Chemical Reaction and Reactor Engineering (1987)
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Ongki PurwantaChemical Reaction and Reactor Engineering (1987)
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CHEMICAL INDUSTRIES
A Series ofReference Books and Text books
Consulting Editor
HEINZ HEINEMANN
Heinz Heinemann, Inc.,
Berkeley, California
Volume I: Fluid Catalytic Cracking with Zeolite Catalysts,
Paul B. Venuto and E. Thomas Habib, Jr.
Volume 2: Ethylene: Keystone to the Petrochemical Industry,
Ludwig Kniel, Olaf Winter, and Karl Stork
Volume 3: The Chemistry and Technology of Petroleum,
James G. Speight
Volume 4: The Desulfurization of Heavy Oils and Residua,
James G. Speight
Volume 5: Catalysis of Organic Reactions,
edited by William R. Moser
Volume 6: Acetylene-Based Chemicals from Coal and Other Natural
Resources, Robert J. Tedeschi
Volume 7: Chemically Resistant Masonry,
Walter Lee Sheppard, Jr.
Volume 8: Compressors and Expanders: Selection and Application
for the Process Industry, Heinz P. Bloch, Joseph A.
Cameron, Frank M. Danowski, Jr., Ralph James, Jr.,
Judson S. Swearingen, and Marilyn E. Weightman
Volume 9: Metering Pumps: Selection and Application,
James P. Poynton
Volume JO: Hydrocarbons from Methanol,
Clarence D. Chang
Volume 11: Foam Flotation: Theory and Applications,
Ann N. Clarke and David J. Wilson
Volume 12: The Chemistry and Technology of Coal,
James G. Speight
Volume 13: Pneumatic and Hydraulic Conveying of Solids,
0. A. Williams
Volume 14: Catalyst Manufacture: Laboratory and Commercial
Preparations, Alvin B. Stiles
Volume 15: Characterization of Heterogeneous Catalysts,
edited by Francis Delannay
Volume 16: BASIC Programs for Chemical Engineering Design,
James H. Weber
Volume 17: Catalyst Poisoning,
L. Louis Hegedus and Robert W. McCabe
Volume 18: Catalysis of Organic Reactions,
edited by John R. Kosak
Volume 19: Adsorption Technology: A Step-by-Step Approach
to Process Evaluation and Application, edited by
Frank L. Slejko
Volume 20: Deactivation and Poisoning of Catalysts,
edited by Jacques Oudar and Henry Wise
Volume 21: Catalysis and Surface Science: Developments in
Chemicals from Methanol, Hydrotreating of
Hydrocarbons, Catalyst Preparation, Monomers
and Polymers, Photocatalysis and Photovoltaics
edited by Heinz Heinemann and Gabor A. Somorjai
Volume 22: Catalysis of Organic Reactions,
edited by Robert L. Augustine
Volume 23: Modern Control Techniques for the Processing Industries,
T. H. Tsai, J. W. Lane, and C S. Lin
Volume 24: Temperature-Programmed Reduction for Solid Materials
Characterization, Alan Jones and Brian McNicol
Volume 25: Catalytic Cracking: Catalysts, Chemistry, and Kinetics,
Bohdan W. Wojciechowski and Avelino Corma
Volume 26: Chemical Reaction and Reactor Engineering, edited
by James J. Carberry and Arvind Varma
Volume 27: Filtration: Principles and Practices, second edition,
edited by Michael J. Matteson and Qyde Orr
Additional Volumes in Preparation
Catalysis and Surface Properties of Liquid Metals and
Alloys, Y oshisada Ogino
Catalyst Deactivation, edited by Eugene E. Petersen
and Alexis T. Bell
Chemical Reaction and
Reactor Engineering
edited by
James J. Carberry / Arvind Varma
Department of Chemical Engineering, University of Notre Dame
Notre Dame, Indiana
Marcel Dekker New York
Library of Congress Cataloging in Publication Data
Chemical reaction and reactor engineering.
(Chemical industries ; 26)
Includes index.
1. Chemical reactors. I. Carberry, James J.
II. Varma, Arvind
TPi57 .C416 1986 660. 2'83 86-19673
ISBN 0-8247-7543-0
COPYRIGHT© 1987 by MARCEL DEKKER, INC. ALL RIGHTS RESERVED
Neither this book nor any part may be reproduced or transmitted in any
form or by any means, electronic or mechanical, including photocopying,
microfilming, and recording, or by any information storage and retrieval
system, without permission in writing from the publisher.
MARCEL DEKKER
270 Madison Avenue, New York, New York 10016
Current printing (last digit):
10 9 8 7 6 5 4 3
Preface
There exist few, if any, Solomons in our midst capable of single- handedly
fashioning a comprehensive treatise embracing the diverse aspects of
chemical reaction and reactor engineering. This topic, by its very
scope and complexity, inevitably demands that each subdiscipline be treated
individually by recognized authorities. Thus the genesis of this volume.
Herein leading authorities set forth their knowing analyses of the many
facets of the general topic. It is hoped that this compilation, while hardly
a textbook or a handbook, will prove to be of value to academic and in-
dustrial practitioners of the art and science of chemical reaction engineer-
ing, a field which, by definition, must embrace the signal complexities of
chemical reaction and reactor systems.
The scope of this treatise is general, hardly universal. New insights
will, in time, emerge. Chemical Reaction and Reactor Engineering presents
an authoritative progress report that will remain germane to the topic and,
we trust, prove to be a substantial inspiration to further progress.
James J. Carberry
Arvind Varma
iii
Contributors
RUTHERFORD ARIS Department of Chemical Engineering and
Materials Science, University of Minnesota, Minneapolis, Minnesota
SERGIO CARRA Dipartimento di Chimica Fisica Applicata, Politecnico di
Milano , Milan , Italy
ALBERTO E. CASSANO Instituto de Desarrollo Tecnol6gico para la
Industria Quimfca-INTEC, Universidad Nacional del Litoral-Consejo
Nacional de Investigaciones Cientiffcas y Tecnicas, Santa Fe, Argentina
MARIA A. CLARIA Instituto de Desarrollo Techn6logico para la Industria
Qufmica-INTEC, Universidad Nacional del Litoral--Consejo Nacional de
Investigaciones Cientiffcas y Tecnicas, Santa Fe, Argentina
ELIANA R. DE BERNARDEZ Instituto de Desarrollo Tecnol6gico para la
Industria Qufmica--INTEC, Universidad Nacional del Litoral-Consejo
Nacional de Investigaciones Cientfficas y Tecnicas, Santa Fe, Argentina
W. NICHOLAS DE LG ASS School of Chemical Engineering, Purdue University,
West Lafayette, Indiana
MORTON M. DENN Department of Chemical Engineering, University of
California, Berkeley, California
L. K. DORAISWAMY National Chemical Laboratory, Pune, India
VICTORIA EDWARDS Department of Chemical Engineering, University of
California, and Materials and Molecular Research Division, Lawrence
Berkeley Laboratory, Berkeley, California
LARRY E. ERICKSON Department of Chemical Engineering, Kansas State
University, Manhattan, Kansas
vi Contributors
GILBERT F. FROMENT Laboratorium Voor Petrochemische Techniek,
Rijksuniversiteit, Gent, Belgium
RAFAEL GALVAN Department of Chemical Engineering and Materials
Science, University of Minnesota, Minneapolis, Minnesota
HANNS P. K. HOFMANN Institut fiir Technische Chemie I (Reaktionstech-
nik), Universitat Erlangen-Niirnberg, Erlangen, Federal Republic of
Germany
B. D. KULKARNI Chemical Engineering Division, National Chemical
Laboratory, Pune, India
ROBERT L. LAURENCE Department of Chemical Engineering, Univer-
sity of Massachusetts, Amherst, Massachusetts
DAN LUSS Department of Chemical Engineering, University of
Houston, Houston, Texas
MICHAEL L. MICHELSEN Instituttet for Kemiteknik, Danmarks
Tekniske Hc:6jskole, Lyngby, Denmark
MASSIMO MORBIDELLI Dipartimento di Chimica Fisica Applicata,
Politecnico di Milano, Milan, Italy
JOHN S. NEWMAN Department of Chemical Engineering, University
of California, and Materials and Molecular Research Division,
Lawerence Berkeley Laboratory, Berkeley, California
PETER N. ROWE Department of Chemical and Biochemical Engineering,
University College London, London, England
YATISH T. SHAH Department of Chemical and Petroleum Engineering,
University of Pittsburgh, Pittsburgh, Pennsylvania
MAN MOHAN SHARMA Department of Chemical Technology, University
of Bombay, Bombay, India
REUEL SHINNAR Department of Chemical Engineering, The City College
of the City University of New York, New York, New York
GREGORY STEPHANOPOULOS* Department of Chemical Engineering,
California Institute of Technology, Pasadena, California
MATTHEW TIRRELL Department of Chemical Engineering and Materials
Science, University of Minnesota, Minneapolis, Minnesota
*Current affiliation: Department of Chemical Engineering, Massachu-
setts Institute of Technology, Cambridge, Massachusetts
Contributors vii
GARY G. TROST* Department of Chemical Engineering, University of Cal-
ifornia, and Lawrence Berkeley Laboratory, Berkeley, California
ARVIND VARMA Department of Chemical Engineering, University of
Notre Dame, Notre Dame, Indiana
JOHN VILLADSEN Instituttet for Kemiteknik, Danmarks Tekniske
H0jskole, Lyngby, Denmark
EDUARDO E. WOLF Department of Chemical Engineering, University of
Notre Dame, Notre Dame, Indiana
JOHN G. YATES Department of Chemical and Biochemical Engineering,
University College London, London, England
*Current affiliation: Raychem Corporation, Menlo Park, California
Contents
Preface iii
Contributors V
1. Numerical Methods in Reaction Engineering 1
John Villadsen and Michael L. Michelsen
2. Use of Residence- and Contact-Time Distributions in
Reactor Design 63
Reuel Shinnar
3. Catalytic Surfaces and Catalyst Characterization Methods 151
W. Nicholas Delgass and Eduardo E. Wolf
4. Diffusion-Reaction Interactions in Catalyst Pellets 239
Dan Luss
5. Gas-Solid Noncatalytic Reactions 293
L. K. Doraiswamy and B. D. Kulkarni
6. Design of Fixed-Bed Gas-Solid Catalytic Reactors 373
Gilbert F. Froment and Hanns P. K. Hofmann
7. Fluidized-Bed Reactors 441
Peter N. Rowe and John G. Yates
i:r
X Contents
8. Coal Gasification Reactors 499
Morton M. Denn and Reuel Shinnar
9. Gas-Liquid Reactors 545
Sergio Carra and Massimo Morbidelli
10. Gas-Liquid-Solid Reactors 667
Yatish T. Shah and Man Mohan Sharma
11. Polymerization Reactors 735
Matthew Tirrell, Rafael Galvan, and Robert L. Laurence
12. Biological Reactors 779
Larry E. Erickson and Gregory Stephanopoulos
13. Analysis and Design of Photoreactors 839
Eliana R. De Bernardez, Mar(a A. Clarici, and
Alberto E. Cassano
14. Electrochemical Reaction Engineering 923
Gary G. Trost, Victoria Edwards, and John Newman
15. Reactor Steady-State Multiplicity and Stability 973
Massimo Morbidelli, Arvind Varma, and Rutherford Aris
Index 1055
Chemical Reaction and
Reactor Engineering
1
Numerical Methods in Reaction
Engineering
JOHN VI LLADSEN and MICHAEL L. MICHELSEN Instituttet for Kemiteknik,
Danmarks Tekniske Hdjskole, Lyngby, Denmark
INTRODUCTION
Mathematical modeling is an integral part of reaction engineering and a
working knowledge of a range of numerical methods is as essential to the
engineer as is a set of keys to a locksmith.
Numerical problems crop up in many forms. Trivial numerical methods
are used almost unconsciously by the professional engineer to solve routine
problems, while much more elaborate methcds-some only recently described
in the literature-are finding applications in the solution of complex re-
search problems or in industrial design problems.
Much of. this chapter deals with numerical methods that were developed
to solve rather difficult problems-most of them relatep. to research in re-
action engineering in our group at Lyngby, but hopefully reminiscent of
problems faced by others. With this in mind, it is befitting to start with
some philosophical remarks that may perhaps appear to contradict the main
body of the text, but which are still important:
1. The large majority of numerical problems in reaction engineering
can be solved by primitive, ad hoc methods if these are used in a
sensible way. Model simplifications frequently point to limiting
solutions that can be computed on a pocket calculator. These limit-
ing solutions may indicate what further insight one may gain into
the problem by a full-scale numerical attack. Also, the limiting
solutions are extremely valuable when it comes to checking the re-
sults of more elaborate calculations.
2. It is a regrettable observation that many numerical techniques are
stretched to the limit of their applicability in order to solve prob-
lems which are physically unrealistic. It is a barren victory to
file a stack of computer output, obtained after endless modifications
of a basic algorithm, when it is discovered that the phenomenon
which was finally tracked down numerically could be neglected al-
together because it exists only for unreasonable parameter values.
1
2 Villadsen and Michelsen
To stress the importance of ad hoc methods, we shall give three exam-
ples which together contain embryonic forms of all the numerical methods
to be treated in the following.
Example 1 The rate of deacylation of a O. 250 M solution of penicillin V
on a commercial immobilized enzyme is given by
2
r = 3.20m [(1 - x) + 1.065(1 - x) ] mol/h ( 1)
C
where x is conversion and me is the amount of immobilized enzyme in kilo-
grams. It is desired to obtain 90% conversion of v = 670 L/h penicillin
solution in two continuous tank reactors, each with me/ 2 kg of enzyme.
The intermediate conversion x 1 and the required catalyst weight are calcu-
lated from
vc:x 1 = 167.5x 1 = 3.20mc/2[(1 - x) + 1.065(1 - x 1) 2]
vc:(0.9 - x) = 167.5(0.9 - x 1 ) = 3.20mc/2[0.1 + 1.065(0.1) 2)
or
( 2)
0.9 0.11065
There are many ways in which Eq. (2) can be solved for x 1 , and some
are definitely better than others. Following are three possibilities:
1. xl = f(x1) = 9.037(0.9 - x1HO - x) + 1.065(1 - x1)] 2 . A value
of x1 is inserted on the right-hand side. x 1 is calculated and re-
inserted on the right-hand side to give a successive substitution
algorithm. 3 2
2. F(x1) = 0 = x1 3. 839x 1 + 4. 688x1 - 1. 745. After reformulation
of Eq. ( 2) into a polynomial expression for xi, one applies a gen-
eral routine to find the zeros of F(x1).
3. The left-hand side of Eq. (2) is plotted against the right-hand side.
For a quick estimate of x1, one would choose method 3. For O < x1 <
0. 9, the left-hand side of Eq. ( 2) increases with increasing x1, while the
right-hand side decreases with increasing x1, A nice intersection (x 1 =
0. 7028, me = 187 kg) is easily obtained.
Algorithm 2 is unwieldy compared to algorithm 3, while algorithm 1 does
not work at all since (df/dx 1)x 1=0. 702 = -6. 48, and a successive approx-
imation algorithm diverges at any point where I df/dx I > 1.
The moral is that even a simple problem may be confounded by the
choice of a poor numerical scheme. It is particularly important to choose
the right numerical formulation when the dimensionality of the problem in-
creases-as will be shown later in many of our examples.
Example 2 Ketene (A) is absorbed in acetone (B), where it reacts-
with H 2so 4 as catalyst-to form isopropenyl acetate by an elementary bi-
molecular reaction. At 37°C the rate constant is k = 0.0128 mol/L•min.
Numerical Methods in Reaction Engineering 3
The reaction is carried out in a flask which initially contains 150 L of pure
acetone (c~ = 13. 62 mol/L). The reactor is equipped with a reflux conden-
ser. For a constant flow of F = ( 7. 5 mol of ketene /min + 7. 5 mol of meth-
ane /min) to the reactor, no ketene can be traced in the outlet stream until
the liquid is saturated with ketene-which indicates that the reflux of
acetone is sufficient to reabsorb all ketene from the outlet stream. The
solubility of ketene in acetone (and in mixtures of acetone, isopropenyl
acetate, and H2SO 4) is taken to be 0.834 mol/L at PA= 0.5 atm and T =
37°C.
It is desired to calculate the time t* until the liquid is saturated with
ketene:
( 3)
0 O
where cA = 0, cB = 13.62 mol/L; and F/V = 7.5/150 = 0.05 mol/L•min.
Elimination of cB yields
F
- - kc
V A ( Co
B
+ C
A
- !'V_t) ( 4)
If no chemical reaction takes place, the liquid is saturated when t = t 1
t 1 = 0.834/(F/V) = 17 min. If the reaction is very fast, saturation is
reached when all acetone is consumed and the isopropenyl acetate is satu-
rated with ketene [e.g., at t 2 = (0.834 + 13.82)/(F/V) = 289 min]. For a
finite k we obtain t1 < t* < tz. 0
For t = 0 the ketene is consumed with a time constant tr = 1/kcB = 5. 7
min; hence the reaction is fairly rapid, and an explicit integration method
(e.g., Euler's method) is numerically stable only when the time step is com-
parable with tr, This could lead to a substantial number of integration
steps. With an implicit integration method a single differential equation can
be integrated in large steps. Consequently, cA(t) is computed such that
f(cA) is small. A much simpler interpretation of the limit lit -+ is the 00
quasi-stationarity principle, by which
( 5)
Inserting cA = 0.834 yields t = t* = 195.4 min (and cB = 4.68 mol/L).
An improvement in this result is obtained by setting d2cA /dt2 = 0 for
t = t*:
0 ( 6)
Inserting CA = 0. 834 at t 195.4 yields an estimate for dcA/dtl t=t*·
ddc: I "' 0.0076 = !'.V - kcA (c; + cA - ; t)
t=t*
4 Villadsen and Michelsen
by Eq. ( 4). Hence t* = 209. 5 min, which is almost the same as the result
t* = 208. 5 min obtained with a fourth-order Runge-Kutta method using
tit = 5 min.
Example 3 A batch reactor contains Mo kilograms of solvent + catalyst.
Reactant A is poured into the reactor at constant speed n1,. /tf (kg/min)
during the time interval [0,tf]. At time = 0, reactant and solvent are at
the temperature T 1 of the surroundings, and natural convection carries the
heat of reaction (-t.H kcal/kg) away. Heat capacity cp (kcal/kg K) and
density p(kg/m3) are independent of T and of conversion 1 - nA/nA =
1 - y. The reaction is first order in A.
It is desired to calculate the reaction temperature T(t) for given values
of the operating parameters Mo, n.A/Mo, T1, and tf,
Mass balance:
for T < 1
(y 0, T = 0) ( 7)
for T;?, 1
Energy balance:
dT
dT
( 8)
3ht/T - T ) 1. 25
0
1 (nA /Mo)b
(T - T 1)
p2/3cpMO[l + (nA/M 0)rn] 1/3
0 0
1 + (nAJM 0)w
where
< <
T = T1 at T = O; a= { ~/T
T
T;;,,
1
1 b ={ ~ T
T;;,,
1
1
The heat transfer coefficient h 'v 5 kcal/m 2 •h •K 1 / 4 and the heat transfer area is
taken to be 3(M/p)2/3; M = Mo(l + n1/Mow). The kinetic parameters k(T1) and
y = E/RT1 and the thermodynamic parameters (-t.H) and Cp have given values.
A crude numerical method (e.g., an explicit Euler method) may be
used to solve the important design problem of finding the maximum permis-
sible Mo (to avoid temperature runaway) for given nA/Mo, tf, and T 1 .
A higher-order method (e.g., an explicit fourth-order Runge-Kutta
method) may give a shorter computation time for the same accuracy, but it
is unnecessary to use an implicit method. The reason is that the structure
of Eqs. (7) and (8) is such that numerical instability of an explicit integra-
tion method is not a problem. When the numerical method becomes unstable,
it is a reflection of the inherent physical instability of the problem: for
Mo larger than a certain critical value, the whole batch will eventually
ignite and T increases to a value close to (-t.H/cp)nA/(nA + M0).
Many problems in reaction engineering can be handled with such crude
tools and it becomes a matter of experience to recognize those situations
where the more elaborate methods to be discussed in the following sections
have to be utilized.
Numerical Methods in Reaction Engineering 5
ELEMENTS OF NUMERICAL WORK
The three introductory examples illustrated ad hoc solutions of two stand-
ard numerical problems:
1. Solution of algebraic equations
2. Solution of coupled first-order differential equations
It is difficult to imagine a simulation job in reaction engineering which can -
not be analyzed in terms of these fundamental numerical problems. As a
preliminary to a more systematic discussion of typical reaction engineering
simulation problems, we shall briefly comment on the techniques that we
recommend for solution of the two problem types.
Solution of Algebraic Equations
Systems of Linear Algebraic Equations
The most efficient technique for solving
Ax = b (9)
=-
is probably Gaussian elimination (with pivotation of rows and perhaps
equilibration before each elimination step) in the particular version where
A is factorized into a lower triangular matrix ~ and an upper triangular
matrix ~-
~= ldl (10)
1 0 0 0 all a12 alN
( 1)
c2 1 0 0 (1) (1)
0 a22 a2N
~= ( 1) ( 2)
1 0
u =
a ( 22) ( 2)
c3 c3 0 0
. .. . .... 33 •· • a 3N
cN
(1) . • • cN(N-1)1 0 0
(N-1)
• aNN
where Q and the subdiagonal elements of b are stored in
elimination constants for the kth elimination step:
~- c.
1
(k)
are the
(k-1)
. .N -
{
aik k = 1, 2, 1
(k)
c. =
1 (k-1) i = k + 1, .N
akk
and Q is the triangular matrix that appears after the N - 1 elimination
steps on matrix ~-
With ~ = Ml ,-the solution of Eq. (10) follows a two-step procedure:
~z = b and subsequently Ux
=-
= z (11)
6 Villadsen and Michelsen
In an iterative or multistep process,
k = 1, 2, . . . , M (12)
with a constant matrix ~, the LU decomposition followed by M applications
of Eq. (11) is preferable to any alternative method [e.g., ~k = ~-l~(~k-l)].
The specific problem
Ax = AX (13)
has a nontrivial solution only when A is one of the N eigenvalues of ,b.
The solution (~,Ai), i = 1, 2, . . . N, is found by diagonalization of A
using ( most efficiently) a QR alogorithm for a general nonsymmetric ~. -
Using only real arithmetic, one arrives at
(14)
If all eigenvalues are real and distinct, ~ = diag {;\i} and ~i is the ith
eigenvector ~i• while the eigenrows ~ rows in y-1. If C\.,A.+l) forms
a complex pair of eigenvalues, fl has a ( 2 x 2) block J J
D
=
= ( a
-b
b)
a
(15)
on the main diagonal in rows j and j + 1 and (Ai, Aj+ 1) = a ± ib. A typical
computer code based on the QR algorithm is discussed in (Villadsen and
Michelsen, 1978).
Nonlinear Systems of Algebraic Equations
In a majority of problems, the multidimensional Newton's method (Newton-
Raphson's method) has been our preferred choice. To solve !:'._(~) = Q_,
the iteration
clF.
1
x = x - _q with J .. = (16)
-k+l -k l] ax.
J ~~k
is carried out until 11 ~k+l - ~k 11 < s.
The elements of the Jacobian matrix ;[ depend on the current value of
x, and in principle ;[ must be reevaluated in each iteration step, although
one may possibly reduce the computational work by taking a few successive
substitution steps ( 12) before updating and refactorizing !!_. Frequently,
the elements of !!_ can be calculated quite simply from Fi-in particular,
this is true when the algebraic equations result from discretization of
boundary value problems with a nonlinear kinetic expression. Here the
nonlinearities are confined to the main diagonal of !!_ and reevaluation of !!_
is trivial (but not, of course, the refactorization of J). -
As with any other algorithm for solution of nonlinear algebraic equations,
Newton's method does not guarantee convergence for all initial guesses ~o,
but in the vicinity of the solution x convergence is very rapid except in
pathological cases where g; has one or more eigenvalues equal to zero at x.
Numerical Methods in Reaction Engineering 7
Calculations on a simplified model are often useful in selecting a proper
~O· When the solution is known for one set of parameters !2.0 close to the
set that is currently being investigated, an excellent ~ 0 is found by means
of the sensitivity of ~ to a variation in !2. at !2. = !2.0· This important
numerical approach is discussed later in this section.
In large problems it may be advantageous to expend considerable
effort in selecting an optimal structuring of the equations before a solu-
tion is attempted. Considerations concerning partitioning of the equations
are given below.
Solution of Coupled Ordinary Differential Equations
First-Order Differential Equations with Constant Coefficients
Together with Eqs. ( 9) and ( 13), the following problem is a key element
in many numerical calculations.
(17)
Factorizing A as in Eq. ( 14) leads to
dy -1
dt = :k1~:k1 y + b
or
dz
-1
dt = ~~ + ~1 with ~(t = O) = 1T y0 ( 18)
where ~ = !J- 1y and ~l = !}-lb. Hence the components of z are found by
solution of either
dz.
dt
l
= A.Z.
l l + bli (19)
or
(_: c1· )
z.
d
=
l
( 20)
dt zi+l :)( ::+J + bl:+l
The solution of the individual problems ( 19) and ( 20) is trivial and the
final solution of Eq. (17) is
( 21)
For a nonsingular ~, one obtains the explicit form
where fl is diagonal except for the ( 2 x 2) blocks ( 15):
8 Villadsen and Michelsen
Sl.. = exp(\.t) ( 22a)
11 1
or
( Sl.. ) = ( co_s bt sin bt) ( 22b)
11 -sm bt cos bt exp(at)
and .9.. is the solution of ~.9 = e_.
Runge-Kutta (or "Single-Step 11 ) Methods
To integrate the set of N autonomous nonlinear first-order equations
( 23)
one step forward from 41 to Li+ 1 with ll t = h, the algorithm ( 24)- ( 25) is
used:
M
l.n+ 1 = l.n + l: Ri~i ( 24)
i=l
~i = h!'_ (l.n +
j=l
~ ( 25)
When bij = 0 for j > i - 1, the method is explicit and the M Runge- Kutta
constants ~i are found one by one, starting with i = 1. In the explicit
Euler method (M = 1), R 1 = 1 and b11 = 0. The fourth-order Runge-
Kutta-Gill method,
0 0 0 0
½ 0 0 0
Q =
½(/2 - 1) ½(2 - V2) 0 0
0 -½12 ½(2 + /2) 0
( 26)
R =
1
il, 2 - 12, 2 + 12, 1)
has better round-off properties than the slightly simpler "classical" Runge-
Kutta method, where the elements of £ are zero except for
b. l . = ( ½, ½, 1) i = 1, 2, 3
1+ ,1
( 27)
1
~ = i l , 2, 2, 1)
If the N right-hand sides depend on t, one extra equation,
dyN+l ( 28)
= 1 Y = t
dt N+l,n n
Numerical Methods in Reaction Engineering 9
is added to the N original equations to give a set of N + 1 autonomous
equations of the form ( 23).
In a truly implicit method all elements in Q can in principle be nonzero.
Here the determination of ~.i, i = 1, 2, • • . ;- M, requires simultaneous
solution of (N x M) nonlinear algebraic equations, an exasperating compu-
tation within each integration step which should be avoided except when
required by the structure of the problem (even though the order of the
implicit method may be as high as 2M).
An implicit integration is necessary when at Yn the Jacobian i of !_
has a set of widely separated, negative eigenvalues. The existence of
positive eigenvalues (or eigenvalues with positive real part) indicates that
the system is physically unstable, and the numerical solution diverges in
response to this inherent instability. When all "i have real negative parts the
numerical solution should converge to some finite value, but this does not
happen for explicit methods unless h is smaller than some constant multi-
plied by I "NI -1, where "N is the eigenvalue of largest modulus. The
natural time scale of the problem is, however, given by I ;i.. 1 1 -1, where
"l is the eigenvalue of the smallest modulus. Thus
h < cl I "NI -1 to avoid numerical instability
( 29)
nh > c 2 I A1 1 - 1 to reach the required integration time
c 1 is 2 for the explicit Euler method and 2. 83 . • • for the explicit fourth-
order Runge-Kutta method.
With eigenvalues spanning many orders of magnitude, the computation
time of an explicit method becomes intolerably large, and this is where
implicit methods should be used since these can be made numerically stable
for any h.
Typical applications of implicit methods are:
1. Integration of kinetic equations for radical reactions
2. Integration of a discretized version of a parabolic partial differen-
tial equation (e.g., for transient diffusion/reaction problems with
nonlinear kinetics).
3. Differential equations coupled with algebraic equations.
The following approximation does, however, give an implicit method that
works almost as an explicit method.
Consider a method where the bij in Eq. ( 25) are zero for j > i (i.e. ,
where the equation for ~i involves ~j, j = 1, 2, . . • , i) . Rather than
solving Eq. (25) by Newton iteration, one expands
i i
!. <!) = f ( Xn + L from z
-0
= y
-n
+ I: b ..k.
11-1
j=l j=l
which results in
f(z
- -0
)+a(: 1y )z.i-1k. ( 30)
10 Villadsen and Michelsen
or
(l - ah~)~ 1. = h!_ (¥...n + ~l b ..k.) ( 31)
j=l 11-1
The constant a is determined such that the method integrates f(y) = AY
correctly for A + - 00 , while the remaining constants in Eqs. ( 31) and
( 24) are fixed by the requirement that a certain order of truncation error
should be obtained. Details on the fitting of Runge-Kutta constants in
general are given in, for example, Gear ( 1971).
The point is that Eqs. (31) and (24) work like an implicit method, but
compared to an explicit method, the only additional work is a factorization
of the matrix Cl - ahJ) at the beginning of each integration step followed
by a number o:fback-substitution steps (12) (this is, of course, not a
trivial complication, but it is still much simpler than solution of N x M non-
linear equations in each step).
Our preferred choice of a semi-implicit method [the nomenclature used
for an algorithm of the type ( 31) and ( 24)] was first derived by Caillaud
and Padmanabhan (1971). It is a third-order method [M = 3, integration
error from t = 0 to tfinal "-' O(h3)] , and instead of the last function evalua-
tion in Eq. ( 31) , one takes ~ 3 to be a linear combination of ~ 1 and ~ 2 ·
Thus the method is defined as follows:
( 32)
( 33)
( 34)
3
t
¥...n+l = ¥...n + '"" R.k.
1-1
+ 0 (h 4) ( 35)
Values for b2, b 31 , b32, R 1 , R 2 , R 3 , and a are given in (Villadsen and
Michelsen, 1978, p. 320 and the computer code STIFF3 on p. 322).
A semi-implicit method is equally suitable for solving N 1 differential
equations coupled to N 2 algebraic equations:
( 36)
¥... 2 ( with dimension N 2)] .
¥_ = [r 1 ( with dimension N 1 ), Equation ( 36)
can be interpreted as a limiting case of
for s + 0
Numerical Methods in Reaction Engineering 11
Let { be the Jacobian of ~ at ~n• let ~ = q - ahp, and define !_3* as
B multiplied by a diagonal matrix:
l - ahf -ahf
=yl =y2
e:+O
~* =~ diag (1, 1, ... , 1, E:, e:, ••• 'e:)
-ahg -ahg
Nl N2 -yl =Y
2
where f is 'iH/ay 1 , g is 3rY/3y_ 1 , and so on. When the device is
-Y1 - - -yl .!2.
applied to the semi-implicit Runge-Kutta method [Eqs. (32) to (34)], it is
seen that multiplication by e: from both sides of Eqs. ( 32) and ( 33):
( 37)
while
b 32-2,:i
k 1)
In Eq. (37) ~l,y and ~ 2 ,y are the first N 1 components of ~l and ~ 2 ,
respectively. -1 -1
· Any semi-implicit (or implicit) Runge-Kutta method, and the implicit
versions of multistep methods to be discussed below (Gear, 1971, p. 226),
can be extended to solve a set of N 1 differential equations and N 2 alge-
braic equations. It is advantageous to treat the algebraic equations and
the differential equations in the same manner, since all components of the
solution vector ~ are found with the same, specified accuracy.
The STIFF3 algorithm based on Eqs. (32) to (35) (Villadsen and
Michelsen, 1978, pp. 316-322), and the STIFFALG algorithm (Michelsen
and Villadsen, 1981) with a slight modification [Eqs. (36)-(37)], control
the step length h by integrating the differential equations twice in every
integration interval. First the step length h is used to get Yn+l(h) and
the next two steps h/2 are taken to obtain Yn+1(h/2). The difference be-
tween the two estimates~= ~n+l(h/2) - ~~+ 1 Ch) is first used to check
the accuracy by comparing ~ with ff, the tolerance for the ith component
of y. If the step length h is accepted, a suitable value for h in the next
step is predicted, and by extrapolation of ~n+1Ch/2) to ~il+l = ~n+l(h/2) +
e/7, one obtains a result Yri+l with single-step accuracy 'v0(h5). A step-
size selection strategy can-also be based on integration from tn to tn+l,
first with a formula of order M and next with a formula of order M - 1.
This is the method used in the IMSL subroutine DVERK and in the ver-
sions of Gear's method that are discussed briefly below.
Multivalue ( or Multistep) Methods
For k = 1, 2, . . . , N, let the kth component of y and of f(y) be given
at M previous values oft: tn, tn-1• . . . , tn-i• .-. ., 1n-M-:;:;: These
values are ordered in vector -n,
v k with 2M components:
12 Villadsen and Michelsen
Using Eq. (38), where the elements of the (2M x 2M) matrix ~ are known
for any particular multistep method, one may update ~n ,k to ~n+l,k:
v == Bv ( 38)
-n+l,k ==-n,k
The N vectors Vn+l,k are arranged in an (N x 2M) matrix Yn+l'
Take the first and the (M + 1) column ~1 and ~M+l of ¥n+l and
compute the residual Q_ of the N differential equations:
(39)
Correct ¥n+l by means of the vector product of G and the constant vec-
tor c:
Vn+l
__ :== V ( 40)
== n+l + --
Ge
Reevaluate Eq. (39), and iterate between Eqs. (39) and (40) until II GIi <
e:, or solve G == 0 by a Newton method (which is the safer approach).
This is in principle the multistep method described by Gear ( 1971, p.
102, 215). There are explicit and implicit versions, and they are incor-
porated into very popular integration packages by Gear and by Hindmarsh
[GEAR, GEARB for a band structure of the Jacobian of f, and GEARIB , a
strictly implicit method that can also be used to solve ~(y)f 1) == f(y),
at least when ~ is a slowly varying function of y]. Byrne ( 1981) -reviews
several commercial packages based on multistep :integration of the differ-
ential equations. It is our experience that STIFF3 and the implicit GEAR
packages work equally well on many different problems. This is also the
conclusion of Finlayson ( 1980, p. 54).
Sensitivity Functions
We shall introduce the sensitivity functions and point to their application
in parametric studies to solve three major problems: algebraic equations,
initial value problems, and boundary value problems.
First consider a set of N algebraic equations that contain M parameters
r<~.:e> == 2. ( 41)
The solution ~O of Eq. (41) is known for :e_ = :e._ 0 , and we desire to
compute the variation of the solution x - ~O as a function of :e -
:e._ 0 .
Now, with the constraint ( 41),
-aF I aFI
dF = 0
ax- -dx +
ai n==p
( 42)
-x==x
-0 "- -0
Numerical Methods in Reaction Engineering 13
-
/:). X = X
-
- X
-0
~ ( -J)
= X
-1 a~
-
clp
I (p -
-
p )
-0
(43)
-o - Eo
where !! is the Jacobian of ~ evaluated at (~ o •E 0) and is available when a
Newton- method has been used to solve Eq. (41) with E. = E.o· Consequently,
as long as sI is reasonably well conditioned, one obtains an excellent start-
ing value !£-for solution of Eq. ( 41) at E. by
!£ = !£o + b,.x where i l:).x = - a;
clF
<:e - 12. 0) ( 44)
Next, let x_ be the N-dimensional solution of the initial value problem
ctr
dt = !:_(:r,;e) x_<t = O) = X.o<:e>' E. = E.o ( 45)
Assume that the variation of x_ with respect to the parameters J2. is de-
sired-the essential problem in parameter estimation. The sensitivity
functions !k(t), k = 1, 2, • • • , M, are calculated as the solution of M
sets of N coupled differential equations.
( 46)
with !k(t = 0) = d:ro/dpk.
The differential equations for the sensitivities are all linear in the de-
pendent variable !k· If Eq. (45) is solved for J2. = E.o from ~ to ~+l
by an implicit method, the Jacobian of !:_ is available at tn+l when X,n+l
has been determined with the required accuracy. Subsequent solution of
the M sets of sensitivity equations ( 46) now follows from Eqs. ( 19) and
( 20) by relatively trivial operations. Only one diagonalization ( 14) is
necessary since the coefficient matrix is the same for all M sets of equa-
tions, while the constant vector b in Eq. (17) depends on Pk• The im-
plicit version of Gear's method has proved to be well suited for this type
of calculation if the Jacobian is computed with sufficient accuracy. Other
implicit methods (e.g., collocation) are also suitable. A semi-implicit
Runge-Kutta method is less satisfactory, for the following reasons. One
may integrate Eq. ( 45) from t = 0 to tfinal with a fixed E.o and thereafter
solve the M sets of equations in ( 46) from t = 0 to tfinal. This would re-
quire storage of a vast amount of data, and no step-length control is pos-
sible since the sequence of t values is fixed by the solution of Eq. ( 45).
On the other hand, one may simultaneously integrate Eq. (45) and
dz g(y,p,z)
=f+fz= (47)
dt p y
where fp is a short notation for a_! /cl E and fy a short notation for ~-
This would, however, require that f and f be calculated to form the
PY YY
14 Villadsen and Michelsen
Jacobian for the N(M + 1) systems of equations, and this is hardly attrac-
tive compared to an implicit solution of Eq. ( 45), followed by solution of
Eq. ( 46) with the correct fy and f at l.n+l •
The application of sensitivity ?unctions in the solution of boundary
value problems is also very important. One may consider a typical situa-
tion where it is desired to solve Eq. ( 48) by an initial value technique:
d2 ( 1)
~ = f(x,y,y ) (48)
dx
a dy + y = a
1 dx
at x = 0 and a dy + y
2 dx
=b at x =1
To integrate Eq. ( 48) as an initial value problem, the initial element
(y, dy/dx) at x = 0 is required. Let the estimated value of Yx=0 be YO•
Then the boundary condition at x = 0 yields (dy/dx)x=O = (lfo1)(a - yo),
and the integration can be performed resulting in (y,dy/dx) at x = 1.
The value of YO must be chosen such that the second boundary condi-
tion is satisfied:
b*(y )
0
2 (a2 ~
dx
+ y)
x=l
= b
The correct value of Yo is determined iteratively (e.g., by Newton itera-
tion). Differentiation of Eq. ( 48) with respect to Yo yields the following
differential equation for z = '<Jy/'<Jyo:
d 2z af af dz
2
= ay z + -(1) dx <49 )
dx ay
with (z = 1, dz/dx = -lfo1 ) at x = 0.
Equation ( 49) is integrated simultaneously with Eq. ( 48). The desired
derivative is
and a corrected estimate of Yo is found from
(b* - b)
y 0 : = y 0 - db*/ dy (50)
0
The method is easily extended to a case with an N-component solution
vector y and N guessed initial values at x = 0. Also, one might find the
sensitivity of y to a parameter p which appears in the differential equation
and determine p
to satisfy given side conditions at x = 0 and x = 1.
Several applications will be shown in the following.
Numerical Methods in Reaction Engineering 15
Partitioning of Large Problems
A large problem should very rarely be attacked numerically before a care-
ful analysis of its structure has shown the following:
1. That the problem is well posed
2. That the proposed numerical method is applied to a reai:,onable
formulation of the model
A number of algorithms exist for testing the consistency of the model-
no missing equations or no duplication of equations-and these automatic
procedures are definitely helpful, since the models can rapidly become too
large and obscure to make a manual check safe enough. An algorithm by
S<.6rensen ( 1982) specifically treats reacting systems. He divides the key
reactant species (those that cannot be obtained from stoichiometric balances)
into four groups:
1. Mobile species: When set up in a stationary coordinate system
the mass balances must include convective or diffusive outflow
of these species from the volume element.
2. Immobile species: The net outflow of these species from the
stationary volume element is neglected.
3, 4. In either group one may find species given by either equilibria
or by kinetic equations with finite time constants.
S<.6rensen's algorithm makes a systematic search of any reaction model
posed in these very general terms and checks it for consistency, ending
up with some minimum set of key species, which is, however, not neces-
sarily the set that is best suited for the numerical solution of the model.
Concerning optimal formulation of the numerical solution scheme, it
may sometimes be advantageous to divide the model into blocks which are
solved in a nested fashion. Let f(~) = 0 be partitioned into two sets of
equations:
!_(~1' ~2) = O
( 51)
g_(~l' ~2) = O
where the dimension of !_ and of ~l is N 1 and the dimension of ~ 2 and of
~is N 2 . For a set of linear equations
Ax +Ax +a=O
=1-1 =2-2 - ( 52)
Bx +Bx +b-O
=1-1 =2-2 -
partitioning leads to the explicit solution
-1 -1
{~1 - i2~2 ~1 }~1 = i2~2 ~ - a
-1 ( 53)
~2 = ~2 (-~l~l ~)
16 Villadsen and Michelsen
which compared to the straightforward procedure [Eqs. (10) and (11)],
is advantageous only when the matrix ( !1 :2) has a pronounced banded
structure in ~l or ~ 2 . 1 2
An algoritl'im for nested iterative solution of a set of nonlinear equa-
tions ( 51) may work in the following way. First g_(:! 1 ,:! 2) = O is solved
for a fixed :!l:
:!2 := :!2 - g_ (54)
Next, the sensitivity of the solution :! 2 is calculated:
( 55)
The matrix gx is available when the iteration ( 54) has converged, and
=-2
the (N 2 x Ni) matrix (cl:! 2 /a:!l)g=O is found by N 1 applications of the
back substitution procedure ( 12). - -
In the third step the outer iteration !_ = Q_ is performed once:
( cl!_-)
clx
fix =-f
-1 -
( 56)
-1 g=Q
or by the chain rule for differentiation,
{(acl;lt
-2
+ (acl;Jx
-1
G::) } .s:.=Q
fix = -f
(57)
Now Eq. (54) is repeated with the new :!l and the nested iteration ends
by a final correction of :! 2 :
!-2 := !-2 + (::2) fixl ( 58)
-1 _g_=Q
to get the same accuracy of !.i and !_ 2 ,
Having obtained the solution <!i,! 2), one may determine its sensitivity
with respect to a set of parameters E. which appear in !_ and .[, First,
the sensitivity is found by solution of Eq. (59) with (cl!.fcl!i)g=O given in
Eqs. (56) and (57): - -
(:J,t,C!t~=~ = -G!t =
(59)
{( cl!_) ( cl!_ ) (cl:!2 \ (
cl E_ X X
-1'-2
+ cl ~ 2
X
cl E_ / =0
fr -
J
-1
Numerical Methods in Reaction Engineering 17
where (a! 2 laE)g=Q is the solution of
(60)
Finally, the sensitivity of !. 2 is calculated from
( 61)
The treatment of a set of N equations by nested iteration is in prin-
ciple not different from what has already been shown [see Eqs. (41) to
( 44)] • The method is, however, less stringently defined than a straight-
forward approach [should Eq. (54) be solved until convergence has been
reached, as suggested by S0rensen (1982, Chap. 4), or should one itera-
tion in the inner loop be followed by one iteration in the outer loop?], and
it may be questioned whether an individual treatment of each problem is
advantageous on the most modern computing machinery (e.g. , a vector
processor) .
Certain problems in reactor simulation do, however, appear to lend
themselves quite naturally to solution in a nested fashion:
1. Some variables appear locally and the structure of the problem is
somewhat like
. ,x.,.
-1
( 62)
k = 2, 3, • • • , M ( 63)
This could typically be a combination of fluid balances (0 and
pellet balances (_g-_) which may be solved individually as M - 1
inner-loop problems for given values of the outer-loop variables
!.l. A sequence of reactors where the inlet conditions to reactor
k + 1 form the only tie between reactor k and reactor k + 1 is
another example that greatly resembles the catalyst pellet-fluid
phase problem. Here the concept of "tearing" is, however, com-
monly recognized as a useful tool.
2. Frequently, modifications of a well-established program system can
be made via nested iterations. A reactor simulation package can
easily be modified to include diffusion restriction in catalyst pellets
through addition of another well-tested program for effectiveness
factor calculation.
The choice of !_ and _g_ can only be made for the individual problem, and
considerable effort may have to be spent in selecting the best partitioning
of the system. If numerical difficulties can be associated with the solution
of a small set of equations, these might be selected as _g_, especially if the
outer-loop variables !.1 are relatively insensitive to variations in !. 2 ; but
a general rule of thumb cannot be given.
18 Villadsen and Michelsen
SIMULATION OF REACTION ENGINEERING MODELS
A number of fundamental numerical techniques were presented in the pre-
ceding section. We consider next some standard numerical problems which
occur specifically in reaction engineering: boundary value problems (ex-
emplified by "catalyst pellet" problems), parabolic partial differential equa-
tions ("the steady-state fixed-bed reactor"), and hyperbolic equations
with a dispersive element ("moving-front problems," exemplified by
"transient fixed-bed reactor models").
Having presented our views on the proper numerical treatment of these
simulation problems, in the final section of the chapter we discuss how
parameters can be fitted to standard reaction engineering models.
Boundary Value Problems
The archetypal boundary value problem in reaction engineering is given
by the simultaneous mass and heat balances for reaction and diffusion on
catalyst pellets. With a very simplified model for the diffusion fluxes [see
Jackson (1977) for a detailed discussion of realistic physical models], one
obtains.
i = 1, 2, • • . , M ( 64)
( 65)
where
v2 = x-s ! (xs :x) s = 0, 1, or 2 in three standard pellet
geometries
dyi
dx + BiM ,l. ( y.l - Yb ,l. ) = 0 at X = 1 (66)
at X = 1 (67)
0 and y. are finite at x = 0 ( 68)
l
where
Yb,i = fluid-phase concentration relative to a reference concentration
Cr, which may be the inlet concentration of a specific react-
ing species
Yi = pellet-phase concentration of species i relative to cr
(0b,0) = temperatures relative to a reference temperature Tr
The M mass balances ( 64) correspond to the M independent reactions
in M key species. The rate terms are also functions of non-key species
(k = M + 1, . . . , Mmax>. The concentrations of these species (Ck, k =
M + 1, . . . , Mmax> can be expressed in terms of their fluid-phase values
Numerical Methods in Reaction Engineering 19
and the pellet concentrations of key species. Similarly, the energy
balance can be eliminated (i.e. , 0 is expressed in terms of 0 b and Yk,
k = 1, 2, • • • , M).
Consequently, the fully reduced pellet model contains only the M mass
balances ( 64) expressed as M nonlinear coupled boundary value problems
in Yi (i = 1, 2, . . . , M), Yb i (i = 1, 2, . . . , Mmax), and 0b, They
are solved with the linear boundary conditions ( 66), i = 1, 2,. . . , M,
and the condition that the Yi are finite at x = 0.
The pellet model is thoroughly discussed in Aris (1975) and elsewhere
in this book and hardly needs further explanation.
<I\ = Thiele modulus for ith mass balance
1\ = adiabatic temperature rise for reaction i
D.L kL
= ...2_12_ and = __£_
BiM. BiH
,1 hM.
,1 pcphH
Collocation was originally introduced to handle simple versions of Eqs.
( 64)- ( 68) (Villadsen and Stewart, 1967). Since then orthogonal collocation
has been proved to handle many boundary value problems-especially those
occurring in reaction engineering-in a very efficient way. The reader is
referred to Villadsen (1970), Finlayson (1972, 1974, 1980), Villadsen and
Michelsen ( 1978), Michelsen and Villadsen ( 1981), and S<hrensen ( 1982) for
detailed discussions of the method. The paper by Michelsen and Villadsen
( 1981) firmly establishes polynominal orthogonal collocation as a close rela-
tive of Galerkin's method.
Basically, what (polynomial) collocation does is to interpolate each
concentration profile Yi (x) by a polynomial with N interior interpolation
points [ defined as the collocation points, and chosen as zeros of certain
Jacobi polynomials PN(a, 13) (x) which are given through a choice of a, 13,
and NJ and one or two extra interpolation points, at x = 1 [to include the
boundary condition ( 66)] and possibly at x = 0 (if the symmetry of the
problem is not used to eliminate the boundary condition at x = 0).
When Yi (x) has been approximated by an Nth-degree polynomial (in x
or in u = x2), the derivatives can be written exactly as linear combinations
of the N unknown interpolation ordinates and the boundary ordinate(s).
After discretizing Eq. ( 64) by inserting these linear combinations of ordi-
nates for the derivatives at each interior interpolation point and equating
Eq. (64) to zero at xi (or ui), i = 1, 2, . . . , N, the original set of M
boundary value problems is converted into N x M algebraic equations in
Yi,j (i = 1, 2, . . . , M; j = 1, 2, . . . , N). The structure of the equa-
tions is dense along the main diagonal (blocks of N x N full matrices) and
sparse elsewhere (see Villadsen and Michelsen, 1978, Chap. 8) and may
be suitable for solution by partitioning.
For a problem in one of the three standard pellet geometries (u = x2)
and a single mass balance, one obtains
dy} ( 69)
du
20 Villadsen and Michelsen
where s = 0 (planar), s = 1 (cylinder), and s = 2 (spherical) geometry.
At collocation point j, j = 1, 2, . . . , N:
x_=(yi, Y2, . • . 'YN+l =y(u = 1))
I _
" 2y u-u. = 4 { u.B
J-J
T
. + -s +2- 1 -J
A.T} v
,t_
c.T ,t_
= -J v ( 70)
J
where Bji and Aji are coefficients to Yi in the linear combinations of ordi-
nates that are used to express the second and first derivative of the inter-
polation polynomial for y(u) at collocation point j.
The final result is the set of N algebraic equations
N
2
C:l:y. cp R(y.) + b. = 0 = 1, 2, N
Jl l J J '
1
Cj ,N+lAN+l,i Cj ,N+lBiMyb
C:I: = c.. d
b, =
2d
( 71)
Jl Jl J
B'lM
d = AN+l,N+l + -2-
Equation ( 71) is particularly well suited for solution by Newton's method
since the nonlinearities appear only in the main diagonal of the Jacobian,
while the remaining elements are constants = C~.
When the catalyst pellet model is solved as part of a fixed-bed reactor
simulation, all that is needed is the flux of reactant at the pellet surface
or equivalently the average rate of reaction on the pellet:
n = pellet effectiveness factor = ( 72)
where R(yb) is the rate taken at bulk-phase conditions.
The appendixes of Villadsen and Michelsen (1978) contain a well-tested
(nonproprietary) package of subroutines that can be arranged to solve
pellet simulation problems as exemplified by Eqs. ( 69) to ( 72). Other
programs are published in Finlayson (1980). In general, these programs
can be expected to work well as long as the pellet profile y(u) can be
reasonably well approximated by a polynomial. A severe diffusion resistance
(i.e., the case where most of the pellet is inactive) is perhaps better
solved using other methods (e.g., asymptotic methods), but collocation
variants that treat these situations have also been developed. Some com-
ments on these methods are given below.
Spline collocation [or "collocation on finite elements" in the nomenclature
of Finlayson ( 1980)] combines the property of finite-difference methods to
represent a rapidly varying function by a series of connected curve seg-
ments with the accurate approximation of the function within each interval
by interpolation based on orthogonal polynomials.
Numerical Methods in Reaction Engineering 21
The interval 0 ~ x ~ 1 is divided into subintervals. Collocation is
applied to each subinterval and the M - 1 spline point ordinates are de-
termined by extra equations that impose continuity of the first derivative
of y(x) at each spline point. With Nk collocation points in the interval of
length ok to the left of spline point k and Nk+l collocation points in the
interval of length ok+l to the right of spline point k, one obtains
1 N
k (k) (k) 1
-r-(1:AN +lli+AN +lN +lYs =-o-
) (NLk+l Ali(k+l) yi+Al(k+l) )
1 Ys <73 )
k 1 k ' k ' k k+1 2 ' '
where Ys is the spline point ordinate and ~ (k) and !!- (k+l) are discretiza-
tion matrices for the first derivative to the left and to the right of the
spline point respectively.
The collocation equations are written up for each subinterval and the
final collocation procedure with N = N 1 + N 2 + • • • + NM-1 + NM colloca-
tion points becomes a set of N + M - 1 algebraic equations with a pronounced
diagonal block structure. The diagonal elements of Q* and of ~ are
usually larger than the other elements, which means -that the spline point
equations may retain their position, and factorization of the coefficient
matrix can be done block by block, with a resulting reduction of computa-
tional effort .
Quite often, one spline point may be enough to represent an outer
pellet region with rapid reaction followed by an inner, almost inactive re-
gion. In recent publications these "penetration front" problems have
frequently been solved by one-point spline collocation (typical examples
are transient gas-solid reactions where the gaseous reactant is used up in
an outer core of the pellet until the solid reactant concentration has de-
creased appreciably).
The original idea derives from Patterson and Cresswell (1971), who
proposed to equate y and the derivative of y to zero at the spline point
Us (or Xs) and determine the spline point position and the effectiveness
factor by collocation in the outer interval. An improvement was suggested
in Villadsen and Michelsen ( 1978, Chap. 7). Here only the derivative of
y was equated to zero at xs, while the position of xs was chosen somewhat
arbitrarily (e.g., by solution of a linearized problem). For a first-order
irreversible, exothermic reaction on spheres, one obtains
sinh A x
y 1 (x) = - - - -r - where "r -- cpexp [ 2( 1yS
+ S) ] (74)
xsinh A x
r
if the linearization of R(y) is made at y = 0, which is quite reasonable
when the major part of the catalyst pellet is inactive. The spline point
may be chosen as the x value where y 1 (x) = 0. 05yb, and collocation with
N = 5 - 6 in the interval (xs, 1) usually gives an excellent value for the
true flux at the pellet surface, at least if the solution y(x) in the truncated
interval satisfies y(xs) < 0. 05yb.
If the original interval is split up into only two parts with Na collocation
points to the left of xs and Nb collocation points to the right of Xs, it is not
difficult to express Ys is terms of the N = Na + Nb collocation ordinates
and y (x = 1). Explicit formulas are given in Holk-Nielsen and Villadsen
22 Villadsen and Michelsen
( 19.83) and their final method is indistinguishable from a global collocation
solution of order Na + Nb.
Hyperbolic collocation is another variant of collocation, which is specific-
ally developed to treat the wedge-shaped profiles associated with near-
asymptotic behavior of the pellet model. This method was originally pro-
posed by Guertin et al. (1977) for one-dimensional homogeneous reactor
problems when these are solved by collocation, applied to the total reactor
length. The method is fully developed and explained in Sibrensen and
Stewart (1982) and Sibrensen (1982).
The rate expression for M key species may be expanded from a refer-
ence state YR [as exemplified in Eq. ( 7 4)] :
clR
B:_(y) = B:_(yR) + cl~ I (y - yR) ( 75)
YR
This gives a linearized version of Eq. ( 64):
(76)
which may be solved by standard methods, analogously to Eqs. ( 17) to
( 22), as a linear combination of sinh( ArX) /x (for spherical geometry and
Ar distinct and nonzero). The eigenvalues of i!:, are /\; and Ar = I i\r I are
used to construct the approximation functions.
If there are many independent reactions, the Ar may give a sufficient
number of approximation functions sinh( ArX) /x to provide an accurate ap-
proximation for y. If the number of independent reactions is small (there
may be only one reaction) , the hyperbolic approximation functions are
augmented by new functions which appear by differentiation of the original
set with respec_t to Ar· For typical pellet problems, Sibrensen ( 1982) sug-
gests ( 1 - x2)J, j = 1, 2, . . . , as multipliers in the higher approxima-
tion functions. When Ar ~ 0. 5, the hyperbolic functions are easily repre-
sented by low-order polynomials, and hyperbolic collocation merges into
the better known polynomial collocation method; but clearly the method is
a valuable generalization of the original collocation method, since the ap-
proximate solution is based on the structure of the individual problem,
rather than on a fixed set of approximation functions.
S0rensen and Stewart ( 1982) and Sibrensen ( 1982) illustrate the applica-
tion of hyperbolic collocation on some very complicated problems, and the
literature contains numerous examples of the application of high-order poly-
nomial collocation. Consequently, we shall be content with two illustrations.
In the first illustration the one-point collocation method is discussed as a
valuable link between heterogeneous models and homogeneous models for
reactors (e.g., a stirred-tank approximation for a pellet). In the second
illustration collocation is applied to solve the pellet equations in a fixed-bed
reactor model.
Numerical Methods in Reaction Engineering 23
Example 4 One-Point collocation Consider a first-order exothermic
reaction on catalyst pellets, and let the pellet model ( 64) to ( 68) be ap-
proximated by one interior interpolation point at ( u 1, Y1):
(77)
where
0 1 + 13y 1 =constant= 0(1) + 13y(l) (78)
2 d (y)
du 0 u=l
= (-qy + qy(l)) = (BiM(l - y(l)))
-q0\ + q0(1) BiH ( 1 - 0 ( 1))
( 79)
where q = 2/( 1 - u 1 )
Equations ( 78) and ( 79) with Yb = 0b = 1 are used to express 01 and
0 (1), y(l) in terms of Y1=
0(1) = (80)
(81)
Now the collocation equation (77) is simplified to
-Cl(l - yl) = (¢*)2yl exp[yl3* 1 + :*-(;1_ Y1)] =
(82)
(¢*)2R*(y )
1
13* = 13
1 + q/BiH
1 + q/BiM
and ¢* = (1 + ~)
B1M
1/2
cp (83)
Finally,
n = fO1 ~
R(yb)
dxs+l = f01 y exp [y(l - -0~)] dxs+l
( 84)
The left half of Table 1 shows the values of the collocation constants
(u 1 ,-c 1 ) which are needed to construct a one-point collocation solution of
Eq. (77) . u 1 1s· t h e zero of P (Oi(s-1)/ 2)( u ) , wh ere s 1s
' th e geome t ry
1
factor.
24 Villadsen and Michelsen
TABLE 1 Parameters for One-Point Collocation
BiH' B~ finite BiH' BiM -+ 00
s ul -Cl q ul -Cl wl w2
0 1/3 3 3 1/5 5/2 5/6 1/6
1 1/2 8 4 1/3 6 3/4 1/4
2 3/5 15 5 3/7 21/2 7/10 3/10
In the specific case BiH = BiM -+ 00 , the zero of P 1 (l,(s-l)/ 2)(u) is
preferred and n is approximated by a more accurate two-point quadrature
formula:
R(y1)
n = wl R(yb) + w2 (85)
Constants for this specific situation (from Villadsen and Michelsen, 1978,
Chap. 5) are shown on the right-hand side of Table 1.
Equation (82) is an approximate solution of the general catalyst pellet
problem. There is only one unknown (y1), and the form of the equation
is the same as one would obtain from a stirred-tank reactor model. A
graphical or algebraic solution can be found for any value of the param-
eters, but the solution is reasonable only when y(u) can be represented
by a fairly low order polynomial. Note in Eq. ( 83) that the original S
[= cr(-LiH)D/kT rl is modified by a factor that can be very large when
BiH is small. Typical values of BiH and BiM in a fixed-bed reactor are 2
and 40, respectively (an industrial SO2 converter) and with spherical
catalyst particles, Eq. ( 83) predicts amplification by a factor 3. 11.
The application of Eq. (82) will be illustrated by two numerical exam-
ples. First consider the trivial case of a first-order isothermal reaction
with BiH = BiM -+ 00 on spherical pellets. The collocation equation has the
explicit solution
21 7 21 3
and +- (86)
n = 10 21 + 2q> 2 10
For q> = 1, one obtains n = O. 93913, which to the first four figures agrees
with the exact solution n = 3 /q> 2 ( q> coth q> - 1) = 0. 93911.
Also, at the much higher value q> = 4, one obtains a good approximation
to n:
q> = 4: y(¾) = o. 3962 and n = 0. 577 <n exac t=0.563)
When q> is as large as 4, one may safely use an asymptotic formula [e.g. ,
the general formula of Wedel and Luss ( 1980) for an nth order reaction on
spheres]:
Numerical Methods in Reaction Engineering 25
12 -2
¢ ( 87)
n+3
which gives n = 0. 5625 for n = 1 and ¢ = 4. Thus the whole region
0 < ¢ < 00 is nicely covered with the two simple formulas ( 86) and ( 87).
We shall next consider the solution of Eq. (64) for a first-order ir-
reversible reaction and the following set of parameters:
13 = 0.05, y = 30, BiH = 2, and BiM = 40 ( 88)
The curve marked "e" on Fig. 1 is the "exact" solution n versus ¢ obtained
by high-order collocation. The surface temperature 8( 1) increases along
the curve from 1 at (n,¢) = (1,0) to 1 + 13(BiM/BiH) = 2 on the upper,
ignited branch of the curve where the effectiveness factor reaches extra-
ordinary high values [max(n) = 2366] before its final decline, proportional
to ¢-2 when ¢ + 00
log 11
FIGURE 1 Effectiveness factor n versus Thiele modulus ¢ for a first-
order nonisothermal reaction. y = 30, 13 = 0. 05, BiM = 40, BiH = 2.
Curve e: exact solution by high-order collocation; merges with curve
marked BiH for large 0. Curve c: one point collocation. Curve BiH:
isothermal pellet; pellet temperature 0 P. = surface temperature 0 ( 1).
Curve BiH: 0 p > 0 ( 1); BiH calculatetl from Eqs. ( 91) and ( 92).
26 Villadsen and Michelsen
The lower branch of the n versus <P curve is well approximated by
one-point collocation (curve marked "c" on Fig. 1). For example, at point
A, where ¢2 = 1.2, one obtains (¢*)2 = 1.35, and inserting the modified
value of 13 [13* = 0.05 • 28/9 = 0.1555] in Eq. (82), one obtains Yl = 0.8468
and n "' R(y 1 ) = 1. 702, which may be compared with the exact result,
1. 683. The value of 0 1 = 1. 0238, while 0 ( 1) is 1. 0170. One-point colloca-
tion breaks down near the first bifurcation point, where the parabolic ap-
proximation for the concentration profile inside the pellet becomes very
poor.
There is another model approximation that appears to give remarkably
good results. The energy balance (65) is integrated over the pellet volume,
and if 13 is small, one may assume that the pellet is nearly isothermal, in
which case the first-order rate expression can be integrated analytically to
give the right-hand side of Eq. ( 89):
¢ 1 coth ¢ 1 - 1
(89)
¢1 = <P exp [f(1 elp)] ( 90)
and 0 is a representative pellet temperature.
lfpwe are on the upper branch of the n versus ¢ curve of Fig. 1, the
pellet temperature is so far above the bulk temperature 1 that the reaction
is complete in a thin boundary layer. Here the representative pellet tem-
perature Gp should be equated to 0 (1) and (89) is an equation to deter-
mine 0(1) = Gp.
On the lower branch of the curve, most of the reaction occurs in the
bulk of the pellet. The case ¢2 = 1. 2 illustrates the difference between
0 ( 1) = 1. 017 and Gp, which in the one-point collocation approximation is
taken to be 0 1 = 1. 0238. In Villadsen and Michelsen ( 1978, p. 28 and
Chap. 6) it is shown that the factor 0 (1) - 1 on the left-hand side of
Eq. (89) can be replaced by the larger factor Gp - 1 if at the same time
BiM is replaced by a smaller, modified value BiH defined by
Bi H [ 0 ( 1) - 1] =
-
BiH ( 6 - 1) ( 91)
where BiH is found by perturbation analysis to be
1
= a=-- s = 0, 1, or 2 (92)
s + 3
Thus, also for a modest reaction rate, one obtains an algebraic equation
for the representative pellet temperature Gp. Whether Gp is taken to be
0 ( 1) or the left- hand side of Eq. ( 89) is replaced by Eq. ( 91) to deter-
mine a Gp > 0 (1), the effectiveness factor is calculated by
3BiM ¢ 1 coth ¢ 1 - 1
n= "7 ¢ 1 coth ¢ 1 + BiM - 1
( 93)
Numerical Methods in Reaction Engineering 27
For 0 p larger than 'v 1. 2, one obtains values of ¢ 1 in excess of 10 and
coth h % 1. Now Eq. (89) can be solved explicitly for ¢ as a function
of 0p:
¢ = exp [- ½(1 ~
- 0 ) ] { 1 + BiM q : pl ~ ~p } ( 94)
which is easily differentiated to obtain (0p,<P) at the point where dq>/d0p =
0 (i.e., at the upper "nose" of the n versus ¢ curve). For q = 1, one
obtains
.£:L
d0
= 0 at 0
p
= 1. 7291 ¢ = 0.1946 and n = 2310 ( 95)
p
Also,
~ = 0 at 0 = 1. 765 ¢ = 0.1970 and n = 2366
d0 p
p
For practical applications of the present model all that is really needed is
calculated from very simple formulas; by one-point collocation, or the ap-
proximation Eqs. ( 89) and ( 91) to ( 93) , the lower branch of the n versus
¢ curve can be calculated.
The upper branch of the curve is found by Eqs. ( 89) and ( 93). The
lower limit of the ignited branch is found with high accuracy by Eq. ( 95),
while the upper limit of the quenched branch is found with reasonable ac-
curacy by one-point collocation.
Example 5 The catalytic reaction
is carried out in a reactor with a given space time T0 = VcAo/FAO· The
conversion A is xA = 1 - cAs/cAO• while the conversion to B is xB =
cBs/cAO· cAs and cBs are fluid-phase concentrations of A and B at a
given position in the reactor. Inside the catalyst particle the reactant
concentrations are cA and cB, respectively. The effective diffusivity D
is the same for A and B .
It is desired to design a reactor with the proper TO to achieve the
¢:
largest possible yield of component B for given values of ¢~ = L;(k 1 /D)
and = L~(k 2cA 0 /D). LP = VP/SP and the particles are described by
slab geometry.
One obtains the following mass balances for the particle phase:
cosh ¢ 1 z;;
= = (96)
cosh ¢ 1
28 Villadsen and Michelsen
2
d (cB /cAs) d2y 2 [cosh ¢ 1 r; 2
= = -¢1 h ¢ - a (1
dc;2 dc;2 cos l
CB XB CB XB
y = = and y(l) =
cAs 1 - XA CBS 1 - XA
The fluid balances are
dxA CA 'OD
= T k -- = (1 - x A) ¢ l tanh ¢ l ( 98)
dT 0 1 CAO L2
p
i]
1
dxB
dT -
dxA [1 -
¢2 (1 - X )
2 A
where y
2
=
f y2 de;
( 99)
dT ¢ 1 tanh ¢ 1 0
The value of , 0 that is required to give a certain xA value is
( 100)
while the xB value is obtained by integration of
I
dy /de; c;=l
( 101)
¢ 1 tanh ¢ 1
from (xA,xB) = (0,0).
For moderate values of ¢1 and ¢2 (e.g., <5) solution of Eq. (97) by
a straightforward collocation method causes no problems. Every evaluation
of the right- hand side of ( 101) is, however, expensive since it requires
solution of the nonlinear boundary value problem ( 97) transformed into N
coupled nonlinear algebraic equations. After having solved the collocation
equations, it is advantageous to find the sensitivity of the collocation
ordinates with respect to XA in order to obtain good starting values for
the ordinates at the next value of xA. Hence the linear boundary value
problem (102) is solved by collocation before XA is changed:
2
d z 2 2
= ¢ 2 [2y(l xA)z - y l
dr;2
( 102)
!L_ (1) XB
z - z = 0 at r; = 0 and z = at r; = 1
3xA 2
(1 - X )
A
Numerical Methods in Reaction Engineering 29
Throughout the calculations values of (cosh ¢i l)cosh ¢1) at the collocation
abscissas are, of course, stored in a table.
Numerical difficulties arise for fast reactions. Figure 2 shows profiles
y(i:;) for <1> 1 = <1> 2 = 10, six collocation points, and different xA values.
For xA = 0 the profile increases to a sharp maximum at c; = smax (the
overall rate of production of B is zero in the inner part of the pellet),
then decreases through an inflection point (where the local rate of produc-
tion of B is zero) to a long ,_!lat part in the interior of the pellet. To
obtain an accurate value of y 2 , six collocation points may not be enough
and spline collocation or some other method may have to be used.
The time-consuming iterations on high-order collocation equations are
avoided if the problem is treated as two differential equations ( 98) and ( 99)
coupled to N + 1 algebraic equations:
N+l
'°'
L.J C .. y. + [p. - a 2y.2(1 ( 103)
i=l Jl l J J
1.6
1.2
.8
.4
0 .2 .4 .6 .8
FIGURE 2 Pellet concentration profiles for component B in
klcA k2cB 2
A - B - - - - C. Parameter on curves: xA = fluid phase con-
version of A. Maximum yield of B is obtained for x A "-' 0. 7 5 where the
pellet profile has zero slope at c; = 1.
30 Villadsen and Michelsen
= 0 (104)
dyN+2
= 1 ( 105)
dt
= (106)
dt
where
YN+2 = XA' YN+3 = XB
t = dummy integration variable
pi = pretabulated values of cosh ¢ 1 s/cosh ¢ 1
The boundary ordinate YN+l is eliminated and the resulting set of N + 2
differential-algebraic equations is solved [e.g. , by the STIFFALG package
based on Eqs. ( 36) and ( 37)] . Initial values of Yi, i = 1, 2,. . . , N, are
found by solution of Eq. (103) with YN+l = YN+2 = YN+ 3 = 0. When 10 or
12 collocation points are used, the optimum (xA,xB) = (0.7514,0.3232) for
¢ 1 = 10 and a = 1 is found with four- to five-digit accuracy.
The advantages of the present method are easily summed up: no un-
necessary computation is spent in solving Eq. (97) "exactly" at every in-
tegration step, and all components Yl, y 2 , . . . , YN+2• YN+ 3 are calculated
with a balanced accuracy.
For q, 1 -->- 00 at a fixed value of a, the pellet equation cannot be solved
by collocation as it stands in Eq. ( 97). An asymptotic solution is, how-
ever, easily derived using the following transformation. Let u = ¢ 1 ( 1 - I;;)
and rewrite ( 97) as
d2 2
_:f_ = -exp( -u) + a (1 (107)
du 2
with y(u = 0) = xB/(1 - xA) and y(u ➔ 00 ) = 0,
-
-
dyI
du u=0
( 108)
The boundary condition at "u -->- 00 " can be applied at two different u values,
say u = 5 and 8, and Eq. (107) is solved by collocation for each of these
values. If there is no appreciable change in dy / du[ u=0, the solution is
accepted; otherwise, u > 8 is tried. Alternatively, one may make a second
transformation to obtain a finite interval:
-2
v = (1 + u) where v = 1 at u = 0 and v = 0 at u -->- 00 ( 109)
Numerical Methods in Reaction Engineering 31
FIGURE 3 Maximum yield of B as a function of s 2 = k1/cAok2 and of ¢ =
Lp(k 1 /D)½ .. Curves for¢= 0, 1, and co are shown, and points with s2 =
0, 1, . . . , 10 are connected. Compare with Fig. 7. 7 of Leven spiel ( 1972)
for consecutive first-order reactions, ¢ = 0.
The transformation ( 109) is well chosen in the present example since from
Eq. (107) it is easily seen that y "' u-2 for large u.
Figure 3 shows the boundary curves ¢ 1 = 0 and ¢ 1 + co for the optimum
(xA,xB) as a function of l/a2 [which is called s 2 in the classical paper of
Wheeler (1951) on first-order consecutive reactions]. A dashed line indi-
cates the locus of the ¢ 1 = 1 optimum solutions, and at seven different
values of l/a2 (10, 5, 2, 1, 0.5, 0.2, and 0.1) other dashed lines connect
solutions with the same value of lfa2. The solution was found by the
technique (103) to (106), using Eq. (97) to obtain the collocation equations
for ¢1 < 20 and Eq. (107) when ¢1 + co. The asymptotic solution ¢i + co
is a good approximation when ¢1 > 10.
Even though in the present example a collocation solution could be
found for all ¢ 1 values, it is worthwhile to remember than an accurate
solution of the boundary value problem can also be obtained by forward
integration from z; = 0 or from z; = 1. There are positive eigenvalues in
the Jacobian of f, and the solution may easily diverge, but an explicit
Runge-Kutta method is just as good as an implicit method.
To find the solution that satisfies y( 1) = xB /( 1 - XA), one proceeds as
in Eqs. ( 48) to ( 50), integrating Eq. ( 97) together with the sensitivity
equation for zy = 8y/8y0 :
0
32 Villadsen and Michelsen
d 2z
Yo
= 2<1>~ic1 - xA)yz (110)
dr,;2 Yo
with
z = 1 and
dzYo I = 0
y 0( i:;=O) di:; 0
Having obtained the correct value of Yo for a given (XA,XB), a single
integration of Eqs. ( 97) and ( 111) from i;; = 0 to i:; = 1 gives the sensitivity
of y with respect to xA:
= 0 (111)
From the computed values of zx ( i;; = 1) and dzx /di;;I _ 1 , one may obtain
A A i:;-
the second derivative of xB with respect to xA. First, calculate dy 0 /dxA,
using the following equivalent expressions for dy(l):
1 dxB]
+ ----- dx
1 -xA dxA A
(112a)
or
dy(l) = [zxA (1) + z (1) - d
dyo] dxA ( 112b)
Yo xA
from which Eq. ( 113) is obtained:
y(l) + dxB/dxA z-1
= [ -z (1) + 1 - X
xA A Yo(l) (113)
Next,
( 114)
and finally ,
( 115)
Numerical Methods in Reaction Engineering 33
where f 1(xA) = -(¢ 1 tanh ¢ 1 )-l dy/d1;I 1;=1• and f/ 1 >cx 1) is found from
( 114).
As a comment on the procedure of Eqs. ( 97) and ( 110) to ( 115), one
might add that for explicit integration of the differential equation ( 97), it
is computationally simpler to find YO by the secant method. Also, for an
explicit integration it may be preferable to calculate zXA by numerical per-
turbation of Eq. ( 97) rather than by Eq. ( 111). The computational cost is
the same and the computer program is simpler.
Very difficult catalyst pellet problems have recently been solved by in-
genious forward integration techniques: Kaza et al. (1980; methanation on
nonisothermal pellets), Sundaresan and Amundson (1980; diffusion and re-
action in a boundary layer surrounding a carbon particle), and Holk and
Villadsen ( 1983; absorption followed by exothermic reaction in a liquid film).
Other examples are given in Villadsen and Michelsen (1978, Chaps. 5 and 9).
We may conclude that the model for a single reaction on a catalyst pellet can
be treated by a standard numerical approach: finite-difference methods,
collocation, or forward integration from the center of the particle, as the
case may be. Examples with several independent reactions will frequently
require a numerical technique which is tuned to the specific problem. Ex-
ample 5 has shown some of the methods that can be used to construct an
efficient numerical solution, and the references given above illustrate other
techniques.
As a final comment it should be acknowledged that the catalyst pellet
model is virtually the same as the model used to calculate absorption with
chemical reaction. In particular, the catalyst effectiveness factor is closely
related to the enhancement factor which is used in the film model for chemi-
cal absorption.
The design of multicomponent countercurrent gas-liquid absorbers [or
moving-bed reactors, as in Peytz et al. (1982)] presents some nasty numeri-
cal problems-far more difficult than those encountered in the boundary
value problems associated with catalyst pellets. A set of exit concentrations
in the gas phase must be guessed, and after integration of the gas-phase
and liquid-phase mass balances through the column, one makes a comparison
with the inlet gas composition to obtain an iterative calculation procedure.
The differential equations are often very stiff, and it requires careful
programming to achieve a stable iteration.
Steady-State Tubular or Fixed-Bed Reactor Models
Detailed discussion of reactor models appears in other chapters of this book;
our task is to bring up some of the common techniques which are applicable
in a numerical study of the models. For this purpose we need only one
mass balance ( 116) and the energy balance ( 117). Axial diffusion terms can
be neglected in the steady-state model since they are small compared to the
convective terms.
.£X.) -
V
z ay = LD _!_ 2.._ ( x _l R (116)
V
av
aZ 2 X ax ax V
av
rtvav
34 Villadsen and Michelsen
V L(-8.H)c
V
z ae
av
az
=
2
Lk
rt v ac pc p
X
1 a
ax ( X ~!) + v pc T
av p r
r
R ( 117)
where
z = axial distance in reactor relative to the total reactor
length L
X = radial coordinate relative to the tube radius rt
y,e = fluid-phase reactant concentration and temperature relative
to a reference state with concentration cr and temperature
Tr
R = reaction rate divided by the reference concentration cr
V radial velocity distribution in the reactor tube
z
~D radial diffusivity of heat and mass
pc '
p
In a "homogeneous" reactor model R is a function of fluid-phase
properties only; the tubular reactor with or without an inert solid packing
is described by this type of model. The catalytic fixed- bed reactor is
described by a "heterogeneous" model in which R is a function of particle-
phase temperature and concentration, but these extra variables do not
appear explicitly, and in the numerical treatment of a catalytic fixed- bed
reactor model, the pellet problem is treated separately from the fluid-phase
model [Eqs. (116) and (117)]-an ideal case for solution by partitioning.
The influence of pellet-phase variables on the total model appears only in
terms of the effectiveness factor n, and R is an implicit function of the
fluid-phase variablas y md e. Calculation of n may be more or less com-
plicated, ranging from the solution of simple algebraic equations for a sur-
face reaction on impervious pellets to the solution of coupled nonlinear
boundary value problems, as in examples 4 and 5 earlier in this section.
In all circumstances one should try to reduce the complexity of the pellet
model as far as possible (Example 4 showed us how far one can get in this
respect without sacrificing any important feature of the pellet model). The
fluid-phase model is itself quite complicated, and the influence of reactor
macrovariables (e.g., the large temperature gradients which occur radially
in the tubes of a reforming reactor) can be studied with sufficient accuracy
without too many details in the pellet-phase description.
If the rate of reaction is moderate, the radial diffusion terms are small
compared to the axial gradients, and one may reduce Eqs. (116) and (117)
to a one-dimensional model. There are certainly situations where this
approximation may lead to loss of major features of the model, but the
potential reduction in computer expenditure is so significant that we feel
it necessary to comment on proper averaging techniques for the radial
gradients before we discuss suitable numerical techniques for solution of the
full model.
Averaging of the Steady-State Model over the
Cross Section of the Tube
Assume that the physical properties k / pcp and D are independent of x and
integrate over the cross section of the tube to obtain two coupled ordinary
Numerical Methods in Reaction Engineering 35
differential equations ( 118) and ( 119) for the averages of y and 0 at
reactor position z:
~ L (118)
dz = R
V
av
1 2
where R = J0 Rdx, which is approximated by R(y,0):
L(-liH)c
d0 2LU r (119)
= (0 - 6x=l) + v pc T R
dz rtv av pc p w
av p r
where 0w is the value of 0 at the reactor wall and Elx=l is the value of 0
just inside the wall. In the same manner in which we introduced a modified
pellet heat transfer coeff~ient in Eq. ( 91) we shall define a modified wall
heat transfer coefficient U:
~ ~, = U(0 - 0 _ ) - U(0 0) ( 120)
rt ax x=l w x-1 w
Expression ( 120) is inserted in Eq. ( 119) and now only 0 and y appear in
the approximate reactor model, which can be solved by integration from
z=0toz=l.
It remains to calculate U in terms of U and the radial heat conductivity
k. In general, U is obtained from
1
( 121)
u
where the constant a depends on the radial velocity distribution. Villadsen
and Michelsen (1978, Chap. 6) discuss a perturbation technique by which
a may be calculated. The value of a will fall between 1/4 for a flat velocity
profile Vz = Vav and 11/24 = 0. 4583 for the parabolic velocity profile of the
laminar flow tubular reactor. Typical results between these values are
V
19 z
a= 48 = 0.3958 for
V
av
an almost flat profile, and
495b 2 + 234b + 31
V
z 6(1 - x 2)(x 2 + b)
a = - - - - - - - - for =
3b + 1
120( 3b + 1) 2
V
av
For b = 1/4 this profile has a mm1mum at x = 0 and a maximum at x 'v 0. 7,
a feature that is observed in many experimental studies on packed-bed
velocity distributions. a= 0. 3277 for b = 1/4.
The result ( 118) obtained by straightforward averaging of the mass
balance can be improved by including one more term in perturbation
analysis from R = 0. For a first-order, isothermal reaction (R = kR c/cr)
36 Villadsen and Michelsen
in a tubular reactor with parabolic velocity distribution, one obtains, in-
stead of Eq. ( 118) ,
(122)
where Da = kRLlvav and the numerical constant 1/48 is calculated by
perturbation analysis as discussed in Villadsen and Michelsen ( 197 8, p. 2 71) .
This result was first given in a famous paper by Sir Geoffrey Taylor ( 1953).
Qualitatively speaking, he interpreted the radial diffusion term in Eq. ( 116)
where D is now a true molecular diffusivity-in terms of fictitious "axial
dispersion term" in a one-dimensional model:
kL 2-
dy r - 1 dy
= -vy+ (123)
dz Peef
av dz 2
where
Peef = 48 ~ = 192~
2 2
V
avrt vavdt
Equation (123) m~ be solved using the simple "semi-infinite" boundary
condition (e.g. , y = 1 at z = 0 and finite for z + 00 ) or with the more
complicated boundary condition
-y(O) + -1- -dyl
Peef dz z=O
= 1 and dyl
dz z=l
= 0
In both cases, one obtains
y(z = 1) = exp [-Da (1 - p~:J] (p~:J
+ 0
2 (124)
which is the same result as that obtained by perturbation analysis ( 122).
The final result ( 124) is well known from elementary textbooks in re-
action engineering [e.g., Levenspiel (1972, pp. 283-287)], where a
"dispersion number"
Def 1
=
V L 192
av
is used to correct "near plug flow" data obtained in a tubular reactor.
The improvement is substantial, at least for small values of the dispersion
number. Thus at Da = 1, where Eq. (118) yields the result y(z = 1) =
exp(-1) = 0. 3679 regardless of the contribution from the radial dispersion,
one obtains the following results from Eq. ( 124):
Numerical Methods in Reaction Engineering 37
Def
192
V L
av 1 2 5 10 co
y by Eq. ( 124) 0.3752 0.3818 0.3892 0.4179
y by a "true model" 0.3750 0.3809 0.3919 0.4038 (o. 443)
The bottom line of the table is calculated by high-order collocation-as
described below-applied to Eqs. (116) for a first-order isothermal reaction
= v avL 1 cl ( cly)
192Def ; ax x ax - Da y ( 125)
1 2
y(z = 1) = 4(1 - x )y(z = 1,x)x dx
0
The case Def + co (which may be interpreted as D 'v 0) corresponds to a
completely segregated flow with no cross-sectional mixing caused by radial
gradients.
Numerical Solution of Steady-State Reactor Model
When Eqs. (116) and (117) are discretized in the x direction, there appears
a set of coupled ordinary differential equations (j = 1, 2, . . . , N):
dy. T L
dzJ = ci...C. y -
lVJ-J -
-
V av
R(y.,8.)
J J
( 126)
d8. (I'.. T)
_J = max
R(y., 8.) (127)
dz T J J
r
The coefficients Cji are defined in Eq. ( 70). They have different values
depending on the method of discretization. Ordinary finite-difference
methods, global collocation, Galerkin's method, or spline collocation have
been used by various authors in numerous computer studies over the last
20 to 25 years.
Equations ( 126) and ( 127) can be solved from z = 0 by any of the
standard packages for coupled initial value problems. An implicit or a
semi-implicit method is preferable to an explicit method because of the large
spread of the eigenvalues of g. This is true in particular when orthogonal
collocation is used to discretize the radial derivative; even for a relatively
low order method (N = 4 or 5) the ratio between the largest and the small-
est eigenvalue can be of the order of 1000. The structure on the right-
hand sides of Eqs. (126) and (127) is, however, so simple that the Jacobian
can be computed very easily.
It is also possible to discretize Eqs. (126) and ( 127) in the z direction
to obtain a so-called double-collocation method. This method was originally
proposed by Villadsen and Scfrensen ( 1969), but it was only recently
38 Villadsen and Michelsen
elaborated into efficient computer codes by S0rensen ( 1982). These codes
appear to be particularly suitable when applied in a parameter estimation
problem.
A situation that lends itself quite naturally to solution by double col-
location is that of a wall-catalyzed chemical reaction: the rate term appears
in the boundary condition of an otherwise linear partial differential equa-
tion [Eqs. (116) and (117) without the rate terms]. Michelsen and Villadsen
( 1981) give a detailed discussion of this particular type of chemical reactor
model, which may be solved either by double collocation or by the STIFFALG
routine [Eqs. (36) and (37)]; there is one nonlinear algebraic equation
(the boundary condition) and N linear differential equations which can be
transformed into the diagonal form ( 18) and used in this form throughout
the calculation.
The solution of Eqs. (116) and (117) for a rate expression which is
linear in y and 8 (or has been linearized from a given reference state)
deserves particular attention. Crank (1957) has discussed the multitude
of practical problems in reaction engineering which are generated from the
same basic equation, the linear "diffusion equation." Numerically, all these
different problems are handled by the same general technique, but with
slight modifications for different boundary conditions.
Let us use a linear mass balance as our "standard problem":
v(u) az
ay
= 4u
(l-s)/2 a ( (s+l)/2 'dy)
3u u 3u _ Da Y ( 128)
where u = x 2 and s = 0, 1, and 2. When s = 1 and v(u) is the radial
velocity distribution, we have a steady-state tubular reactor problem.
When v( u) = 1 and z is interpreted as contact time, we have a linear
transient pellet problem. Here we use cp2 = kRrp 2 /D instead of Da = kRL/
v av as the dimensionless group of parameters.
Equation (128) is discretized by Nth-order collocation:
(129)
y is diagonal with Vjj = v(uj), and the (C~, bj) are given in Eq. (71).
Different side conditions at u = UN+l = 1 lead to different problem modifica-
tions. _1
Diagonalization of \YI = y (g* - DaD yields the standard form ( 18).
Michelsen and Villadsen ( 1981) prove that all eigenvalues of \YI are real and
distinct if collocation is made at the zeros of P~O,O)(u), and -the boundary
condition at u = 1 is any of the linear expressions discussed in Crank
( 1957).
The solution appears as an N-term expansion in eigenfunctions exp( Aj z),
and the modified Fourier coefficients are found by simple matrix-vector
manipulations [ see Villadsen and Michelsen ( 1978, Chap. 4) for the solution
of a particular example] .
For the case Da = 0, Michelsen (1979) proves that the eigenvalues and
eigenfunctions of Eq. ( 128) with boundary condition
dy BiM
du + - 2- y = constant at u = 1 ( 130)
Numerical Methods in Reaction Engineering 39
can be derived for any value of BiM by a simple algorithm that utilizes the
eigenvalues and eigenfunctions obtained at any specific reference value
(BiM )r, which, for example, may be either zero or infinite. This leads to
substantial savings in computer time when estimating the value of BiM (and
a diffusivity) from a series of measurements of y at different z and x.
When Da ;/; 0, the diagonalization of ~ must, however, be performed for
each value of Da. -
Another important special case, that of a finite exterior medium, is
treated in Sotirchos and Villadsen (1981). The boundary condition at u = 1
is given by an overall mass balance
q yb(z) + J1 y(x,z) dxs+l = a - Jz (J1 R dxs+l) dz' = a - f ( 131)
0 0 0
Outside the reaction medium of volume 1 (or the catalyst pellets as the case
may be) there is a radially well mixed volume q into which the reactant may
diffuse. The reactant concentration is Yb in the finite exterior medium at
position z (or at contact time t). In Eq. (131) the total "mass" in the re-
actor and the outer medium is equated to the initial "mass" a, less the total
amount of reacted material. Concentrations in the two media are connected
by a boundary condition of type (130) where the right-hand-side "con-
stant" =(BiM/2)yb(z).
Let v( u) = 1 and write the jth collocation equation,
dy. N b.
dz) = L _l f -
q
R(y.) + b. a
J J q
( 132)
i=l
where f is given in Eq. (131).
- w.
b ( ___! + 2AN+ l ,l·)
j q BiM
= 4/ B ~ A ) _ _B_1_·M_ _ __
bj \ui j ,N+l + 2 j ,N+l 2AN+l,N+l + B¼
f1 y dxs+l
N
- I:l w.y.
l l
0
For a nonlinear reaction rate the N equations ( 132) are solved together with
an equation for the average rate of reaction:
df = Jl N
- Ll w.R(y.) ( 133)
dz O l l
but for a first-order reaction the numerical approach is just like that used
in Eq. ( 12 9) :
40 Villadsen and Michelsen
dY
= MY + b*
dz =-
( 134)
T
,bN' 0}
In Eqs. ( 132) to ( 134) the unfortunate misprints in Sotirchos and Villadsen
(1981) have been corrected. A number of important applications of Eq.
(132), (133), or (134) can be easily listed:
1. Absorption of a reactant gas from a gas phase and reaction in the
liquid phase [ gas flow rate va(m 3 /h), liquid flow rate vL(m 3 /h),
and q = VL/va].
2. Determination of reaction rate constant and pellet diffusivity by
concentration measurements in a finite volume of well stirred liquid
in which the catalyst particles are suspended. All reactant is
originally in the fluid outside the particles.
3. Analysis of membrane reactors: a certain amount of reactant
v(m3/h) flows in a tube coated with a catalyst layer of thickness cS.
Reactant diffuses into the catalyst layer and reacts there. It is
desired to calculate the length of tube required to obtain a certain
average concentration in the flowing liquid.
As a final illustration of the general numerical approach to linear steady-
state reactor models, one may consider Eqs. ( 128) and ( 130) with the addi-
tion of a small axial diffusion term (1/PeM) (a2y/az2) on the right-hand
side of Eq. (128). The problem has only marginal interest in industrial
reactor design (radial diffusion may be accounted for by a fictitious axial
dispersion term as discussed earlier, but an axial diffusion term per se is
almost always insignificant). Addition of the second derivative with re-
spect to z in the partial differential equation ( 128) does, however, lead to
formidable numerical complications which have intrigued many authors [see,
e.g., Papoutsakis et al. (1980) or Michelsen and Villadsen (1981)].
It is interesting that with the exception of the inlet zone of the reactor,
one may study the influence of an axial diffusion term ( 1/P~) ( a 2y /cl z2)
on the solution of Eq. ( 128), using only the eigenfunctions and eigenvalues
of the radial diffusion operator. The technique and its application to the
"extended Graetz problem" discussed here and to the much more interesting
asymptotic stability analysis of catalyst pellet models are developed in
Villadsen and Michelsen (1978, Chap. 9).
Every one of the numerical methods that have been described in this
section have been based on an approximation of the x profile by a poly-
nomial. High-order methods such as collocation will not be able to handle
the near discontinuities that appear in the profiles close to the reactor
entrance (the inlet concentration may be 1 at all interior points and zero
at u = 1 for z = o+). Spline collocation with a spline point that gradually
moves away from u = 1 as z increases has been successful in the computa-
tion of "penetration fronts" in the inlet zone of the reactor. One example
Numerical Methods in Reaction Engineering 41
is given in Holk-Nielsen and Villadsen (1983), and other examples are shown
in Villadsen and Michelsen ( 1978, Chap. 7) .
Another, quite different but apparently versatile approach is to intro-
duce a variable transformation n = f( z ,x) which as far as possible describes
the combined influence of z and x on the solution near z = 0. This is
called "similarity transformation" and is treated in most textbooks on partial
differential equations. The reduction of the model into a problem with only
one independent variable succeeds only in trivial cases, and one will usual-
ly end up with two independent variables n and z in the transformed equa-
tion as well as in the boundary conditions. If, however, n has been
judiciously chosen, a perturbation analysis of the transformed equation
from z = 0 will give an accurate solution of the original problem in the inlet
zone. There are several examples in Villadsen and Michelsen (1978, Chap.
4) where this technique has been used to solve linear reactor problems,
and a pellet model with a concentration dependent diffusivity is treated in
the same reference p. 339).
Unsteady-State Fixed-Bed Reactor Models
Except for regions of hot spots, the steady-state axial temperature and
concentration profiles in a fixed bed are smooth functions of z, and the
radial profiles can almost always be represented by low-order polynomials-
if they are not averaged away as discussed in the preceeding section.
Thus steady-state reactor simulation is a rather modest affair on a high-
speed computer, requiring at most a couple of seconds computing time to
obtain 0(x,z) and y(x,z).
When a time derivative is included in Eqs. ( 116) and ( 117) there is a
fundamental change in the nature of the solution. Sharp concentration and
temperature fronts may be formed, and these fronts move slowly through
the reactor. · To simulate the dynamic response of the reactor to a control
action in the inlet (e.g., a jump in reactant concentration), one has to fol-
low the reactor profiles of the dependent variables through many thousands
of fluid-phase time constants. This, of course, means that the amount of
computation increases drastically, and 25 to 40 sec of computer time per
simulation is not at all extravagant. Quite apart from the cost of the com-
putation, the time it takes to make a computer simulation of the unsteady-
state reactor makes it very difficult to use the result, for instance, in a
computer control of the reactor.
A compromise must be made between the demand for accurate modeling
of the reactor and a reasonable computational effort. The literature on un-
steady-state reactor simulation offers a bewildering array of model simplifi-
cations and numerical shortcuts. Some of the simplifications are justified
and should certainly be generally accepted, but others are downright silly
and will lead to order-of-magnitude errors in, for example, the break-
through time of a catalyst poison.
Thus for gaseous reactants it is reasonable to neglect accumulation
terms in the reactor fluid-phase mass and energy balances and in the pellet
mass balances. The time constant for convective transport of mass through
the reactor and for diffusion into the pellet are orders-of-magnitude smaller
than the velocity of the reaction zone. The pellet temperature is taken to
be independent of position in the pellet (as in Example 4), and while the
pellet time constant for energy transport is certainly larger than the time
constant for mass transport, it is still much smaller than the thermal
42 Villadsen and Michelsen
residence time for the bed, an observation that may justify a further as-
sumption that Sp = eg at any time. To reduce the dimensionality of the
problem, it is common practice to neglect the cross-sectional conductive
term in Eq. (117) when solving unsteady-state reactor models. This may
be justifiable when the diameter-to- length ratio of the bed is larger than
20, but a radial gradient can also be incorporated as a fictitious axial
dispersion term and there is experimental evidence that true axial conduc-
tive terms may have to be taken into account in modeling of transient fixed-
bed reactor behavior.
It is usually dangerous to tamper with the rate expression to obtain
computational advantages. If it is reasonable to suspect a substantial re-
sistance to mass transfer in the pellets, it will not do to neglect this dis-
persing effect, since breakthrough times that are much different from those
observed experimentally are likely to be calculated. Our discussion of the
pellet problem for a single reaction has also shown that a complicated rate
expression is treated with almost the same effort as a simpler rate expres-
sion. Therefore, it is usually not advisable to jeopardize the trustworthi-
ness of the simulation by neglecting the influence of one or more reactants
on the rate of reaction.
Unsteady-state reactor models display such a variation in complexity
that it becomes impossible to discuss suitable solution techniques in general.
At one end of the spectrum one finds the one-component isothermal gas
adsorption unit which can be treated analytically (Aris and Amundson,
1973). At the other end of the spectrum there are studies of reactor con-
trol with several independent variables, steep temperature fro'nts, and with
time-changing kinetic and transport parameters. Simulation of reactors for
reduction of mineral ore and simulation of explosion fronts are other com-
plex problems.
An example that illustrates major features of unsteady-state reactor
behavior without being very complicated is discussed in Michelsen et al.
(1973) and Villadsen and Michelsen (1978, Chap. 9): The reaction takes
place in the fluid phase, but the inert packing material of the reactor in-
troduces a large thermal residence time. After linearization the model is
analyzed in terms of transfer functions, using collocation to account for the
axial variation of the variables y and e.
In the present chapter we use an example of moderate complexity to
illustrate certain numerical techniques which we believe can also be applied
in many other situations.
Example 6: Simulation of coke burning in a fixed-bed reactor A re-
forming catalyst is slowly deactivated due to deposition of tarry material in
the pores. This so-called "coke" has to be burned off periodically, and a
reliable simulation is important to minimize the length of the burn-off period
without sintering the metal crystallites by excessive overheating of the
pellets. Originally, the coke is homogeneously distributed on the particles
with concentration Ceo. Nitrogen containing a small proportion of oxygen
( concentration Coi) is fed to the reactor inlet at temperature T gi ·
A reaction zone develops and moves slowly through the reactor. When
the reaction zone passes out of the reactor the burn is complete, and it is
successful if only a small residual coke concentration cc( z) is left behind
and if the temperature at no time has exceeded Tmax anywhere in the re-
actor, During the operation of the reactor a temperature wave passes
through the bed. It may move faster or slower than the reaction zone-
the inlet oxygen concentration c . can be used to control the relative
01
Numerical Methods in Reaction Engineering 43
movement of the two fronts. Both fronts move exceedingly slowly compared
to the gas residence time in the reactor. Typical velocities are O. 1 m/h for
the reaction zone and O. 9 m /h for the temperature front.
A model with three equations [ ( 135) to ( 137)] for the pellet phase and
two [ ( 138) and ( 139)] for the fluid phase was proposed by Liaw et al.
(1982).
[y (1 f-)]
C
exp yc = cC = 1 at t =0 ( 135)
p co
( 136)
ae T T
tH __E._ = H (e - ep ) + S ny g 8 =_E._ 8 = __g ( 137)
ax p g
Da
p T. g Tgi
gi
cly C
......::..K = - Da ny = og ( 138)
az . g yg C •
01
ae
____g: = H (8 - 8 ) ( 139)
az p p g
The many constants in Eqs. (135) to (139) (tn = characteristic reaction
time, tH = thermal residence time, Hp = fluid-to-pellet heat transfer units,
Cle = moles of o 2 consumed per mole coke burned) are all defined in Liaw
et al. (1982).
There are three reference concentrations: Ceo is used to scale the
coke concentration Cc, and c0 i is used to scale the fluid -phase oxygen con -
centration c 0 g at position z and time t. Finally, in the local oxygen
balance ( 136) c 0 g is used as a reference concentration. It had been easier
to read the model if c 0 i had also been used to scale the pellet oxygen con -
centration c 0 p, but we have used the same scaling procedure as in Liaw
et al. ( 1982) to facilitate cross-reference to the published paper.
The inlet gas temperature T gi is used to scale T g as well as Tp.
There is no temperature variation in the pellet. The previously mentioned
model simplifications (no energy or mass accumulation in fluid phase, no
mass accumulation in the pellets and no radial or axial conductive terms)
have all been used, and the model is still quite formidable.
There is a large oxygen gradient in those pellets which are close to
the reaction zone, and a much too sharp burn front will result if the burn -
ing rate is expressed as kc c rather than kc c This is one of the
c og c op
44 Villadsen and Michelsen
less justified assumptions that have been made in previous studies of the
problem. The present model does not assume "a constant burning rate,"
low-temperature burning" (where cp ~ cg), or "diffusion-controlled burn-
ing" (where the rate is almost independent of temperature), and conse-
quently the predicted burnout history is close to that obtained in laboratory
experiments.
The model has recently been critically reviewed from a numerical point
of view by Funder (1982), and as a result the computation time per burn-
out simulation was reduced from about 5 min in Liaw et al. ( 1982) to about
35 to 40 s. We shall review some of his conclusions.
1. It is meaningless to simplify the model by the assumption 8g =
8s = 8. This is frequently done in numerical studies of unsteady-state
reactor models, and the resulting "homogeneous" model with
ae 1
az = tH SDany
g
(140)
instead of Eqs. (137) and (139) is amenable to solution by the method of
characteristics using increments related by
dt =t dz = dS ( 141)
H SDany
g
There may be about 10% saving in computer time when this approximation
is made, but significant errors in the temperature peak may also occur.
2. The implicit three-point integration scheme suggested by Christian-
sen and Andersen ( 1980) is very suitable for integration of the fluid
balances in a rectangular grid. The pellet mass balance is approximated
by collocation [ using PN ( 0, 0) ( x2) with N = 3 or 4) , and the resulting
equations for Yg, 8g, Sp, and {(yp,Yc); j = 1, 2, . . . ,N} are solved
by a Newton method for each grid point. All z values at a given t are
treated before t is increased.
3. Funder (1982) points to an interesting model approximation: where-
as it is incorrect to assume a constant oxygen level in the pellets ( except
when the pellet is far from the reaction zone), it is quite reasonable to
assume a constant coke level or a coke profile that changes in a few steps.
When Ye is assumed to be piecewise constant in the pellet, it is possible
to solve the pellet model analytically, and since n is the only "output" of
the pellet mass balance, the problem is reduced from one in 2N + 3 vari-
ables to (ideally) one in four or five variables. The resulting reduction
in computer time is very significant (from 35 to 4 to 6 s per burnout
simulation) and the results are only a few percentage points different from
those obtained by the full model, probably because the sharply decreasing
oxygen profile in the pellet is very little influenced by the coke profile as
long as the correct average coke concentration is used.
Characteristically, the solution of the unsteady-state reactor model is
smooth except in the reaction zone and in the temperature front. In Exam-
ple 6 the oxygen concentration is zero downstream from the reaction zone,
and it increases rapidly to the inlet value c i at positions upstream from the
reaction zone . 0
Global collocation does not give a satisfactory representation of the
profile when two, more or less flat parts are joined by a steep front.
Numerical Methods in Reaction Engineering 45
Spline collocation is a possibility, but a suitable algorithm must be con-
structed to move the zone with many collocation points at the same speed
as the reaction zone. With several reacting species and an energy balance,
the fronts will move with different speeds, and unless the program auto-
matically follows each of the fronts, spline collocation will also be impractical.
An ideal code should:
1. Ensure that each front is followed by a sufficient number of nodal
points.
2. Move nodal points in and out of the fronts-not too fast (since
otherwise all nodes would be sucked into the fronts) and not too
slow (the fronts will be inaccurately represented)
When the profiles are given in terms of Yj(t) at positions Zj(t) [e.g.,
as a set of piecewise linear functions between (Yj , Zj) and (Yj+1 , ~+ 1 )] , one
must require that ( Yj , zj) quickly settle down to become smooth functions of
t. This certainly requires that condition 1 is satisified. If a number of
nodes pass quickly through the front, the profiles ( Yj , Zj) will oscillate
wildly with t.
Since the equations that determine the (Yj, Zj) are surely going to be
"stiff," an implicit or semi-implicit integration method in t must be used.
The most promising recent development toward a general algorithm
for solving problems with steep fronts (or schocks) is due to Miller and
coworkers (Miller and Miller, 1981). Their method employs a complicated
system of "spring forces" and "viscosity forces" to move the nodes-quickly
but not too quickly-in and out of the fronts. Computing times (with an
implicit Gear method to solve the differential equations for the time develop-
ment of the profiles) appear to be remarkably small. We have used the in-
formation given in the published articles to test their method, both on
Burgers' equation (their test example) and on a chromatographic separation
example. Our computation times are, however, three to four times as high
as stated by Miller, but undoubtedly the method deserves further study,
since the basic ideas seem to be just right for solution of some extremely
complicated problems of great practical interest.
PARAMETER FITTING IN REACTION ENGINEERING MODELS
Up to this point we have presented various numerical techniques which are
suitable for reactor simulation (i.e. , computation of reactant concentration,
temperature, etc.) as functions of the independent variables in the reactor
model.
We shall now apply these techniques to determine a set of parameters
in a postulated rate expression, heat transfer model, or reactor model.
At n specified values of the (possibly multidimensional) independent variable
x, there are measurements of some or all the components of the M-dimen-
sional state variables in the postulated model. The experimental values
are <Y1,Y2, ... ,YM)k for k = 1, 2, . . . , n. They are collected into an
experimental state vector ~e. The experimental values of !. are supposed
to be free of experimental error, while the experimental error of ~e is sup-
posed to be normally distributed with a mean of zero (this is possibly not
true, but it is often as good as any other guess, and the bias in the
estimated E. that results if the assumption is incorrect will be difficult to
assess).
46 Villadsen and Michelsen
The postulated model contains m parameters (P1,P2, . • . , p ) = E_,
and for a given value of E. the model can be used to calculate vr:fiues l.s
of the state vector at the experimental positions x.
The parameters will be determined by minimization of an object function
<P(X.e•ls•(J2.)) with respect to E.· Weighted least squares, maximum likeli-
hood fitting, or any of the statistical principles advanced in textbooks on
statistics may be used.
Our choice of object function will be
( 142)
The (n x n) covariance matrix 1; for the experimental data is assumed to
be diagonal (uncorrelated data) -and the diagonal elements are Eii = V(yi) =
ri,1
the variance of the ith experimental point. ~ is assumed to be known
2
except for a scalar a
Differentiation of ,p with respect to E. yields the following algorithm for
improvement of an initial estimate E_o for 12.:
where
This is the Gauss-Newton algorithm, which can be applied iteratively until
I !). p I <
e: and p = P, the maximum likelihood estimate for p.
-The variance-covariance matrix y is obtained from the estimate Q(~
for the Hessian matrix that results after convergence has been reached in
Eq. (143):
T
X= E[(E_ - E_) <12. - E_)]
A A
(144)
where
2 A2 2 1
a 'v a =s = - - - ( 145)
n - m
Gauss-Newton's algorithm is at least linearly convergent, but it may fail to
converge even when excellent starting values E.o are provided. Most stand-
ard codes for parameter estimation with an explicit object function employ
one of the several variants of Levenberg-Marquardt's restricted step
algorithms. The simplest version is that in which Q + v!_ is used instead
of Q in Eq. ( 143), but an arbitrary positive-definite matrix may be used
instead of the identity matrix !_. At the start of the iteration a rather
large value is chosen for the Levenberg parameter v, and v is gradually
reduced when !).p + 0. Thus the method starts as a steepest-descent
method and it may end as a Gauss-Newton method in the last iterations.
It is robust and often works well, although it is not spectacularly fast.
A good, recent description of Levenberg-Marquardt methods is Fletcher
Numerical Methods in Reaction Engineering 47
(1980, Chaps. 5 and 6). In the following we assume that one of the
Levenberg-Marquardt library codes (e.g., IMSL or Harwell) with externally
calculated values of -y s and of its gradient ay-s / a-p is available.
The parameters to be determined fall in two groups:
1. Kinetic parameters (rate constants and equilibrium constants)
2. Reactor parameters [residence-time distribution (RTD), cross-
sectional velocity-and heat conductivity distribution, wall heat
transfer coefficients, pellet-to-fluid transfer parameters, axial
dispersion , etc. ]
The measurements can be of wildly different complexity. They may
include:
1. Direct measurement of the reaction rate at given conversion and
space time (recirculation reactor)
2. Measurement of the average conversion and temperature profiles
in the axial direction of a fixed- bed reactor, or profiles of con -
version versus time in a batch reactor
3. Radial and axial temperature and (possibly) concentration profiles
in a fixed-bed reactor at different values of time
The easiest experiments to analyze are those obtained in a recirculation
reactor. The experimental procedure is slow compared to batch reactor
experiments-only one set of outlet concentration and temperature is found
for each steady-state experiment-but in principle it is possible to obtain
a complete picture of the rate expression without worrying about inter-
ference from the reactor parameters. Experiments over the whole range of
conversion should be used to distinguish as far as possible between differ-
ent kinetic parameters. Thus, for oxidation of CO, the pure first-order
behavior is seen for measurements taken at conversion close to 1, while the
"negative order kinetics" (i.e. , the influence of CO inhibition) is observed
for small conversion and large inlet CO concentration.
Intraparticle mass transfer resistance is measured on pellets of differ-
ent size. Jackson (1977, Chap. 10) reviews the subject of diffusivity
measurements by steady-state methods as well as by transient methods.
It may be safer to measure the transport parameters under reacting condi-
tions. One or more standard reactions with known (and simple) kinetics
may be used, but in many studies it has also been proved that kinetic
parameters can be found simultaneously with the pellet mass transfer re-
sistance.
Similarly, the pellet heat conductivity can be measured independently,
followed by measurements of the pellet-to-fluid phase transfer properties,
radial heat conductivity, wall heat transfer coefficient, and so on, in the
packed bed operated as a heat recuperator. Unfortunately, different ex-
perimental methods may give very different values of these parameters
(see, e.g., Hoffmann et al., 1978), and many authors doubt that the
parameters can also be applied for simulation of the reactor under reacting
conditions.
A word of warning should finally be given concerning recirculation re-
actor experiments: when the conversion is very high, the recirculation
ratio is likely to be too small, and for measurements at small conversion the
amount of catalyst may be too small to give a homogeneous bed-or there
48 Villadsen and Michelsen
may be severe short-circuiting in the reactor itself. Wedel and Villadsen
( 1983) show some nasty systematic errors that may arise in the interpreta-
tion of recirculation reactor data errors which could not be avoided by
including R TD measurements in the data analysis.
Still, as far as possible, one should try to proceed as indicated above,
using different equipment to extract information regarding different groups
of parameters. It is far more difficult, from both an experimental and from
a simulation point of view, to determine kinetic and transport parameters
simultaneously. The most probable outcome is that the physical parameters
(which frequently have a much smaller influence on the conversion than
the kinetic parameters) will be determined very poorly. Many authors
(see, e.g. , Clement and J~rgensen ( 1983)) have observed that the param-
eters obtained by the "building- block" approach fail to give satisfactory
prediction of the reactor performance under reacting conditions. Hence
they feel that it is necessary to determine all (or most) of the parameters
simultaneously in order to give a reactor model that can be used for inter-
polation and for control purposes. One may argue that the failure of the
building- block method must indicate that there is some misconception of the
kinetic model or of the flow pattern in the reactor, and that these un -
certainties had better be resolved. If there are errors in the model, the
predicted parameters are of dubious value for large-scale extrapolation, and
for control purposes a very simple but self-adapting algorithm is satisfactory
if the disturbances are small in magnitude.
The final goal of the model work is to understand the underlying
physics and chemistry of the system, and this goal will not he reached un -
less the complete reactor performance can be patched together by the build-
ing block method.
Numerical Techniques
The library routines for parameter estimation require that <P and d<P I d:e_
be generated externally, and consequently the state vector ~c and its gra-
dient dys/dp must be calculated for given p. It is often claimed that it is
more difficult to extract ys from a plug-flow or batch reactor model than
from a recirculation reactor model, but this is not the case when there is
only one reaction. In the schematic representation shown in Table 2, the
steps that lead to p are shown for both recirculation reactor experiments
anf for plug-flow reactor experiments. The state vector is a set of n con-
versions .5. = ~s measured at given values of space time, Ti (i = 1, 2, . .
n). In both cases n algebraic equations must be solved to find Si at the
known values of T = Ti. The only difference is that evaluation of the
integral in the plug-flow reactor model requires a subroutine for numerical
quadrature, and excellent codes based on Gauss quadrature are available
for this purpose.
When there is more than one component in the state vector, the analogy
between the backmix reactor model and the plug-flow (batch) reactor model
becomes less apparent. The procedure for the backmix reactor is the same;
there are now M coupled algebraic equations which have to be solved for
x_s at each i (i = 1, 2, . . . , n), but this is in principle not different
from the case of one reaction. Solution of M coupled differential equations
in the plug-flow reactor model to find x_s at Ti (i = 1, 2, . . . , n) is
much more difficult than evaluating n quadratures.
Numerical Methods in Reaction Engineering 49
TABLE 2 Steps leading to :e_
Recirculation ( or backmix) Plug- flow ( or batch)
reactor model reactor model
i;
Model: i; = TR(i;,:e_) T= J0 dz;;
R( c;,:e_)
Algebraic si i;i de;
equation:
F.
1
= T. R( i;. ,p)
1 -
=0 F.
1
= T.1 - ~ R( z;;,:e_)
-· 0
1
i = 1, 2, n i = 1, 2, n
dF. dF.
Derivative 1 1 1 1
of F.: di;i
= T. dRI
di;i
1
= R( i;. ,p) = R.
1 1 di; i;. 1 - 1
1
Iteration: si .- i;i -
(dFrdi;: Fi i;. := i;. + R.F.
1 1 1 1
For each i repeat the calculation of Fi, dFi/di;i, and 6. Si until
convergence. This leads to f = Ys at the given :e_ = :e_ 0 •
Next, update p using the following procedure with a diagonal
matrix ( cl E'._/ cl f):
Gradient
of y: G!), .p
-s -0
for both reactor models
(:!), ,p
-s -0
C (:!), -s -0
,p (:!), ,p
-s -0
(~)d
cl :e_ c;
Finally, use Eq. ( 143) or a similar formula to update :e_.
50 Villadsen and Michelsen
Still, a close analogy exists if the differential equation model is approx-
imated by a discrete model from T = 0 to Tmax• This can be done, for
example, by global collocation. If the collocation order N is high enough,
the discrete model is an adequate representation of the original model, and
the solution :l.sc is clos~ to :l_s. Hence, when there is the usual no_!se in
the data, the estimate E. is not statistically inferior to the estimate E. which
would be obtained by an "exact" solution of the model.
When the Nth-order collocation model is solved to machine accuracy,
the sensitivities are calculated with only a small extra effort, and they are
based on the exact solution of the (approximate) model at Ti, just as is the
case for solution of the (exact) algebraic equation model which describes
recirculation reactor data. This is important: if there is an inconsistency
between y s and a y / a p, the parameter-fitting algorithm converges slowly
or not aCall. A re::iark on this point was made earlier in the section on
sensitivity functions. Most automatic integration routines, whether they
are based on explicit or semi-implicit Runge-Kutta procedures or on Gear's
method, operate with a fixed accuracy in each step or with some other de-
vice that is outside the user's control, and it is difficult to obtain cor-
responding values of :l.s and cJ:l_s/a .e_.
A truly implicit, stepwise integration routine will give consistent sen-
sitivities when the sensitivity equations are solved one by one after con-
vergence of :l.s has been reached in the step [ see Eq. ( 46)] .
When using an explicit or a semi-implicit integration method, one should
solve the state equations together with m numerically perturbed equations
(:e_ = Pl, P2, . . . , Pm). This is no more difficult than the.procedure
( 46) when the method is explicit. For a semi-implicit method where all
(m + l)M equations have to be solved simultaneously, it is highly profitable
to modify the LU decomposition routine to utilize the (M x M) block diagonal
structure of the [M(m + 1))-dimensional Jacobian matrix.
Collocation applied to parameter estimation in differential equations was
first proposed by Van den Bosch and Hellinckx (1974). As explained
above, it may be an excellent approach to transform each differential equa-
tion into N collocation equations, but unfortunately a number of misconcep-
tions about the proper use of the method are apparent from the literature,
the most misleading being that "the experimental points should be chosen
at values of the independent variable ( axial position, etc. ) which are zeros
of a specific Jacobi polynomial." Obviously, the N collocation points should
be chosen to make the approximate solution :l_sc as close to :l.s as possible.
The collocation order N in one particular coordinate may have to be much
higher than the available number of data points n in this direction-a
situation that occurs if y s is not a smooth function of this particular in -
dependent variable. After having solved the model by a sufficiently high
order collocation method, one may ( without loss of accuracy) interpolate
the solution to the values of the independent variable where the experimental
values Ye are available.
If, on the other hand, there are many more experiments than required
for comparison with a collocation solution of sufficiently high order N (this
may be the case if the experimental results are recorded automatically), one
applies Nth-order polynomial least-squares fitting of the original data to
obtain a synthetic data base :l.ec at the same values of the independent
variable where the collocation solution is constructed.
Baden and Villadsen ( 1982) give a critical review of collocation- based
parameter estimation methods. They emphasize the importance of choosing
Numerical Methods in Reaction Engineering 51
a collocation method that gives the best possible fit between the solution
l.sc to the approximate model and the (unknown) solution I.s of the exact
model. Their model B is the same as that proposed above: solve the
collocation equations, find the gradient dl_sc/dp_, and update p_. One may
either choose to solve the collocation equations to machine accuracy before
calculating lip or take just one step in the iteration toward the solution of
the collocation equations before updating p. A particular variant (their
method A) may be valuable to find good starting values E_ for the param-
eters. If the differential equation model is linear in the parameters ( or
only slightly nonlinear), a situation that frequently occurs, one obtains a
very good estimate for p_ by
[(',:N)\ (\a:)] ( 146)
ON is the residual of the differential equations when the dependent variable
y_ is replaced by Y.ec, the "synthetic" data base referred to the collocation
points as described above, Yr
1 is an estimate for the dispersion matrix for
the residual ON. It is only- a weak function of p_ and may be evaluated at
any reasonable point Eo.
aoN E(aoN)T]-l
[ (147)
cly = cly
- - .x=Y.ec
The general collocation method may, however, be applied for models that
are nonlinear· in the parameters as well as in the state variable y. It is
equally applicable for parameter estimation in nonlinear coupled ordinary-
differential-equation models (where it competes with the explicit or semi-
implicit initial value techniques) and for parameter estimation in boundary
value problems.
The best documented general code for parameter estimation using col-
location is developed by S<,ilrensen and Stewart. The software is shown
in appendixes to S<.ilrensen ( 1982).
Special attention should be given to the linear boundary value problems
which are the basis for Fourier expansion of linear PDE [e.g. , variants of
Eq. (128)], since these models occur so frequently.
Michelsen (1979) convincingly demonstrated that the transport param-
eters (radial dispersion and a wall transfer number) can be estimated with
only one diagonalization of the collocation matrix (for BiM ➔ 00 ) and sen-
sitivities calculated analytically from the eigenvalues and eigenvectors of
g. The resulting reduction of computer time compared to previous calcula-
tions on the same data base was at least by a factor of 20.
When v z(x) = 1, a situation that certainly occurs in pellet problems,
one may find the radial transport parameter, the wall transport parameter,
and Da simultaneously. There are only trival modifications in the proce-
dure of Michelsen ( 1979): The solution with Da -:/: 0 is simply
Y.(T,Da) = exp(-DaT)Y.(T, Da = 0) ( 148)
52 Villadsen and Michelsen
where dy/d, = (Q -- DaDy and y(,, Da = 0) is found by the procedure
( 128) and ( 129) with Da- = 0.
When v z(x) depends on x, a new diagonalization is required for each
value of Da, but the sensitivity with respect to Da can still be derived
quite inexpensively. Consider the system
DaD
with solution
-1
y = exp(~'IT)y 0 = ~ exp(~,)~ Yo ( 149)
The sensitivity zna with respect to Da is found by solution of the inhomo-
geneous linear differential equation
where zD (, = 0) = 0 ( 150)
- a
with solution
~Da
r
where
-1
:\.) [exp(:\.,) - exp(,\..,)]r.. for i -f.
1 ] 1 l]
s..l] = ( 151)
Tr~.
11
exp(:\.,)
1
for i =j
and
r .. is an element of
l]
r = ~ -1¥-1~
When the rate term is nonlinear in y s, one proceeds more or less as
described above for the linear partial differential equation. Collocation is
used to discretize the PDE in the x direction, but now the collocation equa-
tions are integrated in the , direction, either by collocation as proposed
by Sc.frensen ( 1982) or by a stepwise procedure.
Sensitivities can be calculated by numerical perturbation, but at least
for the case of a single reaction it is also possible to use a semi-implicit
Runge-Kutta routine to integrate the N state equations and the N x m
analytically derived sensitivity equations. The calculation of the two higher
derivatives fyy and fpy in Eq. ( 47) is not difficult since, in contrast to
the case of M coupled independent reactions, the collocation differential
equations have a very simple structure. The nonlinearities are found only
in the main diagonal of the Jacobian ;[, whereas all the other elements in J
are constants. - -
It is nearly impossible to give a balanced picture of the subject of
parameter estimation within the framework of one section of one chapter in
a book. So many things are involved, and most of them have more to do
with common sense engineering that with mathematics: the proper choice
Numerical Methods in Reaction Engineering 53
of experimental equipment and analytical method, planning of experiments,
and a general pessimism concerning the influence of all the variables which
for one reason or another were not included in the investigation.
The methods that we have chosen to discuss have been used by us and
by others in many different situations, but still many topics have been
left out. It is hoped that Examples 7 and 8, which mark the end of our
review, will also emphasize some of the facets of parameter estimation that
could not be adequately covered in the preceding text.
Example 7: Determination of a first-order rate constant and a disper-
sion coefficient from experiments in a laminar flow tubular reactor Consider
the mass balance (125) with zero mass flux at the wall, and consider a
series of experiments in which the velocity-averaged outlet concentration y
in Eq. ( 125) has been measured at different axial positions z in a reactor
tube of given diameter. It is desired to estimate the rate constant kR and
the radial diffusivity D. Experimental results of this kind were obtained
by Cleland and Wilhelm (1956), who determined D assuming that kR was
known. The experimental setup is also described by Seinfeld ( 1969), Sein-
feld and Lapidus (1974), and Vari den Bosch and Hellinckx (1974), where
kR was to be determined while the dispersion number was assumed to be
known from independent measurements.
We shall consider the possibility of simultaneous estimation of the two
parameters. Write Eq. (125) as
( 152)
2
where 1/J = D/kRrt. The solution of Eq. (152) by collocation is averaged to
give
N
y = ~ c. exp( A.Da z) ( 153)
1 1 1
where the constants ci and Ai are functions of 1/J only.
A set of equivalent experiments would comprise variation of vav at
fixed total reactor length and diameter. Let Dar= kRL/vav,r and
V
av,r
Da z = Da z' where z' = z - - - ( 154)
r v
av
and the outlet , z = 1 , the value of z' = vav r /vav.
Numerical values of Ci and of Ai are calc'ulated for 1/J = 0.1, the value
used by Seinfeld (1969) and Lapidus and Seinfeld (1974):
i A. c.
1 1
1 -0.8429 o. 9211
2 -2.30 0.069
3 -5.26 0.007
54 Villadsen and Michelsen
A perturbation analysis for large 1jJ [see Eq. (122) for the first term]
yields
A = -1 + - 1- -
1 481/J
(155)
C = 1 - l
l 768i
while Ai 'v
O{ijJ-1) and ci 'v
O(f 2) for i > 1.
When 1jJ is large enough to allow terms in 1/J- 2 to be neglected (1/J = 0.1
is barely large enough to permit this approximation), the expansion ( 153)
can be truncated after the first term:
y'v exp[Dar(-1 + 4!1/J) z'] ( 156)
and measurements of y alone are not sufficient to determine separate
values of D~ and 1/J. Only the product Dar (-1 + 1/481/J) will be found by
plotting ln y versus z' .
We have constructed the following "measurements" of y for Dar = 2 and
1jJ = 0.1 by high-order collocation of Eq. (152) and truncating the results
after the third digit:
z' y -ln y -In y/z'
0.1 0.826 0.1912 1. 912
0.2 0.687 0.3752 1. 877
0.3 0.555 0.5551 1.850
0.4 0.481 0.7319 1.830
0.5 0.404 0.9063 1. 813
0.6 0.340 1.079 1. 798
0.7 0.286 1.252 1. 788
0.8 0.241 1. 423 1.779
0.9 0.203 1.595 1. 772
1 0.172 1. 760 1.760
According to Eq. (156), the ratio ln y/z' should be constant, and since
this is not quite so, we may be able to determine both parameters Dar and
1/J.
Linear regression of the data with z' > 0. 5 yields ln y = -- 0. 053 - 1. 71z'
and now, from Eq. ( 153), truncated after the first term (which is certainly
adequate for large z', say z' > 0. 5), one obtains initial estimates for Dar
and ijJ:
y'v(l--l) 768i
exp [-Da z' (1 - - 1 + - 1 )]
r 481/J 192ol
( 157)
Numerical Methods in Reaction Engineering 55
The result is 12.o = (D3r,1/l)o = (1.93,0.157).
These values are used as initial values in a complete least-squares pro-
cedure based on Eq. ( 152) , which i~ solved by three-point collocation, and
on all the "experimental" points (z' ,y).
The sensitivity with respect to D3r is found by differentiation of Eq.
( 152):
N
d
~ >..z'c. exp(A.Da z') ( 158)
dDa l l l r
r 1
while the sensitivity with respect to 1jJ is found by numerical perturbation
(although analytical differentiation could also be used).
Convergence is obtained in a few iterations, and total computing time
(WATFIV compiler, Harwell VBO lAD parameter estimation program) is O. 2
s. The results are
Da = 1.994 ± 0.1%
r (159)
1jJ = 0.104 ± 2%
The error of 1jJ is substantial, considering that the data are accurate to
three digits, an accuracy that is not likely to be found in practice. The
rate constant is, however, determined with the expected small standard
deviation. The two parameters are strongly correlated (correlation coef-
ficient O. 95) and this, combined with the large standard deviation of ijJ,
shows that the use of laminar flow reactor data for y are unsuitable for
determination of ijJ, based on a "known" value of Da. A small error in
the rate constant will be strongly magnified when iμ is estimated. Converse-
ly, an approximate value for 1jJ is all we need to determine a very good
estimate for the rate constant, using exactly the same data.
Finally, it should be mentioned that concentration measurements at
the exit of the tube, but at the centerline (i.e. , measurements on samples
taken through a small-bore tube which is centrally placed in the reactor
tube) will be much better suited for determination of the two parameters.
We have repeated the estimation, but based on 10 "measurements" taken at
x = 0 and with the same "experimental error." Now 1jJ is found to 0.1004
with a standard deviation of only 0. 4%, while the value of Da is 1. 997 and
has the same standard deviation ( 0. 4%) as before.
The result, which is obtained by a simple numerical analysis of the
model from which the parameters are to be extracted, illustrates how an
experimental program can be guided by simulation studies.
Example 8: Kinetics of a homogeneous liquid-phase substitution reaction
("the Dow Chemical Company test problem") In 1981, Blau et al. from the
Dow Chemical Company published the formulation of a multi-response-
parameter estimation problem. The problem is concerned with an industrial
reaction, "hidden" behind the following symbolic nomenclature:
HA + 2BM = AB + HMBM ( 160)
It is a liquid-phase reaction catalyzed by QM, which is fully dissociated to
M- and Q+.
56 Villadsen and Michelsen
The problem was given to a number of research groups in the United
States and in Europe who were supposed to contribute with a solution. A
comparison of the solutions would, it was hoped, give a review of the state
of the art in parameter fitting for reaction engineering models. Here we
summarize the more general conclusions from the solution that was sub-
mitted by our group (Sarup, 1982).
The postulated mechanism is (Blau et al., 1981):
K2
HA--A-+ H+
K K3
A- + BM _!_ ABM- _____,_ HABM(-H)+
M
kl
--
+ BM ----MBM
k_l
-
+M
K
- + 1
MBM + H - - - HMBM
The reaction is carried out in a batch reactor. Table 3 summarizes the
concentration-time profiles for one of the three temperatures used in the
experimental work.
There are three rate constants, k1, k_ 1 , and k 2 , and there are three
equilibrium constants, K 1 , K 2 , and K 3 . Activation energy and frequency
factor for the three rate constants and values of the three temperature in -
dependent equilibrium constants are desired. +
The 10 species HA, BM, HABM, AB, HMBM, M-, A-, H , ABM , and
MBM- are given by mass balances-six ordinary differential equations
coupled with three equilibrium relations and one condition that expresses
electroneutrality. At t = 0 only HA and BM are present with a small
amount of catalyst QM.
Initial estimates for all parameters are given by Blau et al. (1981). _17
From the set of initial estimates, we shall mention only that K 1 = K 3 = 10
and K 2 = 10- 11 .
Our solution of the problem proceeds in the following three steps:
1. Analysis of the original data. A closer study of the data in Table
2 reveals an alarming fit of the mass balance for B. Except for obvious
misprints it is seen that
cBM = cBM - cHABM - 2cAB (161)
The data were analyzed by the method of Box ( 1973) and it was found that
there is not only one, but two linear relations between the "original" data.
Correspondence with Blau gave the following supplementary information:
a. cBM was not measured, but back-calculated from the mass balance
( 161).
b. The concentrations of HA, HABM, and AB were all measured, but
their sum was normalized to agree with a "known" initial concentra-
tion of HA:
Numerical Methods in Reaction Engineering 57
TABLE 3 Concentration Versus Time Profiles for
The Dow Chemical Company Test Example (T = 40°C)
Concentrations (g mol/kg)
Time
(hrs) BM HA HABM AB
0.00 8.3200 1. 7066 0.0000 0.0000
0.08 8.3065 1. 6960 0.0077 0.0029
0.58 8.2954 1.6826 0.0234 0.0006
1. 58 8.2730 1. 6596 0.0470
2.75 8.2437 1.6305 0.0763
3.75 8.2277 1.6143 0.0923
4.75 8.2026 1. 5892 0.1174
5.75 8.1781 1. 5673 0.1371 0.0024
8.75 8.1265 1.5133 0.1935
23.05 8.0167 1. 4075 0.2949 0.0042
21. 75 7.8440 1. 2308 0.4760
28.75 7. 6977 1.0931 0.6047 0.0088
46.25 7.3234 0.7268 0.9530 0.0268
52.25 7.1495 0.5773 0.0881 0.0412
76.25 6.6123 0.2065 1. 2929 0.2074
106.25 6.2309 0.0650 1.1941 0.4475
124. 25 6.1220 0.0391 1.1370 0.5305
147.75 6.0084 0.0244 1.0528 0.6294
172.25 5.9193 0.0145 0.9835 0.7086
196.25 5.8556 0.0083 0.9326 0.7659
219.75 5.8037 0.0074 0.8821 0.8171
240.25 5.7680 0.0050 0.8492 0.8514
274.25 5.7222 0.0047 0.8064 0.8957
292.25 5.7021 0.0042 0.7869 0.9155
316.25 5.6722 0.0015 0.7628 0.9425
340.75 5.6593 0.0017 0.7495 0.9556
364.25 5.6351 0.7263 o. 9793
386.75 5.6176 0.7112 0.9956
412.25 5.6131 0.7063 1. 0003
442.75 5.5991 0.6927 1.0141
460.75 5.5959 0.6871 1.0195
58 Villadsen and Michelsen
TABLE 2 ( Continued)
Concentrations ( g mol/kg)
Time
(hrs) BM HA HABM AB
483.75 5.5905 0.6837 1. 0229
507.25 5.57.36 0.6672 1. 0396
553.75 5.5568 0.6494 1.0574
580.75 5.5631 0.0046 0.6467 1.0551
651.25 5.5472 0.6408 1.0660
673.25 5.5516 0.6452 1. 0616
842.75 5.5465 0.6397 1. 0669
Source: Blau (1981).
CHA = CHA + CHABM + CAB ( 162)
This normalization is common practice in analysis of chromatographic
data and the error is not as "crude" as that involved in (a). Still,
when normalized measurements are used, the error structure of the
true measurements is completely distorted and one may use a stand-
ard least-squares approach rather than one of the more sophisticated
statistical criteria.
The comments regarding the data base should not be construed as a
criticism of the author of the problem. A preliminary analysis of the raw
data is always valuable, and the flaws in the original data material are
probably typical for what can be expected in practice.
Our conclusion has been to delete the concentration measurements of
cBM from the data base since they contain no independent information.
2. Preliminary analysis of the model. Total mass balances for A, B,
and M and the three equilibrium relations can be used to eliminate 6 out of
10 dependent variables to give a set of three coupled differential equations
and one algebraic equation.
The postulated values of the dissociation constants K1, K 2 , and K 3 are
so small that the acids are almost totally undissociated. One might assume
that the concentration of H+ is nearly zero, and this reduces the model to
three differential equations in three components, chosen as HA, BM, and
M-. cA-, cABM -, and cMBM- are given by
-1
K 3 cHABM K 1 cHMBM)
cA- = (1 + - + - (c + - CM-)
K2 CHA K2 CHA Q
( 163)
Numerical Methods in Reaction Engineering 59
K 1 cHMBMcA-
cHBM- = K2 cHA
while cHABM, cAB, and cHMBM are calculated from the total mass balances
for A, B , and M. Except for the assumption CH+ "' 0, there are no ap-
proximations involved relative to the original model, and we have checked
that our results for the parameters are virtually unaffected by the assump-
tion CH+ "' 0.
With this assumption-which appears to be quite realistic-it is impos-
sible to find absolute values for the equilibrium constants Ki, K 2 , and K 3 .
Only their ratios K3/K2 and K1/K2 can be found.
If these ratios are as small (ca. 10-6) as indicated in the problem
description, the system is extremely stiff: cHA will decrease almost to
zero, following pseudo- zero-order kinetics. When cHA has become of the
order of K1/K2, the rate expression changes to pseudo first order in cHA.
All HA would essentially have to react before the "dead-end" reaction to
HABM reverses direction and starts to send ABM- back into the main reac-
tion sequence.
3. Simulation and parameter estimation. To simulate the solution y of
the model, we used the IMSL routine DGEAR, which was modified to include
algebraic ("exact") evaluation of the sensitivities with respect to the param-
eters.
There are in all eight parameters in k1, k_ 1 , k 2 , K1/K2, and K3/K2,
but sensitivities with respect to activation energy Ej and frequency factor
ai of the rate constants ki can easily be computed from the sensitivities
with respect to kj:
ay
aa
~ak
= ·a k a a = exp (-~) ~
T ak
( 164)
~
clE
= ~~ =
elk clE
- ~ exp (- ~) a Y
T T ak
With this simple device the original 3(2•3 + 2) = 24 sensitivity equations
are reduced to 15 equations.
Also, it is important to rescale the parameters since the magnitude of
a and E are so different that it becomes difficult to harmonize the sensitivi-
ties. Instead of a and E, we use k(T 0) and E /T O defined by
( 165)
where T O is a suitable reference temperature ( chosen as the middle of the
three temperatures used in the experimental investigation). With the re-
scaled parameters a large part of the inherent correlation between the two
parameters involved in k is removed.
In general, if a new parameter p 1 = f(p 0) is introduced instead of p 0 ,
one obtains the sensitivity with respect to p 1 by the simple algorithm
60 Villadsen and Michelsen
(166)
The Harwell code VB0lAD was used for the least-squares minimization.
The routine is based on the Levenberg-Marquardt method, and it requires
analytic derivatives of the error vector with respect to the parameters.
There was no difficulty in obtaining the minimum of the sum of least
squares-about 10 s of CPU time to determine all eight parameters (which
corresponds to ca. 0. 5 s per integration of the model and the 15 sensitivity
differential equations).
It is remarkable that the integration of the three equations for CHA,
cBM, and CM-together with all the sensitivity equations-requires only
twice the time used for the three quations of the state vector. Here it is
much better to use exactly derived sensitivity equations than to use numeri-
cal perturbation of the parameters, which is considerably slower (by a fac-
tor of 6) and requires a much higher integration accuracy to give meaning-
ful results.
Also, a comment on the initial values of K3/K 1 and K1/K2 is necessary.
To obtain the best estimates for these parameters ( 1. 43 and 0. 0672, re-
spectively) it was necessary to start with an initial estimate of K1/K 2
which was decidedly larger than the small value 10-6 suggested by Blau
( 1981).
It is not difficult to see from Table 3 that cHABM starts to decrease
much before HA has been consumed, and consequently that K 1 /K 2 has to
be larger than 10- 6 . It is, however, not at all obvious that the routine
fails to predict the correct values of q 1 = K1/K 2 and q 3 = K 3 /K 2 if the
original estimate of the parameters is used. The reason is that the object
function is affected only by the ratio q3/q1, not by their absolute values
when they are as small as 10- 6 , and it becomes impossible for the routine
to drag the parameter values all the way from 10-6 to their correct values
of about 10- 1.
The integration routine is much faster when (K1/K 2 ,K3/K 2) are of the
order of 1 than when they are ca. 10-6. The reason is the sudden increase
of stiffness that occurs when cHA "' 0, and the apparent reaction order of
the reaction A- + BM + ABM- changes from zero to 1. The problem may
occur quite frequently in the application of standard "kinetic codes," and
it may be illustrated by the simple rate expression ( 167):
R = with k "- 1 and K "' 10- 6 (167)
Even a good numerical integration routine (e.g., DGEAR) will fail to notice
the rapid change in the structure of the solution when YA "' 10-6 and will
happily integrate to negative concentrations of A. This may have a disas-
terous effect on the computation of other reaction species, which may be
heavily influenced by the concentration level of component A.
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Numerical Methods in Reaction Engineering 61
Aris, R. , and N. R. Amundson, First Order Partial Differential Equations
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Baden, N. , and J. Villadsen, A Family of collocation based methods for
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Blau, G., L. Kirkby, and M. Marks, An industrial kinetics problem for
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Box, G. E. P., W. G. Hunter, J. McGregor, and J. Erjavec, Some
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Byrne, C. D. , Some software for solving ordinary differential equations, in
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Caillaud, J. B. and L. Padmanhaban, An improved semi-implicit Runge-
Kutta method for stiff systems, Chem. Eng. J., 2, 227 (1971).
Christiansen, L. J. and S. L. Andersen, Transient profiles in sulphur
poisoning of steam reformers, Chem. Eng. Sci., 35, 314 ( 1980).
Cleland, F. A. and R. H. Wilhelm, Diffusion and reaction in viscous flow
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Clement, K. and S. B. J0rgensen, Experimental investigation of axial and
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(1983).
Crank, J., Mathematics of Diffusion, Clarendon Press, Oxford (1957).
Finlayson, B. A., The Method of Weighted Residuals and Variational
Principles, Academic Press, New York (1972).
Finlayson, B. A. , Orthogonal collocation in chemical reaction engineering,
Catal. Rev. Sci. Eng., 10, 69 (1974).
Finlayson, B.A., Nonlinear Analysis in Chemical Engineering, McGraw-Hill,
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Fletcher, R., Unconstrained Optimization, Wiley, New York, (1980).
Funder, C. R., M.Sc. thesis (in Danish), Instituttet for Kemiteknik (1982).
Gear, C. W., Numerical Initial Value Problems in Ordinary Differential
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Hoffman, U. , G. Emig, and H. Hofmann, Comparison of different methods
for determination of effective thermal conductivity of porous catalysts,
ACS Symp. Ser., 65, 189 (1978).
Holk-Nielsen, P., and J. Villadsen, Absorption with exothermic reaction
in a falling film column, Chem. Eng. Sci., 38, 1439 (1983).
Jackson, R. , Transport in Porous Catalysts, Elsevier, Amsterdam ( 1977).
Kaza, K. R., Villadsen, J., and R. Jackson, Intraparticle diffusion effects
in the methanation reaction, Chem. Eng. Sci. , 35, 17 (1980).
Levenspiel, 0., Chemical Reaction Engineering, 2nd ed., Wiley, New York,
(1972).
Liaw, W. K. , J. Villadsen, and R. Jackson, A simulation of coke burning
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Michelsen, M. L., A fast solution technique for a class of linear PDE,
and Estimation of heat transfer parameters in packed beds from radial
temperature measurements, Chem. Eng. J., 18, 59, 67 (1979).
Michelsen, M. L. and J. V. Villadsen, Polynomial solution of differential
equations, in Foundations of Computer-Aided Chemical Process Design,
62 Villadsen and Michelsen
Vol. 1, S. H. Mah and W. D. Seider, eds. , Engineering Foundation,
New York, 1981, p. 341.
Michelsen, M. L., H. B. Vakil, and A. S. Foss, State space formulation
of fixed bed reactor dynamics, Ind. Eng. Chem. Fundam., 12, 323
(1973).
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18, 1010, 1033 (1981).
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problem with prescribed wall flux, AIChE J., 26, 779 (1980).
Patterson, W. R. , and D. L. Cresswell, A Simple method for the calcula-
tion of effectiveness factors, Chem. Eng. Sci. , 26, 605 ( 1971).
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dual reactor system with liquid catalyst, Chem. Eng. Sci. , 37, 1095
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Sarup, B. , M.Sc. thesis (in Danish), Instituttet for Kemiteknik ( 1982).
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fication, Prentice-Hall, Englewood Cliffs, N .J. ( 1974).
Sotirchos, S. V. and J. Villadsen, Diffusion and reaction with a limited
amount of reactant, Chem. Eng. Commun., 13, 145 (1981).
Sundaresan, S. and N. R. Amundson, Diffusion and reaction in a stagnant
boundary layer about a carbon particle, Ind. Eng. Chem. Fundam.,
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Sr$rensen, J. P., Simulation, Regression, and Control of Chemical Reactors
by Collocation Techniques, Polyteknisk Forlag, Lyngby, Denmark
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diffusion and reactions in porous catalysts, Chem. Eng. Sci., 37,
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Models by Polynomial Approximation, Prentice-Hall, Englewood Cliffs,
N.J. (1978).
Villadsen, J. and W. E. Stewart, Solution of boundary-value problems by
orthogonal collocation, Chem. Eng. Sci. , 22, 1483 ( 1967).
Villadsen, J. and J. P. Sr$rensen, Solution of parabolic PDE by a double
collocation method, Chem. Eng. Sci., 24, 1337 (1969).
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Wedel, S. and J. Villadsen, Falsification of kinetic parameters by incorrect
treatment of recirculation reactor data, Chem. Eng. Sci. , 24, 1346 (1983).
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3, 316 (1951).
2
Use of Residence- and Contact-Time
Distributions in Reactor Design
REUEL SHINNAR The City College of the City University of New York,
New York, New York
INTRODUCTION
Tracer experiments and residence-time distributions measurements have
been used by reaction engineers for 50 years. They are a powerful tool
with an increasing number of applications. The first rigorous presentation
was given by Danckwerts ( 1953). Since then a large body of literature has
accumulated and the topics are discussed in several textbooks (Froment and
Bischoff, 1979; Himmelblau and Bischoff, 1968; Seinfeld and Lapidus, 1974;
Nauman, 1983; Levenspiel and Bischoff, 1963) and review articles (Shinnar,
1977; Petho and Noble, 1982; Nauman, 1981; Weinstein and Adler, 1967).
Tracer experiments and residence-time distributions are useful to re-
action engineers in several ways. They provide a diagnostic tool for the
detection of maldistributions and the flow pattern inside a reactor. They
are useful in experimentally measuring the parameters of simplified flow
models and provide ideas and guidelines for creating and testing such
models. Finally, understanding the concept of residence-time distribution
greatly simplifies the solution of many problems in reactor design, including
the choice of reactor configuration, optimization, and scaleup, and allows
one to solve them without complex and time-consuming computations.
One must, however, be careful not to expect more from the techniques
than they can deliver. It is extremely rare that one can either construct
a reactor model or predict a reactor performance based solely on a residence -
time distribution (Shinnar, 1978) in a situation involving complex flows.
Most reactors are heterogeneous, and the theory as presented in most text-
books is rigorously applicable only to homogeneous reactors. It is therefore
important to understand the advantages as well as the limitations of the
method.
This writer has been involved both in developing some of the theoretical
concepts related to their use and in their practical applications (N aor and
Shinnar, 1963; Shinnar and Naor, 1967; Krambeck et al., 1969; Shinnar
et al., 1972; Naor et al., 1972; Zvirin and Shinnar, 1975; Glasser et al.,
1973; Krambeck et al., 1967; Silverstein and Shinnar, 1975; Shinnar et al.,
1973). In the following sections I try to present the subject in a way that
63
64 Shinnar
stresses practical applications, discussing both advantages and pitfalls.
Thus, by necessity, I must exclude a large amount of theoretical work
which may become useful in the future but has yet to prove its applicability
in practice, and in that sense this chapter presents a personal viewpoint
based on my own experience. Although I try to provide the reader with
references to the literature, no attempt will be made to give full proper
credits to original papers or to historical development.
The theoretical concepts for homogeneous systems are derived in the
following section. Then we discuss experimental techniques for their
measurements and their use and applications in reactor modeling and in the
testing of industrial reactors. Next, we deal with applications to the design
of homogeneous reactions and with multiphase systems and the use of mul-
tiple tracers. Following that, we introduce contact-time distributions, a
concept similar to residence-time distribution that is useful in catalytic re-
actors. Finally we summarize the use of residence-time and contact-time
distributions in catalytic reactor design.
DEFINITIONS OF THE RESIDENCE-TIME DISTRIBUTION,
AGE, AND FUTURE LIFETIME DISTRIBUTION
Residence-Time Distribution
Consider a homogeneous reactor as shown in Figure 1. Assume that the
flow is stable and steady and that the inlet and outlet streams are completely
mixed. Let us now assume that each fluid particle is equipped· with a timer
that is activated when it enters the reactor and stops when it exits. It is
important to define a single exit from which the particle cannot return to
the reactor. Each particle at the exit has a time t associated with it, which
measures the time it spent in the reactor. This quantity is defined as the
residence time for that particle. As with any scalar property, one can de-
fine the distribution of this property by the fraction of the particles for
which the residence time is less than a given value t (see Fig. 2). This
fraction F(t) is defined as the residence-time distribution. [Alternatively,
one can define the residence-time distribution as the fraction of particles
or molecules which has a residence time larger than t, simply 1 - F(t).]
Clearly, F(O) = 0 and F(t) must be a monotonically increasing function with
F(oo) = 1.
Density Function
For any probability distribution, F(t), the derivative that is defined by
f(t) = dF(t) ( 1)
dt
REACTOR Outlet flow Q
Inlet flow Q
volume V
FIGURE 1 Steady-state homogeneous reactor.
Residence- and Contact-Time Distributions 65
1.0
I.J...
z 0.8
0
1--
:::,
(I)
a: 0.6
1--
(/)
0
w F - Fraction of particles
:\!,
j:: 0.4 with residence time in
w the reactor less than(!)
u
z
w
0
(/) 0.2
w
a:
0.0
0.0 1.0 2.0 3.0 4.0 5.0
TIME ( t)
(a)
0.8
k k
A_].B~C
0.7
0.6
0
<(
'
m
::iE 0.5
:::,
:E
X
<(
::iE 0.4
0.3
0.2
IDEAL
STIRRED TANK
0.1
0.0 1.0 2.0 3.0 4.0 5,0
k2
ki
(b)
FIGURE 2 Definition of residence-time distribution.
66 Shinnar
is called the density function and is often of great interest. In the case
where F(t) is a residence-time distribution, f(t) dt corresponds to the frac-
tion of fluid particles whose residence time is between t and t + dt. Some
typical distributions of F(t) and f(t) are given in Figure 3. The way such
distributions are measured and computed will be shown in the next section.
Some properties of the function will be discussed next.
One should note that in the chemical engineering literature the density
function f(t) is often designated E(t) and is sometimes called the residence-
time distribution. [1 - F(t)] is often designated as I(t). As there is a
large literature on the mathematical properties of residence-time distribution
outside the chemical engineering literature, the standard notation F(t) and
f(t) will be used in this chapter.
Mean, Variance, and Moments of f(t)
The expected value or mean of the density function f(t) is defined by
=f f
00 00
= E (t) tf(t) dt = [1 - F(t)] dt ( 2)
f 0 0
This is also equal to the first moment of f(t) and is a widely accepted
measure of the central value of a distribution. In reactor systems with con-
stant density, it is equal to the volume or liquid holdup of the reaction,
divided by the flow rate:
V
T = (2a)
Q
and is also known as the time constant of the system. For purposes of com-
parison, it is often useful to normalize the residence-time distribution such
that the time constant or mean value is unity. Therefore, we define
e = t (2b)
T
where 0 is a dimensionless normalized variable. Most of the graphs in this
chapter use e.
Another important measure is the variance of a distribution, Vf( t) ,
which is defined by
f
00
= [t - E/t>l 2f(t) dt = E/t 2) ( 3)
0
Vf(t) can also be computed directly from F(t) by
00
= 2 ~ t[l - F(t)] dt (3a)
The variance (or the second moment with respect to the average) measures
the dispersion of a distribution. Relative disperison is also frequently
characterized by the coefficient of variation,
Residence- and Contact-Time Distributions 67
/ .,.... -----
1.0
0.8
;;>;
2·/
'/
0.6
/.'
F(B) I/
II
- - Stirred Tank
0.4
I
// - - - 10 Stirred Tanks in Series
- - - - One Dim. Diffusion
//
I
Pe = 10
0.2 I
,1/
I
/./,
0.0
0 2 3 4
e
(a)
1.50
l. 2 5
I. /\.\
1.00
/(\ \ \
,I \\'
f (8)
I,
I
0.75 I, \ \
\ '
0.50 I '~ \
(j
/,
.
0.25 I,
ij
/,
0.0
0 2 3 4
e
(b)
FIGURE 3 (a) Residence-time distribution, (b) residence-time density
function for some simple theoretical flow models.
68 Shinnar
y(t) = ( 4)
When needed, higher moments can be computed using standard methods.
The rth moment of the density function f(t) is defined as
= f0
00
t
r
f(t) dt = y
f 00
t
y-1
[l _ F(t)] dt ( 5)
0
It should be stressed that the functions f, F, and ( 1 - F) refer to the
distribution of the residence times of particles as they appear at the exit
of the flow system.
Linear Properties of Residence-Time Distributions
Residence-time distributions have the properties of linear functions. Thus
if two systems are put in series (see Fig. 4a), the density function of the
total system is the convolution of the two systems, and if they are parallel,
it is the weighted average (Fig. 4b). Thus for mathematical operations it
is useful to apply the Laplace transform of f(t),
f
00
L[f(t)] = f(s) = e- st f(t) dt (6)
0
The Laplace transform can also be used as a moment-generating function.
The rth moment of f(t), µr, is then given by
(6a)
Flow systems are nonlinear systems insofar as the Navier-Stokes equa-
tion is nonlinear. The fact that residence-time distributions have the prop-
erties of a linear system indicates that they provide an incomplete descrip-
tion of the flow process in the reactor. Therefore, they cannot completely
describe the flow, but represent only some important properties of it. If
one designates the complete hydrodynamic description of all the flows and
mass transfer processes in the reactor as M, then F is a linear property
associated with M. While the transformation of M into F is unique, the
opposite is not true. As F is an incomplete description of M, a single F
can have an infinite number of functions M associated with it. In other
words, there can be a large number of completely different hydrodynamic
flow systems with the same residence-time distribution.
Intensity Function or Escape Probability
A residence-time distribution is a deterministic property of the flow system.
It is sometimes advantageous to interpret it probabilistically. One can also
look at F(t) as the probability that a single molecule will have a residence
Residence- and Contact-Time Distributions 69
Q REACTOR I Q REACTOR II
Q
VOLUME V 1 VOLUME v2
RTD - F1 (t) RTD - F2 (t)
DENSITY FUNCTION: DENSITY FUNCTION:
fl ( t ) f2( t )
RTD OF TOTAL SYSTEM:
t
f (l+ 2 ) (t) = ft, (t-T) t 2 (T) d T
0
OR IN LAPLACE DOMAIN:
f(l+ 2 l(s) = t1 (s) * t2 (s)
AVERAGE RESIDENCE TIME:
(a)
Ql REACTOR I Ql
11 (t ), v1
Q
Q2 = Q -Q, REACTOR II Q2
12 ( t ), V2
-f
Q
F1 (t)
AVERAGE RESIDENCE TIME: r
( b)
FIGURE 4 Residence-time distribution of two reactors: (a) in series;
(b) in parallel.
70 Shinnar
time less than t in the reactor. This presents the information contained in
F(t) in a more accessible way. Consider a system characterized by the
residence-time density f(t). In probability terms, f(t) can be interpreted
as follows. If a particle enters the system at time t = 0, the probability
of its leaving the system within the time interval (t to t + dt) is equal to
f(t) dt. However, a slightly different problem may be posed. A particle
has already stayed in the system for a time t; one wishes to know the
probability of its leaving the system within the next time element dt. Let
this probability be denoted by A(t) dt. The function A(t) may be evaluated
as follows. The probability of a particle leaving the system between time t
and t + dt equals f(t) dt. This probability is the product of two terms:
The probability of the particle not leaving before t, which is 1 - F(t), and
the probability of its leaving between t and t + dt, assuming that it is still
in the system and has not left before-this was defined as A(t) dt.
Thus we obtain
f(t) dt = [1 - F(t)]A(t) dt (7)
and by simple rearrangement A(t) is derived as
F(t) -d ln[ 1 - F(t) J
A(t) = 1 - F(t) = (8)
dt
A(t) is the conditional probability distribution and is also known as the in-
tensity function or the escape probability. It must be stressed that there
exists a one-to-one correspondence between A(t) and f(t). Indeed, the
transformation of A(t) into f(t) is governed by
f(t) = A(t) exp [- {t A(t') at'] ( Sa)
Physically, A(t) dt is a measure of the probability of escape for a
particle that has stayed in the system for a period t during the time inter-
val t and t + dt. Thus, in the case of an ideally (exponentially) mixed
vessel, one expects the intensity function A to be a constant, as the chance
of escape during any time interval dt is independent of previous history
and is equal to dt/T. This is indeed the case. Although there is a one-
to-one correspondence between f(t), F(t), and A(t), information about the
properties of the residence-time distribution and the nature of the flow
system is more easily accessible from A(t).
Utilizing the intensity function, it is easy to demonstrate a previously
mentioned problem with residence-time distributions, namely, that the rela-
tion between F and M is not unique. This is illustrated in Figure 5, which
describes the properties of a number of theoretical flow models. Thus, for
an ideal uniformly stirred tank, A(t) must be a constant (see Fig. 5a,
curve A). However, the converse is not true. A A(t) that is constant im-
plies that the escape probability of a particle is independent of its previous
history. In other words, the information as to how long a particle has
been in the system tells us nothing about its future behavior. The fact
that a system has this property does not prove or indicate that it is an
ideally stirred reactor. The latter also implies that the concentration of
Residence- and Contact-Time Distributions 71
,02 . - - - - - - - . - - - - - - - - - - - - - - - - - - - - ,
,cI
I
l B~--- - - - - - -
:/
A<Bl
yI '
,I
/iI
10
0
1-ic....+--------------------1
I A
101
0.50 2.50 4.50 6.50
8
(a)
,oo
I
I I
1-F(B)
i \
I ,
A
cl \s
I\
I I
I \
I
,02 - - - - - ~ - ~ - - ~ - - - - ~ - - - - ~
0.0 2 3 4
8
(b)
FIGURE 5 (a) Intensity function for some simple flow models: . A, stirred
tank; B, approach to plug flow (estimated by 30 tanks in series); C, ideal
plug flow ( o function at e = 1). (b) Cumulative residence-time distribution
for the models in part (a).
72 Shinnar
all different species in the reactor is completely uniform at all points,
which is not a necessary condition for A(t) to be constant.
In many reactors, such as packed beds or baffled fluid- bed reactors,
one wishes to approach plug flow as closely as possible. In reality, one
cannot achieve ideal plug flow and the escape probability will resemble the
one shown in Fig. 5a, curve B. This condition will be called near plug
flow. Such a flow can be modeled by either a series of stirred tanks or
by a one-dimensional diffusion model. Both of these share one property,
which is physically very well represented by the escape probability. For
values of t that are small compared to the average residence time (t << T),
the escape probability is close to zero. As t approaches T the escape
probability rises until it reaches a final constant value. Physically, that
means that for t » T the probability of the molecule being near the exit
if it is still in the system is high. In a series of stirred tanks one can
therefore assume that for t » T the particle is probably in the last tank
and its escape probability is the probability of escaping from the last tank
(see Fig. 6a, curve A). It can be shown (see Shinnar and Naor, 1967),
that in a series of stirred tanks with forward and backward flow between
the tanks (Fig. 7), the escape probability has a similar form. The same
applies to the one-dimensional diffusion model (Fig. 6a, curve B).
In a real packed bed the flow is not necessarily one-dimensional. There
might be a flow maldistribution due to a bad distributor. If there are re-
gions in which the fluid flows faster, then to maintain the same average re-
sidence time, there must also be regions of slower flow. Three such models
are given in Figure 8. In such a case, if t » T, the particle is probably
in the slow region and has a lower escape probability. The same is true if
we consider a system in which there are stagnant regions which particles
can diffuse in and out of, or if there are adsorption phenomena (Fig. 8a,
curve B). Whenever any A( t) has a maximum and then decreases, it implies
that the system either has regions of fast and slow flows or stagnant re-
gions in which a particle can get trapped. Curve C in Fig. 8a shows that
adsorption phenomena do not necessarily lead to decreasing values of A.
If the mass transfer processes are rapid compared to the overall flow
velocity, no stagnation will be occur and the escape probabilities will not
be significantly affected.
The exact value of the intensity function is often less important than
its form, which provides physical insight into the nature of the flow. The
critical features of A(t) are recognizable from the form of ln(l - F) versus
t as A(t) is the derivative of -ln(l - F). This can be seen from Figs. 6b
and 8b, where ln( 1 - F) plotted versus t for the flow models given in Figs.
6a and 8a. Figure 8c illustrates f(t) for cases with stagnancy. Note that
it is much harder to interpret f(t) then ln(l - F) or A(t).
Age Distribution
Consider the thought experiment where a timer is attached to all the parti-
cles entering the system. Instead of collecting them at the outlet, the
whole system is stopped at some time to to collect all the particles inside
the reactor. One can then construct a distribution G(t) such that G(t)
measures the fraction of particles inside the reactor that entered after
to - t. G(t) expresses the probability that a particle chosen at random
inside the reactor has an age less than t. It is also called the age distribu-
tion. G(t) is related to F(t) by the relation
Residence- and Contact-Time Distributions 73
3.0
B ,,,.-------------------
/.
2.0
I A
A(B)
I
1.0
I
'
0.0
0 2 3 4 5 6
8
(a)
10°
~'
1-F(B)
16 2 L . __ _ _L____ _ ____,c___ _~ - - - ~ - - - ~ - ~
0.0 0.5 1.0 7.5 2.0 2.5
8
(b)
FIGURE 6 (a) Intensity function for some simple flow models: A, three
stirred tanks in series; B, one-dimensional diffusion model. (b) Cumulative
residence-time distribution for the models in part (a).
74 Shinnar
FIGURE 7 Schematic diagram for a series of stirred tanks in series with
forward and backward flow between the tanks.
g(t) = 1 - F(t) ( 9)
E/t)
where g(t) is the density function of G(t).
In a multistage system, one can examine a single stage Z and define a
local age distribution Gz with respect to the inlet in the same way as one
defines a local residence-time distribution Fz (see Shinnar and Naor, 1967;
Zvirin and Shinnar, 1975). The same can be done for a local zone in a re-
actor if the flow is not turbulent and the properties of the reactor are
steady in this zone.
A related function is the future lifetime distribution A(t). Consider
again the thought experiment where all molecules inside the reactor are
1.75
CURVE A
1.50
1.25
/i.(8)
CURVE 8
1.00
0.75
I -~-~ .____ ----
--------
✓---~--~--------
{/
•
0.50
CURVE C
,1/
0.25
1/
0.0
0 2 3 4
0
(a)
FIGURE 8 (a) Intensity function for three simple flow models described
above. (b) Cumulative residence-time distribution for the models in part
(a). (c) Residence-time density function for the models in part (a).
Residence- and Contact-Time Distributions 75
10° , - - - " ' : - - - - - - - - - - - - - - - - - - - ~
1- F (8)
,0-2
0.0 2 3 4
e
(bl
0.6
0.5
0.4
0.3
f (8)
0.2
0.7
0,0
0 2 3 4
e
(cl
FIGURE 8 (Continued)
76 Shinnar
provided with a timer. This time, at t = t 0 set all the timers to zero.
Then record the time t for each molecule as it exits and construct the dis-
tribution A(t). Thus A(t) is the probability that a particle which is in the
reactor at time to has exit~d before t 0 + t.
One can also define another related distribution inside the reactor. Con-
sider the thought experiment where all the particles inside the reactor are
again provided with a timer. At a set time t = 0 all the clocks are set to
0. One can then record the clock times on the particles at the exit and
construct a distribution A(t). A(t) is called the future lifetime distribution.
It can be shown that A(t) is equal to G(t) (see Noar and Shinnar, 1963).
Once again, one can define a local future lifetime distribution Az(t). How-
ever, Az(t) i- Gz(t). Both Az(t) and Gz(t) can be measured and are
sometimes useful in modeling ( Zvirin and Shinnar, 1975), but this is outside
the scope of this chapter.
Multiphase Systems
All the definitions given until now refer to a single fluid. If a fluid is
made up of different components, each of them may have a different resi-
dence-time distribution. In a homogeneous reactor, the differences between
the residence-time distributions are in general negligible. However, in
heterogeneous reactors, the differences may be quite large, as different
compounds may adsorb differently or distribute themselves differently be-
tween the phases in multiphase reactors. Here the initial hypothetical
definition can be very helpful in keeping things straight. The system has
to be steady state and one must be able to tag a particle with a clock such
that it retains its identity in passing through the reactor. If the com-
pounds react, one may have to tag an element that does not change and
obtain a set of residence-time distributions Fi (t) for each such element.
For each Fi(t) the definitions of fi(t) and Ai(t) do not change. The only
relation that does not hold is that 'i• the first moment of f(t), is no longer
equal to V /Q. The holdup or average residence time 'i is now different
for each element and not known a priori. A detailed discussion of this
problem is given in a later section.
TRACER EXPERIMENTS: MEASUREMENT OF
RESIDENCE-TIME DISTRIBUTIONS
Methods of Measurement
Step Changes in Tracer Concentration
The residence-time distribution discussed in the preceding section can be
measured in any steady-state system by use of a suitable tracer. Assume
that at time t = 1 one starts labeling all the particles in the feed. One then
measures the fraction of labeled particles at the exit from the reactor at
time t. Any labeled particle that appears at the exit at time t must have
entered the reactor after time t = 0 since before that time, no particles
were labeled. Similarly, any unlabeled particle must have entered the re-
actor prior to time t = 0 since after that time all particles were labeled.
Therefore, the fraction of labeled particles is, by definition, equal to F(t),
which is the probability of staying in the reactor less than time t and the
fraction of unlabeled particles is equal to (1 - F). For small time intervals
Residence- and Contact-Time Distributions 77
it is easier to measure F, whereas for long time spans it is more convenient
to measure 1 - F.
It is not necessary to label all the particles. Assume that at some in -
stant in time t = 0, instead of labeling all the particles, one starts labeling
a constant fraction Cf of the particles in the feed and then measures the
fraction of labeled particles C (t) at the exit. Clearly,
C(t) = F(t)Cf
Since one is usually more interested in estimating F(t), this is usually
expressed as
F(t) (10)
In this case, the fraction of unlabeled particles is no longer directly re-
lated to ( 1 - F), as some unlabeled particles have entered the reactor
after time t = 0.
If one waits long enough, then as t + F(t) + 1 and C(t) + Cf. In
00 ,
practice, equilibrium is reached when t » T, the time constant of the sys-
tem. At that point the fraction of labeled particles at the exit will equal
Cf, the fraction of labeled particles at the feed. Once the system reaches
equilibrium it is useful to stop suddenly the flow of labeled particles
(tracer). From this point on, the fraction of labeled particles at the exit
will decrease monotonically. The fraction of labeled particles, C ( t) at the
exit, measured from the new t = 0 is then given by
C(t) [1 - F(t)]Cf
or
1 - F(t)
This is identical to the case in the preceding paragraph except that now it
is the labeled particles that have entered the system prior to time t = 0.
A step change in tracer is the most accurate way of measuring a
residence-time distribution. C ( t) /Cf should be measured after the tracer
is introduced until equilibrium is achieved and then after the tracer is
stopped. If one could measure the average concentration <C/Cf> inside
the reactor after a step input at time zero (averaged over the total volume
at each instant of time), this yields an estimate of G(t), the age distribu-
tion of the system. This can be achieved experimentally by using a radio-
active tracer and measuring the total radiation emanating from the reactor.
Pulse Experiments
The step input experiments described in the preceding section directly
measure F(t) and 1 - F(t). Another more commonly used tool is the injec-
tion of a fixed amount m of tracer at t = 0 and then measuring the fraction
of labeled particles C (t) at the exit. This leads to a direct measurement
of the density function f(t) given by
78 Shinnar
mf(t) = QC(t)
or
f(t) = QC(t) ( 11)
m
where m is the amount of tracer injected at t = 0 and Q is the volumetric
flow rate. To have reliable estimates of f(t), one needs independent
measurements of Q and m. The relation
m = Q { ' C(t) dt ( 12)
0
allows an estimate of the consistency of available estimates. In the absence
of accurate knowledge of either Q or m, one can use Eq. (12) to reformu-
late Eq. ( 11) as
C(t) (13)
f(t) =
00
/ C(t) dt
0
This allows an estimate of f(t) from a pulse injection in any steady-state
system directly from the measured fraction C ( t). It is the mcist common
way in which tracer pulse experiments are utilized.
Sinusoidal Inputs
Consider the case where the fraction of labeled particles Cf at the inlet is
varied as a function of time. It can be shown that f(t) is equal to the
linear response function for the tracer, or
C(t) f(t) * C/0 (14)
where C(t) is the outlet concentration, Cf(t) is the inlet concentration, and
* denotes the convolution integral. If one writes Eq. (14) in the Fourier
transform, then
A A
C(jw) = f(jw) x C/jw) (15)
Equation (15) is well known from control theory. One can therefore evalu-
ate f(t) in the same way that one evaluates the process transfer function
in controller design.
In this case Cr( t) is varied in a sinusoidal form. After waiting for all
transients to die out and for steady state oscillation in the output to be
established, the amplitude ratio C (t) /Cf(t) and the phase angle are found
by recording input and output data (see Fig. 9a). The frequency of the
input signal is changed and a new amplitude ratio and phase angle are de-
termined. Thus the complete frequency-response curve is determined ex-
perimentally by varying the input frequency over the range of interest.
These measurements are direct measurements of the Fourier transform of
Residence- and Contact-Time Distributions 79
Q ( t) = Q sin (wt)
q ( t) = q sin (wt+8) 8 = PHASE ANGLE = Te 2 n
Tj
(a)
10 1 . . . . . - - - - - - - - - - - - - - - - - - - - - - - - - - - - ,
-..........,
10°-:j-------.::-::::--~-:::.;-:::-- - - -- -- - -
',\_
AR \
''
'I\
\
.
''
'
\
. \
\
16 2 --1-~~~~~---.--,-,-rrTTTT-+-,r,-m7n,--,---y--rrrrr/\-,---T,,rTTTI
16 2 103
WT
- - - - SINGLE CSTR - - - - - PARALLEL CSTR
---------- 5-CSTRs IN SERIES TRAINS N /
csrn7
- - - SINGLE PFR
B~%
11 1
Q =1
- -PA::.~LEL
~ - 4 4 4
20%
Q =1
50 Yo
(b)
FIGURE 9 (a) Sinusoidal input-output curves, w is frequency of input
signal. (b) Frequency response for some simple flow models-amplitude
ratio. (c) Frequency response for the flow models in part (b)-phase lag.
(d) Laplace transform of the density function for the flow models in part
(b).
80 Shinnar
45.0
0.0
..........
8 \.
\
-90.0
\.
-135.0
WT
(c)
_______
·-----------·---- ---
0
10
~~
,01
"'<----.
..,_____ .. ..
1cs)
' ;--------,_-----------------
'<··...........
"
',''--·----..._____________
-2
10
' ---------
''--'--' ..------ -----.. ----
',
2.0 4.0 6.0 8.0 10.0 12.0 14.0
s
(d)
FIGURE 9 (Continued)
Residence- and Contact-Time Distributions 81
the density function f(jw). One can look at f(ju,) as a vector in polar co-
ordinates (r, cp). The amplitude ratio defines the magnitude of the vector
r for each w, and the phase lag defines cp. If one can measure both the
amplitude ratio and the phase lag over a wide range of frequencies, one
has a good estimate of the Fourier transform of f(t). Some typical forms
of these functions are given in Fig. 9b and c.
Measurement of the Laplace Transform from
Arbitrary Inputs
In some cases it is hard to perform an accurate step or pulse experiment.
One might not be able to feed the tracer directly to the reactor, or one
might have a two-stage system where the inlet concentration to the second
stage can be measured, but the tracer cannot be fed directly to it ((/)ster-
gaard and Michelsen, 1969). For fall such cases, one can utilize Eq. ( 14)
and obtain the Laplace transform f(s) of the density function f(t) by
= C(s)output
f(s) (16)
C(s). t
mpu
As C(t) is a measured function, C(s) must be obtained by numerical integra-
tion. This is illustrated in Fig. 10b for several values of s.
Measurement of f(jw) and f(s) poses a problem. Although in theory it is
possible to obtain f( t) by inversion,
a+o
f(t) = 2 ~j f e st f(s) dt
a-o
(17)
0 jwt
1
J-o
A
f(t) = 21rj e f(jw) d(jw)
the results depend strongly on the valueJll of f(s) as s -+ O or f(jw) as
w -+ 0, which are hard to measure. As f(s) is hard to invert, either one
can try and fit f(s) with a reasonable model and then invert it, or one can
use the measurement of f(s) to evaluate directly the properties of the
residence-time distribution. Some typical forms of f(s) are shown in Fig.
9d.
Indirect Estimates of f(t) and F(t)
Indirect ways of measuring residence-time distribution are discussed later.
These are based on the effect of residence-time distribution on conversion,
especially on product distribution in complex reactions.
Measurement of Moments of Residence- Time Distribution
The moments of the residence-time distribution can be computed from either
f(t) or F(t) by using Eq. (2) or
82 Shinnar
z UNIT: ECLP
0
~ 6
a::
I-
z
w
t)
z INLET
0
t) DETECTOR
Cl) 4
Cl)
w
_J
z
Q
Cl)
z
w 2
::!E
0
0
0.0 0.5 1.0 1.5 2.0 2.5
DIMENSIONLESS TIME
(a)
10°
C (s)
C0 (s)
s
(b)
FIGURE 10 (a) Tracer response of a radioactive gas tracer in an Exxon
Donor Solvent coal liquefication reactor. (b) Laplace transform of the re-
sidence-time distribution from part (a) (top of reactor) obtained by
Residence- and Contact-Time Distributions 83
f
00
r-1
µ (f) = r t (1 - F) dt
r
0
The comments on accuracy made before apply also here and the step re-
sponse has a significant advantage. In homogeneous systems, the first
moment can also often be estimated independently from
V
μ1 = T = Q (18)
where V is the volume of the fluid in the reactor. This is an important
check on the accuracy of the measurement of f(tO. Relation ( 18) can only
be used in homogeneous systems, as in a system where there is adsorption
(or solution in another phase) independent knowledge or estimate of the
holdup is difficult.
In the case where, instead of directly measuring f(t) or F(t), the
Laplace transform f(s) is measured, there are two ways to obtain the mo-
ments. When the Laplace transform is obtained from measuring the response
C2(t) to an arbitrary input signal C1(t) (see Fig. 10), one can get the
moments from the fact that the moments for two systems in series are addi-
tive. Recall that
f(t) = g_
m
C(t) (11)
Thus if one now writes
J
00
,1 = g_ tC(t) dt (19a)
m 0
and
where µ 1 and V 1 are the mean and variance, then
( 19b)
00
f0 1
-st
C(t) dt
f(s) = 00
f0 -st
1 C 0 (t) dt
where C is the concentration at the top and c 0 the concentration at the
inlet. The curve can be fitted by [ 1/ ( 1 + Ts /N)] , where T = 1. 18 and
N = 17. (From Tarmy, 1983.)
84 Shinnar
where V 2 and T 2 are defined anal~gously to Eq. ( 19a). There is another
way to extract the moments from f(s), which is especially important for
cases where f(s) is obtained directly, as will be discussed later.
One can obtain the moments of f(t) directly from f(s) as shown in Eq.
( 17). Unfortunately, it is hard to estimate accurately the higher derivatives
near s -+ 0, but one can usually get a good estimate for the first derivative
by using a Taylor expansion, get a reasonable estimate for V and y, the co-
efficient of variation. If y is small (the flow is close to plug flow), V and
y can be estimated by a filtering model such as
f(s) = - -- 1 -- (19c)
( 1 + ,s/n)n
which is a good approximation for flows that are close to plug flow. Equa-
tion (19c) has the form of transfer function for stirred tanks in series,
but here n is used as a fitting parameter. If one can fit f(s) with Eq.
(19c), then
2 1
y (19d)
n
Another way to get the variance from the Laplace transfer for ·cases close
to plug flow can be derived as follows. The measured qu~ntities in Fig. 10
are C1(t) and Cz(t). From this one can derive not only f(s) but also
df/ds:
_1_ df(s) 1 1 ( 20)
=-A--
f(s) ds
where
( 20a)
Evaluation of the derivative of f(s) therefore does not require any numerical
differentiation, but can be evaluated from the concentration curves by in-
tegration. If f(s) can be approximated by Eq. (19c),
-1
1 df(s) (20b)
A
ds -,(1+:s)
f(s)
and
f(s) 1
= ~ (20c)
n T
df(s) /ds
Plotting the left side of Eq. (20c) versus s gives a straight line, the
slope of which is equal to the coefficient of variation.
Residence- and Contact-Time Distributions 85
Required Properties of Reactors and Tracers for
Measurements of Residence-Time Distributions
The most frequent problem the author has encountered in the practical
measurement of residence-time distribution is that not enough though is
given to verify that C(t) /Cf is really an estimate of the residence-time
distribution desired. There are several important conditions that need to
be checked.
The choice of the tracer is very important. It should be accurately
measurable over a wide range of concentrations. There are several other
properties that also affect its choice. Furthermore, there are a number of
other conditions that have to be fulfilled in order that the tracer experi-
ments mentioned earlier will lead to a proper estimate of the residence-time
distribution.
l. The system must be a steady state and stationary in the sense that
C(t) !Cf is independent of the time at which the tracer is introduced into
the feed. As most flows are turbulent, this is not necessarily true for all
reactors. However, if the length-to-diameter ratio is large, the turbulence
effects are averaged out and at the outlet, this condition is satisfied at
least to a first approximation. The same applies to systems equipped with
mechanical agitators. In that case the size of the large eddies is much
smaller than the diameter of the reactor and therefore are often averaged
out independent of the length-to-diameter ratio. This can be tested in two
ways. First, the step response must be monotonous. A response such as
the one shown in Fig. 11 cannot be considered as a residence-time distribu-
tion. The ability to apply this criterion directly is a significant advantage
in using the step resonse. Furthermore, two successive tracer experiments
should give the same result within the expected experimental error. This
condition is not just a question of measurement. The hypothetical experi-
ment of equipping each molecule with a clock had exactly the same require-
ment. It was assumed that it did not matter when the particle entered.
-------------
c/c 0 t
FOR STEP
INPUT
,_
FIGURE 11 Response to step input for a system in which the response to
a tracer is a function of the time of injection. In this case, C(t)/Cr does
not give the residence-time distribution of the system. This may be due
to turbulent mixing, fluctuation in the flow rate, or large bubbles, or other
factors.
86 Shinnar
In Krambeck et al. (1969) the concept of residence-time distribution is ex-
tended to systems that lack this property, but this is outside the scope of
this chapter.
2. The tracer response must be linear in the range of the step change.
If the tracer particles behave exactly as one of the molecular compounds in
the steady-state system, this condition will be fulfilled automatically. If
one can really tag particles in a steady-state flow, it cannot make any dif-
ference how many particles are tagged. As long as the system is in steady
state, it also does not matter if the transport processes are nonlinear.
This also applies to multiphase systems in which one of the compounds is
either adsorbed on a solid surface or dissolved in the liquid phase. As
long as the system is at steady state in the sence defined in the first
criterion, each compound has a residence-time distribution, and if one finds
a real tracer for this compound, its response will be linear, as it cannot
matter how many particles are tagged. However, the only way to obtain
tracers with such properties (at least approximately) is to take the real
reactant feed and mark it by exchanging one of its atoms with an isotope.
Such tracers are seldom used and in most cases one uses tracers that are
inherently different from the fluid at steady state. There is nothing
wrong with this method as long as one recognizes its shortcomings and takes
them into account.
If the tracer is different from the steady state feed, it may upset the
steady-state conditions, and there is no a priori reason for a linear response.
If one wants to obtain a residence-time distribution, one must verify ex-
perimentally that the response is linear. This is accomplished 'by two suc-
cessive tracer experiments with two different step magnitudes which should
give the same response. What one obtains in this case is a residence-time
distribution of the tracer compound, which is not necessarily identical with
the residence-time distribution of the fluid in the reactor. Therefore, one
must add yet another criterion.
3. The tracer should be similar in behavior to the fluid in the reactor.
It is hard to specify this condition in a general way, as it depends strongly
on the specific situation. In a homogeneous stirred tank, almost any tracer
will do, as diffusion processes have negligible effects on F and there is no
potential for adsorption. The tracer is carried along with the liquid. This
applies to most homogeneous reactors. In such cases one seldom has to
worry about linearity. On the other hand, in a fluidized- bed reactor, dif-
fusion and adsorption are very important factors, and the results depend
strongly on the tracer chosen. Which tracer to choose is therefore a ques-
tion not only of availability but also of what information is sought from the
experiment. In multiphase systems it is often appropriate to use several
tracers, each simulating a different compound, or fluid property. This is
discussed in detail later.
Relative Accuracy of Tracer Experiments Utilizing
Step and Pulse Inputs
In principle, f(t) and F(t) contain the same information and each one can be
derived from the other. In practice, the experimental errors are different
for pulse inputs and step inputs. Step inputs tracer experiments have
significant advantages over pulse experiments, provided that they are
carried out in both directions. These advantages include:
Residence- and Contact-Time Distributions 87
1. Immediate recognition of some unsteady phenomena. These are
illustrated in Fig. 11.
2. In a step experiment all one needs is a knowledge of Cf and C(t).
As they are measured by the same instruments, any bias in measur-
ing Cf will also appear in C(t) and will tend to cancel. However,
it is important that the step be carried out in both directions, as it
is difficult to measure C(t)/Cf accurately if it is close to unity
(large t for F and small t for 1 - F).
If one. can do this, a direct estimate of F and 1 - F is obtained. On
the other hand, in a pulse experiment C(t) does not give a direct estimate
of f(t). One must derive it utilizing either Eq. (11) or (13). If one uses
Eq. (13), the problem of bias in measuring C(t) is eliminated, but one
faces the problem of estimating the integral. If the residence-time distribu-
tion is simple and well behaved and has an exponential tail, a fairly accurate
estimate of f(t} is easily obtained. Otherwise, the overall form of f(t) can
usually be derived, but the relative magnitude may not be accurate. One
way to verify the accuracy of the measurements utilizes Eq. (12) and com-
pares 1000 C(t) dt to m/Q. If possible, this should always be done, as it
greatly improves the reliability of the measurement. However, in industrial
reactors it is often impossible or very difficult to measure either Q or m
accurately. A step experiment measures F and 1 - F directly and therefore
also allows a direct measurement of the escape probability. If one plots
ln(l - F) versus time, all the interesting features of the escape probability
(or intensity function) will be directly apparent from the plot. On the other
hand, to derive the intensity function J\.(t) from f(t) using Eq. (7), one
must first compute [ 1 - F(t)] by integration of f(t), which introduces in-
accuracies. In order To minimize the error in estimating 1\. (t), one should
use the relation
C(t)
1\. (t) ( 21)
Joo C(t) dt
t
The value of J0 00 C(t) dt is estimated by plotting C(t) on a logarithmic plot
and approximating the tail by an exponential function. The time constant
of the exponent is then estimated from the tangent of log C(t) for the
largest values of t for which the measurements are still reliable.
In general, the author does not recommend the use of frequency-response
techniques or sinusoidal inputs for measuring residence-time distributions.
The only reason they are discussed is that they might be available from
control studies and can therefore serve as a starting point. The reason
for this broad statement is that whenever such experiments are feasible, a
proper step response in both directions is also feasible, is less time consum-
ing, and provides far better information. In control design the opposite is
true. It is always best to get a direct estimate of the property of the func-
tion required for design. In chemical controller design one needs to know
f(jw) and it is preferable to measure it directly, compared to estimating it
from a step response. On the other hand, to evaluate the flow pattern, one
88 Shinnar
needs to know the escape probability and therefore a direct estimate of
[1 - F(t)] is preferable. Furthermore, the accuracy and the range of w
at which f(jw) is needed is different in the two cases. In controller design,
one needs the overall form of f(jw) and accurate values near the phase lag
of -180°. Accurate estimates of f(jw) for very high and very small w are
of little interest in controller design, but are important in evaluating
residence-time distribution.
In cases where an experiment with an input that reasonably approxi-
mates a step or a pulse cannot be performed, and one must often compro-
mize and utilize other inputs. A practical example is shown in Fig. 10. In
this setting one cannot directly measure F(t) of f(t) but can still measure
an estimate of the Laplace transform. If one has an approximate flow model,
one can fit it directly to f(s) as shown in Fig. 9d. This is less accurate
than estimating [ 1 - F(t)] by a step or pulse experiment. With the latter
one can often get a good estimate of the tail of the function which determines
the moments. On the other hand, to obtain reliable estimates of the tails
from f(s), one needs to have accurate measurements of f(s) for values of s
where s + 0. Estimating the second derivative near s + 0 from experi-
mentally determined f (s) is much more difficult, and therefore estimates of
variance are more difficult and have to be obtained by first fitting a two-
parameter model of f(s) and then estimating the variance from this modeL
This procedure involves some mistakes, but if the variance is small, the re-
sults are often reasonably accurate [Q)stergaard and Michelsen (1969)]. An
example is shown in Fig. 10. If one could plot f(s) in a way equivalent to
an escape probability, it would allow better insight into the meaning of any
deviations of f(s) from the simplified flow models used to fit the experimen-
tal results. However, the author is not aware of any method that would
make this possible.
It is sometimes possible to use Eq. ( 16) ,
~(s}output
f(s) (16)
C(s). t
mpu
to filter out the effects of measurement noise, especially on the tail. It
should be stressed that this method is always one of last resort and that
one always loses significant information. In many cases the most important
information of the tracer experiment is contained in the tail (t + oo) and
there is no way to replace getting an accurate measurement of it. Using
Eq. ( 16) merely obscures the fact that the measurement noise prevented an
accurate measurement of the tail of f(t). The method is sometimes useful
when one knows that the contribution of the tail is small or when one is
interested in bypass phenomena [which depend on the properties of f(t)
near zero]. In all such cases it is important to use an adequate number
of values of s in the range O < s < T, where T is the expected average
residence time. But one should always be aware of the shortcomings of
this method.
Residence- and Contact-Time Distributions 89
USE OF RESIDENCE-TIME DISTRIBUTIONS IN REACTOR
MODELING AND TESTING OF INDUSTRIAL REACTORS
Testing for Maldistribution in Industrial Reactors
Residence-time distributions are an important diagnostic tool inevaluating
the performance of industrial reactors as well as in setting up simplified
flow models. They can be utilized for modeling both homogeneous and
heterogeneous reactors. The most important application is probably checking
for maldistribution in flows. A large number of industrial reactors are de-
signed to approximate either a stirred tank or a plug-flow reactor. In the
first case good mixing is essential. In the second case, such as a packed-
bed reactor, it is very important that the feed is well distributed over the
cross section and that there be no bypassing due to faulty internals or de-
fective catalyst loading. If a reactor does not perform as predicted, it is
important to find out whether the poor performance is due to an inherent
scaleup problem, a faulty catalyst, or a wrong mechanical design. A tracer
experiment can be a valuable tool in distinguishing between these possibilities.
If there are similar reactors in operation which are accessible, one can
conduct a tracer experiment on both reactors and compare the results.
Otherwise, one can compare the results of the tracer experiment to those
predicted by an idealized model. They key question is how one interprets
any deviations between the results of two reactors 0" between the actual
performance and the model. Here the escape probability or intensity func-
tion, I\. (t), is a useful tool, as it provides one with immediate insight as to
what the deviations mean. One does not even always have to actually plot
or compute I\. ( t). With some experience one can recognize the important
features of the escape probability from a plot of ln(l - F) versus t. There-
fore, what is really needed is a reliable estimator of (1 - F) which can usu-
ally be obtained from tracer experiments. The following two examples will
illustrate the method.
Imperfect Mixing and Bypassing in Stirred-Tank Reactors
There are several problems that can occur in the scaleup of stirred-tank
reactors. One of them is that the mixing is insufficient to ensure that the
entering fluid mixes sufficiently rapidly with the contents of the reactor
[ (Evangelista et al., 1969b; Shinnar, 1961). In heterogeneous stirred-tank
reactors there are the additional problems of mass transfer between the
phases, uniformity of turbulence, and the other complicating factors which
are discussed in Shinnar (1961) and Tarmy (1983). Although these prob-
lems can be studied using tracer experiments, they involve methods that
are outside the scope of this chapter. There is one problem that commonly
occurs in the scaleup of a stirred tank reactor and can be effectively dealt
with using the residence-time distribution. This is the case of a design
where the escape probability is to remain constant and is discussed below.
When trying to analyze whether the escape probability is really constant,
consider the type of deviations to be expected. One would always expect
some deviation as t + 0, as there is a minimum finite time for the particle
90 Shinnar
I
''\\.
A(8J
Y'- . . . __ D
I \\ - /"
---------
--
-------------
/
\ I --
('-A~-{....I ------ -.-...
---
C
I ----------------- -
Is
I
/
..-/
0
e
FIGURE 12 Intensity function for imperfectly mixed stirred-tank reactors:
A, short delay between inlet and outlet (normal case); B, delay between
inlet and outlet due to insufficient stirring; C, bypass between inlet and
outlet; D, bypass between inlet and outlet and stagnant regions due to in-
sufficient stirring.
to reach the exit (see Fig. 12, curve A). However, this time is usually
small compared with the average residence time T, and if T is large, one
would not notice it. If the mixing intensity is too low, this initial deviation
might be quite large, especially in tall reactors with viscous fluids. In
that case one would expect J\(t) to look like curve B in Fig. 12. This
could be remedied by increasing the agitator speed or the agitator design.
Another common type of faulty performance is shown by curve C in Fig. 12.
It occurs if the inlet and outlet pipes are close to each other and mixing
intensity is insufficient to distribute the incoming fluid sufficiently fast over
the total reactor. A fraction of the liquid will reach the outlet directly
creating a bypass. For small t one could then expect J\(t) to be significant-
ly higher than the average expected value, as entering particles have a
chance to be in that bypass. If a particle has stayed in the reactor longer
than it takes to reach the exit via the bypass, its chance to exit is now
lower than in the beginning and .I\ ( t) will exhibit a maximum at low values
of t. If the vessel is really badly mixed, A (t) will even have a decreasing
tail (Fig. 12, curve D).
A significant advantage of representing the information contained in the
residence-time distribution by plotting A (t) is that one can plot the expected
form of J\(t) without any computations, as J\(t) corresponds to the physical
concept of the system. An actual example taken from an industrial reactor
is shown in Fig. 13 (Murphree et al., 1964). The conversion in the re-
actor was much lower than expected from the pilot plant results. A step
input tracer experiment was performed and the result is replotted in Fig.
13a, curve E (one impeller). Figure 13b gives ln(l - F) and Fig. 13c the
corresponding curve. The escape probability is similar to curve B, in Fig.
12. It indicates imperfect mixing. The mixer was modified and equipped
with two impellers and again tested by a tracer step input. The results
Residence- and Contact-Time Distributions 91
are also given in Fig. 13, curve G, and the escape probability is similar to
curve A, indicating good mixing. The new mixer also increased the conver-
sion to that expected from the pilot plant.
The tracer results in Fig. 13, illustrate another aspect of the use of
residence-time distributions that is not evident from the escape probability
as plotted. Both curves refer to a reactor with the same volume and volu-
metric feed rate, and therefore the same average residence time , . One
can in both cases estimate , from 1/' (1 - F) dt using an exponential tail
and compare it to its known value. For curve G the estimate is correct,
whereas curve E underestimates , by 30%. The fact that curve E under-
estimates , shows that the reactor is not well perfused and has a strongly
stagnant region which does not appear in the plot. If one could measure
F( t) accurately for long times, curve E must cross curve G for the two in-
tegrals to be equal. The true escape probability would look like curve D in
Fig. 12. If , is equal for the two cases, then curves of F(t) must cross
each other. Therefore, independent knowledge of , provides some important
checks on the accuracy of a tracer experiment.
A fairly constant escape probability, independent of history, which is
characteristic of a well-stirred tank, occurs in quite a number of other situ-
ations, such as solids reacted in fluid beds, and the test described here
applies to all these situations.
Packed-Bed and Trickle-Bed Reactors
In the design of packed-bed and trickle-bed reactors, it is important to
ensure that the feed is well distributed and that the catalyst is arranged in
such a way that there are no preferred pathways with lower pressure drops
ONE
1.0 IMPELLER O o o o o@
0 0
F ( t) 0 0 C\
O O DOD □ 0
0 D DD
0.5 0 □ DD TWO
□
o 0
O o IMPELLERS
8 □
B
0.5 1.0 1.5 2.0
TIME -
(a)
FIGURE 13 Residence-time distribution for reactors with imperfect m1xmg.
(a) Experimental residence-time distribution for a stirred-tank reactor (from)
Woodrow, 1978). The reactor did not match the pilot plant and gave low
conversion. A tracer experiment showed a severe maldistribution of the
flow. A second impeller was installed, which improved the flow pattern as
measured by a residence-time distribution approaching an ideally stirred
tank. The reactor then matched the pilot plant. Here the imperfect mixing
is not directly recognizable from curve E. It can only be recognized by
comparing the estimate of f (1 - F) with the known value of , estimated
from volume divided by flow rate (see the text). This indicates that in
case E the reactor is not well perfused. (b) Cumulative residence-time dis-
tribution. (c) Escape probability (intensity function).
92 Shinnar
10°
©I 8
□
0 □ □
0 □
□
0
□
TWO IMPELLERS
0 □ □
0 □
□
□
0 □
0 □ □ □
0
1- F (t) 0
0
161
0
0
ONE IMPELLER o
1Q2L___L___,_ _ j __ __,__---l.-_---'------ '---__,___ _.__
0 2
TIME-
(bl
3.0
ONE IMPELLER
A(tl 0 0 0 0
000000
2.0
0 0
0 0 0 0 0
1,Q □ □ D D D D D D D D D D D D D D D
TWO IMPELLERS
0.5 1.0 1.5 2.0
TIME -
(cl
FIGURE 13 (Continued)
Residence- and Contact-Time Distributions 93
which create a bypass. Before proceeding with analytical examples, one
must first define the concept of bypass and stagnant regions.
A well-designed packed bed approaches plug flow and will lead to a
J\(t) function such as curve B in Fig. 5a. Most of this is due to the fact
that in a randomly packed bed, the path length for different molecules is
unequal and part of it is due to mixing in the interstices between the par-
ticles. Whenever f( t) is not a delta function, one can in theory represent
the pathways of the individual molecules by an organ pipe model such as
the one shown in Fig. 14. As the pathways are of unequal length, one can
conceive of the shorter one as a bypass. In general, this is not the prime
concern of the diagnostic test. One is looking for much stronger differences
caused by maldistribution of flow. One can utilize the residence-time dis-
tribution in this setting because the typical flow distribution in a packed
bed has a J\ function similar to that of curve B in Fig. 5a with no peaks.
If the maldistribution is strong enough to cause a peak in the J\ function,
it indicates that one is dealing with maldistribution in flow and not simply
a backmixing process.
There are some exceptions to the foregoing statement. If a tracer is
adsorbed, it could lead to a peak in J\ • The same applies if there is a
strong diffusional resistance inside the catalyst particle or a mass transfer
resistance to the particle. Theoretical examples of such cases are illustrated
in Fig. 15, which shows two examples of a packed bed with a significant
chromatographic effect. The residence-time distributions in Fig. 15 are
based on the standard equation used in chromatography or ion exchange
(Shinnar et al., 1972; Hiester and Vermeulen, 1952). These cases demon-
strate that to interpret a residence-time distribution properly, one needs
either a good understanding of the system or a good data base, such as a
tracer experiment from a pilot plant or a similar industrial reactor. Exam-
ples are illustrated in Fig. 16, which shows tracer studies from an indus-
trial trickle· bed used for hydrotreating fuel oil. Curve A is from a pilot
plant and is similar to curve B in Fig. 5a. Curve B is from an industrial
reactor that performs well and shows a small peak in J\ ( t). Curve C is
from an industrial reactor that did not perform well. It shows a strong
peak in J\ and indicates a strong bypass. Shinnar ( 1978) reports that this
bypass was correctable by a change in the design which led to better reactor
performance. If the bypass is really strong, one would expect f( t) to be
double peaked. This occurs rather infrequently and a strong peak in J\ is
a much more sensitive test.
For a packed bed one can also check the flow distribution from the
Laplace transform. For near-plug-flow conditions the Laplace transfer
function should be oJ the form exp[-,P(s)]. One can check the form of
P(s) by plotting ln[f(s) versus s. For one-dimensional diffusion with very
large Peclet numbers,
FIGURE 14 Alternative flow model for a packed bed.
94 Shinnar
f(s) exp(Pe/2)[1 - 1/2
(1 + 4Ts/Pe) ] ( 22)
Equation ( 22) is approximate only for high values of Pe (Pe > 20). One can
check the fit to Eq. (22) by plotting ln[l/f(s)]-1 versus TS{ln[l/f(s)]}-2
1/Pe] , which should give a straight line with slope TS and intercept 1/Pe
(<l>stergaard and Michelsen, 1969). However, plotting ln[f(s)] versus s
might be sufficient and should also be close to a straight line with slope -T
near s -+ 0. If in this plot the slope near zero is less than T or there are
strong changes in the slope (see Fig. 9) , it indicates a strong deviation
from a well-distributed plug-flow reactor. It is extremely difficult to dis-
tinguish solely by means of a tracer experiment between maldistributions
caused by a bad distributor and those caused either by diffusion processes
inside the particle or by adsorption processes (see Figs. 15 and 26). For-
tunately, in an industrial case, one often has a reference case from another
well-performing reactor which can be used for comparison. One should,
2.0 ~ - - - - - - - - - - - - - - - - - - - - - ,
1.6
f ( t)
1~\
I \
1.2 I \
I \
II '\
I \
I \
0.8 I \
I \
I \
f \A= 10
\
0.4 \
\
\
'
0.0 L __ ___,___ ____Jc..___ __,__ _- - - - - ' ~ ~ - ~ - - -
o.o 1.0 2.0 3.0
(a)
FIGURE 15 (a) Residence-time distribution of a chromatographic column:
(From Shinnar et al., 1972; Hiester and Vermeulen, 1952.)
f = e-AT[o(t - T) + ~e-;\(t-T)/r✓ /~TI~;\ ✓ T(\- T)))T=0.5 r = 1
(b) Cumulative residence-time distribution for the column in part (a).
(c) Escape probability (intensity function) for the column in part (a).
Residence- and Contact-Time Distributions 95
100 ~ - - ~ - - - - - - - - - - - - - - - - - - ,
'\.
1-F (t)
""'\
'\
'\
\
\
\
\>.. = 10
\
\
\
\
\
\
10 5 ' - - - - ~ - - - - ' - - - - ~ - - - ' - - - - - ' - - - - ~
0.0 1.0 2.0 3.0
(b)
6~-----------------~
,,,,..,,,,,,,,..,,.,.✓
...... -
//
/
/
/
4
/ -
/.'A.-10
I
A(t)
I
I
I
I
2 I
I
I
I
/ >.. = 1
/
0 '------"'----~----'----~---'--------'
0.0 1.0 2.0 3.0
(c)
FIGURE 15 (Continued)
96 Shinnar
INDUSTRIAL
3
REACTOR (B)
z
0
f-
t) 2
z
::)
A PILOT
1.1.. PLANT
>-
f-
en
z
w
f-
zH INDUSTRIAL
REACTOR (C)
0
0 10 20 30 40
TIME (min)
FIGURE 16 Tracer experiments in a trickle-bed reactor. (From Shinnar
et al. , 1978.)
however, be careful when using pilot plant results as a comparison unless
the pilot plant has the same linear velocity. A change in linear velocity
changes the mass transfer coefficients and therefore also the residence-
time distribution in a packed bed. It also changes the flow regime in a
trickle bed. Often this can be predicted by fluid dynamic conditions.
Use of RTD in Reactor Modeling
Tracer experiments and residence-time distributions are just one of many
tools in studying flow systems in reactors. One seldom starts in a vacuum
and usually has other information about the reactor. In principle, one
wants to understand its fluid dynamics. As F(t) measures a linear property
of a nonlinear system, the information obtainable from it is always incom-
plete, although it can be quite important.
If a reactor model is available, one can compute the expected results
of a tracer experiment and compare it with the actual experimental results.
If one wants only to confirm the model or measure its parameters, doint it
via a residence-time distribution is an unnecessarily complicated technique.
However, the use of residence-time distribution can be of benefit in two
important ways.
Firstly, one never expects models to be completely accurate, so that re-
sults which deviate slightly from the predictions of the model are not sur-
prising. Using !\. (t) gives a physical insight as to the meaning of the de-
viations. Second, f\.(t) gives information in a form that is at least partially
model free. One still has a physical model of steady-state and tracer be-
havior but does not need any a priori assumptions as the the exact flow
model. Interpreting the results in such a way forces one to consider what
Residence- and Contact-Time Distributions 97
other explanations or alternative flow models may be consistent with the
observed data. This type of approach is very important in any reactor
design problem (Overcashier et al., 1959).
As an example, one might cite some of the early tracer experiments in
fluid beds, which are represented in Fig. 17. A low fluid bed has a tracer
response quite similar to a stirred tank, but representing it in the A (t)
domain immediately indicates that one is dealing with a bypass problem,
which was subsequently confirmed in other ways.
It is often useful to have a knowledge of the properties of residence-
time distributions of different flow models. These are shown in Table 1.
One must always remember that transport processes are nonlinear and
cannot be described adequately by simplified models. F(t) is a linear
property of such a model and the only time one can use it to predict re-
actor performance is in first-order reactions in homogeneous systems, a
problem that is not often encountered by the reaction engineer. However,
simplified models are a very valuable tool. In Shinnar (1978) the term
learning models was introduced to distinguish them from models used in
actual design predictions. They provide an understanding of how the trans-
port processes might affect the chemical reactions and give some guidance
for designing the scaleup. Fortunately, many reactions are not very sen-
sitive to scaleup. Nevertheless, it is important to be able to recognize
those cases where significant scaleup problems may be expected. There
is one important case where models derived from tracer experiments are di-
rectly useful in reactor design. In many reactor problems, a plug-flow re-
actor is the optimal configuration or if not optimal, is the only design that
is safe for scaleup. As real reactors are seldom true plug-flow reactors,
one wants to know how closely the design approaches plug-flow and how
the deviations could affect reactor performance. Here one utilizes the fact
that if deviations from plug flow are small, one should get a reasonable
estimate about their impact from any model that has a similar residence-time
distribution. This is equivalent to an asymptotic expansion around a solu-
tion retaining only the first-order terms. In such a case, one could use
either a model based on one-dimensional diffusion or a stirred tank followed
by plug flow or a series of stirred tanks. The latter is preferred as it is
easier to compute, and the additional complexity of a diffusion model is not
justified for cases where the real physical transport processes are not
molecular diffusion. It is also more similar in its form to actual measure
tracer responses, as compared to a single stirred tank followed by a plug-
flow reactor.
It is common to derive these simplified asymptotic models by demanding
that the variance of the residence-time distribution of the model is equal
to that of the actual measured residence-time distribution. The variance 2
is then expressed as an equivalent Peclet number by the relation Pe = 2/y ,
where y2 is the coefficient of variation as defined earlier. For a series of
stirred tanks the equivalent Peclet number is approximately 2n. It will be
shown later that such models give similar kinetic performance as long as the
deviation from plug flow is small.
These relations make sense for Peclet numbers larger than 10 (pre-
ferably 20). For reactors in which the Peclet number is smaller, simplified
models based on one-dimensional diffusion or series of stirred tanks make
no physical sense (unless, of course, one is really dealing with three
stirred tanks hooked up in series).
98 Shinnar
l.O
0.8
0.6
0--
0.4
"""-
""
1-F(B)
~
0.2
""
0.1
""-
0.0 2 3 4
e
(a)
2.0
l.5
A(Bl
1.0
0.5
0.0
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5
e
(b)
FIGURE 17 (a) Experimental cumulative residence-time distribution for a
fluidized bed. (b) Experimental intensity function for a fluidized bed.
Solid line: flow of gas in fluidized-bed reactor; dashed line: completely
mixed reactor (for comparison).
Residence- and Contact-Time Distributions 99
TABLE 1 Properties of Some Theoretical Residence-Time Distributions
Ideally mixed vessel
1 -t/T
Density: f(t) = -e
T
Cumulative distribution: 1 - F(t) = e - th
Expected value:
Coefficient of variation: y = 1
f
Laplace transform: L(f ,s) = E(e -S t ) - 1
- 1 + TS
1
Intensity function: A (t) = -
T
Ideally mixed vessels in series ( T is the parameter of each single vessel)
(th)n-le-t/T
Density: f(t) =
T(n - 1)!
n-l (th}
Cumulative distribution: 1 - F(t) = e
-th
L .,
l.
i=O
Expected value: Er<t) = IlT
1
Coefficient of variation: y =--
f ✓n
L(f,s) - E(e -S t ) = 1
Laplace transform:
1 + TS
n-1
= (th) /(n - 1)!
Intensity function: A (t)
,.,n-1 ( I )i 1.,
T l., i=O t T l.
A ( 0) = 0 }
Special values: 1 (n > 1)
.f\(oo) = -
T
Two nonidentical ideally mixed vessels in series ( T1 and T 2 are the
parameters of the two vessels)
-th
1 (e 1
Density: f(t) = - - -
Tl T2
100 Shinnar
TABLE 1 (Continued)
1 ( T e -t/Tl -th
Cumulative distribution: 1 - F(t) = 1 T2e 2)
'1 '2
Expected value: E/t) = T1 + T2
2 2
T1 + '2
Coefficient of variation: Yr = 2 2
Tl + 2T l T2 + '2
-st 1
Laplace transform: L(f ,s) = E(e ) = -----,-----
( 1 + , 1s)( 1 + T 2s)
-t/, 1 -t/T 2
e_____e_ __
A (t) = __
Intensity function:
-thl -t/T2
T 1e - ''.l
Special values: A(0) = 0
A ( co ) = min (__!__
T '
1
,\)
Plug-flow vessel
Density: f(t) = unit Dirac function
Cumulative distributuon 1 F(t) ={ ~ t < T
t ~ T
Expected value
Coefficient of variation: y = 0
f
Laplace transform:
t :f- T
Intensity function: A(t)={~
t = T
Two parallel, nonidentical, ideally mixed vessels [fraction IT passes through
one vessel with parameter , 1 ; fraction (1 - IT) passes through second
vessel with parameter T21
Density: f(t)
Residence- and Contact-Time Distributions 101
TABLE 1 (Continued)
-t/T -th
Cumulative distribution: 1 - F(t) = Ile l + (1 - II )e 2
Expected value:
2 2
Coefficient T2(1- II)+ T1II(2 - II) - 2T 1 T 2II(l - II)
of variation: y =
f 2 2 2 2
T2(1 - II) + TlII + 2T1T2II(l - II)
-st II 1 - II
Laplace transform: L(f,s) = E(e ) = -1 - - +
+ Tl$ 1 + T 2s
-t/Tl -t/T 2
( II h 1)e + ( 1 - II IT 2)e
Intensity function: A (t) = - - - - - - - - - - - - - -
-th -th
Ile 1 + (1 - II)e 2
Special values:
Two parallel vessels, one ideally mixed, one plug flow [fraction II passes
through plug flow vessel with parameter T1 ; fraction ( 1 - II) passes
through ideally mixed vessel with parameter T2]
-th
1 - II 2
Density: f(t) = - - - e (t -:f. Tl)
T2
f(t) = II x unit Dirac function (t = T1)
{ -th II) t <
Cumulative distribution: F(t) = II + e 2(1 - Tl
1 -
e - t /T 2(1 - II) t ;;i: Tl
Expected value:
Coefficient
of variation:
102 Shinnar
TABLE 1 (Continued)
-st -s,1 1
Laplace transform: L(f,s) = E(e ) = Ile + (1 - II) - - -
1 + , 2s
-ti,
2
[(1 - IIh 2]e
Intensity function: A(t) = t < '1
-th
(1 - II)e 2 + II
1
A(t) = - t > '1
'2
II
Special value: A( 0) = 1 -
'2
Estimation of Model Parameters from
Residence-Time Distribution
As discussed in the preceding section, to estimate the kinetic impact of
small deviations from plug flow, one estimates an equivalent Peclet number
from the coefficient of variation of the residence-time distribution. One
can directly use either f(t) or F(t) [see Eqs. (1) to (3)]. In the litera-
ture, residence-time distributions are often used to estimate simultaneously
several parameters of a complex mocel. The author does not recommend
this.
Residence-time distributions are hard to measure accurately and are
quite constrained. In a homogeneous flow, the first moment is fixed by
V /Q. The limits of experimental accuracy seldom allow one to measure more
than two additional moments. Often only one additional moment, namely the
variance, is all one can reasonably expect to obtain. Therefore, one can-
not estimate more than one or two parameters from such experiments. Fur-
thermore, the models themselves are not accurate, and estimating multiple
parameters for approximate models from a single experiment is a doubtful
procedure at best (Overcashier et al., 1959).
Use of Tracer Experiments in Cold-Flow Models and
Design of Reactor Internals
Tracer experiments and residence-time distributions are becoming a widely
used tool in this area. In principle, there is very little difference in the
approach from that which was discussed in the previous sections. One
wants to make sure that one of the limiting models, such as a stirred tank
or plug flow, is approximated as closely as possible. Quite often one uses
multiple tracers (which will be discussed later), but the principles remain
the same. The following two examples may help illustrate this point. Baf-
fles, especially horizontal baffles, allow one to modify the complex flow in
a fluid bed such that it approaches plug flow quite closely. Properly de-
signed baffles achieve this by breaking up the bubbles and staging the bed,
Residence- and Contact-Time Distributions 103
reducing solid mixing between top and bottom and thereby also reducing
recirculation of gas either adsorbed on the catalyst or entrained in the
dense phase inside particle clusters. An example of this effect and its
measurement by a tracer experiment is given in Fig. 18 [for details, see
Overcashier et al. , 1959].
Figure 19 gives an example of the study of gas distributors in fluid
beds. In Fig. 19 some of the f(t) plots are double peaked, which clearly
indicates a maldistribution. Here both f(t) and the escape probability J\(t)
clearly indicate that the design of the distributor is unsatisfactory and leads
to a maldistribution in the overall reactor, which can be corrected by a
proper design. This example illustrates the importance of a proper base
case in comparing alternatives. Fluid beds, especially short fluid beds,
have maldistributions of flow caused by the formation of larger bubbles.
These are due to inherent hydrodynamic instabilities and cannot be pre-
vented by the design of the distributor. In the cases shown in Fig. 19,
some of the distributor designs give maldistributions which are much more
pronounced compared to the best achievable case, which is a porous plate.
Residence-time distributions cannot distinguish between these two phenomena
and should always be considered only an additional, albeit important diagnos-
tic tool.
BAFFLED
A(8)
UNBAFFLED
0
0 2 3 4
(8)
(a)
FIGURE 18 (a) Experimental residence-time distribution for gas flow in a
fluidized-bed reactor (gas velocity = 1. 6 ft/sec)-intensity function. (From
Overcashier et al., 1959.) (b) Cumulative residence-time distribution for
the flow in part (a).
1.0
0.8
0.6
0.4
0.2
UNBAFFLED
1-F(8)
0.1
0.08
0.06
0.04
0.02
0.01
0 2 3 4
0
(b)
FIGURE 18 (Continued)
f ( t) ss nozzle plate
sandwich gas distributor
porous plate
_u_ = 1.7
Umf
_u_=20
Umf •
FIGURE 19 Residence-time distribution measured with different gas distribu-
tors in a fluid bed, as a function of fluidization indexes u/umf" (From
Woodrow, 1978.)
Residence- and Contact-Time Distributions 105
Measurement of Flow Rates and Reactor
Volume or Holdup
In hydrology and physiology, tracer experiments are widely used to measure
flow rates and volumes [Weinstein and Dudukovic (1975)]. In reaction en-
gineering it is possible in most cases to measure flow rates directly. Excep-
tions are reactors with internal circulation caused by density and pressure
differences, where tracer experiments are sometimes useful to measure flow
rates using Eq. ( 2). It is not a very accurate method and should be used
only as a last resort.
In homogeneous reactors, the volume or holdup is almost always known.
One can then compare the volume estimate from the residence-time distribu-
tion with the known volume. To do this, one has to estimate the contribu-
tion of the tail of either F(t) or f(t) to the first moment. If the volume
estimated from the first moment is significantly smaller than the known
volume, the vessel is not well perfused and has strongly stagnant regions.
An example of this was shown in Fig. 13. In multiphase systems the rela-
tive volume and holdup of solid liquid and gas are sometimes hard to measure,
and here tracer experiments can be valuable, despite the shortcomings men-
tioned above. An example of this use is presented later.
USE OF RESIDENCE-TIME DISTRIBUTIONS IN THE
DESIGN OF HOMOGENEOUS REACTORS
One advantage of using the concept of a residence-time distribution in eval-
uating tracer experiments has already been discussed, namely, the physical
insight into the properties of the system that is gained from the use of the
escape probability fl. (t). Just as important are the direct conceptual in-
sights, which. can help in understanding reactor design problems.
Tracer experiments are very useful in organizing and evaluating alter-
native reactor designs, as well as in designing and evaluating pilot plant
experiments. This requires more than simple algorithmic uses of the dis-
tribution in which one tries to compute performance directly from a residence-
time distribution. However, the conceptual framework which offers guide-
lines for scaleup and scale-down problems is generally worth the effort.
The results in this chapter can be derived rigorously only for homogeneous
reactors, which are a small fraction of the cases met by the design engineer.
However, the guidelines for reactor design derived from them (in contrast
to design algorithms) apply to heterogeneous reactors, as long as one under-
stands the basic principles. The differences are discussed in a later section.
First-Order Isothermal Reactions
Consider the case of a first-order isothermal reaction system. There is a
set of compounds Aj (j == 1, 2, . . • , n) which can undergo composition
changes such that the rate of formation of a compound Aj is given by
n
r(A.) ==
L (-k..A. + k .. A.)
1] ] Jl 1
( 23)
] i==l
In other words, all reactions between two compounds A and B can be ex-
pressed by a set of reactions
106 Shinnar
r(A) (24)
where KAB is the equilibrium constant of the reaction A <=;:, B.
If one starts with an inlet composite Cjo, the outlet composition of a
plug-flow reactor is given (Wei and Prater, 1962) by the equation
n-1
C.(t) == a. +
J JO :E a. exp( - \rt)
Jr
( 25)
r=l
where Cj is the concentration of component j expressed as a mole fraction
and Ar are the (n - 1) nonzero eigenvalues of the system. ajo and ajr
are constants that depend on the initial and equilibrium composition of the
system, and t is the residence time in the homogeneous isothermal plug-flow
reactor (or the reaction time in a homogeneous batch reactor).
Equation (23) and its solution [Eq. (25)] are completely equivalent to a
problem in probability theory describing stochastic systems. Consider a
large set of particles, which can change their state in a di.screte way.
Each particle is associated with a state Aj. The probability of a single
particle being in a specific state Ai is Pi. If the number of particles in the
set is very large, the probability of a partic}e to be in Ai is exactly equiva-
lent to the mole fractions of particles Ai in the system, which in a first-
order system is proportional to the concentration Cj. One ca:n therefore
look at Ci either as a concentration or as the probability of a single particle
(or molecule) to be in state j. The mathematical proof is given in Shinnar
et al. (1973). The reader unfamiliar with probability theory can interpret
Eq. (25) as follows. The concentration Cio of the particles entering the
reactor expresses, for a single particle, the probability of being in state
j. The reactor changes this probability into Cj (t). Each particle behaves
here independently from its neighbor and can undergo changes completely
independent of any other molecule in the reactor. This is the physical
meaning of a first-order reaction system.
Once this is understood, some important results in reaction engineering
become clear without further mathematical derivation. Consider a homo-
geneous isothermal reactor which has a steady-state flow that can be charac-
terized by a residence-time distribution f(t). The inlet concentration is
Cio• One can now perform the following thought experiment. An observer
stands at the outlet of the reactor and collects all the particles and sorts
them into bins according to their residence time. To do so, one has to
divide the residence time into intervals Lt. If Lt is small, all particles in
the bin, t to t + Lt, essentially have the same residence time, t, in the
system. As each molecule in the bin behaves independently of its neighbors,
the concentration in the bin would be the same as at the outlet of a homo-
geneous isothermal plug-flow reactor with residence time t.
n-1
p.(t) C.(t) == a. + Z: a. exp(-\ t) ( 26)
J J JO r=l 3r r
The average concentration at the outlet of the reactor <C .> can be obtained
by averaging over all the bins: J
Residence- and Contact-Time Distributions 107
<c.>
J
= /"f(t) [a. +
O JO r=l
f 1
a. exp(-;,_ t)] dt
Jr r
( 27)
which is equal to
n-1
<c.> L
A
= C. + a. f(A ) ( 28)
J JO Jr r
r=l
where f( Ar) is the Laplace transform of f(t) with Ar substituted for the
transform variable (s). Equation ( 28) is equivalent to the outlet of a
hypothetical reactor described in Fig. 20a, which consists of a set of paral-
lel tubular flow reactors with different residence times t. The fraction of
fluid entering a tube with a residence time between t and t + .6 t is f(t) .6 t.
In practice, a real reactor would hardly look like Fig. 20a, but there is one
case that is equivalent. Consider the case where the reactor feed consists
of separate droplets encapsulated by impermeable membranes which have a
residence-time distribution F(t) in the reactor (it is equivalent to the re-
actor in Fig. 20a). The individual droplets in suspension polymerization
behave this way. In a mixed reactor this is true only in the limiting case
called segregated flow. In a first-order system, by definition, each mole-
cule can be considered such a separate droplet.
The well-known case of an ideally stirred tank will illustrate Eq. (27).
Consider the irreversible reaction A ->- B. In the case of a plug-flow re-
actor, CA(t) = CA 0 e-kt and for a stirred-tank reactor, a mass balance will
give
(a)
--t_ ~t_ ---t~---
(b)
FIGURE 20 Alternative flow models for Zwietering method of bounding the
conversion for a reaction of nth order: (a) segregated flow; (b) maximum
mixedness.
108 Shinnar
QCAO - QCA - VkCA = 0
or (2~
CAO CAO
CA = 1 + Vk/Q = 1 + k,
· -th
For a stirred tank, f(t) is here ( 1/T)e and therefore according to
Eq. (27),
( 30)
In the mass balance [Eq. (26)], it was assumed that the concentration in
the stirred tank is uniform at any point in the tank. For a linear system,
a much weaker assumption is sufficient, namely, that for residence-time dis-
tribution is exponential or that the escape probability is constant. Residence-
time distributions are linear property of the nonlinear model of the trans-
port process in the reactor, and first-order reactions depend only on this
linear property of the flow.
In reality very few reactions are truly linear, but it is a sufficiently
good approximation for many systems. Many reactions are also pseudolinear
in the same sense that while the reaction rates contain nonlinear terms such
as a Langmuir expression, they can be written in a form
( 31)
where Kij is a matrix of linear reaction rate coefficients and ¢(Cjo) is a non-
linear function of inlet concentration and pressure that can be taken out in
front of the reaction rate matrix. Although this is seldom completely cor-
rect, it is often a good approximation. For all those systems residence-time
distributions are an important modeling tool.
Deviation of the Residence-Time Distribution
from Kinetic Experiments
One can also use Eq. (28) in the reverse way. If one has a complex reac-
tion system in which the eigenvalues Ar change over a significantly wide
range, we can use it to reconstruct f(s). Assume that the values of Ar
have been measured from a batch experiment or a plug-flow reactor, and
one now has experimental values for all the concentrations Cj at the outlet
of an industrial reactor. One can then compute the values of Ar and use
them to estimate {( Ar) for the in-9-ustrial reactor. One then has sev~ral
values of the Laplace transform f(s) from which a reconstruction of f(s)
can be attempted. If the Ar are widely spaced, the reconstruction is quite
good. This approach will be discussed in more detail later when we deal
with contact-time distribution in heterogeneous reactors.
Residence- and Contact-Time Distributions 109
Optimal Reactor Concepts for First-Order Reactions
Isothermal Reactors
The concepts derived in the preceding section lead to some important con-
clusions with regard to choosing a reactor configuration. Specifically, they
provide guidelines for cases in which a plug-flow reactor is the preferred
choice and for cases in which other reactor configurations will be preferable.
The principle that a first-order reaction system is completely equivalent to
the case where single molecules undergo changes from one state to other
states, with defined probabilities, simplifies many design problems. Many
optimal problems that are very difficult to deal with analytically become in-
tuitively clear if one understands the foregoing principle and applies it
appropriately.
In the preceding section it was shown that in the case of a first-order
isothermal reaction system of arbitrary complexity, the hypothetical reactor
in Fig. 20a will give identical results to any reactor having the same
residence-time distribution. The outlet concentration is therefore the
average obtained from several plug-flow reactors with different residence
times. Once one recognizes that all one needs to do is average over a num-
ber of plug-flow reactors, optimization is simple. Consider, for example,
the case where <Cj(t)> for a specific value of t has a desirable optimum
minimum or maximum concentration of <Cj>. Then assume that one has
found a reactor with a residence-time distribution f(t) that gives an optimum
yield of Cj. In this reactor the outlet concentration <Cj> is simply the
average of all the different plug-flow reactors. There is a simple algebraic
theorem that says that in any set of numbers with average X , there is at
least one member of the set equal or larger than X and at least one member
equal or smaller than X. If f( t) is a plug flow, one has only a single plug-
flow reactor with t = Ef(t) = , and which has a unique Ci = <Cj>. But if
f(t) is not a plug flow, one has in Fig. 20a different tubes with different
outlet concentration. One of these reactors has an outlet concentration
equal or larger than the average concentration <Cj> and in one of these re-
actors Cj is smaller (or larger) than <Cj>. Therefore, depending on
whether one wishes to maximize or minimize <C?, one can always find a
tubular reactor in Fig. 20 with a uniform residence time which is as good
or better than the reactor with the arbitrary residence time f(t). This is
a simple proof that for first-order systems a plug-flow reactor is optimal in
the sense that one can design a plug-flow reactor with a yield or selectively
as high or higher than any isothermal reactor with arbitrary residence-time
distribution. It results in a very simple but powerful conceptual tool for
reactor design. In all cases where the system is such that one can obtain
the outlet concentration simply by averaging over the bins of different re-
sidence times, then, for any reaction system which has the property that
there is an optimum yield of one compound, a plug- flow reactor is the best
choice. If, for other reasons a simple plug-flow reactor is not feasible or
desirable, one wants a design in which the residence-time distribution ap-
proaches plug flow as closely as possible. For example, F(t) for a series
of stirred tanks approaches plug flow if the number of stirred tanks is
reasonably large. One can judge the required number of tanks simply by
110 Shinnar
the allowable deviation from plug flow. Staged systems in general have a
similar property and one can use the same approach to estimate the number
of stages required.
For averaging to apply, the reaction does not have to be strictly first
order. All one requires is that the reaction behavior of a molecule is not
affected by the nature of its neighbors, as discussed in the preceding sec-
tion. Otherwise, one needs to know not only how long a molecule has been
in the system, but also who its neighbors were. If the outcome is strongly
affected by the nature of its neighbors, a residence-time distribution can-
not provide an answer for the outcome. Nor can one show that plug flow
is optimum, although one can still get some guidelines which will be discussed
in a later section.
In a similar way, if one looks at the conversion of a first-order simple
reaction A<=> B with reaction rate
( 32)
it is given by
(32a)
This is a convex function of t. Again, the outlet concentration of a reactor
with residence-time distribution f(t) is obtained by averaging over the bins,
which really means averaging e -(kl + k2H over f(t). It is easy to see
that a plug-flow reactor with the same average residence time t will have a
lower a - aeq and hence higher conversion than a reactor in which the
bins have different t. (Had the function been concave, the opposite would
have been true.) For high converison in a first-order isothermal system, a
plug-flow reactor will have the lowest residence time. Again, one can evalu-
ate the permissible deviation by some very simple models (such as a series
of stirred tanks) and judge the design by measuring the deviation from
plug flow via a tracer experiment. For small deviations the coefficient of
variation y2 of f(t) is a good criterion. In the literature the Peclet number
is often used instead and is approximately equal to 2/y2. More accurately,
it is given by the expression (see Shinnar and Naor, 1967).
-Pe
2 2[e - (1 - Pe)]
y ( 33)
Pe 2
which for large Pe approaches
2 2
y (Pe + 00 ) (33a)
Pe
But one should be careful not to use Peclet numbers smaller than 10, be-
cause in most cases this is meaningless, as the residence-time distribution
will not fit a one-dimensional diffusion model.
In fact that the results are not sensitive to the form of the deviation
from plug flow is illustrated in Fig. 21, where two cases are plotted. The
Residence- and Contact-Time Distributions 111
100
:,l!
0
90
<(
l._
0
z
0
Cf)
a:
w
> 80
z
0 ' - IDEAL
'-' STIRRED TANK
70
1.0 2.0 3.0 4.0 5.0 6.0
K
(a)
0.8
k k
A_!.. B ~ C
0.7
0.6
0
<(
'-
ID
::'e 0.5
:J
::;;
X
<(
::'e 0.4
0.3
0.2
IDEAL
STIRRED TANK
0.1
0.0 1.0 2.0 3.0 4.0 5.0
(b)
FIGURE 21 (a) Conversion of a first-order irreversible reaction for differ-
ent residence-time distributions. (b) Selectivity of a consecutive first-
order reaction for different residence-time distributuons. 1. Mixed flow;
2, five CSTRs in series; 3, one-dimensional flow, Pe= 8.87; 4, 10 CSTRs
in series; 5, one-dimensional flow, Pe= 20; 6, plug flow.
112 Shinnar
first illustrates an irreversible first-order reaction at high conversion, and
the second shows the selectivity of a consecutive first-order reaction. For
both cases, the limiting cases of plug flow and a stirred tank are given and
two models with equal Peclet number are given. One is a network of equal
stirred tanks in series and the other is a one-dimensional diffusion system
with a Peclet number chosen such that y2 is equal for both cases. For
y 2 = 0. 1, the results are so close that it is impossible to plot the difference.
For y2 = 0. 2 (Peclet number 8. 9 or 5 stirred tanks in series) the difference
is already recognizable but still small. One should not misinterpret this
statement. The results are always sensitive only to the variance of f(t).
In this case only models for which f(t) has a reasonable similar form were
compared. For such cases all models with equal y2 will give similar results,
provided that y2 is sufficiently small. For computation it is therefore ad-
vantageous to use simpler models based on stirred tanks instead of diffusion,
especially since none of the models represents the actual physics accurately.
Nonisothermal Reactors
The arguments in the preceding section can be easily extended to a noniso-
thermal reactor, provided that the temperature profile is imposed from the
outside and is independent of the reactions. For example, consider an
arbitrary network of stirred tanks, each of which is homogeneous and has
a uniform temprature imposed from the outside, although each reactor may
have a different temperature. The reactors are interconnected in an
arbitrary manner. There could be several inlets and outlets.. Again,
each entering molecule is equipped with a clock, but this time a more com-
plex clock is chosen that not only records the time spent in a specific tank,
but also records each step in a specific tank in the order in which it occurs.
If one looks at each clock, one finds a set of times (t1,t2,t5,t1,t2,• . . )
identifying each successive stay in tank i until it leaves the system. One
again collects them into bins, but this time one insists that not only the
total residence time t is constant in each bin, but that all molecules in a
bin have an identical clock history. Thus in each bin not only are the
separate stays in each tank of equal length, but they occur in the same
sequence.
In each stirred tank the reactions are first order with fixed reaction
rate, determined by the temperature of the tank. This means that if one
knows the state of a molecule (or the concentration of each compound)
entering the tank and the length of stay in the tank, the probability dis-
tribution at the time it leaves the tank is known or can be computed.
This means that if one knows the whole history of a molecule in a bin, one
knows the probability of it being in each one of the permissible states,
which in reaction terms means that one knows the concentration of the dif-
ferent compounds in the bin. For those who are somewhat uncomfortable
with probability theory, this concept can be translated as follows. Follow
a blob of molecules that has an equal history. As they travel through each
tank, the concentration of the blob changes in each tank in the same way it
would in a plug-flow reactor with the same temperature and residence time.
There is now only a cascade of plug-flow reactors with different residence
times and temperatures (or reaction rates). Each bin represents a unique
sectional plug-flow reactor of this type (see Fig. 22). It was shown pre-
viously that each stirred tank can be presented in such a way that molecules
with residence time t can be lumped together and treated as if they would
be in a plug-flow reactor of the same residence time t. The average outlet
Residence- and Contact-Time Distributions 113
FIGURE 22 Equivalent representation of a particle history in a nonisother-
mal reactor. Sectionally uniform plug-flow reactor. Ti, temperature of
each section; ti , residence time of each section.
concentration is now the average of all those sectional plug-flow reactors
and it is clear that if one is allowed to average them, one can always find
a single bin (or a plug-flow reaction with a special temperature and time
sequence), which yields a result as good or better than the network of
stirred tanks.
This proof is not limited to networks of stirred tanks. One can take
any arbitrary flow and represent it by such a network if one makes the
stirred tanks small enough. This is therefore true for any arbitrary flow
system provided that:
1. The reaction rates are locally first order in concentration.
2. The temperature profile is independent of the reactions and imposed
from the outside.
If condition 2 is not fulfilled, as for example in an adiabatic reactor, one
can no longer average. The temperature of a tank will depend on its con-
centration, and therefore the reaction rates affecting a single molecule will
depend on the nature of the other molecules in the tank, which violate one
condition for averaging. However, as many reactions are approximately first
order, averaging provides a simple guideline for reactor design. Even more
important, it lets one understand and recognize the exceptions to the rule,
in the cases where plug-flow reactors are not optimal. These in9lude, for
example, all cases in which it is desirable to maximize the contact between
products and reactants.
Bounding Methods for Nonlinear Reactions
For a first-order system, knowledge of the residence-time distribution com-
pletely determines the product composition in a premixed isothermal homo-
geneous reactor. For nonlinear reactions this is not enough, as one needs
to know not only the history of a molecule, but also the property and state
of the molecules in its close neighborhood. However, for a certain class of
nonlinear reactions wehre the reaction rate is of the type
r = -kan ( 34)
A
Zwietering ( 1959) has shown that one can get rigorous bounds on the pos-
sible conversions directly from f(t). Consider again a stirred tank with the
simple irreversible reaction A + B , but this time let the reaction rate be
second order. If the tank is ideally stirred, a mass balance will give
- QC - VkC 2 = 0 (35)
Z A
114 Shinnar
and
( 36)
One can also look at the other extreme idealized case mentioned before,
namely, that the entering fluid enters as separate encapsulated drops that
stay together (which Zwietering terms segregated flow). This case is
equivalent to the reaction in Fig. 13. In each tubular reactor the outlet
concentration will be
1
( 37)
and the average outlet concentration will be simply the average over f(t),
or
00
-u
E.
l
=fQ e u 0/u ( 38)
where Ei is the exponential integral. Note that the two cases lead to dif-
ferent results. However, if kC A O t is not very large, the difference is
small (see Fig. 23).
The reason for the difference is that for a second-order reaction the
probability of a molecule of substance A reacting depends on its probability
of being close to another molecule of A. In the segregated case, this
probability is larger than in the mixed case, as in the latter the entering
molecule is immediately exposed to products that reduce CA in its surround-
ings. Knowledge of the residence-time distribution alone is here insufficient
to compute CA, as one needs to know what happened not only to the mole-
cule but to its neighbors. However, for this simple case of second-order
reaction, Zwietering was able to show that ideal mixing and segregated flow
conditions are extremes and that all other possible mixing situations for
which f(t) is the same will result in an outlet concentration such that
CA (ideal mixing) > CA (segregated flow) (39)
For n = 1/2 or
= -kC 1/2 ( 40)
rA A
the limits become
CA (ideal mixing) 2
(
kt
2~ CAO
)2
2
~
2~ CAO
)
kt
( 41)
Residence- and Contact-Time Distributions 115
0.8
0.4
0.2
o.o
0 2 3 5
FIGURE 23 Conversion of a second-order irreversible reaction (A - B)
in a stirred tank as a function of time for segregated and completely mixed
flow.
and
2
.
CA (segregated flow) = CAO [ 1 + 2 ( kt ) ( 42)
2✓ CAO
Note that CA for the ideal stirred tank is less than CA for segregated flow.
Here the presence of molecules of A reduces the reaction rate and mixing
with products improves conversion. However, one has to be very careful
with such arguments when applied to reactions of fractional order. They
arise normally from Langmuir-type reaction rate expressions. Expressing
them as a fractional order is correct only over a limited range of concentra-
tions. There is a high probability that in integrating the results for Eq.
( 40), one may go outside the range where this is applicable, and therefore
one must verify that the final result is not sensitive to this mistake. The
results for a nonlinear reaction therefore depend not only on f(t) but on a
more complete description of the mixing phenomena which Zwietering terms
micromixing.
Swietering has also shown that these results can be extended to any
arbitrary residence-time distribution as long as the reaction is a simple re-
action of order n. In that case CAICAo will always be bounded by two ex-
treme cases: the case of segregated flow given in Fig. 20a and another
case defined as maximum mixedness, which is illustrated in Fig. 20b. Where -
as in Fig. 20a each tubular reactor is separate, in Fig. 20b, there is inter-
mixing between them and the feed inlets are arranged such that the expected
116 Shinnar
future life is constant for all molecules in a given cross section. Physically,
one could realize the arrangement of Fig. 20b by designing a plug flow re-
actor in which additional feed is introduced at different points along the
tube. For a reaction of order n the two limits or bounds on conversion
are segregated flow and maximum mixedness. For the case of segregated
flow,
f
00
[l + (n - l)R] l/l-n f(t) dt ( 43)
0
R = _-_k_t_
1-n
CAO
For the case of maximum mixedness, <CA> JC A O has to be obtained by solv-
ing the differential equation
( 44)
where ;\ is an integration variable and A(;\) is the escape probability as de-
fined by Eq. ( 8). Equation ( 44) can be integrated numerically, although
for certain values of n and certain values of A ( ;\) it has analytical solutions.
Here one sees another useful property of the escape probability and why
one wants to measure the residence-time distribution in such a way that
A (t) can be computed reliably. For reactors close to plug-flow reactors,
the bounds are very close and one does not have to worry about micro-
mixing which is important mainly in stirred-tank reactors.
Strictly speaking, the results of Eq. ( 43) apply only to simple reaction
of order n, in homogeneous ideally stirred reactors, which is a rather rare
design problem. However, the concepts of bounding the outlet composition
of a reactor is an essential tool of reaction engineering. It is really a form
of performing a sensitivity analysis on a design. Consider the example of a
stirred tank. A priori one knowns that this is an idealized model that can-
not be fully realized. However, one can approach it in the sense that the
time a droplet of feed spends in the reactor before it becomes totally mixed
is very small compared to the total residence time (Evangelista et al. , 1969b;
Shinnar, 1961). One also knows that during scaleup the residence time
stays constant, whereas the mixing time always increases (Evangelista et al. ,
1969a, b; Shinnar, 1961; Weinstein and Dudkovic, 1975). For a second-order
single reaction, Zwietering' s results show that one probably does not need
to worry about this, as the completely mixed case is the worst (least de-
sirable) case. There are many other cases for which this is not true. One
wants to know how important such deviations from complete mixing are. To
answer this, the two limiting cases for any arbitrary reaction system are
determined. If the reactions are complex and nonlinear, these two limiting
cases (segregated flow and complete mixing) will not give rigorous bounds
but will indicate if the system is sensitive to mixing and what penalties are
incurred for incomplete mixing. In scaleup, one cannot achieve segregated
flow, so the case of complete mixing must be satisfactory or the design must
be changed. If the system is sensitive to mixing, one can estimate the per-
missible mixing time by using models for incomplete mixing that simulate
Residence- and Contact-Time Distributions 117
small deviations from incomplete mixing (Evangelista et al. , 1969a, b; Belevi
et al. , 1981).
If, in a stirred-tank reactor, segregated flow leads to improved results,
a plug-flow reactor will normally be even better. If one requires the stir-
ring, one can approach plug flow by putting several such stirred tanks in
series. Experiments that demonstrate the sensitivity to deviations in mixing
can also be performed in a pilot plant. For example, one can design a
pilot plant similar to the one shown in Fig. 24 despite the fact that the
final reactor is completely mixed. There have been a number of models
proposed that look at micromixing for more complex flow conditions over a
wider range of micromixing [see, e.g., Weinstein and Adler (1967); Ng and
Rippin ( 1965)]. These models, which are reviewed in detail in Nauman
( 1981), are more in the nature of learning models than design models, and
are therefore outside the scope of this chapter.
Similar considerations apply to packed- bed and fluid- bed reactors. For
nonlinear reactions the only safe way to scale them up is to approach plug
flow as closely as possible. Again, one wants to know how closely plug
flow must be approached and what the penalty is for small deviations. One
can again perform experiments which experimentally check the sensitivity
of the reaction system to deviations from plug flow and design the reactor
accordingly. Here residence-time distributions are directly useful, since
for small deviations from plug flow, one can estimate the deviation from
plug flow from the tracer response by measuring y2. A simple model will
give reasonably reliable bounds as to the possible impact of such small de-
viations, even if the reactions are highly nonlinear. If the sensitivity is
large, one should take a safety coefficient with respect to the allowable co-
efficient of variation. This is illustrated in Fig. 25, where the effect of
small deviations from plug flow on several reactions are compared. One is
simply the irreversible reaction A + B of second order, and the other is a
nonlinear case very sensitive to mixing. In both cases the results are in-
distinguishable, and for y2 = 0. 2 (five stirred tanks in series, or a Peclet
number of 10) the results are reasonably close. In both cases we also give
the limiting cases of plug flow and a stirred tank to indicate the sensitivity
to back mixing. The comments made with regard to Fig. 22 apply here
FIGURE 24 Simulation of finite mixing in a pilot plant.
118 Shinnar
equally well. The results are not unique functions of y2. However, for
small deviations from plug flow, the results are not model sensitive as long
as the residence-time distributions are reasonably similar. For simulation
purposes, a model based on stirred tanks is therefore preferable, as it is
much easier to compute. The fact that y2 alone is not sufficient to charac-
terize the system unless y2 is very small is illustrated in Fig. 25c where
two other models with y 2 = 0. 1 are compared to a series of stirred tanks.
For a reaction sensitive to mixing, such as the one shown in Fig. 25b, the
differences are very large and a much smaller y2 is necessary for them to
become negligible. Such reactions therefore require extra care in scaleup
and a close approach to plug flow (or a stirred tank).
80
70
:,!!
0
<[ -
~
0
z 60
0
Cf)
a:
w
>
z
0 50
u
40
30
1.0 2.0 3.0 4.0
(a)
FIGURE 25 (a) Conversion of a second-order irreversible reaction for dif-
ferent flow models. (b) Comparison of product yield in a consecutive non-
linear reaction for different flow models. Reaction A+ B + C first order;
reaction A + C + D second order. Inlet concentration of A, 1. 0 ( dimension-
less units). 1, Mixed flow; 2, five CSTRs in series; 3, one-dimensional
flow, Pe= 8.87; 4, 10 CSTRs in series; 5, one-dimensional flow, Pe= 20;
6, plug flow. (c) Same as in part (b) for different flow models:
(I) +C=:J +Ll_J + (II) 10 stirred tanks in series (Ill) +Ll_J+C=:J+
V PF = 0. 69 V, V ST = 0. 31.
Residence- and Contact-Time Distributions 119
0.05
A~B~C
A+CO.l D
0 0.04
w
w
u..
z
<(
w 0.03
....I
0
2
----
0
u.. 0.02
0
CJ)
w
....I
0
2
0.01
0.00
1.0 2.0 3.0 4.0
TIME-
(b)
0.04
A .2..s-2..c
A+C~D
0.03
0
LL
0
Cl)
w
....I
0
:l!: 0.02
PLUG FLOW
0.01
0.00 '-----'-------'--------"------'---~~--~
1.0 2.0 3.0 4.0
TIME--
(c)
FIGURE 25 (Continued)
120 Shinnar
There is another area in which the concept of a residence-time distribu-
tion is useful in organizing ones thinking and experimentation. Thinking
in terms of residence times and joint probabilities is helpful in deciding
what reactor types to choose. For all linear and pseudolinear systems, iso-
thermal as well as nonisothermal, plug-flow reactors are always preferable.
The case where backmixing or a stirred tank has a positive influence is
when there are complex interactions between products and reactants. Ex-
amples are autocatalytic reactions, autothermic reactions (heat can be con-
sidered a product), or reactions of the types
A+ B + C
A+C+D
If D is desirable, a mixed reactor is preferable, as can be seen from Fig.
25. If D is undesirable, a plug-flow reactor is preferable. An example
of this reaction discussed in Renick et al. ( 1982):
Methanol + olefines + aromatics + paraffins
Aromatics + methanol + durene
If Durene formation is to be avoided, the reactor should be as close as
possible to plug flow. This result can be derived without reference to
residence-time distribution, but thinking in terms of residence_ time pro-
vides a useful framework.
There are a number of cases in which the desirable configuration is
neither plug flow nor a stirred tank. Combustion is an example. But here
one can often break down the optimal or desired flow system into configura-
tions composed of well-defined flows. If, on the other hand, the flow is
complex, residence-time distributions may provide diagnostic tests, but one
can neither model nor scale such cases solely on the basis of residence-time
distributions.
It should be emphasized that at the present state of knowledge, there
is no way that one can reliably scale up a reactor if the reactor is sensitive
to the form of f(t) and the reactor does not approach one of the well-
defined ideal cases.
HETEROGENEOUS REACTORS AND MULTl PHASE SYSTEMS
Properties of Tracer Experiments in Multiphase Systems
Residence-time distributions provide a powerful method for the analysis of
homogeneous isothermal reactors. Unfortunately, very few real reactors
used are truly homogeneous. Those few that are seldom provide serious
difficulties in design or scaleup. The majority of the reactors used are
heterogeneous, either gas-solid, gas-liquid, or triple phase. Catalytic re-
actors are almost always heterogeneous, even in homogeneous catalysis,
where most of industriral reactors deal with gas-liquid reactions.
If the use of residence-time distributions was restricted to homogeneous
reactors, their usefulness would be rather limited. Luckily, most of the
concepts derived in the previous sections can with some care, be applied
to heterogeneous reactors. One must, however, be careful to take into
account the heterogeneous nature of the system. This rules out many of
Residence- and Contact-Time Distributions 121
the algorithmic uses of residence-time distributions. One cannot simply
measure a residence-time distribution and predict the performance of a com-
plex reactor. Even the concept of a residence-time distribution is not sim-
ple any more, as different reactants may have totally different residence-
time distributions. In a heterogeneous reaction one cannot measure reaction
rates and residence-time distributions independently and reliably predict re-
actor performance even for first-order systems. But the main uses focused
on in the preceding section remain.
1. · The intensity function is still a useful tool to diagnose maldistribu-
tions in the flow and provide clues to the nature of the flows in
the system. Of special importance is that it allows one to check how
closely a design approaches plug flow (or an ideally stirred tank).
It is also useful in cold-flow models, where it can be used to test
the efficiency of flow distributions or baffles. The examples given
earlier were from heterogeneous reactors.
2. Residence-time distributions still provide a powerful conceptual tool
for design and scaleup. Although often one cannot get accurate
predictions, one can derive a better understanding of the scaleup
problem.
3. Residence-time distributions in multiphase systems allow measurement
of the holdup of each phase.
There are some important differences between tracer experiments in homo-
geneous and heterogeneous systems. It is important to understand these
differences not only in evaluating tracer experiments, but also because they
are related to design and scaleup. In a heterogeneous system, different
compounds may have strongly different residence-time distributions. In a
homogeneous reactor the difference in residence-time distributions between
different compounds is, in most cases, negligible. This is especially so if
the mixing process is turbulent. The only exceptions are slow laminar flows,
where molecular diffusion will be important. Thus in most homogeneous re-
actors the nature of the tracer compounds is of small importance. On the
other hand, in heterogeneous systems, there can be large differences be-
tween the response of different tracers, and therefore between the response
of a tracer and that of a reactant. Even different compounds in the feed
or different products may have different residence-time distributions. An
example of this is shown in Fig. 26 (see also Orth and Schiigerl, 1972).
Figure 26 illustrates data taken from a packed-bed Fischer-Tropsch reactor
in which CO and H2 were reacted over a Ni catalyst. The reactor was
operated at steady state and a step input of CO containing 13c was intro-
duced together with a step input of helium. The helium concentration was
kept very small so as not to disturb the steady state. The response of
the 13c in the CO is plug flow with a longer residence time, which shows
that the CO is adsorbed but that the interchange of the adsorbed CO with
the CO in the gas phase is very fast. On the other hand, both the CH4
and C 3H 6 product behave like a stirred tank in series with a plug flow.
This indicated not only strong adsorption but that, in this case, the inter-
change between the adsorbed phase and the gas phase for the product is
slow and has a characteristic time similar to the residence time. The re-
sults could also have been the reverse (slow interchange of the reactant
and fast interchange of the product). In a reacting system the concept
of a residence-time distribution itself becomes rather complex to define.
122 Shinnar
1.0
,/He
I
I
I
I
I
I
I
0.5 I
I
I
I
I
I
I
I
I
I
I
0
0 100 200 300 400
t, sec
FIGURE 26 Response of a packed-bed Fischer-Tropsch reactor, fed with
CO and Hz, to a step input of 13co and He. Reactor kept at steady state.
(From Biloen et al., 1983.)
One can always define it with respect to specific elements such as C in Fig.
26 (or molecular combinations that do not change such as benzene rings),
but the only way to measure this would be by means of proper isotope
markers. In Fig. 26 the tracer response is given separately for 13CO and
13CH4. From the original data one could have measured a tracer response
for 13c, which would give a residence-time distribution for carbon atoms.
It is a proper residence-time distribution, containing valuable information,
but its interpretation is more difficult. It is not only a function of the
flow pattern but also a function of conversion (or catalyst reactivity). To
measure maldistribution in flow, a nonreactive tracer is often preferable.
The average residence time of a single tracer is not necessarily equal
to total reactor volume divided by the flow rate. It is therefore hard to
estimate independently the average residence time, which due to adsorption
or similar phenomena, can vary by a factor of 5 or more between dif-
ferent tracers. Furthermore, not all tracers give linear responses. This
makes the choice of a proper tracer much more critical than in a homo-
geneous system. Residence-time distributions are by definition linear func-
tions. At steady state all compounds in a reactor have a measurable resi-
dence-time distribution regardless of the nonlinearity of the flow, nonlinear
adsorption phenomena, and so on. If one can properly mark a compound
(e.g., using an isotope), the tracer experiment will result in a residence-
time distribution. But if one introduces a tracer that is not present in the
system, it could behave in a nonlinear way, and the result could be very
dependent on the amount of tracer introduced. Furthermore, one does not
always want a tracer that behaves similar to the reactant. For example, in
some cases where one is studying reactor internals in a packed bed, non-
adsorbing tracers are preferable, as they are more sensitive to a maldistribu-
tion in the flow. This can be seen from Fig. 26. A helium tracer would
have given a much better indication of a maldistribution in gas flow than
using 13co and measuring the total amount of 13c leaving. The proper
choice of tracers is discussed in more detail in the next section.
Residence-time distributions cannot be used directly to predict outlet
composition even for linear reaction systems. Reaction rates in catalytic
reactors are measured and reported on the basis of either reactor volume,
Residence- and Contact-Time Distributions 123
catalyst volume, or catalyst weight. In a homogeneous system this has the
same time scale as the residence-time distribution. In a heterogeneous sys-
tem this relationship is not valid( due to adsorption, absorption, different
solubilities, etc. ) , and the difference in time scale can be a factor of 5 or
more. The ratio is different for different reactants. Consider, for exam-
ple, a packed-bed reactor. The estimates of kinetics are based in most
cases on overall residence times of mole reactantJlb catalyst per hour. The
real residence-time distribution of the gas is in most cases unknown because
the holdup of the gas depends on adsorption. If one could really tag a re-
actant one would not necessarily get plug flow in a tubular laboratory re-
actor (see Fig. 26). However, the kinetic data underlying the scaleup
assumed plug flow in the lab reactor. The rate expressions are really not
molecular kinetic expressions describing real molecular events but represent
overall relations allowing one to scale up a lab reactor to an industrial
packed bed.
This approach works very well even if the reactant is strongly adsorb-
ing and the reactions are highly nonlinear. The fact that for a highly
adsorbing reactant the real residence time of a molecule is, in reality, far
from plug flow, and different for all reactants, does not affect the useful-
ness of such overall kinetic relations for steady-state design. It may, how-
ever, strongly affect the dynamic behavior of the reactor and one has to be
careful when using rate expressions obtained from steady-state experiments
to describe the dynamic behavior of a reactor ( Shinnar, 197 8; Biloen et al. ,
1983). This also prevents one from using such methods as the boundary
methods of Zwietering, unless once again one is dealing with small perturba-
tions.
In catalytic reactors, reactivity can change with position even in iso-
thermal reactors. In some catalytic reactions, especially at high tempera-
tures, reactions occur in the gas phase as well as at the catalytic surface.
There is therefore no unique correlation between residence time and the
state of the molecule, which is a problem already encountered in the case
of the nonisothermal reactor. While a residence-time distribution can give
important information about the flow, one would need additional information
to predict the outlet composition, even if the reactor is isothermal and first
order.
The concept of a residence-time distribution is still helpful in the sense
outlined in the beginning, as long as one is careful to recognize the differ-
ences. This will be discussed in detail at the end of the section. First,
some techniques that are especially applicable to heterogeneous reactors will
be discussed, namely, multiple tracer experiments and contact-time
distributions.
Multiple Tracer Experiments
As in heterogeneous systems, different compounds may have different re-
sidence times. Independent knowledge of the residence-time distribution of
several tracer compounds gives a better description of the system. If the
feed contains different compounds, one may wish to use markers for each
of them to study the system. One can also learn a considerable amount
about the system by using a number of different tracers, even if they are
completely different from the reactant fluid (Shinnar et al., 1972; Nauman,
1981; Orth and Schiigerl, 1972). However, one is really measuring the
residence-time distribution of the specific tracer, which is not necessarily
124 Shinnar
representative of the system. If several tracers of strongly varying
properties are utilized, the residence-time distributions of the compounds
in the system can be bracketed. One should note, however, that even if
one uses an isotope of a reactant, one still cannot call this a residence-time
distribution of the system, as in a heterogeneous system different reactants
may have totally different residence-time distributions.
One does not always want a tracer that behaves like the reactant fluid.
Consider, for example, a packed- bed reactor. To measure maldistributions
of the gas flow, one wants a tracer that does not diffuse into the catalyst
and does not get adsorbed. In this case the transport processes inside
the catalyst particles and adsorption processes are irrelevant for scaleup or
reactor performance in the sense that one deals with scaleup of a pilot plant
with identical catalyst particles. The main problem one needs to consider
is that mass transport processes to and from the particle to not change as
the linear velocity in the large reactor increases. Tracer experiments are
not sensitive enough to check this property, but there are other methods
to ensure this. The main use of a tracer experiment is to test that there
are no maldistributions in the overall flow. An example of this was shown
in Fig. 16. In a packed bed, if there are maldistributions, one can use
the result of a tracer experiment with a nonadsorbing tracer to estimate
their impact on conversion and product distribution. In trickle beds one
must worry about both liquid and gas distribution, and would therefore
want two tracers, one for each phase. In all these cases, /\ (t) is the most
sensitive way to check for a maldistribution, but in a trickle b~d one must
be careful. Strong deviations from plug flow can occur due to fluid dynamic
effects and one therefore needs a good reference case (Mills and Dudukovic,
1981). In fluid-bed reactors the situation is more complex. If the solid
phase is not stationary but is fed and removed from the bed (as in the
treatment of solids in an FCC cracker), one may want to use a solid tracer
to check if the solid has the desired residence-time distribution. In a
single stage one probably wants complete mixing of the solids or a constant
/\ (t), whereas in a multistage bed and for treatment of solids, one wants
the residence-time distribution for the solid to correspond to a series of
stirred tanks, or to approach plug flow.
In some trickle beds, part of the feed evaporates. In this case, to
study the flow properly, it is recommended that both an evaporating and
nonevaporating fraction of the liquid be tagged. An example of such a
multiple tracer experiment is shown in Fig. 27, which illustrates results ob-
tained in a hydrotreater for fuel oil (Snow, 1983). Three tracers are used.
The Cg compound enters in the gas phase. The C16 compound represents
a compound that under the conditions of this hydrotreater is present in both
phases, whereas the C32 compound stays mainly in the liquid phase. Tracer
results are given for two reactors operating under similar conditions. Re-
actor A contains a 1/8-in. extrudate hydrotreating catalyst, whereas reactor
B operates with a 1/16-in. extrudate. Reactor B showed a better perform-
ance at high conversion, allowing a 50% higher throughput at 99% conversion.
The results give a good illustration of the advantage of using proper multiple
tracers. The most interesting information in Fig. 27 is not the form of the
individual tracer response but the relative position of the individual tracer
responses. In a trickle bed, one would expect that the residence time of
the lqiuid is larger than that of the gas. The results bear this out, as
the average residence time of the C 32 response is larger in both reactors
then in the Cg tracer. In reactor B the C32 tracer appears 3 min after
the Cg tracer. However, looking at Fig. 27a one notices immediately
Residence- and Contact-Time Distributions 125
.16
f ( t) Unit A
.12
/
I . Cs
\\
I •
I
.08 !j \~~
I.
"c~,~
If
.
' .
.04 I. ',~..... ......
:0
/•
......
0
0 4 8 12 16 20
.32
f ( t) Unit B
.24 -
.16
.08
0
0 4 8 12 16 20
(a)
FIGURE 27 Multiple tracer experiments in two industrial fuel oil hydro-
treaters. (Private communication with A. I. Snow, Arco Petroleum Co. ,
1983.) Three compounds tagged with 13c introduced simultaneously in feed
(pulse experiment) and measured at reactor outlet. (a) Residence-time
density function; (b) intensity function (escape probability) of unit A; (c)
intensity function (escape probability) of unit B; (d) cumulative residence-
time distribution (unit A); (e) cumulative residence-time distribution (unit
B).
126 Shinnar
0.30
Unit A
ACtl
c,6
0.15
---
0.00 '-----~___JL_____JL__---l_----'-----'-----'--~-~--
0 6 12 18
(b)
ACtl Unit B
0.60
0.30
0.00 l-.....~.L..---1-- --L------'------- -'--------1..---'-- --'---~~
0 6 12 18
( C)
FIGURE 27 (Continued)
Residence- and Contact-Time Distributions 127
100~----~ ----------- -------
1- F Unit A
Ca
16 2 ' - - - - - - L - - - - ' - - - - - - - - L - - - . . . L . ._ _ ____.J_ _ __J
0 8 16 24
(d)
1()3L__..l__..L.__-- '-----L---.l.-___J_ _,____ _.___ _,___~
0 6 12 18
(e)
FIGURE 27 (Continued)
128 Shinnar
that the C 32 tracer in reactor A appears about 1 min before the C 8 tracer.
This shows a significant difference between the two reactors and shows that
something is wrong with reactor A which explains its lower performance.
If one examines in detail at the escape probability (Fig. 27c and d), one
also notes that the C32 response shows a strong maldistribution in reactor
A and good liquid distribution in reactor B. Interestingly, reactor B has
a maldistribution in the gas flow (Cg) which is not evident in reactor A.
But it is apparently not significant enough to cause problems.
These tracer results contain some very interesting information about
what happens inside these reactors, and having simultaneous information
from both a liquid and gas tracer greatly adds to their value. However,
the interpretation of these results is in no way unique, as the maldistribu-
tion of the C 32 response in reactor A could be due to several causes. It
could be caused by a mechanical problem resulting in a nonuniform liquid
distribution, or by inherent flow problems, or by the different catalyst
size. Some reactor modeling could indicate which of these explanations is
more likely.
It is important to note that in such a multiphase system, there is no
way to deduce from a single tracer experiment if a maldistribution such as
the C32 response in reactor A (Fig. 27) is caused by a bad distributor or
by bypass phenomena inherent in the flow regime of this specific reactor
or by phenomena inside the catalyst particle. Trickle beds, by their nature,
do not scale equally well in different flow regimes, which are determined
by various flow parameters, such as gas velocity and density, liquid proper-
ties, and liquid-to-gas ratio. This problem was already encountered in the
discussion of the fluid bed, and it is important to realize this. However,
often one has two reactors operating under similar conditions and, in such
a case, a difference in tracer response clearly indicates a mechanical
problem.
In studying the gas flow in a fluid bed, one faces a problem not en-
countered in packed beds. If the reactant is adsorbed, it will move with
the solid. In an isothermal or adiabatic packed bed, if a pilot plant and
a large plant have the same residence-time distribution for a nonadsorbing
tracer, one would expect them to behave similarly. In a fluid bed one can-
not make the same assumption, as the mixing processes of the solid and the
adsorbed reactant with it are different for the two cases.
The only time that one can reliably scale a fluid bed and predict its
performance from a pilot plant is where in both cases the gas flow approaches
plug flow as closely as possible. One way to achieve this is by using baf-
fles in the fluid bed. Baffles here have a double purpose. They prevent
bypassing of gas due to large bubbles by breaking up the bubbles, and re-
duce solid circulation, thereby also reducing the backmixing of gas by
moment of reactants adsorbed on the catalyst.
In cases where one wants to test whether the flow distributor operates
well, a nonadsorbing tracer is a more sensitive tool (see Fig. 19). When
there are baffles in a fluid bed, the problem becomes more complex. A
good case can be made that an adsorbing tracer is more sensitive, as it
shows if adsorbed tracer is recycled by the catalyst to the bottom of the
reactor. Therefore, if a baffled fluid bed approaches plug flow with a
strongly adsorbing rracer, it gives one better confidence in the design.
However, one has to be careful to check that the tracer behaves linearly.
To check this, one always needs comparative results from a packed-bed
Residence- and Contact-Time Distributions 129
reactor. SF 6 has been reported to have desirable properties, and its ad-
sorption can be changed in a cold-flow model over a wide range, as the
adsorption equilibrium is a function of the water content of the air. If a
properly baffled design gives a residence-time distribution with a high
Peclet number (low coefficient of variation) for both a nonadsorbing and
an adsorbing tracer, this improves the confidence in the scalability of the
design.
Understanding the effect of adsorption on the residence-time distribu-
tion is helpful in another way. It explains why different reactions may
have different sensitivity to scaleup in the same fluid bed. To understand
this concept, one must first consider the evaluation of tracer experiments
with adsorptive tracers in a more rigorous way. The approach used is de-
scribed in detail in Shinnar et al. ( 1972). Consider a packed bed or a
chromatographic column in which a tracer can be adsorbed inside a porous
particle. One can now perform a tracer experiment with a nonadsorbing
tracer which can also diffuse into the porous particles and has the same co-
efficient of diffusion inside the particles. For simplicity a pulse tracer ex-
periment will be used. The density function of the nonadsorbing tracer is
designated fo and that of the adsorbing tracer fa. Also assume that the
adsorption equilibrium is linear and the amount of tracer adsorbed at
equilibrium per unit volume of Co gas phase is dC 0 , where Co is the con-
centration in the gas phase. Consider the case where ideal plug-flow con-
ditiond exist. Then fo(t) for the nonadsorbing tracer is a delta function
at t = T. One can then measure fa (t) for different values of T and define
a function 1/Jn ( t) .
1/J (t) = f (t - T) ( 45a)
a a
which gives the sojourn-time distribution of the adsorbing tracer in the
adsorbed state. The simplest case is if the tracer adsorbs in a way that
the rate of adsorption and desorption is very fast. In this case
1/J (t) =
a
o (en) ( 45b)
and for the general case where a is a constant, that gives the ratio of the
residence time in the adsorbed phase to that in the continuous phase.
( 45c)
If adsorption and desorption have finite rates, Eq ( 45c) will not hold.
However, if the bed has uniform properties and the flow in the gas phase
is plug flow, 1/Ja(t) must be a unique function of Tin the continuous phase.
One can further show that for various values of T
={
t
1/Ja(t/Tl + T2) 1/Jap(8/Tl)1/Jap([l - 8]/T2)d8 ( 46a)
where 1/Jap(t/T1) is the function 1/Jap(t) given that T for the continuous
phase is Tl. The subscript p was added to indicate that the flow in the
continuous phase is plug flow. If Eq. ( 46) holds, one can also show that
the Laplace transfer of 1/Ja(t) must have the form [Shinnar et al., 1972)
130 Shinnar
e
- TP (s) ( 46b)
~ap (~) =
and therefore
-(T 1+T 2)p(s)
= e ( 46c)
p(s) therefore characterizes the adsorption process or in a more general
way the transport processes in an outer phase not reachable for the tracer
use for fo• A
In Eq. (45c) it was assumed that p(s) = as. If one assumes a finite
rate of adsorption and desorption, then in the example given p(s) becomes
as
( 47a)
A
P ( s) = _1_+_(_a_/!:_-)-s
where ;\ is a normalized exchange coefficient. For understanding the gen-
eral concepts, one does not need more complex forms of p(s). The reader
should consult Shinnar et al. (1972) for more details. If p(s) is given by
Eq. ( 47a), then
A
_ -aTs/[l+(a/,\)s] ( 47b)
1/J ( s) - e -
ap
which is a well-known function used in chromatography. To derive it, one
must not only assume that fo(t) is a plug flow, but also assume that the
catalyst bed has uniform properties and that the catalyst is stationary.
This means that any molecule that got adsorbed returned to the same place
it left. In the limiting case where !:. + [Eq. ( 45c)] , the last assumption
00
is not needed. However, the assumption of uniformity is still necessary.
If the bed is uniform in its properties and each particle returns to the
same place in the gas phase, Eq. ( 46) can be generalized to the case where
fo(t) is not plug flow. For any such case with arbitrary fo(t),
t
~a(t) = f0 fQ(T)l/J
t
- dT
ap T
( 48a)
t
f (t) =
a f
Q
f (T)l/J ( ~ ) dT
O ap T
( 48b)
and
~a (s) = r0(p(s)) ( 49a)
where p(s) has been substituted for the variable s in f(s). Similarly,
( 49b)
Note that in the previous simplified case,
Residence- and Contact-Time Distributions 131
* ( 49c)
The results of Eq. ( 49c) are experimentally testable, as one can measure
as/(1 + as/A) in a packed-bed reactor under conditions approaching plug
flow. However, there are strong restrictions on its applicability. Equation
( 49) also allows computation of ~a (s) and therefore of lf!a (t) from measure-
ments of fa(t) and fo(t) in other cases where the adsorbed particle returns
to the same place. The only other case where this direct computation is
possible is when there is no correlation between the total residence time of
a particle in the adsorbed phase and its residence time in the gas phase.
In this case
f Ct) = f 0 (t)
a
* l/J Ct)
a
( 50)
where * is again the convolution integral. Unfortunately, this is a rather
unrealistic case for a catalytic reactor. In real cases when can Eq. (49)
be used? One case is a packed bed with back diffusion. The other is a
stirred tank reactor in which both the continuous and gas phase are mixed
(such as in a Berty reactor). In that case all molecules in the continuous
phase have equivalent location and therefore Eq. ( 49) holds. There are
additional important implications that can be deduced from Eqs. ( 48) and
(49). Consider the special case of a packed-bed reactor in which the flow
r
in the internal phase is plug flow or 0 (s) = e-,os. Further assume that
all reactants and products have the same rate of adsorption and desorption
and also the same adsorption equilibrium. Therefore, l/Ja(t) is constant for
all compounds. Finally, assume that a first-order complex reaction occurs
in the adsorb.ed phase. In that case one can write an equivalent of Eq.
( 28) for the product distribution:
n-1
L
A
* <c.> = a. 0 + a. l/! (A ) ( 51)
J J r=l Jr a r
which for a packed- bed reactor can be written
n-1
* <c.> = a. + L (51a)
J JO r=l
In standard kinetic practice one neglects adsorption processes and
simply assumes that the reactor is plug flow and one writes an equivalent
of Eq. (26):
n-1 -T Ar*
p
P.(t)
J
= C.(t) = a. 0
J J
+ I: ( 52)
r=l
where >..t are eigenvalues based on phenomenological rate constants. Tp is
a time constant that has the dimensions of time but does not refer to
any real measurable time. It is expressed in lb feed/lb catalyst per hour
(or lb mol feed/lb catalyst per hour). Note that
132 Shinnar
= T A* ( 53)
p r
Equation ( 53) implies that it is always possible to describe a first-order re-
action occurring in the adsorbed phase of a catalyst by assuming that the
reactor is a plug-flow reactor. The reaction rates will not relate to any
real reaction rates at the catalyst surface, but this is not important in
phenomenological rate equations in reactor design. Normally, tha kineticist
is interested in eliminating from A; transport resistances that deal with
transport to and from the catalyst particles and diffusion in the macropores,
as well as back diffusion in the reactor. This can be achieved by assuming
that the catalyst particles are small enough and that the microreactor used
is long enough [Silverstein and Shinnar, 1975).
In this special case, one can then estimate the conversion of an iso-
thermal packed-bed reactor in which fo(t) deviates from plug flow (either
due to diffusional resistances or due to maldistributions) , by measuring
f 0 (t) with an inert tracer and then computing the effect of the deviation
from plug flow just as one did in a homogeneous reactor. This is the re-
sult of deriving Eq. ( 53) from Eq. ( 51) . One must, however, note that
fo(t) has a different time scale than Eq. (53). One must therefore non-
dimensionalize f 0(t) and scale it such that the new first moment is the
same as that used in computing A;. This is particularly important, as
kineticists often use different definitions for 'P in computing A;.
Equation ( 49) to ( 53) also imply that for a first-order reaction, one can
predict the behavior of a packed bed by getting kinetic measurements in a
completely mixed reactor such as a Berty reactor, and vice versa. One
cannot, however, predict the outcome of any reactor for which Eq. (49)
does not hold, such as a fluid bed in which the catalyst moves. If the
movement of the catalyst is slow compared to the adsorption-desorption
processes of all reactants, one can get approximate predictions. For exam-
ple, if the fluid bed is staged by vertical baffles , it approaches a series of
stirred tanks or, for practical purposes, the reactants return to the same
place. The outcome can then be predicted using a packed-bed reactor (or
another fluid bed close to plug flow) as a model.
The relationship between Eqs. ( 51) and ( 52) was derived for the case
where 1/Ja(t) is equal for all reactants. This is not a very likely case but
was used for didactic reasons. However, the principle that one can pre-
dict the outcome of a first-order reaction in a reactor for which Eq. ( 49)
holds by measuring fo(t) and the overall kinetics in a packed-bed reactor
is valid for arbitrary sojourn-time distributions in the adsorbed phase, even
when they are different for each compound. The concept therefore has
much broader applicability. To prove the validity of the more general
principle, one can use an argument similar to the one used earlier when we
discussed optimal reactor concepts for nonisothermal reactors.
For any first-order reaction one can derive a phenomenological equation
such as Eq. ( 52). Kineticists define a first-order reaction by this condition
as they do not measure real reaction rates in the adsorbed phase. Consider
such a case in which 1/Ja(t) is different for all compounds. The average
sojourn-time distribution of the molecules will now depend on their state
and therefore on the reactivity of the catalyst. This is included in A*·
Once again, the hypothetical observer stands at the outlet of a plug-flow
reactor and collects the molecules. The molecules are now sorted into bins.
The molecules in each bin have a unique sojourn time e in the continuous
Residence- and Contact-Time Distributions 133
phase. In each bin, given 8 one can compute PjC 8) , the probability of
being in state j given 8. As the number of molecules is large, Pj( 8) is
equal to Ci( 8). Averaging over all the histories yields <p? or <C? or
the outlet concentration. Note that if the conditions leading to Eq. ( 49)
hold [namely, the catalyst has uniform properties and a molecule always re-
turns to the same place in the space of fo(t)], then <C·> is a unique func-
tion of the residence time t of the molecule in the nonadsorbed phase. If
one looks at molecules with different sojourn times in the nonadsorbed phase,
their probability of being in state j should be the same as that of a molecule
passing a plug-flow reactor with residence time t in the nonadsorbed phase.
The previous arguments should therefore hold regardless of the fact that
all compounds have different adsorption desorption behavior as long as the
system is linear and fulfills the basic assumptions.
The previous discussion leads to the disconcerting conclusion that in
order to predict the behavior of a first-order reaction, one does not want
a true residence-time distribution. A more accurate measure will be given
by a nonadosrbing tracer that measures fo(t). Thus the choice of tracer
can be crucial in predicting the outcome even of a first-order reaction.
There are cases where the "true" residence-time distribution will not cor-
rectly predict the outcome of even a fir•st-order reaction. This has im-
portant implications for the scaleup of first-order reactions. It was shown
that there is a fundamental similarity between a mixed reactor and a plug-
flow reactor and that one can always scale up from one to the other regard-
less of how the reactants behave in the adsorbed phase. However, one
cannot apply the kinetic data obtained from either one to predict the outcome
in a fluid-bed reactor. This has important implications for the scaleup of
first-order reactions, as it indicates a fundamental similarity between a
mixed reactor and a plug-flow reactor in terms of arbitrary behavior in the
adsorbed phase.
An important exception is the limiting case of a fluid bed which is
reasonably uniform and approximates plug flow. This will occur when either
~ is very large or the mixing of the solid is slow compared to the time
scale of ;\. ( Tmixing > 1 /'!:_). Otherwise, i)!a (t) would depend on both ~
and solid mixing. Unbaffled fluid beds in the bubbling range are not very
uniform and are often modeled by a two-phase model. Here, Eq. ( 49) does
not apply even if ;\ is large. One can, however, use an adsorbing tracer
with a large value of ~ to test how close the bed approaches the desired
condition, namely, that the bed has no bypass of gas that does not contact
the solid and approaches plug flow. Adsorbing tracers are an effective
tool to test whether the system approaches plug flow or not.
In a packed- bed reactor one can measure ;\. In fact, if one uses
tracers with lower values of ;\ and still gets a-good approximation to plug
flow, one can then get an estimate of the solid backmixing. To estimate
its impact on the reaction, one would have to bound ;\ for all the reactants
and products, which can in principle be done by using tracer methods
similar to those used in Fig. 26.
There is one essential point to remember in testing for maldistribution
of flow or for the effectiveness of internals in fluid beds and trickle beds.
This is the need for a good comparison case of a well-performing reactor.
If the residence-time distribution obtained by a tracer experiment deviates
strongly from plug flow, it does not necessarily indicate a maldistribution
of flow due to bad design. It could be a fluid dynamic instability phenome-
non which is common in fluid beds and which can also occur in large
134 Shinnar
trickle-bed reactors. In trickle-bed reactors it can be due to diffusion and
adsorption phenomena in the liquid phase. Input output tracer experiments
cannot distinguish between the two cases. What they can do is provide com-
parisons between two reactors and give clues to the effectiveness of correc-
tive measures such as baffles, which is a very valuable tool properly used.
Measurement of Holdup in Multiphase Systems
In multiphase systems the separate holdup of each phase may be unknown.
If the system is simply solid gas or liquid gas, the holdup of the solid or
liquid might be obtained by a pressure difference. The holdup of the gas
is more difficult to measure, as it may dissolve in the liquid or adsorb on a
solid. Here tracer experiments can be very helpful. One has to be careful
with the choice of the tracer. For a solid tracer it is important to find
particles that do not separate and have the same size distribution and den-
sity as the solid studied. For best results the solid should be impregnated
with the tracer when possible. If the liquid does not adsorb or evaporate
almost any tracer will do, but if it does, it is best to tag the liquid or part
of it. Choice of a proper tracer from the gas phase presents similar prob-
lems. If the gas adsorbs or is soluble in the liquid, one needs a tracer
with similar properties or preferably an isotope of the real compound. This
is sometimes the only direct way to measure holdup. When a suitable tracer
is available, two further requirements must be met.
1. Accurate measurement of total feed rate for the flow of the phase
measured
2. Accurate measurement of the amount of tracer introduced
In a pulse experiment one should always carefully check that the inte-
gral !0 00 QC(t) is equal to the amount of tracer introduced with an accuracy
better than 95%. In this case, one should never use Eq. (13). The first
moment of f(t) will then give an estimate of the holdup. In a step experi-
ment one can use !000 (1 - F) dt to estimate the holdup. The estimate of
the holdup obtained is one that includes adsorption phenomena. Therefore,
if the tracer is not an isotope of the real flow ,compound, one has to be
very careful in its interpretation.
The example given in Fig. 10 can serve to illustrate these problems.
It is based on data supplied to the author by Exxon (Mills and Dudukovic,
1981) from a study of the Exxon Donor Solvent Reactor. The tracer experi-
ments here were performed to measure holdup of the three phases. The
system illustrated is a three-phase system. The reacting gas is a mixture
of hydrogen and hydrocarbons, and the liquid is a mixture of dissolved
coal liquids and recycled solvent. The solid phase is ash and coal particles.
The tracer used to measure gas holdup was an isotope of argon which dis-
solves in the coal liquid, and it is this experiment that is shown in Fig. 10.
The solubility of the tracer at the reactor temperature and pressure can be
measured and, at equilibrium, the mole fraction of argon in the gas is five
times the mole fraction of argon in the liquid.
In Fig. 10 the Laplace transform of the residence-time distribution com-
puted from the tracer response was plotted. The first moment can be ob-
tained from it by estimating the tangent of f(s) as s + O. This is
Residence- and Contact-Time Distributions 135
A
relatively easy here, as the flow is close to plug flow and therefore ln[f(s)]
versus (s) is almost a straight line (see Fig. 10b), the slope of which is
equal to the first moment. The variance has to be estimated from the
second derivative near zero. This is not easy, but if the coefficient of
variation is small, one can do it by model fitting using
A
1
f(s) (19c)
(1 + , s/n)n
where n in here is a curve-fitting parameter. This approach was discussed
earlier. There are several problems caused by the fact that the gas tracer
is soluble in the liquid. What one really wants to know is not the holdup
of the tracer, but an estimate of the gas volume in the reactor. If the co-
efficient of variation y is large, there is no way that one can reliably esti-
mate the gas holdup. Fortunately, in this particular case, y is small and
the estimate could be obtained. The small y could be due to several
reasons. Either the gas- liquid mass transfer coefficient is small or it is
very large. If the mass transfer coefficient is small, adsorption in the
liquid phase has only a very small impact on C2(t), in the range of accurate
measurements because it mainly affects C2(t) for t + 00 (or s + 0). The
coefficient of variation is then in reality large, but this is not appreciated
when computed from the measured form of f(s). One can then get a large
error in the estimate of µ and y2. In the example given, the mass trans-
fer coefficient could be measured independently and this alternative could
be ruled out. It is therefore reasonable to assume that the mass transfer
is fast, which allows one to assume that the gas adsorbed in the liquid
phase is in equilibrium with the gas phase. If one knows the liquid holdup
and the solubility of the gas, a condition for the effects of absorption can
be made. Note that if y2 was not very small, there is no reliable way to
make any such correction, and it would have to be difficult to estimate the
volume of the gas phase in the reactor.
CONTACT-TIME DISTRIBUTIONS
The term contact-time distribution has been used in the literature in two
ways. One is a sojourn -type distribution in the active phase which is ob-
tained by using a slightly adsorbing tracer as well as a nonadsorbing inert
tracer. If one designates f(t) of the adsorbing tracer as fa(t) and of the
nonadsorbing tracer as f 0 (t), then, for pure plug flow, one can define
the density function of a sojourn -time distribution in the adsorbed phase
as
\/J (t) = f (t - , 0)
a a
where , 0 is the first moment of f 0(t). This distribution was discussed in
the preceding section, where it was shown that the function \/Ja(t) can be
measured not only for plug flow but also for a limited number of other
cases. However, although this distribution is useful for reactor modeling
and for diagnosing maldistributions, it is not directly useful for estimating
the behavior of a first-order reaction.
The kinetic relations assume plug flow in a packed bed, whereas tracer
experiments with a proper isotope tracer will not necessarily give plug flow
136 Shinnar
( see Fig. 26) . A close examination of Fig. 26 will demonstrate that one can -
not use the real residence-time distribution of the reactants to reliably pre-
dict the behavior of a heterogeneous reactor. In Fig. 26 the overall flow
is plug flow. However, the residence time of the 13c tracer is not plug
flow and has a large coefficient of variation. For other reactants the dif-
ference could even be larger. If one applies the kinetic relations which
are based on the assumption of plug flow to a model based on the actual
residence-time distribution, one would obtain very erroneous results. More
meaningful results can be obtained by using the data from the helium
tracer. The helium tracer has a residence-time distribution similar to fo(t)
but dissimilar to the true overall residence-time distribution of any of the
reactants. If the actual reactor is a fluid bed, one can no longer rely on
the results from a helium tracer, nor can one rely on the true residence-
time distribution. However, if the true residence-time distribution for both
the fluid bed and the packed bed are available and they are very close to
each other, one could deduce that the reaction should scale up safely. In
all other cases, one cannot directly apply the information.
A more useful definition of contact-time distribution is based on the re-
lation between the product distribution of first-order reactions and the
residence-time distribution of the system. Earlier it was shown that knowl-
edge of the product distribution defines the Laplace transform of the
residence-time distribution density function [Eq. (28)]. For a first-order
irreversible reaction A + B with a reaction rate r(A) = - ka, the outlet
concentration in a homogeneous system
f(k) ( 54)
where f(k) is the Laplace transform of f(t) with the reaction rate k sub-
stituted for s. For a first-order reaction occurring in Aa heterogeneous re-
actor, one can use Eq. ( 28) to define the distribution .!J!. by
n-1
<c. > I:
A
* ajO + a. \/JO) ( 55)
JP Jr- r
r=l
which is an equivalent of Eq. (28). This distribution, originally proposed
by Orcutt (Orcutt et al., 1962) and Glasser (Glasser et al., 1973), is not
a real distribution of sojourn times but has the same dimensions and proper-
ties. Regardless of the real sojourn-time distribution, Ar is defined and
measured by assuming that 2tOr) is plug flow for a packed-bed reactor.
For a complex first-order reaction occurring in a packed- bed reactor,
one can determine Ar for each r. If the reaction then occurs in a different
reactor such as a fluid bed, one can obtain measurements of Cj. The in -
formation from Cj andAthe Ar from the packed-bed reactor giv~s estimates
for several values of .!J!.( Ar). To obtain the complete function .!J!.( Ar), one
would have to use curve-fitting functions. However, in practice this is
often not needed, as sufficient information is available from the linear
values of Si!_( Ar) . In this case, Ar corresponds to the Laplace transform
variable of iµ(t) even though iµ(t) is an artificial constraint defined by Eq.
( 55) with no physical meaning.
Another way of measuring i<
Ar) is to vary k in Eq. ( 54). In a catalytic
reactor, this can be done by either changing the temperature of the reactor
or the reactivity of the catalyst. One can then use an equivalent of Eq. ( 54)
Residence- and Contact-Time Distributions 137
( 56)
to define $. It has the same meaning as the definition in Eq. ( 55) with k re-
placing ;\;, But it may not have the identical numerical form. Changing
temperature or reactivity may change the complex transport process as well as
the adsorption and desorption rates inside the catalyst particles. Therefore,
the values of $(k) obtained in this way will not be identical to those obtained
using ~Or) as defined in Eq. (55). However, the form will be similar.
Assume that one measures $(k) or ~( Ar) in a packed bed and then re-
peats these experiments in a fluidized bed keeping the space velocity constant,
and measures the conversion for each (k). The highest conversion possible
at each (k) is the same as in a plug-flow reactor. If, for any (k), the con-
version is higher [or f (k) smaller], it follows that either the reaction is not
first order, or the reactor is not isothermal, or the initial small packed-bed
reactor was diffusion controlled. If the conversions for all values of (k) are
equal to that of the packed bed, the fluid is essentially described by a plug
flow. If not, the conversion at each point is a measure of the way the fluid
bed deviates from the packed bed. If a/ao for the two cases is plotted vs.
(k), one can interpret the curves as plots of i_(k) for the two reactors. 1(k)
for the packed bed is by definition plug flow. Much can be learned from the
nature of the plot. In Fig. 28 an experimental contact-time distribution for a
relatively short bubbling fluid bed is given and compared with a plug-flow re-
actor and a stirred tank. Note that i(k) of the fluid bed is larger than f(k)
of the packed-bed reactor (plug-flow case) for all values of (k). At large
values of (k), f(k), for the fluid bed, is very flat and, within expArimental
accuracy, almost parallel. This indicates that part of the material essentially
bypasses the reactor. In fact, a simple bypass model
i(k) = a exp(-kT) + b ( 57)
fits the experimental results quite well. Figure 28 also gives $(k) for a stirred
tank. Note that it fits the experimental data less well. f(k) ~ larger than that
1.0
.8
.6
i(k}
.4
.2
0
0 5 10 15 20 25
k
FIGURE 28 Experimental contact-time distribution for a fluid-bed (Orcutt
et al., 1962). Comparison with various models: - - -- - - , stirred-tank
reactor; - - - - - plug-flow reactor; - - - - plug-flow reactor allowing
for bypass and stagnancy (experimental). (From Glasser et al., 1973.)
~(k) is measured here by conversion of ozone in fluid bed over an iron
catalyst. k is varied by dilating the catalyst with inerts.
138 Shinnar
of a stirred tank for small and large values of (k) . For intermediate range
i!_(k) is smaller than for a stirred tank, which is typical of some bypass
phenomena.
The $(k) for the fluid bed shown in Fig. 27 has another interesting proper-
ty that iscommon to most fluid beds. The slope of ~(k) near k + 0 is smaller
than for a plug-flow reactor. (The only way to know this is to measure the
reaction in a packed bed with the same catalyst under isothermal conditions.)
This indicates that not only does the bed have a bypass in the bubble phase,
but that part of the catalyst phase is not well contacted. In the author's ex-
perience properly baffled (or turbulent) fluid beds do not show any bypass
in the gas phase but will share the problem that the dense catalyst phase is
not perfused. Such baffled beds behave like near-plug-flow reactors with a
smaller effective catalyst volume (about 50 to 70% of real catalyst holdup).
[A possible explanation is given in Krambeck et al. ( 1967).]
If one could really measure the slope of ii!_ (k) for very small (k), it
would approach T as k + 0. This is the same problem that was illustrated
in Fig. 13 when measuring the tail of F(t). If a region of the reactor is
not well perfused, T will be underestimated. If an independent estimate of
Tis available, underestimating Tusing this technique is evidence that the
reactor is not well perfused. For the case shown in Fig. 13, one could
estimate T from the volume of the reactor and the feed rate. In the case
of ¢(k), the only way to estimate the first moment is by using a packed-
bed reactor for comparison. Note that i!_(k) here yields some valuable in-
formation directly applicable to reactor design. One can compare the
information obtained from Fig. 27 with that obtained by tracer experiments
in similar fluid beds ( see Fig. 17) . Figure 17 for a similar bed also clearly
indicates a bypass phenomenon. The escape probability /\ (t) measured from
the tracer response of a nonadsorbing tracer shows a clear maximum, indicat-
ing a bypass or stagnancy.
The method shown in Fig. 17 has one significant advantage. It allows
one to plot /\ (t) which gives direct physical insight into the nature of the
transport process. There is as yet no equivalent way to extract equivalent
information directly from inspection of ~(k). If f(t) is measured, computa-
tion of f( s) or f(k) is straightforward and relatively easy. The opposite
is not true. i<k) is hard to invert accurately, and therefore it js hard to
obtain an accurate estimate of the escape probability /\ (t) from lj!(k).
There are ways of inverting ¢(k) either by numerical inversion or by
fitting it with a theoretical model-;- but both methods are inaccurate. How-
ever, i<k) is a valuable tool since it contains the information in a form that
allows conclusions about the impact of the mixing processes on first-order
chemical reactions. Note that the time scale of ~(k) does not refer to any
real sojourn time. _i,_(k) is really a linear operator that changes the product
distribution of a linear reaction system in a packed- bed reactor to that of
fluid bed (or other) reactor. The properties of this linear operator are
conceptually similar to a residence-time distribution and one can derive
from it similar intuitive deductions about the nature of the transport
processes in the reactor. In most heterogeneous catalytic reactions one
desires plug flow in the reactor itself. i•(k) is therefore a useful tool for
checking internals in a cold flow model or verifying how closely the reactor
approaches plug flow, provided that one can find a suitable reaction. Both
ozone and hydrogen peroxide decomposition have been proposed (Nauman
and Buffham, 1983) and used.
The main advantage of using the i<k) as gefined here compared to
l/Ja(t) defined in the preceding section is that .!l!_(k) is measurable in any
heterogeneous catalytic reactor with a first-order reaction. On the other
Residence- and Contact-Time Distributions 139
hand, i/Ja(t) is uniquely measurable only in these cases where the absorbed
tracer particles return to the same place, in other words, where adsorption
does not change the residence-time distribution in the continuous phase.
As this condition is often not met, $(k) provides a useful alternative.
Unfortunately, i(k) suffers from the same problem as i/Ja(t). That is,
although it is useful in modeling, it cannot be used for scaleup, as the
$(k) depends on adsorption behavior and would be different for different
first-order reactions. One must therefore be careful when applying ~(k)
to actual scaleup problems. It will, in a cold flow model, give good indica-
tions of bypass phenomena. There is, however, no guarantee that the
real reacJ:ant will have the same behavior as reactions used in the cold flow
model. ijJ(k) is useful in studying maldistributions of flow in actual indus-
trial reactors. If an industrial reactor does not perform up to expectations,
one can often obtain several values of i<k) by changing the temperature
and thereby (k). One can then compare the effect of changing (k) in the
industrial reactor to pilot plant results or similar industrial reactors. From
this one can then infer ~ (k) and possible reasons for the poor performance.
This is a powerful diagnostic tool, complementing or substituting for tracer
studies in industrial reactors. One can get similar results even if the re-
action is nonlinear and complex involving several compounds. One starts
with the assumption of a plug-flow reactor, estimates a set of rate constants,
and then obtains expressions completely equivalent to Eqs. (16) and (20).
In this case, unlike the homogeneous case, one cannot use f(t) or f(t) to
compute the outlet composition. The outlet composition can still be used to
estimate $(k), as $(k) is an operator transforming the results of a plug-
flow reactor into our reactor. Note that reliable design requires that $(k)
be close to plug flow.
An especially interesting case is one of consecutive reactions with equal
reaction rates. Consider, for example, the case
The solution of this case is given in Table 2. If the values of the re-
action rates are equal, one gets an estimate not only of $(k) but also of
the higher derivatives of i(k) or (dni_(k) /dkn)k=ki. Even if the values
of (k) are different, the values of Ci give a good approximation of the
derivatives as long as the differences are small. If estimates of the
derivatives are available, $(k) can be reconstructed from a Taylor series
expansion around (k) (see Glasset et al., 1973). It is hard to use such a
reaction in a cold flow model. However, if an industrial reactor has a con-
secutive reaction, one can compare the product distribution to that of a
packed-bed reactor. If significant deviations are found, this allows some
conclusions as to the nature of the flow. A good base case, preferably an
isothermal packed-bed reactor, is essential as well as a well-performing re-
actor of a similar type. One does not always want to reconstruct $(k)
(although this is possible). The nature and magnitude of the deviations
give some immediate qualitative information about the nature and magnitude
of the deviation from plug flow, which can be interpreted by looking at
some simple flow models and styding their effect on product distribution.
An example is given in Table 3. In these examples, the overall residence
time T is kept constant for all cases. The reaction rate k is varied for
each flow model so as to keep the outlet concentration of A (A/Ao) con-
stant. This is done to make the example more consistent with actual
practice. In many cases, catalyst activity changes and is compensated for
140 Shinnar
TABLE 2 Dependence of the Product Distribution of a First-Order
Consecutive Reaction on the Residence-Time or Contact-Time
Distributiona
Reaction:
Reactor with residence-
Plug-flow reactor time distribution f(t)
2 -k.T f(k 1)
L
B 2
..!!_=k e 1 -=k L - - - -
A0 1 ._ 1 II (k. - k.) Ao 1 ._ 1 II (k. - k.)
1- ·-1 2 J 1 1- j=l, 2 J
]- ' 1
j;l:1 j;l:i
A
-k.T C 3 f(k 1 )
_g_=kk
A0
L
1 2 ._ 1 3
e 1
II (k. - k.) -=kk L - - - -
Ao 1 2 ._ 1 II (k. - k.)
1- ' j=l, 3 J 1 1- j=l, 3 . J 1
j;l:i j=l=i
_Q_=l-A-B-C D =1-A-B-C
AO AO
3 k.
D
-=1-L e- iT
k
II
k.
J D =1 - L f(k ) II J
. 1 3 k. - k.
AO i=l,3 j=l,3 \ - ki AO i=l l J= ' J 1
j;l:i j;l:i
~or contact-time distribution, substitute (k) for f(k).
by changing the reactor temperature. In practice one would therefore
compare the results of the industrial reactor to the pilot plant at constant
A I Ao. One does the same if the conversion is reduced due to a ,naldistribution
in the flow. Here the concentration of various products of a consecutive re-
action, which are a function of the residence-time distribution, can clearly
show if the reduced conversion is due to a change in catalyst activity or due
to a maldistribution in flow (provided, of course, that one can confirm in the
pilot plant that catalyst reactivity does not strongly affect selectivity). The
results for the case of consecutive reactions A + B + C + D where all reac-
tion rates are equal are given in Table 3. The results in this example are
very sensitive to the residence-time and contact-time distributions.
Residence- and Contact-Time Distributions 141
k1 k2 k3
A--- B--- C--► D
k =k =k =k
1 2 3
Reactor with residence-
Plug-flow reactor time distribution f(t)
-kT A A
= e = f(k 1)
AO
= k,e
-k, B
= -k df(k) I
AO 1 dk k=k
1
k2
C 1 d 2:f(k)
= 2!
AO dk 2
k=k
1
D
= 1-A-B-C = 1-A-B-C
AO
D
AO
= 1 -[ t
i=O
(k.~)i] e -k,
1.
APPLICATIONS OF CONTACT- AND RESIDENCE-TIME
DISTRIBUTIONS TO THE DESIGN OF
HETEROGENEOUS REACTORS
Earlier, rigorous concepts as to how residence-time distributions affect the
conversion and contact-time distribution in isothermal homogeneous reactors
were discussed. Unfortunately, very few reactions are truly homogeneous
and fewer are isothermal. In the previous sections it was shown that these
principles cannot be applied to heterogeneous reactors in straightforward
way. However, the main applications are still valid if one is careful to
recognize the special features of residence-time distributions in heterogeneous
,.,.
,I>.
TABLE 3 Dependence of the Product Distribution of a First-Order Consecutive Reaction on Residence-Time l\:,
( Contact-Time) Distribution: Numerical Example
kl k2 k3
A - - - B ---c - D
k =k =k =k
1 2 3
Average residence K
Flow model time (h) (h-1) A!A 0 B!B 0 C!C 0 D!D 0
1. Plug flow 1.0 1.0 0.368 0.368 0.184 0.08
2. Ten stirred tanks in series 1.0 1.05 0. 368 0.35 0.183 0.099
3. 1.0 1.068 0.368 0.336 0.192 0.104
~Et 0.9 T- 1.9
4. ~7~. 1.0 1. 36 0.368 0.236 0.191 0.205
T = 1. 39
--
--
T = 8
5. _hQ__-l I I 1-- 1.0 4.03 0.368 0.33 0.147 0.156
C/)
0.91 ,= 0.222, :2' .
;::I
;::I
Q
•
Residence- and Contact-Time Distributions 143
reactors. In this section the concepts presented earlier will be extended
to the more general case of heterogeneous reactors.
In the present state of knowledge, rigorous algorithmic use of residence-
time distributions to predict product distribution in heterogeneous reactors
is very restricted, even for first-order reactions. There is no real good
algorithmic equivalent of Zwieterin g's method.
Fortunately, the concept of bounding the outlet composition is still
valid. Utilizing different models, one can still evaluate whether the reaction
performance is sensitive to the actual flow model. The residence-time and
contact-time distributions can then be used to place constraints on the
range of flow models that one should consider. If the reactor is close to
plug flow, one can evaluate bounds by measuring the deviation from plug
flow by means of a tracer experiment. This works well only if the devia-
tion from plug flow is small.
The conceptual uses of residence-time distributions given earlier are
still valid. Plug-flow reactors or staged reactors approaching plug flow are
optimal for all first-order reactions and for all reactions in which contact
between products and reactants should be minimized. In fact, the example
mentioned earlier was from catalytic heterogeneous reactors (Belevi et al. ,
1981). Also noteworthy is the conceptual use of the contact-time distribu-
tion ~ (k) in reactor design and scaleup. Recall that ~ (k) was really an
operator that showed quantitatively the way the transport process in the
reactor modify the product distribution as compared to a packed-bed reactor.
Its time scale was the reaction rate used to predict the results of a packed-
bed reactor, which is simply the overall reaction rate per unit volume or
per unit weight of catalyst. It therefore has the same time scale as the in -
verse of the space velocity.
In a packed-bed reactor with a good flow distribution, it is possible to
i
keep both (k) and fo(t), the residence-time distribution in the gas phase,
constant. However, during scaleup, this is not automatically guaranteed.
fo(t) will normally stay constant and close to the plug flow if the microre-
actor or pVot plant is sufficiently long [ Silverstein and 'shinnar, 1975).
However, 2l!_ (k) will stay constant only if there is no mass transfer resistance
between the gas phase and the catalyst particle. Otherwise, increasing re-
actor length will change the mass transfer coefficient, which will change
i (t) and therefore $ (k).
- Another interesting conceptual conclusion can be derived from the con-
cept of a contact-time distribution. It can be seen from Eqs. ( 48) to ( 50)
that, for certain classes of systems, l/Ja(t) and ia(s) can be uniquely de-
rived from two sets of information.
1. The residence-time distribution fo(t) in the continuous phase
2. The residence-time distribution fa(t) of an adsorbing tracer in a
plug-flow reactor
Consider a first-order reaction that occurs in the adsorbed phase. As
each of the different reactants has a different adsorption behavior (its
adsorptive equilibrium may be different, as well as the rate at which it
adsorbs or desorbs), each species has a different ijJ (t) or Q(s). To proper-
ly model the system, one would need an exact tracer (isotope) for each re-
actant. However, for the special case described, one could predict ijJ(t)
or jJ_ ( s) for each of the species, given the tracer results from a plug-flow
reactor and fo(t), which is common to all species. If one follows a molecule
144 Shinnar
undergoing a first-order reaction, one can conceptually measure for each
molecule a total sojourn time in the adsorbed phase. To compute its
residence-time distribution, one must also know the reaction rates in order
to determine how much time it spends in each of the various states it can
assume. This is similar to the concept used earlier to deal with first-order
reactions in nonisothermal homogeneous system.
The above is equivalent to changing the nature of p(
s) in Eq. ( 49a).
Although one cannot make this computation without detailed knowledge of
adsorption kinetics, one can use the concept to derive an importan cri-
terion in reaction engineering: namely, that for all cases for which Eqs.
( 48) to ( 50) apply, one can use the pseudokinetics obtained from a packed-
bed reactor and apply it to all cases, using fo(t) to compute the results.
This allows one to deal with dispersion and recycling in packed beds. It
also shows that for a first-order reaction, the result of a stirred-tank
catalytic reactor is directly scalable to a packed-bed reactor, and vice
versa, as a stirred tank is one of the few cases with moving catalyst for
which Eq. ( 48) applies. This scaling is possilbe despite the fact that one
is really measuring a pseudokinetic first-order reaction rate based on
space velocity and not the actual kinetics based on real residence times.
This concept can be extended qualitatively to second-order reactions
in a catalytic reactor. In reactors of this type, micromixing is not impor-
tant. However, it is often important to know whether the product distribu-
tion can be predicted reasonalby from fo(t). For cases where Eq. ( 48)
applies, the Berty reactor provides a simple test. If a stirred-tank cataly-
tic reactor yields kinetic relations that predict well the behavior of a
packed-bed reactor, then nonlinear interactions between products and
reactants are not important and fo(t) can be used to predict the effect of
dispersion in scaleup.
The comparison above is often important in the design of complex re-
actors. It is therefore important to understand the principles by which
Eqs. ( 48) and ( 49) were derived. The main assumptions were:
1. The system is spatially uniform.
2. An adsorbed particle (or a particle diffusing into a catalyst particle)
always returns to the same place [or to a place equivalent to it in
terms of fo(t)] .
These assumptions are not always valid. Nevertheless, there are many
cases where one wants to predict the performance of a heterogeneous re-
actor which is not a packed bed from either a small packed-bed reactor or
a pilot plant. This applies to fluid beds as well as transport reactors such
as a riser cracker. If one compares such a reactor to a packed bed, it is
impossible to keep both fo(t) and i_ 0(k) constant. For example, the first
moment of fo(t) will be much larger for the riser. If the reaction occurs
only at the solid surface of this catalyst , this should not matter. But in
many complex reaction systems catalytic surface reactions compete and inter-
act with gas-phase reactions. The catalyst or solid may also act as an in-
hibitor for the gas-phase reactions. In some catalytic reactions, intermedi-
ates formed at the surface will either diffuse through the gas phase or re-
act in the gas phase. One should therefore be careful in such cases, and
evaluate the possible impact of changes in fo(t) relative to 1/Ja(t).
Rigorously, it is not enough that fo(t) and 1/Ja(t) stay constant. The
distribution of single stays in either phase should also stay constant. If
Residence- and Contact-Time Distributions 145
one cannot assume this to be true, one can experimentally test the sen-
sitivity of the reactions to variations in fo(t), keeping 1/Ja(t) constant.
This technique is a simple and powerful conceptual tool for organizing one's
thinking about the pitfalls of a given scaleup problem. Consider, for ex-
ample, a catalytic fluid-bed cracker in which the cracking really occurs in
the dilute phase riser. At low temperatures, gas-phase reactions are slow
and the results correlate very well with those obtained in a dense-phase
bed at the same space velocity. At higher temperatures, the gas-phase re-
actions become significant and the correlation is poorer. As these gas-
phase reactions are undesirable, it is important to reduce the average
residence time of fo(t), keeping the space velocity constant.
Another important example is the case of a dense-phase catalytic fluid
bed. Equations ( 48) and ( 49) do not apply rigorously in a fluid bed for
two reasons:
1. The gas phase is nonuniform, as part of the gas is in bubbles and
part in a dense phase around the catalyst.
2. The solid circulation and adsorbed reactants circulate with it. The
sojourn-time distribution at each reactant depends on the rate at
which it adsorbs and desorbs from the catalyst.
One can, however, design a fluid bed such that Eq. ( 48) approximately
applies. For example, one can see to it that fo(t) approaches plug flow.
One can also use an adsorbing tracer with fast exchange and design the re-
actor such that fa(t) approaches plug flow. That would occur only if all
gas particles are adsorbed and desorbed many times. This then approaches
the condition of spatial uniformity despite the pressure of bubbles. One
can achieve this either by working in the turbulent fluidization regime or
by using properly designed baffles. Designing the turbulent flow regime
only helps condition 1. The second condition can be approached only by
baffling or staging the bed. One can always approach plug flow by a suf-
ficient number of stages. If the catalyst circulation between the stages is
slow compared to the rate of adsorption and desorption of reactants, one
approaches condition 2, namely, that each molecule always returns to a
place such that its residence time in the continuous phase is not changed.
These arguments allow one to understand on theoretical grounds the
importance of baffles in scaleup. Baffles give added confidence to the scale-
up even if the fluidization is turbulent and a tracer experiment shows that
one approaches plug flow without baffles. This is so because solid mixing
in a fluid bed always increases during scaleup even when the pilot plant is
reasonably large. It is important that the baffles really reduce solid mixing
and divide the solid catalyst phase into stages. Vertical baffles, which are
often used, do not achieve this goal and therefore do not provide the needed
safety net for scaleup which can be achieved using horizontal baffles.
We will conclude with one final example. Recently, flash hydrogenation
of coal, in which coal is devolatilized and partially gasified in the presence
of hydrogen at high pressure, has received considerable attention. A
simplified kinetic scheme of the reaction is
H2 H H2
Coal - h e a v y liquids~ BTX ---methane
( 1) ( 2) ( 3)
146 Shinnar
Steps 2 and 3 can occur in the gas phase and are also catalyzed by the
coal ash as well as by the char. As this is a consecutive reaction, plug
flow of the gas is required for good selectivity, and it is also important to
control the residence time in a narrow optimal range. Kinetic and thermo-
dynamic considerations require the reactor to be as isothermal as possible,
and the easiest way to achieve this is by backmixing of solids. It has
therefore been suggested that fluid-bed reactors or risers with high solid
circulation would have significant advantages for such a design. However,
all present experimental data were obtained in current dilute phase reactors
in which the solid/gas ratio is an order of magnitude lower than would pre-
vail in a riser with solid recirculation. There is no way to estimate reliably
from data in a dilute-phase cocurrent reactor what would happen in riser
with higher concentration of solids. One cannot keep residence time and
contact time constant simultaneously. For any design estimates one would
need data from a system in which both contact time and residence time are
similar to the desired design. Or one would need evidence that one of
these two has no impact on the reaction.
These simple examples should be sufficient to illustrate the varied ap-
plications of contact- and residence-time distributions to the design of
heterogeneous reactor. They provide guidelines for dealing with the diffi-
cult problems of reactor scaleup in complex reactors.
NOTATION
a concentration of compound A
name of compound j
future life distribution of particle inside the reactor fraction of
particles inside the reactor that will leave it before time t
CA concentration of compound A in product stream
CAf concentration of product f in feed stream
C(t) concentration of tracer in exit stream
Cr<t) concentration of tracer in feed stream
Er<tn) expected value of tn or r000 tnf(t) dt
f(s) Laplace transform of f(t)
F(t) residence-time distribution: fraction of particle entering at time
zero that leave the reactor before time t
f(t) density function of residence time distribution: fraction of
particles exiting between t and t + ll t = f( t) ll t
g(t) density function of G(t)
G(t) internal age distribution: fraction of particles which are in the
reactor at a given time of observation that have been inside the
reactor less than time t
k kinetic rate constant
k.. rate constant of reaction A. + A.
lJ l J
Residence- and Contact-Time Distributions 147
K.. equilibrium constant of reaction Ai + Ai
l]
m amount of tracer introduced in pulse experiment
probability of molecule or particle to be in state
Peclet number
volumetric flow rate
time
volume of reactor
variance of density function f(t) = J000 (t - T) 2f(t) dt
Greek Letters
a. constants in Eq. (25)
Jr
~ coefficient of variation of f(t)
y = T
I\ eigenvalues of first-order kinetic systems [ see Eq. ( 25)]
r
/\ ( t) escape probability or intensity function of residence-time
distribution
r
µ r = E/t ) = rth moment of f(t)
T average residence time in homogeneous reactor = V /Q
Laplace transform of contact-time distribution
sojourn-time distribution density function of stay in the adsorbed
phase [see Eq. (46)]
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3
Catalytic Surfaces and Catalyst
Characterization Methods
W. NI CHO LAS DELGASS Purdue University, West Lafayette, Indiana
EDUARDO E. WOLF University of Notre Dame, Notre Dame, Indiana
INTRODUCTION
Catalysis is a complex phenomenon in which a multitude of interesting
variables intervene. A review of the principles and factors involved in
determining catalytic activity is beyond the scope of this chapter. We have
focused on the characterization of catalytic properties to enhance our un-
derstanding of the underlying processes. Emphasis is given to the modern
surface analysis techniques, which can provide new insights for interpret-
ing catalytic phenomena. Such methods, which were often first applied to
study model surfaces, are now being used to analyze the more complex sur-
faces found. on technical heterogeneous catalysts. Two types of characteri-
zation techniques are discussed in this chapter: (a) physical characteriza-
tion, and (b) physicochemical characterization. The first type refers to
total surface area and pore size distribution. Total area is relevant in de-
termining the contact between the catalytic agent and reactants. Porosity
is significant in controlling the transport of the catalytic agent into the
support during catalyst preparation, as well as the transport of reactants
and products between the bulk fluid phase and the active sites during re-
action. Since surface area and pore volume are related, a balance between
these two variables is a key factor in catalyst design. The BET adsorption
method to measure total surface area and methods to measure pore size dis-
tribution are discussed in the following two sections.
Other important variables that characterize a supported catalyst are
the area of the active catalytic component (i.e., metal area in the case of
a supported metal catalyst) and the crystallite size distribution of the active
phase. Many reactions are sensitive to the crystallite size, and they are
termed structure-sensitive or demanding reactions. Various factors are in-
volved in this structure sensitivity. The occurrence of a particular crystal
phase, the ratio of edge to corner sites, the structure of the surface, and
the stability of overlayers can all depend on crystallite size. A distinctive
chemical feature of crystallites in the size region 0. 5 to 5 nm is the low
coordination number of the surface atoms. Later sections describe selective
151
152 Delgass and Wolf
chemisorption of gases as a method to measure total metal area and x-ray
diffraction and transmission electron microscopy as methods to determine
average crystallite size and size distribution.
Although the methods mentioned previously have been known for many
years, their development for chemical analysis of surfaces is more recent.
As knowledge of the principles of operation, capabilities, and limitations of
surface analysis methods expands, the interpretation of catalytic phenomena
will become accordingly more sophisticated. Ultimately, this new knowledge
of surface chemical behavior will support the search for and design of new
catalysts. Knowledge of the composition of a surface is a prerequisite for
understanding its chemistry. X-ray photoelectron spectroscopy (XPS),
Auger electron spectroscopy (AES), and ion scattering spectroscopy (ISS)
provide quantitative analysis of surfaces or thin surface layers. This in-
formation can reveal surface enrichment in alloys, the surface concentration
of promoters in multicomponent supported catalysts, and the composition of
the surface of mixed oxides. These methods can also detect impurities and
poisons and, in general, follow changes in the catalyst surface after expo-
sure to the reaction environment. Oxidation state and phase identification
come most readily from XPS and, for selected elements, from the Mossbauer
effect. The current frontier in surface analysis is the measurement of local
surface composition and structure by application of (a) extended x-ray
absorption of fine structure (EXAFS) , and (b) secondary ion mass spectros-
copy (SIMS). We discuss these analytical tools and magnetic resonance in
relation to the determination of surface composition and structure.
The distribution of a catalytic material, or a poison within ·a support,
can be a key variable in catalyst performance. Slight changes in procedure
during catalyst preparation may introduce significant changes in the distri-
bution of catalytic materials inside the pellets. We discuss the use of elec-
tron microprobes and electron microscopes equipped with analytical capabili-
ties to assess the distribution of materials inside pellets.
To complete the chemical characterization of a surface, one must examine
its interaction with adsorbing and reacting gases. We discuss methods by
which the effects of gas-solid contact on the composition and chemistry of
the solid surface can be examined. The influence of the surface on the
adsorbed molecules is usually probed with vibrational spectroscopy (IR or
Raman) and can be investigated with a magnetic resonance (NMR or ESR).
Another measure of gas-surface interaction is the strength of the adsorbate
bond. Sabatier suggested long ago that this bond must be strong enough
to perturb the molecule but not so strong as to form an unreactive surface
compound. Temperature-programmed desorption and reaction methods for
studying surface bonding are discussed, along with vibrational spectroscopic
techniques for examining the adsorbate molecules themselves. These adsor-
bate studies can serve either as a direct probe of the reaction itself or as
an additional means of chemical characterization of the catalytic surface.
The techniques reviewed in this chapter are those best developed and
most commonly applied or most promising at this time. The presentation
emphasizes the essential concepts and features of each technique and major
applications in catalysis. We have attempted to avoid excessive use of
jargon to keep the discussions understandable to the nonspecialist. Refer-
ences to more detailed descriptions are given in each section. We note,
finally, that thorough characterization of catalysts often requires use of
combinations of techniques chosen to give complementary information, and
Catalytic Surfaces 153
that characterization of the catalyst surface encompasses only half of the
information necessary to fully understand a catalytic system. The other
half is the evaluation of the elementary kinetic steps of the reaction which
are the manifestations of the influence of the catalyst surface on the react-
ing molecules.
TOTAL SURFACE AREA: BET METHOD
There are several techniques to estimate the total surface area and pore
size distribution of porous materials. Various review articles concerning
such measurements have been published (Emmett, 1954; Innes, 1968). The
BET method is, however, the most common technique employed today for
such measurements; consequently, it is the only technique discussed here.
The reader is directed elsewhere in reference to other techniques (Innes,
1968).
BET Adsorption
Many physical adsorption isotherms exhibit S shapes which are inconsistent
with the Langmuir isotherm based on monolayer adsorption-desorption
equilibrium. Brunauer, Emmett, and Teller (1938) proposed an explanation
based on the assumption that multilayer adsorption could occur. The BET
model also postulates surface homogeneity and no intermolecular interaction
between adsorbed species. The most common form of the BET adsortpion
isotherm also assumes that an infinite number of multilayers can be ad-
sorbed. The resulting linearized BET isotherm has the form
p 1 C - 1 P
= +~p ( 1)
V d (P 0 - P) V C
a s · m m 0
where Vads is the volume at STP occupied by molecules adsorbed at a pres-
sure, P, Vm is the volume corresponding to monolayer coverage, C is a
constant, and Po is the saturation vapor pressure of the adsorbate over a
plane surface. A plot of P/Vads(Po - P) versus P/Po is a straight line
with slope S = (C - 1)/VmC and intercept I= 1/VmC. Knowing Sand I
permits calculation of Vm and therefore the number of gas molecules ad-
sorbed in a monolayer, which, when multiplied by the cross-sectional area
of the adsorbate, gives the total surface area of the solid. The following
cross-sectional areas (in square angstroms per molecule) give reasonably
self-consistent total areas: N2 = 16.2, O2 = 14.1, Ar= 13.8, Kr= 19.4
(Adamson, 1976). N 2 is the preferred adsorbate, but Ar and Kr are also
commonly used.
The most common experimental configurations used to measure BET iso-
therms (Innes, 1968; Everett and Otterwill, 1970) are (a) the classical
volumetric static apparatus used by Emmett, in which pressure associated
with incremental volumes of gas is measured; (b) a recirculating batch
flow system with helium dilutent; and (c) a pulse chromatographic dynamic
flow system.
Several commercial systems based on static or dynamic techniques are
available (Everett and Otterwill, 1970). The experimental objective in every
case is to determine Vads as a function of the adsorbate pressure. These
values are then substituted into Eq. ( 1) so that the intercept and the
154 Delgass and Wolf
slope of the linearized BET isotherm can be determined. The region of
best fit for the isotherm is in the P /Po range 0. 05 to 0. 3.
Continuous and automatic systems have also been designed and differ
from batch systems in that the gas is added continuously to the system at
a very low rate instead of in large increments. Continuous addition per-
mits automation, which, when coupled with microcomputers, provides direct
calculation of surface area and pore size distribution. Major factors in all
BET measurements are proper degassing of the sample and equilibration.
Other techniques used for calculation of total surface area, such as gravi-
metric techniques, selective adsorption from liquids, and small-angle x-ray
scattering, are briefly summarized by Innes ( 1968).
PORE SIZE AND DISTRIBUTION
The distribution of pore sizes is one of the important characteristics of sup-
ported catalysts since it is related to the value of the effective transport
coefficients, and consequently it can affect activity, selectivity, and rates
of deactivation. Catalyst pellets have a complex pore structure which pre-
sents a wide distribution of sizes. Pores between 10 and 100 A are re-
ferred to as micropores, those between 1000 A and 10 µm are called macro-
pores, and those of intermediate size are called mesopores. The micropores
are usually characteristic of the support porosity, whereas macropores can
originate in the interparticle space created during formation of the pellets.
A material exhibiting both micropores and macropores is described as having
a bimodal pore distribution. Detailed discussions of pore structure and its
determination have been presented in various textbooks and monographs
(Everett and Otterwill, 1970; Gregg and Singh, 1967; Parfitt and Singh,
1976).
A first-order approximation or estimate of the average pore size can
be performed by assuming that all pores are nonintersecting cylinders of
uniform length L and radius rp; then
Pore surface s = 2
Pore volume = V r
( 2)
p p
or
2V
r
p = ___E_
s
where Vp is the total pore volume and S the total surface area.
For materials with a distribution of pore sizes, it is necessary to know
the pore volume at various pore sizes. The derivative of the pore volume
curve with respect to the radius gives the pore size distribution. The
two most common techniques used to determine pore volumes are the BJH
method (Barrett et al., 1951), based on the use of either adsorption iso-
therms or porosimetry.
Pore Size Distribution from Physical Adsorption Isotherms
If a physical adsorption isotherm is extended to the region in which P /Po
is about 1, a rapid increase of V d occurs due to condensation of the
a s
Catalytic Surfaces 155
adsorbate on !he pore walls. Conversely, a decrease in pressure results
in evaporation of the adsorbed or condensed liquid. Kelvin derived the
following relation between the vapor pressure reduction over a liquid con-
tained in a cylindrical capillary and the radius r:
2Vo ( 3)
== - rRT cos cp
where Po is the saturation pressure, o the surface tension of the liquid,
¢ the contact angle (for simplicity assumed to be 0°), and V the molar
volume of the liquid. The Kelvin equation can be used in principle to
calculate r for any corresponding value of P /Po. However, several com-
plications arise: ( a) a hysteresis loop is often observed in adsorption
isotherms; (b) the pores are not cylindrical and have varying radii; and
(c) an adsorbate film of varying thickness decreases the effective Kelvin
radius. A discussion of the various theories that have been proposed to
account for the factors cited above is given by Gregg and Singh (1967).
A detailed calculation procedure, known as the BJH method, has been
reported by Barrett, Joyner, and Halenda ( 1951). The method consists of
stepwise calculations based on the data obtained from the desorption branch
of the isotherm about the region where P /Po ~ 1. The calculations yield
a cumulative pore volume versus pore radius which is then differentiated
with respect to the radius to obtain the pore size distribution.
Mercury Porosimeter
In this case the pore volume is measured directly by forcing a nonwetting
liquid, mercury, into the pores. A force balance between external pres-
sure and surface tension in a cylindrical pore gives
r =
2o cos e ( 4)
p
or for Hg,
7500
r =
p
Equation ( 4) allows direct calculation of the pore radius at a given pres-
sure. After plotting the cumulative pore volume, which equals the volume
of Hg forced into the pores, versus pore radius, one can obtain the pore
size distribution by differentiation with respect to r.
With proper experimentation, both N 2 desorption and Hg porosimetry
generally agree well. The N 2 desorption method is adequate for small
pores ( 2 to 30 nm), whereas large pores are preferentially measured by
low-pressure Hg porosimetry. With some materials high-pressure Hg pene-
tration modifies the pore structure by breaking pores, which can lead to
spurious results.
DETERMINATION OF METAL AREA BY SELECTIVE
CHEMISORPTION OF GASES
The most common method employed to determine metal area is selective chemi-
sorption of gases. The method has been discussed in review articles and
156 Delgass and Wolf
textbooks (Whyte, 1973; Anderson, 1975). It consists of measuring the
volume of gas adsorbed at monolayer coverage as in the case of BET ad-
sorption; however, gases that chemisorb selectively on the surface under
study are used instead of those that physisorb. Table 1 lists a number
of metals and gases that form chemisorbed monolayers. Since for selected
gases chemisorption is irreversible, fast, and usually single layer, mono-
layer coverage is determined from the plateau of the isotherm, extrapolated
to zero pressure.
A simple stoichiometry is required to relate the number of gas molecules
adsorbed with the number of surface atoms. For a given metal, an average
site density can be calculated for the crystallographic planes exposed.
From the site density, an area per surface atom (Si) is calculated. For
example, for Pt the densities of the ( 100) and ( 110) planes are 1. 31 x 1015
sites/cm2 and 0. 93 x 1015 sites/cm2 or 1.12 x 1015 sites/cm2 on the
average ( 50-50 distribution). This corresponds to an average area of 8. 9
A 2/atom. The total metal area per gram of catalyst (SM) is then calculated
as
s.vv d (6.023 x 10 23 )
1 a s ( 5)
=
22,400 m
where vis the adsorption stoichiometry (surface atoms/number of adsorbed
molecules , Vads the volume of gas adsorbed at monolayer coverage and
standard temperature pressure, and m the mass of catalyst used.
TABLE 1 Selective Chemisorption of Gases on Metalsa
Gases
Metals 02 C2H2 C2H4 co H2 CO 2 N2
Ti, Zr, Hf, V, Nb, + + + + + + +
Ta, Cr, Mo, w,
Fe, Ru, Os
Ni, Co + + + + + +
Rh, Pd, Pt, Ir + + + + +
Mn, Cu + + + + ±
Al, Au + + + +
Li, Na, K + +
Mg, Ag, Zn, Cd, +
In, Si, Ge, Sn,
Pb, As, Sb, Bi
a+, Strong chemisorption occurs; ± chemisorption is weak; chemisorp-
tion is unobservable.
Catalytic Surfaces 157
The metal fraction exposed, or dispersion, is calculated as
vµ.M
metal surface atoms 1
( 6)
D = =
total metal atoms mw
where M is the molecular weight of the metal, w the fractional metal load-
ing, and µi the uptake in micromoles. The average crystallite size is cal-
culated by assuming that crystallites are of the same regular uniform
shape (i.e. , crystallites are often assumed to be cubes with five faces ex-
posed and the sixth being in contact with the support). For this
geometry
( 7)
where PM is the density and d the average crystallite size.
Spenadel and Boudart ( 1960) demonstrated that H 2 chemisorption on
Pt black (10 torr, 25°C) agreed well with BET data. Agreement between
H2 chemisorption and x-ray diffraction results was also obtained in the
case of a Pt supported on alumina catalyst. A variation of the direct
chemisorption technique is titration of preadsorbed 02 with H2 (Gruber,
1962). Benson and Boudart ( 1965) proposed that the titration stoichiometry
is
which allows for the uptake of three hydrogen atoms per Pt atom, thus in -
creasing the· sensitivity of the technique. Mears and Hansford ( 1967)
found that a different Pt-H2 stoichiometry appeared to be applicable to
their results. The dilemma was resolved by Wilson and Hall (1970), who
found that the stoichiometry of oxygen chemisorption depended on crystal-
lite size. For this reason, titration techniques are not used with samples
having very small sizes.
The use of CO chemisorption has also been proposed to determine
metal surface areas (Hughes et al., 1962). However, the relative contribu-
tion of the linear and bridged forms of CO must first be assessed to es-
tablish the proper stoichiometry. Other gases, such as NO, have been
used to evaluate the metal surface area of Ru (Ramamoorthy and Gonzalez,
1979).
The experimental techniques to measure Vads have not been mentioned
above, but in most references a static or volumetric technique similar
to the one used in BET absorption has been used. A flow pulse tech-
niuqe that permits rapid determination of Vads has been described by
several authors (Gruber, 1962; Benesi et al,, 1971; Huasen and Gruber,
1971). The effect of sample volume, amount of catalyst, pretreatment,
and so on, on the value obtained for Vads using the pulse technique has
been reported. Pulse results agree well with the static techniques if ad-
sorption is very fast and irreversible. Reversible adsorption introduces
tailing on the emerging peaks, which can lead to errors (Wanke et al. ,
1979). A stringent requirement of the pulse technique is the use of clean
158 Delgass and Wolf
ultrahigh-purity gases and various traps to eliminate trace impurities.
Sarkany and Gonzalez (1982b) have discussed conditions for proper use
of the pulse technique, in particular, linearity of the TC cell response
and the effect of reversible adsorption. Appropriately used, the flow
technique gives good and expedient results and the apparatus is easy to
build. For a new catalyst it is advisable first to establish the operating
conditions in which reproducibility with the static or other techniques is
attained.
DETERMINATION OF AVERAGE CRYSTALLITE
SIZE AND CRYSTALLITE SIZE DISTRIBUTION
X-ray Diffraction
X rays have often been used in catalytic work in relation to the estimation
of crystallite size and to obtain information on the bulk crystallographic
structure of catalytic materials. A number of monographs exist on x-ray
diffraction (Klug and Alexander, 1974; Cohen and Schwartz, 1977; Cullity,
1978; Schultz, 1982) and the subject is so extensive that it can be treated
here only in basic terms.
Nature of X rays
X rays are electromagnetic radiation with wavelengths in the angstrom
range. Consequently, they can penetrate matter and therefore are
especially well suited to probe the structure of solids. X rays are com-
monly generated by bombarding a solid (target) with high-energy electrons
to create inner-shell electron vacancies. Two types of x rays are thus
generated: (a) a continuous spectrum, and (b) a characteristic line
spectrum. The continuous spectrum arises from the deceleration of the
incoming high-speed electrons by the target. Line spectra occur when an
electron from a high-energy orbital fills a low-energy vacancy in the inner
electron orbitals. The line spectrum is characteristic of the emitting materi-
al and use used for x-ray spectroscopy, which will be discussed in detail
later. The peaks of the line spectra are designated by the orbital (shell)
into which the electrons fall (K, L, M, N) and a Greek letter indicating the
original orbital ( a, 13, etc). Due to the characteristic well-defined energy,
the x-ray lines are used as a quasimonochromatic x-ray source in diffraction
equipment.
X-ray Diffraction
Diffraction occurs when a wave interferes with an array of scattering cen-
ters, causing the outcoming waves to reinforce each other (constructive
interference) or to be out of phase and cancel each other (destructive
interference) (see Fig. la). X rays are scattered by the electrons of the
irradiated matter. Elastically scattered x rays have the same frequency
as the incoming x rays (coherent scattering); the opposite is true for in-
elastic scattering (incoherent scattering). Elastically scattered x rays,
which are important in diffraction, can be depicted as reflected by the
scattering atom.
Bragg used the reflection analogy to explain x-ray diffraction. Fig-
ure lb shows a monochromatic x-ray beam of wavelength A directed on
two successive planes of a crystal. The reflected beam (i.e., scattered)
Catalytic Surfaces 159
SOURCE
SOURCE
CONSTRUCTIVE DESTRUCTIVE
(a)
(b)
FIGURE 1 Schematic representation of (a) constructive (in phase) and
destructive (out of phase) interference when a wave motion is scattered
by slits, and (b) Bragg's reflection analogy for x-ray diffraction showing
constructive interference.
and associated wavelengths are also shown. If the reflected rays are to be
in phase, the path difference of the two successive incoming rays, CB +
BD = 2d sin 0, must be equal to an integral number of wavelengths, that
is,
2d sin 0 = NA ( 8)
The equation above, known as Bragg's law, relates the d spacing of the
crystal with the angle of incidence and wavelength of the incoming x rays.
N is known as the order of the reflection. Equation ( 8) indicates that
measuring the intensity of the diffracted beam as a function of the incident
angle gives a diffraction pattern which is characteristic of the crystallo-
graphic structure of the irradiated sample. Such measurements, which
constitute one of the many methods of XRD analysis, are most easily at-
tained with an x-ray diffractometer.
160 Delgass and Wolf
An x-ray diffractometer consists of a circular table with a stationary
x-ray source and a moving detector located in the circumference of the
table with the sample set at the center. The moving detector, usually a
proportional counter, records the intensity of the reflected beam as a
function of the reflected angle 28. A straightforward application of XRD
is the use of the XRD patterns to identify the various phases existing in
a material. Diffraction patterns of powders are compiled in the Powder
Diffraction File Search Manual (Berry, 1975).
Crystallite Size Determination from XRD Line Broadening
Diffraction lines should, in principle, be very narrow; however, when the
crystallite size of a polycrystalline material falls below 1000 A, broadening
of the diffraction lines is observed. Instrumental limitations and lattice
strain can also cause line broadening.
Line broadening due to particle size only arises because of incomplete
destructive interference. When the incident beam is slightly off the Bragg
angle, the reflected ray which would nullify it originates from N planes
inside the crystal. If the crystal is smaller than about 1000 A , most
planes do not have their destructive counterparts N planes away, so that
finite diffracted lines will be observed at the off-Bragg angle setting,
causing line broadening. Various measures of the peak broadening are
used, the most common being the width at half peak intensity [3 1 , and the
e •
integrated breadth, f3. = J8 2 Id8/I where I is the observed intensity
of the diffracted beam1. 1 max
The relation between line broadening and crystallite size for a stress
free material, known as the Scherrer formula, is
( 9)
f3hkl cos 8
where K is a constant that depends on the definition of f3 used and the
crystal geometry. The constant K varies from 0. 98 to 1. 39, but because
of experimental uncertainties, the constant is often set equal to 1. When
S is defined as the integral breadth, <L> is a volume average crystallite
size.
In the absence of lattice stress, broadening also occurs due to experi-
mental limitations such as nonparallel and nonmonochromatic irradiation.
Other experimental factors also contribute to broadening, even if the
specimen is of "infinite size" (i.e., larger than 1000 A). Consequently,
for the correct estimation of crystallite size using Scherrer's formula, the
experimental contribution to line broadening must be separated to obtain
the pure diffraction broadening. Although various procedures exist, two
are outlined here: (a) a simplified procedure, and (b) an accurate
Fourier transform method.
Simplified Procedure: In this case the sample is mixed with a standard
that has particle sizes greater than 1000 A and produces a diffraction line
near the line of the sample under analysis. Alternatively, diffraction pat-
terns of the sample and of another sample of the same material containing
crystallites larger than 1000 A can be used. In either case, if B is the
width of the sample containing small crystallites and b the width of the
Catalytic Surfaces 161
standard sample with large crystallites ()1000 A), the breadth or broaden-
ing of the pure diffraction pattern S is estimated by
( 10)
or
S=B - b ( 11)
The first correction is derived by assuming that the shape of the peak is
gaussian, whereas the second one corresponds to a Cauchy profile. Here
S would be either B½ or Bi. Over the years, the gaussian approximation
has been widely used, although some evidence indicates that the pure dif-
fraction profile is better approximated by the Cauchy form when a distribu-
tion of particle size exists (Klug and Alexander, 1974). However, either
correction can be used. It must be emphasized that because the shape of
the profiles must be assumed, the simplified procedures give speedily re-
sults of good relative accuracy but have restricted absolute significance.
Fourier Transform Method: The theory of this method is beyond the
scope of this outline and the reader is referred to the specialized literature
(Klug and Alexander, 197 4; Cohen and Schwartz, 1977). The experimen-
tal determinations are similar to those outlined above, but the pure diffrac-
tion profile is calculated from the Fourier synthesis of the sample profile,
h( E:), and a reference profile obtained with a reference sample of infinite
size, g( E:), where E: is the angular change through the peak.
The Fourier transform coefficients of the true diffraction profiles are
calculated from the real and imaginary Fourier series calculated from the
intensities of sample and reference profiles measured at various angular
intervals of the broadened peaks. Computation procedures are given
Ganeson et a:l. ( 1978) and Sashital et al. ( 1977). The crystallite size can
be calculated using the breadth of the reconstructed profile and Scherrer's
formula or directly using the Fourier coefficients. Warren and Averbach
(1950) related the crystallite size to the first derivative of the Fourier
coefficients with respect to the Fourier harmonic. Furthermore, a plot of
the second derivative of the Fourier coefficient is proportional to the dis-
tribution of crystallite sizes. Figure 2 shows results of Sashital et al.
(1977) obtained using the Fourier transform method, including strain and
imperfection corrections. Table 2 summarizes the average crystallite size
for the various crystal planes along with dispersion results obtained from
hydrogen chemisorption techniques. It can be seen that the Fourier
transform calculations agree well with the chemisorption results.
Transmission Electron Microscopy
The most common use of an electron microscopy (EM) in catalysis is to
measure the distribution of crystallite sizes as well as the morphology of
supported or unsupported active materials. However, new analytical elec-
tron microscopes, which combine EM with spectroscopic analysis, also re-
veal information about the chemical nature of the crystallites. To under-
stand the possibilities of EM beyond that of taking pictures, it is
necessary to have a basic understanding of EM. A detailed description of
the subject is presented in various textbooks (Heidenreich, 1964; Hawkes,
1972) and review articles (Beer, 1980; Schmidt et al., 1982).
162 Delgass and Wolf
3 ~
''
''''
? '' (L)III
02
>(
b ~.
N
¢'
,,
C:
"O
'
<1.c: I ,b 0.
N
"O ,9 '1,,
Q,
p c,,,
Jf "O
0
0 10 20 30 40 50
L= na 3 , &
(a)
8
3
P, 7
:'
''
!\
'' ' : 6
/:,' o''
( L)IOO N
-0
2 1, '=' 5
1~ ( Ll3,1
>(
N
C:
'! 'a. N 4
C:
C: /, "O
~
C: 'q ~3
<1. /5 <1. ~
N
/5 ~ N
2 ' b,
"O "O
~
r Q
Q,
"- a,
p 0 'o
0
O'
0
i 0,,
'
0 10 20 30 40 50 0 10 20 30 40
0 0
L= no 3 , A L=na 3 ,A
(b) (c)
FIGURE 2 Particle size distribution for a catalyst containing 40% Pt on
Si0 2 prepared by impregnation of chloroplatinic acid: (a) < 111> direction;
(b) <100> direction; (c) <311> direction.
An electron microscope differs from an optical microscope in that the
electron beam replaces the light beam and electromagnetic lenses replace
the optical lenses. The use of an electron beam improves the resolution
of the microscope, which is proportional to the wavelength ,\ of the inci-
dent beam, in accord with (Heidenreich, 1964)
(12)
where x is the resolution (i.e. , the mm1mum size that can be distinguished
in the microscope) and c 8 is the spherical aberration of the incident beam.
Relation (12) illustrates the advantage of using an electron beam ( ,\ =
0. 5 to 10 A) instead of light ( ,\ = 4000 to 7000 A).
Catalytic Surfaces 163
TABLE 2 Particle Sizes <L>hkl and Dispersion
<L>lll <L>100 <L>110 <L> 311 Dx Dh
Catalysta (A) (A) (A) (A) ( %) ( %)
7.1-SiO -PtCl-S
(1) 2 131 82 108 81 10 7.1
( 2) 111 75 12 7.1
21. 5-SiOrlonX-L
( 1) 49 43 45 47 25 21. 5
( 2) 48 43 45 47 25
27-SiO2-IonX-S
( 1) 43 39 42 31 27 27.3
( 2) 40 39 39 39 29
40-SiOrPtCl-S
(1) 30 26 22 20 44 39.8
( 2) 25 23 47
a7.1, 21.5, 27, and 40 indicate percent of Pt loading on SiO2. PtCl and
IonX indicate preparation via chloroplatinic acid impregnation and ion ex-
change, S and L refer to SiO2 with small (120 to 140) and large ( 70 to 80)
mesh size. Dx is the dispersion obtained from x-ray line broadening, and
Dh is the value obtained from hydrogen chemisorption.
Two fundamental models of operation are used in EM: transmission
electron microscopy ( TEM) and scanning electron microscopy ( SEM). A
third, hybrid mode, scanning transmission electron microscopy (STEM), is
also used. Figure 3 depicts the schematics of the various modes of opera-
tion together with the fundamental components involved in each case.
In transmission electron microscopy ( TEM) the electron beam, generated
by a heated filament (electron gun), passes through two electrodes and a
condenser lens. Parallel rays thus created impinge on the specimen, where
they are scattered as a result of the spatially variable refractive index.
Scattered rays from the same point in the specimen are brought to the
same point in the image formed by the objective lens. The overall effect
is equivalent to transmisssion of primary electrons through the sample.
Electrons are also diffracted (as in the case of x rays), thus producing
rays which are slightly off the angle of rays formed by transmitted elec-
trons. Thus, by selecting the proper aperture, an image of the trans-
mitted (bright field) or diffracted electrons (dark field) is obtained
after the electrons pass through intermediate and projector lenses and
impinge on a fluorescent screen or a photographic plate. A typical con-
ventional electron microscope operates at 100 kV, a vacuum of 10-5 to
10-6 torr, and is capable of 4. 5-A point-to-point resolution and mangifica-
tion of 300,000. Dedicated high-resolution electron microscopes are capable
of resolution of 2. 5 A with magnifications of 800, 000 to 1,000,000.
An important aspect of TEM is that a three-dimensional sample yields a
two-dimensional TEM image which might be difficult to interpret. Further-
more, the contrast between the support and the active component might
164 Delgass and Wolf
ELECTRON ELECTRON SOURCE
SOURCE
~ "'"'""'"' ''12l
SPECIMEN
~ OBJECTIVE
L:::".:,f LENS
AMPLIFIER
OPTICAL
MICROSCOPE
APERTURE ----- l>
SCANNING
CO I L S ~ ~
~ INTERMEDIATE ~ ~ FINAL LENS
~ LENS lz::J
ELECTRON
DETECTOR
SPECIMEN
---'Vvv---i~:~TOR
ENERGY DISPERSIVE
SPECTROMETER
( 0) ( bl ( C)
TEM SEM EPMA
FIGURE 3 Schematics of (a) transmission electron microscope (TEM): (b)
scanning electron microscope (SEM), and (c) electron probe microanalyzer
(EPMA).
not be sufficient to distinguish the metal crystallites. In this case, dark-
field images are useful since electrons diffract preferentially from the
crystallites, thus producing brighter spots from them compared to the
weak diffraction from the nearly amorphous support.
Supported Catalysts
Figure 4 shows bright- and dark-field images of a supported 5% Pt /SiO2
catalyst. The sample is prepared by mortar grinding the catalyst particles
( 200 mesh) to ultrafine powder, which is then dispersed in a liquid (water,
alcohol). A droplet of the solution is then deposited on an EM grid. The
liquid evaporates, leaving on the grid microscopic particles which are thin
enough for electron transmission. The micro graphs shown in Fig. 4a were
obtained with a 100 JEOL STEM operating at a magnification of 400,000.
In this case, the contrast is relatively low because of the presence of the
support. Counting and sizing the crystallites in both the bright- and
dark-field images is often difficult, and many micrographs are required to
obtain a statistically meaningful size distribution. A major limitation here
can be the presence of small crystallites that cannot be seen under the
conditions used. Furthermore, in some cases the diffraction pattern of
the metal cannot be distinguished from that of the support (Schmidt et al.,
Catalytic Surfaces 165
(a)
FIGURE 4 TEM photographs, all at magnification 400,000; 1 cm = 250 A:
(a) 5% Pt/Si02; (b) model sample, Pt sputtered on SiO2 film; and (c)
model sample, Pt impregnated on SiO2 film with chloroplatinic acid. All
catalysts were reduced in H2 at 300°C.
166 Delgass and Wolf
(b)
FIGURE 4 (Continued)
Catalytic Surfaces 167
(c)
FIGURE 4 (Continued)
1982). It is always recommended that one check the electron diffraction
pattern to determine the relative role of the support and active metal in
dark-field studies. Charging of the sample by the electron beam is a com-
mon problem with catalysts in which the support is an insulator. Charging
can be reduced by coating the sample with a carbon or gold film. Higher
metal loadings ( 5 to 10%) and higher beam voltages result in better con-
trasts; however, sample damage can be caused by the electron beam. Sam-
ple preparation procedures are given by Baker et al. (1979) Glass! et al.
(1980) report artifacts introduced due to sample preparation. The particle
size distribution is obtained by the method described by Underwood (1970)
or by means of an automatic sizing and counting device.
Model Samples
Schmidt and coworkers (Schmidt et al., 1982), among others, have dis-
cussed the advantages of using model samples in which the catalyst is
168 Delgass and Wolf
deposited on a planar nonporous substrate of amorphous silica. A thin
flake of silica is prepared by vacuum deposition of silica followed by
vacuum deposition of the metals (e.g. , Ni, Rh) onto the substrate. This
technique avoids particle overlap and produces high contrast between the
metal particles and the support. Figure 4b shows TEM results obtained
by sputtering Pt onto a model silicon grid and Fig. 4c shows similar re-
sults obtained by impregnating the grid with H2PtCL6 and then reducing
it in Hz at 400°C. The disadvantage of the technique is that the total
active area is low for reaction studies. Furthermore, the morphology of
the particles deposited on the model, nonporous support, may be different
than when the metal is deposited on porous silica.
Although TEM has been used extensively to study catalysts, in conven-
tional operation it views samples in a vacuum environment, pre or post re-
action. A technique that allows one to use TEM in a reactive environment
is controlled atmosphere transmission electron microscopy (CATEM). De-
tails of the CATEM technique have been documented in a review article
by R. T. K. Baker ( 1979), who has introduced the technique to catalytic
researchers. In CATEM, the specimen is mounted in a gas reaction cell
which is fixed to the translational manipulator of the sample. With this
arrangement it is possible to operate at gas pressures of the order of
several torr within the cell and at temperatures up to 1300°C. This con-
trol of sample environment requires some sacrifice of resolution. Changes
occurring during reaction are recorded by a TV video system. Baker's
excellent paper (1979) illustrates the use of CATEM in studying gas-solid
systems where the reaction produces carbon deposits or during gasification
of the deposits, which induces motion of small metal particles and changes
in the structure of the specimen. Extraordinary movies have been pro-
duced showing the growth of carbon filaments as well as the movements of
metal particles during carbon gasification. Such information has revealed
the complexity of the dynamics of gas- solid interactions.
COMPOSITION AND STRUCTURE OF
SURFACES AND SOLIDS
Since the 1960s, several techniques have been developed to characterize
surfaces. A great deal of effort has been spent on the measurement of
basic properties of model surfaces (such as single crystals) to establish
the theory and validity of each surface analysis method. These studies
have led, in some cases, to interpretation of catalytic activity in terms of
fundamental properties and have demonstrated the potential of these tech-
niques in studies of technological interest. The discussion that follows is
presented in the context of the application of these techniques in the
interpretation of surface processes related to catalysis. Theoretical as-
pects are treated only on the most basic terms needed for interpretation of
data. The reader is referred to the specialized literature for further de-
tail concerning theory .and for detailed discussion of equipment and opera-
tion.
Most of the techniques now commercially available are based on the ex-
citation of the sample by an incoming beam of particles or electromagnetic
energy. Following such excitation are de-excitation processes, which result
in the emission of electrons or photons of discrete energy which can then
be measured by a suitable energy analyzer. Figure 5 shows the schematics
Catalytic Surfaces 169
Visible or
UV Source
'I.,.. ~~~~~~~~
"'--.... ½½½27/21/4 ( oy
- - - - - - - - - - - - - FL
e- Photo Electron
7ZlZ?27ZZZZZ( b )
--•-•---•----•--L3
---~---L2
X-ray Source _ ____,.....,>---- LI
~ ------ e- X- r a y
--------- ~ . Ph Ot Oe IeCt r On ( X p S )
~-~ K
(a)
EXCITED IONIZED ATOM
Photon De-excitation/ ~ Electron De-excitation
K oc. 1 Radiation
7ZTflZ(( a) ½½½½(a)
/21/J½(b) ½Z½½ ( b y - KL2,L3
/ Transition
•••• • • • o L3
--------L2
I
I
•
I
--~1----- K
Ko< 1 X-ray Flourescence KLL Auger Emission
(b)
FIGURE 5 Schematics of (a) photon excitation and de-excitation by photo-
electron emission, and (b) de-excitation processes leading to x-ray and
Auger electron emission
of the two excitation and de-excitation processes most commonly used for
surface analysis, together with the name and acronym of the analysis tech-
nique (XPS-AES). While several of the techniques discussed in this section
yield similar information, the type of instrumentation and data interpreta-
tion varies. For the sake of clarity, each technique is discussed separately;
however, there are many aspects that are common or complementary among
them. One such common factor is the need for using ultrahigh vacuum
(UHV). At 10-6 torr, about 1015 molecules of gas strike 1 cm2 of the sur-
face per second. At 10- 9 torr, monolayer coverage occurs in about 15 min
if every. molecule that hits sticks; thus a clean surface can be attained
only at -UHV conditions.
The first technique described below is XPS (also known as ESCA,
electron spectroscopy for chemical analysis) which corresponds to the
170 Delgass and Wolf
case where the excitation source is x-ray photons, and the result is elec-
tron emission .
X-ray Photoelectron Spectroscopy
X-ray photoelectron spectroscopy (XPS) was developed in the early 1960s
by Kai Siegbahn (Siegbahn et al., 1967) to characterize solids, liquids, and
gases. Because the technique probes the top atomic layers of a solid, it
has become one of the main tools for surface analysis. Several books,
monographs (Siegbahn et al., 1967; Carlson, 1967; Ertl and Kuppers, 1979;
Briggs, 1977; Delgass et al., 1979), and review articles (Palmberg, 1975;
Hercules and Carver, 197 4; Delgass et al. , 1970; Hercules and Hercules,
1974) have been published describing theory and applications, with a few
articles focusing on applied heterogeneous catalysts (Hercules and Carver,
1974; Delgass et al., 1970; Bhasin, 1981).
Photoelectron Emission (PE) or Photoionization
While the detailed physics of electron emission by photoexcitation, is quite
complex, the basic principle is straightforward and has been known for
decades. Emission of electrons occurs when matter is exposed to or ex-
cited by electromagnetic radiation or photons. If the photons have energies
in the ultraviolet range, they cause ·ejection of the less tightly bound
valence electrons that emerge at discrete energies [ultraviolet photoelectron
spectroscopy (UPS)] . If the incoming photons are x rays of. suitable en-
ergies ( 1 to 3 keV or soft x rays), ejection of inner or core electrons
occurs. If the energy of the incoming photons is known, analysis of the
energy of the emitted electrons permits calculation of core electron binding
energies. Since the electron binding energies are quantized, the emitted
electrons have discrete energies that reflect the electronic structure of the
parent atom and thus identify the irradiated element.
Energy Relationships
The basic energy relationship occurring during photoionization was first
proposed by Einstein. It states that the energy of the incoming photons,
hv, equals the kinetic energy of the ejected electron (Ek) plus its binding
energy, Eb (or photoionization energy):
(13)
In practice, relation ( 13) must be modified to account for additional
potentials existing in the spectrometer. Figure 6 shows the energies of
electron binding measurements in solids. Once the electron is free from
its core level (Eb) and reaches the Fermi level, it must spend some energy
to free itself from the solid matrix (work function ¢s). The remainder
energy appears as a kinetic energy Ek which is slightly changed to Ek by
the contact potential between the sample and the spectrometer. Since the
Fermi level of the spectrometer ( ¢sp) is equal to that of the sample be-
cause they are in electrical contact, one can write
hv = E + ¢ + E' (14)
b sp k
Catalytic Surfaces 171
hv
EXCITING
PHOTONS
(a)
~-r CORE ELECTRON LEVEL
;ETECTOR~ Al 2p (a 3 , 4 )
;-(,-RAY L!B
Si 2p(a 1, 2 )
Si2p(a 3 ,4 )
Al 2p(a 1 2 )
~ (M;g Ka) • Na 2S (al,2)
l
e- //
CQ
I
__,JI SAMPLE
U
Al2p(a 3 , 4 )
RETARDING J '--K-IN_E_T_I_C_E_N_E_R_G_Y__
LENS . ♦
(b)
FIGURE 6 (a) Energetics of electron binding in solids. hv, excitation
photon energy; Eb, electron binding energy; ¢s, sample work function;
Ek, kinetic energy as ejected from the sample; Ek, kinetic energy as
measured by the spectrometer; FL, Fermi level; CB and VB, conduction and
valence bands. (b) Schematic of basic components of an x-ray photo-
electron spectrometer with data for a Y zeolite. (From Delgass et al.,
1979.)
In most applications, relative binding energies or changes in their values
are the relevant information. For each measurement, it is only necessary
that ¢sp remain constant; conversely, the instrument can be calibrated
using as a reference an element of known binding energy (Au or C, for
example).
When the sample is irradiated, electrons emitted from various levels,
and therefore possessing various kinetic energies, are emitted. A photo-
electron spectrum consists of the number of photoelectrons emitted at a
given energy level, N(E), versus their kinetic or binding energy (see Fig.
6b). From the spectral lines or peaks, which are designated in accord
with the energy level from which electrons are ejected, Eb is calculated
using Eq. ( 14) and the values compared with theoretical or experimental
values (Wagner et al. , 1978; Fadley et al. , 1968). Thus XPS can be
used for chemical identification of elements, but more significantly it can
be used for chemical analysis of surfaces because of its surface sensitivity.
Although, in principle, a single spectral line would be observed when a
172 Delgass and Wolf
core electron is ejected, often one finds additional lines of lower intensity
known as satellites. One type of satellite is the "shake-up" line. This
occurs when the energy of the x-ray photon causes both photoemission and
excitation of a valence electron to a low-lying bound state. A second com-
mon satellite line is a discrete energy loss line caused, for example, when
the photoelectron excites a plasmon oscillation in the electrons in the
sample.
Surface Sensitivity
Although x rays can penetrate solids far beyond the surface, the mean
free path of electrons with energies between 10 and 1000 eV is of the
order of 10 to 30 A. Consequently, only electrons of atoms located near
the surface obey the energy conversion equation [Eq. (14)] and are anal-
yzed by the spectrometer. The relation between mean free path (or
escape depth) of electrons as a function of energy is shown in Fig. 7. It
can be seen that the mean free path is affected by the substrate, and for
most elements the escape depth of photoelectrons comes from the top one
to three atomic layers near the surface. The ability to select electrons
ejected near the surface is what makes XPS a surface-sensitive technique.
Another important characteristic of XPS is its ability to produce an
adequate spectrum even though the absolute amount of material present is
of the order of 10- 6 to 10- 8 g. Fractions of monolayer as small as O. 01
can be detected in favorable cases.
Chemical Shifts
While the electron binding energies of particular elements are sufficiently
invariant to provide chemical identification of the element, small but measur-
able shifts in binding energies occur when the XPS spectra of various com-
pounds of the same element are measured (Siegbahn et al., 1967). The observed
100
~
~ Au
J:
I-
Au / ~
Q.
Lu
Au \ .
0 '... -Mo
Ag •-..__w
I
Lu
Q. Ag
ct
u
V)
10
Lu
z Ag
0
Cl::
I-
u
Lu Fe Ni
.....I
Lu Ag
I
I 10 100 1000 10,000
ELECTRON ENERGY (eV)
FIGURE 7 Mean free path or escape depth of electrons as obtained from
Auger and photoelectron spectroscopy data. (From Delgass et al., 1979.)
Catalytic Surfaces 173
shifts in Eb, or chemical shifts, can be explained in terms of changes in electro-
static forces which participate in electron binding (Siegbahn et al. , 1967;
Fadley et al., 1968). A core electron is subjected to attractive nuclear
forces which are proportional to the atomic number and are also affected
by the presence of the outer valence electrons. If an electron is removed
from the outer shell, the core electrons feel an increased attractive force
from the nucleus and therefore Eb increases. Conversely, a gain of an
outer electron has the opposite effect.
Although various theories have been proposed to obtain a priori infor-
mation on chemical shifts, not all the contributions to shifts on solid sam-
ples can be evaluated accurately. However, sufficient data have now been
compiled to make use of chemical shifts as an indicator of the oxidation
state of many elements (Wagner et al., 1978).
Instrumentation
The majority of the x-ray photoelectron spectrometers consist of the follow-
ing five basic components: (a) source, (b) sample mount, (c) electron
energy analyzer, (d) detector, and (e) data acquisition system. The
source is an x-ray tube of conventional design consisting of a heated
cathode or electron gun from which electrons are accelerated to a cooled
anode or target. Al and Mg with Ka lines located at 1486. 6 and 1253. 6 eV
are the most commonly used anodes. The sample region must be maintained
at pressures lower than 10- 9 torr to avoid contamination of the sample.
This restriction is more severe than the 10- 5 torr maximum pressure in the
spectrometer required to minimize electron energy loss on collision with
gaseous molecules.
Improvements in electron energy analyzers led to the development of
XPS. Although various types of analyzers have been used, the most com-
mon types in .use today are electrostatic analyzers (also known as S-spec-
trometers or monochromators). They consist of two concentric bodies
(spheres, cylinders) onto which a voltage is superimposed. Electrons en-
tering the space between the bodies follow trajectories that depend on
electron energy. Thus for a given voltage only those electrons which have
a specific kinetic energy will reach the detector. Figure 8 shows the
schematics of an XPS spectrometer with a cylindrical mirror analyzer ( CMA).
The CMA consists of two concentric cylinders with a slit permitting elec-
trons with energies proportional to the applied voltage to reach the de-
tector. Generally, the analyzer is set at 100 eV and the photoelectrons
are retarded by a negative potential applied to a lens system in front of
the energy analyzer. The complete spectrum is produced by sweeping
the retarding voltage. A data acquisition system is used to collect electron
counts at the detector as a function of electron kinetic energy. Accumula-
tion of counts during repetitive scanning improves the signal-to-noise ratio.
The spectral lines are often superimposed on a raising background which
occurs due to secondary and inelastically scattered electrons. Powdered
samples can be spread uniformly into a self-adhesive material which is
attached to the mount or pressed into self-supporting wafers. Charging of
the sample is not as severe as in the case of excitation by electron impact
and is usually compensated by flooding the sample region with low-energy
electrons. For this reason, XPS is the preferred surface analysis tech-
nique for supported catalysts.
174 Delgass and Wolf
COMPUTER
ANALYZER
SYSTEM
CONTROL
PULSE
COUNTING
DETECTION
7
X-RAY MAGNETIC
SOURCE SHIELD
\
FIRST ANGULAR RESOLVED \_SECOND
APERTURE APERTURE APERTURE
FIGURE 8 Schematic representation of a combined ESCA-Auger-SAM sys-
tem using a double-pass cylindrical mirror analyzer (PHI model 550).
(From Wagner et al., 1978.)
Applications
Applications of XPS are numerous, and many articles have been published
in various areas of materials science, surface science, and catalysis. The
XPS chapter by Delgass et al (1979) presents and discusses several exam-
ples of XPS applications. Rather than enumerating the many examples
published in the literature, the major areas of application related to cataly-
tic activity are discussed below in terms of qualitative and quantitative
analysis
Qualitative Analysis
A straightforward application is a survey of elements existing on a catalyst.
This is particularly important in connection with catalyst poisoning by
impurities contained in the feed, for example, sulfur compounds or metals
(Bhasin, 1981).
Chemical shifts provide an important clue about the oxidation state of
the active component of a catalyst and its modification by pretreatment,
reaction environment, and support. Several studies are reported by Del-
gass et al. (1979) in which chemical shifts have been used to determine
the oxidation state of W supported on SiO2 and Al2O3, Cr supported on
SiO 2, and Co-Mo/Al2O 3 hydrodesulfurizatio n catalysts. Other studies on
supported metals include Pt/Al2O3, Pt Au/C, NiO, FeV2O3, CuO/Al2O3,
and Rh/C, among many other examples. The spectra of a 2% Pd sup-
ported on a ZSM-5 zeolite illustrating the use of chemical shifts arising
from different oxidation states of Pd are shown in Fig. 9.
Quantitative Analysis
The areas under the XPS peaks carry quantitative information; however,
accurate interpretation requires a structural model of the surface layer.
Catalytic Surfaces 175
335.4
337.2 ,,
,".
~
I I
'l
f I
>- I
t- I
(f) I
z I
w I
1---
z I
I
\ I
\.
356 350 344 338 332 326
BE.(eV)
FIGURE 9 XPS spectra of Pd 3d transition of a 2% Pd/Na-ZSM-5
catalyst. Dashed line: oxidized; solid line: freshly reduced. (From
Saha and Wolf, 1984.)
For a homogeneous solid with a flat surface, the following relation has
been derived (Carlson, 1975):
I = Kon>-.F (15)
where K is a·spectrometer constant, a the photoelectron cross section for
a given shell, n the concentration of atoms undergoing photoelectron ejec-
tion, F the x-ray flux, and >-. the electron mean free path for inelastic col-
lision. Other models considering angular energy dependence have also
been proposed (Fraser et al., 1973). In the case of porous materials
such as supported metal catalysts, the model leading to the integrated in-
tensity should consider metal crystallite size distribution, distribution of
the metal within the pore structure, and the effect of surface roughness
on an angle dependence. Some si!Ilplified models for quantitative analysis
of supported catalyst have been proposed (Angevine et al., 1977).
Many of the various factors involved in the expression of the integrated
intensity cancel out when the ratios of intensities of two key components
are compared. For example, for a completely uniformly and monatomic dis-
persed material, the ratio I tal/I t derived from the integrated
me suppor
areas corrected for cross section should be proportional to the ratio of the
number of metal atoms per unit area of support (Fraser et al., 1973). If
the intensity ratio is higher than expected from the metal surface density,
it indicates migration of the metal to the external surface, and if it is
lower, it suggests particle growth or preferential deposition in small pores
not easily seen from the exterior of the particle. Another case wherein
relative comparison can give quantitative information is in analysis of metal-
lic or polymetallic catalysts, where the integrated intensity ratios, cor-
rected for photoelectron cross section, can be compared with the atomic
176 Delgass and Wolf
ratio of the metals as loaded into the catalysts. Deviation from a 1: 1 cor-
respondence would suggest surface enrichment of one metal in preference
to the other (Liao and Wolf, 1982).
In a few cases it has been possible to correlate the catalytic activity
with the intensity of a particular XPS signal. Brinen and Melera ( 1972)
correlated the activity of a Rh/C catalyst with the ratio of Rh in oxidized
to metal form. Several studies of adsorbate metal interaction in clean metal
surfaces have been published in connection with this application.
In closing this brief introduction of the utilization of XPS to study
catalysis, the main applications are summarized. XPS is a useful tool in
qualitative analysis of surfaces to identify contaminants and promoters,
and to determine the oxidation state of metals and examine metal-support
interactions in supported catalysts. Accurate absolute quantitative analysis
requires a model of the surface layer, a difficult task with supported
catalysts. However, relative corrected integrated intensity ratios are a
useful clue to understanding surface enrichment and surface composition in
polymetallic catalysts.
Nearly all catalyst applications require careful handling of the sample,
including in situ pretreatment in a preparation chamber attached to the
spectrometer. A comparison of XPS with other surface analysis techniques
(Powell, 1982) concludes that XPS analysis causes the least damage to the
sample during analysis and is the technique for which the most extensive
procedures for qualitative and quantitative analysis have been reported.
Auger Electron Spectroscopy
Another tool now routinely used for surface analysis is Auger electron
spectroscopy (AES). While the application of XPS to characterize catalysts
has now become well established, AES has been a useful tool in applications
involving flat surfaces such as single crystals. For this reason, less
space will be devoted to AES than to XPS. However, since most of these
techniques are in constant development, the potential applications of AES
to catalysis are still quite open. As in the case of XPS, the principles of
AES are briefly described, but emphasis is given to the possible applica-
tions of AES to heterogeneous catalysis. The reader is referred to the
various review articles and books (Palmberg, 1975; Hercules, 1978; Chang,
197 4; Davis et al. , 1976; McGuire, 1979; Bhasin, 1976) on the subject for
a more detailed theoretical discussion.
Auger Effect
Auger electron spectroscopy (AES) is named after its discoverer, Pierre
Auger, who in 1925 discovered in a Wilson chamber that a two-electron emis-
sion occurred when argon atoms were excited by x rays. One of the elec-
trons was a photoelectron ejected as described in Fig. 5a in the case of
photoelectron emission. The second electron, known as the Auger electron,
originates from another deexcitation process, which competes with photo-
electron emission. When a primary excitation process, such as x ray or
electron bombardment, causes the creation of a vacancy in an inner electron
shell, for example, the K shell, deexcitation of the ionized atom can occur
via the dropping of an electron from an outer level (i.e., L1) to the
vacated inner level. The excess energy is equilibrated by ejection of the
second electron from an upper energy level (i.e. , L 2) ; this Auger
Catalytic Surfaces 177
transition is then known as KL1L 2 . The kinetic energy of the ejected
Auger electron is approximately equal to EK - EL 1 - EL 2 and is character-
istic of the irradiated element. Moreover, the energy of the Auger transi-
tions is independent of the energy of the incident beam. The number of
Auger transitions possessed by an atom increases with the atomic number
of the element. An atom generally possesses one or two strong Auger
transitions.
Whereas Auger electrons can be generated by using both x rays and
electron beams, the latter mode of operation has become the most common
type used in AES because the capability of electron beams to be focused
in a very small surface area ( 1.0 to 1.00 µm in diameter) provides better
spatial resolution thar. do x rays. X-ray excitation is only used in con-
junction with XPS analysis. An Auger spectrum consists of a plot of the
number of electrons emitted, N(E), as a function of energy. Auger emis-
sion occurs accompanied by secondary and scattered primary electrons;
consequently, Auger transitions are not very prominent in such N(E) ver-
sus E plots. To enhance the Auger signal and remove the background
caused by other electrons, the derivative dN(E) /dE is usually plotted as
a function of E. Figure 1.0 shows both integral and differential spectra for
Ag. The minimum of the differential signal is usually used to characterize
the energy of the Auger transitions. The Auger spectra of all the elements
(except Hz and He) have been obtained and compiled (Davis et al., 1976).
Surface Sensitivity
Similar arguments given for XPS photoelectron escape depth are also valid
for AES. The literature indicates that for Auger electrons with energies
between 50 and 2000 eV, the escape depth is of the order of 4 to 20 A
(Palmberg, 1975). For most elements with Auger transitions below 1000 eV,
the escape depth is only a few atomic layers. The greater surface sen-
sitivity sometimes cited for AES versus XPS results because many elements
have Auger lines at 100 eV kinetic energy, the minimum in Fig. 7.
dN(E)
dE
N(E)
or
dN(E)
dE
0 200 400 600 800 1000
ELECTRON ENERGY (eV)
FIGURE 10 Secondary electron energy distribution curves from a silver
sample: (A) N(E) versus E; (b) 1.0 x N(e) versus E; (c) dN(E)/dE
versus E. (From Bhasin, 1976.)
178 Delgass and Wolf
Chemical Shifts
As in the case of XPS, chemical shifts have also been observed in AES.
However, their interpretation is not well understood at present. Chemical
shifts of many light elements ( Z < 40) have been observed and have been
related to oxidation state. In general, Auger lines involving only core elec-
trons are easiest to interpret. In some cases the shape of the Auger peaks
is also affected by structural factors; for example, carbide and g-raphitic
carbon peaks deposited on stainless steel are strikingly different (Siegbahn
et al., 1967). Such lines are coupled to the valence level and thus carry de-
tailed bonding information. Complex Auger line shapes can also be used to
fingerprint the identity of adsorbed molecules (Grant and Hooker, 1976).
Scanning Auger
The ability to focus an electron beam to a very fine diameter ( ca. 5 ].fill)
which can be scanned across a surface as in scanning electron microscopy
is the basis for scanning Auger electron spectroscopy. Most AES instru-
ments are equipped with low-resolution SEM (2000x magnification) capabilities
to select an area for analysis. Furthermore, by locking the voltage of the
energy analyzer (which is of the same type as in XPS), the detector only
receives electrons coming from the selected element. This capability per-
mits one to obtain a map of the element as the electron beam scans a
selected area on the sample under analysis. This capability is referred to
as a scanning auger microprobe (SAM) and is particularly useful in micro-
electronics.
Depth Profiling
SAM systems can be equipped with an Ar ion gun that can be used to im-
pact (sputter) the surface with high-energy ions that remove atoms from
the top surface layer. If the electron beam is also directed to the same
area, it is possible to analyze the composition of the freshly exposed sub-
layer as a function of depth ( depth profiling) . This capability is important
for detection of selective deposition of impurities, formation of surface
layers, and, in general, to detect compositional changes with depth into
the material (subsurface analysis).
Instrumentation
The basic components of an Auger electron spectrometer are those described
for XPS except that an electron gun replaces the x-ray source with the
optional addition of the ion gun for sputtering or etching, and an additional
electron gun to obtain SEM images of the sample. Since the acquisition of
a spectrum requires energy analysis of electrons, the same type of energy
analyzer used in XPS (cylindrical mirror) can be used for AES. In fact,
some manufacturers offer systems that can do both AES and XPS as well
as other types of analysis (UPS, ISS, etc.).
As pointed out earlier, solid flat surfaces are ideal for AES analysis.
In the case of powders, they must first be pressed into the shape of a
wafer or a flat plate. Degassing and drying the sample is necessary to
retain the UHV (10-8 to 10-9 torr) vacuum required in the analysis cham-
ber. Unfortunately, most catalysts are supported on insulating oxides
(Al2O3, SiO 2) which result in severe surface charging. Although some
remedies for surface charging can be adopted, the problem is often so
severe as to limit the applicability of this technique with technical catalysts.
Catalytic Surfaces 179
Applications
In qualitative analysis, AES is used to survey possible contaminants and
poisons that might affect the catalyst activity. The poisoning of a copper
catalyst by lead, and of a Pd/y-Al2O3 cataiyst by iron, has been reported
by Bhasin ( 1976). AES is used routinely in single-crystal studies to
measure the cleanliness of such surfaces, in particular, to determine car-
bon and oxygen contamination, surface composition, and the presence of
adsorbed layers (Chang, 1974).
As in XPS, quantitative analysis of powders is complicated by surface
roughness and heterogeneity. Further complications arise from crystallite
size distribution and nonuniform distribution of the metals in the support.
Approximate analysis can be done in terms of relative intensities between
the sample and a known standard. The atomic concentration of an element
Ci in the sample is given approximately by
I.
1
C. = C. I-- ( 16)
1
1Std iStd
where Ii and Iistd are the peak-to-peak Auger currents of the sample and
standard, respectively, and Cistd the surface concentration of the standard.
Relation ( 16) assumes that escape depth from the sample and standard are
similar and that the standard is homogeneously distributed in the sample.
Auger sensitivity factors with respect to the sensitivity to oxygen have
been given in the literature (Palmberg, 1975). These factors must be used
when the concentrations of different elements are compared. Although many
papers describing the use of AES in single-crystal studies have been pub-
lished [about 300 are listed by Chang (1974)], papers in relation to applica-
tions of AES to heterogeneous catalysis are limited, presumably due to
charging problems. A comparison of the various spectroscopic techniques
for surface analysis and results compiled by the ASTM committee for sur-
face analysis, have recently been published (Powell et al., 1979; 1982).
In summary, AES renders information similar to XPS, and similar prob-
lems can be studied with this technique. AES has a major advantage in
lateral spatial resolution and sublayer analysis that is not yet available in
XPS. As a disadvantage, AES presents serious charging problems with
heterogeneous catalysts supported on insulating materials and chemical
shifts are not as easily interpreted in AES as in XPS.
Ion Scattering Spectroscopy
In ion scattering spectroscopy (ISS), measurement of the energy of pri-
mary ions scattered by the solid sample provides the data from which
sample composition is calculated. At medium and high energies (102 to
103 keV), ions penetrate deep into the solid. The elastic collision with
an atomic core is governed by the mass of that atom, while interactions be-
tween the ion and electrons in the sample cause a loss of ion energy which
is proportional to the distance traveled in the solid. At these energies,
the scattering cross section is governed by simple nuclear potentials and
the experiment is called Rutherford scattering. At energies from 0. 5 to
10 keV, scattering cross sections and neutralization probabilities are so
180 Delgass and Wolf
high that ions are scattered only by the first one or two atomic layers.
Thus low-energy ion scattering is a true surface technique. With proper
calibration, peaks in the scattered ion spectrum identify masses and
amounts of elements present in the surface. This is a relatively new tech-
nique to catalysis, but in combination with ion etching offers both quantita-
tive and structural analysis of complex surfaces.
Principles
The two important parameters in low-energy ISS (LEISS) are the energy
and intensity of the scattered ions. Calculation of the mass from the
energy of the peak is straightforward. Quantitative interpretation of in-
tensity is more difficult.
The energy of the scattered primary ion is governed by momentum and
kinetic energy conservation in the two-body collision between the primary
ion and a single atom in the solid sample. The energy E1 of the ion scat-
tered at angle eL is given by
2
2 )1121
+ ( : : - sin 2 eL ( 17)
where m2 is the target atom mass, E 0 the initial primary ion energy, and
m1 its mass (Buck, 1975). At eL = 90°, a common experimental value,
Eq. ( 17) reduces to
(18)
The simplicity of this analysis is possible, in part, because of the relative-
ly high energy of the collision. Multiple scattering effects do occur, but
theory and experiment show that the binary collision mechanism dominates
the scattering of the particles that remain ionized (Poate and Buck, 1976)
and, except for possible resolution problems, Eq. (17) or ( 18) provides
assignment of masses to the corresponding peaks. As is clear from these
equations, m1 can approach m2 to improve resolution.
To be quantitative about surface composition, one needs either a
theoretical description of the collision cross section and the ion neutraliza-
tion probability along the ion path or a method to calibrate these effects
empirically. The well-defined Rutherford scattering law, which describes
the higher-energy cross sections, is complicated in the 1-keV region by
the fact that the nuclear potentials are partially screened by the electrons.
A Thomas-Fermi potential is often used to account for this screening ef-
fect (Poate and Buck, 1976), but others are also used (Taglauer and
Reiland, 1976).
The ion neutralization process is equally important and difficult to
model. The extra time spent by a low-energy ion in scattering from sub-
surface levels appears to be sufficient to allow substantial neutralization,
preventing its detection. The charge transfer process depends on ion
energy and identity as well as on substrate material and target atom. At
Catalytic Surfaces 181
present there is not a theoretical method that predicts these effects re-
liably. Thus one must turn to experimental calibration methods.
If the relation between surface composition and ISS signal is linear for
a given primary ion and energy, calibration is straightforward. Linear re-
lationships have been found for alloys (Smith, 1971) and for sulfur and
oxygen on nickel (Taglauer and Heiland, 1974, 1975). Surface properties
such as work function can be expected to affect ion neutralization, how-
ever, and nonlinearities in calibration functions have been observed
(Niehus and Bauer, 1975). In practice, some of the most useful informa-
tion is obtained by observing ion ratios as a function of the number of
surface layers removed by ion etching. Changes in ion ratio are taken
to indicate changes in relative concentration (Taglauer and Heiland, 1975).
This approach assumes that any changes in cross section or neutralization
probability accompanying chemical changes from layer to layer cancel out
in the ion yield ratio.
Experiment
The essential components of the ISS instrument, shown in Fig. 11, are
the ion beam, the sample, and the energy analyzer, all enclosed in a UHV
scattering chamber. The 0. 5- to 5-keV He, Ne, or Ar beams used for
low-energy ISS are typically formed by electron impact on the gas at
5 x 10-6 to 10-3 torr (Buck, 1975). The ion gun is differentially pumped,
delivers a beam with a stable ion current of 10 to 200 nA, a spot size on
the order of 1 mm in diameter, and an energy spread of the order of 1 eV.
The beam may also be mass filtered. The scattering chamber is a typical
ultrahigh-vacuum bell jar with a base pressure of ,.;; 10-10 torr and operat-
ing pressure <10-8 torr. As with other particle spectroscopies, an at-
tached catalyst pretreatment chamber is especially useful. The sample is
mounted in the scattering chamber on a manipulator to facilitate other
analytical experiments in the same instrument and possible angular-de-
pendent studies. Insulator samples can accumulate a positive charge during
ION GUN
ELECmOSTATIC
ENERGY ANALYZER
DETECTOR
FIGURE 11 Schematic of an ion scattering spectrometer.
182 Delgass and Wolf
an experiment. This charge is removed by the electron flooding technique
familiar in XPS and SIMS. Ion etching of the surface can be done with
the primary beam itself or, preferably, with a second higher current beam.
In any case it is important to avoid edge effects when substantial etching
is done. Generally, one monitors only a small central portion of the etched
region.
Electrostatic ion energy analyzers are used in low-energy scattering.
Energy resolution L'l E /E on the order of 1% is typical. Thus Auger or XPS
electron monochrometers are candidates for this task, provided that collima-
tion can establish an unique scattering angle eL.
Applications
The power of this method is its ability to give quantitative or at least
semiquantitative analysis of the uppermost layer of a surface. Its surface
sensitivity surpasses both XPS and AES, and this makes the tool especially
well suited to studies of phenomena such as surface enrichment in alloys
and the structure of the upper layers of more complex surfaces. The
work of Brongersma et al. (1978b) nicely illustrates the use of low-energy
ISS for surface enrichment studies. They show strong surface enrichment
in Cu for both CuNi and CuPt and illustrate effects of temperature in an-
nealing and quenching surface compositions. Analysis of the data confirms
the efficacy of calibration by the pure compounds and shows the necessity
for truly clean surfaces since adsorbed layers can differentially shadow
metal atoms. More direct applications in catalysis have emphasized mixed
oxides and supported oxides. ISS analysis of the transition metal cation
content of spinel surfaces has been found by Shelef et al. ( 1975) to be in
good quantitative agreement with titration of the surface by NO adsorption.
Studies of supported CoMo (Delannay et al., 1980a,b) and NiMo (Knozinger
et al., 1981; Canosa Rodrigo et al., 1981; Abart et al., 1982; Jeziorowski
et al., 1983) oxides on alumina offer excellent examples of the ability of
ISS, coupled with ion etching, to examine surface structure in these hydro-
sulfurization catalyst precursors. For the NiMo system, Mo/ Al and Ni /Mo
intensity ratios as a function of etching time indicate essentially single-
layer coverage of Al2O 3 by Mo with Ni concentrated at the Mo-Al interface
after calcination at 870 K (Jeziorowski et al. , 1983). The ISS spectra
shown in Fig. 12 show a low Al intensity at the outset, indicating that
the Al2O 3 surface is covered, and a maximum in the Ni /Mo intensity ratio
with sputtering time, indicating the enhanced concentration of Ni below
the surface. The order of addition of Ni and Mo was also found to affect
the position of the Ni (Abart et al. , 1982). If Ni was impregnated on the
Al2O 3 first, then the Ni /Mo intensity increased with etching time, showing
Ni to be enhanced near the Mo/Al2O3 interface. If Ni was added after
Mo, its concentration was maximum at the outermost surface of the catalyst.
Applications to catalysis also include studies of Bi2MoO6 (Brongersma et al.,
1978a) and individual metals of Al2O3 (Wu and Hercules, 1979; Chin and
Hercules, 1982a,b; Zingg et al., 1980). The technique is relatively new,
but progress is sufficient to mark the method as worthy of continued
attention.
The features of this method that make it attractive for catalysis also
apply in surface science. Here ordered or even just flat surfaces allow
a more suitable use of the shadowing or blocking effects caused by the
relative positions of atoms on the surface. The relative intensities of 0
and C, for example, show CO to bond carbon down on Ni (Smith, 1967).
Catalytic Surfaces 183
0 Al N1 Mo
I I I I
1oss
1
240s1 1
345s
1s100s
0.5 1.0
E / E0
FIGURE 12 Ion scattering spectra of Ni3Mol2/Al2O3 as a function of increas-
ing bombardment time. (From Jeziorowski et al., 1983.)
Quantitative analysis of shadowing effects on intensity as a function of
azimuthal angle have also been used to determine the structure of ordered
adlayers (Reiland and Taglauer, 1972).
Secondary Ion Mass Spectrometry
Secondary ion mass spectrometry (SIMS) is a particle spectroscopy using
200 to 5000-eV Ar+ primary ions to bombard the sample surface and cause
ejection of secondary ions which are detected by mass spectrometry. Fig-
ure 13 is a schematic representation of the experiment. The pressure in
the spectrometer must be low enough to avoid significant ion /molecule col-
lisions. Normal operating pressures vary from 10-6 to 10- ll torr.
184 Delgass and Wolf
MASS~v
o/)
ClllAIHFOLE A
N
CETECToo
l A-:
[jENERGY FILTER
+ +
~cor,()ARY
AmBn- IONS
AB SAMPLE
FIGURE 13 Schematic of a secondary ion mass spectrometer.
Materials scientists and engineers have for some time used dynamic (high
primary ion flux) SIMS for depth profiling in metals and semiconductors
(McHugh, 1975; Werner, 1975). Introduction of the static mode (Benning-
hoven, 1973), in which low primary ion fluxes cause removal of only a frac-
tion of a monolayer during the experiment, has made SIMS a relatively re-
cent entrant as a surface science and catalytic tool. The unique feature
of this method is that the combinations of elements that appear in the clus-
ter ions recorded in the spectra are representative of local environments
on the surface. Thus SIMS stands with EXAFS as one of the· few methods
with the potential to provide proximity, local composition, and ultimately,
local structure information.
Principles
The primary ion brings a large amount of energy to a small surface region
and starts a collision cascade that affects hundreds of atoms and can cause
ejection of as many as 10 or more atoms from the surface. The energy
spectrum of the secondary ion peaks at about 2 eV, so only a small frac-
tion of the primary energy finds its way to the secondary ions that com-
prise the SIMS spectrum. There are, of course, some high-energy
secondary and primary ions, but these are filtered out and not detected.
A thermodynamic model of the SIMS process appears to be successful in
quantitative analysis of dynamic SIMS (Anderson and Hinthorne, 1973).
A complete, quantitative foundation for static SIMS has not yet emerged,
but many characteristics of the process are known. ·The secondary ion
yield has both kinematic components, which account for energy transfer
in the collision cascade, and electronic components, which govern the
probability that an ejected particle will be ionized or remain ionized until
detected.
The kinematic effects have been modeled by classical dynamic calcula-
tions which include all pairwise interactions in an integration of the equa-
tions of motion describing the collision of the primary ion with the solid
(Harrison et al., 1978; Winograd and Garrison, 1980). These calculations
show that for metals and metal/adsorbate systems, cluster ions form pri-
marily over the surface by recombination of atoms that were close neighbors
but not necessarily contiguous (Garrison et al., 1978). Strongly bonded
species such as CO or C6H6 are shown to be ejected intact, however
(Garrison et al., 1980; Garrison, 1980). The clearest demonstration of
Catalytic Surfaces 185
strong electronic influences on the SIMS spectrum is the observation that
positive monomer ion yields from a metal can change by more than three
orders of magnitude when oxygen is chemisorbed on the surface. The
presence of oxygen raises the work function, favoring positive charge emis-
sion and retarding electrons. The importance of initial ion charge (Day
et al., 1980) and electron exchange in the near-surface region (Lin and
Garrison, 1982) has also been demonstrated.
Perhaps the most important issue concerning SIMS is the degree to
which structural information is prese,rved in the spectrum. Extensive work
on molecular solids shows that when intramolecular bonding is stronger
than bonding between molecules, emission of intact molecules is the rule
rather than the exception (Day et al., 1980). Spectra of materials such
as quaternary amines show intact emission and some gas-phase ion frag-
mentation but little evidence for molecular damage during emission (Day
et al. , 1979). Highly ionic solids can give large ions (Barlak et al.,
1982), while recombination over the surface is the dominant cluster ion
mechanism for metals (Garrison et al., 1978). The utility of the SIMS
method for identification of molecular species and element proximity on sur-
face will continue to increase as the reliability of structural interpretation
advances. Significant advances in understanding and control of the ioniza-
tion process will be needed before the method can be truly quantitative.
Experiment
A SIMS spectrometer consists of an ion gun, sample, secondary ion energy
filter, mass analyzer, and detector, all of which are enclosed in an ultra-
high-vacuum chamber and controlled by a digital data acquisition system.
The ion gun is differentially pumped and can deliver ions at energies from
a few hundred e V to about 5000 e V at currents ranging from 10-10 to 10- 5
A. The bea.m diameter at the sample is of the order of 1 mm. In some
cases the beam is mass filtered and may be rastered over the surface.
The sample is mounted on a manipulator. It is not uncommon to have
other analytical devices, (e.g., AES, XPS) in the chamber and the sample
is moved from one analysis position to another on the manipulator. Ability
to heat and cool the sample in the analysis position and to dose adsorbing
gases on it is highly desirable. For catalyst studies, a pretreatment cham-
ber designed for clean transfer to and from the main chamber is a neces-
sity (e.g. , Ott et al. , 197 9) . Catalysts can then be pretreated or reacted
just prior to analysis. Insulating samples such as supported catalysts
often charge up during an experiment. Such charging seriously degrades
the spectrum and must be avoided. Electron-beam charge compensation is
often an acceptable solution (Witmaack, 1979; Reuter et al., 1980). In
some cases charging can also be avoided by proper sample preparation.
Burnishing a very thin sample layer onto a metal foil, mixing the sample or
with a conductor such as metal powder or graphite, scratching the surface
of a thick coating to expose some of the metal backing plate will have all
been successful (Day et al., 1980).
The prefilter conditions the ions for optimum mass analysis, usually by
a quadrupole filter. In fast ion bombardment ( FAB) , the primary ion
beam is neutralized so that the sample can ride at a high potential and a
high-resolution magnetic mass analyzer can be used (Barber et al., 1981).
Secondary ion mass spectra are often intense enough to be collected in an
analog mode, but capability for pulse counting is necessary for the study
186 Delgass and Wolf
of weak signals. The time needed to collect a spectrum depends on many
factors but is generally of order 1 min to 1 hr.
Added features especially useful in surface science applications are
energy selection of the secondary ions and capability of azimuthal and
polar angle resolution of the secondary ions (Winograd and Garrison, 1980).
In catalytic experiments, good charge compensation and convenience and
effectiveness of sample pretreatment are prime considerations.
Applications
Since this technique is still developing, SIMS applications are seldom routine.
The strengths of the method are (a) high sensitivity (ca. 10-6 monolayer
in the highly favorable case of alkalai metals) and restriction to the upper-
most surface layer, (b) ability to detect hydrogen, (c) sensitivity to iso-
topes, (d) detection of adsorbed molecular species, (e) indication of element
proximity on a multicomponent surface, and ( f) the possibility of structural
analysis. The main weaknesses of the method are the difficulty of quan-
titization and the characteristic of most particle spectroscopies that they
require low ambient pressure and see only the external surface of a porous
catalyst.
Applications of SIMS to catalysis have been relatively few, but FeRu+
ions have indicated the formation of FeRu alloys on SiO2 (Delgass et al.,
1982). For cobalt on alumina catalysts, Alco+ ions have shown the inti-
mate mixing and low coverage of Co on the Al2O 3 at low Co loadings ( Chin
and Hercules, 1982b). These ions were replaced by Coo2+, characteristic
of Co3O 4 , when the Al 2O3 surface was heavily loaded with Co. Molecular
species on catalyst surfaces have shown up as a variety of C2 to C5 car-
boxylates in the negative-ion spectrum of a commercial silver catalyst used
for ethylene oxidation (Benninghoven, 1973) and as the protonated molecu-
lar ion for isobutene and pyridine adsorbed on Si and Al oxides (Schu-
macher, 1983). Structural analysis of oxides, potentially a very interest-
ing area, has begun with evaluation of MgCuAl oxides (Barber et al.,
1976) and Fe aluminates (Buhl and Preisinger, 1975). The spectra have
been interpreted as indicating oxide structure. The potential of the method
for analysis of heterogenized homogeneous catalysts have been demon-
strated by the observation of structurally significant secondary ions from
transition metal complexes (Pierce et al., 1982).
Studies on well-defined metal surfaces show the utility of the method
for surface reaction studies. Drechsler et al. (1979) have used SIMS to
identify NH as the most abundant surface intermediate in NH3 decomposi-
tion on Fe( 110) . Other studies identify surface species present during
decomposition of formic acid on nickel (Mohri et al., 1978) and during
flash desorption of C2H4 from Ru(00l) (Lauderback and Delgass, 1984).
SIMS has also confirmed the ethylidyne structure for ethylene adsorbed
on Pt ( 111) (Creighton and White, 1983). Figure 14 shows direct SIMS
observation of associative and dissociative adsorption of CO on Ru( 001)
(Lauderback and Delgass, 1983). The molecular state is indicated by
Ruco+ and Ru 2co+ ions. Finally, the angular-dependent SIMS measure-
ments of Winograd and coworkers for adsorbate /metal crystal systems
show strong angle-dependent variations in SIMS intensity characteristic
of surface symmetry (Gibbs et al., 1982). These measurements, together
with the classical dynamic calculations, suggest new SIMS methods for de-
tailed surface structure determinations (Winograd, 1981).
Catalytic Surfaces 187
Ru
Ru2
(•10)
RuC13 Ru2C13 B
(•100)
(•100) 520 K
I
>-
I-
H
(J)
z
w RuC18O
I-
z <•10)
Ru2
H Ru RuC Ru2C18O
<•100)
r--,
(•10)
<•100) A
18
FIGURE 14 Positive-ion SIMS spectra of CO on Ru( 001) after (A) 9. 0L C 0
at 320 K, and (B) 480L 13 co at 520 K. (From Lauderback and Delgass,
1983.)
Extended X-ray Absorption Fine Structure
Active sites on a catalyst surface are defined by local structure. The
average surface composition of a catalyst, as determined by XPS, Auger
electron spectroscopy, or ISS, is information important in differentiation
of catalysts and in following changes occurring during activation and de-
activation. These tools can only imply local structure, however. A more
direct measure is needed. Extended x-ray absorption fine structure
(EXAFS), although not the complete answer to this local structure need,
offers information on atomic arrangements in catalysts. The method has
several important characteristics. It is element specific (i.e. , one can
individually examine x-ray absorption edges characteristic of the various
elements in a multicomponent catalyst) and does not require crystallinity.
Analysis of the extended fine structure of these edges gives the inter-
atomic distances, to ca. 0. 01 A for subsequent shells; the occupation of
the shells (coordination number), with a current accuracy not better than
±20%; and the mean-square displacement of the atom in question (Joyner,
1980). Although a relatively new and not yet fully developed technique,
EXAFS has shown low coordination numbers but relatively unchanged bond
distances for highly dispersed supported metals (Via et al., 1979), con-
firmed the Cu surface coating model for supported CuRu clusters (Sinfelt
et al., 1980), and shown sulfided Mo(AlzO3 and CoMoAI 2O 3) to contain
small domain MoS 2 structures (Clausen et al., 1981a). In the United
States, experiments are best done at the synchrotron radiation facilities
at Stanford, Cornell, or Brookhaven (Rowe, 1981).
188 Delgass and Wolf
Principles
EXAFS begins with the measurement of transmitted x-ray intensity as a
function of frequency. From these data one can calculate the x-ray ab-
sorption cross section as a function of energy. Each time the energy
reaches the threshold for photoemission of a core electron in the sample
material, the absorption cross section increases dramatically. Thus a
broad scan of energy, as shown in Fig. 15, produces an absorption spec-
trum with steps or "edges" characteristic of the binding energies of core
electrons in the sample. Except for accidental overlaps, each edge cor- ,
responds to a particular element. Close examination of a given edge shows
that for several hundred eV to the high-energy side of the steps, the ab-
sorption initially oscillates with energy. The oscillations beginning 50 to
100 eV above the edge, the extended fine structure, result from the con-
structive and destructive interference between the outgoing photoelectron
wave and its component backscattered from near neighbors. A pebble
dropped among reeds in a still pond produces a classical analog of this
effect.
Because of its origin, the detailed structure of the EXAFS spectrum
co_ntains information on the number and location of the neighbors surround-
ing a particular type of atom. Extraction of this information is complex
but tractable and still developing (Teo and Joy, 1981; Hayes and Boyce,
1982; Einstein, 1982; Sandstrom and Lytle, 1979). First the nonoscillatory
part of the absorption is removed by curve fitting and the EXAFS function
x(k) is formed from the equation
x(k) (19)
Ir L111
1-
z
w
oiii'
-1-
u.-
u.z
w::,
o>
CJa:
z<C
oa:
-I-
i- -
a.m
a;a:
0~
u,
m
<C
11 12 13 14
ENERGY, Kev
FIGURE 15 X-ray absorption spectrum at 100 K in the region of the L
absorption edges of Ir and Pt for a Ptlr-SiO2 catalyst containing 10 wt %
of each metal. (From Sinfelt et al., 1982.)
Catalytic Surfaces 189
where k = ( 2mE) ½/n, m is the mass of an electron h is Planck's constant
by 27T, E is the kinetic energy of the photoelectron, µ the natural log of
the ratio of the incident and transmitted x-ray photon flux, and µ 0 the
absorption coefficient of the free atom. Theories based on single scatter-
ing of the photoelectron by atoms in the coordination shells surrounding
the absorbing atom give
x(k) = 1:A.(k) sin[2kr. + o.(k)] ( 20)
j J J J
where the summation is over the coordination shells, rj is the radial dis-
tance from the absorbing atom to atoms in the j shell and cSj(k) the total
phase shift for emission and scattering, Aj(k) is an amplitude function
that depends on the number of atoms in a given shell; rj, a backscattering
amplitude; and the root-mean-square deviation about rj. With proper ac-
counting for phase shifts and the k = 0 point, Fourier transformation of a
kn weighting of x(k) (Stern et al., 1975), produces a radial structure
function that reflects the positions and number of atoms for each coordina-
tion shell as shown in Fig. 16. These are the data from which initial
structural assignments are made. One method of refinement of structural
parameters is to retransform a small region of radial space (say, the
nearest-neighbor-shell) back into k space. The process acts as a Fourier
filter which removes all but the nearest-neighbor contribution to the x(k)
function. Nonlinear least-squares techniques can then be used to fit the
structural parameters to this function (Via et al., 1981).
This discussion shows the origin of the EXAFS function and the radial
structure function. Further details of the theory and data reduction pro-
cedure are given in the references cited above, but a few additional com-
ments about the technique are included here. The EXAFs phenomenon re-
sults from backscattering of the excited photoelectron. X-ray absorption
is one of several ways to detect the occurrence of this effect. Alternative
ways of detecting x-ray absorption include x-ray fluorescence and Auger
electron measurements. Stimulation of core electron emission may also be
by electron bombardment (Hayes and Boyce, 1982; Einstein, 1982). The
low mean free path of electrons in solids offers opportunity for EXAFS
analysis accentuating surface structure (Landman and Adams, 1976; Einstein,
1982). Among the avenues opened by the use of electron stimulation is
the observation of extended electron energy loss fine structure (EXELFS)
in an electron microscope. This experiment gives both local structure and
high spatial resolution over a sample (Leapman et al. , 1981).
Experimental Methods
The alternative approaches mentioned above may eventually provide
routine access to EXAFS-type information. X-ray absorption measurements
can be made with conventional x-ray sources (Knapp et al., 1978; del
Cueto and Shevchik, 1977) but counting times are generally long compared
to those obtained with the intense beams available from synchroton radia-
tion (Hayes and Boyce, 1982). Since absorption must be scanned as a
function of energy, a broad continuous band of radiation is needed and
the sharp emission lines of the conventional x-ray source must be avoided.
A synchrotron or storage ring produces this radiation by the curved orbit
of a beam of high-energy electrons. This, or the Bremstrahlung
190 Delgass and Wolf
20 Ru/Si0 2 10
10 5
0 0
20 20
Ru-Cu/Si0 2
+
1
Ru-Cu/Si0 2 02
"',....,
0 10 10
X
::e
er
0
LL
VJ
2
<l: 0 0
er
f--
LL Cu/Si0 2
0
w
40 20 +
0
::,
02
f--
2
c.:,
<l:
::e 20 10
0 0
20
Cu-Ru/Si0 2
10
10
5
o-+-~~~-r-~--.-'---~
0 2 4 6 8
0
R, A
FIGURE 16 Effect of exposure of silica-supported ruthenium, ruthenium-
copper, and copper catalysts to oxygen ( 1% oxygen in helium) at room
temperature on the properties of the catalysts as shown by Fourier trans-
forms of EXAFS data at 100 K for the catalysts in the absence and
presence of oxygen. The transforms in the upper half of the figure are
for the K absorption edge of ruthenium. Those in the lower half are for
the Cu K edge. (From Sinfelt et al., 1980.)
Catalytic Surfaces 191
background radiation of an x-ray tube, is passed through a monochromator
and then through an incident flux detector, the sample, and a transmitted
flux detector. X-ray energy is scanned with the monochromator. The
raw data, transmitted intensity ratio as a function of energy, are then
treated as described in the preceding section. As with any work on
catalysts, proper cells for pretreating the sample and maintaining its en-
vironment during the measurement are essential (Via et al., 1979). Sam-
ples are often maintained at low temperatures ( 80 to 100 K) to decrease
the mean-square displacement of the atoms and improve resolution.
Applications
EXAFS structural studies of interest in catalysis have ranged from examina-
tion of supported metal carbonyl clusters (Besson et al., 1980) to analysis
of transition metal coordination in zeolites (Morrison et al., 1980). To
illustrate the method, we focus on applications to supported metals and
HDS catalysts.
In a series of papers, Sinfelt, Via, and Lytle report EXAFS of sup-
ported metals and bimetallic clusters. Studies of OS, Ir, and Pt on
silica and alumina (Via et al., 1979) utilized samples with 1 wt % metal
loadings and percent metal exposed ( dispersion) of 70 to 100% and com-
pared results to values for the pure metals. Nearest-neighbor distances
for the supported metals were within 0. 02 A of the pure metal values. Co-
ordination numbers for the nearest-neighbor shell were 7 to 10 for the
catalysts, lower than the bulk value of 12 because of the high dispersion
of the metals. The high surface-to-volume ratio of the metals also caused
high root-mean-square displacement values for the catalysts compared to
the bulk metals. In general, the close agreement between the interatomic
distances for the catalysts and the bulk metal speaks against structural
rearrangement of the small metal clusters (Burton, 197 4). Distortions in
structure have been observed, however. Moraweck et al. (1979) report
Pt nearest-neighbor distances shortened by 0.12 A for 12-A Pt particles
in Y zeolite. Interestingly, this value returned to the Pt-Pt bulk distance
after adsorption of hydrogen. Joyner ( 1980), in discussing the data of
Via et al. (1979), notes that the radial structure functions for Pt and Ir
on silica are consistent with three-dimensional face-centered-cubic particles,
but Ir and especially Pt on Al2O3 appear to have variations in peak in-
tensities beyond the first neighbor distance that are best described by
rafts with ( 100) orientation.
EXAFS of supported bimetallic clusters has included the RuCu (Sinfelt
et al. , 1980) Os Cu ( Sinfelt et al. , 1981), Ptlr ( Sin felt et al. , 1982), and
RhCu (Meitzner et al., 1983) systems. Here a new dimension is added to
the power of the technique because EXAFS of edges corresponding to each
element can be compared to analyze element proximity. For both RuCu
and OsCu, where the metals are essentially immiscible, copper coats the
group VIII metal. Ru(Os) in these catalysts has interactomic distances
corresponding primarily to Ru(Os) neighbors. The Cu, on the other hand,
is coordinated extensively to Ru(Os) as well as to Cu. Figure 16 shows
the effects of 02 on the transform of the weighted EXAFS function for both
Cu and Ru. Note that the data are taken at low temperature to improve
resolution. The intensities of lines below 2 A are suppressed in this data
because of the restricted region of k space used for the transform. Thus
the interpretation of the results is based mainly on the major metal-metal
192 Delgass and Wolf
nearest-neighbor peak. For Ru/SiO2, oxygen exposure at room tempera-
ture significantly reduces the number of Ru-Ru neighbors. This peak is
essentially unchanged after oxygen exposure of the RuCu/SiO2 catalysts.
Thus Cu shields Ru from oxidation as expected from the Cu coating model.
The copper data in the bottom four spectra of Fig. 16 show that Cu in
Cu/SiO2 is only partially oxidized by 02 (the core of the particle is pro-
tected by an oxide skin) but that Cu in the thin layer on Ru in CuRu/
Si02 is completely altered by oxygen exposure. The RhCu and Ptlr sys-
tems also show surface segregation phenomena but indicate more intermix-
ing of the elements, in accord with the greater miscibility of these systems.
For a 50-A metal particles in Ptlr /SiO 2, x-ray diffraction is consistent
with homogeneous alloy formation, but EXAFS shows the particles to consist
of Pt-rich and Ir-rich regions.
The structure of supported cobalt-molybdenum hydrodesulfurization
catalysts has been a topic of interest approached by many analytical tech-
niques. Recent EXAFS studies have contributed significant new informa-
tion. Clausen et al. ( 1981b) have used the Mo K edge to examine the local
structure around Mo in sulfided Mo/Al03 and CoMo/Al 2O3 catalysts. Com-
parison of results for well-crystallized MoS2 and the two catalysts shows
that Co has little effect on the Mo environment, the first coordination
shell of Mo is essentially the same in all three materials, and the second
coordination shell occurs at the same distance for the three samples but
its population is significantly lower for the catalysts. MoS2 shows struc-
ture at high interatomic distances, but the catalysts do not. The authors
interpret these data to indicate that Mo has the same sulfur coordination
in the catalysts as in MoS2 and that the catalytic species is not an oxysul-
fide. The low amplitude of the peaks corresponding to larger interatomic
distances is interpreted as indicating very small MoS2 crystallites (on the
order of 10 A). Studies of EXAFS following the Co K edge for the sul-
fided C0Mo/Al2O3 catalysts show that Co is surrounded by sulfur, but the
lack of any more distant peaks suggests a highly disordered environment
and that Co is located at the surface of the small MoS2 crystallites
(Clausen et al., 1981a). Finally, we note that EXAFS of Mo has also been
used to confirm an Mos 2 structure for a propene methathesis catalyst pre-
pared by reaction of Mo2(1r-C 3H 5) 4 with the OH groups of y-A1 2o 3 (Sato
et al., 1982).
At this time, catalytic materials most amenable to EXAFS study are the
ones in which the element of intest is in a single environment. The struc-
ture and composition of the first coordination sphere is the information
most readily attained. Developing experimental methods will undoubtedly
widen the scope of this technique, while improved analysis increases the
sophistication of interpretation and allows solution of increasingly complex
structural problems.
Mossbauer Spectroscopy
The Mossbauer effect is a nuclear gamma-ray resonance with such high
precision that spectral features reflect the chemical state of the correspond-
ing atom. The requirement of a relatively low- lying nuclear excited state
restricts the number of isotopes convenient and possible for use in cataly-
tic experiments to those shown in Table 3. Isotopic abundances indicate
the fraction of the naturally occurring element which is the Mossbauer
active isotope. When the technique applies, it is a powerful method for
Catalytic Surfaces 193
TABLE 3
Mossbauer Natural
Mossbauer Parent .\-ray energy abundanqe
isotope Parenta half-lifeb (keV) ( %)
57Fe 57co 270d 14.4 2.2
119Sn 119msn 245d 23.9 8.6
151Eu 151Sm 93y 21. 6 47. 8
121Sb 121msn 75y 37.2 57.2
125Te 1251 57d 35.5 7.0
1271 127mTe 105d 57.6 100
197Au 197Pt 20h 77.3 100
99Ru 99Rh 16d 90 12.7
193lr 1930 s 32h 73 62.7
195Pt 195Au 192d 98.8 33.8
83Kr 83Rb 83d 9.3 11. 6
181Ta 181w 140d 6.25 100
aOther parents are sometimes available.
bd, day; y, year; h, hour.
measuring oxidation state, local symmetry, magnetic ordering, and crystal-
lite size effects for specific Mossbauer elements bound to or within solid
matrices. For isotopes not requiring low temperature in order to observe
a spectrum, the technique can be applied in situ to catalysts operating in
the reaction environment. Applications have included use of 57 Co, 119sn,
151Eu, 121sb, 197Au, and 99Ru, but by far the largest number of studies
have been on 5 7Fe. The reader is referred to Dumesic and Tops<;fo ( 1976)
and Delgass et al. ( 1979) for detailed reviews of catalytic applications,
and to Wertheim (1964) and Greenwood and Gibb (1971) for reference
books on the Mossbauer effect itself.
Principles
The Mossbauer effect can be thought of as the nuclear equivalent of opti-
cal spectroscopy. The source of radiation is generally a metastable iso-
tope which decays to the nuclear excited state of the Mossbauer isotope.
Decay from this excited state to the ground state emits the Mossbauer
y ray. Resonant absorption can then occur if this y ray impinges on a
nucleus of the Mossbauer isotope in its ground state. Since the y-ray
energies are high ( 104 to 105 eV), the Mossbauer atoms must be bound
to a solid to prevent the recoil "kick" from destroying the resonance.
The area under a Mossbauer absorption line is a measure of the probability
of 11 recoil-free 11 emission and absorption, which in turn is related to the
coupling of the Mossbauer atom to the solid. This relation is complex
(Debrunner and Frauenfelder, 1971), but spectral areas can be used as
194 Delgass and Wolf
indicators of changes in bonding of a Mossbauer atom to a catalyst matrix
(Garten et al., 1970). Since the width of the Mossbauer line is of order
10- 9 eV, the precision of the measurement is so high that it reveals the
very small perturbations made on the nuclear energy levels by the atomic
electrons. These nuclear hyperfine interactions project chemical informa-
tion to the nucleus and hence to the Mossbauer spectrum.
Three spectral parameters are of particular interest. The isomer shift
(IS), measured in simple cases by the centroid of the spectrum (Kalvius,
1971), indicates relative electron density at the nucleus. Only s and
relativistic p electrons contribute directly to this term; other electrons
affect its value because of shielding. For example, isomer shift between
high spin Fe3+ and Fe2+ is about 0. 8 mm/s or about three line widths.
Fe3+ has a higher electron density at the nucleus than does Fe 2+ because
it has only five 3d electrons while Fe2+ has six to shield the ls, 2s, and
3s electrons. Covalent bonding can complicate interpretation of isomer
shifts of 57Fe because the 4s character of the bond increases the electron
density at the nucleus while non-s character decreases it. Nevertheless,
assignment of oxidation state for iron in oxides and other ionic compounds
is usually straightforward.
The second spectral parameter is quadrupole splitting (QS). This
effect removes the magnitude but not the sign degeneracy of the nuclear
spin states. In 57Fe, for example, the I = 3/2 excited state is split into
lz = ±3/2 and lz = ±1/2 states. The ground state, with I = 1/2, is un-
split. A quadrupole split spectrum for 57Fe in an isotropic powered sam-
ple has two lines of equal density (Greenwood and Gibb, 1971). The size
of the splitting depends on the nuclear quadrupole moment (a constant)
and the electric field gradient (EFG) at the nucleus. The EFG is a meas-
ure of the symmetry of the electronic environment of the atom. It is zero
for cubic and tetrahedral symmetry, but increases in magnitude for more
highly asymmetric arrangements. There are two important contributions
to the EFG. The lattice component arises from the surroundings of the
atom. The electronic component is a result of the valence election config-
uration of the atom itself. High-spin Fe3+ has an electron EFG of zero.
The extra d electron on Fe2+ causes a strong, temperature-dependent
quadrupole splitting when 57Fe is in a low-symmetry environment (Wertheim,
1964). The combined effects of isomer shift and quadrupole splitting are
shown in Fig. 17, which illustrates oxidation /reduction of Fe /Y- zeolite
(Garten et al., 1970). Spectrum 17a shows two ferrous states, with
spectra corresponding to a large outer and smaller inner doublet. Spec-
trum 17b corresponds to Fe3+ and spectrum 17d to ferrous ions whose
bonding to the zeolite has been weakened by hydration.
When the net electron spin of an atom is greater than zero and is
fixed in space longer than 10-7 s, the nucleus feels an effective magnetic
field and all the ( 21 + 1) nuclear sublevels are split. For 57Fe, the
selection rules allow six transitions with relative intensity 3: 2: 1: 1: 2: 3 for
an isotopic powder sample (Greenwood and Gibb, 1971). The six-line,
magnetic dipole splitting is characteristic of iron in any magnetically
ordered material. The splitting of the outer lines is proportional to the
effective magnetic field at the nucleus, a parameter often useful for
phase identification (Tops@e et al., 1973). Because the effective magnetic
field is measured at the atomic site, antiferro and ferri- as well as ferro-
magnetic states are detected. Different crystallographic sites in a given
Catalytic Surfaces 195
I.02'r------1,-.. ----.......- -.......- - . . . . - - - - - -
0.98
• "'
I •
• •
.
• • •
• (a)
0.96
,
.•,•
0.94
• •• .
............~.:. .•.,,.
• ••
-. •~.;
'
.,#_,,.
1.00
•• •
w
t- 0.98 >
•I \•
-.:
<(
a:
t-
z •
::i 0.96 • ( b)
0
u • •
0
w
••
•
N
...J
0.94
..~-
<(
:!!:
a:
0
z ,,,,,tt::;:
tfl; ~
,
I
0.98
•• ••
~ \
• •
• • • •
:-
( c)
0.96
• •
• • •
.,.'• ••
-
0.94
••
••
( d)
0.98
0.96, _ _ _L.__ __JL....--......L--...L.---'. ......,,.-+-,,--,!,-,,--...,,....,
-2.00 -1.00 0.00 1.00 2.00 3.00 4.00 5.00
VE LOCI TY (mm/sec)
FIGURE 17 Oxidation/reductio n of iron Y zeolite: (a) Fe 2+-Y dehydrated
at 673 K; (b) oxidized at 673 K; (c) reduced in Hz at 673 K; (d) exposed
to 15 torr HzO. All spectra at room temperature and on the same sample.
(From Garten et al., 1970.)
196 Delgass and Wolf
material can also have different effective magnetic fields. This is the case
for x-carbide (Fez. 5c) where three different sites produce 18 overlapping
lines. When the volume of a magnetically ordered crystallite becomes small
enough, thermal energy, kT, may be sufficient to flip the entire coupled
spin system fast enough to cancel out the magnetic field at the nucleus.
The Mossbauer effect shows this conversion from a magnetic to a super-
paramagnetic state when particle diameters are of the order 30 to 150 A ,
depending on the material and the temperature of the measurement (Morup
et al. , 1980).
Experiment
In the typical Mossbauer experiment, y rays pass from the source, through
the catalyst absorber wafer, to the detector. The source is mounted on
an electromechanical drive which imparts a back-and-forth motion with a
carefully programmed velocity along the y-ray path. The velocity causes
a Doppler shift in the energy of the y ray and is thus the means of scan-
ning energy. A periodic triangular velocity versus time function is common.
The Doppler shift corresponding to velocities ranging from -10 to + 10 mm/
s is sufficient to scan the full range of 57Fe shifts and splittings. The
detected count rate (number of counts in a fixed dwell time) is collected in
a multichannel analyzer or minicomputer whose repetitive sweep is synchro-
nized so that each channel corresponds to a given source velocity. By
convention, spectra are plotted as percent transmission versus velocity,
with positive velocity indicating motion of the source toward the absorber.
Sources must have a strong, narrow, single emission line. They con-
sist of the parent of the Mossbauer isotope well bonded in a cubic matrix
and are available commercially. 57Co diffused into a Rh foil is typical for
57Fe experiments. The detectors are usually proportional or scintillation
counters, but solid-state devices are also used. Full systems, including·
the drive, alignment track, detector, data accumulation, and output device,
and all associated electronics are commercially available. Absorber cells
for control of the catalyst environment are also available, but are often
custom made (Delgass et al., 1976; Shen et al., 1981; Clausen et al., 1979).
The cell is a vacuum-tight enclosure with facility to heat and cool the
catalyst wafer in a selected gas environment and Be windows for transmis-
sion of the y rays. Special dewars are necessary if both source and ab-
sorber must be cooled to liquid-helium temperature, as for 99Ru (Clausen
and Good, 1977).
In the transmission mode discussed above, the optimum sample size is
1Ql8 atoms of 57Fe atoms per cm2 for each line in the spectrum. A 5 / S-
in. -diameter wafer typically contains 0.1 to O. 8 g of catalyst. This value
gives signals in the transmission range 90 to 99%, big enough to see, but
not so big as to cause excessive broadening due to reabsorption (Margulies
and Ehrman, 1961). Iron loading below 1 wt % usually require use of iron
enriched in 57Fe, available from Oak Ridge National Laboratories. The
time required to obtain a spectrum depends on the strength of the source
and varies from 10 min to 2 4 h, with 4 to 6 h being common. Transient
effects are best followed by operating the spectrometer in the constant-
velocity mode and following the intensity of a given peak as a function of
time (Raupp and Delgass, 1979).
An alternative to the approach just described is the source mode.
Here the catalyst must be made with the radioactive parent isotope. It is
Catalytic Surfaces 197
then placed in a reaction/pretreatment cell and used as the y-ray source
while the drive moves a standard single-line absorber to scan energy and
generate the spectrum (Topsoe et al., 1981). Surface sensitivity of the
Mossbauer effect can also be enhanced by using the backscattering geom-
etry. Phillips et al. (1980) have used this method to follow the decomposi-
tion of Fe(CO)5 on oriented graphite foils.
Applications
The Mossbauer effect is a seasoned tool in catalysis research and accounts
for advances in the understanding of bulk solids (Topsoe et al., 1973),
supported metals and alloys (Garten, 1976), oxides (Lund and Dumesic,
1982), sulfides (Topsoe et al., 1981), carbides (Amelse et al., 1978;
Niemantsverdriet et al., 1980), catalyst genesis and activation (Boudart
et al., 1977), oxidation-reduction behavior (Garten et al., 1970), support
interactions (Tatarchuk and Dumesic, 1981), and the dynamics of some
catalytic processes (Raupp and Delgass, 1979).
In deciding what information the Mossbauer effect can provide about
a catalyst, one must bear in mind that the radiation penetrates the sample
completely and, generally, all Mossbauer atoms in the .sample contribute to
the spectrum. As the fraction exposed ( dispersion) of the phase contain-
ing the Mossbauer atom increases, the Mossbauer effect becomes more sen-
sitive to the surface. Surface sensitivity is probably best checked experi-
mentally by observing the spectral perturbations caused by adsorbed
gases.
A few specific examples of Mossbauer studies are outlined here. Gar-
ten (1976), Garten and Sinfelt (1980), and Vannice et al. (1978), have
shown that iron forms bimetallic clusters on SiO2 and Al2O3 with a variety
of metals, including Pd, Pt, Ir, and Ru. Lund and Dumesic (1982), have
observed a support interaction between Fe and SiO2 that involves SiO2
migration over the iron phase, and Tatarchuk and Dumesic ( 1981), have
reported one between Fe and Ti02 involving dissolution of Fe in the TiO2
phase. The role of Sn in a supported PtSn steam dehydrogenation catalyst
has been carefully detailed by Gray and Farha (1976). The recent 57co
source experiments of Topsoe et al. (1981) use the Mossbauer parameters
to identify a mixed CoMo sulfide as the active site for hydrodesulfurization.
It is of interest in this study that 57Fe-doped into CoMo catalysts does
not probe the correct cobalt chemistry (Clausen et al., 1978).
Figure 18 illustrates information obtained on supported iron-cobalt alloy
catalysts by Stanfield and Delgass ( 1981). Spectra A to C show nearly
complete reduction of iron since paramagnetic Fe2+ or Fe3+ states would
contribute extra spectral intensity in the region 0 to 2 mm. The change
in splitting of the outer lines shows that the effective magnetic field fol-
lows the expected composition variation and that iron-cobalt alloys with
the nominal composition have been formed successfully. Other spectra show
that improper pretreatment can completely prevent alloy formation. Spectra
D to F show that increasing Co concentration supresses carburization of
the catalyst during Fischer-Tropsch synthesis. The complex spectra of
the carbides lie between - 4 and +4 mm /s. Constant-velocity data taken
in situ at the velocity of the rightmost FeO line can give a dynamic trace
of the amount of carburization as a function of time.
198 Delgass and Wolf
100
96
92
88
100
98
96
94
100
Cl
99
UJ
I-
98
I- 97
i:
en
96
z 95
cc 94
a::
I-
100
-.. ... .,.,. . ...
I-
z 98 ~
UJ
.. :' .:.. ...
u 96
·... ·"· :" "· & ,.
a::
UJ
Q_
94
92
100 ..;,......·. .. ,. ,.,...._-...,
99
98
97
,. :···.··
.,..... -: , -:.....
..
i • • ..
96
100
99
98
97
96
95
-7.0 o.o 7.0
VELOCITY IN MM/SEC
FIGURE 18 Room-temperature Mossbauer spectra of reduced and reacted
vacuum-dried catalysts: (A) l0Fe/Si02, reduced 8 h; (B) 8. 95 Fel.05Co/
SiO2, reduced 8 h; (C) 7.4Fe2.6Co/SiO2, reduced 8 h; (D) l0Fe/SiO2, re-
acted 6 h; (E) 8.95Fel.05Co/SiO2, reacted 6 h; (F) 7.4Fe2.6Co/Si02, re-
acted 6 h. (From Stanfield and Delgass, 1981.)
Magnetic Resonance
Nuclear magnetic resonance (NMR) accurately measures the properties of
a nuclear spin system. To an even greater extent than with the Mossbauer
effect, these nuclear properties can reflect detailed chemical structure and
bonding information. Electron spin resonance (ESR) measures the energies
of the valence electron spin system directly and thus provides a sensitive
measure of the chemical state of species having a net electron spin. In
both measurements an applied magnetic field orients the spins, and transi-
tions between spin states are observed by absorption of electromagnetic
radiation. NMR absorptions are in the radio-frequency region, while ESR
is in the microwave.
Catalytic Surfaces 199
The high sensitivity of these two magnetic resonance techniques to
subtle chemical changes makes the methods at once potentially powerful
probes of chemical reactivity and techniques demanding thorough under-
standing of the underlying quantum mechanical effects in order to extract
the full measure of information available. ESR has a long history of ap-
plications in catalysis. It has been successful in studies of the environ -
ment of paramagnetic transition metal cations in catalysts, in observing the
chemical properties of electrons trapped in defects in oxide catalysts, and
using the paramagnetic probe molecule NO, in examining the interactions
of adsorbed molecules with surfaces (Lunsford, 1972, 1979a). Recently,
ESR has been particularly important in identifying and characterizing
o- and other oxygen anions on catalytic surfaces ( Che and Tench, 1982)
and in examining mobility of adsorbed species (Howe, 1982).
NMR has made significant contributions to catalysis research both in
the identification of chemical species and in measurements of species
mobility (Lunsford, 1979b). Magic angle spinning (Andrew, 1981) and
other recent advances in solid-state NMR make this technique one of the
most promising for future catalysis research. High-resolution 29si NMR,
for example, can quantitatively measure the numbers of Si ions with zero,
one, two, three, or four Al next-nearest neighbors and thus has provided
new understanding of Si-Al ordering in zeolites (Ramdas et al., 1981;
Magi et al., 1981; Nagy et al., 1981). A complete review of magnetic
resonance is well beyond the scope of this chapter. Our main purpose is
to point out some of the most recent developments in NMR that suggest
that an investment of time to understand magnetic resonance tools may be
worthwhile.
Principles
The magnetic resonance effect is easiest to visualize for a spin-1/2 system.
In the presence of a magnetic field, the magnetic moment associated with
the spin will precess about the magnetic field direction. This motion is
quantized and for a spin 1 /2 system only two z components of the spin vec-
tor are allowed, the +l/2 and the --1/2 states. The energy of the spin
system in the presence of the magnetic field is proportional to the product
of the size of the field and the z component of the spin. Thus, as the
magnetic field increases, the energy separation between the +l/2 and -1/2
states increases proportionately. At a given magnetic field strength,
resonant absorption of energy will occur when the frequency v of the ap-
plied electromagnetic radiation is such that hv is equal to the energy sepa-
ration between the +1 /2 and --1 /2 states, as shown in Fig. 19. In real
systems spins are not isolated in free space, but reside in atomic or nu-
clear environments which are generally not isotropic and can provide a
variety of perturbations that affect the energy of the system. In general,
one must write down a spin Hamiltonian that describes the appropriate
interactions and use it in fitting the data obtained.
In ESR the proportionality between the electron spin and the magnetic
field is indicated by the g tensor. This tensor has three principal values,
which deviate from the free electron value because of the interaction be-
tween the electron spin and orbital motion. Account must also be taken
of the fact that the powder samples typical of catalysts have crystallites
at all possible orientations with respect to the applied magnetic field
(Lunsford, 1972). Hyperfine interactions, the coupling of electron and
nuclear spins, cause additional splittings in ESR spectra and can be
200 Delgass and Wolf
I
I
I
I >-
J~
I~
lw
z
IS
I en
1z
I~
I
I
FIGURE 19 Splitting of a spin-1/2 nucleus in a magnetic field.
100 gauss
.______,
160160
170160
...__._----'_ _._____.__ _.__~~~~~~P7o i10
FIGURE 20 First derivative ESR spectrum of Oz on the surface of high-
surface-area MgO. The field increases from left to right and the gain has
been reduced fivefold for the central line; a small portion of the high-
field spectrum is overmodulated to show the outermost lines. For clarity
no attempt has been made in this diagram to insert levels for the lines
around g1. (From Tench and Holroyd, 1968.)
Catalytic Surfaces 201
helpful in defining the environment of an electron spin. As shown in
Fig. 20, the isotope 170, with a nuclear spin of 5/2 shows 6 line splittings
for 170160 but 11 line splittings for 1702 (Tench and Holroyd, 1968).
Note that the spectrum is displayed as the derivative of the energy ab-
sorption curve, as is standard in ESR spectroscopy.
NMR has sensitivity to chemical bonding through shielding effects.
The more free electrons around the nucleus of interest are to circulate in
response to the applied magnetic field, the more they decrease the strength
of the field felt by the nuclear spin. The range of chemical shifts in-
duced by this shielding is generally large with respect to NMR line widths
in liquids, giving the method high chemical sensitivity. Spin-spin coupl-
ings between nonequivalent nuclei also occur, giving NMR further capabil-
ity for defining the chemical environment of a given type of nucleus. In
liquids, many interactions are averaged to zero because of the rapid mo-
tion of the molecules.
In solids, however, relaxation times are long and direct-dipole coupling
of the spins and anisotropy of the chemical shift tensor both tend to
broaden lines to such an extent that meaningful chemical shift information
cannot be obtained from a standard spectrum. Analysis of these two in-
teractions shows that if the sample is spinning on an axis 54° 44' to the
magnetic field direction, the static components of the dipole-dipole inter-
action and the chemical shift anisotropy both become zero (Andrew, 1981).
Sidebands, whose positions depend on rotational frequency, still appear
but do not obscure the spectrum. This technique, called magic angle
spinning, dramatically improves the resolution of NMR of solids (Andrew,
1981). Further improvements can be made with spin decoupling, cross
polarization (Yannoni, 1982), and multiple pulse techniques (Taylor et al.,
1980; Ryan et al., 1980). In the past, NMR has been a powerful tool for
chemical structure analysis. The potential of the new NMR methods is to
bring such detailed structural information to the study of catalytic solids.
NMR Applications
Magic angle spinning NMR has provided a variety of new opportunities
for studying the detailed structure of zeolites. As shown in Fig. 21, 29si
NMR clearly resolves Si with zero to four Al neighbors bonded through
oxygen bridges. In this work by Ramdas et al. (1981), the distribution
of Al neighbors around Si was studied as a function of Si/Al ratio for
synthetic faujasites. They found that Loewenstein's rule forbidding Al
atoms from occupying neighboring tetrahedral sites was obeyed. As the
Si/Al ratio approached 1, the NMR spectrum became a single line cor-
responding four Al neighbors around Si. By analyzing the relative in-
tensities of lines as a function Si/Al ratio, the authors constructed an
ordering scheme for Al placement in the faujasite lattice. The onset of
para positioning for Al in the hexagonal rings facing the supercages was
found to begin at a Si/Al ratio of about 1. 4. The simulation in Figure 21
is based on this structural model. It is interesting to note that
Loewenstien's rule appears to be broken for zeolite A (Bursill et al.,
1980). Thomas and coworkers have also used solid-state NMR to show
the similarity of ZSM-5 and Silicalite (Fyfe et al., 1982). Nagy et al.
( 1981) have observed that the chemical shifts for ZSM- 5 and similar zeolites
are more negative than those of the faujasites and have ascribed that dif-
ference to the presence of the five-membered rings. In another study,
202 Delgass and Wolf
4
0
3
Si/Al = 1.35
80 90 100 110
o[p.p.m.]
FIGURE 21 Observed (at 79. 6 MHz) (upper) and simulated (lower) high-
resolution 29si NMR spectra with magic angle spinning for a Si/Al ratio
of 1. 35 in synthetic faujasite. (From Ramdas et al. , 1981.)
Nagy et al. ( 1982), used cross polarization (coupling of the proton and
29Si resonances) to identify silanol groups in the spectrum of ZSM-5.
Although magic angle spinning is certainly important to applications
of solid-state NMR to catalysts, it is not always necessary. Slichter
( 1981) has reported a very interesting set of 195pt NMR experiments on
Pt/Al2O3 samples supplied by Sinfelt. The data were obtained by the
spin echo technique. The lines observed were very broad, about 4. 5
kG, the range of chemical shift between diamagnetic Pt compounds and Pt
metal. The large shift of metallic Pt, called the Knight shift, arises from
the polarization of the spins of the conduction electrons. Analysis of the
peak shape as a function of Pt dispersion (fraction exposed) shows that
the amount of diamagnetic Pt is directly related to dispersion. The
spectra were interpreted to indicate that adsorption of gases on the sur-
face ties up the otherwise free electrons of. the metal and effectively
demetallizes the surface atoms. Direct observation of such fundamentally
important phenomena can have a great impact on our understanding of
catalysis.
Fourier transform l3c-NMR of species adsorbed on catalyst surfaces
has also been effective. Nagy et al. (1982) have been able to follow the
isomerization of 1- butene to 2- butenes on a tin - antimony oxide catalyst.
Gay (197 4) observed a variety of molecules adsorbed on silica and ex-
amined their mobility. Cirillo et al. (1980) have used proton NMR to
Catalytic Surfaces 203
identify three types of low-temperature H2 adsorption on alumina and
molybdenum /alumina catalysts.
DISTRIBUTION OF CATALYTIC MATERIALS WITHIN CATALYST
PELLETS: ELECTRON MICROPROBE, SCANNING ELECTRON
MICROSCOPY, AND ANALYTICAL MICROSCOPY
An important variable in the performance of a catalyst is the distribution
of catalytic and noncatalytic materials inside the pellets. The latter is
significant in the case of catalyst poisoning due to metal deposition. The
main tools now available to provide such analysis are the electron probe
microanalyzer (EPMA), scanning electron microscope (SEM), and scanning
transmission electron microscope (STEM). The principle of operation in all
three cases is the same, but the EPMA is designed to give best resolution
for chemical analysis, whereas the electron microscopes are designed to
give high magnification and good spatial and depth resolution, with chemi-
cal analysis being an added capability. The SEM produces two-dimensional
images from electrons backscattered from the material instead of from elec-
trons transmitted through the material, as is the case in TEM. A STEM
is a TEM with scanning capabilities and can also be used for chemical
analysis. The synopsis that follows will briefly describe the principle of
x-ray emission used for chemical analysis in these instruments and then
present a description of scanning electron microscopy. A brief compari-
son of the EPMA and SEM is also presented. Finally, applications to
catalysis are described.
Principles of X-ray Emission or X-ray Fluorescence
Chemical mic:r-oanalysis is carried out by analysis of the energy of x rays
emitted when a sample is excited by electron impact or x rays. The
phenomenon has already been referred to in previous sections in connec-
tion with sources for x-ray diffraction and photoelectron emission. When
x rays are used as the excitation source, the technique is called x--ray
fluorescence analysis. Such instruments are used primarily for chemical
analysis of bulk samples because x rays are difficult to focus and there-
fore the spatial resolution is not as good as when electron impact is used
as the excitation source. Electron beams can be focused to diameters
ranging from 25 to 1000 A. Furthermore, since electron beams are the
primary excitation source in electron microscopy, x-ray analysis constitutes
a natural additional capability for such instruments.
Figure 5b shows that when an electron is removed from an inner shell
of an atom, creating a vacancy, it may be filled by an electron from an
outer shell. The energy released by the transition may be emitted as an
x-ray photon. Deexcitation by Auger electron emission can also occur.
Since the energy levels are quantized, it follows that the energy of the
emitted x-ray photon is also a discrete quantity and is characteristic of
the element from which it was emitted. Consequently, knowledge of the
emitted x-ray energy can be used for chemical characterization of the
element. If the vacancy occurred in the K level and the transition occurs
from the L level, the photon is designated as Ka (Ka, 1 and Ka,2 exist due
to differences in spin). Such emission gives rise to characteristic lines
204 Delgass and Wolf
superimposed on a continuous spectrum. The characteristic lines produce
quasi-monochromatic x rays which are used as the source in XRD. When
x rays are used as an excitation source (x-ray fluorescence), no con-
tinuous spectrum is observed, and the background is very low, which is
especially suited for energy analysis.
The additional processes resulting from electron impact are shown
schematically in Figure 22. Secondary and transmitted electrons are used
to produce images in SEM and TEM, respectively. Auger electrons are
used to obtain surface chemical information. Energy analysis of the char-
acteristic x rays also provides such information. Also shown in Fig. 22 is
the depth of escape of the various deexcitation processes. It can be seen
that the escape depth of x rays is on the order of micrometers; there-
fore, they do not contain surface information ( as in the case of Auger
electrons). X-ray emission is generated in a volume of about 1 µm3,
which makes x-ray analysis a microanalytical tool.
Two methods are used to analyze the energy of the emitted x rays:
(a) wavelength dispersive spectrometry (WDS), and (b) energy dispersive
spectrometry (EDS). In the former method, the energy of the x ray is
obtained from knowing its wavelength (E = hv = he/),.). A is determined
using a crystal of known crystal spacing which diffracts (disperses) the
incoming x rays, allowing only one wavelength element to reach the de-
tector. The principle is the same as described in XRD, and Bragg's law
is used to determine A. Energy dispersive analysis (EDS) is accomplished
by using a semiconductor crystal that absorbs x rays, thereby exciting
the crystal's electrons into the conduction band, producing ari electric
pulse proportional to the energy of the x rays. These pulses are then
counted and sorted in a multichannel analyzer, and a display of intensity
of the signal versus its energy gives the desired spectrum ( see Fig. 23a).
The advantages and disadvantages of these two types of x-ray energy
analyzers are summarized in Table 4.
Incident Beam
BSE Ill CXR
Surface
Auger Electrons
(AE) 11--+--+---"l't---Back Scattered Electrons
( BSE) I micron
Characteristic X- ray
(CXR)
X- ray Continuum
(XRC)
FIGURE 22 Schematic of various signals originated by electron impact,
showing the corresponding volume of primary excitation.
Catalytic Surfaces 205
Co Ka
Si Ka
>-
1-
vi
z
w
1-
z
ENERGY
(al
iii
>,
0
0u 0.20 o - SMALL PORE, 8v = 0.15
"'E
u • - LARGE PORE, 8v = 0.20
'Cl 0.16
z
Q 0.12
~
a:
I-
z 0.08
w
(.)
z
0
(.) 0.04
~
:J
0 0
<l 1.0 0.8 0.6 0.4
j FRACTIONAL RADIUS
( bl
FIGURE 23 (a) X-ray spectrum of a sample containing Si, K, Co, and Ti
obtained by EDS. (b) Vanadium concentration profiles on a 1/16" extrudate
catalyst during hydrotreating of a heavy oil residuum. Effect of pore
diameter. (From Tamm et al., 1979.)
TABLE 4 Comparison of EDS and WDS
Advantages of energy dispersive spectroscopy
Compact; low cost
Rapid (qualitative analysis)
Simultaneous multielement analysis of the full x-ray spectrum (Na upward)
Display of the entire spectrum in digital format
High collection efficiency
Low sensitivity to geometric effects
Lack of higher-order lines which are generated in crystal diffraction
Digitally produced outputs for element line scans and distribution maps
Advantages of wavelength-dispersive spectroscopy
Higher inherent element separation (resolution)
High count rate on individual elements
Analysis can be highly quantitative
Better peak-to-background ratios
Analysis of a wide range of elements (Be to U)
Higher sensitivity
Operates at room temperature
206 Delgass and Wolf
Instrumentation
A brief discussion of the major components of the various instruments used
in electron probe microanalysis and SEM is given below; several books
(Postek et al., 1980; Goldstein and Yakowitz, 1975; Thornton, 1968) and
review articles (Sargent and Embury, 1976; Johari and Samudra, 1974) on
SEM, and EPMA (Heinrich, 1980; Purdy and Anderson, 1976) are available
for a more detailed description.
Figure 3 shows the schematics of a TEM, an electron probe microanalyzer
(EPMA), and a SEM. These instruments are equipped with a system to
produce and focus an electron beam and with a system for detection and
analysis of x rays. The EPMA is designed primarily for x-ray analysis, with
an electron- beam intensity which optimizes the x-ray yield and a low-magnifi-
cation optical microscope for viewing the sample. The SEM, on the other
hand, is designed to obtain images which, under ideal conditions, can be
magnified in the 20x to 100, 000x range with resolutions of 70 to 100 A.
Because of the greater versatility of the SEM, it is described in more de-
tail in the following paragraphs.
The SEM differs from the TEM in that images are produced from second-
ary electrons generated by the electron beam. Thus the sample need not
be transparent to electron transmission as in TEM. Electron impact creates
a volume of primary excitation (see Fig. 22) from which elastically scat-
tered ( backscattered) and inelastically scattered electrons or secondary
electrons are emitted. Secondary electrons have low energy (less than
50 eV), and therefore only those electrons near the surface can be emitted
and detected. Secondary and backscattered electrons are emitted outward
in all directions. An electron detector system is used to collect both
types of emitted electrons and produce a signal proportional to their in-
tensity. The detection of secondary electrons depends on the sample
topography. Electrons emitted from the specimen surfaces facing the de-
tector will show a bright face, whereas those emitted from surfaces facing
away from the detector will not be detected, creating a shadowing effect.
Furthermore, as the name indicates, an SEM is equipped with deflecting
coils which permit scanning the electron beam over the sample in a raster
mode. The raster pattern of the primary electron beam is synchronized
with the scanning pattern of a cathode ray tube (CRT) used to display
the detector signal so that a two-dimensional image of the scanned area is
produced. Images are produced in the CRT or a TV, and permanent
records can be obtained directly from the CRT using an instant camera or
by videotape recording from a TV.
Of the two types of x-ray energy analyzers, WDS is the preferred mode
of analysis from the standpoint of x-ray spectroscopy and is used exclusive-
ly in x-ray spectrometers as well as on EPMA instruments. WDS analyzes
one wavelength element at a time and requires mechanical components to
rotate the crystal as well as electrical components. Crystal alignment is
quite important, and WDS is difficult to use with rough surfaces. EDS
analyzers are used in most SEMs and in some electron probes. EDS pro-
vides a faster and easier survey analysis of the elements but at lower
energy resolution and lower sensitivity, and it does not cover the entire
spectrum, especially of light elements such as carbon. Clearly, for
versatility one would like to have an SEM capable of using high beam
intensities such as in EPMA and equipped with both WDS and EDS
analyzers. For high-resolution microscopy work or x-ray spectroscopy
work, separate instruments are preferred. Figure 23a shows the x-ray
Catalytic Surfaces 207
spectra of one spot on the sample. However, the beam can be scanned
over the sample with the analyzer fixed on a certain energy so that only
x rays corresponding to a specific element are displayed. This mode of
operation produces an x-ray map of the element in question over a line
(line scan) or area under analysis. Another way of obtaining elemental
distribution is to move the sample under the fixed electron beam. This
technique is particularly useful when analyzing catalyst pellets because it
permits one to scan the entire width of the pellet.
For electron microanalysis, the sample must have a flat surface. For
powders, the sample is first embedded onto a plastic medium, which,
after drying, is ground to reveal the cross section of its interior. Con-
ductive coatings ( C, Au) are evaporated onto the surface of nonconductive
materials (Purdy and Anderson, 1976). For SEM, the sample is mounted
on a small stub coated with adhesive which holds the particles as received
or after fracturing to reveal the interior.
Applications
Specific applications of SEM and EPMA to catalysis are discussed by
Sargent and Embury (1976) and Purdy and Anderson (1976). SEM is
used in general for physical characterization of catalyst particles, such as
particle size, shape, surface structure and porosity, makeup of aggregates,
and dispersion of one phase into another. The practical magnification and
resolution of the SEM is relatively low compared with the TEM and STEM,
which are preferentially used for examining crystallites in the size range
1 to 10 mm.
X-ray emission capabilities of the electron microprobe or SEM instru-
ments are used to obtain bulk chemical information about the materials
present in the sample. The most important application is to measure the
distribution of catalytic materials or impurities over the cross section of
catalyst pellets. A classical example is the effect of catalyst preparation
in the distribution of the active catalyst inside pellets. The metal profiles
inside the pellets can be followed as a function of preparation conditions.
Depending on the method used, the catalyst can be deposited uniformly
inside the pellet, or it can concentrate toward the external face of the
pellet. Extension of this application will increase our understanding of
catalyst preparation.
Another classical application is the study of metal deposition occurring
during dehydrodesulfurization of heavy residuum (Tamm et al., 1979).
Figure 23b shows the V content of a catalyst as a function of position in-
side the pellet, as obtained using an EPMA. The poisoning of catalysts
due to impurities is an area of study in which EPMA and SEM are partic-
ularly useful tools.
ADSORBED SPECIES ON SURFACES
Infrared Spectroscopy
Unlike the surface analysis techniques based on electron spectroscopy,
infrared (IR) spectroscopy is a well-seasoned tool for catalytic research,
as witnessed by the various books (Little, 1976; Hair, 1967; Clark and
Hester, 1974-1982) and review articles (Delgass et al., 1979; Eichens and
Pliskin, 1958) published on the subject. IR spectroscopy was first
208 Delgass and Wolf
developed to study the chemical structure of bulk compounds, but it was
soon realized that it can also be used to gain structural information about
species adsorbed on solid surfaces. The books by Hair ( 1967) and Little
( 1976) contain a good introductory description of IR together with many ap-
plications. The review article by Eichens and Pliskin ( 1958) has withstood
the test of time and remains one of the most quoted references. The more
recent review articles (Delgass et al., 1979; Basila, 1968; Blyholder, 1968;
Pritchard and Catterick, 1976) emphasize newer developments. The descrip-
tion given here covers only the most fundamental aspects of IR spectroscopy
and its major applications to catalytic research.
IR spectroscopy gives qualitative information about the way adsorbed
molecules are bonded to surfaces , .as well as structural information on solids.
It can also be used to measure the amount of materials adsorbed, and in
some cases it can be used to study the rate at which certain surface
processes occur.
Principles of Vibrational Spectroscopy
When an atom or molecule is placed in an electromagnetic field, there is a
transfer of energy between the field and the quantized energy levels of the
molecules. When energy is adsorbed, measurement of the transmitted energy
versus the frequency of the radiation produces a spectrum unique to the
excited molecule. If the frequency of the incoming radiation is in the IR
range, the spectrum is due to transitions in vibrational and rotational energy
levels. In each electronic energy level there is a series of vibrational
transitions, and for each vibrational level there is a series of rotational
transitions. Transition in electronic energy levels occurs when the excita-
tions have frequencies in the UV or visible range. Selection rules govern
the permissible transitions among the various energy levels.
Diatomic Molecule: Vibrational spectra arise from the motion of one atom
relative to another. While a detailed group theory has been developed to
describe the phenomena, a simple explanation in which a diatomic molecule
is modeled as an harmonic oscillator is often adequate to describe the first-
order processes involved.
The energy and frequency of an electromagnetic wave are related by
E = hv, where h is Planck's constant. Since Av = c, where c is the speed
of light, it has become a common practice to report spectra in terms of
frequency instead of A. The unit most commonly used is the wave number
= 104/A (micrometers), which has units of cm-1. The IR spectrum is
divided into near IR, 10,000 to 5,000 cm-1 (A: 1 to 2 µm); mid IR 5000 to
200 cm-1 (A: 2 to 50 µm), and far IR, 200 to 10 cm-1 ( ;>..: 50 to 1000 µm).
Solving the classical mechanical equations describing the oscillations of
two masses, m1,m 2 , attached to a perfect spring which obeys Hooke's law,
one can calculate the change in potential energy associated with the oscilla-
tions as
kr 2
u =
2
( 21)
where k is the force constant that measures the stiffness of the spring and
r is the displacement from the center of mass. The motion of this system
is sinusoidal and the frequency is given by v = (21r)-l ✓ k/µ, where µ =
m1m2 /(m 1 + m2) is the reduced mass. The simple result of the harmonic
Catalytic Surfaces 209
oscillator has immediate practical applications in the interpretation of spectra.
Knowing v, one can calculate the force constant k; conversely, changes in
v upon adsorption reflect weakening (lower v) or strengthening (higher v)
of the bond.
Another application of the result obtained for the simple diatomic oscil-
lator is in connection with changes in frequency due to isotopic substitution.
If the force constant remains the same, then upon isotopic substitution of
species with reduced mass 111 and a frequency v1 by an isotope of reduced
mass 112, a frequency change predicted by
( 22)
should be observed. Failure to observe a frequency change indicates that
the assumed species or group is not involved in the vibration being ob-
served, and another structure must be postulated [ see Delgass et al. (1979)
and Hair (1967) for illustrations of this application]. The potential energy
diagram described by Eq. ( 21) is similar to the lower region of the energy
diagram of a real diatomic molecule. For this reason, the quantized form of
the harmonic oscillator analogy is adequate for a simple description of
vibrational spectroscopy.
To account for quantum effects, the potential energy function of the
harmonic oscillator is substituted into Schrodinger's wave equation. The
solution of this equation gives the energy of the quantized vibration as
E = hv (v + ½) ( 23)
where v is the vibrational quantum number. Certain selection rules are
used to ascertain the probability of transitions between energy levels. For
harmonic oscillators, only transitions between 6 v = ±1 are permissible.
Since at room temperature most molecules are in the ground state, vibration-
al transitions between ground state and the first energy level are usually
observed. Another important selection rule requires that a change in
dipole moment with vibration must exist in order to couple the vibration to
the electromagnetic radiation. In the absence of such a dipole moment
change, as in the case of linear diatomic molecules containing the same atom
(i.e. , N 2), no vibrational energy transitions are observed. A corollary of
the foregoing selection rule is that IR inactive molecules may give rise to
dipoles when they are adsorbed on a surface and therefore exhibit an IR
spectrum.
Rotational transitions often occur simultaneously with vibrational transi-
tions. The combined vibrational-rotational energy relationship is of the
form
E ( 24)
where I is the moment of inertia of the molecule and m is a rotational quan-
tum number that can have values ±1, ±2, and so on. The center of the
vibrational-rotational band is at v 0 ; thus the second term in Eq. (24)
210 Delgass and Wolf
defines the rotational fine structure. Depending on whether m is positive
or negative, two branches, known as P and R branches, are produced
in the high- and low-frequency sides of vo, Another branch, known as
the Q branch, may appear in the vicinity of v 0 due to changes in angular
momentum about the axis joining the nuclei or due to unpaired electrons.
Figure 24 shows, in addition to adsorbed CO, the high-resolution absorb-
ance spectrum of gaseous CO, depicting the R and P branches resolved
into specific lines due to rotational transitions. Lower resistance spectra
will show only two broad bands about vo, For CO adsorbed on a metal surface,
the rotational fine structure disappears and give rise to a single band.
Polyatomic Molecules: Diatomic molecules exhibit only one vibrational
mode, but as more atoms are added to a molecule, additional vibrations
are possible. For a nonlinear polyatomic molecule containing n atoms,
3n - 6 vibrations are possible ( 3n - 5 for linear molecules). For these ,
n - 1 can be defined as stretching (opposite movement of atoms) and
2n - 5 are bending or deformation vibrations (atoms move at an angle to
each other) . In some cases, the vibrations correspond to a similar type
90..-------.....----~--~--~---~-~
78
66
o 54
0
w"
~ 42
<l
CD
a:
0
~ 30
<l
-5'----'----'------'------'---L------'
2400 2250 2100 1950 1800 1650 1500
WAVE NUMBERS ( cm- 1)
FIGURE 24 Infrared spectrum of CO in the gas plase and adsorbed on a
5% Pt /SiO 2 catalysts. The data were collected at a resolution of 2 cm - l
wave number in a single scan in a FTIR instrument. The fine structure
superimposed into the broad peaks (P, R branches) represents rotational
transitions. The sharp peak at 2070 cm-1 corresponds to adsorbed CO.
Catalytic Surfaces 211
of motion and can be distinguished only because they are perpendicular to
each other (degenerate vibrations). Hair (1967) discusses in detail the
number of possible vibrations in polyatomic molecules.
Group Frequencies: While any vibrational mode involves all atoms in a
molecule, much of the motion is dominated by a few atoms or group of atoms .
Thus, whenever a characteristic combination of atoms is present on a com-
pound , the same characteristic frequency appears more or less independent
of the structure of the rest of the molecule. Group frequencies permit one
to identify structural groups from the IR spectra. Group frequencies often
involve terminal atoms of small mass such as C-H,O-H, N-H, or inter-
nal atoms connected by bonds which have a distinctive force constant.
Extensive tabulations and discussions regarding the use of group frequen-
cies for chemical identification are available (Alpert et al., 1970).
The identification of the spectra of adsorbed species often consists of
matching the surface spectra with those of known compounds. Furthermore,
infrared bands that are forbidden for molecules in the gas phase on
grounds of symmetry may be possible when the molecule is adsorbed and
perturbed by surface forces. The frequency of the adsorbed species shifts
with surface coverage, coadsorption of other molecules, particle size, or,
in general, with changes in the electronic environment of the metal-adsorbate
interaction.
Band Intensities: If radiation of intensity Io impinges on a media of
thickness d containing a concentration of molecules C, the intensity of the
transmitted radiation is given by the Beer-Lambert law,
IO
A= ln 1 = i:::Cd ( 25)
where £ is the extinction coefficient and A the absorbance. For adsorbed
molecules, the extinction coefficient can be larger or smaller than in the gas
phase (Little, 1976). If £ is constant with coverage, there is a linear re-
lation between absorbance and coverage which can be used for quantitative
analysis. The best approach to measuring extinction coefficients is tc.· meas-
ure independently the amount of gas adsorbed along with the IR absorbance.
Recent approaches have used a pulse technique (Sarkany and Gonzalez,
1982a) and mass spectroscopy (Savatsky and Bell, 1982) for evaluation of
the amount adsorbed. If the band width of the adsorption peak changes,
it is recommended to use an integrated absorbance over the full frequency
range.
Band intensity increases with increasing metal loading and sample thick-
ness. However, scattering and absorption by the support sets an upper
limit to the amount of metal and material that can be used. Scattering is
proportional to the cube of particle size and inversely proportional to the
fourth power of the wavelength. It has been found that good transmission
results are obtained if particle sizes are less than 1 µm. Thus, a choice
of support with a particle size of <1 µm will facilitate IR studies.
Experimental
In the past, the majority of IR studies have been carried out using disper-
sive IR instruments operating in a transmission mode. However, Fourier
transform infrared (FTIR) spectroscopy offers a number of advantages over
212 Delgass and Wolf
dispersive instruments, in particular in catalytic applications. Reflection
spectroscopy (specular, diffuse) is also available to study opaque samples
and is especially suited to use with flat, opaque surfaces (foils, single
crystals) in combination with other spectroscopic techniques. The descrip-
tion that follows compares the various modes of IR utilization and summarizes
briefly advantages and disadvantages.
Dispersive Versus Fourier Transform IR: The classical IR instrument is
a dispersive instrument consisting of a source producing a reference and a
sample beam, a sample chamber, an optical system to combine the beams and
separate the various frequencies, and a detector. Frequency discrimination
depends on dispersion of the radiation by a grating system. A brief but
clear description of dispersion instruments is presented by Bell ( 1980) and
is available from the technical literature for commercial instruments. Fourier
transform instruments operate on an entirely different principle to separate
the frequencies. A single beam of IR radiation from the source is sent into
a Michelson interferometer, which, by the displacement of a mirror, produces
an interferogram containing all the frequencies within the desired IR spec-
trum. The details and principles of FTIR spectroscopy are presented in
Griffith's (1975) book on the subject and are also summarized in Bell's (1980)
review article. The information contained in the interferogram is converted
into a frequency versus absorbance or transmittance spectrum by using a
Fourier transform inversion. The transformation is carried out by a dedicated
minicomputer which also operates the spectrometre and is used to display spec-
tra. FTIR has two major advantages over grating spectrometer~. First, the
interferometer observes all spectral resolution elements simultaneously, where-
as a monochrometer spends only a fraction of the total time observing each
resolution element. Consequently, under identical conditions, the FT spectrom-
eter can acquire spectra much faster than the dispersive spectrometer (this is
known as Felgett's advantage). Conversely, for the same time of data collec-
tion, the FT spectrometer can produce spectra of much better signal-to-noise
ratio. The second fundamental advantage of an FT spectrometer over a grat-
ing spectrometer is the increased optical thoughput of an interferometer com-
pared to a grating monochrometer (Jacquinot's advantage). Griffith ( 1975)
has presented a quantitative comparison between dispersive and FTS instru-
ments which has been summarized by Bell ( 1980). Furthermore, FTS data
acquisition and computer data storage capability provide an additional advan-
tage over dispersive IR instruments, although it must be pointed out that
similar computer capabilities are now being added to dispersive units. The
main disadvantage of FTS instruments is their higher cost; however, new
models with restricted capabilities are now being introduced in the market at
prices that are comparable to those of dispersive units. In general, the higher
IR throughput and smaller data collection time required for FTIR instruments
make them especially suited for catalytic studies.
Transmission Versus Reflection and Emission: One of the most widely
used methods of IR spectroscopy is the transmission mode, where in the IR
beam is transmitted through the sample, which must be partially transparent
to IR radiation. Many oxides, such as silica, alumina, zeolites, and stoichio-
metric zinc oxide, are IR transparent. The sample is pressed in the form
of a thin disk (0. 3 to 0.1 mm thick) with a density between 10 and 100 mg/
cm2. The preparation of the wafer is often the key to successful experimen-
tation. Although specific values depend on the material in question, there
Catalytic Surfaces 213
are certain general guidelines. The disk is pressed in a die which must
have highly polished surfaces to prevent the disk from adhering to the die
surfaces. In some cases it is convenient to condition the powders with a
certain degree of moisture and temperature prior to pressing. Transparency
increases when the crystallites of the powders are very small (silica and
alumina prepared by hydrolysis of the chlorides in a HrO2 flame produces
small particles). An open pore structure (i.e., low die pressure) is de-
sirable to facilitate transport of reactants inside the disk. In the case of
supported catalysts, metal loading should be such that crystallite size
should not exceed 100 A. Pt can be loaded from 5 to 10% on silica ( Cabosil)
or alumina aerogel and still give a good absorbance spectra. The support
should not absorb in the same frequency as the adsorbate. Other methods
of sample preparation include evaporation of the metal onto an IR window,
forming a thin film; however, the sensitivity is much less than when the
metal is highly dispersed in a porous support (Pritchard and Catterick,
1968). The books of Little (1976) and Hair (1967) contain details of disk
preparation, and the IR chapter in the Delgass et al. (197 9) book also con -
tains useful information in this regard.
In transmission experiments, the disk is placed in a cell containing
special IR windows ( CaF2, sapphire, etc.) and equipped to meet the pres-
sure and temperature requirements of the experiment. Several cells de-
signs are reproduced by Little (1976) and Hair ( 1967). Newer designs
for transient experiments consist of small-volume cells capable of rapid
response to changes in feed concentration and temperature (Savatsky and
Bell, 1982; Kaul and Wolf, 1984) .
When the solid is completely opaque to IR, the pressed salt method can
be used. The opaque solid is first ground and mixed with a halide trans-
parent to IR (KBr, CsI) and can then be pressed into a self-supporting
disk. Depending on the material, dilutions of 1/100 to 1/400 sample per
halide are used. The disadvantage of this technique is that access to the
surface by gases is lost and therefore adsorption or desorption studies are
no longer possible. However, the technique is useful when analysis of the
structure of the catalysts rather than the adsorbate-surface interaction is
sought. Other methods that have been used are deposition on a liquid
matrix and in a solid argon matrix (Pritchard and Catterick, 1976).
Reflectance techniques have been used with opaque samples that do not
permit transmission. Specular reflection has been used in the case of metal
mirrors such as single crystals or foils and, in principle, provides an attrac-
tive combination with other spectroscopic techniques involving flat surfaces.
Diffuse reflectance spectroscopy (DRS) is used when the reflecting surface
is rough and the incident radiation is reflected (scattered) diffusely. Such
radiation must be collected by a hemispherical or elliptical reflector and
focused into the detector. Klier (1980) summarizes the literature, theory,
and application of DRS to the study of adsorbed species on catalysts.
New developments in vibrational spectroscopy (excluding IR excitation)
are reviewed in the monograph by Bell and Hair ( 1980). They include
electron energy loss spectroscopy (EELS), which is useful with single crys-
tals or metallic foils; inelastic electron tunneling spectroscopy (IETS), used
to study metal-insulator junctions; and neutron scattering spectroscopy
(NSS).
Applications
Rather than an extensive listing of the many IR studies published in the
literature, the major classes of applications in connection with catalysts are
214 Delgass and Wolf
summarized below. The reader is referred to the several review papers for
specific applications.
Bulk Structures: Studies of the structure of silica surfaces and acid
oxide surfaces, including ::-.lumina, silica-alumina, and molecular sieves, are
summarized by Hair ( 1967). A classical example of the use of IR in struc-
tural analysis is the work of Flanigan et al. (1971), who, using KBr-zeolite
disks, compared the spectra of various A, X, and Y zeolites and hydroxy-
sodalite and assigned IR bands to specific structural groups on each zeolite.
In more recent studies (Pichat et al., 1974), the degree of crystallinity of
the zeolite has been related to the IR bands occurring near 560 to 380 cm-1.
A relation between degree of crystallinity (as obtained from IR) and crystal
size (obtained from XRD) has also been attained.
IR Studies of Adsorbed Molecules: A great deal of the IR work relevant
to catalysis has been done with adsorbed molecules. The review of Eichens
and Pliskin (1958) summarizes studies of hydrocarbons (ethylene, ethane,
acetylene, olefins) on nickel and CO chemisorption on Pd, Pt, iron, and
rhodium. Much of this work consisted of structural assigment of the ob-
served IR bands to elucidate the type of bonding involved. In the case of
CO chemisorption, IR can be used to detect the number of metal atoms
bonded to CO by the observation of frequencies corresponding to linear CO
(CO/M = 1), bridged CO (CO/M = 1/2, or two CO per metal (CO/Rh= 2).
Observation of frequency shifts with surface coverage, crystallite size, and
so on, are also important in the elucidation of the CO-metal interaction. IR
studies of NO adsorbed on metals and oxides have also been used as a probe
to elucidate the type of sites existing on supported catalysts (Peri, 1974).
Significant frequency shifts have been observed when hydrogen, from
hydrogen-containing molecules, is bonded to the OH groups of silica. Such
frequency shifts are interpreted in terms of charge transfer or changes in
the OH dipole due to the presence of the adsorbed molecule (Basila, 1968).
One of the classical examples in the use of IR spectroscopy to examine
the nature of active sites is the differentiation of Brl$nsted or proton donor
acid sites and Lewis or electron acceptor acid sites. Ammonia (or nitrogen-
containing molecules gives absorption bands near 3333 and 1639 cm-1 if in
the NH3 configuration (Lewis acid) and near 3125 and 1428 cm- 1 if the NH:
form (Brl$nsted acid). The frequencies of the coordinatively bonded mole-
cules usually shift with coverage, which is interpreted in terms of the
strength of the acid sites. Basila (1968) presents a review of IR studies
of the acidity of silica-alumina and zeolites, together with frequency assign-
ments for ammonia and pyridine.
It has already been mentioned that isotopic substitution can be used to
elucidate the structure of surface complexes; H2 on ZnO, ethylene-oxygen
on Ag, and propylene on ZnO are a few examples discussed in some detail
in the book by Delgass et al. ( 197 9) .
Infrared Kinetic Studies: If the rate of reaction can be correlated with
the rate of formation or disappearance of an IR band, it can be concluded
that such species is a reaction intermediate. If the reaction is carried out
in a batch cell under transient conditions, and if the IR spectrometer is
capable of measuring spectra in the time scale of the reaction experiments,
transient IR experiments premit one to determine the kinetics of surface
species and the reaction mechanism. The use of transient techniques in
catalysis, although proposed some time ago by Tamaru ( 1964), has been the
subject of various review articles (Tamaru, 1964, 1978; Bennett, 1976;
Kobayashi and Kobayashi, 1974).
Catalytic Surfaces 215
A combination of IR transient studies with isotopic labeling has been re-
ported by Kokes et al. (1972) for 1-butene isomerization on ZnO. Band as-
signment was first resolved by isotopic substitution; then the IR bands were
followed as a function of time and compared with gas-phase kinetic data.
Simultaneous measurement of surface and gas phase composition, together
with isotopic substitution, have also been carried out py Tamaru (1978)
during the water-gas shift reaction catalyzed by ZnO.
The use of fast FTIR spectrometers has expanded the use of transient
studies to catalytic systems more active than ZnO. Bennett ( 1982) describes
examples of the use of pulses, steps, and cycled feed to study transient
catalysis using IR spectroscopy. The reactions of carbon monoxide on Pt
and iron have been studied using transient IR. The effect of transport
processes and dynamics of chemisorption have been analyzed by Ho and
Hegedus (1982). The dynamics of three-way catalysts have been studied by
Herz ( 1982) using IR diode laser spectroscopy. Studies of self-sustained
oscillations using FTIR have been carried out by Kaul and Wolf (1985). In
most applications, the time constant associated with the transient surface
processes must be of the order of that for IR data collection (about 0.1 to
1 s for FTIR spectrometers). Time-resolved FTIR spectroscopy has also
been used to measure fast chemical reactions (Durana and Mantz, 1969);
however, the technique has not yet been applied to surface studies.
In closing the synopsis on the fundamentals and applications of IR spec-
troscopy to catalysis, it is clear that this is a mature and necessary tool
in catalytic research. New frontiers are now being opened with the use of
transient techniques. The development of reflection and new vibrational
spectroscopies will be useful in fundamental studies using flat or opaque
surfaces.
Raman Spec_troscopy
Raman spectroscopy has much in common with infrared spectroscopy, but
since it records vibrational spectra from scattered rather than absorbed
radiation, it gives slightly different and often complementary information.
The availability of intense, monochromatic laser light sources compensates
for the low scattering cross sections, and commercial spectrometers are
capable of recording Raman spectra of catalytic materials and adsorbed
species. The main advantage of this technique is that absorption by the
solid matrix does not interfere with the low-frequency bands. Thus vibra-
tional modes of the catalyst itself and of the bond between the adsorbate
and the catalyst are accessible by Raman spectroscopy. Since the effect
requires a change in polarizability with vibration rather that a change in
dipole moment, spectra show strong peaks for nonionic bonds and sym-
metric vibrations. The method has been particularly successful for the
study of hydrodesulfurization catalysts containing molybdenum. It has
also been used to study adsorbed aromatic molecules and electrochemical sur-
faces. Theory, experimental considerations, and examples of applications
are discussed below. Review articles by Hendra ( 197 4) , Cooney et al.
( 1975), Egerton and Hardin ( 1975), and Haller ( 1979) provide further
information.
Principles
Electromagnetic radiation induces a dipole moment in a molecule. The size
of the dipole moment is proportional to the magnitude of the electric field.
The proportionality constant is the molecular polarizability. If the
216 Delgass and Wolf
distribution of charge in the molecule changes during a particular vibration,
the polarizability will also vary with the vibrational motion, and the vibration
will be Raman active. Analysis of the interaction between the oscillating
electric field of the exciting radiation and the induced dipole oscillating with
the vibrational motion reveals three main scattering terms (Haller, 1979).
The first is the elastic or Rayleigh scattering, which occurs at the fre-
quency of the exciting radiation. The second and third terms, 10- 9 times
the intensity of the Rayleigh scattering, represent inelastic scattering in
which energy is exchanged between the radiation and the molecule. These
terms have frequencies vo - vm and vo + Vm, where vo is the frequency
of the exciting radiation and Vm is the frequency of the molecular vibration.
They are called the Stokes and anti-Stokes Raman lines, respectively
(Chantry, 1971). The intensities of these lines depend on the change in
polarizability with the vibration and, for symmetric vibrations, can be re-
lated to bond order (Hendra and Stratton, 1969). For molecules with a
center of symmetry, vibrations that are symmetric about the center of sym-
metry change the polarizability and are Raman active, as shown for CO2 in
Fig. 25. Asymmetric vibrations of such molecules are Raman inactive. These
sensitivities are exactly opposite to those governing IR activity for such
molecules, but IR and Raman activity need not be mutually exclusive for
more complex molecular symmetries. The vibrational selection rules are the
same for Raman and IR (i.e. , I::,. U = ±1 for harmonic oscillators) •
A special case of Raman spectroscopy must be mentioned in a discussion of
catalyst surfaces. Jeanmarie and Van Duyne (1977) and Albrecht and Creigh-
ton (1977) reported that pyridine adsorbed on silver in an electrochemical cell
showed scattering cross sections 105 to 106 higher than for pyridine in solu-
tion. This phenomenon of surface-enhanced Raman spectroscopy (SERS) is
still not completely understood (Furtak and Reyes, 1980; Van Duyne, 1979;
Aravind and Metiu, 1983), but for Ag, Cu, and Au, the metals for which
it has been observed, it offers a signal enhancement which makes study of
molecules adsorbed on foils and other low-surface-area samples straight-
forward. Applications have been made in electrochemistry (Birke et al.,
1983) and should also be possible in catalysis. The technique is particularly
attractive because, with an optical multichannel analyzer, surface spectra
can be recorded every 20 msec (Weaver et al. , 1983).
Experimental Methods
A Raman spectrometer consists of a light source, the sample scattering
chamber, a monochrometer, and a detector. A laser light source is essential
for surface work. Argon ion (514.5 nm and 488.0 nm), helium-neon (632.8
nm), and krypton ion ( 647. 1 nm) lasers are in current use. This light is
highly collimated or passed through an interference filter to remove back-
ground radiation accompanying the laser line.
The light scattered from the sample can be viewed at any angle, but
0°, 90°, or 180° are commonly used. Cells are typically glass with an
optically flat window. Because of the relative high power of the laser
light, care must be taken to avoid sample decomposition or excessive heat-
ing by the exciting radiation. The light can be scanned across the sample
(Zimmerer and Kiefer, 1974) or the sample can be rotated (Cheng et al.,
1980) to avoid this problem.
To obtain the Raman spectrum, the scattered intensity must be
measured as a function of frequency. A monochrometer accomplishes this
Catalytic Surfaces 217
t
C
0
{
C
t
0
Antisymmetrical Stretching, 112
\
0 0
/
I
C
\ 0 0
Bending, 113
FIGURE 25 Polarizability changes during the vibration of carbon dioxide
(not to scale). (From Tobias, 1967.)
218 Delgass and Wolf
task. The light passing through the monochrometer system at a given
energy is recorded by counting photons with a photoelectric detector.
In some cases, species present in catalyst samples are excited by the
laser light and emit a fluorescence spectrum that can obscure weak Raman
lines. When organic impurities are the source of this problem, the fluores-
cence background can often be removed by heating the sample in Oz
(Egerton et al., 197 4) or treating it with hydrogen peroxide or concentrated
nitric acid (Adams et al. , 1976). Other fluorescence rejection schemes use
time resolution to eliminate the relatively long lifetime fluorescence signal
(Van Duyne et al., 1974). Note that fluorescence radiation is easily identi-
fied by the lack of dependence of its frequency on the frequency of the
exciting radiation.
Applications
Raman spectroscopy applies to the study of vibrations within the catalyst
itself and to those of adsorbed molecules at the surface. The utility of the
method for studying catalysts themselves is well illustrated by the growing
literature on the genesis, precursors, and sulfided forms of molybdenum-
containing hydrodesulfurization catalysts.
Molybdenum is usually added to the alumina support by impregnation
with an aqueous solution of (NH 4) 6Mo 7O24 to the point of incipient wetness.
As summarized by Wang and Hall ( 1980), the metal deposition process is
complex. At high pH, the molybdenum species in solution is monometric
Moo}-, while the polymolybdate species Mo 7o 24 6- predominates at low pH.
Furthermore, the local pH in the pores can be modified by the buffer
capacity of the alumina and by the evolution of ammonia. Spectra of both
wet (Fig. 26) and dried catalysts prepared at carefully controlled pH of
8. 6, 3. 9, and 1. 0 show the ability of the Raman spectroscopy to follow the
molybdenum chemistry (Wang and Hall, 1980). At pH 8.6, peaks at 326
cm-1 and 905 cm-1 identify the major species as MoO42-. Bands at 215 cm-1
and 365 cm-1 show Mo 7o 2 46- to dominate at pH 3.9 and 1.0.
Raman spectra also yield much information about calcined or oxidized
catalysts. Zingg et al. (1980) have used the chracteristic spectra of MoO 3
and Alz(MoO4) 3 to show the appearance of MoO 3 when molybdenum sup-
ported on alumina exceeds monolayer coverage and that increased calcination
temperature or duration converts MoO3 to Alz(MoO4) or another tetrahedral
Mo species. A number of authors have reported on the interactions of Mo
with alumina (Brown et al., 1977a,b; Jeziorowski and Knozinger, 1979; and
Dufresne et al., 1981). In general increasing Mo coverage of the surface in-
creases the two-dimensional aggregation of octahedral Mo species, as indicated
by increasing frequency of the Raman bands. The aggregated Mo species in-
teracting with alumina support has a characteristic Raman line in the
950-cm- 1 region. Details of the effects of addition of Ni and Co to MoO /
AlzO3 catalysts have also been elaborated (Cheng and Schrader, 1979a;
Jeziorowoski and Knozinger, 1980; Knozinger et al. , 1981).
Schrader and Cheng (1982) reported that sulfiding of Mo/Al2O3 in 10%
HzS /Hz at 400°C produces a sample with a Raman spectrum characteristic
of MoSz, although slightly broadened and shifted. Studies by these
authors of the effects of Mo loading, sulfiding temperature, and susceptibility
of the sulfide to reoxidation show MoO3 to be difficult to sulfide at low
temperature, isolated Mo species to be the most difficult to sulfide, and
polymolybdate species to sulfide most easily but to produce vacancies
caused by reduced Mo. Brown et al. ( 1977b) and Payen et al. ( 1982) also
Catalytic Surfaces 219
955
1100 1000 900 800 700 600 500 400 300 200 100
CM-1
FIGURE 26 Raman spectra of wet catalysts prepared by impregnation of
alumina with (NH4) 6 Mo 7o 24 at pH (a) 8.6, (b) 3.9, and (c) 1.0. (From
Wang and Hall, 1980.)
report Mos 2 spectra from sulfided catalysts. The latter paper demonstrates
the spatial resolution of the Raman microprobe, which takes advantage of
the ca. 1 µm spot size of the laser radiation.
The Raman literature on adsorbed molecules is not large, but a number
of interesting findings have been reported. Studies of molecules with
aromatic rings offer good examples of the utility of the Raman measurement .
Raman spectra of benzene adsorbed on silica show only slight peak shifts
from the spectrum for liquid benzene, but the intensity of the 994-cm- 1
ring breathing band is significantly reduced. Egerton et al. (1974) in-
terpret this result as a decrease in polarization of the TI electrons and an
indication of TI bonding of the silica surface. Surprisingly, thiophene shows
similar TI interaction with surface SiOH groups by loss of intensity in the
ring breathing vibration at 834 cm-1 (Tam et al. , 1975). Pyridine, on the
other hand, indicates heteroat0rn interaction with a silica surface by a fre-
quency shift in the ring breathing mode from 922 cm-1 in the liquid to
1007 cm-1 at low coverage, where hydrogen bonding dominates (Hendra
et al., 1971; Egerton et al., 1974). In addition, these studies report
220 Delgass and Wolf
coordinative bonding of pyridine to Lewis sites on alumina. Pyridine adsorp-
tion on hydrodesulfurization catalysts gives Raman spectra characteristic of
physisorbed species and a specific chemisorbed species with a peak in the
region 1008 to 1014 cm-1 (Cheng and Schrader, 1979b; Payen et al., 1982).
Raman spectroscopy has also elucidated surface reactions of adsorbed
molecules. Kuiper et al. (1973) have combined Raman and IR results to
show that benzaldehyde is converted to benzoate and benzyl alcoholate on
an alumina surface. Turner et al. ( 1976) used Raman spectroscopy to ob-
serve the isomerization of 1-hexene to 2- hexene on alumina activated at
1200 K.
Most of the applications of surface-enhanced Raman spectroscopy have
been in an electrochemical environment, but it is clear that the technique
does apply to the interaction of gases with clean metals which show the
effect. SERS spectra of carbon monoxide (Wood and Klein, 1980), ethylene
(Moskovits and Dilella, 1980), and water (Pockrand, 1982) adsorbed on sil-
ver at low temperature have all been reported. For ethylene on silver, the
Raman spectra contain bands for vibrational modes that are Raman inactive
in the gas phase. Thus adsorption alters the symmetry of the molecule.
Moscovits and Dilella interpret the band intensities and shifts as suggesting
that both ethylene and propylene are 'ff bonded to the silver surface.
Thus we see that, in general, Raman spectroscopy has been effective in
identifying surface phases and coordination. It can reflect details of ad-
sorbate bonding and gas-surface reaction, and in the surface-enhanced
mode, it can give this information on submonolayers of adsorbates on flat
surfaces. Applications to catalysis have been significant, but 'this is a
technique in the process of being developed for catalysis research. In-
creasing use can be expected.
Temperature-Programmed Desorption and
Temperature-Programmed Reaction
Although many experiments in catalysis demand isothermal conditions, the
unsteady state produced by a rapid, programmed change in temperature
can yield a wealth of information about a catalytic system. Perhaps the
simplest version of this experiment is what is often called flash desorption
spectroscopy (FDS) or thermal desorption spectroscopy in the surface
science literature (King, 1975). In this experiment, gas is irreversibly
adsorbed on a foil or single-crystal surface at low temperature. The
temperature of the sample is then raised linearly at a typical rate of 10 K /
sec. The desorption spectrum, usually recorded by a mass spectrometer
in the vacuum system, shows peaks at temperatures related to the heats of
adsorption of the various adsorbed states. Temperature-programmed de-
sorption (TDS) (Cvetanovic and Amenomiya, 1972) is essentially the same
experiment on a catalyst sample, but extra care must be taken to account
for possible influence of heat transfer, diffusion, or readsorption of the
gas in the porous sample. Temperature-programming rates are usually
slower in TPD and most experiments are done in a carrier gas instead of
a vacuum. The concept of using temperature to scan the energies of in-
teraction of molecules with surfaces is a useful one and has appeared in
many variations, including temperature-programmed reduction (Hurst
et al., 1982), temperature-programmed oxidation (Miura et al., 1975), and
temperature-programmed reaction (TPR) (Falconer and Schwarz, 1983),
Catalytic Surfaces 221
In all of these techniques, the appearance of more than one peak in the
spectrum indicates heterogeneity in the reaction energetics of the surface
or the adlayer. Quantitative interpretation of these results can be difficult
(Gorte, 1982), but detailed analysis of data is possible (Falconer and
Schwarz, 1983) and even fingerprinting of such complex phenomena on
catalysts can be very helpful in differentiating and developing new catalysts.
Principles
In flash desorption spectroscopy, molecules desorb from the surface directly
and are pumped from the vacuum system. If the ratio of pumping speed to
system volume is high and the heating rate is not excessive, the desorption
rate is proportional to the pressure in the system or to the mass spectrome-
ter signal above background. In the absence of readsorption
n
d0 -kd,00
= ---'--- ( 26)
dT s
where 0 is the fractional coverage of the surface, n the order of the desorp-
tion, S the heating rate dT /dt, kd, o the preexponential factor of the de-
sorption rate constant, Ed the activation energy for desorption, T the
absolute temperature, and R the gas constant. In general, kct, o, Ed, and
even n can be a function of coverage. If these factors are constant and
the measured signal is p:roportional to d0/dt, then setting the derivative of
Eq. (26) equal to zero produces the following relation describing the peak
maximum:
( 27)
Here 8m and Tm refer to values at the peak maximum. Note that for first-
order reactions Tm does not depend on 0, and Ed can be calculated if S
and kd,0 are known. A rough estimate for Ed (kcal/g mol) is given by
Tm/16 (Madix, 1980).
At high carrier gas flows and in the absence of readsorption and dif-
fusion limitations, TPD is equivalent to FDS. Increasing degrees of
sophistication must be added to the analysis when coverage dependence of
the parameters, readsorption, or diffusion limitations apply. As outlined
succinctly by Falconer and Schwartz ( 1983), variation of heating rate and
initial coverage; partial integrations of curves to produce desorption rate
isotherms; detailed analyses of peak width, shape, and skewness; and
direct curve fitting provide a variety of approaches for maximizing the re-
turn from TPD experiments. Intrusion of transport and readsorption
problems cannot always be avoided, but recent analyses have provided
quantitative guidelines for optimizing the design of the experiment (Herz
et al., 1982; Lee and Schwartz, 1982; Gorte, 1982). Even under ideal
experimental conditions, fast interconversion between various surface
states can hide information from view by temperature-programmed methods.
Nevertheless, this approach creates a useful family of tools for characteriz-
ing gas-surface energetics and surface reactivity.
222 Delgass and Wolf
Experimental Methods
TPD /TPR began as a simple and inexpensive experiment. Purified carrier
gas or reactant passes through one side of a thermal conductivity cell, over
the catalyst, and through the other side of the cell. In the absence of
desorption or reaction, the thermal conductivity cell is balanced and gives
a zero reading. When a linear temperature program is applied to the fur-
nace around the sample, the temperature of the small catalyst charge is re-
corded by a delicate thermocouple placed in the bed and a desorption or
reaction event is recorded by the imbalance in the thermal conductivity cell,
which is mounted near the reactor exit to minimize the delay time. Higher
sensitivity can be gained by using a flame ionization detector, but a more
flexible apparatus is created when the detector can identify the composition
of the reactor effluent. Since analysis must be done at the speed of the
temperature program, a mass spectrometer is the most versatile detector
and quadrupole mass spectrometers are often used. Accuracy and fast re-
sponse require a well-designed inlet system connecting the atmospheric
pressure reactor effluent to the low-pressure environment needed for ioniza-
tion and mass detection. Further details of experimental design and opera-
tion are discussed by Falconer and Schwarz (1983).
Applications
Temperature-programmed techniques have been widely applied to catalysts.
Falconer and Schwarz ( 1983) cite over 100 references. Our purpose here
is to illustrate temperature-programmed desorption, reduction, ·reoxidation,
and reaction with a few representative examples.
Temperature Programmed Desorption: Anderson et al. ( 1979) have ex-
amined H2 desorption from Pt as a function of metal dispersion (fraction
exposed) on different supports and of alloying with Au on silica. Broaden-
ing of the H2 desorption profile with increasing dispersion was attributed
to an increase in the number of high-energy sites at high dispersion. Al-
loying of Pt with Au decreased the amount of H2 desorption but not the
peak position, showing that Au acted only as an inert diluent in the Pt sur-
face. For some metals, adsorption of hydrogen can be activated. H2 TPD
as a function of adsorption temperature has revealed strong activated ad-
sorption effects for a variety of cobalt catalysts ( Zowtiak et al. , 1983).
CO shows complex, multipeaked desorption spectra for many metals. In
studies of the effects of sulfur poisoning on CO desorption from Ni/SiO2,
Zagli and Falconer ( 1983) showed that sulfur preferentially removes the
highest-energy CO adsorption sites. In an interesting contrast to the find-
ings for H2 desorption, Foger and Anderson ( 1979) showed that alloying
Au with Pt changed the CO desorption spectrum significantly even though
pure Au does not adsorb CO ( see Fig. 2 7) .
Temperature- Programmed Reduction: This experiment is based on the
premise that the reducibility of metals on a catalyst surface can be a sen-
sitive function of the surface chemical environment (Holm and Clark, 1968).
Reducibility is typically measured by H2 consumption during a linear tem-
perature program. In the first application of this method to supported
catalysts, Robertson et al. ( 1975) elucidated the conditions favoring alloying
of Cu and Ni on SiO2. Precalcination tended to maintain separate phases
with identifiable reduction peaks for each metal. After direct reduction
and intervening calcination, temperature-programmed reduction showed one
Catalytic Surfaces 223
395K
♦
r,..
/
.I '· ' ·,
----
720K
. ' ♦ r
I ' ....... _.,,.... ----......._ '.
"'
~
C) I. ii
ii
~
i '\
\ ci
1~K
.0
\
0 E
:G ~
...."tl0
C
0
I• t\
t
~
~
·;::; 573K
. . ~j!\ a.
Cl)
.; ♦
a. • .\
E
0 !!l
....0
C
Cl)
u
,::, E c.E
C Cll
.,. · .. \
C CL>+-'~ •
8 ····· "tl
··.\
C
_____ _ ----------
...... -· Cl)
···~·,;.;
400 500 600 700 900
temperature/K
FIGURE 27 Temperature-p rogrammed desorption profiles for carbon monoxide
from platinum-gold/ aerosil catalysts. Catalyst Pt15, Au85: _ _ , CO; ----,
CO 2 , both components by mass spectrometry. Catalyst Pt76 Au24 -·-·-,
CO; ••. , CO2; both components by mass spectrometry. Samples: platinum-
gold/aerosol (Pt15, Au85), 0.43 g. Platinum-gold/ aerosol (Pt76, Au24),
0.43 g. (From Foger and Anderson, 1979.)
main reduction peak, corresponding to rereduction of both Cu and Ni. In-
teractions of Pt with Ge and Re on y-Al2O3 have also been studied (Mc-
Nicol, 1980). A calcined 0.375 wt% Pt 0.25 wt% Ge/y-AI2O 3 reforming
catalyst showed Pt4+ to PtO reduction at 553 K and Ge4+ to Ge2+ reduction
at 873 K. Oxidation-stat e changes were calculated from the H2 uptake per
metal atom. Rereduction after reoxidation showed both Pt and Ge reduction
occurring below 553 K and only a small residual peak at 873 K. H2 chemi-
sorption after interruption of the TPR cycle showed that the H2 uptake on
Pt was diminished in concert with the onset of Ge reduction. This result
was interpreted as a coating of the Pt surface by Ge.
Temperature-P rogrammed Oxidation: Partial oxidation over mixed-oxide
catalysts often involves an oxidation-redu ction sequence in the surface layer.
Temperature-p rogrammed reaction is applicable to the study of the surface
redox properties and has been used to advantage to study reoxidation of
prereduced surfaces. Miura et al. (1975) and Uda et al. (1980) found two
reoxidation peaks for bismuth molybdate and associated the higher tempera-
ture ( 600 K) peak with catalyst activity. In the latter study, Auger
electron spectroscopy was used to assign the low-temperatu re peak to Mo4+
to Mo6+ conversion and a partial reoxidation of the bismuth. The high-
temperature reoxidation, necessary for conversion of propylene to acrolein,
completed the conversion of bismuth to Bi3+.
The !ability of sulfur in hydrodesulfuri zation catalysts is also amenable
to temperature-pr ogrammed studies. Nag et al. (1980) have shown a
224 Delgass and Wolf
correspondence between activity and decreasing temperature of H 2s appear-
ance in an HrHe stream passing over a sulfided catalyst.
Temperature-Programmed Reaction: These studies can include decompo-
sition of adsorbed gases or surface complexes, reaction of adsorbates or
reactive surface layers with gas-phase reactants, and reaction of coadsorbed
species.
Falconer and Wise ( 1976) used temperature-programmed methods to study
hydrazine and ammonia decomposition on Ir/Al2O3. The similarities in nitro-
gen evolution from the N2H2 and NH3 dosed surfaces suggested that the
N - N bonds are broken in N 2H 2 decomposition. Preadsorbed oxygen was
found to shift the N 2 desorption peak dramatically.
CO /H 2 reactions have been a focal point for many TPR studies. Zagli
et al. ( 1979) examined the temperature response of coadsorbed CO and H 2 ;
and H2 reaction with preadsorbed CO on supported nickel catalysts. Meth-
ane desorbed in a temperature range much narrower than that for CO de-
sorption. Water desorbed in the same temperature range. CO2 adsorption
was found to be activated and dissociative on Ni/SiO2. Temperature program-
ming of adsorbed CO2 in hydrogen gave methanation behavior identical to
that for CO (Falconer and Zagli, 1980).
McCarty and Wise ( 1979) deposited carbon on Ni/Al2O3 by CO dispro-
portionation at 550 K and studied its temperature-programmed reaction in
hydrogen. This method is termed temperature-programmed surface re-
action (TPSR). They observed methane production at room temperature as
well as in the region expected from the CO /H2 results. Even .more carbon
reactive at room temperature was found in TPSR on Ru/SiO2 (Low and Bell,
1979). Both studies showed that thermal aging of the carbon reduces its
reactivity.
Wolf and Kaul (1985) have developed a technique that combines tempera-
ture and concentration programming with transient FTIR spectroscopy.
With its added control and observation of important variables, this technique
has proven to be a powerful tool for studying catalytic reactions under
transient conditions.
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4
Diffusion-Reaction Interactions
in Catalyst Pellets
DAN LUSS University of Houston, Houston, Texas
INTRODUCTION
The reactants within a porous catalytic pellet are consumed by chemical re-
actions and replenished by transport processes. Competitive kinetic and
transport rate processes affect the observable rate and selectivity of a
catalyst. The engineering implications of this interaction between the diffu-
sional transport and chemical reactions were pointed out first by Damkonler
(1937), Zeldovich (1939), Thiele (1939), Wheeler (1951), and Weisz and
Prater ( 1954). The most comprehensive review of the subject is the mono-
graph by Aris (1975).
A porous medium consists of a complex matrix of many interconnected
channels of v·arying diameters and lengths, through which the reactant
species have to diffuse in order to reach the active catalytic sites. Ob-
viously, accurate geometric models of a porous structure cannot be devel-
oped. A proper analysis of the performance of a catalyst requires use of
a reasonable, simplified model which incorporates the essential chemical and
physical properties of the pellet. This is usually accomplished by use of
a single-phase pseudohomogeneous model. This crude representation elimi-
nates the distinction between the solid and fluid phases within the pellet
and simplifies considerably the prediction of most properties which are of
engineering importance.
We describe here methods of predicting the impact of the coupling be-
tween the chemical and transport rate processes on the activity and selectiv-
ity of porous catalytic pellets. This information is essential for the rational
selection, testing, development and application of catalysts. We start with
a review of the rate of transport within and to porous materials.
TRANSPORT WITHIN AND TO POROUS MEDIA
Transport of Gases Within Porous Media
There exists at present no flux relation with a completely sound theoretical
basis capable of describing transport of gases in porous media over a wide
range of pore sizes and pressures. A comprehensive review of the subject
239
240 Luss
can be found in the monograph by Jackson ( 1977). Existing transport
models, which relate the flux to local gradients in the compositions, pres-
sure, and temperature, assume that a porous medium can be described
either as a matrix of interconnected channels or as an assembly of station-
ary dust particles dispersed in the gas.
Flux models for capillary networks are naturally based on known trans-
port laws for a single capillary. Molecular-wall collisions is the mechanism
responsible for transport within an isothermal, isobasic, narrow capillary,
whose diameter is small in comparison with the mean free path of the gaseous
species. The flux relation for this Knudsen flow is
DKA
RT grad PA (1)
r·
NA
2rp ( 8RT 5 2 ( 2)
DKA = 3 TIMA 3 rpuA
where PA is the partial pressure of species A and uA is the corresponding
average molecular velocity.
Gaseous diffusion is the dominant transport mechanism in a wide capil-
lary with a diameter much larger than the mean-free-path length. The
corresponding isobaric, isothermal fluxes satisfy the Stefan-Maxwell relations
n x.N. - x.N.
_p_ grad x. = ) 1 1 )
( 3)
RT 1 ~ D ..
i=l l]
i:fj
where Dij is the binary gaseous diffusion coefficient. According to the
simple kinetic theory of gases, the self-diffusion coefficient is obtained as
AU.
1
D .. = ( 4)
11 3
Very accurate predictions of binary diffusion coefficients can be obtained
from the Chapman -Enskog formula, which can be found in standard text
and reference books (e.g., Bird et al., 1960, pp. 504-513; Perry, 1973,
Chap. 3, pp. 230-234; Reid et al., 1977, pp. 548-564). n Stefan-Maxwell
relations may be written for an n-component mixture, but only n - 1 of
these are independent.
The viscous flow of a pure component substance through a circular
capillary satisfies the relation
2
rpp dp
N = ( 5)
8µRT dz
where µ is the viscosity of the gas.
A porous media may be considered to be a complicated matrix of inter-
connected channels. It is reasonable to speculate that if all the channels
Diffusion-Reaction Interactions 241
are small compared with the mean-free-path length, the local averaged flux
vector, which describes the flow per unit total cross section, is related to
the interstitial local average concentration gradient in the following way:
( 6)
The effective Knudsen diffusivity is defined as
(7)
Ep is the pellet void fraction, and <rp>, the mean pore diameter, is com-
puted as
<r > =
p
f
O
00
r f[ E(r ) ] dr ""'
p p p
2E
pbSg
(8)
where f[ E( rp)] drp is the fraction of the void volume with pores of radius
rp to rp + drp. The tortuosity factor, , , accounts for the tortous path
of the molecules in the porous medium and the varying pore cross section.
This empirical factor depends mainly on the porous material, its porosity,
and the method of preparation. The value of , is usually in the range 2
to 7. Wohlfahrt ( 1982) presented correlations of , for several types of
porous catalysts. The data for catalysts prepared from compacted powders
were correlated as
( 9)
where m depends on the porous material. Typical data and values of the
parameter m for several catalysts are described in Fig. 1. Additional data
were reported by Probst and Wholfahrt (1979). Feng and Stewart (1973) pre-
dicted that , should be about 3 for isotropic systems with no dead-end
branches.
It is reasonable to assume that the fluxes in a porous media, with pores
that are wide compared to the mean free path length, still satisfy the
Stefan-Maxwell relations if the binary diffusion coefficients are replaced by
effective diffusion coefficients
(10)
Omata and Brown ( 1972) pointed out that the tortuosity factor is not neces-
sarily the same for both Knudsen and molecular diffusion. However, with-
out detailed measurements, this is a necessary assumption.
Similarly, it is reasonable to expect that the forced flow through a
porous media satisfies the relation
N =
BoP ~
( 11)
µRT dz
242 Luss
Aff.( __
-----,------,------,----~o
m
._ t::. 0.70 V-qxide col. (S02 -oxid) 1
Y 0.85 Ni0-col. unsintered
._ x 0.95 corb.onyl-iron pellets. 5 μ.m ~!</~/
__ 2
+ 1.05 porous Ag. 65 μ.m ~•xf 2
//✓.• tn(E /T)
o
j
~ 1.10 boehemite, 90 μ.m /", ~ __ 3
D 1.60 porous boehmite 70μ.m / ~/
/
" ' 1.65 .., ""· " " ' " ~ - -4
- -5
'- - -6
-
'
-3
/
/(
/
-2
- fn (E/(2-E))
I
-I
- -7
FIGURE 1 Dependence of the tortuosity factor on the porosity for several
materials. (From Wohlfahrt, 1982.)
where the permeability of the medium, Bo, depends on the geometry and
structure of the pores.
A method of finding the flux relations in the intermediate situations,
where the three transport mechanisms may be of comparable importance,
was proposed by Mason and Evans ( 1969). They suggested that the rate
of momentum transfer by collision with the walls and among molecules
should be combined additively. This leads to a set of n independent equa-
D
tions for the diffusive fluxes N. :
l
ND D D
n x.N. x.N.
1
RT grad pi - --
e
l
+I: ] l l ]
(12)
Dki j=l D~.
l]
i=j
In the special case of a binary mixture, Eq. (12) reduces to
De
A
RT grad PA ( 13)
where
1 - (1 + O'.)XA
1 1
-= --+ (14)
De e e
A DKA DAB
Diffusion-Reaction Interactions 243
and
Cl. = ( 15)
Solving the n equations Eq. ( 12) gives
1 n
N~ = RT LG .. grad p. ( 16)
1 j lJ 1
-1
where the elements of Gij are those of the matrix F . The entries of F
are
x.
1
F.. = for i :f- j
lJ
D~.
lJ
( 17)
n x.
F ..
11
= --
1
e + :E _J_ for i = j
Dki j=l D~.
lJ
i:f-j
Mason and Evans assumed that the total flux is the sum of the diffusive
flux and viscous flow:
N. = N~ +
1 1
N':1 ( 18)
where
= (19)
Substitution of Eqs. (18) and (19) in Eq. (12) gives a relation for the
total fluxes:
N. n x.N. - x.N. x.B 0p
1 ]
RT grad pi
= _1_
e + :E 1 1 ]
+ 1
e
grad p ( 20)
Dki j=l D~. DkiµRT
lJ
i:f-j
An electrical analog of the additivity procedure proposed by Mason
and Evans is shown in Fig. 2. It is remarkable that identical additivity
rules are obtained by a rigorous analysis based on the dusty- gas model
(Mason et al. , 1967).
Figure 3 enables a rapid rough estimate of the dependence of the dif-
fusional regime on the average pore size and operating pressure. For
example, when the pore size is about 100 A, Knudsen flow is a dominant
mechanism for pressures below 5 x 105 Pa, while gaseous diffusion is the
main contributor for pressures above 5 x 106 Pa.
244 Luss
(ADD FLOWS)
NV
-1
"'
_J
~
a:_-, BULK
N
..__,.,
-0 -0 DIFFUSION
+z
§ VISCOUS
~ FLOW
a:.- IN
..__,.,
-0 -0
KNUDSEN
a:.-, ..
-0 -0
DIFFUSION
DIFFUSIVE
FLOW
FIGURE 2 Electrical analog for the additivity rules for the gaseous fluxes
according to the dusty-gas model. (From Mason et al., 1967.)
10,000 Bulk
diffusion
1,000
~
a,
E 100
0
0
a
a,
a. 10
t Typical
1 molecular
♦ s,ze
Pressure , Pascals
FIGURE 3 Transition between bulk and Knudsen diffusion for typical cata-
lysts. (From Andrew, 1981.)
Diffusion-Reaction Interactions 245
The isobaric flux relations are usually not applicable under reaction
conditions. The reason is that the set of isobaric fluxes through a porous
medium has to satisfy the Grahm relation,
n
:E N. /M. = 0 ( 21)
i=l 1 1
which is usually inconsistent with the stoichiometric requirement of
n
:E N.M. = 0
1 1
( 22)
i=l
Consequently, a pressure gradient usually exists in a porous pellet in
which a chemical reaction occurs. Although this pressure gradient may be
small, it may have an important influence on the species fluxes.
A very general transport model was formulated by Feng and Stewart
( 1973), who assumed that a porous medium may be represented by a closely
interconnected network of cylindrical pores and that the dusty-gas model
describes the flux in each pore with D~A, D~B, and B O having values ap-
propriate for a straight cylindrical pore of radius rp. Their model predicts
that if the pores are isotropically oriented, the torhtosity factor is inde-
pendent of pore size and surface diffusion is negligible, then
2
n x.<r > p
N. _E_"'"""
LJ g.. (r )grad p. - -1~p~ - grad p ( 23)
1 TRT j=l lJ p J 8µRT
where
g .. (r ) G .. (r )f[ ic:(r )] dr
lJ p l] p p p
{~
( 24)
2
r f[ic:(r )] dr
p p p
0
and Gij(rp) are the entries of the matrix G for a cylindrical capillary of
radius rp. Feng et al. (1974) have shown that the integrals in Eq. (24)
may be described rather closely by a two-term approximation even for
pellets with a wide pore size distribution. This avoids the need to com-
pute Gij for a wide range of rp and simplifies considerably the application
of this model. A major advantage of this model is that it incorporates
information about the structure of the porous medium into the determination
of the empirical transport coefficients. A comparison of the predictions of
this model with experimental data was presented by Feng et al. (1974).
For isobaric binary systems Eq. ( 23) reduces to Eq. (13) with
1 - ( 1 + a)x ]-1
______ A f[E(rp)] drp ( 25)
DAB
246 Luss
It is sometimes desired to compare the flux relations of the dusty-gas
model with those obtained using a pseudo-Knudsen diffusion coefficient.
Schneider ( 1976) suggested that when a single chemical reaction
k
L v.A. = 0
1 1
( 26)
i=l
occurs in a porous pellet, in which the total pressure gradient is negligible,
the following approximation should be used:
1
v. k V.x. - v.x. n x.
L L
1 1 l J 1 1
= --+ + V. i = 1, 2, k
D.
1
e e
Dki j=l D:.
l]
1
j=k+l D:.
1]
'
( 27)
k V.
-
1
= -x.L _]_
i = k+l, n
D: 1
1 j=l D:.
l]
'
Wakao and Smith ( 1962) developed a completely predictive model for the
binary, isobaric flux in compressed powder catalysts which have a bimodal
pore size distribution. They refer to the small pores within the powder
particles as micropores and to the interstices between the particles as
macropores. Wakao and Smith assume that the one-dimensional flux con-
sists of three contributions: (a) flux through macropores having a radius
of ra, (b) flux through micropores which have a radius of ri, and (c)
flux through a series of micropores and macropores. They denoted the
Knudsen coefficient and void fraction corresponding to the macro and micro-
pores by DKAa, DKAi, Ea, and q, respectively. Their model predicts
that
De = E2D + (1 - E ) 2D. + 4E (1 - E {.!_+
_l ]-1 ( 28)
A a a a 1 a a D D.
a 1
where
2 2
DAB DAB Ei. / (1 - Ea)
D
a = 1 - axA + DAB/DKA
D. =
1 1 - axA + DAB/DKA.
( 29)
a 1
The main advantage of this model is that it contains no adjustable param-
eters. Its main deficiency is that it is not clear how to incorporate into
the model pressure gradients (which are usually present in reactive sys-
tems) or how to generalize it for multicomponent mixtures.
Several steady-state and transient experimental techniques have been
developed for determining the effective diffusivity of porous pellets and
of the parameters appearing in the transport models. The most commonly
used steady-state method is that in which either a cylindrical (Wicke and
Kallenbach, 1941) or spherical (Weisz, 1957) pellet in a special cell is
exposed to two gas streams having the same pressure and temperature
but different compositions. The net diffusive flux is determined from the
change in the composition of the gas streams.
Diffusion-Reaction Interactions 247
For a binary mixture the one-dimensional flux satisfies the relation
(Satterfield, 1970, p. 44).
e e
1 (1 + a)xA (L) + DAB /DKA
== ln ( 30)
RTL(l + a)
1
where
( 31)
Noting that
Hp ( 32)
e e
the values of DKA and DAB are determined by measuring the flux at
several pressures. This technique is very sensitive to leaks next to the
wall and this prevents its use at high temperatures.
The most widely used transient technique is the pulse response of either
a chromatographic column ( Cerro and Smith, 1970; Haynes and Sarma, 1973)
or a single pellet (Suzuki and Smith, 1972; Dogu and Smith, 1976). The
main advantages of this method are that it can be applied to particles of
arbitrary shapes, it accounts for the contribution of dead-end pores, and
it can be used to measure the diffusivity at high temperatures and pressures.
Its main disadvantage is that the interpretation of the data is based on
simplifying assumptions which are not always valid.
The chromatographic technique consists of measuring the first and
second moments of a tracer that has been injected into a packed bed of
porous pellets at several different flow rates of the inert carrier gas. The
theory used to interpret the measurements is described in detail by Cerro
and Smith (1970). The accuracy of this method is higher for adsorbable
gases and improves with increasing particle size and bed length and with
decreasing effective dispersion in the bed.
Experimental measurements and theoretical predictions of gaseous trans-
port through porous media are usually dominated by the flux through large-
diameter pores. However, most catalytic sites are present in micropores,
and it is questionable whether the effective diffusivity is adequate for
characterizing the transport under reaction conditions.
Surface Diffusion
Most gases are adsorbed to some extent on solid surfaces. The migration of
the adsorbed species is referred to as surface diffusion and is particularly
important for porous materials with large surface area and for strongly
adsorbed species. The surface diffusion fluxes combine additively with the
gaseous diffusive fluxes and therefore can be computed separately. The
surface diffusive flux may be determined from a Wicke-Kallenbach diffusion
cell operating at low pressures, so that the gaseous diffusion is of the
248 Luss
Knudsen type. A separate measurement with a nonadsorbing gas is used
to determine the contribution of this Knudsen flow to the total flux.
Assuming that the surface and bulk concentration satisfy the equilibrium
relation
( 33)
the surface diffusion flux may be expressed as
s
DApbS o-
= ___i:,__ grad Cs ( 34)
T A
For sufficiently low gas concentration, the adsorption equilibrium approaches
linearity and Eq. ( 34) simplies to
Ds p S
= A b g K (T) grad CA ( 35)
T A
where the adsorption equilibrium constant, KA (T), usually decreases with
increasing temperatures according to an Arrhenius temperature dependence
( 36)
For low surface coverage the diffusivity may be computed from the site
hopping mechanism,
s :\ 2 :\ 2v ( EAd)
DA = 2T* = -2- exp - RT ( 37)
where :\ is the average hopping distance, T* the lingering time, and v the
vibrational frequency of the adsorbed molecules. Combining Eqs. ( 35),
( 36), and ( 37) gives
( 38)
Thus the surface diffusive flux increases with decreasing pore size (increas-
ing Sg) and may either increase or decrease with temperature, depending
on the sign of E~ - E1.
The surface diffusivity usually depends on surface coverage and hence
on the pressure and composition of the gas phase. Higashi et al. (1963)
predicted that
Ds(e = O)
= ( 39)
1 - e
Diffusion-Reaction Interactions 249
where e is the fractional surface coverage. This relation properly predicts
an increase in the diffusivity with surface coverage, but is not expected to
be valid for e > 0. 9. Yang et al. (1973) derived a modified relation for
high values of e. Sladek et al. (1974) have shown that surface diffusivity
depends on the strength of the adsorption and can be correlated with the
differential heat of adsorption.
The surface diffusivity of physically adsorbed molecules at room tempera-
ture is in the range ,1i0-3 to 10-6 cm2/s. Measured values were reported by
Barrer ( 1967, p. 557), Reed and Butt ( 1971), Schneider and Smith ( 1968),
and Sladek et al. ( 1974). In most gas-solid reaction surface diffusion is not
an important factor.
Diffusion in Zeolites
Many important industrial catalysts consist of small aluminosilicate ( zeolite)
crystals incorporated in a porous matrix. These crystals have narrow ( 5
to 10 A diameter) structured channels through which the reactants and
products have to migrate. The diameter of the pores is often close to the
molecular dimension of the reacting species. Therefore, small differences
in the shape of a molecule can have a large impact on the migration rate,
and this can be utilized to create large differences in the catalytic selectivity
of the catalyst. The diffusional processes in zeolites can affect significantly
the selectivity of catalysts as only molecules which are smaller than a
critical size can enter the pores and only products smaller than this size can
leave the pores. Moreover, the restricted size of the cavities prevent forma-
tion of large intermediates. Consequently, by a proper design of the pore
size it is possible to engineer a shape selective catalyst which will produce
a desired species at a concentration which exceeds significantly the equilib-
rium concentration. This will occur if the desired product can leave the
cavity, at which it is being formed, at a much faster rate than the other
products. For example, when xylene is produced by the alkylation of
toluene with methanol on a conventional catalyst, three different isomers
of xylene are obtained. When the same reaction is carried out over certain
zeolites, the product is essentially pure para-xylene, as the effective dif-
fusivities of the ortho and meta isomers are smaller than those of the para
isomer by three orders of magnitude.
It is customary to assume that the rate of migration in zeolites can be
described by an activated diffusional process so that
e
NA = - DA grad CA ( 40)
even though this is probably not the proper functional dependence. The
reason is that the movement in the narrow pores of the zeolite is definitely
not random, as it should be for a diffusional process, as the potential
energy of a migrating molecule must be influenced by the attractive forces
of the lattice at least when they pass through the openings between the
cavities. Moreover, in the case of counterdiffusion the flux in one direction
may be strongly hindered by that in the opposite direction, even though
this effect is not predicted by Eq. ( 40).
The values of the effective diffusivity are usually determined by gravi-
metric sorption experiments [see, e.g., Goring (1973)]. Riekart ( 1971)
presented a theoretical analysis of this method and its pitfalls. Eberly
250 Luss
( 1969) used the chromatographic technique to measure the diffusivities of
various gases in zeolites. A review of the various methods used to de-
termine the effective diffusivity in zeolites was presented by Eberley ( 1976).
The reported values of the effective diffusivities are in the wide range
10-6 to 10-14 cm2/s. The temperature dependence of these diffusivities is
stronger than that for bulk diffusion and is usually described by an Arrhen-
ius temperature dependence. Goring (1973) found that the activation energy
for diffusion of various hydrocarbon species varied in the range 10 to 60
kJ /mol.
There exists at present no reliable method for predicting the effective
diffusivity in zeolites. The difficulties involved in the development of such
a theory are brought out by Fig. 4, which describes the dependence of the
diffusivity in a potassium T zeolite on the carbon chain length of normal
paraffins. The experiments by Goring ( 1973) show that an n-dodecane
molecule moves through the zeolite lattice at about 140 times the velocity of
an n-octane molecule, despite the difference in size. Thus the interactions
of the molecules with the zeolite lattice and cations must be the major factor
affecting the diffusion, while molecule-molecule interactions are likely to be
weak and determine mainly if a given path is free or blocked.
u
I \'
Cl)
\
en
\
"''Eu
\ I
\ I
c v-- \ I \
-
Cl)
·;:; I
..::::
I
u
Cl)
0
I\\
I
I \
C
·en
0
i
-~ ~ - ·-
H
-
I
.2
ci \ I
\ i/
\ w
10·13
0 I 2 3 4 5 6
\_
7
~
8 9 10 II 12 13 14
Carbon Number of n -Alkane
FIGURE 4 Diffusion coefficients of n-alkanes in potassium T zeolite at
300°C. (From Goring, 1973.)
Diffusion-Reaction Interactions 251
Diffusion in Liquid-Filled Pores
The transport in liquid-filled pores is usually described by a Fickian diffu-
sion relation with an effective diffusion coefficient
EDAB
= ( 41)
T
The bulk binary diffusion coefficient is computed by one of the standard
available correlations (Reid et al., 1977, pp. 567-595). Surface diffusion
may become important with strongly adsorbing molecules, and this contribu-
tion has then to be added to that in the pores. Komiyama and Smith ( 1974)
described a case in which surface diffusion was the main contribution to
the species flux.
In certain applications the sizes of the diffusing molecules and the pores
are of the same order of magnitude. The interaction between the walls and
the molecules tends to decrease the effective diffusion coefficient, which has
to be computed by the equation
( 42)
T
The equilibrium partition factor, KP, is the ratio between the concen-
tration of species A inside and outside the pore and depends on A, the
ratio of pore to molecule diameter. For small solvent molecules, Kp satisfies
the relation (Ferry, 1936)
K = (1 - >..) 2 (43)
p .
When either the solute or the solvent adsorb on the surface Kp may be
much smaller than the value predicted by Eq. ( 43). For example, Satter-
field et al. (1973) measured a partition factor of 1/ 183 for A of 0. 38.
The resistance caused by drag exerted on the moving molecules by the
walls is expressed through the drag coefficient,
K = (1 - A)m+ 2 (44)
r
where m is between O and 2. Combining Eqs. ( 42), ( 43), and ( 44) gives
ED AB (1 - A) 4+m
e
DAB= ( 45)
T
The values of Kp and Kr are strongly affected by the shape of the
molecule and any interaction between the surface and either the solute or
the solvent. Thus Eq. ( 45) is just a rough approximation for the influence
of A on the restricted diffusion coefficient. Recent experimental measure-
ments and correlations of restricted diffusion coefficients were presented by
Chantong and Massoth ( 1983) and Baltus and Anderson (1983).
252 Luss
Effective Thermal Conductivity
Intraparticle temperature gradients may have an important influence on the
activity and selectivity of porous catalysts. A small number of experimental
measurements of the effective thermal conductivity of pellets have been re-
ported in the literature and a compilation of most of them can be found in
Satterfield (1980, pp. 344-348). The data indicate that the effective con-
ductivity is usually rather insensitive to changes in the porosity, pore size
distribution, and the impregnated metal. A comparison of different methods
for determining the effective thermal conductivity was presented by Hoffman
et al. (1978).
At present there exists no general theory capable of predicting the ef-
fective conductivity of porous pellets as the mechanism of heat transport is
rather complex. Butt (1965) generalized the random pore model of Wakao
and Smith (1962) and developed a theory that is capable of correlating the
effect of changes in the gas temperature and porosity on the thermal con-
ductivity. Fortunately, the temperature profile within most catalytic pellets
is rather uniform, so that the uncertainty concerning the value of the con-
ductivity does not have an important impact on our ability to predict the
performance of porous catalysts.
Mass and Heat Transfer Coefficient
A mass transfer coefficient is used to compute the flux of species between
the ambient fluid and the surface of the catalyst. For a binary system
( 46)
where x is the bulk-flow correction factor, which accounts for the influence
of the convective flux. This factor is equal to unity for equimolar counter-
diffusion and is close to unity for dilute mixtures. In applications the factor
is often assumed to be unity. Its exact value is given by the relation
(Geankopolis, 1972, p. 254)
X = ( 47)
where
( 48)
and (RN - XA)LM is the ln mean of RN - XAs and RN - XAb. The special
case of diffusion through a stagnant film Eq. ( 47) reduces to
The prediction of mass transfer coefficients for multicomponent mixtures is
quite complex, as the coefficients depend on the concentrations of the vari-
Diffusion-Reaction Interactions 253
ous species in the mixture. In general, approximate methods must be used
in this case, and a survey of the subject is presented in the monograph
by Cussler (1976, Chap. 9).
The mass and heat transfer coefficients between the pellet and the
ambient fluid are determined by empirical correlations, as the processes are
too complex to analyze in detail. It is customary to correlate the data in
terms of j factors, which depend on the Reynolds number, the geometry of
the pellet, and the boundary conditions. These factors are defined as
k 2/3
( 50)
jD = : (pD:B)
( 51)
Dwivedi and Upadhay (1977) found that the following relations represented
well most of the available data about mass transfer between a fluid and pel-
lets in packed beds:
{ 1. 1068Re-O. 72 for Re< 10 ( 52)
"bjn =
0. 4548Re -O. 4069 for Re> 10 ( 53)
where
upd
__ p
Re = ]J
( 54)
The heat flux to a particle satisfies the equation
( 55)
This relation is useful for predicting the temperature difference between
the surface of a pellet and the ambient fluid. The value of the heat trans-
fer coefficient is computed from the jH factor for all cases in which the
heat exchange by radiation can be neglected. Experimental data show that
the values of jH and jD are essentially equal (Gupta and Thodos, 1962).
IMPACT OF MASS TRANSPORT LIMITATIONS
Determination of the Effectiveness Factor
The reactants within a porous catalytic pellet are consumed by the reaction
and replenished by diffusion. When the time constant of the diffusion is
small relative to that of the reaction, the concentration of the reactant is
rather uniform throughout the pellet. However, when the time constant
of the chemical reaction is small compared to that of diffusion, the concen-
tration of the reactant within the pellet is expected to be lower than that
254 Luss
close to the exterior surface, so that the average reaction rate (per unit
volume of catalyst) depends on the diffusion-reaction interaction. Thus
we expect the observable (or net) reaction rate to depend on the ratio be-
tween the time constants of the chemical reaction and the diffusion within
the pellet.
The overall impact of the diffusional resistances is usually assessed by
computing the effectiveness factor, n, which is defined as the ratio between
the observed reaction rate to that obtained when neither concentration nor
temperature gradients exist between the ambient phase and any point with-
in the pellet. Clearly, the larger the deviation of the effectiveness factor
from unity, the more important is the influence of the transport resistances.
A comprehensive survey of the literature about the effectiveness factor can
be found in the monograph by Aris (1975).
We illustrate the procedure of computing the effectiveness factor by con-
sidering the case of a first-order, isothermal, irreversible A -+ B reaction
occurring within a spherical catalytic pellet. For the sake of compactness,
we denote from now on by C and De the concentration and effective dif-
fusivity of species A. The concentration of the reactant satisfies the
equation
De ~(r2 dC) - kC = 0 ( 56)
2 dr dr 1
r
C = C at r = R ( 57)
s
dC
0 at r = 0 ( 58)
dr
Solving Eq. ( 56) subject to Eqs. ( 57) and ( 58) we get
sinh ¢s
( 59)
s sinh ¢
where
s= r
-
R
¢ = R ~IT ( 60)
"De
The parameter ¢ is defined as the Thiele modulus and is the square
root of the ratio between the time canstant for diffusion ( TD = R2 /De) and
that for the chemical reaction [TR = CAslr(CAs) = 1/k]. The Thiele modu-
lus is independent of the surface concentration of the reactant only in the
special case of a first-order reaction. The inset in Fig. 5 describes the
concentration profiles for several values of the Thiele modulus. For ¢
smaller than about 0. 3 ( 'D < 0, l'IR) the concentration throughout the pellet
is close to that at the surface. This region is referred to as the kinetic-
controlled regime. For large ¢ ( TD > 10,R) the concentration decreases
exponentially with distance from the surface. We refer to these conditions
as the diffusion-controlled or diffusion-limited regime. Here the reaction
rate in the interior of the catalyst is rather low compared to that at the
exterior shell. The region close to ¢ = 1 or 'D = 'R is referred to as
the intermediate region.
Diffusion-Reaction Interactions 255
1.0 - - - - - - -
0.5
0.2
0.1
0.05
0.02
0.01 '----'--~~~-~-~-~~~-~-1~00
0.1 I 10
cp = R..,/k71)e
FIGURE 5 Dependence of the effectiveness factor on the Thiele modulus for
a first-order reaction in a spherical pellet. Inset describes corresponding
concentration profiles.
The effectiveness factor for this case is given by the expression
n = 23 ( ¢ coth ¢ - 1) (61)
¢
The logarithmic graph of n versus ¢ is shown in Fig. 5, As expected,
for small ¢ the impact of diffusion is small and n is close to unity. For
large ¢ diffusional limitations reduce significantly the observed reaction rate
and n approaches asymptotically 3/¢.
The effectiveness factor has been computed for pellets of various geo-
metrical shapes (Aris, 1975, Chap. 3). Fortunately, a rapid estimate of
the value of n for particles of complex geometries can be obtained by
capitalizing on the fact that if Vp /Sx is used as the characteristic length
of a generalized Thiele modulus A, then the graph of n versus A is rather
insensitive to changes in the geometry (Aris, 1957). Thus the graph for
the spherical pellet can be used to predict the value of n for pellets of
other geometries. The adequacy of this approximation is illustrated by Fig.
6, which compares the n versus A graph for a first-order reaction in a
sphere with those for a semi-infinite slab and cylinder.
Similarly, by use of a properly normalized Thiele modulus,
Vr(C)[
A = p Sx s 2De lq C ]-0.
s r(C) dC
5
( 62)
one obtains a graph of n versus ¢ which is independent of the form of the
kinetics rate expression for either large or small A (Aris, 1965; Bischoff,
1965; Petersen, 1965). For an nth-order reaction, the normalized Thiele
modulus is
256 Luss
1.0
0.8
f:"
0.6
iu Slab
if 0.4
en
en Spher cal pellet
Cl)
C
Cl)
-~ lnfinit C ind r
u 0.2
J!
w
0.4 0.6 1.0 20 4.0 6.0 100
FIGURE 6 Dependence of the effectiveness factors for slab, cylindrical,
and spherical pellets on the generalized Thiele modulus. (From Petersen,
1965.)
(n + l)kCn-l
VP s
A ( 63)
sX
and Fig. 7 shows that the n versus qi graph for a first-order reaction ap-
proximates closely those of reactions with different orders.
When the reaction rate is a nonmonotonic function of the concentration
of the limiting reactant, such as the Langmuir-Hinshelwood rate expression
1.0
8
6
f:" .5
ls .4
0
~ 3
en
en
Cl)
C 2
Cl)
tu
-w
Cl)
01
0.1 05 1.0 5 10
FIGURE 7 Dependence of the effectiveness factor on the generalized
Thiele modulus for several nth-order reactions.
Diffusion-Reaction Interactions 257
r(C) = kC (64)
(l + KC) 2
the effectiveness factor may exceed unity for some intermediate values of
the Thiele modulus (Roberts and Satterfield, 1966). This occurs when the
surface concentration exceeds the value corresponding to the maximum rate.
In these cases a reduction in the concentration of the reactant by the dif-
fusional limitations can increase the reaction rate over that corresponding
to the surface concentration and the corresponding n may exceed unity.
For certain rate expressions the interaction between transport and chemical
rate processes can lead to steady-state multiplicity over a bounded range
of the Thiele modulus, so that several values of the effectiveness factor
may be obtained for certain kinetic parameters and pellet dimensions. This
behavior is rather uncommon and it can be proven (Luss, 1971) that it can-
not occur for any rate expression that satisfies the condition
(Cs - C) (- ~~ ) < r( C) for all O < C < Cs ( 65)
where r(C) is the rate of consumption of the reactant A. For example,
condition (65) is satisfied by the rate expression defined by Eq. (64) for
all C < Cs if and only if KCs < 8. Clearly, condition ( 65) is satisfied for
any rate expression that is monotonically increasing function of the con-
centration of the reactant.
Many repetitive calculations of the effectiveness factor need to be car-
ried out in computer simultations of packed-bed reactors and parameter es-
timation of rival rate expressions. Several methods have been developed
for getting a rapid approximation of n. These include the single-point
collocation method of Stewart and Villadsen ( 1969) and several methods that
capitalize on knowledge of the asymptotic value of n (Churchill, 1977; Wedel
and Luss, 1980; Gottifredi et al., 1981a,b).
Several investigators computed the effectiveness factor using the dusty-
gas model to describe the transport within the pellet (e.g., Abed and
Rinker, 1973; Wong and Denny, 1975). It is of interest to know the differ-
ence between the results obtained using this model and that obtained using
a pseudo-Knudsen diffusion model. Unfortunately, this difference depends
on the value chosen for the effective diffusion coefficient and there exists
no unambigious way of predicting its value. One possible scheme is the
use of Eq. ( 27). The few available computations for gaseous mixtures seem
to indicate that use of an effective Knudsen diffusion coefficient usually
gives a reasonable approximation to the effectiveness factor computed by
the dusty-gas model. This is probably due to the fact that diffusion co-
efficients of most gases are of similar magnitude. However, this point re-
quires further analysis.
Many catalytic reactions involve a change in the number of moles and
hence in volume. Rigorous calculations of the effectiveness factor for
such cases are rather cumbersome, as they require use of the dusty-gas
flux relations to account for the changes in both the composition and total
pressure within the pellet. Calculations by Kehoe and Aris (1973) indicate
that ignoring the momentum balance and total pressure gradient does not
usually introduce a large error in the value of the effectiveness factor.
Weekman and Goring ( 1965) computed the effectiveness factor for sym-
metric pellets in which the reaction A + mB occurs, ignoring the influence
258 Luss
of the pressure gradient on the transport within the pellet. This simplified
model enables a rapid computation of the ratio between the effectiveness
factor that accounts for the volume changes (n') to that which ignores it
( n). Typical results for a second-order reaction are shown in Fig. 8.
They indicate that when the reaction decreases the number of moles (m < 1),
the bulk flow toward the center of the pellet increases the effectiveness fac-
tor above that obtained when the volume change is not taken into account
(i.e., n' > n). On the other hand, when the reaction increases the num-
ber of moles (m > 1), the outward bulk flow causes n' to be smaller than
n. The influence of the change in volume is decreased by the presence of
inerts (i.e., by a decrease in xAs, the mole fraction of the reactant at the
surface).
When the influence of external mass transfer is not negligible, the
boundary condition on the surface of the catalyst becomes
( 66)
where n is a vector normal to the surface. For a symmetric pellet the sur-
face concentration is uniform and it can be shown that for a first-order
reaction (Aris, 1975)
1 1 /1.2
n
==
nD(/1.)
+ --
Bi (67)
m
1.6
A-mB
Second-order reaction
1.4 spherical pellet
1.2
T)'
1.0
7i 0.5
0.8
0.6
Ci)
10
0.4
-I 0 2 3
Volume Change Modulus, (m-1) XAs
FIGURE 8 Dependence of the ratio n' /n on the volume change modulus for
a second-order reaction. (From Weekman and Goring, 1965.)
Diffusion-Reaction Interactions 259
where
( 68)
Bi
m
and nn (A) is the effectiveness factor for the case of negligible external
mass transfer resistance (i.e., when Bim is infinite). It follows that the
effectiveness factor is the sum of an internal resistance, which is the re-
ciprocal of n in the absence of an external mass transfer resistance, and
an external transport resistance of A 2/Bim. Note that in the presence of
a mass transfer resistance, the asymptotic value of n for large A is Bim / A 2
rather than 1 / A •
Aris (1975, Sec. 3. 9) has proven the remarkable result that Eq. (67)
is valid for reactions with arbitrary kinetic expressions for large values
of the Thiele modulus. Yortsos and Tsotsis (1982) have generalized this
result for pellets with nonuniform catalytic activity.
In most practical problems Bim exceeds 10. Thus, according to Eq.
( 67), the value of n may be affected by the external mass transfer re-
sistance only when nn is considerably smaller than unity. This observation
led to the development of a rule of thumb that it is possible to encounter
cases in which the external mass transfer resistance is negligible while the
internal diffusional resistance is appreciable, but the converse does not oc-
cur. Note that this conclusion would not be valid if Bim could attain small
values.
In trickle-bed reactors one has often to compute the effectiveness fac-
tor of a liquid-filled catalytic pellet, of which only a fraction f of the ex-
terior surface is wetted by the liquid. Tan and Smith ( 1980) and Mills
and Dudukovic ( 1980) have shown that the corresponding effectiveness fac-
tor for a first-order reaction can be approximated by the relation
1 - f
n= + ( 69)
where CL is the concentration of the reactant in the bulk fluid, CL* the
liquid phase concentration of the reactant in equilibrium with the bulk gas
concentration, and Biw and Bin the mass transfer Biot numbers for the wet
and dry parts of the pellet, respectively. Herskowitz and Smith ( 1983) pre-
sented a comprehensive review of the influence of wetting on the effective-
ness factor of liquid-filled catalysts.
Diffusion Disguise of Intrinsic Kinetics
Kinetic expressions are based on experiments in which the rate is measured
as a function of the concentration of the reactants and the temperature. If
the influence of the diffusional resistance on the observed rate is not taken
into account, erroneous or disguised rate expressions are obtained.
The temperature dependence of the rate constant can usually be de-
scribed by the Arrhenius relation
k(T) = k(To) exp [i ( Tlo - ½)] ( 70)
260 Luss
When the rate expression is of a separable form, that is,
r(T,C) == k(T)f(C) ( 71)
the apparent or observed activation energy is determined from the slope of
the natural logarithm of the measured rate at a specific conversion against
the reciprocal of the absolute temperature, that is,
d ln r
m
E == -R ( 72)
a
The measured reaction rate satisfies the relation
rm == k(T)f(C)n ( 73)
Differentiation of Eq. ( 73) and substitution in Eq. ( 72) gives
E == E + O. 5 d ln 11 (E + R d ln De) ( 74)
a d In <jJ dT-1
In the kinetic-controlled regime (small <jJ), the effectiveness factor is es-
sentially independent of the Thiele modulus and according to Eq. ( 74) the
apparent and intrinsic activation energies are equal. In the diffusion-
controlled regime(¢> 3), d ln 11/d ln <jJ + -1, so that
e
d ln DA
Ea == 0. 5E - 0. 5R ( 75)
dT-l
The effective diffusivity is proportional to Tm, so that the last term on the
left-hand side of Eq. (75) is equal to 0. 5mRT, which is usually very small
in comparison to 0. 5E. We conclude that the apparent activation energy in
the diffusion-controlled regime is about half its intrinsic value. When the
external mass transfer resistance is not negligible, d ln T) /d ln <jJ + - 2 for
large <jJ, so that
E ( 76)
a
In this case the apparent activation energy is very small and is independent
of the intrinsic activation energy.
We conclude that transport intrusions mask and decrease the observed
activation energy. The reason for this effect is that increasing the tempera-
ture decreases the time constant for the chemical reaction and the effective-
ness factor. This, in turn, decreases the sensitivity of the reaction rate
to changes in the temperature. This behavior is clearly illustrated in Fig.
9, which describes the logarithm of the rate of cumene cracking at various
temperatures for catalysts of different sizes (Weisz and Prater, 1954). The
Diffusion-Reaction Interactions 261
u
Q)
(/)
-9/ . O Experimental Values
'E
~
u
10-G
t,
fr
·029
~
c,,, 0
0 :t "·Os ' "o,
"', .....
0:: ,3 C
..... 0
C:
' 'o ....
.Q
u ' "o, .... ,o
....
0
Q)
0:: fr~' 1?5
'
"o, 'o'~'
..... .....
Ctr, O'--...
"'O
', ''
~ '
:::,
(/)
---- ---- 'o :
0
Q)
',,
~ 10- 7 0 ----
----
----
420°c 400°C 380°C
I I I
13 1.4 1.5 1.6
Temperature - - 1- xl0 3
T° K
FIGURE 9 Influence of temperature and particle size on the cracking rate
of cumene on Si0 2-A1 2o 3 catalyst. (From Weisz and Prater, 1954.)
data show that the slope of the graphs, or equivalently the apparent activa-
tion energy, decreases by a factor of about 2 as the particle's radius in-
creases from ·o.0056 cm to 0.175 cm.
Diffusional intrusions may also disguise the functional form of the rate
expression. Consider as an illustration the case of an nth-order reaction
for which the external resistance is negligible. Here
r m == ( 77)
The slope of the logarithmic graph of the observed rate against the concen-
tration of the reactant is defined as the apparent reaction order n':
d log r
log De )
(n _ 1 _ d
m == n + .!_ d log n
n' == ( 78)
d log C 2 d log A d log C
It follows that the apparent and true orders are equal if the experi-
ments are carried out in the kinetic-controlled regime in which n is essen-
tially independent of A. In the diffusion-controlled regime the asymptotic
slope of d log n /d log A is -1 and the apparent order depends on the re-
lation between the concentration of the limiting reactant and the effective
diffusivity. When the changes in the concentration of the reactant do not
affect ne, Eq. (78) predicts that
I n + 1 ( 79)
n == - - -
2
262 Luss
Thus the apparent and true orders are different for all but first-order re-
actions. The diffusional intrusions disguise the true order and shift it
toward unity. For example, a second-order reaction behaves as if it is of
order 1. 5.
When the changes in the reactant's concentration are accomplished by
varying the total pressure of a gaseous mixture and if gaseous bulk diffu-
sion is the dominant mechanism, then
d log De d log De =
= -1 ( 80)
d log C d log p
Substituting Eq. (80) into Eq. (78) we get that for large A,
n' = ~ ( 81)
2
Thus in this case diffusional intrusions disguise the order of all but zero-
order reactions.
We conclude that it is essential to account properly for the influence of
diffusion to avoid pitfalls in the analysis and modeling of kinetic data.
Experimental Detection and Determination of
Diffusional Limitations
Several experimental methods exist for detecting diffusional limitations and
predicting the effectiveness factor. The most direct (but lengthy) method
consists of determining the isothermal reaction rate for pellets of different
sizes at a fixed mixture composition. The experiments are continued until
pellets of two different sizes have the same activity, which is assumed to
be the intrinsic one. The effectiveness factor for larger pellets is the
ratio between their activity and the intrinsic one. The experiments can be
carried out either in a differential reactor or a well-stirred heterogeneous
reactor or a recycle reactor.
This test is meaningful only if all the pellets have the same intrinsic
activity. This can be accomplished by crushing large particles to smaller
sizes. This method may lead to pitfalls when the pellets have a nonuniform
activity profile. For example, if a catalyst has a very narrow active ex-
terior shell and an inert core, cutting the pellets does not affect the ob-
served activity even if diffusion limits the rate in the exterior shell.
A more efficient method of determining 11 is based on the fact that if
an isothermal reaction is carried out in spherical pellets of two different
sizes, then
( 82)
It follows from Eq. (61) that for a first-order reaction the ratio between
the two observed rates satisfies the relation
3A l coth 3A l 1
(83)
3A 2 coth 3A 2 1
Diffusion-Reaction Interactions 263
The two equations ( 82) and ( 83) can be solved for A 1 and A 2, which in
turn can be used to compute 11 1 and 11 2 . The method is very sensitive to
experimental errors if both experiments are conducted in the diffusion -
controlled regime [i.e., when (rm)l/(rm) 2 "' R 2 /R1]. In this case addi-
tional experiments with smaller pellets need to be carried out. The advantage
of this method is that, in principle, two experiments suffice to determine the
effectiveness factor. However, to minimize the influence of inherent experi-
mental errors, it is preferable to conduct experiments with three or four
different particle sizes and determine the Thiele modulus and effectiveness
factor that fit best all the experimental data.
Equation ( 83) is rigorously correct only for a first-order reaction. How-
ever, when the generalized definition of the Thiele modulus is used [Eq.
( 62)] , the effectiveness factor is a rather insensitive function of the kinetic
expression if the rate is a monotonic function of the reactant's concentration.
Thus this method gives a reasonable estimate of 11 for many non-first-order
reactions.
Weisz and Prater (1954, p. 167) have shown that the effectiveness fac-
tor for an nth-order reaction could always be related to the parameter
b.
<P= (3V )2
_E_ ( 84)
sX
which contains only measurable quantities. They noted that for reactions
of order zero, one, and two, 17 exceeds 0.95 if <P is smaller than 6, 0.6,
and O. 3, respectively. Thus they suggested that <P < 1 be used as a
rapid diagnostic for the absence of important diffusional limitations. The
major advantage of this criterion is that it does not require any information
about the rate expression or the kinetic parameters. Unfortunately, this
useful criterion fails for rate expressions that are very sensitive to changes
in Cs. Using singular perturbations (Wedel and Luss, 1980), it can be
shown that 11 deviates from unity by less than 5% for a spherical pellet if
<P < O. 75/R'( 1) ( 85)
where R(CA/CAs) is a dimensionless normalized rate [i.e., R(l) = 1] and
R' is its derivative with respect to the dimensionless concentration CA/CA
s
Note that for a first-order reaction, R'(l) = 1 and Eq. (85) is essentially
equal to the Weisz- Prater criterion.
Horak ( 1967) suggested that 11 > 0. 9 if
cp < 6~ ( 86)
where ~ is the conversion for which the reaction rate is 0. 9 of r(Cs> · For
example, ~ is 0.1 for a first-order reaction, so that according to Eq. (86),
17 > 0. 9 if <P < O. 6, which is in close agreement with the Weisz-Prater
criterion (85). The agreement between the two criteria is not always close,
as illustrated by the reaction
CO 2 + C + 2CO
264 Luss
the rate of which satisfies the equation
r = (87)
1 + 4PCO + 50, 000P CO
2
For a feed of pure carbon dioxide at 1 atm, I; is equal to 0. 55 x 10-5 and
Eq. (86) predicts that n > 0. 9 only if <l> < 3. 3 x 10-5, while Eq. (85) pre-
dicts that n > 0. 95 only if <l> < 3. 75 x 10- 5 . Both predictions are much
smaller than the value of unity predicted by the Weisz-Prater diagnostic.
We conclude that (a) if <l> is larger than unity, diffusional limitations
definitely exist; (b) if <l> is much smaller than unity, diffusional intrusions
are absent; and (c) if <l> is slightly smaller than unity, knowledge of the
form of the rate expression is needed to decide if diffusional limitations
affect the observed rate.
The presence of diffusional intrusions may sometimes be detected by
changing the effective diffusion coefficient. This may be accomplished
when gaseous diffusion dominates by using reaction mixtures containing a
large excess of an inert diluent. If the same rate is obtained for mixtures
with inerts of widely different molecular weights, and hence binary diffu-
sion coefficients, it can be assumed that intraparticle diffusion is not limit-
ing the rate. This test cannot be used for nonisothermal reactions since
the difference in the inerts leads to differences in the heat transfer co-
efficients, and the difference in the pellet temperatures may mask the
results.
Koros and Nowak ( 1967) proposed to use as a diagnostic test for the
presence of diffusional limitations the fact that the reaction rate can be pro-
portional to the number of catalytic sites only in the kinetic regime. They
suggested to prepare catalysts with different number of active sites but
similar diffusional properties either by pelleti zing mixtures of catalyst parti -
cles with inert powder or by inpregnating the catalyst with different amount
of the active component. Certain reactions are structure sensitive, so that
their intrinsic activity depends on the crystallite sizes. Thus a failure to
satisfy this test does not always imply the presence of diffusional limitations.
A detailed discussion and illustration of the application of this test was pre-
sented by Madon and Boudart ( 1982).
The external mass transfer resistance is assumed to be negligible if the
conversion does not change upon an increase in the linear velocity in an
isothermal packed-bed reactor the length of which is adjusted to give a con-
stant residence time. In nonisothermal cases thermal gradients may mask
the results of this test.
In gas-liquid slurry reactors the test consists of checking the con-
stancy of the rate as the agitation is increased. Chambers and Boudart
( 1966) pointed out that at the low Reynolds numbers encountered in many
laboratory reactors, the transport coefficients may be rather insensitive to
changes in the flow rate, and this diagnostic test may lead to erroneous con-
clusions. Figure 10 illustrates the application of this diagnostic test to the
oxidation of SO2 using catalyst particles of two different sizes and beds of
two different lengths. The external mass transfer resistance is negligible
in these cases, as changes in the velocity do not affect the conversion.
Pore diffusion limitations are present at 470°C, as the conversion depends
on the size of the pellets.
Diffusion-Reaction Interactions 265
0
Cf)
"' PARTICLE BED V0L(ml)
DIAM (mm) 20. I 0.
f--
w 60 5.88 0 D
...J I 14 e ■
~
LL
0
z 40
0
1n
0::
w
z> 20
0
u
0
50 100 150 200
W/F, g CAT./(M0L S02 /HR)
FIGURE 10 Influence of linear velocity and particle size on the conversion
of SO2. (From Dowden and Bridger, 1957.)
Mears (1971b) has shown that for an nth-order reaction the interphase
concentration gradient can be ignored if
V
Sp< 0.05 ( 88)
X
It is sometimes difficult to predict the value of the mass transfer coefficient
at the low velocities used in laboratory reactors. This value may be deter-
mined from a mass-transfer-limited reaction rate measured at elevated
temperatures.
Influence of Diffusion on Multi reaction Networks
A comprehensive analysis of the diffusion-reaction interaction for all possible
reaction networks and kinetics is obviously an impossible task. Following
Wheeler ( 1951), we examine the impact of diffusion limitations on the yield
of a desired product for three typical isothermal two-reaction networks and
illustrate how the knowledge of the single-reaction case may be exploited
to predict the qualitative features of more complex reaction networks.
Consider first two parallel, independent, first-order reactions of which
only the first is desirable:
kl
A -Pl
k2
B -P2
266 Luss
An example of such a case is the hydrogenation of olefins in the presence
of aromatic compounds. We define the selectivity as
(89)
In any useful catalyst k 1 » k 2 , so that the time constant for the fast re-
action is much smaller than that for the second reaction and the rate of
the desired reaction is affected by the diffusional limitations much more than
is the rate of the undesired reaction. In the absence of diffusional limita-
tions n 1 = n 2 = 1, so that
( 90)
When diffusion limits both reactions,
( 91)
and the selectivity is given by the relation
( 92)
Thus the diffusional resistance taxes the desired reaction at a higher rate
than it does the undesired reaction. We conclude that it is essential to
minimize the diffusional resistance to get a high selectivity for this reaction
network.
Next consider two consecutive first-order reactions
The species balances are described by the differential equations
( 93)
2
2 /1.lCl
17 2c = /\.2C2 ( 94)
2 8
where
#
V
I\.,
1
= ___E.
s i = 1,2 ( 95)
X
i
Diffusion-Reaction Interactions 267
8 =
The corresponding boundary conditions are
C. = C. i = 1, 2 ( 96)
1 18
Solution of Eqs. (93) and (94) gives the point ratio of the two fluxes (i.e.,
the differential yield of component 2) as
dC 2 dC2s
-8
dC 1 = dCls
( 97)
s
where
kl /\2
1
s = = ( 98)
k2 8 /\ 2
2
and n. is the effectiveness factor for a single first-order reaction having a
Thiele1 modulus of /\i.
When diffusional resistances are negligible, lli + 1 and Eq. ( 97) predicts
that
dC2s
---- = ( 99)
dCls
and as expected the differential yield is independent of the diffusional
processes. However, in the diffusion-controlled regime, lli /\? + /\i (for
i = 1, 2) and the point yield approaches asymptotically the \ialue
( 100)
For all useful catalysts s » 1 and the asymptotic yield in the diffusion -
controlled regime is much lower than that obtained in the kinetic regime.
Equation ( 97) indicates that the differential yield depends on the local
C2 8 /C1 8 ratio. The concentration of the desired intermediate at the exit
of an isothermal plug-flow reactor is found by integration of Eq. (97) to be
268 Luss
where
p = ( 102)
P is equal to 1 /s when the diffusional resistances are negligible and to
/"8Ts in the diffusion-controlled regime. An experimental illustration of
the shift with increasing diffusional resistance of the integral yield (at a
fixed conversion level) from one asymptote to another is shown in Fig. 11
for the oxidehydrogenation reaction
Butene -->- butadiene -->- CO 2 + cracked products
By differentiation of Eq. (101) we find that the maximal yield of c 2 is
obtained when
s p - 8
P( 8 s 1) p - 1
( 103)
C/0) 8
s p -
---+
c 1 (0) 8s 1 p - 1
Note that when 8 = 1, the expressions for C 2(L) IC 1 ( 0) in Eqs. (101) and
(103) simplify considerably. An increase in the diffusional resistances (in-
creasing /\i) decreases the conversion at which the maximal yield is ob-
tained and reduces its value, as illustrated by the example shown in Fig.
12. Thus it is not possible to compensate for loss of yield due to diffu-
sional limitations by increasing the conversion or equivalently the reactor
~
0.
C:
90
0
'iii
:;;
>
C:
0
(_) 80
0~
I[)
r<)
0 70
Q.)
C:
Q.)
'o
0
:i 60 Butene - Butad iene - CO 2
co
0
"C
ai 50
;;:: 0 2 4 6 8 10
Particle Diameter, mm
FIGURE 11 Dependence of the yield of butadiene on iron oxide catalyst
particle size at 620°C. (From Voge and Morgan, 1972.)
Diffusion-Reaction Interactions 269
A1~ A2~'A3
.8 S = 16
§ 8 =I
u
- .6
C2 (0) = 0 P="i
'
...J
~N
u .4
.2 DIFFUSION
CONTROL
.4 .6 .8
Conversion
FIGURE 12 Dependence of the yield of the desired product on the con-
version in the kinetic and diffusion-controlled regimes. (From Carberry,
1962.)
length. We conclude that the impact of mass transport resistance on the
selectivity may be much more critical than its effect on the conversion.
When the interparticle mass transfer resistance is not negligible, the
yield for symmetric pellets may be expressed in terms of the effectiveness
factor for a single reaction. The yield is found by integration of Eq. ( 104),
which is a simple modification of Eq. ( 97) (Carberry, 1962):
dC2s
--=---
8s c2s
{ - s [ ~
n1J\ (Biml
-+--- 1+-- - - -
dCls 8s - 1 els 8s - 1 Biml Bim 2
(104)
Van de Vusse ( 1966) has presented a similar analysis for cases in which
the first reaction is of order n while the second is of order m, where
n, m = 0, 1, 2.
The analysis above indicates that the yield for two consecutive first-
order reactions can be expressed as a function of the effectiveness factor
for a single first-order reaction. Wei (1962) was the first to develop a scheme
for predicting the yield for a general network of first-order reactions in terms
of the effectiveness factor for a single reaction. A different approach to the
solution of the same problem was presented by Aris (1975, p. 345).
Consider now the two simultaneous reactions
(desired, of order n)
(undesired, of order m)
270 Luss
occurring in a porous catalyst. As an analog to Eq. (90), we define the
selectivity to be the ratio between the rate of formation of the desired to
the undesired product:
f klAn dv f (A/As)n dv
V V
p
s = = so ( 105)
f k2Am dv f (A/As)m dv
V V
p p
where So the intrinsic selectivity is defined as
k
so = k_!_(A
2 s
)n-m (106)
When both reactions are of the same order, the ratio between the rate
of formation of P 1 and P 2 is independent of the concentration of A, and the
selectivity is equal to k 1 /k 2 . In this case the diffusional resistances affect
only the rate of consumption of the reactant.
When the two reactions are of different orders, the selectivity is equal
to the intrinsic one only when no diffusional limitations exist (i.e., when
the concentration of the reactant is uniform throughout the pellet). How-
ever, when diffusional limitations exist, we expect them to tax at a higher
rate the reaction with the higher order. Thus diffusional resistances can
either increase or decrease the selectivity, depending on the sign of m - n.
The intuitive guess is verified by Eq. ( 105), which shows that the selec-
tivity is enhanced by diffusional limitations if the order of the desired re-
action is less than that of the undesired one. The converse is true when
n is larger than m.
It is not possible to obtain a general, explicit expression for the
selectivity of this reaction network. Roberts ( 1972) derived some explicit
asymptotic expressions for the selectivity and the interested reader is re-
ferred to that paper.
The analysis of the three two-reaction networks illustrates that it is
often possible to predict the qualitative influence of diffusion on the yield
of a desired product from knowledge of its impact in the single-reaction
case. This ability to predict the qualitative influence of various variables
on the yield is very useful. Obviously, a quantitative prediction of the
yield requires a numerical solution of the governing species balances.
Numerical procedures for solving these equations are described in Chapter 1.
In certain molecular sieve catalysts ( zeolites) the effective diffusion
coefficients of some species may differ by several orders of magnitude from
those of the other. In these cases diffusional limitations may have a pro-
found influence on the product distribution and on the yield of the desired
product. For example, the xylene mixture produced by alkylation of toluene
on a zeolite ZCM-5 catalyst can have para-xylene far in excess of the bulk
gas-phase equilibrium concentration. Wei (1982) has analyzed this selectivity
enhancement and showed that it was caused by the large difference in the
diffusivity between the para-xylene and the ortho- and meta-xylenes.
Diffusion-Reaction Interactions 271
INFLUENCE OF TEMPERATURE EFFECTS
Heat release or consumption by chemical reactions may lead to intraparticle
and interphase temperature gradients, which can have an important impact
on the activity and selectivity of catalytic pellets. The impact of these
temperature gradients may be more pronounced than that of the concentra-
tion gradients.
When a single chemical reaction occurs in a symmetric catalytic pellet,
the maximal intraparticle temperature Max(T) and the surface temperature
Ts must satisfy the relations (Lee and Luss, 1969; Carberry, 1976, p. 231)
Max(T) - T
______ s < Sb (1 - q, *) ( 107)
Tb
T Tb
s ( 108)
== S*q, *
Tb
where
(-t.H)DeCb
S* == (-t.H)kcCb
Sb ==
;\eT hTb
b
( 109)
k ;i._e Bi V
S* m
r == h
C
Bih
Bi
h
== _E_
S
== Sb De ==
X
Note that air the terms on the right-hand side of Eqs. (107) and (108) are
observable quantities. When q,* == 1, Max(T) ~ Ts and Ts+ Tb(l + S*)
(i.e., the pellet has a uniform temperature which exceeds by S*Tb that of
the bulk phase). When q,* + 0, Max(T) < Tb(l + Sb) and Ts ~ Tb and
most of the temperature rise is within the pellet. Dividing Eq. (108) by
Eq. (107) gives a bound on the ratio between the inter- and intraphase
temperature gradients,
Ts - Tb fq,*
,--,---,--,--- ~ --- (110)
Max ( T) - T 1 - q,*
s
In practice the anticipated values of Sb are in the range 10-3 to 0. 3, while
those of r are in the range 10 to 104 for gas-solid systems and 10-4 to
10-l for liquid-solid systems (Carberry, 1976, p. 230). It follows from
Eqs ( 110) and ( 109) that in gas-solid systems a large temperature difference
may exist between the surface of the pellet and the bulk gas. For example,
Maymo and Smith ( 1966) measured a 300°C interphase temperature gradient
during the oxidation of hydrogen over a platinum catalyst. In liquid-solid
systems the interphase temperature gradient is usually small because of the
low value of r , and most of the thermal resistance is within the catalytic
pellet. This intrapellet temperature gradient is usually small, as the value
of Sb is rather small for liquid-solid systems.
272 Luss
The foregoing criteria are most useful for estimating whether any of the
temperature gradients are negligible. This information is very useful, as
the analysis of a limiting case in which either the intrapellet or the inter-
phase temperature gradients are negligible is much simpler than that of the
general case.
Single-Reaction Case
Interphase temperature gradients are usually the dominant ones for gas-
solid reactions. We examine here the impact of the interphase gradients on
an nth-order catalytic reaction A + B occurring in a porous pellet in which
the intraparticle gradients are negligible. The corresponding species and
energy balances are
S k (Cb - C ) = V r(C , T ) ( 111)
XC S p S S
( 112)
Combining the two equations gives
1 + B* - y s
( 113)
B*
where
(114)
Substitution of Eq. ( 113) into Eq. (112) gives a single equation describ-
ing the steady-state temperature. For example, for a first-order reaction
with an Arrhenius temperature dependence the dimensionless steady-state
temperature satisfies the equation
Ys - 1 = Da(l + B* - y )X(y )
s s
6
= f(y )
s
( 115)
where
k(Tb)V
Da = p (116)
y =
k S
C X
We define the effectiveness factor to be the ratio between the observed
rate and that obtained at bulk fluid conditions. Thus if intraparticle gra-
dients are absent,
r
m
( 117)
To illustrate the calculation of 17, we consider the case of an irrever-
sible nth-order reaction for which Eq. (117) becomes
Diffusion-Reaction Interactions 273
(118)
Equation (111) may be rewritten as
C
s 1 - q,* ( 119)
Cb=
Substitution of this result and Eq. (108) into Eq. (118) gives
(120)
Figure 13 describes the dependence of the effectiveness factor for a
first-order reaction on the observable parameter q, *. It is apparent that
in certain cases the effectiveness factor exceeds unity, as the increase in
the reaction rate constant due to the interphase temperature gradient over-
compensates for the decrease in the rate due to the concentration gradient.
This surprising effect is encountered mainly in highly exothermic reactions.
The external transport resistances in laboratory and pilot plant packed-
bed reactors are larger than those in industrial reactors, as the former
operate usually at a much lower linear velocity. Thus it is essential to
account properly for the impact of temperature gradients in the analysis of
kinetic data and reactor design.
100 , - - - - - - - - - - - - - - - - - - - - - ,
E
Y=--=20
RTb
LINEAR KINETICS
i3 .c 10
2...
......
I-~
u
U>
!=""
.I L----'----'----'-.L..L-U..U--'--'-~~~-~~~~~
.001 .01 .I
q/= ;b:c (~: )
FIGURE 13 Dependence of the external effectiveness factor on q, * and S*.
(From Carberry and Kulkarni, 1973.)
274 Luss
The interaction between the external gradients and the intrinsic
kinetics may lead to the existence of multiple steady-state solutions for
the same set of parameters. For example, if for a first-order reaction
( 121)
three steady-state solutions exist for all Damkohler numbers in the region
ymm·-1
> Da > yfmax- 1 ( 122)
f(ymin) (ymax)
where
= y( 2 + S*) ± lyS*[yS* 4(1 + S*) l
Ymax,min ( 123)
2(1 + S*)
Similar criteria may be derived for reactions with different rate expressions
(Chang and Calo, 1979; Tsotsis and Schmitz, 1979; Leib and Luss, 1981;
Luss, 1980).
The existence of steady-state multiplicity may lead to a hysteresis in
the reaction rate or surface temperature when one of the operating condi-
tions, such as the ambient concentration or temperature, is slowly changed.
Figure 14 illustrates this behavior for the oxidation of butane on a platinum
wire ( Cardoso and Luss, 1969). The gas temperatures at which a sudden
increase or decrease in the wire's temperature occurs upon a slight change
900 % Butane 1.5%
700
ci
.,E
I-
., 500
u
't
::,
(/)
Cf)
I-
300
100 G •25.6 gm/cm min
0 100 200 300
Tb , Ambient Gas Temperature
FIGURE 14 Dependence of catalyst wire surface temperatures on gas tempera-
tures and butane concentrations. (From Cardoso and Luss, 1969.)
Diffusion-Reaction Interactions 275
in the ambient conditions are referred to as the ignition and extinction
temperatures, respectively.
We examine next the more common case in which the pellet temperature
is uniform but different from the ambient one, while the intraparticle con-
centration gradients are not negligible. The species and energy balances
for an nth-order reaction are
(124)
S h(T
X S
- Tb) = (-LiH) f k(Ts)Cn dv (125)
V
p
Combining Eqs. (124) and ( 125) gives
1 + S* - y
s
= ( 126)
S*
Substitution of Eq. (126) into Eq. (125) and rearrangement gives the
following equation for the dimensionless surface temperature:
Ys - 1 = S*DaX(y )
s
C +
S* -
S*
n
y s) n.[/\.(y )l
1 S
( 127)
where
V · k(T )Cn-l ( __E_)' k(Tb )Cn-l
b b b
Da =__E_ /\. 2( 1) =
sX k
C
S
X
D
e
(128)
n-1
2 2 ( 1 + S* - y s )
/\. (ys) = /\. (l)X(ys) S*
and ni(/\.) is the effectiveness factor for an nth-order isothermal reaction.
Equation ( 127) can be solved for y s and the corresponding /\. and n,.
An analysis of this model indicates that most of its qualitative fe~tures
are similar to those of the lumped-parameter model Eq. ( 115) . The overall
effectiveness factor is the ratio between the observed to ambient reaction
rates,
k(T )C nn. S* -
S S 1
n = ( 129)
n S*
k(Tb)Cb
and its value may exceed unity. The main influence of the pore diffusion
limitations is to reduce ni from the value predicted in their absence.
The model predicts that steady-state multiplicity may exi'st in certain
cases. It is difficult to derive simple, explicit criteria predicting the
276 Luss
parameters for which the uniqueness-multiplicity transition occurs, but it
is relatively easy to obtain bounds on the parameters for which either
uniqueness or multiplicity exists. For example, for a first-order reaction a
unique solution exists for all Da and A ( 1) if (Van den Bosch and Luss,
1977)
y < 4 ( 1 + 13~) (130)
while multiplicity exists for some Da and A ( 1) if
(131)
Sharper bounds may be obtained for specific A ( 1) and similar criteria may
be derived for nth-order reactions. Studies by Nielsen and Villadsen (1984)
and Hu et al. (1985a,b) have revealed that this model predicts that up to
five steady-state solutions exist for some nth-order reactions and set of
parameters. In contrast, the lumped model predicts that at most three
solutions can exist for any nth-order reaction.
When the interphase concentration and temperature gradients are
negligible, the steady-state species and energy balances are
Dev 2c - r(C,T) = 0 ( 132)
\ev 2T + (-llH)r(C,T) = 0 ( 133)
subject to the boundary conditions
C = Cs and T = Ts on the surface (134)
Combining the two equations gives
C 1 + 13 - y
c = 13
( 135)
s
where
( -fl H)C De
s T
13 = y - - ( 136)
T
s
Thus the steady state is the solution of a single equation of the form
(137)
where
2 r(C , T )
R s s ( 138)
C De
s
Diffusion-Reaction Interactions 277
1000 o - - - - ~ - - ~ - - - . - - - - ,
6
u
~
.,"'"'
.,
C:
>
:;:
u
.2'
w
.01 ~~~~~~~~~~~~
.I I 10 100 1000
cp = Rfi75°
FIGURE 15 Nonisothermal effectiveness factors for a first-order reaction
in a spherical pellet. (From Weisz and Hicks, 1962.)
r(y,T)
r(C,T) s
f(y) = ( 139)
r(C , T ) r(l, T )
s s s
The corresponding effectiveness factor is
17
V
1
f f(y) dv ( 140)
p V
p
Numerical calculations of the effectiveness factor for a first-order re-
action in a sphere by Weisz and Hicks (1962) (Fig. 15) indicate that the
effectiveness factor may exceed unity, due to the competing influences of
the intraparticle temperature and the concentration gradients. Moreover,
steady-state multiplicity may be caused by the interaction of the diffusion-
reaction rate processes.
Luss ( 1968) has shown that a sufficient condition for the existence of a
unique solution for all ¢2 is that
( _ l) d ln f(y) < l for all 1< y< 1 + S ( 141)
y dy
For the case of a first-order reaction, criterion ( 141) guarantees unique-
ness for all ¢ if
( 142)
278 Luss
This criterion is usually satisfied, as 13 is most cases rather small. Methods
of bounding the values of ¢ for which multiplicity exists were presented by
Luss ( 1971).
When the temperature of the pellet is uniform, no more than five steady-
state solutions are obtained for a first-order reaction. However, an arbitrary
large number of solutions may be found for a first-order reaction occurring
in a spherical pellet with intraparticle temperature and concentration gra-
dients (Villadsen and Ivanov, 1978). This behavior is found for extremely
high values of y and 13 which are not encountered in practice (Copelowitz
and Aris, 1970). When both the interphase and intraparticle gradients
have to be accounted for, one needs to solve the two equations (132) and
( 133) subject to the boundary conditions
k (Cb - C ) = DenVC ( 143)
C S -
h(Tb - T ) = ;\enVT ( 144)
s -
The behavioral features of this case are similar to those found for the limit-
ing models discussed before (i.e. , the effectiveness factor may exceed
unity and multiplicity occurs for certain values of the parameters). The
interaction between the interphase and intraparticle gradients may cause
the appearance of two distinct regions of multiplicity, as shown in Fig. 16.
The two multiplicity regions may overlap, giving five steady-state solutions.
IOOO
y•27
/Jb• I /3
Bim•30
Bih" I 0
i::-- 100
::;
ua
LJ..
.,"'"'
.,
C
>
·.;::
0 10
.!!!
w
I c__=,::____ ____1__ _j___..J...__ _____L_,______J
-Vp&
.I 10
Thiele Modulus -
Sx D8
FIGURE 16 Effectiveness factor as a function of the Thiele modulus for a
first-order reaction in a slab catalyst. (From Aris and Hatfield, 1968.)
Diffusion-Reaction Interactions 279
It is rather difficult to derive exact criteria predicting explicitly the
set of parameters for which multiplicity exists in this case. Sufficient con-
ditions for uniqueness were presented by Jackson (1972).
The analysis above indicates that either intra- or interphase tempera-
ture gradients may cause the effectiveness factor to exceed unity and lead
to steady-state multiplicity. Estimation of the magnitude of these gradients
is useful for deciding which of the limiting models should be used in a
specific application.
Multireaction Networks
Temperature gradients may have a significant influence on the yield of a
desired product in a multireaction network. Whenever the activation ener-
gies of the various reactions are not equal, thermal gradients affect the
ratio among the rates of the different reactions and hence the intrinsic
yield. The temperature gradients also affect the ratio among the time con-
stants for diffusion and reaction and hence the influence of diffusion on
the yield.
It is impossible to analyze the behavior of all reaction networks and
rate expressions. Thus we shall discuss just two typical two-reaction net-
works and comment on the behavior of more intricate networks.
We start by examining a case of two consecutive reactions, Ai + A2 +
A3. To simplify the analysis, we ignore intraparticle concentration and
temperature gradients and assume that only interphase gradients exist.
The corresponding steady-state species and energy balances are
( 145)
( 146)
( 147)
The three equations may be combined to give the following equation for the
dimensionless temperature:
( 148)
where
k.V (-L'IH.)k .C.b
Da. - _2__E... !3* =
l - k .s
Cl X i
l
hTb
Cl I
( 149)
Equation (148) is a highly nonlinear function of Ys, as each of the Damkohler
numbers includes a temperature-dependent rate constant.
The corresponding yield is given by the equation (Cassiere and Carberry
1973)
280 Luss
dB klCls - k2C2s nik2 C2b
= = n* - ( 150)
dA klCls 2 n1k1 Clb
where
1
n:I' = i = 1, 2
1 1 + Da.
1
When both Damkohler numbers are very small (D~ << 1), the external
effectiveness factors n:I' are close to unity and Eq. (150) becomes
1
dB
= ( 151)
dA
In this case the temperature gradients affect the yield only by changing
the ratio ki/k 2 .. When E1 > E 2 the temperature gradients enhance the
yield, while the converse occurs if E 2 > E 1 . When the Damkohler numbers
are not small, temperature gradients affect the rate constants as well as the
diffusional limitations.
An analysis of Eq. (150) indicates that it may have up to five different
solutions, even though at most three exist when only one reaction occurs.
Balakotaiah and Luss ( 1982a) have proven that multiplicity can exist for
some Damkonler numbers if and only if at least one of the two .reactions is
exothermic and the set Yi, Si, and o satisfies at least one of five conditions
given in that work. Moreover, they showed how to determine the Damkohler
number for which multiplicity exists. The interested reader is referred to
that work.
When multiple steady states exist in this system , the bifurcation diagrams ,
which describe the yield or surface temperature as a function of a slowly
changing state variable, may be much more intricate than those found for
the single-reaction case. Moreover, the number of different types of bi-
furcation diagrams tends to increase rapidly with the number of the re-
actions (Balakotaiah and Luss, 1982b, 1983b; Harold and Luss, 1985).
Figure 17 describes a case in which two hysteresis loops are completely
nested within a large one. Obviously, it would be easy to miss the internal
nested loop in an experimental study, unless there exists some theoretical
guidance about its existence. The existence of these "exotic" bifurcation
diagrams points out the need for a thorough analysis of the impact of ther-
mal gradients, to avoid pitfalls in the design and operation of the reactor.
When the influence of intraparticle concentration gradients is taken into
account, the equations that describe the dimensionless steady-state tempera-
ture becomes more intricate (McGreavy and Thornton, 1970) and their analy-
sis is more tedious. We shall not discuss this case here.
Intraparticle temperature and concentration gradients may have an im-
portant influence on the yield of the desired intermediate A2 for this re-
action network. Butt ( 1966) has shown that even when the activation
energies of both reactions are equal, the intraparticle gradients may affect
the yield when both reactions are exothermic. In some extreme cases, the
temperature gradients may even change the sign of the yield, so that
instead of producing the desired species the reaction consumes it. When
E 1 = E2 the temperature gradients do not affect the ratio between the two
Diffusion-Reaction Interactions 281
3.9 % co
500 4.2 % C2 H6
G
!!...
w
er
=> 400
!,c 11
er
w
a.. 11
::::;:
~
w 300
.....
.....
w
....J
....J
w
a.. 200
'
I
.....0 .
100100 120 140 160 180 200 220
T9 -GAS TEMPERATURE (°C)
FIGURE 17 Dependence of the temperature of a catalytic pellet on the
gas temperature during the simultaneous oxidation of CO and c 2H 6 . (From
Harold and Luss, 1982.)
rate constants k1 and k 2 . However, the increase in the values of these
rate constants with rising temperatures increases the deleterious impact of
the concentration gradients, which tax the desired fast reaction (A1 + A2)
more than they do the slower undesired reaction (A2 + A 3 ). On the other
hand, the yield may be improved by thermal gradients when E1 = E2 for
endothermic reactions. This is, however, accompanied by a large decrease
in the reaction rate.
When the activation energy of the desired reaction is larger than that of
the undesired one (E1 > E2), thermal gradients tend to improve the yield
for exothermic reactions, as the increased ratio of k2/k1 overcompensates
for the larger diffusional resistances. The inverse occurs when E 2 > E1.
Consider now a single reactant that is consumed by two simultaneous
first-order reactions. When intraparticle gradients can be ignored, the
local selectivity is defined as
(152)
so that the impact of the temperature gradients depends on its influence on
the ratio k1(Ts)/k 2(Ts). Thus the selectivity is improved by thermal gradi-
ents if the reaction is exothermic and E 1 > E 2 or if the reaction is endo-
thermic and E2 > E1.
The interaction between the chemical reaction and the interpellet tempera-
ture gradients leads to steady-state multiplicity for some Damkohler numbers
in this case if at least one of the following three conditions is satisfied
(Michelsen, 1977):
( 153)
282 Luss
(154)
(y
2
- y )(13* -- 13*)
1 2 1
> 4(1 + 13*)(1 + 13*)
1 2
( 155)
The last condition [Eq. (155)] may be satisfied even if both reactions are
endothermic-a rather surprising result in view of the fact that multiplicity
cannot occur for a single, first-order endothermic reaction.
When intraparticle concentration and temperature gradients exist, the
species and energy balances can be solved numerically and the selectivity
is computed from
f k 1(T)C dv
V
p
s = (156)
f k/T)l•' dv
V
p
When the intraparticle resistances are small ( ¢ << 1), the selectivity ap-
proaches asymptotically the value of k1(Ts)/k2(Ts). For large diffusional
resistances the selectivity approaches a different asymptotic value which
depends on the reaction heats and activation energies of both reactions. Fig-
ure 18 illustrates some typical results obtained by <Z>stergaard ( 1965) for two
exothermic reactions. As expected, the asymptotic selectivity in this case is
enhanced by temperature gradients when the activation energy of the de-
sired reaction exceeds that of the undesired one (i.e. , E 1 /E 2 > 1).
The impact of the thermal gradients on the intrinsic selectivity of any
multireaction network can be determined rapidly by use of the external re-
sistances model. When all the reactions are either exothermic or endothermic,
Y1 /Y2 =1.4
2.0...._---------+--+-----------,
kI B
A~
~c
(f)
,;=30
A=2 0
Sx Voe
FIGURE 18 Dependence of the yield for two simultaneous first-order re-
actions in a slab on the Thiele modulus. (From <Z>stergaard, 1965.)
Diffusion-Reaction Interactions 283
the qualitative effect of the intraparticle temperature and concentration
gradients can usually be predicted from knowledge of the influence of the
diffusional resistance in the single-reaction case. The information about
the impact of the interphase thermal gradients on the intrinsic selectivity
and of the intraparticle diffusional limitations can be used to estimate the
qualitative effect of temperature gradients in multireaction systems. Ob-
viously, the quantitative prediction of the influence of thermal gradients
requires a numerical solution of a set of nonlinear differential equations
that describe the system. Balakotaiah and Luss ( 1983a) have devised a
procedure for getting sufficient multiplicity criteria for networks of many
irreversible first-order reactions.
Diagnostic Tests for Temperature Gradients
Criteria ( 107) and ( 108) enable a rapid prediction of the magnitude of the
temperature gradients based on observable quantities. Several criteria
have been proposed for predicting whether thermal resistances have an
important influence on the intrinsic reaction rate. Obviously, the impact
of temperature gradients depends on the exothermicity of the reaction, the
sensitivity of the reaction rate to changes in the temperature, the rate and
the transport coefficients.
Anderson ( 1963) predicted that intraparticle temperature gradients
cause the observed rate to deviate by less than 5% from the value obtained
under isothermal conditions if
cfl 13y < 1 (157)
Kubota and Yamanaka ( 1969) predicted that for positive-order reactions
the combined effect of concentration and intraparticle temperature gradients
is less than- 5% if
1
cf) < n Sy
( 158)
When n - 13y is close to zero, the perturbation approach used to derive Eq.
(158) is no longer applicable. In this case the asymptotic expansion of the
effectiveness factor for large values of cp (Petersen, 1965) can be used to
derive a different criterion. Mears (1971b) suggested using a value of 13
for the right-hand side of Eq. (158) when both n and yl3 are close to
unity. Criterion ( 85) can also be used in this case to predict when the
intraparticle gradients do not affect the rate by more than 5%.
The major resistance to heat transfer is in the boundary layer for gas-
solid reactions. Mears (1971a) has shown that interphase temperature gra-
dients cause less than a 5% deviation in the rate if
cfl* Ybl 13*1 < 0.05 (159)
A comparison of criteria ( 157) and ( 159) indicates that interphase gradients
limit the rate before the intraparticle gradients do if
V
Bl. = h _E_ <22
S . ( 160)
a Ae x
284 Luss
This condition is usually satisfied in laboratory .reactors due to the low
flow rates and heat transfer coefficients.
A comparison of criteria ( 88) and (159) indicates that the external
temperature gradients affect the rate before the external mass transfer
does if
( 161)
This condition is satisfied by many highly exothermic or endothermic
reactions.
Mears (1971b) has shown that for an nth-order reaction, the combined
intraparticle-interphase gradients affect the rate by less than 5% if
( 162)
cp < In - Yb 1\ I (1 + n cD *)
This criterion reduces to Eq. (158) when the external resistances are
negligible ( cp « 1).
Although the diagnostic tests are very useful, the estimation of some
of the relevant parameters may be difficult at times. In such cases direct
experimental tests may have to be carried out to check for the impact of
the thermal gradients.
A common test for external gradient is checking for the influence of the
flow rate on the conversion at a fixed space velocity. If no effect is found,
it is concluded that the external resistances are not important. Unfortunately
radial temperature gradients usually affect the conversion in an integral
packed-bed reactor more than do the interphase gradients. Thus this test
does not provide a conclusive answer as to whether the interphase resistance
is important. A direct examination of the influence of the interphase gra-
dients can be carried out either in a well-stirred heterogeneous catalytic
reactor, sueh as the Berty reactor, or in a recycle reactor in which radial
temperature gradients can be eliminated.
ACKNOWLEDGMENTS
I wish to thank John Villadsen, Arvind Varma, and Stig Wedel for helpful
comments.
NOTATION
Bi Biot number for heat transfer kVp / (A eSx)
a
Bi Biot number for mass transfer kcV /(Des )
m p X
BO, Bl, B2 structural parameters
cp specific heat
C concentration corresponding to chemical equilibrium
eq
C. molar concentration of species j
J
CL concentration of reactant in bulk fluid
Diffusion-Reaction Interactions 285
C*L liquid-phase concentration in equilibrium with bulk gas
concentration
d diameter of particle
p
D .. binary molecular diffusivity
l]
DK Knudsen diffusion coefficient
De effective diffusivity
Ds surface diffusivity
Da Damkobler number, defined by Eq. ( 116)
E activation energy
E apparent activation energy
a
Ea activation energy for adsorption of species A
A
Ed activation energy for desportion of species A
A
f fraction of wetted exterior surface of pellet
f(C A) surface adsorption isotherms
f(r) pore size density function
F .. element of a matrix defined by Eq. (17)
l]
g.. element of matrix defined by Eq. ( 24)
l]
G .• element of the matrix F-l
1]
h heat transfer coefficient
H proportionality coefficient, defined by Eq. ( 32)
jD factor for mass transfer, defined by Eq. ( 50)
jH factor for heat transfer, defined by Eq. (51)
k reaction rate constant
mass transfer coefficient
adsorption equilibrium constant
equilibrium partition factor
increased drag factor
L half thickness of slab
m exponent in correlation
M molecular weight
n reaction order; number of moles
n' apparent reaction order
n normal outward unit vector
N.1 total molar flux of species i
ND diffusive flux of species i
i
NY1 viscous molar flux of species i
286 Luss
p pressure
p quantity defined by Eq. (102)
r radial position
r measured reaction rate
m
r pore diameter
p
r(C) reaction rate
R particle radius; universal gas constant
RN ratio of molar fluxes, defined by Eq. ( 48)
Re Reynolds number defined by Eq. ( 54)
s ratio of rate constants k 1 /k 2
s selectivity
sg surface area per unit weight of catalyst
s external surface area of catalyst
X
t time
T temperature
T surface temperature
s
u bulk fluid velocity
u. average molecular velocity of species i
1
V volume of catalyst
C
V volume of pellet
p
XA mole fraction of A
y dimensionless temperature, defined by Eq. (136)
Ymax quantity defined by Eq. ( 123)
ymin quantity defined by Eq. (123)
Ys dimensionless surface temperature, defined by Eq. (114)
z length coordinate
Greek Letters
Cl ratio of molar fluxes, defined by Eq. (15)
B Prater number, defined by Eq. (136)
Bb Prater number, defined by Eq. ( 109)
B* Prater number, defined by Eq. (109)
y Arrhenius number, defined by Eq. ( 116)
r ratio of Biot numbers, defined by Eq. ( 109)
0 ratio of effective diffu sivities, De/De
2 1
-LiH heat of reaction
Diffusion-Reaction Interactions 287
E porosity of pellet
1) bed voidage fraction
t: dimensionless length, r /R
n effectiveness factor
n* external effectiveness factor = 1 / ( 1 + Da)
8 fraction of surface covered
:\ ratio of molecule to pore diameter; average hopping distance
Af thermal conductivity of fluid
:\e effective thermal conductivity
A normalized Thiele modulus, defined by Eq. (62)
11 viscosity
\! vibrational frequency
\!. stoichiometric coefficient
1
s conversion at which rate is 0. 9 of initial rate
p density
Pb bulk catalyst density
0 ratio of heats of reaction = fl H 2 /ll H 1
T tortuosity factor for
T* lingering time
¢ Thiele modulus with R as characteristic length
qi observable modulus defined by Eq. (84)
qi* observable modulus defined by Eq. ( 88)
X bulk-flow correction factor
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5
Gas-Solid Noncatalytic Reactions
L. K. DORAISWAMY and B. D. KULKARNI National Chemical Laboratory,
Pune, India
INTRODUCTION
Reactions between gases and solids play a major role in the materials
processing industries, encompassing a broad range of operations, such as
extractive metallurgy, combustion of solid fuels, environmental control,
energy generation, and catalyst manufacture and regeneration. Several ex-
amples of gas-solid reactions of industrial importance are cited in Table 1.
The breadth and diversity of systems encountered in gas-solid reactions, as
evident from the table, suggests that any attempt at formulating a unifying
theme for the design of gas-solid reactors would not meet with much success.
However, one can recognize a number of common steps in the overall design
of gas-solid reactions, a combination of which may be used in the develop-
ment of models and formulation of design strategies for these systems. It
is in this spirit that the present chapter attempts to thread together the
otherwise diverse systems.
The foremost consideration in the analysis and design of these systems
is the mode of contact. The number of reactor types (or modes of contact)
is very large in the chemical industry. Even for the same operation, for
example, calcination of lime, different types of reactors ( e. g. , rotary kiln ,
flat hearth, fluidized bed, moving bed) are used. A similar situation pre-
vails in many other gas-solid reactions involving calcination, decomposition,
roasting, and so on. The fixed-, fluidized-, and moving-bed techniques
appear to be most commonly employed and have received greater attention
from both the theoretical and practical points of view. The other modes of
contact, less commonly employed, include horizontal moving bed, pneumatic
conveyor, rotating cylinder, and flat hearth furnace. Although a priori
selection of the mode of contact is difficult, a choice will have to be made
at as early a stage as possible-certainly before any significant effort is
put into the detailed design.
This makes it necessary to undertake an experimental program with a
view to obtaining some qualitative and semiquantitative information regarding
the system. The tools of mathematical modeling should be invoked at this
293
""c:o
,4'>.
TABLE 1 Examples of Gas-Solid Reactions
System Type of reactor Remarks References
1. Reduction of hematite Fixed bed Consecutive reaction Spitzer et al. ( 1968)
of solids
Fixed bed Ohmi et al. (1978)
Moving bed Tsay et al. ( 1976)
Multistage fluid bed Doheim (1973)
Fluid bed Ahner and Feinman ( 1964) t,
0
2. Coal gasification Moving bed Complex reaction Yoon et al. (1979)
afii'
Fluidized bed Ubhayakar et al. (1977) ;
~
3
~
Yoshida and Kunii (1974)
~
;:l
3. Selective chlorination of i::l.
Fluidized bed Reaction of two solids Doraiswamy et al. ( 1959) ;
ilmenite :,,::
with the same gas Fuwa et al. ( 1978) i::
;;;:
Regeneration of coked Ramachandran et al. ( 1975) ~
catalyst
~-
4. Reduction of iron ore with Moving bed Reaction of two gases Tsay et al. (1976) G
Q
CO and/or H 2 with same solid (J)
Fixed bed Osman et al. ( 1966); Barner I
et al. ( 1963) ~A.
5. Oxidation of ZnS Fluid bed Simple reaction Natesan and Philbrook ( 1969); z
0
Yoshida and Wen (1972) ;:1
c:,
Q
Multistage fluid bed Fukunaka et al. ( 1976) ...
Q
~
Fixed bed Beveridge and Kawamura ( 1974) ...o·
6. Reduction of metal chlorides Homogeneous- hetero- Rao (1981) ::ti
(l)
with hydrogen Q
geneous reaction c:,
...5·
;:1
7. Reduction of cobalt sulfide Gaseous product of Fahim et al. ( 1978) (J)
in presence of Cao first reaction react-
ing with a second
solid
Decomposition of potassium Gokhale et al. ( 1975); Kulkarni
benzoate and Doraiswamy ( 1980a)
8. Simultaneous oxidation and Solid product of first Bourgeois et al. (1974)
sulfation of cuprous oxide reaction reacting with
a second gas
~
""'c:r,
296 Doraiswamy and Kulkarni
stage to further substantiate the final choice. Focusing on the phenomena
taking place in the reactor (i.e. , the reaction, and transfer of heat, mass,
and momentum), one can reduce the apparent diversity to a small number
of models or basic reactor types. The modeling and design of reactors is
then based on the equations describing these phenomena.
After a tentative choice of the mode of contact is made, the next im-
mediate problem concerns the particles-their physical and chemical inter-
actions with the surroundings. The variability involved here could be
from one extreme set of conditions to another. The particles may be
packed, as in a fixed-bed reactor, or completely mixed or moving in plug
flow, as in a fluidized- or moving-bed reactor. The gas phase could be
in plug flow or in a state of complete mixing. Intermediate stages of mix-
ing are also possible. Additionally, the chemical interactions could involve
simple single-step reactions or multistep reactions with or without changes
in the volume of the phases and heat effects. The particles themselves
could be porous or nonporous or may become porous during the reaction;
they may also change their size, and significant alterations in the structure
might accompany the chemical reaction. No single model can account for
all the possible events listed. In fact, different classes of models, with
one more suitable than the others for a given situation, can be developed.
Clearly, the first step in the rational synthesis of a design strategy is a
full understanding of the particle behavior.
SINGLE-PARTICLE STUDIES
Basic Steps in Gas-Solid Reactions
Despite the bewildering complexities that can occur in the study of a single
particle, the formulation and accounting of these complexities can be sim-
plified if one adheres to and understands the basic steps involved. Figure
1 sketches a solid particle reacting with a gas species to give products of
reaction. The typical elemental steps involved include gas-phase mass
transfer, diffusion inside the pores, adsorption of reactants, and reaction
and desorption of products. Although these steps occur in succession,
any one or more of these might be rate limiting.
The rate of reaction for the particle as a whole for a slowly reacting
system will be influenced by the surface kinetics (the intrinsic rate). For
somewhat faster reactions, pore diffusion intrudes to limit the rate. For
still faster reactions with exothermic effects, the temperature gradient
across the particle dimension or the gas film may become the limiting factor.
In the extreme case of very rapid reactions, mass transfer across the
fluid interface may become the controlling factor. It is necessary to
demarcate these Cf\ntrolling regimes-for in a given situation when, say,
gas film mass transfer is controlling, it would be wasteful to show undue
concern for the detailed reaction mechanism. These considerations are com-
mon to catalytic and noncatalytic gas-solid reactions.
An important point that differentiates gas-solid reactions from their
catalytic counterparts is the fact that here the solid is also involved as a
reactant. The continuous consumption of the solid reactant leads to in-
evitable structural changes during the reaction, and the system as a whole
is always in a transient state. An important implication of this is that
even the controlling regime might continually change with time for the
same particle.
Gas-Solid Noncatalytic Reactions 297
POSITION OF
REACTION ZONE
WITH TIME
'.:2:
...J
LL
(f)
<(
~ - - CA g
(.!)
UNREACTED
SOLID
I
I GAS
I CONCENTRATION
I PROFILE
I
DISTANCE FROM CENTER, r
FIGURE 1 Basic steps when a solid particle reacts with a gas species.
The problem, complex as it is in the case of a single particle, assumes
further dimensions when a reactor is involved. The particle, influenced
by its own microenvironment, determines the controlling regime (and there-
fore the net rate of production per pellet), which at a given instant of
time is different for different particles. This problem, although considered
in greater detail later, here follows logically from a consideration of the
basic steps in gas-solid reactions.
The rates of reaction when gas film mass transfer is controlling can
easily be obtained from a knowledge of the transport coefficient across the
fluid-solid interface. Several correlations for predicting the transport co-
efficients for a fixed or moving solids and a moving gas stream have been
reported in the literature. These correlations should be used with some
caution, for many of them are valid for restricted operating conditions.
The recommended equations for estimating the mass transfer coefficient are
given in a later section.
In the presence of pore diffusion effects, it is customary to invoke the
laws of molecular diffusion and assume that they are applicable to a porous
medium with an effective diffusion parameter. This equivalence is at best
an approximation, and the total flux balance should include, besides the
diffusive flux, the contributions from the pressure gradient and bulk flow
due to diffusion. Conventionally, these contributions are neglected and
perhaps justifiably so. However, in certain instances, such as when multi-
component diffusion is involved, they should be taken into account. The
concept of effective diffusivity as applied here (as distinct from gas-solid
298 Doraiswamy and Kulkarni
catalytic reactions) also needs reconsideration. In most gas-solid systems,
the morphology of the solid changes due to the presence of reaction, tem-
perature gradient, and so on. The typical changes that may accompany a
reaction include pore shrinkage or closure, swelling, softening, or cracking
of the particle. The temperature may affect the sintering of particles,
whereby the density of contact is increased. In view of these influences,
the effective diffusivity would be modified continuously with the progress
of reaction.
Basic Models
The relevance of the basic steps in gas-solid reactions has brought out a
number of features that are more or less unique to these types of reactions.
It is necessary now to model these features such that a further insight
into the behavior of these systems can be gained using numerical experi-
ments. As already mentioned, it is obviously not possible for a single
model to incorporate all the features of gas-solid reactions. In fact, dif-
ferent classes of models have been postulated and used to describe these
systems. In the present section we briefly summarize these basic models,
and in the next present a state-of-the-art discussion of the extension of
these basic models to different situations of greater practical relevance.
A comprehensive review has recently been published on the modeling of
gas-solid reactions by Ramachandran and Doraiswamyr. (1982b) (see also
Doraiswamy and Sharma, 1983).
Sharp Interface Model
The sharp interface model (SIM) is one of the earliest models used and is
well described in the standard textbooks on chemical reaction engineering.
The model is mainly applicable to nonporous or relatively less porous solids
and assumes that the reaction occurs at a sharp interface that separates
the reacted outer shell (or ash layer) and the unreacted inner core of
solid. The steps involved are diffusion through the gas film, diffusion
through the ash layer, and reaction at the interface. The respective rates
of these steps in molls (for a single pellet) are:
Diffusion through gas film:
(1)
Diffusion through ash layer:
( 2)
Chemical reaction at the interface:
2
RA
C
= 4TTR.l k S CA.l ( 3)
The rate of reaction per pellet at any time t accounting for all the three
resistances is obtained simply by summing Eqs. (1) to ( 3) as
Gas-Solid Noncatalytic Reactions 299
1 1 ( 4a)
+--+--
RAd RAc
or
(4b)
This rate of consumption of A can be related to the conversion of B through
a stoichiometric balance on solid B as
( 5)
Integration of this equation subject to the initial radius (=R) at t = 0 leads
to the conversion-time relationship,
Rk
_g_ 2/3
X + [1 - 3(1 - x) + 2(1 - x)]
2D
e
3k 1/3
+ ___g_ [ 1 - (1 - x) ] ( 6)
k
s
The time required for complete conversion can be obtained by setting
x = 1. The equation can also be written in terms of the time required for
complete conversion if any one of the three basic steps were to control the
rate as
t + t + t .
ash react10n
( 7)
where Tf, Ta, and Tr, represent, respectively, the time required for com-
plete conversion if film transfer, ash diffusion, or reaction alone were to
control the rate. The functions fo, f 1 , and f2 and the various T's assume
different forms for different geometries of the particle and are defined in
Table 2 together with other relevant parameters.
It is evident from the relationships present in the table that the time
required for a given conversion x depends on T, which in turn depends
on (a) the radius of the particle R, (b) the concentration in the gas phase
CAg• (c) the molal density of solid PB, and (d) the stoichiometric coeffi-
cient VB, in addition to kg, De, or ks, depending on whether film, ash
diffusion, or reaction controls.
It may be noted that the dependence of T on pellet size is different for
controlling regimes. Thus it is first order in R for reaction control,
second order for ash diffusion control, and 1. 5 to 2 order for film diffusion
control. By varying the size of the particle it is therefore easy to delineate
the controlling regime.
c.,
c::,
c::,
TABLE 2 Time-Conversi on Relationships for SIM for Different Particle Geometriesa
A(g) + vBB(s) + R(g} + S(s)
Controlling Flat
regime plate Cylinder Sphere T
pBR
Film diffusion , X X X
f 0 (x) = vB (8 + l)kgC Ag
2
2 2/3 pBR
Ash diffusion, X x + (1 - x) ln(l - x) 1 - (1 - x) + 2( 1 - x)
f 1 (x) = 2vB (S + l)DeC Ag
t,
1 - pBR 0
Reaction, X (1 _ x)l/2 1 - (1 _ x//3
n ~
f 2(x) = ;;·
vBkSCAg ~
s:l
3
aThe conversion x = 1 - (r/R)S+1, where S = 0, 1, and 2 for flat plate, cylinder, and sphere, respectively. '<
s:l
;::s
i:l.
:,:::
i::
~
s:l
~-
Gas-Solid Noncatalytic Reactions 301
Further, for pellets of different sizes, different controlling mechanisms
can prevail. At the start of the reaction there is no ash layer present.
Also, unless the reaction is extremely rapid, film diffusion is normally not
limiting. The system therefore begins with the rate controlled by the sur-
face reaction. With progress in time, sufficient ash layer builds up and
the system passes to ash diffusion control.
The dependence of T on the gas-phase concentration, while not very
important for a single particle, assumes great significance for particles in
a reactor. As already mentioned, in a reactor the gas-phase concentration
is usually not constant but varies with position. Thus, even for particles
of the same dimensions, we can have different controlling regimes when they
are placed in a reactor. This point is discussed further later.
An alternative approach to the analysis of gas-solid reactions is to ex-
press the results in analogy with catalytic systems, in terms of an effective-
ness factor. Such an approach has been used by Ishida and Wen ( 1968) ,
and for a general nth-order reaction, the effectiveness factor can be simply
expressed as
n = ( 8)
In view of the changing rate RA, the effectiveness factor is also changing
with time and the following general implicit equation can be derived:
1 - R.
l
(9)
R.
l
n-1
where Sh = kgRIDe and Da = ksRCAb / De. The movement of the inter-
face ~ with time appearing in Eq. (9) can be obtained by integrating Eq.
(5), where the term RA on the right-hand side can be replaced by RA
given by Eq. (8).
The case considered thus far assumes linear kinetics. It is possible for
a reaction to follow fractional-order kinetics with respect to the gaseous re-
actant. Typical examples are the reduction of Cr203 by hydrogen (Chu and
Rahmel, 1979) and oxidation of ZnS (Cannon and Denbigh, 1957). In many
instances the reaction rate may also be represented by Hougen-Watson (H-W)
kinetics. In general, in the presence of such nonlinear kinetics, no analyti-
cal expression for the conversion-time relations can be obtained. Numerical
integration procedures for power law kinetics using SIM have been proposed
by Sohn and Szekely (1972) and for H-W kinetics by Ramachandran (1982).
The case of zero-order reaction has been reported by Simonsson ( 1979).
A zero-order reaction typically exhibits sharp transition between the kinetic
and diffusion control regimes. The combination of first- and zero-order
kinetics has been analyzed by Kam et al. ( 1976) for the case for oxidation
of carbon.
SIM is a phenomenological model, and in the extreme case of reaction
control or ash diffusion control requires only one parameter-the relevant
time factor T-to describe the system. The model predicts total conversion
of solid in a finite time and is well suited for many practical systems. But
it cannot account for such features as the leveling off of conversion of the
S-shaped nature of the conversion-time curve.
302 Doraiswamy and Kulkarni
Volume Reaction Model
When the solid is porous , the gas can penetrate the solid and the reaction
may now be assumed to take place all over the volume of the pellet rather
than at a sharp interface. In general, the rate of reaction at the interior
points would be lower than at the surface due to the concentration gradient.
In a special situation when no diffusion resistance exists, the reaction occurs
uniformly all through the particle, leading to the so-called homogeneous
model. The rate of reaction per unit volume of the pellet is represented as
where m and n refer to the orders with respect to the gas and solid, re-
spectively. A distinctive feature of the volume reaction model is that the
rate of chemical reaction depends on the activity and concentration of the
solid reactant. This means that only for certain values of n (n < 1) can
the solid reactant be completely reacted at any point in a particle and its
concentration reduced to zero.
The general conservation equations for the gaseous and solid reactant
species for the volume reaction model illustrated in Fig. 2 can be written
as
( 10)
(11)
and
The boundary conditions required for the solution of the model are
t=O,R=l: (12)
dCA
>
A A
t 0, R = 1: = Sh(l - CA) or CA 1 (13)
dR
A
dCA
t > 0, R 0: A
= 0 (14)
dR
(;')
A
r,,
I
Cl)
£
E:
CAg Bo CAg Bo
r-~ I z
0
;:s
(')
I A
I ...
A
I ~
t=O~ I) ...g·
::0
Cl)
I L--- o A
R (')
0 ...s·
GAS FILM LOW cf> ;:s
r,,
LARGE 4> (----m=I ,-met)
CAg
Bo
Zone I - Ash layer
Large t----+ Zone II - Reaction zone
B
Zone Ill - Zone of unreacted B
R 0 R 0
LOW Cl> LARGE Cl> ( INDICATING THE DEVELOPMENT
OF THREE ZONES)
FIGURE 2 Concentration profiles for the homogeneous model for various Thiele moduli.
c,.,
C
c,.,
304 Doraiswamy and Kulkarni
No analytical solution to this set of equations for arbitrary values of m
and n seems possible, and recourse to numerical methods is necessary. How-
ever, for certain simplified cases analytical solutions can be obtained. Thus
for the case of low values of <P the concentration profile within the pellet will
be nearly uniform and integration of Eq. ( 11) for n = 0 and 1 would lead to
the following simple conversion-time relations:
- exp(-t) for n = 1 (15)
X
for n = 0 (16)
At higher values of <P (</> > 0.2) the concentration profile within the pellet
cannot any more be neglected and both Eqs. ( 10) and ( 11) need to be
solved simultaneously. An especially important case from the practical
standpoint is when the order with respect to the gaseous component is
unity (n = 1). In this situation it is possible to combine Eqs. ( 10) and
( 11) into a single equation by defining a cumulative gas concentration as
The transformed equation for the special case of m = n = 1 can be written
as
2 2
V 1jJ = <P [1 - exp(-ijJ)] (18)
A A
with boundary conditions ijJ(l) = t and (dijJ/dR)ft=O = 0. This transformation,
suggested by Del Borghi et al. ( 1976) and Dudukovic and Lamba (1976), is
extremely useful for systems with no structural variations and for power-
law-type kinetics. This case (m = 1, n = 1) has also been analyzed by
Dudukovic and Lamba ( 1978a); approximate analytical solutions to the prob-
lem have been proposed by Ramachandran and Kulkarni ( 1980) and by Wen
and Wu (1976).
Some of the useful time-conversion relations are presented in Table 3.
The case of m = 0, n = 1 has been analyzed by Dudukovic and Lamba
( 1978b); m being equal to zero in this case, the gas concentration can drop
to zero within the pellet, depending on the value of <P. In fact, a critical
value of <Per = 6/Sh/ ( 2 + Sh) 1/ 2 can be deduced for this case. For <P < <Per,
the concentration would be finite all over the pellet and the simple relation
given by Eq. (15) describes the conversion-time behavior .A ForA <P > <Per,
the governing equations are applicable only in the region Ri < R < 1, and
solutions to this case are provided by Dudukovic and Lamba ( 1978a). A
comparative study of the effects of reation order on the conversion-time rela-
tionship has been presented by these authors and their results are repro-
duced in Fig. 3. It is seen from the figure that the differences are not
very significant.
Other analyses employing different values for n and m have also been
presented in the literature. The case of m = 1, n = 0 has been analyzed
by Ausman and Watson (1962) and by Ishida and Wen (1968). In view of
the zero-order dependency on the solid concentration the local conversion
of the solid in the pellet reaches completion. This leads to distinct zones,
(;)
Q
'1
~A.
1·0, z0
I I I I I ;:I
(')
m n Q
.. --- 1 0
...
Q
z 0•8 ------ 1 I '<
Q 0 I
...5·
II)
----
a: ::,:i
Ill (1)
> Q
(')
z 0·6
0
(.)
...5·
;:I
0 rn
:::i
0
II) 0•4
J
~
z
...Q
(.)
0·2
~
a:
IL
O·O
O•I 1·0 10·0 100•0
DIMENSIONLESS TIME, f
FIGURE 3 Effect of reaction orders on x versus f plots based on volume reaction model
for slab geometry; Bim = 00 • (From Dudukovic and Lamba, 1978b.)
c.,
C
c:n
w
c:,
0,
TABLE 3 Conservation Equations for Heat and Mass for Volume Reaction and Particle-Pellet Models
Model Governing equations
ac
Volume reaction model N A ~~ (i2 acAA)- cp2cmcn exp [ y
1 at - R2 aR (1 - ~)]
aR A B
aT
A
N 2 ~ = aT + A2 --;:;:- + f3 cp2cmcn exp [ y
A2 m AB (1 - ~)]
at aR R aR
A
ac Am"'n
B
~ CACB exp
at
[y(l - ;)]
acA A aT
R = 1: A = Sh(l - CA); --;:::- = Nu( 1 T)
aR aR
A
ac t,
a _ aT _ 0
R = 0: -A - --::;;:- - 0 is
;;;·
aR aR
~
A
t T 3
= O·. CA = 0' = 1' CB = 1 '<
A
;:l
where A..
;,:::
k Cm Cn-lf R 2t t
N = v Ab Bs c ;>;'
A
1 DeB
2.
P C k Cm n-1 2 Q
N = s ps v Ab CBs fOR t ..,,s::,
2 k' I
e C/l
&
A.
(-LiH)DeBCAb ~
0
sm = ;:l
k'T (')
e b
....s::,s::,
2
.:z....
1 ac cl CA 2 acA 2A2 A a' c=;·
--A-
Particle-pellet model N1 A =--+-
<PrGiCA ::0
Cl)
clt aR2 i "R s::,
(')
....
~ s·
a' ..,,;:l
=
N1 ~ a2 2 clT <P2;2
A A
2 A A
T2 +- - + s .c
m G1 A
clt clR R clR
A
clrGi A a'
-A-= -c
A
at
where
exp[y(l - 1/T)]
a' =
1 + DaGrG/1 - rGi) exp[y(l 1/T)]
vfcR~BcAbks
Nl -
1 -
DepSrGO
2
vR p s C _e.sMBCAbk s
Nl -
2 - k'r
e Go c..,
0
--.:i
aThe conversion x =1 - (r/R)S+l, where S = 0, 1, and 2 for flat plate, cylinder, and sphere, respectively.
308 Doraiswamy and Kulkarni
comprising a product zone nearer the surface and a reaction zone within
the pellet.
Ishida and Wen (1968) divided the total reaction time into two periods
(i.e., the constant-rate period and falling-rate period), in analogy with
the drying process. The time-conversion relations for the two periods are
x=--~~--~-~-----
3(<!> coth <I> - l)t
(constant-rate period) ( 19)
<1>2[1 + (1/Sh)(cj> coth <I> - 1)]
and
3 3Ri
A A
x = 1 - R. + -2 [<l>R. coth(cj>R.)] (falling-rate period) ( 20)
l cj> l l
The conversion at the end of constant-rate period is obtained by substitut-
ing f = fer in Eq. ( 19), where fer is the time required for completion of
the constant-rate period is given by
t
A
- ( l + 2- ) --
= l +<1>2 ( 21)
er 6 Sh
Equation ( 20) relates the conversion in the falling-rate period to the
dimensionless interface position in the particle. It is possible. to obtain a
)
relationship between the interface position and time, which is given im-
plicitly as
t = 1 - (, DeB
DeS
ln
Ri sinh
'
sinh cj>R.
A
<I>
l
<I> 2 2 A
+ 6(1 - R.) (1 + 2R.)
1
A
<1>2 3 [DeB
R.) + ( 22)
A
+ 3Sh (1 - Ri ) + Des (1 l
: ~ ] [ <I> coth(<l>I\) - 1]
In the two- zone models described above, when the rate of reaction is
very rapid, the concentration of the gas species drops very sharply in the
reaction zone. The reaction zone can then be further subdivided into two
zones, comprising the actual reaction zone where the bulk of the reaction
occurs and a core of completely unreacted solid. This has led to the de-
velopment of so-called zone models (Bowen and Cheng, 1969; Mantri et al.,
1976). A common feature of these models is the existence of a reaction
zone of thickness !::,, Y which is a function of the Thiele modulus. Mantri
et al. (1976) have prepared a plot of !::,, Y versus <I>, which is reproduced in
Fig. 4. Such a plot is useful in parameter estimation. The width of the
reaction zone (!::,, Y) can be independently determined from measurements
using electron probe microanalysis (see Prasannan and Doraiswamy, 1982).
For extremely large values of <I> , the reaction zone width becomes very nar-
row, leading to the sharp interface model.
Ramachandran and Doraiswamy ( 1982a) considered the case where the
reaction is zero order with respect to both gaseous and solid reactant
Gas-Solid Noncatalytic Reactions 309
1-0~~,--~~~,~~~~--------~---~-~----,
\
\ ''
I !
i I
>- \ ~ .---m =1 ( Mantri et al, 1976)
<l
IJJ
z
•~ ~ i I II
0
~ ! !Ii I:
\\ ~'N
N \' I Ii I
z t-----+---+----+----l-"'---f-+-----+-"~-~'_ _,!_-+--+--+--+-r--t-:_ _ _ ···-
0
1--
ii
u
<!
IJJ 11
0:
lJ.. 0·1
0
(/)
! '
(/)
IJJ
z ·-- --+--+--,-+-+----+---"'>c--+-----+--+---->---ll\-.->rt---+--+-+-----t
::.:: t-----+----+-------+-!----7e--+-~--~-- _____,,,__ _ _--+---+--' -+---+-~->t-----f
,,/\_ -t----------1
~
:z: i =o
\ ~
1-- 1-----+---+---+---+---+---<
i
m
'
_J
<! f-------_j (Dudukovic and Lomba, 1978 b ~ I 1
\/
1-- !
z
I\ ' '
I\
0·01 ~-........,-~~~~-'-'-~-----___,_-~___,____,_'\....,. .._~~---~
2 10 100
THIELE MODULUS, q:,
FIGURE 4 Reaction zone thickness as a function of the Thiele modulus for
the volume reaction model. (From Mantri et al., 1976.)
species. For finite concentrations of gas within the pellet (no severe dif-
fusional limitations), this case leads to the simple solution
X = t ( 23)
When significant resistance to the diffusion of A exists, a case ( depending
on the value of ¢) may arise where the concentration of A actually drops
to zero within the pellet. A simple criterion for this situation to occur (as
already mentioned) is given by
6
cjJ ,,:; ( 24)
er (1 + 2 /Sh) 1/2
For values of cjJ > ¢er, the governing diffusion equation has to be solved
for the zone where the actual reaction occurs and the position of this zone
310 Doraiswamy and Kulkarni
shifts with time. Once the zone is formed, the reaction process occurs
within this zone until the solid there gets completely exhausted. The re-
action then jumps to another zone, where the phenomenon continues. In
this case, therefore, we have a physical picture of where the reaction zone
jumps from one position to another, and Ramachandran and Doraiswamy
(1982a,b) have termed this the jumping zone model. The jumping zone con-
cept is illustrated in Fig. 5.
Grain (Particle-Pellet) Model
In the basic grain model, also referred to as the particle-pellet model, it is
assumed that each pellet consists of several grains of solid. The grains are
spherical and of the same size. It is further assumed that each grain re-
acts according to SIM and that the size of the grain does not change with
reaction (thereby implying no voidage change in the pellet). A diffusion
resistance for the gaseous species exists in the interparticle spaces within
the pellet. The basic features of the model are sketched in Fig. 6.
The mathematical formulation of the model requires consideration of the
rate processes within an individual grain, and the overall mass balance for
the gaseous reactant in the pellet and its stoichiometric relationship with
the extent of solid consumed. As far as the individual grain is concerned,
the rates of diffusion through the reacted portion of the grain and of reac-
tion at the interface can be obtained in analogy with Eqs. (2) and (3) as
24
(f)
lJ..I
z 20
0
N
z
0
I- 16
u
<t
lJ..I
0:::
u.. 12
0
0:::
lJ..I
CD
~ 8
:::)
z
_J
<t
I- 4
0
I-
0 ,,
2 3 4 5 6 7 8 9 10
THIELE MODULUS, 0
FIGURE 5 Number of reaction zone that develop in the pellet for various
values of ¢.
Gas-Solid Noncatalytic Reactions 311
. COMPLETELY REACTED
rGi - RADIUS OF UNREACTED
CORE
rG - RADIUS OF GRAIN AFTER
SOME REACT ION
rGo - INITIAL GRAIN SIZE
GRAIN
SCHEMATIC OF
GAS A PARTIALLY REACTED GRAIN
SCHEMATIC OF
A PARTIALLY REACTED PELLET
FIGURE 6 S.chematic representation of the grain size model.
4TIDeGrGirGO (C
= A - CA1') ( 25)
rGi - rGO s
( 26)
Eliminating the unknown concentration CAi at the interface, we obtain the
overall rate per unit grain as
( 27)
Once the rate of reaction for the individual grain is known, we can proceed
to write the overall pellet equation as
2 3( 1 - f)
I/ CA= RGA 3 ( 28)
4Tir 00
312 Doraiswamy and Kulkarni
where the term in parentheses refers to the total number of grains in the
pellet volume. The term RQA involves a knowledge of the interfacial posi-
tion rm within each grain, which is a function of both the time and position
within the pellet. To evaluate this, a stoichiometric balance on the solid
reactant B can be written in analogy with Eq. (5) for an individual grain
as
The term CA appearing in RaA in this equation fixes the position of the
individual grain in the pellet .
The appropriate boundary conditions to the problem are
dCA
r = R: De dr = kg(CAb - CAs)
dCA
r = 0: --= 0 ( 30)
dr
t = 0:
In general, this set of equations requires numerical solution.
A mathematical analysis of the particle-pellet model has been presented
by Calvelo and Smith (1970) and Szekely and Evans (1971a,b) for a simple
isothermal first-order reaction. An approximate analytical solution has also
been proposed by Evans and Ranade ( 1980). The constant-size grain m0del
has been generalized by Szekely and Propster ( 1975) to include grain size
distribution. The case of nonlinear kinetics has been proposed by Sohn
and Szekely (1973a,b) for reactions following the H-W rate law.
The microscopic visualization of the solid as consisting of grains requires
two parameters to be known for describing the model. Considering the
physical features of the model, the two characteristic times involved are Tg,
the time required for complete conversion of the grain in the CA environ -
ment, and Ta, the time for complete conversion of the particle by diffusion
if the grain conversion process is extremely fast. In the limiting case of
Tg controlling, the diffusional resistance for the gas within the particle is
negligible and the simple homogeneous model results. The individual grains
could follow the shrinking core model with ash diffusion or reaction control-
ling. In view of the processes within the grain determining the system be-
havior, the conversion-time relationship will be independent of the pellet
dimensions. On the other extreme, when diffusion within the pellet controls,
one would observe shrinking core behavior with ash diffusion control, and
typically (see Table 2) the system behavior(niR2) will be dependent on the
pellet dimensions.
In the intermediate region where both Tg and Ta are of the same order
of magnitude (note that Tg is not a specific number but has a distribution
that is commensurate with the CA profile in the pellet, which in turn is
dictated by Ta), one could expect the pellet behavior to lie within the con-
fines of the limiting cases of shrinking core with reaction and ash diffusion
controlling processes.
Gas-Solid Noncatalytic Reactions 313
The model is useful in cases where pellets are formed by compaction of
particles of very fine sizes. This is not so in naturally occurring minerals.
in which case fictitious grains will have to be invoked to apply the model.
Also the model, in its simple form, does not explain the earlier quoted
S-shaped behavior and leveling off of conversion.
Crackling Core Model
Park and Levenspiel ( 1975) proposed the so-called crackling core model
(Fig. 7) to account for the S-shaped behavior of x versus t plots observed
in some systems. In this model the reaction is assumed to occur in two
steps
A(nonporous) + A (porous)
A(porous) + Product
The first stage could represent a simple physical process or may involve a
porous intermediate, formed out of reaction, that further undergoes reaction
according to the second stage. The reduction of hematite and manganese
oxide (De Bruijin et al., 1980) and uranium oxide (Le Page and Fane, 1974)
with hydrogen follows such a sequence:
FeO Fe
The crackling core model has been used successfully in the interpretation
of experimental data for these systems.
The model envisages two stages, each of which is characterized by a·
certain characteristic time, and the model therefore involves at least two
parameters. As before, Tg represents the time required for complete con-
version of the grain, and Tc represents the time required for the original
nonporous particle to become completely porous. In the limiting case of
fast crackling (T << Tc), the controlling processes shift over to individual
grains and one ofiserves a simple homogeneous ·model. The individual grains
FRESH PARTIALLY
PELLET PELLET REACTED PELLET
PELLET
FIGURE 7 Basic stages in a crackling core model.
314 Doraiswamy and Kulkarni
follow the shrinking core model with either reaction or ash diffusion control-
ling. In view of the processes within the grain controlling, the conversion-
time relationship becomes independent of the pellet dimensions. In the
other extreme of slow crackling, the processes within the grain (in the
porous part of the pellet) get over much faster, and for the pellet as a
whole one observes shrinking core behavior with reaction control. Typical
of such situations (see Table 2), the system time constant shows linear
dependence on the size of the pellet.
The study of the limiting cases as observed here makes possible some
comparisons with the earlier particle-pellet model. The case of Tg » Tc is
identical to the case of Tg » Td in the particle-pellet model. For the re-
verse case Tg << Tc, however, SIM with reaction control prevails as against
SIM with ash diffusion for the particle-pellet model. In view of the differ-
ent size dependencies in these regimes, studies with different sizes of
particles can afford a distinction between the two types of models.
In the intermediate regime where both Tg and Tc are of comparable
magnitude, the model yields an algebraic equation for the conversion-time
relationship which can readily be used. The basic feature of this model is
that it predicts the S-shaped curve observed experimentally in some sys-
tems. Also, in the event that Tg -+- 00 , the crackling proceeds faster,
rendering the pellet porous and taking it to some intermediate level of con-
version (xI). Subsequent conversion to 100% cannot, however, be observed
in view of large Tg· The model also explains the leveling off of conversion
below 100%, as observed in some systems.
The simple crackling core model could be extended, for example , by re-
moving the assumption of no diffusion resistance to gas inside the porous
part of the pellet. Also, one might consider a volume reaction model in the
porous part of the pellet rather than a shrinking core model for the in-
dividual grain.
Nucleation Model
An alternative approach to provide an explanation for the observed sigmoid
behavior in some gas-solid systems has been attempted in a class of models
which are generally referred to as nucleation models. Nucleation effects
are often significant in systems such as reduction of metallic oxides. In
these systems the process proceeds with the generation of metallic nuclei,
which subsequently grow and finally overlap. The rates of these individual
processes strongly affect the conversion-time behavior of the system. In
the event that the nuclei generation rate is faster, the whole surface gets
covered with the metallic phase and the reaction proceeds in a topochemical
manner. On the other hand, for a slow generation rate, the metal-oxide
interface is irregular and different considerations prevail in estimating the
conversion-time relations.
An empirical model that relates the conversion to the time has been pro-
posed by Avrami ( 1940) :
x = 1 - exp( -Ct N ) ( 31)
C and N in this equation are constants which can be obtained by fitting
experimental data. The following three-parameter equation in differential
form has been proposed by Erofeev ( 1961):
Gas-Solid Noncatalytic Reactions 315
dx
= kx a (1 - x) b ( 32)
dt
and seems to provide adequate fit to experimental data (N euburg, 1970).
In a more rational approach to nucleation, Ruckenstein and Vavanellos
(1975) considered the existence of germ nuclei in the form of impurities
present and the embryos of the new solid phase. In the process the germ
nucleus is transformed into a growth nucleus, leading finally to product
formation. The growth process is treated as an activated process, and
employing the modified Avrami model, the following conversion-time relation
may be obtained:
1
x = Sk 3 N k f ( exp(-k ft f)(t ( 33)
growth n,o n ) 0 n n
where Nn O is the number of germ nuclei per unit solid volume at the begin-
ning, and' knf and tnf are the rate constant and time required for nucleus
formation, respectively.
Bhatia and Perlmutter ( 1980) have also analyzed this problem using the
population balance approach. The possibility of both homogeneous and hetero-
geneous nucleation around a germ nucleus is considered and the basic Avarami
model has been modified to include a term for the initial volume of a growth
nucleus.
Some experimental data on the formation and growth of nuclei for the oxida-
tion of copper iodate and reduction of wustite have been provided by Neuburg
(1970) and El-Rahaiby and Rao (1979). Some aspects of the theory of nuclea-
tion have also been discussed (Rao, 1979).
Extensions of the Basic Model
The preceding section dealt with simple basic models. In the present section
we extend these models by considering several complexities that are likely to
be present in practical situations. The complexities that can be considered
are those due to the effect of bulk diffusion, existence of pressure gradients
in the pellets, nonisothermal effects, and effects due to structural changes.
The effect of structural changes, being of much greater practical relevance,
will be considered at some length at the end of the section.
Bulk- Flow Effects
Detailed formulations accounting for the effect of bulk flow have been pre-
sented by a number of authors (e.g., Beveridge and Goldie, 1968; Gower,
1971; Sohn and Sohn, 1980) for the sharp interface model. The bulk flow
within the solid assumes greater importance for reactions with volume change,
and typical examples of industrial gas-solid reactions with volume change are
C(s) + C0 2(g) = 2CO(g)
Ni(s) + 4CO(g) = Ni(CO) lg)
FeC1 2(s) + H 2(g) = Fe(s) + 2HC1
316 Doraiswamy and Kulkarni
The conservation equation for the mass of reactant in situations of this type
should include a term for bulk flow and can be represented in analogy with
the gas-solid catalytic systems (Weekman and Gorring, 1965) in dimensionless
form as
( 34)
with the boundary conditions
R = 1: CA= 1 ( 35)
( 36)
8 is a constant, and ¢ and 0 represent, respectively, the Thiele modulus and
volume change modulus in this equation, and are defined as
( 8 + l)V
k p ( 37)
¢ = 2( 8 + l)D
e
( 38)
The concentration profile for the gaseous reactant as obtained from the solu-
tion of Eq. (34) can be related to the consumption of solid as follows:
dR.
1
--;:-=- ( 39)
dt
where
A
t =
p ( 40)
( 8 + l)V t
p
Bearing in mind the relationship between conversion and interfacial position,
X = 1 - ( :i) 8+1 ( 41)
we can calculate the conversion-time relationship. Sohn and Sohn (1980)
have obtained the following asymptotic solution for the conversion-time
behavior:
Gas-Solid Noncatalytic Reactions 317
ln(l + 8) t X) 2/(B+l) -
1 _ CB+ 1)(1 - 2(1 - x)
8 </)2 B - 1
( 42)
= p(x)
In general, the net effect of volume change is to change the time required
to attain a given extent of conversion by a factor 8/ln(l + 8). It is also
possible to incorporate the effect of external mass transfer in the presence
of volume change effects. The conversion-time relationship can now be ob-
tained as
t [l _ (1 _
x
)1/(B+l)l + ¢2[ 8 ( ) + 2(1 + 8)
ln(l + 8) P x Sh
x] ( 43)
In the event that nonisothermal conditions prevail, significant pressure
gradients can exist within the pellet and the simple analysis above is no
longer applicable. In fact, there is a need now to modify the conventional
Fickian law of diffusion, and more sophisticated models for diffusion in
porous media (such as the dusty-gas model of Mason et al. ( 1969) may have
to be invoked. (This has not been attempted so far.)
Even in instances when the bulk-flow effects are not present (no mole
change), pressure gradients may arise due to temperature gradients. In
the presence of pressure gradients it has been shown (Wong et al. , 1976;
Hite and Jackson, 1977) that the conventional Weisz-Prater temperature holds
true only in the case of Knudsen diffusion. Significant alterations occur
when bulk diffusion prevails. In fact, an additional term ( B2 / 4) is included
m
in the equation for maximum temperature rise where Bm refers to the ther-
micity factor. Pressure gradients can thus have a significant effect on the
conversion-time relations, depending on the regime of diffusion. In the
case of gas-solid reactions, the presence of structural effects continually
alters the diffusional regimes. The effects of pressure gradients cannot
therefore be ignored all through the course of conversion. The influence
of pressure gradients in gas-solid reactions following SIM has been examined
by Deb Roy and Abraham (1974) and Turkdogan et al. (1973). Detailed
numerical solutions have been obtained to the pressure gradients that arise
because of Knudsen flow in the ash layer with small pores and due to the re-
actant gas having a diffusivity different from that of the product.
Nonisothermal Effects
When the chemical reaction is accompanied by evolution of heat, temperature
gradients may exist within the pellet. The local reaction rate in the interior
of the particle can thus be higher, and the higher inside temperature can
cause some difficulties, such as sintering. Additionally, depending on the
heat generation /removal rate, the system may exhibit multiplicity behavior.
In the analysis of nonisothermal SIM, equations describing heat trans-
fer through the gas film and ash layer and heat generation due to reaction
at the interface can be written in a manner analogous to the mass transfer
process. Such a formulation affords an easy analysis of the nonisothermal
effects. The approach, however, presumes the validity of the pseudo-
steady-state assumption, which while justifiable for mass transfer processes,
is not a good approximation for heat transfer processes.
318 Doraiswamy and Kulkarni
Luss and Amundson ( 1969) have provided an analysis that incorporates
the transient heat accumulation term and their solution can be represented
as
T.
1
sin µRi
A f(µ)
fl sin
R. R.
1 1
where µ's are the positive roots of the transcendental equation
µ cot µ + Nu - 1 = 0 ( 45)
and the various other parameters are defined as follows:
' - R.1___,,---
f( ') = _______ R~) + !(_!__
13 Sh
- 1) <,3 - R.3)
1
Da exp[y(l - 1/T.) ]
1
( 46)
p k'
B e
P2 = C (47)
MBps psDeCAb
f(µ) =
(Nu - 1) 2 + μ2 ( 48)
2
Nu(Nu - 1) + µ
Equation ( 44) gives the interface temperature in terms of the interfacial
position }½, which can be obtained from
dR.
1
-,.,- = n ( 49)
dt
where n refers to the effectiveness factor under nonisothermal conditions.
For the specific cases of coke regeneration and reaction of carbon with
oxygen and steam, model equations based on SIM have also been developed
by Shettigar and Hughes ( 1972) and Rehmat and Saxena ( 1980). The
problem of thermal instability in gas-solid systems has been discussed by
Cannon and Denbigh (1957). Shen and Smith ( 1963), Aris ( 1967), Ishida
and Wen (1968), and Wen and Wang (1970) for SIM. The phenomenon of
thermal instability leads to sudden transitions in the rate-controlling steps
and has an important bearing on reactor operation, as runaway conditions
may occur.
The nonisothermal SIM is well suited for describing decomposition re-
actions (Narsimhan, 1961; Campbell et al., 1970; Hills, 1968). For a de-
composition reaction
A(s) + B(s) + P(g)
the application of the phase rule suggests one degree of freedom. Each
temperature T d therefore has a fixed value of partial pressure Pd of the
Gas-Solid Noncatalytic Reactions 319
product gas P, and once this value is reached, the reaction starts and the
front moves inside. The process is controlled either by heat or gas diffu-
sion through the product layer and typically yields SIM behavior.
In the event that heat transfer through the ash layer controls, the re-
action interface stays isothermal and the equation for SIM with ash diffusion
control and De replaced by k~ (in the definition of T in Table 2) represents
the conversion-time behavior. Where gas diffusion through the ash layer
is controlling, the variation of De with temperature (De o:: Tl/2 in the
knudsen regime: De o:: TL 5-2 in the bulk diffusion regime) should be ap-
propriately accounted for (Mu and Perlmutter, 1980).
Nonisothermal effects have also been analyzed for the volume reaction
model by Shettigar and Hughes (1972), and for the particle-pellet model by
Calvelo and Smith (1970). The latter analysis is based on the pseudo-steady-
state hypothesis, which is not valid for heat transfer. The governing
transient equations for heat and mass for the volume and grain models are
presented in Table 4 together with the relevant boundary conditions. An
analysis of the complete transients for the particle-pellet model indicates a
shift in the temperature maximum from the surface to the center with
progress of time (Sampath et al., 1975). Nonisothermal effects along with
structural variations have not yet been analyzed.
Effects of Structural Variations
The earlier parts of this section were concerned with the extension of the
basic models to incorporate certain modifications resulting from the nonlinear
nature of chemical reaction, pressure gradients and bulk flow within the
pellet. Here we shall reexamine these models with a view to incorporating
the structural changes that occur within the solid during reaction. The
main structural changes are due to chemical reaction and sintering. The
differences _in the molal volumes of the reactant and product lead to varia-
tions in the particle voidage and effective diffusivity during the course of
reaction. To account for these effects it is necessary to formulate a rela-
tionship between the voidage, diffusivity, and extent of conversion. A
large number of such relationships to account for these effects have been
proposed using different models, and the more important of these are sum-
marized in Table 5. The incorporation of such effects in the basic models
give rise to conversion -time relationships which show a sigmoid behavior
observed experimentally. Also, where the porosity at the surface of the
pellet becomes zero (pore closure), the governing equations predict incom-
plete conversion. Such behavior has, in fact, been observed in some ex-
perimental systems. Hartman and Coughlin (1974, 1976) and Georgakis
et al. ( 1979) have used a modified grain model to describe pore closure due
to grain swelling in the sulfation of lime.
In a departure from models based on pore behavior, Garza and Duduko-
vic (1982a,b) have proposed a variable-size grain model for systems with
structural changes. Incorporating the diffusivity variations with porosity
for systems with no pore closure, the model first calculates the time re-
quired for complete conversion of the surface layer of the solid. This
product layer then moves inside, toward the center. In systems where
pore closure occurs, the model evaluates the time required for pore closure
and obtains the concentration profile of the unreacted solid at this instant.
Further processes inside the pellet are described by SIM with the incorpora-
tion of a solid concentration profile. Approximate analytical solutions have
c..
c::,
""'
TABLE 4 Typical Diffusivity and Porosity Variations due to Structural Changes in Pellet
Number Relationship Model References
1 f ex: (1 - ~) Volume reaction Fan et al. (1977)
c = f co + 1 B 0 model
-1
D
e
2 = cx: cx: Volume reaction Fan et al. (1977)
D 21exp [1 - (B/ll~)cx:J + 2- 1}
eo model
where ex: 1, cx: 2 , and cx: 3 are constants and B refers to solid concentration
VB + VI
3 f =f +(1-f) Levenspiel (1979)
c co co VB - \! s s
f
D =D ~
e eo f
co t,
0
where VB and Vs refer to molar volumes of species and B and s per mole a
i;;·
of solid. v 1 refers to molar volume of inert per mole of solid B. ~
~
3 '<
1 ...., f A
C ;:l
4 = (:Gao) where rG refers to the radius of the grain Particle-pellet Ramachandran A.
1 - f
co model and Smith :,::
( 1977a) i:::
D f ~
e C A
D- = f
eo co ~-
:;')
Eventually, with progress of time, the pore will be completely A
blocked. The time required for pore closure is obtained as Cl)
~
'
E:
1 1 + z
= Bi1 [ Z zv zv f ) Particle-pellet Georgakis et al. 0
- 1 (1 - f )2/3 ( 1 - . zv co ;:s
p \) model (1979)
co 2
1
A
+ 1 - l 1+-z\)-f ) ~
Z - 1 1 2/3 ] ( ....
t=;·
\) (1 - fco) (l _ fco)l/3 1 -zv co
::0
~
C')
vCpBMC ....
where Zv = v p (1 s·
;:s
B C fc)MB c,,
D 1 - f
e co A 3
5 = 1 - (y - 1)(1 - rGi) Variable grain Garza and
D f
eo co model Dudukovic
( 1982)
where y refers to the ratio of the volume of solid product
formed per unit volume of reactant consumed and refers rm
to the dimensionless position of the shrinking core in the
grain. The time required for pore closure is obtained as
Da { 2 [y + (1 _ y)r\3] 2/3}
T = l - n + - f 1-n +
1 - y
where
f i1'3
co ]
r\ = [1 + (1 - f )(1 - y) c.:,
co ts)
._
Gas-Solid Noncatalytic Reactions 325
been developed by Garza and Dudukovic (1982a,b) and are included in
Table 5 together with the solutions for other models.
A new class of models incorporating structural features such as pore
size distribution have come up in recent years. The simplest of such
models is the single-pore model of Ramachandran and Smith ( 1977a) and
Chrostowski and Georgakis (1978). The model of Ramachandran and Smith,
sketched in Fig. 8, analyzes the changes taking place in a single pore
which is supposed to be representative of the overall pellet. The single
pore is assumed to be cylindrical with the concentric ring of solid B associ-
ated with it. Depending on the molal volumes of the reactant and product,
the pore size increases, decreases, or stays constant with progress of re-
action. The model yields a simple conversion-time relationship and requires
a knowledge of the average structural properties of the solid (pore radius,
length, radius of associated solid). The simple model has been extended to
incorporate the effect of bulk flow and reversibility of reaction (Ulrichson
and Mahoney, 1980).
The use of average structural properties leads to mathematically tract-
able models that are normally adequate for most gas-solid systems. More
rigorous models, however, should include the distribution and variations
in the structural properties with reaction. Thus most solids have an initial
pore size distribution that evolves during the reaction due to pore inter-
section and coalescence. The net reaction surface is therefore a variable,
and any rigorous structural model should account for this variation. Some
of the recent models that account for this will now be discussed.
The model of Christman and Edgar ( 1980) assumes the applicability of
a single-pore model at a local point r in the pellet. The rate of reaction
thus obtained is averaged over the existing pore size distribution, which
is then used in the mass balance equation together with the average values
of other parameters ( effective diffusivity, rate constant, etc.). The mass
balance equation is supplemented by an equation describing the evolution
of pore size distribution with the progress of reaction, and Christman and
Edgar (1980) modeled this process using a population balance approach.
The key feature of this model is that it gives the variation of pore size
distribution with time and position. This additional information can be
used for model verification and selection. A similar approach based on
population balance has been introduced by Gavalas ( 1980).
The model of Simons and Rawlins ( 1980) assumes that each pore within
the solid ends up at the surface of the pellet, where a distribution of pore
radii can exist. The model calculates the flux for a pore of radius rp and
averages it over the surface pore size distribution to obtain an average flux
of the gaseous reactant at the surface. This is then related to the conver-
sion of solid B. The model, though simple, does not account for the varia-
tion of reaction surface with time.
Perhaps the most realistic model is the random pore model of Bhatia
and Perlmutter (1980, 1981b) , which assumes that the actual reaction sur-
face of solid B is the result of the random overlapping of a set of cylindri-
cal surfaces. The development of the reaction surface as envisaged in this
model is sketched in Fig. 9. The model proceeds with calculation of the
actual reaction surface and then the conversion -time relationship in terms
of the intrinsic structural properties of the solid.
The following equations for the conversion-time behavior for the cases
of kinetics and ash diffusion control have been obtained:
c:.,
t-,
0)
PRODUCT C
~ ss/;r-
i
'
I
I
- ~ '
SOLID B
~ -a:: ~SOLIOB
ASSOCIATED
0
a. WITH THE
~1 PORE
l (a) AT TIME ZERO (bl Zv< 1 (cl Zv > 1
t:,
0
AFTER SOME REACT ION
~
;;;·
~
I:)
FIGURE 8 Schematic representation of the single-pore model. 3
'<
I:)
;:1
P..
:,::
s:::
~
I:)
'"'l
2.
Gas-Solid Noncatalytic Reactions 327
\ DIFFUSION LENGTH
\ FOR GAS A
AREA OF UNIFORM
GAS CONCENTRATION
(a ) ( b ) ( C )
FIGURE 9 Development of reaction surface according to the random pore
mode. The shaded area represents unreacted solid B, the dashed area the
product layer. (a) Early stage showing product layer around each pore;
(b) intermediate stage, showing some overlapping reaction surfaces; (c)
later stage, showing full development of product layer and reaction surface
for the particular view chosen. (From Bhatia and Perlmutter, 1981b.)
dx
A = (1 - x)[l - 1/J ln(l - x)] 112 ( 50)
dt
and
1/2
CA ( 1 - x)[ 1 - 1/J ln(l - x)]
A
dx
-;;;-- = ( 51)
dt 1 + S'Z/1/J{[l - 1/J ln(l - x)]l/ 2 - l}
where
1/J = and ( 52)
The parameter S' characterizes the diffusional resistance to the flow of the
gaseous species in the product layer. For 1/J = 0, Eq. ( 50) reduces to the
volume reaction model with n = 1, and for 1/J + 1 the behavior closely ap-
proaches the grain model. It is apparent, therefore, that the concept of
reaction order with respect to solids is closely related to the structure of
the solid, and the random pore model for the first time provides a rational
meaning to the order of reaction with respect to solids. The relation be-
tween 1/J and n is graphically illustrated in Fig. 10.
Several distributions for the parameter 1/J can be assumed, and Bhatia
and Perlmutter ( 1981a) have shown that a uniform pore size leads to the
lowest reactivity of solid. Also, for a given pore size distribution, an
optimal structure exists for highest activity of solid.
328 Doraiswamy and Kulkarni
0-8
z
Q
I-
u 0·6
..,
ct
...a::
0
..,a:: 0•4
0
a::
0
0·2
0 ..,__ _ _ _ _...__ _ _ _ _.___ _ _ ___,....__ _ _ ___,....__ _
0 0·5 1·0 1·5 2·0
PORE STRUCTURE PARAMETER, 'P
FIGURE 10 Relationship between the structural parameter of the random
pore model and the order of reaction with respect to solid in the volume
reaction model. (From Bhatia and Perlmutter, 1980.)
The model of Bhatia and Perlmutter (1980, 1981a,b), discussed above,
considers the pores and reaction surface areas to be equal. Although this
seems to be a good approximation at low levels of conversion, it is less
accurate at high conversion levels. In a subsequent paper, Bhatia and
Perlmutter ( 1983) provided generalization in terms of moving pore and re-
action surface, and for the case of no intraparticle and boundary layer
diffusional resistances, obtained the following relation:
t = + ( 53)
s;
For S' + 0 and this equation reduces to the cases of kinetic control
00 ,
and product layer diffusion control. In this equation S* and refer to
the dimensionless reaction surface area and pore surface area, respectively,
and these quantities can be appropriately evaluated for different models
of the internal structure of the solid. Thus for the grain model,
Gas- Solid N oncatalytic Reactions 329
S*(x) == ( 1 - x)m ( 54)
S*(x) == [1 + (Z - l)x]m ( 55)
p V
while for the random pore model,
S*(x) == (1 - x) ✓ 1 - 1/J ln(l - x) ( 56)
S*(x) == [1 + (Z - l)x] ✓ 1 - 1/; ln[l + (Z - l)x] ( 57)
p V V
Substituting these expressions for S* and s;in Eq. (53) and integrating
leads to the desired conversion-time relationship. A comparison of pre-
dictions obtained using the grain model and the random pore model for a
set of parameter values is illustrated in Fig. 11.
Sintering
The temperature variations within the pellet in the presence of an exother-
mic reaction result in sintering, which causes a decrease in the effective
diffusivity of the pellet. Alternatively, the grain size increases and the
specific surface area of the grain decreases. Simple empirical laws such
as exponential decay of diffusivity with reaction (Evans et al., 1973) or
first-order decay in surface area (Ranade and Harrison, 1979, 1981) can
be used to account for sintering. The primary influence of sintering is to
decrease pore intersection. This causes a decrease in porosity and an in-
crease in the tortuosity factor of the pellet. These effects have been
taken into account by Kim and Smith (1974). Chan and Smith (1976), and
Ramachandran and Smith ( 1977b). The combined effect of chemical reaction
and sinterin'g on the diffusivity in the pellet has been expressed by the
relation
3 2
(1-f)(rGi)](l-f) ( 58)
0 rGO p
where fp represents the fraction of pores removed. Assuming the rate of
removal of pores to be porportional to their availability, the following simple
equation for the variation of fp with time results:
( 59)
where kp, analogous to the conventional rate constant, represents the rate
constant for pore removal.
General Formulation of Model Equations
In the previous sections we described the basic models and considered
their extensions to include more complex cases, such as bulk flow, non -
isothermicity, and so on. In the present section we develop a general
mathematical formulation of these models, including a few case studies.
w
w
0
13' = 1 {3 1 = 10
1·0,- --=
1/
0· 8 I- I! 1
// ✓ /3 = 50
1/',
-
·,
>< -~
; 0·6
0
f/)
0·4l
u
i II /
GRAIN MODEL
0·2
RANDOM PORE MODEL
t:,
0
z
cii'
~
p
0 L - - - - . . . L . . . - - - - - - ' - - - - . . l . - . - - - - - 1 . . - - - _ _ J L . ._ _ _.L_
_ __J
0 2 4 6 8 iO 12 3
14
fl '<
TIME , t p
~
P.
FIGURE 11 Compariso n of conversio n prediction s for several models for various values
~
of S'. Parameter s are ljJ = Zv = 1, ¢ = 0. E.
;>;'
p
~
i::.
Gas-Solid Noncatalytic Reactions 331
It is preferable to begin with the volume reaction model, which is
described by Eqs. ( 10) to ( 14). For a reaction first order in the gaseous
component, these equations can be rewritten as
1
As ~ (ocRS 3
~A) == ¢ 2
dX
A ( 60)
R aR aR at
dx CA
A == (61)
F(x)
dt
where oc refers to the diffusivity ratio DelDeo, x the conversion, ¢ the
Thiele modulus based on the initial diffusivity, and 8 the geometric factor.
Following the general technique developed by Del Borghi et al. ( 1976), the
cumulative gas concentration can be written as
1/J == f t
0
A
CA dt
A
== fx f(x)
0
dx ( 62)
and Eqs. ( 60) and ( 61) then transformed into
( 63)
Substituting for 1/J from Eq. (62) we obtain
d2
f(x) - - + 8 f~x) d; + f'(x)(d: )2 - k(x) == 0 (64)
dit 2 R R dR
Equation ( 64) is an ordinary second-order differential equation of second
degree and its solution directly gives the conversion profiles. The equa-
tion is sufficiently general, since several functional forms [f(x)] suitable
to different models can be chosen. Typical forms of f(x) for some of the
more frequently used models are presented in Table 6. Prasannan et al.
( 1982) has employed a collocation procedure to solve this equation, and the
results obtained by them using the functional forms of f(x) corresponding
to the particle-pellet model, the particle-pellet model with structural varia-
tions, and the nucleation model are reproduced in Fig. 12.
ANALYSIS OF REACTORS
We have so far been concerned with the description of the single-particle
system, and several models attempting to describe qualitatively and semi-
quantitatively the complexities in real systems have been discussed. Newer
models-many of them extensions of the basic model-are constantly appear-
ing in the literature and efforts to quantitatively and realistically describe
the systems continue. Despite these efforts, the single-particle behavior
may continue to involve uncertainties, and the situation becomes even more
332 Doraiswamy and Kulkarni
TABLE 6 Functional Forms for F(x) for Different Gas-Solid Reaction Models
Number Functional form f(x) Reaction model
-n
1 (1 - x) Volume reaction
model
(1 _ x)l/3 + (1 _ x)2/3
2 -l - Sh Grain model
(1-x//3 (1-x)2/3
----- + ------'-----'---- Grain model
3 -l - Sh Sh[Z + (1- z )(1- x)] 1/3
\) \)
with structur-
al variations
(1-n) /n
4
1
n 1 -
1
X
ln ( 1 ~ x) Nucleation
model
Zv= 1- 5
0-8
>C
0-6
z
0
vi
a::
UJ
>
z
0 0-4
u
0-2 n=3
0 L---'---""""=--'----'-----'---'-'_ _..___ __.__ __,__ __,~_ _.___ ___,
0 0-2 0-4 0·6 0-8 1-0 1·2
DIMENSIONLESS TIME, t
FIGURE 12 Solid conversion versus dimensionless reaction time for particle
pellet model with and without structural changes and for nucleation model.
Gas-Solid Noncatalytic Reactions 333
difficult when particle assemblies, as in the case of reactors, are concerned.
The common types of reactors employed in gas-solid noncatalytic systems
are packed-bed, fluidized-bed, and transport-line reactors.
The additional complexities that need to be accounted for in the analysis
of reactors arise out of the fluid flow aspect of the problem. In addition
to the heat and mass transport processes within the pellet, one needs now
to consider the transport processes between the pellets. Also, specific to
each mode of operation, the design criterion may depend quite critically on
the pressure drop-gas flow relationship as in the packed-bed, or on the
minimum fluidization velocity as in the fluidized-bed, or on the terminal
velocities of particles as in the transport-line reactors. The solids feed to
these reactors may be of constant size and shape or may involve a size dis-
tribution. None of these effects manifest themselves in single-particle
studies but become important considerations in the design of reactors. We
present below a discussion of each of these reactor types.
Packed- Bed Reactors
Many gas-solid noncatalytic reactions are carried out in packed-bed reactors,
some important examples being the roasting and sintering of ores, reduction
of metal oxides, production of light weight aggregates, and incineration of
solid wastes. A typical sketch of a packed-bed reactor is shown in Fig. 13.
The conventional packed bed contains a charge of solid reactant and the
gas passes through the voids in the bed. The reaction between the gas
and the solid leads to the formation of a reaction front that gradually moves
along the packed height. This mode of contact is batch with respect to
the solid and is unsuitable for large-scale particle applications. In many in-
stances it is preferable to have solids on a moving grate supplied with gas
blown through the bed on the grate (Fig. 13b). The principal correspond-
ence between these two modes of contact is that the time for the reaction
front in Fig. 13a can be identified with L/u in Fig. 13b, providing justifica-
tion for the work done on conventional transient fixed-bed systems (Szekely,
et al. , 1976).
UNREACTED GAS IN
REGION
REACTION
FRONT
(
REACTED ,._REACTION
REGION FRONT
t
GAS IN
(a) (b)
FIGURE 13 Gas-solid contacting in a fixed-bed arrangement: (a) packed
bed; (b) packed bed with cross-flow contacting.
334 Doraiswamy and Kulkarni
In the packed bed as sketched in Fig. 13a, several nonidealities can
exist. The flow can deviate from the ideal because of radial variation in
velocity and mixing effects brought about by the presence of pellets. Also,
the temperature across the cross section of the packed bed in practical
systems may not be uniform. These problems lead to a consideration of the
variation of system properties in the axial and radial directions. One way
of accounting for these situations is by superimposing an effective trans-
port mechanism on the overall transport by plug flow. The fluxes due to
these additional transport mechanisms are described by the Fick's law of
diffusion for mass and the Fourier law of conduction for heat transfer with
effective system properties. Although this way of representing dispersion
in packed reactors appears quite sound, the resulting equations are in-
variably rather cumbersome in that they involve solution of two-point
boundary value problems. Also; this class of models predicts that the in -
jected pulse of tracer spreads at an infinite velocity in all directions, which
has never been observed experimentally. Chiefly due to these disadvantages,
two other classes of models have been proposed for describing the packed
bed.
In so-called finite-stage models the bed is considered as being composed
of a system of interconnected mixing cells of roughly pellet diemnsions. The
first quantitative study using such a model appeared in a paper by Kramers
and Alberda (1953). Deans and Lapidus (1960a,b) developed a mathematical
model describing mixing characteristics in fixed beds for both reactive and
nonreactive systems. McGuire and Lapidus (1965) analyzed the transient
behavior of packed-bed reactors. The review by Hlavacek and Votruba
( 1977) covers most of the applications of finite-stage models, and it appears
that practically no application to gas-solid noncatalytic systems exists.
The finite-stage models are attractive if only a few stages are involved;
however, for a rigorous description, it is often necessary to consider a
large number of stages--when significant computational advantage is lost.
To overcome this difficulty Hinduja et al. (1980) have developed a cross-
flow model, which divides the void region in the bed into stagnant and flow-
ing parts. The stagnant region corresponds to the wakes of packing ele-
ments, and dispersion is introduced by assuming that there is exchange of
fluid between the stagnant and flowing regions throughout the bed. The
physical situation gives rise to first-order initial value differential equations,
as against recurrence relations in the mixing cell models and second-order
differential equations in the dispersion models. None of these alternative
models have yet been applied to gas-solid noncatalytic systems. In the
present section, therefore, we shall be mainly concerned with dispersion
models.
Before presenting details of the dispersion models, some comments on
their suitability for noncatalytic reactions are in order. The section on
single-pellet studies has amply brought out the fact that the behavior of a
single pellet is characterized by changes in the controlling regime during
the course of its conversion. In the simplest case of SIM, even if one
starts with a reaction-controlled system, the behavior eventually becomes
diffusion controlled, suggesting that unlike in the case of nondecaying
catalytic systems, the effectiveness factor for the pellet is a function of
time. This makes it necessary to consider individual pellets in the reactor
explicitly. In other words, the use of pseudohomogeneous models becomes
Gas-Solid Noncatalytic Reactions 335
inappropriate. Of necessity, therefore, we have to use the one- or two-
dimensional heterogeneous models. These models require a knowledge of
intraparticle and interphase transport properties. In view of the noniso-
tropic nature of the packed bed, the interphase transport properties are
generally different in the axial and radial directions. The models, in
general, are therefore more complex and do not yield analytical solutions
even in simple cases.
In what follows we present a general framework for the development of
these models by considering the one-dimensional heterogeneous model. As
far !_1.S the single pellet is considered, it will be assumed that the process
can be described by the grain model.
Formulation of the Model
The first step in the formulation of the model is writing the mass and en-
ergy balance equations for the external field surrounding the pellets.
These equations are coupled to the mass and energy balance equations for
the individual pellets, where the general chemical reaction
A(g) + B(s) ~ C(g) + D(s) (LIH < 0)
occurs. It is seen from the reaction stoichiometry that there is no change
in moles during the reaction, and therefore bulk-flow effects within the
pellet can be ignored. To simplify the analysis, it is further assumed that
the physical properties of the solid, such as thermal conductivity, heat
capacity, molar density, and so on, are constant. The chemical reaction is
a simple first-order reversible reaction occurring at a sharp interface within
each grain in the pellet and transport resistance through the ash layer in
the individual grains is negligible. The nonisothermal nature of the re-
action does not bring about sintering or agglomeration of solid particles and
the initial physical structure remains unaltered. Also, the solid tempera-
ture is assumed to be uniform throughout the pellet. A rigorous proof for
the isothermality of pellets has been given by Carberry ( 1976).
In the external field it is assumed that axial diffusion terms are
negligible compared to convective flow terms, the concentration and tempera-
ture are constant in the radial direction, and the pressure drop across the
bed is negligible. These assumptions allow the use of the simple one-
dimensional heterogeneous model. The nonisothermicity of reaction affects
the linear velocity and density of gas along the bed length, and these
variations cannot be ignored. Also, the heat generated in the reactor is
lost through the sensible heat carried by the gas leaving the system and
by convection at the outside surface of the reactor wall.
These assumptions simplify the formulation of the mathematical model
although the model becomes somewhat more restrictive. Omitting the de-
tailed material and energy balances, one could write the dimensionless
equations as follows:
Fluid Phase: Reactant:
a
dT
336 Doraiswamy and Kulkarni
Product:
R=l)
"
= 0
( 66)
The initial and boundary conditions associated with these equations ex-
pressed in dimensionless form are:
Initial conditions:
YA (z, T~ 0) =0 ( 67)
Yc(z, T~ 0) = 1.0 (68)
cc ( z, T ~ 0) = 1.0 ( 69)
8( z, T~ 0) = 1.0 ( 70)
Boundary conditions:
YA (z = 0, T > 0) = [YAo +
3A 4( 1 - fB) y A I R=l]/[, + 3A 4(1 - fB)]
8* . 8
( 71)
y' (0,T)
C
=1 - YA (0,T) ( 72)
cc(0,T) = 8( 0, T) ( 73)
8*A (1 - f ) + 1
3 B
= l+A/1-fB) ( 74)
Equations (71) to (74) are obtained by carrying out a molar balance of
gaseous reactant A, an overall molar balance, and an energy balance of
the gaseous mixture at the entrance to the packed-bed reactor.
Pellet Equations:
Product:
( 76)
where the dimensionless radial position of the reaction front inside each
grain is given by
Gas-Solid Noncatalytic Reactions 337
( 77)
and the initial and boundary conditions associated with the internal field
problem are given in dimensionless form as follows:
Initial conditions:
y A (z, R, ,..; 0) =0 ( 78)
Yc<z, R, ,..; 0) =0 (79)
rGi(z, R, ,..; 0) =1 ( 80)
Boundary conditions:
clyA
-,.._-(z,0,T) = 0 (81)
clR
aye
-,.._-(z,0,T) = 0 (82)
clR
cly,.._A(z,1,T) = : 2 [~* YA -- yA(z,1,,)] ( 83)
clR
clyC _ V clyA
-,.._-(z,1,T) - v' -,.._-(z,1,T) ( 84)
clR aR
Energy Balance Equations: Fluid phase:
f ~ = 0~ - ~ (85)
B a, az ex:
az
The change of superficial gas velocity with respect to the axial position is
obtained as
( 86)
where
cx:(0,T) = 0(0,T) (87)
The change of temperature of the reacting pellets at any particular axial
position with respect to time in dimensionless form can be obtained as
cl 0* = A R - 3
A (0* - 0) (88)
cl T 6 1 f 7
p
338 Doraiswamy and Kulkarni
with the initial condition
8*( Z, T ._; 0) = 1 ( 89)
The parameter R defines the extent of reaction and is given by
( 90)
Equations ( 65) to ( 90) completely define the system subject to the as-
sumptions stated earlier. No analytical solution to this set of equations
exists and numerical methods have to be employed. The model involves
formulation of several dimensionless groups which express the rate of one
process in relation to another. For large and small values of these param-
eters, the system approaches one or the other asymptotic limit. In what
follows we shall qualitatively analyze the influence of these dimensionless
groups. ,
The dimensionless group A 6 ( = -t, H /CpsTo) involves the heat of re-
action. In the event that A 6 approaches zero, the system behavior tends
to be isothermal. Even for finite values of A6, isothermal behavior can be
approached if A 5 defines the convective heat transfer through the wall of
the reactor in relation to the axial heat transfer through the gas phase in
the bed. The parameter A4 is a measure of the relative rate of mass trans-
fer across the gas-solid interface to the rate of mass transfer 'through the
gas phase in the bed. For large values of A 4 , the flow through the bed
becomes controlling, and in the limiting case, the gaseous reactant gets
completely consumed at some axial distance in the bed. The sharp inter-
face thus formed moves along the axial coordinate with time. In the other
extreme of very low values of A4, the transfer across the fluid-solid inter-
face takes control. More strictly, at low values of A 4 , the controlling
regime is shifted from the external field to the internal field.
The internal field is specified in terms of two other dimensionless
groups. The group A 1 measures the relative rate of the chemical reaction
in relation to the internal gas diffusion, while the group A 2 measures the
relative importance of external gas film mass transfer to internal diffusion.
For a specified value of A4 depending on the value of A 2 , the bed behavior
approaches either gas-film control (A2 + 0) or a stage where the entire
bed behaves as a single pellet with a uniform environment of gas around
(A2 + large value). The parameter A1, for a specified value of A 4 , de-
termines whether reaction control or diffusion control would prevail in the
system.
The advantages of a skeleton analysis of this type is that it provides
asymptotic solutions to the general model as well as guidelines for the be-
havior of the model. Thus, for isothermal systems (A6 = 0) with a very
small value of the parameter A4, it is seen that any of the three mechanisms
( gas film, internal diffusion, or reaction) in the internal field will govern
the reactor behavior. These equations can be solved analytically to obtain
the following expressions for the extent of reaction ( cj>*) in the bed.
Diffusion Control
In view of constant concentration of gas everywhere in the bed, the pellet
and the bed becomes indistinguishable from each other and the extent of
reaction in the bed is obtained as
Gas-Solid Noncatalytic Reactions 339
¢* == 1 - z 31 ( 91)
where z1 refers to the dimensionless position of the reaction front within
the pellet and is obtained as
3Z~ + 1 ::: TD ::: ( 92)
The mole fraction of gaseous reactant within the pellet is given by
1 - R Zl
1 - YA ::: -:;;--- ( 93)
1 - Zl
R
Reaction control: The extent of reaction in the betl is obtained as
3
( 94)
A
¢* ::: 1 - rGi
where rm refers to the dimensionless position of the reaction front within
each grain and is obtained as
( 95)
Gas film control: The extent of reaction in the bed is given by
¢* ::: T ( 96)
In the other extreme case, where the gas flow through the bed becomes
controlling in relation to its transfer across the gas-solid interface, the con-
trolling regime lies in the external field. This was the case analyzed by
Evans and Song (1974), who considered isothermal and nondispersive condi-
tions in the reactor and spherical pellets with no external mass transfer
resistance. For this case the gas concentration varies with axial position
in the bed and each pellet is subjected to a different environment. A re-
action modulus a analogous to the reaction modulus A 1 was defined, and
their numerical results indicate that after an initial period the plot of the
extent of reaction against position in the bed shows a sigmoid shape which
subsequently travels through the bed at constant velocity. The sigmoid
shape corresponds to the reaction zone width, and the material lying outside
this zone is either completely reacted or unreacted. For higher values of a
the reaction width increases and for sufficiently large values can cover the
entire bed length. The simple model of Evans and Song (197 4) has been
extended further by Ranade and Evans ( 1980) , who additionally considered
the nonisothermal nature of the bed. The variation of velocity and gas
properties with the temperature profile in the bed, as formulated in the
general equations here, has, however, not be accounted for. The authors
used the model to describe the reduction of commercial iron ore (taconite)
with hydrogen, and generally satisfactory simulation was reported. A
340 Doraiswamy and Kulkarni
nonisothermal packed bed has also been analyzed by Beveridge and
Kawamura ( 1974). These authors also neglected the axial and radial m1xmg
in the bed; the behavior of the pellet was accounted for by defining an
effectiveness factor. The model has been applied to the roasting of zinc
sulfide, and the experimental and calculated results show reasonable suc-
cess of the model.
The incorporation of axial and radial dispersion of heat and mass in
the system leads to considerable complications. While the case of axial dis-
persion of heat and mass has been treated by Sampath et al. ( 1975) , the
case of radial variations does not seem to have been attempted in the litera-
ture. In the model of Sampath et al. (1975) the governing equations, which
now include axial Peclet numbers for heat and mass, were simplified using
orthogonal collocation. The authors applied this model to the regeneration
of coked catalyst in a fixed bed. The results of this analysis predicted the
maximum temperature that could be attained in the reactor, and a number
of operating strategies to keep this temperature within permissible limits
were suggested as a consequence of model simulations.
The preceding section discussed some of the basic models for the packed-
bed noncatalytic reactor. Despite the simplifying assumptions made, the
models are unable to present a general qualitative picture of the bed; indeed,
most of these models were developed with a view to obtaining additional in-
formation for specific systems. In real packed beds there exist additional
complexities, such as porosity and velocity distributions. In a randomly
packed bed it has been experimentally observed that the porosity near the
wall differs from the average value (Pillai, 1977; Korolev et al., 1971;
Benenati and Brosilow, 1962). All these authors report an oscillatory be-
havior of porosity near the wall. The significant data on porosity varia-
tions have been correlated by Chandrasekhar and Vortmeyer ( 1979) as
( 97)
This equation is adequate for most practical purposes.
The variation of void fraction near the walls leads to a lower conver-
sion in the wall region than within the bed. In the presence of an exother-
mic reaction, where the local heat liberated depends on the extent of con-
version, the use of average void fraction in the bed can therefore lead to
results significantly different from those actually observed. It is desirable
in such a situation to employ the initial void distribution as given by Eq.
( 97). In many gas-solid noncatalytic reactions where changes in particle
size occur as a result of reaction, it is evident that this initial distribution
will vary and more sophisticated models employing the evolution of porosity
distribution in packed beds with progress of reaction would become neces-
sary. Although no attempts to incorporate any of these features in models
for gas-solid noncatalytic reactors are evident as of now, they should form
part of any further development programs in this area.
Another area of research, where practically no information exists, re-
lates to the dynamic response of packed-bed reactors to minor disturbances
in the feed composition, temperatures, and so on. It is known that in a
reactor the heat flow, fluid flow, and mass flow transients are coupled
and are interacting with each other. A small disturbance sometimes can
cause significant variations in the speeds of propagation of concentration
Gas-Solid Noncatalytic Reactions 341
and temperature fronts in the bed. As is known for catalyst reactors
(Mehta et al., 1981), this can lead to transient high-temperature peaks
which can sinter or damage the bed. It is necessary to know a priori
when such a phenomenon can occur, and predictive criteria for the purpose
are essential. Admittedly, the heterogeneous nature of the packed-bed non-
catalytic reactor does not make it possible to obtain such a criterion for
quick use in practice. However, attempts to obtain simple criteria using
alternative descriptions (such as cell models or cross-flow models) for
packed bed would be noteworthy.
Conventional packed-bed reactors, although suitable for most isothermal
systems, pose problems for highly exothermic or endothermic reactions.
Additionally, these reactors do not offer any advantage from the viewpoint
of solids handling. It is preferable in such instances to employ fluidized-
bed reactors, where a greater case in the handling of solids and uniform
bed temperature can be realized. The fluid-bed reactors, however, are un-
suitable for systems where the possibility of agglomeration of bed material
exists. Also, in view of the nearly complete mixing of solids in these re-
actors, high conversion of solids would require longer residence times.
The moving-bed technique has an advantage here, since solids flow more
or less in a plug-flow manner. However, for highly exothermic reactions
the occurrence of hot spots, and so on, could be a drawback to moving-
bed operations. In a subsequent two sections we briefly describe the
modeling aspects of these reactors.
Moving-Bed Reactors
A number of contacting arrangements can be envisaged for moving bed
systems:
1. Cocurrent flow of gas and solid
2. Countercurrent flow of gas and solid, as in a shaft furnace
3. Cross flow of gas and solid, as in sinter bed operations
In most of these modes of contact the gas and the solids flow pattern
is closer to plug flow; however, deviations from ideality are expected in
certain situations and can easily be accommodated. In many situations the
uptake rate of gas by the solids is marginal in comparison with the net flow,
resulting in an uniform environment of gas all around the bed. In such
situations the conversion of solids leaving the reactor is the same as that of
a single particle exposed to a gas for a time equal to the residence time of
the particle in the reactor.
For the case of varying gas compositions, the model equations under
isothermal conditions can be formulated as follows:
F p (dx/dl)
s s
- R A = 0 ( 98)
M A C
s
2 2
D A p fB(d CA/dl )
g C g
( 99)
M
342 Doraiswamy and Kulkarni
where Ds and Dg refers to the effective axial dispersion coefficients of the
solid gas phases, Fs and F g the volumetric flow rates, Ac the cross-section-
al area, x the conversion of solid, and CA the gas-phase concentration.
The equations can be put in the dimensionless form as
fB pg F
1 d 2x dx _g_ d 2C _ dC)
- + = 0 (100)
Pe dz 1 - f F (p~g dz 2 dz
s dz 2 B PS s
A Z(l fB)
d 2C pg
-1- - - dC C dx
= 0 ( 101)
Peg dz2 dz F ps dT
g
These equations are accompanied by inlet and outlet boundary conditions
given by
1 dx I
X =XO+ Pe ( 102)
s dz z=0
1 dCI
C = co+ ( 103)
Pe dz z=0
g
dx
dz
0 = dC
dz
I z=l (104)
The model as formulated assumes isothermal steady-state conditions, uniform
conditions in the radial direction, negligible mass transfer across gas-solid
interface, and cocurrent movement of the gas and solid phases. With ap-
propriate changes in the boundary conditions and sign of the flow term
according to the direction of flow, the system can be generalized to include
countercurrent operation.
The set of equations (100) to (104) has been solved by Hartman et al.
(1979) to obtain the concentration profiles for the gas and solid reactants.
The specific system considered by the authors was removal of SO2 from flue
gases using calcium sulfate and sodium sulfide particles.
The case of countercurrent movement of gas and solid phases with no
dispersion in the phases has been analyzed by Evans and Song ( 1974), and
illustrative results for conversion as a function of various operating param-
eters were presented. The consideration of nonisothermality of operation
requires additional equations describing heat balances in the gas and solid
phases. Assuming plug-flow conditions, these equations can be easily
formulated as
F p C dT
g g pg ~ = ha(T - T ) ( 105)
MA C dl s g
The equation suggests that the temperature change in the axial direction
is due only to the effect of heat transfer from the pellets. The heat
balance on the solid phase yields
Gas-Solid Noncatalytic Reactions 343
dT
s
(1 - fB) p C = ha(T - T ) + (-llH)RA ( 106)
s ps dl g s
where p C refers to the combined properties of solid reactants and
products" a?ii RA refers to the reaction rate in appropriate units. The
equation assumes that the temperature change in the axial direction occurs
as a result of heat generated in the pellet due to chemical reaction. In
view of the large thermal conductivity of solids, isothermal conditions with-
in the pellet can be assumed. The set of equations needs additional condi-
tions, which can be defined as
T = T 1 0 (107)
g go
Ts TsO 1 = 0 (cocurrent) ( 108)
T Tso 1 = L (countercurrent) ( 109)
s
The case of nonisothermal countercurrent moving-bed reactions has been
analyzed by Tsay et al. (1976), who applied this model to the reduction of
hematite with hydrogen and carbon monoxide. The simulation results indi-
cate that an optimum gaseous feed composition exists for certain range of
operating variables. It is possible to incorporate additional features in the
model, such as a side stream injection ( to adjust temperature and composi-
tion in the bed) , corrections for maldistribution of gas and solid flow
(Yagi and Szekely, 1979), and so on.
It is necessary for larger particles to incorporate the diffusive processes
within the particle. Conventional analyses ignore the mass and heat trans-
fer processes within the particle. Also, for exothermic reactions the axial
and more particularly radial dispersion effects should be included. A com-
plete analysis incorporating these effects is lacking. The dispersion
phenomenon present in the bed is especially important for exothermic or
more specifically nonlinear processes, as it establishes the feedback neces-
sary for the occurrence of nonunique behavior of the bed. The existence
of multiplicity and instability has been established for catalytic reactors.
The literature on noncatalytic systems is relatively scarce and more efforts
in this direction would be fruitful.
Fluidized-Bed Reactors
Fluidized-bed reactors represent a multiphase system consisting of two, or
more correctly, three phases. As a prerequisite to the design of these re-
actors, it is necessary to know the gas flow through the constituent phases
as well as their volume fractions, extent of mixing, and rates of interphase
mass transfer. Several models depicting the behavior of the fluid bed are
available in the literature, and the present treatment presupposes a knowl-
edge of these essentials. Relationships exist between the properties of the
bed and the diameter of bubbles (which grow along the bed due to coales-
cence) , expansion of the bed, and gas transfer from the emulsion phase.
The predictive equations for obtaining these properties of the bed are
listed in the section on estimation of parameter values.
344 Doraiswamy and Kulkarni
The chief features of the fluid bed as used for the noncatalytic reactor
differ from those for the conventional catalytic reactor. The main depar-
tures arise due to different considerations associated with the solid phase.
In noncatalytic systems the solid acts as a reactant and therefore its con-
sumption during the reaction should be accounted for in contrast to cataly-
tic systems. The reaction brings about changes in the size and shape of
these particles which affect the fluidization behavior. Nondecaying catalytic
systems can be operated in the batch mode with respect to the solid, but
the consequences of reaction and solids consumption often require that the
noncatalytic systems be operated on a continuous basis. The solids feed to
these reactors would generally contain a size distribution. Besides its in-
fluence on the fluidization behavior, the size distribution has a direct effect
on the residence-time distribution and therefore on the conversion of the
solid reactant. In catalytic systems, the gas mixing and interchange co-
efficients play an important role in deciding the conversion in the reactor.
In noncatalytic reactions, the degree of backmixing and residence time of
particles are additional important factors. Conventional catalytic reactors
operate with sufficiently fine particles so that processes within the particles
can often be ignored. In noncatalytic reactions with size distribution of
solids, pseudohomogeneous conditions cannot always be assumed and explicit
recognition of the processes within the catalyst particle becomes necessary.
In the discussion that follows we attempt to progressively incorporate some
of these complexities.
Constant Gas-Phase Environment
In this section we analyze the case where the gas-phase concentration is
constant throughout the reactor. Such a case arises for situations where
a large excess of reactant gas is available in the system. The analysis for
conversion now depends mainly on the effect of solids mixing. The mixing
pattern of the solids in most reactors can be assumed to be close to back-
mixing, with the residence-time distribution of the solids given by the
expression
1
E(t) = exp [- ~ ] (110)
t(R.) t(R.)
J J
where t(Rj) is the average residence time for particles of size Rj and E(t)dt
represents the fraction of the particles that have a residence time between
t and t + dt. This information on residence-time distribution can be com-
bined with a suitable model for computing the conversion in a single parti-
cle, to yield the average conversion of solids in the reactor:
FT f
R
M F (R). l [ t ]
x=
00
O x(R)j t(R)j exp - t(R)j dt ( 111)
where RM is the maximum size in the feed and Fs(R)j is the quantity of
particles of size Rj entering with the feed.
However, the analysis ignores any loss of particles due to elutriation.
We shall now consider this effect.
Gas-Solid Noncatalytic Reactions 345
Effect of Elutriation
Elutriation rates from fluidized beds depend on many factors: size distribu-
tion of particles; particle characteristics, such as shape and attrition be-
havior; mode of operation of the reactor; location and type of internals;
feedboard height; and so on. Often, many of these factors are interrelated,
and it is customary to express the rate of elutriation on the basis of an
elutriation constant E* as follows:
Rate of removal of = E* (Weight of that size)
solids of size Rj of solid in the bed
or
Rate of removal of solids of = E* (Fraction of bed weight)
size R. per unit bed area s consisting of size R.
] ]
or
W(R).
= E* ___l (112)
s w
where E! may now be viewed as a specific elutriation constant. The two
quantities E* and E: are related simply as follows:
A
E* = E* c (113)
s w
The following general equation, based on the experimental data for batch
operations with binary mixtures, has been suggested by Wen and Hashinger
( 1960):
E* -5 (u - ut)0.5(d ut)0.725(P - P )1.15
s
= (1.7 X lQ ) --- __E___!_ S g
gdp µ Pg
(114)
The average residence time of solids of size Rj in a fluidized bed can
be predicted in terms of the elutriation constant (Levenspiel, 1979):
(115)
Knowing t(Rj), we can use Eq. ( 115) to predict the solids conversion in
the presence of elutriation.
Other studies on elutriation include those of Sycheva and Donat ( 1974),
Tanaka and Shinohara (1972), Gontanev and Paulin (1975), Lange et al.
( 1977), and Horio et al. ( 1980).
346 Doraiswamy and Kulkarni
Models Based on Particle Growth or Shrinkage
As has been pointed out earlier, change in particle size is a basic feature
of certain gas-solid reactions. In the previous sections, the effect of parti-
cle size distribution was included by defining an average residence time for
each particle size, leading finally to Eq. (111). An alternative approach
is to account for change in particle size by assuming a simple topochemical
model for particle growth or shrinkage as a first approximation. Equations
can then be developed for the quantity of material leaving the reactor as
well as for particle size distribution in the existing stream.
The rate of change of particle radius can be represented for most
practical cases by a simple linear model or an inverse shrinkage model as
dR
dt = - k = constant ( 116)
dR k
dt = R
(117)
The parameter k in the first case is related to the rate constant ks for the
SIM by
vksCAiMB
k = ----- (118)
PB
The latter case arises for a gas-film-controlled reaction (e.g., oxidation of
carbon).
The equations to predict changing particle size can be utilized to calcu-
late the quantity of material of a given size (Fs 1) leaving the reactor,
For a system with feed Fs o having a size distribution ¢(R), an exit stream
Fs,1 with a size distributi~n ¢1(R), an elutriation stream Fs 2 , and an
arbitrary rate law for the changing particle size, a material balance on
solids of size between R and (R + dR) yields
growth of mass
Solids solids solids leaving solids in increase
in in in elutriation and out of solid
( 119)
feed outflow stream of the + within the = 0
(kg /s) (kg/s) (kg /s) interval interval
(kg/s) (kg/s)
On the assumption of complete backmixing of the solid, this equation can
be written as
( 120)
The terms E*(R), (SF), and r(R) represent, respectively, the elutria-
tion constant defined by Eq. ( 113) , the shape factor of the particles, and
Gas-Solid Noncatalytic Reactions 347
the rate of change of particle size. Equation ( 120), valid for a particular
size range, can be supplemented by a balance over all sizes to give
F s,2 + F s, l F
s,0
== (SF)W JR ¢(R)r(R)
R
dR ( 121)
RM
Equation ( 121) assumes positive or negative values depending on whether
the particle grows or shrinks. Equations ( 120) and ( 121) can be rear-
ranged to obtain the outflow stream in terms of the input stream as
W (R R3 [iR (122)
~o
s,
== LRM r(R) I R
M
The corresponding outflow size distribution is given by
F R3
s,0 ( 123)
Wr(R)
In these equations RM represents the smallest feed size for a growing
particle or largest size for a shrinking particle, and I is an integral de-
fined as
Fs,1/W + E*(R) dR]
( 124)
r(R)
The set of Eqs. ( 122) to ( 124) cannot in general be solved analytically.
However, they represent a total generalization with respect to feed size
distribution, reaction kinetics, and presence of an elutriation stream. For
specific situations, such as constant size feed, linear kinetics, or no elutria-
tion, these equations can be simplified to obtain analytical solutions.
Levenspiel ( 1979) has summarized some of these analytical solutions.
Analysis for Systems with Varying Gas-Phase Composition
The assumption of known and constant gas environment in the reactor
simplified the treatment considerably, since an analysis based on the solid
phase alone could be used to describe the bed behavior. Many practical
systems using large particle beds fluidized with a large excess of gas con-
form to this situation. In many other systems ( such as vigorously fluidized
beds of fine particles) , however, the composition of gas varies with position
in the reactor. A simple analysis as above would then be inapplicable. In
these instances, it is necessary to include separate equations for the bubble
and cloud-wake phases.
A number of models to depict the behavior of the bed are available,
and some of these have been extended to gas-solid noncatalytic reactors.
Thus the two-phase model of Davidson and Harrison ( 1963) has been
used by Campbell and Davidson (1975) to analyze the data on the com-
bustion of carbon particles for short periods of combustion in a
348 Doraiswamy and Kulkarni
batch reactor. The model has also been used and considerably extended
by Amundson (see Bukur et al., 1977). Tigrel and Pyle (1971) have used
this model for the not-too-different problem of catalyst deactivation. Kunii
and Levenspiel (1969) and Kato and Wen (1969) have extended their models
to gas-solid noncatalytic systems. A general model for noncatalytic beds
should take account of variation in both size and density of particles. No
model that takes account of all the realities in the bed is however available.
A particularly useful model that takes account of some of the complexities
in practical systems has been suggested by Chen and Saxena ( 1978).
Based on a more rigorous description of the bed, Chen and Saxena
have shown that the solids in the emulsion phase may have a net downward,
stationary, or net upward movement, depending on the rate of solids feed.
As a result, other parameters, such as bubble volume fraction and rise
velocity, become dependent on the solids feed rate. A detailed solids popu-
lation balance has been formulated and a computer simulation program has
been presented by these authors. The results show that the extent of
gas bypassing through bubbles is reduced when the solids feed rate is in-
creased.
These authors have also proposed a criterion to predict the direction
of solids movement in the emulsion phase. An illustrative plot of this
criterion is reporduced in Fig. 14. The quantities Fcl and Fez in this
figure are defined as follows:
p AC (1 -
S
f mf)s W b PsAcswb (1 - fmf)( 1 ~ 0 - swb O)
Fcl == u - u
1 + swbfmf mf 1 + swbfmf
dW ( 125)
r
dt
and
OS - 1 + o dW
r
wb ( 126)
F = F +
cl cl 1 -- o dt
where Wr is the weight of the solids in the reactor and p the average
particle density over the entire bed.
If F 0 < Fc1, the solids move down in the emulsion, whereas for Fo >
F c 2 , them move upward.
Modeling of Shallow- Bed Reactors
The modeling of gas-solid noncatalytic fluid-bed reactors followed the de-
velopments in catalytic systems and in most cases these models were de-
rived as their extensions. Adequate for qualitative purposes, these models
are really applicable only for tall beds (L /dt > 1). Most industrial fluid
beds, however, operate with small L /dt ( <1), and the use of these models
becomes restrictive. The essential differences between the two types of
beds arise due to the changed flow profiles. Thus in tall beds it is justi-
fiable to assume no radial variations of concentration and temperature.
The measurements on lateral mixing of solids in shallow beds, however,
indicate a much lower value than the axial mixing coefficients. This implies
that the lateral variations cannot generally be ignored. Thus it is likely
that strong temperature and concentration gradients in the radial direction
Gas-Solid Noncatalytic Reactions 349
.,u
"'
'Eu
w
(/)
<!
J:
Cl.
z
0
(/)
u
:::J
~
w
w
J:
I-
z
0
>-
I-
u
0
_J
w
> A B C
0
_J
( DOWN FLOW ( NO NET FLOW OF ( UPFLOW OF
0 OF SOLIDS ) SOLIDS ) SOLIDS)
(/)
SOLID FEED RATE, g /sec
FIGURE 14 Classification of fluidizations according to the solids feed rate.
exist in shallow fluidized beds (Highley and Merrick, 1971; Chavarie, 1973;
Fan et al., 1979; Fan and Chang, 1980; Grace, 1980). The remarks, gen-
erally applicable to gas-solid catalytic and noncatalytic systems, are much
more pertinent to the latter case in view of the solids being involved as a
reactant. A rigorous model for the gas-solid fluid-bed reactor therefore
should account for the radial dispersion of gas and solid reactant and for
temperature distribution. These considerations would lead to a far more
complex formulation, which may be difficult to use practically. However,
simplifying assumptions, suitable to each case, can be made to get the
qualitative behavior of the bed, which will be far more realistic than that
obtained using the models for tall beds.
Thus one might consider the applicability of the simple two-phase
theory with the emulsion phase at minimum fluidization conditions and com-
pletely mixed--in this case, only in the axial direction. The bubble phase
would be considered to move in plug flow. The solids could be introduced
at the center or at the bottom and overflow occurs at the farther end. The
solid and gas feed temperatures can be identical or might differ, depending
on the specific case. The formulation of the model requires accounting of
the gas in the bubble phase. In the interest of generality, an overall heat
balance to take care of nonisothermal situations can also be readily written.
350 Doraiswamy and Kulkarni
Emulsion Phase
Solid reactant: The material balance on solid S in the emulsion phase
over the control volume can be written as
rate of
net rate of net rate of disappearance solid B
Accumulation B in by B in by of solid B in feed
of solid B dispersion +
convection due to stream
reaction
or in equivalent mathematical form as
3CB) F
3x - rB + H(l o)
where CB is the concentration of solid B, DeB the effective diffusivity of
solid species B, rB the rate of consumption of solid B, F the molal feed
rate of solid per unit area of feeder, H the height of bed, and o the bub-
ble fraction in the bed.
Gaseous reactant: The material balance on the gaseous component A
in the emuli,don phase can be written as
exchange
net rate
Accumulation net rate of of gas consumption
of A
of gaseous = + A in by + with the due to
in by
species A convection bubble reaction
diffusion
phase
or in equivalent mathematical form as
f 3CA
_ _ e l 3
mf 3t xB 3x
+~
()
!:.
H
f0
H
Bubble Phase: A material balance on the gaseous component A in the
bubble phase can be written in accordance with Davidson's model as
Accumulation net rate of A exchange to emulsion
of A by convection phase
or in equivalent mathematical form as
( 127)
The overall energy balance for the controlled volume can be written
as
Gas-Solid Noncatalytic Reactions 351
net rate of net rate of heat
Accumulation = heat energy heat energy generation
+
energy in by from solids due to
conduction and gas reaction
or in equivalent mathematical notation as
pC aT - _!_ a (ke'XS ~ ) + upCP (T -- T)
p at - x s ax at H go
FMBC
+ H ps (TB O - T) + ( 1 - o)( -L'I H) r A ( 128)
The set of Eqs. (127) and (128) describe the fluid-bed behavior for
a shallow bed. In the form given, these equations are quite complex and
no analytical solution is possible. Chang et al. (1982) have solved these
equations under steady-state conditions on the assumption of isothermality
of operation and no radial variation of concentration of gaseous component.
Also, the reaction rates rA and rB are related through stoichiometry, and
zero-order and first-order dependence on solid concentration was considered.
The analytical results obtained by the authors are summarized in Table 7
and should be useful in a quick estimation of reactor performance.
The general model developed above has been applied to the case of
roasting of zinc sulfide, with the following general conclusions: The lateral
TABLE 7 Exit Concentration of Solid from the Bed
Reaction Solid concentration
A n
cplc Ae
Zero order
2<P3
A
<P2I1(pxf)[Io(p)Kl(p) + Il(p)Ko(p)]
First order (CB)exit = 2 A A A
p [Io(pxf) + Il(pxf)ko(pxf)] [pll(p) + <P3lo(p)]
where n is order with respect to gaseous reactant, if the
dimensionless position of the feeder point, and p, cp 2 , and
<P 3 are constants defined as
2 n n-1
p = <<P
1 Ae
c )112 cpl =
vBkL CAOCBO
DeB
FL 2 FL
cp 2 = (1 - o)HDeBCBO <P3 = DeBCBO(l - o)
352 Doraiswamy and Kulkarni
mixing of solids has a profound influence on the conversion of solids for
beds with smaller bubble dimensions. As such a situation is common in
shallow fluidized beds, the influence of lateral mixing should not be over-
looked. In beds with large-diameter bubbles-where the controlling mech-
anism lies across the bubble/emulsion interface-lateral mixing of solids has
relatively little influence on bed performance,
Staged Fluidized-Bed Reactors
Frequently, from the standpoint of better contact between the gas and the
solid, it becomes necessary to stage the fluid-bed reactor. A three-stage
fluidized bed together with relevant streams is shown in Fig. 15. The
solids in each bed can be considered to be completely mixed. The bed
weight, average residence time of solids, and residence-time distribution
(RTD) of solids may differ from bed to bed.
Elutrioted Partially
solids spent gases
t
ICgl
Cyclones
Fo---,;:
Solids S toge I
teed
IJ ~~II!~ Iii Stage 2
Stage 3
1i--P-r-o•d~:t
Fg I Cgo
Gaseous reductont
FIGURE 15 Schematic representation of a three-stage fluidized reduction
unit.
Gas-Solid Noncatalytic Reactions 353
The RTD function for any particular size of feed solids dp is given by
Eq. ( 110) , where the average residence time of solids of size dp is given
by
t(d ) ( 129)
p
E(dp) in this equation is the elutriation constant appropriately defined tak-
ing account of the parameters in Figure 15 as
F 1S (d )
e P (130)
E(d ) = W S (d )
p 1 1 p
and S 1 and Se are defined by the equations
(131)
and
f (dp)max s 0 (D
p
) d(d )
p
(d)
p
since
( 132)
(d)
/ p max
S(d ) d(d ) = 1
(d ) . . p p
p min
ri ( dR) in Eq. (129) represents the cyclone efficiency.
For an assumed conversion -time relationship, the unconverted fraction
of solids of size dp is given by Eq. (111). Since the bed is composed of
many size fractions, this equation has to be integrated over the size dis-
tribution to obtain mass conversion of solid in the stage. The mass conver-
sion in the stage can be obtained as
2 -1/y.)
1 - X 1 - 3y. + 6y. - e 1 ( 133)
1 1
where
t.(d )
1 p
( 134)
T.(d )
1 p
and ti and Ti represent, respectively, the average residence time of solid
of size dp and the time required for its complete conversion in the ith
stage. It is important to bear in mind that the value of Ti will depend on
the local concentration of gas in the stage. The gas phase could either
have a constant composition through the stage or may be varying. Suitable
balance equations in the gas phase should be written for this purpose.
c:.o
C11
,I>,.
TABLE 8 Recommended Equations for Effective Diffusivity and Flow Permeability
Number Parameter Recommended equation References
1 Effective diffusivity
f
Molecular diffusivity D ~
DAe = AB 'f
where
t,
312 ( _! + 1/2 0
D .. = o. 0018583T .l) ~
l] M.
Pa~.11.. Mi J ;;;·
l] l] ~
i:::i
M molecular weight of species i, 3
= '<
i:::i
a,11 = constants in Lennard-Jones potential ;::s
energy function A.
:,;:
= tortuosity factor E.
'f ;,;'
i:::i
sg = total surface area at porous solid
~-
c;')
19,400f 2 A
('/)
C I
Knudsen diffusivity DAk = Cl)
TfSgps
(- ~t/2 ~
E:
1 1 1 0
z
Effective diffusivity + -- ;:l
D DAe C')
in transition region e DAke A
.....
~
'<::
km .....
;:;·
2 Flow permeability = [, •("K~!) Asaeda and Toei (1979)
kmo ::ti
•15r• (I)
g
.....
where KN, the modified Knudsen number, o·
;:l
is defined as ('/)
c
KN =
nR T)l/ 2(1 - f)
(__g__ µS
8MA fc p
where µ refers to the viscosity of the
gas and S is the specific surface
Vo)
c:n
c:n
c:.,
<:11
0,
TABLE 9 Recommended Equations for Estimating Transport Coefficients
Coefficient Recommended equation Reference
Fluid-particle transport coefficient
Mass transfer coefficient Sh= 2 + 1.1Sc 113Re 0 · 6 Wakao and Funazkri
3 (1978)
< Re < 10,000
Heat transfer coefficient Nu = 2 + 1. 8Re 0 · 5Pr 113 Re > 100 Glidden and Crafield
( 1970)
Nu = 0. 36Re O. 94 Re < 100
t,
2.876 0.3023 0
General correlation for --+ -
flh = - Re -- Gupta et al. ( 1974)
fluidized beds Re 0. 35 ~-
"'~
Q
::l
Bed-to-wall heat transfer = 35. 8(k' ) O. 6d-O. 36 pO. 2 (MKS units) '<
hbw g
Botterill (1975)
p s Q
coefficient ;:J
0..
:,::
7.2k' (1 _ f )2/3 i:::
?;'
Particle-to- horizontal h = f + 26. 6u 0 · 2c p d Zabrodsky et al. ( 1981) Q
.,
stages and tubes d pg g p ;:J
p
c;:i
Interchange coefficients in fluid beds
~
I
Ct.l
u D 1/2)l/2 £
Bubble-emulsion mass and heat mf + 5. 85 (
k be -- 4 · 5 --- bg E:
db d5/2 z
transfer coefficient 0
b ;::s
0
A
Q
h U C k'C
/ g pg::___ g 1/2) 1/2 '<
-be= 4.5 mfg
- pg + 5.851--; Kunii and Levenspiel c;·
-
,5/2
db·, ( 1969) ::0
(I)
A
0
k - (f f U \1/2 Mori and Wen
-s·
;::s
Cloud-emulsion mass and ce - 6. 75 m d! b / (1975) "'
heat transfer coefficient
hce "6.75 ('mi"~:!pgub)l/2
c:.,
c:,,
--..:i
w
<:Tl
Co
TABLE 10 Recommended Equations for Computing Basic Parameters of the Fluidized Bed
Parameter Equation Reference
g( PS - P )d
g p o. 85 (~) o. 13
1. Minimum fluidization 2.4 X 10 5 [ μ2 + 33. 7 Broadhurst
2
velocity p g u mf pgg(ps p g )dp3 J pg and
Becker
( 1975)
0. 01 < Remf < 1000, 500 < p /p < 50, 000
s g
3 t,
p g(p - P ) d 0
s s g p ~
1 < < 10 1;,·
2 ~
]J
Q
3
'<
2. Bubble diameter d = ct_ - ( d - d ) expL O· 3 Z ) Q
~o bm bm bO \ dt ;::I
A.
:,:::
where
E.
;,.'
Q
¾m = 0.652[A/Uo - umf)lo. 4
~-
c;)
a__ i::i
[A (U - U )JO. 4 ('/J
7::>0 = 0. 347 C O mf I
ti)
no S:.
5:
<:
3. Bubble velocity ub = u umf + o.n1 lgdb 0
0- ;:s
0
i::i
i::i
-
u0 - umf ~
4. Bubble fraction in bed 8 = -o·
Ub
::0
Cl)
§
oocb fmfub
=
5. Cloud fraction in bed 8
C ocb 1 ocb = Umf
-s·
;:s
('/J
6. Solid mixing rate = (U - U )A f (1 - f ) 0.067 < f < 0.3 Rajan and
0 mf cm mf s m
Wen
(1980)
K(Uo - umf)
7. Attrition rate = 2.73 x 10- 8 <K< 9.11 x 10- 8 Merrick and
M
Highley
( 1974)
w
c:n
co
360 Doraiswamy and Kulkarni
PARAMETER ESTIMATION OF THE MODELS
The preceding section was concerned with models for gas-solid noncatalytic
reactors. These models were formulated in terms of dimensionless groups
which consist of the physical quantities and structural parameters of the
system. The present section is devoted to the estimation of these proper-
ties. Some of the physical quantities can be measured directly or are
readily available in the literature. On the other hand, certain other proper-
ties, such as effective diffusivity and heat and mass transfer coefficients,
have to be obtained using proven relationships. Several of these param-
eters are not specific to gas-solid noncatalytic reactors, but occur very
often in operations of gaseous mass transfer in porous materials such as
catalytic reaction, adsorption-desorption, drying, and so on. Consequently,
a large volume of literature exists on the estimation of these properties un-
der a variety of conditions. We present in Tables 8 to 10 the recommended
equations for these properties for use in design.
NOTATION
a interfacial area for transfer, cm 2I cm 3
A general notation for gaseous reactant species
Al dimensionless group defined as k RID
s .e
A2 dimensionless group defined as k RID
g e
A3 dimensionless group defined as hRgT O/PCpUO
A4 dimensionless group defined as k g/UO
A5 dimensionless group defined as h R T 0 tu 0PC
w g p
A6 dimensionless group defined as -LlH/C' T
ps 0
A7 dimensionless group defined as hR/D C' TO
e ps
A cross sectional area of the bed, cm 2
C
A area of pellet , cm 2
p
B general notation for the solid reactant species
C dimensionless concentration of gas in the bed
CA' CB concentration of species A, B, mollcm 3
CAb concentration of gaseous species A in the bulk or
in the bubble phase, mol/cm3
CAe concentration of gaseous species A in emulsion
phase, mol/cm3
CAi concentration of gaseous species A at the interface,
mol/cm3
CAs concentration of gaseous species A at the surface,
mol/cm3
CBO initial concentration of species b, mol /cm 3
Gas-Solid Nonca,t.alytic Reactions 361
C specific heat of gaseous species, cal/g•s
p
C specific heat of solid, cal/g•s
ps
c•ps molar specific heat of solid, cal/mol•s
cAP average specific heat of gaseous stream, cal/g•s
CA, CB dimensionless concentration of species A, B
D. effective diffusivity of gaseous species A in the
e solid, cm2/s
DeB effective diffusivity of gaseous species A in the
solid B, cm2/s
DeG effective diffusivity of gaseous species A in the
grain, cm 2 /s
Des effective diffusivity of gaseous species A in the
soHd S, cm2/ s
D effective axial dispersion coefficient of gas in the
g
bed, cm2/s
2
Dk Knudsen diffusivity, cm /s
D effective axial dispersion coefficient of solid in
s
bed, cm2/s
Da Damkohler number
E activation energy, cal /mol
E*, E* elutriation constant
s
E(t) residence-time distribution function defined by Eq.
(110)
f, f pellet voidage
C
fo initial porosity
f 0(x), f 1 (x), f 2(x) functions of conversion defined in Table 2
fB void fraction in bed
fmf voidage at minimum fluidization
f fraction of pores removed
p
Fcl' Fc2 parameters defined by Eq. ( 125)
3
F volumetric flow rate of gas phase, cm /s
g
F volumetric flow rate of solid, cm 3 /s
s
F s. O' F s, 1' F s, 2 volumetric feed rate of the entering, leaving, and
elutriating streams in fluid-bed reactor, cm3/s
F(F) function of fraction of pores removed
p
h heat transfer coefficient, cal/s •cm 2 °C0
2
h heat transfer coefficient at the wall, calls •cm •°C
w
H total height of the bed, cm
362 Doraiswamy and Kulkarni
k general notation for rate constant, (cm3 /mol)n-1
s-1
k' effective thermal conductivity of solid, cal/s •cm •°C
e
k phenomenological mass transfer coefficient, cm/ s
g
k rate constant for pore removal
p
k surface reaction rate constant, cm /s
s
k* dimensionless reaction rate constant, k/k(T 0)
K equilibrium constant
interchange coefficient across bubble-emulsion
phase, cm/s
m general notation for order of reaction with respect
to solid species
molecular weight of species B
n general notation for order of reaction with respect
to gaseous species
p partial pressure of species
p pressure: also used to denote product species
pd decomposition pressure
rG radial position in the grain, cm
rGi radial position of interface in the grain, cm
rGO initial radius of the grain, cm
R radius of pellet, cm
RA general notation for rate of reaction, molls
RAc rate of chemical reaction at the interface, molls
RAd rate of diffusion through ash layer, mol/ s
RAg rate of diffusion through gas film, mol/s
R e-as constant
g
RGA rate of reaction per grain, mol/cm 3
R. radius of the interface, cm
1
R. radius of the ith particle
Al
R dimensionless radial position
R. dimensionless radial position of the interface
1
R extent of reaction parameter defined by Eq. ( 90)
volume fraction of solids in wake per unit volume
of bubble
S* dimensionless pore surface area
p
S* dimensionless reaction surface area
Gas-Solid Noncatalytic Reactions 363
SF shape factor of solid
t time
t(R.) average residence time for particle of size R.
] ]
f dimensionlei:,s time as variedly defined in text
t dimensionless time defined by Eq. ( 21)
er
T temperature variable
Tb' TO temperature in the bulk
TBO' TgO inlet temperature of solid and gaseous streams
T temperature in the gas phase
g
T. temperature at the interface
l
T temperature at the solid surface
,..s
T. dimensionless temperature at the interface
l
u superficial velocity in the bed, cm /s
uo initial velocity in the bed, cm/ s
Ub bubble rise velocity, cm /s
0 mf minimum fluidization velocity, cm/s
V volume of the pellet, cm 3
p
w weight of feed
Wl dimensionless ratio of the pellet size to grain size,
R/rGO
w2 dimensionless ratio of reactor length to pellet size,
L/R
w3 dimensionless ratio of reactor length to reactor
radius, 2L /db
YA mole fraction of gaseous reactant within the pellet
y' mole fraction of gaseous reactant in the gas mixture
A
entering the bed
Ye mole fraction of gaseous product within the pellet
y' mole fraction of gaseous product in the gas mixture
C
entering the bed
z dimensionless axial distance in the reactor
zl defined by Eq. ( 92)
Greek Letters
CJ, diffusivity ratio, De/Deo= also refers to dimensionless
superficial gas velocity in Eq. ( 65)
s shape factor equal to O, 1, and 2 for slab, cylinder, and
sphere, respectively
364 Doraiswamy and Kulkarni
Sm exothermicity factor
y Arrhenius parameter, defined as E /R gTb
Y1 molar density of gas to that of the solid
0 volume fraction of bubbles in the bed
ll H heat of reaction , cal/ g mol
T1 effectiveness factor as defined by Eq. ( 8)
e dimensionless gas temperature in the bed, T g /T 0
eC dimensionless coolent temperature, Tc /T 0
8* dimensionless solid temperature in the bed, Ts /T 0
]J roots of transcendental equation Eq. (45)
\) dimensionless diffusivity of gaseous D eA /D eA, 0
\!A, \!B stoichiometric coefficients
\)' dimensionless diffusivity of gaseous product D ID 0
3 e e
PB density of solid species B, g /cm
0 reaction modulus
T dimensionless time relative to the process in- the pellet,
defined as Det /R2
T time required for complete conversion if ash diffusion
a
alone controls
T the original nonporous material to become completely
C
porous
Td time required for complete conversion for diffusion-
controlled processes
TD dimensionless time relative to the in tern al diffusion con-
trolled process
T time required for complete conversion of grain
g
Tf time required for complete conversion if film diffusion
alone controls
T time required for complete conversion if reaction alone
r
controls
¢* Thiele modulus defined in Eq. (11)
¢ extent of reaction in the bed
¢1, ¢2 parameters defined in Table 7
¢er critical values of Thiele modulus
¢o(R), ¢/R) size distribution of particles in the entering and leaving
streams, respectively
Gas-Solid Noncatalytic Reactions 365
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6
Design of Fixed-Bed Gas-Solid
Catalytic Reactors
GILBERT F. FROMENT Rijksuniversiteit, Gent, Belgium
HANNS P. K. HOFMANN Universitat Erlangen-Niirnberg, Erlangen,
Federal Republic of Germany
INTRODUCTION
At present, the majority of commercial gas-phase catalytic processes are
carried out in fixed-bed reactors. Important exceptions, for which fluidized-
bed operation is preferred-either to continuously regenerate the catalyst
or to improve heat removal--are the catalytic cracking of gas-oil, the syn-
theses of acrylonitrile and ethylene dichloride, and naphthalene oxidation
into phthalic anhydride.
Fixed-bed reactors are preferred because of simpler technology and ease
of operation. This is particularly true for adiabatic reactors. When the
process has a pronounced heat effect, simple adiabatic operation is not al-
ways applicable, however. With very exothermic reactions the temperature
rise may become excessive and harm the selectivity or the catalyst, shift
the equilibrium to the wrong side, or cause safety problems. Very endo-
thermic reactions, on the other hand, may be extinguished when carried
out in a single adiabatic reactor. This is why multibed adiabatic reactors
with interstage heat exchange, direct or indirect, internal or external, are
frequently encountered. Examples are ammonia, methanol, and sulfuric acid
synthesis; carbon monoxide conversion; and catalytic reforming of naphtha.
The flow in such reactors is generally axial, but when a fraction of the ef-
fluent is recycled, it may be advantageous to use radial flow and to spread
the catalyst out over a larger surface to reduce the pressure drop.
With multibed adiabatic reactors, interstage injection with the reacting
gases is possible only between the beds. The temperature profile is of the
sawtooth type and usually suboptimal. Theoretically, only continuous heat
exchange permits a close approximation of the optimum temperature profile,
but the heat exchange coefficients required to obtain this often take values
beyond those that can be reached in practice.
Continuous heat exchange is achieved in two types of fixed-bed reac-
tor. In the first, the catalyst is packed inside a number of parallel tubes
surrounded by a heat-exchanging fluid. In the second, the tubes through
which the heat-exchanging fluid flows are inserted into a massive bed of
373
374 Froment and Hofmann
catalyst. The first type is referred to in this chll.pter as a multitubular
fixed-bed reactor and is encountered, for example, in a-xylene oxidation
to phthalic anhydride, steam reforming, and Fischer-Tropsch synthesis.
The second type is referred to as a fixed-bed reactor with internal heat
exchange and is encountered in ammonia and methanol synthesis.
In the strongly exothermic a-xylene oxidation, the tubes have an inter-
nal diameter of only 2. 5 cm. They are filled with catalyst and cooled by
means of circulating molten salt. One vessel may contain 20,000 tubes.
For endothermic steam reforming the tubes are inserted into a gas-fired
furnace. In ammonia synthesis a bed of 1. 8 m internal diameter for a daily
production of 200 metric tons, which is rather low by today's standards,
may contain 750 cooling tubes. The feed flows through these tubes and is
preheated by the reacting gases before entering the catalyst bed. The
process can be operated in an autothermal way.
Exothermic equilibrium reactions can reach higher conversions at lower
temperature levels, because of more favorable equilibrium conditions. At
low temperatures the reaction rate is too low, however, so that excessive
amounts of catalyst would be required. Nonisothermal operation is pre-
ferred in this case and the optimum temperature profile decreases toward
the exit. Such an optimum profile is better approximated in a multitubular
reactor than in a multibed reactor, at the expense of a considerably more
complicated internal design and flow patterns, however. The effluent
temperature may even be sufficient for partially preheating the feed and for
producing high-pressure steam, as is done in ammonia synthesis. To avoid
heat losses, but also for safety reasons, the boiler is preferably inserted
into the high-pressure vessel. High-pressure reactors may reach a con-
siderable level of sophistication.
Another reason for imposing a certain temperature profile may be the
reaction sequence. Take, for example, a consecutive reaction scheme con-
sisting of two steps. When the second step has an activation energy that
is higher than that of the first step and the intermediate product is the
desired one, the selectivity for this intermediate is favored by a decreasing
temperature profile.
Fixed- bed reactors can be scaled up in several ways. Similarity theory
is of little use in this matter. It is general practice to proceed from the
laboratory to the commercial scale gradually, involving at least two inter-
mediate scales: the pilot and demonstration units. Even large pilots cannot
be expected to behave exactly like the ultimate commercial reactor, so that
further insight is sometimes required. Mockups are useful for providing
information on hydrodynamics, for example, on the redistribution over a
downstream stage of a multibed reactor of gases coming from an external
heat exchanger, a problem encountered in sulfuric acid synthesis. To date
it has been inconceivable to proceed with reactor scaleup without at least
a certain degree of modeling. The modeling can be fundamental and rely
on separate observation of various aspects of the process, tied together
and cast into a set of equations simulating the reactor, or it can be semi-
empirical, thereby relying on pilot experimentation for tuning so-called
"effective" parameters of the model.
The approach followed in this chapter is fundamental. Obstacles en-
countered in such an approach are complex hydrodynamics and the lack of
sufficiently detailed and accurate chemical kinetics (a chronic problem with
complex reactions and complex feedstocks). Modern aspects of kinetic
analysis of complex porcesses have been discussed in recent years by
Fixed-Bed Gas-Solid Catalytic Reactors 375
Froment ( 1975, 1976b), Froment and Hosten ( 1981), Hosten and Froment
(1984), and Hoffmann and Hofmann (1976a,b). Additional difficulties arise
when internal diffusion is limiting. It is generally too complicated-if not
impossible-to derive both the kinetic equation and the diffusional parameters
simultaneously from the usual kinetic experimentation. The intrinsic kinet-
ics should be obtained first and in the absence of any diffusional limitations.
The diffusional parameters are determined in a second stage by experimenta-
tion with particles of larger size (Dumez and Froment, 1976) or by purely
physical measurements using, for example, the Wicke-Kallenbach cell or the
gas chromatographic technique (De Deken et al. , 1982). Other complications
arise from catalyst deactivation by coking, poisoning, and sintering. Sev-
eral reviews deaJ with this phenomenon (Froment, 1976a, 1980a, 1982; Butt,
1978, 1980, 1982; Delmon and Grange, 1980; Pommersheim and Dixit, 1981).
It should be emphasized here that the main deficiencies in the modeling
of fixed-bed catalytic processes originate from incomplete and inaccurate
chemical kinetics. Unfortunately, this is insufficiently recognized by those
who have the background to contribute to this area: the chemical engineers.
After this brief discussion of qualitative design aspects and of problem areas
encountered in the quantitative design based on the fundamental approach,
the latter will now be dealt with in detail.
CLASSIFICATION OF MODELS
Table 1 shows the classification of models for fixed-bed tubular reactor
models proposed by Froment (1972a, 1972b, 1979) and widely accepted
since. The classification contains two categories: the pseudohomogeneous
and heterogeneous models. The latter distinguish between temperatures and
concentrations in the bulk gas phase and those inside, or at the surface of
the solid. The former do not. Each category contains two- and one-
dimensional models, to account, in more or less detail, for gradients on the
reactor scale. The basic model, AI, postualtes plug flow through the bed.
It is one-dimensional because it assumes uniformity in a section perpendicu -
lar to flow, except in a very thin layer near the wall, when heat is ex-
changed with the surroundings. A first complication, leading to model All ,
is to account for deviations from plug flow by superimposing mixing or "dis-
persion" in the axial direction (i.e., in the flow direction). When disper-
sion is also considered in the radial direction (i.e., in a cross section),
because of the occurrence of temperature gradients, the model becomes two-
dimensional.
TABLE 1 Classification of Models for Fixed-Bed Tubular Reactors
Pseudohomogeneous Heterogeneous
T=T·C=C T -:f- TS; C -:f- CS
S' S
One-dimensional AI Basic, ideal BI + interfacial
gradients
All + axial dispersion BIi + intraparticle
gradients
Two-dimensional AIII + radial dispersion BIil + radial dispersion
376 Froment and Hofmann
The first model of the heterogeneous category is derived from the basic
pseudohomogeneous model AI by considering temperature and concentration
gradients over the film surrounding the catalyst particles. The second
model, BII, still one-dimensional, adds gradients inside the catalyst particle
to the preceding model. Finally model BIII considers axial and radial gra-
dients in the reactor as well as inter- and intraparticle local gradients.
The problem is now that of quantitatively expressing these phenomena,
particularly the dispersion. This is generally done in terms of a continuum-
type model, but so-called cell models, accounting for the two-phase nature
of the reactor, have also been used. In continuum models the overall flow
is considered to follow parallel streamlines, although not necessarily at a
uniform velocity. Any mixing caused by the presence of the packing is
modeled in terms of a Fickian, diffusion-type mechanism. This requires the
flux of a component between two points to result from a large number of
steps, each independent of the preceding one, as in a random walk. The
flux resulting from such a mechanism is proportional to the gradient, just
as in molecular or turbulent diffusion. The proportionality factor between
the flux and the gradient is lumped with the molecular and turbulent dif-
fusivities into an "effective" diffusivity or dispersion coefficient. Whereas
the basic model AI leads to first-order differential equations (ordinary for
steady state, partial for transient operation), the models including disper-
sion lead to second-order differential equations.
For nonisothermal situations, heat transfer has to be included in the
model. In the basic pseudohomogeneous model, AI, heat is considered to
be transferred by the overall convection only. When axial and/or radial
dispersion is added, yielding models All or AIII, heat is also transferred
by effective conduction. This is a mode of heat transfer occurring in a
pseudosolid that lumps the fluid and solid and therefore the mechanisms as-
sociated with each phase.
In heterogeneous models, heat and mass transfer from the bulk to the
catalyst surface is described in terms of convective mechanisms. Transport
mechanisms inside the particle are expressed in terms of effective diffusion
and conduction, with the appropriate effective diffusivities and conductivities.
In model BIII the dispersion in the bed is accounted for in a way analogous
to that used in the pseudohomogeneous equivalent, AIU, but the mechanisms
are separated into those occurring in the fluid and solid phases, respectively.
Because of their nature, continuum models, based on effective transport
mechanisms and leading to differential equations, are adequate only from a
certain bed depth and a certain ratio of bed to particle diameter onward.
The first cell models were one-dimensional and consisted simply of a
series of completely mixed tanks, each associated with a single particle.
They lead to algebraic equations for the steady state and to ordinary dif-
ferential equations for transient situations. Unlike continuum models, these
cell models cannot generate backmixing. This feature was only introduced
later by the backflow cell models. Although the properties of this type of
cell model were thoroughly analyzed (Roemer and Durbin, 1967), their ap-
plication seems to be lagging behind. However, Deckwer (1974) has ap-
plied them to nonisothermal reactors.
Cell models contain the property of infinite speed of propagation of a
signal. To avoid this, a time delay would have to be introduced between
the cells, but this has not been done so far (Sundaresan et al., 1980).
Any sophistication of the model, such as allowing for a coupling between
the particles by radiation or by considering a cell to contain the back half
Fixed-Bed Gas-Solid Catalytic Reactors 377
of a particle and the front half of a particle in the next row, destroys the
simplicity of the computation.
Cell models can also be used for heterogeneous situations, when, for
example, heat transfer resistance in the external film and mass transfer
resistance inside the particle have to be accounted for. Two-dimensional
cell models were introduced by Deans and Lapidus ( 1960). In these models
the cells of a given row are connected to the next, downstream row, which
is offset one-half cell width, thus causing radial mixing. Generally, heat
is considered to be transferred through the fluid phase only. This has
been shown to lead to serious errors, however (De Wasch and Froment,
1971). Kunii and Furusawa ( 1972) have accounted for all possible heat
transfer mechanisms in a fixed bed, according to the lines set by Yagi and
Kunii ( 1957) and Kunii and Smith ( 1960), to be discussed further in this
chapter, but the computational advantage of the original cell models with re-
spect to the continuum models is then completely lost.
The equivalence between the predictions of continuum and cell models
has been studied extensively for both one- and two-dimensional cases (Aris
and Amundson, 1957; Olbrich et al., 1966; Sundaresan et al., 1980; Varma,
1980). It should not be forgotten that the cell models were developed for
mathematical convenience. In spite of their seemingly closer relation to
reality, they are still far from true hydrodynamic models. The cell size,
for example, is not the void fraction between particles: it is calculated to
match the results of residence-time-distribution experiments. To achieve
this, the cell size in the radial direction has to be O. 9 times the particle
diameter.
The models used in this chapter are exclusively of the continuum type.
With present-day numerical techniques and computers, integration of differ-
ential equations no longer presents great challenges. The methods available
for this will be mentioned briefly in the appropriate sections.
MODEL EQUATIONS AND THEIR APPLICATIONS
Pseudohomogeneous Models
Basic Model with Plug Flow
General Model Equations: In this and the following sections the model
equations will be written for constant density of the fluid phase, constant
number of moles, and for one reaction only, to avoid obscuring the essen -
tial features. More complicated features will be dealt with, when necessary,
in specific examples.
The model equations for a nonisothermal, nonisobaric reactor with axial
flow, operating in the steady state, may be written
( 1)
ai
4 dt (T - Tw) - (-.6.H)pBrA = 0 (2)
2
fp u
= ~ ( 3)
gd
p
378 Froment and Hofmann
with initial conditions: at z == 0, C == Co, T == To, and Pt == PtO· The
coupling of Eqs. (1) and ( 2) is evident. The coupling of these with Eq.
( 3) results from the total pressure dependence of the rate and the variation
of Pg with temperature and the number of moles. The set of equations
(1) to (3) is easily integrated using Runge-Kutta techniques.
In Eq. (2) Tw is the internal wall temperature and °i is a heat trans-
fer coefficient between the bed and the internal wall for which Leva (1948)
proposed the following correlations. When the reaction mixture is heated
from the wall ,
d G)O. 9 -6(d /d )
0.813 ( _E__ e P t ( 4)
µ
when it is cooled from the wall
d G)O. 7 -4. 6(d /dt)
(
== 3 . 50 _E__ e P
µ ( 5)
The ratio dp /dt determines the void fraction, particularly in the vicinity of
the wall and therefore the flow conditions in that region and is introduced
in an empirical way. The range of application of these equations is limited,
however, since they predict a zero value of ai at zero Reynolds number
dpG /µ, thereby ignoring the contribution of the solid phase and of natural
convection.
De Wasch and Froment ( 1972), who measured heat transfer over a range
of Reynolds numbers extending from 30 to 1000, correlated their results
as follows:
a?d c µ d G
== _!.___.E.
;\ + 0 . 033 -;\-
p p
-μ- ( 6)
g g
where a;
== 2. 44A~r/dt 413 and -¼r is calculated from a correlation to be
presented in the section on the two-dimensional pseudohomogeneous model.
Equation (3) is the pressure-drop equation for turbulent flow, to be
used in conjunction with the friction factor correlations discussed below.
The friction factor f is generally correlated in the following form versus
the void fraction and the Reynolds number:
1 - s (a + b1--- -
f==---
3 Re
€) ( 7)
€
Hicks ( 1970) proposed a different form of correlation for spheres:
) 1. 2 0 2
f==6.8 (1 - s Re-· for 300 < Re < 60,000 ( 8)
3 1 - €
€
which implies that a and b are not true constants, in agreement with
Tallmadge ( 1970).
~
~
(l)
i::i.
tb
(l)
i::i.
c;)
A
Cl)
TABLE 2 Values of Parameters in Ergun-Type Friction Factor Correlations I
Cl)
Reference a b Flow range
&
i::i.
C":l
A
.....
Ergun ( 1952) 1. 75 150 Re < 500 A
1 - E ~
.....
g·
Handley and Heggs ( 1968) 1. 24 368 ::ti
1000 < l ~e E < 5000 (l)
A
(')
0
McDonald et al. (1979) 1. 8 (smooth particles) 180 Re < 10,000 ~
1 - E
4. 0 (rough)
2
4 d
Mehta and Hawley ( 1969) 1.75 [1 + ¼(1 ~PE)d] 150 1 + - ___E.
6 (1 - E)dt
t
Re
Tallmadg-e ( 1970) 1. 75 4. 2 Re 516 0.1 < -1-- < 10,000
- E
c;.,
--:i
co
380 Froment and Hofmann
For nonspherical geometries the particle diameter is replaced by an
equivalent diameter,
V
d' = 6 _£
p sp
where Vp and Sp are the volume and surface area of the particle. With
hollow rings, however, this correction factor is not accurate enough.
Brauer (1957) introduced the following groups to relate the results for hol-
low rings to cylinders:
V
d = 6 ___£x_! En ( 9)
p 8 cyl
with
V S
E = P cv1 and n
S V
p cyl
according to Reichelt and Blasz ( 1971). The void fraction E in packed beds
of spheres has been correlated by Haughey and Beveridge ( 1969) in the
following way:
(10)
The basic pseudohomogeneous model is applied in the following sections to
a number of typical fixed-bed reactor problems encountered in industrial
practice. These applications are intended as illustrations of the fundamen-
tal approach advocated in this chapter.
The various aspects of reactor design and operation illustrated here
may require, in specific cases, more appropriate models. Even then the
simulation by means of this relatively simple model will be a valuable guide
for the selection of the ultimate higher-level model, because it will reveal
essential features about the process and the reactor behavior. The criteria
for the escalation to the higher- level models listed in Table 1 are given in
each corresponding section.
Application to Adiabatic and Multibed Adiabatic Reactors: Equations
( 1) to ( 3) are also applicable to adiabatic reactors by putting a.i equal to
zero in Eq. ( 2). A useful relation, valid in isobaric adiabatic reactors, is
obtained by combining Eqs. ( 1) and ( 2):
( 11)
Douglas and Eagleton (1962) have integrated Eqs. (1) and ( 2) (with a.i = 0)
for zero-, first-, and second-order kinetics and expressed the results in
terms of exponential integrals, which are tabulated functions.
Fixed-Bed Gas-Solid Catalytic Reactors 381
As mentioned earlier, it is of importance to reduce the pressure drop
through the catalyst bed, in particular when a fraction of the effluent has
to be recycled, as in catalytic reforming or ammonia synthesis. This re-
quires rather shallow bed arrangements, but care has to be taken to achieve
a good distribution of the feed. When this condition is satisfied, it is evi-
dent from the continuity equation that for isothermal conditions at least and
for equal total pressure, the same conversion will be obtained when W/FAo
in the shallow bed equals that in the deep bed. To avoid impractical re-
actor configurations and dimensions, radial flow is sometimes substituted
for axial flow. The question then rises if centrifugal or centripetal flow is
preferable. It follows from the detailed theoretical study of Balakotaiah
and Luss ( 1981) that, for plug-flow, isothermal, and isobaric operation,
the conversion is independent of the flow direction.
Marin and Froment ( 1982) recently compared axial with both centrifugal
and centripetal radial flow in the catalytic reforming of a c 6 stream, under
conditions and in configurations suggested by industrial catalytic reforming.
For radial flow the continuity equations for the components are written as
follows. The continuity equations for a feed component i, when the axis
is oriented in the flow direction and the origin of r is at the inlet of the
catalyst bed, are written
d(u C.r)
S 1
Z a .. p 8 r. (12)
dr . l] J
J
where j is one of the reactions in which component i is involved. Introduc-
ing the conversion
x. =
1
I
with Fi =
Za .. p 8 r.
dx. . l] J
1 r ,_J_ __
dr u p R
so g 0
for both centrifugal and centripetal flow. The radial axis is directed in
the flow direction and Ro is the radial distance, measured from the reactor
vertical axis on ward, where the feed enters the bed.
The energy equation can be written
r Za .. (--LlH)p 8 r.
dT j l] J
(13)
dr c u P R0
p so g
The pressure drop is still calculated from Eq. ( 3) with f as given in Eq.
( 7), but with us in the Reynolds number varying with position. The
boundary conditions are obvious.
382 Froment and Hofmann
TABLE 3 Simulation of Reactors with Axial and with Radial Flow for the
Reforming of a c 6 Stream
Makeup feed rates
(kg /h) Feed rate recycle
CCC4 67,808
Dimethylbutanes 10,164
Methylpentanes 17,279
n-Hexane 40,656
Methylcyclopentane 20,845
Benzene 11,056
Hydrogen 9,986
100,000 77,794
Total hydrocarbon feed rate: 167,808 kg /h
Molar ratio recycle/He feed: 6.00
Molar ratio H 2 /HC feed: 4. 20
Weight of catalyst: 63,000 kg
Axial flow Centripetal
Bed diameter internal (m) 8 2.00
Bed diameter external (m) 8 5.04
Bed height (m) 2.02 6.03
Inlet temperature ( °C) 495 495
Exit temperature (°C) 460.5 459.01
Inlet pressure (bar) 15 15
Exit pressure (bar) 14.96 14.98
Effluent flow rates, C 1-c 4 70,343 70,192
(kg /h)
Dimethylbutanes 7,599 7,659
Methylpentanes 26,763 26,454
n-Hexane 34,275 34,611
Methylcyclopentane 6,300 6,672
Benzene 21,765 21,478
Hydrogen 10,684 10,667
Fixed-Bed Gas-Solid Catalytic Reactors 383
The simulation results are given in Table 3. The selected radial con-
figuration leads to a pressure drop which is slightly lower than the axial,
yields the same product distribution, and looks acceptable from a practical
point of view.
For several reasons already referred to, multibed operation is required
when the temperature effects of the process are too pronounced. The dis-
tribution of the catalyst over the various beds and the inlet temperatures
to each of these are design variables. Well-establishe d rigorous techniques
such as dynamic programming (Bellman, 1957; Aris, 1960) can be used to
derive optimal values for these variables. Examples have been published
for ammonia and sulfuric acid synthesis and CO conversion by the water-
gas shift reaction. Figure 1 shows the result for SO3 synthesis using
Capelli's rate equation (Froment and Bischoff, 1979). Analogous results
and a comparison of several optimization techniques were presented by
Chartrand and Crowe ( 1969).
A conversion versus temperature diagram is a convenient way to repre-
sent the operation of a reactor for the case of a single reaction. It does
not, of course, contain any information as to where in the reactor a given
set (x, T) is reached. For an adiabatic bed the relation (x, T) is obtained
from the equivalent of Eq. ( 11). In Fig. 1, the curve re represents the
equilibrium line, the curve r Am the locus of optimum reaction rates in an
adiabatic bed, and the curves r 1 , r 2 , r 3 and r r 1. 2, 3
r are loci of
--------
0.8
0.6 .<__~ r.
' / ~
--✓~
'
./ '-
0.4 '' /.
/ ''
y,· .._.. r.
., m
/ '
'
'
0.2 ''
,K [ r ]kmol/kg cat hr
'' r~m
600 650 700 750 800 850 900 T<"Kl
FIGURE 1 Optimal conversion versus temperature trajectories in SO 2
oxidation. (After Froment and Bischoff, 1979.)
384 Froment and Hofmann
optimum inlet and outlet conditions for each of the three beds. The profit
function includes the benefit resulting from the conversion and the penalty
associated with the cost of catalyst and operation. To achieve optimal oper-
ation with an exothermic equilibrium reaction, the temperature has to be
lowered as the conversion increases. The multibed adiabatic reactor per-
mits only a sawtooth temperature profile. Optimal reaction rate in each
point can only be obtained by following the rm curve, and this can only be
attempted in a reactor with continuous heat exchange, either of the multi-
tubular type or of the internal heat exchanger type, as mentioned earlier.
Tubular Reactors with Continuous Heat Exchange: Multitubular reactors
with catalyst inside the tubes are generally modeled by considering only
one tube, supposed to be representative for all of them. This is generally
justified when the heat-exchanging medium is either well stirred or flows
along or across the tubes in a single pass. When, however, the shell side
of the bundle is baffled and the heat transfer medium flows through it in
several passes, the complete bundle has to be considered, to account for
the different conditions in each tube and for the interaction between tubes.
The latter case will not be considered here; let it suffice to refer to work
by McGreavy and Dunbobbin ( 1976, 1978).
One problem that is of particular importance when exothermic reactions
are carried out in reactors of the type considered here is the occurrence
of temperature peaks, called hot spots. The operating conditions, such as
the feed concentration and temperature, or the coolant temperature and the
tube diameter, have to be chosen judiciously to keep the hot spot within
limits. What this limit is can be decided on by external constraints such
as safety or catalyst stability, or by what Van Welsenaere and Froment
(1970) called intrinsic constraints or criteria, related to the nature and the
parameters of the reaction and to the operating conditions.
Bilous and Amundson ( 1956) were among the first to draw attention to
the sensitivity of temperature profiles to the properties of the reaction or
to the operating conditions. Barkelew (1959) derived, from an extensive
set of simulations, simple intrinsic rules that are useful in early stages of
design to select ranges of safe operation and to set limits on the geometry.
Unfortunately, the results were obtained for a distorted temperature de-
pendence of the rate coefficient. The problem was taken up later, with
the Arrhenius dependence of the rate coefficient, by Dente and Collina
(1964), Marek et al. (1969) (also Hlavacek, 1970), and Van Welsenaere and
Froment ( 1970). The latter compared the various results in a diagram repre-
sented in Fig. 2.
The approach followed by Van Welsenaere and Froment has been ex-
tended to first-order reactions carried out in the presence of interfacial
temperature gradients and intraparticle concentration gradients (model BI!)
by Rayadhyaksha et al. ( 1975). Recently, Morbidelli and Varma ( 1982)
derived simple criteria for all positive-order reactions. The procedure for
obtaining the critical values is explicit but requires a (single) numerical
integration of a differential equation. All other parameters being equal,
runaway is more likely the lower the reaction order.
The detailed design or simulation of a reactor requires numerical integra-
tion to generate the various profiles inside the tubes. An example of one
aspect of the design is given in Fig. 3, which shows reactor temperature
profiles in axial direction and their sensitivity with respect to the salt bath
temperature in a-xylene oxidation over a V 2o 5 catalyst (Froment, 1967).
Fixed-Bed Gas-Solid Catalytic Reactors 385
2.5
N
s
2.0
INSENSITIVE
1.5
/.
/ RUNAWAY
/
/ ,
/
/ , 'I A- - B
4/ / 2 1st order
1.0 1/
l lo = lw
4 6 10 20 40 60 100
FIGURE 2 Comparison of criteria for parametric sensitivity and runaway
based on one-dimensional pseudohomogeneous model with plug flow. (After
Froment, 1974.)
6T 374•c
80
z = z'/dp
FIGURE 3 Parametric sensitivity in a-xylene air oxidation. Effect of salt
bath temperature. Curve at 374°C with diluted bed. (After Froment,
1967.)
386 Froment and Hofmann
The figure shows how, beyond a certain salt bath temperature, runaway
leading to an almost adiabatic temperature rise occurs. The phenomenon
illustrated here is parametric sensitivity, not instability sensu strictu. The
latter cannot be generated by this type of reactor model when the wall
temperature is constant.
The parametric sensitivity of a multitubular reactor with coolant in co-
current flow and varying in temperature was recently studied by Soria
Lopez et al. ( 1981). In certain cases it is important to optimize the temper-
ature profile when a sequence of reactions with different temperature de-
pendencies is taking place or when the process is reversible and exothermic,
as in ammonia, methanol, and so 3 synthesis. Again this is best illustrated
in a conversion versus temperature diagram such as the one presented in
Fig. 1 for S03 synthesis. In this diagram the rm curve represents the
sets (x, T) associated with maximum rates, so that following this set (x, T)
in the reactor ensures maximum conversion with a minimum amount of cata-
lyst. The temperature profile that achieves this can be obtained through
the use of Pontryagin's (1969) maximum principle. Murase et al. ( 1970)
performed such calculations for an ammonia-synthesis reactor, but the
practical realization is not so simple, because unrealistic heat transfer rates
are required. Optimal temperature profiles may also be obtained by appro-
priate dilution of the catalyst bed with inert particles (Butt and Weng,
1976; Froment, 1971; Narsimhan, 1976).
Autothermal operation becomes possible when the heat of reaction is
sufficient to heat the feed to the reaction temperature. In modern multi-
bed adiabatic ammonia synthesis reactors the effluent and the 'feed exchange
heat in an external heat exchanger. Internal heat exchangers whereby
heat is exchanged between feed and reacting gases are also encountered,
again in ammonia synthesis. The equations for the simulation and design
of such reactors are given below.
For autothermal operation in a multibed adiabatic reactor for a single
reaction with key component A (Fig. 4):
Catalyst bed:
(14)
dT
dz up c
s g p
External heat exchanger:
Boundary conditions:
Catalyst bed: x A ( 0) == xi
~
~
(1)
0..
I
OJ
(1)
0..
c;-:i
i::i
Cl)
I
T(Z) :T2 (Z') Cll
~
0..
z:O C")
i::i
i::i
-
~
T2 (0) = Te
-o·
::0
T(O) i . - - - - - - - - - - - - - - - - , T 1 (Z') :T0 (1)
z:Z i::i
(')
0-
~
z':z'
r,
z'=O
l r1coi = ~
...A(0): X, &.-o::::::::=-------------'-------------__jL.._~
T. Te I Z: 0 Z : Z z': Z' z' = 0
I
FIGURE 4 Autothermal operation of an adiabatic reactor with external heat exchanger.
c:.,
Oo
""I
388 Froment and Hofmann
Heat exchanger: T 1 (0) = Ti
T 2(0)=Te
T iZ') = T(Z)
For autothermal operation in a multitubular reactor (Fig. 5):
(-llH)pBrA T - T
dT
= - 4
u 1
(15)
dz uspgcp dt uspgcp
dT l T - T
-4 _Q_ 1
= p
dz dt U C
s g p
Boundary conditions:
xA = xi at z = 0
z = 0
z = z
Notice that U is an overall heat transfer coefficient, not to be confused
with ai in Eq. (2).
The feedback of heat introduces a feature hitherto not encountered in
this chapter, namely the possibility of multiple steady states. This
z::0
T1 :: T
z::Z
xA(O):: x i " ' - - - - - - - - - - - - _ . _ _ -
z:: 0 Z:Z
FIGURE 5 Autothermal operation of a multitubular reactor.
Fixed-Bed Gas-Solid Catalytic Reactors 389
x(Z)
III
T-l T(O) T(Z)Ti T(O) T(Z) T
FIGURE 6 Steady-state operating points in an autothermal multibed
adiabatic reactor.
phenomenon is readily understood on the basis of a now classical diagram
(Liljenroth, 1918; Van Heerden, 1953) shown in Fig. 6.
In an x-T plane the sigmoidal curve is a measure of the heat produced
by an exothermic equilibrium reaction, while the straight line is a measure
of the amount of heat exchanged between, for example, the feed to an
adiabatic bed and the effluent. The slope of this straight line is given by
the ratio \/[1 + (U,rdt/mcp)L]. For a certain range of inlet temperatures
and for certain values of this slope, therefore of operating conditions and
configuration, three intersections (i.e., three steady states are possible)
instead of one. The intersection leading to an intermediate temperature
and conversion corresponds to an unstable steady state, the upper and the
lower to stable steady states. The usual operation of an ammonia-synthesis
reactor is represented by a straight line nearly tangent to the sigmoidal
curve. Slight variations in the feed conditions may therefore cause extinc-
tion of the reactor, with the associated drastic cooling and possible mech-
anical damage to the catalyst and reactor. Consequently, autothermal re-
actors can run away either because of parametric sensitivity, already
encountered in the simple tubular reactor without feedback, or because of
instabilities sensu strictu, associated with the existence of multiple steady
states.
Evidently, computer simulations permit locating ranges of operation in
which such undesirable situations could develop. Yet it is always conven-
ient to have an analytical criterion for this purpose. Such a criterion was
developed by Inoue (1978) for nth-order reactions:
N > Sr y - n for irreversible reactions
with K = 1 ; K for reversible reactions
where
C
4U AO
N (16)
dt cppgrA(T 0)pB
390 Froment and Hofmann
and Sr is the dimensionless adiabatic temperature rise in the reactor.
There is no risk of instability with nth-order irreversible reactions when
Sry < 8 and for first-order reversible reactions when Sr y < 8K.
The optimal operating conditions for autothermal reactions are close to
the blow-off conditions, beyond which an external heat supply is required.
For first-order reactions, irreversible or reversible, Ampaya and Rinker
( 1977a, b) related the critical feed temperature, TF, leading to blow-off and
the critical bed inlet temperature, T O, to the operating and design param-
eters. At blow-off the following equation is valid for a first-order irrever-
sible reaction:
(y - l)T exp (y) = 1 ( 17)
where
The required degree of preheating then follows from
4UL 1
( 18)
u sC p p g dt y - 1
When transients have to be accounted for, the time derivative also en-
ters into the models. Most dynamic studies have been carried out by means
of the one-dimensional model with plug flow [Eqs. (1) to (3)]. Even then
the computational requirements become important. The dynamics of fixed-
bed reactors were discussed by Ray (1972). An interesting case of tran-
sients was studied analytically by Mehta et al. ( 1981)--so-called wrong-way
behavior-a reduction of the feed temperature may lead to a transient
temperature rise because of the different speeds of propagation of concen-
tration and temperature disturbances in the bed. The cold feed cools the
upstream section of the reactor and decreases the reaction rates and there-
fore the conversion in that region. The less converted cold fluid then con-
tacts hot catalyst, thus leading to a substantial temperature rise. Again,
the key parameters determining the magnitude of the response are the
adiabatic temperature rise, the activation energy, the heat transfer capacity,
the coolant temperatures, the magnitude of the disturbance, and the reac-
tor length. For a first-order reaction carried out in an adiabatic reactor
and for a zero-order reaction in a cooled reactor, simple expressions can
be derived for the maximum temperature rise. For the first case the expres-
sion is as follows:
(Sr+ w) exp (sry+ w) - w
(19)
where w represents the ratio of the temperature of the feed after and be-
fore the disturbance.
Fixed-Bed Gas-Solid Catalytic Reactors 391
For dynamic situations, however, it may be necessary to distinguish
between gas and solid, because of the difference in heat capacity of the
two phases. This will be illustrated later when we deal with the one-
dimensional heterogeneous model with interfacial gradients. The cyclic
variation of the feed concentration or temperature has been shown, in cer-
tain cases, to be beneficial for the conversion and selectivity but has not
been adopted yet in industrial practice. Reviews on this subject have
been presented by Schadlich et al. (1983) and Renken (1982).
Axial Dispersion Model
It is clear that the flow conditions in fixed-bed reactors deviate to a cer-
tain extent from plug flow. Since it is impossible-or too complicated-to
rigorously describe the true flow pattern, the deviation in mass and heat
transport is described in terms of diffusion-and conduction-like mech-
anisms that operate in superposition on transport by plug flow. The fluxes
of these mechanisms are expressed by Fick- and Fourier-type equations.
Consequently, a temperature peak will generate a heat flux in the upstream
direction in addition to that caused by radiation. The magnitude of this
flux depends on the gradient and on the effective conductivity appearing
in the Fourier-type law. Hiby ( 1963) has shown that this effect would
extend to only about one particle diameter and according to Wicke ( 1960,
1975) and Sundaresan et al. (1980), it would be overestimated by the cor-
relations that are presently available for the model parameters.
The reactor model equations are as follows, with the assumptions and
restrictions already made:
= 0 ( 20)
0:.
dT
A - U p C 4 d: (T - Tw) + (-liH)pBrA = 0 ( 21)
ea dz2 s g p dz
and the pressure-drop equation ( 3). The boundary conditions are
at z = 0
dT
u p c (TO - T) -),_
s g p ea dz
dC dT
= 0 at z = L
dz dz
These boundary conditions have been extensively discussed (Wicke, 1975).
Mathematically, they lead to a two-point boundary value problem, for which
an appropriate integration algorithm is recommended.
Each term in Eq. ( 20) has dimensions kmol/m 3 •h and (D ) is based
r ea s
on the superficial flow velocity. Notice, however, that the effective axial
dispersion coefficient is obtained from correlations Perna versus Re in which
the Peclet group usually contains ui. These correlations therefore yield
392 Froment and Hofmann
(Deah = (Dea)s IE:. For gases, Perna approaches a value of 2 at the Re
numbers usually encountered in commercial fixed-bed reactors (Froment
and Bischoff, 1979, p. 527). The effective axial thermal conductivity, Aea,
is obtained from correlations Peha versus Re in which the former contains
Us. These correlations show considerable spread, however (Dixon and
Cresswell, 1979). Yagi et al. (1960) derived the following correlation from
their experimental data at Re < 20:
:\ :\ o
ea ea
( 22)
:\ :\
g g
with 1./Ja = 1/Pema of the order of 0. 75 and A~a/Ag of the order of 8 to 10,
which is close to values measured for A~r/ Ag, to be discussed later. This
would lead to a value for
u p c d
s g p p
:\
ea
of the order of 2. A theoretical derivation by Bischoff (1962), based on
axial mass dispersion and radial velocity profiles in packed beds, leads to
a dependence on Reynolds, which is more complicated than that of Eq. ( 22).
Extensive experimental data of Votruba et al. (1972), extending to Re = 150
and higher, lead to considerably lower Peha, of the order of 0. 5 (i.e., Aea
roughly four times higher than those of Yagi et al.).
Axial dispersion effects may be neglected when the following criteria,
derived by Young and Finlayson (1973), are satisfied. For situations in
which the rate is monotonically decreasing with bed length (isothermal opera-
tion, adiabatic operation of an endothermic reaction, exothermic reaction with
excessive cooling), the criteria are set up for inlet conditions.
Axial dispersion effects are negligible at the inlet when
« Pe
ma
( 23)
and
(-L'iH)rA pBd
0 p
- - - - - - - - <<
(TO - T )u p c
Pe
ha
w s g p
Even when effects are noticeable at the inlet they are not necessarily felt
at the exit when total or equilibrium conversion is achieved inside the re-
actor, of course, but intermediate states may be affected. When the rate
of reaction is maximum at some intermediate position (e.g., because of a
hot spot) the criteria above are inadequate. Evidently, the steepness of the
temperature peak or of the concentration gradient determines whether or
not axial dispersion has to be accounted for, but generally, a priori criteria
are not available. Again according to Young and Finlayson ( 1973), axial
dispersion is negligible when
Fixed-Bed Gas-Solid Catalytic Reactors 393
dx
«
I
max Pe
d(z/d ) ma
p
( 24)
max I dT
d( z/d )
p
« Peha
The gradients can be approximated from a simulation based on the one-
dimensional pseudohomogeneous model with plug flow, AI. In industrial re-
actors with moderate temperature peaks, the flow velocities and reactor
length are such that axial dispersion effects may be neglected. In their
simulation of the TVA ammonium synthesis reactor, Baddour et al. (1965)
observed that axial dispersion of heat altered the steady-state temperature
profile by less than 0. 6°C from that computed by means of the basic model,
AI. Van Welsenaere and Froment ( 1970) simulated hydrocarbon oxidation
close to runaway conditions, with a hot spot of 50°C and a conversion of
some 70% in the first meter. Even for such a severe situation the criteria
(23) and (24) were satisfied. More drastic cases are generally not realistic
and have to be avoided for reasons of selectivity.
The structure of the model equations ( 20) and ( 21) introduces the pos-
sibility of multiple steady states. Consider, for illustrative purposes, the
adiabatic version of these equations and let Aea = (Dea>s. Combining the
equations leads to
dT
Pe~a dz' + f(T) = 0 ( 25)
where
z
z' = Pe' =
d ma
p
2
k(T
f(T) = (D )0)L ( E ) ( TO)
pB(Tad - T) exp R'To l - T
ea s
This equation may lead to a monotonic relation between T(Z) and To, yield-
ing unique steady-state profiles or, for a certain range of parameter values,
to a relation as shown in Fig. 7.
With such a relation three steady-state profiles are possible for inlet
temperatures (To)3 < To < (To)1, Of the three values of exit temperatures,
T(Z), corresponding to a To inside that range, only the outer two are
stable and can be observed without external action. The runaway associ-
ated with multiplicity of steady states has different properties from that
generated by parametric sensitivity, discussed under the basic plug-flow
model, AI.
Indeed, as To is increased along branch A, the exit temperature, T( Z) ,
increases progressively up to T(Z) 1 . For a value slightly exceeding (To)1,
the exit temperature T(Z) jumps to T(Z)2. Notice the discontinuity in
T ( Z): whereas in the parametric sensitivity case any exit' temperature can
be achieved, in the present case the range T(Z) 1 < T(Z) < T(Z)2 is
394 Froment and Hofmann
I
I
I
I
----+--------
1
I
I
I
I
I
I
I
--r-----;----r--------+-----+-- -
T(Z) 2 T(Zl
FIGURE 7 Relation of feed and exit temperatures in an adiabatic fixed-bed
reactor with axial mixing leading to the possibility of three steady-state
profiles. (From Froment, 1980b.)
excluded for the C O and flow rate that were selected. This is clearly an
instability in the restricted sense. Indeed, if the inlet temperature is
lowered from (To)2 onward, T(Z) will progressively decrease along branch
C until a value T(Z)3 is reached. If T(Z) is further reduced, T(Z) will
jump downward to T(Z)4, a value that differs from T(Z)3. The temperature
history exhibits a hysteresis, which is typical for an unstable system.
Several criteria for detecting multiplicity have been derived, either through
an analytical approach or through numerical computations. It is clear from
Fig. 7 that a necessary and sufficient condition for uniqueness is the ab-
sence of a hump, or in mathematical terms that no bifurcation occurs. The
hump is not a sufficient condition for multiplicity, however, since this is
possible for a certain range of To values only. In short, multiplicity
would be possible only for strongly exothermic processes with a very high
activation energy, carried out in reactors with considerable influence of
axial mixing.
According to Hlavacek and Hofmann ( 1970), for first-order reactions
multiplicity would be possible as soon as
sry > ~
4y
where Sr is the dimensionless adiabatic temperature rise in the reactor,
(-llH)ColPgCpTo, and y the dimensionless activation energy, E/RT 0 .
Figure 8 shows that even when this condition is satisfied, multiplicity can
occur only when Perna is smaller than a certain value, depending on the
ratio
Fixed-Bed Gas-Solid Catalytic Reactors 395
400r-----------------,
t:8
Bo
II 200
4
uil
--
Dea
100
2
0.05 0.1
n -1
k(T0 )C 0 L
Da: - - - - - -
FIGURE 8 Areas of multiplicity of steady-state profiles in an adiabatic
tubular reactor with axial mixing. Sry = 10; y = 20; t = Aea/DeaPgCp·
(From Hlavac"ek and Votruba, 1977.)
Pe A
ma ea
Peha
and between two values of the first Damkohler number, k(To)L/ui.
The value of Sr of 0. 5 is exceeded in ammonia-methanol and oxy syn-
thesis. Values of Aeal(Dea)sPgCp range from 1 to 4. Even for the maxi-
mum value, a value of Pehia of 200, corresponding to a bed depth of
roughly 100 particles, would exclude multiplicity. Industrial reactors
typically lead to Pe~a of 600 to 2000. These values were confirmed in a
very extensive analysis of this problem by Jensen and Ray ( 1982), who
concluded further that oscillations caused by axial dispersion are totally
unlikely in fixed - bed reactors .
It should be added that multiplicity of steady states has been observed
in laboratory tubular reactors, for some extreme conditions. Even if axial
dispersion is relatively more important in laboratory reactors, it now looks
as if other phenomena are responsible for this behavior: intraparticle gra-
dients, a particular form of rate equation, or surface phenomena on the
catalyst. These causes will be dealt with in later sections.
396 Froment and Hofmann
Two-Dimensional Pseudohomogeneous Model
When reactions with a pronounced heat effect, such as ethylene, benzene,
xylene, and naphthalene oxidation, are carried out in multitubular reactors,
radial temperature and cor,sequent concentration gradients develop. It then
becomes necessary to extend the one-dimensional model AI to account for
these gradients, caused by finite rates of heat and mass transfer in radial
direction. In fixed beds the resistance to heat transfer is not limited to
a very thin layer in the immediate vicinity of the wall, but extends through-
out the cross section. The flux in radial direction of heat and mass is super-
imposed on the flux in axial direction by plug flow and is again expressed
in terms of effective diffusion and conduction, obeying Fick's and Fourier's
law. The effective dispersion coefficient contains contributions from molecu-
lar and turbulent diffusion and from the dispersion caused by the catalyst
particles. The effective thermal conductivity contains various contributions,
such as conduction in the solid and in the fluid, radiation between gas-
filled voids and between solids, convection from the fluid to the solid, and
conduction through stagnant fluid in the vicinity of contact surfaces be-
tween solid particles. It has been derived from experiments that the effec-
tive thermal conductivity Aer is relatively constant in the core of the bed,
but rapidly decreases toward the wall-as if supplementary resistance
operates close to this boundary. This is not surprising: it is known that
the packing-and therefore the flow characteristics-in that region are
quite different from those in the core. Rather than using point values,
Aer has generally been considered to be constant up to the wall and a
second parameter, accounting for the heat transfer at the wall, aw, has
been introduced. It is defined by
clT
-;\ = a (T - T ) at r = R ( 26)
er clr w w
This wall heat transfer coefficient should not be confused with the heat
transfer coefficient, ai, of the one-dimensional model, which lumps the re-
sistance to heat transfer completely in the film near the wall.
Since in industrial reactors the flow rate is generally high, the contri-
bution of axial effective diffusion can be neglected. The model equations
can then be written, for steady state, in an isobaric reactor and no change
in number of moles:
(D cl 2C 1 cl C
er)s (3r2 + r 8r ) = 0 ( 27)
( 28)
with boundary conditions
at z = 0, 0 < r < R
( 29)
at r = 0 and r = R
Fixed-Bed Gas-Solid Catalytic Reactors 397
3T
3r =0 at r =0
( 29)
C(
3T w
3r = ~ ( T - Tw) at r =R
er
Notice that axial effective diffusion has been neglected in this model for
the reasons explained in the preceding section.
Like Dea, the effective radial diffusivity is obtained from correlations
Pemr versus Re. In Pemr the velocity is the interstitial, so that (Der)i is
derived from this. Again, (Der)s = E(Derh• Correlations for Der have
been derived from experiments. According to Fahien and Smith (1955),
for Re > 10,
Pe
____m_r____ = 10
1 + 19.4(dp/dt) 2
The denominator contains the ratio dp/dt, to account for the radial non-
homogeneity of the packing.
For heat transfer De Wasch and Froment ( 1972) obtained the following
correlation for air and a V2O5-TiO2 catalyst:
0.0025
t.. \ 0 + -------Re ( 30)
er 1 + 46(d /d ) 2
er
p t
0. 0115dt
C( = a 0 ·+ - - - - R e ( 31)
w w d
p
Yagi and Kunii ( 1957) and Kunii and Smith ( 1960) developed models
for calculating Aer and aw from fundamentals. In these models the flux by
effective conduction is considered to consist of two contributions: the first
static, independent of flow conditions, the second dynamic,
( 32)
The model for the calculation of A~r contains the mechanisms mentioned
above. Zehner and Schliinder (1970) developed a slightly different con-
cept yielding the following equation:
\0
er = ( 1 - /l"=s) (1 + E C(~sgdp) + _ _ _ _ _ 2_✓_1_-_E
_ _ _ _e
t..g /\ 1 + [(a d /A ) - B](\ /A )
rs p g g s
( 33)
398 Froment and Hofmann
f{1
with
+ [(ars d p />.. g ) 1] (A />.. ) }B 1 + a d />..
rs p s
e= g s ln
{{1+ [(a d
rs p
/A )
g
Bl(>.. />.. )}
g s
2 B(A /A)
g s
a d
B - 1 ~ ( ~ -
1 + [(a d />.. ) - B](A />.. ) + 2B >..
rs p g g s g
where B = b[(l - s)/s]l0/9 with b = 1.25 for spheres and 2.5 for cylin-
ders and Raschig rings.
The dynamic contribution >.. t is obtained from
er
1/J PrRe ( 34)
r
where 1/Jr = 1/Pemr· From the heat transfer experiments of De Wasch and
Froment ( 1972), the following correlation for 1/Jr can be derived:
0.14
( 35)
whereas Yagi and Kunii ( 1957) obtained values between 0.10 and 0.14
Yagi and Wakao (1959) and Yagi and Kunii (1960) also derived the following
correlation for Cl.w and developed a model along the lines adopted for the
modeling of Aer to predict this parameter:
a d
~ ( 36)
>..
g
where 1/Jw = 0. 041. Values of a~dp /Ag in cylindrical beds are of the order
Of 3. 0, depending on the solid, its size, and the ratio dt /dp. Hennecke
and Schlunder ( 1973) also presented a correlation for aw. based on an ex-
tensive set of experimental data. Spechia et al. (1980) have presented new
data and correlations, both for >.. t and a . The numerical problems asso-
er w
ciated with the solution of sets of second-order nonlinear partial differential
equations have been thoroughly investigated and various techniques, such
as the implicit Crank-Nicolson scheme (Grosjean and Froment, 1962) and
orthogonal collocation (Finlayson, 1971), have been used and compared with
one another (Mihail and Jordache, 1976). Computer programs for their
application are available (Hoffmann et al. (1977); Lerou and Froment,
1982; Dente et al. ( 1972). Yet for situations that are very demanding in
computational efforts, such as those involving transients, it may still be of
interest to use a model with a structure requiring less computation, but
containing, nevertheless, certain features of the two-dimensional model.
An "equivalent" one-dimensional model has been developed that aims at re-
producing- the radially averaged concentrations and temperatures generated
by the two-dimensional model. By matching temperature profiles in the
Fixed-Bed Gas-Solid Catalytic Reactors 399
absence of reaction, Froment ( 1961) derived the following relation from
which the parameters a.. of the equivalent one-dimension al model can be
calculated: 1
1 1 dt
= --+ ( 37)
a.. a. 8A
l w er
Slightly different but analogous relations were derived by Crider and
Foss (1965), Hlava&ek (1970), and Finlayson (1971). A comparison of both
model predictions was made by Froment (1967) for o-xylene oxidation. For
severe but still realistic operating conditions, the deviations between both
models become important. And, of course, the values in the axis may still
significantly differ from the radially averaged value, necessitating a more
detailed model.
Examples of simulations based on the two-dimension al pseudohomoge neous
model have been presented by Froment ( 1967), Hawthorn et al. ( 1968) ,
Carberry and White (1969) and Garcia-Ochoa et al. (1981), among others.
These simulations reveal that the radial profiles are not very sensitive to
the Peclet number for radial mass transfer, but that, on the other hand,
for severe conditions, Aer and a.w have to be known with great accuracy.
Figure 9 shows measured and computed temperatures in a cross section
halfway between two tubular reactors for the endothermic dehydrogenati on
of methylcyclohe xane on a Pt/Al2O 3 catalyst (Hawthorn et al., 1968). The
parameters in the two-dimension al model were independently determined.
The reactor with internal tube diameter 1. 6S cm leads to a temperature dif-
ference between the wall and the axis of 34°C. This D. T is made up of two
30
25
20
T-To(°C)
15
10
I
I
I
--- -------'
5
0.2 0.4 0.6 0.8
r
R
FIGURE 9 Measured and computed radial temperature profiles in a methyl-
cyclohexane dehydrogenati on reactor. Solid line: I.D. tube, 1. 65 cm;
awdt/2Aer = 2.9; dashed line: I.D. tube, 0.71 cm; awdt/2A = 1.1.
(From Hawthorn et al., 1968.) er
400 Froment and Hofmann
nearly equal parts and the reaction rate is significantly varying with
radial position, while the temperature profile is deviating from parabolic.
In the reactor with internal tube diameter 0. 71 cm, the D. T is 13°C, with
nearly two-third accounted for by the wall film resistance; the reaction
rate is nearly uniform in the cross section and the temperature profile is
very nearly parabolic. In this case a one-dimensional model would be suf-
ficient to successfully simulate the reactor, provided that the heat transfer
coefficient elf would be adapted to account for the influence of the radial
temperature profile, as is done in Eq. ( 36).
Hofmann and coworkers (Hofmann, 1979) studied reactions with widely
different heat effects in a sophisticated bench-scale tubular reactor allowing
axial and radial profiles of conversion and temperature to be measured.
This work again emphasizes the high degree of accuracy required in the
modeling of reaction and heat transfer under severe conditions. The ex-
pressions for the static contributions to >..er and ¾ contain a number of
parameters which are not always available with a sufficient accuracy: even
the apparently trivial solid conductivity, As, is a problem, in particular
with complex catalysts (Hoffmann et al., 1978).
Discrepancies between observed and predicted parameter values are more
likely also at low dt /dp, for which the reported data show a wide scatter
and for which deviations from plug flow should no longer be described by
a Fickian mechanism. Recently, a non- Fickian model was developed by
Chang ( 1982) , but much remains to be done in this area.
Little has been done also to account for the radial variation in the
velocity caused by the nonuniform void fraction. The latter has a value of
1 at the wall and decreases in an oscillating way to a rather constant value
around the central axis. The following empirical correlation was derived
for the void fraction in a bed of spheres by Martin (1978) from the experi-
mental data of Benenati and Brosilow ( 1962):
E.
m1n
+(1- E •
mm
)r 12 -1 ,.;; r' < 0
{
E(r')
-0. 25r' 7T
E
oo
+ (E •
min
- Eoo )e cos a- r' r' ;;;, 0
where r' = 2(r/dp) - 1 and a = 0. 816 for dt/dp = 00 and 0. 876 for dt/dp =
20.3. Emin occurs at a distance of (1/2)dp from the wall, while Eoo re-
fers to the value in the axis. For beds of spheres Emin equals 0.2 and Eoo
roughly 0.4, depending on dt/dp. For a dt/dp of 8, Schwartz and Smith
(1953) measured velocities near the wall twice as high as those in the axis.
Accounting for the point values of the flow velocity into the treatment of
their radial heat transfer data, Lerou and Froment ( 1977) came to values
for >..er very close to those predicted by the correlation ( 30), in which the
dependence on the Reynolds number was arrived at through the variation
of the global flow rate.
Figure 10 shows a comparison of radial temperature profiles in an
o-xylene oxidation reactor, computed on the basis of uniform flow velocity
and a flow velocity distribution induced by the local void fraction (Lerou
and Froment, 1977).
Again it is clear that considerable sophistication is required in the
modeling of demanding situations. It is unrealistic to believe that gross
Fixed-Bed Gas-Solid Catalytic Reactors 401
100
Tw:: 361 °C
axis
radial ml!an
wall
----------
1.4 1.6 1.8 2.0
REACTOR LENGTH(m)
FIGURE 10 Effect of flow velocity profile on radially averaged temperature,
and conversion profiles in a tubular reactor for o-xylene oxidation. dp =
0.0045 m; dt = 0.025 m; T = 361°C. Dotted line, model with radial velocity
profile; solid line, model with uniform velocity. (After Lerou and Froment,
1977.)
models would be sufficient for the modeling of a reactor, just because it
is industrial and geometrically relatively simple. To decide whether or not
a two-dimensional model is required, Mears (1971a) proposed to evaluate
the group
I tiHI rA(T)pBd:E
( 37)
( 1 + a d8 /;\
4;\ R 1T 2 w p er
er w
at the hot spot predicted by the one-dimensional simulation. If the value
of the group exceeds 0. 4, the simulation should be extended to the pseudo-
homogeneous two-dimensional model. The idea behind the criterion is that
if the cross section is to be uniform in temperature, the radially averaged
rate in the hot-spot location should not deviate from the rate taken at the
wall temperature by more than 5%. For exothermic reactions the criterion
is somewhat optimistic, since the temperature predicted by the one-
dimensional model at a given bed depth is lower than the radial average
of the two-dimensional temperature profile.
402 Froment and Hofmann
Clearly, there are cases where there is no justification for not using a
two-dimensional model in designing or simulating a reactor. And from the
work of Hofmann and coworkers (Hofmann, 1979), this would seem to be
true for kinetic analysis also, when pronounced hot spots are inevitable.
Finally, it should be added that the mathematical structure of the reactor
model as presented here cannot generate multiple steady states (Young and
Finlayson, 1974). The parametric sensitivity of the model has been investi-
gated numerically along the Barkelew approach by Agnew and Potter ( 1966).
Heterogeneous Models
Plug-Flow Model with Interfacial Gradients
Model Equations and Correlations for the Parameters: When the trans-
fer of heat and mass from the bulk gas phase to the catalyst involves
significant gradients in the vicinity of the surface of the particle, the
model commonly used to describe such a situation in a fixed-bed reactor
is of the heterogeneous type. It is written, in the steady state, for a
single reaction, constant density, and isobaric operation:
Fluid phase:
dC ( 38)
-us dz = k gv
a (C
4a.
I
( 39)
Solid phase:
( 40)
( 41)
with initial conditions C = Co, T = To at z = 0. The algebraic equations
( 40) and ( 41) are· first iteratively solved, yielding the values of Cs and Ts
s s
which enter into the right-hand sides of the differential equations for the
fluid. These are then solved by a Runge-Kutta routine. Notice that this
model does not explicity contain any axial coupling between the solid phase;
heat and mass are transferred in the axial direction through the gas phase
only.
The correlations for the mass and heat transfer coefficients have been
reviewed by Schliinder ( 1978). A frequently used correlation for kg is
that of Petrovic and Thodos ( 1968) :
3 ,.; Re ,.; 2000 ( 42)
Fixed-Bed Gas-Solid Catalytic Reactors 403
whereas for heat transfer Whitaker ( 1972) proposed
( 43)
and Gelbin et al. (1976):
0.563
ENU= 1.oo(REe) Pr 0 • 33 ( 44)
Evidently, these transfer coefficients between bulk gas and a bed of parti-
cles differ from those between a gas and a single particle, but Martin
( 1978) and Gnielinski ( 1982) expressed Nu in terms of that for a single
particle, Nusp, which is in turn first related to laminar and turbulent con-
tributions:
( 45)
with
= 0. 664 3/Fr /Re'
and
up
s g
Js7;
p
and Re'
].! E
The Nusselt' number for the packed bed is then calculated from
Nu = f Nu ( 46)
a sp
with the shape factor, fa = 1. 0 for spheres, 1. 6 for cylinders, 2. 3 for
Berl-Saddles, and 2.1 for Raschig rings. Relation (46) and the shape fac-
tors also hold for the Sherwood number. Gnielinski's correlation fits a
large number of experimental data of various authors, except at low values
of Peh = PrRe. Martin ( 1978) and Schliinder ( 1978) explained this by the
error introduced by assuming uniform radial flow velocity in the deviation
of hf from the experimental data and derived an asymptotic relation valid
when Peh + 0.
The fluid-solid heat transfer coefficient derived from experiments in
packed beds heated from the wall is really a conglomerate resulting
from several mechanisms. Three contributions are considered by
Balakrishnan and Pei ( 1979): the true fluid to solid heat transfer coeffi-
cient, the particle-to-particle heat transfer coefficient, and the coefficient
for heat transfer through the solid. Using microwaves to heat the solid
enabled Bhattacharyya and Pei ( 1975) to measure the true fluid to solid
heat transfer coefficient. As mentioned already, the model equations (38)
404 Froment and Hofmann
to ( 41) do not contain any coupling between particles. Therefore, for
fixed beds exchanging heat through the wall, the use of the global hf, ob-
tained from the correlations ( 43), ( 44) or ( 46) is consistent with the
model, although it is not necessarily the most accurate way of dealing with
the phenomenon. Interfacial gradients develop when the rate of reaction
is high, the heat effect pronounced, and the flow velocity relatively low
The most likely gradient is a temperature gradient.
Mears ( 1971b) derived the following criterion for neglecting interfacial
concentration gradients in the presence of an irreversible reaction with
order n:
rApSdJ2. < 0.15
( 47)
2Ck n
g
For a less than 5% deviation in the rate equation, due to interfacial tempera-
ture gradients alone, he derived ( 1971a)
_(-11H)rApSdp
< 0.15 R'T ( 48)
2hfT E
Interfacial gradients are generally not of concern in industrial reactors,
since the flow velocity is high. In ammonia synthesis Baddour et al.
(1965) simulated a 11 T of 2. 3°C between gas and solid at the top of the re-
actor, where the rate is maximum and 0. 4°C at the outlet. In methanol
synthesis, Cappelli et al. (1972) calculated a 11 T of maximum 1. 5°C. In
phthalic anhydride synthesis. Froment and Bischoff ( 197 9) calculated a LT
of maximum 3°C for normal operating conditions and in steam reforming of
natural gas, De Deken et al. ( 1982) obtained less than 4°C. There are excep-
tions, however, for example, when a component of the catalyst itself is involved
in the reaction, as in catalyst reoxidation or catalyst regeneration by burning
off the coke formed by side reactions.
Example of Application: An illustration of the need for heterogeneous
models with interfacial gradients is provided by Hatcher et al. ( 1978). The
case dealt with is the reoxidation of a nickel catalyst in the secondary re-
former of an ammonia plant, prior to opening the reactor for maintenance.
During normal operation the gases coming from the primary reformer are
fed at 1100°C and exit at 900°C. The reactor is adiabatic. When it has
to be opened, the first step in stabilizing the catalyst is to circulate steam
through the bed until the exit has cooled down to 250°C. During the
cooling period the steam strips hydrogen from the catalyst support, but it
does not remove hydrogen adsorbed on the nickel surface. At this point,
nitrogen, containing small amounts of oxygen only, is fed to the reactor.
The oxygen reacts with the adsorbed hydrogen and also partially oxidizes
the nickel catalyst. Both reactions are very exothermic and a thermal
wave travels through the bed. The reactor simulation equations have to
account for the non-steady-state nature of the operation. The continuity
equation for the oxygen in the gas phase may be written
GR' T ( 3p A + ~ cl p A) = ( 49)
M pta k 3z G 3t pA
m V g S
Fixed-Bed Gas-Solid Catalytic Reactors 405
The energy equation for the gas phase is
sp
+__:_g:_- aT)
=T -T ( 50)
G at s
The continuity equation for oxygen in the solid phase is
k
~(PA ( 51)
where the term in brackets is simply ro 2 .
Since the rate of hydrogen oxidation is instantaneous and the phenome-
non is therefore mass-transfer limited, the oxygen present on the surface
is essentially zero as long as there is hydrogen on the surface, so that
d
= -12 p ( 52)
12 s
with cH 2 is the concentration of adsorbed hydrogen, in kmol/kg cat. The
energy equation for the solid phase is written
d aT
hrCTs - T) + f csps at
s
( 53)
The initial and boundary conditions are
t = 0, z ;;i: 0:
t ,f: 0, z = 0: PA -p
- A '
T=T
0
0
The rate equation for nickel reoxidation, derived from bench-scale experi-
mentation, was written as
k'KApAc!i
( 54)
rNi = 1 + KApA
with rNi in kmol/kg cat•h, CNi in kmol/kg catalyst, and k' in kmol/kg
catalyst •h. The simulation was carried out for a reactor with a diameter
of 1. 8 m and a length of 2. 5 m, operated adiabatically. The reoxidation
gas was fed at 250°C and at an absolute pressure of 1. 5 bar. The oxygen
partial pressure in the feed was 0. 075 atm. Its mass flow velocity amounted
to 1342.8 kg/m2•h. The equivalent catalyst diameter was 0.014 m and the
catalyst bed density 950 kg/m3 reactor. The initial Ni concentration was
0.00624 kmol/kg cat, and the hydrogen concentration, 0.00093 kmol/kg
cat. The set of equations was integrated along the characteristics by
406 Froment and Hofmann
means of a Runge-Kutta-Gill routine. The results are represented in the
Figs. 11 and 12.
The simulation illustrates the combined effect of too high an oxygen
content and too low a flow velocity, which led to the fusion of the catalyst
from a bed depth of 1. 46 m onward. This requires a temperature exceed-
ing 1400°C. Figure 11 shows how the simulation predicts a temperature of
1400°C, reached between 1. 2 and 1. 3 m, in excellent agreement with the
observation. Figure 12 illustrates that the difference between gas and solid
temperatures can reach 100°C. Clearly, a reactor model accounting for
interfacial gradients is required here. Notice from Fig. 12 how the solid
temperature exceeds the gas temperature at positions already passed by
the thermal wave and how the difference rapidly increases on the back
slope of the wave. Near the peak of the wave the difference becomes
smaller. In front of the wave the gas temperature exceeds the catalyst
temperature. It is also observed that after a certain time the wave travels
at a nearly constant rate. Analogous equations are used to simulate the
regeneration of coked catalysts and similar results are obtained (Olson
et al. , 1968).
0
T5 , C CURVE TIME HRS
1400 7 1 0.2
2 0.4
3 66
4 08
1200 5 10
6 I 2
7 11.
1000
lb2 = 0 075atm.
800 G = 131.2.8 kg/m 2 hr
600
400
200
0+---------r-----------,,--------,----
ns 1.0 1 s Z,m
(a)
FIGURE 11 Reoxidation of a steam reforming catalyst in an adiabatic
secondary reformer, simulated by means of the heterogeneous one-dimension-
al model with interfacial gradients. (a) Solid temperature profiles; (b)
Nickel and hydrogen concentration profiles. (After Hatcher et al., 1978.)
Fixed-Bed Gas-Solid Catalytic Reactors 407
0.5
0~-------,--------r-------r-::-4"
o 0.5 1.0 1.5 Z.m
CHi Po2 = 0.075 aim
::-0 G = 1342 .8 kg/m2hr
CH2
1.0 r r
0.5
0+----~-~- ~-...__...__ ........__~
0 0.5 1.0 1.5 Z,m
(b)
FIGURE 11 (Continued)
Multiplicity of Steady States: Ever since the work of Wicke ( 1960),
Liu and Amundson (1962) and Liu et al. (1963), there has been intensive
academic interest in multiplicity of steady states generated by the existence
of gradients at the fluid-solid interface in exothermic processes. The pur-
pose of the present section is to describe this phenomenon in simple terms
and to evaluate whether it is likely to occur or not in industrial tubular
reactions.
Consider a single reaction and a catalyst particle with uniform tempera-
ture Ts and concentration Cs of a key component. The bulk fluid surround-
ing it is at a temperature T and concentration C. At steady state the heat
408 Froment and Hofmann
100
0.L HOURS
-100t---------;:,-::------~------~--
o 0.5 1.0 1.5 Z,m
100
0. 8 HOURS
o-1-------
-100t--------------~------~----
0 0.5 1.0 1.5 Z,m
FIGURE 12 Simulated temperature difference between solid and gas in the
reoxidation of a steam reforming catalyst. (After Hatcher et al. , 1978.)
generated by reaction QR= (-llH)rAPB has to equal the heat transferred
from the particle to the bulk fluid, QT = hfav(Ts - T). It can be seen
from Fig. 13 that QR has a sigmoidal shape when plotted versus Ts, where-
as QT leads to a straight line. When the intersection of Qr and QT occurs
in A, the corresponding values of Ts are low, whereas intersection in C
requires a higher fluid temperature and leads to a high temperature for the
solid. For a certain range of T , three intersections are possible, the outer
two corresponding to stable, the intermediate to unstable operation. Which
one of the two stable steady states is selected by the system depends on the
fluid temperature and on the previous history.
Suppose that the system operates in a point on branch A. As soon as
the gas temperature is increased above a value leading to the solid tempera-
ture (Ts) 1 , the latter will jump to a value (Ts) 2 . For the history just
Fixed-Bed Gas-Solid Catalytic Reactors 409
FIGURE 13 Heat production and transfer rates for various gas and
catalyst temperatures.
described, the points in the range (Ts)1, (Ts)2 do not correspond to a
steady state for Ts, If the particle is initially at (Ts)2 and its tempera-
ture is slightly lowered below (Ts)3, the temperature will drop to (Ts)4
and extinction will occur. With this history the range (Ts)3 to (Ts)4 does
not correspond to a steady state for the solid temperature. The hysteresis
involved in the description above is shown in Fig. 14.
Extending this reasoning from a single particle to a fixed-bed reactor
leads to the conclusion that the concentration and temperature profile in a
reactor-even without feed-effluent heat exchange-would not only depend
on the feed conditions and the wall temperature, but also on the tempera-
ture profile at the time the feed is initially admitted to the reactor.
Figure 15 shows simulated temperature profiles in an adiabatic reactor
with interfacial gradients (Liu and Amundson, 1962a, b). Figure 15a relates
to a situation in which multiplicity is not possible and in which runaway
would result solely from parametric sensitivity. Upon removal of the per-
turbation causing the runaway, the original profile would be recovered.
Any intermediate temperature profile would be possible with an appropriate
selection of operating conditions. Figure 15b, on the other hand, relates
to multiplicity of steady states and true instability. Notice the much higher
feed concentration required to achieve this. In case A the initial bed
temperature is lower than 393°C. Up to 0. 27 m the particles are in the
lower steady state. The temperature then rises very steeply over a few
410 Froment and Hofmann
-----=-=.;-__...,_-
FIGURE 14 Temperature hysteresis in catalyst temperature upon variations
in bulk gas temperature for the case of multiple steady state.
1200
800 .08 \,. ......--r
T p T 1000
I
/ B
.06 Ps Ts
Ts
I
(OC) (atm) (OC) 800 I
I
600 .04
I
600 I
/ .02 I
/,
/, I
,I.
""' 400
400
0 .1 .2 .3 .4 0 .1 .2 .3 .4
z Im) z (m)
(a) (b)
FIGURE 15 Simulated temperature profiles in an adiabatic tubular reactor
with interfacial gradients for a first-order reaction. {a) Nonunique steady-
state case: PO= 0.15 atm, To= 393°C; initial Ts for A: 393°C; for B:
560°C. (b) Unique steady state; PO= 0.007 atm, To= 449°C. (After
Lee and Amundson, 1962.)
Fixed-Bed Gas-Solid Catalytic Reactors 411
layers of catalyst to reach the upper steady state. In case B the initial
bed temperature is 560°C. The feed is rapidly heated from 393°C onward
and it takes only a few centimeters to ignite the reactor to the upper
steady state.
Experimentally, the characteristics associated with Fig. 15 would have
to be checked to distinguish between the causes of runaway: parametric
sensitivity or multiplicity of steady states. Similar, although less drastic
behavior would be calculated for orders higher than one. For the more gen-
eral Hougen-Watson-type rate equations, which account for adsorption of the
reacting components, the results may differ in some aspects (Cardoso and
Luss, 1969).
The analysis of the multiplicity of steady states caused by interfacial
gradients proceeds along the lines described earlier. A priori criteria for
testing multiplicity associated with interfacial gradients were reviewed by
Luss ( 1976). Briefly, for exothermic reactions uniqueness is guaranteed
in a cross section in the reactor with bulk conditions (C, T) when
For orders O ,( n ,( 2, the function f( Br,n) is bounded between 1 (for
n = 0 and Bf = 0) and 5. 82 (for n = 2 and Sf = 0). For large Br the
function value asymptotically approaches 4, for all n. For n = 1 the func-
tions f( Br,n) equals 4, for all Sf· When Sn /1 + Bf exceeds the value of
f( Br,n), multiplicity is possible for some values of the dimensionless
parameter
V k(T) cn-l
p ps
C( = ~------
s k Sn--l
p g f
(Van den Bosch and Luss, 1977).
Recently, Tsotsis et al. ( 1982) presented criteria for Hougen-Watson-
type rate equations. In this case multiplicity may also occur with endo-
thermic reactions and for isothermal situations ( Br = 0). In ammonia,
methanol, and oxo synthesis, values of Bn/1 + Bf exceeding 10 may be en-
countered. Yet for realistic operating conditions, fl T of 2. 5°C and less
were simulated by Baddour et al. (1965) and Capelli et al. (1972) in
ammonia and methanol synthesis. Such low fl T values cannot generate
multiplicity.
It has already been mentioned that the model [Eqs. ( 38) to ( 41)] does
not contain any axial coupling between the particles, a serious simplification
when steep gradients occur over a few layers of catalyst particles only.
Eigenberger (1972a,b) extended the model to account for this and found a
significantly different behavior in the range of multiplicity. The backward
flow of heat prevents some parts of the reactor to be in the lower steady
state and others in the high steady state, which would be possible if there
were no coupling. If the reactor is in the high steady state at the exit,
it will be so at the inlet, too, so that the temperature peak is right at the
entrance. Vanderveen et al. ( 1968) analyzed such a situation by means
of a cell model.
412 Froment and Hofmann
Plug-Flow Model with Interfacial and Intraparticle Gradients
Model Equations and Parameters: Many industrial processes make use
of catalysts and operating conditions leading to intraparticle gradients. In
the present section a rather general model will be given first, before enter-
ing into the possibility of simplifying it. The equations can be written
accounting for the already mentioned assumptions:
Fluid phase:
dC ( 55)
-us dz = k a (C
g V
( 56)
Solid phase, with spherical particles:
D
( 2 dCs)
e d
( 57)
s2 ds s ds
( 58)
with boundary conditions
z=0: C=C 0 ,T=T 0
dC dT
s= 0:
ds
s
=
ds
s
== 0
( 59)
d dC
k (Cs - C) = -D s
s = _E_:
2 g s e ds
dT
h (Ts - s
T) = -1c
f s e ds
The effective diffusivity De is usually related to the molecular and Knudsen
diffusion inside the pores of the catalyst by means of the Bosanquet
relation:
s
D = ____s_ _ __ ( 60)
e T(l/Dm + 1/DK)
which is strictly speaking valid for equimolar countercurrent diffusion in a
binary mixture only.
Bulk flow due to a pressure gradient or surface diffusion can generally
be neglected. The internal void fraction of the catalyst, ss , enters into
this formula because the diffusion evidently occurs in the pores only and the
Fixed-Bed Gas-Solid Catalytic Reactors 413
tortuosity, T, because these are randomly oriented (i.e., not along the
normal from the surface to the center). De can be measured using the
steady-state Wicke-Kallenbach method (1941) or the transient gas chroma-
tographic technique, which also accounts for the contribution of dead and
pores (Van Deemter et al., 1956).
Probst and Wohlfahrt ( 1979) presented empirical methods for estimating
De, Several pore structure models have been proposed for calculating De
(or T), since reliable correlations are available for Dm and DK and since
Es is easily measured. No such models are available for Ae, except that
of Butt ( 1965), based on the simple pore model of Wakao and Smith ( 1962),
but temperature effects inside the particle are generally negligible when
the reaction does not involve any component of the solid. The numerical
effort introduced by the integration of the system of second-order (non-
linear) differential equations for the solid phase in each of the nodes
used in the integration of the fluid-phase equations is substantial, in
particular for complex reactions, even with modern collocation methods.
It has been shown, both by calculations and experimentally, that intra-
particle temperature gradients are generally negligible, so that Eq. ( 58)
can be dropped. Also, when there are external gradients, these are gen-
erally only temperature gradients. The system of equations then reduces
to:
Fluid phase:
dC
-us dz ( 61)
s
h,.a (T - T) (62)
I V S
Solid phase:
(63)
with boundary conditions for the solid:
d
At E;, = _£_,
2 . -D
dC
= p s r A (C ss , T ss )
e dt;,
dC
h (Ts
f s
T) = -(-b.H)D e -
dt;,
( 64)
dC
s
At E;, = 0: dt;, =0
and the usual boundary conditions for the fluid phase. Clearly, the
problem is considerably further simplified for first-order reactions, for
which an analytical solution for Eq. (63) is possible. The result is gen-
erally cast into the following convenient form:
414 Froment and Hofmann
1 3¢ coth 3¢ - 1
11 = ( 65)
¢ 3¢
where 11, the effectiveness factor, is the ratio of the actual rate to that in
the absence of diffusional limitations, that is, when the surface conditions
prevail throughout the particle and
is a modified Thiele modulus, which, like the original Thiele modulus, con-
tains the rate coefficient and the effective diffusivity and therefore varies
with position in the reactor whenever there is a temperature profile. The
use of ¢ leads to a unique relation between 11 and ¢, whatever the shape
of the particles, for both low and high values of the modulus and to dif-
ferences between cylinders and spheres smaller than 15% for intermediate
values, as shown in Fig. 16.
The 11 concept allows replacing Eq. ( 57) [ or Eq. ( 63)] , and when it
is included, Eq. ( 58), by the algebraic equations
k a (C - Cs) ( 66)
g V S
s
hfa (T - T) ( 67)
V S
When the particle is nonisothermal, 11 may exceed 1. It cannot be obtained
analytically, but Eq. ( 71) can still be used for the sake of uniformity and
abbreviation of the equations.
0.6
0.4
0.2
0 ~L-1_ _i.__O_j._2_ _...L.._0..1..4_...L.._01....6__J.__0.1...8....__1...-_ _..1_---'2--__J._--4J.._----'-----'6:--J.._81.......11•10
FIGURE 16 Effectiveness factor versus Thiele modulus ¢ = (Vp/Sp)/kps/De·
S, slab; P, sphere; C, cylinder.
Fixed-Bed Gas-Solid Catalytic Reactors 415
In the treatment above, the rate r A is taken at surface condition
(Cs, Ts). Sometimes it is referred to the bulk-phase conditions, rA(C, T).
s s
In other words, the external concentration gradient is included into the
11 value. The analytical expression for the isothermal effectiveness factor
for first-order reaction then becomes
3 Sh cash sinh <jJ
7
<jJ <jJ -
17 = ( 68)
G </l cash </l + (Sh - l)sinh <jJ
where Sh = kgo /De* and o is the film thickness.
The use of llG further reduces the system Eqs. ( 55), ( 56), ( 66), and
( 67) into
( 69)
( 70)
The structure of these model equations is identical to that of the basic
pseudohomogeneous model, AI .
For orders different from one, 11 and llG cannot be obtained analytically.
In those cases Eqs. (71) and (74) can still be used, but the 11 concept
does not introduce any gain any more, since obtaining 17 numerically in
each integration node is not any different from solving Eqs. ( 57) and ( 58).
This is why approximate solutions for the relation 11 versus <jJ have been
worked out _by Aris (1965), Bischoff (1965), and Petersen ( 1965b), based
on the introduction of
</l =
12 sp
s
V rA(C ,T )p
P s s s
s
[f c:
C
so
D 'A(Cs ,Ts)p dCJ-1/2
e s s s
( 71)
The use of this "generalized modulus" extends the application of Eq. (65)
to any shape and to any type of rate equation, even the Hougen-Watson
form, but still only for a single reaction. Equation ( 71) also shows that
for orders different from one, the surface concentration enters into the
modulus, so that 11 is a paint value, varying in the reactor, even when
the latter is isothermal. Evidently, the use of 11 does not yield the con-
centration profile inside the particles, but this is generally not of concern
in the reactor design stage. When it is of importance to have information
on intraparticle g-radients-for example, when coke or /and poison are
*The ratio of a convective coefficient to an internal diffusivity or con-
ductivity is more properly termed a Biot number for mass and heat.
416 Froment and Hofmann
deposited inside the catalyst and an insight is required into the relation
between the catalyst structure and penetration depth of coke or poison,
as exemplified by work of Summers and Hegedus and co-workers in auto-
mobile exhaust purification (Summers and Hegedus, 1979)-the required
calculations can be disconnected from the reactor design and can be carried
out for surface values generated in the reactor simulation. Various criteria
have been derived for evaluating, on the basis of observables, whether or
not it is necessary to account for intraparticle gradients. A rather extensive
set of proposed criteria is given by Butt (1980). A few only are given here.
For the absence of concentration gradients in an isothermal particle-in other
words, to have a value of n > 0.95-Weisz and Prater (1959) proposed
2
rAp s d p 6.0 for zero-order reactions
< 0.6 for first-order reactions ( 72)
4D Cs 0.3 for second-order reactions
e s
in which r A is the observed rate.
For first-order reactions, this criterion is slightly more conservative
than that previously proposed by Weisz and Prater (1953) and requiring
the left- hand side to be smaller than 1. For the absence of temperature
gradients (i.e., the observed rate differs by no more than 5% from the
rate prevailing in an isothermal particle), Anderson ( 1963) derived
I fl.HI rAp s d p2 TsR,
s
< E
( 73)
41t Ts
e s
or
2
rAp d 1
s p
<
D Cs SP y
e s
with Sp and y taken at surface conditions Cs and Ts. For the absence of
s s
combined intraparticle and interfacial gradients ( n == 1 ± 0. 05), Mears
(1971a,b) proposed
1 + 0.33y[(-fl.H)rAp d /2hfT]
s p (74)
n - S y[l+ 0.33n(rAp d /2k C)]
p s p g
with Sp and y evaluated at bulk gas conditions, C and T.
Multiplicity of Steady States: In recent years great attention has been
paid to the mathematical features of the solid-phase equations ( 57) and ( 58).
For certain ranges of the parameter values, more than one steady-state
profile would be possible for given geometry and operating conditions.
Again the approach used to derive criteria for uniqueness or multiplicity
in a cross section of the bed is the one mentioned earlier. The condition
for uniqueness arrived at by Luss ( 1977) and by Van der Bosch and Luss
( 1977) for a first-order irreversible reaction as regards a particle with
Fixed-Bed Gas-Solid Catalytic Reactors 417
concentration and temperature gradients and a particle having internal
concentration gradients and interfacial concentration and temperature
gradients can be written in the same form , Sy/ (1 + S) < 4, with S = S
in the first and S = Es Sf in the second case. If this condition is violafed,
multiplicity may exist for a certain range of values of the Thiele modulus
in the first case and of the Sherwood number, Es(kglDeHVp/Sp), in the
second case. In the second case no simple analytical expressions can be
given for these ranges. Internal concentration gradients reduce the region
in parameter space for which multiplicity of steady states is possible, as
compared to the situation in which only interfacial gradients occur. In iso-
thermal particles, multiplicity would still be possible with rate equations
that are not monotonic with respect to the conversion (e.g, Hougen-Watson-
type rate equations with very high values for the adsorption coefficients
of one of the reactants).
The rate equations for air oxidation of CO or H 2 on platinum/ alumina
are examples of this. Multiplicity has indeed been observed in laboratory
studies of these reactions (Smith, 1975; Hegedus et al., 1977). Whether
this is really caused by the interaction between reaction and interfacial and
intraparticle gradients or by some different phenomenon has not been
settled unequivocally, however. According to Keil and Wicke ( 1980), the
multiplicity observed in their work on CO oxidation is kinetically induced
(i.e., would result from an interaction between reaction and adsorption).
Eigenberger (1976, 1978) has modeled this interpretation and its conse-
quences. A realistic review of the area of multiplicity of steady states has
been presented by Schmitz ( 1975). It should be stressed that multiplicity
has not been reported yet for industrial operation of tubular reactors with-
out feedback.
Examples of Application: There are very few examples of design
studies which explicitly include internal diffusion limitations into the model.
The first reason for this is that very few kinetic studies of catalytic
processes went into sufficient depth to permit a quantitative expression for
the intraparticle diffusional limitations to be derived. The second reason
is the computational effort involved in the integration of the full set of
equations ( 55) to ( 58). What has generally been done is to use an "effec-
tive" rate equation, based on bulk gas phase conditions only and assumed
to account implicitly for these effects, so that the reactor model is re-
duced to the pseudohomogeneous base case AI. The accuracy of such an
"effective"-in reality distorted-rate equation may be seriously questioned,
however.
In an optimization study of 1-butene dehydrogenation on a chromia-
alumina catalyst, requiring a large number of reactor simulations, Dumez
and Froment (1976, 1977) circumvented the necessity of integrating the
solid-phase equations (57) and (58) in a far more rigorous way. Having
determined actual reaction rates, rE, for various particle sizes, they
plotted these versus the true, intrinsic rates, rH , obtained with finely
crushed catalyst under corresponding bulk gas phase compositions. A
unique curve was derived which could be expressed as
rE = 0.0034 + ✓ o.00685(rH + 0.0017) ( 75)
When both sides of this equation are divided by rH, the resulting equation
asymptotically behaves like the relation between 11 and ¢ [Eq. (65)], since
418 Froment and Hofmann
0.5
0.1 +-------,---,---.-.--.--.---r-r,-----,---.---,----,--,-- ----,~....,-,---------,--•
0.001 o.005 0.01 o.o5 0.1 rH
FIGURE 17 Effectiveness factor versus intrinsic rate of 1-butene dehydro-
genation. (After Dumez and Froment, 1977.)
rr;
!'E tends toward rtt as the latter goes to zero and becomes proportional to
as rH tends to infinity. The relation n = rE /rH versus rH is shown in
Fig. 17.
Dumez and Froment ( 1976) also considered the full set of equations
( 55) to ( 58). They derived a value of 5 for T from rate measurements at
various sizes and the knowledge of the intrinsic rate. With Dm and DK
calculated from published correlations and s s determined by physical
measurements, De was calculated from Eq. ( 60). The model equations ( 57)
and ( 58) were integrated in each node used in the integration of the fluid
field equation by collocation. In their work on steam reforming of natural
gas on a nickel-alumina catalyst, De Deken et al. (1982) obtained a T of
4. 5 from the gas chromatographic technique, using finely crushed catalyst
as a column material. The effectiveness factor was very low with this
very active catalyst: on the order of 0. 02 to 0. 04. The reaction was con-
fined to a very thin layer near the surface, but nevertheless still repre-
senting an internal area of about 1000 times the external surface area.
The model used in the reactor simulation considered interfacial tempera-
ture and intraparticle concentration gradients, leading to equations (61) to
( 63). Two continuity equations were required to define the composition of
the reaction mixture. The rate equations were of the Hougen-Watson type
and the generalized modulus concept [Eq. (71)] was used. Strictly speak-
ing, this concept is limited to a single reaction, but an approximate relation
could be established between the two independent reactions determining
the process. Figure 18 shows the variation of nctt 4 and nco along the
reactor for typical operating condition. The discontinuity at a bed depth
of 6 m results from the use of a different catalyst size farther downstream.
Notice that both n are essentially zero at the inlet, where the reaction
rates are extremely high. The L'i T over the external film surrounding the
catalyst is very small: 4°C up to 6 m, 3°C from there onward, and 2°C
Fixed-Bed Gas-Solid Catalytic Reactors 419
0.07
0.06
0
u
""
0
z 0.05
<(
'St
I
u
""
(/)
a:
0
f-
u
<(
lL
(/)
0.03
(/)
w
z
w
>
i== 0.02
u
w
lL
lL
w
0.01
0
0 2 4 6 B 10 12
AXIAL REACTOR COORDINATE [ml
FIGURE 18 Steam reforming of natural gas. Variation of the effectiveness
factor for methane conversion and for CO production with bed depth.
(After De Deken et al., 1982.)
and less from 10 m onward. Neglecting this t:,,. T would further simplify the
set of model equations without significantly modifying the results.
Two-Dimensional Heterogeneous Model
The model equations, considering axial and radial gradients in the reactor,
interfacial and intraparticle concentration, and temperature gradients, can
be written, when use is made of the effectiveness factor 17 , either in its
analytical expression or just formally, to abbreviate the system of equations
(De Wasch and Froment, 1971):
Fluid phase:
(D ( cl 2C + .!_ ac)
) u
ac = k a (C - Cs) ( 76)
er s cl r2 r clr s dZ g V s
;x/er ( cl 2T + .!_
ar2 r
!'a!_) __
r
U p C
s g p az
clT
= hrv(T - Ts)
s
( 77)
420 Froment and Hofmann
Solid phase:
k a (C - Cs) = llP r ( 78)
g V s B A
hfa (Ts -- T) ( 79)
V S
with boundary conditions
C = co at z = 0, all r
T = TO
clC
clr =0 at r O, all z
clT
clT s
clr = clr =0
clC
= 0
clr
r:/w(T w T) = / clT
er clr
at r R, all z
clT
s
clw(T w T) = As
s er clr
The second term in the right-hand size of Eq. ( 79) expresses heat trans-
fer in radial direction involving both the solid and fluid phases. The two-
phase character of the model is also reflected in the boundary condition for
heat transfer at the wall. The model parameters are now D , 1c f 1c s
er er' er'
f s
a , and a .
w w
The effective conductivity and wall heat transfer coefficient concept,
used in the two-dimensional pseudohomogeneous model (Yagi and Kunii,
1957; Kunii and Smith, 1960; Zehner and Schliinder, 1970), is not directly
applicable here. In this concept the heat transfer mechanisms are lumped
according to static and dynamic contributions (Re = 0 and -f. 0, respectively)
and not according to phase, as was done by Singer and Wilhelm ( 1950).
However, Yagi and Kunii (1957) considered the following heat transfer
mechanisms, grouped here according to phase:
Fluid phase:
1. Conduction
2. Convection
3. Transfer from fluid to solid
4. Radiation from void to void
Fixed-Bed Gas-Solid Catalytic Reactors 421
Solid phase:
1. Conduction
2. Conduction from particle to particle through contact surfaces
3. Conduction through the stagnant film surrounding the contact
surfaces
4. Radiation from particle to particle
Combining these mechanisms in the appropriate way and expressing them
in terms of the heat transfer formulas lead to (De Wasch and Froment,
1971)
,/er = s(;\
g
+ Bd Cl
p rv
+ p C D
g p er
) ( 80)
>- s = B(l - s)
(81)
er (y/A ) + {1/[(;\ /¢,) + hfdp + Cl d l}
s g rs p
where B is a coefficient comprised between O. 9 and 1. 0, a rv and a rs are
radiation coefficients between voids and solids, respectively, and ¢, can be
calculated from a formula presented by Kunii and Smith ( 1960). Based on
the model of Yagi and Kunii (1960) for wall heat transfer, the following re-
lations can be written for i and as, provided that T and T are not too
different: w w s
f
/er
Cl = - - Cl ( 82)
w >- w
er
>- s
s er
Cl =--Cl ( 83)
w >- w
er
Dixon and Cresswell ( 1979) discussed experimental heat transfer correlations
and derived relations between the pseudohomogeneous parameters >-er and
f s f s
a and the parameters of the heterogeneous model, A , A , a , and a .
w er er w w
De Wasch and Froment (1971) simulated a hydrocarbon oxidation reactor and
obtained the radial temperature profiles shown in Fig. 19, for conditions
whereby 17 = 1. The t,, T between solid and fluid does not exceed 2°C, al-
though the reaction is very exothermic. Figure 20 compares radial mean
temperatures as a function of bed depth, calculated by various models dis-
cussed in this chapter and for typical industrial operating conditions.
Curves 1 and 2 were obtained by means of the one-dimensional models,
pseudohomogeneous (AI) and heterogeneous, but with 17 = 1 (BI), curves
3 and 4, by the two-dimensional models AIII and BIII, respectively. Curve
5, which predicts an excessive hot spot, was obtained by means of a model
neglecting heat transfer through the solid. For the conditions of the exam-
ple, some 25% of the radial heat flux occurs through the solid phase.
420
Ts
s
T
400
C°C)
JB0L----0....1_25
_ _ _ _0.....5_0_ _ _0.....75_ _ __,
r
R
FIGURE 19 Simulation of hydrocarbon oxidation by means of two-dimension-
al heterogeneous model. Gas and solid radial temperature profiles. (After
De Wasch and Froment, 1971.)
0.75
z (ml
FIGURE 20 Hydrocarbon oxidation. Simulation by means of various models:
1, basic pseudohomogeneous one-dimensional model; 2, one-dimensional
heterogeneous model with interfacial gradients; 3, pseudohomogeneous two-
dimensional model; 4, two-dimensional heterogeneous model; 5, two-
dimensional heterogeneous model with heat transfer in radial direction
through gas phase only. (After De Wasch and Froment, 1971.)
422
Fixed-Bed Gas-Solid Catalytic Reactors 423
The heterogeneous nature of the case dealt with here results from
interfacial gradients, but again these were shown to be negligible. De
Deken et al. ( 1982) used a two-dimensional model to simulate a process in
which the interfacial gradients could be neglected, but not the intra-
particle concentration gradient-the steam reforming dealt with earlier.
Figure 21 shows radial temperature profiles at various bed depths.
The maximum difference in process gas temperature between the centerline
and the inner tube wall amounts to 33°C, which is not excessive and per-
mits the radially averaged temperature to be simulated accurately by means
of the corresponding one-dimensional model with a heat transfer coefficient
calculated from Eq. ( 37).
Note that the model is really a heterogeneous model, but that since
there are no interfacial gradients and since the intraparticle concentration
gradient is accounted for by means of the effectiveness factor concept, its
structure is that of the pseudohomogeneous two-dimensional model AIII,
750 z = 9m
___ ..........
u
2....
,;·
~ f--
f-- w
w er
er :J
f--
:J <(
f--
<( er
er w
a.
w
a.
z = 6m
:a:
:a:
w
w
f--
f-- -'
en -'
s:
<( <(
Cl
en w
en co
w :J
u 150 f--
0 er
er w
a.
z
~
z = 3m
sooL------
o ~ ~ ~ M W
NORMALIZED DISTANCE FROM REACTOR CENTERLINE
FIGURE 21 Steam reforming of natural gas. Simulation of radial tempera-
ture profiles at various bed depths by means of two-dimensional hetero-
geneous model with intraparticle concentration gradient only. Comparison
of radially averaged values with prediction of temperature by means of
one-dimensional model with intraparticle concentration gradient. (After
De Deken et al. , 1982.)
424 Froment and Hofmann
with n multiplying the rate term rAPB. Again because there are no inter-
facial gradients and because the particles are isothermal, the radial heat
transfer parameters are those of the pseudohomogeneous model, Aer and a.w.
SPECIAL CASE: THE MONOLITH CONVERTER
The monolith converter consists of an array of ducts with catalyst coating
on the walls. It is used for control of automotive emission and is being con-
sidered for waste abatement. The discussion of reactor design and opera-
tion in the previous sections was oriented exclusively toward reactors for
production processes. The catalytic muffler does not fall in this category,
but since there may be a potential use for monolith converters in other
areas and since its simulation makes use of reactor models described in this
chapter, it is discussed briefly below, mainly from the simulation point of
view.
More detailed discussions were published by Wei (1975), who reviewed
some of the reaction engineering aspects and early models for CO oxidation.
Lee and Aris ( 1976) also reviewed the features of possible models, whereas
Hegedus and coworkers (Hegedus et al., 1980) significantly contributed to
the mathematical modeling of the phenomena at the level of the catalyst
particle, in particular of instabilities and oscillations. Below, models are
given for the comparison of the performance of a monolith converter, along
the lines set by Young and Finlayson (1974). They are written, for the
sake of generality, for transient operation, which is also the most typical
type of operation for the catalytic muffler. Since the transient response is
determined mainly by the thermal response of the solid, all other time
derivatives are set equal to zero. The reaction considered is CO oxidation.
Diffusional limitations in the thin catalytic layer is neglected, although it
could-formally, at least-easily be incorporated into the model equations by
means of the effectiveness factor n. A cell comprising a cylindrical duct
and surrounding solid is chosen. The operation of the cell is adiabatic;
that is, the flow rate is the same over all ducts and the solid temperature
at any cross section of the monolith is uniform. Axial conduction in the
solid is neglected, as is axial diffusion in the fluid since the Peclet number,
based on the length of the duct, exceeds 500. The first model dealt with
by Young and Finlayson is a one-dimensional heterogeneous model with plug
flow and interfacial gradients (BI in the terminology used here). The con-
tinuity equation for CO is written, in terms of mol fractions,
k
u 3y = 4J.(y -y) ( 84)
3z dt s
and the energy equation for the fluid,
h
U p C 3 T = 4 __i (T - T) ( 85)
s g p 3z dt s
g
At the wall surface, where the reaction occurs (and with the rate of disap-
pearance of CO taken to be positive),
Fixed-Bed Gas-Solid Catalytic Reactors 425
p
k _g_ (y - y ) = r (86)
g Mm s CO
( 87)
where Ss represents the surface area per volume of solid in the monolith
cell. The boundary and initial conditions are
T = T 0 (t) at z = 0
y = Yo(t) (88)
T = T s. (z) at t = 0
s
l
The second model is of the two-dimensional type, but with laminar flow,
since the Reynolds number in the duct ranges from 20 to 400. Continuity
equation for CO:
D 1 cl ( cly)
mrarrar (89)
Energy equation for the fluid:
( 90)
and at the wall surface:
D ~ cly
m M clr
m
r=R
clT
A clT
g
ar Ir=R = (-LiH)rCO + at
s
( 91)
where rco is expressed in kmol/h and unit wall surface area. The boundary
and initial conditions are
T T at r = R, all z
s =
T T at t = 0
s = s.
l
T = TO(t) at z = 0
y = y 0(t)
426 Froment and Hofmann
The one-dimensional model may have multiple steady states, but the
two-dimensional may not. Figure 22 shows that the lower steady-state pro-
files of Ts and T of the one-dimensional model are obtained when the mono-
lith is heated from an initial low temperature, while the higher steady state
profiles are reached when the converter is cooled from some initial high
temperature. For intermediate initial temperatures the final steady state
may lie between those shown. The unique Ts and T profiles of the two-
dimensional model are closer to those corresponding to the lower steady
state of the one-dimensional model.
The two-dimensional model is definitely a more realistic model of the
monolith, but it is computationally much more demanding. This is why it
is of interest to investigate whether or not it is possible to approximate it
by means of the one-dimensional model-overlooking for a while the multi-
plicity of steady states associated with the latter. The curves related to
the one-dimensional model in Fig. 22 were calculated for constant values of
the Sherwood and Nusselt numbers, kgdt/Dm and hfdt /Ag, respectively.
To come to an exact fit, however, these numbers have to continuously
vary along the reactor. The Nu number, for example, would have to be
calculated, for each axial position, from the temperature gradient at the
wall, generated by the two-dimensional model:
j
8.0
Nu,Sh '
4.36
5.0
11 3.0
0 2.5 50 7.5 10
Z(cm)
FIGURE 22 One- and two-dimensional simulation of monolith converter.
Solid line, one-dimensional heterogeneous model; dashed line, two-dimensional
model. (After Young and Finlayson, 1974.)
Fixed-Bed Gas-Solid Catalytic Reactors 427
= 2(aT/3r)lr=R
Nu ( 92)
Ts - T
where T is the cup m1xmg temperature of the fluid. The Sherwood num-
ber would be obtained in an analogous way. Figure 22 also shows how
Nu and Sh, taken to be identical in this case, vary with axial position.
Also shown is the ratio of the reaction rate at wall conditions to that at
mixing cup conditions. This ratio varies strongly with position and be-
comes infinite when the gas reaches the wall temperature, in the reaction
zone, after light off.
To avoid the two-dimensional simulation as a prerequisite for one-
dimensional calculations, Heck et al. (1976) approximated the Nu profile
before the discontinuity by the value for pure heat transfer with constant
heat flux and that beyond the discontinuity by the value corresponding to
constant wall temperature. Sundaram and Froment (1979, 1980) derived
the local Nu for laminar flow and in the absence of reaction from a large
number of two-dimensional simulations. They came to the following correla-
tions:
-0. 778 ( 93)
Nu= 3.655 + 0.1450Z exp(-7.158Z)
The asymptotic value of Nu of 3. 655 completely agrees with the experimen-
tal value.
For turbulent flow, Whitaker ( 1972) obtained the following correlation:
Nu= Nu 00 + a 1 exp ( a 2Z)z
o. 743 ( 94)
with
where Nuoo is the asymptotic Nu number (e.g., 2.28 x 10- 2Re 0 · 8 , in agree-
ment with the Dittus-Boelter correlation). Sundaram and Fromont (1979,
1980) also showed that Nu depends strongly on the properties of the reac-
tion. For endothermic reactions and both laminar and turbulent flow they
correlated the Nusselt profile versus the dimensionless adiabatic tempera-
ture rise, the Lewis number, and the dimensionless activation energy. The
discontinuity in the ratio ( 92) for exothermic reactions at T = Ts precludes
a correlation that would be as accurate as that given for endothermic
reactions.
The preceding discussion once again illustrates the importance of a repre-
sentative model, not only to come to the highest possible accuracy, but also
to avoid the prediction of a behavior that may not be real at all. The
question of whether or not multiplicity is possible in a monolith converter
remains largely unanswered, even if Hlavacek and Votruba (1974) pre-
sented experimental evidence for it. This has been explained in terms of
axial heat transfer in the wall. It is more likely, however, to result from
428 Froment and Hofmann
phenomena at the catalyst surface instead of transport phenomena. Sur-
face phenomena causing multiplicity would be reflected by more than one
rate-determining step and rate equations more complicated than those used
in the work of Young and Finlayson. Multiplicity would then, of course,
also become possible with the two-dimensional model.
CONCLUSION
In this chapter the design or simulation of fixed-bed reactors is based on
fundamental models. These combine the hydrodynamic and heat transfer
phenomena with the chemical reaction aspects by means of a set of mathe-
matical equations of varying complexity. With the present computational
facilities and numerical techniques, the solution of these equations is no
longer an obstacle to the application of these models to the real problems
and configurations encountered in industrial operation.
Evidently, no model will ever represent the reactor behavior in an ab-
solutely rigorous way. The equations contain a number of parameters, some
of which are "effective" in the sense that they lump the effects of phenome-
na that would otherwise have to be expressed by means of additional equa-
tions, to be solved simultaneously in the reactor simulation. Admittedly,
considerable improvement and extension of existing correlations is required
for severe reaction conditions or unusual reactor configurations. Indeed,
for convenience, correlations for these parameters were generally obtained
from purely physical experiments, possibly without sufficient ·testing under
conditions similar to those encountered in the presence of reaction. Under
reaction conditions the parameter values may then turn out to be inaccurate,
even when the underlying description of the phenomenon is correct. But
the parameters should not be tuned arbitrarily on the basis of experimental
testing of the reactor model, to avoid inconsistency and violation of their
physicochemical background.
The models developed here are all of the continuum type. This dispute
between the advocates of continuum and cell models is mainly of academic
interest, except perhaps for very severe reaction conditions. An escalation
of model sophistication is presented and criteria are given for the selection
of the appropriate model. Which model is "appropriate" depends in the
first place on the reactor, the operating conditions, and the reactions, but
also on the required accuracy and on the availability and precision of the
required fundamental information. Some of the models presented here are
a bare minimum for a realistic description of the reactor operation, others
may look too refined and of academic interest only. Nevertheless, it is
safe to predict that what may seem to be too refined today may well be the
minimum level of modeling tomorrow, particularly for demanding conditions.
Models will certainly continue to be refined, but realism should be a guide
in this development.
It should never be forgotten, however, that advanced reactor modeling
requires first, accurate kinetics, not only on fresh, but also on gradually
deactivating catalysts. In the past this has been the main obstacle to the
fundamental approach in reactor design. It will continue to be a serious
challenge in the future, because it requires a considerable experimental
effort of a team with both broad scientific and technical background which
is seldom put together at the right time (i.e., at an early stage of
development).
Fixed-Bed Gas-Solid Catalytic Reactors 429
NOTATION
. reactor volume, m2/ m 3
external particle sur f ace area per umt
a
V p r
C gas phase concentration, kmol/m 3
g
co concentration of A in feed, kmol/m 3
C specific heat of gas, kJ /kg• K
p
CPS
specific heat of gas inside the solid, kJ /kg•K
cs specific heat of solid, kJ /kg•K
C concentration inside catalyst, kmol Im 3
s 3 g
cs surface concentration, kmollm
s g
d. internal diameter of catalyst ring, m
1 p
d particle diameter , m
p p
dt internal tube diameter, m
r
3
D effective diffusivity inside catalyst, m Im •s
e g p
DK Knudsen diffusivity, m 2 Is
D molecular diffusivity, m 2 Is
m
(D )s effective diffusivity in axial bed direction based on superfacial
ea
flow velocity, m3 Im •s
g r
(D ) effective diffusivity in radial bed direction based on superfacial
er s
flow velocity, m3 Im •s
g r 3
E activation energy, kJ lkmol or m •atm lkmol •K
E. exponential integral
1
f friction factor
FA molar feed rate of component A, kmol •A Is
0
g acceleration of gravity, mls 2
2
superficial mass flow velocity, kg Im s
r
superficial mass flow velocity of component i, kg i Im 2 •s
r 2
gas-to-solid heat transfer coefficient in a fixed bed, kJ Im •s •K
3 p
reaction rate coefficient; for first order, e.g., m glkg cat•s
3 2
gas-to-solid mass transfer coefficient in a fixed bed, m Im •s
g p
equilibrium constant,
adsorption constant of component A, 1 latm
total length of reactor, m
r
m mass flow rate, kg Is
M molecular weight of mixture, kg lkmol
m
n order of reaction
Nu
430 Froment and Hofmann
partial pressure of component A, atm
total pressure , atm
Peclet number for radial effective diffusion, [ d u. /D ]
p 1 er
Peclet number for axial effective diffusion in fixed bed,
[d u. /(D ).]
p 1 ea 1
Pe' Peclet number for axial effective diffusion in fixed bed, [d /L/(D ) 1.]
ma p ea
Pr Prandtl number (c µ /").. )
p g
r radial position, m
rA rate of reaction of A per unit catalyst weight, kmol/kg cat •s
rE effective rate of dehydrogenation of 1-butene, kmol/kg cat•s
rH intrinsic rate of dehydrogenation of 1-butene, kmol/kg cat •s
R tube radius, m
R' gas constant, kJ /kmol •K or m 3 •atm /kmol •K
Re Reynolds number (d G/µ)
p
scyl external surface area of cylinder with same external diameter
and height as the ring-shaped catalyst, m2
p
sp surface area of a particle , m2
ss surface area per volume of solid in monolith cell, ~ 2 /m 3
Sh Sherwood number (k dt /D )
g m
t time, s
T, Tl process gas temperature, K
T2 coolant temperature, K
TO feed temperature of gas, K
T solid temperature, K
s
TS solid surface temperature, K
s
u velocity in the axis of monolith duct, mis
ax
u. interstitial flow velocity, m /s
l r 2
u superficial flow velocity, m3 /m •s
s g r 2
u overall heat transfer coefficient, kJ /m •s •K
V volume of cylinder with same external diameter and height as ring-
cyl
shaped catalyst, m3
p
V particle volume, m3
p p
X conversion
y mole fraction
z, z' axial distance in reactor (respectively, heat exchanger), m
r
z, Z' length of reactor (respectively, heat exchanger), m
r
Fixed-Bed Gas-Solid Catalytic Reactors 431
Greek Letters
CL bed-to-wall heat transfer coefficient in one-dimensional model,
1
kJ/m2•s•K
a .. stoichiometric coefficient of component i in reaction
1]
a radiation coefficient between particles, kJ /m 2 •s •K
rs
radiation coefficient between voids, kJ /m 2 •s •K
wall heat transfer coefficient in two-dimensional model, kJ /m 2 •s• K
static contribution to a , kJ /m 2 •s•K
w
dimensionless Tad in a film surrounding a particle [kg( -t, H)C I
hfT]
dimensionless T din a particle [D Cs(-t,H) /A Ts]
a e s e s
dimensionless adiabatic temperature rise in a reactor
[(-L',H)Co/pgcpT O]
y dimensionless activation energy (E/RT 0 , E/RT, E/RT:)
(-t,H) heat of reaction, kJ /kmol
adiabatic temperature rise, K
void fraction of bed, m3 /m 3
g r
E.: void fraction of particle, m3 /m3
s g p
a group (M L/u p ) , m 3 •s/kmol
m s g r
catalyst effectiveness factor based on surface conditions (Cs, Ts)
s s
catalyst effectiveness factor based on bulk gas conditions ( C, T)
effective conductivity inside a particle, kJ/m•s•K
A effective axial conductivity of bed+ gas, kJ/m•s•K
ea
Ao static contribution to the effective axial conductivity kJ /m •s ·K
ea
A effective radial conductivity of bed + gas, kJ /m •s •K
er
Ao static contribution to the effective radial conductivity, kJ /m •s •K
er
Af effective radial conductivity for gas phase, kJ /m •s •K
er
As effective radial conductivity for solid phase, kJ /m •s •K
er
A gas conductivity, kJ /m •s •K
g
].l dynamic viscosity, kg /m •s
inside particle, oriented toward surface coordinate , m
p
bulk density of bed, kg cat Im!
gas phase density, kg/m 3
g
3
catalyst density, kg cat/m
p
T tortuosity
Thiele modulus [= (V /S )(k/D )]
p p e
432 Froment and Hofmann
1/Pe
ma
1/Pe
mr
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7
Fluidized-Bed Reactors
PETER N. ROWE and JOHN G. YATES University College London,
London, England
INTRODUCTION
Industrial reactors in which solid particles are maintained in a fluidized
state by an upward-flowing gas stream were first applied on a wide scale
in the 1940s in the fluidized catalytic cracking (FCC) process for the pro-
duction of gasoline, although a more localized use of the technique had
been practiced in Germany 10 years earlier in the Winkler coal gasification
process. The main aim of those who developed the FCC process was to
devise a method of engineering the catalytic cracking reaction of gas oil,
discovered by Houdry, without using fixed-bed reactors that not only suf-
fered from considerable operational problems but also were strongly pro-
tected by patents (Jahnig et al. , 1980). The success of the development
work on the FCC process may be judged from the short time span of four
years between its initial conception and the startup of full-scale plant and
it is apparent with hindsight that a major reason for this success was the
eminent suitability of the cracking process for operation in fluidized-bed
reactors. For example, the relative ease of transfer of the finely powdered
catalyst between reactor and regenerator overcame the difficulty of cyclic
operation of fixed beds and at the same time solved the problem of trans-
ferring heat from the exothermic regeneration to the endothermic cracking
reaction. Furthermore, the high throughputs that it was possible to main-
tain gave the FCC process an enormous advantage over its competitors and
it is not surprising that some 40 years later it remains one of the most
important and elegant catalytic processes in all industry.
Subsequent developments in the field of industrial fluidized-bed re-
actors, however, did not always result in the same degree of success for
the processes to which they were applied and it rapidly became clear that
more needed to be understood about the basic physics of gas-solid fluidiza-
tion before large-scale reactors could with confidence be designed or
scaled up from smaller units, and during the last three decades with this aim
in view a great deal of research has been carried out on the fundamentals
of the subject.
441
442 Rowe and Yates
The type of information required for the design of a fluidized-bed re-
actor is not markedly different from that needed for any other gas-solid
reactor and relates to chemical kinetics and the mode and extent of contact
between the gas and solid phases. The way in which this information is
assembled constitutes the reactor model. Consider the general scheme
shown in Fig. 1, where gas enters at the base and rises through the bed
at a superficial velocity U, in excess of the minimum, Umf, required just
to fluidize the particles. Under these conditions it is generally observed
that the bed divides into two phases and each accommodates a proportion
of the total flow (Fig. lb). The interstitial emulsion-phase flow Qi passes
at a velocity close to Umf through the space between the fluidized particles,
while the excess, Qb, flows in the form of rapidly moving voids or "bub-
bles" which are essentially free of particles and grow by coalescence as
they rise through the bed. Gas flowing interstitially is in intimate contact
with particles and, if the chemical kinetics are favorable, the efficiency of
the chemical conversion in this phase will be high. Bubble-phase gas, how-
ever, does not make good contact with solids, so reaction here will be in-
efficient. There is some exchange between the two phases, but the extent
of this, QE, is determined mainly by the size of the bubbles and decreases
as they become larger.
The extent to which a reactant gas is converted to products as it
passes through the bed is therefore determined by the following factors:
1. The division of flow between the two phases
2. The contacting pattern of gas and solids within each phase
~ Products
Cyclone
separator
Freeboard
space
Inter
Interstitial phase bubble
Interstitial phase exchange phase
phase
OE
t
fluidizing
gas
Total flow= Ot
at velocity U
(a) (b)
FIGURE 1 Flow distribution in a fluidized bed. (a) Cross section through
a fluidized bed. (b) Schematic of gas flow division.
Fluidized-Bed Reactors 443
3, Interphase exchange
4. Chemical kinetics
The three hydrodynamic factors are discussed in detail below, but first it
will be useful to consider some of the more basic features of gas-fluidized
beds that have important implications for their use as chemical reactors.
BASIC FEATURES OF GAS-SOLID FLUIDIZATION
Minimum Fluidization Velocity
A bed of particles is normally load bearing because any impressed force is
ultimately resisted by static friction between grains in contact and is
spread over a volume of the whole. Thus one can walk over dry sand, al-
though sinking a little at each step as the grains rearrange to provide
frictional resistance. If a fluid, liquid, or gas, is passed upward through
a particle bed, relative motion causes an upward drag force on each parti-
cle, effectively reducing its apparent weight. At a critical velocity drag
force equals gravitational force, each particle is individually supported
and they no longer rest upon one other. This condition can be written
d3( p p )g
ii
-- 'IT
p s - f (1)
for uniformly sized spherical particles. In this condition there is no
static friction between particles and the whole ceases to be load bearing.
It behaves like a fluid with shear forces resisted essentially by the vis-
cosity of the interstitial fluid-hence the origin of the descriptive name
fluidized b~d. The fluid velocity at which this condition is first reached
is called the minimum fluidization velocity Umf• It is conventional and con-
venient to express this as a superficial velocity,
Qmf
umf =-
A
( 2)
where A is the cross-sectional area of the bed.
Light bodies will float on fluidized particles and heavy ones sink. The
bed surface remains level although subject to wave motion and splashing,
just as a liquid. The whole can be readily stirred and particles will flow
through orifices in the side or bottom of the containing vessel. The above
applies whether the fluid is a liquid or a gas, but the effects are more
dramatic and initially surprising in the latter case.
The essential condition of Eq. (1) can be expressed differently by con-
sidering the bed as a whole rather than individual particles. The bed be-
comes fluidized when the upward flow of fluid produces a pressure drop
equivalent to the bed weight. In a parallel-sided vessel,
( 3)
is the necessary condition for fluidization. Generally, in gas-fluidized sys-
tems Ps >> Pf, and the latter can ususally be neglected.
The bulk density of dry powder in a vessel of constant cross-sectional
area is given by
444 Rowe and Yates
M ( 4)
pbulk = HA
and bulk density is related to the individual particle density by
( 5)
so that
M
H(l - E) = Ap ( 6)
s
from which it is seen that the product H(l - E) in Eq. (3) is constant.
Equation ( 6) also shows how bed voidage and its variation is calculated
from the measurement of bed height. A difficulty arises in measuring
particle density Ps when the particles are porous, as is commonly the case
with materials such as catalysts (Knight et al., 1980; Knight and Rowe,
1980). The density required for this purpose is the ratio of particle mass
to the volume enclosing all solid material together with gas contained in all
pores and cavities (i.e., gas that is not part of the flowing stream).
Up to the point of fluidization the bed behaves as a packed bed and
pressure drop can be calculated from well-known semiempirical equations.
For fine particles where the local Reynolds number is small, the Carman-
Kozeny equation is suitable and can be written for minimum fluidization
conditions (Richardson, 1971)
3
Emf tip
umf = - - - - - 2 - ( 7)
5( 1 - Emf)
where S is the particle specific surface. Combining this with Eq. (3)
yields
( 8)
For uniformly sized spherical particles S = 6/dp and Emf= 0.4, so
2
0. 0006d ( p - pf) g
U = p s ( 9)
mf µ
It is useful from this to remember the way in which Umf varies with size,
density, and viscosity, but it is not an accurate predictor for most pow-
ders of practical interest. It should be noted that when considering a
fluidized-bed chemical reactor, fluid density and viscosity and the particle
density will generally be fixed by chemical and thermodynamic considera-
tions. Umf will then be determined solely by particle size to which it is
quite sensitive, at least with finely divided particles.
Fluidized-Bed Reactors 445
A more general pressure-drop equation applicable to larger particles
and Reynolds numbers is that due to Ergun ( 1952) , which can be written
for the present purpose
The two terms on the right-hand side correspond, respectively, to the
viscous or skin friction component and the turbulent or form drag con -
tribution and thus span a wide Reynolds number range. The first term
is the same as Eq. (7), although with a slightly different constant. Sub-
stituting from Eq. (3) and rearranging yields
Defining
(12)
and Galileo number,
Ga= ( 13)
we have
Ga = 150 (' s!:mf) Re mf + 75 (s!,) Re!,
1.
(14)
Thus Remf (containing the required Umf) is quadratic in Ga, which is a
combination of the physical properties of particles and fluid. For the
particular case of uniform spheres, Emf = 0. 4:
2
Remf + 51. 4 Remf - 0. 0366Ga = O (15)
or
-5 1/2
Remf = 25. 7[ (1 + 5. 53 x 10 Ga) - 1] (16)
Equation (14) is quite a good and reliable predictor, although a little
clumsy to use. Most powders of practical interest include a range of
particle sizes in which case the surface mean diameter should be used.
Nonspherical particles can be characterized by the diameter of a sphere
with the same specific surface, but it must be kept in mind that particles
446 Rowe and Yates
differing greatly from spheres in overall shape (e.g, plates and needles)
may not be readily fluidized.
A purely empirical correlation due to Leva ( 1959) becomes, in SI units,
7.9 ) 0. 94
X pf
( 17)
0.88
]J
and is valid for Remf < 10. At higher values the result of Eq. (17) is
multiplied by the correction factor shown in Fig. 2. Leva's equation is
simple to use and reasonably reliable but not as good as Eq. (14).
A little insight comes from considering the experiments of Rowe ( 1961).
The drag force was measured on an isolated spherical particle held in a
fluid stream and the result expressed as drag coefficient varying with
Reynolds number. Similar measurements were made under identical condi-
tions except that the observed spherical particle was closely surrounded
by similar particles also held stationary. The results are summarized in
Fig. 3, from which it is seen that at a given Reynolds number drag co-
efficient is increased by a factor of about 70 when an isolated particle is
surrounded by close neighbors.
If a particle is to be held stationary in an upward-flowing stream, the
conditions of Eq. ( 1) must apply whether the particle is isolated or one
within a fluidized bed. The product CDU2 must be the same for these
two cases:
( 18)
a:
0
I-
u
<(
u..
z
0
j::
u
UJ
a:
a:
0
u
CJ)
<i: 02
>
UJ
-l
o,o 100 1000
FIGURE 2 Leva's correction factor as a function of Reynolds number at
minimum fluidization.
Fluidized-Bed Reactors 447
105
o0 o
104 u 0 o 0 oo
---+ 0 o®uo
. F
i
Co
103
/
0 0 000
...
00
102
'' CLOSE PACKED
''
- ''
10
u
"' 'ISOLATED
''
''
,0-1
10-1
'' NEWTON, Co=0.44
10 102 10 3 104 105
Re-
FIGURE 3 Drag coefficient as a function of Reynolds number.
where c 01 and CDmf refer to the drag coefficients under isolated and mini-
mum fluidization (closed packed) conditions, respectively. The relationship
between these two is revealed by Fig. 3.
As is further seen from Fig. 3,
(19)
and
( 20)
The form of this functional relationship is not easy to express mathematical-
ly because of the varying contributions of skin friction and form drag as
Reynolds number changes. There are various empirical equations to de-
scribe it, but they are not helpful for the present purpose. The two end
conditions can be treated analytically.
Stokes' regime lies at Re < 0. 2 when form drag can be neglected and in
this case
24
( 21)
Re
It follows from Eq. (1) that
which is a well-known expression. From Eqs. (18) to (20),
70 X U ( 23)
mf
448 Rowe and Yates
and therefore,
2
0.0008g(ps pf)d
umf =
p ( 24)
µ
which is similar to Eq. (9) but with a slightly different constant.
Newton's regime applies at Re > 103 when
::: 0.44 ( 25)
From Eq. (1) it follows that
( 26)
and again from Eqs. (18) to ( 20) that
UT = ffo umf ( 27)
= 8. 4Umf ( 28)
Thus
0 _206 gl/2(p _ )1/2dl/2
U = ______s_ _P_f_ _--=-P-
( 29)
mf 1/2
pf
It is now seen that, excepting those expressions that treat skin friction
and from drag as additive, equations for predicting minimum fluidization
velocity are of the form
U f = kg( p ( 30)
m s
and Table 1 compares the various equations in this way. In particular it
shows that Leva's empirical equation is a compromise at a Reynolds number
that is evidently near the average of practical systems examined
TABLE 1
K a b C d
Stokes 0.0008 1 2 0 -1 Increasing
Re
Carman-Kozeny 0.0006 1 2 0 -1 mf
Leva (0. 805) 0.94 1. 82 0 -0.88
Ergun
Newton 0.066
½
½
l.
2
l.
2
-½
-½
0
0
j
Fluidized-Bed Reactors 449
TABLE 2
-m
ReT m UT/Umf = smf
0.1 4.65 71 70 from Eq. ( 23)
1 4.35 53
10 3.53 26
100 2.81 13
1000 2.39 8.9 8. 4 from Eq. ( 28)
Apart from the insight given by the approach above, it shows the re-
lationship between Umf and UT, which is of considerable practical importance.
It is fundamental to any consideration of a fluidized-bed chemical reactor
that it should be operated at a fluid velocity greater than Umf but not in
excess of UT if particles are to be retained in the bed. Practical powders
are generally made up of a range of particle sizes, so there is a correspond-
ing range of UT (but not of Umf). The above is therefore only a guide to
an estimate of elutriation, but it is a useful one.
Intermediate values of the ratios given by Eqs. ( 23) and ( 28) can be
derived from the work of Richardson and Zaki ( 1954). As is mentioned in
the next section, liquid fluidized beds expand uniformly as liquid velocity
increases, and the relationship between voidage and velocity can be
described by
where m is constant for a given system but varies with ReT. A particular
case of Eq. ( 31) is
and this has been evaluated in Table 2 for the case of uniform spheres,
where Smf = 0. 4 and using values of m found by Richardson and Zaki
(1954). The end conditions agree well with the previously described and
quite independent experimental measurement.
Particulate Fluidization
The subject of this chapter is gas fluidized beds, but it is necessary
briefly to refer to the special case of liquid fluidization because under cer-
tain conditions dry beds can behave as if liquid fluidized.
Once they have been fluidized, particles generally behave differently
depending on whether the fluid stream is a liquid or a gas. Liquid
fluidized beds expand uniformly as velocity is increased. The particles
separate to accommodate more liquid flow between them while retaining the
same drag force. As is implied by Fig. 3, the drag coefficient diminishes
450 Rowe and Yates
as particle spacing increases, but Cn U 2 remains constant. The same rela-
tionship is expressed differently by Eq. ( 31). Between Eqs. ( 6) and ( 3)
if follows that
u
log -
UT
= m log [1 - (H:p )]
s
( 33)
from which it is seen how bed height varies with velocity when plotted
against logarithmic coordinates.
Uniform expansion of this kind is generally referred to as particulate
fluidization and for most purposes it can be regarded as of uniform particle
concentration throughout. The particles are not stationary but mix fairly
rapidly by a process akin to eddy diffusion. The (modified) eddies in the
liquid carry particles with them causing both lateral and longitudinal disper-
sion.
Solids Classification
The observation that certain powders undergo considerable expansion be-
yond the point of minimum fluidization and only begin to bubble when an-
other critical gas velocity, Umb, is exceeded has led to the acceptance of
the principle that such powders should be grouped together and their
fluidization properties considered separately from those materials that show
more "normal" behavior and begin to bubble at Umf · Moveover, experience
with a wide range of particulate solids in gas fluidized beds has shown there
to be other modes of behavior that are different from those of the foregoing
materials, and as a result it has been found convenient to divide all pow-
ders into four groups according to criteria of particle size and density.
Such a scheme of classification was suggested originally by Geldart (1973)
and it has now become firmly established. It classifies powders as belong-
ing to Groups A, B, C, or D as given in Table 3. Although in practice
the divisions between the groups are somewhat diffuse, making it difficult
in some cases to assign a powder firmly to one group or another, the clas-
sification does nevertheless provide a broad guide to the type of behavior
that may be expected from a given powder. It is useful to represent the
four groups of materials on a "phase diagram" showing the density differ-
ence ( Ps - Pg) plotted against particle diameter dp (Fig. 4). Here the
boundaries between groups C and A and groups B and D are entirely
empirical. The A /B boundary, however, may be defined on the basis of
whether or not a powder begins to form bubbles at its minimum fluidzation
velocity. For group A materials, Umf/Umb ,( 1, while for group B, Umf/
Umb > 1; a convenient dividing line would thus be one for which Umf /Umb =
1. Baeyens and Geldart ( 1973) correlated Umf and Umb with particle and
gas properties for a wide range of commonly used powders and showed that
for air at ambient conditions the A /B boundary is given approximately by
the line
d (p - p ) = 2 x 10 5 ( 34)
p s g
where ~ (µm) is the surface mean diameter of the particles. Equation
( 34) is plotted as line XY on Fig. 4.
~
i:
15:
N.
(I)
0.
I
tl:I
(I)
0.
::0
TABLE 3 Solids Classification for Fluidized Beds (I)
0
0
Range of Range of 0
-s
(/)
particle size particle density
Group (μm) (kg/m3) Behavior when fluidized Examples
A 30-200 5000-800 "Abnormal" bed expansion between Cracking catalyst
Umf and Umb followed by bed
collapse Umb > Umf, Ub > Ui,
Ej_ > Emf
B 50-1000 4000-1000 Normal behavior Umb = Umf• Sand, glass
Ei = Emf ballotini
C <30 Any value Cohesive powders, difficult to Talc, flour, cement
fluidize, prone to channeling
D >400 >1000 Prone to slugging, bubbles Steel shot, dried
ill-defined, Ub < Ui peas
Source: Baeyens and Geldart ( 1973).
,IS.
g)
452 Rowe and Yates
'15000
~
012000
9-Vl
~1000
u
C
11: 500
-~
1J
~
.gi 200
(1.)
0
100'------'------'------'---_L_L_J_J__L.L_ __JL-_L__L_JLLLLL-'--------'------'
10 20 50 100 200 500 1000
Mean particle size (μm)
FIGURE 4 Powder classification diagram for fluidization with air at ambient
conditions. (Based on Baeyens and Geldart, 1973.)
Gas Fluidization and the Two-Phase Theory
When the fluid velocity is increased above Umf, gas fluidized· beds begin to
bubble and look remarkably like boiling opaque liquids. They are sometimes
called boiling beds, which is certainly descriptive. In contrast to "particu-
late," this has been referred to as aggregative fluidization, but that is not
a very descriptive name and boiling or bubbling is to be preferred.
The two-phase theory states essentially that the gas flow divides into
that which flows interstitially among the closely packed particles and that
which takes part in bubble flow. That is,
( 35)
As generally expressed, the two-phase theory further assumes that Qi ==
Qmf, which here will be referred to as the simple two-phase theory. This
can conveniently be written
QB
-==U-U ( 36)
A mf
which gives an immediate estimate of the bubble flow for any operating
velocity.
The two-phase theory is fundamental to most models of fluidized-bed
chemical reactors. Gas in each of the two phases has a different residence
time and pattern of contacting with the particles. In realistic situations there
is generally some exchange between the phases.
Two obvious corrections are necessary to Eq. (36), although they are
often small enough to be neglected. First, as the bed fills with bubbles
the overall average height increases but the cross-sectional area available
for interstitial flow is reduced. Second, there is necessarily a pressure
Fluidized-Bed Reactors 453
drop across the bed and therefore gas must expand as it rises. Volumetric
flow and therefore gas velocity consequently increases with height. As
Table 2 shows, Umf is largely independent of gas density (or varies in-
versely as its square root for large particles), so that the excess flow avail-
able for bubbles (U - Umf) increases with height. It can be shown (Rowe,
1978b) that these two corrections lead to
( 37)
where the suffices D and H refer, respectively, to the distributor plane
and a plane height H above it. The expansion correction is usually neces-
sary only for deep beds of dense material or when operating at subatmos-
pheric pressure. Even in a vigorously fluidized bed, fB is rarely greater
than about 30% and, especially when Un » Umf, this correction also is com-
monly very small.
The simple two-phase theory is essentially correct for many powders,
particularly for those with mean particle size greater than about 100 µm.
From consideration of the minimum fluidization conditions as implied, for
example, in Eq. (11), it follows that the interstitial gas velocity must remain
at Umf if the voidage of the dense phase remains at Emf. It is difficult to
imagine that particles may become closer spaced after fluidization, but they
may separate more widely, thus causing the dense phase to be more per-
meable. It is thus to be expected and there are indeed cases when inter-
stitial flow is greater than Umf and the two-phase theory needs modification.
Three situations have been observed experimentally where Ui > Umf·
1. Beds of fine particles of group A (Geldart, 1973) (typically the
partic1e size is less than 100 µm).
2. When operating at high gas pressure
3. In the bottom several centimeters of the bed, where it appears to
take measurable time for the flows to come to equilibrium
These special cases will be discussed in the following sections.
Properties of Bubbles
In many ways the bubbles in gas fluidized beds have similar properties to
bubbles in a true liquid. They have a roughly similar shape, they rise at
about the same velocity, disturb the surrounding medium in much the same
way, and coalesce and break up. However, they differ in several points of
detail and the analogy must be drawn with care. Bubbles are fundamental
to the behavior of gas fluidized-bed reactors, so it is important properly to
understand their properties as much is now known about them from research
experiments.
In any realistic reactor there will be many bubbles, but it is helpful
first to examine the properties of single bubbles in isolation. Because the
dense phase of closely spaced powder particles is opaque, bubbles cannot
normally be seen within the bed and special experimental techniques are
required to reveal them. One such technique is the so-called two-dimension-
al bed, where the powder is confined between glass plates perhaps 1 cm
apart. This effectively exposes a thin slice of the bed and the bubbles
454 Rowe and Yates
C) '-
----- --- /
FIGURE 5 Undisturbed gas bubble in a fluidized bed.
can be seen by suitable lighting and recorded photographically (Rowe,
1971). Bubble shape, rise velocity, and some other properties are changed
a little by this constraint within two dimensions; nevertheless, the tech-
nique reveals many essential features and gives much insight. Another
technique with different limitations is x-ray cine photography.
Undisturbed bubbles are spherical with an indented base, as shown in
Fig. 5. The boundary is quite definite and the interior is empty of parti-
cles. They rise by particles flowing around them in streamlines rather as a
bluff body moves through a true fluid at low Reynolds number.
Bubble rise velocity can be described by the Davies-Taylor expression
(Davies and Taylor, 1950), which can be written
( 38)
The standard deviation of a single observation is very high and even under
ideal experimental conditions prediction of velocity for a particular bubble is
subject to much error. Even with large numbers of observations it is not
possible to confirm that Eq. ( 38) is the correct form and it is chosen simply
on the basis of analogy with bubbles in liquids. From many data it is clear
that the constant of proportionality in Eq. ( 38) is unity within the limits of
experimental error. For the purpose of reaction engineering it is behavior
of the average bubble that is of interest, and for this, Eq. (38) is adequate
and as good as any other. From this equation it is seen that bubbles rise
at a few tens of cm /s and the practical range of velocities is less than one
order of magnitude.
The indentation at the bottom of a bubble is a wake of particles travel-
ing with it and roughly circulating as indicated in Fig. 6. It is very like
the attached vortices behind a bluff body moving through a liquid at
10 < Re < 100. The wake grows as further particles are captured until it
becomes unstably large, when a large portion is shed-again closely
analogous to behavior in a true liquid. Pursuing this analogy suggests that
the fluidized particles have a viscosity of 10- 2 N •s /m2, but it can be mis-
leading to attribute a true Newtonian viscosity to the fluidized system. At
high shear rates particles will come in contact with each other, and apparent
viscosity will change abruptly to elasticity. The system has been treated
as a rheological fluid (Rietema, 1967), but such an approach has not ad-
vanced our understanding very far.
The continuous growth and discontinuous shedding of wakes accounts
in part for the variability of velocity. It also accounts for the fact that
instantaneous pictures of bubbles show a variety of wake sizes. The
Fluidized-Bed Reactors 455
FIGURE 6 Particle circulation in bubble wake.
average wake volume is about one-third of the bubble volume or one-fourth
of the whole sphere volume.
VB
V
w = 3
( 39)
3
nd B
= 24
( 40)
Additionally, the wake fraction increases with the absolute size of the bub-
ble so that bigger bubbles appear flatter, but this is a fairly small effect
and for most practical purposes Eq. ( 39) is adequate. Both wake fraction
and velocity appear to be independent of particle properties.
Gas Flow Within the Bed
Gas flow within the interstitial phase is essentially streamline because the
closely spaced particles suppress turbulence and prevent the development
of eddies any larger than interstitial space. This is at first surprising
because the immediate impression on seeing a bubbling fluidized bed is that
it is well mixed. As far as gas is concerned, this is quite wrong and with
nonporous particles there is very little gas mixing, and reactors that feed
reactant gases separately usually perform very badly because of this. A
limited degree of gas mixing occurs with porous particles simply because they
absorb gas, move, and release it elsewhere.
It has been mentioned above that gas velocity in the interstitial phase,
Ui, remains at minimum fluidization value Umf except in some special circum-
stances when it may be exceeded to a limited degree. Reynolds number
based on particle diameter and interstitial velocity is usually quite small.
For example, for particles of diameter, dp = 100 µm fluidized by gas at
NTP Rei is of order 10-1. This supports the observation that gas mixing
is poor and also indicates that the heat and mass transfer coefficient be-
tween particles and gas will be near their lower limiting values.
456 Rowe and Yates
As is fairly obvious and is explained fully below, particles move in the
bed as bubbles pass among them. The particles move as a whole in a fairly
orderly way and in so doing move gas with them while the relative velocity
or slip remains at Ui. Th:is gas may follow a tortuous path from bottom to
top but without mixing.
There is a pressure drop from bottom to top of a fluidized bed as given
by Eq. ( 3), and consequently the pressure just below a bubble is greater
than that just above it. This pressure difference is the hydrostatic pres-
sure change over the bubble height, just as for a bubble in a liquid. There
is no material resistance to gas flow through the empty space of the bubble
where the pressure is constant and therefore gas must flow upward through
it.
When bubbles rise slowly relative to interstitial gas, they offer an easy
flow route and gas converges on these regions of high permeability and by-
passes some dense phase as it flows through the bed. Figure 7 illustrates
qualitatively the type of path gas may follow in these circumstances. The
streamlines are distorted by the bubbles in much the same way that magnetic
lines of force are distorted by soft-iron bodies in the magnetic field and for
much the same reason. For the purpose of reaction engineering it is neces-
sary to know the residence time of elements of gas in the dense interstitial
phase and in the interior of bubbles.
When bubbles rise quickly relative to interstitial gas, a quite different
situation develops. Gas must still flow upward through the empty space
because of the pressure difference, but as it flows out through the bubble
roof, it enters a region of fast-moving particles flowing round the bubble
as in Fig. 6. In consequence, gas is swept around the top of the bubble,
down the sides, and near the lower half it is pushed back into the empty
space by excess pressure in the dense phase. Hence gas is trapped and
forms a spherical vortex or cloud around the bubble as it rises, as illus-
trated in Fig. 8, The overall result under these circumstances is that each
bubble becomes surrounded by a cloud, as indicated in Fig. 9, The gas
has how divided into two phases, that flowing interstitially and that per-
mentaly associated with the bubbles.
Considering the gas enclosed by the outer boundary shown in Fig. 9,
only that part in the annular region between outer and bubble boundaries
FIGURE 7 Gas flow through slow-moving bubbles.
Fluidized-Bed Reactors 457
•
: - - FLOWING PARTICLES
••
PRESSURE DIFFERENCE
• /DRAG GAS WITH THEM
CAUSES UPWARD FLOW
TO COMPLETE THE
CIRCULATION PATH
OF TRAPPED GAS
_ AND EXCESS PRESSURE
••• •
RETURNS IT TO THE
BUBBLE
•
••
••
•
•
FIGURE 8
'
Formation of gas cloud around fast-moving bubble.
is actually in contact with particles. Only this fraction of gas can react at
any instant, although since the whole is circulating, each element will have
a limited period of reaction time. Furthermore, since a necessary condition
for this hydrodynamic situation is that UB > Ui, gas forming the cloud has
a shorter residence time than interstitial gas. Plainly these limitations have
important consequences in reaction engineering and the mechanism described
above forms a basis for reactor modeling.
It is evident that the two velocities, UB and Ui, are important param-
eters in determining the nature of gas flow through the bed. They are
independent of each other. UB depends only on bubble size, as shown by
Eq. ( 38). Ui is proportional to Umf, which in turn depends on the gas
and particle properties as given by Eq. ( 9), (14) , or (17). For small
values of Umf, when clouds are likely to form, interstitial gas velocity de-
pends primarily on particle size, roughly as d§. The important ratio UB /Ui
is then proportional to d! 12 /d;. It should be noted that conventionally, Umf
is expressed as a superficial velocity
FIGURE 9 Bubble with captive cloud.
458 Rowe and Yates
Qmf
umf = -
A
( 41)
and therefore when the simple two-phase theory applies,
(42)
Clouds form around the bubbles whenever UB > Ui, that is, when the
ratio
a. =
u.l > 1 ( 43)
A simple but elegant theory (Davidson and Harrison, 1963) treats the bub-
bles as perfect circles around which concentric clouds form the diameter,
being given by
= ( ~ ) 1/2 ( 44)
a. - 1
for a two-dimensional or disklike bubble (the only case observable experi-
mentally) or
d
C = (~)1/3 ( 45)
dB a. - 1
for three-dimensional or spherical bubbles. These equations are shown
graphically in Fig. 10. From this it is seen that when a. < 1, the cloud is
of infinite extent, or in other words, is open to through-flow.
16
15
14
IXI
-::!
c.> 13
""
12
11
10
rn 2 3 4 5 6 7 8 9 10
o<.
FIGURE 10 Ratio of cloud to bubble diameter as a function of the dimension-
less parameter a..
Fluidized-Bed Reactors 459
Equation ( 45) gives an estimate that is useful in calculating contacting
efficiency in reactor modeling, but a better estimate is given by the semi-
empirical equation (Partridge and Rowe, 1966)
1.17
( 46)
a - 1
In gas fluidized beds of particles where dp ~ 100 µm, values of the
velocity ratio are commonly in the rage 10 < a < 100. From Eq. ( 46) it
is then seen that the cloud volume is between 13 and 1% greater than bub-
ble volume. That is, only between 13 and 1% of gas in the bubble or
cloud phase is in contact with solid particles at any instant. This is very
poor contacting and explains the performance of reactors that operate un-
der such ill-chosen conditions.
Bubbles usually form initially at the distributor plane and unless there
is change in the volumetric gas flow with height, the bubble population
changes thereafter only by coalescence and splitting. There is, however,
an initial or formation zone in which this is not true.
Distributor and Bubble Formation
In an industrial reactor the distributor plate usually contains a number of
regularly spaced holes which may or may not be capped in some way to
prevent solids falling through on shut down and to help distribute the flow
uniformly. Gas velocity through individual holes can be considerable
(typically tens of m/sec), yet under all realistic conditions gas enters the
bed from them in the form of bubbles (Rowe et al., 1979). The gas momen-
tum is effectively zero and even with horizontal entry, bubbles rise ver-
tically from the source. The mode of entry is very similar to the way bub-
bles form when gas is blown into a liquid.
In one important respect gas entering a fluidized bed differs from that
entering a liquid. With increasing flow rate the frequency remains approx-
imately constant at eight per second and the size of bubble at detachment
increases. Into a liquid the reverse is true at least at modest flow rates.
This is an important and useful fact, as it enables initial bubble size
to be calculated. If it is assumed that the total gas flow is equally divided
between the holes, the bubble volume at detachment follows from the ob-
served frequency. However, this is subject to the correction mentioned
below.
From x-ray observation it is seen that the size of bubble at detachment
multiplied by observed frequency accounts for only about one- half of the
known flow through the distributor orifice. That is, the bubbles are only
about half the expected volume. These newly formed bubbles continue to
grow after detachment and by the time their centers are about two diame-
ters above the hole, they are of a size and frequency to account for all
the flow as depicted in Fig. 11. It is now seen that the initial bubble size
is given by
( 47)
460 Rowe and Yates
~
e:.:=:1 Va=~ ]:d~~Q_
36 8
ca.2xds
FIGURE 11 Bubble formation at an orifice.
where Qo is the flow through a single orifice in m3 /s. At the moment of
detachment the bubble is spherical but quickly develops a wake, as shown
in Fig. 11.
If for a proposed design of distributor the calculation of Eq. (47) gives
an impossibly small diameter (e.g. , less than the hole size or markedly less
than 100 particle diameters), it is evident that the design is unsatisfactory
and not all holes will operate. Similarly, if the bubble size and hole spac-
ing is such that gross overlap occurs, the holes will not operate independ-
ently. These considerations, together with the well-known empirical rule
that pressure drop across the plate should be about one-third of that
across the bed to ensure stability, are essential guides to successful dis-
tributor design.
The facts described above can be explained in a semiqualitative way
that is important in modeling chemical reactor behavior in the shallow dis-
tributor zone. Unlike a bubble forming in a liquid, one in a fluidized bed
can grow only by gas flowing perpendicularly across the bubble boundary.
This is the only way in which a force can be applied to individual particles
to cause them to move and so extend the boundary. After time t the still
attached bubble may have grown to diameter dB, as shown in Figure 12,
FIGURE 12 Region of gas penetration during bubble formation.
Fluidized-Bed Reactors 461
but during this time the gas has advanced as far as the dashed line
indicated. The volume within the outer boundary is Qt plus the volume
occupied by particles in the eccentric annular region.
This annular region now contains excess gas, and therefore the local
powder voidage, E, must increase. Such increase is unstable and evidently
when the bubble detaches and begins to rise through the unstable ex-
panded region, it relaxes and the excess gas pours back into the bubble,
almost certainly through its base. The experimental evidence shows that
this is completed by the time the bubble has traveled little more than one
diameter. Since eight bubbles form each second, it is a very rapid se-
quence of events and hydrodynamic equilibrium is achieved in a time of
order 10-1 s.
Referring again to Fig. 11, the upper bubble is now stable and will
have formed a cloud around itself if the velocity ratio is appropriate. Half
the gas in this cloud and bubble first passed into the dense phase and then
returned to form a stable bubble. This brief but efficient contact between
gas and particles can lead to good reactor performance in this shallow layer,
and a model for this is developed later in this chapter.
Bubble Coalescence and Average Size
Bubbles coalesce readily for although the fluidized powder has a property
equivalent to surface tension, it is small. The rate of coal~scence depends
essentially on the closeness or concentration of bubbles. From this it is
possible to postulate the way in which bubble concentration will change
with height, and combining this with the assumption that the bubble flow
remains constant, bubble size can be estimated. The empirical constant is
fitted from the data, leading to (Rowe, 1976)
(U + h )3/4
0
( 48)
1/4
g
ho in Eq. ( 48) arises as a constant of integration and its physical meaning
is clear by reference to Fig. 13. It is that imaginary distance beneath
the distributor where the bubbles would be of zero size. It is related to
initial bubble diameter by
d4/3 1/3
B(O)g
(49)
(U - U )2/3
mf
and so can be estimated from Eq. ( 47). In practice, ho is usually only a
few centimeters and can· often be neglected when estimating bubble size in
beds of reasonable depth.
For bubbles to achieve an average size at a given height and flow rate,
it is obvious that the containing vessel must be big enough. If not, the
bed will slug and Eq. ( 48) is useful in indicating when this condition will
begin, an important point in reactor modeling (Rowe, 1978a).
Another expression for bubble size that is based on slightly different
reasoning is (Darton et al. , 1977)
462 Rowe and Yates
i
m
"O
er
w
1---
w
2
<(
0
\d
w
_J
m
m
:::J
m
z 8 = ( U-Umi)112 ( h+h 0 / 14
<(
w
2 g1/4
r---;
ds<o) ✓✓
~.✓ O-c.1----------------------
-ho_o BED HEIGHT h _____.
FIGURE 13 Variation of bubble diameter with bed height.
U ) 0. 4
mf
d = ( 50)
e 0.2
g
where de is the equivalent sphere diameter [de = (3/4) 113dB] and Ao is
the catchment area for a bubble stream at the distributor plate. The two
equations ( 48) and ( 50) are very similar numerically and, within the limits
of observational error, describe the data equally well.
Bubbles also split by instabilities that develop as "fingers" from the
roof which may grow rapidly enough to divide the bubble usually into two
unequal parts. It is quite common for the two parts subsequently to
coalesce. On average, small daughter bubbles persist as individuals for
some time, so that the size distribution becomes positive skewed with an ex-
cess of small sizes. A well-designed distributor with uniform holes pro-
duces initially a more or less mono-sized distribution, but by coalescence
and splitting this develops toward an exponential distribution with height
which is equivalent to time.
Within a region where there are many bubbles and frequent coalescence,
average bubble velocity is increased by the accelerations accompanying
coalescence. It has already been pointed out that even with isolated and
undisturbed bubbles, there is a high error variance in estimating velocity
from bubble size. This variance is increased when many bubbles are
present, so that from the data it is not clear that there is any correlation
at all. It is, however, apparent that velocity increases with gas flow rate,
and a commonly used expression that takes this into account is
( 51)
which is probably satisfactory for most reaction engineering purposes.
Fluidized-Bed Reactors 463
Equation ( 48) can be expressed as average bubble volume using the
bubble shape and proportions given by Eq. ( 39) and ( 40). If the two-
phase theory applies as given by Eq. ( 36), the volumetric flow is constant
and this can be written
( 52)
where n is the frequency with which bubbles cross a horizontal plane
through the bed. Combining these equations gives an expression for this
frequency,
n 8g3/4
= ( 53)
A TI(U - U )1/2(h + h )9/4
mf 0
Bubble concentration is related to frequency by
n
N= ( 54)
8 3/4
( 55)
+ h )9/4
0
from which it is seen that bubble concentration falls rapidly with increas-
ing height. A large industrial-scale reactor operated at a fairly high gas
velocity may bubble furiously near the bottom but appear almost quiescent
at the top. ·Under these conditions bubbles can be treated as isolated in
much of the upper part of the reactor.
The question is commonly asked: Is there a maximum bubble size?
But it is an academic question without much practical importance. Equation
( 48) implies growth without limit and, while it is based on coalescence fre-
quency observed on a fairly small scale, on an industrial scale it does fit
the few data there are. Certainly, bubbles of diameter in the region of
1 m have been reported from more than one source. Rate of coalescence
falls off rapidly with concentration so that rate of growth declines with
height, and it requires an impossibly large and deep bed to observe bub-
bles much more than 1 m in diameter. It is inconceivable that close bubbles
should fail to coalesce just because the distributor plane is far below. Cer-
tainly, big bubbles tend to break up, but then the fragments all too com-
monly recoalesce. Evidence and logic suggest there is no upper limit, and
the possibility of experimental proof seems remote.
On the contrary, there is surely a lower size limit. A bubble of parti-
cle size is meaningless. The bubble has reality only when particles can
flow around is as a pseudofluid. This suggests a lower limit of order 102 x
dp. There is no experimental evidence for bubbles less than about 1 cm
in diameter, but observation would be difficult.
Particle Mixing and Segregation
The transport of a wake and streamline motion of particles causes a largely
predictable displacement of material. This can be demonstrated by preparing
464 Rowe and Yates
a bed initially with, say, black particles forming the lower half and white
ones above with a horizontal interface between (Rowe et al., 1965b).
Figure 14 indicates the kind of displacement that occurs as first one
and then successive bubbles disturb the initial arrangement. Each bubble
carries wake material to the surface, spilling some enroute while streamline
motion draws up a spout or drift profile. Repetition complicates the pat-
tern and the whole quickly becomes well mixed. If bubbles tend to rise
in the center, the overall motion is a convection pattern, up the center
and down the sides. This reverses if bubbles rise near the walls and
more complicated patterns occur in large beds.
It is important to realize from these demonstrations that particle mixing
is caused solely by displacement by the bubbles. Without bubbles there
can be no mixing. There is no mechanism equivalent to molecular diffusion
whereby neighboring particles may jostle and exchange positions-except in
the wake. In spite of appearances to the contrary, particle movement is
relatively orderly and predicable to a limited degree.
It follows from this that the rate of particle mixing depends on the
bubbling rate. It is directly related to the excess gas flow rate (U - Umf),
as seen from Eq. (35). In most realistic circumstances, the bubbling rate
is such that mixing occurs rapidly, and in the majority of cases it is appro-
priate to treat the particles as perfectly mixed. The circulation rate can
be estimated roughly (Rowe, 1973) from
Ahwf
t
C
=------'-'------- ( 56)
0. 6 QB [1 - (QB /AUB)
where tc is a measure of the time taken for a particle to make a circuit of
the bed. If in a chemical reactor where the particles are changing composi-
tion the rate of chemical change is small compared with circulation rate, the
solids system can justifiably be treated as perfectly mixed, and the above
is a simple test to check the correctness of the assumption. The over-
simplified nature of Eq. ( 56) still leaves it quite suitable for this purpose.
Uneven gas distribution quickly leads to convection patterns of solids
motion, and the type of pattern is. not difficult to imagine with the fore-
going mechanism in mind. Sometimes this is done deliberately to induce a
a) Initially b) After 1 bubble c) After several bubbles
FIGURE 14 Particle mixing caused by rising bubbles.
Fluidized-Bed Reactors 465
desired circulation. As it is not easy to ensure uniform distribution over
a large area, it may occur involuntarily and unwanted in industrial reactors.
Bulk movement of particles in some kind of circulation pattern will af-
fect bubble velocity and processes such as coalescence. Equations such as
( 48) and ( 51) must be used with caution in reactors where appreciable con-
vection is known or suspected to occur.
If the powder to be fluidized contains grains of different types, segre-
gation may occur. Shape differences seem to be unimportant and the only
relevant differences between particles are size and density. Of these,
density is much the more important. In contrast with mechanical powder
mixers, fluidized beds will tolerate a very wide range in particle size with-
out appreciable segregation.
Minimum fluidization velocity varies with mean particle size, so that if
the size composition of a mixture changes, so does Umf· If fines are
elutriated or if agglomeration occurs, Umf increases and at a constant gas
flow rate the vigor of fluidization decreases. This may eventually cause
segregation because, as explained above, the rate of mixing depends on the
bubbling rate, which declines with increasing Umf according to Eq. ( 36).
Again in contrast with mechanical mixers, particles of different density
can readily segregate in a fluidized bed. While there is usually a spectrum
of particle sizes in powders pf industrial interest, there are rarely more
than two or three different densities and most commonly only two. The
majority of research studies are confined to binary systems.
If two powders made up of particles differing only in density are well
mixed and then gently fluidized, the dense component settles to the bottom
as jetsam. It forms a pure layer, but a small portion remains uniformly
mixed in the less dense flotsam above it. With increasing gas velocity
( bubbling rate), the proportion of jetsam dispersed in the flotsam increases,
and eventually it may be possible to achieve an overall uniform mix. This
is illustrated graphically in Fig. 15.
The ratio M = x Ix
as defined by Fig. 15 is a simple mixing index, zero
for complete segregation and unity for perfect mixing. It is a function of
velocity, of density ratio, and to a small extent, of size ratio. A simple
empirical relationship is (Rowe and Nienow, 1976)
TOP
I INCREASING
lru-Umtl
i
BED X I
HEIGHT
h I
I
I
BOTTOM+---+----+
0 x 1 x O x
FRACTION OF JETSAM-----+
(U-Um1)-O ( U-Umi)-SMALL ( U-Um1)-LARGE
I
PERFECT SEGREGATION PARTIAL SEGREGATION I PERFECT MIXING I
FIGURE 15 Segregation patterns for binary mixtures of solids.
466 Rowe and Yates
5/2 (dd12) 1/2
M = f(U) ( :; ) ( 57)
where (d 1 Jd 2) > 1. This shows quantitatively the relative importance of
density and size difference. The variation with velocity, f(U), is compli-
cated by the above-mentioned fact that Umf varies with composition. It is
of the double exponential form shown in Fig. 16. For each binary system
there is a critical velocity UTO below which the system rapidly segregates
and above which it rapidly mixes. An empirical equation from which this
can be estimated is
)1.1 )0.7
[ (U:;);
(U ) ]1.2 P
+ 0.9(P; - 1
d
(d: - 2.2x 112 (H*) (58)
where H* is a reduced bed height defined by
H* = 1- exp (- !) ( 59)
Like mixing segregation is brought about by the bubbles. A bubble
passing through a region of jetsam enables it to descend through neighbor-
ing flotsam. Similarly, the bubbles cause mixing by lifting jetsam in their
wakes, carrying it to the upper part of the bed. The two processes are
in competition, but mixing increases more rapidly than does segregation.
From the point of view of chemical reaction engineering, interest lies
in knowing the distribution of material in cases where segregation may
occur. Complete mixing is often desired and the equations above give a
guide as to whether or not this will occur.
Heat and Mass Transfer
Two quite different and independent heat transfer coefficients apply to a
fluidized bed. hG /S refers to heat transfer between gas and solid particles
PERF~'fl1 - ----+--~-
I
i
MIXING
I
INDEX
M
COMPLETE
SEGREGATION 0_,.-~:______L__ _ _ _ _ __
Umt Uro
GAS VELOCITY U -
FIGURE 16 Variation of mixing index with gas velocity.
Fluidized-Bed Reactors 467
and hB /W refers to heat transfer between the bed and its containing walls
or immersed surfaces.
Heat transfer between gas and particles is usually very rapid but only
because of the enormous surface area presented by finely divided solids and
because of their large heat capacity on a volume basis compared with that
of the gas. The transfer coefficient hG /S is small, near its lower limiting
value, because the local Reynolds number is small, as explained earlier.
The local number can be estimated from (Rowe and Claxton, 1965)
Nu ( 60)
= A + BPr 113 Ren (61)
where
2
A = ( 62)
1 - (1 - E) 1/3
2
B = ( 63)
3E
and
--0 28
(2 - 3n) / ( 3n -- 1) = 4. 6 5Re · ( 64)
Consider the case where fluidizing gas enters the bed at a different
temperature from the particles. Assume that the particles are uniform
spheres and are perfectly mixed by bubble disturbance as described above.
Further assuming no heat loss and that the solids have a much greater
heat capacity per unit volume than gas, it is readily shown that the depth
of bed over which 90% of the gas change in temperature occurs is given by
( 65)
If this is evaluated for a typical gas-solid fluidized system with hG /S calcu-
lated from Eq. (61), it is seen that this layer is only a few particle diam-
eters thick. That is, virtually all heat transfer occurs in a very shallow
bottom layer. Experimental attempts to detect a temperature gradient at
the bottom of the bed invariably fail, which is in accordance with Eq. (65).
This follows from three simple facts: the particles are well mixed, they
have much larger volumetric heat capacity than gas, and they offer a lot
of surface area for heat transfer.
It is well known that a vigorously bubbling gas fluidized bed is re-
markably uniform in temperature even when highly energetic reactions are
occurring. This all follows from what is written above and is not a con-
squence of a high transfer coefficient when this is considered on an in-
dividual particle basis.
Heat transfer from bed to walls is also generally very high, and this is
expressed by a high value of the coefficient hB /W when, as is logical, it
is defined in terms of wall area. The magnitude of the coefficient is usually
comparable with that for heat transfer to a boiling liquid, and often the
468 Rowe and Yates
overall coefficient is limited by conditions on the other side of the wall.
Numerical values depend on particle and gas properties in a complicated
way that has been well documented (Botterill, 1975).
The reason for high heat transfer rates is easily explained. It follows
from the fact that particles are well mixed and of uniform temperature.
The temperature profile across a section of the bed is flat, and therefore
there is a very steep gradient or driving force against the containing
walls. Another way of saying this is that hot particles from the center
are continually brought to the cold walls and then moved on before they
have time to cool appreciably. The requirement for good heat transfer is
simply that the particles keep moving.
The foregoing also applies to surfaces immersed in the bed, but diffi-
culties can arise when these interfere with fluidization, the rise of bubbles,
and the consequential movement of particles. It is easy in these general
terms to understand why a submerged heat exchanger may not perform
well, but improvement depends on engineering empiricism with this model
kept in mind.
There is no realistic equivalent of mass transfer between surfaces and
the bed but an obvious one between the particles and the gas. On an in-
dividual particle basis this is closely analogous to heat transfer and Eqs.
( 60) and ( 61) simply become
i
d
Sh = kG/S ( 66)
= A + BSc 113 Ren (67)
with A, B, and n defined as before by Eqs. ( 62) to ( 64).
There is very little more to say about mass transfer, although the
simpleminded often seek an overall coefficient that will yield conversion in
a reactor from facts such as the inlet conditions and the bed temperature.
There is no simple answer of this kind. Overall conversion follows from an
integration of all the histories experienced by elements of gas in their pas-
sage through the bed, in bubbles, in interstitial flow, or as part of a
cloud. The local reaction rate will depend on local concentration and on
the transfer coefficient given by Eq. (67). But this is the basis of the
reactor models dealt with later in this chapter.
Fine Powders
Fine powders behave differently from coarser ones in ways that are important
for reaction engineering, and some of the previous description requires
modification. Fine powder in this context means Geldart's group A powders
(Geldart, 1973), which are roughly defined as lying in the range
( ps pf)d~ > 10 6
( 68)
(p
s
-- p )d
f p
< 2 x 10 5
when density is expressed in kg /m 3 and particle diameter in µm. Thus
solids of density 103 kg /m 3 show group A behavior when in the range
Fluidized-Bed Reactors 469
30 < dp < 200 µm. Below this size they are very difficult to fluidize
uniformly and tend to channel ( group C) , and above it they behave as
hitherto described ( group B). The classification is approximate at best,
depends also on other poorly understood particle properties, and there is
a gradation of behavior and not abrupt change. Most powders clearly
show group A behavior when dp < 100 µm.
The distinguishing feature of group A powders is that they expand uni-
formly when fluidized at low gas velocities and do not begin to bubble until
a higher velocity, Umb, is reached. For group A powders Umb /Umf > 1.
This is illustrated by Fig. 17, which shows how bed height changes with
gas velocity.
The uniformly expanded state is quite stable. There is no hysteresis
and the same height is observed whether gas velocity has increased or de-
creased. The first appearance of bubbles is a breakdown of this stability,
and observations around Umb are not very reproducible, making it diffi-
cult to determine with precision.
Behavior in the region Umf < U < Umb is closely akin to that of liquid
fluidized beds as described briefly earlier. The height or bed voidage
varies with velocity as Eq. ( 31) except that the constant of proportionality
is less than UT. As a corollary, the exponent m is greater than observed
with liquids at the same Reynolds number.
With decreasing average particle size this group A behavior becomes
more marked. Bed heirht can double before bubbling begins when Umb/
Umf i
3. Expansion is increased by the addition of fines to the powder,
which has the effect of reducing mean particle size dp·
Many catalyst powders prepared for use in fluidized-bed reactors be-
have as group A and fluid-bed cracking catalyst (FCC) is a good example.
Expansion of the dense phase and increased interstitial flow above Umf has
important consequences in reactor behavior and modeling. Since this oc-
curs only with fine powders where interstitial flow is necessarily small, in-
crease in this very effective phase can increase reactor performance
markedly.
~ I
~
- h ..,.._ _ __,, I I BUBBLING
1◄ ~
WI O UNIFORMLY FLUIDISED BED
I
8
EXPANDED
-~PA~C""K~E_D~-.~LUIDISE~ILJ
CD E I BED
I UNSTABLE
REGION
o-+--------1----t---------1,-------
0 Umt Umb
GAS VELOCITY u--.
FIGURE 17 Variation of bed height with gas velocity for group A
powders.
470 Rowe and Yates
i
0
~
LL }
GROUP A
POWDERS
_J
<r:
i=
i=
t.f) INCREASING
0::: FINES CONTENT
w
f-
z I IDEAL.: 2 PHASE THEORY ( GROUP B POWDER)
I
I
I
Omt
o--------'-----------------
0 TOTAL FLOW 0---
►
FIGURE 18 Variation of interstitial flow with total flow as a function of
fines content for group A powders.
Although observation is difficult, there is evidence that the dense
phase remains expanded after bubbling begins and more gas than Qmf
flows interstitially in a vigorously fluidized bed of group A powder (Rowe
et al. , 1978). Figure 18 shows how interstitial flow increases for group A
powders as the fines content is increased (dp decreased). Only limited
data are so far available, and it is not yet possible to quantify the informa-
tion of Fig. 18 for a previously untested powder. It should be noted that
interstitial flow will decrease and reactor performance will consequently fall
as fines are elutriated from the bed. Such is commonly observed by plant
operators.
Effect of Increasinq Pressure
Most fluidized-bed reactors operate at or a little above atmospheric pressure,
but there are cases when it is required to operate at higher pressures.
Fluidized coal combustion under pressure, for example, gives improved ef-
ficiency because of the reduced volume of the plant for a given duty and
because of the opportunity to recover further energy by expanding hot
gases through a turbine ( Roberts et al. , 1980) . For this application, pres-
sures up to 20 bar are feasible. There are, additionally, chemical
processes where it is thermodynamically desirable to operate at high
pressure.
At the same mass flow rate it is obvious that velocity will decrease with
increasing pressure, so there will be fewer and smaller bubbles with an
increasing proportion of interstitial flow. It is of more interest to compare
Fluidized-Bed Reactors 471
behavior at the same volumetric flow rate as pressure increases and this
is the condition in all that follows.
It is commonly reported by plant operators that fluidization is "smoother"
as pressure increases, and this is said to be because the bubbles are
smaller. The evidence for this is very slender because of the difficulty of
observation, but the conclusion is widely accepted. Data from research ob-
servations under pressure are scarce, again because of the difficulty of
observation, but what little evidence there is points to the conclusion that
proportionately more gas flows interstitially as pressure increases (Rowe
and MacGillivray, 1980).
The ratio Umb /Umf for class A powders does increase with increasing
pressure but not dramatically, about 25% for a fivefold increase in pressure
(Rowe et al. , 1982). Certainly, some group B powders show group A be-
havior as pressure increases, and this is not predicted by the criteria of
Eq. (68). An alumina powder of dp = 450 µm that is typically group B at
NTP began to show group A behav10r at pressures as low as 2 bar and
showed it markedly at higher pressures (Rowe et al., 1983). X-ray cine
photographs of this powder fluidized with nitrogen show that as expected,
bubble size decreases with pressure and the average volume is halved at
around 60 bar. Again, this is not a dramatic change. Bubble frequency
increases and the visible bubble flow varies approximately in proportion
with A(U - Umb). The bubble velocity coefficient ✓ uB /( 1/2)gdB increases
by about 50% at 30 bar and thereafter changes little.
It should be noted that Umf falls with increasing pressure as predicted
by Eq. (14). Terminal falling velocity, UT, also falls with pressure. The
change can be considerable, and for the 450 µm alumina referred to above,
Umf falls to one-third of its atmospheric value at about 60 bar. UT falls
to about one-fifth over the same range. The change increases with parti-
cle size. Equation (14) fits the presently available data very well up to
pressures of 100 bar.
Change of Umf with pressure means that at constant volumetric flow
rate the bed will be fluidized at a greater multiple of Umf as pressure in-
creases. The development of group A behavior means that a larger pro-
portion of gas will flow interstitially, and the net result may be a reduction
in bubble flow with consequently smaller bubbles. These changes would
improve reactor performance.
With the 450-µm alumina (the only material so far to be studied system-
atically in this way), dramatic changes do occur at pressures greater than
about 80 bar. As this pressure is approached, the wake obtrudes more
deeply into the bubble and they begin to break up by wake reaching to
the roof, a mode of breakup never observed at lower pressures. At 80 bar
the bubbles are no longer clearly observable, and it may be that the system
has changed toward particulate fluidization.
Entrainment and Elutriation
When fluidized beds are operated at gas velocities in excess of the mm1mum
fluidization value, the eruption of gas bubbles at the bed surface causes
particles to be carried upward into th.e free board region. It is generally
accepted that these particles originate from the bubble wake region (George
and Grace, 1978) and that the height to which they are carried above the
surface before falling back is a function of their size and density as well
as of the velocity of the fluidizing gas.
472 Rowe and Yates
Under conditions of operation in which the superficial gas velocity
exceeds the terminal fall velocity of the bed particles, entrainment leads
to elutriation and particles are carried out of the system completely. Thus
there is usually a concentration gradient in the freeboard, with the larger
denser particles being carried some way above the surface before returning
to it, and the smaller, lighter particles being removed from the system.
The height above the surface at which the particle concentration becomes
constant is known as the transport disengaging height (TDH).
It is clearly important from a design point of view to be able to predict
how much bed material will be elutriated for a given set of operating con-
ditions, since this has a strong bearing on cyclone and filter specification.
A basic assumption generally made is that entrainment is a first-order
process and the rate of elutriation of particles in a particular size range
is directly proportional to the mass fraction x. of those particles in the
bed: 1
( 69)
where A is the bed area, M the bed mass, and K* (kg/m2•s) a first-order
rate constant. Then for an approximately constant bed mass,
xi = exp (- KM*At) ( 70)
xiO
where Xi0 is the initial mass fraction of elutriable particles. A great deal
of work has been carried out to establish relationships between K * and the
properties of fluidizing gas and bed particles, and as a result a number of
correlations have been devised and some are listed in Table 4. It must be
TABLE 4 Some Published Correlations for Elutriation from Fluidized Beds
Yagi and Aochi ( 1955):
K*gd 2
p
0.0015Re~· 6 + 0.01Re~· 2
Zenz and Weil ( 1958):
10'( :~ ,)""
u2
0 -3
39,1 X ¾ 581, 8 X 10
2
g PPS gd P
p s
-K*
--
pgUO 1.15
2
u2
0 -3
7, 02 • 10 3 ( : O 2 ) ;;;, 581, 8 X 10
d 2
g PPS g pps
Fluidized-Bed Reactors 473
TABLE 4 (Continued)
Wen and Hasinger (1960):
K*
Tanaka et al. ( 1972):
o. 5
K*
= 4.6 x 10-2 ~
(U -U )2
0 gdp ts J p
Re~.3 ( s Pg
-p
g) 0.15
Merrick and Highley ( 1974):
_mi mf )
u )o.5 u 0.25]
K~=A+130exp [ -10.4 ( ;s (u
Pg O O O
Geldart et al. (1979):
P=~o = 23.7 exp [-5.4(u;;)]
Pe = p + l: p. ( p. = solid loading of ith size fraction in exit gas)
g l l
Colakyan et al. (1979):
K*" 33 (1 - ':::) 2
Bachovchin et al. ( 1979):
K* = 3. 35 x 10 5 - -_( U
0 - )4. 67 (p_g )1. 62(L ) (D~
;x-)1.15
~ PS d d
pg p p
where
d = average size of particle elutriated
p
X = fraction of fines at the bed surface
s
Lin et al. ( 1980):
2 1. 65
= 9.43 X lQ- 4 (:d:)
474 Rowe and Yates
TABLE 5 Experimental Conditions for Entrainment or Elutriation of Fines
from Fluidized Beds (from Chen and Wen, 1982)
Column
diameter, De
bed height, L;
Investigator Experiments freeboard, H ( m) Gas Distributor
Yagi and Elutriation D = 0.052-0.071 Air Fixed bed
C
Aochi two and of steel
L = 0.031-0.12
( 1955) multicomponents, balls
batch operations
Zenz and Entrainment of D =0.051x0.61 Air, mean
C
Weil FCC catalyst, grid
H = 0.254-2.80
( 1960) steady-state pressure
operation 8 atm
Wen and Elutriation, D = 0. 067 Air, He Filter cloth
C
Hashinger two and multi -
L+H=2.08, 1. 83
(1960) components,
batch operation
Tanaka Elutriation, D = 0.067 Air Perforated
C
et al. two components, plate
L + H = 1.80
( 1972) batch and
continuous
Merrick and Elutriation, D =0.90x0.45 Air
C
Highley steady-state
L = 0.61-1.22
( 197 4) operation
L + H = 3. 96
Geldart Elutriation, D = 0.076 Air Filter paper
C
et al. multicomponents, covered
L=0.35-0.45
( 1979) batch operation by wire
L + H = 3.80 mesh
Colakyan Elutriation, D =0.90x0.90 Air Perforated
C
et al. multicomponents, plate
L + H = 6. 30
(1979) batch operation
Bachovchin Entrainment, D = 0.1524 Air Perforated
C
et al. multicomponents, plate
L = 0. 23-0. 25
( 1979) steady-state
operation H = 0.75-4.00
Lin et al. Entrainment D = 0. 60 X 0,60 Air Grid
C
( 1980) and elutriation,
L = 0. 25
multicomponents,
steady-state H = 0. 63-3. 27
operation
Fluidized-Bed Reactors 475
Size of Size of Initial
fines coarse weight Superficial
to be solids in fraction gas
entrained parent bed of fines velocity
Particles (µm) (µm) ( %) (m/sec) Internals
Sand, glass 85-500 310-1640 5-20 0. 92-1. 62 None
seed,
refractory
FCC catalyst 20-150 o. 30-0. 72 None
with size
distribution
Glass spheres, 40-140 100-280 6-10 0.22-1.32 None
coal powder
Glass beads , 60-800 141-2300 1. 28-2. 70 None
sand, stainless
balls, lead balls,
Neobeads
Coal ash 0--1400 1400-3170 0. 61-2. 44 None
with size
distribution
Sand, shot, 38-327 150-355 5-75 o. 60-3. 00 None
alumina
Sand with size 37-356 356-2360 10 0.90-3.60 With or with-
distribution out immersed
heat trans-
fer tubes
Sand 22-180 Coarse: 10-20 0.61-1.25 None
443-1095;
Medium:
22-1095
Sand/char with 0--125 125-419 0. 01-1 0.10-0. 30 None
size distribution (char)
476 Rowe and Yates
I //
~MERRICK AND
20 HIGHLEY
/ /---COLAKYAN ET AL.
10 )/ -,rn, A<D wm
5 WEN AND
HASHINGER AND
0 TANAKA ET AL.
~
(/)
(\J
E 2
---Ol
.x
•~
0.5
02
0.1 ~ - ~ - ~ - - ~ - - _ L _ - - - '
0.3 05 1 2 5
U (m/s)
FIGURE 19 Specific elutriation rate constant versus gas velocity for
64- µm size fraction. (From George and Grace, 1981.)
emphasized, however, that owing to the physical complexity of the elutria-
tion process, these correlations are frequently inapplicable outside the
range of conditions for which they were determined. Furthermore, there
is evidence that wall effects can have an influence on particle carryover,
so that bed diameter should be included in a correlation as an important
variable; this is seldom done, however. Table 5 indicates the range of con-
ditions, particle size, and so on, for which the previously listed correlations
were obtained.
A number of investigators have compared the elutriation correlations
with their own experimental results and in many cases have found poor
agreement (see, e.g., Gugnoni and Zenz, 1980). George and Grace (1981),
however, found the Zenz-Weil correlation to fit their data quite well over
a range of conditions, whereas the relationships of Merrick and Highley
( 1972) and Colakyan et al. (1979) were generally poor (Fig. 19). It would
thus seem that a mechanistic model independent of empirical measurements
would be preferable for predicting elutriation rates under any foreseeable
circumstances, but despite some attempts to establish such a model ( see
Chen and Wen, 1982; George and Grace, 1981), progress so far has been
limited.
INTERPHASE GAS EXCHANGE
It is generally accepted that gas bubbles in fluidized beds are devoid of
particles and that except in the cloud and wake regions, the opportunity
Fluidized-Bed Reactors 477
for gas-solid interaction is limited. As a result of the "porous" nature of
the bubble-cloud boundary, however, gas exchange can occur between the
unreactive bubble phase and the reactive dense phase, and this can lead to
a significant increase in the extent of conversion in a fluidized-bed reactor.
The precise mechanism of the gas-exchange process has been the object of
much speculation, and a number of methods have been proposed for calculat-
ing its magnitude under given conditions. There is, however, a second
mechanism by means of which bubble gas can contact bed particles, and
this is during the coalescence process when gas "leaks" from a trailing to a
leading bubble through the intervening dense phase. It will be convenient
first to examine the proposed transfer mechanisms for single bubbles and
then to consider what modifications need to be made to take account of
bubble coalescence.
Gas Exchange from Single Bubbles
Chavarie and Grace (1976) identified three "classical" models of mass trans-
fer from single bubbles that have been discussed in the literature. The
first is based on the assumption that transfer is controlled by diffusion
across the boundary between the cloud and interstitial phase, and was
developed principally by Rowe et al. (1966, 1971), Toei et al. (1969), and
Chiba and Kobayashi ( 1970). The Rowe approach, for example, assumes
gas in the bubble and cloud to be completely mixed and the transfer rate
to be a function of a single coefficient kgc (m/s):
-dVb Cbc
dt = k S .(Cb - C.) molls ( 71)
gc Cl C 1
where Vbc i.s the volume of the bubble plus cloud, Sci the surface area of the
cloud-dense phase interface, and Cbc and Ci the concentrations of gas in the
bubble-cloud and interstitial phases, respectively. The gas-solid system
is then modeled on the basis of transfer from a drop of one immiscible
liquid rising through another, the drop diameter being equal to the cloud
diameter de. The Sherwood number, She, for mass transfer from a
sphere of uniform composition in the appropriate range of Reynolds number
( 30 < Rec < 2000) is given, according to Rowe et al. ( 1965a) , by the
expression
k d
ShC = ~ - 2 + 0.69 Sc 113Re 112 ( 72)
D - c
where the Schmidt number,
Sc = µ ( 73)
pD
and the Reynolds number,
Re (74)
C
with D being the molecular diffusivity of the gas and UR the relative veloc-
ity between bubble and interstitial gas: UR = Ub - Ui. The bubble
478 Rowe and Yates
cloud-to-interstitial phase exchange rate (volume of gas per unit volume
of bubble per second) is then
2
k 1rd s
gc C
Qbci =
vbc
( 75)
3. 9sD Sh
C
v2/ 3
be
A second approach to interphase gas exchange was explored by David-
son and Harrison (1963), who disregarded the bubble cloud and considered
transfer to occur directly between bubble and interstitial phases by a com-
bination of convective and diffusive flow. The molar gas exchange rate is
( 76)
where the convective term, q, is given for a spherical bubble by
q = 31r U d2 ( 77)
4 mf b
db being the bubble diameter, Vb the bubble volume, and Sbi the inter-
phase surface area.
The mass transfer coefficient kbi is evaluated on the basis of the
analogy with diffusion from a gas bubble rising in a liquid:
( 78)
The overall rate of exchange is then given by
( 79)
+ 5.85
(
Dl/2 1/4)
5~4 ( 80)
db
The third "classical" model is that of Kunii and Levenspiel ( 1969), who
combined elements of the foregoing two methods and considered the ex-
change process to take place in two stages. The first stage involves
transfer from the bubble to the cloud region and is described in terms of
a coefficient Qbc identical with the bubble-to-interstitial phase coefficient
Qbi of Davidson and Harrison. In the second stage gas is considered to
be transferred from cloud to interstitial phase by a diffusive process,
described by the coefficient Qci, which may be evaluated on the basis of
the penetration theory of Higbie ( 1935):
Fluidized-Bed Reactors 479
BU 112
Q . = 6. 78(Emr b) ( 81)
Cl d3
b
The two transfer processes are assumed to occur in series, so that the
overall flow rate of gas from bubble to interstitial phase, Qbi, is given by
1 1
= -- + ( 82)
Qbi Qbc
Although the Kunii-Levenspiel model assumes separate resistances to flow
at the bubble-cloud interface and at the cloud-dense phase boundary, in
practice the latter is normally the dominant factor, so the model predictions
are not very different from those derived from the purely diffusive models.
This is shown by the values given in Table 6, where exchange coefficients
from the three models are calculated for a system in which a single spheri-
cal bubble of ozone (Do = 2 x 10-5 m2/s) with a diameter of 0.10 m is
assumed to be injected into a bed of particles of Umf = 0. 053 m/s incipiently
fluidized with air.
It is apparent that the model of Davidson and Harrison in which the con-
vective through-flow term is dominant over the diffusion term gives a value
an order of magnitude greater than those derived on the basis of the mainly
diffusive models.
Charvarie and Grace (1976) and Sit and Grace (1978) carried out gas
exchange experiments in a two-dimensional bed into which bubbles of air
containing low concentrations of ozone were injected. They found values
of overall transfer coefficients, corrected for unsteady bubble growth and
entrance effects, that were somewhere between those predicted by the
through-flow- and diffusion-dominated models. They concluded that for
TABLE 6 Predicted Interphase Gas Exchange Coefficients for Ozone
Bubbles in an Air-Fluidized Bed
Calculated
value
Model Exchange coefficient cs- 1)
3. 9ED Sh
C
Partridge Qbci = v2/3
0.245
and Rowe
(1966) be
(Dl/2gl/4)
Davidson Qbi = 4.5(°::) +
d5/4
3.21
and Harrison
b
(1963)
QbcQci
Kunii and Qbi = 0.466
Levenspiel Qbc + Qci
(1969)
Source: After Charvarie and Grace (1976).
480 Rowe and Yates
single bubbles the best agreement with experiment was shown by the
model of Murray (1965, 1966) (which ascribes a modest value to the
through-flow), modified on the basis of penetration theory to give an over-
all transfer coefficient for spherical bubbles of
12
+ -- ( 83)
d3/2 7T
b
The value of Qbi from Eq. ( 83) calculated for the ozone-air system con -
sidered in Table 6 is 1. 34 s- 1.
Gas Exchange in Systems of Multiple Bubbles
As already mentioned, interphase gas exchange can increase considerably
during the process of bubble coalescence, so that in vigorously bubbling
beds the extent of gas-solid contact leading to chemical reaction can be
expected to be greater than would be predicted on the basis of the single-
bubble models discussed in the preceding section. Single-bubble models
are n'.:lvertheless useful in suggesting a basic mechanism of transfer into
which the effects of coalescence may subsequently be incorporated.
There is as yet no convincing theory to account for all the complexities
of bubble coalescence. It is known, however, that the process normally
proceeds by a trailing bubble accelerating into the rear of a leading one
and producing a single bubble whose volume is greater than the sum of
the volumes of the original pair. In a continuation of the study mentioned
earlier, Sit and Grace (1981) investigated the interphase transfer of ozone
during coalescence in a two-dimensional bed. From cine film of the
process, they divided coalescence into four periods:
1. An approach period between the time of bubble formation and the
point of contact of the nose of the trailer with the wake region of
the leader
2. An encroachment period when the .1ose of the trailer passed
through the wake region and touched the lower edge of the leader
3. A period during which coalescence proceeded
4. A postcoalescence period
They found the greatest change in ozone concentration to occur during
the approach and encroachment periods and that 77% of the gas transfer
occurred within the first 50% of the total time span. Furthermore, they
estimated the mass transfer coefficient of the leading bubble to be two to
three times greater during the approach period than when the bubble was
in isolation.
On the basis of these observations, Sit and Grace proposed that during
coalescence the convective through-flow process is increased while the dif-
fusive processes are little affected. They thus proposed applying an empiri-
cal enhancement factor of 1. 8 to the through-flow term in the expression
for Qbi based on the Murray theory [Eq. ( 83)]. However, since from
visual observation 40% of the bubbles are at any instant in the early stages
of coalescence, a more realistic estimate of the enhancement factor was
Fluidized-Bed Reactors 481
suggested to be ( 1. 8 x 0. 4 + 0. 6) = 1. 32, giving the modified expression
for the exchange coefficient:
( 84)
where Ub is the mean velocity of bubbles in the bed and db their mean
diameter. Equation (84) appears to give the best estimate of the inter-
phase transfer coefficient in freely bubbling, three-dimensional beds of
nonabsorbing particles.
REACTOR MODELS
A large number of fluidized-bed reactor models have been described in
the literature during the last three decades, and although most of them
are designed for application to gas-solid catalytic reactions, suitable modifi-
cations for noncatalytic processes are relatively easily incorporated (Kunii
and Levenspiel, 1969). The essential feature of all the models is the
description given of the bed hydrodynamics, and since this involves the
interplay of a number of physical variables, the number of possible permu-
tations and combinations and hence the number of models, is quite large.
Several reviews have been published and these should be referred to for
detailed comparisons (Pyle, 1970; Grace, 1971; Rowe, 1972; Yates, 1975;
Horio and Wen, 1977; van Swaaij, 1978). In general, the starting point
of any model is a consideration of the division of flow between the dense
phase and the lean or bubble phase, and in the majority of cases the two-
phase theory· is assumed to apply (i.e., it is assumed that all gas flowing
into the bed in excess of that required for minimum fluidization passes
through in the form of bubbles). It is then necessary to consider the ex-
tent of conversion in each phase, the amount of transfer between phases
as gas flows through, and finally how the two streams are combined at the
bed surface to give the outlet reactant concentration. In addition to the
events taking place in the bed itself under conditions of steady two-phase
flow , it is necessary for completeness to examine the possiblity of chemical
reaction occurring in both the grid zone, where fresh gas enters the bed
and bubbles are in embryonic form, and in the freeboard region above
the bed surface, where high concentrations of active entrained particles
can be found. We will, however, examine first some of the purely two-
phase models and defer a consideration of the effect of these end zones.
The models to be considered have been chosen to represent three
approaches to the problem of reactor design. The first (Davidson and
Harrison, 1963) models bed performance from first principles and uses the
minimum amount of empirical information. The second (Kunii and Levenspiel,
1969), while based on two-phase theory, imposes an operating condition on
the bed (an artifically controlled bubble size) that enables a relatively
simple solution to be obtained. The third model (due to the Shell company)
incorporates theory with a large amount of empirical information obtained
from pilot plant experiments and is a fairly typical example of industrial
methodology.
482 Rowe and Yates
Model of Davidson and Harrison ( 1963)
This was one of the earliest models to be based on the two-phase theory,
and although its basic assumptions represent an oversimplification of the
physics of fluidization, it has been successfully applied in a number of
cases. The assumptions on which the model is based are as follows:
1. Gas bubbles are evenly distributed throughout the bed and are
of equal size.
2. Reaction occurs only in the dense phase, where gas flowing at U f
is either completely mixed or in plug flow. m
3. Gas is exchanged between the bubble and dense phases by the
convection-diffusion mechanism discussed earlier.
A material balance on reactant A, with initial concentration CAo, leav-
ing the interstitial phase in the case where this is assumed to be completely
mixed gives the concentration, CA·, in terms of three dimensionless param-
1
eters, X the interphase exchange term, S the bubble fraction, and k' the
reaction kinetic term:
( 85)
1 - Se
-x + k'
where
QbiH
X -- ( 86)
ubvb
umf
s 1 -
u
( 87)
and
k' ( 88)
Here H is the expanded bed height, Hmf the height at mm1mum fluidization,
Ub the bubble velocity, Vb the bubble volume, and k a first-order reaction
rate constant. The interphase transfer coefficient Qbi is given by Eq.
( 80) and this leads to an expression for X in terms of the bubble diameter
db:
X =
H
[4. 50 (:mf) + ( 89)
p
For reactions involving mixtures of gases, Davidson and Harrison recom-
mended the use of the methods of Arnold or Hirschfelder (Reid and Sher-
wood, 1958) for the estimation of the gas-phase diffusion coefficients, D.
Fluidized-Bed Reactors 483
A separate mass balance on the bubble phase leads to
( 90)
and the overall outlet concentration of A, CA, is then found by substitut-
ing for CAi and CAb from Eqs. (85) and (90) in
( 91)
giving the overall fraction of reactant unconverted:
Se
-x (1 - Se -x) 2
( 92)
+
1 -- Se
-x + k'
Inspection of Eq. ( 92) shows that for large values of the interphase ex-
change term X, the model, as would be expected, reduces to that of a
CSTR. Furthermore, Eq. (92) predicts that conversion can never be com-
plete even for very fast values of k':
Se
-x
as a result of the bypassing action of bubble gas.
If the dense-phase gas is assumed to be in plug flow, mass balance
equations on both phases lead to the following expression for the fraction
of reactant leaving the bed unconverted:
m2e -m 1H ( 1 -- :tumf)]
( 93)
m 1 and m 2 being found from
2H(l - S)m = (X + k') ± [(X + k 1 ) 2 - 4k'X(l - S)]l/ 2 ( 94)
where m = m1 with the positive sign and m = m2 with the negative sign.
In both forms of the model the variable playing the most important role is
the bubble diameter, db, since it determines, among other things, the ex-
tent of interphase gas transfer. In the earlier publications an average
value of db for the whole bed was estimated from the reaction data of
other workers, but more recently, Darton ( 1979) has proposed a method
whereby the variation in bubble diameter with bed height may be allowed
for. The method is based on a deterministic model of bubble growth by
stagewise coalescence and leads to the following expression for the inter-
phase transfer term:
484 Rowe and Yates
sl/ 2D 1 /2gl /10
X = 32. 0
f
_m_f_ _ _ _ _ __
(U _ U )7/lOAl/5
( 95)
mf 0
In this equation A 0 is the area of distributor plate per orifice and H is
the expanded bed height estimated by iteration from
(4A
-vlm: )3/5] l)( 96)
The use of Eq. (95) in conjunction with the "dense phase completely mixed"
equation ( 92) was shown by Darton to give reasonably good predictions of
the conversions measured by Fryer and Potter ( 1976) using a 0. 229-m-
diameter reactor fitted with a bubble cap distributor with 61 caps, giving
Ao = 675 mm2.
Model of Kunii and Levenspiel ( 1969)
This model is designed specifically for beds that are vigorously bubbling
but not slugging and in which the bubble size is controlled at a uniform
value throughout by the use of internals. As with the foregoin·g model of
Davidson and Harrison, the average bubble diameter is the single most
important parameter since it determines the bubble velocity by Eq. ( 51)
and the extent of interphase gas exchange by Eq. ( 80). Conversion in
the interstitial phase at gas velocities in excess of about 3Umf is considered
to be negligible, the great majority of gas flowing as bubbles. The bubble
gas is assumed to be in plug flow and the fraction of reactant emerging un-
converted at the bed surface is
( 97)
where kf is an effective overall rate constant given by
( 98)
Here kr is the first-order reaction rate constant, Qbc and Qci are the
interphase exchange rates defined in Eqs. (8) (Qbi = Qbc) and (81),
and the y terms represent the ratios of solids dispersed in bubbles, Yb,
clouds, Ye, and interstitial phase, Yi, to the total volume of bubbles
in the bed:
(99)
Fluidized-Bed Reactors 485
fb is the fraction of bed occupied by bubbles, a term also dependent on
bubble diameter:
( 100)
The degree of gas-solid contact, and hence the extent of reaction, depends
strongly on the values of the y terms, and the model in its simplest form
takes Yb = 0 while y c is calculated from
( 101)
where the ratio of bubble volume Vb to wake volume Vw is found from the
empirical correlation of Rowe and Partridge ( 1965). The value of Yi is
found by substitution of Yb and Ye in Eq. (99). The Kunii-Levenspiel
model was found by Chavarie and Grace ( 1975) to show the best agreement
of all the several models they tested against experimental results of the
ozone decomposition reaction in a large two-dimensional fluidized bed, al-
though they found some of its simplifying assumptions to be self-compensat-
ing.
A much more sophisticated treatment of the same basic model has been
developed by Potter and his co-workers who included a consideration of
reaction in the dense phase of the bed and incorporated equations to allow
for the change in bubble size with bed height. Their so-called counter-
current back mixing model has been well reviewed by Potter ( 1978).
Shell Model
The two models discussed earlier although firmly based on the two-phase
theory of fluidization, do incorporate empirical relationships derived from
experiments with laboratory-scale equipment, and this has caused the
validity of their application to large industrial units to be questioned. A
number of different approaches to the modeling of large beds have there-
fore been explored, and although most remain hidden behind the cloak of
industrial secrecy, one such approach has been discussed fairly fully in
the open literature (van Swaaij and Zuiderweg, 1972, 1973; de Vries et al.,
1972). The Shell company, faced with designing of fluidized bed reactor
for their solid-catalysed hydrogen chloride oxidation process, adopted a
combined theoretical and empirical attack on the problem in which data from
a number of beds of increasing diameter were used to obtain scaleup corre-
lations. The theoretical basis was the two-phase theory model of van
Deemter ( 1967), which assumes that:
1. Bubble gas is in plug flow.
2. Gas through-flow in the dense phase is negligible.
3. Gas mixes in the dense phase by a process of eddy diffusion.
As with the Davidson-Harrison model, mass balances on reactant gas flow-
ing into the two phases leads to an equation for the bubble phase:
486 Rowe and Yates
clCAb
+ N (CA CA.) 0 (102)
3 !; a b 1
32
CA
1 b
N (C CA ) + N r CA.1 = 0 (103)
a A. NE 3 !; 2
1 b
Here !; is the dimensionless bed height (h/H), and Na, NE, and Nr are
dimensionless groups defined as follows:
1. The number of interphase transfer units, Na= k' H/U, where k'
is a mass transfer coefficient g g
2. The number of interstitial phase mixing units, NE = UH/fiE where
fi is the volume fraction of bed occupied by interstitial gas and E
is a mixing coefficient
3. The number of reaction units, Nr = k'H /U, where k' is an effective
rate constant for dense phase
The two hydrodynamic groups Na and NE were found from the results of
tracer experiments in beds 0. 3, 0. 6, and 1. 5 m in diameter. Thus from
the residence-time distribution of tracer gas, the following expression for
the height of a transfer unit, Ha, was obtained:
1. 06) ( 3. 5 - 2. 5 ) ( 104)
Ha= ( 1. 8 - Dl/4 Hl/4
Then Na = H /Ha, Equation (104) was predicted to be valid for the micro-
spheroidal catalyst in beds with heights and diameters of up to 10 m. The
term NE was found from values of E measured in experiments with labeled
solid particles in pilot-scale beds up to 3 m in diameter; E is plotted as a
function of bed diameter in Fig. 20, and values of Nr and Na are given
as functions of solids fines content and gas velocity in Table 7. The
dimensions of the full-scale reactor were calculated in the following way.
Bed diameter was found in a straightforward way from known stoichiometry
of the process and a realistic value of the fluidizing gas velocity. An
estimated figure for bed height was put into Eq. (104) and a value of Ha,
and hence Na, calculated. The latter, along with the empirical NE and Nr
terms, were then substituted into the solutions of the two simultaneous
equations (102) and (103) and an overall reactant conversion calculated.
The difference between this calculated conversion and the required value
was then adjusted by choosing a second value of the bed height and re-
peating the calculation. The method, although costly in terms of pilot
plant work was claimed to result in a satisfactory final design.
Model for Reaction in the Distributor Region
As mentioned earlier, there is experimental evidence to show that up to
the point of detachment of a bubble from an orifice in the distributor of a
fluidized bed, the volumetric flow of gas through the orifice is greater
than that leading to the formation of a visible bubble, and furthermore
Fluidized-Bed Reactors 487
E(m%)
2
(SPRAY-DRIED
1.0 (CRACKING SILICA,24'/o
8 CATALYST FINES)
MAY)
6
0.1
8
6
2
•
0 ·010:---~1~-~2--~3---'-4----,'5
D(m)
FIGURE 20 Mixing coefficient as a function of bed diameter. (From
de Vries et al., 1972.)
that equalization of flow is observed only after the bubble has risen some
distance into the bed. The sequence of events is illustrated in Figs. 11
and 12, and the conclusion that is drawn from the visual evidence is that
during the period up to the time of detachment of the bubble, td, the un-
accounted or· invisible gas has passed into the dense phase, causing the
particles to expand to a void fraction E: in excess of Emf. The time td is
clearly related to the frequency of bubble formation n (Hz) by
1
== ( 105)
n
TABLE 7 Empirical Parameters Used in Shell Chlorine Process Model
Conversion
Percent u relative to H Ha
fines (mis) equilibrium (m) Nr Na (m)
20 0.2 95.7 10.0 15 4.0 2.50
17 0.22 95.0 10.4 20 3.5 2.97
12 0.2 93.5 9.7 33 3.0 3.26
7 0.2 91. 0 10.0 34 2.56 3.86
Source: de Vries et al. ( 1972).
488 Rowe and Yates
and during this period the volume of gas entering the dense phase and re-
acting is Qotd(l - xo), where xo is the fraction of flow that forms the
visible bubble. Further, if we assume that the gas entering the dense
phase undergoes a pseudohomogeneous first-order reaction with the particles
at a rate given by
(106)
where ks is the first-order rate constant, the fraction of reactant A re-
maining unconverted after time t is
= exp [ - (1 - c:)k t] ( 107)
s
Now if the time taken for the bubble gas to reach equilibrium (i.e.,
the time for the bubble to form completely) is te and if the mean residence
time of the gas in the expanded dense phase is 0. 5te, then Eq. (107)
becomes
exp[-0. 5(1 - c:)k t J ( 108)
s e
When the bubble has formed completely, the gas it contains will be made
up partly of that which has been in contact with the dense phase and
partly of that which has not, so that at equilibrium the fraction of A re-
maining unreacted inside the bubble will be
CAb QOtdxO + QOtd(l - xO)(CA/CAO)
= ( 109)
CAO Q~d
= x 0 + (1 - x 0) exp[-0. 5(1 - c:)kste]
Assuming that a value of the rate constant ks is available from auxiliary
experiments in, for example, a fixed-bed reactor, the bubble-phase concen-
tration of reactant gas may be calculated once the three remaining parame-
ters xo, c:, and te are known.
In the present work the proportion of incoming gas appearing as a
visible bubble at the orifice (xo = 0. 36) and at a position 25 cm above the
orifice (x25 = O. 79) have been measured, so by a linear extrapolation from
these two values the height at which x = 1. 0, and hence at which the bub-
ble gas has reached equilibrium, may be found. If this height is He, the
time for the bubble to reach equilibrium is clearly
t = (110)
e
so that if the bubble velocity is known, the residence time of gas in the
expanded phase may be calculated. Now the velocity of a bubble in a
Fluidized-Bed Reactors 489
fluidized bed is normally expressed in terms of its diameter, db, by the
Davies-Taylor relationship
( 111)
the observed coefficient of proportionality being unity. As approximately
one-fourth of the volume of the sphere centered on the bubble is occupied
by bubble wake, the volume of gas forming the bubble is
3 rr 3
( 112)
Vb 46 db
Qor
= XO (113)
nb
Hence
db (!f /\~/3 (114)
Ub = (f/ /2(% fl\~16 ( 115)
= 0. 259V~/ 6 ( 116)
and combining Eqs. ( 110) , ( 113), and ( 116), we have
1/6
te = 3.86He(::) ( 117)
The value of the third parameter in Eq. ( 109), the voidage of the
expanded dense phase, s, is at present unknown, but reasonable values
in the range 0. 4 to 0. 7 may be assumed for the purpose of an illustrative
calculation. Combining Eqs. ( 109) and ( 117) , the fraction of reactant A
remaining unreacted in the bubble phase at a height He above the distribu-
tor is
6
CAb x 0 + (1 - x 0) exp [ -1.93(1 -
- C = s)k H (nb)l/
- ] (118)
AO s e QO
Example The value of He calculated from the foregoing measurements
of visible bubble volume at two bed heights (0 and 0.25 m above the
orifice) is 0. 375 m. Other values used in the calculation are as follows:
= 7 Hz
490 Rowe and Yates
= 5xl0- 4 m3 /s
-1
= 1, 5, 10 s
E = 0.4, 0.5, 0.6, 0.7
Table 8 gives the calculated values of CAblCAo at height He above the
distributor and it is clear that, particularly in the case of fast reactions,
the model predicts considerable conversion in the distributor zone.
Reactions in the Freeboard
When bubbles burst at the surface of a fluidized bed, the solid particles
released into the freeboard can cause further reaction to take place with
any gas that has passed through the bed unreacted. Reaction in the free-
board region is not subject to the same constraints as that which occurs
in the bed itself, and it can give rise to severe temperature excursions in
the gas space above the surface, leading to damage of both bed structures
and catalyst particles.
It is well known, for example, that uncontrolled reactions in the free-
board of fluidized-bed phthalic anhydride plants were the cause of con-
siderable problems, as also were afterburning reactions in catalytic cracker
regenerators.
Yates and Rowe ( 1977) developed a simple model of a catalytic reaction
based on the assumption that the freeboard contained perfectly mixed,
equally dispersed particles derived from bubble wakes. The physical form
of the model is illustrated in Fig. 21. Assuming the two-phase theory to
apply to the fluidized bed and the fraction of wake particles ejected above
the surface to be f, the rate of particle ejection is
f(U - umf)A(l - Emf)
( 119)
3
TABLE 8 Calculated Fraction Unconverted Leaving
Distributor Zone
-1 -1 -1
E k
s =1 s ks =5 s k
s = 10 s
0.40 0.876 0.577 0.434
0.50 0.895 0.620 0.466
0.60 0.914 0.672 0.512
0.70 0.934 0.733 0.577
Fluidized-Bed Reactors 491
. t. Volume fx1vsx(1-E:mtl
::/{~wr~of particles entrained
.,-:·,.-,.-.. 1
.,\:/·,-:\-. Volume (1-f) x :3Vsx (1-emt)
~fG~~s~~~ \\\(}:'-returns to bed
bubble ~ -~ Bed surface
·Q.·.
.
. .
Bubble
. . volume,Vs
.
.
. .- .·_ .. ·__ ._· _· .· . :.·_.
:..· -.:Y' :-/-\:.-. .· · travelling
···.·:·,:--··
P~rttcle ~ak~
wrth
· · · . . the bubble,
volume.1.Vs
.... 3 .
Particle of
volume Vp
CAH i
Reactant .
concentration
CA
FIGURE 21 Basis of freeboard reaction model. (From Yates and Rowe,
1977.)
where QB is the volumetric flow rate of bubble gas and A is the bed cross-
sectional area. The total holdup of particles in the freeboard, V, is
(U _
f _ - _umf)A(l
_ _3_ _- _Emf)
__
V = (120)
where Hp is the freeboard height and UT is the particle terminal fall
velocity. The freeboard voidage is then
( 121)
Now if the particles are equally spaced, the volume Vc of the gas cell
surrounding each particle is given by
492 Rowe and Yates
3V
p
V (122)
C
where Vp is the particle volume. The rate of change of concentration of
reactant A within a cell is a function of the particle surface area Ap, the
concentration driving force (CAh - CAp), and a mass transfer coefficient
hM:
(123)
while the rate of change of CA at the particle surface is determined by the
rate of chemical reaction. If the freeboard gas is assumed to be in plug
flow, the equations lead to the following expression for the fraction of re-
actant unconverted at any height h above the bed surface:
j 1
r
C Ah fh
CA, a exp 3(U - UT) [61\,(:P_ 'mf) + ~])
where CAs is the reactant concentration at the bed surface and k is an
assumed first-order reaction rate constant. The corresponding equation
for mixed flow of gas in the freeboard is
1
( 125)
3(U -
The mass transfer coefficient hM may be found from the expression of Rowe
et al. (1965a):
Sh = 2 + O. 69Sc 113 Re~ 12 ( 126)
where the Sherwood number,
= hMdp
Sh ( 127)
D
the Schmidt number,
Sc= ..l!.__ ( 128)
pD
Fluidized-Bed Reactors 493
Fluid Bed Freeboard
10 , - - - - - - ~ - - - - - ~ ~ - - - - -
Entrainment
Froction,f
0.8
- - - Plug Flow
- - - - Complete Mixing
02
00 0.2 04 0.6 0.8 lO 12 14 16 18 20
H
Hr
-1
FIGURE 22 Conversion versus bed height for k = 5 s
and the Reynolds number,
( 129)
The terminal fall velocity may be obtained from graphical correlations be-
tween ReT and the velocity independent group 2dp pg( Ps - Pg) /3µ2
(Kunii and Levenspiel, 1969) , and hence the Sherwood number and hM may
be calculated .from Eqs. ( 128) and ( 129).
Solutions to the equations were obtained for various combinations of the
parameters, and it was shown that under some circumstances a greater level
of conversion can be obtained in the freeboard than in the fluidized bed it-
self (Fig. 22). Experimental support for these conclusions has been pro-
vided by Miyauchi and Furusaki (1974) and Furusaki et al. (1976), who
have also developed theoretical mac.els of the effect.
Conclusions
It would seem from the discussion presented in this section that three zones
need to be considered in the design of a fluidized-bed reactor: First, the
entry zone near the distributor where fresh reactant gas first comes into
contact with bed particles and where bubbles are in the early stages of
development; second, the fluidized bed itself, where in general reaction is
controlled by mass transfer between the bubble and interstitial phases;
and third, the freeboard zone above the bed surface. The necessary de-
sign equations for each zone are quite different and must be examined
thoroughly for the full range of potential operating variables before the
overall performance of a reactor can be predicted with confidence.
NOTATION
c /s area of bed, m2
3
concentration of reactant A, mol/m
494 Rowe and Yates
TI 2 1 2
drag coefficient (single particle) = F / 4 dp 2 pfu
specific heat of gas, J /mol •K
molecular diffusivity, m2 / s
bed diameter, m
particle diameter, µm
volume fraction bubble holdup
drag force on a single particle, N
g acceleration of gravity, m/s 2
h height above distributor, m
hB/w heat transfer coefficient: bed to wall, Wtm 2 •K
2
hG/s heat transfer coefficient: gas to solids, W/m •K
H total bed height above distributor, m
K thermal conductivity, W/m•K
K a constant
KG/s mass transfer coefficient, m / s
m exponent in Eq. (31)
M total mass of bed, kg
M simple mixing index == X /x (Fig. 13)
-1
n bubble frequency crossing horizontal plane, s
n exponent in Eq. ( 45)
-3
N bubble number concentration, m
p absolute pressure, N tm 2
Q volumetric flow rate, m2/s
-1
s particle external surface per unit volume, m
u superficial fluid velocity, m/s
3
VB bubble volume, m
Greek Letters
a velocity ratio (UB /Ui)
/\.p pressure drop across the bed, N tm 2
E bed voidage
µ fluid viscosity, N •s tm 2
3
powder bulk density, kg /m
fluid density, kg /m 3
particle density, kg /m 3
Fluidized-Bed Reactors 495
Special Numbers
Nu Nusselt number (hG/sdp/K)
Pr Prandtl number (CGµ /K)
Re Reynolds number (Ud p /µ)
p
Sc Schmidt number (µ /p D)
Sh Sherwood number (KG /sdp /D)
Subscripts
B bubble
C cloud
D distributor plane
f fluid
F flotsam
G gas
H plane at height h
i interstitial
I isolated
J jetsam
mf minimum fluidization
mb minimum bubbling
s solid (particle)
T terminal falling
W wake
REFERENCES
Bachovchin, D. M., J. M. Beer, and A. F. Sarofim, Elutriation from
fluidized beds, AIChE 72nd Meet., San Francisco (1979).
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496 Rowe and Yates
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8
Coal Gasification Reactors
MORTON M. DENN University of California, Berkeley, California
REUEL SHI NNAR The City College of the City University of New York,
New York, New York
INTRODUCTION
Coal gasification reactors are devices that contact coal with reactive gases,
usually oxygen and steam, to produce gaseous products, generally CO and
hydrogen or methane. Proposed or existing configurations include fluidized
and countercurrent moving (nonfluidized) beds and entrained flow reactors;
product compositions depend on the coal type and the reactor configuration.
The dry ash free composition of a typical eastern United States bituminous
coal is roughly CHo. sOo.1• In excess of 40 wt% of this material will volatilize
with slow heating, yielding a product containing tars, oils, water, methane,
hydrogen, CO, CO2, and other gaseous products. More of the coal may
volatilize with very rapid heating.· The porous residue, or char, consists
mostly of carbon and inorganic ash.
Typical proximate and ultimate analyses of Illinois No. 6 bituminous coal,
an eastern U.S. coal which is used subsequently for illustrative purposes,
are shown in Table 1. The following primary reactions can be expected to
take place between the carbon in the char and the gaseous reactants:
Oxidation:
C+ ½o 2 t CO !aH = -26. 4 (1)
C + o 2 :t CO 2 LiH = -94.2 (2)
Gasification:
C + H 20 t CO + H 2 LiH = +32.2 ( 3)
C + CO 2 t_ 2CO LiH = +41. 4 ( 4)
C + 2H 2 t CH 4 LiH = -20.2 (5)
C Ho -+1 1 LiH = +1.4
+ 2 + 2 CH4 + 2 CO2 ( 6)
499
500 Denn and Shinnar
TABLE 1 Typical Analysis of Illinois No. 6 Coal
Wt %
Proximate
Ash 9.6
Moisture 4.2
Volatile matter 34.2
Fixed carbon 52.0
Wt %
dry ash free basis
Ultimate
C 77.3
H 5.9
N 1.4
s 4.3
0 11.1
In addition, three important gas-phase reactions may take place:
Water- gas shift: H 20 + CO ➔
+- H 2 + CO 2 l\H = -9.2 ( 7)
Methanation 3H 2 + CO ➔
+- H 2o + CH 4 ll H -52.4 (8)
1
Oxidation: H2 +
➔
H 20 L'IH = -58. 6 ( 9)
2 °2 +-
Reactions (7) and (8) can also take place between the same species in the
devolatilization products; in addition, the volatiles are combustible, and the
higher-molecular-weight constituents might crack. The catalytic activity of
the ash, which differs from coal to coal, is likely to affect the rates of
both the heterogeneous and gas-phase reactions.
Many other reactions between the major species might also occur, but
other reactions of possible interest are derivable from this basic set. The
methanation reaction
➔
+- .!.3 CH 4 + ~co
3
is simply the sum of one-third reaction (5) and two-thirds reaction ( 3), for
example. Only four reactions are, in fact, independent for the seven chemi-
cal species made up of three elements, but the remaining five are included
here because of their possible importance. Reactions (1) to (3) and (5) and
(2) to (5) and (7) form useful independent sets.
USES OF MEDI UM-BTU GAS
This chapter is concerned mainly with medium- btu gasifiers, a generic
name for gasifiers in which the gasification medium is a mixture of steam
Coal Gasification Reactors 501
and oxygen. Air- blown gasifiers, which are normally an integrated part
of power plants, will not be treated here. The gas obtained from medium-
btu gasifiers has several uses, each of which requires a different gas com-
position and hence affects design considerations.
Fuel Gas Production
Medium-btu gas is a clean fuel that can directly substitute for natural gas
in existing boilers and many other industrial applications and is also suitable
for combined-cycle power piants. The disadvantage of medium-btu gas for
fuel gas use is that it is expensive to pump over long distances.
For fuel gas uses the major criterion is the lower heating value, which
is approximately proportional to the number of moles of CO + 0. 85H2 +
2. 85CH4 produced per mole of carbon or coal. A high CO content is there-
fore preferable, and the shift reaction (7) is undesirable. (It is still com-
mon practice to use the higher heating value, which is proportional to
CO + H2 + 3CH4, and we shall sometimes follow this practice. Efficiency
based on lower heating value is close in value for coal conversion processes
to the efficiency based on available free energy. )
SNG
Although interest in pure SNG production has presently subsided, it was
the main driving force for many recent developments in gasification tech-
nology. There are two criteria that distinguish SNG production from fuel
gas and syngas gasifiers, based on the fact that the total yield of methane
per mole of coal is proportional to CO + H2 + 4CH4:
1. Maximizing CH4 in the outlet of the gasifier reduces gas cleanup
and• methanation cost.
2. The ratio of H2/CO has to be larger than unity, and higher ratios
are preferable. Otherwise, the gas has to be shifted.
Syngas
CO and H 2 are used in the manufacture of many chemicals. They can also
be converted to transportation fuels, either via a Fischer-Tropsch process
or via methanol and further conversion of methanol by zeolites. For each
use a special H2 /CO ratio is required. In all such cases any methane
formed in the gasifier is a by-product that has to be separated from the
product. This by-product mBthane can either be sold or reformed to
syngas.
The need to separate methane does not necessarily imply that for syn-
gas it is always desirable to minimize methane production. As we will show
later, gasifiers with high thermal efficiency always produce significant
amounts of methane, and eliminating methane production imposes severe
penalties on the design. These penalties therefore have to be weighed
against the cost of separating the methane from the final product. The
penalty is very low in the production of methanol and in some Fischer-
Tropsch processes, but is significant for many chemicals. The separation
penalty also depends on the scale of the plant and the value of the
methane by-product.
In a synfuel plant that is coproducing SNG and liquid fuels, the total
clean fuel has a higher heating value that is proportional to CO + H2 + 4CH4,
502 Denn and Shinnar
and it is interesting that this is almost independent of the fuel consumption
as long as we deal with pure hydrocarbons.
GASIFICATION AND PARTIAL COMBUSTION
It is useful to draw a distinction between gasification and partial combus-
tion, since they correspond to different modes of reactor operation. By
partial combustion we mean a process in which the oxygen supplied to the
gasifier is sufficient to convert all carbon to CO. In that case, the role
of steam in the feed is simply to shift a portion of the product to hydrogen.
In contrast, steam is required for conversion of at least a portion of the
carbon in gasification.
Consider a coal with a composition CHaOb; a is typically O. 8; b is
ty!'_)ically O.1 for an eastern U.S. bituminous coal and O. 2 for a western
U.S. subbituminous coal. Linear combination of the basis reactions (1) to
( 3) and ( 5) leads to the overall equation
SuR - b - 2m)CO
+ (2R + SuR + b + m -l)CO 2 + (suR + i- 2m)H 2 + mCH 4
+ SpRH 2o ( 10)
R is the molar ratio of oxygen in the feed to carbon in the coal. Su + Sp
is the feed steam-to-oxygen ratio; Su denotes steam utilized for gasification
or the shift reaction, while Sp denotes unreacted steam that leaves with
the product gas. m is the molar production rate of methane, either through
reaction or through volatile evolution.
This overall reaction system has an important invariant: the total
molar production of syngas (CO plus H2) plus four times the methane pro-
duction per mole of carbon feed. We denote this invariant by I:
I = (11)
For a given coal (a and b fixed) and essentially complete carbon conversion,
this combination of products is uniquely fixed by the oxygen-to-carbon
feed ratio and is independent of gasifier type. An alternative form when
there is no CO2 in the feed , based only on product gas mole fractions , is
CO + H 2 + 4CH 4
I = (12)
CO + CO 2 + CH 4
This relation must be modified slightly if carbon conversion is not complete
or if the feed contains CO2.
The reactor operates as a partial combuster when Eq. (10) can be
balanced without the need to utilize steam or feed CO2 to effect complete
carbon conversion. For purposes of our discussion here, it is most
Coal Gasification Reactors 503
convenient to neglect methane formation. In that case the criterion for
partial combustion is
1 - b
R ;;,
2
The minimum oxygen rate for partial combustion, which we denote Re, is
then
1 - b
R = (13)
C 2
[We could attempt to be more precise in the definition of Re by accounting
for methane produced by devolatilization and considering the maximum
amount of carbon that could be gasified by devolatilization in the presence
of Hz. To do so would make the discussion dependent on reactor configura-
tion. Equation (13) is conservative in that a reactor that operates as a
partial combuster under this definition is a partial combuster under any
more stringent definition, and it is thus useful for reactor classification.]
We wish to emphasize that the definition of Re is strictly stoichiometric.
If R > Re, we could in principle reach the final composition by first totally
gasifying the coal with oxygen and then reacting the gaseous products with
steam. The fact that in reality the oxygen-coal reaction may lead to CO2
and the coal will later react with CO2 and HzO is not relevant here. The
value of Re will typically be between 0. 40 and 0. 45. The kinetic processes
occurring in the reactor are fundamentally different depending on whether
R is greater or less than Re; in the former case, carbon conversion will
be largely by oxidation, and the steam is simply used to shift the product,
while direct steam (and perhaps CO2) gasification of carbon must occur in
the latter case. Combination of Eqs. (11) and (13) leads to the following
equality, based solely on coal and product gas compositions:
(14)
It is particularly important that pilot studies be carried out in the same
Re - R regime as the planned commercial process, to ensure that scaleup
occurs under comparable kinetic conditions. We shall return to this point
in foe discussion of specific gasifers.
The gross molar heating values of hydrogen and CO are nearly the
same, and approximately one-third that of methane. Thus the gross
product heating value per mole of carbon fed is approximately proportional
to 3m plus the sum of the coefficients of CO and H 2 in Eq. ( 10); we donate
this sum as h:
2(R - R) = I - m ( 15)
C
The significance of methane formation in a reactor for the production of
syngas is illustrated in Eq. (15). I is fixed entirely by the oxygen-to-
carbon ratio. For a given amount of oxygen, production of methane is
detrimental to the heating value of fuel or syngas, and the methane forma-
tion is of value only if it reduces the amount of oxygen required. As we
504 Denn and Shinnar
shall see when we discuss stoichiometry in more detail, formation of
methane significantly reduces oxygen requirements because reaction ( 6)
has a much lower heat of reaction than reaction ( 3).
Finally, as we shall discuss further below, overall efficiency is greatly
affected by the cost of feed steam and oxygen, with 1 mol of oxygen cost-
ing about four times as much as 1 mol of steam. This cost is proportional
to R(4 + Su+ Sp), and economic optimization of a syngas process includes
making this quantity small while making Re - R large. Minimizing R
might be of less importance in the overall optimization than minimizing Sp,
the unused steam appearing in the product. It readily follows from the re-
quirement that CO and CO2 have positive stoichiometric coefficients in Eq.
(10) that the steam requirement for gasification and shift (without methane
formation) is bounded as follows:
2
R c
2(
- (R - R) ,.:; Su ,.:; - R -
R c
1)
R + -
2
(16)
Comparison of the actual feed steam-to-oxygen ratio to the upper bound in
Eq. ( 16) provides a minimum estimate of the excess steam. Excess steam
is required either to moderate temperature or due to inherent thermody-
namic limitations.
CASI Fl ER TYPES
There are four broad classes of reactor configurations: moving (or "fixed")
bed, entrained flow, fluidized bed, and molten bath. The last of these is
fundamentally different from the first three and is not discussed here.
Numerous designs have been proposed within each class, and we will focus
here on generally applicable principles and a few representative designs
that are in or near commercial use. There is a complete compilation of re-
actor descriptions, operating ranges, and operating histories in Nowacki
(1981), and very useful descriptions in Bissett (1978) and the proceedings
of an EPRI conference on synfuels (EPRI, 1981). We focus here on reactor
design principles as applicable to coal gasifiers.
Countercurrent Moving Bed
The prototypical moving-bed gasifier is the Lurgi dry ash pressurized gasi-
fier, as shown schematically in Fig. 1, which was first put into commercial
operation in 1936. The antecedents of this reactor can be traced to non-
pressurized town gas producers that have long been in use. Coal with a
particle size range of about 6 to 30 mm (the reactor cannot accept coal fines
that are formed during grinding) is fed through a lock hopper and moves
under gravity countercurrent to the rising gas stream. Steam and oxygen,
air, or enriched air are fed through the bottom and distributed through the
rotating grate, which is used to remove powdered ash. A similar reactor
configuration developed at the U.S. Department of Energy Morgantown
Energy Technology Center and implemented as well in the General Electric
GEGAS reactor does not have a water-cooled wall but does have a stirrer
that can be moved through the coal bed. A typical effluent composition
from gasification of Illinois No. 6 bituminous coal with steam and oxygen in
a Lurgi reactor is shown in Table 2. Illinois No. 6 is a low reactivity,
Coal Gasification Reactors 505
♦ Feed Coo I
Cool Lock
Tor
Distributor ~
Gos
G role
Grote
Drive
FIGURE 1 Schematic of dry ash Lurgi pressurized gasifier.
TABLE 2 Effluent Composition for Oxygen-Blown Pressurized
Gasification of Illinois No. 6 Coal
Dry ash Lurgi Texaco
(Woodall-Duckham Ltd., 1974) (McDaniel, 1981)
H2 39.1 37. 5
co 17 .3 39.5
CO 2 31.2 21. 5
CH 4 9.4
C2H6 0.7
HS+
s
cos 1.1 1.1
Inert 1.2 0.4
506 Denn and Shinnar
caking coal, and the choice of this particular example is for comparative
purposes only. The current applications of this type of gasifier, such as
at SASOL, are limited to reactive, noncaking coals, although successful
gasification of caking coals has been reported in stirrer-equipped reactors.
The moving- bed gasifier can be conceived as operating as shown in
Fig. 2. The coal first contacts hot product gases and is dried. The
volatiles are then driven off by relatively slow heating. Next, the char
contacts a hot, oxygen-free gas, enabling the endothermic gasification re-
actions ( 3) and ( 4) to occur. Finally, the remaining char enters a region
of oxygen-rich gas, allowing combustion to take place.
There are two important consequences of this reactor configuration.
First, the volatiles are released in such a way that they cannot react with
oxygen. Thus the methane, CO, and hydrogen from the volatiles appears
in the product gas, as does the tar. The condensible liquids are generally
cool product
gos
Drying Zone
(moisture driven off}
En dot herm ic
Devolotilizotion Zone
( cool gos, tor, and)
oil driven off
Thermally Neutral
Gasification Zone
GI (Ii t t I e or no oxygen }
~ Endothermic
N
C
-
0
u
0
GI
0:: Combustion Zone
(oxygen rich gos}
Exothermic
ash
' steam
+ +
unreoc ted air or
carbon oxygen
FIGURE 2 Schematic of moving-bed gasifier.
Coal Gasification Reactors 507
undesirable in the product gas and must be separated by quenching.
(The wastewater treatment can be quite expensive, particularly in a small
installation. In larger installations the tars could in principle be recovered
as a valuable byproduct. One of the most important challenges in gasifica-
tion research is to overcome this problem and devolatilize the coal without
tar formation. This might be done by decomposing the tar in a catalytic
reactor before condensing the steam.) Devolatilization is the primary
source of methane in this reactor, since direct methanation of char is rela-
tively slow, although some product methane undoubtedly comes from one or
more of the methane-forming reactions. Second, good control of the maxi-
mum temperature in the bed is essential to ensure that the inorganic ash
remains in a dry state for removal by the grate and does not become sticky
and agglomerate. The ash softening temperature is approximately 1200°C
(but highly dependent on coal type), and large amounts of excess steam
(typically 7 mol of steam per mole of oxygen) are required to keep the
temperature in the combustion region below this value. The excess steam
is the primary reason for the relative thermal inefficiency of this type of
gasifier. The excess steam requirement for high-reactivity coals is less
than for low-reactivity coals, which partly explains why the gasifier is
used mainly for the former. The data in Tables 1 and 2 lead to a value of
Re - R of 0.13 for the Lurgi with eastern coal (and a higher value if
methane formation is included in the definition of Re); thus this reactor
clearly operates in the gasification regime.
The excess steam can be reduced in principle if the grate is replaced
with a hearth and the steam-to-oxygen ratio is reduced to a level that al-
lows the maximum temperature in the combustion region to rise above the
point at which ash is a freely running liquid; this temperature is typically
about 1450°C but is highly dependent on coal type and fluxing agent. A
schematic of the British Gas Corporation/Lurgi slagging gasifier is shown
in Fig. 3. This system has not yet been commercialized. Reported data
(Scott, 1981) for the slagger for gasification of a Pittsburg No. 8 bitumin-
ous coal with a molar steam-to-oxygen ratio of between 1.1 and 1. 2 show
considerably more CO and less hydrogen than in the dry ash Lurgi at
nearly the same pressure (Woodall-Duckham Ltd., 1974), and little COz.
This is to be expected from the equilibrium of the water-gas shift reaction
(7), in view of the substantially reduced steam content. Less methane was
produced in the slagger. The slagger has a value of Re -- R that is close
to zero, but slightly in the gasification regime. The moving beds are the
only reactors in commercial or near-commercial operation that are true
gasifiers in the sense defined above (Re - R > 0) .
Entrained Flow Reactor
Entrained flow reactors are devices in which coal particles that are typically
about 100 µm in diameter are fed cocurrently with the steam and the oxidant.
The coal may be transported either in a gas stream or in a water slurry;
in the latter case the suspending water provides the steam for gasification.
Bissett (1978) has provided a comprehensive review of the characteristics
of entrained flow reactors.
Two entrained flow gasifiers have reached major commercial status. The
Koppers-Totzek atmospheric reactor, shown schematically in Fig. 4, was
first put into operation in 1952. The coal is fed through opposing jets.
The steam-to-oxygen ratio is less than unity, and the combustion zone is
508 Denn and Shinnar
Cool Lock
Cool Distributor Drive '--..
- - - - Dusty tor recycle
,~---Steam
t-Wosh Cool"
Cool Distributor
and Stirrer
Ceramic Lining _ _ ___,
(-Gas
Water Jacket - - - -
Gosif icotion Medium
Tuyere - - - • - Steam and Oxygen
- - - - - Quench Water
Slog Lock-----
FIGURE 3 Schematic of slagging pressurized gasifier.
above the slagging temperature. A pressurized gasifier of this type is
under development by Shell and Koppers.
The Texaco pressurized gasification reactor, shown schematically in Fig.
5, is a modification of an established reactor for the partial combustion of
crude oil residual. The first major commercial installations were under way
at the end of 1982, although Bissett (1978) gives a detailed description of
a semicommercial-scale Texaco gasifier that operated from 1956 to 1958.
The coal is fed in a water slurry, which has been reported to contain up
to 70% solids by weight. The result is a steam-to-oxygen ratio of close to
unity, and the ash slags. Pilot plant data for gasification of Illinois No. 6
coal are shown in Table 2. These data illustrate the fundamental difference
between the Texaco and Lurgi gasifiers. The value of Re - R for the
Texaco gasifier is -0. 09, and the reactor operates as a partial combustor.
[The same result is obtained for the data of Dillingham et al. (1982). In
both cases the value of R computed from Eqs. (11) and (12) is 0. 52, indi-
cating excellent carbon material balance closure.] The Koppers-Totzek and
Shell- Koppers gasifiers both also operate with slightly negative values of
Re - R, based on data compiled in Shinnar and Kuo (1978).
Devolatilization takes place in these entrained flow reactors in a region
that is oxygen-rich. Thus combustion of the volatiles .occurs, and there is
Coal Gasification Reactors 509
-
H.P.
Gas Steam Orum
Outlet
Steam-
Boiler -
L. P. 1--~----.--n:
Steam
Drum
Coo I Feed (111'~!!:=:!;::====!==!~~
Screw
t
Oxygen
Boiler Feed
Water
Quench
Tonk
FIGURE 4 Schematic of Koppers-Totzek reactor.
Cool-Water Slurry
- Synthesis Gas
Generator
Refractory Lining
- Water In
Water Quench
Section Slurry Out
FIGURE 5 Schematic of Texaco pressurized gasifier.
510 Denn and Shinnar
little or no methane or condensible liquid in the product gas. The gas
need not be quenched prior to heat exchange. An entrained flow reactor
configuration that causes devolatilization to occur after combustion, and
hence maximizes methane production, is embodied in the design of the high-
pressure Bi-Gas reactor, but it has never been successfully carried beyond
the pilot stage.
Fluidized Bed
No pressurized fluidized-bed gasifier is as well developed as the examples
cited above of other gasifier configurations, and it is therfore appropriate
to discuss here some of the problems faced in the design and scaleup of a
fluid-bed gasifier.
The only economically available fluid-bed gasifier is the atmospheric
pressure Winkler, which was developed in the 1920s for German Braunkohle.
The reactor operates only with very reactive coals, and carbon conversion
is limited to 90%. Typical effluent data are shown in Table 3. Ruhr
Chemie has developed a pressurized version that will operate at 30 atm,
and a demonstration plant is planned. The published estimates claim that
overall performance characteristics will be identical to the old Winkler, but
with 95% carbon conversion.
A fluidized bed can in principle be staged, and it therefore has a po-
tential advantage over a true countercurrent reactor. Conditions in the
devolatilization zone can be adjusted independently of those in the reaction
zone in order to crack tars and maximize methane production; the tempera-
ture profile in a countercurrent reactor cannot be controlled, and the
residence time in the devolatilization zone is quite short. There are also
several inherent disadvantages relative to a reactor like the slagger. One
is that the gasification zone temperature is limited by the need to prevent
agglomeration. No good data exist on the maximum permissible temperature.
The second is that a significant amount of carbon must be maintained in
the gasification zone in order to achieve reasonable reaction rates. If this
TABLE 3 Effluent Data for Oxygen-Blown
Gasification of German Braukohle in a
Winkler Gasifier at 2 atm and 1700°C
H2 38.44
co 33.36
CO 2 21.4
CH 4 1.8
R = O2 /C 0. 96
Steam/O 2 1. 52
Cold gas efficiency 74. 7
Net efficiency 56.8
Coal Gasification Reactors 511
zone is mixed, the ash leaving the reactor will contain excess carbon; this
is the reason for the limited conversion in the Winkler.
There are two further problems that affect the Winkler and all other
fluid-bed gasifiers under development:
1. Some of the partially converted coal disintegrates into fines. Fines
are difficult to convert, as shown in Chapter 5, and they are swept from
the gasifier and tend to adhere to the wall of the cyclone. If fed back to
the bed, buildup of fines could reduce the bed density. Reducing the load
on the cyclone requires a low bed velocity that is high enough to prevent
ash agglomeration. This problem is solved in the Winkler by adding oxygen
near the top of the bed, raising the temperature of the dilute phase and
preferentially combusting the fines. (There are no detailed data to indicate
if the fines really combust, or if the combustion is in the gas phase and
the fines convert because the increased temperature.) The net result is
that the Winkler operates as a partial combuster, with R < Re.
2. The combustion reaction near the oxygen inlet is much faster than
can be dissipated either by the gasification reaction or by the mixing of
the fluid bed. The method used to date to overcome this fast reaction and
prevent agglomeration and high temperatures is to dilute the oxygen with
either steam or cold recycle gas to act as a heat sink. The Higas and Syn-
thane reactors developed in the United States required as much steam as a
diluent as the dry ash Lurgi, eliminating most potential economic advantage.
An alternative way to overcome the problem is to increase the mixing in-
tensity near the nozzle.
Recent American development work has concentrated on two pilot plants,
the UGas gasifier of IGT and the Westinghouse fluid-bed reactor. Both are
currently conceived as single-stage gasifiers (e.g., Schwartz et al., 1982)
in that the coal is fed directly to the fluid bed and there is no separate
zone for devolatilization. They therefore produce less methane than a gasi-
fier designed to have a separate devolatilization zone with independent
temperature control, although not all of the methane formed by devolatiliza-
tion is reformed. The major achievement of these programs has been the
development of an ash agglomerating zone at the bottom of the gasifier. The
ash agglomerates grow much larger than coal particles and hence separate
out at the bottom of the bed and can be removed selectively. A high
fluidization velocity is required to prevent agglomeration of the coal parti-
cles, especially in caking coals; this permits a reasonably high coal concen-
tration to be maintained in the bed, while removing ash at the bottom having
a much lower carbon content.
Both the UGas and Westinghouse reactors have demonstrated the feasibil-
ity of ash agglomeration and segregation. The Westinghouse has operated
thus far with coal conversions below 90%, and usually below 85%, mainly
because of carbon loss due to imperfect fines recovery. The Westinghouse
has also operated with large heat losses, both because of nonadiabatic
operation and heat losses in the fines recycle. Pilot data for R - Re are
therefore quite negative (-0. 2), although Westinghouse claims that the com-
mercial gasifier is projected to operate with a positive value of R - Re
comparable to that of the dry ash Lurgi. The UGas has operated until now
only at low pressure (ca. 3 atm), but claims to have achieved 95% coal con-
version. Results of both gasifiers were significantly better for reactive
coals than for bituminous coals, as would be expected from simple kinetic
considerations.
512 Denn and Shinnar
STOICHIOMETRIC ANALYSIS
Some useful principles regarding gasifier operation can be obtained by
examining overall stoichiometric constraints and energy balances under
idealized conditions. We will consider only the gasification of char, which
is taken as consisting entirely of carbon. Any effect of the presence of
volatiles can be added afterward in this analysis.
Reactions of char to form methane in the absence of a suitable catalyst
are generally much slower kinetically than combustion or steam and CO2
gasification. It therefore suffices in the first approximation to neglect any
methanation and to remove reaction (5) from the set of reactions under con-
sideration. Reactions ( 1) to ( 3) then form a basis from which to construct
all other reactions to form CO, CO 2 , and hydrogen from carbon, water,
and oxygen.
The three species fed to the reactor are conveniently represented in
Fig. 6 as the vertices of a triangular diagram on which each point repre-
sents the mole fraction of reactants. The feed compositions for reactions
(1) to (3) are shown on the axes. It is readily established that incomplete
carbon conversion will occur for starting compositions that lie above the line
connecting C + (1/2)02 and C + H 2o, while incomplete oxygen conversion
will occur for compositions below the line connecting C + 02 to the H20
vertex. A gasifier would operate ideally with no excess steam. It can be
shown by linear combination of the basis reactions [ twice ( 3) plus ( 2) minus
twice ( 1)] that steam must appear in the effluent for starting compositions
that lie below the line connecting C + o 2 with the reaction
LiH == +23.0 ( 17)
FIGURE 6 Triangular diagram for reactor feed conditions.
Coal Gasification Reactors 513
[Some steam will, of course, appear in the effluent for starting formulations
above this line, since the analysis assumes complete conversion and neglects
any possible chemical equilibria, including that of the water-gas shift re-
action (7).] The shaded trapezium area thus represents the most desirable
area for gasifier operation.
The operating range can be further restricted by the condition of auto-
thermal operation (overall thermal neutrality): the exothermic reactions
must produce just sufficient reaction enthalpy to drive the endothermic re-
actions (assuming that an external heating source, such as a nuclear re-
actor, is not to be used). We suppose that the inlet and outlet streams for
char gasification are at the same temperature, which we will take to be 700°C
for this discussion. Let X 1, X 2, and 1 - X 1 - X 2 represent the fractional
conversion of carbon through each of the basis reactions ( 1), ( 2), and ( 3),
respectively. Thermal neutrality is then represented by
(-26.4)X 1 + (-94.2)X 2 + (+32.2)(1 - x1 - X 2) = 0
and the thermal efficiency based on the lower heating value (LHV) of the
feed char at 700°F will be 100%. The overall reaction for thermal neutrality
is the one-parameter family
C + (0.255 + 0.036X 1)o 2 + (0.745 0,536X 1)H 20 +
(0.745 + 0.464X 1)CO + (0.255 0,464X 1)c0 2 + (0.795 - 0.536X 1)H 2
or, in terms of the basis reactions,
(0.255 0.464X 1)(C + o2 + CO 2)
(0.745 0, 536X 1}(C + H 20 + CO + H 2)
This reaction family lies along line AB in Fig. 6. Point A corresponds to
Xi= 0.55, with reactions (1) and (3) in the following proportions:
O. 82C + O. 82H 20 + 0.82CO + 0.82H 2
x 1 cannot exceed 0. 55, or else CO2 will be required as a feed. Point B
corresponds to X1 = -1.61 and represents the minimum value for which it
is possible in principle to produce a product gas without steam. It is most
convenient to express point B in terms of reactions ( 2) and ( 17) as
C + o2 + CO 2
4.09C + 8.17H 20 + 0.82CO + 0.82H 2
514 Denn and Shinnar
Values of X 1 below - 1. 61 would require CO as a feed in this simplified
analysis. The H2/CO ratio in the product gas varies from 0.45 at point A
to infinity (no CO) at point B. Conversely, point A has no CO2 in the
product, while the H2/CO2 ratio at point B is 2.
This simple stoichiometric analysis, which neglects all kinetic and
equilibrium limitations, is generally instructive but is misleading in one
important regard: the thermal efficiency of all points along line AB based
on the lower heating value at 700°F is the same. A more realistic picture
is obtained by accounting for the energy required to product the feed
steam and oxygen at the assumed pressure of 400 psi. It can be shown
(Shinnar and Kuo, 1978) that production of 1 mol of oxygen at 700°F and
400 psi requires the same energy as 4.1 mol of steam at the same conditions.
The overall reactions at points A and B are, respectively,
A: C + 0.27502 + 0.45H 2o + CO+ 0.45H 2
B: C + 0.1950 2 + 1.61H 2O +CO 2 + 1.16H 2
Point A requires the energy equivalent of 1. 58 mol of steam to convert one
mol of carbon, while point B requires the equivalent of 2. 41 mol of steam.
There is thus a net energy loss equal to the production of 0. 83 mol of
steam in passing from point A to point B, which is equivalent to 9% based
on the lower heating value of reactants. When the energy required to pre-
pare steam and oxygen is taken into account, the efficiencies .for the idealized
processes at points A and B drop to 81% and 72%, respectively. Line AB
can be parameterized by the feed steam-to-oxygen ratio; the computed ef-
ficiency as a function of steam-to-oxygen ratio for autothermal operation is
shown in Fig. 7.
An equivalent analysis can be carried out by assuming that methanation
will take place and that the reaction products are only CO, CO2, and CH4.
This limit is unrealistic in the absence of the appropriate catalysts, but helps
in defining the performance that might be obtained. Combinations of the
100 e--,----,-----,--,----~•---,
A: I B
l
'- ......._ Loss due to steom feed
>,
0
C:
90
'--------J
r--- --- --- --- --•
Q)
·;:;
A
w 80 Loss due to oxygen B
0
+ feed
E
~
Q)
..c:
I- 70 B
60
0 2 4 6 8 10
Steam/Oxygen (Molar)
FIGURE 7 Efficiency as a function of molar steam-to-oxygen ratio. (From
Shinnar and Kuo, 1978.)
TABLE 4 Thermal Efficiency of Limiting Cases in Char Gasifiers with Stoichiometric and Energy Constraintsa
Point A Point B Point E Point F
Overall reaction C + 0. 2750 2 + O. 45H 2o -+ C + 0.1950 2 + 1.61H 2O-+ C + 0. 0150 2 + O. 985H 2O -+ C + 0.180 2 + 0. 428H 2O -+
CO + 0.45H 2 CO 2 + 1.61H 2 0. 4925CH 4 + 0. 5075CO 2 0. 213CH 4 + 0. 788CO
Steam-to-oxygen ratio 1.6 8.2 64.5 2.4
Steam requirements 47.8 170.9 104.7 45.4
[lb /MMBtu (LHV)
gas]
Steam (MBtu/lb mol 9.2 32.7 20.0 8.7
carbon)
Oxygen requirements 611 ( 190) 411 (124) 35 ( 10) 405 (126)
[scf/MMBtu gas
( scf / mscf)]
Oxygen (MBtu/lb mol 23.0 14. 9 1. 3 15.0
carbon)
Thermal efficiency 81 72 87 86
aConditions: feed and outlet temperature, 700°F; no heat recovery from products below 7000F; Btu requirements of feeds, 220
Btu/scf oxygen, 1130 Btu/lb steam, both at 700°F and 400 psia.
Source: Shinnar and Kuo ( 1978).
516 Denn and Shinnar
FIGURE 8 Region of autothermal operation with methane formation.
two limiting analysis leads to the operating diagram shown in Fig. 8. The
quadrilateral ABEF bounds the autothermal region and lies within the region
of possible complete utilization of carbon and steam. The characteristics of
the corner points are summarized in Table 4. If methanation could be car-
ried out within the gasifier, it is clear that operation should be along line
EF. Kinetic constraints, to be discussed subsequently, currently preclude
this option, however. Thus it is clear that the desirable region for opera-
tion of a gasification reactor is close to point A.
The assumption in this analysis that all reactions go to completion is
not as restrictive as it might appear. The oxygen and steam utilized to con-
vert carbon must satisfy the constraints outlined here, which thus define
upper bounds on efficiency. Equilibrium, kinetic, and transport limitations
provide information regarding excess steam. Oxygen utilization will always
be essentially complete.
THERMODYNAMIC AND PROCESS CONSTRAINTS
The net efficiency of a gasification process depends strongly on the energy
required to prepare the feed, which is approximately proportional to the
moles of steam plus 4.1 times the moles of oxygen (Shinnar and Kuo, 1978).
The ratio of irrecoverable energy used in preparing the feed to the lower
heating value of the product gas is therefore a useful measure of gasifier
efficiency; we denote this ratio as EL:
(18)
CO+ 0.85H 2 + 2.85CH 4
The lower EL, the higher the net efficiency. (For an SNG plant we would
replace the denominator with CO + H 2 + 4CH 4 .) Points E and F in Table 4
Coal Gasification Reactors 517
are clearly superior to points A and B in having lower values of EL, but
there are several reasons why this stoichiometric limit cannot be approached.
The first is a process constraint. The calculations in Table 4 assume
that product gas can be heat exchanged with the feeds and only consider
the heat requirements of chemical reactions. The actual heat requirements
are greater. Gasification requires high temperatures (>1500°F) without a
catalyst. It is impractical to heat exchange a high-temperature product
stream, for two reasons:
1. Heat transfer at high pressure from streams containing H 2S is
limited by material constraints to temperatures below 1100°F.
2. Gasifier product streams often contain tars and solids which will
coke and cover heat exchanger surfaces.
In present commercial gasifiers the only way in which heat is fed back
from the product gas to the gasifier feed is by countercurrent gasifiers.
This exchange recovers a large fraction of the sensible heat of the product
gases and hence gives an inherent advantage to countercurrent gasifiers,
since they require less heat to be supplied to the gasification zone and
therefore less oxygen. In a cocurrent or well-mixed single-stage gasifier
the only way in which the sensible heat of the product gases can be re-
covered is a process steam. Since the steam can also be produced directly
from a combustion of coal, we suffer the penalty incurred in separating the
incremental oxygen that is required to supply the heat to raise the product
to gasifier temperature.
The second reason that points E and F are inaccessible with current
gasifiers is the thermodynamic consequence of the kinetic rates of the dif-
ferent gasification reactions. These points require methane formation by
reaction ( 6), where no H 2 is produced. Reactions ( 3), ( 4), and ( 8) are
all faster thah reaction ( 6) at normal gasification conditions, and reaction
( 7) is generally much faster than all the others. Thus, while the equilibri-
um conversion of reaction (6) is high at high temperatures, the other
product gases will also be present in the reactor and the global equilibrium
must be taken into account. Methane yield at global equilibrium is low at
temperatures above 1100°F, except at very high pressures (Shinnar et al.,
1982). At low temperatures, where methane is the dominant product, steam
conversion is approximately 50%, and the increased steam requirement re-
moves any advantage over point A (at least for fuel gas).
It is important to emphasize that the inability to obtain a high methane
yield at high temperatures is not a rigorous thermodynamic constraint but
is a consequence of the fact that the primary gasification reaction is
C + H2O + CO + H2. Methane is formed mainly by consecutive processes
involving reactions ( 5) and ( 8); in neither case could the product exceed
the equilibrium composition. If, on the other hand, one could find a
catalyst that promoted reaction (6) or some other reaction (e.g., 1.5C +
H2O + 0. 5CH4 + CO) via a surface mechanism that does not first require
formation of molecular hydrogen, there is no thermodynamic reason why
methane yield consistent with the equilibrium yields of these latter reactions
could not be approached. Present catalysts, such as potassium carbonate,
do not allow this, at least not as presently applied, and very high pressure
operation would only present means of obtaining a high methane yield with
high steam conversion.
EL is shown as a function of temperature i.n Figs. 9 and 10 under
equilibrium conditions for an eastern and western U.S. coal, respectively,
518 Denn and Shinnar
T (Kl
IOOO 1200 1400 1600 1800
3.00-......----,-----,,-----,----,---,
\ O Dry Ash Lurgi
\ 0 x Slagger
\ + Texaco
\ A Shell - Koppers
'<I" \ \ A
\.\ \
I D Koppers -Totzek
u
cf~ 2.00
N .\ D
<i +
+
0
I "'
I()
~,\ \ \
+
"' 00
0 C \, '-, A
1-----:'·--.;:..:.::..=::.::::.=-------:i
..
I
+ 1.00 - · - · - . - . ~ - - - -
0
u D --:.::::::-.-:.:_--.-
_ _ _ _x_
...J
w
0 L-.-.....1.--....L..--..I----''------'----'
1200 1800 2400 3000
T (°F)
FIGURE 9 EL as a function of gasifier temperature for an eastern U.S.
coal. A, well-mixed reactor, no methane formation; B, countercurrent
reactor, no methane formation; C, well-mixed reactor, methane at global
equilibrium; D, countercurrent reactor, methane at global equilibrium.
T (Kl
I000 1200 1400 1600 1800
3.00 ..;.::.;:..:...._..:...,.:_ ___,,-----,----,---,
\
\
...---.. \ 0 Winkler
'<I" \A x Dry Ash Lurgi
I + Shel I - Koppers
0
"'U \
0
I()
2.00 '. \
\
00
<i N \
+ + '8 \ X
o"'~ ' \.
''
I ICl
00
ci '
+ '"-. C -._
0
u
..____.. 1.00 - - - ',
o·-.::::::::_.,~-~-----
...J
w
0 L.__ _J__ _..J.__ __jl...----'-----'-----'
1200 1800 2400 3000
T (°F)
FIGURE 10 EL as a function of gasifier temperature for a Western U.S.
coal. Symbols as in Figure 9.
Coal Gasification Reactors 519
at 400 psi with steam and oxygen fed at 1100°F and coal at ambient tempera-
ture. There are four calculations: the reactor is assumed to be either
well mixed or countercurrent, and methane is either formed and is at the
global equilibrium composition or is not formed at all. Gases formed during
devolatilization in the countercurrent gasifier do not affect the equilibrium,
while in the well -mixed or cocurrent gasifier they reduce the maximum
steam conversion. There appears to be a broad minimum in all cases around
200°F, corresponding to optimal thermal efficiency for fuel gas. The
presence or absence of methane has little effect on the location of the mini-
mum, nor does the gasifier configuration. EL increases at lower tempera-
tures, but the increase is much less steep for the cases with methane pro-
duction. If one had to operate at lower temperatures for process reasons,
methane formation would be essential for high efficiency.
The actual values of EL for several gasifiers operating on eastern coal
are also plotted in Fig. 9. We note that the slagger approaches to theoreti-
cal minimum quite closely. (The devolatilization compositions used for the
countercurrent calculations were derived from data on the slagger, so the
countercurrent reactor curve must pass near the slagger point. This has
no bearing on the discussion of relative reactor efficiencies.) The Texaco
gasifier, by contrast, lies well above the thermodynamic equilibrium line,
in part because the reactor uses a water slurry as a feed and requires
excess oxygen to supply heat for vaporization. The Shell- Koppers and
Koppers-Totzek cocurrent gasifiers, which use steam instead of water, also
lie above the optimum; the short residence time apparently precludes attain-
ment of equilibrium. EL for the dry ash Lurgi is also very large, despite
the fact that it is countercurrent. This reactor is not suitable for eastern
U.S. coal because of the high steam-to-oxygen ratio required to keep the
ash below the fusion temperature.
As shown in Fig. 10, the dry ash Lurgi performs much better on
western coal~ where the more rapid endothermic gasification reactions aid
in moderating the temperature and reduce the excess steam requirement.
There are no data available for the slagging moving bed, and none of the
commercial or semicommercial reactors have achieved results as good as
those of the slagger for eastern coal. The Texaco gasifier is not suitable
for these coals at present because the heating value is too low to permit
efficient slurrying with water.
Calculations of R under the same four assumptions are shown in Figs.
11 and 12 for eastern and western coals, respectively, together with Re
and data for the same gasifiers. R never reaches Re for any of the calcu-
lations, regardless of CH4 formation, and there is no optimum near the mini-
mum of EL. The minimum of EL is a consequence of the fact that R increases
with temperature, whereas steam requirements decrease. R is approximately
equal to Re for the Texaco, Shell-Koppers, Koppers-Totzek, and Winkler
gasifiers. The reason for this high value of R is kinetic and is not a
thermodynamic constraint; these reactors use oxygen for partial combustion
because steam gasification is too slow under their process conditions. This
is easiest to see for the Texaco and rather puzzling for the fluid bed, but
we lack any reliable data to explain the latter. R is close to the equilibrium
limit for the slagger and is still low for the dry ash Lurgi; the moving beds
are therefore the only gasifiers that operate presently at true gasification
conditions, and the slagger is the only gasifier that operates close to the
thermodynamic optimum .
520 Denn and Shinnar
T (Kl
1000 1200 1400 1600 1800
□
0.40
~ 0.30
(\J
0
O Dry Ash Lurgi
x Slagger
+ Texaco
tc. Shell-Koppers
□ Koppers-Totzek
QL-_ _J__ _..L.__ _L___-L.._ _..L__ ___,l
1200 1800 2400 3000
T (°F)
FIGURE 11 R as a function of gasifier temperature for an eastern U.S.
coal. Symbols as in Fig. 9.
T (K)
0.50 1000 1200 1400 1600 1800
0
+
0 0.30 /
/
---- --
'
0
(\J
~--c---::::=-:~~----
a:: 0. 20
_/o
- - - /X/ ----·
o Winkler
x Dry Ash Lurgi
0.10 / + Shel I - Koppers
/
0 l.-_ __j_ _-1..._ _.,L___ _.L.,_._ ___,l_ __ ,
1200 1800 2400 3000
T (°F)
FIGURE 12 R as a function of gasifier temperature for a western U.S.
coal. Symbols as in Fig. 9.
Coal Gasification Reactors 521
It is important to note that methane formation by itself is not always
beneficial, but depends on where it occurs. If methane is formed in the
gasification zone it reduces the heat requirement, and therefore R, and
also improves steam conversion. If it is formed in the low-temperature
zone of a countercurrent gasifier, the value depends on the mechanism.
Methane formation by devolatilization or by reaction of H2 and steam with
tar and coal are beneficial, since they reduce the char feed to the gasifier.
The heating value of methane formed from these reactions is larger than
the heating value of the hydrogen formed in the gasification zone (Shinnar
et al., 1982). On the other hand, the impact is negative if methane is
formed by reaction of CO or CO2 with H2, since the reaction is highly exo-
thermic and the heat of reaction is not fed back to the gasification zone.
The heating value of the methane formed in this way is lower than that of
the syngas reacted. Such methane formation can occur in the lower tem-
perature zone since fresh iron oxide and other ash constituents are methana-
tion catalysts which are later poisoned by the HzS. This problem also
causes difficulties in the evaluation of pilot plant results. Steel and stain-
less steel catalyze methanation as well as shift, and can therefore lead to
outlet compositions which contain more CH4 and Hz than would be obtained
in a commercial gasifier where surface effects are much smaller.
KINETICS-FREE CALCULATIONS
It is often possible to estimate reactor performance by the use of kinetics-
free calculations; such calculations assume that key reactions occur in-
finitely fast, and hence go to completion or to thermodynamic equilibrium,
or that they do not occur at all. (Assumptions are thus made both about
relative kinetic rates and about residence times, so such calculations are
only apparently free of kinetics.) The procedure is the same for all re-
actor types, but the detailed calculations differ slightly depending on
whether or not the volatiles are released in an oxygen-rich environment.
Thus it is convenient to consider co- and countercurrent reactors separately
for illustrative purposes.
Countercurrent Moving Bed
Consider the moving-bed reactor, shown schematically in Figs. 1 to 3. We
will focus on the reaction zone, below the regions where devolatilization and
drying take place. Direct hydrogenation to form methane is usually slow
and will initially be neglected in this elementary analysis. Oxygen reactivity
is assumed to be infinitely fast, and oxygen attack on the fixed carbon is
irreversible and is completed before any other reaction begins. Steam
gasification, reaction ( 3), is taken to be sufficiently fast to reach equilibri-
um or completion at the top of the reaction zone. The water-gas shift,
reaction ( 7), is taken to be instantaneous and always at equilibrium. Reac-
tions ( 1), ( 3) , and ( 7) form a fundamental set for overall balances without
methanation, and are therefore the only reactions that need be considered.
Two general types of behavior can exist, depending on relative feed
rates. If the coal feed rate is too large to utilize all the steam, reactions
(3) and (7) [and hence also reaction (4)] will be in equilibrium at the top
of the reaction zone and there will be unreacted carbon in the ash at the
bottom of the reactor. Reduction in the carbon feed rate relative to steam
522 Denn and Shinnar
will lead to reduced amounts of carbon in the ash, while maintaining the
equilibria at the top. The carbon in the ash will reach zero at a critical
carbon rate. At carbon feed rates below this critical value there will be
an excess of steam and the carbon-steam reaction can no longer be at
equilibrium at the top of the gasification zone, although the equilibrium of
reaction ( 7) will be maintained. (This behavior is contrary to the intuition
of many people and is a consequence of the countercurrent operation.)
The overall mass and energy balances and the equilibrium equations
are sufficient to define the compositions and temperatures of the effluents
( with the additional assumption that the solid and gas temperatures are
equal). The calculation therefore requires only the solution of a set of
algebraic equations. The fixed carbon-to-ash ratio must be given, since
the ash is included in the energy balance, and we use a ratio of 5: 1 as
typical of Illinois No. 6 coal. The calculations shown in Fig. 13 from Yoon
et al. (1979a) are for a gas feed temperature of 700°F and an operating
pressure of 25 atm. The solid lines are lines of constant fraction of un-
reacted carbon in the ash. The line of zero unreacted carbon represents
the case in which feed rates of carbon, steam, and oxygen are such that
the carbon-steam reaction reaches equilibrium at the top of the reaction
zone without unreacted carbon at the bottom; this line, and all points below,
are characterized by complete utilization of carbon, first by oxygen and
then by steam.
There is a noticeable change in slope of the lines of constant unreacted
carbon at a steam-to-oxygen molar ratio of about 1. 2. To the left of the
change in slope the equilibrium of the carbon-steam reaction is far to the
FIGURE 13 Lines of constant fraction of unreacted fixed carbon (solid),
and increase in gas sensible heat (dashed, kcal/mol fixed carbon) for a
countercurrent moving-bed reactor. (After Yoon et al., 1979a.)
Coal Gasification Reactors 523
right, and this reaction as well as oxidation can be taken to be essentially
irreversible. The line of complete carbon conversion in this region is thus
very close to the line connecting reactions ( 1) and ( 3) in Figs. 6 and 8.
The region to the right of the break represents an excess of steam. The
excess steam lowers the temperature, and sufficient excess steams brings
the peak temperature below the ash melting point and allows operation of a
dry ash reactor. The lines of constant carbon in the ash in this region
approximate lines of constant oxygen -to-carbon molar feed ratios.
The dashed lines in Fig. 13 are lines of constant increase in gas sensible
heat in kcal/g mol of fixed carbon. Autothermal operation for char gasifica-
tion lies to the right of the line of complete carbon conversion. A coal con-
taining 10% moisture will require about 5 kcal/ g mol of carbon for heating
and drying; if we presume that the gas exit temperature must be at least
700°F to prevent condensation of tars, operation in the region to the right
of the 5-kcal/mol line is excluded because of the need to add heat to the
gasifier. Operating points to the left of the 5- kcal line will represent an
appreciable loss of energy unless the sensible heat can be conveniently re-
covered downstream, which will be difficult in a gas stream containing con-
densibles that will foul a heat exchanger. The intersection of the 5-kcal/
mol sensible heat line with the complete carbon conversion line thus repre-
sents the most efficient operating point. (This is slightly to the left of
point A in Fig. 6, which was determined on the basis of a dry, hot char
feed.) This intersection occurs near a steam-to-oxygen ratio of 1.2, which,
as noted above, is typical of the feed to the ECG /Lurgi slagger. The com-
plete carbon conversion line is close to the 10-kcal/mol sensible heat line at
a steam-to-oxygen ratio of about 7, which is typical of a dry ash Lurgi re-
actor; this represents an additional loss of efficiency of about 5%. The net
thermal efficiency (Shinnar and Kuo, 1978) is shown as a function of steam-
to-oxygen ratio at complete carbon conversion in Fig. 14. (This calculation
90
Constraints
0~
>,
- Equilibrium
<.)
C 80 - - Kinetic
Q)
........w
<.)
0 70
...
E
Q)
.c
I-
-:0
z 60
5 0 ' - - - - - - - - - - - -.........- - - - ~ - - - -......
0 2 4 6 8
Steam /Oxygen (Molar)
FIGURE 14 Thermal efficiency for a countercurrent moving-bed reactor as
a function of molar steam-to-oxygen ratio. (From Shinnar and Kuo, 1978.)
524 Denn and Shinnar
is at 400 psi.) The dashed line is for an equilibrium constant that is only
10% of the true value as a means of attempting to account for kinetic effects.
This approach to kinetir. and transport constraints in a moving-bed gasifier
has been used by Gumz (1950) and Woodmansee ( 1976).
One further useful conclusion can be drawn from this analysis. The
steam gasification reaction ( 3) is not equimolar in gaseous species, so the
equilibrium will be pressure dependent. The effect of decreasing the pres-
sure is to make the reverse reaction more unfavorable, and hence to move
the break point on the line of complete carbon conversion to the right along
the line connecting the reactions (1) and ( 3) in Fig. 6. Since all points to
the left of the break correspond to essentially complete utilization of steam,
it can be concluded that slagging moving-bed gasification will be insensitive
to decreasing pressure; this phenomenon has been observed by Ellman
et al. (1977) in pilot plant studies. Conversely, at pressures substantially
higher than 370 psi, the breakpoint would move sufficiently far to the left
to cause excessive unreacted carbon.
There is no conceptual or computational difficulty in repeating these
calculations with reaction ( 5) included in the basis in order to account for
methanation. The line of complete carbon conversion with methanation
equilibrium is shown in Fig. 15, together with the corresponding line with-
out methanation. The two lines converge at steam-to-oxygen ratios of order
unity, which is the region of slagger operation. The high temperatures
here drive the equilibrium far to the left and suppress methane formation.
Thus, for slagging operation the methanation reactions need not be con-
sidered. At the higher steam-to-oxygen ratios and lower temperatures
characteristic of dry ash moving-bed reactors, however, methanation is
thermodynamically favorable. As noted in Table 4 and in the preceding sec-
tion, formation of methane in the reaction zone increases the efficiency.
This is because methanation is exothermic and enables gasification to be
carried out with less utilization of oxygen.
Methanation Equilibrium
FIGURE 15 Lines of complete carbon conversion with and without methanation
for a countercurrent moving-bed reactor. (After Yoon et al., 1979a.)
Coal Gasification Reactors 525
There are competing thermodynamic effects with pressure at the high
steam-to-oxygen rations in dry ash operation. Methanation is favored by in-
creased pressure, but we have already noted that increased pressure will
lower the efficiency of steam gasification. This observation is consistent with
the preliminary report from the Ruhr 100 dry ash Lurgi gasifier (Lohman and
Langhoff, 1981; Lohmann, 1982), which is intended for operation at up to
100 atm. A pressure increase from 25 to 50 atm (with a change in ash
content of the coal) showed an increase in raw gas methane from 9.1 to
13. 5% (but little change in other hydrocarbons), with decreases in hydro-
gen and CO from 39.1 to 37.9% and 16.1 to 15.0%, respectively, and an in-
crease in raw gas heating value of 13%. There was also a 5% increase in carbon
conversion and a 5% decrease in oxygen consumption. Thus the optimal
pressure will depend on the reactivity of the coal. Reactivity of methana-
tion reactions seems generally to be low at intermediate pressure; the
methane yields shown in Table 5 for moving-bed gasifiers operating at 30
atm and less are not significantly greater than would be expected solely
from the volatiles. The methane yield from the gasification of coke probably
represents the maximum methane obtainable in the reaction zone (adjusted
for pressure if compared to the other data). The slightly higher yields in
the dry ash reactor relative to the slagger may reflect the lower tempera-
tures in the gasification zone of the former, which are thus more favorable
to methane formation. The increased methane production at 50 atm is ac-
companied by a decrease in oxygen utilization corresponding roughly to a
trade-off between the exothermic reaction ( 5) and reactions (1) and ( 2) in a
3: 1 ratio, and methane formation in the reaction zone (rather than a change
in the devolatilization process) is a plausible explanation for the increased
methane production.
The trapezemium of autothermal operation in the reaction zone (ABEF) is
also included in Fig. 15. The neighborhood of line EF, which is carbon con-
version to methane, CO, and CO2, and contains the highest efficiencies, is
quite far removed from the line of complete carbon conversion with methane
equilibrium. This region around line EF therefore appears not to be obtain-
able. Selective catalysts that provide a kinetic pathway approaching global
equilibrium by a trajectory passing through the neighborhood of line EF
would be required, as discussed by Shinnar et al. ( 1982).
The analysis above also pinpoints the deficiencies of a kinetics-free
analysis. It fits the slagger quite well and explains certain trends for the
dry ash Lurgi, but it misses the main feature that controls the design of
the dry ash reactor. The steam-to-oxygen ratio in a dry ash Lurgi is con-
trolled by the relative selection rates of combustion ( which is diffusion con -
trolled) and reaction ( 3). Nonreactive coals therefore require a much higher
steam-to-oxygen ratio, as discussed below in the section on modeling. In
the slagger this is of no consequence, and therefore the assumption that
combustion is infinitely fast has no effect on the steam requirements. It is
always important in any design or development effort to understand clearly
what is the critical constraint, and the case above is a good example of how
constraints can shift by changes in design.
Cocurrent Entrained Flow
An analogous "kinetics-free" analysis can be carried out for any reactor con-
figuration. We do so here, with less detail, for the cocurrent entrained flow
~
0:,
TABLE 5 Methane Production of Various Moving-Bed Gasifiers
scf Methane per lb
Gasifier Coal Steam/oxygen Pressure (atm) dry ash free coala
Dry ash Lurgi Wyoming (western U.S.) 7.5 27 4.2
Dry ash Lurgi Illinois No. 6 (eastern U.S.) 8.5 30 3.85
Dry ash Ruhr-100 Lurgi German Long Flame 7.7 25 4.0
Dry ash Ruhr-100 Lurgi German Long Flame 6.5 50 5.4
Grand Forks Slagger Lignite 1.0 27 2.1
BCG /Lurgi Slagger Scottish Frances 1. 3 30 2.65
Solihull Slagger Avenue No. 2 coke 1.17 20 0.3
al scf CnHm converted to equivalent scf CH4 by ratio of heats of combustion. ti
Cl)
Source: Compiled by Shinnar and Kuo (1978), except data on _the Solihull slagger, which are from Lacey (1969), and ;:s
;:s
the Ruhr-100 gasifier, which are from Lohmann and Langhoff (1981). i:i
;:s
1:2.
Cl)
~
s·;:s
i:i
"'l
Coal Gasification Reactors 527
reactor without char recycle, such as the Texaco gasifier (Fig. 5). The
volatiles are driven off in an oxygen-rich environment in this type of re-
actor, and combustion of the volatiles is expected to occur even before
oxygen attack on the remaining fixed carbon. The volatiles must therefore
be included in the material and energy balances, and the graphical con-
structions will be specific to each coal.
It is easiest for comparison to use the fixed carbon in the coal as the
basis for calculations on the triangular diagram. The lines defining the
broad bounds of the operating region are thus shifted somewhat from those
in Fig. 6. The corresponding lines connecting reactions (1) and (3) and
reaction (2) and the H 2o vertex are drawn in Fig. 16 for a coal with the
analysis in Table 1.
The pulverized coal is fed to the Texaco gasifier in a water slurry.
The maximum slurry concentration is limited by current technology to about
70% solids by weight. This limit is shown as a straight line emanating
from the O 2 vertex. The gasifier must operate to the right of this line. A
gasifier in which the coal feed is transported solely by gas could operate
anywhere to the right of the C-0 2 axis. The 50% solids slurry line, which
is probably the practical lower limit for operation, is also shown in Fig. 16.
The effluent temperature and composition can be estimated by making
assumptions about relative kinetic rates and the available residence time.
Reaction ( 1) is assumed to occur first, and to go to completion. Since such
reactors always operate with slightly more oxygen than required to utilize
all of the carbon through reaction ( 1) , the excess oxygen is assumed to re-
act to form CO2, The residence time is then assumed to be sufficiently long
to achieve equilibrium in the gas phase. The reactor operates in the slag-
ging regime, and methanation is not expected at the high temperatures, so
FIGURE 16 Operating diagram for a Texaco entrained flow gasifier, Illinois
No. 6 coal. (After Denn and Wei, 1982.)
528 Denn and Shinnar
reaction ( 5) need not be included in the basis. The calculations shown
here, from Denn and Wei (1982), were carried out for an operating pressure
of 620 psi and an oxygen feed temperature of 300°F.
Lines of constant effluent temperatures of 2280 and 3000°F are shown on
Fig. 16. The former is the minimum temperature that will ensure slagging,
while the latter probably represents an absolute upper bound on the system
temperature because of materials limitations. The effluent composition is
summarized in lines of constant efficiency, from 60 to 90%. Efficiency in
this figure is defined as the ratio of the higher, or gross heating value of
the product gas to the higher heating value of the coal. As shown in Eq.
(15) (with m = 0), lines of constant higher heating value are lines of con-
stant carbon-to-oxygen ratio, increasing in efficiency with decreasing oxy-
gen (and hence with decreasing effluent CO2). It is clear that for a given
slurry concentration, the maximum efficiency will be obtained by operating at
the lowest permissible effluent temperature. The maximum obtainable gross
efficiency, without taking any kinetic constraints into account, is slightly
over O. 8 with the limitation of a 70% slurry. This must be reduced when
the maximum temperature in the reaction zone is incorporated in the analysis.
It is important to note that all present cocurrent gasifiers operate in
the partial combustion regime (R - Re > 0). This can be predicted from
thermodynamic considerations for a Texaco gasifier with a coal-water slurry
containing 30% water if we assume a minimum operating temperature of
2700°F. It follows from Figs 11 and 12, on the other hand, that R - Re
need not be positive for a cocurrent gasifier with dry feed, and yet all
published data for such gasifiers are also in the partial combustion regime.
This is a consequence of the use of sufficient steam with the coal feed to
require a high oxygen-to-coal ratio in order to reach the operating tempera-
ture. The steam is used here only as a coolant. and not as a reactant for
the gasification reactions, and it serves only to shift the product gas. This
seems to indicate that the steam-carbon reaction is too slow even at these
high temperatures for significant reaction to occur in the short residence
time in such reactors. The assumption of equilibrium in a cocurrent reactor
seems therefore to be justified only if R - R0 > 0, and even then it is
questionable since it gives possible operating regimes but does not predict
the operating conditions. It is very important to understand this limitation
when we deal with kinetic models.
DETAILED REACTOR MODELING
The stoichiometric and kinetics-free calculations define useful bounds on
reactor operating regions, but reactor operability is ultimately determined
by the detailed temperature, composition, and ash-state profiles. We
briefly describe in this section the approaches to such detailed modeling and
the problems that must be dealt with. Detailed models do not seem to have
been utilized in the initial design of any of the existing operating systems,
and their major use will undoubtedly lie in the development of process under-
standing for control, feedstock change, and perhaps design modifications for
increased efficiency (e.g. , Lu and Denn, 1984).
Before undertaking a discussion of detailed reactor modeling, it is well
to say a few words about model validation. Most data have been obtained on
reactor effluents, and effluent conditions are extremely insensitive to the
details of the model. Data are generally obtained under successful operating
Coal Gasification Reactors 529
conditions, which means nearly complete carbon conversion. Given the
facts that combustion and water-gas shift are fast and that complete carbon
conversion implies a sufficient residence time for any necessary steam or
CO 2 gasification, the effluent is essentially fixed by feed conditions. (It is
only a slight overstatement to insist that it is difficult to construct a model
of a successful gasifier that will not predict the effluent correctly. Many
of the models in the literature, especially for high-temperature gasifiers,
are simply complex ways to do thermodynamic calculations.) Temperature
and composition profiles would be sensitive tests, but only limited and in-
complete data are available from pilot- and full-scale units, and these do
not seem to have been used in any modeling study.
Reaction Rates
All detailed reactor models require a description of the solid-gas reactions,
using models of varying degrees of detail to describe the physicochemical
phenomena in the neighborhood of a coal or char particle. The kinetic data
in the literature indicate considerable variation with coal rank in reactivity
to steam and CO2, but less variability in the rate of oxygen attack. It is
generally agreed that reactions ( 3) and ( 4), steam and CO2 gasification,
proceed at roughly the same rate, and considerably slower than oxidation.
Some published data on steam gasification rates are shown in Fig. 17.
The data represent a range of coals, pressures, and steam and hydrogen
mole fractions, so absolute rate magnitudes are not directly comparable, but
each line is at constant gas composition and pressure. The variability in
reported activation energies is a cause for concern and must affect any
modeling study. Lupa and Kliesch ( 1979) have compiled and evaluated the
available rate data. Typical data showing relative magnitudes of the several
gas-solid reaction rates in a constant environment are plotted in Fig. 18; the
combustion data are from Sergent and Smith ( 1973) and the gasification data
from Gibson and Euker ( 1975). The diffusion limits are based on a shell-
progressive model for a 10-mm-diameter particle at 2000°F and 50% carbon
conversion, which is typical of conditions in the combustion zone of a moving
bed gasifier. Gasification may be comparable in rate to combustion under
these conditions.
One of the important, still unresolved differences in the kinetic expres-
sions employed in moving-bed models is whether to include reaction ( 9), the
formation of water from hydrogen and oxygen. This free-radical reaction
would be expected to occur very rapidly in the combustion zone, but there
may be sufficient char and ash surface present to quench the reaction. The
presence or absence of gas-phase oxidation has little effect on reactor efflu -
ent properties, but it will greatly affect the computed maximum temperature
and hence the range of operability.
Moving-Bed Models
Moving-bed reactor models are of two basic types: homogeneous and
heterogeneous. The equations for the former take the gas and solid tempera-
tures to be equal, and average over the two phases, while the latter treat
gas and solid phases separately. Steady-state multiplicity and limit cycles
have been observed only with heterogeneous models. The major differences
between models are in the choice of reactions to be considered, sources of
kinetic data, details of single-particle models, treatment of devolatilization,
530 Denn and Shinnar
T (°F)
1900 1800 1700 1600 1500
1.0
..c
'C
_g.... 10-I
0
0
.0
'C
0
....
.0
0
0
CJ) ,0-2 Blackwood
E and Gray
0
0 (1978)
.0
a, Gibson and
0 Euker (1975)
0::
Johnson
(1974)
10- 4 1..-_ _ _ _ _...L,__ _ _ _ _ _ _. _ _ .
0.41 0.45 0.50
[1/T (0 R)] x 10- 3
FIGURE 17 Published data on steam gasification rates.
and inclusion of radial variations and heat transfer. All models assume a
single particle size and plug flow of the gas. The published moving-bed
models are summarized in Table 6. * A one-dimensional, adiabatic analysis
is adequate to establish the important operating features of a full-scale
gasifier with wall cooling at normal throughput, since the penetration dis-
tance of the wall thermal boundary layer can be estimated to be only a small
*Stillman's ( 1979, 1981) model contains an error in the energy balance which
results in computations equivalent to replacing the heat capacity Cp by
cp(l + d ln cp/d ln T). This introduces a position-dependent error in the
heat capacity that can exceed 50% in the gas phase in the region of steepest
temperature profiles. The error is unlikely to change the qualitative re-
sults published using the model, but detailed steady-state and transient
profiles are unreliable.
Coal Gasification Reactors 531
T (°F)
10 _2 _4.;.;o:;.;o:;.;o"-r--=20=-.o;;..;oa......;.1,...50;;..o;;...__1o"'To'""o____
75T"o_,
Carbon-Steam Reaction
;Rate Limited by Diffusion
Combustion Limited
_ _ / by Diffusion _
Carbon-Steam
(Wyoming)
Carbon-Steam
(Illinois)
10-G....___._ __._.....__._...._......._ ..___.__ _
0.2 0.4 0.6 0.8 1.0 1.2 I .4 1.6
(1/T) x 1000, T (K)
FIGURE 18 Rates of combustion and gasification reactions.
fraction of the diameter (Yoon et al,, 1978). Wall cooling and radial varia-
tion will be important in a small-diameter pilot reactor or in a full-scale
reactor at low throughput or in a banked (hot standby) state.
All moving-bed models that have been compared with plant effluent data
have shown generally good agreement. Table 7 show results of two simula-
tions of the Westfield test on Illinois No. 6 coal in an oxygen-blown Lurgi
gasifier. The difference between the two simulations seems to be the result of
different means of treating volatile evolution and reaction, which is the
source of nearly all the methane in both cases, and is not a consequence of
the fact that one model is homogeneous and one is heterogeneous . The
effluents all satisfy the invariant relation defined by Eq. ( 12) (adjusted
to account for the H2S and C2H5). Yoon's calculations agree with the plant
data to within the uncertainty of the oxygen plant purity, but we have
already noted that effluent properties are not a reliable means of model
validation. The computed maximum temperatures are at the upper end of
the dry ash range, which is where the plant would be expected to operate,
but the maximum temperature is very sensitive to the assumptions made re-
garding the CO /CO2 selectivity of oxidation (Denn et al., 1979), while the
effluent is insensitive to this parameter. Reliable model validation would
require detailed axial profiles, which are extremely difficult to obtain in a
pressurized moving bed. Profile data of Hebden et al. ( 1954) are notable,
and have apparently not been used. Woodmansee and Floess ( 1975) have
reported data on the inside wall temperature profile in the GEGAS reactor,
but these data may not be representative of the interior.
tll
c.,
t-.:,
TABLE 6 Published Models of Moving-Bed Gasifiers
Homogeneous One-dimensional Detailed Computer
Steady-state or or radial single-particle code
References or transient heterogeneous dependence model available
Amundson and Arri ( 1978) s-s Hetero 1-D Yes
Biba et al. (1976, 1978) s-s Hetero 1-D No
Caram and Fuentes ( 1982) s-s Hetero 1-D No
Cho and Joseph ( 1981) s-s Hetero 1-D No
Cwiklinski et al. (1981) s-s Hetero 1-D Yes
Daniel (1982) T Homo 1-D No
Desai and Wen ( 1978) s-s Homo 1-D No DOE
Kim and Joseph ( 1982) T Hetero 1-D No
Stillman (1979, 1981) S-S and T Hetero 1-D No IBM
t:,
t1)
Yoon et al. (1978, 1979b) S-S and pseudo- Homo 1-D + core/ ;:I
No EPRI ;:I
s-s boundary layer A
;:I
A.
Yu et al. ( 1982, 1983) S-S and T Homo 2-D No EPRI Cl)
....;:I'
;:I
;:I
A
'"S
Coal Gasification Reactors 533
TABLE 7 Simulation of Pressurized Lurgi
Gasification of Illinois No. 6 Coal at Westfield
Using Models of Yoon et al. ( 1978) and Cho
and Joseph ( 1981)a
Cho and Westfield plant
Yoon et al. Joseph datab
CO 2 32.9 27.5 31.2
co 13.8 19.5 17.3
H2 42.4 44.4 39.1
CH 4 8.6 6.5 9.4
C2H6 0.7 0.7
H 2S 1. 0 2.1 1.1
Inert 0.5 1. 2
a
Steam/oxygen molar ratio= 9.6, fixed carbon/
oxygen molar ratio = 2. 73.
bPlant data are from Woodall-Duckham Ltd. (1974).
Typical temperature profiles computed with the model of Yu et al. ( 1983) ,
which includes Yoon's model as a special case, are shown in Fig. 19 for
gasification of Illinois No. 6 coal in an air-blown 12-ft-diameter dry ash
Lurgi gasifier. The cold zone near the wall is the source of nearly all the
unreacted carbon. The effect of blast temperature is shown in Fig. 20.
There is a critical blast temperature below which carbon conversion effec-
tively ceases. The model is probably inaccurate in predicting the precise
E, 10
2C 1525---~
t5 8 1545-----
Q)
>
0 1570,-----
.0
<(
6 1605-----
Q)
<J
C 1660-----
.,,
E
4
0
C
><
<(
2
0
2 3 4 5 6
Radial Position (ft)
FIGURE 19 Computed temperature contours for a dry ash Lurgi gasifier.
(From Yu et al., 1983.)
534 Denn and Shinnar
1.0
Radial Position
C
0 I 1-D, adiabatic care
~ 0.8 2 1-0. boundary layer
0 3 25.3%
u
4 88.5%
.,
-0
5 96.5%
u0 0.6
:!:'
C
=> 0.4
0
C
0
u
C
0.2
~
600 800 1000
Blast Temperature (°F)
FIGURE 20 Computed radial distribution of unreacted carbon at the bottom
of a dry ash Lurgi gasifier as a function of blast temperature. (From Yu
et al., 1983.)
value of this critical temperature, since the finite heat transfer rate be-
tween the blast gas and the ash is not taken into account in the homo-
geneous model, but the effect is certainly real and important. There is a
detailed discussion of the interactions between wall cooling and blast
temperature in Yu et al. ( 1982, 1983) .
The dashed line in Fig. 21 is the locus of optimal feed conditions com-
puted by Yoon et al. for Illinois No. 6 coal; it lies very close to the line
in Fig. 13 computed with the kinetics-free approach for complete carbon
conversion and no methanation. Computed lines of maximum temperature
for oxygen-blown gasification of Illinois No. 6 coal are also plotted in Fig.
21. This completes the definition of operability regions. The dry ash
reactor must operate to the right of the ll 75°C contour, but as close to
that line as possible. The point denoted "L" on Fig. 21 represents the
operating point of the Westfield test of Illinois No. 6 coal in a dry ash
Lurgi reactor (Woodall-Duckham Ltd., 1974), and it is consistent with the
reactor model calculations. A slagging reactor must operate to the left of
the ash melting temperature and, as noted previously, ideally close to point
A. Point S is the reported operating point in a BCG/Lurgi slagger at
Westfield (Scott, 1981) for a British Rossington coal that is believed to be
similar to Illinois No. 6. The steam-to-oxygen ratio is essentially the same
as at point A, and corresponds to complete steam utilization, but the carbon-
to-blast gas ratio is lower than would be expected from the model. The
model predicts more unreacted carbon than is observed in the slagger,
probably because of an inadequate description of the region near the
hearth, and this is one possible explanation of the difference in feed ratios.
As a final note on this aspect of modeling, it is useful to return briefly
to the kinetics-free method of analysis. Table 8 shows a comparison of the
gas properties above the reaction zone, but prior to devolatilization, as
computed with the detailed model and by the kinetics-free method, assuming
complete carbon conversion and no methanation with the latter. The
Coal Gasification Reactors 535
Oxygen Breakthrough
FIGURE 21 Operating region and locus of optimal feed conditions computed
for dry ash Lurgi reactor. (After Denn and Wei, 1982.)
TABLE 8 Comparison of Detailed and Kinetics-Free Model Calculations for
Oxygen -Blown Gasification of Illinois and Wyoming Coals in a Dry Ash
Lurgi Gasifier
Illinois coal Wyoming coal
Detailed Kinetics- Detailed Kinetics-
model free model free
H 20 0.68 0.68 0.49 0.45
H2 0.32 0.32 0.45 0.55
co 0.09 0.09 0.22 0.25
CO 2 0.22 0.22 0.30 0.30
CH 4 0.002 0 0.03 0
Exit temperature (OF) 1441 1437 1383 1320
H 2 /CO 3.43 3.52 2.07 2.21
Maximum temperature (OF) 2072 2004 2361 2362
Source: Denn et al. ( 1979).
536 Denn and Shinnar
maximum temperature is estimated from the adiabatic temperature rise of
combustion followed by water-gas shift equilibrium, assuming complete
utilization of oxygen and equal amounts of CO and CO2 as combustion
products. The detailed model calculations assume the same selectivity and
an initial particle size of 20 mm. All of the results, including the estimate
of maximum temperature, are close. Agreement is better with the low-
activity Illinois coal then with the high-activity Wyoming coal, since the
latter allows for more methanation. The kinetics-free approach is clearly
an effective means of estimating process performance if the feed conditions
necessary for complete carbon conversion are known. (The maximum tem-
perature estimated in this way will differ significantly from the kinetics-free
calculation only if the particle size is sufficiently large that the oxidation
rate is limited by mass transfer and becomes comparable to the steam gasifi-
cation rate, or if large amounts of methane are formed.)
There are two time scales that are relevant in the transient response of
a moving-bed gasifier. The first is of the order of the gas residence time,
which is approximately 1 min in the dry ash reactor and 10 s in the slagger.
The response to gas load changes over this time scale is only a consequence
of changing amounts of the hot gas effecting devolatilization and drying.
The temperature profile in the reaction zone is unchanged, so the kinetic
processes remain the same and the steady-state model of the reaction zone
suffices. This short time scale is the important one for changes in gas
demand in a power cycle, and the response can be computed from an overall
energy and mass balance on the drying and devolatilization zones.
There is a second time scale, of order hours, which corresponds to the
movement of a thermal wave through the bed. A pseudo-steady-state analy-
sis can be used to follow the wave propagation through the bed following a
load change, and to compute the effluent properties from the steady-state
model for the given profile, as done by Yoon et al. (1979b). This approach
is not adequate for the large changes associated with startup from, or turn-
down to, a significantly reduced throughput or a hot banked state.
The most important processing result from the full transient model of Yu
et al. (1982) is that the long-term transient response of a dry ash gasifier
is approximately first order, with a time constant that depends on the op-
erating level but (based on limited calculations) seems to be independent of
the magnitude of the change. Typical computed transients for an air-blown
dry ash Lurgi with Illinois No. 6 coal are shown in Fig. 22. The time con-
stant for turndown is about 6 h, while the time constant for a load increase
is about 3 h. The transient time for startup is shorter than for turndown
because an increase in the gas flux increases the flame velocity. Published
experimental data on transients in dry ash gasifiers are not available, but
the long time constants are consistent with the known operating characteris-
tics of these reactors. Yu et al. used the dynamic model to study feed
policies during turndown to maintain the combustion zone in a fixed position,
and concluded that a step change to the new steady-state ratio is effective.
The nature of the transient in a slagger is fundamentally different,
since the low steam-to-oxygen ratio and hot slag tap burner gas always keep
the combustion zone at the hearth. Thus a throughput change does not
cause a thermal wave, and the major dynamic response is in the region close
to the wall, where the greater relative importance of heat loss decreases
the conversion. Response times for load increases and decreases are about
six times as fast as in the dry ash reactor, and effluent compositions are
essentially unchanged. The major transient is the heat transfer between
Coal Gasification Reactors 537
Q)
C o, • 80% of full load
N
0 □ , ■ 50%
C C
t:.,& 30%
o.Q
·.;: .....
"'·-
.c "'
:::,
0 0.40
Ea..
--
0
u-0
Q)
0(/)
L: >,
0.20
-
0-o
0 0
... Cl)
0
8:
Q)
0
<{ ~
-
oz Q)
C 0.10
0
:;:::: .....0
0.08
...
0
0
LL
0.06
0 4 8 12 16 20
Time (h)
FIGURE 22 Computed transient response of a dry ash Lurgi gasifier to
load changes. (After Yu et al. , 1982.)
the bed and the water jacket. Slagger tests at Westfield (Scott, 1981)
show stable operation with large load changes effected over minutes, but
the insensitivity of the effluent, even under transient operation, makes
such experiments inadequate for testing a dynamic model.
Entrained Flow Models
Entrained flow reactor models fall into three general categories: two-
compartment, multicompartment, and two-dimensional turbulence. The
published descriptions are summarized in Table 9. Most models represent
commercial proprietary codes and are noted by the corporate or institutional
name as well as the authors of descriptive papers.
The two compartment models simply assume that the gas hydrodynamics
can be approximated by a well-stirred region immediately downstream of
the nozzle, followed by a plug-flow section, with plug flow throughout of
the solid particles. Volatiles are assumed to evolve and burn in the well-
stirred region. These models show good agreement with published conver-
sion data for the Texaco gasifier, but such agreement is to be expected in
light of the comments made previously about the factors that determine reac-
tor effluents. There is little methane produced, so total syngas ( CO + H 2)
is fixed entirely by the feed oxygen-to-carbon ratio. The steam serves
only to shift the product and determine the CO /H2 ratio; prediction of the
effluent temperature in order to compute the equilibrium of reaction ( 7) is
thus the main result of the model, and the temperature prediction can be
"tuned" by small changes in the assumptions about the size of the well-
stirred region and the heat loss in the plug-flow region.
538 Denn and Shinnar
TABLE 9 Entrained Flow Gasifier Models
Model Reference Type
Avco- Everett Ubhayakar et al. (1977) Multicompartment
Bringham Young 1-DICOG Smoot et al. ( 1979), Multicompartment
Hebden et al. (1981)
Brigham Young PCGC-2 Hebden et al. (1981), Two-dimensional
Martin ( 1982)
Delaware Denn and Wei ( 1982), Two-compartment
Olsen (1981)
Jaycor Ghate and Martin ( 1982) Two-dimensional
Physical Sciences Ghate and Martin ( 1982) Multicompartment
S-Cubed Schneyer et al. ( 1982) Two-dimensional
Texaco Lupa and Kliesch ( 1979), Two-compartment
Lupa ( 1982)
West Virginia Wen and Chuang (1979) Two-compartment
The prediction of the maximum temperature is an important model out-
put, since this value must lie within the bounds established by the ash
slagging temperature and the materials of construction. The region compris-
ing maximum temperatures in the range 2800° to 3000°F computed from the
Delaware model (Denn and Wei, 1982) is added to the triangular operating
diagram in Fig. 23. The shaded region is the feasible operating range for
a slurry-fed, oxygen - blown gasifier with Illinois No. 6 coal, according to
the model calculations, bounded by a maximum temperature of 3000°F, an
effluent gas temperature of 2280°F, and a slurry in the range 50 to 70%
solids by weight. The maximum temperature prediction is very sensitive
to the assumed size of the recirculating zone, however, which depends on
the unknown jet configuration and velocity. In addition, the assumption
of a single well-stirred region must be a poor approximation to the tempera-
ture profile from the jet core to the wall and should be expected to predict
too low a maximum. Lupa and Kliesch ( 1979) note that reactor temperatures
(at an unstated location) predicted by their model differ from plant measure-
ments by several hundred degrees and are systematically low. (The raw
data are proprietary and have not been published.) The transient model
predictions (Lupa, 1982) are generally good with regard to total syngas
production, but they deviate from the component data and fail to predict
the "wrong-way" dynamics observed in some of the reported runs.
The multicompartment models attempt to describe the physical processes
on a finer spatial scale, including kinetic models of devolatilization, but
still use macroscopic approximations to the gas and solid dynamics. The
two-dimensional models solve full continuum descriptions of the momentum,
mass, and energy transport, including detailed kinetic and turbulence
(mixing-length or k- s) models. A considerable data base, including detailed
profiles of the type computed in the two-dimensional models, is not being
developed for model testing on small entrained reactors (Hebden et al., 1981;
Coal Gasification Reactors 539
Tmax=
3000°f
FIGURE 23 Operability region computed for a Texaco entrained flow
gasifier. (After Denn and Wei, 1982.)
Smoot, 1982; Solomon and Hamblen, 1982), but applicability of these com-
plex models to the analysis of full-scale reactors has not been demonstrated
in the open literature.
Fluidized-Bed Models
Several steady-state models of fluidized char gasification have been published
using conventional fluidization models: perfectly mixed, Davidson-Harrison ,
and Kunii-Levenspiel. The most complete such model is that of Caram and
Amundson ( 1979); other, less general treatments include those of Yoshida
and Kunii ( 1974) and Weimer and Clough ( 1980). A model briefly described
by Finson ( 1982) seems similar in concept to that of Caram and Amundson.
Caram and Amundson show good agreement with effluent data from a small
char gasifier, but the model is not applicable to an industrial or demonstra-
tion scale configuration. Finson shows poor agreement with UGas and
Westinghouse reactor data.
A number of "first principle" models to follow detailed two-phase fluid
mechanics, as well as the chemical reactions, are under development and
are described in Ghate and Martin ( 1982). Although these detailed hydro-
dynamic models seem to show the flow characteristics associated with fluidized
beds, the published descriptions indicate that they are still far from provid-
ing an engineering tool for dealing with the problems described earlier re-
garding fluidized gasifier design. The most difficult problem is near the
oxygen nozzle. This is a highly nonisothermal zone in which performance
depends strongly on the relative rates of combustion and solid mixing
around the nozzle. Both rates depend on the properties of the coal and the
540 Denn and Shinnar
state of the char, and an adequate description of this region is beyond
current modeling capabilities. The only reliable way to develop a gasifier
is therefore to have a pilot plant in which the mixing zone is large enough
to be duplicated in the commercial plant by multiplication. Hence both the
nozzle and the region around each oxygen nozzle must be kept constant to
allow reliable scaleup.
A second problem is that the kinetic properties of the char depend on
particle history, and the kinetics measured in a fixed or small fluid bed
might not be applicable to a large bed; the reactivity of a particle alter-
nately exposed to oxidizing and reducing atmospheres is not necessarily the
same as one kept in a constant er-vironment. Finally, the ash agglomeration
process is not sufficiently understood to be modeled reliably or scaled to
different operating conditions.
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9
Gas-Liquid Reactors
SERGIO CARRA and MASSIMO MORBIDELLI Politecnico di Milano,
Milan, Italy
INDUSTRIAL REACTIONS AND TYPES OF REACTORS
Chemical reactions between a gas and a solute dissolved in a liquid are very
common in industry. In Table 1 examples of some important processes per-
formed in gas-liquid reactors are given. In such reactors the gaseous com-
ponents are dissolved in the liquid, where they react with the other
components. The fundamental analysis of these units is very complex as a
consequence of the simultaneous occurrence of diffusion and chemical reac-
tion. The hydrodynamic conditions of the system are also difficult to define.
The overall rate of the process is affected by the rates of mass trans-
fer in the g(ls and liquid phases and by the rate of chemical reaction.
Actually, the diffusivity in the gas phase is some orders of magnitude high-
er than the diffusivity in liquids. It follows that gas-side mass transfer
resistance becomes significant only in the case of very fast chemical reac-
tions.
According to the relative magnitude of mass transfer rate with respect
to reaction rate, two extreme situations can be evidenced:
1. Instantaneous irreversible reaction in which the rate of the overall
process is controlled by the diffusion rates of the reactants.
2. Slow reactions with uniform concentration of reactants in the whole
volume of liquid, while the concentration of the dissolved gas is
determined by phase equilibrium. The rate of the overall process
is controlled by the rate of the chemical reaction.
Some cases of practical importance may be approximated by the men-
tioned asymptotic situations. However, for many important industrial
processes the rate of mass transfer and chemical reactions are comparable.
Therefore, both effects must be accounted for in the design of chemical
reactors.
In a gas-liquid reaction, yield and selectivity are also affected by mass
transfer, the nature of gas-liquid contacting, and residence-time distribution
545
546 Carra and Morbidelli
TABLE 1 Examples of Processes Performed in Gas-Liquid Reactors
Absorption of acid gases Absorption of SO3 in dilute sulfuric acid
Absorption of NO 2 in dilute nitric acid
Removal of CO 2 and H 2s by absorption in
alkaline liquids
Oxidation of organic Oxidation of paraffins to acids
compounds by oxygen
Oxidation of p-xylene to terephthalic acid
or air
Oxidation of cyclohexane to cycloheanone
Oxidation of acetaldehyde to acetic acid
Oxidation of ethylene to acetaldehyde
Chlorination Chlorination of benzene to chlorobenzene
Chlorination of dodecane
Chlorination of toluene to chlorotoluene
Addition of chlorine to ethylene
Hydrogenation of organic Hydrogenation of olefins
compounds
Hydrogenation of esters of fatty acids
Other reactions Absorption of isobutylene by sulfuric acid
Sulfation of alcohols by sulfur trioxide
Polymerization of olefins in organic solvents
in the two phases, For instance, in a consecutive reaction network, the
insufficient rate of mass transfer in the liquid may give rise to a decrease
in selectivity with respect to an intermediate desired product. This situa-
tion may occur for example, in the chlorination of organic compounds ( van
de Vusse, 1966a, b). The oxidation of hydrocarbons is another gas-liquid
reaction in which mass transport may plan an important role in defining
the selectivity toward the desired product (Carra and Santacesaria, 1980).
The design of a gas-liquid reactor proceeds in two steps:
1. The choice of a suitable type of reactor
2. The definition of reaction conditions and the design of the geometry
parameters
To begin, we consider the first point. Some typical examples of gas-
liquid reactors are illustrated in Fig. 1, and each will be considered in
turn.
Stirred-Tank Reactors
These reactors, which are agitated mechanically, represent versatile equip-
ment for dispersing gases, These units are the best for systems with
Gas-Liquid Reactors 547
G G
G
Jacketed coil cooled external cooling
G G
L----1
..
... ..
"ww: L
G
Bubble column multi staged packed column
....
...
.... L
. ·..
. . ......
G
IL
Spray column ejector reactor ejector Venturi
FIGURE 1 Schematic representation of some industrial gas-liquid reactors.
large heat effects and are particularly useful for performing slow reactions
requiring high liquid holdup.
Bubble Columns
In these columns the gas is supplied at the bottom of a tower whose height
is at least three times its diameter. Gas bubbles rise through the liquid;
the bubbling reaction creates mixing. These units are employed for relative-
ly slow reactions in which the key component is usually in the liquid phase.
They are more economical than stirred tanks.
Packed Columns
In these columns liquid and vapor pass co- or countercurrent to each other
through the passages created by the packing. They are very good for
548 Carril and Morbidelli
service that requires low pressure drop and for corrosive service because
of the wide selection of material of construction. These units are designed
as absorbers and the reaction is viewed as an accelerated absorption.
Plate Columns (Plates: Perforated, with Bubble
Caps or Valves)
Liquid and vapor follow separate paths between stages, and they contact
each other on plates. In these units liquid holdup on plates is advanta-
geous for slow reactions requiring long contact time.
Spray Columns
Liquid is sprayed with nozzles from the top of a column and the gas flows
upward. The unit is empty, and it is required in the case of gas streams
containing solid particles. A high liquid area is created near the nozzles,
but drops coalesce and the area is rapidly reduced. For this reason these
units are generally used for relatively easy absorption duty.
PHASE EQUILIBRIA AND DIFFUSIVITY OF
GASES IN LIQUIDS
The design of gas- liquid reactors requires a knowledge of the distribution
of involved components between phases in a state of thermodynamic equilibri-
um and the rate at which mass transfer occurs. Although complete theo-
retical predictions of the mentioned effects are not possible at present,
some correlations have been proposed to evaluate their role in gas-liquid
contactors. They are used only in the absence of experimental data and
after careful analysis of the conditions of validity.
Phase Equilibria
Thermodynamic equilibrium conditions between the gas and liquid phase
are conveniently expressed through a vaporization factor as
K.(x,y ,P ,T) (1)
1
Standard thermodynamics (Prausnitz, 1969) yields suitable expressions
for the vaporization factor Ki. Two situations must be considered. The
first refers to the case in which some components are present in the vapor ,
phase at a temperature higher than their critical temperature (supercritical
components). It occurs, for instance, when hydrogen or oxygen feed the
gas-liquid reactor. In this case
( 2)
where <Pi is the fugacity coefficient of component i in the vapor phase. If
the nonideal behavior of the gas phase is described through the virial equa-
tion of state, then
Gas-Liquid Reactors 549
1n c/>. =
1
2p g :Ey.B..
. 1 1] - ln(~)
( 3)
] RTp
g
where Bij is the second virial coefficient of the mixture components i and
j, Hi the Henry constant, and Yi the activity coefficient of superficial
component i in the liquid phase. It must satisfy the unsummetrical nor-
malization condition
lim y~= 1 ( 4)
x.+O 1
1
The limiting Henry's constant can be predicted from nonideal solution
behavior, in agreement with the theory of regular solutions (Hildebrand
et al., 1970), through the relation
Hi= pi[exp :~ (t\ - 8) 2] ( 5)
where pf is the extrapolated vapor pressure of component i, and Vi is the
molar volume of the solute gas, often assumed equal to the value of the
liquid volume at 25°C; oi and 8 are the solubility parameters of the solute
i and of the bulk liquid, respectively. The solubility parameter reflects
the influence of forces between the molecules, through the cohesive energy
density expressed by
i'IH . -RT
ev,1
0. = ( 6)
1
V.1
where i'IHev,i is the molar enthalpy of vaporization and Vi is the molar
volume of component i.
If the size of the molecules of the solute i are greatly different from
those of the solvent B, Eq. (5) must be modified as follows:
H. = p? exp
1 1
[ v.RT
- 1- ( 8. -
1
8) 2 ~
v.
+ ln - 1- +
(1 -v. )]
1
~- ( 7)
VB VB
The preceding equations are satisfactory for solutions where both sol-
vent an~ solute are nonpolar or for slightly polar solvents. The values of
oi and o can be obtained either from Reid et al. (1977) or from Wilhem and
Battino (1973). The solubility of some gases in water as a function of
temperature is summarized in Fig. 2. An empirical correlation for nonpolar
gas solubilities in alcohol-water solutions has been proposed by Tokunaga
(1975) in terms of the alcohol volume fraction cp in liquid phase:
ln H = <PO - cp)(A +Be/>+ ccp 2 + ncp 3)
550 Carr{}_ and Morbidelli
z
0
I-
u
er
a:
10-1
162
~
Lt..
w 1c?
_J
0
~
-4
>- 10
I-
_J
Cll
:::,
165
_J
0 He-
(/)
r'
10
-6 c> ~.. .
..... c> c>
c> .....
c>
~
.....
c>
2.4 2.5 2.6 2.7 2.8
LOG TEMPERATURE T IN K
FIGURE 2 Solubility of gases in water. (From Hayduk and Laudie, 1974.)
where the empirical coefficients depend only on the nature of the alcohol
and temperature, not on the nature of the solube gas (02, CO2, N 2 or
even CH4).
At moderate pressure, </Ji ~ 1 and the concentration of the gas in the
liquid phase is small, so that Ki is simply given by the ratio between the
Henry constant and the pressure.
The second situation mentioned refers to a mixture of subcritical com-
ponents. This occurs in units in which a reaction is performed through dis-
tillation of volatile products. In this case,
K. = ( 9)
l
where ff is the fugacity of pure component i and Yi is the activity coefficient
in the liquid phase. It satisfies the symmetric normalization condition:
lim y. = 1 (10)
l
x.+1
l
The influence of electrolytes on the solubility of gases can be estimated
through the following equation proposed by van Krevelen and Hoftijzer
( 1948b):
log 10 HH = hI ( 11)
B
Gas-Liquid Reactors 551
where HB is the value of Henry's constant in pure solvent and I the ionic
strength of the solution:
1" 2 (12)
I = -2 /-J C.Z.
. l l
l
Ci being the concentration of ions of valency Zi; h is a salting coefficient
that can be expressed through the sum of different contributions as
h=h +h +h (13)
g +
hg refers to the species of gas, h+ and h to the species of positive and
negative ions, respectively. The numerical. values of these coefficients for
some gases and ions are given in Tables 2 and 3.
In mixed electrolytes the following equation, suggested by Onda et al.
( 1970), can be applied:
H
loglO H = I:.h.I.
] ] ]
(14)
B
TABLE 2 Salting Coefficients for
Inorganic Ions (L/g mol)
Ion h+ Ion h
H+ -0.1110 Cl 0.3416
Na+ -0.0183 Br 0.3310
K+ -0. 0362 NO 3 0.3230
NH+ -0.0737 OH 0.3875
4
u+ -0. 0416 Hso 3 0.3869
2+
Mg -0. 0568 HS 0. 3718
2+
Zn -0. 0590 HCO 3 0.4286
Ca 2+ -0.0547 co z- 0.3754
3
2+
Ba -0.0473 soi- 0.3446
2+ so 2-
Mn -0. 0624 0.3275
3
Fe 2+ -0. 0602 PO 3- 0.3265
4
Co 2+ -0.0532 C 6H 5O 0.4084
Ni2+ -0. 0520 MnO 4 0.2600
Cr 3+ -0. 0986
Source: Charpentier (1981).
<:11
<:11
ts:,
TABLE 3 Salting Coefficient hg for Gases (L/g mol)
T (°C) H2 02 CO 2 H 2S NH 3 C2H2 C2H4 SO 2 N2
0 - -0.1653 -0. 2110
10 -0.2170
15 -0. 2197 -0.1786 -0. 2222 -0.2124 -0.2003
20 -0.2132 -0.1771
25 -0.2115 -0.1892 -0.2277 -0.2551 -0.2394 -0. 2240 -0.1951 -0.3154 -0.1904
35 -0. 3122
40 -0.2327
Source: Charpentier ( 1981). (j
p
ip,
p
;:s
i:i..
is::
0
~i:i..
~
Gas-Liquid Reactors 553
where Ij is the ionic strength attributable to the jth electrolytic species
and hj is a characteristic coefficient of that electrolyte.
Diffusivity in Liquids
Despite different theoretical treatments available for the description of diffu-
sion in liquids, there are no satisfactory methods to predict the diffusivity
coefficients. Therefore, prediction procedures must be applied only when
experimental data are not available. Such prediction procedures can be
divided in those suitable for nonelectrolytes and those suitable for electro-
lytes. Most studies have focused on the estimation of diffusivities in dilute
solutions (Skelland, 1974). There are two theoretical approaches to the
diffusional theory of nonelectrolytes. The first is known as hydrodynamical
theory, and in it the drag of a large spherical molecule i, moving through
a continuum of small solvent molecules j, is evaluated. The following equa-
tion is derived:
D.. µ.
21..2. = ( 15)
T
where ri is the radius of the molecule i.
In the latter approach, the liquid is treated as a quasi-crystalline lat-
tice in which holes are scattered. The following relation was proposed by
Jost ( 1952):
D .. µ.
-? = f(molecular volumes of mixture) ( 16)
The right-hand side of Eq. (16) has been semiempirically evaluated and a
set of proposed relationships are summarized in Table 4.
The molecular volumes can be estimated by adding up the contributions
of the atoms in the molecule as reported by Liley and Gambill ( 1973), pp.
232-234). The parameter !; which appears in the Wilke-Chang equation
(Eq. 1 in Table 4), is an association factor for the solvent. It is equal to
2. 6 for water, 1. 9 for methanol, 1. 5 for ethanol, and 1 for unassociated
solvents such as hydrocarbons, ethers, and so on. The uncertainity in-
volved in assigning values to !; for the new solvents has resulted in efforts
to eliminate this factor, as in the other equations reported in the table.
The effect of concentration on diffusion coefficients can be accounted
by means of the following equation, proposed by Vignes (1966):
(D.µ.. )
x.
= (D'?.µ.) ](D?.µ.)
x. (
l
d ln
1 + d 1
y.)
l ( 17)
1 13 cone l] J 31 1 n xi
nfj and Dji being the diffusion coefficients in dilute solution; µi, µj, and
µij the viscosities of pure components and of the solution, respectively;
and Yi the activity coefficient of the solute. Equation ( 17) can be applied
to nonassociated solutions or to an associated solution with a constant degree
of association.
In an electrolytic solution both cations and anions diffuse at the same
rate, so that electrical neutrality of the solution is preserved. If complete
554 Carrll and Morbidelli
TABLE 4 Semiempirical Relationships for Diffusivity in Dilute Binary
Solution of Nonelectrolytes
Equation Restriction Equationa
( f,M.) 1/2
Diµij
1 Exclude = 7.4 X 10- 8 - ~ - -
water as
T \7_0.6
1
solute
Diµij _8 1 + <3 v.1v.) 213
2 Exclude = 8. 2 X 10 - - - ~ J _ l_ _
T ~ 1/ 3
water as V.
1
solute
Diµij
3 General
T
being a = 10 for (V./V.)
J 1
< 1. 5
a = 8. 5 for (V./V.)
1 J
> 1.5
D.µ. 8 1.4ocv.1v.)
1
1I3 + (V./V.)
1
4 Organic _l_J = 8.52 X 10-
T
solvents
5 Aqueous
solutions
only
aµ = cP; D = cm 2 /s; V = cm 3 /mol; T = K.
dissociation takes place, the diffusion coefficient can be predicted very
accurately at infinite dilution by using the following equation proposed by
Nerst ( 1888):
flO flO z+ + z-
D'? = 8. 931 x 10- 14 T + - (18)
1 fl~ + fl'.:_ z+z
-
where Df is the diffusivity of electrolyte; fl~ and fl~ the cation and anion
conductances at infinite dilution, respectively (mhos/ equivalent); Z+ and Z
the absolute values of cation and anion valences. Some values of fl+ and
fl'.:_, are given by Liley and Gambill (1973, p. 235). For evaluating the
diffusivities at other than infinite dilution, the following equation has been
recommended by Gordon (1937):
Gas-Liquid Reactors 555
Average error (%)
Organic Water Water
solvents as solvent as solute Overall Reference
27 11 up 250 10 Wilke and Chang
(1955)
25 11 up 250 Scheibe! ( 1954)
15 9 13.5 Reddy and Doraiswamy
18 26 18 ( 1967)
16 Othmer and Thakar
( 1953)
5 Lusis and Ratcliff
( 1968)
1
(Di) cone = Df (19)
c.v.
] ]
m being the molality of the ~ectrolyte, y + the mean activity coefficient of
ions based on molality, and v.] the partial molar volume of solvent.
'
MASS TRANSFER IN GAS-LIQUID CONTACTORS
Balance of a Reacting System
The mass balance equations of a gas-liquid reacting system are written in
terms of phase equilibria, interphase mass transfer, and reaction rate dat1:1;.
556 Carr~ and Morbidelli
gas out
liquid rn
gas rn liquid out
FIGURE 3 Schematic representation of a well-mixed gas-liquid unit.
The role of these factors may be evidenced by considering an idealized
perfectly mixed, two-phase system, as illustrated in Fig. 3, in which a
reaction occurs in the liquid phase. The mass transfer of the volatile com-
ponents involves two steps. The first step is the transfer from the bulk
gas phase to the gas-liquid interface; the second involves the transfer
from the gas-liquid interface to the bulk liquid phase. Equilibrium condi-
tions are assumed to exist at the interface. The mass transfer rate per
unit interfacial area, Ni, of each component i is expressed as a function of
the bulk-phase concentrations:
where
(21a)
C*. = H.C~. (21b)
g'1 1 x,l
The asterisk indicates the gas-liquid interface; Ei is an enhancement
factor which accounts for the influence of chemical reaction on mass trans-
fer, as will be explained later.
Although more rigorous treatments are available (King, 1964), the usual
combined resistance approach is employed to define the overall mass trans-
fer coefficient Kgi in terms of gas-phase and liquid-phase resistances as
follows:
1 1 Hi
----+-- ( 22)
K . - k . k 0 .E.
g'1 g'1 x,l 1
In "bubble-type" gas-liquid reaction system, Ukg is generally small enough
compared with H./k O .E.. The possible exception is the case in which k O .E.
1 x,l 1 x,l 1
Gas-Liquid Reactors 557
is very large because of a fast reaction in the liquid phase. The mass
balance of component i in the unit under consideration may be stated as
QfCf. - Q C . = K .a(C . - H.C 0 .)VR ( 23)
g gI g gI gI gI 1 ;cl
In addition, the mass balance in the liquid phase is given by
( 24)
where Ri is the overall rate of consumption of the ith component.
Effects of Chemical Reactions on Mass Transfer
The differential equation of change in the liquid phase arises from a mass
balance on each component (Danckwerts, 1970; Astarita, 1967). It ex-
presses the phenomenon of simultaneous diffusion and chemical reaction and
may be written as
ac.
1 2
= -y. vc. + D.V C. R. ( 25)
at 1 1 1 1
accumulation convection molecular reaction
transport rate
If the bulk of the liquid is well mixed, the preceding equation needs
to be integrated over the region near the gas-liquid interface. This im-
plies an understanding of the fluid dynamics in such a region. The sim-
plest model relies on the assumption that the velocity vector !:! is parallel
to the interface. In addition, the concentration gradient vector VCi is
assumed to be perpendicular to the interface. As a consequence of these
assumptions, the convective term is dropped. This procedure is accom-
plished in classical film and penetration models. The models contain one
parameter each, which can not be specified theoretically and which reflect
the influence of the prevailing flow pattern (Sherwood et al., 1975). In the
former model the parameter is the film depth o , in which the resistance to
mass transfer J.s confined. In the penetration model, the parameter is the
mean lifetime s of the elements of fluid which are randomly replaced at the
surface.
Both parameters are semiempirically evaluated from experimental values
of the mass transfer coefficient kt without chemical reaction, as
D
0 = s = ( 26)
Attempts have been made to identify the more reliable of the mentioned
models. The general conclusion is that for describing the rate of gas ab-
sorption in the presence of chemical reaction, only small differences exist
between the two models once the same value for the purely physical mass
transfer coefficient kt is assumed. In fact, the accuracy of available
558 Carrc'i and Morbidelli
experimental data is frequently insufficient to discriminate between the two
models, which do not usually differ by more than a few percent. Signifi-
cant differences appear only when the gaseous and liquid reactants have
greatly different diffusivities (Brian et al., 1961) or when a complex re-
action scheme is involved (Tavares da Silva, 1974; Huang et al., 1980).
It follows that the choice between the models is usually made on the basis
of simplicity in describing the reacting system. For these reasons the film
model has been more widely used and will be applied in the following. The
dependence of the mass transfer coefficient on the diffusion coefficient pre-
dicted by the two models is different; the power 0.5, given by the penetra-
tion theory, is recommended.
The occurrence of a chemical reaction in the liquid phase affects the
value of the mass transfer coefficient. This effect can be accounted for
through the introduction of an enhancement factor E or a reaction factor
E*. The former is given by the ratfo between the mass transfer fluxes
with and without reaction, in the same hydrodynamic conditions;
-Di(dCf/ds)s = 0
E. = ( 27)
l kJl,i(C'h - CJl,i)
Instead, the reaction factor is defined as the ratio between the total
mass flux of the component i under examination in the presence of a reaction
and the hypothetical mass flux in the absence of reaction and with zero con-
centration of i in the liquid bulk:
( 28)
The mathematical analysis of gas-liquid reactions is complex as a con-
sequence of the interference of hydrodynamic and chemical factors. It
follows that the possibility of obtaining analytical expressions of the men -
tioned factors is limited to cases of simplified reaction kinetics only.
The type of chemical system which has received the most attention is
that in which the dissolved gas A undergoes an irreversible reaction with
a reactant B dissolved in the liquid. The reaction is described by the fol-
lowing stoichiometric equation:
A + vBB + products ( 29)
The film model assumes that even on a microscopic scale the process
occurs in steady state, so that the term (clCi/clt) in Eq. (25) is dropped.
It follows that the material balances for the two components are
2
d CfA
DA - r = 0
ds 2
0 ~ s ~ o ( 30)
d 2C
fB
DB - vBr = 0
ds 2
Gas-Liquid Reactors 559
r being the reaction rate and s the distance in the liquid from the inter-
face. DA and DB are the qjffusivities of A and B in the liquid.
The boundary conditions are
s = 0 (31)
(32)
To obtain the bulk concentration of component A (i.e., C 2A), it must be
taken into account that some of it reacts within the film and the rest is
transferred across the film. For instance, in a well-mixed reactor, the
following mass balance equation ii, obtained:
(33)
This equation states that the tr&nsfer rate of dissolved gas to the bulk
liquid must be equal to the amount reacted in the bulk plus that which
leaves the reactor in the effluent stream. By integrating the preceding
differential equations, the concentration profiles in the liquid film are ob-
tained, and from there the values of the enhancement and reaction factors
can be evaluated through Eqs. ( 27) and ( 28) , respectively.
Enhancement Factor for Fast Reaction
If the reaction rate is high, it is justifiable to consider the reaction to be
completed in the film. In this case the concentration of the absorbed gas
in the bulk of the liquid is zero. Therefore, the boundary condition (32)
can be simplified as follows:
at s = cS (34)
and the enhancement and reaction factors are then identical.
Although this situation is not fulfilled for many important gas-liquid re-
actions, it is worthwhile to consider it in some detail. Cases in which the
reaction also occurs in the liquid bulk are discussed extensively in the next
section.
The typical form of the concentration profiles of the reagents A and B
of reaction ( 29) is illustrated in Fig. 4a. The reaction is fast and it occurs
completely in the liquid film during the diffusion of component A. For re-
actors in which this situation occurs, high interfacial area is required, while
the liquid holdup is not important. The use of packed columns is thus
recommended. Let us consider, first, the case in which reaction ( 29) takes
palce through a bimolecular reaction of first order with respect to both
560 Carrel and Morbidelli
s s
(al <bl
ClB
s
(C)
FIGURE 4 Concentration profile of gaseous and liquid reactants in the
liquid phase: (a) fast reaction; (b) fast reaction with C,Q,B » c A;
(c) instantaneous reaction.
2
reagents. In this case the enhancement factor can be expressed as a func-
tion of a dimensionless parameter known as the Hatta number:
M ( 35)
and of the concentration diffusion parameter:
== ( 36)
An approximate expression of the enhancement factor E has been pro-
posed by van Krevelen and Hoftijzer ( 1948a). It was obtained through a
linearization technique based on the assumption that the concentration
value of B throughout the film is constant and equal to its value at the
interface. With this assumption the film model equations can be integrated
and the following implicit expression for the enhancement factor is obtained:
1/2
M[(EA. - EA)/(EA. - 1)]
,1n ,1n
== ( 37)
1/2
tanh {M[(E . - EA)/(EA. - 1)] }
a,1n ,1n
EA ,in is the enhancement factor corresponding to an instantaneous reaction
and is given by
Gas-Liquid Reactors 561
EA. (38)
,In
The behavior of the enhancement factor as a function of the param-
eters M and Zn is given in Fig. 5, Two particular cases merit attention,
The first occurs if the concentration of component B in the bulk liquid is
much greater than CfA, as shown in Fig. 4b. In this case the kinetics
of the reaction becomes pseudo-first order with an apparent reaction rate
constant given by kC £B. An exact solution of Eq. ( 30) can thus be ob-
tained, which gives the following expression of the enhancement factor:
M
EA == tanh M ( 39)
If 4 < M < EA in/ 2, the points representing the enhancement factor
are very close to the diagonal in Fig. 5. The second case is the one in
which the reaction rate is so high that the concentration of the reactant B
is less than the solubility of the gas A, because it reacts instantaneously
with component B. This situation occurs when M > lOEA,in· In fact, it
can be seen from Fig. 5 that when the preceding condition occurs, an in-
crease of the Hatta number leads to a limiting value of EA = EA in. Since
the reaction is instantaneous, the liquid phase may be considere'd to be
made up of two subsequent layers in which the resistance to the transforma-
tion is given by the diffusion of the reagents (Fig. 4c). In this case ex-
pression ( 38) for the enhancement factor is obtained .
w
.
a:::
0
1-
u
c:i:
LL
1-
z
w
~
w
u
z
c:i:
:t:
z
w
10 10
M= VOA k C1 8/k1A
FIGURE 5 Enhancement factor for a fast bimolecular second-order
reaction.
562 Carra and Morbidelli
A more general case is that in which reaction ( 29) takes place through
a bimolecular reaction of order m with respect to A and n with respect to
B. This problem was studied by Hikita and Asai (1963), whose basic idea
was to linearize the reaction rate with respect to the gaseous reactant con-
centration through the approximation
(40)
which is obviously exact in the case of m = 1. Introducing this approxima-
tion, the previously mentioned linearization technique can readily be ap-
plied (i.e., assuming CB as constant within the film). This approach leads
to the following analytical implicit expression for the enhancement factor:
n/2
M[(EA ,1n . -
. - EA)/(EA ,1n 1))
( 41)
EA = n/2
tanh{[(EA. . -
- EA)/(EA ,1n 1)] }
,1n
where the Hatta number in this case is defined as
M_1_ [(-2-)kn
=
+
k 9-A m 1 A
C*m-lcn ]
9-A .Q,B
1/2 ( 42)
EA ,in is still given by Eq. (38). The behavior of the enhancement factor
as a function of the parameters is given in Fig. 6 for various values of n,
with fixed m = 1. The accuracy of expression (40) is sufficient for engi-
neering calculations. In Fig. 7, for a pseudo-mth-order reaction (i.e.,
100
6
4
2
w"
t 10 --::::::::::===:::::::::::::::=====:: EA.in
=10
6
4
n=1 2 3 5 10
10 2 4 6 100 2 4 6 1000
1.0
-M
FIGURE 6 Enhancement factor for a fast bimolecular reaction of first order
with respect to the gaseous reactant and nth order with respect to the
liquid reactant.
Gas-Liquid Reactors 563
110~-----------------,
106
L
.&:.
C:
"' 102
'L
'i.J 0.98
t 0.94
0.1 0.2 0.4 0.6 0.8 lO 2 4 6 810 20
-M
FIGURE 7 Ratio of the true enhancemen t factor numerically calculated, EA
to the approximate factor calculated by Eqs. ( 39) and ( 42), in the case
of a pseudo mth-order reaction.
where CB is constant) the ratio between the approximate and the numerically
calculated enhancemen t factors is reported for various values of m as a func-
tion of the Hatta number. The same kind of accuracy is also exhibited by
Eq. ( 40) in the case of reaction ( 29) of mth order with respect to A and
nth order with respect to B.
It is worth mentioning here the large amount of literature devoted to
the definition of explicit expressions of the enhancemen t factor under the
assumption of complete gaseous reactant depletion in the liquid bulk, C Q,A ==
0. For reaction (29), first order with respect to both reactants, it has
been reviewed by Wellek et al. ( 1978), who recommende d the use of the
expression proposed by Yeramian et al. (1970):
2
M2 { [ 4(EA . _ _
1 + ---'•_m - _
l)EA . _tanh~J
_-"-,1_n _ __
. -
2(EA ,1n l)tanh 2 M M2
where Mand EA,in are given by Eqs. (35) and (38), respectively . In the
present section we have considered a particular situation for the gas-liquid
reactor which allows the neglecting of the reaction in the liquid bulk, since
this is not reached by the gaseous reactant. Deeper analysis of the problem
requires the coupling of the film equations with those describing the reac-
tor behavior. This is developed later and more general approximate expres-
sions of the reaction factor are also given.
MEASUREM ENTS OF INTERFACI AL AREAS AND
MASS TRANSFER COEFFICIEN TS
Gas holdup E:g, interfacial area a, and mass transfer coefficients are impor-
tant parameters determining the mass transfer rates in gas-liquid reactors.
Different procedures have been proposed for their measuremen t, which can
be classified in two categories: local measuremen ts with physical techniques
564 Carra and Morbidelli
and global measurements with chemical procedures. A detailed analysis of
the procedures has been given by Charpentier ( 1981).
Physical Methods
The gas holdup is directly determined by measuring the height of the
aerated liquid and that of the clear liquid without reaction (Fair et al.,
1962; Marrucci and Nicodemo, 1967; Hughmark, 1967; Yoshida et al., 1970;
Eissa and Schiigerl, 1975; Yoshida and Akita, 1965; Miller, 1974). This
procedure is rapid but not very accurate. A more precise technique, in
which the gas holdup is obtained from measurements of the clear liquid
height in the dispersion at successive manometric taps on the side of the
froth container, has been proposed and employed by Burgess and Calder-
bank (1975a, b).
An electrical technique, proposed by Linek and Mayrhoferova ( 1969),
can also be used. It involves the measurements of the surface elevation at
certain selected points by means of an electrically conducting probe. The
height is determined by the vertical position of the tip at which the sum of
the contact times equals one-half of the measurement period. The y-ray
transmission technique has also been employed to determine the local gas
holdup in gas-liquid contactors (Calderbank, 1958; Calderbank and Rennie,
1962; Bernard and Sargent, 1966; Hwa and Beckmann, 1960).
From the gas holdup, the specific interfacial area can be calculated as
6s
a = __g_ ( 44)
d
sv
where dsv is the volume surface mean diameter or Sauter mean diameter, de-
fined as
~nid~
1
d = ( 45)
SV
~nid~
1
db is the diameter of the single bubble (or drop) and ni the number of bub-
bles (or drops) of diameter db. The value of d 8 v can be directly evaluated
through a statistical analysis of high-speed photomicrographs performed in
the dispersion (Calderbank and Rennie, 1962; Vermeulen et al., 1955; Porter
et al. , 1966; Akita and Yoshida, 1973; Ashley and Haselden, 1972).
The local interfacial contact area is directly evaluated by light transmis-
sion and reflection techniques. A parallel beam of light is passed through
the dispersion and a photocell is placed at some distance from it (Vermeulen,
1955). Only the unscattered part of the incident parallel beam is recorded
by the photocell. It has been shown by Calderbank (1958) that for bubbles
the scattering cross section is equal to its projected area. The total inter-
facial area per unit volume of the dispersion is related to the intensity ratio
of the radiation through the following equation:
( 46)
Gas-Liquid Reactors 565
where £ is the optical path length and Io/I the intensity ratio between the
incident beam of radiation and the transmitted beam.
Chemical Methods
The chemical methods are derived from the theory of mass transfer with
chemical reaction, previously illustrated. A gas is absorbed into a liquid,
where it reacts with a dissolved species. An excellent review of such
methods has been published by Sharma and Danchwerts (1970). By choos-
ing a reactant with adequate solubility and a suitable reaction rate, either
the products k 9,a, kga, or the interfacial area can be deduced from the
overall rate of gas absorption.
The determination of the interfacial area relies on the fact that when
the reaction between the two components in the liquid phase is mth order
in A and nth order in B if
EA.
4<M<~
2
( 47)
where M is defined by Eq. ( 42), the rate of absorption is given by
( 48)
This equation shows that the specific absorption rate is independent of
hydrodynamic conditions. Therefore, if the solubility, the diffusivity, and
the reaction kinetics are known, the specific interfacial area can be deter-
mined from the experimentally determined total absorption rate.
Interfacial areas determined from the physical and chemical methods may
differ by more than 100%. A careful analysis reveals that the results of
the photographic method and the sulfite oxidation method (a specific chemi-
cal method discussed later) show large variations at high gas velocities.
For homogeneous bubbly flow, Schumpe and Deckwer ( 1980) have found that
a p h Ot O = 1. 35a SUlf't ( 49)
1 e
For churn-turbulent flow, the difference is even larger. These results re-
veal that the photographic method is not very reliable.
The analytic determination of the absorption rates can be performed in
two limiting situations, the transport or reaction -controlled cases. In
the former case, which corresponds to instantaneous reaction regime, the
chemical systems employed are indicated in Table 5. In the latter case,
which corresponds to slow reaction regime, the employed chemical systems
are shown in Table 6.
Of course, the interpretation of experimental data relies on the model
employed to describe the gas-liquid dispersion, and customarily it is as-
sumed that the liquid phase is perfectly mixed, while the gas phase is
either in plug flow or perfectly mixed. This subject has been critically
examined by Midoux et al. (1980), who proposed a flow model for gas dis-
persion into liquids inhibiting coalescence that seems more realistic than the
plug-flow model.
566 Carra. and Morbidelli
TABLE 5 Chemical Systems Employed to Determine kJla in the
Instantaneous Reaction Regime
Solute gas Reactant Reference
NH 3 H 2so 4 Sharma and Danckwerts ( 1970)
so 2 , Cl 2 , HCl NaQH Sharma and Danckwerts ( 1970)
H 2S, HCl, CO 2 Amines Sharma and Danckwerts ( 1970)
02 N2S204 Jhaveri and Sharma (1968)
Oxygen absorption into sodium sulfite in the presence of copper ions
as catalyst has been widely used for the determination of absorption rates
in packed columns, bubble columns, and mechanically agitated vessels.
The absorption occurs through the reaction
( 50)
An extended review on its use as a model reaction of known kinetics in
determining accurately mass transfer characteristics of gas-liquid contactors
has been published by Linek and Vacek ( 1981).
TABLE 6 Chemical Systems Employed to Determine kJla in the Slow Reaction
Regime
Solute gas Reactant Catalyst References
NaClO Danckwerts and Sharma ( 1966)
Danckwerts and Gillham ( 1966)
o 2 diluted Cu Cl Jhaveri and Sharma (1967)
with air
o 2 diluted Na 2so 3 CuSO 4 De Waal and Okeson (1966)
with air Wesselingh and Van't Hoog (1970)
Astarita et al. ( 1964)
o 2 diluted Na 2so 3 CoSO 4 Linek ( 1966)
with air Linek and Mayrhoferova ( 1970)
Onda et al. ( 1972)
B utadiene Maleic-anhydride Neelakantan and Gehlawat ( 1982)
Gas-Liquid Reactors 567
MODELING OF ISOTHERMAL GAS-LIQUID REACTORS
Similarly to most chemical reactors, reliable sizing and selection of optimal
operating conditions for gas-liquid reactors require the use of suitable
mathematical models. The hydrodynamics of industrial gas-liquid reactors
is quite complex, due to the presence of two phases, one dispersed and the
other continuous, in relative motion, in some cases through a stationary
solid packing. In particular, mixing in both phases can significantly affect
the reactor performance in terms of reactant conversion and product selec-
tivity. Wen and Fan (1975) and Shah et al. ( 1978) have reviewed back-
mixing in empty and packed gas-liquid reactors.
The most common technique used to define the extent of backmixing in
a given unit is first to measure the residence-time distribution (RTD) of a
suitable tracer in each phase and then to fit the obtained data with an ap-
propriate model. A number of such models have been proposed in the litera-
ture, and some of these are summarized in Table 7. They can be divided
into two main groups: pseudocontinuous models and cell models, leading to
differential and algebraic equations, respectively. Each model is character-
ized by one or more parameters, which are usually tuned in order to re-
produce the experimental RTD data.
The simplest pseudocontinuous model is the axial dispersion model,
where backmixing is characterized by a one-dimensional diffusional term,
which also includes the effects of both radial dispersion and nonuniform
TABLE 7 Backmixing Models
Adjustable
parameters Reference
Pseudocontinuous models
Axial dispersion model 1 Levenspiel ( 1972)
Multistaged dispersion model 2 Nishiwaki and Kato (1974)
Modified mixing cell model 2 Deans ( 1963)
Cross-flow model 2 Hochman and Effron (1969)
Piston diffusion 3 van Swaaij et al. (1969)
exchange model
Cell models
Series of stirred-tank 1 Dean and Lapidus (1960a,b)
model
Modified series of 3 Bang and Cholette (1973)
stirred-tank model
Backflow model Variable Miyauchi and Vermeulen
( 1963)
Dispersion backflow model Variable Nishiwaki et al. (1973)
568 Carra and Morbidelli
velocity profile. It is equivalent to the series of CSTRs models, where
backmixing is again characterized by only one parameter: the number of
tanks in the series. In the other models listed in Table 7, some more
parameters are introduced in order into account the possible simultaneous
presence of flow with axial dispersion, bypass, and a fraction of stagnant
fluid. Although they give a better representation of experimental RTD
data, when used to describe the kinetic performance of a gas-liquid reactor,
they lead to complex mathematical equations, which can be of limited use
for reactor simulation or design. Therefore, in the following we consider
only the axial dispersion model for both the gas and liquid phases. Ob-
viously, a model of this type can describe only macromixing situations inter-
mediate between plug flow and perfect mixing. More complex situations can
be examined by modeling the unit under examination as a combination of
suitable smaller units, each described by the axial dispersion model, with
different values of the dispersion coefficients. This model can then be re-
garded as the fundamental unit for building more complex models, such as
those presented by Wolf and Resnick ( 1963) or those mentioned in Table 7.
We will first outline the most general form of the axial dispersion model,
which can be used to simulate most gas- liquid reactors, provided that
suitable values are given for the involved parameters. The CSTR model,
which is also the limiting situation for infinite axial dispersion, is examined
in detail due to its very frequent application. Two modes of operation will
be considered: both phases continuous and batch for the liquid phase.
As in most industrial applications, the chemical reactions are assumed to
occur only in the liquid phase.
The mathematical model of a gas-liquid reactor is constituted of two
interacting portions. The first describes the diffusion and reaction
process within the liquid film, depending on the concentration values in
the bulk of the two phases in relative motion. The second describes the
time or space evolution of the bulk concentrations, taking into account the
operating mode, hydrodynamics, and macromixing in each phase.
Liquid Film Model
Considering a generic ith component, its dimensionless steady-state mass
balance in the liquid film, where NR reactions occur, is written as follows:
2
[,.
1
d cpfi
dx
2
= -Ha
2 NR
L v .. p.f.
l] JJ
X € (0,1) ( 51)
j=l
with boundary conditions (BCs)
X = Q: q> fi = q> ii ( 51a)
X = 1: q> fi = q> ,Q,i ( 51b)
where </>fi, ¢ ti• and ¢Q,i indicate the dimensionless concentration of the ith
component in the liquid film, bulk, and gas-liquid interface, respectively;
the other quantities are defined as follows:
Gas-Liquid Reactors 569
D.
~- = 1
1 DA
ro
Ha 2 = p = J. ( 52)
j 1J.
r. D.
1
f. == ...1. k Q,i == 6
J r:'
]
where the subscript A indicates the gaseous reactant and the superscript 0
indicates a reference condition, usually corresponding to the feed stream or
the initial condition for continuous or batch operations, respectively.
It is worthwhile to recall that the last of equations ( 52) is a result of
the film theory, but it is not verified in practice since from experimental
measurements the purely physical mass transfer coefficient k Q,i appears to
be proportional to the square root of the diffusion coefficient Di.
In the solution of the liquid film model, it is only necessary to calculate
the mass flux of the ith component across the gas-liquid film (x == 0) and
the liquid film-liquid bulk (x == 1) interfaces. The first is given by
* *x-1
kn .E. C n. = k . ( C .
*
C .) (53)
x-1 1 gI gI gI
where the reaction factor E;I', defined by Eq. (28), using Eqs. (52) reduces
to 1
E.* = (
d<Pfi) (54)
1
dx x==O
The last equality in Eq. (53) is based on also using the film theory for the
gas-side mass transfer process, and in dimensionless form leads to
* <P gi
<P . = ( 55)
gi 1 + y.E.*/H;!'
1 1 1
where
H;i' (56)
1
and the gas-liquid equilibrium at the interface [(Eq. (21b)] reduces to
"*
't' gi
== H*"*
i 't' Q,i ( 57)
The material fluxes at the liquid boundaries can be calculated, using Eqs.
(51), (53), and (55), through the relationships
570 Carril and Morbidelli
k,Q,.Ct</J .(E:l'/H;I')
1 fQ 1 1
(N ) = ( 58)
i s=0 1 + y.E;l'/H:"
1 1 1
(N)
i s=o
=
k ,Q,f ,Q,
0
[ I gt.(ENH'l
l l
1 + y .E;l'/H:l'
1 1 1
Ha 2
+--
si
NR
j=l
L V
l]
pf
J 0
f.
J
dx] ( 59)
as a function of the bulk concentrations <Pgi and <P ,Q,i. These can be evalu-
ated through the macroscopic balances examined later, depending on the re-
actor hydrodynamics and operation mode.
Axial Dispersion Model
Using the axial dispersion model for both phases, the isothermal, steady-
state, dimensionless material balances for the ith component are, in the
liquid phase,
2
d <P ,Q,i
- - + n*
dz 2
( 60)
z s (0,1)
and in the gas phase,
d(v ¢ .)
g g1 z s ( 0, 1)
- (J.) 0 = 0
dz 1 x=
where besides those defined in Eqs. ( 52), the following dimensionless quan-
tities have been introduced:
C u,Q, u
<P • = __g!_ z = ~ =uo- V = __g_
gt co L
V
,Q, g uo
g ,Q, g
Lak,Q,i Lak u 0,Q, L
St,Q,i uo-
-- St . = ____g!_
uo Pe,Q, = ao) ( 61)
gt E,Q,(1 E:
g
,Q, g
u0 L 1 - E: ao
_g_ g
Pe = a=
g E E: ao
g g
n * = 1, -1 indicates countercurrent and cocurrent flow, respectively. The
dimensionless interfacial material fluxes are given, using Eqs. ( 55), ( 58),
and (59), by
( 63)
Gas-Liquid Reactors 571
_
(Ji)x=l - 8t ti
[
cf> .(E:"/H:")
g'l l l Ha2 NR
1 + y.E:"/H:" + - 1 : - L
v .. p.
il ] f. dx ( 64)
l l l "i j=l lJ J O J
When, as in Eqs. ( 60), the variation of the superficial velocities v t and
vg along the reactor axis must be taken into account, the equation of state
of each phase should be introduced. However, for most usual applications
the liquid superficial velocity can be assumed constant along the reactor
axis, while for the gas phase the ideal gas law can be used:
(65)
which introduced in Eqs. (61) and (63) leads to
d(v P/P 0 ) NC
(66)
g + "LJ 0
dz
i=l
where P 0 is the pressure value at the reference conditions, which in this
case are those relative to the feed stream (i.e., po /RT = C 0 = E~C Cf.).
g i=l gi
According to Deckwer ( 1976), the pressure gradient can significantly affect
reactor behavior and should then be taken into account through the relation-
ship
p = 1 + a( 1 - z) ( 67)
PT
where a= p tgL(l - Eg) /PT and PT is the pressure at the reactor top. Note
that, using Eq. (67), the first term in Eq. (66) vanishes.
The boundary conditions for Eqs. ( 60) and ( 61) depend on the reactor
operation mode: cocurrent (n* = -1) or countercurrent (n* = 1):
Liquid phase:
1 + n* f f 1 dcjl ti f
z = vtcpti = vtcpii vt = vt (68a)
2 Pet dz
def> ti
z = 1 - n*: = 0 (68b)
dz
Gas phase:
z = 0: vf <Pf. = V cf>. -
1 ~ V =v
f
(69a)
g g'l g gi Pe dz g g
g
z = 1: ~ = 0 (69b)
dz
572 Carro and Morbidelli
TABLE 8 Mass Balances for the CSTR Model
Liquid phase:
L
2 NR
St.Q,
a - - Ha v ..p.f. - (J1.)x=l
~i lJ J J
j=l
Gas phase:
NC
L
f
vg = vg + (Ji)x=O
i=l
Special cases of this model, particularly used in practice, are the
CSTR and the PFR models, which are obtained assuming infinite (Pe + 0)
and zero (Pe + 00 ) axial dispersion coefficients, respectively. The equa-
tions for the CSTR model are summarized in Table 8, where constant pres-
sure is assumed in the reactor. For the PFR model, the equations readily
derive from those of the axial dispersion model, by simply deleting all the
terms containing the Peclet numbers and the boundary conditions at the
reactor outlet.
Semiflow Batch Model
A common operation mode for gas-liquid reactors is to continuously flow the
gas phase through the liquid phase held inside the reactor. The liquid con -
centrations are then time dependent, but not space dependent, since the
liquid can usually be considered well mixed. For the liquid phase, the fol-
lowing material balances can be written
0 > 0 (70)
in
with the initial conditions, cjJ .Q,i = ¢ti at e= 0, and where
tktAa
0 = ------
1 E: ao
g
(71)
The total mass flux of the ith component entering the liquid bulk, (Ji)x=l'
is given by
( 72)
Gas-Liquid Reactors 573
where (Ji)x=l is given by Eq. (64) as a function of the gas-phase composi-
tion, which for Peg =f- 0 depends on the reactor axis z according to Eq.
( 61).
Usually, pseudo-steady-state conditions can be assumed for the gaseous
phase (Schaftlein and Russel, 1968), so that the mass balances in this
phase are identical to those previously described for the axial dispersion
model.
Variation of I nterfacial Area and Gas Holdup
In all previous models it is assumed that the gas-liquid interfacial area and
the gas holdup are constant along the reactor axis. Although experimental
results do not fully confirm this assumption (Deckwer, 1977; Deckwer et al.
1978; Kolbel et al., 1972), sufficient data have not yet been collected to
derive reliable correlations. However, in some applications (i.e. , dead-end
reactors) the variation of the gas flow rate due to absorption is such that
changes in interfacial area and gas holdup cannot be neglected. To this
end, Schaftlein and Russel ( 1968) and Shaikh and Varma ( 1983b) have sug-
gested the following relationships:
-a -_
a
f
(V_g_)
V
f
213
(73a)
g
E: V
_g:_ - _g_ (73b)
f - f
E: V
g g
where the ratio between the value of a (or Eg) with and without (i.e., at
feed conditions, vg = vi) absorption is related to the superficial gas veloc-
ity. These equations are based on the assumption that the dispersed gas
phase is constituted by a swarm of spherical bubbles flowing with no break-
age or coalescence and no shape variation during shrinkage.
ESTIMATION OF CHARACTERISTIC PARAMETERS
The use of mathematical models for the simulation of various types of indus-
trial gas-liquid reactors requires a suitable evaluation procedure of all the
parameters appearing in the model equations. In this section recommended
semiempirical relationships for the three most widely used reactor types-
sparged, packed, and mechanically agitated reactors-are reported.
Sparged Reactors
These are empty reactors where the gas-liquid m1xmg energy is predomi-
nantly introduced with the gas phase, which can be dispersed into the
liquid phase through various sparger types: single orifices, pipes with
holes, sieve and porous plates, and two-phase nozzle spargers of injector
and ejector type (Mersmann, 1978; Fair, 1967a). Main advantages of these
units are the absence of moving parts, eliminating the need for seals (less
maintenance and cost); solids handling ability; large heat transfer rate per
574 Carra. and Morbidelli
unit reactor volume; and large values of the gas-liquid mass transfer co-
efficients. The disadvantages are backmixing, particularly in the liquid
phase; high pressure drop (significant particularly at low pressure); and
the reduction of interfacial area due to bubble coalescence, significant for
Lide > 12.
Vertical bubble columns are the sparged gas-liquid reactors most widely
used in industry. Some modifications have been introduced to improve their
performance: sectionalized bubble columns (low backmixing and bubble
coalescence), horizontal bubble columns (low pressure drop), downflow bub-
ble columns (large residence time), and plate columns (large number of
transfer units). General review articles on hydrodynamics and mass and
heat transport have been reported by Fair et al. (1973), Pohorecki ( 1976),
Stichlmair and Mersmann ( 1977), Charpentier ( 1981) , and Zahradnik et al.
(1982) for plate columns, and Joshi and Sharma (1976, 1978) for horizontal
bubble columns.
Various studies on the design and simulation of bubble columns have
been reported in the literature ( Shulman and Molstad, 1950; Sideman et al. ,
1966; Fair, 1967a,b; Sharma and Mashelkar, 1968; Cichy et al., 1969; Cichy
and Russel, 1969; Mashelkar, 1970; Deckwer, 1977; Mersmann, 1978).
Shah et al. ( 1982) have published an extensive survey on the characteristic
parameters estimation for bubble columns.
These parameters are affected by the column regime, which changes by
increasing the upflow gas velocity as follows:
1. Bubble flow, characterized by uniform flow of equally sized bubbles;
it occurs approximately at ug < 0.05 m/s (Fair, 1967a).
2. Churn turbulent flow, where large and small bubbles are present
with different rise velocities leading to an unsteady flow; it is the
most common in industrial units.
3. Slug flow, where the bubble occupies the entire column cross sec-
tion; it occurs at large upflow gas velocity, with columns diameter,
de:;; 0.15 m.
The a priori definition of the flow regime is difficult, since it is affected
by many parameters, such as sparger type, physical properties, and
velocity of the liquid phase. An approximate map of flow regimes is shown
in Fig. 8.
The recommended empirical equations for the evaluation of the character-
istic parameters of a bubble column are reported in Table 9, The volume-
surface mean diameter of the swarm of bubbles, defined by Eq. (45) can be
evaluated through Calderbank's ( 1967) correlation when gas is sparged by
two-phase nozzles and the energy dissipation rate is given by Pt /V d ==
UgPR.(1 - Eg)g. For less effective gas spargers, such as perforated plates
and single orifices, the correlation proposed by Akita and Yoshida ( 1974)
can be used. In sparged reactors the bubble size is controlled by the
equilibrium between breakup and coalescence rates. For low-viscous aqueous
solutions, in the bubbly flow regime, the bubble size stability diagram
shown in Fig. 9 has been proposed by Berghams ( 1973). In it the critical
Weber number, which corresponds to the mentioned equilibrium, separating
the stable and unstable regions, is shown. Pressure values up to 1. 6 MPa
do not affect the bubble diameter if the gas velocity is corrected to take
into account the pressure in the column (Kolbel et al. , 1961).
Gas-Liquid Reactors 575
0.15
Slug Flow
0.10 Churn Turbulent
Flow
Bubbly Flow
0.05 0.1 0.2 05 1.0 1.2
--de
(a)
BUBBLY FLOW CHURN SLUG FLOW
TURBULENT
b
FLOW
• 0
~
0
00 0 0
.0°0'
p
0 00 0 0 O 0
0 0 0 0 O O • 0
0 0 O
0 00 0 00
· •Oo
0 0, O ,
Oo O 0
·a 0 0
?~:oo 0
0 0
0 0 o 0 o O.
0 o 0
0 o O0
o0 o0 o0 o0 o
(b)
FIGURE 8 (a) Approximate dependency of flow regime on gas velocity ug
and column ·diameter de. (b) Schematic representation of flow regimes in
bubble columns.
1.4
Unstable reg ion
1.2
1.0
QJ
3::: Critical Weber
0.8 Stable region number
1 0.6
0.4
P, gct;, Pl U~oodvs
We= Bd=
0.2 4 a, 20,
0 0.2 0.4 0.6 0.8 10
--Bd
FIGURE 9 Stability diagram for low-viscous aqueous solutions in the bub-
bly flow regime.
en
~
TABLE 9 Semiempirical Expressions for Bubble Columns 0)
Bubble diameter Calderbank ( 1967)
0.6
OJI, En (µg)0.25
d 0.4 0.2 g µi + c2
vs =Cl
(PT/Vd) P51,
C 1 = 2. 25; n = 0. 40; C 2 = 0 for aqueous solutions of electrolytes
C 1 = 1. 90; n = 0. 65; C 2 = 0 for aqueous solutions of alcohols
c1 = 4.15; n = 0.50; c2 = 0.0009 m for pure liquids
0 12
gdcp!I,
2 ~-0.5(gdcp!I,
3 2)- • ( u )-0.12
d = 26d -- -- _lL
Akita and Yoshida ( 1974)
VS C
~ OJI, 2
µ JI,
V!td
g C
0,07 < d < 0.6 m; if d > 0.6 m, used = 0.6 m; u < 0.42 m/s;
C C C g
E < 0,3
g
(")
Terminal bubble rise velocity i::i
Clift et al. ( 1978) -s
;1
Re = M-O.l 49 (J - G.857) i::i
boo ~
P..
J = 0.94H0, 747 (2 < H < 59.3)
~
J = 3. 42HO. 441 (H > 59. 3) ~
P..
H = ! E M-0.149( / )-0.14
3 0 µ JI, µw E
4 c;'.l
p
gµ /P,Q, - pg) d u p Cl.)
00 I
< 10- 3 = vs b ,Q, > 0. l
M= 2 3 Re boo r
µ ,Q, ..o·
P ,Q,o,Q,
E.
A.
-
:i::i
E = g( p ,Q, pg:) d!s ct,
p
0 < 40 0
a,Q, ....0
;;i
Gas holdup Akita and Yoshida (1973)
1/ 8 1/12
s
_g -
-C (gd!p
-- ,Q,)
4 a,Q,
(1 - s ) (:;:) (~)
g
C = 0. 20 for nonelectrolyte solutions
C = 0. 25 for electrolyte solutions
0.15 < d < 0.6 m; u < 0.42 mis s < 0.3
C g g
3
u µ,Q,)0.578(µ!g )-O.l l(P )0.062(µ )0.107
s = 0. 672f ( _g:___!<'.,_ -- ~ ___g_ Hikita et al. (1980)
g o,Q, P 3 p,Q, µ,Q,
,Q,a,Q,
f = 1 for pure liquid or nonelectrolyte solutions
f = 10°· 0414 for I< 1 kg ion/m 3
f = 1. 1 for I > 1 kg ion/ m3
I = ionic strength of the solution
en
"'l
d = 0.1 m; 0.042 < u < 0.38 mis "'l
C g
c:n
TABLE 9 (Continued) ~
\0. 0346 ( \0. 254 ~-1
'• = ~ + 0.06855 (1 - ,.,,.112 ( : ;; : ;-; Fro. 36We o. 543J Friedel et al. (1980)
e:*0.395
u
e:* = g_
Ug + UJI,
F2
Fr =
2
gdcpJI,
F 2d
C
We=
a,11,P,11,
F = P,11,U,11, + pgug
148 < F < 336 kg/m2•s; 0.003 < E* < 0.24; 0.004 < e: < 0.3
g
184 < pJl,/pg < 5340; 37 < µJl,/µg < 2220; 0,055 < OJI,< 0,074 N/m
Interfacial area per reactor volume C".l
A
2
i
A
0.5( 3)0.1 ;:1
a= _1_ ( gdcpJl,1 gdc /.13 s:i.
3d a 2 g Akita and Yoshida (1974)
C JI, \) JI, :;:::
0
J
0.07 < d < 0.6 m; if d > 0.6 m, used = 0.6 m; u < 0.4 m/s; e: < 0.14
C C C g g
i
c;)
a= 48.7(ug/µeff)0.51 Schumpe and Deckwer ( 1981) i::i
Cl)
d = 0.14 m; u > 0.02 m/s .o·t!..
C g E.
0..
Volumetric liquid mass transfer coefficient
::0
(!)
3 i::i
0
O 5( 2 )0.62 ( d3 2)o: l
_ D ,Q, µ ,Q, • gdC p ,Q, g c p ,Q, / •1 0
( -
k,Q,a - 0.6 2 - 0- ) -- 2 g Akita and Yoshida ( 1973) ~
d P,Q, ,Q, a,Q, µ,Q,
C
0.15 < d < 0.6 m; if d > 0.6 m; used = 0.6 m; u < 0.33 m/s; E < 0.3
C C C g g
k ,Q,a = bu g0 • 8 Deckwer et al. (1974)
Sparger Liquid phase b
-3
--
Cross of nozzles ( 10 m), Tap water 0.467
d = 0.2 m; 0.003 < u < 0.08 m/s Salt solutions 0.460
C g
Sintered plates Tap water 1.174
0.1 < d < 0.15 m; 0.003 < u < 0.08 mis Salt solutions 1. 445
C g
k,Q,a = 0.00315u~· 59 µ~~· 84 Dekwer et al. (1982)
u =0.08m/s;d =0.14m
g C
Liquid-side mass transfer coefficient Calderbank and Moo-Young (1961)
3 1/3
k,Q,dvs _ [dvs ( P ,Q, - Pg) g] . -3
- 2 + 0. 31 D , d
vs
< 2. 5 x 10 m
D,Q, µ ,Q, ,Q, <:Tl
.....,,
<:o
<:Jl
TABLE 9 (Continued) Oo
C
µ 1/2 td3 1/3
k!/.,dvs = 0.42 ( ~-!/.,-) vsp!/.,(p!/., - Pg)g] -3
d > 2. 5 x 10 m
D!/., p!/.,D!/., 2 ; vs
µ !/.,
6
k!/.,dvs µ !/.,
0. 546 (dvsusp!/., )0. 779 ( d g 1/ 3)0. l1
2 + a - -)
~ --- _v_s_ _ Hughmark ( 1967)
n;-= p!/.,D!/., µ.Q, D2/3
.Q,
a = 0. 061 for single bubbles
a = 0. 0187 for swarms of bubbles
0.025 < dC < 1.1 m; Un < - uo/(1 - E )
,, x,
0.12 m/s; u S = u g /E g g
Gas-side mass transfer coefficient Geddes ( 1946)
d vs ( _JLg_
D
kg= T (1 _ y) 0.083 + 6.58 d 2
T)
g . vs
'g = L/ub; ub == bubble velocity C')
Q
y = gas mole fraction of diffusing component
1
Q
;::s
k d (d u p ) O. 756 ~
~ VS = 3.29 X 10-4 VS g g Shilimkan and Stepanek ( 1978) ~
g μa 0
0.01 < d < 0.02 m; 1 < u < 5 m/s
s:
~
C g
~
Liquid-ph ase axial dispersion coefficien t C)
Deckwer et al. (1974) 0
(/,)
I
E 0 = 0.678dl. 4u 0 · 3 r
x., C g .a·
S.
0..
dl. 4u 0 • 3 < 400
C g ~
(t)
0
0
E,Q, = 0.33dc(uc + u,Q,) Joshi ( 1980) 0
;j
1/3
Uc= 1.31 [gdc (ug - l ~gEg u,Q, - EgUboo)]
0.1 < d < 1.1 m; 0.003 < u < 0.45 m/s; 0.12 0.002 m/s
C g < u ,Q, <
Gas-phase axial dispersion coefficien t
Diboun and Schiigerl ( 1967)
E = 5u d
g r C
u = relative velocity between the gas and liquid phase
r
E = 50d 1. 5 ( u / E ) 3
g C g g Mangartz and Pilhofer ( 1980)
33
E = 56.4dl. (u /E ) 3 · 56
g C g g Field and Davidson ( 1980)
O. 08 < d < 3 m; 0. 008 < u < 0.1 m/ s
C g
Heat transfer cmifficien t
Deckwer ( 1980)
h
w 2 -0. 25
= 0.1(3-eFrP r )
p,Q,Cp,Q,ug
2 c:r.
Re= ugdvspiµ ,Q,; Fr= uigdvs; Pr= Cp,Q,µ,Q,/kT,Q, Oo
.....
~
ts:,
TABLE 9 (Continued)
2
0.03 < (ReFrPr ) < 7; 6 < Pr < 985
308
h. µ
~_w__ = 0. 411 (u
__g__!_ 851( µ 4g ( k )2/3
_JI,_ T JI,
a
)-o. 3
)o. C µ Hikita et al. ( 1981a)
JI, pJl,aJI, p!I, JI,
-4 -2
5.4 x 10 < uguJl,/051, < 7.6 x 10
4.9< CpJl,µJl,/kTJI, < 93
-12 4 3 -6
7,7 X 10 < µ Jl,g/pJl,OJI, < 1,6 X 10
C")
A
i
A
;:I
A,
s&
I
Gas-Liquid Reactors 583
The choice of one expression for the evaluation of the gas holdup is
quite difficult, due to its sensitivity to the material system, including trace
impurities. The gas holdup depends on the superficial gas velocity to the
power 0. 7 to 1. 2 in the bubble flow regime, and 0. 4 to 0. 7 in the churn
turbulent one. On the other hand, it is almost independent of pressure
values up to 1. 6 MPa (K61bel et al., 1961), of the presence of internals (mainly
for heat transfer), and of the column diameter for de > 0.15 m. It is then
convenient, particularly for noncoalescing or non-Newtonian liquids, to
evaluate Eg through a simple experimental measurement in a laboratory-scale
column ( de > 0. 15 m), with the desired material system and gas velocity.
The most accurate correlations seem those proposed by Akita and Yoshida
( 1973) and Hikita et al. ( 1980), valid for single- or multinozzle spargers
with diameter of about 1 mm or larger and for low-viscous ( µ Q, < 0. 02 Pa •s)
and coalescing liquids. Such systems are characterized by the following
condition (Mersmann, 1978):
1 dcr Q,
- - ,;;; 1 ( 74)
I':,, (5 dx
where x indicates the mole fraction of the component of lower surface ten-
sion, and I':,, 0 is the difference in the surface tension of the two components
of the binary mixture. If condition ( 74) is violated, foaming occurs in the
column and the gas holdup increases, as in the case of aqueous solutions of
electrolytes (Deckwer et al., 1974). For downflow bubble columns the rela-
tionships proposed by Friedel et al. (1980) are recommended.
The gas-liquid interfacial area per unit reactor volume, a, can be calcu-
lated from Eq. (44) using the correlations mentioned for gas holdup and bub-
ble size. In particular, the correlation proposed by Akita and Yoshida
( 1974) is recommended, which has been derived for less effective spargers
(with one or· more distributors) and can then be used in general at least
for a conservative estimation. In the case of 0.14 < Eg < 0.3, the value
of a should be calculated from Eq. ( 44) using the expressions for E g and
dvs proposed by the same authors and reported in Table 9. A more general
correlation specifically tested for two-phase nozzle spargers is shown in Fig.
10 (Nagel et al. , 1978) . The direction of flow, up or down does not
1000
500
200
"' 100
! 50
20
10
0.1 0.2 05 2 5 10 20 50 100 200 500
--Pr/Vd (KW/m 3 )
FIGURE 10 Specific interfacial areas in bubble columns; •, vertical pipe;
x, horizontal pipe.
584 Carrii and Morbidelli
substantially affect the interfacial area in cocurrent flow (Shilimkan and
Stepanek, 1978). Finally, for non-Newtonian highly viscous media and
columns operating in the slug regime, as it is usually the case for such
media at ug > 0.02 m/s, Schumpe and Deckwer (1981) developed a useful
correlation. The effective liquid viscosity 11eff is calculated according to
Nishikawa et al. ( 1977).
The volumetric liquid-side mass transfer coefficient depends on gas
velocity, sparger type, and liquid physicochemical properties, while they
are unaffected by the liquid velocity and the column diameter, above de =
0.15 m. Also, in this case the correlation proposed by Akita and Yoshida
( 1973) applies to less effective spargers, and the one proposed by Deckwer
et al. (1982) to non-Newtonian highly viscous media. The k,11,a values ob-
tained from Akita and Yoshida's equation are conservative values; much
higher values can be obtained using sintered plates or two-phase nozzles
for gas sparging [Deckwer ( 1977) suggests, as a rule of thumb, a correc-
tion factor of about 4 to 5]. This same equation can also be used for multi-
stage columns. A more general expression is given by Deckwer et al.
( 1974), where the constant b is quite sensitive to sparger type and material
system. This same expression can be used for downflow bubble columns
(Herbrechtsmeier and Steiner, 1978).
Gas-side mass transfer resistance is usually negligible, and it becomes
important only in the case of fast or instantaneous chemical reactions. Ac-
curate correlations are not available; those reported in Table 9 are the
most widely used. It is worthwhile reiterating that for all the parameters
described up to this point, the effect of the column diameter de becomes in-
significant for de values larger than 0.15 m for less viscous liquids, and
larger than 0.30 m for highly viscous liquids (11,11, > 0.02 Pa•s).
The liquid-phase axial dispersion coefficient E ,11, depends on the gas
velocity and column diameter and geometry, whereas it is independent of
the liquid velocity, at least up to u JI, = 0. 03 m/ s. Rectangular columns ex-
hibit larger backmixing than cylindrical ones (Striegel and Shah, 1977a).
In a coiled column, E JI, depends on liquid velocity and approaches the same
degree of axial mixing as in a single liquid-phase column for Reynolds num-
ber of the order of 400 to 2000. Information about backmixing in horizontal
columns, in multistage columns partitioned with orifice and perforated plates,
and in spray columns can be found in the review of Shah et al. ( 1978).
In nonisothermal bubble columns it is necessary to take into account the
heat exchange with the surroundings. It is remarkable that for Newtonian
liquids the heat transfer coefficients from the reactor wall and from immersed
coils are almost identical. For non-Newtonian liquids, the latter is larger,
and then it is advantageous to use coils. Also, the location of the heat
transfer section along the column axis does not appear to affect the heat
transfer coefficient (Hikita et al., 1981a).
Packed Columns
The presence of packings inside the column limits bubbles coalescence,
leading to smaller bubbles, which rise with lower velocity. As a consequence,
backmixing decreases in both phases, and interfacial area and gas holdup
increase with respect to empty bubble columns. The pressure drop in-
creases, but usually not significantly (Carleton et al., 1967). High-porosity
packings, such as screen packings ( Ep 2:_ 0. 90), are particularly efficient
Gas-Liquid Reactors 585
(Chen and Vallabh, 1970). Packed columns are specifically indicated when
handling corrosive materials and when no significant heat exchange is
required.
Two main flow patterns can be operated in a packed column: trickle
flow, where the gas forms a continuous phase while the liquid phase flows
downward as a film over the solid packing and its level is below the pack-
ing; and bubble flow, where the gas flows as bubbles through the liquid,
whose level is now above the packing. A detailed description of the column
hydrodynamics and the packing characteristics is reported by Fair et al.
( 1971) and Treybal ( 1968). In Table 10 approximate values of the void frac-
tion Ep and the total dry surface area per unit packed volume at are reported
for some packings. The characteristic packing dimension is defined as
follows:
6( 1 - E )
p
d ( 75)
p
which is not normally the same as the nominal diameter dn.
The recommended relationships for the evaluation of the characteristic
parameter will be examined below in terms of the operation mode and the
specific flow patterns. Useful surveys have recently been reported by
Charpentier (1976, 1978) on mass transfer, by Shah et al. ( 1978) on back-
mixing in packed columns, and by Satterfield (1975) on trickle-bed reactors.
Countercurrent Packed Columns
These units are usually operated in the trickle-flow regime, that is, below
the loading zone. For such situations the various involved parameters can
be evaluated with the expressions reported in Table 11. Little information
is available on columns operated countercurrently in the bubble-flow regime
(Carleton et al., 1967; Sahay and Sharma, 1973).
The liquid holdup is given by the sum of two contributions: s ,Q, = s~ +
s~; the static holdup, s~, given by the liquid retained by the drained pack-
ings, and the operational holdup, s~. The values of the adjustable param-
eters appearing in the correlation developed by Shulman et al. (1955) are
reported in Table 12 for some packings. For other types of packing the
procedure proposed by Dombrowski and Brownell ( 1954) can be applied
The evaluation of the interfacial area per unit of packed volume, ap,
and the liquid-side mass transfer coefficient k,Q, can be obtained, for tfie
packings and operating conditions summarized in Table 10, from Figs. 11
and 12 as a function of the liquid superficial velocity. The gas velocity
does not affect the reported curves. For situations not included in these
figures, the relationships reported in Table 11 can be used. The values of
the critical surface tension, CTc for various materials, including polypropylene
and polyethylene hydrophilized by treatment with chromosulfuric acid
(Linek et al., 1977), are reported in Table 13. Note that the expression
proposed by Onda et al. ( 1968) assumes that the gas-liquid interfacial area
ap identifies the packing wetted surface area aw, which is not true when a
portion of the liquid is dispersed as small droplets or rivulets, as for Pall
rings (in this case the interfacial area may be underestimated by 50%).
en
00
0)
TABLE 10 Packing Characteristics and Operating Conditions for the Data Shown in Figs. 11 and 12
Packing Number of
particles per
Nominal Column unit of Dry packing Void
diameter, Temperature diameter packed column area, at fraction,
Type dn (in.) (OC) de (m-3) (cm-1) €
p
A Ceramic Intalox saddles 1/2 25 4 in. 630,000 4.7 0.78
B Ceramic Pall rings 1/2 25 4 in. 360,000 4.2
C Steel Pall rings 5/8 25 6 in. 220,000 3.5 0.93
D Ceramic Raschig rings 3/8 30 10 and 1,070,000 5.1 0.68 C")
20 cm i::i
,
E Ceramic Raschig rings 3/8 30 4. 37 cm 980,000 - - a,
i::i
Ceramic Intalox rings ;:J
F 1/2 30 io cm 385,000 - - i::i.
G Ceramic Raschig rings 1/2 25 4 in. 370,000 3.8 0.64 is:
0
H 1 Ceramic Pall rings 1 25 9 in. 49,000 2.2 - s:
i::i.
H 2 Inox steel Pall rings 1 25 20 cm 49,000 2.0 0.94 ~
H 3 Polypropylene Pall rings 1 25 20 cm 51,000 2.0 0.90 c;"}
i::i
11 Ceramic lntalox saddles 1 25 9 in. 84,000 2.5 0.77 "'I:"'I
Ceramic lntalox saddles 1 25 20 cm 75,300 2.5 0.77
..o·
12 s.Q.
Polypropylene lntalox 1 25 20 cm 53,500 2.0 :-
13 ~
Cl)
J Ceramic Raschig rings 1 25 12 in. 2.03 i::i
- - Q
K
...
0
Ceramic Raschig rings 1 25 9 in. 48,000 1.8 - ~
Ceramic Raschig rings 1 25 20 cm 50,600 1.9 0.74
PVC Raschig rings 1 25 20 cm 51,400 1. 9
L Ceramic Raschig rings 1 1/2 20 18 in. 14,000 1. 3 0.71
M Ceramic lntalox saddles 1 1/2 11-34 0.5 m 21,000 1.6 0.80
N Ceramic Raschig rings 1 1/ 2 11-34 0.5 m 13,000 1.3 0.71
0 Polypropylene Pall rings 1 1/ 2 11-34 0.5 m 15,500 1.3 0.91
p Polypropylene lntalox 2 11-34 0.5 m 6,200 1.1
saddles
<:ii
Oo
-..;i
TABLE 11 Semiempirical Expressions for Countercurrent Packed Columns <:11
Co
Co
Liquid holdup Otake and Kunigita
( 1958)
p u d 0.676(d 3gp 2)-0.44 -4
E = 6. 28 £ £ p) ~ 3. 8 X lQ
£ ~ µ 2 + d
£ µ p
£
c2 c3
Clµ£ cri
ES = Shulman et al. ( 1955)
£ 0.37
pi
u2 )l/2
r:;O (;µ U
)1/3
£ = 2,2-1:_!.. + 1.8-£
~ Buchanan (1967)
gp d2 gd
£ n n
d = nominal packing size (Table 10)
n
Interfacial area per unit of packed volume Onda et al. ( 1968)
(")
a
5 2 )0.2] A
crc 0.75( uipi)0.1(ui2a)-o.o
t ( u£p£ "".I
....E.. = 1 - exp [ -1.45( - ) - - - ;1
at cri atµ£ g criat A
;:$
at = total dry area of the packing per unit of packed volume A..
:s::
0
a 2 0 33 ~
o. uipi 041 ( uipi) · 1 ( crc ) 0 . 182 A..
....E.. = 1.045--
( -- - Puranik and Vogelpohl
at
~ atµ£ criat cri ~
( 1974)
2 -2 c;":l
0.25 < p,Q,u,Q, < 12 kg/m •s; 10 < dp < 0.0375 m p
Cl)
I
t-<
0.3 < 0,Q,/CTc < 1.3; 0.08 < ap/at < 0.8; .o·
S.
A.
Volumetric liquid mass transfer coefficient Mohunta et al. (1969) ::0
Cl)
p
Q
9 4 0
gp,Q, )2/3 (g2p,Q,)1/ (µ,Q,u!a:)l/ ( µ,Q, ~-1/2 '-:I
k a = 0.0025-- -- --- -- Cl)
,Q, p ~atµ ,Q, µ ,Q, 2 p ,Q, D ,Q,
g p,Q,
2 2
0.1< u,Q,p,Q, < 42kg/m •s; 0.015 <ugpg< 1.22kg/m •s;
0.006 < d < 0.05 m; 0.06 < d < 0.5 m
p C
Liquid-side mass transfer coefficient Onda et al. (1968)
1/3 2/3 -1/2
k = 0.0051(µ,Q,g) (u,Q,p,Q,) (~) (ad )o. 4
,Q, P,Q, awµ,Q, p,Q,D,Q, t p
0.0063 < dp < 0.051 m; 1 < (u,Q,p,Q,/awµ,Q,) < 500
a = a (as given by the same authors in this table)
w p
Gas-side mass transfer coefficient Onda et al. (1968)
0. 7 1/ 3
k
_g_ = f(pgug) (J_) (ad )-- 2
atDg atµ p D t p
g g g
<:.rt
Co
f = 2. 0 for d < 0. 013 m <o
p
c:.,,
co
C,
TABLE 11 (Continued)
f = 5. 2 for d > O. 013 m
p
0.0063 < d < 0.051 m; 5 < u p /atµ < 500
p g g g
Liquid-phase axial dispersion coefficient Sater and Levenspiel
( 1966)
(Pei/Et)= 0.00758 Re~· 703
0.007 < d < 0.016 m
p
Pei = 836Re; 0 • 317Re; 2 · 01 Linek et al. (1978)
2 x 10-5 < Re -0. 317Re-2. 01 < 2 x 10-3
g i
Pei= u 1 d/Et; Re 1 = piuidp/µ 1 ; Reg= pgugdp/µg
Gas-phase axial dispersion coefficient De Maria and White
( 1960)
) ()
P e , /( E -E 2 4R e -0.2
=. X 10-(0.013-0.088 d p /dC )Ren,., A
g p i g "'S
is,
Pe' = 1.l5Re0.139Re 1 0.16 x 10 -0.131 Re 1 0.385 Linek et al. ( 1978) A
g g ;:s
$:l.
Pe' = u d /E ; 5 < Re < 50; Ren < 100 is::
g gp g g ,., 0
~
~
TABLE 12 Values of the Adjustable Parameters Appearing in Shulman's
Equation, Reported in Table 11, for Various Packings
Packing
Nominal diameter,
Type dn (in.) Cl c2 c3
Carbon Rashig rings 1 1.35 0.02 0.23
Ceramic Rashig rings 1 2.75 0.02 0.99
Ceramic Berl saddles 1 0.904 0.04 0.55
300
ia.
200
0.005 0.01 0.015 0.02
-U1
FIGURE 11 Interfacial area per unit packed volume, ap in countercurrent
packed columns for the packing illustrated in Table 10.
0.004 0.008 0.012
-U1
FIGURE 12 Liquid-side mass transfer coefficient ki in countercurrent
packed columns for the packing illustrated in Table 10.
592 Carra and Morbidelli
TABLE 13 Critical Surface Tension for Some
Packing Materials
Material CTC X 10 3 (N /m)
Carbon 56
Ceramic 61
Glass 73
Paraffin 20
Polyethylene 33
Polyvinyl chloride 40
Steel 75
Polypropylene and polyethylene 54
hydrophylyzed
Axial dispersion is usually present in both phases, although it is
larger in the liquid phase [roughly one order of magnitude in the Peclet
number; Dunn et al. (1977)]. Reliable semiempirical expressions are not
available for this parameter, due to discrepancies obtained using different
experimental approaches (steady-state or transient) or different evaluation
methods of the experimental response curves. In Table 11 the most widely
used expressions are reported; the correlations proposed by Linek et al.
( 1978) appear particularly accurate, although they are limited to a 0.139-m-
diameter column packed with 15-mm ceramic Raschig rings.
Cocurrent Packed Columns
In these units, since flooding cannot occur, unlimited flow rates can be
used. So, unlike countercurrently operated columns, they do not exhibit
capacity limitations and at a given gas and liquid flow rate, the pressure
drop is lower. Obviously, due to reduced average interphase mass trans-
fer driving force, their application is limited primarily to columns with fast
chemical reactions. For small gas flow rates in a downward cocurrent column,
the trickle or bubbly flow can be present, depending on the magnitude of
the liquid flow rate. For increasing gas velocity, in both cases a transi-
tion to pulse flow, and subsequently to spray flow, takes place. Flow pat-
terns and transitions from one form to another, as a function of the gas
and liquid flow rates, are reported graphically by various authors, with
reference to specific systems (Charpentier et al., 1969; Beimesch and
Kessler, 1971; Charpentier and Favier, 1975). Trickle flow cannot be
realized in upflow columns.
The recommended expressions for the evaluation of characteristic param-
eters are summarized in Table 14. In the expression developed by Larkins
et al. ( 1961), which is not valid in the trickle flow regime, the pressure
drop for each phase is calculated through the following Ergun-type
equation:
c;)
TABLE 14 Semiempirical Expressions for Cocurrent Packed Columns l:l
a,
f<
Liquid holdup and pressure drop Larkins et al. (1961) ..o·
I::
.....
2 A..
log (sisp) = -0.744 + 0.525 log x - 0.109(log x)
:,;i
(1)
l:l
(')
b.PLG = o. 416 ....0
log b.P + b.P G ;;"l
L (log x) 2 + 0. 666
0. 05 < x = (b.P L /b.P G// 2 < 30
Liquid holdup Bakos and Charpentier ( 1970)
-2
log( s / sp) = a 1 + a 2 log x + aa<log x)
0. 05 < x = ( uu 1 p 1 L LG + 1 < 100
gpg pgg
Rashig rings
rep r,,
Spheres Pellets
al -0. 570 -0.280 -0.363
a2 0.165 0.175 0.168
a3 -0.095 -0.047 -0.043
d > 0.002 m
p
Interfacial area per unit of packed volume
a Cll
-a co
....E.. = aly 2 c..,
at
c:n
co
>I.
TABLE 14 (Continued)
~PLG E
y = ~h
L at
y > 12 Pa, a 1 = 0.25, a2 = 0.5 Gianetto et al. ( 1970)
y < 12 Pa, a 1 = 0.05, a2 = 1.2 Charpentier ( 1976)
E < 0.5
p
Volumetric liquid mass transfer coefficient
- a2
ktap = a 1 (EtDt/Dw)
u ~p
E - i LG 3 -9 2 (')
i - W/m ; D = 2.4 x 10 m /s p
L w
- 3
l
p
Et > 80 W/m, a 1 = 0.0173, a 2 = 0.5 Reiss ( 1967) ;::s
Q..
3 El::
5 < -E i < 100 W/m , a 1 = 0. 0011, a2 = 1. 0 Charpentier ( 1976) 0
~
Q..
- 3
Ei < 5 W/ m , a 1 = 0. 008, a2 =0 ~
c;)
Volumetric gas mass transfer coefficient Reiss (1967) p
Cl>
k a = 2 +
i:l-
g p
o. 07 Eg 213 .o·
~
....0..
u .6.P
~
E = g LG W/m3 (I)
p
g L n
0
....,
Liquid-phase axial dispersion coefficient Co and Bibaud ( 1971) Cl>
uQ,dp = 0.0165(UQ,pQ,dp)0.4313
EQ,EQ, µo
d 0.245 d -0.16
utdp
= 0.128 (PQ,UQ, p) (pgug p) (ad )0.53 Stiegel and Shah (1977b)
EQ,E Q, µQ, µg tp
Gas-phase axial dispersion coefficient Hochman and Effron ( 1969)
u d u p
d ]-0.7
K._£ 1.8 [ g P g x 10 -0.005pQ,u 0 d /µ 0 (1-E )
= µg( 1 - Ep) ,., p ,., p
(E - E )E
p g g
en
co
en
596 Carra and Morbidelli
!:.P ( 76)
L
where h1 and h2 are given in Table 15 for various packings. In the case
of trickling liquid, S,Q, is given by the equation developed by Bakos and
Charpentier (1970), and the pressure drop can be estimated from Eq. ( 76)
by replacing the packing porosity Eu with ( Sp - S,Q,) to account for the
liquid film. Note that the relationsnips reported in Table 15 for the evalua-
tion of pressure drop and liquid holdup are not valid for saddles and Pall
rings; for these packings useful data are reported by Dodds et al. ( 1960),
Wen et al. ( 1963), and Reiss ( 1967). Extensive data on downflow packed
beds with foaming and nonfoaming materials are reported by Midoux et al.
( 1976). The same relationships proposed for downflow columns also give
reasonably accurate results for upflow columns (Carleton et al., 1967).
The evaluation of mass transfer coefficients and effective interfacial
areas is highly affected by the flow regime, which in turn depends on the
energy dissipation rate. In the relationship proposed by Reiss ( 1967) for
the evaluation of k ,Q, ap in liquids more viscous than water, the complementary
correction D ,Q, µ ~ • 8 = constant for constant temperature, should be applied.
In the case of kg ap, the expression developed by Reiss ( 1967) is not
valid for the trickle flow regime, where the same equation reported in Table
11 for the countercurrent case gives conservative results. Mitchell and
Perona (1979) found, for high-porosity packings (sp > 0. 7), interfacial
area values significantly larger than those given by the relationship pro-
posed by Gianetto et al. ( 1970) and Charpentier ( 1976). For upflow
TABLE 15 Values of Parameters h 1 and h 2 in
Eq. (76) for Various Packings
Packing
Nominal diameter,
Type dn (in.) hl h2
Dumped 1/ 2 3.06 0.340
Stacked 1/2 2.33 0.039
Dumped 1 2.56 0.918
Stacked 1 3.58 0.0195
Stacked 3 3.39 0.018
Intalox 1 3.75 0.333
Cylinder 1/8 4.17 0.292
Sphere 3/8 3.28 0.167
Raschig ring 3/8 7.39 0.388
Source: Reiss (1967).
Gas-Liquid Reactors 597
columns the k ,Q,ap values are roughly 100% larger than those calculated
using the relationships reported in Table 14 (Specchia et al., 1974); in the
bubbly regime a conservative value, k ,Q,ap = 0. 15 s- 1 is recommended
(Charpentier, 1976).
Axial dispersion in the liquid phase can be described using the relation-
ships developed by Co and Bibaud (1971) and Stiegel and Shah (1977b) for
trickle beds and bubble-packed columns, respectively. For the gas phase,
the relationship developed by Hochman and Effron ( 1969) applies only to
trickle flow [for Re ,Q, > 650 the dispersion coefficient is independent of the
liquid flow rate; Woodburn (1974)]. For bubble-packed columns no data
are available on gas-phase axial dispersion, which can be expected to be
smaller than in upacked bubble columns under equivalent flow conditions.
Mechanically Agitated Reactors
Stirred tanks are particularly suitable for viscous liquids, large liquid
volumes, and low gas flow rates. Noticeable is the flexibility of these units
with respect to the heat transfer rate and the liquid residence time. Princi-
pal drawbacks are the large backmixing in both phases and the high cost
of the mechanical agitator, particularly in the case of highly corrosive
liquids. As a rule of thumb with noncorrosive liquids, the mechanically
agitated reactor is most economical when the overall reaction rate is five
times larger than the mass transfer rate in a bubble column. If a large
fraction of gas needs to be absorbed, stirred-tank reactors are not recom-
mended. Recent reviews on these units have been reported by Calderbank
(1967), Charpentier (1981), and Joshi et al. (1982).
In Table 16 a list of the most important agitator types is given, together
with their main characteristics [uAM and µ,Q,M indicate the maximum allowable
values of the agitator tip velocity and of the liquid viscosity, respectively
(Steiff et al., 1981)]. The most common agitator for dispersing gas into
liquids is the six-flat-blade turbine, while a pitched-blade turbine is to be
preferred when suspension of solid particles is required. Baffles in the
vessel change the liquid flow patterns, improving the gas-liquid mass trans-
fer. The baffling recommended is four 90° baffles, dR/12 in width, offset
from the vessel wall one-sixth of the baffle width. In a single impeller unit,
values such as H/dR = 1, dAldR = 0.4 to 0.5, and hAldR = 0.33 to 0.5 are
recommended, where dA and hA indicate the agitator diameter and height
off the tank bottom, respectively. Gas sparging can be realized with an
inexpensive perforated plate (at least in the turbulent regime, where the
bubble size is regulated by the coalescence and breakup phenomena). The
sparger is located just below the agitator, with a diameter 0. 8 to 1 of the
impeller diameter. An even gas distribution, in the case of a sparge ring,
can be obtained by arranging the size and number of holes so that the gas
velocity through the holes is at least three times that through the pipe
used as sparging ring. The use of a disk-mounted turbine is suitable,
particularly at low agitation speed in order to prevent bubbles crossing a
hub-mounted impeller instead of being dispersed. Further information on
reactor design is given by Bates et al. (1966) and Nagata (1975).
In these units the gas-liquid dispersion is realized using not only the
energy associated with the gas inlet flow rate, as in sparged reactors, but
also a significant contribution is by mechanical agitation. The latter is
largely predominant when the agitation speed exceeds a critical value N O,
which corresponds roughly to a tip velocity of about 2.25 m/s, and is given
by
en
<o
co
TABLE 16 Qualitative Information on the Application of the Most Common Agitators in Multiphase Systemsa
Heat transfer
uAM µLM Gas-liquid Liquid-solid
Stirrer design dA/dR (m/s) (Pa•s) Baffled Wall Coil dispersion dispersion
Propeller 0.15-0.4 15 5 Yes gg g gg gg
Disk flat-blade turbine 0.2-0.45 15 10 Yes gg g gg g
Pitched-blade turbine 0.2-0.45 12 20 Yes gg gg gg gg
Impeller 0.5-0.7 12 20 Yes gg g g
Paddle mixer 0. 4-0. 5 5 50 Yes gg gg g bg
Anchor impeller o. 9-0. 98 5 50 No gg g bg
Helical mixer o. 9-0. 98 1 1000 No gg C')
I:)
a ""l
gg, Highly suitable; g, suitable; bg, conditionally suitable. J
p
;:l
.:l.
;;::
0
~
.:l.
E
Gas-Liquid Reactors 599
(77)
where a and b depend on the agitator type: a = 1. 22 and b = 1. 25 for
turbine impellers; a = 2. 25 and b = 0. 68 for two- and four-blade agitators
(Westerterp et al., 1963). Further details on the hydrodynamics and flow
patterns of agitated gas-liquid reactors, including the estimation of the
agitator flooding conditions, are reported by Rushton and Bimbinet ( 1968),
John (1971), Nagata (1975), Hicks and Gates (1976), Joshi et al. (1982),
and Rietema ( 1982).
Another critical agitation speed, Ne, can be defined beyond which gas
above the free liquid surface is entrapped by the liquid. It can be evalu-
ated from the following relationship (Joshi et al., 1982):
dl.1 0.19 0,031 0,625
R
N = 1.65 N;0.125(::g) (:;) (:;) (78)
C dl. 98
A
where Np is the power number and WA the impeller blade width.
Due to the strong dependence of mass and heat transfer parameters on
liquid viscosity, surface tension, coalescenc;e characteristics ( such as solu-
tion ionic strength), and foam ability, it is very difficult to predict a priori
these parameters (Elstner and Onken, 1981). Therefore, the semiempirical
expressions reported in Table 17, developed primarily for the air-water sys-
tem, should be used with caution.
The power absorbed by a mechanical stirrer in an unaerated liquid, P 0 ,
can easily b_e calculated (Bates et al., 1966; Nagata, 1975). The reduced
power consumption in gas-liquid systems can be evaluated according to the
relationships reported in Table 17. The correlation developed by Hughmark
(1980) is based on experimental data of various authors; it refers to flat-
blade turbines, Newtonian fluids , and does not account for the power con-
tribution of gas sparging. Further experimental results are reported by
Hassan and Robinson ( 1977).
The correlations developed by Sridhar and Potter (1980a,b) for inter-
facial area and gas holdup constitute extensions of the corresponding cor-
relations by Calderbank (1958), to account for larger gas flows and operating
pressures beyond atmospheric. In such cases the contributions of the
kinetic power Pk and the gas expansion power Pq are comparable to the
mechanical agitation power Pg, At atmospheric pressure, Pt ~ Pg and
Pg ~ Pa, and these equations reduce to those developed by Calderbank
(1958). Mean bubble diameters can be estimated using Eq. ( 44) and suitable
correlations are reported in Table 17.
Specific interfacial area values are highly sensitive to the solution ionic
strength. In fact, the inhibition of bubble coalescence by ionic solutes,
even if present in very small amounts (Elstner and Onken, 1981), leads to
larger values of a. The expressions proposed by Van't Riet (1979), valid
for aqueous solution and for agitation speed beyond the critical value No,
account for this effect.
The volumetric liquid mass transfer coefficient is not affected by the
agitator type, location, and number and by the sparger type and position,
0)
TABLE 17 Semiempirical Expressions for Mechanically Agitated Reactors c:,
c:,
Impeller power consumption Hughmark ( 1980)
5
p (Q )-1/4( N2d4 )-l/
-f = 0.10 if- t3
0 Jl gwAVJl
3
0.87 < pJl < 1.6 kg/m ; 0,0008 < µJl < 0.028 Pa•s; 0.025 < a!l < 0.072.N/m;
0.1 < dR < 1 m; 0.25 < dA/dR < 0.46; 0.31 <Pg/Po< 0.8
Total power consumption Gray et al. (1982)
2 11/4 1/4
PT g hA dR ail
N 3d!p, = o.,. (cu,ie,)'N 2d! CJ
h A = agitator height off the tank bottom;
0.15 < dR < 0.45 m; 0.25 < dA/dR < 0.45; 0.75 < hA/dA < 1.5
(j
a s::i
Gas holdup Hughmark ( 1980)
l
s::i
2 ;::s
Q )1/2( N2d4 ¾N p
2d! Jl)l/4 A.
s =
g
O. 74 ~__JL
NV Jl
A
2/3
)l/ (
V 2/3 ~
gw Av Jl a!l Jl
~
A.
-3 -2 3
¾=2.5x1Q m;lO <VJl<51m;ug<0.053m/s
....~
c;)
Q
a,
Eu )1/2 [(P /V )0.4P0.2j(u )0.5(p ) (p )0.16
E = ( .JL.g_ + o. 000216 g JI, JI, _g: _'.!_ :__g:_ Sridhar and Potter ( 1980a) ~
g ub 0.6 ub P p .5·
ail g a i:::
E:
ub = 0.265 m/s; pa = density of air at operating conditions ~
Cl)
g
2 0
-
~
PT=P g +Pk+P q ;Pk=0.5Qpu;
g g s
P = P n ghLQ ; u = gas velocity at sparger exit
q J<, g s
Interfacial area per reactor volume Hughmark ( 198ol
= ~gp !l)l/2(~)1/3( N2d! )O. 592(¾N2d!p Jl,)O. l 87
a 1. 38 a NV 2/3 2/3
!l !l gwAV!l a!lV!l
-3 -2 3
¾= 2.5 x 10 m; 10 <Vil< 51 m; ug < 0.053 m/s
(P /V ) 0. 4P 0. 21(u )0. 5(p ) (p )0.16
a = 1. 44 [ g JI, JI, _g: _'.!_ J Sridhar and Potter ( 1980b)
0.6 ¾ p p
ail g a
symbols as for gas holdup correlation
Volumetric liquid mass transfer coefficient Chandrasekharan and Calderbank
(1981)
0.551 r:;-
0. 0248 (p ) 0. 551/v dR
ka=--_g: Q
!l d4 Vil g 0)
R C
.....
Cl)
TABLE 17 (Continued) c:::,
~
3 -3 -2
90 < P g/V JI, < 1700 WIm ; 2. 6 x 10 < ug < 1. 8 x 10 m/ s; 0. 3 < dR < 1. 2 m
P )m
- ( _g_ n Van't Riet (1979)
k!/,a - b 0 V !l ug
For pure water: b 0 = 0. 026; m = O. 4; n = 0. 5
For ionic solutions: b 0 = 0.002; m= 0.7; n= 0.2
2 x 10- 3 <VJ/,< 4.4 m3 ; 500 <Pg/VJ/,< 10,000 W/m 3
Liquid-side mass transfer coefficient Prasher and Willis ( 1973)
1/ 2 - 1/4
k!/, = 0,592D!/, (Ep!/,/µ!/,)
8N 3d 5 <j) Q
-E:= - 2 -
A- q=~
dRhL Nd 3
A
<P = 1 - 1.26q for q < 0.035
C"'l
A
<P = 0.62 - 1.85q for q > 0.035
- 2 3
i
A
dA/dR = 1/3; 0.006 < E < 0.4 m Is ;::s
s:i.
is::
0
Gas-side mass transfer coefficient Newman (1931)
~
s:i.
(t)
kg = 6. 5s[a.vs<:g_ YJ --~
Ci)
y = gas mole fraction of diffusing component
&lI
I:"'
Liquid-phase axial dispersion coefficient Joshi ( 1980) .o·
~
...
s::l.
(dR + H) 2N]
~
ER-= 0.116 [ 2 (l)
(dR/dA) §
8"
H = clear liquid height; valid for disk turbine impeller ;!
Heat transfer coefficient Rao and Murti ( 1973)
h d (µ )-0.14
~ = b Re mPr 0 · 33Fr -O. l _.:!!..
kTQ, µQ,
b = 1. 35; m = 0. 59 for jacket
b = 0.87; m = 0.64 for coil
_ dApR- C Q,µQ,
Re = - - (dAN + 4u ) ; Pr = T
µQ, g TR-
N2d
Fr = __A_; µ (µ ) = liquid viscosity at inside vessel (coil) wall temperature
g W C
10 3 < Re< 5 x 10 5 ; 2 <Pr< 266; 0.008 <Fr< 0.53
1. 02 < µw/ µ Q, < 1. 50 for coil; 0.18 < µw/ µ Q, < 0. 98 for jacket
aThese relationships have been corrected with respect to the original version according to Hughmark ( 1982).
0:,
C
c:..,
604 Carra and Morbidelli
as long as the indicative conditions on sparger diameter and agitator loca-
tion previously mentioned are satisfied (Van't Riet, 1979). When operating
at large flow rates, the gas sparging power contribution should also be con-
sidered together with mechanical power Pg in the evaluation of kia (Botton
et al., 1980). Extensions to systems other than O2-water can be made as
suggested by Fair ( 1967a):
(79)
where D = 2.4 x 10- 9 m 2 /s. No general correlation is available
Orwater
for non-Newtonian liquids; experimental data reported by Hocker et al.
( 1981) can be useful. The correlations for gas- and liquid-side mass trans-
fer coefficients are not very accurate; for the latter the relationship pro-
posed by Calderbank and Moo-Young (1961) reported in Table 9, can be
used.
The axial dispersion coefficients in both phases, Eg and Ei, are
greatly enhanced by mechanical agitation, so that the expressions reported
fo.r sparged reactors give in this case conservative estimates. Perfect mix-
ing can reasonably be assumed at stirring speeds above NO· Further in-
formation about liquid-phase backmixing in mechanically agitated contactors
is reported by Sideman et al. (1966) for single-stage systems and by Sul-
livan and Treybal ( 1970) and Joshi ( 1980) for multistage systems.
In Table 17 semiempirical correlations for the evaluation of the heat
transfer coefficients, for both the coil-aerated liquid and the wall-aerated
liquid heat transfer, are reported. These relationships, obtained using a
flat-blade turbine as agitator, are of general validity, since the type of
,a,~---.------.----.-----,
Reg=ugdAP1/μ1 :
Pr1=1J1 Cp1/kn
Fr9 = u~/gdA; St= h/u 9 P1 Cpl
-~
10°
• □-,__
Vl 101
I o.e,6.£=Jacket
o. ■ =Coil
ti~
□~~
~
System; water-air
Baffled tank; H :dR
10·1 10° 101
-< Reg Fr 9 Pd> 113
FIGURE 13 Correlation of heat transfer data in aerated stirred vessels.
Gas-Liquid Reactors 605
impeller has little effect on heat transfer (Joshi et al., 1982). As in the
case of mass transfer, the effect of gas sparging on the heat transfer co-
efficient decreases at higher agitation speed; in any case, it never causes
variations with respect to the ungassed case (Uhl, 1966; Nagata, 1975)
larger than about 25 to 30%. In Fig. 13 the data obtained by various
2 5
authors for the air-water system at high stirring intensity (NdA p Q, /µ Q, > 10 )
are shown (Steiff et al., 1981).
APPROXIMATE SOLUTIONS FOR ISOTHERMAL MODELS
The complete model of a gas-liquid reactor is obtained by coupling the
suitable macroscopic material balances with the liquid film model. The lat-
ter must then be solved for different values of the bulk concentrations <Pgi
and cp Q,i, which vary along the reactor axis (steady-state axial dispersion
model) or during time (semiflow batch model). The solution in general re-
quires numerical techniques. Since boundary value differential equations
are involved, the weighted residual methods (Finlayson, 1972; Villadsen
and Michelsen, 1978) and the implicit difference methods, such as the one
proposed by Lee ( 1968), are particularly convenient. Comments on their
application to problems of this type are reported by Huang et al. (1980),
Shah and Paraskos ( 1975), and Ho and Lee ( 1980) for the orthogonal col-
location method; by Szeri et al. ( 1976) for the Galerkin method; and by
Deckwer ( 1976) for the Lee method.
It is apparent that numerical solution of the complete models, although
always feasible, is quite complex and time consuming. It is therefore use-
ful to develop approximate solutions, valid only in limited situations, which
can be applied for first-trial reactor design and optimization. Such solu-
tions are developed below for the film and the reactor models separately.
Approximate Solutions of the Liquid Film Model
As already discussed, the only information relative to the film model that
is required for the solution of the reactor model are the material fluxes at
the interfaces (Ji)x=o (or Ef) and (Ji)x=l as a function of the bulk concen-
trations <Pgi and cjJ Q,i, Approximate relationships for (Ji)x=O and (Ji)x=l as
functions of <Pgi and cjJ Q,i for various kinetic schemes are reported in the
following.
Some relationships of this type have already been reported, but they
were all obtained assuming zero concentration in the liquid phase for the
gaseous reactant (i.e. , cp Q,A = 0), and therefore their use is confined to
cases where the reactor is operating in the fast reaction regime, as dis-
cussed later. It is evident that this assumption depends on the reactor
performance, which is obviously not known a priori, and therefore, if not
used with caution it can lead to serious pitfalls in the simulation of gas-
liquid reactors as shown by Shaikh and Varma ( 1983c).
Teramoto et al. (1969, 1973) modified the original expression of van
Krevelen and Hoftijzer (1948a) for consecutive reactions to account for
<P Q,A -:f. 0 and the general reaction order, using the approximation ( 40) de-
veloped by Hikita and Asai ( 1963). This has been extended by Morbidelli
et al. ( 1984b) to a complex scheme of consecutive reactions and compared with
the exact numerical solution. The approximate solution is reported in Table
18 and applies to the following scheme of multiple irreversible reactions:
606 Carra and Morbidelli
A + B. -+ = 1, 2, . . NR ( 80)
J
where the rate of the generic jth reaction is given by
m. n.
r = k C le J ( 81)
j j fA fj
The isothermal liquid film model equations are used, the only exception
being the boundary condition ( 51a) for the liquid reactants (Bj and Pj),
which, since only the gaseous reactant A is considered to be volatile, is
replaced by (d</Jfj/dx)x=O = 0, In Fig. 14 the characteristic multistep be-
havior of the reaction factor EA as a function of the Hatta number in the
case of three reactions of first order with respect to both reactants (NR =
3, mi = nj = 1) is shown. Extensive comparison with the exact numerical
solution for the case of a CSTR have been performed by Morbidelli et al.
( 1984b). The percentage error of the approximate solution never exceeds a
few percent, except for multiple reactions characterized by small values of
the selectivity, where it can be of the order of 20%, The approximate solu-
tion is exact for reactions of first order with respect to the gaseous re-
actant (m = 1) and zeroth order with respect to the liquid reactant (n = 0).
For other reaction orders the accuracy of the approximate solution is more
sensitive to deviations of m from unity than of n from zero. In conclusion,
the approximate expressions reported in Table 18 are sufficiently accurate
for reactor modeling. The only exception is for multiple reactions, where
the gaseous reactant exhibits different reaction orders (i.e., mi -=I- mj); in
this case percentage errors of the order of 100% for the selectivity, also
in the range where its value is not very small, can be found.
15
a:10; Stl-oo, p1=1
i;, =!;2=!;3=1
-3
<l>t2= 4h= 10 ;<l>t,= 1
<l>t,/<!>l:= 4
10
3 3
• <t P2=10,p3=10
w
t
5
~Ha
FIGURE 14 Behavior of the reaction factor, EA as a function of the Hatta
number Ha in the case of three consecutive bimolecular reactions of first
order with respect to both reactants.
Gas-Liquid Reactors 607
TABLE 18 Approximate Liquid Film Model Solution for the Kinetic
Scheme (80)
Volatile reactant, A:
E = y' (1 - ¢,9.,A/¢,!A)
A tanh y' cosh y'
yAEA/HA
Nonvolatile reactant , B . :
J
Ej = 0; (Jj)x=O = 0
(Jj)x=l = -S t tj y' t:~h y' (¢,9.,A + ¢,£A) ( 1 - co!h y')
¢,£A exp(-y') ]
y' shy'
where
NR
y'2 = Ha2 L pi m. +
2
1 "'*9..A
'¥
m.-1
J "'*tj
'¥
n.
J.'
j=l J
Ha 2 ( 2 m.-1 n. 2 m. 1 -1 n. 1 )
r·= -c- p. ~ "'*tA J "'*tJ· J -pi·-1 - - -
m. + 1 <l>fA J- <l>fJ· J-
"'i
'I' 'I'
J J mj J-1
Using a similar technique, Onda et al. (1972), Hikita et al. (1977), and
Zarzycki et al. ( 1981) have developed approximate solutions for the kinetic
schemes reported in Table 19. All the reacting components are considered
nonvolatile, the only exception being the gaseous reactants A and A'; the
boundary condition (51b) has also been used at the liquid film-liquid bulk
interface (i.e., ¢, 9.,A '4 0). The approximate solutions are reported in Table
20 in the form of a system of nonlinear algebraic equations. The unknowns
are, in addition to the reaction factors EA and EA, (if A' is present), the
dimensionless concentrations of all the nonvolatile reactants at the gas-liquid
interface, ¢,1i. Comparison of the approximate values of the reaction fac-
tor with those obtained by numerical integration of the relevant equations,
for various situations, have shown that the errors never exceed a few per-
cent. It is remarkable that very similar results can be obtained for all the
kinetic schemes in Table 19 using the penetration and the surface renewal
608 Carra and Morbidelli
TABLE 19 Kinetic Schemes Considered in Table 20
Reaction Reaction rate
kl m n
(a) A+ vBB -product rl == klCA CB
kl m n
(b) A + v BB ~ v EE + v FF rl ==klCACB
k2
r2 == k 2cPcq
E F
kl m n
(c) A+ vBB - vCC + product r == klCACB
1
k2
v A' A'+ v' C C - v BB
r 2 == k 2c~,c6
(d) A+ VA 1A' --product rl == klCACA'
kl m n
(e) A+ vBB -product r == klCA CB
1
k2
A + vcf - product r 2 == k 2C~C6
kl m n
(f) A + vBB - product r == klCACB
1
k2
v A'A' + vBB - product r2 == k 2C~,C~
models (Onda et al., 1972). This confirms the substantial equivalence of
the three models, already discussed.
Finally, it is worthwhile mentioning the study of Pangarkar ( 1974) and
Shaikh and Varma (1983c) on the effect of liquid reactant volatility, of
Karlsson and Bjerle ( 1980) on the effect of the gas-side mass transfer re-
sistance, and various analyses of mass transfer enhancement in the case of
complex kinetic schemes (Chandhari et al., 1975; Carmichael and Chang,
1980; Zarzycki et al., 1981; Astarita and Savage, 1982).
Another way to obtain approximate solutions for the liquid film model
is to assume a specific operating regime for the reactor. According to
Astarita ( 1967) and Danckwerts ( 1970), and considering, for example, the
(m,n)th-order reaction (i.e., mth order with respect to A and nth order
with respect to B) :
A + vB + liquid products (82)
characterized by the following kinetic expression:
m n
r == kC ACB (83)
Ci)
TABLE 20 Approximate Solution of the Film Model for the Kinetic Schemes Reported in Table 19 i:l
a,
I
Reaction Approximate solution M1 and M 1 .o·t-<
E.
Q.
(a) E* = q,
A :ti
(I)
Mcj>* n/2
f;B rn
0
E* = 1 q + - q (1 -
...g.,
A A B a,
vB
<P*.rn )
(1 - qA)(l + f;E/vET) + (f;E/vE)[(qA/T) - qBcj>Jrn](l - sech M1 ) v T )1/ 2
(b) E* = - - - - - - - - - - - - - - - - - - - - - - - - - - Mcj>* n/2 ( 1 + _!_
A 1 + (tanh M1 /M 1 )f;E/vET rn f;E
f;B f;E
EA - (l - qA) = vB qB(l - <PlB) = vE qBC<PlE - cj>Jrn)
f;F
= - q (cj>* cp R.F)
vF B ,Q,F
(c) E*=<J:>·E* =<J:>' Mcj>*rn n/2 and M'cj>* q/2
A ' A' ,Q,C
f;A' <PR.A' f;B
<l:>-(1-q ) = - --[<J:>'-(1-q )]+-q(l-cj>*)
A vA, <Pi.A A' vB R.B
vC,f;A,<P1A' [<J:>' - (1 - qA,)] E;c
-- vCvA, <P*R.A
vC qB<<Pw - <Pfo)
cosh M1 - qA v C*
(d) M"' S A' R.A 0)
EA = sinh M1 Hal c:::,
f;A,CfA, (0
0:,
.....
0
TABLE 20 (Continued)
Reaction Approximate solution M 1 and M 1
V A'CQ,A
E* = 1 + (EA* + qA - 1) < C* - qA'
A' '""A' Q,A'
(e) E* = 1>
A
sB sc
E* = 1 - q + - q (1 - ¢* ) + - q (¢ - ¢* ) M(¢*n + V¢*q)
A A VB B Q,B vC B Q,C Q,C Q,B Q,C'
¢ic ( vcsB 1 - ¢iB)-i
--= l+-- U
¢ Q,C VB sc ¢9-B
(f) E*=<t>·E* =1>' M"'* n/2 d M""'* q/2
A ' A' '+' Q,B an '+' Q,B
sB
E* = 1 - q + - q (1 - ¢* ) s A, ¢ 1A' [ii>, - (1 - q A,)]
A A VB B Q,B -- ¢*
VA' Q,A (j
Q
'"'$
where
6
A, A'= gaseous reactant Q
;:;l
i:i..
B, C, E, F = liquid reactant, nonvolatile
i:'l::
0
¢9-i = C'.R,/Crn; ¢,Q,i = CQ,i/Crn; si = D/DA; qA = CQ,A/CQ,A; qA' = CQ,A'/CR-A'; ~
i:i..
qB = crn1c1A E
c;:i
i::,
Ml M'1 Cl>
I
<P == tanh M1 (1- qA sech Ml); <Ii'== tanh M\ (l - qA' sech M\) I:"'
.s·
s.
i:l.
k2 m + 1 (p+q-m-n) (p+q-n-1) (p-1) * q *n :,;,
T == k p + 1 c1A qB · <Ph <PiF l<Prn Cl)
i::,
1 (')
...
0
k
V == _! C*(p+q-m-n) (q-n) m + 1 ~
k 1 JiA qB p + 1
M 2 == - 2- k D C*(m-l) en / k 2
m+l lA JiA JiB JiA
,2 _ 2 *(p-1) q 2
M - p+1 vA,k2DA,cJiA CJl,C/kJiA'
M 112 - - 2- k D C*(p-l)Cq /k 2
- p + 1 v A' 2 A' JiA' JiB JiA'
JiA
M1112 -- k lDA C*JiA' /k 2
U == V<P*(q-1) /<P*(n-1)
w rn
!;A,CR,A' 1 - q
l - qA') A - E*A
s (
1 - 3El + 3E*
A
0)
........
612 Carra and Morbidelli
the following parameter can be introduced:
M2 = _2_ (84)
m + 1
which is the Hatta number defined at the liquid bulk conditions and repre-
sents the ratio of the characteristic times of the diffusion and reaction
processes. Its value can then be used to define the reactor regime.
Slow Reaction Regime
In this case the reaction in the liquid film is negligible, and the reaction
factor identifies with the purely physical diffusion value:
E:I' = (85)
l
The material fluxes at the interfaces can then be calculated as follows:
y./H:I'
(J ) St l l ( H*) = (86)
l. x= 0 = gl' 1 + y./
l H':"
,I, - ,I,
l 't' D'i
,,,. 't' Jl,i i
( 87)
The gas-liquid interface concentration values are given by Eq. (57) and
<jl.+y.<jln•
*- gl 1)\,1 (88)
<jlgi - 1 + y./H:I'
l l
Equations ( 86) to ( 88) represent the liquid film model solution under the
condition
(89)
Such conditions has been further specified by Barona ( 1979) for a CSTR
model with a (1,1)-th order reaction of type (82) as M < 0.1.
It is worth mentioning that two subregimes can be identified with the
slow reaction regime depending, in addition to Eq. (89), on the following
conditions:
Kinetic Subregime
al.Vl2 « 1 ( 90)
In this case the chemical reaction is the rate-determining step, so that the
gaseous reactant concentration is <PR-A = <P £A, independent of the reaction
Gas-Liquid Reactors 613
rate. The gas- liquid reactor then behaves as a homogeneous reactor, where
only the liquid reactant concentrations change with time or position.
Diffusional Subregime
( 91)
In this case the gas-liquid mass transfer is the rate-determining step, so
that the liquid concentration of the gaseous reactant vanishes. The total
amount absorbed from the gas stream can then be calculated by solving the
only gaseous phase mass balance. The interfacial material fluxes are easily
evaluated from Eqs. ( 86) and ( 87) with ¢ Q,A = 0, leading to a linear expres-
sion for the sink term in the gas-phase mass balance of the gaseous
reactant.
Fast Reaction Regime
In this case it is assumed that the reaction is completed within the liquid
film, so that the liquid bulk concentration of the gaseous reactant vanishes,
<P £A = 0. This simplification is of great utility in practice, since the liquid-
phase mass balance of the gaseous reactant is not needed, and the approxi-
mate expressions for the reaction factor EA reported earlier can now be
used. This regime is established for
M2 » 1 ( 92)
In Figs. 15 and 16, a comparison between the two approximate solutions
developed above and the complete liquid film model solution for two reactions
of type ( 80) of first order with respect to both reactants (i.e., NR = 2,
mj = nj = 1) in a CSTR is shown. It is apparent that the two approximations
3-------------------,
<llt1/¢i°A= 4
-complete film model
---slow reaction approximation
P1=P2=1
---last reaction approximation -'
~, =~2=1
-3
¢ll=J;¢l2=10
2 Sh= oo
. .,
Lu
0.1 2 3
-M
FIGURE 15 Comparison of the reaction factor, EA calculated with the com-
plete model and the slow and fast reaction approximations.
614 Carril and Morbidelli
~':, 0.5
"'
Sil= 00
$l1 /$l~=4
P, =P2=1
~, =~2=1
$l1 =1; $L2=10- 3
0!--c--,--'----.,__......_......_.i...;.i.~_::i:::::...-._....,c....u..._L____;:..:t:31,..
0.01
* calculated with the
FIGURE 16 Comparison of the concentration ratio c/> !1,A I cp !1,A
complete model and the slow reaction approximation.
are quite accurate in the appropriate intervals of M values, while a lack of ac-
curacy appears for both of them for intermediate M values, depending on the
liquid holdup value a, defined by Eq. (62). It should be remarked that the
value of M is not known a priori, since in general it depends on the reactor
operating conditions through the bulk reactant concentrations (and then it is
a function of the reactor axis in the steady-state axial dispersion model, and
of time in the semiflow batch model). Therefore, care must be exercised to en-
sure that all possible values of M along the reactor axis or during time are such
as to satisfy conditions ( 89) or ( 92). Obviously, this is not true for the approx-
imate solutions reported in Tables 18 and 20, which can be applied for all re-
actor regimes.
The available solutions, valid for a specific reactor regime, and the possible
model simplifications arising from limiting values of the dimensionless charac-
teristic parameters are reviewed below for each reactor model reported earlier.
Approximate Solutions of the Axial Dispersion Model
The macromixing effects on reactor performance are taken into account in
each phase separately through the introduction of a Peclet number. In Fig. 17
the effect of Peg on the reactor outlet conversion, in the case of a pseudo-
first-order reaction in the slow regime, is shown. Extensive calculations for
this system, performed by Pavlica and Olson (1970), have shown that the
Peclet number affects the reactor conversion by no more than 10%, except
in the interval 0.1 < Pe < 20. Such a conclusion, valid for each phase
independently, has been also verified in the fast reaction regime by Deckwer
( 1976). For Pe < 0. 1 and Pe > 20, the CSTR and PFR models can be ap-
plied, respectively. Also, a PFR model can generally be assumed for the
gaseous phase for small bubbles columns (de < 0. 5 m)
Frequently, gas-liquid reactors can be described using a CSTR model
for the liquid phase and a PFR or an axial dispersion model for the gaseous
phase. In this case the reactor model can be obtained by suitably combin-
ing the appropriate equations of the models presented earlier. The only
difference is that in the CSTR model the local material flux entering the
Gas-Liquid Reactors 615
0 1.0
X
aHa2=1
X
's
'
~
X
I.,
0
0.5
0 ~Pel~ oo
4>tA =O ; 4>:A =1
X
a.. 0
~ 0.1 1.0 10 100
t -Peg
FIGURE 17 Effect of the gaseous phase Peclet number Peg on the outlet
reactor conversion, in the case of a pseudo-first-order reaction in the slow
reaction regime.
liquid bulk (Ji)x=l must be replaced by the average one, (Ji)x=l' defined
by Eq. (72), as done in the semiflow batch model.
A useful simplification of the axial dispersion term has been proposed by
Hlavacek and Hofmann ( 1970).
1 d2¢ d¢
- - 2+ ~
-(A p )¢ ( 93)
Pe dz Pe 4
dz 2
where
A Pe
tgA = ( 94)
A2 - Pe 2 /4
Since such an approximation correctly approaches the CS TR model as Pe -+ 0,
while obviously it does not approach the PFR model as Pe -+ oo, its applica-
tion should be limited to situations with relatively small Pe values.
Another important aspect of the axial dispersion model is the variation
of the superficial gas velocity along the reactor axis. Gas expansion due
to reduced pressure and gas shrinkage due to gas absorption cause opposite
variations on the gas velocity and thus on the reactor performance. This is
quantified in Fig. 18, where the effect of a
and the inlet gaseous reactant
mole fraction y~ on the reactor conversion for a first-order reaction in the
fast reaction regime is shown. From the results reported by Deckwer ( 1976),
it can be concluded that the hydrostatic head variation can be neglected for
a < 0. 1 (in particular, for large pressure values, P > 20 atm) , while the
f
gas absorption effect can be neglected when y A < 0. 2.
Slow Reaction Regime
The model is given by Eqs. ( 60), ( 61), ( 66) to ( 69), ( 86), and ( 87), where
the only nonlinearity is due to the gas velocity variation along the reactor
axis and to the chemical reaction in the liquid bulk.
616 Carra and Morbidelli
.
C
0
·.;
L-
>
C
0
u
0.5L.....__.1..---'---'-=--- ,-'--,~----,'
~y;
0 0.2 0.4 06 0.8 1.0
FIGURE 18 Influence of the hydrostatic head variation a and the reactant
mole fraction in the feed y~ on its conversion. The dashed line indicates
the solution where the gas velocity is assumed constant.
For a reaction type (82) with the reaction rate given by Eq. (83), if
the gas velocity is assumed constant (v = vf = 1) and the kinetics of
g g
pseudo first order, the model becomes linear. The analytical solution can
then be obtained by standard techniques (Pavlica and Olson, 1970). In
Table 21 the solution obtained assuming a PFR model for both phases (Peg,
Pe£ -+ 00 ) is reported ( Cichy et al. , 1969) . In the same table the solution
in the case of a gaseous phase constituted of pure reactant A is also re-
ported.
Of particular practical interest is the case where the liquid phase is
described by the CSTR model and the gaseous phase by the axial dispersion
model. Then ¢ ti is independent of the axial position, so the mass balances
in the gaseous phase can be solved analytically. Those in the liquid phase
require the introduction of the average fluxes (Ji)x=l defined by Eq. (72).
Since the reaction in the liquid film is negligible, (Ni)s=o = (Ni)s=O' which
in dimensionless form can be rewritten as
St n.
(J ) -.)
(J x,l
i x=l = l X= 0
(95)
y. St .
l gl
where (J.) 0 can be evaluated from Eq. (72), using Eqs. (61) and (69) as
follows: 1 x=
( 96)
Gas-Liquid Reactors 617
TABLE 21 PFR Model with the Bimolecular Reaction (82) of Pseudo
First Order (v = 1 v = 1)
g ' JI,
for n* = -1
cp~A (1 + A+)edA+ - HA cp~A
for n* = 1
(1 + ;\)edA+ _ (1 + A_)edA_
A = -[q - n*(p + 1) ± (q 2 + p 2 + 2p + 1 + 2n*pq - 2n*q) 112
± 2q
Case of gaseous phase of pure A:
f = d(p + 1)
q
618 Carra and Morbidelli
TABLE 22 Liquid-Phase CSTR, Gaseous-Phase Axial Dispersion Model
(v = 1)
g
Pe /2
4q(g/. - b/d)e g
b
cf>gi(l) = +-
2 Pe q/2 2 -Pe q/2 d
(1 + q) e g - (1 - q) e g
f
v!l<f>ti =
For Peg + co:
cf>gi(l) = (cf>~ - ~)e-d + ~
Y/Hi
d = Stgi 1 + y / Hf
b = dH{cf>.Q,i
Assuming constant gas velocity (i.e., vg = 1), the model reduces to the sys-
tem of nonlinear algebraic equations reported in Table 22, which can be
solved by standard techniques. Note that this procedure applies to all
kinetic schemes and rate expressions, including reversible reactions. In the
case of a nonvolatile component, the equations in Table 22 still hold with
H:l'
1
= O and cf>f.
gi
= 0, which lead to cf> .(1)
gi
= O.
Fast Reaction Regime
In this case the mass balance of the gaseous reactant in the liquid phase is
not necessary, since it is assumed that cf> £A = 0. Under the conditions of
constant velocity, v g = 1, and reaction factor independent of the axial posi-
tion, the mass balance of the gaseous reactant in the gas phase can be
solved analytically as follows:
cf>~ __2_(1_+_q_)_e_x_p_[_P~e~(_1_-_q_)_z_l_2]_-_2(~1--_q_)_ex_p_[_-_P_e~_ _..,___ _ __
cf>~A - (1 + q) 2 - (1 - q) 2 exp(-Pegq)
( 97)
Gas-Liquid Reactors 619
where
St 5
_ + ~ YA E*A /H*A ) O. ( 98)
q - (1 4 Pe 1 + y E* /H*
g A A A
The assumption EA = const. is quite restrictive in practice, However,
it is valid in the case of a reaction of type ( 82), first order with respect
to A and nth order with respect to B, with component B nonvolatile and
the liquid phase well mixed. Thus, according to Eq. ( 39), if 4 < M <
EA,in/2, in the reactor factor is given by
(kD en )0.5
A 9,B
EA = M = _ _k_!l_A_ __ ( 99)
which is constant along the reactor axis, because the liquid phase is well
mixed, (i.e., C !lB = con st.) . In the fast reaction regime, the gaseous re-
actant is depleted within the liquid film and therefore at steady state it
follows that vB(NA)s=O = -(NB)s=o' which in dimensionless form leads to
( 100)
where (J A)x=O can readily be evaluated, using Eqs. (61) and (69), as
follows:
( 101)
The final system of nonlinear algebraic equations which constitutes the
model is reported in Table 23.
With reference to the same reacting system, in the case of PFR model
for the gaseous phase, the reactor model can be greatly simplified, although
taking into account the variation of the superficial gas velocity (Deckwer,
1976). The final version of the model is reported in Table 24. Moreover,
extensive calculations performed by Deckwer ( 1977) enable us to account for
the effect of the gas-phase axial dispersion on the outlet reactor conversion.
In Fig. 19 the ratio of the reactor lengths calculated using the axial disper-
sion model, Lpe (Peg= finite), and the PFR model, L 00 (Peg+ 00 ) , to ob-
tain a given value of the outlet conversion is shown. The results are shown
for various values of the Pec!._et number, Peg. It is remarkable that the
hydrostatic head parameter, a, and the gaseous reactant mole fraction in the
feed stream, yi, although affecting the gas velocity appreciably, do not
significantly alter the results of Fig. 19. That is, the effect of axial dis-
persion seems almost independent of the variation of the gas velocity along
the reactor axis.
620 Carra. and Morbidelli
TABLE 23 Liquid-Phase CSTR, Gaseous-Phase
Axial Dispersion Model , with the Bimolecular
Reaction (82) of (1,n)-th Order (vg = 1;
B Nonvolatile)
f Pe /2
4cj> Aqe g
cj>gA (l) = 2 Pe q/2 2 -Pe q/2
(1 + q) e g - (1 - q) e g
cj>R,A = 0
f VB 8t tA f
V cj> = V cj> + - - - - [ cj> cj> ( 1)]
R, rn R, rn y A StgA gA - gA
For Pe + oo:
g
E* = H ,i.n/2
A a'l'R,B
TABLE 24 Liquid-Phase CSTR, Gaseous-Phase PFR
Model with the Bimolecular Reaction ( 82) of
(1,n)th-Order (B Nonvolatile)
f
s = _ct>.._gA_ _<_v_..g_cp.,_gA_)_z_=_l V
f
= 1
f g
cpgA
(a+ 1)(1 - A) l
vg(l) = 1 g
- (a+ l)cj>gA (1)
cj> tA = 0
f vB 8t tA f
VR,cj>R,B = VR,cj>R,B + yAStgA scj>gA
E* = H ,i.n/2
A a'l'R-B
Gas-Liquid Reactors 621
1s~------,--- --,-----f;---- ;a;;---~---,
Peg J.A.._....__ 0.1 0.5 1.0
0.1 0 • •
0.3 I:. + ■
0.6 ◊ • •
' ,f
_J
I
1
0.01 0.05
-conversion
FIGURE 19 Influence of the gaseous-phase Peclet number Peg on the _
reactor length necessary to obtain a given conversion. The effect of a
and y~ is examined at Peg = 2.
The effect of the gaseous reactant order on reactor performance can be
investigated through the relationships developed by Mhaskar ( 1974). They
concern an (m,n)th-order reaction of type (82), with component B non-
volatile and plug flow for both gaseous and liquid phases. Also in this case,
assuming that 4 < M < EA . / 2, the reaction is given by
,1n
( 102)
In Table 25 the analytical solutions obtained by Mhaskar (1974) for
various values of the reaction orders m and n are reported, assuming plug
flow in both phases (i.e., Peg, Pe JI, ➔ oo), negligible gas-side mass transfer
resistance (i.e., YAEA./Hl << 1), and constant superficial velocities (i.e.,
VJI, = vg = 1). Four situations have been considered: cocurrent flow (n* =
-1), countercurren t flow (n* = 1), the case where the gaseous reactant con-
centration ct>gA does not vary appreciably along the reactor ( ct>gA = 1), and
finally the case where the liquid reactant concentration cj> Jl,B does not vary
appreciably along the reactor ( cj> Jl,B = 1). It is worth mentioning also the
approximate solutions obtained by Szeri et al. (1976) for a (1, l)th-order
reaction in the fast and instantaneous reaction regimes. Such solutions are
valid in the range of large and small Peclet number and have been obtained
using the perturbation and Galerkin methods, respectively.
Approximate Solutions of the CSTR Model
The equations that constitute the model are summarized in Table 8. Since
these are algebraic equations, the problem here is only to simplify the liquid
film model. In the case of consecutive reactions ( 80) of general order, the
approximation reported in Table 18 can be used. The resulting nonlinear
algebraic system can be solved through various methods, as reported by
Hashimoto et al. (1968), Teramoto et al. (1973), Morbidelli et al. (1984), and
Shaikh and Varma (1983b). In the last reference, a (1,l)th-order reaction
is considered, taking into account the gas holdup and interfacial area variation
622 Carra and Morbidelli
TABLE 25 PFR Model with the Bimolecular Reaction (82) of (m,n)-th Order
(B Nonvolatile, v g v R, =
1, y A El/HA « 1) =
m n Cocurrent (n* = -1)
1 2 <PgA = d/ [1 - (1- d) exp(dd~\)] (q 'l=-1)
1 2 c/JgA = 1/(bz + 1) (q = 1)
1 1 <P = d + d [1 - lg='"ltan(bz/g-=-i/2)] 2 (q >)
gA [ ~ + tan(bz/q=l/2)] 2
1 1 c/JgA = 1/(1 + bz/2) 2 (q = 1)
1 1 cp = d _ d [1 + ~+ (1 - /T="q) exp(-bz~)] 2
gA [1 + /T=q- (1 - v'l="q°) exp(-bzil=q")] 2
(q < 1)
lq(c/J A - 1) + 1 - [4(q - l)(qcp A - q + 1)]1/ 4.+ ~
1 1/2 1 g g
n ,------- 1/4
lq(c/JgA - 1) + 1 + [4(q - l)(qcjJgA - q + 1)] + v7C:t=-i
[ 4( q - 1)( q cp A - q + 1)] 1/ 4
+ 2 arctan g r;;- 1/4
= -bz v i (q - 1)
/q=1 - ____
✓-q-(_c/J 1)_+_1
gA
4( 1)] 1/ 4 1/4 fa=-i
+arctan [ q - +lnl-[ 4 (q-l)] + q-l (q>l)
/q::-r - 1 1 + [4(q - 1)] 114 + /q::-r
1 1/2 <P = 1 (q = 1)
gA [(bz + 4) /4] 4
1/4 1/4 1/4
[q(cjJA-1)+1] -(1-·q) [q(cp -1)+1]
1 1/2 ln g + 2 arctan _ _g_A_ ____,_ _
[q(cpgA - 1) + 1]1/4 + (1 - q)l/4 (1 - q)l/4
1/ 4 1- (1- ) l/ 4 1
= -bz(l- q) + ln 9 114 + 2arctan 114 (q < 1)
1+(1-q) (1-q)
-/:-1 0 <P = [1 + bz(m - 1)/2] 2 /(l-m)
gA
1 0 <PgA = exp(-bz)
Gas-Liquid Reactors 623
TABLE 25 (Continued)
m n Cocurrent (n * = -1)
0 2 <P A= d {1 +la+ (1 - la) exp[-bz la/(1 - d)] ~2 (q > l)
g {1 + l a - (1 - Id) exp[-bz/ci/(1 - d)]}
0 2 <P =--1_ __ (q = 1)
gA (1 + bz/2) 2
2
0 2 <P = -d[l - v-d tan(bqz/-=-a./2] (q < 1)
gA ✓ -d + tan (bqzl'=a/2)
0 1 /<t,gA= (1 + IT"=ci) exp(-bz(Vq/2) - /<t,gA - d (q I= 1)
0 1 <PgA=exp(-bz) (q=l)
The liquid concentration of B is given by
m n Countercurrent (n* = 1)
1 2 ¢ gA = ~ {1 - 1/ [ 1 + <ti} exp ( - bhz)] }
j l
qc- [✓h
h [Vh - ~B - (v'h + ✓~) exp(b v'h z)] 2
1 1
<PgA = - ~ + (Vh + ~ ) exp(b Vh z)J 2 '
h 1/ 4 + (h _
"' ) 1/ 4 1/4
q4'gA h-q¢A\ 1/4
1 1/ 2 ln - - - - - - - - - " ' - - - - 2 arctan ( h g J = b zh
hl/4 _ (h _ q¢ )1/4
gA
¢ 0 )1/ 4 hl/4 + ¢ 0 1/4
(
-2 arctan hB + ln 114 B l/ 4
h - q,O
B
0 ¢gA = [l+bz(m - 1)/2] 2 /(l-m)
1 0 ¢ gA = exp( -bz)
0 2
<P = ~ [,/h/q - 1 - 1) exp(-bzv'hq)J 2
(,/h/q +
gA q [/h/q - 1 + (/h/q + 1) exp(-bz/hq)] 2
624 Carra and Morbidelli
TABLE 25 (Continued)
m n Cocurrent (n * = -1)
0 1 <P A=!:!_ [ ✓ q/h cos(bz ✓q/2) - ✓ 1 - q/h sin(bz ✓q/2)] 2
g q
The liquid concentration of B is given by
<Prn = <Prn< 0 > + q(l - <PgA)
¢ rn ( 0) = 1 - q[ 1 - ¢ gA (1)]
m n Cocurrent and pure A (n* = -1; ¢ = 1)
A
Any <Prn = [l+bqz(n - 2)/21 21 <2-n)
Any 2 ¢ rn = exp(-bqz)
m n Negligible consumption (¢ ,(l,B = 1)
41 Any <PgA = [1 + bz(m - 1)/2] 2 /(l-m)
1 Any <PgA = exp(-bz)
St A y A Ha
b = ___,g"-----
H* (m+l) /2
A
d = c1 - 1)/q; h = q + <PB; <PB= <Prn<O)
f f
¢ gA = 1; ¢ Q,B = 1
Gas-Liquid Reactors 625
due to gas absorption according to Eqs. (73). In Figs. 20 and 21 the con-
versions of the gaseous and the liquid reactants, XA and XB, are shown as
a function of the residence time, operating with fixed gas and liquid flow
rate, respectively. The behavior represented can be explained considering
the actual reactor regime, which is defined by the value of the parameter M
defined by Eq. ( 84) (not by Mf, which is the M value calculated using the
feed concentrations).
Similarly, for the kinetic schemes reported in Table 19, the approximate
solutions of the film model listed in Table 20 can be used, thus reducing
the reactor model to a system of algebraic equations. Some useful approxi-
mations for the model solution, based on the specific reactor regime, are
given next.
Slow Reaction Regime
Assuming constant gas velocity (vg = 1), the model equations reduce to
those reported in Table 26. In general, this is a system of nonlinear equa-
tions with the liquid bulk concentrations qi Q,i as unknowns.
Fast Reaction Regime
In the case of a (m,n)th-order irreversible reaction of type (82), assuming
component B nonvolatile and 4 < M < EA,in/ 2, the reaction factor is given
by Eq. ( 102) • In this case the model equations can be rewritten as shown
in Table 27.
Approximate Solutions of the Semiflow Batch Model
The mass balance in the liquid phase for these models is given by Eqs. ( 70)
to ( 72). From comparison with the mass balance equations in the liquid
phase of the CSTR model reported in Table 8, it appears that the two set
of equations are identical, the only exception being that the accumulation
term d¢£i/d8 in the batch model is replaced by the convective term (vQ,¢£i
vQ,¢1i) ~i/StQ,i in the CSTR model.
In semiflow batch models the gaseous phase is usually described by the
steady-state axial dispersion model, with various levels of backmixin g.
Therefore, all the solutions reported in Tables 22 to 24, 26, and 27, where
the CSTR model is assumed for the liquid phase and the axial dispersion or
the CSTR model for the gaseous phase, can be used in this case as well.
In particular, the solutions for the semiflow batch models are valid under
the same conditions and are obtained from those reported in the above-
f
mentioned tables, by simply replacing the term (vQ,qiQ,i - vQ,qiQ,i )(~i/StQ,i)
by the derivative dqi Q,/ d8. Systems of ordinary differential equations, in-
stead of algebraic equations, are then obtained. For illustrative purposes,
the solution reported in Table 22 for the case of M << 1 and vg = 1 is
examined. In the case of an (m,n)th-order reaction of type (82) with A
the only volatile component, the equations reported in Table 22 for the
liquid mass balance reduce to
( 103)
626 Carra and Morbidelli
10
'Cg =5s 1.0
.
0.8 1
0.05
0.8 0.6
X
t 0.4 0.02
X
. 0.6 0.2
0 2
-1:t (min)
3 4
t 0.4
0.2
0
0 100 200 300 400 500
-1:l=VR El/Ql (min)
(a)
1.0
0.8
0.6
111·
X
t 0.4
0.2
0
0 100 200 300 400 500
(b)
FIGURE 20 Conversion of the gaseous reactant XA as a function of the
liquid residence time , 9,. (b) Conversion of the liquid reactant XB as a
f 1/2
function of the liquid residence time , 9,. Mf = (kDB C 9,B) /k 9,A
Gas-Liquid Reactors 627
0.2
1t=20 min
0
0 01 0.2 0.3 0.4 0.5
- i: 9: VR£ 9 /Q9 (min)
(a)
1.0
1t=20 min
"'
t
0 0.1 0.2 0.3 0.4 0.5
(b)
FIGURE 21 (a) Conversion of the gaseous reactant XA as a function of
the gas residence time, Tg· (b) Conversion of the liquid reactant x 8 as
a function of the gase residence time T . Mf = (kD AC frn) 1/2 /k9.,A.
g
628 Carra and Morbidelli
TABLE 26 CSTR Model in the Slow Reaction Regime
with Constant Velocities (v g = v !I, = 1)
v ..p.f.
lJ J J
Y/H{
(½_ = Sto-i
e,•
1 +yi /H*
i
TABLE 27 CSTR Model in the Fast Reaction Regime
with the Bimolecular Reaction ( 82) of (m, n)th Order
1 + y E* /H*
A A A
1/ 2
EA = Ha~! 1 <Pf~-l<P!;J
yAEA/HA
vg = 1 - StgA 1 + yAEA/HA <PgA
Gas-Liquid Reactors 629
TABLE 28 Semiflow Batch Model in the Slow Reaction Regime, with the
Bimolecular Reaction ( 82) of Pseudo First Order (v = 1)
•
( <j)m - - 0 ) exp(-a 8)
a
1A a1 1
where
Pe I 2 2 Pe q / 2 2 - Pe q / 2
h = 4qe g /[ (1 + q) e g - (1 - q) e g ]
[forPe + 00 ,h=exp(-d)]
g
1 f
<j)gA (1 - h)
y A StgA
yA/HA
d = StgA
l + yA/HA
q = (1 + 4d/Pe ) 112
g
(104)
while those for the gas mass balance are unchanged. In the case of pseudo-
first-order kinetics (i.e. , m = 1, n = 0) , the analytical solution is possible
and is reported in Table 28.
A useful approximation has been proposed by Barona and Prengle ( 1973),
valid for slow reactions, such that aM2 < 0. 25. It consists of evaluating
¢ 1B ( 8) from Eq. (104), assuming that ¢ tA = ¢ fA, and then calculating ¢ tA
from Eq. (103) where the time derivative is neglected (i.e., d¢tA/d8 == 0).
630 Carra and Morbidelli
TABLE 29 Semiflow Batch Model in the Slow Reaction
Regime, with the Bimolecular Reaction (82) of (m,n)th
Order (vg = 1; aM2 < O. 25). Approximation of
Barona and Prengle ( 1973)
(n f=. 1)
(n = 1)
2 m n
aHa <j) :lA <P :lB
where the parameters h and a 2 are defined as in
Table 28.
The gas-liquid interface mass flux can be obtained by noting from Eqs.
( 87), ( 95), and ( 96) that
( 105)
Using these approximations, the model reduces to the system of non-
linear algebraic equations reported in Table 29. This solution is adequate
for cases such as the chlorination of benzene to monochlorobenzene at 80°C
and the auto-oxidation of p-toluic acid in acetic acid solution, catalyzed by
cobalt and manganese bromide, where the reactions are (1, l)th order
(Agnello and Williams, 1960; Groggins, 1958) and (0.5,l)th order (Ravens,
1959), respectively. In these cases the equations reported in Table 29 can
easily be solved analytically.
NONI SOTHERMAL GAS-LIQUID REACTORS
Modeling Nonisothermal Gas-Liquid Reactors
Gas-Liquid reactors are widely used for temperature-sensitive processes,
such as oxidation, hydrogenation, alkylation, chlorination, sulfonation, and
so on, which are all accompanied by large heat effects. In fact, owing to
the high heat capacity of the liquid phase and the large dispersion prevailing
Gas-Liquid Reactors 631
in gas-liquid reactors, the temperature is almost constant in the entire re-
actor volume and can easily be controlled. To this end, heat is usually
removed through the vessel wall or through a coil immersed in the liquid
volume. In both cases, the process-side heat transfer coefficient is much
larger than in the absence of bubbles, due to the increased turbulence pro-
voked by bubbles in the liquid film at the heating surface.
The joint effect of the heat of absorption and the heat of reaction can
lead to significant temperature gradients within the liquid film, which can
largely affect the total mass absorption rate and, in the case of a complex
kinetic scheme, also the process selectivity.
Thermal effects in gas absorption without reaction have been studied by
Chiang and Toor (1964) and Verma and Delancey (1975) by coupling the
energy and mass balances in the surface renewal model. The latter con -
sidered the influence of heat of absorption, volume changes in the liquid
phase, variable liquid density, and the pseudo-Dofour effect; they con-
cluded that while for the accurate prediction of the surface temperature rise
the first two mentioned phenomena must be taken into account, if only the
interphase mass flow is to be evaluated, excellent estimates are obtained
using the isothermal model. This is largely due to the equivalence between
the enhancing effect of the liquid volume change and the depressing effect
of the heat of absorption, which leads to larger superficial temperature and
then to lower solubility of the gaseous reactant. This study, where gas-
side resistances are always assumed negligible, has been verified experi-
mentally for the systems ammonia-water and propane-decane.
If a chemical reaction is present, its thermal contribution must also be
taken into account. While the heat of absorption is released only at the
gas-liquid interface, the heat of reaction is released in the entire liquid
film, and in the case of slow reaction, also in the liquid bulk. Thus the
estimation of the temperature profile requires the solution of both energy
and mass balances in the liquid film. An upper limit of the superficial
temperature values has been reported by Danckwerts ( 1970), assuming that
all the heat of reaction, as well as the heat of absorption, is liberated at
the interface:
( 106)
Accurate analyses have been made in the case of a first-order reaction
using both the penetration theory model [Danckwerts (1952, 1967) and Shah
( 1972) examined the effect of the temperature rise on reactant solubility,
diffusion coefficient, and reaction rate constant] and the film model (Mann
and Moyes, 1977). In the latter it was concluded that for pseudo-first-
order kinetics in the fast reaction regime (i.e., C iA = 0), the nonisothermal
reaction factor, defined as the ratio between the absorption rate with reac-
tion heat effects and the purely physical absorption rate with zero heat of
solution, is given by
ctA (T*) Ha*
E* = - - - - - - - - - (107)
A Ha*
ClA (T 9.,) tanh
632 Carri! and Morbidelli
where TR, and T* indicate the liquid bulk and the gas-liquid interface
temperature, respectively. The latter can be evaluated through the
equation
( 108)
which must be coupled with a suitable expression of the gaseous reactant
solubility as a function of temperature C*(T) = f(T).
As pointed out by Clegg and Mann (1969), from Eq. (107) it appears
that the solubility decrease due to the interfacial temperature rise can re-
duce the interface absorption flows even below those obtained under condi-
tions of purely physical isothermal absorption (i.e., E_A < 1). In these
approaches the only heat effect on the surface temperature, and consequently
on the gaseous reactant solubility, is taken into account. Therefore, such
results can be applied with confidence to cases where heat effects are small
or absorption rates as well as solubilities are low. If the converse is true,
a deeper analysis of the problem is necessary.
The most complete treatment of nonisothermal gas-liquid mass transfer
has been given by Tamir et al. ( 1975) and Tamir and Taitel ( 1975) using a
penetration-type model for gas absorption into a laminar liquid stream. In
it the solvent volatility is taken into account, together with the gas-side
mass transfer resistance. A boundary layer model is assumed for the fluid
mechanical behavior of the gas phase, and in the liquid phase the transverse
bulk-flow contribution, ignored in previous works, is taken into account.
This is found to affect the interface absorption flow only for low reaction
rates or contact times (i.e., when the reaction contribution is small); under
these conditions the decrease with respect to the isothermal case is limited,
and the same situation depicted previously for purely physical absorption is
obtained. At large reaction rates or contact times, the solvent evaporation
and the gaseous environment effects are of the same order of magnitude as
the heat effect, leading to serious decreases of the mass flux with respect
to the isothermal case. The effect of heat conduction from the liquid film
to the gaseous phase is negligible compared to other heat contributions. It
is worth pointing out that for increasing reaction rates the interfacial ab-
sorption flow decreases, which is contrary to the trend obtained under iso-
thermal conditions. In the case of absorption with chemical reaction of
chlorine in toluene, experimentally investigated by Mann and Clegg (1975),
this analysis shows that the effect of the gaseous environment is to decrease
the total absorption flux of chlorine by 25% more than what is predicted us-
ing the simplified models mentioned previously, which take into account only
the heat effect on the interfacial temperature.
The complete model of a nonisothermal gas-liquid reactor, including the
detailed description of the nonisothermal liquid film, would be quite com-
plicated, so, usually, several simplifications are introduced in order to model
such units. In the first place, the gas- and liquid-phase temperatures are
generally assumed to be identical at any given axial position. This assump-
tion can be verified ~sing the relationship for the heat transfer coefficient
developed by Calderbank and Moo-Young (1961) for small bubbles (dvs <
0. 0025 m, as is true in almost all industrial gas-liquid contactors):
( 109)
Gas-Liquid Reactors 633
Only one energy balance is then required for these reactors, which us-
ing the axial dispersion model (assuming the gas and liquid velocities con-
stant along the reactor axis, and the physical properties of the gas and
liquid and the heats of reaction, absorption, and evaporation independent
of temperature) is given by
d 2T
ET
dy2
NC (110)
+ a L
i=l
where on the right- hand side three contributions are present: heat exchange
with heating or cooling devices (ac is the heat exchange surface area of
coils or jacket, per unit reactor volume), heat liberated ~r ab~orbed by
evaporation or solution of the liquid [ (Ni)s=O < 0 and 1'. H = 1'. Hev] or the
gaseous [(Ni)s==O > 0 and 1'.H == 1'.Hal reactants, respectively, and finally,
the heat of reaction per unit reactor volume. This last term, in the case of
only one reaction with one gaseous reactant [see Eq. (82)], can be evalu-
ated as follows:
( 111)
The overall heat transfer coefficient can be calculated as usual through
the following relationship:
1
( 112)
h
C
where the process-side heat transfer coefficient hw can be evaluated as
shown earlier, and the cooling (or heating) side heat transfer coefficient he
using standard techniques (Kern, 1950).
Little information is available on the evaluation of effective axial thermal
conductivity ET. However, since the mechanisms for axial heat transfer are
widely accepted to be responsible also for axial mass transfer (i.e. , turbulent
mixing due to liquid circulation, natural convection, and conduction), it is
reasonable to assume equal effective axial diffusivity for mass and heat:
(113)
where the index d refers to the gas-liquid dispersion. Chen and McMillian
(1982) have recently shown that Eq. (113) is reasonably accurate for batch
bubble columns, while for packed columns it gives slightly lower values for
the effective axial thermal conductivity, due to the additional heat conduc-
tion through the solid packings.
In many cases of practical interest, as shown by Fair et al. (1962) using
a 1-m-diameter column with superficial gas velocities over 0,006 m/s, liquid
634 Carril and Morbidelli
backmixing is quite extensive, leading to temperature uniformity. In this
case (ET + 00 ) the CSTR model can be applied for the energy balance:
(QgpgCpg + Q,11,P Jl,cp,11,)(Tf - T) = UacVR(T - Tc)
(114)
NC
+ aVR E (Ni)s=O(-liHi)
i=l
where U is given by Eq. (112), and qR, in the case of one reaction involv-
ing the only gaseous reactant A, can be evaluated as
(115)
Models of this type have been used in several theoretical studies of noniso-
thermal gas-liquid reactors (Hoffman et al., 1975; Sharma et al., 1976;
Raghuram et al., 1979; Huang and Varma, 1981c,d).
Finally, it is worth mentioning the shortcut and rigorous design calcula-
tion procedures for packed gas absorbers involving large heat effects pro-
posed by Stockar and Wilke (1977a,b) and Feintuch and Treybal (1978) and
applied to cases such as the absorption in aqueous solutions of air gaseous
streams containing ammonia or acetone or hydrogen chloride.
Steady-State Multiplicity
The steady state obtained in isothermal backmixed gas-liquid reactors is
usually unique and stable. This is not true for nonisothermal reactors,
where the interaction between the chemical reaction, the heat and mass trans-
port resistances, and the gaseous reactant solubility causes the occurrence
of multiple steady states.
Experimentally, up to three steady states have been found by Ding et
al. (1974) in a CSTR during chlorination of n-decane, while Hancock and
Kenney (1972, 1977) showed unusual dynamic phenomena, such as sustained
periodic oxcillation, in a semiflow stirred-tank column during methanol
chlorination, with hydrochloric acid in the presence of ZnCl2 catalyst, to
methyl chloride.
Earlier theoretical analyses of steady-state multiplicity and stability
were presented by Schmitz and Amundson ( 1963a-d) and Luss and Amund-
son (1967) using reactor models which assume that the chemical reaction and
the interphase mass transfer are two independent, noninteracting processes.
Thus these analyses are restricted to the case of slow reaction. Hoffman
et al. (1975) and Huang and Varma (1981d) have examined the steady-state
multiplicity for the bimolecular reaction ( 82) of ( 1, l)th order in an adiabatic
and a nonadiabatic reactor, respectively. In both cases the CS TR model
for both phases and the energy balance ( 114) has been used, and the agree-
ment with the experimental results reported by Ding et al. (1974) is satis-
factory. It is concluded that an isola with up to five steady states can occur
in an adiabatic CSTR, while in the corresponding nonadiabatic case (even
with a small heat loss) only three steady states can exist. In the case of
two consecutive reactions of the same kind, Sharma et al. ( 1976) have shown
Gas-Liquid Reactors 635
the possible existence of up to seven steady states. Note that these are
unique features of gas-liquid reactors, as in a single-phase adiabatic CSTR
a maximum of three and five steady states can occur for one or two con-
secutive reactions, respectively. Also the occurrence of an isola is not
possible in adiabatic reactors.
Analytically necessary and sufficient criteria for steady-state multi-
plicity, uniqueness, and local stability have been developed for CSTR re-
actors with pseudo-first-order reactions in the fast reaction regime
(Raghuram and Shah, 1977; Raghuram et al., 1979; Huang and Varma,
1981b; Singh et al., 1982). Under these conditions, the occurrence of
limit cycles is usually not possible. It is worthwhile mentioning the signifi-
cant usefulness of steady-state multiplicity analysis as a tool for discriminat-
ing among rival models and for the accurate evaluation of some parameters
of these models (Hoffman et al., 1975; Huang and Varma, 1981e). In the
latter work surprising agreement between the multiplicity regions predicted
by the pseudo-first-order reaction model in the fast reaction regime and the
complete (1, l)th-order model was found.
Finally, Huang and Varma (1981c) and Aluko and Chang (1982) have
examined the steady-state multiplicity of nonadiabatic bubble columns with
fast pseudo-nth-order reactions, assuming the liquid phase well mixed, the
gas phase in plug flow, and the energy balance in the form of Eq. ( 114).
Every multiplicity pattern observed in a gas-liquid CSTR is also possible
in a bubble column, and the possibility of multiplicity in the bubble column
is always higher than that in the CSTR for equivalent system parameters.
Analytic criteria are developed for the prediction of uniqueness and multi-
plicity of the steady states as a function of the system physicochemical
parameters.
Stagewise Nonisothermal Models
Stagewise models are widely used in the simulation of nonisothermal gas-
liquid contactors. Resorting to a stagewise, tray-tower analogy, they can
describe not only plate columns but also packed columns. Following Carra
et al. (1979b), the model equations are summarized in Table 30. In each
stage the gas-liquid system is assumed to be more or less close to the equi-
librium conditions, depending on the value of the Murphree efficiency EM.
This parameter takes into account the possible influence of mass transfer
resistances for the various components. In some cases, a similar approach
can be used to describe the effect of the heat transfer resistance leading
to different temperature values for the gas and liquid streams (Bourne
et al. , 197 4a) on the jth stage:
. l + EMT(T x,,J
T g,J. = T g,J- O • - . 1)
T g,J+ (116)
Murphree efficiencies can be esitmated following several correlations, as
reported by Stichlmair and Mersmann ( 1977) and Pohorecki (1976). How-
ever, since the model results can be quite sensitive to the value of such
quantities, Bourne et al. (1974b) suggested determining the Murphree
efficiency values as a function of the operating conditions through suitable
measurements conducted on a single plate of the same design as those of
the unit under consideration.
As it appears from Table 30, stagewise models lead to a system of non-
linear algebraic equations. Several numerical techniques are available for
636 Carra and Morbidelli
TABLE 30 Stagewise Nonisothermal Model Equations
Material balances of the ith component on the kth stage:
v . .r. k
1 'J J'
Equilibrium conditions for the ith component on the kth stage:
Enthalpy balance on the kth stage: ·
~f ~
FkHk + Gk+lHg,k+l GkH g, k
NR
+ V Q,,k L (- ti HR ,J. ) r. k - qk = 0
J'
j=l
Overall material balance on the kth stage:
NC NR
v . . t. k = 0
1 ,l J,
i=l j=l
Stoichiometric equation on the kth stage:
NC
:E (x. k -
1,
y. k) = 0
1,
j=l
the solution of these systems, and most of them have been reviewed by
Hunek et al. (1976) and Holland (1981). The global Newton-Raphson
method has been successfully used for the case of distillation columns with
chemical reactions (Carra et al., 1979b ,d). On the other hand, a dynamic
simulation method was found by Bourne et al. (1974a) to be particularly
efficient in the case of gas absorbers.
The use of distillation columns with chemical reactions is quite common
in chemical industry. Mayer and Worz ( 1980) give useful suggestions on
the optimal selection, from the standpoint of energy savings, of either a
reaction column or a batch reactor mounted by a column, depending on
the relative volatilities and the reaction rates of the compounds involved.
Coupling distillation with chemical reaction is particularly useful when it
is necessary to displace the chemical equilibrium in order to increase the
desired product yield, as in esterification and transesterification re.actions
(Baratella et al., 1974). In the case of two consecutive reactions in the
Gas-Liquid Reactors 637
Xw, Yw •Yepy
0 0.5
1
4 I
I
I
yW - - :I
II
~
a..
I
16
20
0 0.001 . 02
- Xa 13' Xay' "vty' YawYay
FIGURE 22 Profiles of some liquid-phase mole fractions Xi (solid lines)
and some vapor-phase mole fractions Yi (dashed lines) along a column for
the synthesis of epichlorohydrin.
liquid phase, where the intermediate desired product is highly volatile, the
use of a distillation column reactor can significantly improve the process
selectivity. This is the case in epichlorohydrin (Carra et al., 1979a) and
propylene oxide ( Carra et al. , 1979c) synthesis by dehydrochlorination,
which both follow the following simplified kinetic scheme: chlorohydrins ➔
epoxide ➔ hydrolysis products. In the case of epichlorohydrin synthesis
0.20
0.95 0.15
>- 0.90 ~
0.10 <.!)
a..
w
f 0.85 0.05
f
0.80 0
0 50 100 150 200 250 300 350
-Vi(cm 3 )
FIGURE 23 Yields of epichlorohydrin and glicidol as a function of the liquid
volume of the column plate V R,• EPY, (distilled epychlorohydrin) /(reacted
dichlorohydrins); GLY, (glycidol produced) /(fed dichlorohydrins).
638 Carra and Morbidelli
from a mixture of aS- and ay-dichlorohydrins, the calculated concentration
profiles along the column and yields to the main product and the by-
product (glycidol) as a function of the liquid volume on the plate of a
pilot column are shown in Figs. 22 and 23, respectively (Carra et al., 1979b).
Finally, the application of stagewise models to the simulation of gas
absorption in nonisothermal plate columns is worth mentioning. The model
results have been verified accurately through comparison with experimental
concentration and temperature profiles (including the column startup and
shutdown transients) for the case of the air-ammonia-water systems in two
different columns: one with five bubble cap plates and the other one with
11 sieve plates (Bourne et al., 1974a,b).
REACTOR CHOICE AND SCALEUP
Reactor selection for a given process is usually performed on the basis of
previous experience or analogies with similar existing processes. In fact,
especially in the first stages of the research, limited information is available;
in gas-liquid reactors, several basic operations which could require differ-
ent reactor types must often be performed simultaneously. Thus a rigorous
selection procedure is not available, although some useful guidelines can be
given. In Table 31 the characteristic values of the hydrodynamic and mass
transfer parameters of various types of industrial reactors are reported.
Such values, coupled with physical and kinetic information about the system
under consideration, using the reactor models reported earlier, can lead
to reactor selection. A procedure of this kind has been proposed by Nagel
et al. ( 1978).
The main scope of a gas-liquid contactor is to produce suitably large
values of the mass (and/or heat) transfer parameters kg, k51,, and a, using
some kind of energy ( gas sparging or mechanical agitation). Among these,
only the mass transfer area can vary through several orders of magnitude
depending on the choice of the engineering parameters, thus allowing the
achievement of the desired reactor performance. Thus once the process re-
quirements, in terms of mass transfer surface area, are known, the reactor
choice can be made with the use of Fig. 24, where the surface area values
attainable with various reactors, and the relative energy cost, are shown.
The values in the figure are referred to the gas flow rate Qg, since for a
given reacting system, the depletion of the gaseous reactant concentration
within the reactor is basically defined by the only parameter (a/Qg) (Nagel
et al., 1973, 1978).
In the case of mechanically agitated reactors, a useful procedure for
the selection of commercially available turbine agitators has been presented
by Hicks and Gates (1976). In Tables 32 and 33, the turbine prime-mover
power and shaft speed, which uniquely identify a commercial turbine, are
reported as a function of three parameters characterizing the gas-liquid
dispersion process. These are the equivalent liquid volume Veq_ =
(p51,/Pw)V51,, the superficial gas velocity ug, and the scale of agitation index.
The latter is evaluated using the gas-dispersion agitation scale reported in
Table 34; where the index ranges from 1 to 10, and O indicates any con-
dition producing a flooded impeller, never used in chemical processes.
This procedure is valid for baffled reactors, designed according to the sug-
gestions given earlier and equipped with a sparge ring and a six-flat-blade
turbine whose prime-mover power is fully invested in the gassed conditions.
c;')
t:l
TABLE 31 0
Hydrodynamic and Mass Transfer Parameters Values in Industrial Reactors I
l02kR, a
104k g 102kia
.o·i::t'"<
(s-1)
....A.
Type of reactor ER, (mol/cm2•s•atm) (cm/ s) (cm-1)
!=,;J
(I)
Packed columns t:l
~
Countercurrent 2-25 0.03-2 0.4-2 0.1-3.5 0.04-7
....0
~
Cocurrent 2-95 0.1-3 0.4-6 0.1-17 0.04-102 0
Plate columns
Bubble cap 10-95 0.5-2 1-5 1-4 1-20
Sieve plates 10-95 0.5-6 1-20 1-2 1-40
Bubble columns 60-98 0.5-2 1-4 0.5-6 0.5-24
Packed bubble columns 60-98 0.5-2 1-4 0.5-3 o. 5-12
Tube reactors
Horizontal and coiled 5-95 0.5-4 1-10 0.5-7 0.5-70
Vertical 5-95 0.5-8 2-5 1-10 2-100
Spray columns 2-20 0.5-2 0.7-1.5 0.1-1 0.07-1. 5
Mechanically agitated bubble 20-95 - 0.3-4 1-20 o. 3-80
reactors
Submerged and plunging jet 94-99 - 0.15-0. 5 o. 2-1. 2 o. 03-0.6
Hydrocyclone 70-93 - 10-30 o. 2-0. 5 2-15
Ejector reactor - - - 1-20
Venturi 5-30 2-10 5-10 1.6-25 8-25
-- C)
t.:)
<:o
640 Carra and Morbidelli
~ 10,,___ _ _ _ __
'e
.c
c:,"'
'100 _ _ _ _ ,,
,:ff
"'
1
100 101 ,02 ,oJ 104
- P r / Q 9 (KW s m- 3 >
FIGURE 24 Approximate dependency of interfacial area on the power
dissipation density for various types of reactors.
Therefore, for systems that are gassed at some times and ungassed at
others, the agitator must be equipped with a two-speed motor to prevent
dangerous overload when the gas flow ceases. Finally, the agitator diam-
eter, expressed in meters, can be evaluated as
(117)
where Hp and N are the prime-mover power and the agitation speed re-
ported in Tables 32 and 33 and expressed in hp and rpm, respectively;
P /Po is evaluated as follows:
Q )0.833
1+ 235.B~N:!)
Q 2.667]
ln
[ 9.155( ~ (118)
NdA
In the case of multiple impeller systems the same procedure can be ap-
plied, as reported by Hicks and Gates (1976). It is worthwhile mentioning
the alternative approach based on the Pfaudler agitation scale described by
Barona ( 1979).
The reactor dimensioning can be performed using either a modeling or
an experimental approach. In the first case, a first trial value of the geo-
metric dimensions and the operating parameters (such as pressure, tempera-
ture, and feed stream characteristics) must be selected to initiate the pro-
cedure. The process specific parameters (i.e., physical and kinetic data
of the system under examination) are then calculated or measured independent-
ly, and the self-adjusting parameters (relative to the hydrodynamics, mass,
c;)
TABLE 32 Prime-Mover Power (hp) and Agitator Speed (rpm) for Superficial Gas Velocity, u~ = 0. 021 m/s A
en
I
t"'
Equivalent volume, Veq (gal) .E"
Scale of i:::
agitation 750 1,500 3,000 5,000 10,000 20,000
E:
50,000 75,000
~
(!)
A
1 1. 5/ 125 2/56 5/84 7.5/68 15/56 30/45 100/56 150/ 45 0
15/155 25/100 50/84 125/68 200/ 68
...
0
-s
en
2 1. 5/84 2/45 7.5/125 10/84 20/68 40/56 154/84 250/84
7.5/45 14/45 200/125
30/125
3 2/45 3/84 7.5/68 10/45 25/84 50/68 250/155 300/100
2/84 3/68 5/45 10/56 25/56 75/125 125/45 350/125
2/125 3/56 7.5/84 20/45 50/45 200/45
5/56 50/56
4 3/84 5/125 10/84 15/68 30/100 60/84 150/45 250/56
3/68 5/84 10/100 20/100 40/155 75/100 200/68 300/68
5/100 10/45 15/84 30/68 60/56 150/56 300/45
5/45 10/56 20/68 40/84 75/68 200/45
5 3/56 7.5/125 15/155 25/125 50/100 100/155 250/84 350/84
7.5/155 15/68 25/84 50/68 100/100 250/56 400/100
7.5/68 15/84 25/100 50/84 100/56 350/45
7.5/84 15/45 25/56 50/45 100/68 400/56
6 5/125 10/84 20/100 30/155 60/125 125/125 300/100 500/68
5/84 10/100 20/68 30/100 60/155 125/68 350/125
5/100 20/45 30/125 60/84 125/45 300/68
30/68 60/56 350/84
7 7.5/155 10/56 25/125 40/155 75/190 150/155 400/100 600/84
25/84 40/84 75/100 150/84 400/56 0:,
,I>.
....
0:,
,i:..
t-:,
TABLE 32 ( Continued)
Equivalent volurr.e, Veq ( gal)
Scale of
agitation 750 1,500 3,000 5,000 10,000 20,000 50,000 75,000
7 (cont.) 25/100 40/100 75/125 150/100
25/56 40/56 75/68 150/45
8 7.5/125 15/155 30/155 50/100 100/155 200/125 500/68
7.5/68 15/84 30/100 50/68 100/100 200/68
7.5/84 30/125 50/84 100/56 200/45
50/45 100/68
9 10/100 15/68 30/68 60/125 125/125 250/155 600/84
60/155 125/68 250/84
60/84 125/45 250/56
60/56
10 10/84 20/100 40/156 75/190 150/155 300/100
15/155 20/68 40/84 75/100 150/84 350/125 (")
r:l
20/100 75/125 150/100 300/68 "'S
"'S
s::l,
r:l
;:s
i;l.
Sa'::
0
....t5'
i;l.
s;
c;)
A
(ll
TABLE 33 Prime-Mover Power (hp) and Agitator Speed (rpm) for Superficial Gas Velocity, u 0 = 0.061 m/s I
g t"'
..Ei"
Equivalent volume, Veq ( gal) ....s:::A.
Scale of
agitation 750 1,500 3,000 5,000 10,000 20,000 50,000 75,000 ::0
(t)
A
(')
1 1. 5/84 3/56 7.5/68 10/45 30/68 50/45 150/45 ....0
"l
10/100 60/155 60/56 250/84 (ll
2 1. 5/56 3/45 15/155 15/68 40/84 75/68 300/100
20/100 100/100 350/125
3 2/84 5/100 10/84 25/125 75/190 125/125 200/56
7.5/45
4 3/84 5/84 10/45 30/155 50/100 150/155 200/45 300/45
3/68 7.5/155 10/56 20/68 40/56 75/45
5/56 15/45 30/45
15/56
5 3/56 7.5/125 15/68 25/84 60/125 100/56 300/68 350/45
7.5/68 15/84 25/100 50/68 100/68 400/56
7.5/84 15/45 25/56 50/84
15/56 50/45
6 5/125 10/84 20/100 30/100 60/84 125/68 350/84 500/68
5/84 10/100 20/68 30/125 60/56 125/45 350/45
5/100 30/68 60/68 300/45
30/45
7 7.5/155 10/56 25/125 40/155 75/100 150/84 400/100 600/84
25/84 25/84 75/125 150/100 400/56
25/100 40/100 75/68 150/45
25/56 40/56 75/84 150/56 0)
ti>,.
c..,
0:,
""""
TABLE 33 ( Continued )
Equivalen t volume, Veq ( gal)
Scale of
agitation 750 1,500 3,000 5,000 10,000 20,000 50,000 75,000
8 7.5/125 15/155 30/155 50/100 100/155 200/125 500/68
7.5/84 15/84 30/100 50/68 100/100 200/68
30/125 50/84 100/56 200/45
50/56 100/68
9 10/100 15/68 30/68 60/125 125/125 250/155 600/84
60/155 125/68 250/84
60/84 125/45 250/56
60/56
10 15/155 25/125 40/155 75/190 150/155 300/100
25/84 40/84 75/100 150/84 300/68
75/125 150/100
(')
Q
~
o,
Q
;::$
Q.
s::
0
~
Q.
ct)
-·~
Gm::-Liquid Reactors 645
TABLE 34 Scale of Agitation for Dispersing Gas into Liquids
Scale of
agitation Description
0 Agitation level of zero indicates a flooded impeller. Not
recommended in CPI service.
1-2 Agitation levels 1-2 characterize applications in which the
degree of gas dispersion is not critical.
Agitators capable of scale level 2 will:
Provide nonflooded impeller conditions for coarse dispersion
of gas in the liquid system.
Be typical of applications that are not mass transfer limited.
3-5 Agitation levels 3- 5 characterize applications in which the
degree of gas dispersion is moderate.
Agitators capable of scale level 5 will:
Drive fine bubbles completely to vessel wall.
Provide recirculation of dispersed bubbles back into
impeller.
6-10 Agitation levels 6-10 characterize critical gas-liquid reactors
where rapid mass transfer is required.
Agitators capable of scale level 10 will:
Maximize interfacial area and recirculation of dispersed
bubbles back into impeller.
and heat transfer) are calculated as shown earlier. All the values so ob-
tained are fed to the suitable mathematical model, whose solution leads to
the estimation of the reactor performance and then to its dimensioning and
optimization (Deckwer, 1977). The most uncertain steps of this procedure
concern the correct evaluation of the self-adjusting parameters, particularly
for bubble columns and mechanically stirred contactors, and the related
problem of the correct reactor model selection. Also, the complete physical
(solubility and diffusivity of the solute in the reacting mixture) and kinetic
(rate constant of all the involved reactions) characterization of the system
can be difficult and uncertain.
An experimental procedure can overcome these difficulties, leading to
more accurate results. In this case the equations reported earlier can be
very useful to define the kind of dependence among the various parameters.
Small-scale experiments are performed on the same gas-liquid system using
a laboratory apparatus similar in shape, agitation, and contact time to the
chosen industrial reactor. The scaling rule, which ensures the same
specific interfacial area, is to maintain constant the total power input per
unit liquid volume; that is, Pt /V 9, and uf are constant in a mechanically
g
agitated contactor, and p 9,gug is constant in a tubular sparged reactor
(Reith, 1970). Note that using this scaleup criterion, the heat transfer
coefficient hw has roughly the same values in the model and in the prototype,
.
since 1·t d ecreases f or 1ncreas1ng
. . - l/ 9 •
reactor d"iameter as dR There f ore, on
scaleup of agitated reactors with significant heat transfer, installation of
646 Carril and Morbidelli
additional heating or cooling devices is usually necessary, since the con -
tents increase with the cube and the heat exchange with the square of the
reactor diameter (Steiff et al., 1981). Since the interfacial area (and then
the reactor performance) increases for increasing values of the power in-
put per unit liquid volume, and the operating costs are directly proportion-
al to the power input, the reactor volume selection should be based on the
minimum total cost.
A useful scaleup procedure, based on constant depletion of the re-
actant gaseous concentration, has been proposed by Nagel et al. (1973, 1978).
It allows, through the use of suitable working diagrams, defining the opti-
mal reactor volume using as a scaleup criterion a constant value of the
quantity a/Qg, An alternative scaleup procedure for bubble columns has
been propose a by Kastanek et al. ( 1980).
An alternative experimental approach is the simulation of industrial
units using laboratory-scale apparatuses, with the same gas-liquid system
(so avoiding determination of kinetic, solubility, and diffusivity parameters)
and a different mean of liquid agitation. It is based on the observation
that if the purely physical mass transfer coefficients in the two units are
equal, the absorption rates per unit interfacial area, also in the presence of
the reaction, are identical. This fact appears quite reasonable noticing that
the predicted effect of chemical reaction on the rate of absorption differs
little whether the film or surface renewal-type models are used as a basis
for calculations, provided that the same value of the purely physical mass
transfer coefficient k,Q, is assumed in all models (Danckwerts, 1970). When
the absorption process involves a dilute solute in the gas phase (i.e.,
significant gas-phase transfer resistance is present), the gaseous mass
transfer coefficient kg must be the same in both units. Finally, for slow
reactions that do not completely occur in the liquid film, the ratio a/E,Q, must
be the same in both units, to account for the liquid bulk reaction contribu-
tion. So, in general, the three criteria for simulation (i.e. , to reproduce
the same absorption rate per unit interfacial area) are identical values of
k,Q,, kg, and a/E,Q, in the industrial and laboratory absorber,
The procedure can then be outlined as follows:
1. Measurement or calculation of k,Q,, kg, and a/f:.,Q, in the industrial
unit
2. Reproduction of the same values in the laboratory unit
3. Measurement of the interfacial mass flux in the laboratory unit,
which is the same in the industrial unit
To accomplish the last two steps, it is necessary to use laboratory-scale
absorbers where the interfacial area is known with good accuracy and the
values of the three parameters k,Q,, kg, and alc.,Q, can be varied over a reason-
ably wide range of values. The first one is usually varied by mechanical liquid
agitation, the second one by independent mechanical gas agitation, or simply
by changing the relative gas-liquid velocity. The control of the third param-
eter requires more complex apparatus, such as a string of spheres with pools
at the top (Alper and Danckwerts, 1976) or the modified stirred cell proposed
by Levenspiel and Godfrey (1974). However, few applications of the third
criterion are known in the literature, since usually only fast reactions have been
examplined. In Table 35 and Fig. 25, the most important types of laboratory
equipment have been summarized together with the relative values of the
c;)
p
Cl)
I
t"'
..a"
E.
i:i..
TABLE 35 Values of the Characteristic Parameters of the Laborabory Models Sketched in Fig. 25
::0
(1)
p
(')
Model
0
-
J
Wetted wall column String Modified
Laminar of Stirred Rotating stirred
Parameter jet Cylinder Sphere Cone disks cell drum cell
Contact time 10- 3 10- 1 10- 1 2 X 10-l 10- 1 6 X 10- 2 2 X 10- 4 2 X 10- 2
(s) 10- 1 2 1 1 2 10 10- 1 10
Interfacial 0.3 10 10 30 4 2 2
area, A (cm 2 )
1.0 100 40 80 360 80 100 80
-1 -2 -3
k,Q, (cm•s ) 1.6 X 10 3.6 X 10- 3 5 X lQ- 3 5 X 10- 3 3. 6 X 10 1.6 X 10- 3 1.6 X 10- 2 2 X lQ- 3
X X
-2
1.6 10-l 1.6 10- 2 1.6 X 10- 2 1.1 X 10 1.6 X 10- 2 2, 1 X 10- 2 3.56 X 10-l 2 X 10- 2
10 5 kg (mol •cm-2 10 1 1 1 1 1 - 1
-1 -1
s atm ) 40 9 9 9 25 15 - 15
-1
A/V ,Q, (cm ) 20 25 20 40 20 2 X 10-3 100 2 X 10- 3
80 60 60 70 60 5.4 X 10-l 1250 10- 1
0.,
,IS.
~
0:,
>IS.
Oo
WETTED WALL COLUMN
MODEL LAMINAR JET STRING OF ROTATING MODIFIED
r CYLINDER SPHERE CONE DISKS
I STIRRED CELL □ ~UM STIRRED CELL
liquid l1qu1d
liquid
l1qu1d gas
SCHEME
Ire ~q-!'i
to
i°"llJ. Ii'f ~~ ~~~:u,~ ~: ~
L1auld
ll tfr TlJ l1qu1d I
BJERLE ET AL ROBERTS AND DAVIDSON AND DANCKWERTS LEVEN SPIEL
REFERENCE \
I DANCKWERTS (1970) STEPHEN AND IDANCKWERTS
DANCKWERTS CULLEN MORRIS A ND ALPER AND KENNEDY AND GODFREY
(1972 l (1957)
(1962) (1951 l (1975) (1958 l (1974 l
FIGURE 25 Schematic representation of some laboratory equipments.
(')
Q
"'$
;1
Q
;:l
Q.
;s::
0
~
Q.
~
Gas-Liquid Reactors 649
relevant parameters. These, coupled with Table 31, can lead to the choice
of the most suitable laboratory unit for the simulation of a given industrial
unit (Charpentier and Laurent, 1974). Note that this equipment is usually
employed for the determination of kinetic rate constants, diffusivities, and
solubilities (Lauret et al., 1975).
A classic example of the procedure described above is the simulation of
a packed column with a stirred cell for reactions occurring in liquid film
(Danckwerts and Gillham, 1966; Charpentier, 1978; and references therein).
In this case a mutual correspondence can be determined between the agita-
tor speeds in the gas and liquid phases in the model unit (which define kg
and k Jl, respectively) and the gas and liquid superficial velocities in the
packed column, respectively.
The interfacial mass flow values measured in the laboratory unit can
be used to perform a differential or an integral simulation of an industrial
tubular reactor. In the first case, the material flux is evaluated at the
various concentration values present along the column, and reactor be-
havior is then predicted through a numerical integration (Danckwerts and
Alper, 1975; Laurent and Charpentier, 1977; and references therein). In
the case of multiple liquid or gaseous reactants or when the reaction con -
tribution in the liquid bulk is significant, the differential simulation is not
feasible, and only the integral one can be pursued, In this case the column
is simulated as a whole, using the laboratory model unit described above.
The global absorption rate in the model is measured at the same operating
conditions, including the outlet and inlet concentration values, at which
the industrial unit is operated. The global absorption rate in the industrial
unit is then given by the product of the global absorption rate in the labora-
tory unit and the ratio between the liquid flow rates in the industrial and
model units, respectively (Alper and Danckwerts, 1976). It is noticeable that
both these types of simulation procedures exhibit, in all literature applications
(Laurent and Charpentier, 1977), errors that never exceed 20%.
NOTATION
a interfacial area per unit reactor volume
a heat exchange surface per unit reactor volume
C
a interfacial area per unit packed volume
p
at total dry surface area of packing per unit packed volume
A, A' gaseous reactant
B liquid reactant
C liquid reactant
C. concentration of the ith component
1
C
p specific heat
dA, de' dR diameter of agitator, columns, reactor
d , d characteristic and nominal packing diameter
p n
d Sauter mean bubble diameter, defined by Eq. (45)
vs
D diffusion coefficient
650 Carra and Morbidelli
E, E* enhancement and reaction factor, defined by Eqs. ( 27) and
( 28), respectively
E axial effective mass dispersion in the gas and liquid phases
g' E,Q,
E. reaction factor for an instantaneous reaction
ln
EM' EMT Murphree efficiency for mass and heat transfer
ET axial effective heat dispersion
f fugacity
f r/r 0
F feed molar flow rate
g gravitational acceleration
G gas molar flow rate
hA agitator height off the reactor bottom
hc,hw coil and wall bed heat transfer coefficients
h,Q, gas-liquid heat transfer coefficient
H interfacial equilibrium ratio, defined by Eq. (21a)
H liquid height
H* dimensionless Henry's constant, defined by Eq .. ( 56)
H molar enthalpy
H Henry's constant
Ha Hatta number, defined by Eq. ( 52)
I solution ionic strength, defined by Eq. (12)
J dimensionless mass flux
k reaction rate constant
kB Boltzmann's constant
kg, k,Q, gas-side and liquid-side mass transfer coefficients
kT thermal conductivity
K equilibrium ratio, defined by Eq. ( 1)
K overall mass transfer coefficient, defined by Eq. ( 22)
g
L reactor length
L liquid molar flow rate
m reaction order
m. molality of the ith component
l
M Hatta number, defined by Eq. ( 84)
n reaction order
n* flow index; 1 == countercurrent, -1 == cocurrent
N agitation speed
Gas-Liquid Reactors 651
N. mass flux of the ith component (positive if leaving the gas
l
phase)
N power number
p
NC component number
NR reaction number
pj rr/r 1
po vapor pressure
p pressure
Po power input in unaerated reactor
Pt, p g total and mechanical power input
Pe Peclet number, defined by Eq. (62)
Q volumetric flow rate
r reaction rate
R universal gas constant
Re Reynolds number
R.l overall rate of consumption of the ith component
s distance into the liquid phase
SC wall or coil width
sg specific gravity
St Stanton number, defined by Eq. (62)
t time
T temperature
u superficial velocity
u overall heat transfer coefficient
V dimensionless superficial velocity
V volume
VR reactor volume
WA agitator blade width
X s/o
x. mole fraction of the ith component in the liquid phase
l
y axial coordinate
Y1 mole fraction of the ith component in the gas phase
z y/L
z. mole fraction of the ith component in the feed stream
l
ZD concentration diffusion parameter, defined by Eq. ( 36)
652 Carra and Morbidelli
Greek Letters
ratio of the bulk liquid volume to film volume, defined
by Eq, (62)
dimensionless parameter defined by Eq. (67)
y activity coefficient
y dimensionless parameter defined by Eq. ( 56)
0 film thickness
~H a '~H ev '~HR molar heat of absorption, evaporation and reaction
(negative if exothermic)
Eg' EJI, fractional gas and liquid holdup
Ep packing void fraction
0 dimensionless time, defined by Eq. ( 71)
µ viscosity
vB stoichiometric coefficient of reactant B, positive
v .. stoichiometric coefficient of the ith component in the jth
l]
reaction
~ D/DA
p density
a surface tension
<P dimensionless concentration
<P fugacity coefficient
Special Operators
V gradient operator
v2 Laplacian operator
Subscripts
d dispersion
f film
g gas
i component index
reaction index
k stage index
JI, liquid
s solid
w water
vector
Gas-Liquid Reactors 653
Superscripts
f feed
in initial
0 reference condition (feed for continuous and initial for batch reactors)
molar
* surface
partial molar
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Gas-Liquid Reactors 665
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666 Carra and Morbidelli
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10
Gas-Liquid-Solid Reactors
YATISH T. SHAH University of Pittsburgh, Pittsburgh, Pennsylvania
MAN MOHAN SHARMA University of Bombay, Bombay, India
INTRODUCTION: CLASSIFICATIONS: EXAMPLES
OF INDUSTRIAL IMPORTANCE
Three-phase reactors, involving gas, liquid, and solid phases, are widely
encountered in industrial practice. Several examples are illustrated in
Table 1. Other examples are given by 0stergaard ( 1968), Shah ( 1979),
Shah et al. (1982), and Doraiswamy and Sharma (1983). As can be seen
from this table, solid phase can be either reactant or product or it could
be catalyst. In some cases we may have four phases, either through two
immiscible liquid phases (either as reactants and /or products) or through
two solid phases, one reactant or product and other catalyst. Although,
three-phase· systems are found in chemical, polymer, biochemical, and
petroleum industries, they are best known in hydroprocessing operations.
Two main categories of three-phase reactors are fixed- bed reactors,
which are normally used when catalyst particles are larger than 10- 3 m,
and slurry reactors, wherein the solid phase is in suspension. The most
common type of fixed-bed reactor used in industry is the trickle-bed reac-
tor, wherein liquid trickles over a fixed bed of catalyst while gas flows co-
currently downward as a continuous phase. Fixed-bed reactors are often
operated in the bubble flow regime, wherein both gas and liquid flow cocur-
rently upward and gas is the dispersed phase. In some processes, such
as for hydrodemetallization of high-metal-content heavy crude, the catalyst
needs to be replaced frequently, and a moving fixed-bed reactor is used.
In such reactors, a pulsating flow regime may prevail in the bottom part of
the reactor. As pointed out by 0stergaard ( 1968), in true slurry reactors,
solid particles are very fine ( generally less than 10- 3 m) and gas flows
mainly in and out of the reactor. In many cases, slurry reactors can be
mechanically agitated. If solid particles are large such that they form a
discrete phase within the reactor and if the liquid-solid mixture flows in
and out of the reactor, the reactor is often called a three-phase fluidized-
bed reactor. In the present chapter we concentrate on slurry reactors
(with fine catalyst particles) with some allowance for slurry flow in and
out of the reactor. Several types of fixed-bed and slurry reactors used
in industrial practice are illustrated in Fig. 1.
667
668 Shah and Sharma
TABLE 1 (a) Examples of Fluid-Fluid-Solid Systems: Solids
Sparingly Soluble
Absorption of co 2 in aqueous suspension of lime and Ba(OH) 2
Absorption of CO 2 in a suspension of BaS
Absorption of lean so 2 in a slurry of Caco 3
Absorption of lean H2s, COC1 2 , Cl 2 , etc., in an aqueous suspension of
lime
Absorption of CO in a suspension of lime in the manufacture of (HCOO) 2Ca
(b) Examples of Fluid-Fluid-Solid Systems: Solid Particles Insoluble in
The Medium
Absorption of CO 2 in a suspension of MgO
Absorption of CO 2 in a suspension of CaS
Absorption of so 2
in a suspension of Caco 3
Chlorination of wood pulp
Hydrogenation of styrene- butadiene rubber latex and other polymeric
substances suspended in solvents
Hydrogenation of sodium particles suspended in mineral oil to give NaH
Chlorination of suspended polyethylene (and PVC) particles in water
Manufacture of zinc dithionite by reaction between so 2 and zinc particles
suspended in water
(c) Examples of Fluid-Fluid-Solid (Catalytic) Reactions
System Catalyst Type of reactor
Hydrogenation of unsaturated fats Raney nickel SR
Hydrogenation of nitrobenzene Pd, Pt, Ni, etc., SR
sulfonic acid (potassium salt), based catalyst
nitrophenols, etc., in aqueous
solutions
Hydrogenation and hydrocracking Ni catalyst SR
of a-cellulose ( also powdered
coal) to liquid and gaseous fuels
Hydrogenation of nitriles Ni-based catalyst SR
Hydroisomerization of butene-1 Undisclosed TBR: packed
to butene-2 bubble column
(up- flow)
Hydroformylation and hydrogenation Nobel metal SR
of monoolefins , methyl sorbate, (Rh)-based
etc. catalyst
Gas-Liquid-Solid Reactors 669
TABLE 1 (Continued)
System Catalyst Type of reactor
Hydrogenation of xylose; Raney Nickel; Ru SR
hydrogenolysis of saccharides
Fischer-Tropsh synthesis: Ni-MgO SR
conversion of CO+H 2 to CH 4 ,
:paraffins, etc.
Conversion of CO+H 2 to methanol Cu-Zn oxide (Three-phase)
fluidized- bed
reactor
Reaction between nitrite and H2 Noble metal (Pd) SR
to give hydroxylamine salts; on carbon
reaction between NH4NO3, H3PO4,
and H2 to give hydroxylamine
phosphate
Reduction of sodium chlorate in Not disclosed TBR
(diaphragm cell) aqueous caustic
liquor with H2
Hydrogenation of iodine dissolved Ru or Rh SR
in aqueous II
Reduction of uranyl(VI) to PD based TBR: packed
uranyl(IV) in aqueous solutions bubble col-
with H 2 umn reactor
Reduction of UF5 dissolved in Pt-based catalyst SR
molten LiF- BeF 2-ThF 2 melt with
H2
Deuterium exchange between Pt on carbon TBR
H 2 and water
Air oxidation of ethanol to acetic Pd- based catalyst, TBR; SR
acid; conversion of primary CdO, ZnO, etc.
alcohols to the corresponding
sodium salt of the acid
Oxidation of isobutylene glycol Pt on carbon SR
to a.-hydroxyisobutyric acid
Amination of monoethanolamine Undisclosed TBR
to ethylene diamine
Isomerization of propylene oxide Li3PO4 suspended SR
to allyl alcohol; rearrangement in diphenyl;
of oxirane compounds SiOrAl2O3
Oxidation of glucose to Pt on carbon SR
K - gluconate
Hydrogenation of 1-bromo, Pd on carbon SR
2, 4-dichlorobenzene to
1, 3-dichlorobenzene
670 Shah and Sharma
TABLE 1 (Continued)
System Catalyst Type of reactor
Alkylation of benzene with Phosphoric acid TBR
propylene
Reaction between isobutylene and TBR
aqueous formaldehyde (a step in
the manufacture of synthetic
isoprene)
Reaction between isobutylene and Ion-exchange Multitubular
methanol to give methyl-tert- resins packed - bed
butyl ether reactor
Epoxidation of ethylene to ethylene Silver oxide on SR
oxide silica gel
suspended in
dibutyl phthalate
Epoxidation of propylene with Mo sulfide /oxides SR
tert-butyl hydroperoxide, ethyl
benzene hydroperoxide, etc. ;
Epoxidation of styrene and
a-olefins with cumene hydroper-
oxide
Slurry polymerization Organometallic SR
compounds
Oxidation of S02 to H2S04 in water; Active carbon TBR, SR
absorption of H2S from stack
gases in alkaline solutions ;
osication of aqueous sodium
sulfide (black liquor)
Air oxidation of dilute formic Copper oxide- zinc TBR
acid and acetic acid solutions oxide ; ferric oxide
(treatment of waste streams)
Hydrodesulphurization and Molybdenum- and TBR
hydrocracking of petroleum tungsten - based
fractions catalyst
Conversion of propylene to Tungstic oxide- TBR
isopropanol based catalyst
Acrylamide from acrylonitrile Copper chromite TBR
Dehydrogenation of secondary filor copp~ SR
alcohols to ketones chrome
Dehydrogenation of isoborneol Cu-Ni-Mn SR
to camphor
Hydrogenation of polymeric Raney Ni; Pd/C SR
substances
Gas-Liquid-Solid Reactors 671
TABLE 1 (Continued)
System Catalyst Type of reactor
Hydrogenation of epoxides of Raney Ni SR
styrene, a-olefins, etc. , in the
presence of water as a second
liquid phase
Hydrogenation of 2-methyl nitro- Pt/C SR
benzene in cone. H2S04 medium
to 4-amino- 3-methyl phenol
Absorption of NOx (at low ppm) Patented alloy TBR
in water gauge packing
Coal liquefaction Ni-Co-Mo SR
Organic substitution reactions Quarternary SR
via phase transfer catalysis ammonium or
phosphenium
salts bound to
cross -linked
polystyrene
resins , resin -
bound linear poly-
ethers, resins-sup-
ported oligooxyethlenes,
poly(vinyl pyridine)-
bound polymers
The nature of the gas- liquid solid reaction may often be complex. The
product of the reaction is usually soluble in the liquid phase but in several
instances the product may be insoluble in the liquid phase. In slurry and
fixed-bed reactors the liquid phase may be a reactant or may simply be a
solvent. In a special case of the slurry reactor, the particles may simply
be adsorbents. In some uncommon cases, such as demetallization of heavier
petroleum fractions, the catalyst gets laden with the product (metals in the
case of heavier petroleum fractions) .
Solid-bound catalysts and reactants have gained importance in recent
years and here both slurry and fixed- bed reactors are used. There is
an incentive to use heterogenized- homogeneous catalysts, as the problem
of the recovery of the catalyst can easily be handled using such catalysts.
There are special reasons to immobilize a soluble reactant; the objective may
be to achieve high selectivity or to avoid product contamination. In fact,
ionic reactants exchanted on ion-exchange resins have also been considered
in the literature. The solid particles may be reactant, which may be soluble/
sparingly soluble /insoluble in the liquid phase, and if insoluble, may exist
on the solid reactant as a product layer or as a discrete phase.
A variety of two-phase reactions involving a sparingly soluble reactant
can be carried out successfully using the technique of phase transfer
catalysis. Here the catalyst (PTC) forms a complex with the reactive
672 Shah and Sharma
i
Gas
l V'
) ) )>-,>
l l i r
Gas Liquid
Trickle-bed reactor Packed bubble
column reactor
Liquid Gas
i i
T
Trickle
flow
pulsating+
flow
Solid catalyst
Moving fixed-bed reactor
(a)
FIGURE 1 Various types of (a) fixed-bed reactors, and (b) slurry
reactors.
Gas-Liquid-Solid Reactors 673
L, L1 L1
Go Go Go
Single Stage Multi Staged Multi Channel With Static Mixers
G1 G1
L1
•Q•O. 0 0 0 L1
••o Oo 0
oo:o:o~
O•o •o o
o o •·o·
0 Gj
0 Oo
I I
Loop Reactor Loop Reactor Jet Reactor Downflow Bubble
( External ) (Internal) Column
Pipe Line
Slurry reactor
L, Go
3-Phase Flu id ized Slurry R~actor
Bed Reactor
(b)
FIGURE 1 (Continued)
674 Shah and Sharma
species from the aqueous or solid phase and transports it across the inter-
face into the organic phase, where the reaction talces place. The main
drawbacks of the technique involve the separation and recovery of the
costly PTC, but these can probably be overcome by employing a solid-
supported PTC. This type of catalysis was termed triphase catalysis by
Regen (1975). The special feature of triphase catalysis is that the two re-
acting species are located in two different phases and the solid catalyst
forms the third phase.
Finally, in recent years, three-phase electrochemical reactions have
also gained some importance. Both slurry and fixed - bed reactors have
been considered where gas-liquid-solid and liquid-liquid-solid systems are
encountered, and some new designs have been suggested. In this chapter
we attempt to cover briefly the main features of gas-liquid-solid reactors,
with the principal emphasis on conventional fixed and slurry- bed reactors.
HYDRODYNAMICS, MIXING, AND TRANSPORT
CHARACTERISTICS OF FIXED-BED REACTORS
Three-phase catalytic fixed-bed reactors are generally operated with
downward or upward cocurrent flow of liquid and gas. The most pre-
dominant flow regime encountered in commercial operations is the trickle
flow regime, in which gas and liquid flow cocurrently downward over a
fixed bed of catalyst. As shown by Satterfield (1975), in many hydro-
processing operations, flow conditions are such that the reactor is operated
at the boundary of trickle flow and pulsating flow regimes. The pulsating
flow regime can also be achieved when gas and liquid flow cocurrently up-
ward at high velocities. Some commercial reactors are operated under a
bubble flow regime wherein gas and liquid flow cocurrently upward through
a fixed bed of catalyst. Finally, hydrodemetallization of heavy crude is
carried out in moving fixed-bed reactors with cocurrent downward gas-
liquid flow due to rapid aging of the catalyst. The flow regime in such
reactor can change from trickle flow at the top to pulsating flow at the bot-
tom. The discussion presented below is therefore restricted to ( a) trickle
flow, (b) pulsating flow, (c) packed bubble flow, and (d) moving fixed-bed
reactors.
Flow Regime Boundaries
In all work on two-phase downflow over packed beds before 1975, flow
regimes were considered to be functions only of gas and liquid flow rates.
The flow regime boundaries have been obtained in terms of superficial mass
flow rates of air and water. The coordinates for the flow maps, showing
flow regime boundaries, have been either Ga versus GL (Weekman and
Myers, 1964, 1965; Beimesch and Kessler 1971; Sato et al., 1973b; Satter-
field, 1975; Chou et al., 1977; Charpentier et al. 1969; Hoffmann, 1978;
Sicardi et al., 1979) or GL versus Ga (Turpin and Huntington, 1967).
Sato et al. (1973b) noted that the boundary between continuous and pulse
gas flow moves to low liquid flow rates and returns to high liquid flow
rates as the particle size is increased.
Charpentier and Favier ( 1975) introduced the effects of density,
viscosity, and surface tension and the foaming nature of liquid of the flow
regime boundaries and presented a flow map using Balcer's coordinates for
gas-liquid flow in an empty tube. Their results are shown in Fig. 2.
Gas-Liquid-Solid Reactors 675
1000 System Packing Key
Water - air Spherical catalyst 0
Cyclohexane -air Spherical catalyst ()
Water-air Cylindrical catalyst 1 □
Cyc lo hexane-nitrogen Cylindrical catalyst 2 t:,.
➔
-< 10 Gasoline-carbon dioxide Cylindrical catalyst 2
•
Gasol ine-n itrogen Cylindrical catalyst 2 ■
Gasoline-helium Cylindrical catalyst Z A
Petroleum ether-nitrogen Cylindrical catalyst 2
Spray
flow Petroleum ether-carbon-dioxide Cylindrical catalyst 2 i
0•1 ....._...._......._..._-'--.....L-........L-.....L--'
0•01 0•1 O• 1
GG/).
(a)
System Packing Key
Kerosene-air Spherical catalyst ()
Foaming
Desulfurized gas oil-carbon Cylindrical catalyst 2 +
dioxide
:,;,.-,, .. ,.. ,
pulsed Desulfurized gas oil-air Cylindrical catalyst 2 X
Desulfuri zed gas oil-helium Cylindrical catalyst 2 A
100
Trickle \';<'. flow
Nondesulfurized gas oil-carbon Cylindrical catalyst 2 *
dioxide
Nondesulfurized gas oi I-air Cylindrical catalyst 2 /\
.
l!I flow ','\
',,:'\
10
......
<!>
Nondesulturized gas oil-helium Cylindrical catalyst 2 J.
1,
(!)
Kerosene-air Cylindrical catalyst 2 ◊
Specchio and Baldi Kerosene-nitrogen Cylindrical catalyst 2 ♦
)..:
G A
[ _,_L_
Jo.,,y: CTwat
f'wat Pair C"L
(b)
FIGURE 2 Flow-regime boundaries for (a) foaming and (b) nonfoaming
liquids. (After Charpentier and Favier, 1975.)
676 Shah and Sharma
GAS CONTINUOUS
(Blurring flow, Spray Flow)
Upper Boundary
For Pulsing
-
..J
I
0
I
Ill
C)
0 TWO CONTINUOUS
PHASES
·-u...
- GI
E
::,
Lower Boundary
For Pulsing
'o 2 LIQUID CONTINUOUS___,_______......________________
1___________,__
> ( DisP,ersed Bubbles l
·1 ·2 ·4 ·6 1·0 2 4 6 10 20 40 100 200 400 1000
Inertia + Gravity forces = 1+ (1 /Fr)
Interface+ Viscous Resistances We+( 1/Re)
600
GAS CONTINUOUS
-
.~400 (Blurring flow, Spray flow)
&200 Upper boundary
"O --~-f...:.o r p u Ising
·-100
::,
CT 60
..J
-
I 40
0
I
I ll
20
g FOAM.ING
AND
..
.u..
GI
E
PULSING
:, Lowerbou~
0
2 tor pulsing FOAMING
>
1
·1 ·2 ·4 -6 1·0 2 4 6 10 20 40 60 100 200 400 1000
Inertia+ Gravity Forces _ 1+ ( 1 /Fr)
Interface +Viscous Resistances - We+( 1/ Re)
FIGURE 3 Flow maps: two-phase downflow through packed beds: (top)
nonfoaming liquids; (bottom) foaming liquids. (From Shah et al., 1981.)
Gas-Liquid-Solid Reactors 677
Talmor (1977) presented flow maps (Fig. 3) for foaming and nonfoaming
liquids using a superficial volumetric gas-to-liquid ratio versus a ratio of
driving force to resistance force. Clements and Halfacre (1979) showed
that the data of Chou et al. (1977) for aqueous solution of alcohol, and
their own data for air-isopropanol aqueous solution (0 to 48 wt %) , were
correlated by the flow maps of Talmor ( 1977) but not by the flow maps of
Charpentier and Favier ( 1975). These workers also concluded that surface
tension exerts the dominant influence over flow pattern transitions and foam-
ing in the packed bed. A Talmor flow map has been used by Patil and
Sharma ( 1981) for a tube packed with Pall rings and multifilament wire
gauge packings.
The flow regime boundaries for cocurrent upflow over a fixed bed in
terms of gas and liquid mass flow rates have been reported by several
workers (Ford, 1960; Turpin and Huntington, 1967; Specchia et al,, 1974;
Sato et al., 1974; Pittsburgh Energy Research Center, 1976). The results
of the latter study are shown in Fig. 4. Saada (1975) obtained data charac-
terizing the flow regime for small particles (d < 0. 2 cm). He also modified
the coordinates of flow maps to include the e~ects of densities and viscos-
ities of gas and liquid and bed porosity. In Saada's work, flow is divided
into two regimes. At relatively high gas flow rates, the pores of the pack-
ing are considered to be traversed by both phases together, whereas at low
,"
--
N
'E Gos-continuous or spo/..-:
u
Cl
flow ✓
I
, ,,,,,,,-
I
,✓
I
Pulsed or {
u
0 slug flow )
"ii
>
,,I
----
,,,
Ill
Ill
0 Surging flow
E
Ill
~ 0•1L.------a-u"'"b_b_l_eflow
0·1 1·0 10
Llqui d moss velocity ,GL ( g cni 2 ,-, )
- - - Pittsburgh energy - - - - Soto et ol.(1974)
re nor ch center ( 1976) dp- 1•22cm spherical
dp - 1,9 cm x 1·9 cm particle shape
cylindrical particle shape
FIGURE 4 Flow regime boundaries of water-air upflow through a packed
bed. (From Pittsburgh Energy Research Center, 1976.)
678 Shah and Sharma
gas flow rates each phase is considered to flow seperately through the
pores. The former is referred to as a two-phase pore-flow regime and the
latter as a single-phase pore-flow regime. This flow map is shown in Fig.
5. Generalized flow maps such as those of Talmor (1977), for downflow
over packed beds, are not available for the cocurrent upflow case.
Pressure Drop
Reported data on pressure drop in two-phase flow over a fixed bed cover
various flow regimes and a large range of design and operating variables.
However, most of these studies are for air-water systems. Other gas-
liquid systems have also been investigated (Clements and Schmidt, 1976,
1980b; Larkins et al., 1961; Specchia and Baldi, 1977), but more data on
hydrocarbon and foaming systems are needed. The data base of Larkin
Regime of
two-phase
pore flow
...JI
:t.. :t.
I.!)
1 Regime of
\ single-phase
\POre flow
\
\
\
\
0•01 \
\
\
\
\
\
\
0·0001 \
\
\
\
FIGURE 5 Correlation of flow transition by Saada ( 1975).
Gas-Liquid-Solid Reactors 679
et al. 's ( 1961) correlation is relatively large and close to the conditions in
a commercial reactor and therefore is more commonly used,
In the correlation of pressure-drop data for two-phase flow in packed
beds, basically two approaches have been used, In one approach, the vari-
ables are lumped into various dimensionless groups, such as Reynolds num-
bers for gas and liquid, Weber numbers, and so on, and the pressure drop
or friction factor is expressed in terms of these dimensionless groups. The
use of Tallmadge or Lockhart-Martinelli parameters is included in this ap-
proach (Turpin and Huntington, 1967; Specchia and Baldi, 1977). The
other approach is to correlate the two-phase pressure drop with the pres-
sure drops of energy losses for individual phases in single-phase flows
under identical conditions.
Ford (1960) measured pressure drop in packed beds for cocurrent up-
flow and identified the flow regimes based on the flow that takes place in-
side the pores: namely, single-phase pore flow and two-phase pore flow.
He presented correlations having the form
1 ( tiP) (1)
gpL "i:z LG =
The values of a., x, y, and z depend on the type of flow regime. Different
values of a., x, y, and z have accordingly been suggested for the two
regimes. Saada (1975) modified the Ford correlation and replaced the µLil.ta
term by dp/dc (i.e., the ratio of the particle and column diameters),
A large number of data points obtained by the Pittsburgh Energy Re-
search Center (PERC) (1976) in highly pulsed and spray flow regimes have
been correlated by Tallmadge's correlation (1970). Sato et al. (1974), on
the other hand, correlated their data with the Lockhard-Martinelli type of
relation in all three flow regimes (i.e., bubble, pulsed, and spray).
The more widely used correlation of Larkins et al. (1961), for cocurrent
downflow is based on the second approach. It correlates the overall two-
phase energy loss for the gas and liquid passing through the reactor to the
two individual single-phase energy losses as follows:
( 2)
where og is the gas-phase energy loss, oL the liquid-phase energy loss,
OLG the two-phase energy loss, and X = (oL/oa)l/2, The constants K1
and K2 have the values 0.416 and 0.66, respectively.
Larkins et al. (1961) defined the two-phase pressure gradient
(tiP/tiZ)LG as follows:
(t~)LG = oLG - PM ( 3)
where
( 4)
680 Shah and Sharma
Several other workers have used Eq. (3) directly (Abbot et al., 1967) or
in modified form (Reiss, 1967; Sato et al., 1973a) for correlation of their
data. Charpentier et al. (1969) derived pressure-drop correlations by
comparing two-phase pressure loss tiPLG with that for single-phase flow,
in terms of the energy-based dimensionless groups. Clements and Schmidt
(1976, 1980a,b) combined the foregoing two approaches and gave the cor-
relation for pressure drop in two-phase cocurrent downflow in terms of
Reynolds numbers of gas and liquid phases, gas-phase Weber number, and
pressure drop for the gas phase alone. Clements (1978) also gave a theo-
retical justification for this approach. Theoretical correlations for pressure
drop under trickle flow conditions have been proposed by Hutton and Leung
(1974) and Specchia and Baldi (1977).
It is important to note that in most of the studies reported, Reynolds
numbers for liquid and gas phases are considered to be the controlling
dimensionless groups. However, those studies that use systems other than
air-water recognized the role of surface tension on the pressure drop and
used either an empirical correction factor (Specchia and Baldi, 1977) or the
dimensionless Weber number (Clements and Schmidt, 1976, 1980a, b). More
data over a larger range of Weber numbers are needed.
Phase Holdups
Liquid Holdup
Total liquid holdup in a fixed-bed column is the sum of the operating and
static holdups. Static holdup, the amount of liquid in the bed after the
liquid inlet is shutt off and the column is allowed to drain, represents the
liquid retained in the pore volume of the catalyst and its packing. Operat-
ing holdup, the liquid external to the catalyst particles, depends on the
liquid and gas flow rates, their properties, and the nature of catalyst
packing. 2
Static holdup is often correlated by Eotvos number, Eo (=pLgd/ crL,
where dp is the nominal particle diameter and g the gravitational accelera-
tion). The correlation of Van Swaaij et al. (1969) indicates that smaller
particle diameter and fluid density and larger surface tension give larger
static liquid holdup. The correlation also indicates that a porous material
gives a larger static liquid holdup than does a nonporous material.
Basically, two types of correlations for the dynamic or total liquid
holdup are reported in the literature. Some investigators have correlated
the liquid holdup directly with the liquid velocity and fluid properties by
either dimensional or dimensionless relations. In more recent investigations,
liquid holdup is correlated to the Lockhart-Martinelli parameter tiPL/tiPa
or its equivalent.
For cocurrent downflow, the dimensional correlations (Satterfield and
Way, 1972; Jesser and Elgin, 1943) are very few. Most of the correlations
are in the following dimensionless form (Clements and Schmidt, 1980a;
Otake and Okada, 1963; Michell and Furzer, 1972; Buchanan, 1967; Gelbe,
1968; Mohunta and Laddha, 1965; Van Swaaij et al., 1969; Specchia and
Baldi, 1977; Davidson et al., 1959):
(5)
The values of a, 13, y, and n obtained by different workers differ.
Gas-Liquid-Solid Reactors 681
Many correlations using the Lockhart-Martinelli parameter or its
equivalent are also reported in the literature (Abbott et al., 1967; Larkins
et al., 1961; Sato et al., 1973a; Bakos and Charpentier, 1970; Midoux et al.
1976). The correlations of Midoux et al. ( 1976), in terms of energy based
dimensionless groups, for nonfoaming and foaming liquids are recommended
for use in the case of hydrocarbon liquids.
For cocurrent upflow a large amount of experimental data were obtained
by the Pittsburgh Energy Research Center ( 1976). The average liquid
holdup was found to be a very strong function of actual gas velocity and a
relatively mild function of liquid velocity. Various dimensionless correlations
are available for cocurrent upflow reactors. The modified correlation of
Ford ( 1960) has been given by Saada (1975) in the form
( 6)
where a and S depend on the flow regime. Stiegel and Shah (1977b) pro-
posed a correlation which is in a more general form:
( 7)
Sato et al. (1974) correlated their data in terms of the Lockhart-
Martinelli parameter. A theoretical model of the liquid holdup for cocurrent
upflow through a packed column was proposed by Hutton and Leung ( 197 4).
With the help of their model, these workers showed that cocurrent upflow
operation gives higher liquid holdup than cocurrent downflow operation
under the same gas and liquid flow conditions, a fact demonstrated experi-
mentally by Turpin and Huntington (1967), and shown in Fig. 6.
The range of variables and physical properties examined in the litera-
ture can be roughly stated as 0. 3 < ReL < 3000, 0. 4 mm < dp < 50 mm,
Turpin and
Huntington (1967)
a.
j
"C
0
.r:.
"C
·5
r:T
0·25
....I
:.
~-'-=o_.__.._........... .,.2. 1.-o,...-L----'----'--3...L·o..,......JL....1___J_4.....J.Lo...J.._...J.._...J.._s....J.L-o
(GL/Gs>°"24
FIGURE 6 Liquid holdup for cocurrent upflow versus cocurrent downflow
through a packed bed.
682 Shah and Sharma
2. 6 < asdp < 6. 02, and 14 < GaL < 320 for particle shapes consisting of
Raschig rmgs. Berl saddles, spheres, and irregular granules. Both foam-
ing and nonfoaming liquids have been examined. Although there are signifi-
cant discrepancies in the predictions of various correlations, qualitatively
they all indicate that the liquid holdup under trickle flow conditions in-
creases with liquid velocity and is essentially independent of gas flow rate.
Although not completely clear, an increase in particle size appears to de-
crease the liquid holdup. An increase in Galileo number for the liquid also
decreases the liquid holdup. These statements are generally verified by
three theoretical models: those of Hutton and Lueng ( 197 4), Reynier and
Charpentier (1971), and Clements (1978). It is important to note that none
of the controlling dimensionless groups (ReL, Rea, GaL, and asdp) in
liquid holdup correlations include a surface tension term (i.e., the liquid
holdup is considered to be independent of surface tension). This conclusion
needs to be verified in view of the observed dependence of flow regimes
and pressure drop on surface tension.
Gas Holdup
In a packed-bed column, the gas holdup can be evaluated if the total liquid
holdup and void volume of the column are known. However, in cases where
the gas holdup is small, it is more desirable to evaluate it directly rather
than through the difference. For cocurrent upflow in a bubble flow regime,
Ford ( 1960) suggested the relation
R 0. 2( )0. 24
E = 21.2 '( -eL
-) µL-
- ( 8)
G Rea µG
whereas Achwal and Stepanek (1976) proposed two correlations for the
bubble flow regime: one based on the homogeneous flow model and the
other based on force balance on the column.
Axial Dispersion
Liquid Phase
While in most commercial trickle-bed operations, the liquid phase is believed
to move in plug flow, in pilot-scale operations, the liquid phase can be
backmixed. As shown in Fig. 7, the axial dispersion in the liquid phase
under trickle flow conditions can be an order of magnitude higher than that
in the single phase. For trickle flow, the correlation of Hochman and
Effron ( 1969),
PeL = 0.042Re~· 5 (9)
where ReL = UoLPLdp/µL(l - E), is recommended. For the cocurrent up-
flow packed bubble column, the correlation shown in Fig. 8 is recommended.
No similar correlation for the pulsating flow regime is presently available.
Gas Phase
Just as for the liquid phase, the axial dispersion in the gas phase under
trickle flow conditions is higher than that under single-phase flow conditions.
The correlation of Hochman and Effron ( 1969),
Gas-Liquid-Solid Reactors 683
Two-phase
trickle-flow
0 -'I ...J
-::,0
FIGURE 7 Pe and ReL relations for single-phase and trickle flow. (After
Hofmann, 1977.)
a-,
C 'i
c:Pc ic
D
'Jnl6
cl!,
cIll
C
,P O o 0
C f,, 06. C
....
Zl ' 6.
...J
GI tl )..6. ~ t •
0.
'-...J ~
w ',
-- -- Hei I mann and Hofmann(1"TI)',
fl,i, □ Data of Stiegel and Shah(1977a,~
'
fl Max.gas flow rate} cylindrical'
fl Min. gas flow rate column
10_1L--
□..J....._R..Je_c..Jta--1..n.i.gu....L...Lla.1.r.Lc~o-l_u...Jm'-n---'---'-'-...L...I..L.L......,__ _,
10 103 10'
//!" 3-3
Rell,c.G dp
FIGURE 8 Heilmann-Hofmann correlation for backmixing in a cocurrent up-
flow packed bubble column. (After Stiegel and Shah, 1977a.)
684 Shah and Sharma
( 10)
where PeG = UGdp/DG' ReG = GGdp/µg(l - i::), and ReL = GLdp/µL(l - i::)
for trickle flow conditions, is recommended. No similar correlations for the
bubble flow and pulsating flow regimes are presently available.
Mass Transfer
Gas-Liquid
Just as for liquid holdup, the correlations for the mass transfer coefficient
(KLaL) are reported in two ways. Some investigators correlate KLaL with
liquid and gas velocities in dimensional (Gianetto et al., 1970; Goto and
Smith, 1975; Goto et al., 1976) or dimensionless (Goto and Smith, 1975)
forms, whereas others (Charpentier, 1976; Reiss, 1967; Satterfield, 1975)
have presented energy correlations.
The dimensional correlations assume that KLaL cc U~U~, where the
value of r
and s depend on the types of packings (Shah, 1979). For very
small gas and liquid velocities Goto and Smith (1975) and Goto et al. (1976)
gave more accurate predictions. Charpentier ( 1976), Reiss ( 1967), Gian-
netto et al. (1970), and Specchia et al. (1974) gave relations between KLaL,
aL, and KL and the energy parameter. Reiss (1967) gave a correlation
KLaL = 0.173 [(t.P/t,Z)LGUoL]0,5, which was subsequently modified by
Satterfield ( 1975) and later by Charpentier ( 1976) to account for the liquid
properties. Specchia et al. (1974) gave energy correlations for both up-
flow and downflow, as shown in Figs. 9 to 11, and indicated that for the
same value of energy parameters, upflow gives a better transfer coefficient
and interfacial area than does downflow.
Better values of KL are obtained for slower liquid velocities in upflow
compared to downflow, presumably due to an increase in circulation inside
6x16 2r---.--..--,--.-,-,-,..,..,---r--..-~~~---~
...J
0
:::i 2
---....
iU)
FIGURE 9 Energy correlations for kL. (After Specchia et al., 1974.)
Gas-Liquid-Solid Reactors 685
4....----.----~--~--.---.----~~
1
0·8
0·6
0,5....__...__..__...__ _. . . J - - - - L -........__.,__......,
0·5
FIGURE 10 Energy correlations for aL /as. (After Specchia et al., 1974.)
the liquid drops, caused among other things, by the greater slip velocity
between the liquid and gas phases. Specchia et al. (1974) also showed
that the upflow values of KLaL are, on the average, two times that of down-
flow values in pulsed and spray flow regimes because the gravitational
force leads to higher liquid holdup and pressure drop.
3 ....--~-~~~--~-~~----,---.---.--,
2
--
"j"I/I
_. 10
_,
~ 8
.x 6
4
2 4 6810 2 4 6810 2 4 Sx102
t.P )
(- t.Z ( -3 -1 )
UOL kgf m m s
LG
FIGURE 11 Energy correlations for kLaL. (After Specchia et al., 1974.)
686 Shah and Sharma
Charpentier (1976) suggested that if no reliable data or correlations for
a given packing are available, as a conservative approximation, KLaL can
be taken to be 0 .15 s-1 in the bubble flow regime. He also suggested that
the gas-liquid interfacial area varies with about 0. 5 power of the superficial
gas velocity, regardless of the packing size and type, column diameter, and
superficial liquid velocity. Morsi and Charpentier (1981) indicated that the
mass transfer properties of hydrocarbon systems are substantially different
from those of air-water systems. Also, the interfacial area (aL) for hydro-
carbon systems is much less than that for air-water systems. The effective
interfacial area and the liquid-side mass transfer coefficient for trickle-bed
reactors packed with a variety of packings and for organic liquids have
also been measured by Mahajani and Sharma ( 1979, 1980). Future work must
be directed toward systems other than air-water and under high-temperature
and high-pressure conditions.
Liquid-Solid
Under trickle flow conditions, the liquid-solid mass transfer coefficient can
be estimated using the correlation of Goto et al. ( 1975) (see Fig. 12) or
that of Dharwadkar and Sylvester ( 1977). In the pulsating flow regime the
correlation of Lemay et al. (1975) is recommended. For the packed bubble
flow column, the correlation of Kirillov and Nasamanyan (1976) is recom-
mended for large particles (dp > 3 mm) and the correlation presented in
Fig. 12 is recommended for small particles (dp < 3 mm).
10
5
3
1
data
0•7 Data were taken for
dp=0·241 cm,
0•5 0·108 cm
0•0541 cm
0.3....__..___ _ _...._____..___ _.........__....___ __.__ _.__..___ __
0·2 0·3 0,5 0-7 2 3 S 7 10 20
Liquid Reynolds number,ReL
FIGURE 12 JD versus ReL correlation for cocurrent upflow. (After Goto
et al., 1975.)
Gas-Liquid-Solid Reactors 687
Heat Transfer
The data reported on heat transfer in trickle-bed reactors are sparse.
Weekman and Myers (1965) measured wall-to-bed heat transfer coefficients
in a cocurrent air-water downward flow through packed column. Their re-
sults are discussed by Shah ( 197 9). A more recent work on heat transfer
in trickle-bed reactors is that by Specchia and Baldi (1979). In the low-
interaction regime, they proposed a correlation between Nusselt number and
Prandtl number and a modified liquid Reynolds number. In the high-inter-
action regime, the heat transfer coefficient was found to be independent of
gas flow rate and packing size and shape. Specchai and Baldi (1979) also
obtained some results for the effective thermal conductivity of the bed in
both low- and high-interaction regimes.
Scaleup Considerations
Experiments on the laboratory or pilot scale are invariably conducted with
25-mm-I.D. and 0.5- to 2-m-long reactors at about the same liquid hourly
space velocity as in the industrial reactor. However, the latter reactor
may have a height of 20 to 25 m. Thus the superficial liquid velocity in
the pilot reactor may be merely about 10% of the industrial unit and one
may have different flow regimes in the two cases; if this is the case, the
reactor scaleup may be seriously jeopardized. We have already emphasized
the importance of different flow regimes, in particular the different func-
tional dependence of various design variables , on operating parameters. In
fact, if the proper precautions are not taken, one may get a situation where
external mass transfer resistance may become important or dominant in the
pilot reactor but may be unimportant in the industrial reactor. There may
also be different residence-time distributions for gas and liquid phases in
the two cases~ One may often benefit by replacing expensive catalyst with
inexpensive support material of equivalent dimension when solid-liquid or
gas-liquid film resistance is important.
General Remarks
Very little is known on the hydrodynamic, mixing, and transport character-
istics of moving fixed-bed reactors. It is suggested that such reactors
should be divided on the basis of the prevailing flow regime and approximate
correlations for each flow regime should then be applied.
HYDRODYNAMIC, MIXING, AND TRANSPORT
CHARACTERISTICS OF SLURRY REACTORS
As shown in Fig. 1, a variety of slurry reactors are used in industrial
practice. Some of these are:
1. Gas sparged (including vibrating) reactor
2. Mechanically agitated (including gas inducing) reactor
3. Three-phase fluidized reactor
4. Transport reactor
5. Multitubular reactor
6. Loop reactor
688 Shah and Sharma
7. Plate column reactor
8, Pipe reactor
9. Spouted bed reactor
Some novel distillation column reactors for MTBE and for some hydro-
genation reactions, such as the conversion of isophorone to trimethylcyclo-
hexanone and trimethylcyclohexanol, have also been reported (Smith and
Huddleston, 1982; Schmitt, 1960),
In the following we discuss primarily reactor types 1 and 2. Some de-
tails are, however, applicable to other types of reactors, and these are
noted.
Flow Regime Boundaries
In gas sparged, vertical bubble columns, flow regime maps have been
described by a number of researchers and are discussed by Sh~h et al,
( 1982). As an approximate evaluation of the flow regime in a vertical
slurry reactor, Fig. 13 can be used. It should be, noted, however, that
the type of sparger used, liquid velocity, physicochemical properties of the
liquid, and the presence of solid may also affect the flow regime boundaries.
Wallis (1962, 1969) has suggested the use of flow regime charts based on
the drift flux approach. Kara (1981) and Kelkar (1982) have recently
shown that this approach can be applied to three-phase slurry reactor sys-
tems. The flow regime for gas-liquid flow in horizontal pipe has been dis-
cussed at great length by Govier and Aziz (1972). No similar flow maps
for three-phase flow are presently available.
I
II
0•15
~
Slug flow Hete,ogeneou,
O•lO Chu,n-Tu,bulent Flow
l
~ 0•05
J ~
~~~~
Homogeneous
{Bubbly) Flow
0---------....,.....-----,,--------__,_-----....,..---
0•025 0•05 0•1 0•2 0•5 1•0
de. m .,
FIGURE 13 Approximate dependency of flow regime on gas velocity and
column diameter (water and dilute aqueous solutions). (From Shah et al.,
1982.)
Gas-Liquid-Solid Reactors 689
Bubble Dynamics
Bubble size and its distribution and bubble rise velocity have a direct bear-
ing on the performance of the bubble columns. A brief review of this sub-
ject has been given by Shah et al. ( 1981, 1982). When gas is sparged by
single orifices or perforated or sintered plates, the following correlation of
Aldta and Yoshida (1974) can be used as first approximation for the estima-
tion of average bubble size:
= (11)
Relation ( 11) has not been tested for three-phase systems. For a stirred
vessel the correlation of Calderbank ( 1967),
( 12)
may be used as a first approximation. Here constants C and n depend on
the stirrer type and the type of liquid phase. P /VD represents the energy
dissipation rate per unit volume of dispersion.
The bubble size distribution is often given in terms of large bubbles
and small bubbles. The definition of large and small bubbles has been
based on the dynamic bubble disengagement technique described by Sriram
and Mann (1977), Schumpe (1981), and Vermeer and Krishna (1981), among
others. Based on this technique, the fraction of gas throughput carried
by large bubbles as a function of gas velocity obtained by Beinhauer ( 1971)
is shown in Fig. 14. For slurry reactors, such a plot should depend on the
lI
....:::, 1-0------.----r-----r----.------,---,----,
Q.
0•8
41 0·6
E
3 Ill
0 41
>-
Ill 2 0•4
0 :::,
O'I .c
·--~ ~0-2
~-
~
0
~
41 ....
0 o.,______..___..___~-------------~
0•02 0•06 0•1 0•14
l..loG. m/s ►
FIGURE 14 Fraction of volume throughput of large bubbles. (Calculated
from Beinhauer, 1971.)
690 Shah and Sharma
physical properties of liquid, solids particle size, nature, and concentration,
a relationship not yet been developed in the literature.
Kara (1981) and Kelkar (1982) found that Zuber and Findlay's modifica-
tion of drift flux theory predicted meaningful bubble size, bubble rise
velocity, and radial distribution of gas holdup in three-phase slurry re-
actors. The bubble size evaluation for the gas-liquid flow in horizontal
pipes is given by Govier and Aziz (1972). A similar evaluation of the
mechanically agitated contactor is given by Joshi et al. (1982).
Minimum Gas and Liquid Velocities Required
for Fluidi zation
In a three-phase system the particles form the fluidized phase, with the
liquid as the fluidizing medium. The gas passing through the system im-
parts the requisite energy to the liquid to keep the particles suspended.
The bed is fluidized when the superficial velocity past the particles is
greater than their settling velocity. Kato (1963), Roy et al. (1964),
Imafuku et al. (1968), Narayanan et al. (1969), and Begovich and Watson
(1978) studied the minimum gas velocity required to suspend particles in
a stagnant liquid medium. These works are reviewed by Shah ( 1979) and
Shah et al. (1982).
Begovich and Watson (1978) measured the minimum gas and liquid vel-
ocities required to fluidize various types of solids as a function of particle
size, particle density, and liquid viscosity. No effect of the initial bed
height or column diameter was found. In mechanically agitated contactors,
some minimum impeller speed is required to keep the particles in suspen-
sion. For liquid-solid suspensions (in the absence of gas), Zwietering
(1958) proposed such a correlation. Arbiter et al. (1976) and Subbarao
and Taneja ( 1979) have shown that the value of minimum speed is higher
in the presence of gas then in the absence of gas. Smith and coworkers
(Smith, 1980) have studied the effect of cavity formation, behind the im-
peller blades, on the impeller speeds required for suspension of solid
particles in gas-liquid-solid systems. More discussion of this subject is
given by Joshi et al. (1982).
Phase Holdup
The available correlations for the gas holdup in two- and three-phase bub-
ble columns are reviewed by Shah et al. ( 1982). For slurry reactors, the
gas holdup depends mainly on the superficial gas velocity and is often
very sensitive to the physical properties of the liquid. The dependence of
the gas holdup on gas velocity is generally of the form
( 13)
where 0. 7 < n < 1. 2 for bubbly flow and O. 4 < n < 0. 7 for churn turbu-
lent flow.
A large number of correlations for gas holdup have been reported in the
literature, however, the large scatter in the reported data does not allow
a single correlation. Some of the important correlations are reported by
Shah et al. (1982). The large scatter (Schiigerl et al., 1977; Bach and
Pilhofer, 1978) is due mainly to the extreme sensitivity of the holdup to
Gas-Liquid-Solid Reactors 691
the material system and to the trace impurities, which is not well under-
stood. The easily available physical properties, such as density, viscosity,
and surface tension, are not necessarily sufficient to expalin the scatter
observed. The effect of gas properties on the gas holdup is shown to be
small (Hikita et al. , 1980). Kolbel et al. ( 1961) and Deckwer et al. ( 1980a)
have also shown a very small effect of pressure on the gas holdup .
Jeffrey and Acrivos (1976) found that for particles as small as a few
(<10) micrometers, suspensions behave macroscopically as non-Newtonian
fluids. Therefore-gas holdup values involving non-Newtonian liquids might
be useful in analyzing gas-slurry systems.
Gas holdup data in non-Newtonian media have been reported by
Nishikawa et al. (1977), Buchholz et al. ( 1978), Nakanoh and Yoshida
(1980), and Schumpe et al. (1981). Gas holdup values higher than pre-
dicted by the correlation of Akita and Yoshida (1973) were obtained. The
effect of spargers was found to be insignificant in the slug flow regime.
Hikita et al. ( 1980) compared their data with those predicted from dif-
ferent correlations and attributed the disagreement between theories partly
to the differences in the design of gas sparges. They concluded that at low
gas velocities, the single-nozzle gas sparger gives lower values of gas hold-
up than does a multi.nozzle or a porous plate sparger. Zahradnik and
Kastanek (1979) carried out experiments with sieve piates of different hole
diameters and observed that the critical gas velocity corresponding to the
onset of stable performance of a plate depends on the plate hole diameter.
Numerous data for different kinds of spargers and various liquid media
(synthetic fermentation media) have been reported by Schiigerl et al. (1977)
Oels et al. (1978). Hills (1974) and Ueyama et al. (1980) reported pro-
nounced radial holdup profiles, and Kobayashi et al. ( 1970) proposed an
empirical correlation to evaluate such a radial distribution.
Shah ( 1979) has critically reviewed the published information on individu-
al phase holdups and has recommended the correlations of Kim et al. (1972,
1975) and Hovmand and Davidson ( 1968). More recently, Dhanuka and
Stepanek ( 1978) measured and theoretically predicted the individual phase
holdups in the 0.05-m-I.D. column. Begovich and Watson (1978) determined
the individual phase holdups from O. 076- and 0.152-m-l.D. columns and
developed correlations which cover their own data and those reported by
0stergaard (1965), 0stergaard and Thiesen (1966), fl)stergaard and Michel-
sen (1968), Michelsen and fl)stergaard ( 1970), Rigby and Capes (1970),
Efremov and Vakhrusev (1970), Dakshinamurthy et al. (1971), Bhatia and
Epstein (1974), and Kim et al. (1975).
Kato et al. (1972) and Kato and Nishiwaki (1972), Ying et al. (1980a),
and Vasalos et al. ( 1980) investigated the effect of solids concentration and
concluded that an increase in solids concentration generally decreases the
gas holdup but that the effect becomes insignificant at high gas velocities
(>O .1 m Is). Ying et al. ( 1980a) also applied the correlation of Akita and
Yoshida (1973) to their data and concluded that the correlation of Akita
and Yoshida is equally adequate for the three-phase system. Kojima and
Asano (1980) measured the fractional gas holdup and average bubble diam-
eter from 0.055- and 0.095-m-I.D. contactors. The particle size was varied
in the range of 105 to 2000 µm. The liquid viscosity was varied from 1 x
10- 3 to 18. 8 x 10-3 Pa •s. The results were empirically correlated.
Liquid fluidized beds of small particles have been found to contract
upon the introduction of gas (Stewart and Davidson, 1964; 0stergaard and
Thiesan, 1966; Kim et al., 1972), while the reverse trend occurs with large
particles. The contraction can be explained by considering liquid wakes
692 Shah and Sharma
behind the gas bubbles. The liquid in the wake moved at a much faster
rate than the continuous liquid phase. As a result, the average velocity
of the bulk liquid phase decreases and the bed contracts, causing an in-
crease in the solid holdup. The large particles can cause a bubble break-
up by virtue of their inertia and hence result in an expansion in fluidized
beds. Bhatia et al. ( 1972) and Armstrong et al. (1976a) studied the effect
of solids wettability on the behavior of three-phase fluidized beds of small
and large particles, respectively. They have also qualitatively described
the role of wakes and bubbles in such bed. Kim et al. ( 1975) have re-
ported the existence of two distinct types of three-phase fluidization, which
may be termed as bubble coalescing and bubble disintegrating. The former
occurs when the particles are smaller than a critical size and the latter oc-
curs when they are larger.
Axial solid concentration has been studied by Cova ( 1966) , Imafuku
et al. (1968), Farkas and Leblond (1969), Narayanan et al. (1969), Yaman-
aka et al. (1970), and Govindrao (1975). Cova (1966) reported that high
gas and liquid velocities and high viscosities tend to give more uniform
solid distribution. Imafuku et al. ( 1968) observed that the critical gas
velocity for complete suspension depends mostly on the liquid flow near the
gas distributor, while Govindrao (1975) pointed out that particle diameter
and bed volume have a strong influence on the axial distribution of solids.
As a rule of thumb, in a cocurrent column, particles less than 100 µm in
diameter can form a pseudohomogeneous slurry, while particles greater than
that will result in some axial solids distribution.
In multistage columns Schiigerl et al. (1977) observed higher values of
gas holdup than in a single-stage column. They also noted a strong effect
of the distributor design in multistage columns for a noncoalescing medium.
However, in an air-water medium, Zahradnik et al. (1974) and Zahradnik
and Kastanek ( 197 4) observed very little effect of the distributor design
and the liquid velocity in multistage columns. Freedman and Davidson
(1969) and Botton et al. (1978) carried out experiments with ·draught tubes
and observed insignificant effects of the draught tube on the holdup values.
Wieland (1978) reported that in a bubble column with an external loop, the
holdup values are comparable to the values in a single-stage bubble column.
As a rule of thumb, it can be concluded that the effect of internals on the
gas holdup is negligible, and any correlation that fairly represents the
values of holdup in a single-stage bubble column can be used to calculate
the values in the presence of internals. As a first approximation the same
conclusion should apply to three-phase systems. The phase holdups in
mechanically agitated contactor is discussed by Joshi et al. (1982).
Axial Dispersion
Liquid Phase
The effects of suspended solid particles on liquid-phase backmixing have
been studied by Schiigerl ( 1967), lmafuku et al. ( 1968), Vail et al. ( 1968),
Michelsen and 0stergaard ( 1970), Kato et al. ( 1972), 0stergaard ( 1978),
and El-Temtamy et al. ( 1979). Shah et al. (1978) have critically reviewed
the literature and outlined the present state of the art. The correlation
reported by Kato et al. (1972) is suitable for cases where the particle size
is relatively small. The experimental observations may be summarized as
follows:
Gas-Liquid-Solid Reactors 693
1. When the particles are very small and/or the difference between the
densities of liquid and solid is small and /or the solid loading is
relatively small, the extent of liquid-phase axial mixing in three-
phase systems is practically the same as that for gas-liquid systems.
The liquid-phase axial dispersion coefficient varies with column
diameter and gas velocity, and under turbulent conditions it is
practically independent of liquid velocity and particle diameter.
2. When the particle size is large and the density difference is high,
the dispersion coefficient depends on the particle size and the
superficial gas and liquid velocities (Michelsen and Q)stergaard,
(1970).
Joshi (1980) has shown that the observation of Michelsen and q)stergaard
(1970) can be explained if the average liquid circulation velocity (Vc) is
selected as the correlating parameter. When the rate of energy input is
higher than that dissipated at the gas-liquid and liquid-solid interfaces,
recirculation of liquid occurs. The data reported by Kato et al. ( 1972),
Michelsen and q)stergaard (1970), Q)stergaard (1978) and Vail et al. (1968)
were analyzed by Joshi ( 1980). From an accuracy point of view, only
those data were analyzed for which at least 20% of the input energy is
dissipated in the liquid motion. Based on the analysis, the following equa-
tion with a standard deviation of 16% was obtained:
(14)
Riquarts (1981) made use of another theoretical approach. In analogy
to the well-known Pe = 2 relation for fixed beds, Riquarts assumed that
this relation is also valid for bubble columns. The liquid-phase dispersion
coefficient is. given by
(15)
and introducing appropriate expressions for the bubble rise velocity and
bubble diameter, he arrived at the equation
Fr~ )1/8
( (16)
PeL = 14. 7 ReL
where
2
UOL
=-- (17)
gd
C
Equation (16) describes measured data with accuracy similar to that of
other correlations reported in the literature.
The effect of solid particles on the liquid dispersion coefficient is not
clearly understood due to the lack of enough experimental evidence. At
high solid concentrations, Ying et al. (1980b) observed large discrepencies
between actual and theoretical values of dispersion coefficients predicted
694 Shah and Sharma
with the help of different existing correlations. They also observed the
effect of liquid velocity on dispersion coefficients. The observations are
supported by Kara et al. ( 1982) and Kelkar ( 1982), who noted that the
dispersion coefficients are lower at high liquid velocities than those ob-
served in the absence of solids.
Solid Phase
Kato et al. (1972) studied solid-phase backmixing under a wide range of
conditions. They found that for small particle sizes in small-diameter col-
umns, the axial dispersion coefficient for solids is the same as that for the
liquid. For relatively large particle sizes (up to 0.177 mm) the dispersion
coefficient depends on the particle Reynolds number (Shah, 1979). More
experimental investigations pertaining to solid-phase backmixing in the
presence of large particles (>O. 2 mm) are needed.
Gas Phase
The gas-phase backmixing in gas-liquid-solid systems have been measured
by Schiigerl (1967), 0stergaard and Michelsen (1968), and Michelsen and
0stergaard ( 1970). Schiigerl ( 1967) reported that at low liquid velocities,
the gas-phase Peclet number increases with the gas rate, but at high liquid
velocities, the Peclet number shows a maximum with respect to gas rate.
From Schiigerl's data, the effect of liquid velocity on the gas-phase Peclet
number is unclear, although at low velocities, the gas-phase Peclet number
appears to decrease with increase in liquid velocity. Based on studies of
many nonaqueous and aqueous systems, in 0.1- and 0.15-m-I.D. bubble
columns, Mangartz and Pilhofer ( 1980) reported the following equation for
the gas-phase dispersion coefficient :
D = 50dl.5 (UOG)3 ( 18)
G C EG
where Dais in m2/s, de is in meters, Uoa in m/s, and ca is fractional
gas holdup in the presence of solids. Field and Davidson (1980), who con-
ducted measurements on gas-phase dispersion in a large-diameter ( 32 times
that used by Pilhofer et al. (1978)] column, slightly modified Eq. (18) and
proposed the empirical correlation
u )3.56
D = 56.4d1. 33 ( OG (19)
G c e:G
Although the predictions of Eqs. (18) and (19) may differ up to 50%, both
correlations are recommended due to lack of sufficient literature data. More
data on three-phase systems are needed.
Mass Transfer
Gas-Liquid
Gas-liquid mass transfer in a bubble column has been reviewed extensively
by Shah et al. (1982). In three-phase bubble column reactors, KLaL can
Gas-Liquid-Solid Reactors 695
be affected by the presence of solids. Investigations of various authors
(Voyer and Miller, 1968; Slesser et al., 1968; Sharma and Mashelkar, 1968;
Kato et al., 1973; Juvekar and Sharma, 1973; Sittig, 1977; Zlokarnik, 1979)
indicate that the degree of influence of suspended particles on kLaL depends
on the particle concentration, the particle size, the liquid solid density
difference, the geometrical sizes, and the operating conditions of the reactor
(i.e., gas and liquid velocities). Nguyen-Tien and Deckwer (1981) showed
that at high liquid velocities (UoL = 0.093 m/s) and low gas velocities, the
kLaL values are slightly higher in the presence of solids. A small increase
in kLaL was also reported by Sittig ( 1977) for the solids (various plastic
particles) concentrations below 15 wt % and particle sizes between 50 and
200 µm. With rising gas velocities and decreasing liquid velocities, the
particle distribution becomes increasingly nonuniform and the kLaL values
are lower than the ones without the solids. The influence of the solid con-
centration on kLaL depends largely on the liquid and gas velocities. Kato
et al. (1973) have also shown that for higher solid concentration a steep
decrease in kLaL is found, which is caused by a decrease in aL. It has
been shown by Dhanuka and Stepanek ( 1980) that with an increase in parti-
cle size, kLaL decreases because of a decrease in a. For the typical
operating conditions prevailing in Fischer-Tropsch synthesis in the slurry
phase, Zaidi et al. (1979) and Deckwer et al. (1980) have shown that the
presence of solid particles ( diameter less than 50 µm, concentrations of
solids <16 wt %) has a negligible effect on kLaL.
Weiland ( 1978) investigated mass transfer in a bubble column with an
external loop. He reported an agreement of kLaL data for water-O2 with
the data reported by Yoshida and Akita (1965) and Lin et al. (1976). In
the absence of other data, these data should be used as a first approxima-
tion for three-phase systems.
Voigt et al. (1979, 1980) and Hecht et al. (1980) have studied mass
transfer in a· multistage bubble column for electrolyte solutions and highly
viscous Newtonian and non-Newtonian (carboxymethyl cellulose and poly-
acrylate) solutions. They have recommended use of multistage columns for
a coalescence promoting medium, although for non - Newtonian solutions bet-
ter mass transfer can be achieved in single-stage bubble columns (Voigt
et al., 1980). Hydrogenation of dissolved elastomeric materials may show
pronounced non-Newtonian behavior (Falk, 1976). Mass transfer in such
systems has been reviewed by Kumar et al. (1978) and Mashelkar and
Chavan (1973). Fan et al. ( 1976) and Wang and Fan ( 1978) studies
oxygen transfer in a bubble column packed with Koch motionless mixers.
They reported a significant increase (as high as twofold) in kLaL and de-
pendence of kLaL values with Koch mixers than the ones with sieve trays
in bubble columns. Orazen and Erickson ( 1979) reported significantly
larger kLaL in the two-stage airlift tower for a gas velocity between O. 20
and 0. 45 m/s. No difference in kLaL was apparent at superficial gas vel-
ocities from 0.12 to 0.20 m/s. Lin et al. (1976) have shown that in tower
cycling fermenters for volatile substrates, higher mass transfer rates can
be achieved. Fujie et al. (1980) observed higher volumetric oxygen trans-
fer coefficients in a downflow bubble column compared to those in conven-
tional upflow systems.
The average liquid-side volumetric mass transfer coefficient depends on
the average bubble diameter and their rise velocity. The bubble dynamics
in a cocurrent-upflow, three-phase fluidized-bed system have been studied
by Massimilla et al. (1959, 1961), ~stergaard (1966), and Lee (1965).
696 Shah and Sharma
Massimilla et al. ( 1961) found that the bubble size and the rate of bubble
coalescence decreased with increasing fluidization intensity. These results
were in agreement with a subsequent study of 0stergaard ( 1966). Adling-
ton and Thompson (1965) found that the gas-liquid interfacial area de-
creased with decreasing bed porosity and was less sensitive to changes in
particle size. However, for large particles and large bubbles, Lee (1965)
showed that the gas-liquid interfacial area increased with increasing dis-
tance away from the gas distributor.
The adosrption rate depends on the gas-liquid interfacial area, the gas
residence time, and the gas- liquid mass transfer coefficient. It is the first
factor that has an important and complex effect on the mass transfer rate
in three-phase fluidized-bed systems. The study of 0stergaard and
Suchozebrski ( 1968) showed that the volumetric mass transfer coefficient
(i.e., KLaL) increased with increasing gas flow rate but was uninfluenced
by variations in the liquid velocity. Particle size was observed to have a
pronounced effect on the adsorption rate. 0stergaard and coworkers also
showed that an increase in the superficial liquid velocity had no effect on
the absorption rate in beds of 6-mm particles and in solid-free bubble
columns. In beds of 1-mm particles, however, an increase in liquid velocity
caused a marked increase in the volumetric mass transfer coefficient. These
results agreed well with the fact that both the gas holdup and bubble size,
in beds of 6-mm particles and in the solid-free bubble column, were inde-
pendent of liquid velocity, whereas in beds of 1-mm particles (1$stergaard,
1966, 1971b) an increase in the liquid velocity caused a marked reduction
in bubble size and an increase in gas holdup. The rate of bubble coales-
cence was higher at low liquid velocities than at high liquid velocities in
beds of 1-mm particles (0stergaard, 1966). An increase in the gas velocity
increases the volumetric mass transfer coefficient.
Shah ( 1979) reviewed the studies on mass transfer across the gas-liquid
interface. The best up-to-date work is reported by Joosten et al. ( 1977).
They showed that in the absence of solids, the volumetric mass transfer
coefficient can be well correlated to the total power, dissipated by stirrer
and gas, per unit volume. However, the correlation with power dissipated
by the stirrer alone was poor. Joosten et al. (1977) also found that for a
given stirrer power input and superficial gas velocity, the volumetric mass
transfer coefficient first increased with the volume of solids added. Al-
though this is in qualitative agreement with the observations of Slesser
et al. ( 1968) and Chandrasekaran and Sharma ( 1977), unlike these authors ,
Joosten et al. ( 1977), found the increase to be rather small (between 10
and 20%). Furthermore, as more solids were added, the volumetric mass
transfer coefficient remained constant at first and then started to decline
at a specific concentration that depended on solid type and particle size.
Joosten et al. (1977) explained the data based on the increase in the ap-
parent viscosity of the slurry by the addition of solids. Mass transfer in
mechanically agitated contactor is discussed further in Joshi et al. (1982).
Liquid-Solid
In three-phase bubble column slurry reactors, the mass transfer from
bulk liquid to the solid surface can play an important role in the overall
apparent reaction rate ( Choudhari and Ramchandran, 1980). Liquid-solid
mass transfer is based on the slip velocity (boundary layer) between two
phases, and in general, leads to such expressions as
Gas- Liquid-So lid Reactors 697
( 20)
Frossling ( 1938) and Ranz and Marshall (1952) showed that for large
values of Re, a= 0.6, m = 1/3, and n = 1/2. Shah (1979) has discussed
in detail the recommendations of various investigators (Friedlander, 1957,
1961; Harriot, 1962; Levich, 1962; Brian and Hales, 1969) for evaluating
the particle Reynolds number
u d
Re = _E__.12_ ( 21)
V
where ur is the relative velocity between two phases. In the case of bub-
ble columns where the solid particles are suspended, this velocity is diffi-
cult to determine. Kolmogoroff' s theory of isotropic turbulence avoids
this problem, as discussed by Shah et al. ( 1982).
Only a few experimental studies (Kamawura and Sasano, 1965; Sano
et al., 1974; Sanger and Deckwer, 1981) have been carried out in three-
phase vertical bubble columns. These investigations and the proposed
correlations using Kolmogoroff's characteristic parameters are outlined by
Shah et al. (1982). The data of Sano et al. (197 4) covers a range of
Schmidt numbers from 200 to 1400. Sanger and Deckwer ( 1981) have pro-
vided the data for Schmidt numbers ranging from 137 to 50,000. The
measured data deviated at low Reynolds numbers because the assumption
of isotropic turbulence is not justified, as discussed by Levins and Glaston-
bury ( 1972). Figure 15 illustrates that the data of these three investiga-
tors are consistent. The difference in three curves is due partly to
100
10
Sano et al.,1976
Songer and Deckwer, 1981
0 ~.~1....;_---~,----~,o=----~ ,o~o=---~,'-="000
4 3 1/3
( edp /vL )
FIGURE 15 Correlations of liquid-solid mass transfer coefficients in
bubble columns. (From Shah et al., 1982.)
698 Shah and Sharma
uncertainties in the estimation of diffusivities. The figure also demon-
strates the usefulness and applicability of the theory of isotropic turbu-
lence. This is advantageous, as the energy dissipation can be easily
measured in bubble columns. The liquid-solid mass transfer in bubble
columns with and without internals have also been measured by Sharma
and coworkers (Sharma, 1982) using Cu-dichromate system.
The equation by Sanger and Deckwer ( 1981) is recommended for the
calculation of liquid-solid mass transfer since it covers a wide range of
experimental parameters. More recommendations for mechanically agitated
contactors are given by Joshi et al. ( 1982).
Heat Transfer
Heat transfer from the reactor wall and inserted rods and coils to the
vertical flowing gas in liquid dispersion has been the subject of many in-
vestigations, and suitable correlations have been reported (Kolbel et al. ,
1958, 1960; Muller, 1958; Martins, 1959; Kast, 1963; Shaykhutdinov et al.,
1971; Burkel, 1972; Mersmann, 1975; Hart, 1976; Steiff and Weinspach,
1978; Deckwer, 1980; Deckwer et al., 1980; Joshi et al., 1980; Kato et al.,
1981). A summary of the published data collected on bubble columns and
stirred vessels is presented by Steiff and Weinspach ( 1978).
Muller (1958), Kolbel et al. ( 1958, 1960), Viswanathan et al. ( 1965),
Armstrong et al. (1976b), and Zaidi et al. (1979) measured heat transfer
coefficients from the inserted heat source to the bed (gas-liquid-solid
dispersion) or between the column wall and the bed. Analysis of the re-
ported data indicate the following behavior of gas- liquid-solid systems:
1. The values of the heat transfer coefficient hw are at least 10 to
100 times higher then that for single-phase ( gas or liquid) flow,
0. 9 to 1. 3 times higher than for bubble columns, and 1. 2 to 25
times higher than for gas-solid fluidized beds.
2. The values of hw are practically independent of the column diam-
eter and dimensions of heat transfer element.
3. In general, hw increases with an increase in particle diameter up
to 3 mm. However, for particle sizes larger than 3 mm, hw be-
comes essentially independent of the particle diameter (Armstrong
et al., 1976b).
4. When the solid concentration ss is increased from zero, at the be-
ginning hw increases with an increase in ss, reaches a maximum
value at a certain value of s s, and then falls.
. 0. 25 ..
5. h w varies as u00 . Zaidi et al. ( 1979) have reported that above
a Uoa of 0.1 m/s, hw is independent of Uoa in a 0.1-m-I.D.
column. This behavior was not observed by Armstrong et al.
(1976b) up to a Uoa of 0. 23 m/s in a 0. 24-m-I.D. column.
6. The design of gas sprager has no effect on hw.
For suspensions of Kieselguhr in water and oil, Ko1bel et al. ( 1958,
1960) reported separate correlations for laminar and turbulent regions.
Their results are discussed by Shah ( 1979). Vishwanathan et al. ( 1965)
and Arstrong et al. ( 1976b) reported their experimental data in the form
of graphs and correlations are not proposed.
Gas-Liquid-Solid Reactors 699
Deckwer (1980) has analyzed the problem of heat transfer on the
basis of Higbie's penetration theory together with Kolmogoroff's theory of
isotropic turbulence and proposed the correlation
2 -1/4 ( 22)
St = a(ReFrPr )
where
h
St= _ _w__ C µ
Fr= Pr= __E__
pCpUOG K
where k, p, Cp, and µ are the thermal conductivity, density, specific
heat, and viscosity of the gas-liquid-solid system. These are calculated
by the following equations:
k = k p = EsPs + ~PL ( 23)
L
µ = µL(l + 4.5ES)
Zaidi et al. ( 1979) have shown that the data reported by Muller ( 1958),
Kolbel et al. ( 1958, 1960), and Zaidi et al. ( 1979) can be correlated with
Eq. (22) within 20%, and the value of a is reported to be 0.1.
For design purposes, Eq. ( 22) is recommended. However, a pre-
caution is desirable for cases where no more than 80% of the input energy
is dissipated at the gas-liquid and liquid-solid interfaces and at the
column wall. Further Eq. (22) was proposed for slurry reactors, and
therefore for the case of three-phase fluidized beds, Uoa may be replaced
to get the form
h
w
(24)
Joshi et al. ( 1980) have proposed a new correlation based on the circula-
tion cell model (Joshi, 1980). They reported that in some gas-liquid-
solid systems, all the input energy due to the gas flow is dissipated at the
gas-liquid and solid-liquid interface rather than in the liquid motion. By
using the method of average recirculation velocity (Joshi, 1980), they pro-
posed the following equation to calculate the wall bed heat transfer co-
~f"
efficient:
h d
W C
k
= (0. 48)
_d_~_·3_3_g_o_.3_3_<_~-:--E_G_u_b_oo_)_P_1_,, C~L) X (
(25)
This equation is based on the analogy between mechanically agitated con-
tactors and bubble columns. Joshi et al. ( 1980) showed that the apparent
700 Shah and Sharma
discrepancy between the deterministic (Joshi, 1980) and the stochastic
(Deckwer, 1980) approach is immaterial and that both physical concepts
are equally capable of representing transfer phenomena in the liquid
phase of bubble columns and an be regarded as limiting cases of a more
general model. This subject is discussed in more detail by Joshi et al.
( 1982).
Scaleup Considerations
Laboratory experiments are invariably made in 70- to 150-mm reactors,
and in the case of gas sparged reactors, the height-to-diameter ratio may
be 3: 10. In large industrial reactors we often have a low height-to-
diameter ratio of 1: 2, and in the case of gas sparged reactors we also
normally have lower values of superficial gas velocity. Even though the
height-to-diameter ratio is low in industrial reactors, one may encounter
problems associated with the hydrostatic head of the liquid and low values
of superficial gas velocity. In particular, we have to ensure that the
solid particles concentration is uniform throughout the reactor. In some
cases we may encounter a substantial change in the superficial gas velocity
from bottom to top, but such cases have received very little attention.
When backmixing in the gas phase is relevant, one needs to ascertain
this more closely. This problem may be particularly important in mechan-
ically agitated reactors.
One must bear in mind that just as for the fixed- bed reactor, if ex-
pensive catalysts are used (say, those based on noble metals) and the re-
sistance is essentially located in the solid-liquid film or gas- liquid film,
one may benefit substantially by replacing a part of the catalyst with an
equivalent support material (say, alumina or zeolite or activated carbon)
but without the noble metal.
CALCULATIONS OF ABSORPTION /DESORPTION RATES
The calculation of absorption /desorption rates for a three-phase system
when the solid phase is a catalyst is discussed at great length by Shah
( 1979), Shah and Sharma (1976), and Choudhary and Ramchandran ( 1980)
and will not be repeated here. The film theory analysis illustrated in
these references can be applied to more complex reaction systems. Here
we restrict our discussion to novel reaction systems such as micellar cata -
lysis used in liquid-liquid reactions, catalytic reactions in which catalyst
particles are smaller than diffusion film thickness, and slurry reactors in -
valving reactive solids. Some detailed mathematics of the last two cases
is given by Choudhary and Ramchandran (1980).
Micellar Catalysis
Micellar catalysis has been shown to have a remarkable effect on the rate
of a variety of liquid- liquid reactions. Micelles are aggregates of surfac-
tants formed in aqueous solutions, where the apolar groups extend into
the interior of the aggregate and the head groups are located at the
interface with water. Typically, micelles have an average radii of 12-30
A and contain 20 to 100 monomers. These micelles can solubilize large quan-
tities of materials which otherwise have a low solubility in the aqueous
phase.
Gas-Liquid-So lid Reactors 701
Rate acceleration or inhibition of organic reactions in micellar solutions
arises from the different rates of reaction of the substrate in the micellar
medium and in the bulk phase and the distribution of substrates between
these two phases. Typical reactions that have been studied in presence
of micelles include hydrolysis reactions and nucleophilic substitutions.
Fendler and Fendler (1975) give a good summary of the work done on
micellar systems up to 1975. Most of these systems involved slow reactions
where the mass transfer of the reactants is fast compared to the reaction
rate and hence need not be considered. Menger and Portnoy (1967) de-
veloped a pseudophase model for unimolecular reaction systems. By assum-
ing the total rate to be the sum of the rates of reactions occurring in the
micellar and the aqueous pseudophases, they obtained an expression for
the overall observed first-order rate constant:
k + k K (D )
w
k = - - -m- -s n
-- ( 26)
obs 1 + k (D )
s n
where kw and km are the true first-order rate constants in the aqueous
and micellar pseudophases, Ks the binding constant of the reactant to the
micelle, and (Dn) the concentration of micellized surfactant.
The pseudophase model has also been applied to bimolecular reactions
by considering the distribution of both reactants between the micellar and
water phases (Bunton, 1979). For these systems the micellar effects may
be due either to the increased concentration of reactants in the micellar
medium (proximity effect) or to increased reactivity in the micellar medium
over that in the aqueous phase (medium effect). Dilution effects may come
into play when micellar concentrations are made very high because of the
decreased probability of finding both the reactants in the same micelle, and
this leads to· reduced reaction rates.
Recently, Janakiram and Sharma ( 1982) have considered the case of
slow and fast liquid-liquid reactions when mass transfer of reactant is
important. The film theory applied to mass transfer with chemical reaction
was used, wherein it was assumed that all the resistance to mass transfer
existed in a thin film near the interface (called diffusion films). The re-
action was assumed to occur in the aqueous phase only, which contained
the micelles and the reactant B. The hydrophobic reactant A was assumed
to have a low solubility in the aqueous phase. Because of their small size,
the micelles are present in the film and as A diffuses through the film, it
is taken up simultaneously by the micelles, where it reacts with the micellar
bound B. The micelles thus steepen the concentration profile of A in the
film and lead to higher mass transfer rates. By writing down transport
equations for A and B in the film and considering micellar incorporation
to be a parallel step, equations have been derived to predict mass trans-
fer rates of A in micellar systems for different regimes (Janakiraman and
Sharma, 1982).
Catalyst Particles Smaller than Film Thickness:
Reaction Occurs in the Diffusion Film and Is
Catalyzed by Solid Particles
We can conceive if situations where catalyst particles are sufficiently small
in size (say, below 20 µm) to be smaller than the gas-liquid diffusion film
702 Shah and Sharma
thickness. In such cases a parallel model of transport has to be considered .
In the established practice of slurry reactors, the steps associated with
gas-liquid artd liquid-solid mass transfer are taken in series. Further, the
indigenous reaction may be sufficiently fast to occur partially or wholly in
the diffusion film, yet it is further amenable to catalysis by fine particles.
Pal et al. (1982) have considered this situation. Earlier work in this area
has been carried out by Deckwer, Alper, and coworkers. There is con-
siderable practical significance for such cases, as not only may one get
marked increase in the specific rate of absorption but one may also realize
the desired selectivity. In the case of magnetic catalyst particles such as
Fe, Ni, and CO, or those that can be magnetized, we have a powerful
method of recovering fine catalyst particles efficiently via high-gradient
magnetic separation. This subject merits further attention. A brief
mathematical analysis is presented below. Since the reaction is fast enough
to occur in the diffusion film wihtout a catalyst, it is logical to assume that
in the presence of fine catalyst particles, the transport of dissolved gas to
the catalyst particles will control the rate due to catalyst. For a reaction
that is first order in the dissolved gas and dissolved reactive, species,
the governing equations are
( 27)
where
The second term on the right-hand side of Eq. (27) accounts for the
reaction in the film due to catalyst particles. A solution for the absorp-
tion rate of A with the boundary conditions
dCB
z = 0: CA = C*A' dz =0
( 28)
z = oL: CA =0
can be given as
= _c_A_*_I_D_M_A_k_l_+_D_M_A_k_s_a-=-p-
( 29)
z=O tanh (/DMAkl :lDMAksap)
Here the contribution due to the parallel reaction in the film is unimportant
as the particle is relatively very coarse, leading to low values of ap and
k 8 (in the particle size range relevant here, k 8 will be inversely propor-
tional to the particle size).
When DMAkl + DMAksap/k 1 > 3, Eq. (29) can be expressed as
( 30)
Gas-Liquid-Solid Reactors 703
2
For small dp' where ksdp/DMA = 2, a plot of [(1/DMA)(NA/CA) - k 1]
against DMAw for a specified particle size should be a straight line through
the origin having a slope of 12/ p d 2 . Thus data pertaining to different
p p
temperatures can be accommodated in a single plot. Pal et al. ( 1982) have
verified this theory for absorption of 02 in aqueous solutions of sodium
sulfide at elevated temperature and pressure with fine activated carbon
particles as catalyst.
Slurry Reactors Involving Reactive Solids
In this category we can visualize two distinct situations: (a) particles are
sparingly soluble in the medium and the reaction occurs between the dis-
solved gas and the dissolved reactive species obtained from the dissolution
of solid particles (the product of the reaction may be soluble or insoluble
in the medium), or (b) particles are insoluble in the medium (the product
of the reaction may be soluble or insoluble in the medium).
Solid Particles Sparingly in the Medium
This situation is commonly encountered in practice and we can think of two
distinctly different situations: (a) solid particles are larger than the thick-
ness of the liquid film (this thickness is that of diffusion film within which
the resistance to mass transfer is confined in the absence of chemical re-
actions, or (b) solid particles are smaller than the liquid film thickness.
Particles Larger Than the Liquid Film Thickness. It is quite easy to
deal with this problem as the constituent steps; namely, diffusion of dis-
solved gas from the interface into the liquid phase and dissolution of solid
particles in series (Fig. 16). We can predict the specific rate of mass trans-
fer for any of the controlling regimes. It may well be that in view of the
particle size and loading, the bulk liquid phase may be saturated with re-
spect to the dissolved solid species. However, even if we have a "finite"
slurry that causes bulk concentration to be lower than the saturation con-
centration, we can solve the problem analytically.
Particles Smaller Than the Liquid Film Thickness. Depending on the
type of gas-liquid contactor, we may have a liquid film thickness ( diffusion
film thickness) in the range 2 to 40 µm. Thus if we have particles smaller
than the film thickness, we can conceivably have the step of dissolution of
solid particles in parallel to that of diffusion of dissolved gas from the
gas-liquid interface to the bulk liquid phase. Depending on the relative
rates of diffusion and chemical reaction, the entire amount of dissolved gas
may be consumed in the film. Further, depending on the controlling
regime, the concentration of dissolved reactive species in the liquid film
may be uniform or may be zero close to the gas-liquid interface (see Figs.
17 and 18).
When the concentration of dissolved solid species is uniform in the film,
the simultaneous dissolution of solid particles in the film will not affect the
specific rate of mass transfer. However, if we have depletion of the re-
active species, the simultaneous dissolution of solid particles can lead to a
situation where the depletion is entirely overcome and concentration becomes
uniform in the film .
The most exciting situation arises when the reaction is instantaneous
and the concentration of both species, namely the dissolved gas and
GAS LIQUID
GAS LIQUID
FILM FILM
LIQUID FILM IS
SURROUNDING THE SOLID
c"B
- - - PSEUDO- FIRST- ORDER
REACTION
-DEPLETION REGIME
0 6
LIQUID
p*
GAS
FILM
LIQUID FILM ILIBULK
Q.UID ILIQUID-FILM
t SURROUNDING
THE SOLID
FIGURE 16 Concentration profiles based on the film theory for two gas-
liquid-solid systems when the solid dissolution in the film is unimportant.
- - --CONCENTRATION PROF IL ES FOR SOLUTION
CONTAINING NO SUSPENDED SOLIDS
- - CONCENTRATION PROFILES FOR SOLUTION
CONTAINING SUSPENDED FINE PARTICLES
I
I
0 6
FIG URE 17 Concentration profiles for an instantaneous reaction when the
solid dissolution in the film is important.
Gas-Liquid-Solid Reactors 705
~
lil ~¼ CBS
C:: fl
0
c*
A
. I
1/ I
'., '
<(
(bl I MODEL BY UCHIDA tl ill
u.. I
0
\ I -·-·- RAMACHANDRAN AND SHARMA'S MODEL
z \ '\. I I -- --- FILM MODEL FOR NO SOLID
0
'
I I
\ SUSPENSION
~ \CA ' /CB I
a::
f-
z \ "' /
I
I
w
a
u
\
"\
" v
I
I
I
/'-
u
. I. ' I
0
0 A J..' ' X' 6
0
(a)
FIGURE 18 Concentration profiles of A and B O., ;\ 1 , ;\" are the main re-
action planes for these models): (a) in liquid film near gas-liquid interface;
(b) in the neighborhood of solid particles present in the region z = 0 to
z = ;>..,
dissolved solid, is zero at a reaction plane that is very close to the gas-
liquid interface. Here the concentration of dissolved species drops to zero
from the bulk concentration, which may well be the same as the saturation
concentration. The simultaneous dissolution of the solid particles in the
film will obviously augment the flux of the dissolved solid species and hence
the specific rate of absorption will increase. Ultimately, the reaction plane
may coincide with the gas-liquid interface and we will get a very interesting
situation where the specific rate of absorption will be proportional to the
square root of the particle area. Since for very small particles the solid-
liquid mass transfer coefficient is inversely proportional to the particle size
(Sherwood number = 2), we can conceivably get a situation where the
specific rate of mass transfer will be inversely proportional to the particle
size.
The simultaneous dissolution of very fine solid particles in the film may
lead to a situation where the "instantaneous" reaction-controlled mechanism
(but having known value of rate constant) changes over to the case of de-
pletion of reactants and eventually to fast pseudo-mth-order reaction-con-
trolled mechanism.
We also think of situations where the interfacial concentration of the
dissolved gas is comparable or even higher than the saturation concentration
of the solid particles, and in such cases we will have significant enhance-
ment in the rate of dissolution of solid particles in the film due to the in-
stantaneous reaction (Fig. 18).
The mathematics associated with those cases is evaluated by Ramachandran
and Sharma ( 1969). Sada and coworkers ( 1977, 1980) and Uchida and co-
workers ( 1975) have also applied the theory to the absorption of so 2 in
slurries of CaC03 and Ca(0H)2,
Solid Particles Insoluble in the Medium
Particles of Unchanging Size. Here the product is insoluble in the
medium and stays with the particle, and the reactant has to diffuse through
the product layer. Figure 19 shows typical concentration profiles.
706 Shah and Sharma
....J
- ~
0
e~ ....J a::
0
~:) 0 w
::::l....J ....J d l/l I-
d- ;::i _ <(
::i LL i:o ....J
~
:W
~
0
LL :C
I-
w
O:c I-
Wt/1 u
0 I- <( <(
- 0:: u
::::i <( ww
~LLJ
<( a: 0::
LLJ Cl:: Zo
a:
~ CA ....JZ 0 ::::iu
~
CAS
~ CAR
FIGURE 19 Concentration profiles for gas-liquid-solid systems where
solids are reacting but insoluble in liquid; solids of constant size.
TABLE 2 Controlling Mechanisms for Constant Size Particles
Controlling Controlling
mechanism rate term Remarks
Mass transfer kLaL XBCl.t Hydrodynamic factors
from phase A are very important
to phase B
Solid-liquid k XBCl.t Hydrodynamic factors
s
mass transfer have some effect
in the turbulent
regime
Diffusion D ta[(l - X ) 213 Hydrodynamic factors
ms B
through solid are likely to be
+(1-xB)] unimportant, effect
of temperature
should be
insignificant
Chemical reaction Effect of temperature
very significant;
no effect of
hydrodynamic
factors
Gas-Liquid-Solid Reactors 707
0
_J
0
::E l/l w
u
e~
:::, _J
~
_J
-
0
:::,
:::w
I.LI
I-
0
_u..
_J
<(
0::
0- :::,~ o:::,
:::::; LL ID _J ea:
:::, <(
l/l lfl
Qw
_J z
FIGURE 20 Concentration profiles for gas-liquid-solid systems where solids
are reacting but insoluble in the liquid; solids of changing size.
It is possible to follow systematic procedures which will allow the con-
trolling mechanism to be clearly discerned. Table 2 brings out the salient
features of different controlling regimes.
Particles of Changing Size. Here the product of the reaction is soluble
in the medium and hence the reactant shrinks. Figure 20 shows the concen-
tration profiles and Table 3 shows the pertinent features of different con-
trolling regimes.
Hydrome~allurgy provides a variety of examples which fall in this
category of reactions. Oxidative leaching of copper, cobalt, and silver are
some typical examples. A novel case is that of the manufacture of alkali
hydrides by hydrogenation of alkali metals suspended in a hydrocarbon sol-
vent. Chlorination of wood pulp provides another example.
TABLE 3 Controlling Mechanisms for Particles of Changing Size
Relation
between time
Controlling Controlling and fractional
mechanism rate term conversion Remarks
Mass transfer from Hydrodynamic factors
phase A to are very important
phase B
Mass transfer to k Hydrodynamic factors
s
solid particles have some effect in
the turbulent regime
Chemical reaction Effect of temperature
at the surface significant; no effect
of hydrodynamic
factors
708 Shah and Sharma
MODELS FOR FIXED-BED CATALYTIC REACTORS
Isothermal Models
A generalized isothermal steady-state model for the fixed-bed catalytic re-
actor can be written as
2
d C..
D.. __!J_ ± T .. ± R.. = 0 ( 31)
lJ dz2 lJ lJ
where the subscript i refers to the phase and j refers to the species. Equa-
tion ( 31) is a one-dimensional model which is generally applicable to the
fixed- bed systems. If the reactor is to be operated under transient condi-
tions, the right-hand side of Eq. ( 31) will have a time-dependent concen-
tration term. In Eq. ( 31) , Dij is the axial dispersion coefficient for species
j in phase i, Ui the superficial velocity of phase i, and Tij the transfer in
and /or out of species j from phase i to other phases. For example, for a
gaseous reactant j in the liquid phase, Tij can be expressed as
T .. = KLaL(C 0 . - CL.) - K .a (CL, - C .) ( 32)
lJ J J SJ S J SJ
Here i = L and the species is transferred in from the gas phase and trans-
ferred out to the solid catalyst phase. ~j is the reaction rate of species in
the phase i. The + sign indicates generation and the - sign indicates de-
pletion. For the fixed- bed reactor, the first two terms on the left- hand
side of Eq. ( 31) drop out. The first term on the left- hand side also drops
out for the gas phase. If the gas velocities of each phase vary along the
length of the reactor, this can be evaluated by taking a total material
balance on each phase. In general, the total number of equations that
need to be solved simultaneously equal the sum of component balances for
each phase plus the total number of overall material balances. It should be
noted that Eq. ( 31) assumes that the dispersion model applies to the reac-
tor, an assumption generally found to be reasonable. Equation ( 31) is
subjected to the boundary conditions
dC ..
D .. -22.
d -- U.(C .. C?.) at z = 0 ( 33)
lJ Z 1 lJ lJ
and
dC ..
-22. = 0 at z = L ( 34)
dz
where L is the length of the reactor. Various cases of this generalized
model have been examined in the literature, and these are reviewed by
Shah (1979).
In an evaluation of pilot-scale trickle-bed reactors the model described
above is often not applicable due to flow anamolies such as incomplete
catalyst wetting, insufficient liquid holdup, backmixing, and so on. Shah
( 1979) has reviewed at great length the reported modeling of pilot-scale
hydroprocessing trickle- bed reactors.
Gas-Liquid-Solid Reactors 709
Nonisothermal Models
Many industrial hydroprocessing reactors such as those for hydrodesulfuriza-
tion and hydrocracking operate under adiabatic or close to adiabatic condi-
tions. Since hydrodesulfurization, hydrocracking, and hydrogenation
reactions are highly exothermic, the temperature rise in such reactors is
frequently controlled by the injection of quench streams at one or more
positions along the length of the reactor. These fixed-bed (under trickle
flow conditions) reactors are usually operated under plug-flow conditions
and the reactor temperature profile exhibits discontinuities at the position
of the quenches. The maximum temperature rise in commercial trickle- bed
reactors is controlled by the amount of nature of the quench and its posi-
tion along the length of the reactor.
In commercial hydrodesulfurization reactor the catalyst bed deactivates
nonuniformly due to the deposition of metals. The catalyst deactivation is
usually counterbalanced by the increase in feed temperature in order to
maintain the constant quality of the product. This process is continued
until the temperature in any part of the reactor reaches the maximum allow-
able temperature based on the metallurgical limit. At this point, the re-
actor is shut down and the catalyst is regenerated. The time required to
achieve this maximum allowable temperature is called the reactor cycle life.
Shah et al. (1976) and Mhaskar et al. (1978) have pointed out that the re-
actor cycle life depends on the locations of quench positions (for one and
two quenches) and that by properly choosing the quench positions, one
can significantly improve the reactor cycle life. Abichandani et al. (1980)
evaluated the problem for a more generalized nonadiabatic reactor. These
studies illustrate that in industrial fixed- bed hydroprocessing reactors,
catalyst activity can be maintained at a higher level over a longer period of
time by properly controlling the temperature distribution in the reactor.
The thermal .behavior of a fixed-bed hydrocracking reactor with one or more
quenches has been evaluated by Yan (1980).
Generally, commercial fixed-bed reactors have a large catalyst bed
length-to-particle diameter ratio and they are operated under plug-flow con-
ditions. The criteria for axial dispersion effects in adiabatic trickle-bed
hydroprocessing reactors for ( a) residual hydrodesulfurization, (b) hydro-
cracking of gas oils, and (c) denitrogenation of shale oils were derived by
Shah and Paraskos ( 1975). These criteria indicate that at high conversions,
an adiabatic reactor produces a larger axial dispersion effect than the iso-
thermal operation. At low conversions, the opposite results are obtained.
Some experimental verifications of these analytical criteria are needed.
MODELS FOR SLURRY REACTORS
Isothermal Models
A generalized model for the fixed-bed catalytic reactor described in the
preceding section is applicable for both the gas and liquid phases in slurry
reactors. If the solid particles are very fine (less than 100 µm), the
liquid-solid slurry is often assumed to form pseudohomogeneous slurry and
the separate material balances for the solid phase may not be required. A
model of the slurry reactor wherein solid concentration gradient prevails
within the reactor has been evaluated by Govindarao ( 1975) and discussed
by Shah (1979). Some aspects of steady-state behavior of three-phase
710 Shah and Sharma
fluidized-bed reactor as applied to coal liquefaction are discussed by
Parulekar and Shah (1980) and Shah (1981). This model should be, in
general, applicable to other three-phase systems.
The modeling of a three-phase slurry reactor with solid as a reactant is
a more difficult task. Joshi et al. (1981) modeled the performance of an
oxydesulfurization reactor wherein the sulfur in coal particles is oxidized to
form sulfuric acid. When the solid phase dissolves or reacts substantially,
its volume fraction along the reactor changes. This problem has not been
evaluated in the literature.
The selectivity problem in the operation of a slurry reactor has also
not been yet completely evaluated. For example, the liquid-phase half-
hydrogenation of 2,4-dinitrotoluene (DNT) can lead to different isomer dis-
tribution depending on the presence or absence of mass transfer resistances
(Acres and Cooper, 1972). Even more interesting is the case of obtaining
stereospecific product depending on the presence /absence of pore diffusional
resistance (Woerde et al., 1982). Selectivity is also very important in coal
liquefaction and FT synthesis. These types of problems need to be evalu-
ated in the future.
Nonisothermal Models
The steady-state thermal behavior of an adiabatic three-phase coal liquefac-
tion reactor operated under slow and fast hydrogen consumption reaction
regimes have been analyzed by Parulekar and Shah ( 1980, 1982). The
theoretical calculations were based on the axial dispersion model, and the
predictions of the model for steady-state temperature distribution in the
presence as well as the absence of quench were found to agree well with
those measured experimentally (Shah, 1981). It should be noted that un-
like in plug-flow reactor, in a backmix reactor the temperature continuity
at the quench location is maintained; and as shown by Krishnamurthy and
Shah (1979) and Singh et al. (1981), the quench gas flattens the tempera-
ture profile in the entire backmixed reactor.
The multiple steady states in adiabatic reactors have been investigated
by Singh et al. (1980). Nunez et al. (1982) studied the effects of preheater
variables on the multiple steady state in an adiabatic coal liquefaction re-
actor. Shah and Singh ( 1981) presented some experimental data in a
laboratory adiabatic reactor and showed that significant temperature excur-
sions could occur under practical ranges of operations.
Parulekar et al. (1980) examined a first-order reaction in a three-phase
bubble column reactor with the help of an axial dispersion model. For the
extreme case of a continuous-stirred-tank reactor, these authors identified
a fairly large region of five steady states for a nonzero concentration of the
gaseous reactant in the liquid phase, a fact previously observed for an
adiabatic gas-liquid CSTR (Raghuram and Shah, 1977). For the case of
partially backmixed bubble column reactors, the authors derived criteria
for the uniqueness of steady states.
SELECTION OF REACTORS
A variety of reactors have been used for gas-liquid-solid systems, and
Satterfield (1970), Shah (1979), and Doraiswamy and Sharma (1983) have
considered several aspects of these reactors. As indicated elsewhere, the
main classification of reactors may be based on solid particles being very
Gas-Liquid-Solid Reactors 711
fine when we have slurry reactors and solid particles being coarse when we
usually adopt fixed-bed reactors. The selection of a reactor for a specified
duty will depend on a number of factors, and Table 4 lists the important
points.
Slurry Versus Fixed-Bed Reactors
The relative merits of slurry and fixed-bed reactors have been reported by
several of the authors listed above. Slurry reactors operate as thermal fly-
wheels and maintenance of isothermal conditions is relatively easy. The
slurry can be pumped and regeneration can be conveniently accomplished.
Further powdered catalysts are generally cheaper and fine catalyst particles
whould show a negligible to small resistance to isothermal diffusion. Slurry
reactors measure up very well with respect to the important points listed in
Table 4. The main disadvantage of slurry reactors is associated with re-
moval of the catalyst particles from the product stream. In case the prod-
ucts are volatile and are stripped under operating conditions (e.g., in
Fischer-Tropsch operations for CH4 and lower hydrocarbons), the question
of catalyst removal does not arise except for purposes of catalyst regenera-
tion /replacement. This disadvantage is liely to be relatively unimportant
for catalyst particles, such as those based on Fe, Ni, Cr, and Co, which
TABLE 4 Gas-Liquid Solid Reactors:
Checklist for Selection of Reactor
Residence time of liquid phase
Allowable pressure drop
Relative flow rates of gas and liquid
Scale of operation
Recycle of gas
Changes in type of feedstock
Countercurrent or cocurrent mode of operation
Corrosion
Foaming behavior
Rheological behavior
Micromixing
Selectivity
Heat removal /supply
Solid particles as reactant or catalyst
Particles fine or coarse
Product of reaction soluble in insoluble
Specification of solid product
Fouling of catalyst
712 Shah and Sharma
are magnetic, or particles that can be magnetized, as the catalyst separa-
tion (HGMS). Recent reports indicate that many noble metal catalysts can
be prepared on mangetized supports and that HGMS can even deal with sub-
micron particles .
For very large scale operation for relatively cheap materials such as in
hydroprocessing of petroleum fractions , slurry reactors may prove to be
unwiedly and expensive. However, for vacuum residua or bottom fractions
of heavy crude oils , which contain relatively very high amounts of organo-
metallic compounds , fouling may be severe and slurry reactors have a clear
edge over fixed- bed reactors.
In slurry reactors the liquid phase is essentially backmixed; the gas
phase may be plug flow or partially backmixed. In fixed-bed reactors,
depending on the regime of operation, we may approach plug-flow behavior
for both phases.
In fixed- bed reactors, the trickle flow gives a relatively very low
residence time for liquid, and slow to very slow reactions, which require a
long residence time, cannot be conviently conducted. It is possible to over-
come this problem to some extent by using packed bubble column reactors.
Fixed-bed reactors are not generally suited for application, where the
feed consists of a slurry, or one of the products of reaction is solid, as
this may be lead to excessive pressure drop and maloperation of the column.
Gas Sparged Versus Mechanically Agitated Slurry Reactors
Having decided to use slurry reactors, we can adopt different· versions de-
pending on circumstances. The process may call for relatively small amounts
of gas , and in case gas sparged reactors are considered, the problem of
catalyst suspension may become severe and we may be forced to opt for a
mechanically agitated version. It is possible to use much higher flow rates
of gas and to recycle the unreacted gas in case we are dealing with pure
gas , which is the case in a variety of hydrogenations. In large reactors
there is definite merit in opting for gas sparged reactors, as the problems
of shaft seal, shaft stability, and so on, can be avoided. Values of the
heat transfer coefficient are comparable in the two types of contactors.
However, when the heat load is very high we can have a pump-around
system as in a loop reactor. We also have the option of a heat exchanger
of the multitubular reactor type, where the slurry passes through tubes
together with the gas ; heat transfer fluid is circulated through the shell.
In gas sparged reactors, depending on the solids loading, particle size, and
density, we may approach three-phase fluidized-bed behavior.
Mechanically agitated contactors can be operated using the "dead-end"
system. Here, pure gas is introduced in the head space and the pressure
is maintained at a specified level; no reaction product is volatile. Such
a system is used extensively in hydrogenation of a variety of edible and non-
edible unsaturated oils. This operation is very large worldwide; a few mil-
lion tons per year are processed in this way. A variety of feedstocks are
used and frequent changes in feedstock become necessary. Further, in
the case of edible fats, the product has to meet fairly stringent require-
ments. For the foregoing reasons, the mechanically agitated contactor has
remained a "workhorse" in this industry despite large-scale operation and
other benefits of continuous operation in fixed-bed reactors with respect to
heat recovery. Some improvement may be possible in mechanically agitated
contactors by using a smaller impeller (size about 40% of that of the main
impeller) at a distance from the interface roughly equal to its own diameter.
Gas-Liquid-Solid Reactors 713
This arrangement should improve gas dispersion and hence gas- liquid inter-
facial area.
Recent work indicates that with better control strategies and faster
analytical techniques it may become possible to use fixed-bed reactors for
the hydrogenation of edible and nonedible oils.
WORKED EXAMPLE: MANUFACTURE OF HYDROXYLAMINE
PHOSPHATE IN A SLURRY REACTOR
Design a continuous bubble column (slurry) reactor for the production of
100 metric ton per day of hydroxylamine phosphate (HYAM) based on the
reduction of aqueous ammonium nitrate-phosphate buffer. A palladium-based
catalyst will be employed.
Data
Temperature = 70°C
Pressure = 4 atm at the top
(solutions for pressures of 8, 10, 15, and 20 atm at the top will also
be considered)
Superficial gas velocity at the top = 1 cm/s
(solutions for superficial gas velocities at the top of 0.5 and 2 cm/s
will also be considered)
Concentration of NH 4No 3 in feed = 20 wt %
Concentration of H3PO 4 in feed = 23 wt %
Desired con:'ersion of NH 4No 3 to HYAM = 80%
Hydrogen rate at the bottom = 10% excess over the theoretical requirements
-7 3
Henry's coefficient for hydrogen, H = 4. 63 x 10 mol/cm •atm
Catalyst = 2% palladium on carbon
-3 3
Concentration of active palladium, Cpd = 1 x 10 g /cm of solution
Particle size of the catalyst = 8 x 10- 3 cm
Density of catalyst = O. 6 g /cm 3
Diffusivity of dissolved hydrogen = 5.24 x 10- 5 cm 2 /s
Reaction
Solution
Rate of production of hydroxylamine phosphate
100 X 10 6
=
24 X 3600 X 131
714 Shah and Sharma
= 8. 84 mol/s
0_
NH 4No 3 required in the feed= 8 884 = 11.05 mol/s or 884 g/s
Concentration of NH 4No 3 in the feed = 20 wt %
Feed rate= 884/0.2 = 4420 g/s
Hydrogen requirements = 8. 84 x 3 = 26. 52 mol/s
Hydrogen supplied is 10% over the theoretical requirements: = 26. 52 x
1.1 = 29.17 mol/s
Volumetric flow rate of hydrogen at the top
3 273 + 70 1
= 2.652 X 0.1 X 22.4 X 10 X ---- X -
273 4
= 1. 86 x 10 4 cm 3 /s
Superficial gas velocity at the top = 1 cm /s
Cross sectional area of the column = 1. 86 x 10 4 cm 2
Diameter of the column = 1. 54 m
4420
Superficial liquid velocity = - - - - - - - - = 0.194 cm/s
1. 22 X 1.86 X 10 4
Determination of Rate-Controlling Step in
the HY AM Formation
The following steps are involved in the reaction between hydrogen and am-
monium nitrate:
1. Transfer of hydrogen to the bulk liquid
2. Transfer of hydrogen and ammonium nitrate from bulk liquid to the
catalyst surface
3. Reaction of hydrogen and ammonium nitrate on the catalyst surface
The relative importance of different resistances will be considered at
the top of the column. The following assumptions have been made to
simplify the problem:
1. The gas holdup and the (volumetric) liquid-side mass transfer co-
efficient are uniform throughout the reactor. (the value of E is
calculated by using an average value of VG at the top and the bot-
tom of the column. )
2. The vapor pressure of water over the solution has been ignored,
as this is insignificant in practically all cases.
3. The catalyst particles are homogeneously dispersed throughout the
reactor.
4. The liquid phase is completely backmixed.
Transfer of H2 to the Bulk Liquid
If this is the rate-controlling step, the rate of absorption of hydrogen will
be given by the equation
Gas-Liquid-Solid Reactors 715
R' == k a[A*] (units of~== cm 2 /cm 3 of solution)
A L-
From the data of de Rooij et al. (1977), we have
kL (at v0 == 1.0 cm/s) == 2 x 10- 2 cm/s
kL kL -2
= 0.1 or dB == - = 2. 22 x 10 cm
dB 0.9
de Rooij et al. (1977) have reported some data on fractional gas holdup for
the same system under consideration and the data can be correlated by the
following equation in the range 1.0 < v 0 < 10, cm/s:
1. 5V G
E: ==
G 30 + 2VG
( 35)
== 0.0485 (at v0 == 1.0 cm/s)
Effective interfacial area:
6
~ ==
dB(l sG)
6 X 0.0485
== ( 36)
-2
2.22 X 10 X (1 - 0.0485)
· 2 3
== 13. 77 cm /cm of solution
(This value of ~ is high, but for the specific system under consideration it
appears to be reasonable. )
RA' == k a[A *]
L-
== 2 10
-2 13. 77
7
X X X 4 X 4. 63 X 10- ( 37)
-7 3
= 5.1 x 10 mol/cm of solution
Transfer of Hydrogen from Bulk Liquid to
the Catalyst Surface
Sano et al. (197 4) have given the following equation for the calculation of
a true solid-liquid mass transfer coefficient.
kSLdp
Sh = DA
( 38)
4 1/4
= [2 + 0.4c)>) Scl/ 3] ¢c
716 Shah and Sharma
where
E = rate of energy dissipation per unit mass of liquid
= VG gX
= 981 cm 2 Js 3 , at the top
= diameter of catalyst particle = 8 x 10
-3
cm
= shape factor; here its value is assumed to be equal to 1
= kinematic viscosity= 4.2 x 10- 2 cm 2 /s
Substitution in Eq. ( 38) gives
Sh= 2.02
and
kSL = 1. 32 x 10- 2 cm/s
Thus the Sherwood number is very close to 2 and this situation will be
valid for other operating conditions considered in this example.
Concentration of catalyst:
1 x 10- 3 g active Pd/cm 3 of solution
w =
2 g active Pd /100 g catalyst
= 0. 05 g /cm 3 solution
(Note: wt% of Pd on C is 2 and concentration of active Pd is 1 x 10- 3
g /cm3 of solution.)
Solid-liquid effective interfacial area:
6w
a
-p = pd
p
6 X 0.05
= ( 39)
0.6 X 8 X 10- 3
= 62.5 cm 2 /cm 3 solution
-1
kSL~p = 0. 825 s
For this step to be rate controlling, RA will be given by
0,825 X 4 X 4.63 X 10- 7 ( 40)
15.28 x 10- 7 mol/(cm 3 of solution)•s
Gas-Liquid-Solid Reactors 717
Reaction of Hydrogen and Ammonium Nitrate on
the Catalyst Surface
de Rooij et al. (1977) have given the following empirical equation for the
rate of reaction of hydrogen in aqueous NH4NO3-H3PO4 buffer:
R' = ka C [A*]0. 34 ( 41)
A c pd
where k is the reaction rate constant and is given by the following equation:
k = 1.696 x 10 4 exp(-;~ 4 )
= 1.696 x 10 4 exp [-7674
1 _987 x (273 + 70)]
(mol) O. 66(cm) 1. 02
= 0.218 .a..-~-~-~-
(g active Pd) •s
where
a = relative activity of the catalyst and is assumed to be equal to
C
0.8
concentration of active palladium, 1 x 10-- 3 g active Pd/cm 3
of solution
R' = 0.218 X 0.8 X 1 X 10- 3(4 X 4.63 X 10- 7 ) 0 • 34
A
19.61 x 10- 7 mol/(cm 3 solution) •s
From the. individual values of RA above it can be seen that at the top
of the column, all three steps contribute to the overall resistance. As we
go toward the bottom of the column, the value of [A*] increases because of
the increase in the static head of the liquid. Further, the absorption of
gas is accompanied by considerable bubble shrinkage and the value of a is
likely to decrease along the height of the column (as we go up the column).
For the calculation of~ it is assumed that Eqs. (35) and (36) are valid.
Due to the two factors above, the rate of gas-liquid mass transfer increases
as we go toward the bottom because of the increase in both [A*] and a.
For the case under consideration we have assumed, as stated earlier, that
we have uniform values of E: and kL a throughout the reactor.
Since, in bubble column slurry reactors the liquid phase is expected to
be completely backmixed, the values of dissolved hydrogen concentration
and the hydrogen concentration at the catalyst surface will be uniform
throughout the contactor. As a result, the rate of solid-liquid mass trans-
fer will be constant (the variations in the value of ksL in the range of VG
encountered in the reactor were found to be small and hence the value of
ksL~p has been assumed to be constant).
When all the three steps contribute to the overall resistance, the rate
of dissolution of hydrogen in the liquid bulk is given by the equation
( 42)
The rate of transfer of hydrogen from bulk liquid to the catalyst sur-
face is given by the equation
718 Shah and Sharma
R'A = kSLa ([A ] - [A s ]) ( 43)
-p o
The rate of reaction of ammonium nitrate and hydrogen on the catalyst
surface is given by the equation
R' = ka C [A
A C pd s
1°· 34 ( 44)
(The relative importance of surface reaction in relation to gas-liquid and
liquid-solid mass transfer resistance will depend on the pressure, as the
intrinsic kinetics shows O. 34 order in dissolved hydrogen.)
Since the liquid phase has been assumed to be completely backmixed,
the values of [Ao] and [Asl remain uniform throughout the contactor.
Elimination of [Asl from Eqs. ( 43) and ( 44) gives
R'A
[Aol = k a ( 45)
SL-p
The overall material balance across the contactor gives
G. - G
R' = 1 o (46)
A Sh/1 - s)
where ht is the height of dispersion. Substitution of Eq. ( 46) in Eq. ( 45)
gives [Aol
G. - G G. _ G 1/0.34
1 0
0 ( 47)
+ ~hyka;(l - s0 )Cpd]
The material balance with respect to hydrogen over a differential
height dhd gives the following ordinary differential equation:
= RA X S(l - E) ( 48)
( 49)
where
[A*] = H(PT + ijJhd)
(1 ( 50)
dP EG) p
1jJ = dhd
= 1033
Substitution of Eq. ( 50) in Eq. ( 49) takes the form
dG
= a+ Sh ( 51)
dhd
Gas-Liquid-Solid Reactors 719
where
a kL~S(1 - E:G) {HPT - [A 0 ] } (52)
S = kL~SHljJ(l - EG) ( 53)
and [A 0 ] is given by Eq. ( 47). The boundary conditions are
At the top: h = 0, G = G = 2,652 (54)
0
At the bottom: h = ht, G=G.=29.17 (55)
l
Integration of Eq. (51) gives
Sh 2
t
G. G = a.ht + -2- ( 56)
l 0
or
-a+ ✓ a.2 + 2S(Gi - G )
0
= (57)
ht s
Procedure for the Calculation of Height
The procedure is essentially trial and error:
1. Assume the height of the column and calculate [A 0 ] using Eq. (47).
2. Calculate the value of KL~ from Eqs. (35) and (36) based on the
aver.age value of VG.
3. Knowing [A 0 ] and kL~' calculate a and S using Eqs. (52) and
( 53).
4. Calculate ht from Eq. (57)
5. If the calculated value of ht is greater/smaller than the initial
guess, the next guess should be in between these two values.
The numerical method of partial substitution may be used for quick
convergence.
In case the reaction follows first-order kinetics, the height of dispersion
can be given by the following analytical expression:
-a±~ 1-a. 2 + 2y(G. - G )(1+ S)
1 l O
=
y
where
a = kL~HPTS(l - E: 0 )
s =
k L ~ ( ~ + ka)PJ
SL-p
y = kL~S(1 - E0 )Hl/J
k = cm 3 /(g active Pd)•s
720 Shah and Sharma
TABLE 5 Hydroxylamine Phosphate: Slurry Reactor Details for Different
Operating Conditions
Total
pressure Superficial
at the gas velocity Column Height of Volume of
top at the top diameter dispersion dispersion
No. (atm) (cm/s) (cm) (cm) (m3)
1 4.0 0.5 218 1106 41.27
2 4.0 1.0 154 1878 33.35
3 4.0 2.0 109 3200 29.85
4 8.0 0.5 154 1241 23.15
5 8.0 1.0 109 2202 20.54
6 8.0 2.0 77.1 4303 20.07
7 10.0 0.5 138 1312 19.58
8 10.0 1.0 97.5 2397 17.90
9 10.0 2.0 68.9 4793 17.89
10 15.0 0.5 112.6 1493 14.86
11 15.0 1.0 79.6 2856 14.21
12 15.0 2.0 56.3 5913 14. 71
13 20.0 0.5 97.5 1669 12.46
14 20.0 2.0 68.9 3280 12.24
15 20.0 2.0 48.7 6923 12.92
Height of dispersion = 1787 cm
Volume of dispersion = 33. 35 m 3
The problem was reworked for several values of superficial gas velocity
and total pressure at the top. The results are given in Table 5.
Due to complete backmixing in the liquid phase, the concentration of
dissolved hydrogen remains uniform throughout the contactor. Therefore,
for cases where there is substantial difference in the top and bottom pres-
sures, desorption is likely to occur near the top of the column. It was
found that desorption occurs in all cases for values of superficial gas
velocity at the top of the column greater than 2 cm /s. We should avoid,
as far as possible, designing columns for conditions that are conducive for
desorption.
There is a remarkable effect of pressure on the volume of the contactor.
Since hydrogen is usually available from steam reformers at higher pres-
sures in the range 15 to 25 atm, it is useful to employ a pressure of 20
atm at the top of the contactor. The case of a superficial gas velocity of
0.5 cm/s at the op appears to be most reasonable. We may therefore opt
for a 97. 5-cm-diameter (say, 1. 0 m) column with an effective dispersion
height of 16. 69 m (dispersion volume = 12. 46 m3). The case of a pressure
Gas-Liquid-Solid Reactors 721
10 atm at the top of the contactor with a superficial gas velocity of 0. 5 cm /s at
the top also appears to be attractive with a column diameter of 1. 38 m and an
effective dispersion height of 13. 12 m (dispersion volume = 19. 58 m3).
NOTATION
~ gas-liquid interfacial area
a particle surface area
p
a particle surface area per unit volume in Eq. ( 5) and
s
Figs. 9 to 11.
A*, Ao' A gas-liquid interface, bulk liquid and particle surface
s
concentrations in worked example
C concentration
C specific heat
p
C* solubility
db bubble diameter
d column diameter
C
d particle diameter
p
d average bubble size
VS
D axial dispersion coefficient
D molecular diffusivity
m
D diffusion through solid product layer
ms
D concentration of micellized surfactant [Eq. (26)]
n
e energy consumption in Fig. 15
F Froude number, dimensionless [Eq. (17)]
r
g gravitational constant
G mass velocity
h slurry wall heat transfer coefficient
w
jD j factor in Fig. 12
k liquid-solid mass transfer coefficient
s
Kl' Kr reactor rate constants
KL liquid-side gas-liquid mass transfer coefficient
KLoverall gas-liquid mass transfer coefficient
K binding constant in Eq. ( 26)
s
K
w' Km' Kobs various kinetic constants in Eq. ( 26)
K thermal conductivity
L length of reactor
N
a absorption rate of species A
722 Shah and Sharma
p Pressure
Pe Peclet number, dimensionless
Pr Prandtl number [Eq, (22)]
power per unit volume of dispersion
volumetric gas flow rate
radius of particle
rC radius of unreacted core
Re Reynolds number, dimensionless
Sc Schmidt number ( µ p /Dm)
Sh Sherwood number (k d /D )
s p m
St Stanton number [Eq. (22)]
t time
u velocity
bubble rise velocity
relative velocity between two phases
circulation velocity
w particle loading
We Weber number in Fig. 3
conversion in Tables 2 and 3
axial distance in the reactor or within liquid film
Greek Letters
8 energy loss
oL thickness of liquid film
µ viscosity
b.P pressure drop
b.P
pressure gradient
b. z
E: volume traction
E: void fraction in the fixed bed
8 dL dynamic liquid holdup
parameters in Fig. 2
"- ' 1/J
T, "-' "fn reaction planes in Figs. 17 and 18
'
\) kinematic viscosity
p density
a surface tension
Gas-Liquid-Solid Reactors 723
Subscripts
A refers to species A
air refers to air
B refers to species B
G gas phase
L liquid phase
LG two-phase
M mixture
OL superficial liquid velocity
OG superficial gas velocity
p particle
s solid phase
wat refers to water in Fig. 2
Superscripts
0 bulk condition
* refers to interface condition
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11
Polymerization Reactors
MATTHEW Tl RR ELL and RAFAEL GALVAN University of Minnesota,
Minneapolis, Minnesota
ROBERT L. LAURENCE University of Massachusetts, Amherst,
Massachusetts
INTRODUCTION
A separate chapter on polymerization reactors in any treatise on chemical
reaction engineering is required for several reasons. One is the steady
and considerable glowth in production of polymeric products. In 1985, it
is expected that production of the five leading thermoplastic polymers alone
(polystyrene, polyvinyl chloride, polypropylene, and high- and low-density
polyethylene) will exceed 100 billion pounds worldwide (Webber, 1985).
This total doubles the production of 1975 and amounts to about $40 billion
worth of product. At this scale, even relatively minor efficiencies created
by good engineering are very significant.
Another challenge lies in the unique difficulties of performance optimiza-
tion of polymerization reactors. To optimize a system, we need to know
what optimal is-to define the objective. Polymerization engineering is com-
plicated in this regard since most polymeric products end up as fabricated
materials, so that criteria such as processibility and end-use (mechanical,
etc.) properties are the real reactor performance measures. No truly
analogous situation exists in the design of a reactor for a monomeric prod-
uct.
We can contrast the polymer reactor with a reactor making ammonia, for
example. We know the properties of ammonia. The only design problem is
to make as much of it as fast and economically as possible. We want to
maximize conversion and if there are parallel or sequential reactions in the
synthetic scheme, maximize selectivity. The first point of contrast is that
simply to specify the generic name of a polymer (e.g., polystyrene) is in-
adequate to specify its properties. The second point of contrast is that
polymerization reactions present selectivity problems that are orders of
magnitude more complex than those for the monomeric reactor. An elaborate
set of sequential and parallel reactions occurs. The resulting distribution
of polymeric product, which composes any commercial polymeric material, is
of comparable importance to the chemical structure of the polymer in deter-
mining product performance in end-use properties. The product distribu-
tion, as well as the generic chemical formula, must therefore be described
in any complete specification of a polymer product.
735
736 Tirrell, Galvan, and Laurence
As in other reactor design situations for optimal yield and selectivity,
the factors of reactor configuration-batch or continuous; mixing pattern;
residence-time distribution; recycle; heat transfer-all play roles in deter-
mining the product distribution. The sensitivity of the product distribution
to these factors is enormous. Polymers produced in a batch reactor can
be very different from those produced in a continuous reactor under other-
wise substantially identical chemical conditions.
A final point to be made regarding the distinguishing features of poly-
mer reactors pertains to polymers at the other end of the production scale
from the commodity polymers mentioned in the first paragraph. Those
products not withstanding, many more polymeric products are low-volume
specialty materials, frequently copolymers, designed to perform a specified
function. Efficiency is not the principal design objective for these reactors
(frequently, there is a high margin of profitability). Rather, the need is
for reproducible production of a complex product distribution so that the
polymer performs precisely as required.
Product distribution analysis and control is, therefore, the principal
novel feature and objective of polymerization reactor engineering relative
to other chemical reactors. This chapter is informative but not comprehen-
sive. It is designed to provide an entry into the field by presenting the
main ideas and techniques, by way of some examples and placing the em-
phasis where possible on the most recent ideas, techniques, problems, and
challenges. This is made possible by referring the reader interested in
more comprehensive information on this subject to several other excellent
sources on polymerization reactor engineering (Ray, 1972; Ray and Laurence,
1977; Biesenberger and Sebastian, 1983; Platzer, 1970; Gerrens, 1982).
MATHEMATICAL TECHNIQUES
If the elementary reaction steps of a polymerization mechanism are known
or can be postulated with an adequate degree of certainty, mathematical
analysis is a (somewhat underutilized) tool available to the engineer for
making predictions about product distributions.
There are two alternative generic starting points for the employment
of mathematical analysis in polymerization. One can start from the mass
balance equations on the reactor of interest. This leads to differential or
algebraic difference equations, depending on reactor type, which must be
solved to get the desired information on product distribution. Data are
needed on the rate constants of the model. This is a systematic approach,
readily adapted to the analysis of different reactor types. This method
produces an infinite set of mass balance equations, one for each possible
polymer chain length, 1 to 00 • The solution of any particular set of such
equations may be difficult and involved, but there is a catalog of solution
methods available (Ray and Laurence, 1977).
Alternatively, statistical methods can be useful (Flory, 1936; Schulz,
1935; Lowry, 1970). These rely on picturing the polymer chain as growing
by a process of selecting monomers from the reaction mixture according to
some statistical distribution. The success of this approach depends on a
correct, and frequently intuitively based, correspondence of the polymeriza-
tion process with a postulated stochastic process. It is therefore less
easily adaptable to different reactor configurations since the appropriate cor-
respondence may be difficult to find or, in fact, may not exist. On the
Polymerization Reactors 737
other hand, when statistical methods do work, they usually lead to results
in a comparatively simple way and can sometimes reveal features of a poly-
merization system that a mass balance approach does not. The fully
equipped polymerization engineer should be able to take advantage of both
mass balance and statistical techniques.
Table 1 lays out several approaches to solving infinite sets of mass
balance equations, illustrated with an example from anionic polymerization.
All the techniques in that table have general utility beyond this particular
mechanism. The basic example equation of Table 1 has been simplified
through the use of several generally practical maneuvers.
To illustrate these generic tricks, we go back to the mechanism of
anionic polymerization with no termination and instantaneous initiation
(Szwarc, 1968; Nanda and Jain, 1964). In this case, only the propagation
reaction is of interest.
k
p + M __g___ p (1)
j j+l
At the instant of introduction of initiator (concentration Io) a certain num-
ber of growing chains (concentration Io) are established. They add mono-
mer with rate constant kp until monomer is exhausted. The polymerization
engineer's problem is to determine the distribution of polymer chain lengths
at any specified instant of the reaction. Solution of the mass balance on
Pj, for arbitrary j, gives the answer:
dP.
dtJ = kpMPj-1 k MP. P 1 (0) = 1 0 , all other Pj(O) = o ( 2)
p J
In equations like ( 2), it is frequently useful to scale time with the rate
constant and monomer concentration in order to eliminate kp from explicit
consideration temporarily and to decouple Eq. ( 2) from the monomer balance:
co
dM
= -k M ~P. M(O) = MO ( 3)
dt p £..J J
j=l
This scaling is done by defining a new time variable (Dostal and Mark,
1936):
, =ft kp(t')M(t') dt' (4)
0
or
d, = (5)
Thus temperature variations and monomer depletion are eliminated from
explicit consideration in calculation of the polymer chain-length distribution.
Using Eq. ( 5), Eq. ( 2) becomes
738 Tirrell, Galvan, and Laurence
TABLE 1 Techniques for Solving Polymerization Rate Equations,
Illustrated with Anionic Polymerization
Basic equation: Pj = Pj-l
Techniques
1. Analytical, successive substitution:
2. Numerical: conceptually identical to 1. Used when rate equations
are either impossible to integrate analytically or when a general
form for Pj cannot be found by successive substitution.
3. Laplace transform: converts the infinite set of differential-differ-
ence equations to a single difference equation
L[P.(,)]
J
= P.O.)
J
= fO
00 P.(,)e-;\, dT
J
The rate equation becomes
s
;\P. = -P. + P. l j ~ 2
J J J-
pj = >.. _!- 1 pj-1 ::::;> pj = 1o (;\ ~
From a compilation of Laplace transforms,
n-1
T - , -;\,
(n _ l)! e e d,
Thus
e
-,
Polymerization Reactors 739
TABLE 1 (Continued)
4. Generating function transformation: converts the infinite set to a
single ordinary differential equation (ODE). In principle, can pro-
vide the total MWD. Moments are easily obtained otherwise.
Definition:
00
G(s,T) = L sjPj(T)
j=l
Moments are obtained by noting (see technique 5 below)
ak G(s,T)
(cl 1n s)k
s=l
Using Ej=l
00
s jPj-l = sG ( s, T), the rate equation
. becomes
G(s,T) = -(1 - s)G(s,T) G(s,0) = sI 0
G(s,T) = sI 0e -(l-s)T
Expanding the exponential in power series in s yields
00 ·-1
_ ~ j TJ -T
G(s,T) - Io £.JS (j _ 1)! e
j=l
Comparing with the definition, we obtain
5. Moment generation: uses the definition of the moments of the MWD,
JJk = E; 1 tPj, to convert the infinite set to a few ODEs for the
moments. Used when no analytical solution is possible or when tak-
ing the logarithmic derivative of G(s,T) is cumbersome, and the
information given by moments suffices. The rate equation becomes
00
µk = L .kp
J • 1
J-
- µk µk ( 0) = I
0
j=l
Letting k = 0, 1, 2, . . . gives
μ0 = 0 > ]J
0
(T) = I
0
740 Tirrell, Galvan, and Laurence
TABLE 1 (Continued)
Frequently, only the three leading moments are needed.
6. Continuous variable approximation: assumes the chain sufficiently
long such that the chain length j can be considered to be a con-
tinuous variable. Expanding P._ 1 in a Taylor's series about P.,
the following is obtained: J J
3P.
_] 1
+ -
:)j 2
Truncating after the quadratic term, the rate equation (an infinite
set) is converted to a partial differential equation for P.:
J
3P. 3 P. 2
l 3 P.
__J_ + _] ::: - ___J_
3T 3j 2 3 j2
with solution
P.(T) :::
IO
1/2 exp
r(jl - 2,1 - T) 2 ]
J ( 211 T)
This approximation is valid only for reasonably high molecular
weight, 1/j small, for the Taylor's expansion to be valid. Equiva-
lent to Poisson distribution for large T.
7. Statistical techniques: historically, the first techniques used in
polymerization problems. Can be classified as follows:
Direct approach Flory (1953)
Markov chain theory approach Lowry (1970)
Recursive approach Lopez-Serrano et al. (1980)
P.J ::: P. l -
i-
P.
J
( 6)
where the dot signifies a derivative with respect to T. Techniques for
solving this equation are enumerated in Table 1. Some additional results
on the resulting product distribution are given by Peebles ( 1971).
Implicit in this reaction scheme, and necessary for this time-scaling
procedure to work, is kp independent of j. This is known as the equal
reactivity assumption, meaning that the reactivity of a chain end is un-
influenced by the length of chain to which it is attached (Flory, 1953).
This is an assumption which is very often, but not always, correct. It
Polymerization Reactors 741
has been examined for several different mechanisms and certain exceptions
have been noted, the most important of which are the termination reaction
in free radical polymerization (Coyle et al., 1985) and monomer addition at
high conversion in polycondensation (Gupta and Kumar, 1985).
Certain solution techniques for polymerization equations work better in
certain situations. Only experience teaches this, but some guidelines can
be laid down. Analytical solutions (technique 1, Table 1) are the exception,
not the rule , and are more the province of the academician than of the
engineering practitioner. However, this does not mean that sequential com-
puter numerical solution (technique 2, Table 1) should be called in im-
mediately by those with pragmatic views. Moment generation via techniques
4 and 5 of Table 1 will lead to a set of moment equations that may be solva-
ble analytically, even when the mass balance cannot, and may provide
adequate, though incomplete predictive information about the MWD in the
polymerization reactor. It is important for· the engineer to decide in ad-
vance what level of analysis is appropriate, based on the level of informa-
tion required from the analysis. It is frequently a good idea to set the
simplest information first (i.e., moments) and then move on to attempt
more involved analytical or numerical solutions.
The level and varieties of mathematics required for polymerization
analysis are shown in Table 1. Analysis is not as arcane as it is some-
times made to seem. Solution of ordinary differential equations is funda-
mental. Partial differential equations arise in several ways: (a) when the
continuous variable approximation (Bamford and Tompa, 1954; Bamford
et al., 1958; Zeman and Amundson, 1963, 1965a,b) is made (technique 6,
Table 1); (b) when diffusion limitations are considered (Nagel et al., 1980);
(c) in some applications of generating functions. Difference equations,
particularly of the form Pj = a.Pj-1, arise frequently. It is useful to realize
that the solution to this first-order difference equation is Pj = Kell. In
other words 1 this difference equation has a geometric distribution as its
solution. Clearly, a sine qua non is facility with the ideas of probability
and distribution functions. Series of various types, and their infinite
(and, less often, partial) sums, arise frequently. Familiarity with the
short list of mathematical areas above will provide the engineer with tools
needed to employ modeling profitably. A final caveat on mathematical
analysis is never to let it become more complex than necessary, nor let it
become an end in itself. Two rules help to avoid this. One, mentioned
above, is to have a good idea in advance of the kind of information you
want out of analysis before wading into it too deeply. The second rule is
to look always for a physical interpretation of any derived equation. Fre-
quently, bearing in mind the two generic and complementary modeling ap-
proaches, mass balance and statistical, is helpful in this regard. For
example, the difference equation mentioned above;
P. = aP. l ( 7)
J 3-
arises in many polymerization mass balances. In the anionic polymerization
mechanism of Table 1, but occurring in a steady-state continuous stirred-
tank reactor of average residence time e, a balance on Pj with no Pj in the
feed gives
P.
-1.0 = k p MP.J- l k MP. (8)
p J
742 Tirrell, Galvan, and Laurence
[compare Eq. (2)], which is exactly the form of Eq. (7) with
k M
C( = p ( 9)
1/8 + k M
p
Alternatively, we could arrive at Eq. ( 7) by an equivalent, but at first
sight perhaps different, statistical argument. We can regard the concen-
tration Pj as the probability of forming a polymer of length j. Pj is then
the product of two other probabilities: Pj- 1, the probability of forming a
polymer of length j - 1 times, and a, the reaction probability for adding
a monomer to the growing polymer. Equation (9) then gives an explicit
physical interpretation of this reaction probability. The growing chain has
two choices: (a) add a monomer with rate kpM, or (b) wash out of the
reactor with rate 1/8. Equation (9) gives the probability that it reacts.
Very similar statistical arguments apply to several other polymerization
situations (Lowry, 1970).
POLYMERIZATION REACTIONS
Classification of all polymerization reactions as either step growth or chain
growth has been discussed by Lenz (1968). It is important to note that
this is a classification of reactions, not of the polymers themselves, since
there are instances of polymers that can be made via either step-growth or
chain-growth routes. Generally speaking, however, most important poly-
mers are made exclusively by one or the other.
The principal characteristic distinguishing step-growth and chain-growth
reactions is that each polymer chain grows at a relatively slow rate over a
much longer period of time for the former than for the latter. In step-
growth polymerization there is usually a single type of chemical reaction
that links polymer molecules of all sizes. The reactions are of the same
mechanism that link monomers, oligomers, and polymers. In contrast, a
chain-growth polymerization consists of distinctly different chemical steps:
initiation, which creates a highly reactive polymerization locus; propagation
in which monomer (only) adds to the active center, which grows in length;
(frequently) termination, in which the active center is extinguished and
this polymer chain no longer participates in the reaction; (sometimes) trans-
fer, where the active locus is not extinguished permanently but rather
transferred in location from one growing chain (which becomes dead) to
another species in the medium (monomer, solvent, agent, impurity, etc.),
which then propagates. The existence of the active center in chain-
growth polymerization, in that not every chain has one, is another important
distinction between step growth and chain growth.
In the remaining parts of this section we discuss the characteristic
molecular weight distributions that arise in each of these types of polymer-
ization in a batch reactor. This will further differentiate the two types of
polymerization. Subsequent sections will deal with the modified distribu-
tions produced in other types of reactors.
Step-Growth Polymerization
The most important chemical reaction used for the preparation of polymer
via step-growth polymerization is that of addition and elimination at the
Polymerization Reactors 743
carbonyl double bond of carboxylic acids and their derivatives (Lenz, 1968).
These reactions are the routes to most nylons and polyesters. Other im-
portant step-growth reactions are the urethane-forming double-bond addi-
tion and carbonyl addition-substitution for polyacetals and phenol-formalde-
hyde. Many, but not all step-growth reactions produce a condensation
product (e.g. , water or glycol) that must be removed.
Schematically, for the purposes of molecular weight distribution analysis,
the general step-growth reaction in its least encumbered form can be
represented:
p + p k p n, m 1, . . . ' (10)
n m n+m 00
In step-growth polymerization attention is focused on the end groups of
the polymer chain. Restricting our attention for the moment to bifunctional
monomers, every polymer has exactly one end group of each chemical type
involved in the linkage. Thus fractional conversion of end groups is
directly related to the number of polymer molecules, and therefore also to
the molecular weight and molecular weight distribution of the polymer. In
the case of exact stoichiometric equality of the concentrations of the two
functional groups, we expect that a second-order rate law will govern the
increase in fractional conversion, p, of c 0 initial functional groups:
dp - (11)
dt -
which integrates to
__l _ ::: C kt+ 1 (12)
1 - p 0
Kinetic data from many step-growth polymerizations fit the rate equation
( 12) (Flory, 1953) . One exception occurs in polyesterification with no
added acid catalyst; in this case, acid functional groups participate also
as catalysts and thus the rate law is third order. As we shall show below,
the number-average degree of polymerization in this reaction is 1/( 1 - p).
So a result of this analysis in Eq. ( 12) is that the number-average molecular
weight builds linearly with time over the course of the reaction.
The analysis of the molecular weight distribution in the simplest step-
growth situation of Eq. ( 10) with equal stoichiometry of the two end groups
is most easily done with statistical arguments. The fractional conversion
p is alternatively interpreted as the probability that a functional group
selected at random has reacted to form a linkage. If we inquire after the
probability of finding one molecule containing n monomer units, we realize
that this is a molecule having (n - 1) linkages and one free unreacted
functional group of a particular type. The probability of having (n - 1)
linkages is the product of (n - 1) separate probabilities that an ester link-
age would have been formed, pn-1. So the probability of finding the de-
sired molecule with (n - 1) linkages and one unlinked end is
n-1
pn == (1 - p)p ( 13)
which is the geometric or "most probable" distribution. The average
molecular weights and chain lengths resulting from this distribution are
744 Tirrell, Galvan, and Laurence
given in Ray and Laurence (1977). These authors, following Abraham
(1963) and others (Kilkson, 1964; Szabo and Leathrum, 1969), have shown
how the mass balance approach for the mechanism of Eq. (10) leads to the
same result as Eq. (13).
From an engineering viewpoint one of the most important characteristics
of Eq. (13) is that fractional conversion completely specifies the entire
molecular weight distribution and therefore all the average molecular weights.
Conversion control is the only means of molecular weight control for this
system available to the reactor engineer. The number- and weight-average
degrees of polymerization resulting from the distribution equation ( 13) are
1/ ( 1 - p) and ( 1 + p) / ( 1 - p) , respectively, which show that only as p
nears 1 is a high-molecular-weight product produced. There are two
significant exceptions to this absolute control of the molecular distribution
by conversion. These are interfacial polymerization and nonlinear, that is,
branching or cross-linking, step-growth polymerization both of which are
discussed later.
While Eq. ( 13) gives an accurate global description of many linear step-
growth polymerization processes, in practice there are important additional
effects and complications that often arise. Stoichiometry is sometimes in-
advertently or intentionally unbalanced. Monofunctional species (chain
stoppers) may be added to gain an independent means of control over the
MWD. Equal reactivity may not strictly apply; this is, monomer functional
groups may react more rapidly than identical groups on longer chains,
particularly as conversion gets high. Reversibility of reaction ( 10) can be
an important consideration. Diffusion limitations on the rate of removal
of condensation product or the rate of polymer coupling may dominate the
kinetics at high conversion.
Two of these effects will be considered further here to give a more
complete picture of step-growth polymerization and to illustrate the use of
some of the mathematical modeling techniques of the preceding section. We
shall examine, in turn, the effect of addition of monofunctional agents and
the effect of reversibility of reaction ( 10) , both for the case of the batch
reactor. Reactor configuration effects are considered in a subsequent sec-
tion. This section concludes with brief discussions of interfacial step-
growth polymerization and nonlinear step-growth polymerization.
Effects of Chain Stoppers (Gupta and Kumar, 1985;
Kilkson, 1964)
The practical situation is one in which a monofunctional compound such as
acetic acid is added to a mixture of difunctional amines and acids, or amino
acids, a common practice in nylon-6 manufacture. We now have two dis-
tinguishable kinds of polymers, those with two reactable ends,
( 14)
and those with one end blocked by the monofunctional agent,
p ( 15)
nx
We have, therefore, two kinds of polymer linkage reactions:
+p k
m - - - - Pn+m (16)
p
n
Polymerization Reactors 745
p + p _k_p (17)
n mx (n+m)x
X-terminated molecules cannot react with one another. Mass balances on
the two kinds of polymeric species read:
n-1
dP
dt
n
--= k l: P.P
J n-1
. - kPn ( 2P + Px) P (0) = 0
n
(18)
j=l
n-1
dP
nx
dt
= k L P. p
JX n-j
kP
nx
p P
nx
(0) = 0 (19)
j=l
00
where P (x) = ~n=l Pn(x). (The x in parentheses is used to denote situa-
tions where the same equation applies for Pn or Pnx •) The first terms on
the right-hand sides of each equation give the rate of formation of Pn(x)
by linkages between smaller molecules. The remaining terms give the rates
of dissappearance of Pn(x) by reaction will all other species in the mixture.
The factor of 2 in the second term of Eq. (18) is due to the fact that a
Pn has two distinct ways to couple with any other Pm.
Equations (18) and (19) apply for n ;;,, 2. For n = 1, we have no
formation reactions ; thus
dP 1
dt = -kP 1(2P+Px) ( 20)
dPlx
- - = -kP P p lx(O) = p lx0 ( 21)
dt lx
It is convenient to scale time in a manner similar to Eq. ( 4):
L = it0
k dt ( 22)
For the solution of the set of equations ( 18) to ( 22), we illustrate the
generating function technique, as in technique 4, Table 1. We will need
generating functions for the two distributions:
00
G(s,-r) = L snP
n
( 23)
n=l
00
Gx(s,-r) =
L
n=l
snP
nx (24)
746 Tirrell, Galvan, and Laurence
Adding Eq. (18) to Eq. (20) and Eq. (19) to Eq. (21), multiplying the
two results by sn, and summing as indicated in Eqs. ( 23) and ( 24) gives
two differential equations for the generating functions:
0 G = G2 - G( 2P + P ) G(0) =sP 10 ( 25)
dT X
oG
~=GG-GP G( 0) = sP lx0 ( 26)
cl T X X
Partial derivatives are indicated since G(x) is a function of both s and T.
Note that G( )(1) = Z: 00 1 P ( ) = P( )' Settings= 1 in Eqs. (25) and
(26) gives x n= n x x
dP = -(P2 + pp ) P(0) = plO ( 27)
dT X
dP
~= 0 ( 28)
dT
illustrating that as molecular weight builds, the total number, P, of difunc-
tional monomers decreases but, as expected, the total number, Px, of mono-
functional species remains constant, although these chains do grow in
length. Kilkson (1964) showed that these equations are easily solved using
normalized generating functions:
G
y = p ( 29)
G
X
y = p ( 30)
X
X
to give:
cly
= Py(y - 1) ( 31)
dT
clyx
= Pyx(y - 1) ( 32)
dT
from which it is clear that the two generating functions, and therefore the
two distributions, satisfy the proportionality
p
G = p Gx ( 33)
X
Finally, to make contact and compare with the statistically derived result
Eq. (13) for the simpler situation of no monofunctional agent, it is con-
vient to solve Eqs. ( 31) and ( 32) in terms of conversion of end groups
rather than time. Conversion, p, in this case is defined as
Polymerization Reactors 747
plO - p
p= ( 34)
p 10 + p lx0
as the fractional conversion of all initial groups of the, say, acid type,
including those on the monofunctional agent. The time rate of conversion
can easily be obtained from Eq. ( 27):
( 35)
where r = 1 + (P1xo/P 10 ), always greater than 1, gives the stoichiometry
of the initial addition of monofunctional agent. Dividing Eq. (31) by Eq.
(35) gives
dy = y(y - 1)
y = s at p = 0 (36)
dp 1 - p
leading to
_s(l-p)
y - 1 - ps ( 37)
and by Eq. (33),
- s(l - p)
Yx - 1 - ps ( 38)
so that the normalized distributions of monofunctional and difunctional chains
oo n-1 n
are identical. Recognizing that ax/(1 - bx) = a I:n=l b x , we see by
rewriting Eqs. ( 37) and ( 38) as power series in s that
p p
n nx n-1
p ::: p = (1 - p)p (39)
X
In other words, even in the presence of monofunctional agents, we obtain a
product with a "most probable" or geometric distribution like Eq. (13). The
distribution is still uniquely determined by p, but in this case p is not ex-
clusively a function of time as it is in Eq. (12). Here p is also dependent
on the initial stoichiometry, r. For the simple step-growth case leading to
Eq. (13),
p = 1 ( 40)
With monofunctional agents,
P = (1 - ~ ) .!_ ( 41)
plO r
The effect of molecular weight is important. In both cases
1
DPn = 1 - p ( 42)
748 Tirrell, Galvan, and Laurence
which for the case of added chain stoppers gives
1
DP = ( 43)
n 1 - (1 P /P 10 )(1/r)
In the high conversion limit P + 0 and we find
r
= ( 44)
r - 1
Thus final molecular weight can be influenced not only by reaction time
and conversion but also by addition of monofunctional agent. However,
this addition does not change the overall character or shape of the distri-
bution very much, except to shift the mean to lower degree of polymeriza-
tion.
The similarity and implications of these results for another case of
practical importance, that of unbalanced stoichiometry of the two difunc-
tional monomers, should also be clear.
Effects of Reversibility and Interchange Reactions
In practice, many step-growth polymerizations, polyesterification and poly-
amidation included, are run at elevated temperatures ( 250°C or higher) in
order to force the reaction to completion and to drive off and. extract low-
molecular-weight condensation products (e.g., water or glycol). The same
high temperatures also promote reversibility of the polymerization reaction
as well as interchange reactions, such as transamidation and transesterifica-
tion, between the polymer molecules formed (Lenz, 1968). It is of interest
then to know what effect reversibility has on the molecular weight distribu-
tion. This example will also afford the opportunity to illustrate some
additional useful techniques in polymerization analysis.
The reversible step-growth mechanism is written
p +P ~p ( 45)
n m - n+m
k'
with the understanding that the larger species Pn+m may unlink any of its
n + m - 1 links. The interchange reaction is a simultaneous unlinking
and relinking by two polymers:
k.
p + p ___!_._ ( 46)
n m-
k.
1
Both reactions should be expected to have a similar effect on the molecular
weight distribution. The effect of both reversibility and interchange is to
unlink a polymer at a randomly chosen link. Statistical arguments have
been used to show that a most probable distribution of the form of Eqs.
(13) and ( 39) is obtained when reversibility is an important factor. This
is, in fact, an important general conclusion. Random scission processes,
such as thermal or radiation degradation will also lead ultimately to a most
probable distribution, even starting from a monodisperse product.
Polymerization Reactors 749
Reversibility presents some special difficulties to the mass balance ap-
proach to modeling (Gupta and Kumar, 1985). The mass balance on Pn
resulting from the mechanism (42) is
n-1 00
L
dP
--=
dt
n k
2 L P.P
J n-J
. kPnP - k'(n - l)Pn + 2k' Pj (47)
j=l j=n+l
The first two terms of this equation are identical (aside from the factor-of-
2 difference in the definition of the rate constants here) to the first two
terms in Eq. (18). The third term gives the rate of dissappearance of Pn
by a Pn unlinking any of its (n - 1) bonds. The fourth term gives the
rate of appearance of Pn by larger molecules unlinking, the factor of 2
accounting for the fact that any polymer has two sites at which it can un-
link to give a polymer of some specified shorter length. Mathematically,
the nPn term and the partial sum term due to reversibility pose the dif-
ficulties. Applying the generating function operation of Eq. (23) yields
~
at
= ~ G(G
2
- 2P) - k' fs~ ~
els
- G - G - sP)
1 - s
(48)
Rather than solve this nonlinear first-order partial differential equation,
we shall use it to derive moment equations (see Table 1) by successive
differentiation of Eq. (48) with respect to In s and taking the limit as
s + 1.
dP
= = (49)
dt
dµl
dt = 0 (50)
with initial conditions µk ( 0) = P 10 • Equation ( 50) expresses the fact that
the total number of monomer units, r:=l nPn, in the reaction mixture re-
mains constant. Evidently, Eq. ( 49) and ( 50) can be solved together to
give conversion p and degree of polymerization DPn as functions~ time.
It is found that the most probable distribution relation between DPn and p,
Eq. (42), is obeyed.
Higher moments present the mathematical difficulties. The set of
moment equations is not close in that µ2 depends on µ3, the equation for
µ3 would involve µ4 and so on. This arises from the third term of Eq.
( 48). Terms like this also arise in analysis of other chain scission reactions.
One route to analysis of this type of problem is the moment expansion pro-
cedure discussed by Bamford and Tompa ( 1954) and Hulburt and Katz
(1964). This is an approximation procedure which for the purposes of ob-
taining relations among the moments, replaces the unknown true distribu-
tion by an expansion in Laguerre polynomials about a standard distribution
750 Tirrell, Galvan, and Laurence
for which the relations among the moments can be calculated exactly. These
known relations enable one to express, for example µ 3 , in terms of the
lower moments. Application of the Hulburt-Katz procedure gives
( 52)
In fact, this moment closure approximation has been examined in several
reversible polymerization problems and found to give very accurate numeri-
cal results, 1% error when three to five terms are used (Bamford and
Tompa, 1954; Gupta and Kumar, 1985), for the moments when compared
with the much more laborious complete numerical solution. It could there-
fore be recommended as a generally useful approximation provided that
there is no a priori reason to believe that the distribution will have a very
unusual shape.
In summary, the effect of reversibility can be treated by the means
described here. Reversibility does not change the conclusion reached from
analysis of irreversible linear step-growth polymerization that the product
MWD is most probable with the mean dictated completely by fractional con-
version of end groups. Reversibility does, however, alter the fractional
conversion itself. Means of driving the equilibrium toward higher conver-
sion and therefore higher molecular weight are frequently employed.
Interfacial Polycondensation
The preceeding discussion has illustrated the intimate connection between
conversion, stoichiometry, and molecular weight distribution in linear step-
growth polymerization. Reaction engineers should always seek additional
control handles on MWD. In step-growth polymerization, interfacial reac-
tion provides an alternative to the strict conversion and stoichiometry con-
straints. This has been exploited in polyamide production. The principles
of the technique have been explained by Kilkson ( 1968). It relies on what
he has termed the concept of slow influx.
Consider polymerization of two difunctional monomers of the AA and BB
types (e.g., hexamethylene diamine and adipic acid or its derivatives),
where we start with exact stoichiometric equivalent amounts of the two
monomers. A "normal" polycondensation would be done homogeneously, ad-
ding all of both the monomers at the beginning. This is the situation of
strict conversion and stoichiometry control, where most of the analysis of
this section applies. Imagine now the following alternative. All of the BB
monomer is placed in the reactor and slow addition of AA is begun. As
each increment of AA enters the large excess of BB, it will be immediately
reacted on both ends by BB. This process can be continued until the full
stoichiometric equivalent amount of AA has been added, consuming the last
B group. If the addition has been very slow, the polymer at that point,
will be of essentially infinite molecular weight since all the AA and BB
units have been linked into the polymer. Addition of further AA, in
stoichiometric excess, now serves only to dilute this high-molecular-weight
product, not decrease molecular weight as it would in the case of the homo-
geneous reaction with unbalanced stoichiometry [ see Eq. ( 44)] .
The point is that molecular weight is now influenced strongly by the
monomer addition rate, not exclusively by conversion and stoichiometry.
In interfacial polycondensation, the slow influx of monomer is accomplished
Polymerization Reactors 751
by imposing diffusion limitations. Each monomer is dissolved in one of a
pair of mutually immiscible solvents. Reaction occurs at the interface,
where the monomer supply is limited by diffusion.
In practice, interfacial polymerization is done under mild reaction condi-
tions. Therefore, reactive monomers must be used. Diacid chlorides are
used instead of diacids. Stirring and addition of emulsifier to create and
stabilize large interfacial areas are also important considerations in this
type of reactor.
Nonlinear Step-Growth Polymerization
Not a great deal of literature is available on reactor design for nonlinear
step-growth polymerization. Two factors probably account for this. One
is that nonlinear step-growth polymers have never been produced in very
large volumes. The other is that many of these materials are thermosetting
materials, neither soluble nor fusible once made, so that the "reactor" is
frequently simply a mold of the desired shape. Examples of important non-
linear step-growth polymerizations include phenolic resin manufacture, urea-
formaldehyde resin manufacture, epoxies, and many polyurethanes.
Nonlinear polymerization requires the presence of some monomers with
functionality greater than 2. The amount of multifunctional monomer is
another variable that influences MWD. For example, the number-average
degree of polymerization is given by (Flory, 1953)
2
DP = ( 53)
n 2 - pf
where f is the average functionality of the monomers containing the branch-
ing group. For example, consider a polymerization of AB, BB, and a tri-
functional A monomer, A3. If there is one A3 in every 10 original monomers
containing A· functional groups, then f = 2.1. For linear step growth
f = 2 and Eq. ( 53) reverts to the linear result: 1/ ( 1 - p).
Notice that for f > 2 in Eq. ( 53) DPn becomes infinite at conversions
less than 1. For example, if f = 2.1, D'Y"n diverges at p = O. 952. Thus
even a small amount of multifunctional monomer increases the molecular
weight greatly at conversions less than 1.
Divergence of the molecular weight (i.e., gelation) is the most spectacu-
lar feature of nonlinear polymerization. The "gel" point where this occurs
is most succinctly expressed in terms of the branching probability a, de-
fined by Flory (1953) and discussed in detail by Billmeyer (1971). a is the
probability in a reaction mixture of linking two multifunctional monomers.
This will depend in general upon conversion and stoichiometry of branched
and linear monomers. Consult Flory ( 1953) or Billmeyer ( 1971) for de-
tailed calculations for specific cases. Gelation occurs at a critical value
of a:
1
a, = ( 54)
C f - 1
which corresponds to the divergence of the weight-average molecular
weight.
Analysis of the MWD up to and after gelation is beyond the scope of
this chapter. We simply conclude with a few important observations.
Weight-average molecular weight goes to infinity at the gel point, not the
752 Tirrell, Galvan, and Laurence
number-average molecular weight. This means that there is a "sol" frac-
tion of finite-sized molecules present even after gelation. Historically,
statistical methods of calculating MWD, such as those of Flory ( 1953) and
Stockmayer ( 1943), have been employed. These methods neglect the pos-
sibility of cyclization, that is, different branched units being connected
by two or more chains, which is redundant from the point of view of the
connectivity required for gelation. There is much interest currently in
determining how important this process is in the structure of nonlinear poly-
mers (Family and Landau, 1984). Certainly as a first approximation the
Flory-Stockmayer method is excellent. However, it remains to be decided
if there are subtle but important influences of cyclization on the gel point,
mechanical properties, and scattering.
Finally, the more chemical engineering-oriented mass balance approach
has only recently been applied to nonlinear polymerization (Ver Strate
et al., 1980; Hendriks et al., 1983). This has the advantage of more
ready generalization to different reactor configurations, such as continuous
reactors. In addition, the time evolution of the MWD is more explicit in
the mass balance treatment. Incorporation of cyclization in these methods
is also problematic.
Chain-Growth Polymerization
Chain - growth polymerization is based on the application of a free radical or
ionic reaction to a polymerization chain or macromolecule which results
from the propagation of one kinetic chain reaction (Lenz, 1968). Chain-
growth polymerization is initiated by a reactive species R produced from
an initiator or catalyst. A chain reaction can be initiated by a radical-
producing initiator such as azobisbutyronitrile or benzoyl peroxide. It
can be initiated thermally, photochemically, with cationic and anionic
initiators, or with true catalysts that are not consumed by the reaction
I-nR
1
(In chain-growth polymerization we must distinguish between growing
chains, which we designate R, and dead chains with no active center
attached, which we designate P.) The reaction chain propagates by reac-
tion of a monomer with the active species or radical. The propagation re-
action is simply represented by
This representation does not detail the various methods or mechanisms of
propagation or growth of the active chain. Lenz ( 1968) treats this question
in considerable detail. The kinetic chain can be transferred by several
reactions
Ri + M - P i + R 1 transfer to monomer
Ri + S - P i + R 1 solvent
Ri + A - Pi+ R 1 agent
Ri + pk - pi + Rk polymer
Polymerization Reactors 753
Transfer reactions terminate the active chain and initiate another one. We
will find that transfer reactions do not affect the shape of the distribution,
although they affect strongly the average degree of polymerization. The
polymer transfer reaction in free radical polymerizations leads to branching
(Bamford and Tompa, 1954; Graessley et al., 1969; Nagasubramanian and
Graessley, 1970a,b).
Sooner or later the propagating polymer chain is terminated not by a
transfer reaction, but by annihilation of active groups. Two active groups
react with each other in radical polymerization by (a) combination, and (b)
disproportionation. A shorthand representation of the termination reactions
is
Rj + Rk - P j + k combination
Rj + Rk - P j + Pk disproportionation
The termination reactions occur between two large macromolecular active
species. Such a reaction runs the risk of being strongly diffusion con-
trolled. This leads to a phenomenon termed the gel effect or Trommsdorff
effect (Tulig and Tirrell, 1981). An extensive discussion of the ramifica-
tions of this phenomenon is particularly important in the design of poly-
merization reactors involving chain-growth polymerization taken to high
conversions. Ionic and heterogeneous catalyzed polymerizations suffer
termination by small molecule poisons present accidentally or purposefully
to control molecular weight.
Free Radical
Of the several types of polymerizations classed as chain growth, free
radical initiation has found more general industrial application. This may
be largely historical, but it remains that a significant fraction of polymer
produced today are made by radical mechanisms.
For the sake of simplicity, consider a batch chain-growth polymerization
involving only initiation, propagation, and combination termination. We
must describe the evolution of monomer, M; active polymer species of chain
length j, Rj; dead or inactive polymer of chain length j , Pj ; and initiator,
I. The reaction sequence is given as
kl
I - 2R 1 initiation (55)
k2
M + Rj - R j + l propagation (56)
k3
Rj + Rk - - pj+k combination termination (57)
The material balance on the species of interest are
dI
= - k I (58)
dt 1
754 Tirrell, Galvan, and Laurence
00
( 59)
00
dR.
Tt : : 2fk 110 (j - 1) + k 2M<Rj-l - Rj) - k 3Rj :E R
n
(60)
n:::1
00
dP. k3
_j_
dt -- "'
2 .l..J (j > 2) (61)
n:::1
Note that Pj ::: 0 for j < 2. We use the Dirac delta function o(j - 1) to
designate a term that occurs only when the argument is zero, in this case
when j ::: 1.
The assumptions implicit in this formulation are that:
1. The reaction velocity constants are independent of molecular size.
2. A fraction f of the initiator form active radicals.
3. Isothermal reaction conditions prevail.
The generating function can be used to collapse the infinite set of differ-
ential equations to a finite set:
di
-::: -k I ( 62)
dt 1
dM
- ::: -k MG(l) (63)
dt 2
3G(s) ::: 2fk 1Is - k 2M(l - s)G(s) - k 3G(s)G(l) (64)
at
a H(s) ::: k 3G 2(s) ( 65)
at
30(1) ::: 2fk 1I - k 3G 2(1) (66)
at
where G and H are the generating functions for the R and P distributions,
respectively. These equations can be solved formally subject to initial
conditions at t ::: 0:
G(s, 0) ::: H(s, 0) ::: 0
(67)
M(O) ::: M0 , 1(0) ::: I 0
The procedure is to solve first for I, then for G( 1), M, and finally for
G(s) and H(s). In doing so, most analyses of free radical polymerization
use an assumption known as the quasi-steady-state approximation (QSSA).
Polymerization Reactors 755
Bamford et al. ( 1958) state this fundamental assumption of radical
chain-growth polymerization as "the assumption that the concentration of
radical intermediates remains constant during the polymerization." More
specifically,
00
d
dt L R. = 0
J
( 68)
j=l
or
00
dM
d~L R. « dt
(69)
J
j=l
or that the reaction has proceeded so far that the net rate of change of
concentration of radical intermediates is very much less than both their
rate of production and their rate of destruction.
One can examine more rigorously what the QSSA really means by at-
tempting a rigorous solution of some of the equations and comparing with
the result of assuming Eq. (68).
The equations governing the evolution of total polymer radical [Eq.
(64) with s = 1], the initiator [Eq. (62)], and the monomer [Eq. (63)] can
be solved for an isothermal batch polymerization starting with only monomer
and initiator. The equations are
di
= -k 1I ( 70)
dt
dG(l)
= 2fk I k 3G 2(1) (71)
dt 1
dM = -k~G(l) ( 72)
dt
At t = 0, M = Mo, I = Io, and G(l) = 0. The solution to Eq. (70) can be
obtained readily:
The equation for total polymer radical can be transfermed into a classical
Riccatti equation with the following definitions:
G( 1)
y =--
Io
(74)
Ct =
756 Tirrell, Galvan, and Laurence
Equation ( 71), then, becomes
2 2
..x
d
+~y =.r.__x ( 75)
dx X a
Solution methods for Riccatti equations are well presented in Davis ( 1962).
The substitution
(76)
into Eq. (75) leads to
(77)
The solution is straightforward and leads to the following expression for y:
XY Kl(y)ll(YX) - Kl(YX)Il(y)
y = a K 1(y)I 0 (YX) - K 0 (YXH 1 (y) ( 78)
where Ki and Ii are the modified Bessel functions of order i.. We can make
a comparison of this exact solution to that solution resulting from the quasi-
steady-state approximation (QSSA). If the assumption characterized by
Eq. ( 68) is applied to Eqs. ( 70) and ( 71), the result is
y = YX (79)
s a
This suggests that QSS conditions prevail if y - y s' which requires
( 80)
Saidel and Katz (1967) and Bamford (1965) have shown this to be a
reasonable assumption for values that can be assigned to y for typical
radical chain-growth polymerization. The QSSA leads to the following
representation of the kinetics:
( 81)
2fk )1/ 2
dM = -k MG(l) = -k ( _ _l 1112M ( 82)
dt 2 2 k3
( 83)
Polymerization Reactors 757
d~?) ~ 0 = 2fk 1Is - k~(l - s)G(s) - k 3G(s)G(l) ( 84)
k
dH(s)
= _]_ G(s) 2 ( 85)
dt 2
The quasi-steady-state assumption yields
G(l) = (~1 1) 1/2 ( 86)
and
as
G(s) = ( 87)
1 - bs
where
a= (2fk 1I)[k~ + (2fk 1k 3I)l/ 2]-l
( 88)
b = k~[k~ + (2fk 1k 3I)l/Z]-l
Notice that this is exactly the same form of the generating function as Eq.
(37) found in step-growth polymerization. This is an important general con-
clusion concerning free radical polymerization: the distribution of growing
chains is most probable. This is the same distribution as is found in step-
growth polymerizations, but the parameters of the distribution are con-
trolled by entirely different factors, Here the mean of the MWD changes
with conversion since a and b depend on M and I, The distribution of the
terminated chains is slightly more complex and is discussed below,
Monomer consumption is given by the solution of Eq. ( 82), which can
be rewritten as
d
dt (ln M) = -k 2 ~
1 0 (
2fk I )l/ 2
exp ( 89)
The solution of the monomer equation can be expressed as
(2::
1/2
ln M: = - : ;
10
) [1 - exp(- k!t )] ( 90)
Note that as t -+ oo,
(91)
This is sometimes termed dead-end polymerization, Appropriate choice of
initiator type and amount will avoid this.
758 Tirrell, Galvan, and Laurence
The rate of polymerization is given by
2fk )1/2
dM = -k ( _ _1 1 1/2M ( 92)
dt 2 k3
Here we see the various influences on the kinetics. In chemically initiated
radical chain polymerization the rate is proportional to the 1/2 power of
the initiator concentration and the first power in monomer concentration.
The termination rate constant, k3, occurs in the expression as a -1/2
power term. Should for some reason the termination reaction velocity con-
stant decrease, the polymerization rate will increase. This is the effect
previously mentioned as the Trommsdorff or gel effect. The reaction be-
haves much in the fashion of an autocatalytic reaction.
Regarding the chain-length distribution of the dead chains, we get
that from the distribution of growing chains via Eq. ( 85). We saw that
2fk 1Is
G(s) = - - - - - - - - - - - (93)
k/1(1 - s) + (2fk 1k 3l) 1 / 2
so that for the combination termination scheme
k
dH(s) = _l_ ( as )2 (94)
dt 2 1 - bs
with a and b defined by Eq. ( 88).
Equation (94) can be readily inverted by expanding the right-hand
side as a power series in s in a fashion similar to what was done to Eqs.
( 37) and ( 38) with the result
2
dP; k 3a . 2
dt
-.J..
= -2- bJ- (J' - 1) ( 95)
Since a and b are functions of time, readily determined from the solu-
tions to Eqs. ( 81) and ( 82), the entire distribution for Pj can be directly
obtained by integration of Eq. ( 95).
Our discussions earlier suggested that many polymerization schemes
are best understood in terms of the moments of the distribution. The
moment equations can be readily obtained from the equation for the trans-
form of the chain-length distribution. The moment-generating property
k
_ 1. d G(s)
Jlk - im k (96)
s-+1 d(ln s)
gives the following set of moment equations from the original rate equations:
(97)
2(1 - b) 2
Polymerization Reactors 759
= ( 98)
k a2
= 3 (2 + b) ( 99)
(1 - b)4
One can see that the instantaneous number- and weight-average degree of
polymerization have the simple form (for b near 1, which is necessary for
high-molecular-weight polymer)
dµl 2
= ( 100)
dµO 1 - b
dµ2 3
= ( 101)
dµl 1 - b
The polydispersity of any polymer formed in an instant [the ratio of Eqs.
(100) and (101)] is constant and always 3/2 for the mechanism of combina-
tion termination used in this discussion of radical chain-growth polymeriza-
tion. Notice that b is very similar in its definition to the reaction
probability p of step-growth polymerization [see Eq. ( 13)] , or the a of
Eq. (9).
We have discussed a very simple mechanism for radical chain polymeriza-
tion. It is worth examining briefly what happens when other reactions
occur, chain transfer and branching, for example.
Consider the following mechanisms:
k
I _!___.2R initiation
1
k2
R. +M - - - Rj+l propagation
J
k
R. +M --1_ p + Rl transfer to monomer
J J
k4
R. +A - P . + Rl transfer to solvent or agent
J J
k5
R. + Rk - - - P combination termination
J j+k
The material balances for such a polymerization in a batch reaction are
given by
( 102)
760 Tirrell, Galvan, and Laurence
00
dlVl
dt = -(k2 + k3)M L R.
J
(103)
(•~,1 k~ t
j=l
R,)6(j -
00
dR.
--1. =
dt + Rj + k 4A L 1)
.R.=1
Rj) -(k~ R}j
00
(104)
+ k 2M(Rj-l - + k 4A + k 5 L
n=l
00
k5
~= -
dt 2
(j - 1)
L (105)
k=l
These same equations can be put in the generating function format:
di (106)
- = -k I
dt 1
(107)
dG(s) = [2fk 1I + k 3MG(1) + k 4AG(1)]s - k 2MG(s)(1 - s)
dt ( 108)
- (k 3M + k 4A)G(s) - k 5G(1)G(s)
(109)
(110)
The QSSA can lead to considerable simplification since
( 111)
[ 2fk 1I + (k 3M + k 4A)G(1)] s
G(S) = - - - - - - - - - - - - - (112)
k5G(1) + k:f1 + k 4A + k 2M(1 - s)
The distribution produced by this mechanism is not significantly different
from that prescribed by the simpler mechanism. Only the mean values are
different. G(s) can again be written in the form
Polymerization Reactors 761
as
G(s) = (113)
1 - bs
where
2fk} + (k 3M + k 4A)G(l)
a= (114)
k 5G(l) + k 3M + k 4A + k 2M
Equation ( 110) can be greatly simplified to yield
k 2
dH(s) = _i ( as ) + (k M + k A) as ( 115)
dt 2 1 - bs 3 4 1 - bs
The equation for H(s) can be inverted readily to give the equation for P.:
J
: j = k5a2(j ; 1 bj-2 + Sbj-1) (116)
where
k 3M + k 4A
s= ----- (117)
k5a
Again we should note that the quantities a, b, and S are functions of time,
readily evaluated from the conservation equations for M, S, and I.
Now it might help to examine the moment equations. Let the moments
of the radical and polymer distributions be defined as
00 00
and (118)
We have seen that the distribution for polymer radicals has a most probable
distribution [i.e., Eq. (113)], so that the moments of the polymer radical
distributions are
a
0 o= 1 - b ( 119)
a
0 = (120)
1 (1-b)2
a(l + b)
0 = (121)
2 (1 _ b)3
The equations for the moments of the distribution can be readily derived
from Eq. ( 110) in terms of the moments of the radical polymer distribution
762 Tirrell, Galvan, and Laurence
(122)
( 123)
(124)
The instantaneous weight- and number-average degrees of polymerization
then assume the form
o1 (o 0 + Sa)
( 125)
0 0 (0 0/ 2 + Sa)
(126)
The relations for o0 , o1 , and o2 afford considerable simplification:
dµl
= 1 [ 1 + S(l - b) ] ( 127)
dµO 1 - b 1/ 2 + S(l - b)
dµ2 1 1
= ( 128)
dµl 1 - b [1 + b + l + S(l - b)]
A little exercise will show that as S + 0 (no transfer reactions) the instan-
taneous polydispersity has the same value, 3/2, as the simple mechanism
and that in the limit of dominant transfer S + the polydispersity ap-
00 ,
proaches 2 from below.
Volume Change in Radical Polymerization
Volume change is a common effect in undiluted or bulk polymerization. For
the case of styrene, Hui and Hamielec ( 1972) used a linear correlation be-
tween volume and conversion,
where E is the fractional change in volume of the system between 0 and
100% conversion. E depends also on temperature and may be calculated
reasonably accurately from the individual properties of monomer and poly-
mer, by assuming volume additivity and disregarding molecular weight
dependency. For the case of styrene, values for E range approximately
from -0.16 at 60°C to -0. 22 at 180°C (volume contraction).
The effect of incorporating volume change in the kinetic model can be
evaluated quantiatively. While there are no appreciable changes in the
conversion time relation, it does affect the prediction of average molecular
Polymerization Reactors 763
weights. Errors due to neglect of contraction in the polydispersity may
approach 50% at higher conversions.
Anionic Polymerization
Anionic polymerization is important industrially for various types of co-
polymers and also because the same basic kinetic scheme is found in many
heterogeneously catalyzed polymerizations. In the course of illustrating
many of the techniques of molecular weight distribution analysis, the
simplest version of anionic polymerization (instantaneous initiation, no
termination) has already been examined, This mechanism, which can be
closely approximated in practice with very pure systems, produces the
narrowest possible MWD for any as-polymerized, unfractionated material.
It is instructive to examine what can happen if some of the conditions
of simple ideal anionic polymerization are not achieved. We look briefly
here at the case of slow initiation.
The kinetic scheme for this mechanism might be expressed as
This is still a simple mechanism readily described as before. The species
balances are
di
-= (131)
dt
00
dM
dt
R ( 132)
n
at = k 1IMo (j -
dR.
1) - k 2M(Rj - Rj-l) (133)
This set of equations can be reformulated using both a generating function
and the transformation:
T = (134)
and Eqs. (131) to (134) become
: = -al (135)
dM
- = -al - G(l) ( 136)
764 Tirrell, Galvan, and Laurence
dG(l)= al (137)
d,
dG(s)
- - = als - (1 - s)G(s) (138)
d,
The initial conditions are transformed to 1(0) = lo, M(O) = Mo, and G(s, 0) =
0. A solution to Eq. (138) can be readily written as
s _
aI 0_ (e-a' _ e- (l -s ) -r)
G( S,T ) = _ _
l - a - s
The inversion of G(s) is straightforward, if lengthy, and has been pre-
sented by Nanda and Jain (1964):
00
[(1 - a)T]k
Rj = aI 0e -,(1 - a) - j I : (139)
k!
k=j
This distribution is often termed the Gold distribution and for values
assigned to the parameter a the distribution can vary from very narrow
(Poisson distributed) to very broad at large a for small a.
Cationic Polymerization (Plesch, 1963)
As in most chain- growth polymerizations, in cationic reactions the chain
must be initiated
kl
I+M-R (140)
1
This schematic representation is typical of initiation by proton donor
(protonic acids). Lewis acids form another class of initiators. For such
systems one generally needs a cocatalyst. The initiation is very rapid
and reversible:
I-R ( 141)
---- 1
There are, of course, other means of ionic catalysis, but we will, in our
discussions, restrict ourselves to these two.
The active chain propagates
( 142)
The propagation reaction can be complex as a result of many intramolecular
rearrangements. In our discussion we avoid these but maintain an aware-
ness of their existence.
Polymerization Reactors 765
Transfer reactions occur commonly in cationic polymerizations. They
are often called termination reactions. We avoid that usage since the
kinetic chain is not destroyed.
( 143)
Spontaneous transfer termination can also occur and is described by
(144)
The kinetic chain can be terminated (by combination of the carbonium ion
with the gegenion) and is best represented by
k5
R,-P. (145)
J J
Other transfer reactions are important and should be considered in any
model. The analysis of cationic polymerization is much less complete than
for anionic polymerization due to the more complex kinetic scheme. Equa-
tions ( 140) to ( 145) represent a typical minimum set of reaction equations
that should be analyzed.
Heat and Mass Transfer Effects in Chain-Growth Polymerization
Polymerization reactions are typically strongly exothermic. Moreover, poly-
mers are typically poor thermal conductors. Mass transport by diffusion is
also a slow process in polymer systems. Heats of reaction of 15 to 20
kcal/mol are common, as are thermal diffusivities of 10-4 cm2/s and mass
diffusivities, for small molecules in polymers, of 10-8 cm2/s. For polymers
diffusing in polymer, 10-14 cm2/s is not an unusually low value of the
diffusion coefficient.
Two examples of transport effects that stand out for their practical im-
portance are (a) the autoacceleration or Trommsdorff effect in high-
conversion-bulk free radical polymerization, and (b) the heterogeneous
catalyzed polymerization of ethylene, propylene, and a-olefins. These will
be discussed briefly in turn.
Trommsdorff Effect (Cardenas and O'Driscoll, 1976, 1977a,b;
Ross and Laurence, 1976; Dionisio and O'Driscoll, 1979;
Marten and Hamielec, 1979; Tulig and Tirrell, 1981; Balke
et al,, 1981; Sob and Sundberg, 1981a-d; Chiu et al., 1983)
In a free radical polymerization conducted in bulk or solution, it is found
that monomer consumption follows the exponential approach toward complete
conversion suggested by Eq. ( 92). However, when the reaction has pro-
ceeded to the point that the medium contains 20 to 40% polymer (i.e., 20
to 40% fractional conversion of monomer in bulk polymerization, later in
solution polymerization), there is, in many free radical polymerizations,
an abrupt increase in the rate of polymerization. This occurs, as suggested
under Eq. ( 92) , because the termination rate constant takes a drastic drop.
766 Tirrell, Galvan, and Laurence
The practical implications of this phenomenon are enormous. Due to
the high reaction exothermicity and the relatively low thermal conductivity
of polymeric media, dispensing with this added heat production is difficult
and can lead to significant, even dangerous temperature excursions. The
book by Biesenberger and Sebastian ( 1983) discusses thermal runaway
phenomena extensively. Even without large temperature changes, the
highly nonlinear kinetic behavior can lead to multiple steady states and
other uncommon dynamic phenomena otherwise normally associated with
nonisothermal operation. In addition to these operational control problems,
this autoacceleration changes the nature of the polymeric product signifi-
cantly. Reduction in the termination rate produces long-lived free radicals
and therefore higher-molecular-weight polymer. What is found as the
acceleration sets in is that the molecular weight distribution of the polymer
being produced at that instant of time shifts abruptly to higher average
molecular weight. As this higher-molecular-weight polymer accumulates,
the aggregate molecular weight distribution becomes quite broad and bimodal.
The physical basis of this phenomenon is well understood qualitatively.
It clearly results from an abrupt slowing of the polymer diffusion process.
As polymer concentration builds in the reaction medium, diffusion of large
molecules, like the growing radicals, is going to be retarded more than
that of monomers. Therefore, the termination reaction, which involves two
large molecules, is inhibited more strongly than the propagation reaction
and the overall rate of polymerization goes up.
Converting this qualitative understanding to practical, accurate, quan-
titative, predictive modeling is difficult, but also very important, and is
the subject of much current activity and recent progress. The key points
of any model of this effect are (a) how the onset of the autoacceleration is
handled, and (b) how the rate constants are supposed to vary with polymer
concentration and molecular weight in the reaction medium. It has been
clear for some time that the onset of autoacceleration is not the onset of
diffusion control of the termination reaction. Even at zero polymer concen-
tration (i.e., zero conversion of monomer to polymer), it has been demon-
strated that the termination reaction rate is diffusion controlled, as it scales
directly with monomer or solvent viscosity. What happens at the onset,
then, is an abrupt change in the character of the diffusion control. Re-
cent work has gathered convincing evidence that the onset of acceleration
corresponds to the onset of entanglement in the polymerizating mixture.
A fundamental approach to the modeling of diffusion-controlled reaction
in this onset regime is very difficult since the behavior of the polymer
diffusion coefficient itself is not clearly understood here with respect to its
dependence on concentration and molecular weight. Several authors have
proposed similar, ad hoc means of dealing with the onset, which is to
treat it as a transition, much like the transition from unentangled to en-
tangled behavior seen in rheological properties with increasing concentra-
tion. With minor variations among them, all suggest that the acceleration
onset occurs at a concentration, c 0 , that varies with molecular weight of
the polymer like M-a, where the exponent a is between 1/2 and 1 (Tulig and
Tirrell, 1982). Exponents in this regime are found for the appearance of
entanglement in rheological properties with increasing concentration. Ul-
timately, a smooth transition function from dilute to entangled behavior is
needed, but this will require advances in our fundamental understanding
of entanglement.
There is a wider diversity of approach to how the variation of kt with
conversion and molecular weight is handled after the onset. This part of
Polymerization Reactors 767
the model is the important part for prediction of molecular weight distribu-
tion and the resultant polymer properties. The onset part of the model by
contrast has more bearing on the control of the reactor. There are several
effective empirical or semiempirical approaches to treating the kt variation
(Ross and Laurence, 1976; Cardenas and O'Driscoll, 1976, 1977a,b; Marten
and Hamielec, 1979). Among these several have been developed from the
notion that the termination rate constant should be inversely proportional
to the viscosity of the reaction medium (Marten and Hamielec, 1979). This
hypothesis leads to a particular dependence of kt on polymer concentration
(conversion) and molecular weight. Given that a number of adjustable
parameters are unavoidable in the construction of models like this, these
models can be made to fit experimental data well.
Recently, this kind of model has been criticized on theoretical grounds
and an alternative hypothesis proposed, namely that kt should be propor-
tional to the diffusion coefficient (D) of the free radicals rather than the
viscosity of the entire reaction medium (Tulig and Tirrell, 1982). This
model implies that the concentration and molecular weight dependence of
kt should follow that of D. Experimentally, these dependences of D are
currently in the process of examination. The reptation model (de Gennes,
1976a,b) of polymer diffusion suggests that D varies with the inverse
square power of molecular weight and with concentration to some power be-
tween -3 and -1. 75, depending on the quality of the solvent. Experi-
mental evidence to date supports the predicted molecular weight dependence
of D but suggests that the concentration dependence is much stronger
(Tirrell, 1984) . A model with kt depending on molecular weight and con -
version as suggested by the reptation model has been developed and shown
to fit kinetic, molecular weight, and molecular weight distribution data
well ( Coyle et al., 1985). However, this model, like its predecessors, con-
tains adjustable parameters, so that it is difficult to make a convincing
argument for its superiority based on its predictive power. The bottom
line is that any model where there is an abrupt switch in kt from a mild
to a strong dependence on molecular weight and concentration can be made
to fit the data reasonably well. The behavior, especially conversion ver-
sus time, is simply not very sensitive to the exact forms chosen for these
dependences.
On the other hand, there is some recent evidence to suggest that the
model based on the reptation theory is more fundamentally sound. Experi-
mental measurements of kt have been made in solutions of polymethyl
methacrylate in methyl methacrylate monomer where the molecular weight
and concentration of polymer in the reaction medium can be varied inde-
pendently (Tirrell and Tulig, 1983). In this way, one can examine kt
at fixed concentration and vary the molecular weight of the added polymer
and therefore the viscosity of the reaction medium. On doing this, one
sees that kt is only very weakly dependent on viscosity and molecular
weight of added polymer. This is in contrast with early models but ex-
actly what is expected from the reptation theory, which focuses on diffu-
sion of the radicals. This diffusion rate is expected to be independent of
the molecular weight of surrounding chains as long as they are sufficiently
long and concentrated to be entangled. Only the molecular weight of the
radicals plays a role in the diffusivity.
This area is one of active research currently and should therefore be
watched closely by the engineer who wishes to keep abreast. On the
practical side, it should be mentioned that there are also several completely
768 Tirrell, Galvan, and Laurence
empirical models of autoacceleration cited above that have been used suc-
cessfully for certain modeling purposes. A fundamentally based theory for
the reaction of two macromolecules is clearly more desirable in the long run.
Such a theory would find application not only to the problem of autoaccelera-
tion in free radical polymerization but also possibly to high-conversion step-
growth polymerization and certain branching and cross-linking reactions.
Heterogeneous Polymerization
In several kinds of chain-growth polymerizations the active center may be
in a separate phase, frequently in the form of droplets or particles, from
other components of the reaction medium. Emulsion (Penlidis et al., 1985),
precipitation, and heterogeneously catalyzed polymerizations are all exam-
ples of this. (Suspension polymerization, while multiphasic, contains all
reactive components in one phase and therefore has more in common with
bulk and solution polymerizations than with heterogeneous polymerization.)
These polymerizations share several features. One is that the active
center becomes isolated somewhat by this phase separation and therefore
very long-lived. Very high molecular weights can be produced and fre-
quently chain transfer additives are used to control molecular weight. A
second common feature is that reactants have to diffuse into droplet or
particle form in order to participate in the reaction, opening up the pos-
sibility of diffusion limitations on the rate. Also, heat has to diffuse out
of and be carried away from the reaction particles, presenting the pos-
sibility of local temperature excursions.
These problems have received the most attention in heterogeneously
catalyzed polymerizations, an important class of which are the Ziegler-Natta
(Z-N) catalyzed polymerizations (and copolymerizations) of ethylene, propy-
lene, other a-olefins, and sometimes, dienes. The class of Z-N catalysts
includes transition metal halides (Ti, V, Zr, etc.) complexed with aluminum
alkyls or alkyl halides (Boor, 1979). These catalysts have been developed
to the point that very high rates and yield of polymer (per weight of
catalyst) are obtained (Goodall, 1981). This means that the initial porous
catalyst particle is rapidly fragmented by and buried inside the evolving
polymer.
Interesting morphologies (Boor, 1979) of polymer particles are formed
in this process. How they are formed is incompletely understood, but it
is known that some morphologies are more desirable than others for sub-
sequent processing of the polymer. The morphology of the polymer particle
is obviously very important in regulating diffusion of monomer to the active
site. A very common kind of morphology is one where the polymer particle
is composed of an agglomeration of smaller microparticles, each of which
presumably surrounds a fragment of the original catalyst particle. Diffu -
sion from outside therefore involves moving through the pores of the
macroparticle (between the microparticles) and penetration through the poly-
mer coating of the microparticle to reach the active site.
Several groups have developed diffusion-reaction models for Z-N poly-
merizations, some of which have attempted to account explicitly for the
morphology described above. Stimulus for this modeling has been provided
by the experimental fact that Z-N polymerizations, almost without exception,
produce a broad distribution of molecular weights, even though the chemis-
try at the active site resembles in many ways the anionic polymerization
mechanism and therefore should produce a relatively narrow molecular
weight distribution. Debate has developed about the origin of the broad
Polymerization Reactors 769
molecular weight distribution. Possibilities are that (a) diffusion limitations
produce a variable supply of monomer to different active sites (Schmeal
and Street, 1971; Nagel et al., 1980; Laurence and Chiovetta, 1983); (b)
multiplicity of types and activity of active sites (Caunt, 1981; Keii et al.,
1984; Barbe et al., 1983); and (c) time variation of site activity (i.e.,
deactivation). Diffusion limitations certainly occur, but whether they are
strong enough alone to produce the broad molecular weight distributions
seen is doubtful. Active site heterogeneity and deactivation have both
been documented and are very likely partly responsible for the broad
molecular weight distributions. For example, a recent analysis ( Galvan and
Tirrell, 1985) has shown that the Thiele modulus,
a= ( 146)
where a is a characteristic size of the polymer particle, k is the turnover
rate at the active site, and D is the diffusion coefficient for monomer, must
exceed 10 for there to be significant molecular weight distribution broaden-
ing by diffusion. Data are limited and the model does not correspond ex-
actly to reality in that the chemical mechanism is oversimplified but, speak-
ing approximately, this seems to be on the high end of what might be
found in practice.
Clearly, the relative importance of diffusion limitations will depend on
whether the reaction is occurring in a slurry in liquid diluent or in a gas
phase. Furthermore, Z-N copolymerization, such as that employed to pro-
duce EPDM rubber or linear low-density polyethylene, may experience
diffusion effects on the composition and sequence distributions, even when
the effects on the molecular weight distribution are not particularly impor-
tant.
OPTIMIZATION AND CONTROL
Several unique problems are encountered in the optimal design and control
of polymerization reactors, as discussed briefly earlier. One set of prob-
lems arises from the fact that the performance criteria for such reactors
are not readily defined. Further, such criteria are not universal for a
class of polymerization reactors. Polymerization reactors produce materials
whose quality is assessed in terms of strength, stiffness, processability,
and so on. Even if these ultimate qualities can be reduced to more ab-
stract and readily quantifiable measures (molecular weight distribution,
copolymer composition distribution, sequence distribution), it is unavoidable
that (a) these measures are distributions (or characteristic values thereof)
themselves, and (b) different measures react differently to changes in the
reaction environment. Thus it is not at all apparent at first sight how to
formulate properly a meaningful optimization problem. This problem is
especially severe in the case of copolymerization (Ray and Gall, 1969; Tirrell
and Gromley, 1981; Bejger et al., 1981; Garcia-Rubio et al., 1982). Dis-
tributions of molecular weight, composition, and sequence are all important,
and what optimizes one may degrade another.
Obviously, the informed judgment of a designer is required at some
stage in the optimization process in order to set priorities among objectives
that may be in conflict. The ability to do this relies on accurate information
770 Tirrell, Galvan, and Laurence
about the process from data and modeling. The procedure that has been
used virtually exclusively in polymerization reactor optimization problems
is to formulate a single objective functional which combines all identifiable
performance measures (some of which may be in conflict in the sense that
they react in opposite directions to manipulations of the control variables)
with weighting factors on each measure chosen a priori. This choosing
of weighting factors is one means of exercising judgment.
Several more restricted (i.e., single objective) optimization problems in
polymerization have been treated (Ray and Gall, 1969; Hicks et al., 1969;
Wu et al., 1982). Examination of these cases helps build experience and
an intuitive basis for polymerization optimization. Minimization of the
breadth of the molecular weight distribution in free radical homopolymeriza-
tion has been treated several times. Effective manipulated variables are
addition rate of monomer or initiator and temperature. All of these studies
reach the conclusion that the narrowest possible distribution of molecular
weights is obtained when the reactor produces a constant average molecular
weight at every instant in time. Examination of Eqs. (125) and ( 126) shows
that if initiator concentration is approximately constant, average molecular
weight will tend to decline with increasing conversion because of declining
monomer concentration. Adding monomer can therefore be used to keep
molecular weight constant. Increasing temperature will reduce the in-
stantaneous average molecular weight, so a decreasing temperature policy
could be used to control a downward drift in molecular weight. Even this
simple example, however, demonstrates the types of conflicts inherent in
polymerization reactor optimization: decreasing temperature produces a bet-
ter molecular weight distribution, but at the expense of a slower reaction
and therefore slower production of polymer. Initiator addition can be
effective if conditions are such that initiator concentration is declining
(dead-end polymerization), thereby drifting molecular weight upward.
Copolymerization problems encompass an even larger set of objectives
than homopolymerization. In optimal design and control of copolymerization
reactors, it is useful, indeed important, to understand the trade-offs
among the objectives quantitatively before selecting an "optimum" solution.
Tsoukas et al. (1982) emphasized this in their study of semibatch copoly-
merization. They examined the objectives of simultaneous minimization of
the breadths of the composition and molecular weight distribution using
temperature and monomer feed rate as manipulated variables. The principal
conclusion of their study was that under no circumstances would it be wise
to optimize with the weight very heavily on one or the other of these ob-
jectives. In every copolymerization situation that they examined there was
a policy of adjustment of the manipulated variable (temperature and mono-
mer flow rate) away from the optimum for either individual objective, which
would produce significant improvement in the other objective with very little
damage to the former. The practical lesson is that even when a particular
one of all the possible objectives seems to be dominant, it pays to examine
other relevant objectives to see if some improvement in these can be ob-
tained in addition, at little or no extra cost. This is even more valid if
there are more control variables available to manipulate.
The examples above have been of optimal control designed to combat
drift dispersion, that is, product nonuniformity due to reaction conditions
that change in time. This kind of dispersion occurs in batch reactors
(or with axial position in tubular continuous reactors). There is another
type of dispersion, termed statistical dispersion, about which little can be
Polymerization Reactors 771
done via optimal control. This kind of dispersion results from the poly-
merization mechanism itself and from the reactor in which the polymer is
made. For example, Eqs. (127) and (128) show that 1. 5 is the minimum
possible value of polydispersity for a free radical polymerization. This
could be produced in a CSTR operating at steady state or in a batch re-
actor under time-invariant conditions. Drift broadens the distribution.
Choice of reactor is, of course, another element of polymerization op-
timization. I den tical reactions run in different reactor configurations will
produce products with different molecular weight distributions. This is
easily seen on comparing the results of Table 1 for batch anionic polymeriza-
tion with those of Eqs. ( 7) to ( 9) for anionic polymerization in a CSTR.
The former produces a Poisson distribution, the latter a most probable
distribution. The relative broadening in the CSTR is due to the fact that
flow out of the reactor introduces an effective termination in the reaction
scheme that is absent in ideal batch anionic polymerization. This is one
example of what might be called Denbigh's rule (Denbigh, 1947). This
rule could be phrased in the following way: when the mean lifetime of a
growing chain is long compared to the mean residence time in the CSTR,
the CSTR will produce a broader MWD than the batch reactor. This rule
applies and is borne out in practice in anionic chain-growth and in step-
growth polymerizations. The converse of Denbigh's rule is not always
true. Free radical chain-growth polymerization is an example where the
growing chains are very short- lived compared to the mean residence time.
Here the shift from batch to CSTR usually produces narrowing due to the
elimination of drift dispersion. In the absence of significant drift in the
batch situation, narrowing cannot be achieved in the CSTR since with
such short lifetimes, the growing chains do not have the opportunity to
sense whether they have been made in batch or CSTR. Much work on
other ideal reactor configurations, such as segregated continuous stirred-
tank reactors and recycle reactors, has shown how these modify molecular
weight distribution as well (Mecklenburgh, 1970; Nau man, 1974). Real
reactor behavior can sometimes be represented approximately by these ideal
reactors.
On-line control and optimization is a topic of significant current interest,
facilitated greatly by the rapid evolution of computing equipment. Particu-
lar interest is in adaptive, self-tuning controllers. The idea is to use a
model of the process in the controller. A reduced, aphysical model is
used with parameters that do not necessarily have any physical significance
themselves. However, algorithms are used for continually revising the
parameter values based on comparison of process data with the designed
control trajectory. In this way the parameters of the controller model are
tuned to give optimal performance. This has been shown to be especially
effective for non-steady-state situations where tuning of PID controllers is
difficult. Self-tuning regulators can, however, also be used to set the
gains of PID controllers (Bejger, 1982; Summers, 1985).
On-line optimization requires more computing power and has not yet
been accomplished to any significant extent. This requires a better model
of the process in the on-line computer that can compute updated optimal
control policies based on new data. The problem with this sort of scheme
is not the available computing power, it is the availability of sensors to
monitor the process in an informative way. Currently, on-line data on
polymerization reactors is limited largely to temperatures, crude estimates
of medium viscosity (e.g., agitator motor torque) and perhaps some measures
772 Tirrell, Galvan, and Laurence
of polymer content or conversion (Del Pino et al., 1982). Quantities such
as molecular weight and its distribution, copolymer composition, and se-
quence distribution and particle size distribution in emulsion polymerization
must in turn be estimated from these. Work is progressing on all of these
fronts: on-line light scattering and viscosity for molecular weight, surface
tension and dielectric relaxation for particle size distribution, and gas
chromatography for copolymer composition. On- line gel permeation chroma-
tography for molecular weight distribution remains a desirable but difficult
and distant goal.
REACTOR SELECTION
The polymer "property" that all practicing engineers really strive to opti-
mize is the bottom-line cost per unit production, subject to performance con-
straints. Meeting these performance constraints has been the subject of
most of the first part of this chapter; however, cost can have important
influence on the choice of polymerization reactor. Simplicity and energy
efficiency are major goals along this route.
Considerations beyond cost and polymer product performance enter in
as well. Viscosity of the reaction mixture is a primary consideration. Ef-
ficient mixing depends in part on power input, which in turn depends on
viscosity (Oldshue, et al., 1982). An important caveat here is to take
proper account of possible non-Newtonian rheological properties of the re-
action mixture (Middleman, 1977, Chap. 13). Flow properties largely deter-
mine agitator size, power, and design. Motionless mixers are also an im-
portant possibility to consider (Middleman, 1977, p. 327). Conveying and
pumping equipment must be designed around the flow properties of the re-
action mixture. Extruders can be used as pumps and mixers. In many
cases, the flow properties in the reactor have determined historically the
choice of reactor for particular purpose. The rationale for these choices
is found in the patent literature, which has been reviewed nicely up to the
late 1970s by Gerrens ( 1982).
Separation processes that may have to be accomplished after the poly-
merization reaction can influence the choice of reactor. Two principal
separation operations follow polymerization processes: elimination of mono-
mers or diluents and separation of solid polymer. Devolatilization, to reduce
residual monomer content to negligible levels, is an important example of
the former. Extruders, tower, and wiped film reactors are all used in
processes where devolatilization is a chief concern. There are also many
common design concerns between devolatilization and reactor designs for
driving certain step-growth polymerizations to very high conversion by
removal of condensation product (pressure reduction, surface area regula-
tion). Effective separation of solid product has been one of the important
innovations in certain reactors, such as the Union Carbide fluidized-bed
reactor process for polyolefins. Loop reactors incorporating a settling
portion are also useful for separating solid polymer from slurries.
Temperature and its control are always considerations. Heats of poly-
merization are typically high, as mentioned earlier, so that maintaining de-
sired temperature is not always a simple matter. Temperature can become
spatially nonuniform and globally out of control. The typical consistency
Polymerization Reactors 773
of the reaction medium is again a factor. Normal good heat transfer design
for large heat transfer surface, with coils or corrugated surfaces, is not
effective in polymerization reactors since these surfaces create dead zones
and accumulate material. This can produce nonuniform molecular weight
distribution; foul the heat transfer equipment, exacerbating the heat re-
moval difficulties; and make the reactor very difficult to clean. For these
reasons, smooth heat transfer surfaces are usually preferable, with the
best possible agitation to sweep the fluid clearly over the surface.
An example of these considerations can be seen in high-pressure ethyl-
ene polymerization. This reaction is done commercially in both tubular and
stirred autoclave reactors. Tubular reactors have a high surface-to-volume
ratio, which is good for heat transfer; they have, however, no mixing, which
may produce segregation and inhomogeneity. Stirred-tank reactors have a
comparatively low surface-to-volume ratio, although temperature can be ma-
nipulated somewhat using the feed temperature. Generally, these reactors
have better mixing.
The desired form (pellet, powder, bead, etc.) can influence the re-
actor design. For example, suspension polymerizers produce beads that
may be directly useful in processing. On the other hand, round beads
can be dangerous if spilled and may not have suitable bulk flow properties.
Extruder reactors (Stuber and Tirrell, 1985) are able to produce pellets,
sheets, or coatings quite easily and directly. Safety considerations always
place inviolable constraints on polymerization process design. Venting to
the atmosphere in a safe and environmentally sound manner must always
be designed for. Clearly, the entire process, not exclusively the reaction,
must be considered in any useful polymerization process optimization. The
articles by Platzer (1970) and Gerrens ( 1982) give additional useful informa-
tion and insight into the practical aspects of reactor selection.
CONCLUSION
Polymerization reactors are rich in challenges and opportunities for the
chemical engineer. This richness derives from the complexity of product
distributions in even the simplest polymer reactor, the difficulties of handl-
ing viscous, exothermic reaction masses where informative measurements
are extremely limited, and finally, from the fact that a polymer reactor is
designed to follow a molecular architectural blueprint for a material. Devia-
tion from this blueprint is reflected directly not in the behavior of the re-
actor but in the performance of the material. This is currently a charac-
teristic nearly unique to polymer reactors, but may become an incresingly
important matter to deal with in other materials fabrication reactors, such
as chemical vapor deposition reactors for microelectronics applications.
This chapter, while covering a fair amount of ground, is at best an
introduction to the techniques of analysis and experience on the behavior
of polymerization reactors. In particular, the very important topics of
copolymerization, emulsion polymerization, and varieties of continuous
polymerization have received only superficial attention here. Our hope is
that in the techniques and examples we have presented, the reader will
find the motivation and means to attack new areas of polymerization
engineering.
774 Tirrell, Galvan, and Laurence
NOTATION
initial concentration of functional groups in polycondensation
number-average degree of polymerization
D diffusion coefficient of monomer in polymer
f functionality of reacting mixture (in polycondensation); initiation
efficiency (in free radical polymerization)
G(s, T) generating function for growing chains (see Table 1 for definition)
H(s,T) generating function for "dead" chains
I initiator concentration
k reaction rate constant
M monomer concentration
p conversion of functional groups
P. concentration of growing chains of length j (in polycondensation
J and anionic polymerization); concentration of "dead" chains of
length j (in free radical polymerization)
r stoichiometric ratio
R. concentration of growing chains of length (in free radical
J polymerization)
t time
V volume of polymerizing media
X conversion in free radical polymerization
y normalized generating function , defined in Eq. ( 29)
y normalized generating function for chains with a stopper, defined
X
in Eq. (30)
Greek Letters
a probability of propagation; parameter in Gold distribution; Thiele
modulus, depending on the context
y defined in Eq. (74)
8 Dirac delta function
E fractional change in volume due to reaction
e residence time
kth moment of the MWD of "dead" chains (in free radical polymer-
ization) or growing chains (in anionic polymerization) (see
Table 1 for definition)
kth moment of the MWD of growing radicals in free radical
polymerization
T reduced time, defined in Eq. ( 4)
X defined in Eq. ( 7 4)
Polymerization Reactors 775
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Peebles, L. H., Molecular Weight Distributions in Polymers, Wiley, New
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Penlidis, A.; J. F. MacGregor, and A. E. Hamielec, Dynamic modeling of
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778 Tirrell, Galvan, and Laurence
Soh, S. K. and D. C. Sundberg, Diffusion-controlled vinyl polymerization:
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12
Biological Reactors
LARRY E. ERICKSON Kansas State University, Manhattan, Kansas
GREGORY STEPHANOPOULOS * California Institute of Technology,
Pasadena, California
INTRODUCTION
According to recorded history, some of the first reactors were biological
reactors. Fermentors for the production of alcoholic beverages such as
beer and wine were designed, constructed, and used more than 5000 years
ago (Pederson, 1979, pp. 1-24; Rose, 1959; Amerine, 1964). According
to Pederson (1979, p. 14), the Babylonians made beer as early as 5000-
7000 B .C. The baking of leavened bread may have started in Egypt some
3500 years ago (Pederson, 1979, p. 4). Cheese manufacture also appears
to have been carried out by the Egyptians about 3000 B. C. (Pederson,
1979, p. 6). The science of fermentation advanced significantly in 1857
when Pasteur showed that microorganisms were present and active in fer-
mentations (Aiba et al., 1973, p. 4). Another major advance was the pro-
duction of penicillin in deep aerated tanks during World War II. It was
during this period that Elmer Gaden, the father of modern biochemical en-
gineering, did his Ph.D. research on oxygen transfer to aerobic cultures
(Hixon and Gaden, 1950). Most of the science and engineering advances
in biological reactor design have appeared during the period from World
War II to the present. During this period several books have appeared
in which biological reactor design is an important consideration (Aiba et al.,
1973; Bailey and Ollis, 1977; Pirt, 1975; Wang et al., 1979; Aiba and
Nagai, 1975; and Bekers, 1980). Journals have started which are devoted
to biochemical engineering, such as Biotechnology and Bioengineering, and
many articles on biological reactors are contained in the volumes of Advances
in Biochemical Engineering.
Biological reactors include a wide variety of types, both human-made
and natural. Thus one can find aerobic and anaerobic reactors, well-mixed
or stratified reactors, enzymatic reactors with soluble or immobilized enzymes,
immobilized cell reactors of various configurations, and others that will be
discussed in this chapter. Biological reactor design has been influenced by
several important factors. Strain selections and mutations placed time-
varying specifications on the biological reactors while promoting batch or
*Current affiliation: Department of Chemical Engineering, Massachusetts
Institute of Technology, Cambridge, Massachusetts
779
780 Erickson and Stephanopoulos
fed-batch operation. Rheological conditions may change significantly during
the course of a batch fermentation (van Suijdam et al., 1982). Furthermore,
market forces frequently dictate that the same fermentor be used for the
production of different products by different microorganisms during its oper-
ational life. All these considerations make the problem of optimal design and
operation of bioreactors very important indeed.
Anaerobic reactors are used in the production of ethanol, acetone,
butanol, many food products, and anaerobic waste treatment. Temperature
and pH control are usually important considerations. Reactor design has
received limited attention except for the case of anaerobic digestion, where
mixed culture interactions have been considered extensively (Bailey and
Ollis, 1977; Gould, 1971; Sundstrom and Klei, 1979). A completely mixed
reactor is frequently employed.
The design of aerobic reactors, frequently employed for antibiotic pro-
duction, has primarily considered oxygen mass transfer and oxygen limita-
tion on reactor performance. Gas, liquid, and solid phases are present.
In hydrocarbon fermentations, hydrocarbon transport may also limit growth
(Erickson et al., 1969, 1970, 1975; Shah et al., 1972a,b; Erickson and
Humphrey, 1969a,b; Gutierrez and Erickson, 1978). In aerobic ferementa-
tions in which the organic substrate is insoluble, four phases are important
for biological reactor design. The utilization of solid substrates, such as
cellulose, by microorganisms also requires that transport limitations to
growth be considered (Lee et al., 1980; Avgerinos et al., 1981). Trans-
port and surface area limitations are also important in the bacterial leaching
of ores (Gormely et al., 1975; Chang and Myerson, 1982). In the modeling
of these multiphase growth processes, basic concepts of reaction engineering,
such as residence time, segregation, surface adsorption, transport limita-
tion, and reaction kinetics, have been applied.
Enzymatic reactors is another important category of bioreactors. En-
zymes are presently used and hold a strong promise for future applications
as catalysts of biochemical reactions. In soluble or immobilized form they
are analogous to other homogeneous or heterogeneous catalysts and principles
of reaction and diffusion theories can be applied to optimize bioreactor op-
eration. Enzyme reaction engineering studies have resulted in the develop-
ment of membrane reactors to retain the enzymes (Deeslie and Cheryan,
1982; Cheryan and Deeslie, 1980; and Vieth et al., 1976), fixed-bed re-
actors with immobilized enzymes or immobilized whole cells (Lee et al.,
1976; Vieth et al., 1976; and Tyagi and Ghose, 1982), and fluidized- and
semifluidized-bed reactors (Vieth et al., 1976; Barker et al., 1981; Fan and
Hsu, 1981). Immobilized enzymes have also been used to develop enzyme
electrodes and other enzyme-based sensors in which reactors are used for
instrumentation (Chen et al., 1982; Barker and Somers, 1978). Several
conferences and books have been devoted to enzyme reaction engineering
and the supporting science of enzyme and whole cell immobilization (Wingard,
1972; Pye and Wingard, 1974; Pye and Weetall, 1978; Weetall and Royer,
1980; Wingard et al., 1976, 1980; Zaborsky, 1973).
Media sterilization, enzyme deactivation, and the thermal processing of
foods in canning is another important application of biological reaction
engineering. The activation energy in the Arrhenius expression for temper-
ature dependence of the rate of sterilization is very high (Aiba et al., 1973,
pp. 242-243). Thus high-temperature short-time processing of foods op-
timizes food quality. The design of continuous processes which closely
approximate plug flow requires the application of residence-time distribution
analysis (Aiba et al., 1973, pp. 258-264; Bailey and Ollis, 1977, pp. 551-554).
Biological Reactors 781
There are many different types of biological reactors and biochemical
reactions; however, in many cases, the basic principles of reaction engineer-
ing described in earlier chapters may be applied in designing the reactor
system. To avoid unnecessary duplication, attention will focus on those
aspects that are characteristic of biological systems and processes. The
stoichiometry, kinetics, and energetics of these systems will first be re-
viewed, for they appear to differ from those of simple chemical systems.
Subsequently, the various types of bioreactor configurations will be pre-
sented along with the design equations for the simple ones. Mass transfer
considerations, especially as they apply to oxygen transfer in aerobic
processes and procedures for bioreactor design, will occupy the last two
sections of this chapter. Much of the discussion will be associated with
aerobic microbial growth and product formation, for most of the current
biological reaction engineering research is focused on the optimization of
aerobic fermentation processes.
MICROBIAL GROWTH
The stoichiometry, kinetics, and energetics of a biochemical process must
be known and understood in order to design the reactor system. These
basic concepts as applied to microbial growth processes with product forma-
tion are reviewed in this section. Regularities are introduced because of
the simplification achieved through their application in process analysis and
design.
Stoichiometry and Nutrition
In direct analogy to the case of a single chemical reaction occurring in a
chemical reactor, the processes of growth and product formation are repre-
sented by a chemical reaction in which ammonia (or another nitrogen source)
with a carbon-energy source is converted into biomass, product, carbon
-
dioxide, and water:
+ aNH 3 + bO 2 ybCHpOnNq +
carbon -energy ammonia cell
source (nitrogen source) biomass
( 1)
+ ypCHrOsNt + ydco 2 + cH 2O
product
Reaction ( 1) is true for the case of a single carbon-energy source (or
substrate) and a single product. If complex mixtures of organic substrates
and products are involved, approximate formulas of the type indicated
above are written for the substrate and product. It is further assumed
that cell biomass can be represented by the formula CHpOnNq and that the
biomass composition remains constant during the course of the fermentation.
Although deviations occur, the above is a rather reasonable assumption.
In addition to carbon, hydrogen, oxygen, and nitrogen, on a dry basis,
there is also 3 wt %phosphorus, 1% sulfur, 1% potassium, 1% sodium, less
than 1% calcium, magnesium, chlorine, and iron, and trace amounts of
other elements, such as copper and zinc. All the latter are not represented
in formula ( 1).
782 Erickson and Stephanopoulos
It should be noted that reaction ( 1) is written on the basis of one
carbon atom of substrate. Therefore, Yb• Yp, and Yd give the fraction
of organic substrate converted to biomass, product, and carbon dioxide,
respectively; that is,
Yb + yp +yd= 1,0 (2)
is a carbon balance for the process. Similarly, a nitrogen balance gives
One can also write balances for hydrogen and oxygen involving all
the stoichiometric coefficients of reaction (1). Since the water involved in
the process is not measurable , it is, in general, desirable to eliminate the
stoichiometric coefficient of water c between the hydrogen and oxygen
balances. The result is Eq. ( 4), which may also be interpreted as an
available electron balance (Minkevich and Eroshin, 1973; Erickson et al.,
1978a):
(4)
Equation ( 4) introduces the concept of the degree of reductance of biomass,
product, and substrate, Yb, Yp• and Ys, respectively. The p.egree of
reductance of a substance is defined as the number of equivalents of avail-
able electrons per gram atom of carbon of the substance which would be
transfered to oxygen upon oxidation of the substance to CO2, H 2o, and
NH3. Thus
Yb = 4 + P 2n - 3q (5)
y = 4 + r - 2s - 3t (6)
p
y = 4+ m - 2R- (7)
s
where the valences C = 4, H = 1, 0 = - 2, and N = -3 have been used.
The concept of the degree of reductance is a very useful tool in establish-
ing a unifying treatment of the biological processes of microbial metabolism.
Furthermore, some regularities concerning the degree of reductance of bio-
mass have been observed (Minkevich and Eroshin, 1973; Mikevich et al.,
1977; Erickson, 1980b). By examining various biomass compositions, these
authors found that Yb is relatively constant at an average value of 4. 291
with a coefficient variation of 4%. Another regularity was also observed
concerning the weight fraction of carbon in biomass, Ob. The same
authors observed that ab has an average value of O. 462 with a coefficient
of variation of 5%.
In a typical bioreactor situation the chemical formulas of the substrate
and product are known and that of biomass can be determined by an
elemental analysis. The only remaining unknowns, then, are the stoichio-
metric coefficients of reaction (1), namely a and band Yb, Yp, and Yd•
Notice that these coefficients are directly related to the yields of the
process. The available equations are the carbon balance [Eq. ( 2)] , the
Biological Reactors 783
nitrogen balance [Eq. (3)], and the electron balance [Eq. (4)]. By
measuring the respiratory quotient (i.e., the ratio yd/b) an additional
equation becomes available and the system can be determined in the
absence of product formation. If product(s) is being formed an additional
measurement(s) is needed to close the system. In summary, the balances
above can be used (a) to determine the stoichiometry of a process, in con-
junction with the necessary measurements; (b) to monitor on-line the state
of a bioreactor to provide the appropriate control action (Wang et al.,
1977; Stephanopoulos and San, 1982); and (c) to test the consistency of
measurements (Ferrer and Erickson, 1979) and identify the measurement
that most likely introduces large error (Wang and Stephanopoulos, 1982).
The stoichiometry of a biological process is an important element in
writing the proper macroscopic material balances over a bioreactor, which
is the subject of the following section. However, in addition to mass,
heat is also exchanged in most of the aerobic fermentations. One can
write the following enthalpy balance for the heat of reaction fl. Hr:
fl.H 0 = (fl.H 0 ) - y (1'.H 0 ) - y (1'.H 0 ) (8)
r c substrate b c biomass p c product
where the products of combustion are taken to be C02(g), H20(,Q,), and
NH3 in a dilute aqueous solution, and each of the values of fl. H~ are for
1 atom of carbon.
Equation ( 8) can be utilized in two different ways. If the stoichiomet-
ric coefficients Yb and Yp are known, the heat released during growth can
be calculated and the corresponding cooling requirements determined. Con-
versely, if the reaction heat can be measured, Eq. ( 8) provides an addi-
tional balance for the determination of the unknown yields. The heat of
growth can be measured on-line by using flow microcalorimeters (Eriksson
and Holme, 1973). Alternatively, a correlation may be used that relates
the heat evolved to the amount of oxygen consumed. Thus, approximately,
as shown in Fig. 1,
fl.HO= -27(4b) (9)
r
where fl. H; is in kcal/ g atom of carbon in the substrate. This approximation
is based on the early work of Thornton (1917), Kharasch (1929), and
Kharasch and Sher ( 1925) and the more recent work of Minkevich and
Eroshin (1973), Roels (1981), Cooney et al. (1969), Minkevich et al. (1977),
Erickson et al. ( 1978b), and Patel and Erickson (1981).
For aerobic fermentations the chemical energy per equivalent of avail-
able electrons is about the same for the organic substrate, the biomass,
and the extracellular product. Minkevich and Eroshin (1973) and
Minkevich et al. (1977) found a value of 26. 95 kcal/g equiv of available
electrons ( 112. 8 kJ /Q equiv) for the quantity of energy given up when
dry biomass is oxidized to C02(g), H20(,Q,) and NH3 in a dilute aqueous
solution. Per gram atom of carbon, this yields
( 10)
Now, Eq. (4) can be divided by Ys to yield
E + 17 + Sp = 1.0 (11)
784 Erickson and Stephanopoulos
2400
~ 2000
::l:
E "
0
~
......
0
u
-"
C
0
"iii
:::,
.c
E
0
(.)
0
+-
0
a,
:z:
40
80 100
Equivalents of Available Electrons/Gram Mole
FIGURE 1 Linear variation of heat of combustion of organic compounds
with the number of equivalents of available electrons. (From Patel and
Erickson, 1981.)
where the three quantities E = 4b/ys, n = YbYblYs, and l;p = YpYplYs are
fractions of the available electrons transferred to oxygen, mcorporated into
biomass, and incorporated into extracellular product, respectively. In
view of the regularity mentioned earlier, according to which the chemical
energy per equivalent of available electrons is the same, the quantities
above may also be interpreted as the fractions of substrate energy evolved
as heat, incorporated into biomass, and incorporated into extracellular
products, respectively. In this regard, the electron balance Eq. ( 4) ob-
tains the meaning of an energy balance.
It should be noted that the subject of stoichiometry and yields is
essential in bioreactor design. In biological processes the stoichiometry
is unknown and, unlike chemical systems, may vary during the course of
the process. Consequently, the establishment of the proper stoichiometry,
and the ability to follow any variations on-line, constitute the first objec-
tive in the analysis of a biological process. The second is the determination
of the process kinetics, and this is the subject of the next section.
Biological Reactors 785
Kinetics
The kinetics of biological processes deals with the subject of the determina-
tion of the rates of substrate consumption, biomass growth, and product
formation. Typically, in a chemical reaction, these rates are interrelated
through the reaction stoichiometry. However, the variation of yields in bio-
logical processes complicates the situation.
The starting point is the specific rate of biomass growth, µ. A
variety of models exists of varying degree of complexity. Thus one can
find lumped-parameter models which treat the biomass as one entity,
structured models that distinguish the various types of biomass, segregated
models that recognize the individual nature of each microorganism, and the
possible combinations among them. This discussion focuses on lumped-
parameter models. Various structured and segregated models can be found
in Fredrickson and Tsuchiya ( 1977) and Bailey and Ollis ( 1977). The
typical trade-off with these models is that the number of parameters in-
volved and the mathematical complexity increases dramatically, but more
information becomes available and better dynamic response is achieved.
The lumped-parameter models express the specific growth rate as a func-
tion of key substances of the abiotic medium. To be sure, a large number
of factors affect the growth of a culture. By keeping the concentrations
of all but one above the saturation level, the specific growth rate becomes
a function of the concentrations of this rate-limiting substance. Figures
2 and 3 depict the two basic functional relationships between µ and S.
The characteristics of the function shown in Fig. 2 can be represented
by the rectangular hyperbola of Eq. (12):
!-'-max
1.0 ------------------►
0.8
'.c
::I.. o. 5 JJ-max
o-_._......._____.__......,__.....____.
0 20 40 60 80 100
S(mg;I)
FIGURE 2 Specific growth rate µ plotted as a function of substrate con-
centration s according to the Monad model, where µ max = 1. O h-1 and Ks =
10 mg/L. Note that µ = O. 5 µmax when S = Ks. (From Pirt, 1975, p. 9.)
786 Erickson and Stephanopoulos
Q5
0.4 •
-
"j
....
..c:
0.3
::t. 0.2
0.1
0
0 4 8 12 16 20 24 28
(S Hg acetate/I)
FIGURE 3 Substrate inhibition for growth of Candida utilis on sodium
acetate. (From Aiba and Nagai, 1975, p. 188; Cama and Edwards, 1970.)
µmax 8
µ(S) = (12)
K + S
s
The model is the celebrated Monod model. It is an empirical model, pat-
terned after the Michaelis-Menten kinetics of enzymatic reactions, which
was found to describe adequately the growth kinetics of several microbial
systems (Monod, 1949). This model has also been used repeatedly in a
variety of applications ranging from activated sludge kinetics to the analy-
sis of dynamics of mixed culture systems. It contains the basic features
exhibited by most microbial systems, namely linear dependence at low S
values and saturation at high S values. Furthermore, it is a simple, two-
parameter model and in the absence of indications to the opposite, it is
used to fit data or to study the general dynamic characteristics of a reac-
tor system.
The meaning of the two parameters µmax and Ks is shown in Fig. 2.
These parameters are usually estimated by plotting available data in the
form 1/µ versus 1/S. For many organic substrates the saturation constant
Ks is between O. 1 and 20 mg /L (Bailey and Ollis, 1977, pp. 346, 347; Pirt,
1975, pp. 10-12). Maximum specific growth rates are usually larger for
bacteria than yeast. Values between O. 3 and 1. 0 h-1 are frequently re-
ported; however , both lower and higher values are found (Pirt, 1975, p.
145).
The maximum specific growth rate, µmax, depends on temperature and
pH. Microorganisms are classified as thermophiles, mesophiles, and
psychrophiles with respect to their optimum temperature for growth
(Bailey and Ollis, 1977, p. 344). The optimum temperature for most
mesophylic organisms is about 37°C; as shown in Fig. 4, at temperatures
lower than about 37°C, the common Arrhenius temperature dependence is
observed (Bailey and Ollis, 1977, pp. 132-135, 344; Prokop and Erickson ,
1972). Values of the activation energy have been found to be significantly
different for growth (8. 2 kcal/mol), respiration (17. 8 kcal/mol), and penicil-
lin production ( 26. 8 kcal/mol) for Penicillin chrysogenum (Aiba et al., 1973,
pp. 108-110; Calam et al., 1971).
Biological Reactors 787
Temperature,°C
1.0 50 30 20 10 0
><
0 -1.0
E
::I.
C:
Ot -2.0 A
-3.0
-4.0
-5.0
0.0030 0.0032 0.0034 0.0036
I/T,°K- 1
FIGURE 4 Arrhenius plot for the effect of temperature on the maximum
specific growth rate of a mesophile (E, coli, curve A, E = 25.5 kcal/g mol)
and a psychrophile (Pseudomonas strain 21-3C, curve B, E = 16.2 kcal/g
mol). (Data of Ingraham, 1958,)
As shown in Fig. 5, the optimum pH for growth depends on the or-
ganism. Bacteria frequently grow in the pH range 4 to 8, yeasts grow
in the pH range 3 to 6, molds from 3 to 7, and higher eucaryotic cells
from 6.5 to 7.5 (Wang et al., 1979, pp. 89-90). A rather narrow window
of optimal growth exists around the optimal pH with the growth rate drop-
ping rapidly outside this window. However, there exist organisms, such
as yeast, Escherichia coli, and others, which maintain optimal growth over
a wider pH variation. If it can be assumed that pH affects growth by in -
activating some rate-limiting enzymes through protonation-deprotonation re-
actions, then the primary effect of pH variations is the decrease of \.lmax.
Changes in Ks may also be present, but they are secondary importance.
Temperature and pH control are commonly included in the design of
fermentors.
Some systems exhibit rate inhibition at high substrate concentrations.
This situation is depicted in Fig. 3 and described by the model
).lmaxs
µ(S) = - - - - - - ( 13)
KS + S + s 2 /Ki
Equation (13) has a maximum and exhibits steady-state multiplicity and
very interesting dynamic features when considered in a CSTR situation
(San and Stephanopoulos, 1983).
788 Erickson and Stephanopoulos
1.8 . A
1.6
1.4
'.c 1.2 0.15
'.c
,c
0
E
::I. 1.0 ~-~ ->(
I
' \B\ 0
E
0
u 0.8 I \ 0.10 ::I.
I \ ,n
LL.I ~
0.6 I \ u
I u
0.4 0 0 0.05
0
u
0
>-
.c
0.2 li
~
0 0
4 5 6 7 8 9
pH
FIGURE 5 Effects of medium pH on maximum bacterial specific growth
rates: A, E. coli in anaerobic casein hydrolysate medium (from data
of Gale and Epps, 1942); B, Methylococcus capsulatus grown on methane
(from data of Harwood and Pirt, 1972). (From Pirt, 1975, p.· 145.)
Other models of microbial kinetics have also appeared in the literature.
These models contain various features that occasionally were found to be
important, such as multiple substrate limitation, product inhibition, de-
pendence of µ on biomass concentration, and others. A detailed description
of these models is given by Fredrickson and Tsuchiya (1977) and in tabular
form by Ollis (1977). It should be also pointed out that even though S
usually stands for an organic limiting substrate, it can represent any limit-
ing compound. Johnson (1967), for example, found a value of Ks = 0.0234
mg /L for a Monod model with oxygen rate limiting. Also, expressions com-
pletely analogous to those presented above have been developed for the
velocity of enzymatic reactions.
The rate of nutrient consumption is modeled by the product of the
specific growth rate and the biomass concentration divided by an appropriate
yield. Various possibilities regarding these yields and their variation with
time will be presented when the bioreactor design equations are derived in
a later section.
Product formation is often the objective of carrying out a biological
process. The kinetics of product formation depend on the product or
products that are produced. Some products are associated with the process
of growth, whereas some others are not. The specific (3 per unit amount
of biomass) product formation rate in the first case is proportional to the
specific growth rate; it is constant in the second case of non-growth-asso-
ciated product. Intermediate situations also exist. Leudeking and Piret
(1959) introduced a successful mathematical model which includes all the
foregoing possibilities:
Biological Reactors 789
1 dP (14)
X dt = a + SJJ
The model above has been applied to a number of fermentations where
the parameters a and S, determined experimentally, indicated the extent of
growth association. Some flexibility can be introduced in the model by
providing different parameter values for the different phases of growth.
This certainly extends the applicability of the model but does not alter the
fact that it is an empirical one and results based on this model cannot be
extrapolated in general.
In constructing product formation models with a mechanistic basis, the
classification of the various products in rational categories can be useful.
Gaden (1955, 1959) has proposed a classification scheme which includes
type I products, which are directly associated with primary energy metabo-
lism, such as ethanol; type II products, which are indirectly associated
with primary energy metabolism, such as citric acid; and type III products,
which are complex molecules that are not directly associated with primary
energy metabolism, such as penicillin (Bailey and Ollis, 1977, pp. 371-
375). Wang et al. (1979, pp. 1-45), divide microbial product formation into
biosynthesis of primary metabolites, secondary metabolites, and enzymes
with a fourth category of bioconversions. Primary metabolites are end
products of low moelcular weight that are used as building blocks by cells.
Secondary metabolites are products such as antibiotics which are not re-
quired for growth; they are usually synthesized late in the growth cycle.
Secondary metabolites are usually type III fermentations according to Gaden's
classification. Finally, Deindoerfer (1960), has organized fermentations pat-
terns into four categories, according to the similarity of the formation of
fermentation products to those produced by simple, simultaneous, consecutive,
and stepwise reactions.
In type I fermentations, the last term in Eq. (14) is usually important
and product formation is primarily growth associated. In type II fermenta-
tions, product formation kinetics are frequently complex, with maximum
product formation rates often occurring late in the fermentation at low
specific growth rates.
The rate of product formation, the product yield, and the concentration
of the product in the final broth are important economic considerations.
Product inhibition is an important consideration in many fermentations
because this limits the final product concentration. Pirt (1975, pp. 170-
185) has considered the effect of product inhibition on growth and has
presented the expressions
]Jmaxs
]J = - - - - - - - - (15)
s + K ( 1 + I /K. )
S 1
for competitive product inhibition and
]Jmaxs
]J = - - - - - -+- -- (16)
( S + K )(1 1/K.)
S 1
for noncompetitive product inhibition, respectively. The concentration of
the product which inhibits growth is I, and Ki is the kinetic saturation
790 Erickson and Stephanopoulos
constant. For the production of ethanol, Aiba et al. ( 1968) found that
ethanol inhibits growth by noncompetitive inhibition.
Product formation kinetics have been developed and used in reactor
design and operation for many industrial fermentations. Constantinides
et al. (1970a,b) have used kinetic data for penicillin production to optimize
temperature profiles in batch fermentations to achieve improved yields of
about 15%. Kinetic models for the production of gluconic acid from glucose
have been developed and used to optimize pH and temperature (Constantin-
ides and Rai, 1974). The optimization resulted in improved yields and
rates. Rai and Constantinides ( 197 3) found a time saving of up to 60%
by conducting experiments near the optimal temperature and pH. In these
examples, the kinetic models are first developed and then employed to
optimize batch operation.
One of the deficiencies of the Monod model is its inability to model the
dynamics of growth processes. Structured models in which microbial com-
position is considered are needed to properly represent the dynamic varia-
tions associated with growth which occur because of sudden changes in
environmental conditions. Harder and Roels ( 1982) have recently reviewed
structured models; in much of the work they review, RNA is considered as
a variable in the model. While structured models may be extensively used
in future reactor design work, they have not yet become widely accepted
in industrial practice (Harder and Roels, 1982).
Another developing area which may be much more important in the
future is that of growth kinetic models for mixed cultures. Fredrickson
( 1977) has reviewed the types of interactions and associated dynamics in
mixed cultures. Among others the interaction of competition is receiving
increasing attention and related work is summarized in a recent review
(Fredrickson and Stephanopoulos, 1981). One of the useful kinetic models
of mixed cultures is that of Andrews and Graef (1971), which has been
used in anaerobic digestor control. Bailey and Ollis (1977, pp. 635-743)
present several kinetic models for mixed cultures and discuss mixed cul-
ture applications. Harrison (1978) point out that the number of mixed
cultures in commercial use which are well studied and understood, and
deliberately constituted, is extremely small. Fredrickson and Tsuchiya
(1977) have reviewed mixed culture kinetic models including much of their
own work.
Energetics
In the design of a fermentation process, the energetics must be considered
and energy balances must be made for the process. Aerobic processes may
be limited by the availability of carbon in the organic substrate or by the
quantity of energy in the organic substrate (Erickson, 1981; Linton and
Stephenson, 1978). Figures 6 and 7 show the variation of the biomass
carbon yield, Yb, and the biomass energetic yield, n, as a function of the
reductance degree of the organic substrate. For low values of Ys, these
results show that the growth process is energy limited; however, at a value
of Ys above 4, the results indicate that the availability of carbon becomes
important. For example, Veselov et al. (1974) reported substantially larger
yields with CO2 in the gas fed to the fermentor where n-alkanes were
used as the organic substrate (Ys = 6.1). Figures 6 and 7 are for growth
processes without product formation; the process of product formation may
also be carbon limited or energy limited (Erickson, 1981).
Biological Reactors 791
0.7 00
0
0
0.6
0.5
0.4
>,Sl
0.3
0.2
0.1
o.o
0 2 3 4 5 6 7 8
FIGURE 6 Variation of biomass carbon yield with reductance degree of
organic substrate. (From Erickson, 1981.)
0.7
0.6
0.5
0,4
(::'"
0.3
0.2
0.1
o.o
0 2 3 4 5 6 7 8
ys
FIGURE 7 Variation of biomass energetic yield with reductance degree of
organic substrate. (From Erickson, 1981.)
792 Erickson and Stephanopoulos
The energetics of growth and product formation may be viewed as a
process in which available electrons in the organic substrate are rearranged
into available electrons in biomass and products with similar energy per
available electron. Energy in the form or ATP is used to achieve the re-
max max
arrangement. The parameters YATP and Yp / ATP are measures of the
quantity of biomass and product, respectively, that can be formed from
organic substrates per mole or ATP. Thus, under energy-limited growth
conditions, the maximum biomass energetic yield (Erickson, 1980c), n ,
max
and the maximum product energetic yield, s;ax, are related to Y~~ and
Y;~TP and the efficiency by which ATP is formed (P /0) by
(17)
max
(opyp/12)YP/ATP
!;max=-----~~------------ (18)
p max
(op yp/12)YP/ATP + {2/[(P/O)s + (P/O) 0 ] }
(P/O) is the gram moles of ATP high-energy bonds formed per gram atom
of oxygen consumed and the subscripts s and o refer to substrate-level
phosphorylation and oxidative phosphorylation, respectively. For glucose
as the organic substrate, the theoretically estimated value of Y~;; = 28. 8 g
of cells/mol ATP may be used with the value of 3.167 mol of ATP/g atom of
oxygen for (P /O)s + (P /0) 0 to obtain nmax = O. 88 as the theoretical maxi-
mum biomass energetic yield for aerobic growth with glucose as the organic
substrate (Erickson, 1980c; Stouthamer, 1979). For polysaccharide produc-
tion from glucose, Erickson (1980c) has found a maximum product energetic
yield of !;max = 0. 95. Actual yields should be smaller than the theoretical
p
maximum yield.
By using available electron concepts, Erickson (1979) obtained the fol-
lowing expressions for the energetic yields in terms of nmax, me, and
!;max.
p .
1 1 me sp
= - - + - +--- (19)
n nmax µ /;"max
n,P
max 1 - n m
-
E:
=--- - + _!!_
µ
+ (20)
n
d 1 - (ys/yb)nmax m 1 - (ys/yp)s;ax
e
= + µ- + ~ ( 21)
n nmax n !;max
p
Biological Reactors 793
These equations may be used with parameter estimation methods to estimate
n , m , and /;max from experimental data. The parameter, n , is the
max e p max
true growth yield based on that fraction of the available electrons in the
organic substrate that are associated with growth, /;max is the true product
p
yield based on that fraction of the available electrons that are associated
with product formation, and me is the maintenance parameter.
Values of the parameters nmax and me have been estimated for micro-
bial growth processes without product formation ( Solomon et al. , 1981,
1982; Ferrer and Erickson, 1979, 1980). Equivalent parameters have also
been estimated by others (Pirt, 1975, p. 69; Stouthamer, 1979; Heijnen
and Roels, 1981). Erickson ( 1980a ,c), Erickson and Hess ( 1981), and
Oner et al. (1983) have considered the true product yield /;max in estimat-
p
ing yield parameters. Solomon et al. (1982) and Oner et al. (1983) have
developed parameter estimation methods in which all the data are used
simultaneously in estimating parameters.
TYPES OF BIOLOGICAL REACTORS
Stirred Tanks
Well-stirred reactor systems have traditionally been employed for carrying
out the great majority of fermentation processes. Providing a homogeneous
reactor environment has not been always an easy task. Large residence
times in continuous operation or batch operation are certainly positive fac-
tors in maintaining a liquid phase that is well mixed with respect to the
nutrients. On the other hand, the large size of these reactors and the
complex and time-varying rheological behavior of a multiphase reaction sys-
tem make homogenization in these reactors an energy consuming and, in
general, difficult proposition. Nevertheless, very large ( 200 m3) fermenta-
tion vessels have been built and operated in the pharmaceutical, food,
and chemical industries mainly because of the relative simplicity in their
design and operation.
Because of the need to avoid mutations and maintain the superior
qualities of the genetically developed strain, batch or fed-batch operations
are the rule in most applications. The intrinsic property of continuous
reactor systems to select for the best grower and not for the best product
producer has hindered the expansion of continuous operation. Neverthe-
less, continuous culture operations are of great interest in research
laboratories, for they provide a time-invariant environment at steady state
which facilitates greatly the study of a biological process. Furthermore,
some industrial operations employ continuous reactors, such as the single-
cell protein facility of ICI in Billingham (total reactor volume of about
2300 m3), all waste treatment processes, and others. It should be noted
that it is relatively common to follow a batch process with a period of fed-
batch or continuous operation. Also, batch cultivation is the optimal start-
up procedure for continuous cultivation or fed-batch cultivation in most
cases (Yamane et al., 1979).
Recently, many batch operations have been transformed into fed-batch
(semicontinuous) by introducing the nutrient gradually into the reactor in-
stead of charging everything at the beginning of the operation. The ration-
ale is to optimally control the feed to maximize a composite performance index.
794 Erickson and Stephanopoulos
F ( t)
F max
/ X = Xmax
s* s
(a) (b)
FIG URE 8 Schematic representation of an optimal fed- batch operation:
(a) mutual disposition of specific growth and product formation rates;
(b) feeding schedule. Smax is the maximum substrate concentration allowed
to prevent undesirable side reactions. Xmax is the maximum cell concentra-
tion allowed by mixing and oxygen transfer requirements.
For the case of penicillin fermentation, for example, for which the specific
growth rate and the specific penicillin formation rate are mutually disposed
as shown in Fig. 8a, the optimal feed policy is shown schematically in Fig.
8b. According to this strategy, the fermentation is carried out in two
phases. During the first, cell biomass is built up to the maximum level al-
lowed as quickly as possible. The second is a product formation phase
during which the feed is controlled as an optimal level of high penicillin
production and sufficient biomass growth to make up for the dilution effects.
Other advantages of fed-batch operation include flexibility in the introduc-
tion of growth factors, deliberate variation of the feed concentration, and
similar control actions.
The mass balance equations for all three modes of operation are as
follows:
dX
dt = µX - DX (22)
dS µX (a+ Sµ)X
dt = D(S
o
- S) - - - - mX
ymax s ymax
( 23)
s P/S
dP
dt = -DP + (a+ Sµ)X ( 24)
where D is the dilution rate-equal to zero for batch operation and to F /V £
for continuous operation and for fed-batch operation (notice that in the
latter case, F = dV £/dt),
Biological Reactors 795
In aerobic fermentations a continuous airstream flows through the re-
actor to provide the necessary oxygen for growth. Balances for the liquid-
and gas-phase concentrations of the two main gaseous components, oxygen
and carbon dioxide , are as follows:
dC
0
= (k a')(C* - C ) - Qo X DC + DCf (25)
dt L o o 2 0 0
(26)
in
V dpo Qinpo Qoutpo
_g_ = --- - (k a') (C* - C )V (27)
RT dt RT RT L o o o t
in
V dp Qinpc QoutPc
_g_ C
= + (k La') C (C C - C*)V (28)
RT dt RT RT C R,
where Q02 and Qc 02 are the specified oxygen uptake and carbon dioxide
evolution rates, respectively, defined by
= __μ_ a+ Sµ ( 29)
+ m + ----''--'-
ymax o
0
_ _µ_ a+ Sµ
(30)
max + mD + max
YD YP/D
The dilution rate D in Eqs. (25) and (26) is defined as before. The
values of the non-growth- and growth-associated product formation coef-
ficients, a and S, respectively, depend on nutrient concentration, tempera-
. max max max
ture, and pH. The true growth yield parameters, Y , Y , and YD ,
S 0
are related to the true biomass energetic yield parameter, Tlmax, as has
been shown by Erickson ( 197 9) . The maintenance parameters , ms , m0 ,
and mD, are also related because of the stoichiometry of the maintenance
process (Erickson, 1979; Erickson et al., 1979). Erickson (1979) has also
max max max
shown how the true product yield parameters, Yp IS, Yp /O, and Yp /D, are
related to the true product energetic yield, E;max.
p
A stoichiometry difficulty associated with the use of the Luedeking and
Piret model for product formation in the previous equations has been dis-
cussed by Fredrickson and Tsuchiya ( 1977). These authors point out that
products come from some precursors. If the precursor is the growth-limit-
ing substrate, then, according to Eq. ( 24), product is formed at a finite
rate even after the precursor has been exhausted and is not present in
the system. If the precursor is the biomass itself, this should be accounted
for by adding a sink term in Eq. (22). In either case, some modification
796 Erickson and Stephanopoulos
is needed in the equations or the parameters if the models above are going
to be valid during all phases of growth and product formation.
Steady-state operation can be achieved in a continuous culture system.
The steady-state concentrations of biomass, substrate, product, Oz, and
CO2 in the liquid phase are obtained by setting the left- hand sides of Eqs.
(16), (22), and (26) equal to zero. The possibility of multiple steady
states exists, especially for the more complicated models of the specific
growth rate. Fredrickson and Tsuchiya (1977) have analyzed the dynamics
of various pure and mixed culture systems. Stephanopoulos (1980) pre-
sented a method for quickly analyzing the dynamics of two-population mixed
culture systems. This method makes use of topological arguments and
Poincare index.
Various modifications and extensions of the previous model equations
have appeared in the literature. The purpose of this work has been two-
fold: first, to model various departures from the ideal situation of a per-
fectly mixed vessel, such as wall growth, film formation, and incomplete
rmXJ.ng. Second, to describe some interesting process or hardware con-
figurations, such as cell recycle, vessels in series, film reactors, and so
on. Some of this work has been reviewed by Ollis (1977).
Other Design Considerations
The design equations of the preceding section were developed with the
assumption of well-mixed liquid and gas phases. Even though macroscopic
mixing is a good assumption, microscopic mixing is often hard to achieve.
Dunlop and Ye (1982) have pointed out that in many fermentors the smallest
turbulent eddy has a size of about 50 µm. This, contrasted with an average
size of about 1 to 2 µm for a bacterium, indicates that various cells may
be enclosed in an environment where nutrients are rapidly depleted. In-
creasing the power input has a minimal effect, for the size of the smallest
eddy is inversely proportional to the one-fourth power of the energy input.
The same authors conclude that the length scale of turbulence and the
rates at which eddies are being created and destroyed must be quantified.
Supplying sufficient oxygen and removing the produced carbon dioxide
in the case of aerobic fermentation is probably the single most important
issue in fermentor design. Various air supply mechanisms, impeller de-
signs and modifications of the bioreactor interior (baffles, etc.) have been
proposed to facilitate the transport of these gases. Much of the develop-
ment in this area is proprietary.
The equilibrium concentration ci is usually provided by applying
Henry's law as the phase equilibrium relationship:
P ::: H C* ( 31)
0 0 0
with H0 being the Henry's law constant for oxygen (Perry and Chilton,
197 3, pp. 3- 98; Schumpe et al. , 1978). Similarly, for carbon dioxide,
p ::: H C* ( 32)
C C C
where He is the Henry's law constant for carbon dioxide (Stumm and
Morgan, 1970, p. 148; Perry and Chilton, 197 3, pp. 3- 96).
Biological Reactors 797
Carbon dioxide in the liquid phase is present as dissolved CO 2 , H2co 3 ,
Hco 3-, and co;-. The fraction of bicarbonate and carbonate ions which
are present at equilibrium depends on pH (Stumm and Morgan, 1970, pp.
118-129). At low pH and up to pH 5, most of the CO2 is present as dis-
solved CO2; for the pH range 7 to 9, the bicarbonate ion is strongly
favored, and at pH 11 and above the carbonate ion is strongly favored, as
can be deduced by considering the equilibrium constants:
= 10-6.3 ( 33)
= 10-10. 3 (34)
at 30°C (Pirt, 1975, pp. 76-77; Stumm and Morgan, 1970, pp. 148-150).
Under gas /liquid-phase equilibrium conditions, the total quantity of carbon
in the liquid phase is given by
( 35)
increases with pH above 5 for fixed concentration of CO 2 in the gas phase
as shown in Fig. 9.
Under co;nditions where the bicarbonate ion in the broth is being con-
verted to H2CO3 and the H2CO3 to CO2+ H2O, the rates of chemical reac-
tion should be considered. The reversible chemical reaction
is very fast and may be at equilibrium. Kern (1960) gives a value of
= 2,5 X 10- 4 ( 36)
for the equilibrium constant at 25°C. The chemical reaction
is much slower. Kern (1960) reports average values of k1 = 20 s-l and
k2 = 0.03 s- 1 at 25°C, with activation energies of 16.5 and 15 kcal/mol,
respectively (Stumm and Morgan, 1970, p. 153). If both dissolved CO2
and bicarbonate ion are present within the cell and both diffuse through
798 Erickson and Stephanopoulos
a:::
~
0
::::E
z
0
~
a:::
1-
z
I.LI
u
z
0
u
Cl
.9
4 5 6 7 8 9 10 II
pH
FIGURE 9 Aqueous carbonate equilibrium constant Pco 2 • Water is
equilibrated with the atmosphere (Pco 2 = 10- 3• 5 atm) and the pH is ad-
justed with strong base or strong acid. (From Stumm and Morgan, 1970,
p. 127.)
the membrane rapidly, the bicarbonate ion will need to be converted to
H2CO3 and the HzCO 3 to CO2 in the bulk liquid as a part of the CO2
removal process .
It is clear from the published literature that rate processes associated
with CO2 removal from the broth may be of interest in some industrial
fermentations (Ishizaki et al., 1971a-c, 1973; Barford and Hall, 1979;
Yagi and Yoshida, 1977). Because of rate limitations, concentrations of
CO2, H2CO3, and HC03 may substantially exceed the values that would be
in equilibrium with the exhaust gas from the fermentor.
As microbial cultures are very sensitive systems, they pose high de-
mands on the monitoring and control capabilities of a bioreactor. A
schematic of the instrumentation available for on-line bioreactor monitoring
is shown in Fig. 10. Off-line analysis by liquid chromatography or en-
zymatic assay methods can also be employed for the measurement of sub-
stances associated with the process of growth as substrates or products.
Presently, on-line measurement is basically limited to off-gas analysis (0 2
and CO2) by mass spectrometer or paramagnetic O2 and infrared CO2
analyzers, and to the concentrations of dissolved oxygen and carbon
dioxide. These measurements can be utilized together with the elemental
balances developed earlier to provide on-line estimates for the reactor state
variables, which, in turn, can be used for control or other purposes.
Biological Reactors 799
IBIOCHEMICAL REACTOR INSTRUMENTATION I
[
SHAFT POWER IMPELLER SPEED
Torsion dynomometer (external)] [Generator -type tachometer
RPM \ as V ! but impeller
l
l
Strain gouge meosur. (internal)
tip speed is the some rrD(RPM)
FEED RATE
pH REDOX
Drop count
[ Addition vessel on load cell Glo~reference] [Combined Pt and reference]
[ El t d electrode (measurement
Electromagnetic flowmeter ec ro e hard to interpret)
FOAM DETECTION Interaction with DO.
Capacitance PRESSURE
l
Conductance [Simple /
CONTROL: diaphragm DISSOLVED OXYGEN
Mechanical system gouge
Polorogrophic sterilizoble electrode]
Silicone emulsion ontifoom ] [
0 2 +4H++4e--2H 20
Oil based (sterility problems)
TEMPERATURE
Thermometer bulb]
[ Thermocouple PRODUCT REMOVAL
Thermistors
Overflow, level control,]
[
VISCOSITY load cell.
Shaft
---
Power
FG-GAS FLOW RATE
~
TURBIDITY
Spectrophotometer
[ Biomass measurement
(not for dense cultures)
l
Rotometers ] Paramagnetic 0 2 anal.]
[ [
Moss flowmeters Electrochemical cell SENSORS UNDER DEVELOPMENT
pC0 2 Glucose
Ethanol
[ IR ono lyzer] * =
+ -t+ + +
NH 4 , Mg , K , No , Cu , P0 4
ATP, ADP, AMP
DNA, RNA
NADH
FIGURE 10 Schematic of biochemical reactor instrumentation. Temperature
and pH controls are not shown. Viscosity measurements can be obtained
from the slope of the shaft power versus time graph. Redox measurements
are usually hard to interpret.
800 Erickson and Stephanopoulos
On- line, automated microanalytical methods, as well as various enzyme
probes , are presently being developed for the purpose of providing the
means for monitoring many other reactor variables on-line.
Bioreactor control is presently concerned with the control of the abiotic
culture environment as the latter is described by the temperature, the pH,
the dissolved Oz concentration, and the presence of foam. All the fore-
going parameters are maintained at set points which are optimal for the
process. Manipulative variables are the coolant flow rate for the tempera-
ture, the rate of an acid or alkali addition for pH, agitation speed and
gas flow rate for dissolved Oz, and mechanical foam breakers or agent
addition for foam. In fed-batch operation the feed rate of nutrients is also
controlled according to a predetermined schedule or on-line measurement or
estimate. Certain interaction exists between the various control actions,
but the multivariable control characteristics of these systems has not been
studied. Most of the control is presently carried out by local analog con-
trollers. However, as the reactor systems and processes grow more com-
plex and the monitoring-estimation capabilities increase, more sophisticated
control policies are expected to be introduced in bioreactor operation.
Other Bioreactor Designs
Although the stirred tank has been employed extensively in the past, it is
considered inadequate for more demanding applications. The main factors
against it are technical, but there are also economic and biological reasons
for developing novel bioreactor schemes (Schiigerl, 1982b). Schiigerl
(1982b) summarizes the main reasons for the introduction of new bioreactors
as (a) the inability of stirred-tank scaleup to very large size because of
design difficulties and heat removal problems, often accompanied by high
power requirements and high energy and utility costs; (b) reduction of
specific energy and capital costs; (c) avoidance of cell damage; and (d)
increase of yields and reduction of substrate losses.
Information on these new systems is scarce. Most of the available
knowledge comes from laboratory and pilot plant units and is summarized in
a comprehensive review by Schiigerl (1982b). The discussion below follows
his paper.
The various types of bioreactors are classified into the following
categories according to the method of energy introduction:
1. Reactors with mechanically moved internals
2. External liquid pumping
3. Reactors with gas compression
The tranditional submerged-culture stirred tanks belong to the first
category (Fig. 11). They can have various types of agitation without
( 1. 1) and with ( 1. 2) loop. Other types are mechanically stirred loop reac-
tors (1.3); self-aspirated aerated reactors without (1.4) and with (1.5) loop;
mechanically stirred, self-aspirated, aerated, horizontal loop reactors ( 1. 6);
cascade reactors with rotating mixing elements (1. 7), with axially moving
mixing elements ( 1. 8), or with pulsating liquid ( 1. 9); and finally surface
reactors such as thin-layer reactors (1.10), disk (1.11), and paddlewheel
reactors ( 1. 12).
Types of reactors in which the energy input is by means of an external
pump are shown in Fig. 12. Such submerged-type reactors include plunging
Biological Reactors 801
G G
SB LR LR
G 1.3 G 1.3
With overflow Overfilled
/
/
I
' I
1 . ~- • SZ
_..,,..,..... M
1.4
M-Motor
G-Gas (Air)
1.5
SZ-baffles
LR-conduit tube M Motor
d' 1.6
LR-conduit
SZ-Foam breaker 1-Self-gas agitator
·~
G G Gas (Air)
G
' '
G G
,]}~~
Pulsation W-Roller
1.8 1.9 1.10
i
G G
1.12 1.,,
FIGURE 11 Biochemical reactors in which energy input is by mechanically
moved internals. (From Schiigerl, 1982b.)
802 Erickson and Stephanopoulos
6 G
G G
G
F
F
F G 2.9
2l
6
G
G
ID-Injector nozzle 2.7
GAS SEPARATOR 1.6 SK-Float
FIGURE 12 Biochemical reactors in which energy input is by circulation
using an external pump. (From Schiigerl, 1982b.)
jet reactors (2.1), jet-loop reactors (2.. 2), plunging-channel reactors (2.3),
nozzle loop reactors ( 2. 4), perforated-tray or sieve-tray cascade reactors
(2.5), tubular-loop-reacto rs (2.6), reactors with rotating injector nozzles
( 2. 7), packed-bed (percolating) reactors with counterflow of the phases
( 2. 8) , and bubble column, downflow reactors ( 2. 9). Packed-bed reactors
can also be classified as surface reactors.
The third category, shown in Fig. 13, includes submerged-type reac-
tors in which the energy is introduced by means of compression. In this
category, along with the simple single-stage bubble column ( 3.1), are the
single-stage mammoth loops with centrally arranged draft tubes ( 3. 2), ex-
ternally attached tubular loops ( 3. 3), vertical partition wall ( 3. 4), and
downflow loop ( 3. 5). Between the loop reactors ( 3. 2 and 3. 4) and the
downflow loop reactors ( 3. 5) there is, of course, a certain overlapping.
Bubble columns with static internals belong to this group, including con-
current bubble columns with stage-separating trays ( 3. 6), concurrent
Biological Reactors 803
G G G
r '
G G 3.3 G
G
=1l
ijj
F
G F F G
F
3.4 3.5 3.6
G G
G
3.9
1. Gas valve
2. Static mixer
Valve 1 is periodically opened and closed
F
3.7 3.8
FIGURE 13 Biochemical reactors in which energy input is by compression.
(From Schiigerl, 1982b.)
bubble columns with static mixers (3. 7) and mammoth loop reactors with
stage-separating trays ( 3. 8), and bubble columns with stage-separating
trays with external tubular loops filled with static mixers and with pneu-
matically imposed liquid pulsation ( 3. 9). Schiigerl ( 1982b) also provides
tables with the characteristics of these reactors and references for more
details.
MASS TRANSFER IN AEROBIC FERMENTATIONS
In multiphase processes with chemical reactions, it is common for mass trans-
fer to be an important consideration. The transfer of oxygen to aerobic
cultures and the transfer of carbon dioxide from the culture to the exhaust
gas are probably the two most important mass transfer considerations in
804 Erickson and Stephanopoulos
biochemical engineering. Oxygen transfer from the gas phase into the
liquid phase has been the subject of much research (Moo Young and Blanch,
1981; Schiigerl, 1981; Aiba et al., 1973, pp. 163-217; Bailey and Ollis,
1977, pp. 411-496). The high viscosity of many fermentation broths has
been one of the important reasons for this research. With bacteria and
yeasts, oxygen transfer from the gas phase to the liquid phase is often
the most important mass transfer consideration; however, it is relatively
easy to design industrial equipment in which the desired mass transfer
rates are achieved. As the size of the microorganism increases, oxygen
transfer from the liquid phase to the microorganism becomes more important.
For mold fermentations, it is important to consider oxygen transfer both
from the gas to the liquid and from the liquid to the microbial biomass.
For mold pellets, transport within the pellet is also important.
The transport of CO2 from the broth and the transport of 02 to the
broth should both be considered in the analysis of the mass transfer
associated with an aerobic fermentation. The sa,me gas flow rate is common
to both of these processes. Furthermore, the pressure in the fermentor
affects the dissolved 02 and CO2 concentrations, but in opposite directions.
Increasing the pressure enhances oxygen transfer, but it negatively influ-
ences the rate of CO2 release.
Mass Transfer Coefficient
Mass transfer in gas-liquid systems is treated in detail in Chapter 10. In
addition, mass transfer in biochemical reactors is reviewed by Moo Young
and Blanch (1981). In most fermentors, the mass transfer coefficient in
the liquid phase depends on the Sherwood, Grashof, and Schmidt numbers
because the density difference is the dominant force that causes fluid
motion between the bubble and the liquid. For small rigid bubbles less
than 2.5 mm diameter (Calderbank and Moo Young, 1961; Calderbank,
1958, 1959, 1967),
Sh= 2.0 + 0.31Gr 113sc 113 ( 37)
and for bubbles greater than 2. 5 mm in diameter which are much less
rigid,
Sh = 0.42Gr 113sc 112 ( 38)
where
kLdb
Sh = D (39)
3
dbpLg(pL pg)
Gr = ( 40)
2
]JC
]JC
Sc = pD ( 41)
Biological Reactors 805
Equations ( 37) and ( 38) appear to be applicable to a wide variety of geom-
etries and mixing configurations because the density difference causes
fluid motion near the gas-liquid interface. Fukuda et al. (1978, 1979) have
measured kL in an airlift fermentor and a perforated plate column and
found that Eq. (38) with a constant of 0,50 instead of 0.42 fits their data
very well. This small difference may be due to some properties of the
solutions which are not considered in the correlations and experimental
error.
Equation (37) may also be used to estimate mass transfer coefficients
to microbial biomass. For bacteria and yeast, the expression Sh = 2. 0
provides a useful estimate of the mass transfer coefficient. This expres-
sion shows that mass transfer coefficients are relatively large for very
small objects such as bacteria and yeasts. For mold pellets and other
suspended particles with densities close to that of the continuous phase
where agitation in a stirred mixing vessel creates the dominant force for
relative fluid motion between the phases (Calderbank, 1967)
( 42)
where P /V is the power per unit volume supplied by the agitator.
Surfactants are frequently present in fermentors. Surfactants provide
a barrier for diffusion through the film at the interface; they also act to
give the bubble more rigidity. The mass transfer coefficient may decrease
significantly because of surfactants (Aiba et al., 1973, pp. 184-185).
Swarms of bubbles and non-Newtonian liquid phase flow behavior also
may affect the value of the liquid-phase mass transfer coefficient. Correc-
tions for these factors have been reviewed by Moo Young and Blanch (1981)
and Schiigerl ( 1981).
Interfacial Area
The gas-liquid interfacial area is an important variable in aerobic microbial
growth processes. Because the interfacial area is affected by a large num-
ber of physical properties and other variables, very few correlations that
accurately predict the interfacial area under fermentation conditions are
available. However, knowledge of the effect of various physical properties ,
equipment designs, and operating conditions on the interfacial area is of
considerable importance. The bubble size distribution and the gas-phase
holdup or volume fraction are directly related to the interfacial area per
unit volume of dispersion; that is,
6s
a = __[ (43)
d
s
where sg is the gas phase volume fraction and ds the Sauter mean bubble
diameter;
806 Erickson and Stephanopoulos
d = ( 44)
s
The bubble size frequency distribution, fi, depends on the physical proper-
ties of the broth, equipment design, and operating conditions. Equation
( 43) shows that changes in gas holdup as well as changes in the bubble
size distribution will result in changes in the interfacial area.
The bubble size distribution depends on the gas-liquid interfacial ten-
sion; liquid-phase density, viscosity, and ionic strength; gas flow rate and
holdup; gas distributor; rate of turbulent energy dissipation; and equip-
ment design. The chemical composition of the liquid phase also appears to
be important. Calderbank ( 1967) measured bubble size distributions and
interfacial areas in stirred tanks and sieve tray columns. Recently,
Bhavaraju et al. ( 1978) investigated the effects of viscosity and turbulence
on bubble size and interfacial area. Schiigerl (1981) has reviewed the
literature with respect to bubble size interfacial area and mass transfer in
highly viscous broths. The sparger or gas distributor design and the gas
flow rate through the sparger determine the initial bubble size distribution
in the region of the sparger. For moderately high gas flow rates, Bhavaraju
et al. (1978) found that
d
s = 3 23R -0.lF 0.21 ( 45)
d • eOL ro
0
where d 0 is the nozzle diameter and
(46)
is the orifice Reynolds number based on the volumetric flow rate through
the orifice, Q 0 , and orifice diameter, do. The orifice Froude number is
Fr ( 47)
0
The rate of coalescence influences the bubble size distribution. The
ionic strength and chemical composition of the broth significantly influence
the coalescence frequency and the bubble size distribution (Schiigerl, 1981;
Schiigerl et al., 1978; Zlokarnik, 1978); however, equations that properly
incorporate these variables into expressions for the interfacial area or bub-
ble size distribution for fermentation broths are lacking. This is especially
true for high-viscosity broths.
The level of turbulence greatly influences bubble breakup throughout
the fermentation broth. As viscosity increases a point is reached where
bubble breakup due to turbulence is unimportant. Bhavaraju (1978) have
used the criterion that the scale of the energy containing eddies should be
Biological Reactors 807
200 times larger than the scale of the energy dissipating eddies for turbu-
lent breakup to be important. They found that
<J0.6 (µL)0.1
d = 0.7 - - - - - - ( 48)
s (P/V)0.4p~.2 µG
for the Sauter mean diameter in a gas sparged vessel when turbulent break-
up was important. For mixing vessels with agitators, Calderbank ( 1967)
found that
d = 2.25 ( 49)
s
Schiigerl (1981) found that in viscous fermentation broths small bub-
bles have too long a mean residence time in the broth. As equilibrium con-
ditions are approached, the concentration driving force decreases and oxygen
transfer from the small bubbles to the liquid slows considerably. Renewal
of these small bubbles is very important in highly viscous broths. The
vertical circulation pattern of the airlift fermentor and various multistage
column designs may help achieve improved small bubble renewal rates; how-
ever, further investigation is needed. Because some of the interfacial area
is not effective, Schiigerl has chosen to show correlations in terms of the
combined volumetric mass transfer coefficient.
A number of expressions have been presented for the gas holdup in
aerated mixing vessels (Calderbank, 1967; Hughmark, 1980; Bailey and
Ollis, 1977, p. 436; Aiba et al., 1973, p. 178). For bubble columns,
Hikita et al. ( 1980) and Moo Young and Blanch ( 1981) have recently re-
viewed the literature on gas holdup. Schiirgel (1981) has divided the hold-
up in viscous media into that associated with very small bubbles and that
associated with intermediate and large bubbles. He has presented the re-
sults in a series of graphs.
The interfacial area may be obtained using· expressions for the gas
holdup, Eg, and the Sauter mean bubble diameter, ds, in Eq. ( 43) or by
using correlations for interfacial area. Calderbank ( 1967), Hughmark
(1980), Moo Young and Blanch (1981), and Joshi et al. (1982) have pre-
sented correlations for interfacial area, for example. However, because of
the difficulty of obtaining correlations in which all the important variables
are included, most fermentor design is carried out using correlations in-
volving the volumetric mass transfer coefficient.
Volumetric Mass Transfer Coefficient
It is important to realize that two different volumetric mass transfer co-
efficients are commonly found in the biochemical engineering literature for
gas-liquid mass transfer. The interfacial area per unit volume of gas-
liquid dispersion, a, and the interfacial area per unit volume of liquid, a' ,
are related; that is ,
a'(l - s ) = a (50)
G
808 Erickson and Stephanopoulos
Equation ( 43) leads directly to the interfacial area per unit volume of
dispersion, a; however, in studies where the liquid phase is completely
mixed and the quantity of oxygen added to the liquid phase is measured,
kLa' arises naturally, as shown in Eq. (25), for example. In reviewing
the literature, one must be very careful to determine if the results pre-
sented are for kLa or kLa'.
The flow models selected for data analysis should also be examined in
reviewing data in the literature. The correctness of estimates of the
volumetric mass transfer coefficient depends on the selection of proper flow
models which appropriately fit the experimental system when significant
variations in concentration occur with position.
Bubble Columns
In bubble columns [Fig. 13, (3.1)] the energy to provide turbulence and
bubble breakup is contained in the entering gas; that is, the power
RT P1
P = QP -In - (51)
G M p2
is directly related to the volumetric gas flow rate Q. The volumetric mass
transfer coefficient kLa has been correlated by Akita and Yoshida ( 1973,
1974), who found that
kLdt d _ O SS 0.5B 0.62G 0.31 1.1 (52)
~ a t - . c o a EG
where the Bond number is
and the Galileo number is
These authors also correlated the gas holdup and found
EG 4 = 0.20Bo0.125Ga0.083Fr (53)
(1 - EG)
where the Froude number is
Fr=
Biological Reactors 809
with ua the superficial gas velocity. These two correlations were tested
in large-diameter bubble columns using CO2 and water and it was found
that the effect of column diameter disappeared above about O. 60 m. For
diameters above O. 60 m, the authors and Kataoka et al. ( 1979) recommended
using 0.6 min Eqs. (52) and (53). The authors recommend using these
correlations for superficial gas velocities up to 1500 m /h and gas holdup
up to 30%. These equations are for dispersions in which the viscosity is
sufficiently low for turbulence to play a dominant role in determining the
bubble size distribution and interfacial area. Liquids up to O. 21 poise
were considered by the authors.
Deckwer (1981) has tested Eq. (52) using some of his data and other
literature data (see Fig. 14). He concludes that the correlation is good in
some cases, but that with some spargers larger values of kLa are found.
The effects of salts and organic substances on coalescence are not included
in the correlation.
Schiigerl et al. (1977) have investigated gas holdup, interfacial area,
and mass transfer in bubble columns for a wide variety of model fermenta-
tion media using porous plate, perforated plate, injector nozzle, and ejector
nozzle gas distributors. They point out that higher volumetric mass trans-
fer coefficients than those predicted by Eq. ( 52) can be achieved by using
distributors that produce a bubble size distribution in the entrance zone
which is smaller than the equilibrium bubble size distribution associated
with the turbulence due to the energy dissipation from Eq. ( 51). Additional
energy is required at the distributor to produce these small bubbles. Un-
der the conditions of their experiments, the holdup, interfacial area, and
"'
0
..J
....:
D ( S )0.5( )0.62( 0.31 I.I
2 c Bo Ga) E G
dt
FIGURE 14 Volumetric mass transfer data of Towell et al. (1965) for dt =
40.6 cm, 6; Deckwer et al. (1974) for dt = 20 cm, □; Kastanek (1977)
for dt = 100 cm,◊; and Kataoka et al. (1979) for dt = 550 cm, Oplotted
against the correlation of Akita and Yoshida (1973) using dt = 60 cm for
the larger-diameter columns.
810 Erickson and Stephanopoulos
volumetric mass transfer coefficients varied significantly with the various
media selected. Deckwer (1981) points out that these results are not well
correlated by Eq. ( 52) .
Moo Young and Blanch ( 1981) have reviewed mass transfer correlations
for bubble columns and found that volumetric mass transfer coefficients are
directly proportional to the superficial gas velocity. These results are for
low viscosity broths in which turbulence plays an important role in deter-
mining the bubble size distribution. As viscosity increases, a point is
reached where the behavior at the gas distributor becomes more important
(Bhavaraju et al., 1978). This occurs as the scale of the energy dissipat-
ing eddies becomes larger. At higher viscosities, the results for bubble
columns are not in good agreement. Henzler (1981) correlated the data
of Buchholz et al. (1978a,b) for a 3. 9-m-high bubble column with 0.14-m
diameter for apparent viscosities ranging from 46 to 217 mPa •s. The re-
sult is ( see Fig. 15)
-0.9
0. 06 [ -u~. 333] (54)
(gv)
Deckwer et al. (1982) point out that values of kLa' predicted by this ex-
pression are at least five times larger than those predicted by Nakanoh and
Yoshida (1980). The results of Deckwer et al. ( 1982) for aqueous carboxy-
methyl cellulose ( CMC) solutions are correlated by the equation
kLa = 2.08 x 10-4u0.59µ- -0.84 ( 55)
G
,n
d
0,01 0.1
(
uG
0.333
)2
(gv)
FIGURE 15 Bubble column data of Buchholz et al. (1978a,b) as correlated
by Henzler (1981) to obtain Eq. (54). For aqueous solutions with the fol-
lowing apparent viscosities: 0, 46 to 65 mPa •s; ■, 64 to 95 mPa •s; v, 92
to 140 mPa•s; •, 109 to 172 mPa•s; and □, 130 to 217 mPa•s.
Biological Reactors 811
where ua is mean superficial gas velocity in cm /s and µ is the apparent
viscosity in Pa •s. This correlation predicts results which are smaller than
those of Nakanoh and Yoshida (1980). There are significant differences
which may explain these results. Buchholz et al. (1978a) used a sintered
plate sparger with a mean hole diameter of O. 0175 mm, while Deckwer et al.
( 1982) used a sintered plate with 0. 20-mm holes. The results of Deckwer
et al. (1982) and the results of Voigt et al. (1980) for CMC solutions are
in fairly good agreement for gas velocities above 2 cm /s. Plates of O. 5-,
1.0-, and 3.0-mm hole diameter were used by Voigt et al. (1980) in a
multistage column; however, only one stage was used for the experiments
with CMC. Henzler (1980) correlated the results of Voigt et al. ( 1980) to
obtain:
k La , = C uG
0.6 -1.03
v ( 56)
or
-0.4
k a ( 2 0. 333
_l_ ~) Sc0.5 = 0. 075[ UGO. 33} ( 57)
UG g (gv) J
The results of Deckwer et al. (1982) and those of Buchholz et al. (1978a)
show that the design of the gas distributor may be important for viscous
solutions.
The measure of Bhavaraju et al. ( 1978) for the existence of an internal
subrange in the energy spectrum of turbulence is
0.25
(;) ( 58)
where 1 / nT should be larger than 200 based on their data. Table 1 shows
values of 1 / nT for some of the experiments of Deckwer et al. ( 1982). Some
of the values of 1 /nT at high gas superficial velocity and low CMC concen -
tration are greater than 200. This suggests that turbulence should be
important. However, at 1. 3 and 1. 6 wt % CMC, 1/nT is less than 200 at
all superficial velocities investigated. The form of Eq. (55) suggests that
turbulent forces are important in the experiments of Deckwer et al. ( 1982).
The exponent of 0. 59 for superficial velocity shows that the power input is
important; however, the value of the exponent is smaller than the value
of about 1. 0 for low-viscosity broths. The dependence on viscosity differs
from that found by Akita and Yoshida in Eq. ( 52). Equation ( 55) may be
contrasted with Eq. ( 54) where the distributor appears to have significantly
affected the bubble size distribution. In Eq. ( 54) , kLa' is proportional to
the O. 1 power of superficial velocity.
Viscoelastic fluids in bubble columns have been considered by Hecht
et al. (1980) and Nokanoh and Yoshida (1980). The correlation of Nakanoh
and Yoshida is
( 59)
812 Erickson and Stephanopoulos
TABLE 1 Ratio of the Scale of
Energy-Containing Eddies to
Energy- Dissipating Eddies for
Bubble Column Experiments of
Deckwer et al. ( 1982)
Superficial
gas velocity CMC Ratio
(cm/s) (wt %) 1/nT
0.4 1 139
1.0 1 185
2.0 1 229
3.0 1 260
4.0 1. 3 167
0.4 1.6 55
2.0 1.6 103
4.0 1.6 135
where the Deborah number is De = ub;>._/ds, where ub is the bubble rise
velocity, A the characteristic time of the viscoelastic material, and ds the
Sauter mean bubble diameter. In Eq. ( 59), kLa is proportional to the
superficial gas velocity to the 1.0 power. This may be due to the fact
that Nakanoh and Yoshida used a single nozzle that was 4 mm in diameter
in their 14. 55-cm-diameter column. Under these conditions, almost all of
the surface area must be generated by turbulent forces.
Airlift Columns
Airlift tower fermentors (several different designs are shown in Fig. 13)
have received considerable attention during the last 15 years. The vertical
liquid circulation that occurs because of the upflow and downflow sections
of the airlift column helps to keep surface-active agents distributed through-
out the broth. The cocurrent upflow section is similar to a bubble column
in some respects; however, the cocurrent liquid flow influences the two-
phase flow behavior. The transition from bubble flow occurs at a much
larger superficial gas velocity in an airlift fermentor then in a bubble
column (Hatch, 197 3). Because of this, the power dissipated per unit
volume in the upflow section of the airlift can be considerably greater
under bubble regime operating conditions compared to an aeration tower.
Blenke ( 1979) has reviewed his work and that of others in airlift reactors,
jet loop reactors , and propeller loop reactors ; he has shown that forced
liquid circulation may be used to increase substantially gas holdup and
interfacial area. Correlations for liquid circulation rate, gas holdup, and
volumetric oxygen transfer coefficient have been presented by Bello et al.
(1981); for oxygen transfer,
Biological Reactors 813
(P /V) 0. 8
G
( 60)
where bis 0.000507 for water and 0.000502 for 0.15 M NaCl solution, Po
is the power (watts), V is the total reactor dispersion volume (m3), and
Act/Ar is the ratio of the area of the downcomer to the riser. Blenke
(1979) found that the interfacial area per unit volume of liquid, a', in-
creased with power per unit volume of liquid in the bubble flow regime; to
correlate his data in the bubble flow regime, exponents ranging from O. 85
to 1. O are needed on power per unit volume. At superficial gas velocities
above about 30 cm /s, the dependence on power per unit volume decreases;
this may be due to slug flow. Orazem and Erickson ( 1979) found that the
oxygen transfer coefficient increased linearly with superficial gas velocity
in a two-stage airlift tower. Hatch (197 3) correlated the volumetric mass
transfer coefficient for the up flow region, head region, and downflow
region. At the same sparger gas flow rate, the highest volumetric mass
transfer coefficients are in the head region; those in the draft tube are
slightly higher than those in the downflow region. Moo Young and Blanch
(1981) have reviewed some of their own work and that of Lin (1976) and
found a slightly greater dependence on gas superficial velocity with values
of the exponent ranging from 1. 06 to 1. 29.
Hatch ( 197 3) has shown that volumetric mass transfer coefficients in
the head region are approximately twice as large as those for an aeration
tower under similar sparger gas flow rates. In the downflow section the
gas holdup must be less than that in the upflow section because the liquid
circulation rate depends on the difference in dispersion density between the
two regions. The most common operating condition results in a liquid circu-
lation rate sufficient to entrain small bubbles but not large ones in the
liquid downflow. Under fermentation conditions where coalescence rates are
relatively small, the bubbles in the downflow appear to be segregated with
little coalescence occurring. Very little attention has been directed to re-
search in the downflow section of the airlift fermentor (Orazem et al.,
1979, 1980). Blenke (1979) and Fujui et al. (1980) have investigated some
related cocurrent downflow phenomena.
The effect of viscosity on oxygen transfer in airlift biological reactors
has received very little study. Several investigators have used airlift
fermentors and obtained good results under viscous conditions (Konig et al. ,
1982; Malfait et al., 1981; Barker and Worgan, 1981); however, further re-
search is needed to better appreciate the oxygen transfer limitations as-
sociated with high viscosity in an airlift fermentor. Because higher values
of power per unit volume may be obtained in an airlift compared to a bubble
column, the airlift column should be superior to a bubble column under
high-viscosity conditions.
The effect of the ratio of the downflow area to upflow area on oxygen
transfer has been investigated by Hatch (1973, 1975). Based on the per-
formance ratio, the optimum area ratio is about O. 8.
Columns with Motionless Mixers
As shown in Fig. 13, multistage columns with sieve plates, columns with
Koch motionless mixers, and columns with other stationary internals that
814 Erickson and Stephanopoulos
promote mixing have been investigated (Schiigerl, 1982b). Kitai et al.
(1969, 1972) showed that volumetric mass transfer coefficients in multistage
perforated plate columns were larger than those in aeration towers at high
superficial gas velocities. The column internals help to maintain bubble
flow conditions by removing large bubbles and slugs. K. Hsu et al. (1975,
1977) investigated oxygen transfer in multistage columns with sieve trays
and with Koch motionless mixers; they found that Koch mixers and perfor-
ated plates gave fairly similar results. For both, the performance ratio
was higher when column internals were employed compared to an aeration
tower. These results are very much in agreement with those given above
for bubble columns, where it was pointed out that the gas distributor
could positively influence the volumetric mass transfer coefficient.
Columns with Koch motionless mixers and liquid circulation have been
considered by Fan et al. (1975), H. Hsu et al., (1975a), and Wang (1977).
Wang ( 1977) has developed correlations for the volumetric mass transfer
coefficient which includes the superficial liquid velocity UL, as well as the
superficial gas velocity ua ; he found for 7 AY whole Koch mixers that
u
kLa = 0.120u 0 · 624 G ( 61)
L 1. 99uG + 47. 1
where kLa is in units of s - l and the superficial velocities are in cm /s.
Vertical circulation within the fermentor is often needed to distribute sur-
face-active agents which are carried to the liquid surface by air bubbles.
Foaming problems were encountered in early designs which did not allow
for vertical circulation. Considerable research and the commercial applica-
tion of columns with motionless mixers has been reported in Latvia. This
work has been reviewed by Viesturs et al. (1980, 1981). Better oxygen
transfer efficiencies are reported for 100-m3 columns with stationary inter-
nals.
Schiigerl and coworkers have investigated oxygen transfer in multi-
stage columns with perforated plates at low viscosity (Voigt and Schiigerl,
1979, 1981) and high viscosity (Schiigerl, 1981; Schiigerl et al., 1982a;
Voigt et al., 1980; Hecht et al., 1980). The optimum spacing between
stages depends on the coalescence rate of the bubbles. For rapid rates of
coalescence, the bubble size distribution generated by the distributor needs
to be renewed more frequently, and a shorter distance between plates is
suggested (Voigt and Schiigerl, 1979). For slow rates of coalescence, bub-
ble size distributions generated by the distributor are retained for a longer
time; under these conditions the contribution of the distributor to oxygen
transfer can be greater. Under actual fermentation conditions larger
volumetric mass transfer coefficients are found for the multistage column
(Voigt and Schiigerl, 1981).
Appropriate correlations that account for the contributions of both the
distributor and bulk turbulence to the interfacial area and volumetric mass
transfer coefficient are lacking. The effect of coalescence must be con-
sidered in order to relate the bubble breakup at a gas distributor to the
volumetric mass transfer coefficient throughout the fermentor. The power
dissipated at the gas distributor should also be considered. Zlokarnik
( 1978, 1979) has correlated the volumetric mass transfer coefficient with
the power of a liquid jet of an injector nozzle. He has found ( Zlokarnik,
1978) that
Biological Reactors 815
p /V ] 0. 8
\))0.33 [
k a' ( - = 0.00023 4L0.333 ( 62)
L 2
g p(vg )
or that the volumetric mass transfer coefficient is proportional to the
power per unit volume to the 0. 8 power. Blenke (1979) has also shown
that power supplied at the nozzle of his jet loop reactor should be con-
sidered in correlating interfacial area; that is,
(
p )0. 66
a = 5. 4 x 10 3u~· 4 ~ · (63)
where a is in m- 1, u 0 is in m /s, and PL /V is kW /m 3 of dispersion volume.
Zlokarnik ( 1979) has shown how the coalescence rate influences the volumet-
ric mass transfer coefficient in large-scale systems with injector nozzles.
Mechanically Agitated Systems
Mechanically agitated fermentors (Fig. 11) with air sparged into the vessel
below the agitator are widely used in industry. Volumetric mass transfer
coefficients for such systems have been reviewed by Moo Young and Blanch
( 1981), Joshi et al. (1982), and Schiigerl ( 1981). Moo Young and Blanch
( 1981) and Joshi et al. ( 1982) have presented tables of correlations for the
volumetric mass transfer coefficient from the literature. The agitation power
per unit volume, the superficial gas velocity, and the physical properties
of the broth affect the volumetric mass transfer coefficient. Miller (197 4),
Zlokarnik (1978), Yagi and Yoshida (1975), and Henzler (1980), for example,
have investigated volumetric mass transfer coefficients in agitated vessels.
Yagi and Yoshida developed the correlation
= 0.060 (dtN:f (d(fl9 (~;J:"5
5
( 64)
x (
µ u )0.6(Nd
: G u:) 0.32
[l + 2 (AN)o.5 1-0.67
using both Newtonian and non-Newtonian fluids. The dimensionless groups
are the modified Sherwood number, impeller Reynolds number, Froude num-
ber, Schmidt number, gas flow number, aeration number, and Deborah
number. Henzler (1980) developed the correlation
kLa'VL 0.3 PG Jo. 5 (65)
Q
Sc = 0.045 [ 0 _667
QpL (gv)
using data for water, glucose, and glycerin. For aqueous CMC solutions,
he found that
816 Erickson and Stephanopoulos
p 0.6
kLa'VL
=0.082[ G 0.6671 (66)
Q
QpL(gv) j
Zlokarnik (1978) has examined the effect of coalescence on the volumetric
mass transfer coefficient in agitated vessels.
DESIGN OF BIOLOGICAL REACTORS
There are many factors that must be considered in the design of biological
reactors. Providing the desired environment for the microbial population
at reasonable cost may be accomplished with an available fermentor or by
design of a new fermentor. When a new fermentor is designed, many more
decisions must be made. Decisions that may be made with an existing
mechanically agitated fermentor include the agitation rate, the gas flow
rate, the operating pressure in the fermentor, the liquid volume, the
nutrient composition of the feed, pH, temperature, method of foam control,
and mode of operation (batch, fed batch, or continuous). For a new fer-
mentor , equipment design must also be considered. In both cases, the
rate of oxygen transfer in aerobic fermentations is usually one of the im-
portant concerns.
Economic considerations must be carefully considered in the design
process. Some of the important costs include the capital costs for equip-
ment, the cost of organic substrates and other nutrients, energy cost for
aeration, cooling water or refrigeration costs, product separation costs,
waste treatment costs, and personnel costs. An economic optimum exists
because of the following considerations: The rate of the fermentation
process should be high to reduce fermentor capital costs; however, aera-
tion and cooling costs increase as the rate increases. Microbial growth is
usually most efficient at relatively high specific growth rates. Cell and
product concentrations should be as large as possible to reduce separation
costs; however, aeration, cooling, and nutrient costs (yield) must also be
considered. An optimum gas flow rate and operating pressure need to be
selected in the design process. For a given production rate of the product,
t)J.e net present value of the capital and operating costs should be minimized.
Mechanically Agitated Fermentors
The design of mechanically agitated fermentors is treated by Aiba et al.
(1973, p. 171), Bailey and Ollis (1977, p. 443), and Wang et al. (1979, p.
157). Relationships between the power number, P = P/p N 3d 15 , and the
no c
impeller Reynolds number for agitated liquids are presented in Fig. 16.
Recently, Schiigerl (1981) has presented similar graphs for non-Newtonian
viscous broths. Hughmark (1980) correlated the gassed to ungassed power
ratio and found that for flat- blade turbine impellers,
(67)
Biological Reactors 817
100
SIX-BLADE TURBINE:
., H
RUSHTON BATES
,,.-o 10
z
~u
a:: SIX-BLADE PADDLE_i_S
II.I
III
:I!
:::,
z FOUR-BLADE PADDLE:
a::
II.I
~
a..
PROPELLER:
O. I.._____._L....J.....L.JL..J..L....__...,___._...L..L....L.J..L.Ll.~2-..__....._.L..L...u...L.LL~3-,__...,__L-L.~L.LL.---'----'-_._......__....... 5
+
I 10 10 10 10
Nip
REYNOLDS NUMBER =
FIGURE 16 Correlation of impeller Reynolds number and power number
for different impellers in ungassed liquids. (From Wang et al., 1979,
p. 160.)
Other correlations have been presented by Luong and Volesky ( 1979),
Hassan and Robinson (1977), and Oyama and Endoh (1955). Luong and
Volesky (1979) and Schiigerl (1981) have investigated non-Newtonian CMC
solutions, while Haasan and Robinson investigated electrolytic solutions.
Joshi et al. ( 1982) has recently reviewed the available correlations and
has recommended the correlation of Hughmark ( 1980), which is presented
above.
For a mechanically agitated fermentor, the optimal design for continuous
production of microbial biomass is considered to illustrate the economic de-
cisions that must be made. The specific growth rate µ, the biomass concen-
tration in the fermentor X, the agitation speed N, and the gas flow rate Q,
may be considered as independent decision variables which are to be selected
to minimize the net present value of capital and operating costs per unit of
biomass produced. The biomass energetic yield n is related to the specific
growth rate,
m
1 e
= + µ- (68)
n
and the mass yield is Y s = Os y s n / crb Yb in units of grams of biomass per
gram of organic substrate. The oxygen transfer rate may be found from
the available electron balance to be
818 Erickson and Stephanopoulos
µX = ( 69)
y
0
where Y0 is grams of biomass produced per gram mole of oxygen consumed,
and µ X /YO is gram moles of o 2 transferred per unit volume of liquid per
unit time. The heat that needs to be removed is directly related to the
oxygen transfer rate; that is, Q0 = 112. 8 kJ /equivalent of oxygen or
451.2 kJ/g mole of oxygen; thus
17)µX
451.2 ~x = (70)
1217
0
For Monod kinetics, the exit organic substrate concentration is
μKs
s =----- (71)
11max - 11
and from the yield equation X = Ys<S 0 - S),
X
so= y + S (72)
s
The computational sequence is as follows for a desired productivity rate
P 1 , where
(73)
where F is the liquid volumetric flow rate. First, values of the independent
decision variables µ and X are selected. Then 11 and Ys are found using
Eq. ( 68). Next, the oxygen transfer rate
k a'(C* - C ) = µX (7 4)
L o o Y
0
is calculated using Eq. ( 69). Equation ( 70) is used to estimate the heat
to be removed per unit volume per unit time. The volumetric liquid flow
rate may be found using Eq. (73). Since the specific growth rate equals
the dilution rate, the required liquid volume is
F
V = - (75)
L 11
Equations (71) and (72) may be used to find the organic substrate concen-
trations S and S0 •
From the required liquid volume, the total dispersion volume may be
estimated using the relationship
( 76)
Biological Reactors 819
where the gas holdup e:a is to be estimated initially and calculated more
precisely later from the expression (Hughmark, 1980)
(77)
where the bubble diameter db may be estimated from available correlations,
such as Eq. (49).
The dimensions of the fermentor may now be selected; the height-to-
diameter ratio, the number of impellers, and the type of impeller are in-
dependent variables. The gas flow rate and the agitation speed may also
be viewed as independent variables which may be optimally selected based
on economics. The gas flow rate must be more than sufficient to supply
the oxygen needs of the fermentation; that is, for air,
RTµXVL
Q. ~ ----
m 0.21p. Y
1n o
For 30% consumption of oxygen, for example,
(78)
Qin= (0.3)(0.2l)p. Y
1n o
The optimization of oxygen transfer efficiency in the agitated vessel for
the required oxygen transfer rate involves selecting the height-to-diameter
ratio, number of impellers, type of impeller, gas flow rate, and agitation
speed. For standard impeller designs, this fixes the impeller diameter
and allows one to find the power number using Fig. 3 and the calculated
impeller Reynolds number. The ungassed power P may then be found from
the power number. The gassed power may be found from Eq. (67). Equa-
tion (64) or (65) may be used to calculate the volumetric mass transfer
coefficient, kLa'. Equation (74) may now be used to calculate the driving
force (C; - C0 ), where the dissolved oxygen concentration C0 is usually
chosen to be small; that is, about 0.03 m mol/L or less. Henry's law re-
latesCci to the total pressure p and the gas-phase oxygen mole fraction
y; that is,
yp = HC* (79)
0
The mean mole fraction of oxygen in the exit gas is found from the gas-
phase oxygen balance,
( 80)
For a completely mixed gas phase, the mole fraction oxygen in the fermentor
equals the exit mole fraction, and the required total pressure may be
820 Erickson and Stephanopoulos
calculated using Eq. (79). This is the average pressure within the dis-
persion.
The capital costs, operating costs , and net present value of the costs
per unit of productivity may be calculated. The separation costs depend
primarily on the liquid flow rate F and biomass concentration X. The fer-
mentor costs depend on the total dispersion volume V, the pressure p, ,nd
the number of agitators. The size of the agitator motor and the power
costs associated with it may be determined. The size of the gas compressor
and the power requirements may be determined. The cost of heat transfer
may be determined from the cooling requirements. The cost of organic
substrate may be determined using the quantity of substrate FS0 per unit
time.
The optimization problem involves selecting the values of the independent
variables so as to minimize the net present value of the costs per unit of
productivity. Thus values of specific growth rate, biomass concentration,
height-to-diameter ratio, number of impellers, type of impeller, impeller
speed, and gas flow rate may be varied in the search for an economic
optimum. Of these variables, the height-to-diameter ratio, number of im-
pellers, and type of impeller would probably be selected based on prior
experience.
The example above is presented to illustrate how the many variables
are related to each other in fermentor design. The simplest flow models
have been used by assuming complete mixing in both phases. For the gas
phase a flow model composed of two completely mixed tanks in series may
be more appropriate (Joshi et al., 1982). The assumption of complete mix-
ing of the liquid phase is appropriate. For simplicity, the possibility of
CO 2 inhibition is not included.
Bubble Columns
When a bubble column is designed to be used as an aerobic fermentor,
several important considerations should be taken into account. The super-
ficial gas velocity should be selected such that the bubble two-phase flow
regime is present. The pressure gradient due to the liquid head should
be taken into account in the design. Axial dispersion should be considered.
The effect of segregation may be important because small bubbles have
longer residence times than larger bubbles and they also have greater inter-
facial area per unit volume than large bubbles. The gas-phase molar flow
rate may change with position due to gas absorption; howeve1-, in carbo-
hydrate fermentations the respiratory quotient is nearly unity and the molar
flow rate is approximately constant.
The design of bubble columns has been considered by Deckwer (1976,
1977) and Deckwer et al. (1974, 1977). Shah et al. (1978) have reviewed
axial dispersion or backmixing in bubble columns and other gas-liquid re-
actors. Deckwer (1976, 1977) has presented mathematical models which
take into account axial dispersion and the pressure gradient. Deckwer
recommends including the effect of the pressure gradient when the pressure
at the bottom of the column is more than 30% larger than the pressure at
the top above the liquid phase. Deckwer (1977) found that the effective
value of the volumetric mass transfer coefficient was smaller in large indus-
trial-scale bubble columns compared to smaller columns. Segregation
could account for this. Despite the limitations of Deckwer' s success, the
approach used has considerable merit; however, computationally, numerical
solution of the system of differential equations is required.
Biological Reactors 821
A simpler, less exact approach is to consider dispersion of oxygen in
the axial direction in the liquid phase and either a complete mixing or plug-
flow model for the gas phase. The complete-mixing model is a conservative
one since the exit gas-phase mole fraction of oxygen is used for the entire
vessel. If gas-phase segregation is important, some bubbles will have a
lower mole fraction of oxygen than the value predicted by the complete-
mixing model. Since the liquid-phase superficial velocity is zero (or close
to zero), the oxygen balance is taken to be
( 81)
where X is the height above the bottom of the column:
PTY
C* = [l+a(l-z)] ( 82)
0 H
0
and
( 83)
is the ratio of the liquid head to the pressure at the top of the column,
PT . The boundary conditions are
dC
dx
0
= o. at x =0 and x =L
A dimensionless distance x = x /L and dimensionless concentration c = Co /C oT
*
may be introduced, where c;T = pTy/H 0 is the liquid-phase oxygen con-
centration in equilibrium with the gas phase at the top of the column. The
dimensionless groups
DL
Bl =--- ( 84)
L 2kLa'
and
µX
B2 =Y k a'C*
( 85)
o L T
appear in the dimensionless expression
c = B - 1 - a+ ax (86)
2
822 Erickson and Stephanopoulos
which has the solution
( 87)
where
Ml
o:(e - 1)
(88)
( 89)
and
(90)
Figure 17 shows the effect of dispersion in the axial direction on the
dimensionless dissolved oxygen profile along the length of the column for
o: = 1 and B2 = 1. Figure 17 is also a plot of
A1 -M 1x A 2 M 1x
C
e + -e + 1 - x (91)
0: 0: 0:
for all values of o: and B2 in which c > 0 for x = 1. Note that zero-order
kinetics are used for the dependence of µ on c;
that is , as long as c > 0,
the specific growth rate does not depend on the dis~olved oxygen concen-
tration. The column should be designed such that c > 0 at the top of the
column.
Values of the axial dispersion coefficient DL have been correlated by
Deckwer et al. (1974, 1982) and others (Shah et al., 1978). Deckwer
et al. ( 197 4) found that
( 92)
where units of centimeters and seconds are used.
A design methodology analogous to that used for mechanically agitated
vessels may now be visualized. Four independent variables may be
optimally selected based on economic considerations. The specific growth
rate, µ , and biomass concentration, X, may be selected as independent
variables if continuous biomass production is again considered as the exam-
ple of interest. Complete mixing is assumed for the organic substrate and
biomass in the column; this should be appropriate unless it is necessary to
consider the dispersion of the organic substrate fed to the column.
After values of \1 and X are assumed, values of n and µ X /Y 0 may be
found from Eqs. ( 68) and ( 69). The rate of heat removal may be found
Biological Reactors 823
1.0
QSO
~ Q60
C\J
(I)
+
0:40
lu
0.20
0.60 0.80 1.0
x
FIGURE 17 Effect of axial dispersion and pressure gradient on dimension-
less dissolved oxygen concentration in a bubble column. The parameter is
~ L 2kL a' /DL .. Results are limited to conditions where c ;;,, 0.
using Eq. ( 70) and the organic substrate concentrations from Eqs. ( 71) and
(72). The liquid flow rate may be found from Eq. (73) and the liquid vol-
ume from Eq. ( 75). The fraction of oxygen in the gas phase which is con-
sumed and the superficial gas velocity may be selected as the other two
independent variables. The oxygen balance for a constant molar flow rate,
nT'
µXVL
( 93)
y
0
may be used to find nT. A trail-and-error iteration is required at this
point since the pressure, column diameter, and gas superficial velocity are
all related to the molar gas flow rate. Assuming a pressure, the column
diameter may be found from the relationship
The gas holdup may now be estimated from an appropriate correlation such
as Eq. (53). The total dispersion volume may be found from Eq. (76) and
824 Erickson and Stephanopoulos
the height L of the column may also be found. The volumetric mass trans-
fer coefficient kLa' may be found from an appropriate correlation, such as
Eq. ( 52) . The axial dispersion coefficient DL may be found using Eq. ( 92) .
The value of cat x= 1 may be found from Eq. (87) and compared to the
desired value. The trial-~nd-error iteration involves adjusting the pressure
until a desirable value of c is obtained. The optimal values of µ, X, ua,
and y are to be selected based on economic considerations.
Airlift Fermentors
Airlift fermentors have a well-defined loop for liquid circulation which is
driven by the gas flow. The liquid circulation rate depends on the design
of the airlift column. The extent to which the gas is separated from the
liquid at the top of the column prior to entering the downflow section can
significantly affect the liquid circulation rate. In the work of Hatch (1973)
and Gutierrez and Erickson ( 1977), for example, the dispersion enters the
downflow section with more gas than can be carried downward by the liquid.
Some of the large gas bubbles must rise against the downflow of the disper-
sion and escape. It is necessary for this to happen because the average
gas velocity is much smaller than the liquid velocity in the downflow section,
and only a fraction of the gas in the dispersion entering the downflow re-
gion can be carried downward. For this disengagement process to occur,
the actual liquid velocity in the downflow section must be larger than the
rise velocity of small bubbles and smaller than the rise velocity of large
bubbles; that is, it should be about 10 to 30 cm /s. Hatch (1973) reported
superficial liquid velocities ranging from 10 to 30 cm /s and Orazem et al.
(1979) reported values ranging from 17 to 21 cm/s. Hatch (1973) points
out that the liquid circulation velocity increases with gas superficial velocity
in the upflow section until the liquid circulation velocity is limited by the
gas bubble disengagement process at the top of the downflow section. Fur-
ther increases in gas superficial velocity lead to liquid recirculation within
the up flow section similar to that found in bubble columns.
Hsu and Dudukovic (1980) and Merchuk and Stein (1981b) have investi-
gated the liquid velocity in airlift columns, but in both cases the design
was such that the downflow section was almost free of gas. Merchuk and
Stein found that the actual liquid velocity could be correlated with the
superficial gas velocity to the 0. 41 power. They observed liquid velocities
above 100 cm /s at superficial gas velocities above 20 cm /s. They found
that their data could be correlated by the expression of Zuber and Findley
( 1965); that is,
(94)
where CA= 1.03 and vn = 0.33 m/s. That is, vn = 0.33 m/s is approx-
imately the gas velocity relative to the superficial velocity of the mixture,
UM.
Hsu and Dudukovic (1980) presented an overall momentum balance for
the airlift loop and presented a correlation for the two-phase friction factor.
Their results do not correlate well with the popular Lockhart-Martinelli cor-
relation (Perry and Chilton, 1973, pp. 5-41).
Biological Reactors 825
Hatch ( 1969) found that the optimum ratio of upflow to downflow area
was about 0. 83. Since the upflow liquid velocity increases with superficial
gas velocity, one would expect the optimum area ratio to decrease as super-
ficial gas velocity increases.
Hatch ( 1973) has measured the axial dispersion coefficient DL in the air-
lift upflow section and found that DL is constant at about 58 cm2 /s for low
superficial gas velocities where liquid recirculation within the upflow section
is small. Hatch concludes that the liquid phase may be modeled using a
plug- flow model for both the up flow and downflow sections. Hatch recom-
mends a complete-mixing model for the head region. Merchuk and Stein
( 1981a) have modeled the airlift fermentor using plug flow in the up flow
and downflow regions and complete mixing in the head region. Ho et al.
( 1977) have modeled the airlift fermentor using a tanks-in-series model in
the upflow and downflow regions and a completely mixed tank for the head
region.
The design methodology for the airlift fermentor is analogous to that
described above for bubble columns. The fraction of oxygen consumed,
the feed gas superficial velocity in the draft tube, and the ratio of up flow
to downflow area may be selected as independent variables together with µ
and X. A trial-and-error calculation is required to find the operating pres-
sure that results in an acceptable dissolved oxygen concentration. A
simulation procedure analogous to that of Ho et al. (1977) or Merchuk and
Stein ( 1981a) is needed to determine the dissolved oxygen level in the vari-
ous parts of the airlift fermentor for a particular operating pressure.
The available correlations for use in the design of airlift fermentors are
not as complete and extensive as those for agitated tanks and bubble columns.
Further research is needed to develop such correlations. Airlift fermentors
have been compared to bubble columns and agitated tanks and the mass
transfer efficiency of airlift columns has been demonstrated (Orazem and
Erickson, 1979; Hatch, 1975).
A variety of equipment arrangements involving vertical circulation due
to airlift designs have been reported. The length of the vertical divider
ranges from the short downcomers of Viesturs et al. (1980, 1981) to the
very long downcomers of the deep shaft fermentors (Takamatsu et al.,
198la,b; Kubota et al., 1978; Hosono et al., 1979; Hines et al., 1975).
Further research is needed to develop optimal designs for biological applica-
tions of these systems.
Tower Reactors with Motionless Mixers
The design methods of this chapter can be applied to various tower fermen -
tors with internals such as Koch motionless mixers, sieve trays, and down-
comers. Appropriate flow models should be selected for the proposed system
and the effect of pressure should be considered. Correlations for the
volumetric mass transfer coefficient and the gas holdup are needed. The
work of Viesturs et al. (1980, 1981) has resulted in the industrial-scale
application of such systems; they have compared the performance of several
large-scale systems experimentally. Further research is needed to optimize
mathematically such designs.
ACKNOWLEDGMENT
This work was partially supported by the National Science Foundation.
826 Erickson and Stephanopoulos
NOTATION
a stoichiometric coefficient in Eq. ( 1) ; interfacial area
a' interfacial area per unit volume of liquid
area
stoichiometric coefficient in Eq. ( 1)
dimensionless group defined by Eq. ( 84)
dimensionless group defined by Eq. ( 85)
2
Bond number ( gdt PL /a)
C dimensionless dissolved oxygen, CO /CC)T
molar carbon dioxide concentration in liquid phase
molar oxygen concentration in liquid phase
PTY /H 0 ; equilibrium oxygen concentration in liquid at the top of
the column
bubble diameter
width of impeller blade
impeller diameter
orifice diameter
Sauter mean diameter [see Eq. ( 44)]
tower diameter
dilution rate F /V !l (hr - l); molecular diffusivity
dispersion coefficient for liquid phase
Deborah number (ub;\/ds)
F volumetric flow rate of liquid phase
Fr uG / ~ ; Froude number
Fr Q 2 /d 5 g; orifice Froude number
0 0 0
g gravitational acceleration
Ga gd: /ui; Galileo number
3 2
Gr dbpLg(pL - pg)/µL
He Henry's law constant for CO 2
H Henry's law constant for oxygen
0
H+ hydrogen ion concentration
inhibitor concentration
liquid-phase mass transfer coefficient
saturation constant for product inhibition
saturation constant of Monod kinetic model
maintenance coefficient based on CO 2 , g mol CO 2 ( g biomass) •h
maintenance coefficient, g equiv available electrons substrage/g
Biological Reactors 827
-1
m maintenance coefficient based on oxygen, g mol O 2( g biomass •
0
h-1
maintenance coefficient, g substrate/(g biomass) •h
molecular weight
molar flow rate of gas
impeller speed
Pc partial pressure of CO 2
po partial pressure of oxygen
PT total pressure
p product concentration, g /L
p power
pl productivity in Eq. (73)
PG gassed power
p power number, P/pcN 3d:
no
Q volumetric gas flow rate
Qco 2 specific rate of CO 2 evolution, g mol/(g biomass) •h
Qo2 specific rate of oxygen utilized, g mol o 2 t(g biomass) •h
Qo heat evolved per equivalent of available electrons transferred to
oxygen, kJ /equiv
R gas constant
ReOL 4pL Q0 /1rd0 µL; orifice Reynolds number
Sc µL / PLD; Schmidt number
Sh kLdb/D; Sherwood number; use ds for bubble size distribution
T absolute temperature
bubble rise velocity
gas-phase superficial velocity
liquid-phase superficial velocity
superficial velocity of gas-liquid mixture
dispersion volume
gas volume
liquid volume
height from bottom of the column
biomass concentration, g /L
mole fraction oxygen in gas phase
biomass carbon yield in Eq. ( 1)
carbon dioxide yield in Eq. (1)
product yield in Eq. ( 1)
828 Erickson and Stephanopoulos
true biomass yield, g biomass/g mol ATP
biomass yield based on CO 2 , g biomass/g mol CO 2
true biomass yield based on co 2 , g biomass/g mol CO 2
y biomass yield based on oxygen, g biomass /g mol oxygen
0
ymax true biomass yield based on oxygen, g biomass/g mol oxygen
0
max
yp /ATP true product yield based on ATP, g product/g mol ATP
YP/D
max
true product yield based on co 2 , g product/g mol co 2
max
true product yield based on oxygen, g product/g mol oxygen
YP/0
max
YP/S
true product yield based on substrate, g product /g substrate
YQ biomass yield based on heat evolved, g biomass /kJ
y biomass yield based on organic substrate, g biomass /g substrate
s
Ymax true biomass yield based on substrate, g biomass/ g substrate
s
Greek Letters
a. pressure ratio defined by Eq. ( 83)
a. rate coefficient for product formation, g product/(g biomass) •h
rate coefficient for product formation, g product /g biomass
reductance degree of biomass [see Eq. (4)]
reductance degree of product [see Eq. (7)]
reductance degree of substrate [see Eq. (6)]
standard heat of combustion per gram atom of carbon
heat of reaction per gram atom of substrate carbon
E fraction of available electrons transferred to oxygen
volume fraction of dispersed gas phase
biomass energetic yield
true biomass energetic yield
Kolmogoroff scale [see Eq. (58)]
characteristic time of viscoelastic material
]J specific growth rate, h - l
apparent viscosity
viscosity of gas
viscosity of liquid
Biological Reactors 829
maximum specific growth rate
kinematic viscosity
\) apparent kinematic viscosity
product energetic yield
true product energetic yield
p density
(J surface tension
weight fraction carbon in biomass
weight fraction carbon in product
weight fraction carbon in substrate
Subscripts
b biomass
C continuous phase; CO 2
g gas phase
G gas phase
in inlet condition
L liquid phase
R, liquid phase
0 oxygen; orifice
p product
s organic substrate
Superscript
* equilibrium concentration
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13
Analysis and Design of Photoreactors
ELIANA R. DE BERNARDEZ, MARIA A. CLARIA, and
ALBERTO E. CASSANO Instituto de Desarrollo Tecnol6gico para la
Industria Qu{mica- INT EC, Universidad Nacional del Litoral-Consejo
Nacional de Investigaciones, Cient(ficas y Tecnicas, Santa Fe, Argentina
SIGNIFICANCE AND SCOPE
The advantages of photochemical reactions over thermal or catalytic reac-
tions have frequently been quoted: selectivity, negligible side reactions,
low operating temperature, possibility of carrying out some reactions that
would be thermodynamically infeasible by thermal means due to unfavorable
equilibrium conditions, liquid-phase operation, and so on.
Despite these advantages, photoreactors have been employed industrial-
ly only when either thermal or conventional catalytic reaction paths have
proved to be very difficult. The reasons are: lack of suitable reactor
models and design methods, lack of quantitative information about the per-
tinent physical and chemical parameters, limited variety of equipment avail-
able, and the understandable reluctance of successful industrial companies
to publish design and scaleup procedures. However, many reactions are
suitable for photochemical production.
The most common industrial photoreactions are those that proceed via
chain mechanisms. Among these, photochlorinations are undoubtedly the
most important processes due to their high-energy yields. Thermal clorina-
tions, carried out at high temperatures, produce a variety of different
molecular species which have to be separated; this results from the broad
energy distribution of the thermal field and its effects on reactions with
different activation energies. In contrast to this, in many cases, the
photochemical process may produce only a single product. The synthesis
of y-hexachlorocyclohexane has been one of the photochlorinations of
greatest economic significance.
An industrial process for the preparation of volatile primary mercaptans,
which are commonly used as additives to natural gas, is based on the anti-
Markovnikov addition of hydrogen sulfide to terminal olefins, a free radical
chain reaction initiated by light. Photopolymerizations are another example.
Such chains, started by light, have high energy yields; in addition, no
fragments of initiator molecules remain and production rates by means of
the flow process are extremely fast.
839
840 De Bernardez, Claria, and Cassano
The photooximation of cyclohexane, a reaction with low energy yield,
is currently used to prepare caprolactam, which in its turn is utilized for
the production of nylon-6; nylon-12 is prepared by a similar route. This
reaction involves a free radical mechanism but is not a chain reaction.
Several companies have experimented with this process; however, the first
large-scale use has been reported by the Toyo Rayon Co. of Japan.
The photooxidation of olefins has been investigated extensively in rela-
tion to the "smog" problem that appears in the atmosphere by the photo-
chemical reaction between several atmospheric contaminants. Also, a num-
ber of organic compounds , epoxides , aldehydes, and ketones have been
produced in the laboratory by reaction of oxygen atoms (photochemically
produced) with olefins. Generally, these reactions have high yields and
side reactions are minor (at least for terminal olefins).
There are photochemical reactions with low energy yields that are
generally limited in application to the synthesis of high-priced, low-volume
chemicals such as pharmaceuticals or perfumes. The photosynthesis of
vitamin D2 is the most important example in the pharmaceutical industry.
It is based on the ergosterin photolysis and is the only way to obtain this
vitamin.
We should add that, very often, photochemical processes have been
proposed with the following objectives:
1. Decomposition of water contaminants refractory to other ways of
destruction
2. Sterilization processes
3. Bacteriological treatment of drinkable water
4. Destruction of very dangerous chemicals that may have been pro-
duced either voluntarily or by error, particularly when there are
no other ways of making them harmless
Several more applications can be included, but perhaps the most im-
portant development in the field of photochemistry is the recent emphasis
on photo-assisted catalysis (Childs and Ollis, 1980). Heterogeneous photo-
assisted catalysts are substances that require photo-excited electrons or
holes in the course of a heterogeneously catalyzed reaction. As an example
we can mention several semiconducting oxides, such as TiO2 and ZnO; the
former, when irradiated, becomes active in the selective oxidation of alkanes
to ketones and aldehydes as well as in the dechlorination of polychlorinated
biphenyls; on the other hand, carbon monoxide oxidation occurs over
illuminated ZnO. Several photo-assisted semiconductor electrodes, such as
crystals of SrTiO3 and the perovskite KTaO3, can electrolyze water without
an applied electromotive force. Many other applications could be listed.
Photo-assisted catalysis may become practically useful if a relatively cheap
source of light with appropriate wavelength is available, the sun being
the obvious source. The prospects for solar energy conversion following
this path are particularly appealing.
Despite all these potentialities, photoreactor design is still. a novel
field in reaction engineering, with many important problems still not proper-
ly solved. In fact, up to the present, no reliable design methods have
been made available to the practicing engineer. We believe that a signifi-
cant part of the responsibility for this lack of know-how lies mostly in
considering its analysis as a kinetic variation of a conventional reactor,
Analysis and Design of Photoreactors 841
when in fact it must necessarily include the radiation field as the key view-
point. Consequently, if some progress is to be made, the design of a
photoreactor cannot avoid all the complexities that radiation problems in-
volve.
First, we present a definition of the problem and the requisite theory.
Later, the design methods are shown through four applications, three of
which have already been tested in bench-scale experiments with excellent
agreement. Finally, in two short sections we propose some new reactors
not yet theoretically modeled, and we end with what we believe are the
most important problems still unsolved in the field.
TYPES OF REACTORS
When dealing with the design of the equipment for carrying out a photo-
chemical reaction, several aspects must be considered. Some of them are
common to the design of conventional thermal reactors, such as the kinetic
characteristics of the reactions involved, the phases of the system, the
necessity of temperature control, the requirements about the material of
construction, and so on. Others arise specifically from the selection of
the appropriate radiation source for the reaction under study (i.e. , the
spectral distribution of the emitted light and the geometrical configuration
of the reactor-lamp arrangement). In addition, a certain number of im-
portant photochemical reactions share the common characteristic of present-
ing products and reactants with highly corrosive or dissolving properties;
a typical example is the chlorination of hydrocarbons where the presence
of chlorine, hydrochloric acid, and chlorinated solvents creates difficulties
in the selection of materials for equipments and seals. In the case of
heterogeneous systems, the mixing pattern of the reactor is extremely im-
portant. Another important aspect in the design is the requirement for
temperature control in strongly exothermic or endothermic reactions. We
may add that in some particular cases the design can be improved by add-
ing a reflecting device; its use complicates the analysis of the radiation
field.
Many of these difficulties can be overcome by choosing an appropriate
configuration of the photoreactor system. Among a wide range of possible
reactor-lamp-reflector configurations, those most widely studied in the
literature are the annular reactor, the cylindrical reactor with elliptical
reflector, and the cylindrical reactor with parabolic reflector; they are
described briefly below. Other types of configurations can be used in com-
mercial applications; nevertheless, they arise from different combinations of
the three mentioned above.
Annular Reactor
Annular photoreactors are an excellent approach to what is perhaps the
most practical type of photochemical reactor to be used for commercial
purposes. The utilization of energy can be the maximum expected and,
moreover, they represent the common case of a reaction vessel with a tubu -
lar lamp placed at its axis by means of an immersion well.
Figure 1 shows the main features of the system. The reacting stream
is contained in the annular space that surrounds the lamp. If the reactor
842 De Bernardez, Clarid, and Cassano
FIGURE 1 Annular reactor.
vessel is separated from the lamp, the annular space between them can be
used to cool the lamp and/or control the operating temperature of the re-
actor. However, it must be noted that the requirement of light transmis-
sion introduces some limitations in the heat transfer possibilities because
at least the inner reactor wall must be made of quartz or glass. Since
light transparency is not required in the outer reactor wall, it provides
much more freedom for design purposes, such as cooling, reflection of
nonabsorbed light, and so on. Hence if one desires to improve the absorp-
tion efficiency of the reactor, a reflector surface covering the outer reactor
wall can be used.
In dealing with laboratory research, the annular photoreactor cannot be
recommended for continuous-flow operations due to its unavoidably large
cross-sectional area, which requires the handling of large volumetric flow
rates. On the contrary, this characteristic makes it very appropriate for
commercial - scale operations.
s R
FIGURE 2 Cylindrical reactor with elliptical reflector.
Analysis and Design of Photoreactors 843
-----~- ...
I
', I
'• ~
I
FIGURE 3 Cylindrical reactor irradiated from the bottom.
Cylindrical Reactor with Elliptical Reflector
This system consists of a reactor made with a cylindrical tube placed at
one of the focuses of a cylindrical reflector of elliptical cross section. A
tubular radiation source is placed at the other focus. This particular
arrangement is often called an elliptical photoreactor (Fig. 2).
The possibility of using cylindrical tubular reactors with a small cross-
sectional area together with the generally accepted (but only partially true)
concept of the existence of a uniform irradiation from outside has resulted
in a rather extensive application of this reactor for laboratory and bench-
scale re search work.
On the other hand, since the incidence efficiency of this type of re-
actor-defined as the capacity of concentrating the energy within the reac-
tor boundaries-is not very high, this is not an advisable device for
commercial-scale operation unless other energetic considerations compel its
use.
Cylindrical Reactor with Parabolic Reflector
Another possibility of isolating the reaction system from the radiation source
( which could also simplify the solution of the well -known problem of wall
deposites, generally more severe at the radiation entrance wall) consists
of the use of a cylindrical reactor irradiated from the bottom by a tubular
source located at the focal axis of a cylindrical reflector of parabolic cross
section (Fig. 3). Since the cylindrical reactor may be a perfectly stirred
tank reactor, this device is especially appropriate to carry out liquid or
gas-liquid reactions where vigorous stirring is required. This type of re-
action is indicated for both laboratory and commercial scale work and can
be used in batch, semibatch, or continuous operations. Problems of cor-
rosion and sealing can be more easily handled in this system.
PHOTOREACTOR DESIGN: STATEMENT OF THE PROBLEM
To design a photochemical reactor, an engineer should have the following
information (a) the reaction; (b) the radiation energy demand (generally
844 De Bernardez, Claria, and Cassano
qualitatively defined), which can be satisfied with a radiation source
(lamp) and perhaps a reflector; and (c) a choice of possible reactor con-
figurations ( sometimes with some restrictions). Then the following ques-
tions must be answered:
1. Which is the best source-reactor-reflector arrangement?
2. Which is the optimal value of the spectral distribution and overall
radiation power output to convert reactants into the desired
product?
3. Which is the optimal feed composition?
4. How much conversion can be achieved?
5. Which is the optimal size of the reactor?
6. How much selectivity can be obtained?
The answers to these questions must be treated in a logical sequence
which starts with the knowledge of the rate of a photochemical reaction.
The description of the rate makes it necessary to distinguish between dark-
and radiation-activated steps. To treat dark reactions one uses the same
methodology as for thermal reactions; the main hindrance appears when
evaluating the rate of the initiation step. It is known that the rate of this
step is related to the local volumetric rate of energy absorption (LVREA).
The evaluation of the LVREA is performed stating first a balance of radiant
energy at steady state for a control volume. For simplicity, a nonemitting
medium is generally assumed. Afterward, it is necessary to incorporate a
radiation source model and a constitutive equation in the absorption term.
The source models have been treated by several research teams, which
have developed different proposals to predict radiation profiles inside photo-
reactors. Conceptual approaches may be classified into two well-defined
groups: (a) those which assume a given radiation distribution in the
vicinity of the reactor (incidence models) and (b) those which start from
a proposal of a model for the source (emission models). There is no way
of using incidence models without experimentally adjustable parameters.
The reader interested in this approach can find a critical review in a pre-
vious work (Alfano et al., 1985). However, since we are looking for an
a priori design of photoreactors, attention will only be paid to the emission
models. Their formulation will be presented later.
Once we know how to formulate the rate of a photochemical reaction, we
can progress further ahead with the design problem. Then the mass,
energy and momentum balances must be established. The expression for
the conservation of momentum is similar to that of conventional reactors.
Due to the energetical features of photochemical reactions (very low and
sometimes null "equivalent" activation energy for the global reaction), it
is very frequent to find that the reaction behavior can be accurately
described with the mass balance and the energy balance reduced exclusively
to radiation. However, in some cases, when highly exothermic or endo-
thermic reactions are present, the design of the reactor will unavoidable
require the complete energy equation of change. In any event, even for
the simplest case, the mass and radiation balances are normally coupled
through concentrations of the radiation-absorbing species.
The nature of this coupling is well understood. The local volumetric
rate of energy absorption (LVREA) is generally a function of the radiation
field inside the space of reaction, the concentration of the absorbing species,
and other physicochemical parameters. If species i which is being con -
sidered in the mass balance is an absorbing species, a coupling between the
Analysis and Design of Photoreactors 845
LVREA and the corresponding mass balance equation will take place. Simul-
taneously, the concentration of the absorbing species (i) goes inside an
integral expression, accounting for the radiation attenuation by absorption.
Thus the general problem of modeling a photoreactor presents an integro-
differential mathematical nature. This degree of complexity of the problem
should not be surprising since the physical situation indicates that the
progress of the reaction at a point depends on the LVREA (which is, among
other variables, a function of the radiation attenuation suffered by each
bundle along its path inside the reactor); in its turn, the attenuation suf-
fered by each pencil of radiation ( due to its concentration dependence) is
a function of the reaction extent reached at each one of the points con-
stituting the trajectory of the bundle. We discuss later how to model the
absorption process in the reactor by one or more species, as well as evalua -
ting the LVREA and presenting several applications using the three main
reactor configurations described previously.
To solve the design problem, additional information about the lamp, the
reactor, the reaction, and perhaps, if it is used, the reflector will be
needed. We should state beforehand that we assume that the reaction is
already known. This means that kinetic data are available as well as qual-
itative information regarding radiation requirement. Because of this, the
system will impose some constraints on the selection of radiation sources and
reactor configurations. At the same time the market availability of ultra-
violet- and visible-light lamps and quartz (or Pyrex glass) tubes and plates,
if they are needed, will provide definite guidelines about the type of reac-
tor-lamp combination better suited for each process. In any case, a design
will generally start with a tentatively chosen radiation source. More often
than not, the choice of the lamp considerably reduces the freedom concern -
ing most reactor dimensions.
Thus the problem must begin with a tentative list of needed information,
generally oriented by one's qualitative knowledge of the reaction and pos-
sible reactor configurations. Even if the information is complete, very
often the design will have to be done in an iterative way because of the
limitations imposed on the construction of the reactor by the above-
mentioned market restrictions. Let us list what is needed:
1. About the tentative radiation source:
a. Its power consumption and power output.
b. The spectral distribution of its power output.
c. Its geometrical dimensions.
d. Its operating conditions.
2. About the tentative reactor (assuming that some decision has been
taken about its shape and type of operation):
a. Its geometrical dimensions.
b. In some der 'gn s, the transmission characteristic of the wall
through which the radiation should enter the reactor.
c. The spectral distribution of the wall transmission characteris-
tics.
d. Information about ranges of operating conditions (e.g., pres-
sure, temperature, required production, etc.) .
3. About the reaction :
a. A kinetic sequence with the following characteristics:
( 1) An initiation step that is activated by absorption of
radiation.
846 De Bernardez, Clari6., and Cassano
(2) One or more "dark" reactions. From the industrial point
of view the most important reactions are those recognized
by the name of chain reactions. Starting from an atomic
species or a free radical formed in the initiation step , they
involve the following constituents:
(a) One or more propagation steps.
(b) One or more termination steps.
In some cases it is possible to work with a global kinetics that
relates the absorption of radiation to the formation of products.
Nevertheless, if it is available, it is always better to work with
microkinetic information such as that mentioned in ( 1) and (2).
b. The radiation absorption characteristics of reactants, inerts,
and products.
c. The primary quantum yield of the initiation step (i.e., how
many atomic or free radical species are effectively produced
for each absorbed photon by the appropriate reactant in the
first reaction of the kinetic sequence). If only global kinetic
expressions are available, an overall quantum yield may be
necessary, which is defined according to the reaction scheme
(moles of product formed or reactant consumed/energy
absorbed).
4. About the tentative reflector (if it is used and assuming that its
shape is given):
a. Its geometrical dimensions.
b. Its reflectivity
c. The spectral distribution of its reflectivity.
Here we have pointed out mainly the particular design variables and
the parameters of photochemical reactors. In addition, we must know all
other physicochemical properties or characteristic parameters usually
needed for thermal reactors (densities, diffusivities, thermal properties,
etc.).
In the next sections we derive the theory and show the methods used
to reach an a priori design of a photoreactor, when the problem is posed
as indicated above.
EMISSION MODELS
We begin our analysis of the emission mode:i.s by defining the fundamental
properties of the radiation field. Then the balance of radiant energy for
an absorbing medium will be derived with which we will finally be able to
obtain an expression for the rate of the initiation step for a photochemical
reaction. The concepts introduced here are based on well-accepted defini-
tions in the areas of radiation engineering and radiation gas dynamics.
However, we shall point out some differences between the conventional
thermal applications of radiation (e.g., furnaces) and those that involve
the use of visible, ultraviolet, and even shorter wavelength radiations.
Definitions
Specific Intensity
Radiation engineering generally studies the energy exchange between sur-
faces (Fig. 4). To characterize the amount of energy departing from a
Analysis and Design of Photoreactors 847
FIGURE 4 Geometric representation of the SEES model.
surface, the concept of specific intensity of radiation is used. The
specific intensity of radiation is defined as the amount of energy in the
frequency range between v and v + d v, leaving a surface per unit area
normal to the pencil or rays, per unit solid angle and unit time. From
now on we will simplify our notation and call energy in the frequency in-
terval between v and v + dv simply energy of frequency v. To illustrate
the rise of the specific intensity concept, let d\j!v be the radiant energy
of frequency v per unit time and unit area, leaving a given surface dAe
in the direction ee and contained within a solid angle dwe (Fig. 4); then
d\j!v
::: ( 1)
dw f(8,¢)
e
where f( e, ¢) takes into account the directional characteristics of the emis-
sion (isotropic, diffuse, etc. ) . We must extend this concept to photoreac-
tor engineering, where the energy exchange may involve not only surfaces
but volumes as well.
When the radiation source is a fluorescent lamp, only the external sur-
face of the lamp participates in the emission process. Hence the energy
exchange phenomenon involves two surfaces, one for emission and the other
for reception (Fig. 4). On the other hand, if the radiation source is a
nonfluorescent arc lamp, the emission is volumetric (i.e. , the entire volume
of the lamp participates in the emission process). In this case (Fig. 5)
the energy exchange phenomenon involves an emitting volume (dVe) and a
receiving surface (dAr). The first proposal of an extense model was pub-
lished by Irazoqui et al. ( 1973). It was applied to a nonfluorescent arc
lamp and it is known as the volumetric emission extense source model
(VEES). Stramigioli et al. (1975, 1977) presented the superficial emission
extense source model (SEES) to describe the performance of fluorescent
lamps. Their formulation was an extension of the VEES model.
In spite of the fact that radiation sources have finite spatial dimensions,
many authors have used a third model, which considers the lamp as a line
(Figure 6). This model, first proposed by Jacob and Dranoff (1966, 1968)
is known as the spherical emission linear source model ( SELS). As we shall
see later, the SELS model can be used only in some special-but very im-
portant-reactor designs.
848 De Bernardez, Clariti, and Cassano
FIGURE 5 Geometric representation of the VEES model.
We can now derive a formulation of the specific intensity of radiation
which will account for the type of energy exchange involved; then we
have:
1. Emitting surface-receiving surface (SEES model)
2. Emitting volume-receiving surface (VEES model)
3. Emitting line-receiving surface (SELS model)
When formulating the equations we make the following assumptions:
1. The emitters of the radiation source are uniformly distributed in-
side its extension (be it a volume, a surface, or a line).
2. Any elementary extension of the source emits per unit time, at any
frequency, an amount of energy proportional to its extension.
3. The emission characteristics are constant along the z direction (this
assumption does not imply a constant radiation field in the z direc-
tion).
!!e
dZ
FIGURE 6 Geometric representation of the SELS model.
Analysis and Design of Photoreactors 849
Maintaining the expression ( 1) for the definition of Iv, we may intro-
duce the differences in the energy exchange process in the expression for
di/Jv· Let us use a generic expression for an "energy flux" (d'¥v) which
includes the possibility of emission by either lines, surfaces , or volumes.
The generic extent of the lamp will be indicated by df e, which may have
dimensions of length, area, or volume; depending on the case. Then
dE
V
d'¥ = (2)
V df
e
where d '¥ v is the amount of energy of frequency v per unit time that
leaves an infinitesimal extent of the lamp, characterized by dr e. This
distinction is the definition of the specific intensity of radiation allows us
to achieve complete consistency in a unified theory. Considering Eq. ( 2) ,
the equation for Iv becomes
( 3)
Here a superscript in parentheses indicates the order of the infintesi-
mal quantity. Values of (d) and the expressions of d(d)re for each emis-
sion model are given in Table 1. It is obvious that b = d + 2.
At this point it should be noted that in a diactinic medium (a homo-
geneous nonabsorbing medium) the specific intensity is constant along the
propagation path, and hence independent of distance. On the other hand,
in absorbing and /or nonhomogeneous media the specific intensity will
change ( due .to absorption, scattering, reflection, and refraction) accord-
ing to the physical properties of the medium.
In the following analysis we consider three special cases:
1. When the emission is independent of the direction, it is called
isotropic emission; then f(0,cjJ) = 1.
2. When the emission is diffuse, it follows what is known as the
"cosine law;" then f(0,cjl) = cos 0e.
3. When the directional characteristics of the emission are different
from cases 1 and 2, the model needs the specification of function
f( e, cp).
From now on we consider only the first two cases, isotropic and diffuse
emission. To simplify the treatment of the equations, we can reduce the
two emission cases into a unique expression:
I' ( 4)
V
For isotropic emission, I' = I . In the case of diffuse emission,
V V
I' = I
v v cos 0e ( 5)
850 De Bernardez, Clarici, and Cassano
TABLE 1 Final Equations for the Three Emission Models
I'
V
ld<d\
~v
I
Model d a<d)r r* [Eq. (4)] [Eq. ( 9)]
e e
dE I' dz
=
V V
SELS 1 dz LL dw dz
e p2
2
p dE V
dA cos e dz
r r
dE I' dA
e
SEES 2 dA
e = 21rrLLL dw
V
dA =
V
2 =
e e p
p2 dwr
2 dE I' dw
p V V r
dA
r
cos er dA
e
dE I' dV
2 e
VEES 3 dV
e = ,rrLLL dw
V
dV = V
2 =
e e p
2
p dw dp
r 2 I' dw dp
p dE V V r
dA cos e dV
r r e
However, since the product Iv cos Be is independent of direction, in
both cases I~ is always isotropic. The distinction between the two types
of emission will be introduced in the following derivations only when neces-
sary. Table 1 summarizes the final expressions of I~ for each emission
model.
Finally, for polychromatic sources, the radiation intensity is obtained
integrating the specific intensity over the whole frequency range, as
follows:
(6)
Specific Energy Flux Density Vector
The amount of energy of frequency v passing through a surface of extent
dAr (Figs. 4, 5, and 6), per unit time may be expressed as
(7)
Analysis and Design of Photoreactors 851
Isotropic Diffuse
a a
Isotropic emission, e \) emission Diffuse emission , e emission
\)
[Eq. (29)] K [Eq. (33)] (K)
\) \)
K<J µ \l
ILL dz
E
~
K\l µ \l
f LL
sin 0 dz
E
~
0 p2 41TLL 0 p2 TILL
x exp (- ~;• µU dp) x exp ( - ( µu)dp'
K\)µ\)l ~ sin e
E
2
L,v
81T rLLL
K\l µ \) ff
</l e
sin 2 e cos </J
E
L,v
2 2
21T rLLL
x exp (- ~; µU df 0dj x(-JP*µ dp'
* \)
d0 d</J)
Po
i~ ~ E
L,v
{la~ E
L,v
+(
K\lµ\l sin e K\l µ \l sin 2 e
2 2 2 2
41T rLLL 1T rLLL
µu dp) dp d0 dj X COS Ql x exp ( - { µUdp)
X dp de d</J Po
where d(c)q is the specific energy flux density vector. We do not need to
~\) (
make a distinction between the definition of d c) q for each model because it
~\)
is a properly related to the receiving surface. From Eq. (7) if follows that
= dAr cos e I d(c) q I
r ~" ( 8)
Where I d (c)'.!v I 1s
· th e mo d u l us or the spem"fl1c energy fl ux d ens1·ty vect or.
For both Eqs. (7) and (8) it is clear that c = b - 2 = d.
The relationship between the specific intensity and the modulus of the
specific energy flux density vector can be derived relating Eqs. ( 4) and
( 8):
dA cos 0
dw r r ( 9)
=
e 2
p
852 De Bernardez, Clari6, and Cassano
where we used the geometrical relationship
dA cos 8
r r
dw = (10)
e 2
p
In spite of the fact that Iid) q I and I' have different physical
~V V
meanings, they are often confused in the photoreactor engineering litera-
ture. In a diactinic medium while I~ remains constant, Eq. ( 9) shows that
the modulus of the specific energy flux density vector changes with dis-
tance. Table 1 summarizes the expressions of Eq. ( 9) for each emission
model.
Attenuation Coefficient
The attenuation coefficient is a property of the substance through which
the radiation travels and is related to the process of radiation absorption.
It is defined through a constitutive equation commonly referred to as
Lambert's "law," which can be derived from molecular theory. The con-
stitutive equation states that for an absorbing and homogeneous medium,
the contribution of absorption to the gradient of the specific intensity is
div Ia =
-μ I (11)
dp V V
Equation (11) is valid for any type of emission model with proper use of
the definition of Iv. The left-hand side of Eq. (11) is the directional
derivative of Iv (i.e., the component of the gradient of the scalar function
Iv along the direction of propagation of the ray). Hence Eq. ( 11) may be
rewritten
j • 171 = -μ I (12)
_v vv
where is a unit vector in the direction of each ray. Since f( e, ¢) is in -
dependent of distance p, Eq. ( 12) is also valid for I' .
V
Radiation Balance
We shall state the steady-state radiation balance for a nonemitting, non-
dispersing homogeneous control volume (Fig. 7). The difference between
the energy flux density of frequency v impinging on dAr at position p with
direction ( 8, ¢), and the energy flux density of frequency v leaving the
fixed control volume with the same direction, at position p + d p, is due to
the absorption of radiation:
( 13)
where on the right-hand side the subscript p indicates differentiation with
respect to p.
Analysis and Design of Photoreactors 853
FIGURE 7 Radiation balance in an elementary absorbing volume.
Introducing Eqs. (8) and (10) into Eq. (13), we have
(14)
Combining Eqs. ( 14) and ( 9) yields
( 15)
Substituting the constitutive equation ( 11) into Eq. ( 15) gives us
( 16)
Finally, considering Eqs. ( 9), ( 14), and ( 16), the steady-state radiation
balance becomes
1 ~ ( 21 id) I) ( 17)
2 dp P ~v
p
Rate of the Activation Step
As mentioned earlier, the rate of the activation step is proportional to the
local volumetric rate of energy absorption (LVREA). The LVREA is defined
as follows:
(18)
dV
r
with f = b + 1 - 3 = b 2 = d. Combining Eq. (14) with Eq. (18) and
considering that dVr = p2 dwe dp, we obtain
854 De Bernardez, Clari6, and Cassano
( 19)
Finally, introducing the radiation balance ( 17) into Eq. ( 19) , we have
(20)
To evaluate id)ea we need to know I id)q I From the radiation balance
V ~V
and integrating inside the reacting space (where the absorption of the
radiation process takes place), we obtain (Fig. 8)
P
21ct<d) ~v I P
2
Id (d) q I exp
(1p*(8,¢)
- (21)
o _v o pi(e,¢)
In Eq. (21), I d(d)q_v I o is the modulus of the specific energy flux density
vector for a point W(p*,8,¢) at the surface of entrance of radiation to the
0
reactor volume. To evaluate it, assuming no absorption between the source
surface and point W, we use the equations valid for diactinic media, that
is,
21ct<d) ~v I
P
(22)
I
i /
J.,., ,,,.,,.
,., I ,,..,
/ ._,,,,,
--,.~.;--r- -----t--
.... \ / ----1
I ',.j_. .._
I
I I(p*,8 ,tp} ',.._
....
-------1------'....
'
,, i '
i
I
FIGURE 8 Schematic representation of the attenuation process.
Analysis and Design of Photoreactors 855
Because I~ remains constant in a diactinic medium, Eq. ( 22) may be
written
Po
21a<d)
~v o
I (23)
Combining Eqs. (20), (21), and (23), we obtain
(24)
Finally, the local volumetric rate of energy absorption at frequency v is
obtained by integrating Eq. (24):
I'
a \) ,o
e ::: exp (25)
\) 2
p
In Eq. (25), I~,o must be related to the power output of the radiation
source. From Eq. (4) we have
::: I' dw a<d)r (26)
v ,o e e
for a diactinic medium. Integrating Eq. ( 26) for the whole range of solid
angles and for the whole extension of the emission source, we obtain the
lamp power output at frequency v:
E
L,v = L fr e e
I'
v ,o
dw
e
a<d)r
e
(27)
where we have made the following assumptions:
1. In the case of volumetric emission, each elementary volume is
transparent to the emission of its surroundings.
2. In the case of three-dimensional emission sources, they are sup-
posed to be bounded by mathematical surfaces of zero thickness.
Thus any bundle of radiation coming out of the lamp does not
change its intensity or direction when it crosses this boundary.
To perform the integration in Eq. (27), we may distinguish the two
emission cases:
1. Isotropic emission. Here I' =I , which is constant (independent
v,o v,o
of distance). Then Eq. (27) becomes
E
L,v = I'v,o 4TI r e* ( 28)
856 De Bernardez, Clarid, and Cassano
where the expression of r * for
e
each emission model is condensed
in Table 1. Finally, we have
~ -\- exp (-
p
fp* p* µv dp) (29)
e 0
2. Diffuse emission. In Eq. (27) we must replace I' by I cos 0
v,o v,o e
and then perform the integration:
E
L,v = Iv,o jw cos e
e
dw
e
jr a<d>r
e
(30)
e e
where Iv O is constant (independent of distance). Here, since the
intensity'of radiation follows the cosine law, the emission solid angle
is 21r. Then
E = I 1rf* ( 31)
L,v v,o e
Finally, we have
E
~
I'
\) ,o
= I
v,o
cos 0
e = 1r r * cos ee ( 32)
e
and
cos ee
~
a
e = ( 33)
\) 2
p
e
The final expressions of e~ valid for diffuse emission for each model can
be found in Table 1, where cos Be has been replaced by the appropriate
expression for each model. Equations (29) and (33) are valid for mono-
chromatic light if we deal with polychromatic radiation, these expressions
must be integrated over the entire frequency spectrum, that is,
( 34)
MODELING THE ABSORPTION PROCESS
As mentioned in preceding sections, the main difference between a photo-
chemical and a thermal reaction is due to the presence of a radiation-
activated step. The rate of reaction of this step is proportional to the
local volumetric rate of energy absorption (LVREA). Hence the evaluation
of the LVREA constitutes the most important stage in the analysis and
design of a photochemical reactor.
Analysis and Design of Photoreactors 857
Table 1 illustrates that for each emission model, the LVREA is a func-
tion of the spatial variables, of the physical properties and geometrical
characteristics of the lamp-reactor system, and some physicochemical proper-
ties of the reacting mixture. The LVREA dependence on the geometrical
characteristics of the lamp-reactor system will be studied in detail in the
next section, and it comes from the limits of integration of the LVREA ex-
pression for each emission model. The physical properties of the lamp are
represented by the parameter Kv in the LVREA equations; both are de-
scribed in Table 1 for each model. Finally, the attenuation coefficient µ v
involves the dependence on the physicochemical properties of the reacting
system. This section is devoted to the evaluation of the attenuation coef-
ficient and the local volumetric rate of energy absorption.
Attenuation Coefficient
In the evaluation of this coefficient it is necessary to make a distinction
between homogeneous and heterogeneous media. The latter are encountered
when one attempts to model systems in which gas bubbles are dispersed in
a liquid, or solid particles are incorporated into a gas or liquid phase as
in photocatalytic applications. The distinction arises from the fact that the
presence of heterogeneities introduces unavoidable distortions in the radia-
tion field.
Homogeneous Media
When the medium is homogeneous, the attenuation of radiation changes con-
tinuously. As mentioned before, this variation in the specific intensity due
to absorption inside an elementary volume of homogeneous media may be ex-
pressed by a constitutive equation which involves an attenuation coefficient
µ v. It is a function of the frequency of radiation v and the state variables
such as temperature, composition, and in some cases pressure. The exact
form of the attenuation coefficient function can be determined from the micro-
scopic theory by studying the absorption of a photon by atoms or molecules
exposed to a radiation field. The reader is referred to the specific litera-
ture [e.g., Pai (1966) or Vincenti and Krug·er (1965)].
Macroscopically, the attenuation coefficient is considered to be a linear
function of the concentration of the absorbing species:
= a C
\)
( 35)
where av is the absorption coefficient or absorptivity. When more than one
species participate in the absorption process, Eq. ( 35) may be written as
= ~ a.1, \) C.l ( 36)
i
Both Eqs. ( 35) and ( 36) are strictly valid for dilute solutions. The
range of validity of these equations can be experimentally tested by study-
ing the variation of µ v with concentration by means of a spectrophotometer.
This type of experiment also allows us to obtain values of the absorption
coefficient necessary to model the attenuation process. On the other hand,
858 De Bernardez, Claric:i, and Cassano
for many chemical compounds, values of the absorption coefficient and the
range of validity of Eqs. (35) and (36) can generally be found in standard
handbooks of physics and chemistry. The absorption characteristics of
many other species and mixtures of different compounds may be found in
specialized publications in the field of spectroscopy. Later we will see an
example of a photochemical reaction with an inorganic complex in which the
characteristics of the absorbing species change with composition and the
data required by Eq. (35) are not available. Instead, the attenuation co-
efficient is evaluated as a function of the composition of the absorbing
medium.
Heterogeneous Media
Since homogeneous systems have been the main objective of the research
performed so far in photochemical reactor analysis, the information available
in the literature about modeling the attenuation in heterogeneous media is
particularly scarce. A critical review about this subject can be found in
Alfano et al. ( 1985). The problem can be approached in two different
ways: (a) by modeling the attenuation process taking into account the
scattering of radiation produced by the heterogeneities, or (b) by using
the existing formulation of homogeneous media with an effective attenuation
coefficient. About the first strategy, it can be ascertained that the use
of a rigorous radiation source model having no adjustable parameters, to-
gether with the complexity provided by the heterogeneities of the medium,
have not yet been attempted. On the other hand, the simplitied method
using an effective attenuation coefficient is appropriate to carry out the
calculation of the rate of radiant energy absorption in heterogeneous sys-
tems with a good degree of approximation. Based on these considerations,
if one attempts to design and /or analyze an industrial photochemical reactor,
the second strategy must be followed for the time being.
At present, several correlations have been proposed to evaluate the
effective attenuation coefficient in gas-liquid dispersions. Among them, we
can particularly mention two:
1. The first one, proposed by Otake et al. ( 1981), is a simple empiri-
cal expression which accounts for the absorption effects produced by the
liquid phase and the reflection, refraction, and transmission effects pro-
voked by the gaseous phase. Considering that the latter are proportional
to the specific surface area (a~) , µeff, v may be represented by the follow-
ing correlation :
µeff,v = µ)1 - '
Eg) + kav (37)
where µ v is the attenuation coefficient of the liquid phase, Eg the holdup
of the dispersed phase, and k is an empirical coefficient depending on the
optical properties of the system. Otake et al. (1981) plotted the experimen-
tal information obtained by them and other authors, finding that the values
can be well correlated by using k = 0.125 for µeff v, µ v, and a~ in the
same units (cm-1). '
2. The other correlation proposed by Yokota et al. (1981), in which
the effective attenuation coefficient becomes a function of the attenuation
coefficient in the liquid phase, the bubble diameter, and the gas holdup.
The expression is
Analysis and Design of Photoreactors 859
( 38)
μ
e ff ,V = μ
V
(1 + hi:: g )
and
( 39)
where db is the bubble diameter in mm for µv and µeff, v expressed in
m-1. Both correlations may be used in the case of µv smaller than 40 m-1
When µv is greater than 40 m-1, the dispersing effect of radiation due to
the presence of bubbles may normally be neglected. ·
Later we will see an example of the design of a two-phase photochemi-
cal reactor where the absorption process is modeled using an effective at-
tenuation coefficient. However, no reliable design procedures have yet
been developed for photocatalytic reactors (solid-fluid photoreactors).
Local Volumetric Rate of Energy Absorption
As derived in the preceding section, the integrated expression for the
local volumetric rate of energy absorption may be expressed as
= (40)
for monochromatic radiation for each point I (r1 , s1 , z1) inside the reactor
volume. In Eq. ( 40) the modulus of the energy flux density vector I q I
-V
represents the energy flux arriving from all directions in space and from
the whole volume of the lamp; µ v is the attenuation coefficient, which is a
function of the concentration of the absor.):)ing species at point I.
Figure 8 illustrates the attenuation process undergone by each radiation
bundle before reaching point I inside the reactor volume. To evaluate
I q_v I at point I, every direction ( 0, <P) must be considered. For each direc-
tion ( 0, <P) in the most general case, the ray travels from the emission
source without changing its specific intensity until it reaches the reactor
wall, represented by point W(p*,0,<P) in Fig. 8. In the trajectory between
0
W(p~,0,<P) and l(p*,0,<P) of Fig. 8, the specific intensity changes due to
absorption. This change is represented by the exponential factor
~f
p*(S,</J) )
exp - µ dp' ( 41)
p~(0,</J) V
in the expression of I q~V I for each model. Due to the concentration de-
pendence of the attenuation coefficient, the modulus of the radiation flux
density vector, and hence the LVREA, becomes a functional of the con-
centration field inside the reactor. This functional characteristic of the
LVREA makes the problem of modeling a photochemical reactor more complex
than expected. The complexity is due to the coupling between the radia-
tion field evaluation and the resolution of the mass balance equations. The
860 De Bernardez, Claria and Cassano
of the reaction at each point I depends on the local value of the LVREA,
but the LVREA value is a function of the extent of the reaction reached at
all points in space through which every ray arriving at point I has pre-
viously traveled.
There are some special situations where this complexity is reduced.
Working with a perfectly mixed reactor, the absence of stable species con-
centration gradients inside the reactor volume makes the attenuation co-
efficient uniform in space. In this case the LVREA is no longer a function
of the concentration field but is still spatially dependent through its de-
pendence with I q I.
~\)
This condition may also be attained by working with a photosensitized
reaction independently of the mixing conditions in the reactor. In this
special kind of reaction, the absorbing species does not change its concen-
tration (i.e., it is not consumed). In this case, due to the spatial and
temporal uniformity of the concentration field of the absorbing species, the
link "progress of the reaction attenuation of radiation" is destroyed. In
the liquid phase, photosensitized reactions generally involve large con-
jugate molecules such as benzophenone. In gas-phase work, sulfur dioxide ,
benzene, and other organic molecules are used. In addition, metal vapors
have been particularly useful in gas-phase photosensitized reactions, such
as Na, Zn, Cd, and Hg, of which the latter has been applied most
extensively.
Another situation where the degree of complexity is lessened is in the
modeling of black body reactors. In this type of reactor, almost all the
absorption of radiation occurs in a thin layer close to the entrance of light.
This characteristic may be attained by working with a strongly absorbing
medium. In this case the attenuation can be modeled as occurring on the
reactor wall (i.e. , at the "black" surface). Consequently, the evaluation
of the radiant field is reduced to estimate the energy flux density on the
reactor wall.
EVALUATION OF THE LVREA FOR DIFFERENT REACTORS
The rate of initiation of a photoreaction is proportional to the LVREA (i.e.,
n act = <I>ea); the porportionality constant is the primary quantum yield.
The definition of this yield will depend on the nature of the process
concerned. The primary process may be defined, including both the initial
act of absorption and those immediately following processes which are de-
termined by the properties of the initially excited electronic state. In
almost all cases the primary process leads to a dissociation of the absorbing
molecule. For such cases the primary quantum yield may be defined as
= number of molecules dissociated by the primary process
number of quanta of radiation absorbed
<I> cannot be measured easily; to determine its value we must gain informa-
tion about the relative rates of the other possibilities more likely involved
in the primary process (recombination, physical quenching, etc.). Some-
times, these rates may be obtained by inspection of the absorption spectrum.
Then we may be able to estimate the value of <I> . To illustrate this we can
consider the photochemical dissociation of chlorine molecules: referring to
the potential curves for chlorine (Herzberg, 1950), the inequivocally show
Analysis and Design of Photoreactors 861
that upper states are unstable and the molecule dissociates very rapidly.
Then this process will predominate over all others and we can surely say
that, almost independently of the frequency considered, <i> = 1. Following
the statement of the second photochemical law (Turro, 1967), the maximum
possible value of <i> is unity; therefore, for the great majority of cases its
value may be taken as unity.
In addition, we may use the overall quantum yield as
number of molecules of a given reactant or
product finally decomposed or formed
<i>ov = number of quanta absorbed
This property will generally give an indication of the nature of the reaction
mechanism. If <i>ov is large, a chain mechanism is indicated; if it is small,
either deactivation or recombination is suggested, although other possibilities
must not be overlooked. It can clearly be seen that while <i> can never be
larger than unity, <i> ov can attain very large values. (Depending on the
chain length , it can be as large as 106. )
Expressions for the LVREA for different emission models were presented
earlier. There we mentioned that the integration limits will depend on the
geometrical configuration of the lamp-reactor system and, perhaps, the re-
flector. They constitute the major complexity in the evaluation of the radia-
tion field. For the three types of reactors described earlier, they will be
derived applying the VEES and the SELS models. The SEES model requires
the same equations for the lamp limiting values as the VEES model, with the
exception of the p coordinate, which need not be integrated because the
emission is produced by the surface of the lamp only. The final equations
for the LVREA and I q I also differ in the value of the characteristic con-
~\)
stant of the radiation source Kv (see Table 1).
To simplify the treatment, we will derive the values of I q I for mono-
chromatic radiation and isotropic emission. The extension to polychromatic
radiation and diffuse emission is straightforward.
In addition to the assumption already described for the emission model
and the lamp, we must add the following ones about the reactor (Irazoqui
et al., 1973):
1. The inner wall of the reactor is bounded by a cylindrical mathemati-
cal surface without thickness (i.e. , no reflection or refraction
occurs).
2. The opaque zones at the top and bottom parts of the reactor do
not reflect or emit radiation.
The modulus of the radiation flux density vector at any point in the
reacting space, I(r, S, z), is the energy flux arriving from all directions in
space and from the whole extension of the lamp. It can be obtained after
integration of
I qi ( 42)
The problem that will always be present along this section is centered on
the complexity of the limits for the integrals of Eq. ( 42).
862 De Bernardez, Clari6, and Cassano
Annular Photoreactor
VEES Model
In this case Eq. ( 42) is written as follows (see Table 1):
d 8 d ¢ d p sin 8 exp (f-
p*(i:l,¢)
pi(8,¢)
µ ( 43)
To obtain the integration limits, one starts from the point of reception
I(r,13,z) and investigates all the arriving rays with directions (8,¢). One
must find those that intersect the boundaries of the surface of the cylinder
representing the lamp (Fig. 9).
The limits for variable p are the intersections of this coordinate with
the front and rear parts of the lamp in any 8, ¢ direction:
2 2 2 2) 1 /2
r cos ¢ ± (r cos ¢ r + rL
( 44)
sin 8
The limits for variable 8 are obtained considering that the limiting rays
coming from the lamp and reaching the generic point (r, 13, z) must satisfy
two restrictive conditions: (a) a ray limits the 8 angle when its equation
has a common solution with the equation of the circumference that defines
the nonemitting zones at the upper and lower parts of the lamp; and (b)
the ray will be a limit when the common solution above corresponds to the
intersection of the ray with that portion of the circumference which, limited
by two generatrix lines corresponding to the ¢ limiting angles, is closer to
the generic point (r, 13, z). The second condition is needed because for
any plane at constant ¢, there are two 8 angles that satisfy the first re-
striction for both the upper and lower boundaries (Fig. 10).
FIGURE 9 Geometry and coordinate systems for direct radiation
Analysis and Design of Photoreactors 863
FIGURE 10 Limits of 0 and <P for direct radiation.
In this way, for e1 and e2 we obtain the following expressions
r cos <P - [r 2(cos 2 <P 1) + r~] 1/2
-1
e1(<P) = tan
L - z
(45a)
L
2 2
r cos <P - [r (cos <P - 1) + rL2] 1/2
-1 (45b)
e2(<P) = tan -z
A more rigorous approach should require computation of the reactor
and the lamp wedges. The three-dimensional characteristic of the emission
process causes the reactor to be partially irradiated in the incoming and
out going regions (Fig. 11a) . This fact increases the effective reaction
volume. This effect is more noticeable when the inner reactor wall is close
to the lamp. The expressions for the 0-limiting angles should be modified
in the partially irradiated regions; the reader is referred to Romero et al.
( 1983) for a detailed analysis of the reactor wedge computation. On the
other hand, Fig. 11b shows that the calculations should be corrected to
account for the effective lamp length. If no corrections were introduced,
we would be computing as emission volumes portions of the cylinder that
correspond to regions in the space where there is no emission at all. This
effect is also significant when the inner reactor wall is very close to the
lamp; for a more detailed analysis, the reader is referred to De Bernardez
and Cassano ( 1985).
The limiting rays in the <P direction can be obtained by imposing the
restriction that both intersections of the p coordinate with the lamp boundary
must coincide, that is ,
p = ( 46)
1
864 De Bernardez, Clari6., and Cassano
IRRADIATED
VOLUME
I 1r,/3,z>
s R
(a) (b)
FIGURE 11 ( a) Reactor wedges; (b) lamp wedges.
With Eq. ( 44) and since ¢ can take values only in the closed interval
[-rr /2,rr/2],
( 2 2) 1 /2
-1 r - rL
- ¢ 1 = ¢ 2 = cos r ( 47)
With these limits, Eq. ( 45) can be integrated to obtain
µ dp)
( 48)
SELS Model
In this case Eq. (42) becomes (see Table 1):
I~ I = K i LL d
-1p exp
~- f P*(8) µ dp'
) ( 49)
o p*(S)
0
Let us call
p( 8) cos 8 = r ( 50)
p( 8) sin 8 = z ( 51)
Then we have
dz d8
= ( 52)
2 r
p
Analysis and Design of Photoreactors 865
and finally ,
~-f
p*( 8)
d8 exp ( 53)
p*( 8)
0
where 81 and 82 can be obtained from Eqs. (44) and (45), making rL = 0
and <jJ = O. Again, a more rigorous approach should consider the reactor
wedges (see Fig. lla), as it was mentioned when the VEES model was
discussed.
Cylindrical Photoreactor with Elliptical Reflector
Four additional assumptions may be added to those given earlier ( Cerda
et al., 1973):
1. The reflector is a perfect elliptical cylinder.
2. The lamp is located in such a way that its centerline passes
through one of the focuses of the elliptical reflector (F1).
3. Specular reflection occurs with an average reflection coefficient
that is independent of wavelength and direction. (These restric-
tions could be easily relaxed and are used here for simplicity. )
4. The reflected radiation comes only from the elliptical reflector
(i.e. , the top and bottom parts of the cylinder do not reflect
radiation).
The radiation impinging at any point inside the elliptical cylinder is
made up of two parts: direct radiation and ref1ected radiation. Excluding
direct radiation, a ray could arrive at a point of reception with a given
direction by asingle reflection process or as a result of successive con-
tacts with the elliptical mirror. In the second case, for points located
close to the focus F2, the ray will describe a broken line touching the
surface of the reflector at least three times. The question is whether
it is always possible for a ray coming out of the lamp to undergo so many
reflections and still arrive at the point of interest. It can be answered
by following the ray path in the reverse way (i.e., starting from the point
of reception). A multiply reflected ray will be effective at a given point
in space if and only if, traveling the reverse trajectory previously de-
scribed and in spite of its progressive vertical displacement, it still inter-
sects the surface of the lamp boundary that is seen from the points of
incidence. Through the same reasoning, a multiply reflected ray would
have no real existence if this intersection falls outside the length of the
lamp.
The problem consists in finding the mathematical relationship between
the incident radiant energy flux and the reactor, lamp and reflector dimen-
sions, the optical properties of the reflector and the reactor wall, and the
physical properties of the radiation coming out of the source. The point
of reception (I) on the reactor volume is referred to a cylindrical coordinate
system located at the centerline of the cylindrical reactor with origin at
the reflector bottom (rI, SI, S) .
866 De Bernardez, ClarUi., and Cassano
VEES Model
Direct Radiation: For this case, the limits of integration for variable
p may be obtained in a similar way as for the annular reactor. The results
are (see Fig. 12)
b. cos <P ± [b.2 cos2cp - (b.2 - r~)]l/2
(54)
sin 0
where
(55)
(56)
2 2 . 2 1 /2
_ 1 b. cos <P - (rL - b. sm <f>)
= tan (57)
(l/2)(LRf - LL) - 1';1
. -1 rL
<P = sin - ( 58)
1 b.
(59)
20,_ _ _
1
i-7- ~-
i l/2(LRf+LL) I I
-l - -·-·- LR LR,
i
--iii.
I
FIGURE 12 Variables used in the determination of the limits of
integration.
Analysis and Design of Photoreactors 867
For direct radiation the final expression after integration of Eq. ( 43) is :
(60)
Indirect Radiation with Only One Reflection: The methodology of
analysis for reflected radiation is to follow a ray starting from the point of
reception in order to identify the point of reflection, and from this (apply-
ing the laws of optical physics) to search in the direction of emission. To
understand the analysis it is necessary to locate several key points (Fig.
13): first, the point of incidence of the reflected ray (point of reception
I); second, the point of reflection (P); and finally, the two points of
intersection of the direction of emission with the lamp cylinder (El and E2).
Any ray coming from the lamp will be indicated by an incidence position
vector at the point of reflection ( PE) and a reflection position vector at
the point of reception (PI). The former has its origin at P and the latter
at I. The intersections of PE with the cylinder of the lamp tube define two
vectors, PE, 1 and PE, 2. The details of the geometrical derivations and
definitions of the variables are explained in the appendix to this chapter.
The results are
D cos !; ± (r~ - D 2 sin 2 !;) 112
p = (61)
E 2 ,l sin 0
( 62)
FIGURE 13 Variables involved in the analysis of indirect radiation with
only one reflection.
868 De Bernardez, Claria, and Cassano
+ D cos I; - (r~ - D 2 sin 2 o 112
( 63)
(1/2)(LRf - LL) - z;I
( 64)
Then the integration of Eq. ( 43) in the p coordinate gives us the
following expression for the modulus of the radiation flux density due to
indirect radiation with only one reflection:
d8 exp ( - JPi<e,cp)
p*(8,¢)
µ
(65)
where the attenuation of the radiant beams at the mirror surface was
taken into account using the reflection coefficient of the elliptical mirror
fRf·
Indirect Radiation with Two or More Reflections: As explained earlier,
the mathematical analysis is accomplished by considering the broken trajec-
tories of the rays arriving at the reaction surface after more than one
reflection. The derivation will not be presented here. Details may be
found in Cerda et al. ( 1977).
Asymmetries: An additional problem with this system is originated by
the azimuthal asymmetry. This is due to the overlapping of two effects:
the arrival of direct radiation (only on the points situated in front of the
lamp) and the existence of umbra and penumbra zones, giving rise to non-
uniformities in the indirect radiation. When the characteristics of the re-
actor generate important asymmetries, the addition of angular terms to the
mass balances transforms all problems from two- to three-dimensional.
A previous work (De Bernardez and Cassano, 1982) showed that for
this system the uniform angular distribution will be obtained only if one
works with a reactor diameter /lamp diameter ratio lower than O. 5 and with
an eccentricity as low as possible (about 0. 4). If one wishes to work with
higher eccentricities, the reactor diameter /lamp diameter ratio should be
lower than O. 2. It is recommended that values of the distance between
focuses of the ellipse be as large as possible.
SELS Model
Direct Radiation: The expression of the modulus of the energy flux
density vector for this model is similar to that obtained for the annular
reactor, but r must be replaced by t,, , with t,, given by Eq. ( 55)
= f 182 d 8 exp ~- Jp*(8) )
µ d p' ( 66)
81 pi( 8)
The limits in the 8 coordinate can be obtained from Eqs. ( 56) and ( 57),
making ¢ = 0 and rL = 0.
Analysis and Design of Photoreactors 869
.-----2c---~
FIGURE 14 Projections of reflected ray trajectories.
Indirect Radiation with Only One Reflection: All reflected rays must
lie on planes that also contain the reactor axis. A ray which after reflec-
tion reaches the reactor centerline may be projected on a plane that goes
through the point of emission and is perpendicular to the lamp axis. The
length of this projection is equal to 2a (Fig. 14).
Each one of these planes allows us to define a circumference con-
structed with the locus of all the end points of rectified rays (Fig. 15).
This can be done in this way because the reflector is a cylinder and the
lamp is assumed to be a line parallel to the generatrix line of the mirror.
This circumference may be repeated for each point of emission of the lamp,
giving rise to a cylinder of circular cross section of radius equal to 2a.
This cylinder may be thought like a virtual surface of emission that acts
as a substitute for the linear lamp. Taking a planar cross section going
through the reactor focal axis of the elliptical cylinder, we finally obtain
a situation like the one depicted in Fig. 16. Points such as those
C
D
\ I
\ I
\\ I
B \ /
' \ I
', \ I
I
', \ I
: ..~ i - - - - - 2 0 - - - ~
/ I \
// I \
/// I \
G I \
I \
I \
I \
I \
E
F
FIGURE 15 Locus of end points of rectified rays.
870 De Bernardez, Clari6, and Cassano
I 1
l
I I
LL
2a
I
I
I
2a
J
FIGURE 16 Limiting angles for the 8 coordinate.
designated in Fig. 15 with letters A, B, C, D, and so on, when converted
into straight lines as is done for one cross section in Fig. 16, represent
the way in which the linear lamp would be seen by observers located at
the reactor centerline if they looked in the indicated directions. The pro-
jection of the actual distance travelled by any ray with direction e on the
lamp centerline is
2a
-.--
Sln 8
cos 8 = 2a cot e ( 67)
The key point, as in any emission model, is to know the limits of the
8 angles (i.e. , out of all those 8 directions arriving at the reactor axis
which are really coming out of the "line" source). If the ray effectively
comes out of the lamp (i.e. , if it is a direction that transports energy),
its projection given by Eq. ( 67) must lie within the lamp longitudinal dimen-
sions. This allows us to define the limiting angles for e in the following
manner:
2a - r
-1 I
e1 = tan (1/2)(LRf + LL) - ( 68)
r,:I
2a - r
e2 = tan -1 I
(1/2)(LRf - LL) -
( 69)
r,:I
2a + r 1
03 = tan --1 ( 70)
(1/2)(LRf + LL) - r,: I
2a + r 1
8
4
= tan -1 (1/2)(LRf - LL) - (71)
r,:I
To compute the reflected radiation at point I, we have split the integral
into two parts to account for energy contributions from the whole closed
reflecting surface of the elliptical mirror. The final expression for the
modulus of the radiation flux density of the reflected radiation with the
linear model is
Analysis and Design of Photoreactors 871
+ 2 1 fe4 de exp (- f P*(S) µ dp') ] (72)
a + rl e3 *( 6)
Po
It should be stressed that since it is a linear model, we have lost the
integration in the cp coordinate, which must always be taken into account
when an extense model is used (with finite dimensions for rL).
Cylindrical Photoreactor with Parabolic Reflector
Here again we may have direct and reflected radiation. For the analysis
we will require two coordinate systems. The first one (xF-YF-zF) is
defined with the origin at point F located at the center of the bottom of
the empty cylindrical reactor, with YF, consequently, being its centerline
(Fig. 17). An auxiliary coordinate system parallel to the former is also
needed. Its center is located at the point of incidence designated by I
in Fig. 17 and it can be moved all over the space under analysis.
VEES Model
Direct Radiation: For this case, the limits of integration may be ob-
tained in a similar way as for the annular and elliptical reactors. The
results are
t. 1 sin cp + t. 2 cos cp [r~ - (t. 2 sin cp - t. 1 cos ¢) 2 ] 112
sin e ±----- -------
sin e ----
(73)
FIGURE 17 Geometry of the tubular source with parabolic reflector.
872 De Bernardez, Claria, and Cassano
where
111 = Y1 + 1 - a ( 73)
112 = rl sin r3i (74)
p'
-1 1
01 ( <P) = tan (75)
LL/2 + z1
p'
-1 1
02(<1>) = tan - (76)
LL/2 + z1
P1 = - 11 1 sin <P - 11 2 cos <P [ri - (11 2 sin <P - 11 1 cos <1>) 21112 1
(77)
The limits for <P are obtained from the solution of the implicit equation
r ~ - ( 11 2 sin <P - 11 1 cos <P ) 2 = O (78)
and the final expression for Iq I is
sin <P - 11 1 cos
(79)
x exp - (f P*(0,<j))
µ dp')
p6(0,<j))
Indirect Radiation: The methodology of analysis for this type of radia-
tion is similar to that employed with the elliptical photoreactor and will not
be repeated here. The expression resulting for the modulus of the radia-
tion flux density due to indirect radiation is identical to Eq. (65).
The limits for the p variable are the same as those which were obtained
for the elliptical photoreactor, that is,
D cos E; ± (r~ - n2 sin 2 o 112
(80)
P2,1 = sin 0
But the meaning of the variables in this case is
D = (x2 + y2)1/2 (81)
L L
1
sin E; = D (xL sin <j)E - yL cos <j)E) (82)
Analysis and Design of Photoreactors 873
cos l; = (83)
where
(84)
(85)
-1 (1 - G 2)sin <P - 2G cos <P
<PE = t an (86)
(G 2 - l)cos <P - 2G sin <P
-2a (87)
G =
xp + b. 2
The limits for the e variable are represented by the following
expressions:
2 2 . 2 1/2
-l Pi + D cos l; - (rL - D sm l;)
= tan ---------------- (88)
LL/2 - z1
2 2 . 2"")1/2
-l Pi + D cos l; - (rL - D sin "'
= tan - ---------------- (89)
LL/2 + z1
and
2a tan <P - b. 2 - 2[a 2 (1 + tan 2cp) + a(b. 1 - b. 2 tanq,)] 112
p' = - - - - - - - - - - - - - - - - - - - - - - - - - - (90)
1 cos </l
To obtain the limits for the <P variable, we must solve (as in the case
of the elliptical photoreactor) the following implicit equation:
( 91)
Finally, it should be mentioned that in certain cases it may be neces-
sary to put a protecting cover over the emission system which can also be
used to support the cylindrical reactor (see Figs. 18 and 19). If this is
the case, there will be totally and partially irradiated zones within the re-
action space. Consequently, for each incidence point I, we have to deter-
mine which portion of the parabolic reflector or source is capable of
illuminating the point. From the mathematical point of view, the integration
interval for each point I must be adjusted. To do this, the limiting angles
determined by the circular hole of the lamp-reflector cover system must be
calculated (see Figs. 18 and 19) , and afterward compared with the limiting
angles defined for the integration of the source volume [Eqs. (88) to (91)].
For more detailed information, the reader is referred to Alfano et al.
(1984b).
874 De Bernardez, Claria, and Cassano
FIGURE 18 Illustrative representation of changes needed in the limits for
e due to the shape of the emitting system.
SELS Model
Direct Radiation: The expression for this case is the same as the one
given for the annular reactor, but replacing r by D. with D. given by
(92)
The limits in the e coordinate can be obtained from Eqs. (75) and (76)
making r L = 0 and
'P1
X
''
''
'
'' t
a
FIGURE 19 Illustrative representation of changes needed in the limits for
<P due to the shape of the emitting system.
Analysis and Design of Photoreactors 875
tan <P (93)
Indirect Radiation: Following the same approach as the one derived to
obtain I q I for the elliptical reflector, we get
I gI = Kf Rf
102 1
de p' + p'
I E
~ r•(e)
exp -
p*( 0)
µ dp) (94)
el 0
where
p' + p'
-1 I E
01 = tan (95)
LL/2 - z1
p' + p'
-1 I E ( 96)
02 = tan
LL /2 + ZI
4a(Li 1 +a) Li 2
2 (97)
p' =
I 4a
abd
p' = [(Li 1 - p' )2 + Li;]l/2 (98)
E I
Inability of the Linear Models to Predict the Radiation
Field When Curved Reflecting Surfaces Are Part
of the Emitting System
From previous theoretical developments it is clear that the linear models are
much simpler to use than the extense ones. The computing time is con-
siderably reduced, and consequently they should always be the starting
equations for photoreactor design. Cerda et al. (1978) and Romero et al.
(1983) showed that for certain cases the SELS model provides good results.
For the annular type of reactor, where only direct radiation is involved,
errors are never larger than 15%. A recent work (Claria et al., 1986b)
showed that under no conditions can linear models be used if curved reflect-
ing surfaces combined with tubular lamps are employed. This work con-
firmed experimental results of Alfano et al. ( 1984), regarding the validity
of linear models when a reflector is used. We will not reproduce here the
details of these papers , but we shall present a brief summary of their main
results as well as of their conclusions.
Figures 20 and 21 show computed and experimental results for two
reactions (chlorination of ethane and photodecomposition of uranyl oxalate)
carried out in an elliptical photoreactor. Plots include predictions with
the SELS model and the VEES model. It is obvious that the error of the
linear model is intolerable for any practical purpose. [The details are
given in Claria et al. (1985b; 1986a,b).]
Table 2 clearly shows that when only direct radiation is considered the
differences between the linear model and the extense one are negligible.
876 De Bernardez, Claria, and Cassano
.
60
'· '·'·
'·....... '·Ill
40
.·-·-.• -·,
...............
.......
30 LR=30 cm
% Cl2= 2
% EtH = 4
20 - - SELS Model
-· -· VEES Model
10
0
/200 /600 2000
FIGURE 20 VEES model and SELS model theoretical predictions compared
with experimental results for ethane photochlorination.
Even though there exist conditions where this approximation is not good, it
can be safely used for most engineering purposes (see Claria et al., 1986b).
Table 3 shows experimental verifications performed in a system which
has a cylindrical reflector of parabolic cross section under the following
experimental conditions: measurements of total and only direct radiation
were performed with a precise thermopile; and they were done with the
radiation probe receiving the sum of both direct and indirect radiation and
with the same sensing device but the reflector covered with a copper sheet
completely masked with carbon deposition. The data were obtained for dif-
ferent positions in space and the results compared with predictions made
the SELS model and the VEES model. In all cases previsions were taken in
the computation of the radiation field to account for the orientation and
finite size of the sensor (thermopile). Clearly, in cases like this, the linear
models are useless. [The details may be found in Alfano et al. (1984),]
Without going into the details of the theoretical proof of this inability
of the linear models to predict reflected radiation, let us explain the
reasons in an intuitive way. When the tubular lamp is placed parallel to
the generatrix straight line of the cylindrical reflector and it is modeled as
a straight line, the source does not "recognize" the curvature of the reflect-
ing surface. Hence the concentrating effect of the curved mirror, be it
elliptical or parabolic, cannot be predicted.
Analysis and Design of Photoreactors 877
rR = 0.2 cm
¾Xox LR= 12 cm
cgx = 2.63 10- 3 M
Cur= 0.517 10- 3 M
40
-SELS Model
-•-VEES Model
:,o
'\
t
\
\
20
\
/0
~
·,..........
-~.
--::..-._ ·---·-·-
0 L.=:::::::=:=""""'---'---....1----'-
o 40 80 /20 /60
Q (cm 3 min- 1 )
FIGURE 21 VEES model and SELS model theoretical predictions compared
with experimental results for uranyl oxalate photodecomposition.
TABLE 2 Comparison of the SELS and VEES
Models for Direct Radiation (Elliptical
Reflector System)a
I gl D x 10 7 (einstein/cm 2 •s)
rL/c SELS VEES
0.018 0.031 0.031
0.022 0.047 0.046
0.025 0.058 0.058
0.030 0.083 0.082
0.033 0.102 0.100
0.037 0.127 0.123
0.040 0.143 0.139
0.050 0.215 0.205
878 De Bernardez, Clari<i, and Cassano
TABLE 3 Direct-to-Total Radiation Ratio: Comparison of The SELS and
VEES Models (Cylindrical Reactor Irradiated from the Bottom)a
Contribution of direct radiation to total radiation
Prediction of Prediction of
Cylindrical SELS model VEES model Experimental
coordinate (%) (%) values (%)
yI = 12.02 cm 69. 0 27.7 29.2
r 1 = 2.80 cm
SI = rr / 4
y 1 = 12. 02 cm 69.3 28.1 30.8
r 1 = 1. 69 cm
SI = 0
y 1 = 12.02 cm 69.2 28.0 31.2
r 1 = 2.99 cm
SI= 0
y 1 = 12.02 cm 69.1 27.7 31. 6
r 1 = 4.35 cm
S = 0
I
a
a, 2.1 cm; !l, 8.4 cm; rL, 0.95 cm; LL, 15.2 cm; lamp, GE UA3-360.
Depending on the significance of direct radiation on the total radiation
flux density, the error may go from more than 100%, as in the case of the
parabolic reflector, to up to more than two orders of magnitude for the
case of the elliptical one.
In conclusion: for most practical purposes, when only direct radiation
is involved, the linear models can be used. When reflecting curved surfaces
are present, only the extense source type of model can be used. The
finite size of the radius of the tubular lamp must be incorporated in the
model, and in this way the extent of the emission source will be able to
recognize the curvature of the mirror and its concentrating effects.
PHOTOREACTOR DESIGN: APPLICATIONS
For the photoreactor design problem stated earlier, all the theory has now
been developed. In this section we show how it is possible to perform the
design of a photoreactor. To do so, we have chosen four applications.
The first deals with the design of an annular photoreactor with simple
kinetics. The methodology is applied to a bench-scale reactor and the
Analysis and Design of Photoreactors 879
theoretical results are compared with experimental data. The second is a
gas-phase photochlorination, a typical chain reaction. Again the theory is
presented and applied to a bench-scale photoreactor inside an elliptical
reflector. Results are also compared with experimental data. A third
problem deals with a heterogeneous reaction. Problems related to the gas
absorption, the reaction rates, the radiation field in a two-phase system,
and the mixing states must be taken into account to formulate a rigorous
model. The method is applied to a chain reaction and one must search for
simplifications that could reduce the design problem to a tractable one.
Once more, predictions for a bench-scale system are compared with experi-
mental results. Finally, the optimal design of an annular reactor for con -
secutive photochlorinations is illustrated in the fourth application. Here the
whole process of designing a photoreactor is presented in detail, starting
with the information that a practicing engineer would have at hand to
begin work.
Simple Kinetics in a Continuous Annular Photoreactor
with Almost Monochromatic Radiation
Consider the isothermal steady-state photodecomposition of a solution of
uranyl oxalate flowing through an annular reactor irradiated by an ultra -
violet arc lamp located at its axis. For the bench-scale lamp and reactor
characteristics listed below, we wish to study the incidence of the volumetric
flow rate on the oxalic acid exit conversion.
Reactor characteristics: rin == 2. 3 cm; r 0 u == 2. 7 cm; LR == 30 cm.
Lamp characteristics: GE G15T8 (15 nominal watts); LL== 43 cm; rL ==
1. 25 cm. Uranyl oxalate initial composition (UO2SO4): 1 x 10-6 mol/cm 3 ,
H2C2O4: 5 x 10-6 mol/cm3.
The uranyl oxalate photochemical decomposition is a well-known chemical
actinometer. ·chemists have found that the rate of oxalic acid decomposition
is proportional to the local volumetric rate of energy absorption, where the
proportionality factor is the overall quantum yield, It represents a good
example of a photochemical reaction that can be modeled using an overall
kinetics. To find the relationship between the oxalic acid exit conversion
and the volumetric flow rate, we must solve the mass balance equation for
the oxalic acid.
We can introduce the following assumptions and/or simplifications in the
general equation: (a) negligible thermal effects; (b) steady state
( cl C0 x / cl t == 0) ; (c) physical properties such as velocities, diffusivities, and
densities are constant through the reaction volume; ( d) axial laminar flow;
(e) Newtonian fluid; (f) azimuthal symmetry; and (g) axial diffttsion
negligible when compared with the convective flux. If the hypothesis above
are fulfilled, the mass balance equation for the oxalic acid reduces to
clC l "0 ( clC )
v (r) ~ == D - - - r ~ + &1 ( 99)
z cl z ox r cl r cl r ox
with the following boundary conditions:
clC
OX
v-z ' == 0 (100)
clr
880 De Bernardez, Claria, and Cassano
ac
ox
r = rou' v-z ' = 0 (101)
ar
and
V-r, z = 0, C = co (102)
OX ox
We assume that the velocity profile is fully developed; for example,
allowing the existence of an entrance region, we can express
1 - (r/r. ) 2 + [(1 -
1n
/ln(l/x)] ln(r/r. )
1n
x2>
v (r) = 2<v> - - - - - - - - - - - - - - - - - - (103)
z 1 + x2 - [(1 - x2)/ln(l/x)1
where x = rinlrou·
Finally, to solve the mass balance equation, we need an expression for
the reaction rate rlox· We know that n0 x can be expressed by
n = -cp ea (104)
ox ov
Now we need some data about the absorption characteristics of the
uranyl oxalate solution. Light is absorbed by the uranyl oxalate complexes,
which are decomposed into water, carbon dioxide, carbon monoxide, and
formic acid, while the uranyl ion remains unchanged. The overall reactions
are
2+ 2+
00 2 + H2c 2o 4 + hv - 00 2 +CO 2 + CO+ H 20
2+ 2+
00 2 + H 2cp 4 + hv - - - 00 2 + co 2 + HCOOH
The relative significance of each reaction path depends on the pH of the
solution. Nevertheless, the overall rate of oxalic acid decomposition is pro-
portional to the LVREA and independent of the reaction path.
Eighty-five percent of the radiation power output of the lamp falls into
a single wavelength ( 11. = 2537 A) • The absorption characteristics of the
uranyl-oxalate complex show the following significant variations
-1
11. (A) µ (cm ) cI> (mol/einstein)
ov
2250 16.71 0.56
2950 1. 96 0.57
3450 0.17 0.51
It is then clear that the reactor can be safely modeled as operating with
monochromatic radiation.
The chemical nature of the absorbing species changes with the com-
position of the solution. However, a useful data for solving the modeling
problem would be a plot of the attenuation coefficient versus the oxalic
acid concentration, at constant uranyl ion concentration (Fig. 22). The
Analysis and Design of Photoreactors 881
0
0 2 4 6
Cox (mole cm- 3 l x 108
FIGURE 22 Attenuation coefficient as a function of the oxalic acid
concentration.
plot shows that the attenuation coefficient is not a linear function of the
oxalic acid concentration, which agrees with the fact that the oxalic acid
is not the actual absorbing species. The experimental data were fitted to
give an analytical expression for the concentration dependence of the attenu-
ation coefficient :
2.362 + 3.372 x 10 6c
-1
µ (cm ) = 9. 582 x 10 11c 2
OX ox
(105)
+ l, 286 X 10 17c 3 - 6,527 X 10 21 c 4
ox OX
valid for Cur = 1 x 10-6 mol/cm3, A = 2537 A, and Cox expressed in
mol/cm 3 .
Figure 22 shows that when the molar ratio of oxalic acid to uranyl ion
is 4 or greater, the attenuation coefficient is almost constant (i.e., practical-
ly independent of the oxalic acid concentration). Hence, starting with a
solution of composition uo 2so 4 1 x 10-6 mol/cm3 and H2C2O4 5 x 10-6
mol/cm3, if the reaction proceeds without exceeding a maximum permissible
conversion value of 20%, the attenuation coefficient can be considered to
be constant during the reaction. This characteristic of the actinometer is
generally pointed out in the literature without further analysis. Although
a constant value of the attenuation coefficient allows us to simplify calcula-
tion of the local volumetric rate of energy absorption, we are not able to
use this property in modeling a continuous, segregated flow reactor. In
these reactors, as a result of the unavoidable concentration gradients,
there are regions where the requirement of maximum 20% conversion may be
violated although the average exit conversion does not exceed that value.
Figure 22 also shows that the value of the attenuation coefficient is
greater than O. 4 cm-1 for the whole range of oxalic acid concentration.
Hence, considering the criterion drawn earlier for the absorption process
in heterogeneous media, we can neglect the distortion effect produced by
the presence of CO 2 and CO bubbles.
882 De Bernardez, Claria, and Cassano
The oxalic acid mass balance represented by Eq. ( 99) to ( 102) cannot
be solved analytically. Any of the numerical methods recommended for
parabolic differential equations can be used, combined with an appropriate
integration technique (Gauss, Simpson, etc.) for calculating ea.
Since the GE G 15T 8 is a nonfluorescent ultraviolet arc lamp, the ap-
propriate model to describe the radiation field inside the reactor is the
VEES model with isotropic emission. However, as pointed out earlier, the
SELS model can also be used as a good approximation to predict the radia-
tion field inside an annular reactor because only direct radiation is present.
Using the SELS model with isotropic emission, the computing time required
to evaluate the LVREA is lessened.
Either with the VEES model or with the SELS model the solution strategy
must account for the functional characteristics of the LVREA (i.e. , in order
to evaluate it we need to know the oxalic acid concentration field inside the
whole reactor volume). Generally, the numerical procedure follows the
direction of the flow; in this case, when solving each point, we should com-
pute bundles of radiation traveling through regions already calculated (up-
stream section) together with bundles coming from regions whose concentra-
tion field has not been calculated yet (downstream section). Then, to solve
the problem, we must follow an iterative scheme, until reaching a "steady-
state" oxalic acid concentration field. Finally, after finding the "steady-
state" concentration field, we estimate the oxalic acid exit conversion as
follows:
<c ox >
X 1 - co (106a)
OX
ox
where
<c ox> (106b)
Figure 23 shows a plot of the oxalic acid exit conversion as a function
of the volumetric flow rate calculated using the SELS model together with
Eq. ( 105) for the attenuation coefficient µ ( solid line) . In the same figure
experimental results obtained in our laboratory are depicted.
This example shows that it is possible to perform an a priori design of
a photochemical reactor if we use an appropriate emission model to estimate
the radiation field. The agreement between the experimental results and
the theoretical predictions shown in Fig. 23 corroborates what we have
said. Later we will see that an a priori design of more complex reactions
and reactors can be performed with a similar degree of accuracy. For
more detailed information about the example, the reader may refer to
De Bernardez and Cassano ( 1985).
Complex Kinetics in an Elliptical Photoreactor
with Polychromatic Radiation
A gaseous mixture of N2, Cl2, and C2H5 is fed into a bench -scale elliptical
photoreactor (described in Fig. 2) whose characteristics are listed below.
For the same assumptions made in the preceding example (steady state,
Analysis and Design of Photoreactors 883
50
¾Xox
25
0
0 /00 200 300 400
FIGURE 23 Comparison between theoretical predictions and experimental
results for the photodecomposition of oxalic acid. Effect of the volumetric
flow rate.
laminar flow, isothermal operation, etc.) we wish to study the incidence of
the feed composition on the chlorine conversion for low-percental values of
the chlorine fraction in the feed. (These conditions may be convenient to
overcome undesirable thermal effects and avoid side reactions and conse-
quently improve product selectivity.)
Reactor characteristics: LR = 30 cm, rR = 0. 2 cm; reflector character-
istics: LRf = 59 cm, a= 53.5 cm, e = 0.4; lamp characteristics: GE G30T8
(30 nominal watts), LL= 81.3 cm, rL = 1.25 cm.
Under unrestricted design conditions, the existence of direct radiation
and umbra and penumbra zones for the reflected one originates angular
asymmetries in the radiation field. They induce the same problem in the
concentration field. However, it has been shown (De Bernardez and
Cassano, 1982) that when the ellipse eccentricity is low (,( 0. 4) and the
ratio of rR /rL is small ( <0. 5) azimuthal asymmetries inside the reactor can
be safely neglected. This condition implies that a three-dimensional mass
balance can be avoided, making computations considerably simpler. To
take advantage of this convenience, the conditions above have been fulfilled
in this example. Re and Cassano (1986) showed that under normal practical
conditions (rR > rL), the three-dimensional modeling of the reactor is almost
indespensable. With this exception only, the design method here described
can be applied to any reactor size and configuration.
The proposed low chlorine concentration in the feed, together with the
presence of an inert gas, allow us to safely assume that:
1. The main reaction products will be hydrochloric acid and mono-
chloroethane. This assumption can be easily confirmed with experi-
mental results.
2. Under the stated operating conditions thermal effects will be small.
Hence isothermal behavior is applicable.
884 De Bernardez, Claria, and Cassano
The overall reaction is
Several research groups have made detailed studies of the chlorination
kinetics of saturated hydrocarbons. They have proposed similar reaction
mechanisms. Gosselain et al. (1956) indicated a general mechanism for the
gas-phase halogenation of saturated hydrocarbons for both thermal and
photochemical reactions that include the possibility of using nonpolar sol-
vents. The reaction mechansim has all the possible reaction steps that are
feasible under low chlorine concentrations and temperatures below 600K.
a
Cl 2 ~ 2Cl• Initiation
k 2
-
Cl• + EtH _£_ CIH + Et•
k
p-2
Propagation steps
k 3
Cl + Et• _E_____ ClEt + Cl•
2 ~
p-3
k
Cl• + Cl• + M _!!__ Cl 2 + M
k
Cl• + Et • ~ ClEt Homogeneous termination steps
kt6
Et• + Et• - c 4H 10
The authors also reported that heterogeneous termination reactions (at the
wall) may be safely neglected. This was also precisely shown by Claria
et al. ( 1985a).
Under these conditions, eight species are present, which will be identi-
fied , for simplicity, in the following manner:
Species Cl 2 Cl EtH EtCl Et HCl C 4H 10 N2
Number 1 2 3 4 5 6 7 8
From the momentum balance under the described operating conditions
(fully developed laminar, Newtonian and imcompressible flow), we have
2
vz<r) = 2<v> [1 ( :R) ] (107)
Neglecting thermal effects, we only need the radiation balance for the
LVREA and the mass balance equations. They will be derived under the
Analysis and Design of Photoreactors 885
assumptions and simplifications described in the previous application.
The mass balance for species i is
( 108)
with
z = 0, ¥-r ' C. = C? ( 108a)
1 1
ac.
1
¥-z ' r = 0, = 0 (108b)
ar
ac.
1
¥- r = rR' = 0 ( 108c)
z' ar
If heterogeneous reactions were present, the boundary conditions for
the species at r = rR should be changed to
ac.
D _J = ( 108c')
¥-z ' jm ar
where the summation must include all the heterogeneous steps where
species j participates; Qh is the rate of the h heterogeneous termination
step and Vjh is the stoichiometric coefficient of species j in the h hetero-
geneous step.
In Eq. (108) for the eight homogeneous steps included in the reaction
mechanism we have
r=8
Q.
1 = L V. Q
1r r
(109)
r=l
Hence the rates of formation of species i are
Ql = -<Iie a - k p3clc5 + kt4c8c22 + kp-3c2c 4 (110)
Q2 = 2<Iiea kp2c2c3 + kp-2c5c6 + kp3clc5
(111)
2
-kp-3c2c 4 - 2kt4c2c8 - kt5c2c5
Q3 = -kp2c2c3 + kp-2c5c6 (112)
Q4 = kp3clc5 kp-3c2c 4 + kt5c2c5 (113)
Q5 = kp2c2c3 k p-2c5c6 - kp3clc5 - kt5c2c5
(114)
2kt 6c; + kP_ 3c 2c 4
886 De Bernardez, Claria, and Cassano
S16 = kp2c2c3 (115)
2 ( 116)
S17 = kt6C5
De Bernardez and Cassano ( 1986) and Claria et al. (1985a) showed
that in these systems the local or microscopic steady-state approximation
for intermediate unstable species can be applied without error. Hence
Eq. (111) and (114) can be set equal to zero:
S1. = 0 for i = 2 and 5 (117)
1
These two algebraic equations are still coupled with the mass balance
equations through the reaction rate term. In addition, Eq. ( 110) and ( 111)
clearly show the coupling of the mass balance equations with the radiation
balance through the rate of the activation step.
Since a curved reflecting surface is present, extense models (VEES
or SEES) must necessarily be used. On the other hand, the GE G30T 8 is
a nonfluorescent ultraviolet (UV) arc lamp, so the appropriate model to
describe the emission process is the VEES with isotropic emission.
The reacting system is homogeneous (gas phase) and chlorine is the
only absorbing species in the wavelength of lamp the emission of the lamp.
Hence
= a
V
c1 I q
-V
I (118)
where av is the absorption coefficient of chlorine.
From the emission characteristics of the lamp (see Table 4) approxi-
mately 90% of the output energy falls into the UV region. Out of this
amount, about 95% is emitted in a single wavelength ( 2537 A). However,
we will not consider monochromatic radiation because the absorption by
chlorine in this line is low, having instead much higher values at longer
wavelengths. Thus
(119)
Since the total energy flux density vector results from the contribu-
tions of direct and indirect radiation (the latter with one or more reflec-
tions), in Eq. (119) we have
l<ivl = l~vlD + I <ivlln,1 + ••· + l~vlln,n (120)
When the hypothesis of azimuthal simmetry is used, it can also be
shown that if c is sufficiently large, only indirect radiation with one re-
flection is significant. Hence we can safely consider only this contribution.
Its expression was derived earlier [Eqs. (40) and (65)]:
Analysis and Design of Photoreactors 887
TABLE 4 Spectral Distribution of Power
Output for the GE G 30T 8
Wavelength E;>.. x 107
interval (A) E:>.. (W) (einstein / s)
2200-2400
2400-2600 8.34 174.20
2600-2800 0.01 0.226
2800-2900 0.02 o. 476
2900-3000 0.03 0.739
3000-3100 0.02 o. 510
3100-3200 0.16 4. 211
3200-3400 0.01 0.276
3400-3600 0.01 0.292
3600-3800 0.17 5.255
3800-4000 0.01 0.326
4000-5000 0.66 24.814
5000-6000 0.33 15.164
6000-7000
Source: General Electric Co. (1967).
(121)
For the wavelength range of this application, the quartz transmittance,
the average reflection coefficient and the primary quantum yield are con-
sidered independent of v. For the latter, in addition, its value is taken
equal to 1.
In Eq. (121), only EL,v (lamp specific power output) and av (chlorine
absorptivity) are wavelength dependent. Hence we may write
X f \)=co dv E a,
L,v v exp ( - f p*(0,<jl)
a,VCl dp'
)
v=O pi(0,<jl) ( 122)
888 De Bernardez, Claria, and Cassano
Let us separately analyze the wavelength-dependent integral:
d
V
E
L,V
a
V
exp - (f P*(S,cj>}
(123)
pi(<P' 6)
av exp -
(
f ice, <P >
P
P*(6,cj>}
a" c 1 dp'
)
(124)
= f "2=500oA
dA E a
(
exp -
p*(0,<P)
a C d p'
)
(125)
"1=2200A L,>. " ~~(0,<P) " 1
In Eq. ( 125) the wavelength interval has been reduced to the region
in which we simultaneously have significant absorption by chlorine and
emission from the lamp (see Tables 4 and 5). Furthermore, considering
that the absorption by choroine is continuous (Herzberg, 1950) and the
lamp emission is discrete in very well defined lines, Eq. ( 125) can be written
TABLE 5 Chlorine Absorption Coefficient
lQ- 3 3
[ aCl ] Jl,n x 10-
X
[aCl ] Jl,n
"(A) 2
(cm 2 /mol) "
(A)
2
(cm 2 /mol)
2450 1.08 3750 41.13
2550 3.33 3850 23.49
2650 4.96 3950 14.23
2750 10.62 4050 9.89
2850 28.78 4150 7.22
2950 55.98 4250 5.73
3050 92.33 4350 4.09
3150 127.33 4450 2.94
3250 145.46 4550 2.02
3350 146.59 4650 1.34
3450 123. 11 4570 0.88
3550 93.47 4850 0.66
3650 64.51 4950 0.21
Source: Calvert and Pitts (1966).
Analysis and Design of Photoreactors 889
J
n
( p*(8,¢)
A = L J d;,_ EL .cS (;,_ - A.)o:. exp -
,1 1 1 p6(8,¢)
dp' c\Cl) (126)
i=l
f
n
( p*( 8, ¢) )
= L EL .o:. exp -
,1 1 *( B ¢)
Po '
dp' o:.c 1
1
( 127)
i=l
where n are all the lamp spectral lines of emission and the summation must
be taken over all the n values were o:i i- 0. cS is the Dirac function; EL ,i
and o:i are the values of EL and o: at A = Ai. In going from Eq. ( 126)
to Eq. ( 127) we have made
= EL .cS (A - A.) ( 128)
,1 1
This is equivalent to substitute a polychromatic radiation source by n
hypothetical monochromatic devices, which simultaneously occupy the same
physical space. Each of them emits a single frequency which corresponds
to one of the emission lines of the polychromatic source.
The mass balance equations are solved in a r-z plane. However to
evaluate the LVREA we must consider bundles of radiation coming from
every direction in space and from the whole volume of the lamp. Con-
sequently, rays not belonging to the r-z plane should also be considered
in the calculation. This makes it necessary to evaluate the real distance
traveled by each energy bundle and the sequence of concentrations found
along its path; considering the azimuthal symmetry, it is possible to find
the required_ information by performing a cylindrical projection on the rays
on the plane r- z (Fig. 24). [For further details see Romero et al. ( 1983).]
Substituting Eq. (127) into Eq. (122) and solving Eq. (108) with
Eqs. (110) to (117) we can treat the problem with any conventional numeri-
cal procedure. We should only recall that to obtain the I q I value at
~v
each point, we need to use the methodology indicated in Fig. 24 and the
computation of the radiation field as described earlier. The solution pro-
vides the concentration field for each species i. Finally, the averaged
exit conversion is defined as
c 0 - <c >
1 1
( 129)
X
co
1
and the value of <C1> may be obtained as it was illustrated in the pre-
ceding application [Eq. (106b)].
Claria et al. (1985a,b) solved this system and compared the predicted
values with experimental results obtained in a bench-scale reactor. Some
of their results are shown in Figs. 25 and 26, where the incidence of the
feed composition upon the chlorine conversion is analyzed.
Considering that no adjustable parameters have been used and the
values of < r R?,
<TR>, and EL, v are taken from the specifications provided
by the manufacturing companies, we think that the results are extremely
good.
+..
I ', z
. '
I '
I
i
'''
i ''
i ''
'
i
I
i
i
I
i
i
i
r
FIGURE 24 Cylindrical projection to compute the three-dimensional
attenuation in a two-dimensional grid.
80
Re = 600
% EtH
%X --=2
% CL 2
60
40
20 ~ - - - - - ' - - - - - - - - - " ' - - - - - - - - ' - - -
0 2 4
FIGURE 25 Comparison of theoretical predictions and experimental re-
sults for the chlorination of ethane. Effect of the chlorine inlet con-
centration.
890
Analysis and Design of Photoreactors 891
80
Re= 600
% Cl 2 = 3
%X
60
40
20 L------'-------'-------'-------
0 2 4 6
% EtH
FIGURE 26 Comparison of theoretical predictions and experimental results
for the chlorination of ethane. Effect of the ethane inlet concentration.
Complex Kinetics in a Heterogeneous Semibatch
Reactor Irradiated from the Bottom
The photochlorination of trichloroethylene is carried out in a semibatch
stirred tank reactor irradiated from the bottom by a tubular source located
at the focal axis of a cylindrical reflector of parabolic cross section. The
liquid phase is a homogeneous solution of trichloroethylene and carbon
tetrachloride, while the gas phase is a mixture of chlorine and nitrogen.
The overall reaction is
( 130)
We wish to analyze (a) the possibility of transforming all the CzHC1 3
initially present in the liquid phase into C2HCl5 only, and (b) the effect
of the inlet nitrogen concentration upon selectivity, conversion, and re-
action time.
The modeling problem must be consider the following aspects: the
radiation energy distribution inside the reactor, the reaction rate, the
mixing pattern, and the gas absorption rate. Since the reaction is con-
sidered to occur only in a perfectly stirred liquid phase, the overall
phenomenon involves the following elementary steps:
892 De Bernardez, Claria, and Cassano
1. Diffusion of chlorine from the bulk of the gas phase to the inter-
face, where physical equilibrium is assumed
2. Diffusion of chlorine from the interface to the bulk of the liquid
phase
3. Chemical reaction within the liquid phase
It is useful to point out here that the chemical reaction proceeds through
through a chain mechanism; hence not only are stable species present but
highly reactive intermediates as well. Since the liquid phase is considered
to be perfectly stirred, we can visualize the following mixing characteristics:
1. The concentration field of the stable species is uniform inside the
whole reactor volume.
2. The rate of initiation step (ea) is no longer a functional of the
concentration field as in the previous applications but is still
spatially dependent
3. The spatial distribution of the radiation field together with the
short lifetime of the highly reactive intermediate species suggest
that concentration gradients of these species should be expected.
Moreover, they can be considered to be born, live , and die in the
same place. Alfano and Cassano (1986a,b) showed that this
characteristic corresponds to reality, and perfect mixing for the
short-lived intermediates cannot be assumed. Even though the
liquid phase is perfectly stirred and concentration gradients of
the stable species are not present, the reaction rate is a function
of position due to the spatial distribution of the radiation field
and the short-lived intermediate concentration field. Hence the
mass transfer (with chemical reaction) coefficient may be spatially
dependent.
For simplicity, the species ill be identified in the following way:
Cl• N2
1 2 3 4 5 6 7 8 9
An order-of-magnitude analysis f the characteristic reaction time and
the characteristic absorption time in the liquid film shows that
(131)
and
t
re =--------
if
- 10s (132)
n1cc 1 , x = x )
~ ~max
where we have estimated trc at the interface conditions and in the spatial
position where ea is maximum.
Analysis and Design of Photoreactors 893
This means that the reaction is slow compared with the diffusional
rate. This physical situation was characterized in the literature as the
slow reaction regime (Astarita, 1967) and in this case
k = k0 (133)
L L
That is, the mass transfer with chemical reaction coefficient is equal to the
physical mass transfer absorption coefficient and hence independent of the
spatial position.
The chlorine absorption rate is
N = k 0 (Cif - C ) = (134)
1 Lav 1 1
where
1
=- - = effective diffusion time (135)
k0 a
L V
Cii is the chlorine concentration at the gas-liquid phase, and c 1 is the
chlorine concentration in the bulk of the liquid phase.
The mass balance in the gas phase is posed under the following assump-
tions: (a) pseudo steady state, (b) no reaction in the gas phase, (c)
negligible gas-phase resistance to mass transfer, (d) well-mixed gas phase,
and (e) no accumulation or significant reaction in the liquid film. Hence
we can write
F0 - F = N V = k 0 avV(Ci1f (136)
1 1 1 L
Assumption c must be made mainly because no reliable correlations can
be used to predict the mass transfer rates. It is usually made in problems
related to gas absorption with chemical reaction in spite of the fact that we
known that even if the gas-side resistance to mass transfer may occasionally
be negligible, it is never zero.
Since the inlet gas stream is a mixture of chlorine and nitrogen,
= ( 137a)
If we assume equilibrium conditions at the interface,
if
if pl
C =- = (137b)
1 H
894 De Bernardez, Clarid, and Cassano
Solving Eq. ( 136) together with Eq. ( 137) we obtain
= ½{(F°;d + ~ + cJ-
yOFOt ) 1/2}
_ 4 ~ (C + 1 ed (138)
H 1 V
Finally, the mass balance equations in the bulk of the liquid phase are
dC 1 (t)
( 139a)
dt
dCi (t)
= <n.(x,t)>(t) i = 2, • • • , 5 (139b)
dt I -
aC.(x,t)
J - - j = 6, 7, 8 (139c)
at - nj(!_,t)
where we have considered perfect mixing for the stable species and non -
mixing for the highly reactive intermediate species.
The system of represented by Eqs. (139) must be solved· together with
the following initial conditions:
C.(0) = C!' i = 1, ' 5 (140a)
I I
C.(0) = 0 j = 6, 7, 8 (140b)
]
The reaction scheme involves the following steps:
Initiation:
a
c1 2 ~ 2Cl• (141a)
Propagation:
k2
-c HCI • (141b)
k' 2 4
2
( 141c)
k4
C 2HC1 5 + Cl• - C Cl • + HCI (141d)
~ 2 5
4
(141e)
Analysis and Design of Photoreactors 895
Termination:
k6
2Cl• - Cl 2 (141f)
(141g)
(141h)
( 141i)
klO
Cl• + C 2c1 5 - products (141j)
(141k)
where the possibility of wall reactions has been disregarded.
Considering that the rate of each step of the mechanism has the form
of the mass action law, and applying the local or microscopic steady-state
approximation for the highly reactive intermediate species together with the
long-chain approximation, we obtain
(142)
(143)
(144)
(145)
(146)
n=n=n=o
6 7 8
(147)
and
(148)
k4C3 + k5C 4
(149)
k:f5 + k5Cl
896 De Bernardez, Clarid, and Cassano
( 150)
To complete the reaction rate expressions, the rate of the initiation
step ( qi ea) must be evaluated in a heterogeneous medium. Earlier we
anticipated that a suitable strategy for the modeling problem is to make use
of the LVREA expressions valid for homogeneous media but including an
effective attenuation coefficient to account for the distortions in the radia-
tion field due to the presence of gas bubbles. Since a reflecting surface
is present, we cannot use a linear model; hence either the SEES model for
fluorescent lamps or the VEES model for arc lamps will be required.
Regarding the kinetic sequence, we observe that the overall behavior
is the one corresponding to a series-parallel reaction system, that is
+ Cl 2
A B -HCl C
where the first path (A ➔ B) is an addition reaction and the second path
(B ➔ C) is a substitution reaction. It is known that the characteristic
time for both reactions should be different, that is, tA➔ B << tB ➔ C' Under
this condition it would be possible to obtain high selectivity values for the
intermediate product B (C2HCl5), as it is observed in homogeneous con-
secutive reactions. However, with single-phase systems, only· in exceptional
situations could we expect to achieve 100% selectivity. In a heterogeneous
medium it is possible to improve selectivity by operating on the process con-
ditions so as to change the rate-controlling step as follows.
Let tA ➔ B be the characteristic reaction time for the kinetic path A ➔ B,
and tB ➔ C be the one corresponding to the path B ➔ C. Let ted be the
effective diffusion time calculated as (kL8v) - l and trnf the characteristic
diffusion time estimated with Eq. ( 131). Under the slow reaction regime
(tDif << tA➔ B << tB ➔ C), the following possibilities are present (Astarita
et al. , 1983) :
1. ted << tA➔ B << tB ➔ C' Both reactions are under the kinetic sub-
regime and the overall expected behavior would be similar to that
observed in the homogeneous system A ➔ B ➔ C.
2. tA➔ B << ted << tB ➔ C. The first path A + B is under the diffu-
sional subregime while the second is under the kinetic subregime.
In this case it would be possible to obtain 100% selectivity of C2HCl5
with almost 100% conversion of C 2HCl3 because in practical terms
reactions A + B and B + C do not take place simultaneously.
3. tA+B << tB+C << tea· Both paths are under the diffusional sub-
regime. However, for the reacting system under analysis and the
type of reactor being modeled (perfectly mixed stirred tank reactor),
condition ( 3) cannot be practically achieved. Hence this situation
will not be analyzed here.
Analysis and Design of Photoreactors 897
Let us suppose that condition (2) is fulfilled in the semibatch stirred-
tank reactor under analysis. Hence the reaction would proceed under the
diffusional subregime until almost 100% selectivity of C2HCl5 (B) together
with almost 100% conversion of C2HCl3 (A) are attained. After that, the
overall behavior changes from the diffusional to the kinetic subregime and
reaction B + C becomes more significant. If B is the desired product the
reaction operation should be frozen (by turning off the lamp) before the
transition from the diffusional to the kinetic subregime takes place. Under
the diffusional subregime we may expect the following characteristics for
the concentration distribution:
1. Dependent on the intensity of mixing of the liquid phase
2. Proportional to the interfacial area
3. Independent of the liquid volume
4. Independent of the emission system used to activate the reaction
The latter characteristic allows us to use a low-energy emission source,
decreasing the operating costs. However, there is a minimum permissible
value of the energy output below which the characteristic reaction time of
the path A + B becomes greater than the effective diffusion time and the
overall behavior changes from the diffusional subregime to the kinetic one
[i.e., from case (2) to case (1)], reducing the possibility of achieving 100%
selectivity of C2HCl5 with 100% conversion of C2HCl3.
To illustrate the previous qualitative analysis we will report some of the
results obtained by Alfano and Cassano ( 1986a, b), who carried out bench-
scale experiments in a photoreactor with the following characteristics. Re-
actor: radius, 0.145 m; height, 0.20 m; bottom material, quartz or Pyrex
glass. Lamp: Ge UA 3-360; radius, 0. 0095 m; length, 0. 152 m. Reflector:
characteristic constant of the parabola, 0. 021 m; distance from vertex of
parabolic reflector to bottom of reactor, 0.084 m; cover radius, 0.013 m.
Operating conditions: temperature, 298 K; pressure, 101. 3 kPa; volume of
liquid, 0.002 m3; stirring speed, 800 rpm (nominal).
Theoretical predictions were performed with the VEES model with iso-
tropic emission (the GE UA3-360 emission source is a nonfluorescent UV
arc lamp) and using Yokota et al. 's (1981) correlation [Eqs. (38) and (39)]
to evaluate the effective attenuation coefficient. It is interesting to point
out that any emission model can be used when the reaction is under the dif -
fusional subregime but only extense source models (VEES or SEES) can be
safely used under the kinetic subregime.
The existence of both subregimes needs to be investigated to find the
real possibilities of a very high selectivity. To do so, it is necessary to
change the mass transfer characteristics of the system (to search for the
diffusional subregime) and the kinetics of the reaction by changing the
radiation field, for example (to search for the kinetic subregime). Both
tests can be computationally and experimentally performed and were carried
out by Alfano and Cassano (1986a, b). Their results showed that the first
reaction was sensitive to the stirring speed, while the second one (starting
from pentachloroethane) was almost insensitive to changes in the mass trans-
fer characteristics, but indicated a noticeable response to changes in the
light transmission properties of the reactor bottom. Computational and ex-
perimental results clearly support the idea of two different reacting condi-
tions. The details can be found in the papers cited.
898 De Bernardez, ClarUi, and Cassano
...0 /.0
.
..,........
.
I
E
u
0
E
u 0.5 yr= 0.14
0.0 • _ _ ___.._ _ ____.1..--___~:l!llo...-_ _...J
0.0 30 60 90 120
t (min)
FIGURE 27 Comparison of theoretical predictions and experimental results
for the chlorination of trichloroethylene ( chlorine fraction in the feed, 14%).
Figure 27 shows an example obtained for the case in which the reaction
is conducted using 86% of nitrogen in the feed. Since the first reaction is
in the diffusional subregime the good correspondence between computed and
experimental values only indicates that the mass flow rates of reactant gases
have been properly modeled and the energy input to the reactor is suf-
ficient. In the second reaction we known that it is kinetically controlled
and the agreement must be ascribed to the quality of the radiation field
prediction as well as the kinetics and reactor modeling. It can be observed
that C2HCl5 selectivity is always 100% until almost all C2HCl3 has been con-
sumed (t = 90 min); then C2HCl5 concentration goes down because the sub-
stitution reaction (C2HCl5 + Cl2 + C2Cl5 + HCl) becomes significant. For
this particular reactor- source-reflector configuration , condition 2 is certainly
fulfilled and, in practice, both reaction paths A + B and B + C do not
take place simultaneously. Stopping the reaction at t = 90 min (by turning
off the lamp), it is possible to transform all the C2HCl3 initially present in
the liquid phase into C2HCl5 only. Figure 28 shows the results for the
case in which 60% of nitrogen is used in the feed. Similar conclusions can
be drawn from the selectivity and conversion viewpoints. However, the time
necessary to achieve 100% C2HCl5 selectivity together with almost 100%
C2HCl3 conversion has been reduced to 35 min.
These results clearly show that it is possible to achieve 100% selectivity
for the intermediate species together with almost 100% conversion of C2HCl3
and that the presence of nitrogen does not affect the final product distribu-
tion, but the time needed to reach a given value of conversion. The time
of reaction can be sharply reduced by using pure chlorine in the feed but,
obviously, it is possible that under such conditions the reaction control
will be much more difficult.
Analysis and Design of Photoreactors 899
•
st
0
,c
,-..._
"''e
u
.,
0
----
E
u 05
0.0
•
"----..l.-""""4~--------....1:1--...i
0.0 20 40 60 80 100
t (min)
FIGURE 28 Comparison of theoretical predictions and experimental results
for the chlorination of trichloroethylene (chlorine fraction in the feed, 40 %) .
Consecutive Reactions in a Continuous
Annular Photoreactor
A gaseous mixture of Cl2, CH4, and N2 is flowing through an annular
photoreactor whose inner and outer walls are cooled to avoid large tempera-
ture rises, precluding undesirable overheating and by-product formation.
Moreover, with the same purpose, it is recommended that the chlorine inlet
molar fraction be maintained no higher than 50%. The aim is to perform a
preliminary design of the reactor, including the selection of the emitting
system for an optimal production of chloroform. For safety reasons, the
maximum reaction temperature and pressure are T = 363 K and P = 101. 3
kPa.
In dealing with the design of this photochemical reactor we must answer
the following questions: (a) What is the size of the reactor? (For the
annular reactor, this means the values of rin, r 0 u, and LR.) (b) What are
the operating conditions? (These include inlet composition, flow rate, etc.)
(c) Which is the appropriate emission system to carry out the reaction?
(This involves the spectral distribution of power output, overall power out-
put, and values of rL and LL.) The first two questions are common in
conventional thermal reactor design; the last arises only in photochemical
reactor design and constitutes one of the most important stages in the design
strategy.
To provide an answer to the foregoing questions, we have to solve the
modeling equations several times because the number of variables involved
in the design problem is large. Hence it would be recommended to find a
simple, even though only approximate model to describe the performance of
the photoreactor. This simple model will allow us to (a) choose an emission
system, and (b) find a starting set of values for the main variables to carry
900 De Bernardez, Clari6., and Cassano
out the final design using a reliable (but more complex) model. The simple
model should have the following characteristics:
A simplified kinetic scheme with reaction rate expressions valid for a
wide range of operati~g conditions
A simplified model to describe the reactor operation
A simplified model for the emission process
Simplified Kinetic Scheme
We can use the entire reaction mechanism for which the rate expressions
for the individual steps are known and obtain global kinetic expressions by
introducing some typical simplifications, such as the local steady state ap-
proximation for highly reactive intermediate species.
The reaction mechanism for the chlorination of methane can be summarized
as follows:
Initiation step:
Cl 2 + h v __!____ 2Cl • (151)
Propagation steps:
( 152)
3
CH 3 • + Cl 2 ~ CH 3Cl + Cl• (153)
4
CH 3Cl + Cl· ~ CH 2Cl• + HCl (154)
. 5
CH 2Cl• + Cl 2 ~ CH 2c1 2 + Cl• (155)
6
CH 2c1 2 + Cl• ~ CHC1 2 • + HCl ( 156)
7
CHC1 2 • + Cl 2 ~ CHC1 2 + Cl• ( 157)
8
CHC1 3 + Cl• ~ CC1 3 • + HCl ( 158)
(159)
Homogeneous termination steps:
10
CH 3 • + Cl• - CH 3c1 (160)
11
CH 2Cl• - CH 2c1 2 (161)
12
CHC1 2 • + Cl· - - - - CHC1 3 (162)
CCI•+ Cl· ___!!__CCI (163)
3 4
Analysis and Design of Photoreactors 901
14
Cl•+ Cl• - Cl 2 (164)
15
CH 3 ° + CH 3 ° ---- CH 3 - CH 3 (165)
CH 3 • + CH 2Cl• ~ CH 3 (166)
CH 3 • + CHC1 2 • ___!I___ CH 3 - CHC1 2 ( 167)
18
CH 3 • + cc1 3 • - CH 3 -- CC1 3 (168)
CH 2Cl• + CH 2Cl• ~ CH 2Cl ( 169)
CH 2c1 • + CHC1 2 • - ~ CH 2c1 - CHC1 2 ( 170)
21
CH 2Cl• + CC1 3 ° - CH 2Cl - CC1 3 (171)
CHC1 2 • + CHC1 2 • ~ CHC1 2 - CHC1 2 (172)
23
CHC1 2 • + CC1 3 • - CHC1 2 - CC1 3 ( 173)
24
CC1 3 • + CC1 3 • - CC1 3 - CC1 3 (174)
Heterogeneous termination steps:
25
CH 3 • + wall - products (175)
26
CH 2Cl• + wall - products ( 176)
27
CHC1 2 • + wall - products ( 177)
28
CC1 3 • + wall - products (178)
29
Cl• + wall - - products (179)
We introduce the following simplifications:
1. Disregard the heterogeneous termination steps [Eqs. ( 175) to (179)]
as shown by De Bernardez and Cassano (1986).
2. Disregard the homogeneous termination steps that lead to form
chlorinated derivatives of ethane [Eqs. (165) to (174)], which are
known to be negligible (Kurtz, 1972; De Bernardez and Cassano,
1986).
3. Apply the local steady-state approximation to the unstable intermediate
species together with the long-chain approximation in the remaining
reaction system [Eqs. (151) to (164)].
902 De Bernardez, Claria, and Cassano
Thus the complex chain mechanism is reduced to the following kinetic
scheme:
CH 4 + Cl R-l_ CH Cl + HCl ( 180)
2--- 3
R-2
CH 3Cl + Cl 2 ::;--- CH 2Cl 2 + HCl ( 181)
CH 2c1 2 + Cl 2 ~ CHC1 3 + HCl (182)
R-4
CHC13 + Cl 2 ~ CC1 4 + HCl ( 183)
The reaction rate expressions become a nonlinear function of the con -
centration of the stable species, the individual kinetic constants of each
step of the mechanism, and the local volumetric rate of energy absorption.
Considering that the kinetic expression for each elementary step of the
mechanism has the form of the mass action law, the final expressions are
( 184)
( 185)
( 186)
(187)
where we have identified each species in the following way:
CC1 4 HCl N2
1 2 3 4 5 6 7 8
and in Eqs. (184) to (187) we have
k2C2 + k3C3
( 188)
Kl= k:f 7 + k3Cl
k4C3 + kfp 4
( 189)
K2 = k4C7 + k5Cl
Analysis and Design of Photoreactors 903
k6c4 + k;Fs
( 190)
k6C7 + k7Cl
k8C5+ k9C6
( 191)
k8C7 + k9Cl
and
( 192)
It should be noticed that we have obtained kinetic expressions for the
overall reactions [ Eqs. ( 184) to ( 192)] which do not need any adjustable
parameter if an appropriate emission model is used for evaluating the radia -
tion field. Generally, the kinetic expressions found in the literature make
use of phenomenological rate constants obtained by fitting experimental
data. If appropriate microkinetics data are available, empirical rates do not
seem appropriate for modern design purposes, since they are valid only
for restricted ranges of operating conditions.
Simplified Model for the Reactor Operation
The simplest model to be used for the prediction of the performance of a
continuous reactor is undoubtedly the plug-flow model. However, Romero
et al. ( 1983) have shown that this model is a very poor approximation when
strong radial gradients in the radiation field are present, which could be
the case of the annular photoreactor if we have a medium-to-large optical
density. Moreover, it may provide totally incorrect predictions of the
global kinetic behavior. Nevertheless, we can use the maximum gradient
model under the following assumptions: ( a) isothermal conditions, (b) flat
velocity profile, ( c) negligible axial dispersion, and ( d) negligible radial
dispersion. For steady-state flow, the species i mass balance equation
becomes
V rl.[C(r, z) ,ea(C,r, z)] i = 1, • . . , 7 ( 193)
l - -
and
C = (C 1 • • • C 7 ? ( 194)
with
i = 1, • . • , 7 ( 195)
where
4
n.l =
I:
j=l
v .. n.
l] ]
( 196)
and v .. is the stoichiometric coefficient of species i in reaction j.
l]
904 De Bernardez, Claria, and Cassano
Simplified Emission Model
The first historical step in the development of emission models considered
a line source with emission in parallel planes perpendicular to the lamp axis
(PELS model). This model is very attractive because of its simplicity but
it has very little physical meaning since it requires that all points of the
source emit radiation in planes perpendicular to the lamp axis, with zero
probability of emission in other directions. As for any type of linear
model, it is not recommended for evaluating the radiation field when reflect-
ing surfaces are present. But, on the other hand, it is believed to give
an approximate estimation of the radiation field when only direct radiation
is present (as in the case of annular photoreactors). However, this state-
ment is partially true. At point I(r, S, z) inside the reactor volume (Fig.
8) the radiation arrives from all directions in space and from the whole
volume of the lamp. The attenuation path length changes with the direc-
tion and may be much longer than the characteristic radiation path length
(r0 u - rm). Besides, the radiation field at point I(r,S,z) in the annular
reactor results from the contributions of all rays coming from the hemisphere
containing the lamp volume. As can be observed in Fig. 29, this im-
portant physical situation is not accounted for when the PELS model is used.
In fact, at point l(r, S, z) inside the reactor, the radiation field results
from the contribution of only one ray departing from the lamp; in addition,
the attenuation path length is a representation of just the minimum length
existing in the real process.
Another failure of the PELS model to predict the real radiation field
arises from the fact that it does not account for the reactor wedges ( see
Fig. lla) which may be very significant in an annular reactor whose inner
wall is close to the lamp wall. With these disadvantages the PELS model
is inappropriate to carry out the design of a photoreactor particularly when
the characteristic radiation path length is one of the design parameters.
Hence the simplest model to predict the radiation field is the SELS model,
which at least considers the three-dimensional characteristic of the emission
and attenuation processes.
~ ~----------~~
Icr,/3,z >
i--,t------t--
~~---------~~-~
S R
FIGURE 29 Schematic representation of the attenuation process for the
PELS model.
Analysis and Design of Photoreactors 905
Rigorous Model
For the final computation the model was perfected by incorporating the
following improvements:
1. Regarding the kinetic scheme: The long-chain approximation was
not used.
2. Regarding the reactor model: (a) The parabolic velocity profile
was included, (b) radial diffusion was not neglected, and (c) the
multicomponent diffusion coefficients were calculated with the
Stefan-Maxwell relationships.
3. Regarding the emission model: Extense models (VEES and SEES
models) were used instead of the SELS model.
Design Problem
Although production is generally the goal of an optimal design, when deal-
ing with consecutive reactions, the recommended criterion is selectivity.
However, in order to decrease the cost of the product separation it may
be advisable to operate the reactor with maximum conversion for at least
one of the reactants.
A suitable strategy for solving the design problem consists in stating
an optimization programme in which the independent variables are the de-
sign parameters and the objective function results from a combination of
both criteria: selectivity and conversion.
The design problem, which is described by Eqs. (193) to ( 196), initially
has the following degrees of freedom: inlet composition, c'i, c 2,
and Cg;
volumetric flow rate, Q; inner and outer reactor radiuses, rh1 and r 0 u;
reactor length, LR; and lamp characteristics: radius, length, power out-
put, and spectral distribution of its power output,
However,. only some of these variables are appropriate to perform an
optimization problem. Although they are extremely important in the design
of a photochemical reactor, the emission system characteristics cannot be
varied continuously because only a limited number of lamp types are avail-
able in the market. Hence, in spite of the fact that the parameters related
to the lamp enter into the mass balance equations, they cannot be used as
optimization variables. Nevertheless, the problem may be solved for differ-
ent lamps in order to select the most appropriate one. On the other hand,
operating conditions and geometrical characteristics of the reactor can be
continuously varied. Thus they can be included in the optimization.
Operating the reactor at constant pressure and temperature, the total
inlet concentration is constant. Hence
c1
0 + c2 +
0 C0
8
= C 0 = constant
and the total number of independent variables is reduced. At the same time,
one could set an upper limit to the chlorine inlet fraction:. for example,
not greater than 50% to avoid excessive heating. Thus if we adopt a con-
stant chlorine inlet concentration,
c1 = o. sc 0
the only independent variable representing the inlet composition will be c 2.
906 De Bernardez, Claria, and Cassano
In order to make use of the maximum amount of energy coming out of
the lamp, the reactor length is generally taken equal to the lamp length .
The inner reactor radius is adopted as close to the lamp radius as possible,
leaving a small distance for cooling the lamp and controlling the operating
reactor temperature if needed. Then, in our preliminary design problem
we will adopt a constant value for the inner radius, and equal values for
the lamp and reactor lengths. Finally, the independent variables are:
methane inlet concentration, C~; volumetric flow rate, Q; and outer reactor
radius, rou·
In the preceding paragraphs we mentioned the possibility of solving
the design problem by means of an optimization technique. The following
statement of this optimization problem results:
Maximize S. = i = 3, . • . , 6 ( 197)
1
Subject to
~ < vk < bk k = 1, 2, 3 ( 198)
XJ!, ;:;i, pl!, Q, = 1, 2 ( 199)
h (v, Q_, !_)
m- = 0 m = 1, '
7 ( 200)
where
S.1 = selectivity of the desired chloromethane derivative
<Ci(LR)> = average exit concentration of species i calculated with
Eq. (106b)
V = independent variable array (Q, r
OU
, etc.)
a = lower bound for the independent variable array
b = upper bound for the independent variable array
XJ!, = !!,-reactant conversion
p J!, = minimum permissible value for !!,-reactant conversion
C = chloromethane concentration array
t = array that accounts for the fixed design and operating
parameters (temperature, pressure, rin, C0 , lamp
characteristics, etc . )
Constraints ( 198) define a feasible region for the optimization problem
(i.e., a range of variation for the independent variables). On the other
hand, constraints ( 199) allow us to establish a minimum permissible value
for both reactant conversions so as to assure appreciable exit production.
Finally, equality constraints ( 200) represent the solution of the species
mass balance equations which give a relationship between the independent
Analysis and Design of Photoreactors 907
variables v and the dependent variables C necessary to evaluate Si, Equa-
tions ( 197) to ( 200) define a nonlinear multivariable constrained optimization
problem which can be solved using any of the several algorithms available
in the literature.
To illustrate the design methodology, we solved the optimization problem
for chloroform production using a modified Powell algorithm. The statement
of the optimization problem becomes:
Maximize ( 201)
subject to
( 202a)
0.00005,;;; Q,;;; 0,00100 m 3 /s ( 202b)
0. 04 ,;;; r ,;;; 0. 12 m ( 202c)
OU
X ~ 0 ( 202d)
1
X ~ 0.995 ( 202e)
2
and
k = 1, . . . , 7 ( 203)
and t includes
P = 101.3 kPa ( 204a)
T = 363 K ( 204b)
C0 = 33.6 mol/m3 ( 204c)
r. = 0.03 m ( 204d)
ln
and lamp data. The upper and lower bounds used in constraints ( 202b)
and ( 202c) are typical values for annular photoreactor operation.
Finally, to complete the required information we must decide about the
characteristics of the lamp. Since methane photochlorination is a chain-type
reaction, it should be expected that low-energy radiation sources would be
required. This statement was corroborated by De Bernardez and Cassano
( 1986), who studied the incidence of lamp parameters on selectivity and
conversion in methane photochlorination. The authors found that the re-
action can be carried out using sources of low-energy output such as
germicidal or black-light lamps. Both types of lamps represent a very
attractive solution from an economic point of view. In addition, they are
available in the market in a variety of sizes and output powers. To illus-
trate the lamp selection procedure, we will solve the optimization problem
for two different sources which are amenable to comparison:
908 De Bernardez, Claria, and Cassano
Power Power Spectral range
Emission input output of emission Length
Lamp model (W) (W) (A) (m)
Germicidal VEES 30 8.3 2537 0.91
isotropic
Black light SEES 30 5.4 3200-4200 0.91
diffuse
Both lamps have identical values of energy input and length, but the
output power and spectral distribution are different. The germicidal lamp
emits at a wavelength range where chlorine absorption is poor ( see Table
5), while the emission of the black lamp falls in a wavelength range where
the absorption by chlorine is significantly stronger. Hence a higher re-
actant conversion should be expected when the black light lamp is used.
However, the amount of energy emitted by the germicidal lamp is greater and
consequently there exists the possibility of obtaining a larger product out-
put for the same energy consumption. The final result will show which of
the two characteristics causes a better improvement in conversion. In
other words, we wish to obtain information about the relative s~gnificance
of the quality and the quantity of the energy emitted. Similarly, it is im-
possible to anticipate the effect of both properties (power and spectral dis-
tribution) on chloroform selectivity.
Table 6 summarizes the results of the design problem for ·both lamps.
Due to the characteristics of chlorine light absorption combined with the
spectral distribution of the energy output of both lamps, we can state the
following conclusions:
TABLE 6 Optimization of Chloroform Production:
Design Problem Results
Germicidal Black light
11.3 3.9
SCH3Cl
s 25.0 18.9
CH 2Cl2
40.4 47.0
SCHC1 3
23.3 30. 2
SCCl4
21.8 60.3
XCl2
89.8 95.8
XCH4
7.4 12.8
PCHCl3
(g/s) X 103
c 2 (mol/m3 ) 1. 32 2.83
r (m) 0.050 0.044
OU 3 5
Q(m /s) x 10 13.0 8.5
Analysis and Design of Photoreactors 909
1. The germicidal lamp allows us to use greater equivalent diameters,
but to obtain high methane conversions, the system is forced to
use low hydrocarbon concentration in the feed. This considerably
reduces the output production. With germicidal lamps, chloroform
selectivity would be approximately 40%.
2. Chloroform production and selectivity are greater in the case of
black-light lamp, indicating that in spite of the differences in
power output (more than 50%), what really counts is the quality
of the supplied radiation. With this lamp we get higher selectivity
(close to 50%), very high methane conversion (almost 96%), and
can obtain 73% more output production of chloroform for the same
energy input and reactor length. Perhaps what is even more sur-
prising is that all these advantages are obtained with an equivalent
diameter that is 30% smaller.
Table 6 also shows that the minimum permissible value of methane con-
version could not be reached. However, by working with lamps of greater
energy input we can increase the length of the lamp (and that of the re-
actor), the amount of energy per unit length of the lamp, and obviously,
the mean residence time. This possibility could certainly allow one to ful-
fill the required exit conversion.
To increase the total amount of chloroform produced, several reactors
(in parallel) should be used. Other possibilities are the multitube and the
multitube-multilamp reactors.
These results clearly illustrate that a photochemical reactor provides
new variables for optimization. Although reactant feed composition ratio
and mean residence time are still very important parameters, the optical
thickness (combination of absorptivity, characteristic radiation path, and
absorbing species concentration) as well as the output characteristics of
the radiation. source have a significant effect not only in the exit conversion
but also in the overall production and selectivity.
REACTOR CONFIGURATIONS FOR
INDUSTRIAL APPLICATIONS
Single Lamp-Multitube Reactor
This arrangement (Fig. 30) is a suitable reactor for medium-pressure,
highly exothermic or endothermic gas-phase reactions. It provides good
heat transfer characteristics with the surrounding fluid. The individual
reactors may have rather small diameters and consequently, well-tested
Pyrex glass or quartz tubes can stand pressures up to 1500 kPa. It
could be used for liquid-phase reactors as well. In any case, applications
should be restricted to rather fast reactions (or equivalently low flow
rates) because the reactor tubes will necessarily have length limitations
(mainly motivated by market restrictions in the lamps and safe operating
conditions for the reactor).
Multilamp Reactor
This reactor (Fig. 31) can be recommended for liquid-phase reactions with
small-to-medium heat transfer requirements, which could be improved by
adding cooling coils inside the vessel. The walls of the tank could have
910 De Bernardez, Claria, and Cassano
FIGURE 30 Single lamp-multitube reactor.
reflecting properties, increasing the efficiency of the radiation emitted by
the lamps. Again, it can be used for low and medium reaction pressures,
since restrictions are placed in the diameter of the tubes surrounding the
radiation sources. This reactor is very appropriate for reactions where
energy requirements are rather high or if, in spite of having low-energy
requirements, the optical thickness of the medium is large. In the second
case the same input energy could be distributed in several radiation sources,
obtaining a more useful radiation field distribution inside the tank. It is
also suitable for multiphase reactions since very good stirring is easily
achieved. It is not appropriate for gas-phase reactions.
Pseudoannular Reactor
This reactor (Fig. 32) is a modified version of an annular photoreactor
with the purpose of increasing its heat transfer possibilities and its capa-
bilities for low and medium operating pressures. It is also very suitable
for reactions that may need medium-to-long mean residence times. It
could equally well be used for gas- or liquid-phase reactions.
Analysis and Design of Photoreactors 911
FIGURE 31 . Multilamp reactor.
Multilamp-Multitube Reactor
This reactor (Fig. 33) is perhaps the best arrangement for large-scale
production. The system has good pressure and heat transfer capabilities,
large flexibility regarding energy requirements or optical properties of the
reacting medium, and if there is adequate connection between tubes, good
flexibility to overcome large residence-time requirements. It could not be
used efficiently for multiphase reactions, this limitation being its main
hindrance.
Flat-Plate Reactor
This reactor (Fig. 34) is suitable for reacting media of very high optical
thickness. Its main application could be for decontamination of highly re-
fractory materials to other technologies. In this case the "cleaning" of the
reactor feed (to increase transparency from the optical point of view)
could be infeasible for economic or technical reasons. Hence impurities
will greatly increase the absorption characteristics of "reactants." A re-
duction in the radiation path length would be the only solution and the
flat-plate reactor may be the most practical way to achieve it. Both plates
(upper and bottom parts) should be made with practical provisions for
FIGURE 32
P se ud oa nn ul
ar re ac to r.
FIGURE 33
M ul ti tu be -m ul
ti la m p re ac to
r,
912
Analysis and Design of Photoreactors 913
FIGURE 34 Flat-plate reactor.
fast assembling and reassembling purposes to facilitate unavoidable clean-
ing routines. A second important application may be photo-assisted
catalysis. The modeling of this reactor is an easy extension of our re-
actor irradiated from the bottom (Fig. 34).
Finally, it should be noted regarding wall deposite difficulties that
mechanical cleaning would be difficult only in the pseudoannular reactor.
If chemical methods are used this reactor is one of the easiest to clean.
UNSOLVED PROBLEMS
With regard to photoreactor design, assuming that the reactions are well
known, we recognize several problems where lack of information or reliable
ways of handling them can be observed. The main ones are: modeling
the absorption in heterogeneous systems, dark deposits at the reactor wall
through which the radiation must enter into the reacting space (which re-
duces light transmission and affects yield), and problems related to pres-
surized gas-phase reactors.
Several research groups have made important contributions to the area
of modeling the absorption in heterogeneous media (Otake et al. , 1981;
Yokota et al. , 1981). However, we should point out that the only duly
proved contributions related to the modeling of heterogeneous systems still
require experimentally adjustable parameters. The use of rigorous models
combined with the modeling of the distortions produced by the hetero-
geneities constitutes a particularly attractive problem where additional re-
search work should be performed. These problems have great significance
in the field of photocatalysis where an opaque solid may be present.
The reactions at the wall of the reactor are a serious disadvantage for
the use of photochemical reactors in industrial processes and the main
cause of frequently shutdowns for cleaning routines. It is known that
some of these difficulties have already been overcome by the Toyo Rayon
Co. of Japan in their cyclohexane photonitrosation commercial-scale process.
Some additional work on the subject, proposing novel reactor designs not
yet under the stage of providing results of economic significance, has been
proposed by Lucas ( 1971). The author proposed a "two-zone segregated
reactor" where all deposites are avoided since all secondary reactions after
the initiation step occur in a place different from the one where the radia-
tion is supplied to the system. Nevertheless, appropriate design of the
reactor could provide continuous cleaning by a mechanical scraping of the
wall where the radiation enters the reactor, thus supplying a practical
914 De Bernardez, Claria, and Cassano
solution to the problem. Hopefully, the time will come when fundamental
research on surface chemistry will be able to provide a definite answer.
Since photochemical gas-phase reactors must have at least one quartz
or Pyrex glass wall, there exist some difficulties in working under pressure.
It could be thought as a materials science problem but mainly a challenge
for new reactor designs, which could range from multitubular reactors of
small diameter (often used in industry for heat-release reasons) to the in-
troduction of new technologies such as lasers combined with optical fibers
(see Marinangeli and Ollis, 1977, 1980).
APPENDIX: CYLINDRICAL REACTOR WITH ELLIPTICAL
REFLECTOR. LIMITING VALUES OF THE COORDINATES
FOR INDIRECT RADIATION WITH ONLY ONE REFLECTION
The limiting values for the p coordinate can be obtained as follows (see
Fig. 13). Let S: be the unit vector representing the direction of a ray
that impinges at any point I on the reaction space with direction 0, cp given
by
c: = sin 0 cos ct>i + sin 0 sin cpj + cos 0k (Al)
_1
This ray has previously rebounded on a point P of the elliptical mirror,
whose coordinates referred to point I are:
xp PI sin 0 cos cp
Yp = PI sin 0 sin cp
zp = pl cos 0
where
= -(hb 2 cos cp + ka 2 sin ct>) + ab[cr 2 - (h sin cp - k cos cp) 2] 112
PI 2 . 0
0 Sln
(A2)
and
a2 = b 2 cos 2cp + a 2 sm
. 2
cp
h = c + r 1 cos SI (A3)
k = r 1 sin SI
The expression for the unit normal vector to the reflector at point P
can be written as follows:
xp + h . Yp + k
2 1 + j
a b2 ~
txp
~p = (A4)
: h)
2 (yp + k)2] 1/2
3 + 4
b
Analysis and Design of Photoreactors 915
The unit vector :E representing the direction of the ray before reflec-
tion (i.e., emerging from the lamp) can be obtained from the law of reflec-
tion:
(A5)
~p X : E = ~p X : I
Solving this vectorial equation, the following expression for :E is
obtained:
:E = sin e cos <PE~+ sin e sin <PE~+ cos 6k (A6)
where
2
<PE=
t an -1 (m - 1) sin <P + 2m cos <P (A7)
2m sin ¢ - (m 2 - 1) cos <P
and
2
a (Yp + k)
m = 2 (AS)
b (xp + h)
The two intersections of direction 6, ¢E with the bounding surface of
the radiation source are precisely the limits of p. They are:
D cos ~ ± (r~ - n2 sin 2o 112
p = (A9)
E2,1 sin e
where
D = [(xp + h + c)2 + (yp + k)2]1/2 (AlO)
1
sin ~ = D [(xp + h + c) sin <PE - (Yp + k) cos <PE] (All)
cos~ = (A12)
The limiting values of the 6 coordinate can be defined by means of
(Fig. 12)
cos
(A13)
Using Eqs. (A2) and (A9), the integration limits as a function of cp
result:
2 2 . 2 1/2
- l Pj + D cos ~ - (r L - D sm 0
el = tan ---(-1/.,...2_)_(L_R_f_+_L_L_)___s_I___ (A14)
916 De Bernardez, Claria, and Cassano
2 2 . 2 1/2
= 1
P + D cos i; - ( r L - D sm i;)
tan _ 1 ____________:;;:_________
(A15)
(1/ 2 )(LRf - LL) - l:I
where
-(hb 2 cos ¢ + ka 2 sin ¢) + ab[a 2 - (h sin ¢ - k cos ¢) 2] 112
=
02
t
p1 depends only on ¢.The same can be said for D, ¢E , and i;.
The limiting rays in the ¢ direction for any 8 angle must be tangent
to the lamp boundaries that is,
(A16)
With Eq. (A9) the following expression is obtained:
(A17)
Solving this implicit equation numerically, the limiting values of ¢ can be
determined.
ACKNOWLEDGMENTS
This work reports the photoreactor design methodology developed from re-
search done with my former students, some of them now full professors,
such as Horacio A. Irazoqui, Jaime Cerda, and Jacinto L. Marchetti, and
others that are still on their way to get their doctor's degrees, including
Orlando M. Alfano, Roberto L. Romero, Roberto M. Re, and my two co-
authors, Eliana R. De Bernardez and Maria A. Claria.
The theory has been verified with bench-scale experiments. Thanks
must be given to Pedro G. Guarino, Mario J. J. Didier, Juan C. Garcfa,
Antonio C. Negro, Omar Brizuela, Jose L. Gimenez, and Jose L. Giombi for
their contributions to this part of the work. Credit must also be given to
Yolanda Pereyra for her excellent typing of this monography and to Elsa I.
Grimaldi for the thoroughness of her review of the English used in the
manuscript.
NOTATION
a ellipse semimajor axis or characteristic constant of the parabola, cm
-1
a interfacial area per unit liquid volume, cm
V
-1
a' interfacial area per unit liquid plus gas volume, cm
V
A area, cm 2
b ellipse semiminor axis, cm
C half distance between focuses of the ellipse, cm
C concentration , mol / cm 3
Analysis and Design of Photoreactors 917
bubble diameter, cm
diffusivity, cm 2 /s
ellipse eccentricity, dimensionless
local volumetric rate of energy absorption, einstein /cm 3 •s
E radiant energy flow rate, einstein/s
1
F molar flow rate, mol/s
G value defined by Eq. ( 87) dimensionless
h Planck's constant, J•s. or value defined by Eq. (A3), cm
H Henry's constant, kPa •cm 3 /mol
I intensity of radiation (dimensions are source-model dependent)
I' isotropic intensity of radiation (dimensions are source-model
dependent
j unit vector
k value defined by Eq. (A3), cm
-1 3
k. reaction rate constant for step i, s (first order) or cm /mol•s
1
( second order)
mass transfer with chemical reaction absorption coefficient, cm/ s
physical mass transfer absorption coefficient, cm /s
length, cm
distance from vertex of parabolic reflector to the bottom of the re-
actor,. cm
m value defined by Eq. (A 8) , dimensionless
n unit normal vector
N mass absorption rate, mol/cm3•s
p partial pressure, kPa, or production, g/s
P total pressure, kPa
q radiation flux density vector, einstein /cm 2 •s
Q volumetric flow rate, cm 3 /s
r radial coordinate, cm
R indicates reactor
Re Reynolds number, dimensionless
S selectivity, dimensionless; also indicates radiation source
t time, s
v velocity, cm /s
V volume, cm 3
x rectangular coordinate, cm
X fractional conversion, dimensionless
918 De Bernardez, Claria, and Cassano
y rectangular coordinate, cm or gas-phase molar fraction
z rectangular coordinate, cm
Greek Letters
a absorption coefficient, cm 2 /mol
cylindrical coordinate, rad
emitting extension (dimensions are source-model dependent)
reflection coefficient, dimensionless
Dirac function
value defined by Eqs. ( 55) and ( 92), cm
values defined by Eq. ( 74) , cm
dispersed-phase holdup, dimensionless
axial coordinate , cm
spherical coordinate, rad
K characteristic emission property of the lamp (dimensions are source-
model dependent)
wavelength, cm
11 attenuation coefficient , cm - 1
V frequency, s -l; also stoichiometric coefficient
angle defined by Eqs, (All) and (A12) rad
p spherical coordinate, cm
0 value defined by Eq. (A3), cm
T reactor wall transmittance, dimensionless
cp spherical coordinate, rad
cj) primary quantum yield, mol/einstein
cj) overall quantum yield, mol/einstein
ov
inner radius /outer radius, dimensionless
energy flow rate per unit area, einstein/s•cm 2
radiant energy flow per unit of source extent (dimensions are
source model dependent)
w solid angle, Sr
reaction rate , mol / cm 3 •s
Subscripts
act relative to an activation step
D denotes direct radiation
Dif denotes a property related to diffusion
Analysis and Design of Photoreactors 919
e relative to emission
ed denotes a property related to effective diffusion
eff denotes an effective property
E denotes a property of an emerging ray from the source
F relative to a fixed coordinate system
i denotes species i
in relative to the inner wall of the annular reactor
I denotes an incident point or an incident ray property
In denotes indirect radiation
L denotes a lamp property
m relative to a multicomponent mixture
max denotes maximum value
o denotes a wall property
ou relative to the outer wall of the annular reactor
ox relative to oxalic acid
P denotes point of reflection
r relative to reception
re relative to chemical reaction
R denotes a reactor property
Rf denotes a reflector property
T denotes total value
ur relative to the uranyl ion
z relative to the z axis
1 denotes a lower limit of integration
2 denotes an upper limit of integration
Greek Letters
A denotes a wavelength dependence
v denotes a frequency dependence
p relative to the p coordinate
Superscripts
a relative to absorption
if denotes interface property
o initial value
value projected on the x-y plane
* relative to the attenuation path
920 De Bernardez, Clari6, and Cassano
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photochemical monochlorination of ethane: II. Computed and experimen-
tal results (1985b, submitted for publication.)
Claria, H. , A. Irazoqui, and A. E. Cassano, Modeling and experimental
validation of the radiation field inside an elliptical photoreactor (1986a,
submitted for publication.)
Claria, M. A., H. A. Irazoqui, and A. E. Cassano, The use of linear and
extense source models in photoreactor design (1986b, submitted for publi-
cation.)
De Bernardez, E. R. and A. E. Cassano, Azimuthal asymmetries in tubular
photoreactors, Lat. Am. J. Heat Mass Transfer, 6, 333 (1982).
De Bernardez, E. R. and A. E. Cassano, A priori design of a continuous
annular photochemical reactor. Experimental validation, J. Photochem.
30, 285 (1985).
De Bernardez, E. R. and A. E. Cassano, Optimal selection of the radiation
source for a consecutive-chain type-reactions in a continuous photo-
reactor Ind. Eng. Chem. Process Des. Dev. (1986, in press.)
General Electric Co., Tech. Bull. T .P. 122 (1967).
Gosselain, P. A. , J. Adam, and P. Goldfinter, La specificite des halogena-
tions atomiques: 11. Les regles generales qui determinent le mecanisme
et a. specificite des halogenations atomiques, Bull. Soc. Chem. Belg.,
65, 533 (1956).
Analysis and Design of Photoreactors 921
Herzberg, G., Molecular Spectra and Molecular Structure, Vol. I: Spectra
of Diatomic Molecules, 2nd ed., Van Nostrand Reinhold, New York
( 1950).
Irazoqui, H. a., J. Cerda, and A. E. Cassano, Radiation profiles in an
empty annular photoreactor with a source of finite spatial dimensions,
AIChE J., 19, 460 (1973).
Jacob, S. M. and J. S. Dranoff, Radial scale-up of perfectly mixed photo-
chemical reactors, Chem. Eng. Prog. Symp. Ser., 62, 47 (1966).
Jacob, S. M. and J. S. Dranoff, Design and analysis of perfectly mixed
photochemical reactors, Chem. Eng. Prog. Symp. Ser., 64, 54 (1968).
Kurtz, B. E., Homogeneous kinetics of methyl chloride chloration, Ind. Eng.
Chem. Process Des. Dev., 11, 332 (1972).
Lucas, G, , A new concept in oximation by the nitrosyl chloride molecule,
Inf. Chim., 16, 33 (1971).
Marinangeli, R. E. and D. F. Ollis, Photoassisted heterogeneous catalysis
with optical fibers: I. Isolated single fiber, AIChE J., 23, 415 (1977).
Marinageli, R. E. and D. F. Ollis, Photoassisted heterogeneous catalysis
with optical fibers: II. Nonisothermal single fiber and fiber bundle,
AIChE J., 26, 1000 (1980).
Otake, T. , S. Tone, K. Higuchi, and K. Nakao, Light intensity profile in
gas-liquid dispersion. Applicability of effective absorption coefficient,
Kagaku Kogaku Ronbunshu, 7, 57 ( 1981).
Pai, S., Radiation Gas Dynamics, Springer-Verlag, Berlin (1966).
Re, R. M. and A. E. Cassano, Three-dimensional modeling of a tubular
photoreactor when the radiation field has no angular symmetry (1986,
submitted for publication.)
Romero, R. L. , 0. M. Alfano, J. L. Marchetti, and A. E. Cassano, Model-
ing and parametric sensitivity for an annular photoreactor with complex
kinetics, Chem. Eng. Sci., 38, 1593 (1983).
Stramigioli, c·. , F. Santarelli, and F. P. Foraboschi, Photosensitized reac-
tions in an annular photoreactor, Ing. Chim. Ital., 11, 143 (1975).
Stramigioli, C. , F. Santarelli, and F. P. Foraboschi, Photosensitized reac-
tions in an annular continuous photoreactor, Appl. Sci. Res., 33, 23
(1977).
Turro, N. J., Molecular Photochemistry, W. A. Benjamin, New York (1965).
Vincenti, W. G. and C. H. Kruger, Jr., Introduction to Physical Gas
Dynamics, Wiley, New York (1965).
Yokota, T., T. Iwano, H. Deguchi, and T. Tadaki, Light absorption rate in
a bubble column photochemical reactor, Kagaku Kogaku Ronbunshu, 7,
156 (1981).
14
Electrochemical Reaction Engineering
GARY G. TROST,* VICTORIA EDWARDS, and JOHN S. NEWMAN
University of Califronia and Lawrence Berkeley Laboratory, Berkeley,
California
INTRODUCTION
Electrochemistry is involved to a significant extent in the present-day in-
dustrial economy. Examples are found in primary and secondary batteries
and fuel cells; in the production of aluminum, chlorine, caustic soda, and
other chemicals; in electroplating, electromachining, and electrorefining;
and in corrosion. The electrochemical industries presently consume 6% of
the total electric energy generated in the United States (Darlington and
Woo, 1982; Mantell, 1960). The battery industry amounts to 0.2% of the
total U.S. manufacturing (U.S. Department of Commerce, 1980, p. 14;
National Research Council, 1982, p. 183). Over 3% of the total U.S. elec-
tric energy is consumed by the aluminum industry (Darlington and Woo,
1982; Mantell, 1960), and the chlorine industry consumes 2% of the total
U .s. electric energy (Darlington and Woo, 1982; Mantell, 1960; Beck, 1976;
Bockris et al., 1981). The economic importance of corrosion is evident
from the amount of money spent to protect what has been built and to re-
place what has been destroyed. It has been estimated (Wenglowski, 1966)
that corrosion prevention products amount to 3% of the U.S. electrochemical
industry. The quantity of iron destroyed by corrosion is between 25 and
33% of the total production (Van Muylder, 1981).
In spite of the economic significance of electrochemistry, engineering
design procedures for electrochemical systems have not been developed as
thoroughly as for the mass transfer operations such as distillation. Neverthe-
less, the fundamental laws governing electrochemical systems are known.
The purpose of this chapter is to review the design and analysis of certain
electrochemical systems in relation to these fundamental laws.
One of the difficulties in designing an electrochemical process is that
there are several different types of reactors that can be used. These re-
actors can be broadly classified as either batch or continuous reactors.
For example, many batteries are batch reactors, while fuel cells and many
electrolysis cells are continuous reactors. Naturally, there are several
different reactor geometries within each category. For example, chlorine
*Current affiliation: Raychem Corporation, Menlo Park, California
923
924 Trost, Edwards, and Newman
and caustic soda are produced in any of three types of cells (Bockris et al.,
1981). The diaphragm cell contains a vertical dimensionally stable anode,
where chlorine is evolved, and steel screen cathodes, where hydrogen gas
and hydroxyl ions are produced. The electrode compartments are separated
by a porous diaphragm that allows passage of electric current. The second
type of chlor-alkali cell is the membrane cell. This cell is similar to the
diaphragm cell with the exception of the separator, which, in this case, is
a cation-exchange membrane, which inhibits transfer of chloride and
hydroxyl ions, and does not permit bulk flow of electrolyte. The third
type of cell, the mercury cell, C'Ontains no diaphragm , but achieves separa-
tion of electrode products by the use of a mercury cathode, where sodium
ion is reduced and forms a sodium-mercury amalgam. The amalgam is then
passed to a second cell, where the amalgam is reacted with water to form
sodium hydroxide, hydrogen, and pure mercury, which is recycled to the
electrolyzer.
Another economically significant electrochemical reactor is the Hall-
Heroult cell for the production of aluminum. This process is operated in
the batch mode at high temperature (approximately 1000°C) in a bath of
aluminum oxide or alumina (Al2O3) dissolved in fused cryolite (Na3AlFs),
to which aluminum fluoride is added. The thermal insulation is adjusted to
provide sufficient heat loss to freeze a protective coating of electrolyte on
the inner walls, but not on the bottom, which must make electrical contact
with the molten aluminum cathode. A crust of frozen electrolyte and
alumina covers the molten electrolyte. Electric current enters the cell
through carbon anodes and flows through the electrolyte, forming CO2 at
the anode and aluminum at the cathode. Steel collector bars joined to the
carbon lining at the bottom conduct electric current from the cell. Some
reviews of these and other industrial electrochemical processes can be found
in Bockris et al. (1981), Kuhn (1971), and Houghton and Kuhn (1974).
INTRODUCTION TO DESIGN
Any chemical process requires the evaluation of various alternative routes,
whether they be chemical or electrochemical. Two major tasks in designing
an electrochemical reactor are first to narrow down the choices of reactor
configurations and then to devise an economically optimum final design. As
an example of eliminating some reactor geometries, consider metal-ion re-
moval from dilute waste streams. In this case it would be impractical to
use two plane parallel electrodes because the reactor volume would be very
high, whereas a porous electrode, with its high surface area per unit
volume, would be a good candidate for this application. Porous electrodes
are also more suitable for gas-evolving reactions. On the other hand, the
channel configuration might be very useful for removing valuable metals,
such as silver, from concentrated solutions because the metal would be re-
covered directly as a sheet, rather than being incorporated in a porous
structure.
After choosing some electrode configurations to evaluate, one would
want to estimate the capital and operating costs and the product composition,
or, in the case of a battery, the energy and power output, as a function
of the feed conditions, the cell dimensions, and the operating conditions.
This can sometimes be a very difficult task because there are so many
phenomena that can interact, such as mass transfer, ohmic potential drop,
Electrochemical Reaction Engineering 925
thermodynamics, and electrode kinetics. In many cases, however, the
problem can be greatly simplified by realizing which phenomena dominate
the system behavior. This approach is expedient in choosing design alter-
natives.
In either the crude design or the final design, it is desirable to maxi-
mize profit or minimize cost. Thus one should be aware of the various
economic trade-offs that are important in electrochemical systems. Perhaps
the most obvious trade-off is between capital and operating costs. Usually,
the degree of conversion is specified, and one can meet that specification
either by building a large cell, with a high capital cost, or by using more
power with a smaller cell. There are also other trade-offs; for example,
in a channel flow cell, one can reduce the ohmic drop and increase the
mass transfer rate by making the interelectrode gap very thin, but this
will increase the pressure drop and hence the pumping cost. In addition,
it will lead to fabrication problems and the possibility of shorts.
GOVERNING PHENOMENA
If an electrochemical reactor is to be compared to an alternative, be it
chemical or electrochemical, detailed knowledge for the design and scaleup
is needed. To design an electrochemical system, one needs to consider many
effects, such as migration and diffusion of charged species, fluid dynamics,
thermodynamics, and reaction kinetics on electrode surfaces. An additional
system variable, not present in analyses of most chemical reactors, is the
electric potential. It is the difference in potential between the electrode
and the solution that governs which electrochemical reactions will occur.
In addition, gradients of electric potential and differences in potential be-
tween phases constitute major driving forces for mass transfer and for
electrochemical reactions. Thus a knowledge of the current and potential
distribution is useful in designing a reactor to carry out a desired electro-
chemical reaction.
To describe mass transfer in an electrochemical system, one must con-
sider not only ordinary diffusion, but also migration of charged species in
an electric field. Because it is the flux of charged species that produces
an electric current, one must include the contribution of migration to the
species flux to predict correctly the current flow.
In addition to mass transfer, one must consider thermodynamics in elec-
trochemical systems. Thermodynamics can be used to describe the properties
of electrolytic solutions and their dependence on composition, temperature,
and pressure. Thermodynamics also provides a framework for describing
reaction equilibria, which manifest themselves in equilibrium cell potentials.
Furthermore, the driving forces for irreversible processes are conveniently
expressed in thermodynamic terms.
Departures from equilibrium conditions are inherent in electrochemical
applications. Electrode kinetics concerns the nonequilibrium driving force,
called surface overpotential, necessary to make heterogeneous electrode re-
actions proceed at appreciable rates.
In addition to heterogeneous reactions, there are other interfacial
phenomena at electrode surfaces that can affect the current-potential be-
havior. The most prominent of these is the formation of a thin double layer
near electrode surfaces. This double layer may be on the order of 10 to
100 A ( 1 to 10 nm) in thickness.
926 Trost, Edwards, and Newman
Because there are so many interacting phenomena, it can sometimes be
very difficult to design an electrochemical system. In the present age of
computers, however, many problems that were intractable 30 years ago can
be handled today.
In spite of the power of computers, however, it is still useful to sim -
plify the problem if certain phenomena dominate the system behavior. For
example, there are some systems where it is possible to neglect concentra-
tion variations near the electrodes. The current distribution is then de-
termined by the ohmic potential drop in the solution and by electrode over-
potentials. (The ohmic drop is simply the voltage difference that arises
when current flows through the resistive solution.) Mathematically, this
means that the potential satisfies Laplace's equation, and many results of
potential theory, developed in electrostatics, the flow of inviscid fluids,
and steady heat conduction in solids, are directly applicable. These can
be called "potential-theory problems" (Newman, 1968). The electrode
kinetics provides boundary conditions which are usually different from those
encountered in other applications of potential theory.
There are also systems where the ohmic potential drop can be neglected.
The current distribution is then determined by the same principles which
apply to heat transfer and nonelectrolytic mass transfer. These can be
called "convective-transport problems" (Newman, 1968).
Some systems do not fall into either of the categories mentioned above.
Fortunately, however, some of these complex systems can be treated realis-
tically by using the computer to model the interacting phenomena.
FUNDAMENTAL EQUATIONS
To calculate the current and potential distribution, which is necessary to
design an electrochemical system, one needs a set of fundamental equations
applicable to electrochemical systems. These equations include a description
of the movement of mobile ionic species, an expression for current flow,
material balances, electroneutrality, and equations from fluid mechanics. In
addition, the differential equations describing the electrolytic solution re-
quire boundary conditions describing the thermodynamics and kinetics of
electrode reactions .
In dilute systems, the flux of each species is given by (Newman, 1973a)
(1)
where cjl is the electrostatic potential and Zi is the number of proton
charges carried by ion i. This movement is due, first, to the motion of
the fluid with the bulk velocity v. However, the movement of the species
can deviate from this average velocity by diffusion if there is a concentra-
tion gradient, 'i/ Ci, or by migration if there is an electric field, - 'i/ cjl , and
the species is charged. The migration term is peculiar to electrochemical
systems or systems containing charged species.
The second and third terms on the right side of Eq. (1) are the usual
terms required to describe diffusion and convection in nonelectrolytic sys-
tems. The species will diffuse from regions of high concentration to regions
of lower concentration. The three terms on the right in Eq. (1) thus
represent three mechanisms of mass transfer: migration of a charged species
Electrochemical Reaction Engineering 927
in an electric field, molecular diffusion due to a concentration gradient,
and convection due to the bulk motion of the medium.
Note that Eq. (1) only applies to dilute solutions. A more general
form of Eq. (1) is (Newman, 1973a)
c.c.
c.Vµ. = RT~ _u_ (yJ. - v.) (2)
l l D.. cT ~1
j l]
where µi is the electrochemical potential of species i. This equation must
be applied to systems, such as molten salt systems, where the activity co-
efficients are not close to unity, or to systems where the diffusion flux of
each species can be affected by more than one concentration gradient. The
driving forces for diffusion and migration are both included in the gradient
of the electrochemical potential in Eq. (2). Further details of concentrated
solution theory can be found in Newman ( 1973a).
After writing the appropriate flux equation, one can write an expres-
sion for the current, which is, of course, due to the motion of charged
particles in an electrolytic solution.
z.N. ( 3)
1~1
Here ,! is the current density expressed in amperes per square centimeter,
and ZiF is the charge per mole.
Next we need to state a material balance for any component i:
clc.
l
= -V • N. + R. ( 4)
at ~l l
Since reactions are frequently restricted to the surfaces of electrodes, the
bulk reaction term Ri is often zero in electrochemical systems.
Finally, we can say that the solution is electrically neutral:
z.c. = 0 (5)
~ l l
i
Such electroneutrality is observed in all solutions except in the thin double-
charge layer near electrodes and other boundaries.
These equations provide a consistent description of transport processes
in electrolytic solutions. Equations ( 1) and ( 2) state that species in the
solution can move by migration, diffusion, and convection. Equation (3)
merely says that the sum of fluxes of charged species constitutes an electric
current. Equation ( 4) is a material balance for a species, and Eq. ( 5) is
the condition of electroneutrality. Although the specific description may be
refined, any theory of electrolytic solutions will need to consider these
physical phenomena.
Note that in order to solve the equations describing the mass transfer,
it is necessary to know the convective velocity y. This velocity can be
928 Trost, Edwards, and Newman
found from the equations of fluid mechanics, such as the Navier-Stokes
equation
2 (6)
p(cly/clt + v•'i/v) = -'i/p + µ 'i/ V + pg
and the continuity equation
'i/ •v = 0 ( 7)
Next one needs boundary conditions describing the differences in
potential between phases. These boundary conditions describe the processes
occurring at the electrode interface.
One process that can occur is the adsorption of ions onto the surface.
(Usually, anions are specifically adsorbed.) A double-charge layer is
formed because the ions of one sign are attracted from the solution to the
adsorbed ions of the opposite sign. This attractive force, however, is
balanced by thermal agitation, which tends to make the ions wander.
Therefore, the double-charge layer has a diffuse part in the solution. That
is, the charge density decreases with distance from the interface. The
thickness of this diffuse layer of excess charge density is characterized by
the Debye length,
sRT )1/2
A ( (8)
2
= F Lz.2c.
1 1 100
The Debye length is typically on the order of 10 A. The major effect of
the double layer on the overall behavior of the interface is that it super-
imposes a capacitive effect on top of the electrode kinetics of the electrode
reaction itself. This means that when the potential of the electrode is
varied, the current that flows is partly due to charging the double-layer
capacity, and partly due to the charge-transfer reaction. One can
measure the capacitance of the double layer in several ways (Newman,
1973a; Grahame, 1947). Typically, the double-layer capacity is 10 to 40
µF/cm2 (Bard and Faulkner, 1980), but this capacitance is a function of
potential. The double layer is discussed further in Newman (1973a),
Grahame (1947), Bard and Faulkner (1980), Delahay (1965), and Parsons
(1954).
Although the existence of the double layer should not be neglected, it
is the charge-transfer reactions at the electrodes which are usually of
primary importance in electrochemical systems of practical interest. The
kinetics of these reactions relate the potential driving force to the rate of
reaction. Thus a knowledge of the electrode kinetics is necessary to formu-
late boundary conditions for the differential equations describing the move-
ment of ionic species.
For the purpose of assessing potential variations in a solution, it is
convenient to conceive of placing reference electrodes into the solution at
appropriate locations, usually just outside the diffuse double layer or in
the bulk solution. Figure 1 illustrates the placement of these reference
electrodes (White, 1977). The letter s designates reference electrodes of
the same kind as the working electrode, and the letter g refers to reference
Electrochemical Reaction Engineering 929
Diffuse
Working Bulk
Double Di ff us ion Loyer
Electrode Solution
Layer
® rls @ r 2s
® r lg @ r2g
FIGURE 1 Reference electrodes, which may be imaginary, positioned in
the bulk solution and within the diffusion layer. (From White, 1977.)
electrodes of a given kind. It is important to realize that a reference
electrode of a "given kind" cannot be a reference electrode of any kind.
Instead, the reference electrode must be carefully selected to be as re-
versible and reproducible as possible. The selection of reference electrodes
is discussed in Newman (1973a). One must also realize that a measurement
made by a reference electrode of a given kind must be corrected for any
liquid-junction potentials that might exist between the solution in question
and that within the reference-electrode compartment (see Newman, 1973a,
Sec. 40).
In the absence of concentration variations, the two reference electrodes
shown in Fig. 1 would measure the ohmic potential drop between the two
points labeled 1 and 2. In the presence of concentration variations, the
potential difference between the two reference electrodes will be composed
of an ohmic portion and what is called a concentration overpotential. The
concentration overpotential, nc , reflects the thermodynamic effect of the
difference in concentration between the interface and the bulk solution.
An additional contribution to the overall cell potential is the driving force
required to make the electrode reactions proceed at appreciable rates. This
surface overpotential, ns, is defined as the potential of the working elec-
trode relative to a reference electrode of the same kind, placed in the
solution adjacent to the surface of the working electrode, but just outside
the diffuse double layer. In terms of the notation of Fig. 1, this surface
overpotential for a reaction j would be written
= V - V = V - V (V r 1s V ( 9)
r ls r lg r
or
= V - <!> - U. ( 10)
0 J,O
where <!> 0 = Vr lg is the potential just outside the double layer, as
measured by a reference electrode of a given kind, and
U. = V Vr lg (11)
J ,o r ls
930 Trost, Edwards, and Newman
u.J ,o == (u~ _
J
RT~
n.F .L.J
c.1 0 )
siJ" ln -
Po
e
- ( 0 re
_ RT
n
re
~ s.
F LJ
.
1,re
J i l
(11)
Here the subscript re denotes the reference electrode reaction. The
stoichiometric coefficient , 8ij , refers to species i in a reaction j, written in
the form
( 12)
i
where nj denotes the number of electrons transferred, Mi refers to species
i, and Zi is the charge number of species i.
For a large class of electrochemical reactions, the current density de-
pends exponentially on the surface overpotential according to the Butler-
Volmer equation
i.
J
== i0 j
[ (a
exp
.F
:~ nsj
)
- exp
(-a .F
R~ nsj
)]
(13)
where \>j is the exchange current density for reaction j and depends on the
concentrations Cj_. Usually, this dependence is expressed as.
•
lOJ"
== • II ( cio
OJ,re f 1. -
l • --
c.1,re f
)yij (14)
In Eq. ( 13) , the first exponential term corresponds to the forward reaction
rate for an anodic process, and the second term represents the reverse re-
action rate. Note that if the anodic surface overpotential is large, the re-
verse reaction term can be neglected. This approximation, known as the
Tafel approximation, produces a linear plot of surface overpotential vs. the
logarithm of current density. A more thorough discussion of overpotentials
can be found in Newman (1973a) and White (1977).
We have now introduced enough of the elements to be in a position to
discuss the composition of the overall cell potential. This is due partly to
the ohmic potential drop in the solution. In addition, there is a potential
loss associated with the concentration variations in the solution near elec-
trodes, which we have termed the concentration overpotential. Finally,
there is the surface overpotential due to the limited rates of the electrode
reactions. The sum of these is the cell potential, which can be written
V == <I> (anode) <I>( cathode)
~
== <I> (anode) <I> (cathode) + <I> 2
== ns(anode) + nc(anode) + t:,. <I>ohm - n (cathode) - n (cathode)
C S (15)
where ~ 1 is the value that the potential adjacent to the anode would have
if there were no concentration variations in the solution. The terms nc and
Electrochemical Reaction Engineering 931
Anode Diffusion Bulk Solution Diffusion Cathode
Loyer Loyer
----- --~--
Van
T/s (anode)
+
~~-T
T/c (anode)
<I>,
Current
-17c (cathode)
(positive
charge)
-17s (cathode)
FIGURE 2 Overpotentials in an electrolytic cell. The solid line represents
potential distribution in the absence of concentration variations.
ns for the cathode enter with negative signs because of the conventions that
have been adopted. Since they are generally negative, they make a positive
contribution to the cell potential. Thus none of these terms, ohmic drop or
overpotentials, represents a source of energy. An example of how the vari-
ous overpotentials contribute to the overall cell potential is shown in Fig.
2. The dashed line represents what the potential in the solution would be
if all concentrations were at their bulk values.
Note that this decomposition presumes a bulk solution and a diffusion
layer adjacent to each electrode. In situations where this does not prevail,
such as a cell with overlapping diffusion layers, or a porous electrode, it is
necessary to start over from the basic equations, but the fundamentals re-
main the same.
CHANNEL FLOW CELLS
Channel flow between two parallel planar electrodes is used in many indus-
trial electrochemical processes, such as metal refining, energy storage, and
electro-organic synthesis. Specific examples include copper refining, some
zinc-halogen energy storage cells, and the Monsanto process for conversion
of acrylonitrile to adiponitrile.
932 Trost, Edwards, and Newman
Channel flow cells are very useful, since they provide continuous pro-
duction, they are simple to operate and maintain, and they do not require
a high capital investment (Fitzjohn, 1975). In addition, the analysis of
channel flow cells has been relatively well developed (Sakellaropoulos, 1979;
Sakellaropoulos and Francis, 1979, 1980; Parrish and Newman, 1969, 1970;
Caban and Chapman, 1976; Lee and Selman, 1982; Jorn€, 1982).
A channel flow cell consists of two parallel plates, which serve as the
anode and the cathode for electrochemical reactions. The electrolyte flows
past the electrodes, and the current flow is perpendicular to the fluid flow.
In general, a thin-gap cell with multiple reactions occurring on each
electrode is difficult to analyze. The electrodes cannot be treated separately,
and mass transfer, thermodynamics, and the kinetics of more than one re-
action must be considered simultaneously. This problem can be solved, but
for design purposes, it is useful to see if any simplifications can be made.
One assumption that is commonly used is that the diffusion layers are thin.
In this case, the electrodes can be treated separately. This is known as
the Leveque approximation (Newman, 1973a,b), and it is valid as long as
L
< 0. 0lReSc (16)
h
where
Re == 2 <v>h/v
Sc == v/D (about 1000 for most aqueous systems)
L == length of electrodes
h == spacing between electrodes
Thus we see that the thin-diffusion-layer approximation breaks down only
if the electrodes are very long, the gap is very thin, or the velocity is
very low.
Parrish and Newman ( 1970) used the Leveque approximation to obtain
the current and concentration distributions in a channel flow cell. They
examined the case of a metal deposition and dissolution reaction. Intuitively,
one would expect that mass transfer would not be important near the front
of each electrode, where the ions in solution are still unreacted. Farther
down the channel, however, the solution becomes depleted of metal ions.
Mass transfer then begins to affect the cathodic deposition reaction. The
anodic dissolution reaction, however, is not affected by the concentration of
ions in the solution. Therefore, we would not expect the anodic reaction to
become mass-transfer limited.
In the absence of mass transfer, the current distribution is governed
by the ohmic potential drop and the reaction kinetics. This current dis-
tribution is called the secondary current distribution. If there are no
kinetic limitations, however, the current distribution is called the primary
distribution. To calculate the primary current distribution, one would
solve Laplace's equation for the potential, assuming that the potential ad-
jacent to each electrode is held at a constant value. For two electrodes
embedded in planar channel walls, the primary current density is infinite
at the electrode edges. The secondary current distribution is similar to
the primary distribution, but it is more uniform because there are kinetic
limitations. Therefore, the current density is not infinite anywhere, but
it is still higher at the electrode edges.
Electrochemical Reaction Engineering 933
If mass transfer dominates the current distribution, on the other hand,
the current density is high only at the front of the electrode, and it de-
creases with distance down the channel.
For an anodic dissolution reaction, one would expect that mass transfer
would not be important. Therefore, the current distribution should re-
semble the secondary current distribution. Parrish and Newman found that
this is indeed the case. The cathodic current distribution, however, should
behave like a secondary current distribution near the front of the electrode,
but like a mass-transfer-limited current distribution near the back. In
fact, Parrish and Newman's numerical results show maxima in the cathodic
current densities. These maxima arise from a compromise between the
secondary current distribution and the mass-transfer-limited current dis-
tribution.
Throughout their analysis, Parrish and Newman assumed a single reaction
at each electrode. Very often, this simplifying assumption is valid (Pickett,
1979). Occasionally, however, multiple reactions must be considered
(Sakellaropoulos, 1979; Sakellaropoulos and Francis, 1979, 1980; White and
Newman, 1977). The assumption of a single reaction may be checked by
identifying a single parameter which characterizes the manner in which a
side reaction tends to obscure the limiting-current plateau for a main, or
desired, reaction (White and Newman, 1977). It is the magnitude of the
side reaction relative to the main reaction at potentials in the neighborhood
of the limiting-current plateau which is important.
Figure 3 illustrates this concept for the example of copper deposition
as the main reaction and hydrogen evolution as the side reaction. The
0.1
--------- ----
0 /
/----
/-·
f -u
/
m,ref
?. --; 1am, ref . .
-------- , Morn Cathodic
1,e,o -O . I Main Anodic / Reaction
> -0.2 Reaction -------- /
/ t- us.ref
0
"-§
Q)
---- ----- ---- ---- ---- /·
~ las,ref
/
n. -0.3 ,.___ _ _ _ _ _ _/~-~
0 /
/
-log Am--~~
Q) /
-e
-0 /
-QA /
/
u Side Anodic/
~ ~Us
w -o Reaction/
-o.
-o. ?'---'--/-////_.__/ --'----'------'--~-'-----'----'--l___.__,
-5 -4 -3 -2
-9 -8 -7 -6 -I 0
log Iii (A/cm 2 )
FIGURE 3 Qualitative sketch of the current-potential curves for a main
and a side reaction showing some of the parameters defined in the text.
(From White, 1977.)
934 Trost, Edwards, and Newman
solid line, labeled "main cathodic reaction," is the current-potential curve
of interest. The curves in the figure are plots of the potential difference,
V - ~ 0 , versus the log~rithm of the current density, where V is the
electrode potential and <!l0 is the potential in the solution just outside the
double layer as measured by a reference electrode of the same kind as the
main reaction. Note that the potential difference V - 41 is related to the
surface overpotential by Eq. ( 10). 0
n = V - ~ - U. (10)
Sj O ],O
where Uj ,o is defined by Eq. ( 11).
Figure 3 shows the following four curves:
1. Tafel approximation of main anodic reaction (copper dissolution)
2. Tafel approximation of side anodic reaction (production of hydro-
gen ions)
3. Tafel approximation of side cathodic reaction (hydrogen evolution)
4. Main cathodic reaction (copper deposition)
The heavy line for the main cathodic reaction (curve 4) has two asymptotes:
at high I V - q5 0 I , the reaction is mass-transfer controlled; at low I V - qS O I ,
the reaction is kinetically controlled.
The Tafel approximation is applied to the cathodic reactions, since it is
unlikely that the backward terms in the Butler-Volmer equation are impor-
tant in the neighborhood of the limiting-current plateau, where -ns, m is
large. The anodic reactions are plotted as Tafel lines to illustrate that the
limiting-current plateau is not affected by either anodic reaction. Although
the Tafel approximation is not valid near i = io, we are interested in the
neighborhood of the limiting-current plateau, which is far from io, There-
fore, we only examine the portion of the Tafel curve near the limiting-
current plateau, where the backward terms in the Butler-Volmer equation
can be neglected.
As long as there are no mass-transfer limitations, the plot of V - ~
versus log I i I will remain linear. Note that the solid line for the main
cathodic reaction does start to bend over as mass transfer comes into play.
The side cathodic reaction, hydrogen evolution, however, has no mass
transfer limitations because hydrogen evolution occurs from a solution with
excess hydrogen ion in the supporting electrolyte.
To plot a Tafel line, one needs not only the slope, but also the value
of V - ~ 0 at a single current density, i. If this current density is chosen
as the exchange current density at the reference concentrations, then
V - ~ = U ( 17)
o m.ref
where U f is given by
m,re
um,ref = ue - ue
m re
RT
n F I: s. ln
1m
c.1,ref
+ RT
n F
I: s.1,re ln c.
1,re
m Po re Po
i i
(18)
Electrochemical Reaction Engineering 935
The Tafel approximation can also be written for the main reaction in
the anodic direction. Again, at i ::: iom,ref, IV - ~ol is Um,ref· In
fact, the anodic and cathodic Tafel lines, for any reaction j, intersect at
ioj, ref and Uj ,ref, if the surface concentrations are at their reference
values. Therefore, for any reaction j, if one knows the exchange current
densities ioj, ref, and the anodic and cathodic transfer coefficients, Ctcj and
aaj, one can plot lines similar to those shown in Fig. 3,
The parameters Am and As, also shown in Fig. 3, characterize the
magnitude of the anodic part of a reaction, at the electrode potential for
which the main reaction is beginning to reach the limiting current. This
parameter is defined (White and Newman, 1977), for reaction j, as
1. • f l+aa3./a CJ. ( a .F )
A. = 03,re -1!1_ AU (19)
. exp RT '-' .
J 1m, li m J
It should be noted that if the surface concentrations are not at the
reference values, the Tafel lines will be shifted. For example, if the con-
centration of dissolved hydrogen is less than cH 2 ,ref• the Tafel line for
the anodic side reaction will be shifted to the left. The exact placement of
this line, in this case, however, does not affect the length of the limiting-
current plateau for the main reaction. In fact, neither anodic reaction
affects the length of the limiting-current plateau. Thus, since the limiting-
current region is of greatest interest, the anodic reactions are not important.
The electrode potential, Vm, for which the main reaction is beginning
to reach the limiting current is , in the absence of an ohmic potential drop ,
approximately equal to
-i
RT ln m,lim
V ::: U (20)
m m,ref a F i
cm om,ref
At the potential defined by Eq. (20), the current density for the side re-
action divided by the limiting current density for the main reaction is pro-
portional to exp (-a F t;.U /RT), where
cs s
i i
RT os,ref RT om,ref
t;.Us = U - U ln - ~ - + - - ln - - ' - - (21)
m,ref s ,ref a F -i a F -i
cs m ,lim cm m ,lim
corresponds to the length of the limiting-current plateau, as shown in Fig.
3. The parameter /:;. Us shows that both the exchange current density and
the open-circuit potential determine the relative significance of a side reac-
tion. If the exchange current density is very small or the open-circuit
potential is quite negative, /:;.Us will be large, and the side reaction will not
obscure the limiting-current plateau.
CELL OPTIMIZATION
The goal in designing any reactor is to maximize the profit or to mm1m1ze
the total cost by making an appropriate choice of operating variables and
936 Trost, Edwards, and Newman
cell dimensions. Naturally, there are constraints, such as mass transfer
and current-potential relationships, as well as feed and product specifica-
tions. Usually, however, there are few enough constraints that there is
enough flexibility to perform a cost minimization.
An example of the trade-off between capital and operating costs in a
fuel cell has been discussed by Newman (1979). Ibl and coworkers (lbl,
1977; Ibl and Adam, 1965; Ibl and Robertson, 1973) have also treated the
design and optimization of various electrochemical systems. Alkire et al.
( 1982) have discussed the optimization of electrochemical systems having
many variables. We shall discuss here the example of optimization of
potential and hydrogen utilization in an acid fuel cell.
A fuel cell for commercial power generation consists of a device to re-
form a hydrocarbon fuel to yield hydrogen and an electrochemical reactor,
where this hydrogen is combined with oxygen from the air to produce
water vapor and electric power. In this example, we shall perform a sim-
plified cost analysis, where only the capital costs and the fuel costs will
be included. The fuel cost, denoted Cf, will include all operating costs
which can be associated with or set proportional to the consumption of fuel.
Thus the reformer costs will be included in Cf, The trade-off between
capital and operating costs results because there is an optimum fuel utiliza-
tion beyond which the increase in electrode area costs more than can be
justified by the increase in electric power produced.
To perform the optimization, one must first write an expression for the
cost to be minimized. In this example, we shall write the cost in terms of
the hydrogen utilization u and the cell potential V, where utilization is de-
fined as the fraction of the hydrogen in the feed that is consumed in the
electrochemical reactor. To write the cost in terms of only the variables
u and V, one needs to know how the cell potential depends on current
density and gas consumption. Once the cost is written in terms of u and
V the optimization is performed by simply setting the derivatives of the cost
with respect to u and V equal to zero and solving for u and V.
To calculate the relationship among cell potential, current density and
gas composition, one can assume that the air cathode obeys Tafel kinetics.
At the hydrogen electrode, on the other hand, the surface overpotential is
negligible and the Nernst equation applies, where the anode potential differs
from the potential of the adjacent hydrogen reference electrode mainly be-
cause the hydrogen partial pressure differs from the reference pressure of 1
atm. Finally, one can calculate the ohmic potential drop within the cell and
combine the three equations to obtain the relationship among cell potential,
current density, and gas composition,
RT
V = U' + - ln - R'I (22)
F
The partial pressures of oxygen and hydrogen appearing in Eq. ( 22) are
at the catalyst layers and must be obtained from the values in the flowing
streams by allowance for the gas-phase mass-transfer resistance through
the inert gas in the electrode substrates. These partial pressures are then
substituted into Eq. ( 22) to obtain the desired current-potential relation-
ship.
Next, one needs an expression for the total cost. In this example, the
total cost is the fuel cost plus the capital cost. Let Cf be the value of a
Electrochemical Reaction Engineering 937
unit of hydrogen in the feed, and Ku Cf be the value of hydrogen in the
exit fuel stream after a utilization u, where Cf is expressed in $/C. Let
the capital costs be expressed by Ca, having units of $/s •cm 2 , based on
superficial electrode area. Ca is obtained by multiplying the total capital
cost ( $/cm2) by a factor such as 0. 3 yr-1, representing the effect of in-
terest, depreciation, and taxes. Components with a 5-year life and a 10%
interest rate might give rise to this factor. The total cost can now be ex-
pressed as
cost
(23)
time
where
F = Faraday's constant, 96,487 C/equiv
F = flow rate of inerts on anode side, mol/s
a
Xexit = ratio of moles of H 2 to moles of inerts in the exit stream
H2
XO = ratio of moles of H2 to moles of inerts in the feed stream
H2
2
.A.tot = superficial electrode area, cm
The first term on the right is the cost of the hydrogen feed stream, the
second term is the resale value of the hydrogen exit stream, and the last
term is the capital cost. We are concerned with minimizing the cost per
unit of electric energy, which is the ratio of the cost per unit time to the
electric power produced, where
A
Power = P = [
tot
VIdA (24)
0
Here I is the superficial current density, expressed in A /cm 2 . As a step
toward writing the total cost in terms of u and V, we can relate the flow
rate and consumption of hydrogen to the electric current by Faraday's
law,
2FF (X 8° - X ) = 2FF x 0 u' (25)
a 2 H2 a H2
where u' denotes the value of the utilization u for a local mole ratio x 8 of
hydrogen. Now we can write the total area as 2
A
tot =
2FF X o
a H2
f O
u du'
I
(26)
and the electric power from Eq. ( 24) becomes
P = 2FF X 0 {u V du'
a H2 Jo ( 27)
938 Trost, Edwards, and Newman
By means of these relationships, the power cost takes the form
C C;< (1 - u) + C (u (du' /I)
f - u aj 0
C = ( 28)
e
This equation has been written so that the extensive quantities-power re-
quired, electrode area Atot, and flow rate of the fuel stream- have been
eliminated in favor of the utilization u, an intensive variable.
We restrict ourselves here to the case where the cell potential V is a
constant for all values of the utilization. Now we can set the derivatives
of the power cost in Eq. ( 28) with respect to u and V equal to zero. The
ciu
differentiation with respect to u gives, after some manipulation,
I - K
C u du' dK
= + - - + (1 - u) duu ( 29)
I u u O I
where C = Ca/Cf is the ratio of the capital cost to the fuel cost and has
the units of A/cm2. The differentiation with respect to V gives
(.zl__)
cl V u
du' ( 30)
12
The results of this optimization show that when depleted hydrogen can
be sold at cost, that is, Ku = 1, it is economical to operate with the richest
fuel and airstreams available, as expected. Thus the optimum utilization
obtained from Eq. ( 29) is u = 0. Substituting this into Eq. ( 30) gives
-~(1+!__)=
cl I C
~
I
( 31)
This equation, when coupled with the current-potential relationship gives
the optimum current density or cell potential. For C, the ratio of capital
to fuel cost, approaching infinity, Eq. ( 31) says that the power maximum,
where dVI/dI = 0, is the optimum. As fuel costs become more important
and C decreases, optimum operation is at a current density below ( and a
potential above) the power maximum. The limit Ku = 1 will give the most
favorable power cost.
( 32)
The other extreme is Ku = 0, where waste hydrogen has no value.
This will be the worst case and will yield the highest optimum utilization,
for a given cost ratio C.
Electrochemical Reaction Engineering 939
POROUS ELECTRODES
In the discussion above we have considered a flow channel as a possible
reactor configuration. We wish now to focus attention on porous electrodes
as another class of electrochemical reactors.
Porous electrodes can be used in flow-through configurations as in fuel
cells, redox energy storage systems, and chemical reactors or in closed
configurations as in many primary and secondary batteries. Thus porous
electrodes find potential applications as electrochemical reactors in a variety
of areas. Flow-through porous electrodes are reviewed by Newman and
Tiedemann ( 1978). The mass transfer of reacting species within the fixed
bed and the ohmic potential variation throughout the bed are treated in de-
tail. A second review article treats porous electrodes with regard to bat-
tery applications (Newman and Tiedemann, 1975). A literature survey is
given in each review.
Two distinguishing features of porous electrodes are the intimate con-
tact of the electrode with the solution (and possibly a gaseous phase) and
the high surface area-to-volume ratio that can be obtained. The high
surface area-to-volume ratio is important to applications where the intrinsic
rate of the heterogeneous, electrochemical reaction is slow. In processes
using double-layer adsorption, the high surface area is again important.
Dilute reactants in solution require the close proximity of solution and
electrode to enhance mass transfer to the electrode surface. In battery or
fuel-cell applications, porous electrodes offer a means for storing the
soluble reactants in close proximity to the electrode surface. For non-
conducting reactants of low solubility, another solid phase (as in batteries)
or gas phase ( as in fuel cells) may be incorporated into the system.
Flow-through porous electrodes could find applications in the area of
metal processing. This includes the purification, electrowinning, and
possibly electroplating of aluminum, copper, magnesium, sodium, manganese,
nickel, gold, silver, and chromium. The electrorefining of aluminum from
an aluminum-manganese alloy might involve a flow-through porous anode in
order to prevent the dissolved manganese from reaching the cathode. Solu-
tions too dilute to treat with electrowinning processes may be treated with
a flow-through porous electrode. Dilute aqueous metal removal and recovery
of copper (Bennion and Newman, 1972), silver (Van Zee and Newman, 1977),
and mercury (Matlosz and Newman, 1982) have been studied in fixed-bed,
flow-through porous electrodes. Copper was recovered from feed streams
of 667 ppm with effluent concentrations less than 1 ppm, with simultaneous
production of a concentrated stream of 47, 660 ppm. Copper recovery has
also been investigated in fluidized-bed reactors (Fleischmann et al. , 1971;
Germain and Goodridge, 1976). Gold can readily be recovered from plating
baths which have deteriorated, and streams from processing photographic
emulsions can be reduced to less than 1 ppm silver. Mercury contamination
in brine solutions has been reduced to concentrations as low as 5 ppb from
feed streams of 50 ppm. Reduction of contaminants usually requires
processing of large volumes of dilute solutions. For metal removal, considera-
tion must be made for the periodic removal of material from the matrix.
Oxidation of organic contaminants, however, can proceed with no retention
of solids.
940 Trost, Edwards, and Newman
The use of porous electrodes in electro-organic syntheses may provide
an .economical alternative to other chemical routes. The electrochemical
synthesis may give higher yields under less severe operating constraints.
The ability to control the electrode potential allows optimization for a particu-
lar reaction product, while minimizing side reactions or multiple products.
A bibliography of electro-organic syntheses has been recently compiled by
Swann and Alkire (1980).
Energy storage and conversion systems may use flow-through porous
electrodes. Flow-redox systems, zinc-chloride hydrate storage systems,
and fuel cells are some examples. It has also been shown that the per-
formance of some primary or secondary batteries could be enhanced by a
fresh supply of electrolyte (Wierschem and Tiedemann, 1980; Liebenow,
1897). A promising zinc-bromine secondary battery system uses a flowing
electrolyte.
Flow-through porous electrodes also find applications in fundamental
studies. Appel and Newman (1976) apply a limiting-current method for the
measurement of mass-transfer coefficients at very low Reynolds numbers.
Fedkiw and Newman (1982) summarize mass transfer results of several
workers. The results are correlated by a dual-sized, straight-pore model
for the bed's pore volume.
Governing Equations
The many potential applications of porous electrodes warrant the need for
a mathematical description of the system. One can then scaieup a system
or predict the result of a change in operating parameters. This modeling
can lead to designs that optimize or maximize the desired process. Less de-
tailed modeling can be a guide in screening various alternatives such as
newly proposed battery systems. It is important, then, to develop guide-
lines as to the behavior of the porous electrodes.
Porous electrodes are inherently different from planar electrodes due to
the intimate contact of the solution and matrix phases. Here the current
flows within the matrix and the solution phases and exchanges between the
matrix and solution nonuniformly throughout the bed. An electrical analog
that can help picture the inherent complications is seen in Fig. 4. This
figure shows two porous electrodes operating as an electrolytic cell. The
subscripts 1 and 2 refer to the matrix and solution phases respectively.
Subscripts a and c refer to the anode and cathode, and Rs represents the
resistance due to the separator. When current flows through the porous
electrode, the electrical double-layer capacity (represented by Ca) is
charged. This is a net flow of current through the solution causing a
change in solution composition near the interface. In parallel to this process,
net current flows via a Faradaic reaction where RF represents the charge-
transfer resistance of the electrochemical reaction, These processes occur
nonuniformly throughout the volume of the porous bed. It is cautioned
that this figure is meant to serve as a guide in thinking about the distribu-
tion of reactions in porous electrodes, but is not a substitute for modeling
the porous electrode with the appropriate governing equations. Mass trans-
fer of reacting species, for example, is not considered in the electrical
analog.
The mathematical description of porous electrodes assumes a macrohomo-
geneous system. The porous bed is represented as the superposition of
two continua, a matrix and a solution. The actual geometric detail of the
Electrochemical Reaction Engineering 941
FIGURE 4 Simplified electrical analog of a porous anode and cathode (sub-
scripts a and c, respectively) showing the resistance in the matrix phases
(subscript 1) and solution phases (subscript 2). Also shown are the Faradaic
charge-transfer resistance (RF), electrical double-layer capacity (Ca), and
separator resistance (Rs).
bed is ignored. Average physical parameters such as porosity and surface
area are used. This type of analysis leads to a volume-averaged approach
in the governing differential equations (Gray, 1975; Dunning, 1971).
A schematic of a section of a porous bed is shown in Fig. 5. The
volume-averaged material balance (Dunning, 1971) of a species i within a
flooded porous bed in the absence of homogeneous chemical reactions takes
the form [ compare Eq. ( 4) J
cl (EC.)
1
= aj. 17•N. ( 33)
cl t In ~l
Here three different averages are used. i:: is the porosity or void volume
fraction. a is the specific interfacial area (surface area of pore walls per
unit volume of bed) . c. is the concentration averaged over the volume
1
Porous electrode
i 1= I
Metal
bocking
plate
X=O X=L
FIGURE 5 Schematic of a one-dimensional porous electrode.
942 Trost, Edwards, and Newman
of solution in the pores. sci is then the superficial concentration averaged
over the bed volume (matrix plus pores). hn is the normal component of
the pore wall flux of species i into the solution relative to the velocity of
the pore wall, averaged over the interfacial area. ~i is the average flux of
species i in the pore solution averaged over the cross-sectional area of the
pore plus matrix.
With the flux ~i referenced to the cross-sectional area of the pore plus
matrix, the superficial current density .!i in the solution phase is given as
( 34)
Similarly, 1 i, the current density in the matrix phase, is defined to refer
to the superficial area and not to the area of an individual phase.
The matrix and solution phases are taken to be electrically neutral.
For the solution, then,
z.c. = 0 (35)
1 1
We have assumed that the electrical double layer at the matrix pore inter-
face is a small volume compared to our averaging volume. This assumption
may break down for very dilute solutions and high-surface-area electrodes.
Electroneutrality requires that the divergence of the total current density
(!i + J 2) is zero; charge leaving the matrix must enter the solution. Thus
V•i
~1 +V•i
~2 = 0 (36)
A combination of Eqs. ( 33) to ( 35) gives
V •! 2 = aF L zijin = ai n ( 37)
i
where in is the average transfer current density from the matrix to the
solution phase. V • .i 2 is the transfer current per unit volume of the elec-
trode (A/cm3) and is positive for anodic currents. For a single electrode
reaction represented as
(38)
Faraday's law becomes
aj. = ( 39)
1n
Electrochemical Reaction Engineering 943
Substitution into Eq. ( 33) and neglect of double- layer charging yield
a ( e:c.) s.
1-
---
at = -v •N~i - -
nF
1 V• i
~2
( 40)
A kinetic polarization equation relating the local rate of reaction (transfer
current density) to the surface concentrations and interfacial potential drop
is needed. For the porous electrode , Eq. (13) becomes
V •J 2 = aiJexp ( : ; nJ- exp (-:c; nJ] ( 41)
Porosity changes can be taken into account by a solid-phase material
balance for a single electrode reaction:
a e: = -A V •i ( 42)
at 0 ~2
where
s.M.
AO = L l
pinF
l
( 43)
solid
phases
Transport processes are needed to complete our description. Ohm's law for
the matrix phase is
where cr is an effective matrix conductivity dependent on the composition of
solid phases, the manner in which the granules of the conducting phases
are connected, and the volume fraction of conducting phase or phases.
For a dilute electrolytic solution in the pores, the flux of a mobile
solute can be attributed to diffusion, dispersion, migration, and convection
[compare Eq. (1)]:
N.
~1
vc.
~ l
- = -(D. + D )Ve. - z.u.Fc.V<P 2 + - (45)
E: l a l 11 l e:
where ~ is a corrected ionic mobility and Di is an ionic diffusion coefficient
corrected for the tortuosity of the pores. Da represents the effect of axial
dispersion. A discussion of the effect of axial dispersion on the average
mass transfer coefficient is found in the review article by Newman and
Tiedemann (1978) (see also Fedkiw and Newman, 1978). The current den-
sity in the solution phase can now be represented by
12 = -KV<P 2 - e:F L ziDiVci ( 46)
i
944 Trost, Edwards, and Newman
where K == sF2I:i 21 2uici. The second term in Eq. (46) represents the
diffusion potential. As a consequence of electroneutrality, convection and
dispersion make no contribution to the current density.
We should also recognize here that other forms of the transport equa-
tions may be necessary to describe a system. The appropriate equations
for a concentrated binary electrolyte are given in Newman and Tiedemann
(1975). Two binary molten salts are treated by Pollard and Newman (1979).
When necessary, the full multicomponent transport equations can be used.
[Compare the discussion of Eq. ( 2). ]
In summary, the equations presented above have been found to describe
adequately porous electrodes in many cases. A certain level of complexity
is necessary in order to treat the simultaneous interaction of the physical
processes. Equations ( 3 3) to ( 35) and ( 45) govern the transport , conserva-
tion, and electrical neutrality in the solution phase. Equation ( 44) covers
the transport in the matrix phase. Equations (36) and (41) couple the
species in the bulk phase to the electrochemical processes occurring at the
interface. These equations are normally considered boundary conditions in
systems not involving porous electrodes, but here they are applied through-
out the volume of the bed.
Let us now illustrate an important design principle for flow-through
porous electrodes (Newman and Tiedemann, 1978; Bennion and Newman,
1972). Consider the case of reducing a species i at the limiting current
in an excess of supporting electrolyte. Equation ( 33) becomes
dN.
1
== aj. ( 47)
dx 1n
for a one-dimensional, steady-state material balance. In the absence of
migration in an electric field for the reacting species, the superficial flux
of species i in the direction of the superficial fluid velocity is [from Eq.
( 45)]
de.
N. - s(Di + Da) d; + c.v ( 48)
1 1
The local flux to the wall is given by a local mass transfer coefficient km
such that
== -k c. ( 49)
m 1
where the wall concentration C:io has been set equal to zero at limiting
current. Substitution of Eqs. ( 48) and ( 49) into the continuity equation
( 47) gives
2
de. d c.
1 1
v dx == s(D. + D ) ak c. ( 50)
1 a m 1
dx 2
Equation (50) governs the concentration distribution of species i throughout
the reactor. It is solved subject to the Danckwerts ( 1953) and Wehner and
Wilhelm ( 1956) boundary conditions for the concentration of species i at the
Electrochemical Reaction Engineering 945
inlet (x = 0) and the outlet (x = L) of the reactor. This formulation
assumes that an inert packing extends from the active portion of the bed
in both the upstream and downstream directions. A result of the con-
straints that the concentration of species i cannot increase without bounds
and that the concentration and flux should be continuous is that
de.
1
0 at x = L (51)
dx
For the upstream boundary condition, an inlet concentration of c and
0
continuous concentration and flux give
at X = 0 (52)
Under this condition, the concentration at the inlet of the bed will be less
than c 0 because some of the reactant will have diffused ahead to the active
portion of the bed. The solution to Eq. ( 50) subject to boundary conditions
(51) and (52) is
e--y/B + (D'/B 2)eBy/D' exp[-aL(l/B + B/D')]
e = ( 53)
B + (D'/B 2)(1 - B) exp[-aL(l/B + B/D')]
where we have introduced the quantities
c. ak X E ak
m m
e = C- 1 y = D' = -2- (Di + D a)
0
' V
V
( 54)
ak
1 + ✓ 1 + 4D' m
B = 2
Cl = V
Note that Eq. (53) simply reduces to
C. = Ce
-ax
or e = e-y (55)
1 0
when the effects of axial dispersion and diffusion are ignored,
Substitution of Faraday's law for the local flux to the wall in Eq. ( 49)
governs the behavior of the superficial current density in the solution.
Equation (50) becomes
2
de. d c.
1 1
v dx = E(D. + D ) (56)
1 a
dx 2
For an upstream counterelectrode, the current density i 2 must go to zero
at the back of the electrode as all the current has been transferred to the
matrix and current collector. Using this boundary condition and integrating
Eq. (56) give
946 Trost, Edwards, and Newman
(57)
where the subscript L refers to the exit of the reactor. Ohm's law for the
solution [Eq. ( 46)] is taken as
(58)
The diffusion potential has been ignored here, a good assumption when an
excess of supporting electrolyte is present. Integration of Eq. (58) sub-
ject to Eqs. (57) and (54) gives the local variation of potential through the
bed. This result is expressed as
nFvc
qi (L) - qi (0) = _ _o ~ rB 2 e eaL/B - D' - (aL + 1 + D')0 ] (59)
2 2 sRK akm ~ L B L
Figure 6 shows the nature of the potential variation through the electrode
bed. The potential in the matrix is constant through the length of the bed
if the matrix conductivity is very high. The ohmic potential drop in the
solution causes the variation in solution potential. The potential driving
force at the back of the electrode qi 1 - qi 2(L) must be large enough to
ensure limiting current, while the potential difference at the· front of the
electrode must not be large enough to have secondary reactions, such as
hydrogen evolution. Thus we have a maximum allowable ohmic potential
drop in our reactor. As the bracketed quantity in Eq. (59) is of order
unity, the coefficient of this quantity represents the magnitude of the
potential variation in the porous bed. Thus we see that, for given values
of c and K, side reactions limit the maximum flow rate through the bed.
0
V)
...J
<t
1-
z
w
l-
oQ.
w <1>2 (Ll
0
0
I
~ MATRIX POTENTIAL, <1>
u <I>,~----------------<
1
x=O x=L
CATHODE POSITION, x
FIGURE 6 Variation of solution and matrix potentials as a function of
position through a porous cathode. Matrix conductivity is infinite.
Electrochemical Reaction Engineering 947
Since v /akm represents the order of magnitude of the distance through the
reactor where the reaction occurs to an appreciable extent, a limit on the
velocity therefore limits the useful thickness of the bed. qi 2(L) - qi 2(0)
can be assigned a maximum value based on data that might be taken on a
rotating-disk electrode. Equation ( 59) can then be solved for the velocity v.
What is left to be specified, then, is the length of the electrode. The
length of the electrode is governed by the desired degree of conversion.
Equation (53) can be solved for L if y is replaced by ctL and e is replaced
by 0L, the desired conversion. In the case of neglecting the effects of axial
dispersion and diffusion,
V
L = ln (60)
ak
m
As mentioned above, other configurations of anode placement and current
collector placement can be considered (Trainham and Newman, 1978). Qual-
itatively, an upstream counterelectrode will yield the highest reactant con-
centration and the highest potential driving force at the front of the
electrode. A downstream counterelectrode will have the maximum reactant
concentration where the potential driving force is smallest. Thus the latter
configuration might appear to give a more uniform reaction distribution
throughout the bed. It is important then to consider the best configuration
to achieve a given objective. Calculations show that the best configuration
for achieving low effluent concentrations is with an upstream counterelectrode.
This rule applies for both high or low ratios of cr/K, In fact, a limiting-
current distribution cannot be achieved for a system utilizing a downstream
counterelectrode (except for short reactors). For very high values of cr/K,
the matrix potential is constant, and the placement of the current collector
is not important. For moderate matrix conductivities the optimum placement
of the current collector depends on the particular chemical system being in -
vestigated and the actual value of cr / K.
We have considered above that often a flow-through porous electrode
may be ohmically limited. This suggests an alternative configuration seen
at the bottom of Fig. 7. The flow- by porous electrode configuration has the
advantage that the flow of current is perpendicular to the fluid flow. The
electrodes can be made thin to minimize the ohmic potential drop in the elec-
trodes, and they can be made long to achieve high conversions. The dis-
advantage of the flow-by configuration is the necessity of including a
separator to avoid anolyte and catholyte mixing. The mathematical analysis
is also inherently more complicated due to the two-dimensional nature of the
problem. Two-dimensional modeling work has been done by Alkire and Ng
(1974). They treat a cylindrical packed-bed electrode surrounded by a con-
centric counterelectrode. Trainham and Newman (1981) present an engineer-
ing model that compares the performance on an economic basis of the two
porous electrode configurations for redox energy storage. The results of
the computer optimization show that the flow-by configuration is superior in
this case, where the dimensionless quantity e:nFD 0c 0 /sRK b. qi 2 is large. For
dilute solutions (small values of e:nFDoco/sRK b. qi 2) the flow-through con-
figuration may continue to have merit. Fedkiw (1981) presents a comparison
of the performance of flow-through and flow-by electrodes operated at limit-
ing current. For a given maximum ohmic potential drop and desired conver-
sion, he concludes that a flow-by electrode with a length-to-width aspect
948 Trost, Edwards, and Newman
iSeparator or Gap
i-----..~ Porous Electrodes
(al
Current
V V
t
Direction of Flow
lb) v{][}e"""'
+
Direction of Flow
lei {]0-c,m,t
f t
Direction of Flow
FIGURE 7 Various configurations of electrode placement relative to the
direction of fluid flow. (a) and (b) are flow-through configurations
(current and fluid flow are parallel), and (c) is the flow-by configuration
(current flows perpendicular to fluid flow).
ratio greater than 5 will have a higher processing rate than a flow-through
electrode. An ultimate design of a flow-by electrode must recognize that it
can be run below the limiting current.
It is clear that the flow- by system holds sufficient promise that more
detailed mathematical modeling and scaleup criteria are needed. The zinc-
bromine secondary battery system as well as flow-redox energy storage
systems have evolved to flow-by configurations.
Battery Applications
Let us now focus attention on the use of porous electrodes for battery appli-
cations. Several levels of mathematical sophistication can be used to examine
battery systems. Initially we should like to develop guidelines for screening
prospective systems. As development of a new or old system continues, we
then resort to more sophisticated mathematical models for our design and
scaleup. Before going into details, let us consider some general aspects of
battery systems (Tiedemann, 1978).
We wish to examine desirable characteristics for batteries so that we
may define inherent limitations or areas needing development for new and
existing systems. One recognizes that listing a set of desirable
Electrochemical Reaction Engineering 949
characteristics implies a particular application. In examining a new or old
system we wish to look at advantages and disadvantages in terms of cost
(perhaps amortized cost /cycle), energy and power density, shelf life, re-
versibility, energy and coulombic efficiencies, material utilization efficiency ,
cycle life, reliability, portability, safety, and availability of materials.
One of the first characteristics of a battery to be considered is its
voltage and specific energy. Knowledge of the overall reaction allows calcu-
lation of the open-circuit potential from thermodynamic data. Dividing the
potential by the equivalent weight (kg /C) yields the theoretical specific
energy of the electrode pair. Thus more energetic electrode couples with
lower equivalent weight will increase the theoretical specific energy. From
a practical viewpoint, the advantage of more energetic couples must be
weighed against the more severe materials compatibility requirements in the
more corrosive environment. For new batteries the specific energy quoted
is often a theoretical energy based only on the mass of active materials.
The theoretical specific energy of the lead-acid battery is 218 W•h/kg based
on the active materials PbO 2, Pb, and H280 4. Including the weight of the
solvent (for an initial concentration of 5 molal H2SO4) decreases the energy
to approximately 100 W•h/kg. Addition of the weights of current collectors,
excess active materials, separator, container, and connecting posts de-
creases this value further to approximately 40 W•h/kg. A rule of thumb
that the final specific energy is 25 to 30% of the theoretical specific energy
has been found to be approximately true for several systems. This rule
should be used with caution, but it does illustrate the performance penalties
associated with battery packaging and scaleup.
Knowledge of the specific energy of the system can be used to assess
the promise of a given system. Data on the specific power of the system
are also needed to determine the ability of the battery to deliver energy
at different rates. The maximum specific power that a battery can deliver
can be approximately calculated by (U /2)2/Ri where U is the open-circuit
potential and Ri is the sum of the internal area specific resistances (rl •cm2)
times the loading density of material (kg /cm2). The area specific resistance
can be estimated on the basis of electrolyte conductivity and separator thick-
ness. Battery designs with large current densities should keep overall area
specific resistances down to approximately 1 rl •cm2 and keep area specific
resistances of the separator itself down to about 0. 2 It •cm 2. These calcula-
tions become more refined as we obtain more information on a system. Higher
specific energies and specific powers are important in applications where
total weight or volume are important. In electric vehicle applications, for
example, a battery may not have enough energy or power to carry itself
and its support structure.
Three system efficiencies characterize the performance of a battery.
Coulombic efficiency is a measure of the reversibility of the electrodes or
the presence of side reactions. It is given by the ratio of the number of
coulombs released during discharge to the number of coulombs required to
charge the system back to its initial state. Energy efficiency is calculated
by multiplying the coulombic efficiency by the ratio of average discharge
voltage to average charging voltage. Differences in charge and discharge
voltages are due to irreversibilities associated with the ohmic potential drop
in the solution and matrix, and overpotentials associated with electrode
kinetics and mass transfer resistances. Coulombic efficiencies can often
approach 100%, while energy efficiencies are typically 50 to 80%. The
method of charging and discharging the battery will affect both of these
numbers.
950 Trost, Edwards, and Newman
The material utilization efficiency is the ratio of the actual coulombs
passed during discharge to the theoretical amount of active material avail-
able. Utilizations of 70 to 80% are typical, and again are dependent on the
method of discharge as well as any imposed cutoff voltage. Material utiliza-
tions often decrease with cycling. Among the factors that can lead to
material utilizations less than 100% are the isolation of active materials,
solubility problems with reactants and products, and, as mentioned above,
any imposed voltage cutoff. Isolation of active material can occur when an
insoluble, insulating reaction product covers the active material. Highly
nonuniform reaction distributions can lead to pore blockage. Differences
in the molar volume of reactants and products cause porosity changes
which can lead to matrix fracture.
The solubility of reactants and products is important to material utiliza-
tion as well as cycle life and shelf life. Dunning et al. (1971) identify a
range of approximately 5 x 10-5 to 11. 4 x 10-5 molar for the desirable
solubility range of a sparingly soluble reactant. The lower limit of solu-
bility is based on the need to diffuse the reactant to the active sites from
sparingly soluble crystallites. The ability to store the reactant in close
proximity to the active site was listed as one of the advantages of porous
electrodes. The upper limit of solubility can determine the shelf life of
the cell because of self-discharge processes. In general, a soluble reactant
on discharge will react if it can diffuse to the other electrode, while a
soluble reactant on charge will be substantially inert if it diffuses to the
other electrode. A soluble discharge reactant can be permanently incor-
porated into the other electrode and not be recoverable on charge. The
magnitude of solubility also influences the redistribution of active material.
The relatively high solubility of ZnO in KOH leads to marked concentra-
tion changes on cycling, and these can couple with the fluid flow to pro-
duce zinc shape change (Choi et al., 1976a,b).
We have mentioned above that the method of charging can affect the
efficiencies of a given system. Ideally, the charging process will restore
the battery to its state at the onset of the discharge cycle. In general,
the charging process plays an important role in the cycle life and per-
formance of a battery. Two common charging methods that may be used
are constant current and constant voltage. These can be combined with
voltage or current limits to help minimize side reactions, or for thermal
management. Side reactions, however, often do occur on charge. If
these reactions occur preferentially on one electrode, an imbalance in the
state of charge occurs. The ability of the system to accept overcharge
then becomes important. More sophisticated charging procedures can be
developed, but may be prohibitively expensive depending on specific applica-
tions. In some redox energy storage systems, for example, a third electrode
is used to correct for imbalances in the state of charge.
Porous battery electrodes can be constructed in a variety of configura-
tions. Often individual electrodes are constructed with a highly conducting,
inert substrate (grid) that mechanically holds the porous matrix in place.
It should be strong enough to withstand volume changes on cycling and be
inert over the operating temperature and voltage ranges. For a battery
plate with poorly conducting active materials, the grid is necessary to act
as a current collector to conduct electrons to or from the reaction site.
For moderately conducting active materials it can act as a secondary current
collector. In electrode configurations using grids, the current is collected
from each plate and is connected in parallel with an interconnecting bus.
Electrochemical Reaction Engineering 951
The optimal design of the current collecting grid and intercell connectors
is a scaleup problem that will be considered later. Another battery con-
figuration that can be considered is a bipolar arrangement. Such an ar-
rangement eliminates the need for a separate current collecting grid for
each electrode and may possibly minimize the voltage and weight perfor-
mance penalties associated with the grid. Here the positive and negative
active materials are put on opposite sides of an inert, conducting sub-
strate. Current flows straight through the cell stack and is collected at
the ends. The materials constraints for the conducting substrate are
severe; it must be substantially inert to both the oxidizing and reducing
environment. Corrosion of the substrate will lead to short circuits.
Materials compatibility is often a major problem in new or old battery
systems. Materials constraints may limit cycle life or prohibitively increase
the cost of a system. For example, corrosion of the current collecting grid
is cited as a major failure mechanism for the lead-acid battery. Active
material in ambient temperature Li electrodes becomes electronically isolated
from its substrate, presumably due to reaction with impurities and the
electrolyte itself (Brummer et al., 1980). In general, we look for a bat-
tery system where the active materials are compatible with each other and
the other support materials required in the battery. We require the elec-
trolyte, separator, battery container, interconnecting bus and post, current
collectors, and so on, to be stable over the operating voltage and tempera-
ture ranges of our system while not catalyzing side reactions or otherwise
reacting adversely with the system.
A separator is a major component of the battery package. It is re-
quired to separate the positive and negative electrodes in the battery, so
that they may be in close proximity but not short together. A common
failure mechanism in early battery development is shorting of the positive
and negative electrodes by dendritic growth of material through the separa-
tor (Choi et al., 1976a,b). Separators must be electronic insulators, but
have relatively high ionic conductivities. A separator with a high area
specific resistance (n •cm2) leads to a high ohmic potential drop with sub-
sequent poor performance. Separators may also be required to have other
desirable properties. Often they should be specifically conducting to only
certain ionic species (Choi et al., 1976a,b) or must contain additives that
increase electrolyte wetting.
Costs, of course, must always be considered within a particular applica-
tion. Besides the costs of raw materials, some other factors can be con-
sidered. Costs associated with safety, recycling (particularly if availability
of materials is low), and associated environmental factors need to be
considered. A common basis for comparison of various alternatives of
secondary batteries is the amortized cost of the system in $/W•h•cycle.
Scaleup of porous electrodes is not straightforward. Simply increasing
the thickness of an electrode, for example, does not necessarily bring about
proportional increases in performance. We wish to develop a micromodel of
the porous-electrode system so that we can predict the effects of changing
parameters such as electrode thicknesses on the behavior of the system.
Having this information in hand then leads us to couple the micromodeling
to further scaleup considerations of plate area and lengths of intercell con-
nectors.
In examining the micromodeling of porous electrodes let us first con-
sider the zero-time behavior (Newman and Tobias, 1962) where concentra-
tions are assumed to be uniform throughout the pore volume. Further,
952 Trost, Edwards, and Newman
let us ignore double-layer charging effects. Four dimensionless ratios
govern the current distribution. These can be stated as a dimensionless
current density,
a dimensionless exchange current,
2 FaioL2 (1 1
\! = (ex + ex ) - - - - + -) ( 62)
a C RT K CJ
the ratio of transfer coefficients in the polarization equation, exa/cxc, and
the ratio of effective solution and matrix conductivities K/0. o and v2
are ratios describing the competing effects of ohmic potential drop and
slow electrode kinetics. For large values of o or \! 2, the ohmic effect
dominates with a nonuniform reaction distribution, For small values of
K /cr, the reaction occurs preferentially near the electrode-separator
boundary at the expense of the region near the backing plate.
The nonuniformity of the reaction distribution for Tafel kinetics can be
seen in Fig. 8, For Tafel kinetics the current distribution depends only
Ordinate
8 y = 0.5 y=I
I 0.9594 1.084
10 0.693 1.943
100 0.1693 12.6 9
......N ,
t>
......
'-
__J
o= I
8 = 10
8 = 100
o o.__~...,,.,._,~-="--:--'---::'-cc------::::--;:;-~-;--
0. 2 OA
y=-x./L
FIGURE 8 Reduced current distributions for Tafel kinetics with equal
matrix and solution conductivities.
Electrochemical Reaction Engineering 953
on the parameter o and the ratio K/cr. Curves for linear polarization would
exhibit similar behavior as in Fig. 8. For linear behavior, the distribution
becomes nonuniform for large v and is independent of the total current.
For both cases the ratio of K / cr serves to shift the reaction distribution
from one face to the other.
The distance to which the reaction can penetrate the electrode deter-
mines how thick an electrode can be utilized. This penetration depth is
characterized by
L [ RTKcr ]l/ 2
v = (a
a
+ a ) ai F( K + cr) J
C O
( 63)
Electrodes much thinner than the penetration depth behave like plane elec-
trodes with an enhanced surface area. Electrodes much thicker are not
fully utilized. For high current levels, in the Tafel range, the ratio L/o
will be more characteristic of the penetration of the reaction.
To continue to follow the discharge behavior of a porous electrode
through the transient behavior, we need to consider the time derivative in
Eq. ( 33). Porous electrodes used in primary and secondary batteries in-
variably involve solid reactants and products, and the matrix is changed
during discharge. Consequently, no steady state is strictly possible. We
may nonetheless examine a steady-state operation of a porous electrode.
Just above we have considered the irreversibilities associated with electrode
kinetics and ohmic potential drop. As the reaction proceeds, reactant is
depleted at the pore-solution interface. This then represents an additional
irreversibility. Newman and Tobias (1962) also treat a redox reaction in a
porous electrode. Convection is assumed to be absent, and migration is
neglected due to an excess of supporting electrolyte. The stoichiometric
coefficients of the reactant and product species are taken to be +l and -1.
For a redox reaction Eq. ( 41) is often written as
(64)
Now i 0 is a constant representing the exchange current density at the com-
position c1, c;. The potential difference qi 1 - qi 2 is equal to ns plus an
additive term which depends on the local solution composition, [Compare
this with Eqs. (10) and (11).] A new dimensionless group Yi= 5iIL/
nFEDici can be formed due to the introduction of the diffusion coefficient
of each species and a characteristic concentration. Another special case
that can be treated is deposition from a binary electrolyte. The binary
electrolyte formulation can be applied to sulfuric acid in lead-acid batteries
or to the polysulfide in the sodium-sulfur cell if the melt is taken to be
composed of Na2S and S. This formulation also applies to systems with con-
centrated KOH electrolyte, such as in Ni-Fe and Ni-Zn cells, although the
solubility of ZnO must be ignored.
Often a system cannot be approximated by one of the limiting cases
presented above. Full treatment of the complicated factors governing the
behavior of the porous electrode requires the use of high-speed digital
954 Trost, Edwards, and Newman
computation. Newman and Tiedemann (1975) suggest a computational method
for battery electrodes involving a binary electrolyte. In general, reactant
species are depleted during the course of discharge, and time must be in-
cluded as a variable. Thus the coupled equations are solved simultaneously
at each time step. Pollard and Newman (1981) treat the transient behavior
of the lithium-aluminum, iron sulfide high-temperature battery for a con-
stant current discharge. Concentration distributions across the cell
sandwich are presented at various times throughout the discharge.
In summary we can list a number of factors that can affect the per-
formance of porous electrodes:
1. Charge and discharge methods affect battery efficiencies and cycle
life.
2. The solubility of reactants and products can limit cycle life and
shelf life.
3. Higher current densities yield higher overpotentials, and thus a
given cuttoff potential is reached sooner.
4. The pores may become constricted or even plugged with solid re-
action products. A nonuniform reaction distribution will accentuate
this problem at the mouth of the pores.
5. Utilization of the solid fuel can be limited by covering of the reac-
tion surface with reaction products.
6. Rates of mass transfer between crystallites and the reaction surface
may become more limiting as the discharge exhausts the front part
of the electrode. This could account for changes in the apparent
limit of utilization with current density.
Until now we have considered the mathematical modeling of porous bat-
tery electrodes. Experimental data are needed, of course, to ensure that
our understanding of the system is substantially correct. In constructing
an experimental cell we want to eliminate any scaleup effects not included
in the mathematical modeling so that we can directly compare experimental
and theoretical results. The scaleup effects of current collectors and in -
terconnecting bus and post will then be considered separately.
The experimental system can be arranged in a monocell configuration
with one positive and one negative plate, or as a bicell with a single posi-
tive electrode and two negative electrodes. The bicell arrangement repre-
sents a "section" of a positive and two half negatives that would be found
in the scaled-up battery. The construction and symmetry of discharge of
this cell would be similar to the scaled-up version. The monocell's main
advantage over the bicell may be in the ease and cost of construction.
A schematic of a bicell is shown in Fig. 9. This figure shows heavy,
highly conducting current collecting sheets in the center of the positive
electrode and at the back of the two half negative electrodes. These cur-
rent collectors promote a uniform current distribution across the face of
the electrode by minimizing the ohmic potential drop in the current collect-
ing sheet. This is important for comparison to one-dimensional micromodel-
ing results or for use as data in subsequent scaleup calculations. Separate
voltage and current taps should be used to eliminate any error in voltage
readings due to ohmic potential drop in the cell leads. Reference electrodes
should be used in the experimental cell so that the total cell potential can
be decomposed into contributions associated with the positive and negative
electrodes. Although we will see that this decomposition is not necessary
Electrochemical Reaction Engineering 955
le
RESERVOIR
NICKEL
CURRENT
COLLECTOR
FeS ELECTRODE
S.S SCREEN
BN SEPARATOR_j_-~.-- >~
~c~~
S S. HOUSING
FIGURE 9 Bicell design of a positive and two half negative electrodes
designed to promote a uniform current distribution across the electrode
face.
for our scaleup calculations, resear·ch efforts at improving the battery
need to be largely directed to the limiting electrode. Batteries are often
designed so that the positive electrode limits the battery capacity. This
should then be the case with the experimental cell as well. In general it
is important to use the same electrode thickness, amount of active material,
excess electrolyte, temperature, separator material, and so on, that is be-
ing considered for the scaled-up version. Micromodeling results can be used
as a guide in the selection of some of these parameters. The cross-
sectional area of the test cell is not important since our experiment is de-
signed to be one dimensional.
The apparent open-circuit potential is measured during discharging or
charging with a current-interruptio n technique. The cell potential during
956 Trost, Edwards, and Newman
current flow ( <l>p - <I>n) and after 15 seconds* of interruption is inter-
preted according to the equation
i = Y(U - <!> + <!> ) ( 65)
p n
where i is the current density from negative to positive plate (A/cm2), Y
is the conductance of a cell element cn-Lcm-2), U is the apparent open-
circuit potential (V), <l>p is the potential of the positive plate (V), and <I>n
is the potential of the negative plate (V). This relationship assumes a
linear polarization curve; however it can also be regarded as a step in the
linearization of a nonlinear problem. Values of U and Y can be determined
as a function of the state of charge for a given constant current density.
Data for a lithium-aluminum, iron sulfide high-temperature cell taken at
Argonne National Laboratory (Barney et al., 1981) are shown in Fig. 10.
The use of reference electrodes allows the decomposition of the cell poten-
tial and specific conductance into values for the individual electrodes.
These values are related to the cell values by
u = u
+
u (66)
and
1 1 1
y = -y + y
(67)
+
These results form a basis both for comparison to micromodeling results
and now for scaling up the plate size.
Cost, weight, and volume considerations dictate that the current col-
lectors will not be the heavy plates used in our test cell. The mass of the
current collector that should be used for a given plate area is a scaleup
consideration that is subject to optimization. Our goal is to develop a dis-
charge curve for the plate as a whole (with current collectors) based on
individual cell elements shown in Figure 10. Two common configurations
for the current collector are the sheet current collector and a grid current
collector. Tiedemann and Newman treat the nonuniform current and poten-
tial distributions in composite sheet electrodes (Tiedemann and Newman,
1979c) and in battery plates with grid configurations (Tiedemann and
Newman, 1979a).
The lead-acid battery uses a current collecting grid with the active
material pressed between the ribs. A honeycomb grid has been used in
*When the total external current is interrupted, we can identify three
transients: relaxation of the double- layer capacity, a local equilization of
charge and concentration from front to back of the electrode, and a reduc-
tion of concentration gradients in the whole cell by diffusion across the
separator. In the current-interruption technique, we wish to wait long
enough for double-layer charging to relax. A characteristic time for this is
L2ac /K. The apparent open-circuit potential will continue to rise as the
other transients continue. We choose 15 s here so that we may more closely
approximate the results that would be obtained with a 15-s power test.
Electrochemical Reaction Engineering 957
1.36
1.34
1.32
>
+ 1.30
::::>
1.28
1.26 0.04
>
1.24 a a 0.02 I
_..o....--,<r ::::>
1.22 0
0 C 33 39.4 mA/cm 2
□ C3 8 74.9
C,
Css 39.4
1.0
0.8
N
E
u
Cl 0.6
►
'
0.4
□
0.2 0
0
NEGATIVE
0 100 200 300 400 500 600
DISCHARGE C / cm 2
FIGURE 10 Electrochemical characteristics (U and Y) on discharge for
Lp = 0. 32 cm and 30% excess capacity in the negative electrode.
experiments with the lithium-aluminum, iron sulfide battery. We choose as
an operational current-collector model a rectilinear grid with horizontal and
vertical elements. A one-dimensional micromodel (Tiedemann and Newman,
1979b) or data as in Fig. 10 is coupled to a two-dimensional model of the
grid. Equation (65) can still be used where the current, area, and poten-
tials are now local values for node points on the grid. The polarization
parameters, U and Y, are curve fit as functions of depth of discharge and
local current density. Kirchhoff's law is used with Eq. ( 65) to solve for
the local potential distribution across the face of the plate during discharge.
Results of this analysis give the overall plate behavior as a function of
state of charge. The current distribution across the face of the electrode
is nonuniform at the beginning of discharge and becomes more nearly uniform
958 Trost, Edwards, and Newman
as discharge proceeds because of the dependence of the electrochemical re-
sistance and apparent open-circuit potential on the state of charge. The
overall behavior can now be represented by
(68)
where ti V is the voltage displacement from open circuit, and Rg is the re-
sistance of the grid. Since 1/Y and Rg vary through discharge in ways
that depend on the specific system, a general formulation of results cannot
be made. However, we can consider the zero-time behavior of a system
with constant polarization parameters and formulate the problem. For the
primary variables ti V the voltage displacement from open circuit, I the
total current leaving the grid, A the area of the plate, Y the conductance
of the cell element, M the mass of the grid, cr the grid conductivity, p the
grid density, and Lp the positive electrode thickness, four dimensionless
groups govern the system. One of these, L2 /A, does not have direct
relevance to the problem. We are left with p
I
II =
1 2AYtiV '
II1 represents a ratio of overall conductance I /2ti V to electrochemical con-
ductance AY. Stated another way, II1 is the ratio of the actual current
leaving the tab to the current that would leave the tab if the.re were no
ohmic resistance in the grid. The factor of 2 in II1 reflects the fact that
the total current leaving the grid tab is being collected from both sides
of the plate. II2 represents a ratio of grid conductance Mcr/ pA to electro-
chemical conductance AY. II3 is the volume fraction of grid material.
Other minor dimensionless parameters must now be chosen before the
results of the grid model can be plotted. These include the ratio of the
tab width to plate width, relative tab position, aspect ratio of plate height
to plate width, ratio of total grid material on horizontal elements to that in
vertical elements, and the number of horizontal and vertical elements.
Further, results can be presented for an infinitely conducting negative grid,
a symmetric negative grid with equal conductivity, or a complete descrip-
tion of a positive and negative with different conductivities.
Figure 11 is a plot of dimensionless plate current versus dimensionless
plate area for the beginning of discharge (Tiedemann and Newman, 1979a).
The volume fraction of grid material has been taken to be zero so that Lp
does not enter as a parameter in this figure. Here the horizontal and
vertical grid elements have the same amount of grid material, and a sym-
metric negative grid with equal conductivity is used. Figure 12 is an ex-
ample of an improved grid. Extra conducting material has been added to
the two columns of vertical elements below the tab and the horizontal
elements across the top of the grid. The two center vertical elements are
heavier by a factor of 11, and the top horizontal elements have four times
the mass of the base elements. Figure 13 is a dimensionless graph of
plate current versus plate area for this grid design. Here the negative
grid has been assumed to be infinitely conducting. A comparison of Figs.
11 and 13 shows the improvement in overall conductance for the improved
grid design. This improvement is actually due to two major effects, the
Electrochemical Reaction Engineering 959
0.6--------~-~-~-~~
0.4
0.2 0.4 0.6 0.8
A/PYo
Mer
FIGURE 11 Dimensionless plate current as a function of the dimensionless
plate area. Height-to-width ratio equals O. 8. Ten percent tab is located
30% from the edge of the plate. Lp is taken to be 00 (From Tiedemann
and Newman, 1979a.)
reduction of ohmic potential drop in the improved grid design and the
neglect of ohmic potential drop in the negative grid.
Figure 14 is a dimensionless correlation of the same data as in Fig. 13.
The dimensionless groups have been adjusted so that all the data closely
follow the same curve. Here it is recognized that the grid necessarily
-
Tab
_.---4~
I
,1-
~11/
FIGURE 12 Improved grid design with extra conducting material in the
two vertical elements and top horizontal elements.
960 Trost, Edwards, and Newman
l.2r-------.--~-------,....--~--~--~-~
1.0 No grid resistance, 113 =0
I
I
~0.8 I ,, /
I "7 / /
/'l ,,
I 1/i I
/"/ I I I
I
0 0.6 I I/111//
1,
~
1
/ l1 I 1 1 Plate Size
/ I 0-/._j (cm)
...._.... 04
/ 1ifi-.~15
I I f-i--i___ ----- 12
0.2
I
/ ,,1/11;---a
/
//
I / I ' 1 - - - - - 10
t--~---6
I
I I I I
I I I I I
I II I I
0.0~--------~--~--~--~--~---'
0.0 0.4 1.2
FIGURE 13 Dimensionless plate current as a function of the dimensionless
plate area for the improved grid design.
X=A ~ /I
/Mei- ✓ Ti
I-Yo Rs + Y. R
Xi= 1- (M/pLpAl o 5
0.8
_ 0.6
X
,.!?I
> >'0
~ <(
_N
Plate Size
(cm)
0.4
□ 18
•a 15
12
"
6
10
8
<;J 6
0.2
0 0.2 0.4 0.6
0.8 x2
l+0.8X 2
FIGURE 14 Dimensionless plate conductance versus dimensionless plate
area based on a reduced area for current flow through the matrix bed.
Electrochemical Reaction Engineering 961
displaces some active material, reducing the area for current within the
bed. The active bed cross-sectional area is therefore A - M/pLp. The
area for current flow through the separator is A. Thus we correct the
electrochemical conductance AY0 by an additive contribution of separator
resistance based on area A, and the rest of the electrochemical resistance
based on area A - M/pLP. Thus 1/Y0 is replaced by
1-YR )
...!-_ ( OS +YR
Y0 1 - M/pLPA o s
-1 -2
in plotting Fig. 14. The value of the separator resistance, Rs (Q •cm ) ,
can be estimated on the basis of electrolyte conductivity. The data plotted
in this manner fall very closely on the same curve and have unity inter-
cepts on both the ordinate and abscissa.
As pointed out above, Fig. 14 is strictly valid for zero-time behavior.
Our alternative to performing complex grid calculations to map out the
overall conductance during discharge is to assume Fig. 14 is valid through-
out discharge, replacing Y0 with Y and (l/t.V) 0 by 1/t.V. Here we are
recognizing the dependence of the polarization parameters on the average
depth of discharge, but still assume that they are constant across the
electrode face. Y and U actually depend on the local current density and
local depth of discharge. This method should give a good approximation
to the actual behavior of the plate and reduces to an exact solution to the
complete grid formulation as the current densities become more uniform.
A computer program can now be developed that uses data as in Figs. 10
and 14 to generate scaleup predictions for energy and power.
For a given plate size and grid weight, we can now calculate the
specific energy and specific power through discharge. The calculations
vary the average depth of discharge to a specified cutoff potential for a
4-h discharge rate. The results of these calculations, using the correlation
in Fig. 14 and the data in Fig. 10, are given in Fig. 15. We immediately
see a conflict in trying to optimize simultaneously the battery system for
maximum energy and maximum power. Instead, we choose an intermediate
grid weight that gives a ratio of power to energy equal to the ratio of
maximum power to maximum energy. Alternative compromises could be
selected based on the particular applications at hand.
Having selected a natural system ratio for determining the grid com-
promise, we now recognize that our small plates must still be connected
in parallel with an interconnecting bus, and that the cell must be con-
nected in series to another cell with an interconnecting post. Two impor-
tant new parameters-the length of interconnecting bus and length of
interconnecting post-must now be considered. Figure 16 shows a sym-
metric arrangement of interconnecting buses for three positive electrodes.
Lbus is approximately equal to the sum of the widths of the positive elec-
trode, negative electrode, and two separators. The post represents the
cell terminal plus intercell connector that extends from one cell to the next
cell. In our calculations we take Lpost to represent only that part of the
post associated with one cell (i.e. , the length of the terminal plus half
of the length of intercell connector). The lengths of interconnecting buses
for the positive and negative plates are taken to be the same, as are the
post lengths. Given the post and bus lengths needed to connect our cells,
an optimization of the distribution of conducting material among the parallel
962 Trost, Edwards, and Newman
140~-~-~-~--~-~-~-~
Lbus = L post= 0.0.
<
a,
120
.c
,i:
>-
t::>
a:: 13.6
w
~ 100
u
LL
u
w
a.
CfJ 80 Plate Size
(cm)
D 18
O 12
/; 8
60~-~-~-~--~-~-~-~
80 120 160 200
SPECIFIC POWER (W/kg)
FIGURE 15 Maximum specific energy versus maximum specific power half-
way through discharge.
bus connections and the post connections can be made independently of
other scaleup considerations. The important quantity that results from
this optimization is
1/2
L (Ppost)
post opost
If the density of the bus and post are taken to be equal, we see only the
sum of the bus and post length is important to the scaleup predictions. We
also note that the number of positive electrodes per cell is subject to varia-
tion. The number used will affect the final results for the power and
energy, but does not affect the optimum distribution of material over the
bus and post per cell "section. "
FIGURE 16 Symmetric arrangement of interconnecting buses and inter-
connecting posts for three positive electrodes.
Electrochemical Reaction Engineering 963
For a given plate size and grid weight, the calculated specific energies
versus specific powers will form a loop in the same manner as in Fig. 15
as the mass of the bus and post is varied from very small values to larger
values. Thus, for each plate area and grid weight we can find a mass of
bus and post that maximizes either the specific energy or specific power.
As we investigate different grid weights (and thus different optimum post
and bus weights) we can find values of the mass of grid, bus, and post
that yield the maximum power. Similarly, we search for values of grid
weights and bus and post weights that yield the maximum energy. Now
our compromise ratio is the value of the maximum power to this maximum
energy. Thus for each plate size our compromise design is the values of
the mass of grid, bus, and post that give a power-to-energy ratio equal
to the compromise ratio. More than one combination of grid and bus and
post weight will yield a power-to-energy ratio equal to the compromise
value. The largest values of energy and power are selected from this col-
lection of results to represent the best compromise design for a given plate
area.
Figure 17 represents the composite prediction of specific energy versus
specific power as they relate to the size of plates and lengths of bus and
post. Recall that each point given represents the best compromise of
specific energy and specific power for each plate area as just discussed
above. The performance penalty (weight and voltage) of including the
interconnecting bus and post is readily seen. This graph can now be
used to select the plate area which will give adequate performance at a
suitable cost. The grid weights and plate areas used to generate Fig. 17
are plotted in Fig. 18. Also shown are the grid weights that correspond
to maximum power and maximum energy. This figure, then, yields the grid
weight that gives the maximum power, maximum energy, or compromise for
130~--~---~---~---~
C'
-"'
.......
'~•
l~J.8
7 110 I 10
! 8 6cm
>-
(!)
0: 6cm
w
z
w 6cm
u
Li: 90 Lpost Lbus
u (cm) (cm)
w
a. 6 00 00
(/) D 2.0 1.0
0 5.0 1.0
70
90 110 130 150 170
SPECIFIC POWER (W/kgl
FIGURE 17 Composite, compromise predictions of the specific energy and
specific power for various post and bus lengths and electrode areas.
964 Trost, Edwards, and Newman
Maximum
0.10 Specific Power
0.01 0.10
FIGURE 18 Dimensionless grid weight versus dimensionless plate area
along the maximum specific energy, maximum specific power, or the com-
promise design.
each plate area and length of bus and post. It is seen that the optimum
grid weight is not greatly dependent on the length of the bus and post,
and that this dependence is actually undetectable for maximum specific
power. These results suggest that we can improve our grid design with-
out concern over interaction with the optimum post and bus lengths, and
that improvements may be independent of depth of discharge as well. We
also see that the optimum grid weight should be roughly increased in pro-
portion to A3/2.
We should also note here that no consideration has been given to any
minimum current-collector weight necessary to support the active materials
through cycling. In general, for smaller cells it may be stated that a cur-
rent collector that is large enough to contain the active material will have
a weight large enough to approach or exceed the value corresponding to
the design for maximum power. More detailed scaleup considerations are
needed for bigger plate sizes. Finally, we should note that the value of
the grid weight corresponding to maximum specific energy will depend on
the discharge time. As we decrease the discharge time from the 4- h value
used here, the grid weight will move upward toward the value for maximum
specific power.
In the results presented above, the delivered ampere-hour capacity of
the battery has been a dependent variable. An alternative design sequence
is to specify a value for the total delivered capacity. In this case the
area of the plate is varied until the optimum values of grid weight and bus
and post weight are found so that the specified capacity is reached at the
cutoff voltage.
In summary, we have shown how to account for the performance penal-
ties associated with the grid and interconnecting bus and post.
Electrochemical Reaction Engineering 965
NOTATION
a specific interfacial area per unit volume of porous electrode,
cm-1
2
A cross-sectional area of the plate, cm
A. parameter characterizing magnitude of anodic reaction at the
]
potential where the main reaction is beginning to reach limiting
current [see Eq. (19)]
constant defined by Eq. ( 43)
2
total superficial electrode area, cm
quantity defined in Eq. (54)
3
Ci concentration of species i per unit volume of solution, mol/cm
c. local surface concentration of species i, mol/cm 3
10
C. concentration of species i in the reference electrode compartment,
1,re
mol/cm3
ci,ref reference concentration of species i, mol/cm 3
c.1co concentration of species i in the bulk, mol/cm 3
exit concentration of reactant, mol/cm 3
feed concentration to flow-through electrode, mol/cm 3
ratio of capital cost to fuel cost, A/cm 2
capital cost coefficient, $ /cm 2 •s
2
electrical double- layer capacity, F /cm
electric energy cost, $/J
fuel cost coefficient, $/C
dimensionless dispersion coefficient defined in Eq. ( 54)
D dispersion coefficient, cm 2 /s
a
D.1 diffusion coefficient of species i, cm 2 / s
D.. diffusion coefficient for interaction of species i with species j,
l]
cm2/s
F Faraday's constant, 96487 C /equiv
flow rate of inerts on anode side, mol/s
acceleration of gravity, cm/s 2
spacing between electrodes, cm
i current density, A /cm 2
i 1 superficial current density in the matrix, A/cm 2
2
22 superficial current density in the pore phase, A /cm
i. current density for reaction j, A/cm 2
]
2
i m, Ii m limiting current density for the main reaction, A/cm
966 Trost, Edwards, and Newman
i transfer current per unit of interfacial area, A/cm 2
n
i exchange current density, A/cm 2
0
.
i OJ,re f exchange current density for reaction with reference concentra-
tions, A/cm2
current density, A /cm 2 , or total current leaving tab, A
pore-wall flux of species i, mol/cm 2
coefficient of mass transfer between flowing solution and electrode
surface, cm/s
K resale value of unused but depleted hydrogen, as a fraction of
u
value in feed
L length of planar electrodes, or length of porous electrode, cm
Lbus length of interconnecting bus, cm
LP thickness of positive electrode, cm
L length of interconnecting post, cm
post
M current collector weight, g
M. molecular weight of species i, g /mol
1
n number of electrons transferred in electrode reaction, equiv /mol
n. number of electrons transferred in reaction j, equiv /mol
]
N. flux of species i, or superficial flux of species i, mol/cm 2 •s
~1
p pressure, dyne/cm 2
PH2 partial pressure of hydrogen at the anode, bar
Po 2 partial pressure of oxygen at the cathode, bar
p electric power produced, W
R universal gas constant, 8. 3143 J /mol •K
R anode matrix resistance, S'l •cm 2
a,1
R anolyte solution resistance, S'l •cm 2
a,2
R cathode matrix resistance, S'l •cm 2
c,1
R catholyte solution resistance, S'l •cm 2
c,2
RF Faradaic charge-transfer resistance, :] •cm 2
Rg resistance of grid, S'l •cm 2
R. rate of homogeneous production of species i, mol/cm 3 •s, or the
1
sum of internal area specific resistances, S'l •cm2
R separator resistance, S'l •cm 2
s
R' effective ohmic resistance, S'l •cm 2
Re Reynolds number
s. stoichiometric coefficient of species i in electrode reaction
1
s.. stoichiometric coefficient of species i in reaction j
lJ
Electrochemical Reaction Engineering 967
Sc Schmidt number
t time, s
T absolute temperature, K
u fractional utilization of hydrogen
u.1 mobility of species i, cm 2 •mol/J•s
u apparent open-circuit potential, V
U' constant in Eq. ( 22) , V
u. theoretical open-circuit potential for reaction j at the composition
J ,o
prevailing locally at the electrode surface relative to a reference
electrode of a given kind, V
u.J ,re f theoretical open-circuit potential evaluated with reference con-
centrations, V
u~ standard electrode potential of reaction j, V
]
ue standard potential for the reference electrode reaction, V
re
y solution velocity or superficial fluid velocity, cm /s
<v> average solution velocity, cm /s
V electrode potential or cell potential, V
V electrode potential where main reaction begins to reach limiting
m
current, V
X distance through porous electrode, cm
ratio of moles of H 2 to moles of inerts
= ak x /v, dimensionless distance
m -1 -2
electrochemical conductance, r2 •cm
-1 -2
electrochemical conductance at start of discharge, r2 •cm
valence or charge number of species i
Greek Letters
-1
a. = ak /v, reciprocal reaction distance, cm
m
a. transfer coefficient in anodic direction
a
a. . anodic transfer coefficient for reaction
aJ
a.c transfer coefficient in cathodic direction
a. • cathodic transfer coefficient for reaction
CJ
yij exponent in composition dependence of exchange current density
0 dimensionless current density defined in Eq. (61)
Li us approximate length of the limiting current plateau for the main
reaction before the onset of the side reaction, V
Li V voltage displacement from open circuit, V
Li cJ>o h m ohmic potential drop in the absence of concentration variations, V
968 Trost, Edwards, and Newman
E porosity or void volume fraction, dimensionless, or permittivity,
Flem
concentration overpotential for reaction j , V
surface overpotential, V
surface overpotential for reaction j , V
= c. /c , dimensionless concentration
1 0
= cL/c0 , dimensionless exit concentration
effective conductivity of solution, n- 1 -cm-l
>.. Debye length, cm
µ viscosity, g /cm •s
electrochemical potential of species i, J /mol
kinematic viscosity of the solution, cm 2 /s
dimensionless exchange current given by Eq. (62)
= l/2AYt:. V, dimensionless plate current
= Ma/pYA 2 , ratio of grid to electrochemical conductance, dimen-
sionless
= MI pLp A, volume fraction of grid, dimensionless
density, g/cm 3
pure solvent density, kg /cm 3
effective conductivity of the matrix phase, or the conductivity
of the current collecting grid, n- l •cm-1
electrostatic potential, V
electric potential in the matrix, V
electric potential in the solution, V
potential of the negative plate, V
potential in the bulk solution extrapolated to the electrode sur-
face, V
<I> potential of the positive plate, V
p
Subscripts
g reference electrode of a given kind
i species i
reaction j
m main reaction
o electrode surface, solvent, reactor inlet, or beginning of
discharge
ohm ohmic
Electrochemical Reaction Engineering 969
rl reference electrode located just outside the double layer
r2 reference electrode in the bulk solution
re reference electrode
ref reference concentrations
s side reaction, or reference electrode of the same kind as the
working electrode
oo bulk solution
1 porous electrode matrix phase
2 porous electrode solution phase
Superscripts
exit exit stream
0 feed stream
REFERENCES
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packed - bed electrochemical flow reactor, J. Electrochem. Soc. , 121 ,
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Alkire, R. C. , G. D. Cera, and M. A. Stadtherr, Optimization of electro-
lytic cells having large numbers of variables, J. Electrochem. Soc. ,
129, 1225 (1982).
Appel, P. W. and J. Newman, Application of the limiting current method
to mass transfer in packed beds at very low Reynolds numbers,
AIChE J., 22, 979 (1976).
Bard, A. J. and L. R. Faulkner, Electrochemical Methods, Fundamentals
and Applications, Wiley, New York (1980).
Barney, D. L. and others, Lithium/Iron Sulfide Batteries for Electric-
Vehicle Propulsion and Other Applications, Progress Report for
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Beck, T. R. , Proceedings of the Workshop on Energy Conservation in
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from very dilute solutions, J. Appl. Electrochem. , 2, 113 (1972).
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Comprehensive Treatise of Electrochemistry, Vol. 2: Electrochemical
Processing, Plenum Press, New York ( 1981).
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Caban, R. and T. W. Chapman, Rapid computation of current distribution
by orthogonal collocation, J. Electrochem. Soc., 123, 1036 (1976).
Choi, K. W., D. N. Bennion, and J. Newman, Engineering analysis of
shape change in zinc secondary electrodes: I. Theoretical, J. Electro-
chem. Soc., 123, 1616 (1976a).
970 Trost, Edwards, and Newman
Choi, K. W. , D. Hamby, D. N. Bennion, and J. Newman, Engineering
analysis of shape change in zinc secondary electrodes: II. Experi -
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Danckwerts, P. V. , Continuous flow systems. Distribution of residence
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tries 1981, Report sponsored by the Industrial Electrolytic Division
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York (1965).
Dunning, J. S. , Analysis of Porous Electrodes with Sparingly Soluble
Reactants, Dissertation, University of California, Los Angeles (1971).
Dunning, J. S. , D. N. Bennion, and J. Newman, Analysis of porous
electrodes with sparingly soluble reactants, J. Electrochem. Soc.,
118, 1251 (1971).
Fedkiw, P. S., Ohmic potential drop in flow-through and flow-by
porous electrodes, J. Electrochem. Soc., 128, 831 (1981).
Fedkiw, P. and J. Newman, Low Peclet number behavior of the transfer
rate in packed beds, Chem. Eng. Sci., 33, 1043 (1978).
Fedkiw, P. S. and J. Newman, Mass-transfer coefficients in packed
beds at very low Reynolds numbers, Int. J. Heat Mass Transfer,
25, 935 (1982).
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85 (1975).
Fleischmann, M. , J. W. Oldfield, and L. Tennakoon, Fluidized bed
electrodes: Part IV. Electrodeposition of copper in a fluidized bed
of copper-coated spheres, J. Appl. Electrochem. , 1, 103 ( 1971).
Germain, S. and F. Goodridge, Copper deposition in a fluidised bed cell,
Electrochim. Acta, 21, 545 (1976).
Grahame, D. C. , The electrical double layer and the theory of electro-
capillarity, Chem. Rev. , 41, 441 (1947).
Gray, W. G. , A derivation of the equations for multi-phase transport,
Chem. Eng. Sci., 30, 229 (1975).
Houghton, R. W. and A. T. Kuhn, Mass-transport problems and some
design concepts of electrochemical reactors, J. Appl. Electro-
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lbl, N., Optimization of copper refining, Electrochim. Acta, 22, 465 (1977).
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nik, Chem. - Ing. -Tech. , 37, 573 ( 1965).
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bei variabeler Stromstarke, Z. Elektrochem. , 4, 58 (particularly
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Electrochemical Reaction Engineering 971
Mantell, C. L., Electrochemical Engineering, 4th ed., McGraw-Hill,
New York (1960), p. 391.
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removal of mercury from contaminated brine solutions, Proc.
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National Research Council, Assessment of Research Needs for Advanced
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15
Reactor Steady-State Multiplicity
and Stability
MASSIMO MORBIDELLI Politecnico di Milano, Milan, Italy
ARVIND VARMA University of Notre Dame, Notre Dame, Indiana
RUTHERFORD ARIS University of Minnesota, Minneapolis, Minnesota
INTRODUCTION
Although it is titled broadly, the scope of this chapter is more limited. We
attempt to provide a review of concepts and results related to steady-state
multiplicity and dynamic behavior in two types of reactors: the continuous-
flow stirred-tank reactor (CSTR) and the empty tubular reactor (note that in
qualifying it as "empty," we mean that there is no special reference made to
packing found in a packed-bed reactor; see Chapter 6 for the design of such
reactors). In thus limiting the scope, for reasons of brevity, we therefore
make no direct mention of similar problems that arise and that have been at-
tacked for ot}:ler types of reactors and for single-catalyst pellets. These re-
sults are discussed in other chapters.
Despite the limitation in scope, the two reactor types that are covered
are the most widely treated in the literature and offer a wide spectrum of re-
sults. Many of these results also carry over to other reactors. The CSTR
and the empty tubular reactor thus serve as paradigms for understanding
steady-state multiplicity and dynamic behavior of reactors in general.
In its simplest form, the CSTR is perfectly ·well-mixed; thus there is no
spatial distribution of reagent concentrations or of temperature. In the
simplest model for the tubular reactor, a plug of fluid flows through the
tube and reaction occurs along the length of the tube; there is no fluid
mixing in the axial direction while there is perfect mixing in the radial
direction-the so-called plug-flow model. Since the reaction does occur
along the length of the tube, there is a distribution of reagent concentra-
tions-and also of temperature for nonisothermal cases-along the axial
direction. Fluid mixing can be taken into account by including axial dis-
persion superimposed on the plug flow, and as noted earlier (Varma and
Aris, 1977), the axial dispersion model in the limits of small and large dis-
persion does indeed yield plug-flow and CSTR behavior, respectively.
This chapter may be considered an update of our previous review (Varma
and Aris, 1977). In the interim period, numerous additional results have
appeared in the literature, and this chapter provides us with an opportunity
to collect them in one place.
973
974 Morbidelli, Varma, and Aris
STEADY-STATE MULTIPLICITY
Continuous-Stirred-Tank Reactor
The mass and energy balances for a CSTR under steady-state conditions can
be written as follows (see Varma and Aris, 1977):
q(C 0 - C) - Vf(C,T) = 0 ( 1)
qpC (To - T) + (-LIH)Vf(C,T) - Ua(T -- T ) = 0 (2)
p C
where all the symbols are explained in the notation section. In deriving Eqs.
( 1) and ( 2) , it has been assumed for simplicity that:
1. The flow rate q and the reactor volume V are constant.
2. The fluid thermal and physical parameters, p, C , and LIH are
independent of temperature and composition. p
3. The temperature of the cooling medium, T , is constant.
C
Equations ( 1) and ( 2) can be made dimensionless by introducing the
following quantities:
T E
v=- y=--
T RT
m m
Vf(Co, Tm) Ua
Da = qCO
c5 = qpC
(3)
p
(-LIH)C 0
f(C,T)
s = pC T ( 1 + c5)
r = f(C 0 ,Tm)
p m
The reference temperature Tm is given by the weighted-average value be-
tween the inlet and the cooling temperatures:
T = ( 4)
m
As shown by Kauschus et al. ( 1978), this choice allows the simultaneous
treatment of the adiabatic and the nonadiabatic case and reduces by one the
number of dimensionless parameters.
Substituting Eqs. ( 3) and ( 4) , Eqs. ( 1) and ( 2) reduce to
1 - u - Dar(u,v) = 0 (5)
1 - v + SDar(u,v) = 0 ( 6)
These can be suitably combined to give the dimensionless concentration
1 + f3 - V
u = ( 6)
f3
Reactor Steady-State Multiplicity /Stability 975
which substituted in Eq. (6) leads to
1 - V+ SDar ( l + ! - V ,V) = 0 ( 8)
The problem has then been reduced to the solution of the nonlinear algebraic
equation ( 8) in the only unknown v.
A priori bounds of v, in the case of an exothermic reaction (S > 0),
can readily be derived from Eq. (7), noting that from physical arguments
that O ~ u ~ 1 and
1 ~ v ~ (1 + S) ( 9)
while for an endothermic reaction (S < 0) the same inequality holds with
the signs reversed.
In the following sections, Eq. ( 8) is examined for various expressions
of the dimensionless reaction rate r, to define, a priori, the number of all
possible steady states for any given set of parameter values.
Positive nth-Order Kinetics
Using the reaction rate expression f = k(T)Cn (in dimensionless form, r =
un exp [ y ( 1 - 1 /v)]) , Eq. ( 8) can be rewritten as follows:
sn-l (1 + S - v)n exp [ y ( 1 - -
- - = -'----'---_.__ 1)~ = F(v) (10)
Da v - 1 v
Since in the case of endothermic reactions Eq. (10) admits a unique solu-
tion for all Da, in the following we shall consider only exothermic reactions
(i.e. , S > 0)..
From inspection of Eq. (10), F(l) = +00 , F(l + S) = 0, and F(v) > 0
for v E [1, 1 + S], so that uniqueness is guaranteed for all Da if and only
if (Luss, 1971)
dF
dv
~ O for all v E [ 1, 1 + Bl (11)
If condition ( 11) is violated, multiple steady states will occur for some
value of Da. By differentiating F(v) it can be seen that Eq. (11) leads to
(n - l)v 3 + (S + y + 1 - n)v 2 - y(2 + S)v + y(l + S) > 0 (12)
Based on this relation, Van den Bosch and Luss (1977) derived strong suf-
ficient criteria for both uniqueness and multiplicity, and subsequently,
Tsotsis and Schmitz (1979) defined the corresponding exact necessary and
sufficient conditions. These can be obtained in a more compact form by
rewriting Eq. ( 12), according to Leib and Luss ( 1981), as follows:
(1 + SZ) 2 [1 + Z(n - 1)]
y ~ ~-~~-=-----''------'--=- - G ( Z ; n, S) for all Z E (0, 1) ( 13)
SZ(l - Z)
976 Morbidelli, Varma, and Aris
where the quantity Z = (v - 1) /S has been introduced. From inspection
of Eq. (13) it appears that G(0) = G(l) = +00 , G(Z) > 0 for all Z E (0, 1),
and G' = 0 for values of Z satisfying
-S(n - l)Z 3 + z2(n - 1)(2S + 1) + (2 + B)Z - 1 = o (14)
Since Eq. ( 14) exhibits one and only one root Z in the interval Z E ( 0, 1)
for any value of S and n > 0, it can be concluded that when
y " G = G(Z) (15)
there is uniqueness for all values of Da. On the other hand, if condition
( 15) is violated, the system admits multiple solutions in some range of Da.
The boundaries of such range are called lower and upper bifurcation points:
Da* and Da*. They can be calculated by substituting in Eq. (10) the two
roots Z_ and Z+ (i.e., v_ and v+) of Eq. (13) [i.e., y = G(Z)], thus ob-
taining the following relationships:
-n-1
= _s_ Da* (16)
F(v+)
Thus for y > G the system admits multiplicity for Da* < Da < Da*, and
uniqueness for Da < Da* or Da > Da*. The functions F(v) and G(Z) are
sketched in Fig. 1, where all the above-mentioned features are indicated.
In Fig. 2 the bifurcation curves in the S - y plane are shown for kinetics
of various positive orders.
First-Order Kinetics: In the classical case of first-order reaction, Eq.
(14) can be solved analytically, leading to Z = 1/(2 + S). Then, using
Eqs. (13) and (15), the well-known necessary and sufficient condition for
uniqueness can be derived:
ys..; 4<1 + s> ( 17)
If condition ( 17) is violated, then multiplicity occurs for Da E
where the bifurcation points are given by Eq. ( 16) with
y<2 + 's> ± {yS[yS - 4(1 + s">l }112 (18)
v± =
2cy + "s>
Kauschus et al. ( 1978) have obtained equivalent conditions in terms of
only two parameters: a= (1 + 8)/yS and b = y$Da. This allows us to
characterize the entire steady-state behavior of the system with a single
plot in the a-b plane, as shown in Fig. 3. Parameter values inside the
region enclosed by the two curves representing the bifurcation points lead
to three steady states, while values outside this region can lead to unique-
ness. The point where the two curves merge and vanish is called the
cusp point (a = 1/4; b = 4e-2).
It is worth stressing that the shape of the multiplicity pattern, such
as that depicted in Fig. la, is strongly dependent on the definition of the
Reactor Steady-State Multiplicity /Stability 977
FI XEO : '/3, n
u..
t F ( V _)
v_ 1+$
-v
(a)
FIXED: {3, n
<..'.)
G
Y,
0 z· z Z+
~z=(v-1)/iJ
(b)
FIGURE 1 Schematic representation of functions (a) F(v) and (b) G(z).
y == y 1 , uniqueness; y == y 2 , three or one steady state.
dimensionless parameters used. For practical applications it is convenient
to study the multiplicity pattern with respect to the reactor residence time,
which can easily be varied in a continuous fashion by varying the reactor
inlet flow rate. After the first works of Furusawa and Nishimura (1968)
and Hlavacek et al. (1970), Uppal et al. (1976) reported a detailed study
of the multiplicity pattern in terms of the reactor residence time.
Golubitsky and Keyfitz ( 1980) showed through singularity theory that
the multiplicity pattern, in terms of conversion/residence-time plots, may
assume one of the six different shapes shown in Fig. 4, in addition to
the obvious uniqueness case. Knowledge of these multiplicity patterns is
very important when discussing the problem of attainability of a given steady
state. For example, stable steady states on an isola (see Fig. 4c) that lies
entirely along with a stable continuous branch cannot be reached by chang-
ing only the reactor inlet flow rate (see Huang and Varma, 1980).
978 Morbidelli, Varma, and Aris
ICQ
FIGURE 2 Bifurcation curves for reactions of various positive order:
Below the curve, uniqueness; above the curve, three or one steady state.
Balakotaiah and Luss (1981) developed an a priori procedure for the
definition of the multiplicity pattern. Although it requires a different
definition of parameters cS and S such that the reactor flow rate appears
only in Da, the spirit of this technique can be illustrated briefly using
Eqs. ( 10) and (11) with n = 1. As mentioned above, these equations can
0.6
0.5
04
D 0.3 CD
@
0.2
0.1
0
0 0.1 0.2 0.3
~a
FIGURE 3 Multiplicity behavior for a first-order reaction: a = ( 1 + S) /yB,
b = y S Da. Inside the curves, three steady states; outside, one steady
state.
Reactor Steady-State Multiplicity /Stability 979
(a) (b)
z ( d)
0
(/)
0::
w
>
z
0
u
0
REACTOR RESIDENCE TIME, T
FIGURE 4 Schematic representation of the multiplicity patterns in terms
of outlet conversion versus residence time for a first-order reaction.
be solved simultaneously to give the bifurcation values Da* and Da*. Re-
garding the function F = F(v,Da,E._), where E._ represents the vector of all
parameters but Da, it can be stated on the basis of the implicit function
theorem that the transition from zero to two or four bifurcation points can
occur only when
3F 3F
3v 3 Da
= 0 (19)
3v 2 3v 3Da
which, using Eqs. (10) and (11), can be replaced by either one of the two
conditions
3F
0 or 0 ( 20)
3 Da
Each of these conditions identifies a surface in the parameter space, named
"hysteresis variety" and "isola variety," respectively. According to
Golubitsky and Keyfitz (1980), crossing the first surface through a contin-
uous change of one of the parameters causes the appearance or disappear-
ance of an S (Fig. 4a) or inverse S (Fig. 4b) pattern; similar behavior,
but relative to the isola pattern (Fig. 4c), is observed for the second sur-
face. These two surfaces are represented in the a-B plane shown in
Fig. 5 for the particular case y = 00 and Tc = T O = Tm. They divide the
plane in five regions, each corresponding to a specific multiplicity pattern.
980 Morbidelli, Varma, and Aris
ISOLA ~ I
VARIETY : ,,...,...~
I ISOLA b
I MUSHROOM
I
0
0 UNIQUE I
'
()() SOLUTION I
I 7
'1
HYSTERESIS / f--- S + ISOLA
1/
VARIETY /
I S PATTERN
y==
Tc =To
B=y"fi(l+8)
FIGURE 5 Schematic of the regions in the parameter plane a = o /Da
versus B which lead to the different multiplicity patterns of Fig. 4.
For example, the location of the mushroom pattern region is quite obvious
since by crossing the isola variety it must degenerate into an isola, while
crossing the hysteresis variety it must degenerate into a S-shape pattern.
Note that the inverse S-shape pattern never occurs in the case illustrated
in Fig. 5, since it requires very strong cooling (i.e., Tc< T 0).
Zeroth-Order Kinetics: This particular case differs from the general
one in that G(l) is positive but finite, which reflects the well-known
peculiarity of these reactions that they reach complete conversion with a
positive reaction rate. Since Eq. ( 14) admits the solution Z = 1 /S, it can
be seen from Eq. ( 13) that the uniqueness condition for all Da is given by
y < 4 for S;;,, 1 (21a)
y
o + s)2
< ~---'--'-- for S< 1 (21b)
Nonmonotone Kinetics
An unusual feature of some reactions in catalysis, as well as in other fields,
such as biocatalysis, is to exhibit kinetics which are not monotonically in -
creasing with the reactant concentration. This situation occurs when the
reactant can somehow inhibit the rate of reaction. For example, in the
case of oxidation of CO or various hydrocarbons (see Voltz et al., 1973) or
hydrogenation of olefins (see Sinfelt, 1964; Rogers et al., 1966) over noble
metals, the reactant can be strongly adsorbed on the catalyst active sites,
thus inhibiting the development of the reaction. Similar behavior is en-
countered in biocatalysis for certain substrate-inhibited enzymatic reactions
(see Laidler and Bunting, 1973).
Reactor Steady-State Multiplicity /Stability 981
Of particular interest is the case of oxidation (hydrogenation) reactions,
where oxygen (hydrogen) is present in large excess. This corresponds to
the well-known Langmuir-Hinshelwood kinetics f = kC/(1 + KC)2, where k
is the reaction rate constant and K the reactant adsorption constant. In
dimensionless form
r = exp [y (1 - i)] ( 22)
Tsotsis et al. (1982) have examined in detail the following general form of
nonmonotone kinetics:
r = exp [y (1 - i)] (23)
which reduces to Eq. (22) for p = 1 and q = 2.
Under similar conditions, the intrinsic high nonlinearity of nonmonotone
kinetics leads in general to more complex multiplicity patterns than those
characteristic of monotone kinetics. In fact, in the latter case, the only
source of nonlinearity is in the Arrhenius temperature dependence of the
reaction rate constant, while in the former multiplicity can occur even under
isothermal conditions. Thus for this type of reaction we shall examine
separately the isothermal and the nonisothermal cases.
Isothermal Reactor: In this case v = 1, and only the mass balance Eq.
(5) needs to be considered. Introducing the kinetic expression (23), Eq.
(5) can be rewritten in the form
1 (1 + o)q
= _ F(u) ( 24)
Da (1 - u)
Since F( 0) = 0 and F( 1) = 00 , it is seen that the necessary and sufficient
condition for uniqueness is (Luss, 1971)
dF ~ O for all u e: [ 0, 1] (25)
du
Tsotsis et al. (1982) found that condition (25) is satisfied if and only if
0 ~ p(q - p + 1) + q + 2[pq(q p + 1)]1/2
(26)
(p - q)2
which in the case of a bimolecular Langmuir-Hinshelwood reaction (p = 1,
q = 2) reduces to
a~ 8 ( 27)
As expected, it appears that multiplicity under isothermal conditions occurs
only for sufficiently strong inhibition. If Eq. ( 27) is violated, then in the
interval
982 Morbidelli, Varma, and Aris
1- 1
Da* _ - -
F(u_)
< Da < Da* _
F(u )
(28)
+
where U+ and u are the roots of dF /du = 0, the reactor exhibits three
steady states. Outside this interval the steady state is unique. Thus the
most complex pattern of multiplicity is again of the type 1- 3-1.
Nonisothermal Reactor: Similar to the nth-order kinetics case, the
necessary and sufficient condition for uniqueness is given by Eq. (11),
with F(v) defined as follows:
-p-1
_13_=
Da
(1 + o)q
V - 1
(l + 13 - v)P
[ 1 + 00 + s- v) 1q
exp [y (1 i)] = F(v) (29)
The critical condition dF /dv = 0 leads in this case to a quartic equation in
v, which implies that F(v) can have none, one, or two pairs of extreme
points (one maximum and one minimum). These three possible situations
are illustrated in Fig. 6. It is apparent that by continuously varying the
Damkholer number Da, the following multiplicity patterns can be obtained:
1-3-1 (b), 1-3-1-3-1 (cl), or 1-3-5-3-1 (c2). As expected, this case ex-
hibits the most complex multiplicity pattern among those examined up to
now. This is due to superimposition of the temperature nonlinearity with the
nonmonotonic concentration dependence of the reaction rate. In fact, when
the latter tends to vanish, as for q ...:; p - 1, the system again exhibits at
most the multiplicity pattern 1- 3-1.
(a) ( b)
1-3 -I
>
u.
I+ {3 I+ {3
FIGURE 6 Sketches of function F(v) corresponding to any possible
multiplicity pattern for a nonisothermal CSTR with nonmonotone kinetics
[Eq. (23)].
Reactor Steady-State Multiplicity /Stability 983
Tsotsis et al. (1982) have examined in detail this quartic equation using
Sturm's theorem to obtain a priori criteria for the number of roots in the
interval v E [ 1, 1 + SJ. Their procedure gives the exact number of steady
states of the reactor, but it is too complex to be reported here in detail.
Some simple sufficient conditions for uniqueness by these authors are:
For an overall negative order (i.e., q > p) and endothermic reaction,
the condition is given by Eq. ( 26).
For an overall positive order (p > q) , the condition is given by y :s;; 4
or 13 < 0 (endothermic reaction) .
For the specific case of p = 1 and q = 2, Brown et al. ( 1984) used singu-
larity theory to locate two butterfly singularities, one in the exothermic case
and the other in the endothermic case. Around these singular points, a
maximum of five steady states exist. In Fig. 7a, uniqueness and multiplicity
regions in the S-y plane are shown for various values of the inhibition param-
eter rJ. There is multiplicity, for some Da, to the right of the curves lying
on the $-positive half plane and to the left of those lying on the (3-negative
half plane. For the particular case rJ = 7, all the possible multiplicity patterns
are indicated in Fig. 7b.
More Complex Configurations
For all systems examined above, a complete characterization of the multi-
plicity pattern has been obtained. Following an increasing complexity order,
the next systems to be examined would include either several reactors in
series with a single reaction ( so as to approach the behavior of tubular
3 (Y =0
2
18
IQ:)_ 0 I~ 14
-0.25 I 12
2
-0.50 10
1: I
-0.75 8 2: 1-3-1
3: 1-3-1-3-1
4: 1-3-5·3·1
-1.00
0 4 8 12 16 20 24 28 2 3 4 5 6 7
-Y
--Y
(a) (b)
FIGURE 7 (a) Uniqueness and multiplicity regions in the 13 versus y plane
for various values of the inhibition parameter cr. (b) Multiplicity patterns
in the case rJ = 7.
984 Morbidelli, Varma, and Aris
reactors) or a single reactor with a more complex kinetic scheme-say, a
series and/or parallel sequence of first-order reactions. In both cases the
number of equations of the model and the number of characteristic dimen-
sionless parameters of the system increase rapidly. This leads to a rapid
increase in the complexity of the multiplicity study. In particular, we now
have to deal with a multidimensional parameter space, which prevents an
exhaustive representation of the system behavior in terms of phase plane.
The work in this area is then oriented toward the analysis of some sections
of the parameter space, which are usually selected either on the basis of
some specific practical interest or to identify all the possible qualitative be-
havior of the system.
In the following, two cases of this type that have received particular
attention in the literature are examined. The aim is to give the reader a
feeling for the rapidly increasing complexity and to indicate some of the
techniques used to attack these problems.
Series of Continuous Stirred-Tank Reactors: The interest in examining
a series of CSTR relies on its well-known use for modeling tubular reactors.
The steady-state mass and energy balance for the generic ith reactor of
the series can be written as follows:
u. - Da.r. = 0 1 = 1, 2, ., N ( 30)
1 1 1
v1._ 1 - v. + SDa.r. - cS.(v. - v .) = O i = 1, 2, . . . , N ( 31)
1 1 1 1 1 Cl
where the same parameters defined by Eq. ( 3) have been used, but taking
as reference temperature To instead of Tm, so that uo = 1, vo = 1. More-
over,
T.
Cl
V. =- ( 32)
Cl TQ
In the case of N nonisothermal CSTRs in series with a first-order reaction,
Varma (1980) has shown that at most (2N+l - 1) steady states are possible,
of which however at most (N + 1) are stable. It is worth noting in passing
that this same conclusion applies also to this same system configuration in
the case of a nonmonotone isothermal reaction of the type in Eq. ( 22).
This result can be intuitively understood, noting that each reactor in the
cascade can exhibit three steady states in correspondence to each steady
state exhibited by the previous one. To the number thus obtained, we
should substract all those steady states that imply physically unrealistic
extinction phenomena along the sequence of reactors (i.e. , the transition
from a high-conversion steady state to a low-conversion steady state).
A detailed study of the behavior of this system for the particular case
of only two reactors in series has been performed independently by Kubicek
et al. ( 1980) and Svoronos et al. ( 1982). Even for this simple case the
total number of parameters is quite elevated (Dai, cSi, 13, y, Vci = eight
independent parameters), so that most of the analysis has been dedicated
to the case of two identical CSTRs (i.e., Da = Dai and cSi = 8) in the
limit of the Frank-Kamenetskii approximation of the Arrehnius temperature
dependence of the rate constant, which allows us to eliminate the dimension-
less activation energy parameter y. To simplify the treatment, in the
Reactor Steady-State Multiplicity /Stability 985
following we treat only the case Vci = 1 (i.e., cooling temperature equal to
To for both reactors). After all these approximations, Eqs. (30) and (31)
can be solved, leading to
1 ul
Da = fl[u 1 ;cp] - exp[-¾ (1 - u 1)] (33a)
ul
Da = r[u 1 ,u 2 ;cp,o] -
u
1
- u2
u2
{-4 [ul - u2
exp <P /ul ul
1 -
+ ul(l :\ )] }
(33b)
where
4(1 + o)
<P = ( 34)
Yi3
A particularly important feature of this system is that the behavior of the
second reactor is dictated by the same equation as the first one, but with
proper scaling of the unknown and the involved parameters. This is ap-
parent, noting from Eqs. ( 33a) and ( 33b) that
( 35)
Since the reactor equations can be solved in cascade, this allows us im-
mediately to characterize the behavior of the second reactor once that of the
first is known (i.e., the function fl has been investigated fully). Namely
r exhibits tb,e same behavior as fl, but scaled in the interval O < u2 < u1
and with increased value of the parameter <P /u 1 .
The multiplicity pattern of the first reactor is obtained as in the pre-
ceding section:
For <P > 1: uniqueness for all Da
Da* < Da < Da* multiplicity (36)
For <P < 1: {
Da < Da* or Da > Da* uniqueness
where Da* = fl (m +>, Da* = fl (m_), and
1 ± (1 - <P)l/2
m = (36a)
± 2
Note that Eqs. ( 36) and ( 36a) correspond to Eqs. (17) and ( 18) in the
limit of very large activation energy.
Similarly, for the second reactor it can be shown that
For <P /ul > 1: uniqueness for all Da
{ < Da < Da**
Da** multiplicity (37)
For <P/u 1 < 1:
Da < Da** or Da > Da** uniqueness
986 Morbidelli, Varma, and Aris
0
0
~ 1ki!_
0 0
rb! 0
b2
I
1ld_
I I
~x -x ~x
0
0
1.0
0.8
0 0
~x I
-x
--0-- 0.6
:J\j ;!J)
I 04
0
0 0
0 0.2
0
0 0.5 1.0 1.5 2.0 2.5 3.0 3.5
0 ~3 0
-x -x
0
0
m;;J 0
0 m'
,J\_
) 0
0
Illb
Ji,
J )
'
(_/ I
0 0 0
-x -x ~x
(a)
FIGURE 8 Regions in the ¢ = 4( 1 + cS) /y 13 versus 13 parameter plane,
surrounded by the sketches of the corresponding multiplicity pattern in
the Da versus outlet conversion plane. Solid line: stable steady state;
dashed line: unstable steady state (parameter values: v cl = v c 2 = 1,
Da 1 = Da 2 = Da, cS l = cS 2 = cS).
2 - u 1 ± u 1 (1
n± =-------------
2
(37a)
The impact of the above-mentioned scaling property of the equations ex-
amined is evident by noting that Eqs. (37) and (37a) reduce to Eqs. (36)
and ( 36a) , respectively, as u 1 = uo = 1.
Since space prevents us from analyzing this problem in further detail,
we shall limit our discussion to the final answers for the specific case under
examination. In Fig. 8 the multiplicity pattern is reported through a proper
subdivision of the ¢-cS plane into 23 regions. For each of these, a sketch
of the corresponding Da versus ( 1 - u2) curve is shown on the side of
the figure. It appears that the maximum number of steady states is seven
Reactor Steady-State Multiplicity /Stability 987
r~
0 0
0 0
0 ---X I 0 ---x
g ) 0.80
I ~075
0 __. X
0.70 0
x\\./1 I
\~
0
0
0
(JJ0.65
--- X
0
0
0
~ - - - - 0.60 L _ - L - - L - - - - - - " ' - - - - - - " - - - - ' - - - - ' - - - - '
o ~x 16 2 ~ 8 2.4 2.8 0
0
0
0
0
,(j}) 0
0
Xa ✓7 /
?J
0 0 0
-x --- X ---x
(b)
FIGURE 8 (Continued)
(of which no more than three can be stable), and the total number of pos-
sible multiplicity patterns is much larger than that in the case of a single
reactor.
A more detailed treatment of this problem, including the case v c 1 :f.
v c2 :f. 1, has been reported by Svoronos et al. (1982). Other interesting
features, such as the effect of two different Da values for the reactors or
the influence of the activation energy, have been reported by Kubicek et al.
(1980). Moreover, in the latter work the effect of recirculation from the
second to the first reactor is also examined. It is found that for increasing
recirculation ratios, the multiplicity region tends to disappear.
Complex Kinetic Schemes: When more than one reaction is considered,
the variety of possible configurations is enormously--in fact, infinitely-en-
larged. The only way in which to present some of the modes of attacking
988 Morbidelli, Varma, and Aris
the problem of multiplicity in these cases is to take a simple example, and
the obvious extensions of the single reaction are the parallel reactions,
A + B, A + C, and the sequential A + B + C; we shall concentrate on
the latter. Since there are three reaction parameters (the Damkobler num-
ber, the heat of reaction or Prater number, and the Arrhenius number)
for a single reaction, we should expect six parameters for A + B + C.
In addition, there is in both cases the cooling rate parameter and the
dimensionless coolant temperature. We shall see that the latter may often
be ignored, and that in steady-state problems the cooling rate parameter
can be combined with the heat of reaction, but this leaves six for the
steady state and seven for stability questions. In the face of so many
parameters we can hardly hope to explore every nook and cranny of param-
eter space, but some progress may be made through the use of singularity
theory. The work of Balakotaiah and Luss (1981-1984) has been outstand-
ing in this area, and one cannot get a better account than is given in their
original papers.
If CA, CB , and T denote the two concentrations and the temperature
respectively, the steady-state mass and heat balances give the three
equations:
q(C AO (38a)
(38b)
qpC/To - T) -- UA(T - Tc)+ (-1',Hl)Vkl(T)CA
+ (-L'iH 2)Vk 2 (T)CB ::: 0 (38c)
where all the symbols are as defined in the notation section. It is cus-
tomary to take CEO ::: 0 and use the dimensionless quantities
::: 0 :::
y ::: B::: ( 39)
Ci, ::: \) ::: cS :::
Then
1 ( 40a)
(40b)
-0 + BDau 1 exp( 0 y: y) + BavDau 2 exp(/! 0y)- y(0 - 0c) ::: 0 (40c)
Reactor Steady-State Multiplicity /Stability 989
Replacing To by (To + cSTc) /(1 + cS), we have the same equations but
with 0c = O. This is satisfactory unless either q or U is taken to be the
distinguished parameter. If Tc = To, this difficulty disappears, and this
assumption is commonly made.
Since the equations are linear in u1 and u2 the steady state is usually
found by solving Eq. (40a) for u1 in terms of 0, substituting in Eq. (40b)
and solving for u2 to give, on substitution in Eq. (40c), a single equation
in 0 . This may be written
(1 + 8)0 = BH 1 (0)[1 + aH/0)] ( 41)
where
H/0) = Da exp(y y+G 0 ) / ((1 + Da exp /! 0 )]
( 42)
H/0) = v Da exp(/} 8y) / [(1 + v Da exp 0 A.;'8y)]
This is the form which Bilous and Amundson ( 1955) used and it has the
simple physical interpretation of a heat balance, ( 1 + cS) 0 being propor-
tional to the rate of cooling, and H 1 and H1H 2 to the two rates of heat
generation. Of course, a and B or both can be negative if one step is
endothermic and the other exothermic. Arguing that H 1 and H 2 are curves
with a steplike transition between values near zero and values near 1, most
workers in this field have assumed that at most five steady states can be
obtained. Actually, the subtleties of shape of the right side allow seven, but
only in a very restricted region of parameter space (Farr, 1985). This
phenomenon is lost when y is allowed to become large and the exponential
approximation is used (Jorgensen et al. , 1984). Formally, we let y + 00
in the two ex·ponentials, simplifying them to e0 and eA0 , but this ignores
the presence of y in 0 and B. The true nature of this so-called "positive
exponential approximation" is obscure, but it is probably best to think of it
as implying that the deviations of temperature from To are not large.
Though Eq. ( 41) is a physically appealine: form of the equation that
has to be solved for the steady state, it is in better shape for computation
when regarded as a quadratic for Da given the steady-state temperature 0.
Thus the multiplicity question is to be investigated by exploring the nature
of the equation
F = Da 2vB*(l + a)/l+A) 8 - vDa0eAG (1 + Dae 8 )
0 0
+ B *Dae - 0 (1 + Dae ) = 0 ( 43)
where B * = B /( 1 + cS). Certain combinations emerge from tis form and we
can take
0 1-A r = vDal-A
s = Dae A = (1 + a)vB*Da
giving
A s
l+A
+ B*s - r 0 s A(1 + s) -- 0 (1 + s) = O ( 44)
990 Morbidelli, Varma, and Aris
If ;\ = 1 and 0 is specified, this is a quadratic for s given A, B *, and r ,
and its positive root will give the correspondi ng Da. The usual form of
multiplicity diagram is 0 versus Da, and this may take one of a number of
forms shown in the bottom row of diagrams of Fig. 9. In the upper part
of that figure all parameters except B * and Da are fixed, and the curve
PQRST is the locus of turning points of the 0 -Da curve [i.e. , the points
where d(Da) /d0 = OJ. The branches of this curve are numbered for the
order in which they are encountered in traversing the Da-8 curves shown
below in the direction of increasing Da. The form of the Da- 8 curve is
shown in the lower part of the figure for the appropriate range of B *. For
example, over the square C, any vertical with increasing Da encounters the
branches of the turning-poi nt curve in the order 2143. There are thus
two regions of three possible steady states. For D these overlap and there
is an interval of five states with three on either side. The Da-8 diagrams
for the transitions are shown as vixillae attached to the vertical. Thus
the B JC transition comes about by a so-called "hysteresis point," where
the tangent at a point of inflection is vertical. On the other hand, the
Do
s*= _lL
1+8
e ~
Do
FIGURE 9 Multiplicity diagram for the reaction A + B + C occurring in a
nonisotherm al CSTR.
Reactor Steady-State Multiplicity /Stability 991
C /D transition is made when two turning points are vertically above one
another.
A point on the Da-0 diagram is given by a solution of F = 0 according
to Eq. ( 43). A turning point is given by F = F 0 = 0, and when B * and
the other parameters are held constant, this pair of equations has from
zero to four solutions for Da and 0 . For example, Fig. 9 shows that for
sufficiently small B * there are no roots, while for sufficiently large B *
there are just two. The transitions occur at particular values of B *. Those
that involve vertical tangents at inflation points Q ,R, S are obtained by
solving F = F 0 = F00 = 0 for 0, Da, and B*. The double limit points U,
V, and Ware solutions for 01, 02, Da, and B* of the four equations F(01) =
F 0 (01) = F(02) = F0(G2) = 0, where F(01) = F(0,Da,B*;a,y,;\,v ) with
0 = 0 1 · 0 1 and 0 2 are the ordinates of the turning points that share a
common Da. The surface in parameter space given by eliminating 0 and
Da between F = F 0 = F 0 0 = 0 is called the "hysteresis variety." If 01, 0 2 ,
and Da are eliminated between F(G1) = F0(81) = F(G2) = F0(82) = 0 the
"double limit variety" is obtained. Isolas arise when either the curve loops
back on itself or an entirely new branch is born from an isolated point.
In both cases the direction of the curve F = 0 is indeterminate , so both
F 0 and Fna vanish simultaneously. This does not happen in this particular
case, but if 0 and Da can be eliminated between F = Fe = Fna = 0, we
have the "isola variety."
Following the precepts of singularity theory we look for the points
where as many as possiole of the derivatives vanish. Balakotaiah and Luss
(1982a,b) showed that there are points at which F and its first four deriva-
tives with respect to 0 vanish. For ;\ = 1, y = 00 , these are (0 ,Da,B*,a,
v) = (3,0.1858,3.2154,0. 8660,0.0718) and (3,0.0133,44.7846, -0.8660,
13. 9282). A point where F and its first four derivatives vanish is known
as a "butterfly point" and F is there "contact equivalent" ( see the Ap-
pendix to this chapter) to x5 - A = 0. This means that x is some trans-
formation of 0 and A of the Damkohler number Da, and that a full unfolding
is given by three other parameters a1, a2, and a3 in the form
( 45)
Singularity theory ( subject to appropriate tests) shows that a 1 , a2,
and a3 will be smooth functions of B *, a, and v, although it would be a
work of some magnitude to find them. However, the qualitative picture in
the neighborhood of the "organizing center" must be that of the butterfly.
Thus, for a 3 < 0 there are only two possible 0 -Da diagrams, namely A
and B. The former is obtained when the parameters a 1 and a 2 lie beneath
the parabolic curve shown in the left half of the top part of Fig. 10. Other-
wise, the common phenomenon of three steady states in the intermediate
interval of the Damkobler number is obtained. The situation with a 3 > 0
is more complicated and is shown on the right at the top of Fig. 10. The
various Da-0 diagrams shown below by the letters A, . . . , G are obtained
for a3 > 0 when al and a2 lie in the correspondingly marked region. Re-
ferring back to Fig. 9, where the sequence A, B, C, D, F, G, Bis ob-
tained for increasing B *, we see that it would be quite consistent with this
if a 1 were a monotone-increasin g function of B *, and that a and v were
such that a2 and a 3 were positive, for then the same sequence would be
obtained passing upward along the dashed curve, PQ.
992 Morbidelli, Varma, and Aris
al
al
4
B
B B
a2
a2
B B
A A
B B
A \
a 3<0 5
a 3> o \
\p
0 A F
B C D E G
Do
FIGURE 10 Qualitative bifurcation diagrams for the reaction. A ➔ B ➔ C
occurring in a nonisothermal CSTR, in the neighborhood of the organizing
center.
By working away from the singularity the various regions of multiplicity
can be determined computationally. Thus the curve 1,9,2,3,4,9,5 for
a3 > 0 and the parabolic for a3 < 0 are obtained by generating the hyster-
esis variety, while 2, 8, 7, 6, 8, 4 is the double-limit variety. The loci on
which the points 2, 4, and 9 lie arise when two hysteresis points coincide
(i.e., F == Fe == F00 == F000 == 0), while 6, 7, and 8 are where a turning
point lies vertically above or below a hysteresis point [i.e. , F( 0 1) ==
F0(01) == F00(01) == F(0z) = F0(02) = OJ. In this way the multiplicity
regions can be built up with some confidence that we have a comprehensive
picture.
Further examples are given in the papers of Balakotaiah and Luss already
referred to, and no doubt we shall see many more studies using singularity
theory (see Polizopoulos and Takoudis, in press). The sequence of two
stirred tanks, for example, has been considered by Dangelmayr and
Stewart ( 1984).
Tubular Reactor
The steady-state mass and energy balances in a tubular reactor can be
written as follows (Varma and Aris, 1977):
v ~; - f(C, T) ::: o ( 46)
Reactor Steady-State Multiplicity /Stability 993
dT UP
vpCP dz + (-llH)f(C,T) - A (T - Tc) = 0 ( 47)
together with Danckwerts' boundary conditions (BCs)
D dC = v(C - C ) at z = 0 (48a)
e dz 0
at z =0 (48b)
In deriving these equations the following assumptions have been implicitly
made, in addition to assumptions 2 and 3 reported earlier for the CSTR:
1. Radial gradients of temperature and concentration are negligible.
2. The fluid spatial velocity is constant in the axial direction.
3. The dispersive fluxes of mass and heat can be described through
Fick and Fourier law, respectively, with effective mass and heat
diffusion coefficients.
We shall not pursue any further the classical question of relaxing the above-
mentioned restricti~ns in order to improve the model capability of simulating
experimental reactor behavior ( see Chapter 6) . Our aim is instead to
indicate the multiplicity pattern of this model, usually referred to as the
"axial dispersion model," in connection with various reacting systems. Note
in passing that the occurrence of multiple steady states in tubular reactors
has been experimentally verified in several works, which have been exten-
sively reviewed by Jensen and Ray (1982). Introducing the dimensionless
quantities
T T
C
u = co V = TO V
C = TO
C
s = L~
ucc 0 , T 0) UPL
Da = 8 =
vC 0 AvpCP
( 49)
(-llH)C 0
s = pCpTO
r = f(Cf(C,, TT))
0 0
vLpC
Pe = vL Pe =__ p_ y = RT
E
m D h k 0
e e
the model equations reduce to
1 d 2u du
Dar(u,v) = 0 (50)
Pe ds
m ds 2
co
co
"""
TABLE 1 A Priori Bounds on the Steady-State Temperature of the Axial Disperison Model with Irreversible Reaction
Adiabatic ( o = 0) Nonadiabatic ( o > 0)
V ;;, 1 1 ~ v ~ 1 + B + - 1)
C
o(vC
Exothermic reaction
l~v<l+B
( B > O)
{ V < 1 vc~v<l+B
C
V ;;, 1 Max[0, 1 - I BI ] ~ V ~ V
C C
Endothermic reaction
max[0, 1 - I BI ] < v ~ 1
( B < 0)
~
{ vc < l max[0, 1 - I BI -o(l-v)~v~l
C
0
~i:l.
Source: Varma (1977).
E
-::::
c:l
~
c:l
c:l
;::!
i:l.
::i,..
"':I
;,;·
Reactor Steady-State Multiplicity /Stability 995
dv
ds + 13Dar(u, v) - 5 (v - v c) = 0 ( 51)
with BCs
du dv
ds
= Pe (u -
m
1)
ds
= Peh(v - 1) at s =0 (52a)
du dv
ds = 0
ds = 0 at s =1 (52b)
The a priori bound for the steady-state reactant concentration is obvious
from physical arguments: 0 < u(s) < 1 for all s s [O, 1], while for the
temperature a more detailed analysis is required. This has been developed,
based on the strong maximum principle for elliptic equations, by Varma
(1977) and the obtained bounds are summarized in Table 1.
Uniqueness and Multiplicity Criteria
As a direct consequence of the Danckwerts BCs, the axial dispersion model
reduces to the CSTR and the plug-flow models for very large and very
small axial dispersion (i.e. , Pe + 0 and Pe + respectively. The
00 ) ,
multiplicity pattern of the first limit has been fully characterized in the
preceding section, at least for simple reacting systems. On the other
hand, the plug-flow model does not admit any multiple steady state, since
it is constituted by initial value ordinary differential equations.
However, while the multiplicity behavior of the axial dispersion model
is well characterized for limiting Pe values, it is still not so for inter-
mediate situations (i.e., finite Peclet number values). In particular, there
is a lack of a priori criteria, based on the values of the relevant param -
eters, for the definition of the reactor uniqueness or multiplicity. Al-
though several attempts have been made in the literature, based on com-
parison theorems, fixed-point arguments, perturbation methods, lumping
procedures, and other techniques, a necessary and sufficient criterion for
steady-state uniqueness has not been found.
Next, we summarize briefly the most widely used sufficient or necessary,
or neither but simply approximate, bounds of the multiplicity region which
have been reported in the literature. Since no proofs will be reported,
the interested reader should refer to the original papers or to a previous
review (Varma and Aris, 1977).
Special Case of Adiabatic Reactor: The case of adiabatic reactor
( o = 0) with equal mass and heat Peclet numbers (Pem = Peh = Pe) is of
particular mathematical interest, since it allows to combine Eqs. ( 50) and
( 51) [in the same way we did for the CSTR case and leading to the same
u-v relation given by Eq. ( 7)] , reducing the problem to the single ordinary
differential equation (ODE)
d 2v
ds2
- Pe dv
ds
+ DaPe13r (1+13
-----
13
v v) = 0 ( 53)
with BCs given by the second of Eqs. (52a) and (52b).
996 Morbidelli, Varma, and Aris
Luss (1971) showed that the same condition [Eq. ( 11)] which is neces-
sary and sufficient for uniqueness in lumped systems gives a sufficient
condition in distributed systems of the single-catalyst-particle type. Since
Eq. (53) can be reduced to the latter form (Varma and Amundson, 1973c),
the following sufficient condition for stability is obtained:
dF ,.;; O for any v E: [ 1 , 1 + SJ (54)
dv
where F(v) = r(v) /(v - 1), and the temperature bound for an exothermic
reaction from Table 1 has been used.
An earlier sufficient criterion developed by Luss and Amundson (1967b)
using comparison methods which ensures uniqueness is
Da,.;; _μ__ for any VE: [1, 1 + SJ (55)
Sr'(v)
where µ = A1 /Pe + Pe/4, and Al is the smallest root of the equation
tan fi" = Pe fi" (55a)
A- (Pe 2 /4)
Similarly, two additional sufficient uniqueness criteria developed by
Luss ( 1971) for a slab catalyst particle can readily be applied· to the case
under examination:
1
Da,.;; (56)
F(v+)
Da _μ_
;;i: ( 57)
F(v_)
where v+ and v represent the local maximum and mm1mum of F(v). In
the case of an irreversible first-order reaction, F(v) and v+ are given by
Eqs. (10) (with n = 1) and (18) respectively. Depending on the value of
the Peclet number, either condition ( 55) or condition ( 56) is more sharp.
General Nonadiabatic Case: Using comparison methods, Varma and
Amundson (1972b) have developed the following two sufficient criteria for
uniqueness, which are restricted to reaction rates of positive order. The
first applies only to the case Pem = Peh = Pe; it requires that
Da ..;; µ + 0 for any v E: [1, l+ SJ (58)
Sr' (v) + [ cS (a 1 - a 2) /2µ J
where µ is the same parameter as in Eq. (55), and
a1 = Sup
ar
au >0 (58a)
Note that Eq. ( 58) reduces to Eq. ( 55) for cS = 0. The second criterion
is more general since it applies to Peh -:f. Pem also:
Reactor Steady-State Multiplicity /Stability 997
[-Sµma3 + (µh + cS)a2] + /:J.1/2
Da,.;; (59)
a 3S[2a 2 + a 1 exp <I Peh - Pem I)]
where
/:J. = [Sµma 3 + (µh + cS) 2 + 2Sµm(µm + cS)a1a 3 exp(! Peh - Peml )]
(59a)
a 3 = Sup -
ar
av
and µm and µh are evaluated as µ in the preceding criterion, but using
Pem and Peh in Eq. ( 55), respectively. Note that for the nonadiabatic
case, no upper bound to the region of uniqueness is available.
From the results reported above, at least some qualitative conclusions
can be drawn: for sufficiently large Peclet number Pe and heat transfer
coefficient cS, and for sufficiently small Damkholer number Da and reactor
length L, the axial dispersion model exhibits a unique steady state for any
value of all the other parameters.
Approximate Analysis of Multiplicity Pattern
As shown above, no exact necessary and sufficient criteria for the defini-
tion of the multiplicity pattern of the axial dispersion model are available.
Hlavacek and Hofmann (1970a,b) devleoped a lumping procedure that allows
us to approximate the original set of nonlinear ODEs, with a set of non-
linear algebraic equations, whose multiplicity pattern can be determined
using the methods described in the CSTR section.
The lumping procedure consists of approximating the linear space dif-
ferential operator, say in Eq. ( 53) , with the first term of the series solu-
tion of the corresponding transient problem where the nonlinear reaction
term has been neglected, that is,
(60)
where A1 is given as the smallest root of Eq. ( 55a). Thus for the particu-
lar case of Eq. (53), the problem reduces to
( "l + -Pe4-
2 v) - DaPeSr (1 + S
S - v , v) = O ( 61)
whose multiplicity pattern can be easily determined. Note that this procedure
can also be applied readily to the more general case [i.e., Eqs, ( 50) and
( 51)] , and it is independent of the form of the reaction rate expression
r(u,v).
It may be observed that as expected from the intrinsic nature of the
lumping approximation, Eq. (61) reduces to the correct CSTR model as
Pe + O. However, this is not true for the other limit condition (i.e.,
Pe + 00 ) , where the characteristic uniqueness of the plug-flow model is
not correctly predicted. Therefore, this procedure should be used with
care, since as we will see in more detail in the case of a first-order
998 Morbidelli, Varma, and Aris
reaction, it can lead to erroneous conclusions about the reactor steady-
state multiplicity.
A different lumped model can be obtained by approximating the space
differential operator through a one-point collocation method. Using
Legendre polynomials, so that the collocation point is located at the reactor
center, we obtain
Pe dv = 2 + Pe
----Pev ( 62)
ds 2 + 3Pe/4
which then leads to algebraic nonlinear equations of the same form as Eq.
(61). Jensen and Ray (1982) have noted that this lumping procedure
exhibits similar limiting behavior in terms of Pe as the previous one, and
thus it basically suffers from the same shortcomings.
Irreversible First--Order Reaction in a
Nonadiabatic Reactor
This particular case has been examined numerically in detail by Varma and
Amundson (1973c), Hlavacek et al. (1973), and Kubicek et al. (1979), who
found multiplicity patterns of the type 1- 3-1, 1- 3-1- 3-1, and 1- 3- 5- 3-1.
More recently, Kapila and Poore (1982) have developed an analytical
asymptotic solution of the model in the limit of very large activation energy
(i.e. , y -+
00 ) . This solution is achieved by dividing the reactor into
zones of various reaction intensity, where a simple analytic representation
of the solution can be given, then completing the solution through the
asymptotic matching technique. It has been concluded that whereas the
adiabatic model can exhibit at most three steady states, the nonadiabatic
one can yield up to seven. These findings have been confirmed by the
numerical results reported by Heinemann and Poore ( 1982) . Some of the
obtained results are shown in Fig. 11, in terms of the maximum tempera-
ture along the reactor as a function of the Damkobler number. It appears
that with all other parameters fixed, for increasing values of the dimension-
less activation energy y, the model yields unique solution (y = 25), 1-3-1
multiplicity (y = 40), 1-3-5-3-1 multiplicity (y = 50, 60, 75), and finally
1-3-5-7-5-3-1 multiplicity (y = 100,125). Note that in all cases the inter-
mediate steady states are all unstable; only the lower and upper ones are
asymptotically stable.
The inaccuracy of the lumping approximation [Eq. ( 60)] becomes evi-
dent in the case of a first-order reaction, since the lumped model can, at
most, predict a 1-3-1 multiplicity pattern. Moreover, it has been shown
(Varma and Amundson, 1973c) to predict uniqueness when the distributed
nonadiabatic model exhibits multiplicity, and vice versa. However, in the
adiabatic case with equal Peclet numbers, numerical comparisons seem to
indicate that the lumped model yields a truly sufficient condition for unique-
ness, although no proof is available. Jensen and Ray (1982) have com-
pared the lumping approximation ( 60) and ( 62) with the exact numerical
calculations for adiabatic and nonadiabatic reactors. As shown in Fig. 12,
when the multiplicity regions are compared, both approximation may lead
to erroneous conclusions. In general, Eq. (62) seems to be more
accurate.
120 ( b) r= 125 100
~
~ 1.12
E
~
E
::,
~ l.04
0
~
- Domkohler number, Do
120
( o)
~
::, ',-
\~
/
,,,
......
'- ------ / Q ~ t I 40
"',,
~ \ I
II 2
'l~ ' v-, I /
\\
(I)
a.
E '-' I \~, \I- I
I
~ '-~
25l
E
' ).. ' \ ~\ II
::, Y = 75 -- ', \ \
E
X
104 ' '\ ' \ \' II
0
~
\ I
10- 3 10- 2 10- 1 10°
- ~ Domkohler number , Do
FIGURE 11 Maximum dimensionless temperature as a function of Da for
various activation energy values. (a) y = 25, 40, 50, 60, 75; (b) y =
100, 125 (parameter values: Pem::: Peh = 1.0, cS = 4.0, S::: 0.5, vc = 1.0).
15 - - - - - ~ - - - - - - - -
10
5 ...--------
a
--- ----
__________
~ b
\. ......_
b
0 .____ __._ ____,__ __,__ __.__ ___,
0 20 40 60 80 100
~ Peh
FIGURE 12 Comparison of exact and approximate regions of multiple steady
states in the Sy versus Peh plane; exact ( - ), Eq. (62) (-•-•-), Eq.
(60) (- - -); cS = 0, Pem = Peh (curve a); cS = 0, Pem = 3Peh (curve b);
cS ::: 2, Pem = Peh (curve c).
999
1000 Morbidelli, Varma, and Aris
Nonmonotone Isothermal Reaction
Nonmonotone kinetics were examined in an earlier section. We refer here
to the case of a substrate-inhibited enzyme reaction, of some importance
in biocatalysis, examined in detail by DeVera and Varma (1979). The iso-
thermal axial dispersion model in this case reduces to Eq. ( 50), with
boundary conditions given by the first of Eqs. (52a) and (52b), with
(1 + K + 1/K )u
s
r(u) = - - - - - - - ( 63)
K + u + u2/K
s
where K and Ks represent the adsorption and substrate inhibition dimen-
sionless constants, respectively. Note that Eq. ( 63) is quite similar to
the biomolecular Langmuir- Hinshelwood reaction rate ( 22) examined pre-
viously in the context of a CSTR.
In Fig. 13 the reactor outlet concentration u(l) is shown as a function
of the Damkohler number Da for various Pe. It appears that the reactor
exhibits at most a 1- 3-1 multiplicity pattern. In Fig. 14 the region of mul-
tiple steady states in the Pe-Da plane is shown for fixed values of the
kinetic constants Kand Ks.
The calculated bifurcation values of Da have been compared with the
uniqueness criteria reported above. It is found that Eqs. (56) and (57)
(rewritten for the isothermal model under examination) give conservative
bounds by a factor ranging between 1. 6 to 3. 3 and 1 to 2. 1, respectively.
On the other hand, unlike the case of the adiabatic axial disperison model
with first-order reaction, the lumping approximation fails in predicting the
region of steady-state uniqueness close to the cusp point.
I.O
::, 0.8
<;:
2 0.6
1
<;:
Ql
u
<;: 04
0
u
~ 0.2
::,
0
0
2 3 4 5 6 7
Damkohler number, Do
FIGURE 13 Outlet concentration as a function of Damkobler number for
various Pem values in the case of isothermal substrate-inhibited enzyme
reaction (63) (parameter values: K = 0.01, K = 0.1).
s
Reactor Steady-State Multiplicity /Stability 1001
14
12
E 10
"'
a.
8
0
I 2 3 4 5 6
- -- Do
FIGURE 14 Region of multiple steady states in the Pem versus Da plane.
Parameter values as in Fig. 13.
DYNAMIC BEHAVIOR
In the preceding section we examined several reacting systems and have
shown that under specific conditions these may exhibit one or more steady
states. It is now important to characterize the stability character of these
steady states, which determines whether or not they can be reached in
practice by the reactor, through a suitable starting procedure. However,
in general, the analysis of all the reactor steady states and their stability
character does not exhaustively describe the reactor dynamic behavior.
In particular, the occurrence of periodic or aperiodic solutions has to be
investigated separately. In this section we focus on steady-state stability
and periodic solutions.
Significant contributions have been made to the solution of these prob-
lems in recent years, so that at least from a methodological point of view,
definitive answers are available in some instances. However, a complete
picture of reactor dynamics has been obtained in only a few very simple
cases. Maintaining the same structure as the preceding section, we examine
first the CSTR and then the axial dispersion model tubular reactor (i.e. ,
a lumped-parameter model and a distributed-parame ter model). Subse-
quently, examples of aperiodic solutions will be given through the analysis
of somewhat more complex reacting systems.
Continuous Stirred-Tank Reactor
Stability
The transient mass and energy balances can be readily derived from Eqs.
(1) and (2) by adding on the right-hand side the mass and energy accumu-
lation terms, respectively. However, in making the resulting equations
dimensionless, it is convenient to use the quantities most widely used in
the literature, which are somewhat different from those given by Eq. ( 3).
In particular, using the inlet temperature as reference temperature Tm =
T 0 , and
1002 Morbidelli, Varma, and Aris
V
X = 8 = T = -
q
(64)
t'
t = B =
T
we obtain
dx
dt = -x + Dar (65)
dG
Le - = -8 + BDar - o (8 - 8 ) (66)
dt c
with initial conditions
in
x=x at t = 0 ( 67)
where Da, o, and r are as defined in Eq. (3), while the Lewis number
Le represents the ratio between the time constants of the thermal and
material transport, respectively. As discussed in detail by Ray and
Hastings ( 1980), Le is defined as
(VpC )T
Le= _ ____.P~- (68)
V pC
m p
where V m and (V pCp)T represent the total mass and thermal capacitances
of the reaction unit, respectively.
The first criterion for the stability of the steady state of a CSTR was
developed in a pioneering paper by van Heerden in 1953. It can be ob-
tained from the steady-state version of Eqs. (65) and (66) (i.e., setting
the left-hand side equal to zero) by solving explicitly for x,
8 + o(8 - 8 )
C
X =---B---- (69)
and substituting back in Eq. ( 66) to obtain an equation in the only un-
known 8:
8 + o (8 - 8 C) )
R(G) =8 + o(G -Ge)= BDar ( B ,8 = G(G) ( 70)
The left- and right-hand sides of Eq. ( 70) represent the heat removed
from the reactor through flow and the cooling medium, and the heat pro-
duced inside the reactor by the exothermic reaction, respectively. These
two functions are shown in Fig. 15, for those cases where the reactor
exhibits one ( curve 1) and three ( curve 2) steady states. On physical
grounds, it can be argued that the stability of each steady state depends
on the relative slopes of these two curves. If at steady state the slope
Reactor Steady-State Multiplicity /Stability 1003
Cl)
a::
e
FIGURE 15 Schematic representation of the heat removal R(0) and the
heat generation functions 0(0), defined by Eq. (70) in a CSTR.
of the heat generation curve is larger than that of the heat removal curve,
the steady state is unstable, because for small perturbation of the tempera-
ture value the system evolves away from the steady state itself. Based on
this observation, van Herdeen concluded that the middle steady state in the
case of multiplicity is unstable, while all the others, including the case of
a unique steady state, are stable.
The first rigorous analysis of this problem was presented by Bilous
and Amundson ( 1955), who applied the first method of Liapunov. It con-
sists of linearizing Eqs. (65) and (66) around the steady state, introducing
the two deviation variables
y = 0 - 0 (71)
2 s
and analyzing the stability character of the linearized system. In matrix
form this can be written as follows:
d~
£! ctt = i~ (72)
where ~ = (y 1y 2)T ,£! is the capacitance matrix given by
(73a)
and i is the Jacobian evaluated at steady state defined as
Dar0 ]
(73b)
-1 - o + BDar
0
where rx and re indicate the partial derivatives of the reaction rate, r at
steady state with respect to conversion x and temperature 0, respectively.
1004 Morbidelli, Varma, and Aris
In the case of an irreversible first-order reaction r = (1 - x) exp[0 /
(1 + 0 /y)], the Jacobian reduces to
J
=
= [ ~
X -
Bx
1
(1 + X0 /y) 2
-1 - o+ Bx
]
( 74)
(1 + 0/y) 2
The stability of the linear system ( 72) is dictated by the eigenvalues of
matrix g-l;i:. Assuming that Le = 1 (i.e., f = p, these coincide with the
eigenvalues of i);, which are given by
tr J + /'11 /2
2
l'1 = (tr '.!_) - 4 det J ( 75)
The effect of the Lewis number Le will be examined in detail later.
The necessary and sufficient condition for asymptotic stability (i.e. ,
stability to "small" perturbations from the steady state) is that both
eignevalues have' negative real part, that is,
det i); >0 (76a)
and
tr J < 0 (76b)
From standard linear differential equation theory the following classifica-
tion of the steady state of the linear system ( 72) is obtained:
1. det J < 0: unstable saddle point ( 77a)
2. det i); > 0, tr J > 0: unstable node (1'1 > 0) or focus
( 77b)
(/', < 0)
3. det { > 0, tr J < 0: stable node (/'1 > 0) or focus (1'1 < 0) (77c)
4. det g; > 0, tr J = 0: center (77d)
Liapunov's theorem assures us that the stability character of the nonlinear
system ( 65) and ( 66) is the same as that of the linear one for the first
three cases. For the fourth, further analysis is required.
A few comments on the comparison between the rigorous stability con-
dition ( 76) and the slope condition previously reported are now in order.
It should first be noted that condition ( 76a), using Eqs. ( 70) and ( 73), is
actually identical to the slope condition, since it requires the slope of the
heat removal function to be larger than that of the heat generation function.
Thus van Heerden criterion does actually give only a necessary condition
for stability. This implies that when three steady states occur, the middle
one is certainly unstable, while the lower and upper ones can be stable.
These two, as well as the single steady state in the case of uniqueness,
are in fact asymptotically stable if condition ( 76b) , usually referred as the
dynamic condition, is also satisfied.
Reactor Steady-State Multiplicity /Stability 1005
Finally, it can be shown (see Varma and Aris, 1977) that in the case
of an adiabatic reactor (i.e., cS = 0) condition (76a) implies condition (76b)
automatically. In this case the slope condition becomes necessary and suf-
ficient for asymptotic stability.
Periodic Solutions
To complete the picture of the dynamic behavior of the reactor, it is neces-
sary to characterize fully the occurrence of periodic solutions. A very
large number of papers have appeared in the literature using several
mathematical methods, such as Liapunov' s direct method , averaging tech-
niques, Fourier analysis, and perturbation methods [ see Hlavacek et al.
( 1970) and Uppal et al. (1974) for detailed references]. The most con-
venient approach, which allows us to answer the problem exhaustively, has
been presented by Poore (1973).
This approach is based on the Hopf-Friedrichs bifurcation theorem
(Friedrichs, 1965), which states that bifurcation to a periodic solution occurs
only from the center of the linearized system, and under the restriction
that the trace of the matrix !? = d!l/de: (where e: is the bifurcation param-
eter) does not vanish. Moreover, -this theorem allows the construction of a
function cS (x) whose sign at the bifurcation point allows to estimate both
the direction of the periodic solution and its stability character. It should
be mentioned that in this type of bifurcation, often referred to as Hopf
bifurcation, a pair of complex conjugate eigenvalues change their real part
sign by crossing the imaginary axis, thus implying a change in the system
stability character, since all the other eigenvalues are required to have neg-
ative real part. This should not be confused with the so-called static
bifurcation, where one real eigenvalue changes its sign by passing through
the origin. This is the bifurcation we have been referring to in the sec-
tion on steadr-state multiplicity.
Poore ( 1973) applied this theory to the case of a CSTR with first-order
irreversible reaction and Le = 1, in the limit of infinite activation energy.
To investigate all possible qualitative phase-plane behavior for the system,
he considered the parameter plane B versus cS (with fixed y = 00 , 0c = 0,
and Le = 1) taking Da as the bifurcation parameter (i.e., eventually the only
parameter that changes, while all the others are kept constant, to explore
the bifurcations and/or jumps of the system). The phase plane is then
divided into six regions by three curves, which are defined conceptually
as follows:
1. Curve M. Below this curve m1 and m2 [defined as conversion
values corresponding to the Da bifurcation values shown in Fig. 16
(i.e. , where det i = 0)] are complex, thus det i > 0; above the
curve, det i < 0 for m1 < x < m2 and det i > otherwise. This
curve thus represents the uniqueness condition for any Da, and is
analytically given, for a first-order reaction, by Eq. ( 17).
2. Curve S. It is based on the same concepts as curve M, but with
respect to stability insteady of multiplicity. Indicating with s 1
and s2 the conversion values where the stability character changes
(i.e., tr i
= 0) (see Fig. 16), it follows that below the curve s 1 and
s 2 are complex, thus tr i
< 0; above the curve for s 1 < x < s 2 ,
tr i > 0; while for x < s1 and x :> s 2 , tr i!; < 0.
1006 Morbidelli, Varma, and Aris
Do,._ Do*
--- Do
FIGURE 16 Sketch of outlet conversion as a function of Da at steady
state.
3. Curve SM. This curve establishes the relative location of the
solutions m1, m2 , and s1, s2, In particular, it represents the
locus of points where the m's and s's have the same·values (i.e.,
det J = 0 and tr J = 0).
- -
For the case examined by Poore ( 1973) these curves are described by
particularly simple expressions:
Curve M: B = 4(1 + 0) (78a)
Curve S: B =3 + o + 2 12+8 (78b)
3
Curve SM: B = (l+o)
8
( 78c)
Also, for the above-mentioned function o(x) a simple expression is derived
for x = s 1 and s 2 :
1) + 2b. - Bs. i = 1, 2 ( 79)
l l
2 2
where w. = b.(Bs. - b 1.) and b. = Bs. - 1 - S. It is found that for bi-
1 l l l l
furcation at s 1 ( s 2 ), o1 > 0( o 2 > 0) indicates bifurcation to a stable (un-
stable) periodic solution for Da values larger than the bifurcation value,
and vice versa for o1 < 0( o2 < 0).
The six regions in the S- o plane obtained using the three curves given
by Eq. ( 78) are shown in Fig. 17. The bifurcation behavior corresponding
to each region is illustrated as a function of Da in the side figures, where
the capital letters refer to the various shapes of phase portraits shown in
Fig. 18 (here the symbols filled and open circles indicate stable and un-
stable limit cycles, respectively, and their distance to the steady-state
::i::,
~
Q
X X mb . .. . . X Illa
ma S2 - ______ _. 0
s /'
---- .....
0
m2 m2 -s
' -- ---- ... ,
m1 --" m1 Ooo __ _..
C/J
S1 Da
.....
Da Da Da Da ~
A . A E A B A G B A Q
·~; :~ 0.
"<
I
C/J
30 .....
Q
.....
~
8.5 t :s::
i:::
:: t\ I (Il 7 5 /~l .....
~ ~ -s·
6.5 -- - " §:
CD 1.6 1.8 .....
II: t SM f ~ (1+8) "<
m ......
C/J
I ~~ 0
10 ~ \ ~ I ~
- e
j ~
I
1.5 2.0
:~ 2.5
( I+ 8)
3.0 3.5 4.0 4.5
EVAPORATION )(or.
STABLE ss
~2 . · / S2 _.. ··> s2 .·, S1
UNSTABLE ss
m ~ • .,,,, ~ m2 ',
,,
S1 ••_......... S1 ° .•./ S1 / m1 STABLE
. / ,~,,~
'LL. r~T ·wzc .·/ Uk[ ...... '
LIMIT CYCLE •···
Da . - A__ Da A B A Da A Do
UNSTABLE
LIMIT CYCLE
FIGURE 17 Regions in the parameter plane B versus ( 1 + o), surrounded by the
sketches of the corresponding bifurcation diagrams in the X versus Da plane
(parameter values: y == 00 , Ge = 0, Le = 1). Irreversible first-order reaction in a
CSTR. .....
0
0
-'I
1008 Morbidelli, Varma, and Aris
TYPICAL PHASE PLOTS
CASE A B C D E F G H J
[ NODE
F8cus
J[ STABLE
UNSTABLE
J 1
0
0
1
1
1
1
0
2
0 1
1
2
0 2
0
1
1
JG J
SADDLE POINT 0 0 1 0 1 1 1 1 1
G LIMIT
CYCLES
STABLE
UNSTABLE
0
0
1
0
0
0
1
1
0
0
1
0
1
0
0
1
1
1
TOTAL INVARIANTS 1 2 3 3 3 4 4 4 5
ABSCISSA-CONCENTRATION ORDINATE-TEMPERATURE
~ A B
iif) G H
FIGURE 18 Phase portraits characteristic of various regions in the param-
eter plane shown in Fig. 1 7.
Reactor Steady-State Multiplicity /Stability 1009
curve represents the maximum amplitude of the oscillation). These figures
have been taken from Uppal et al. (1974), who extended Poore (1973) re-
sults to the case of finite activation energy, and completely defined the
CSTR dynamics by following the branches of periodic solutions up to com-
pletion through accurate numerical integration.
The correspondence between the regions in the parameter plane and the
corresponding bifurcation diagram follows directly from the relative position
of each region with respect to the above-mentioned curves. For example,
since bifurcation to a periodic solution occurs only for tr !I. = 0 and det l > 0,
it follows that bifurcation at x = s1 occurs only in regions-IV (0 < s1 < m1 <
m2 < s2 < 1), V (0 < s1 < s 2 < 1, m, and m2 are complex), and VI (0 < m1 <
m2 < s1 < s2 < 1), while bifurcation at x = s 2 can occur also in region III
(0 < m1 < s1 < m2 < s2 < 1).
Several interesting dynamic features of the CSTR have been evidenced
by this analysis. For example, for a set of parameter values inside region
IIIb in Fig. 17, it appears that starting with large Da and decreasing it,
the system goes from a high-conversion steady state to a limit cycle (trans-
ition A-B), whose amplitude increases up to a Da value, where the limit
cycle evaporates and the system precipitates to a low-conversion steady
state (transition F-C). This behavior has been likened by Poore ( 1973) to
the flickering of the flame when turning off a bunsen burner.
Another interesting observation concerns the mechanisms for the limit
cycle disappearance pointed out by Uppal et al. (1974). Three of these
have been observed: shrinking into a steady state, increasing amplitude
up to merging with a separatrix line, and coalescence of a stable and
unstable limit cycle.
Also, about the relative position of limit cycles and steady states some
general conclusions can be drawn. Poore ( 1973) has shown that any
steady state in the uniqueness region has index +l, while in the multiplicity
region the middle steady state has index -1, and the lower and upper ones
have again index +1 (see Gavalas, 1968). Since any periodic solutions must
encircle a number of steady states such that the sum of their indices gives
+l, it can be concluded that a limit cycle can either include the steady
state in the case of uniqueness, or include only the upper steady state or
only the lower or all the three steady states in the case of multiplicity.
This conclusion is confirmed by the phase-plane portraits shown in Fig. 18.
Along this same line, Poore (1973) also proved that if a unique unstable
steady state exists, then a stable periodic orbit must also exist surrounding
the steady state.
As we have already discussed in the multiplicity section, the most con-
venient way to change the Da value in practice is to change the feed
stream flow rate. However, this also affects the cooling parameter o, de-
fined by Eq. (3). So Uppal et al. (1976) redefined the dimensionless
quantities, isolating the feed stream flow rate in the residence-time param-
eter, and explicitly accounting for it as follows:
Da = Da 0 T (80)
The entire bifurcation analysis has then to be repeated, now taking T in-
stead of Da as a bifurcation parameter. As mentioned earlier, the multi-
plicity pattern with respect to the reactor residence time is quite complex,
giving rise to the isola and mushroom shapes, which do not appear when
the Damkho1er number is taken as a bifurcation parameter. Therefore, it
1010 Morbidelli, Varma, and Aris
is not surpnsmg that more complex features and up to 17 different types
of dynamic behavior have been found by Uppal et al. (1976).
It should be noted that the number of possible phase portraits is un-
changed, since these depend only on the parameter steady-state values.
Thus in this case also, the nine portraits shown in Fig. 18 cover all pos-
sible phase-plane shapes.
Effect of the Lewis Number
The Lewis number has been defined in Eq. (68) as the ratio between the
thermal and the mass capacitances of the reactor. Up to this point it has
been assumed that Le = 1; however, while for homogeneous tubular reac-
tors the Lewis number is very close to 1, for packed-bed reactors this is
not true, and in general it tends to be much larger than unity.
Clearly, the Lewis number does not affect the value of the reactor
steady state, only its stability character. In fact, Le appears only as a
multiplier of the thermal accumulation term in the transient model (65) and
( 66). The linearized system ( 72) can be rewritten as
d~
(81)
dt
where ~ = f-li involves the lewis number.
In general, decreasing values of Le enlarge the instability region of the
reactor. For example, in the case of a first-order reaction with y = 00 ,
the conversion values s 1 , 2 , where tr ~ = 0, can be readily calculated from
Eqs. (74) and (81) as follows:
s 1 , 2 = B \~ + o ± 2~ [(B + 1 + o) 2 - 4BLe - 4B(l + 0)) 1 / 2 (82)
where it appears that as Le + 0, s1 decreases while s2 increases. Since
tr ~ > 0 for s1 < x < s 2 , it follows that decreasing values of Le expand
the region where the dynamic stability condition (76b) is violated. The
numerical findings of various authors also go in this direction, showing
that models of this type tend to exhibit periodic solutions for sufficiently
low Le values [see Aris (1975) for the case of a catalyst particle].
Perelson (1976) extending a previous work by Luss (1974), has
examined the effect of the capacitance matrix on the stability of the linear
system ( 81) in a more general way. It was observed that ~ being a posi-
tive definite symmetric matrix, if i is nonsingular and symmetric, then ~
has all real eigenvalues. If i is nonsingular and nonsymmetric, as in the
case under examination, the eigenvalues of ~ can be either real or complex
conjugate, depending on the value of the capacitance parameter. Thus
taking one of the elements of g as bifurcation parameter (in our case, Le),
and applying the above-mentioned Hopf- Friedrichs bifurcation theorem, for
any given steady state of the reactor the value of Le at which periodic
orbits bifurcate can be identified.
In particular, for a system equivalent to the adiabatic CSTR model,
Perelson (1976) found that such a critical value of Le is given by
Reactor Steady-State Multiplicity /Stability 1011
Lee = (x - 1) h- Bx ] ( 83)
[ (1 + 0/y) 2
where x and 0 are evaluated at steady-state conditions, and periodic solu-
tions can occur only for Le < Lee, Since the occurrence of Hopf bifurca-
tion requires det ~ > 0, it can be shown that Lee < 1. This implies that
for adiabatic systems of the type examined, oscillations can occur only for
Le< 1.
This result has been previously reported by Ray et al. (1974), in the
context of multiplicity and stability of catalytic wires. Since wires are
characterized by Lewis number values much larger than 1, it appears that
they cannot oscillate on their own. These findings agree with the analysis
of Edwards et al. (1974) on flickering of catalytic wires. This phenomenon,
characterized by the occurrence of a localized region of very high luminosity
whose intensity changes with time, has been attributed to fluctuations of
the concentrations in the gaseous stream, which can be significantly en-
hanced by the catalytic wire.
Ray and Hastings (1980) have applied bifurcation analysis to the system
of Eqs. ( 65) and ( 66) taking as bifurcation parameter the Lewis number Le.
The procedure is identical to that applied by Upp al et al. (1974, 1976)
taking as bifurcation parameters the Damkobler number and the reactor
residence time, respectively. By inspection of Eqs. (65) and (66) it is
readily seen that by replacing the parameters, B , 6 , and 0 c with the new
quantities
0
1 + 6 A
B A
C
CJ, = B 0C ( 84)
Le Le Le
Eqs. (65) and (66) reduce to the same form used by Uppal et al. (1974) in
the case of Le = 1. Thus, with these parameter changes, the results ob-
tained previously still hold. In particular, the B-& parameter plane [pre-
viously, B - ( 1 + 6 ) ] is again divided into the same six regions, each
leading to a different shape of the conversion versus Damkohler number
bifurcation diagram. This diagram is shown in Fig. 19 for the case y = 00
and 0c = 0, in terms of the new dimensionless parameters accounting for
the effect of Lewis number.
A quite interesting feature of the dynamics of this system can be ob-
served in Fig. 19. Since the reactor steady state for 0 c = 0 is affected
only by the ratio B /(1 + 6), it follows that the same x-Da bifurcation
diagram corresponds to all the points on any straight line going through
the origin. For a given straight line, by decreasing Le we move toward
the upper-right region of the diagram. So, depending on the given value
of the ratio B /(1 + 6), the curve may enter region III (curve 1), V ( curve
2), or even the small region VI. In any event, in either one of these re-
gions, the system can exhibit stable periodic orbits. Thus it appears that
for decreasing values of Le, lower than the critical value Lee where the
straight line enters one of the above-mentioned regions, we have persistent
stable periodic solutions.
Using the same procedure adopted for deriving Eq. (78b), the following
expression for Lee, valid for y = 00 and 0 c = 0, is obtained:
1012 Morbidelli, Varma, and Aris
26
24
20
QJ 16
.J
'
Q)
12
8 @
4
0.5
(l+O)/Le
FIGURE 19 Effect of Lewis number on reactor dynamics (parameter
values as in Fig. 17).
Le
C
= [< 1 +41/J1/J) 2 1)c1+0> (85)
where 1jJ = B/(1 + o).
It should be noted that the specific form of the bifurcation diagram x
versus Le depends on the particular choice of the values for B / ( 1 + o)
and Da. A detailed analysis of all possible situations has been reported by
Ray and Hastings (1980).
These authors have also pointed out that in some cases the periodic
orbits asymptotically approach relaxation oscillations as Le + O. In this
case the characteristic thermal time is so much smaller than that for mass
that the energy balance (66) can be assumed in pseudo-steady-state con-
ditions with respect to the mass balance ( 65). Under these conditions,
relaxation oscillations can occur only if the function 0 = 0 (x), given by the
pseudo-steady-state approximation of Eq. (66) is multivalued (see Gilles
et al., 1978). For example, this is not the case for y = oo, which there-
fore does not exhibit this peculiar type of dynamic behavior.
Some Comparison with Experimental Data
As a conclusion of the analysis of the dynamic behavior of a CSTR, it is
convenient to report some experimental verification of the presented re-
sults. It should be understood that what we are really verifying with such
a comparison is the CSTR model and its ability to simulate real systems.
Several experiments have been reported in the literature of multiplicity,
oscillations, and sensitivity in CSTRs, for both homogeneous and hetero-
geneous reactions. Exhaustive reviews have been presented by Schmitz
( 1975) and Sheintuch and Schmitz ( 1977). We shall here content with few
references, specifically concerning homogeneous reactions in a CSTR,
which explicitly prove some of the features previously described. In
particular, we refer to the experiments reported by Schmitz and coworkers
using a laboratory well-mixed continuous reactor where the second-order
reaction between sodium thiosulfate and hydrogen peroxide occurs.
Reactor Steady-State Multiplicity /Stability 1013
Several of the phase portraits shown in Fig. 16 have been experimen-
tally found using this system. Vejtasa and Schmitz (1970) used an
adiabatic reactor, which we have shown (at least for a first-order reaction)
to belong either to region I or II in Fig. 17. Accordingly, no oscillations
were found and only phase portraits of type A and E were reported. Chang
and Schmitz (1975a,b) used a nonadiabatic unit, which allowed them to ob-
serve oscillatory behavior. Besides type A and E, a phase portrait of type
B was also reported.
Subsequently, the authors of the most significant latest theoretical
and experimental contributions in this area joined together with the aim of
experimentally verifying additional dynamic features of the above-mentioned
reaction system (Schmitz et al. , 1979). Applying the Hopf- Friedrichs bi-
furcation theorem, the dynamic behavior of a CSTR with a second-order re-
action was explored. Again, the same six regions characteristic of the
first-order reaction were found. The qualitative agreement between the
above-mentioned previous experimental results and the model predictions
was complete. Moreover, a fourth type of phase portrait, C was experi-
mentally found, where three steady states are present, but only the low
conversion one is stable. This result was achieved thanks to the dual
nature, theoretical and experimental, of this work. Unfortunately, due to
limitations intrinsic of any experimental apparatus, not all the dynamic
features found theoretically were possible to be reproduced experimentally.
An interesting result regarding the effect of the Lewis number has also
been reported by these authors. The experimental unit was, in fact,
equipped with a jacket, surrounding the reactor wall, which could be filled
with water in order to increase the thermal capacity of the reactor and
thus also the corresponding value of the Lewis number. It was shown that
repeating the experiment relative to the phase portrait of type C, but now
filling the jacket of the reactor with water, a stable high conversion steady
state was obtained. This confirms the previously discussed stabilizing
effect of increasing values of the Lewis number.
Tubular Reactor
Stability
The transient behavior of a tubular reactor is described by the axial dis-
persion model through the following set of parabolic partial differential
equations (PDEs):
au 1 a 2u au
= - Dar(u,v) ( 86)
at Pe 2 as
m as
av 1 a 2v av
Le at =--
Peh as 2 as
+ BDar(u, v) - 0 (V - V )
C
(87)
where the dimensionless parameters
t'n spC + (1 - s) p C
t = .:...1 Le = p s ps
( 88)
V spC
p
1014 Morbidelli, Varma, and Aris
have been added to those previously defined in Eq. ( 49). The Lewis num-
ber is defined as the ratio between the total heat capacitance of the reacting
system (fluid + solid) and that of the fluid. In the case of homogeneous
reactors Le = 1, while it rises up to a few hundred in the case of catalytic
reactors.
Boundary conditions of Eqs. (86) and (87) are the same reported for
the steady-state model [Eq. (52)], while the initial conditions are
in in
u = u (s) V = V (S) at t = 0 ( 89)
It is worth point out that the BCs (52) proposed by Danckwerts in 1953
are valid also under transient conditions only when no mass or heat dis-
persion occurs in the inlet and outlet tubes to and from the reactor
(Wehner and Wilhelm, 1956; van Cauwenberghe, 1966). In the following
we shall always refer to the Danckwerts boundary conditions, and eventual-
ly discuss the effect on reactor stability of the degree of mixing in the
regions before and after the reacting region.
In the preceding section it was shown that Eqs. ( 86) and ( 87) can
admit up to seven steady- state solutions. It is then necessary to discuss
numerical procedures and a priori criteria to define the stability character
of a steady state. Unfortunately, the mathematical apparatus for dealing
with stability of parabolic PDEs is not as well assessed as for ODEs.
Therefore, except for very special situations, strong statements about
steady-state stability, such as those reported for the CSTR,. cannot be
made.
Even though no rigorous mathematical proof is available (of the type
of Liapunov's first theorem for ODEs), it seems quite reasonable to relate
the local stability character of a given steady state of nonlinear system
of parabolic PDEs to that of the corresponding system obtained through
linearization about the steady state. Introducing the perturbation variables
u(s,t) = u(s,t) u (s) (90a)
s
v(s,t) = v(s,t) V (s) (90b)
s
where the index s refers to steady-state condition, and performing the
usual change of variables (Amundson, 1965; Varma and Aris, 1977),
y 1 (s,t) = u(s,t) exp (- Pets) (91a)
y 2 (s,t) = v(s,t) exp (- Pe:s) (91b)
the following linearized version of Eqs. ( 86), ( 87), ( 52), and ( 89) can be
obtained:
1
=
Pe
m
Reactor Steady-State Multiplicity /Stability 1015
Le a;; "P!h aa':; - (P:h + ' - SDar.) Y,+ SDaruY 1 expCPem2 Peh)']
(93)
with BCs
ely 1 Pe el y 2 Peh
m ( 94a)
Y1 == 0 -2-y2 == 0 at s == 0
els 2 cl s
ely 1 Pem cly2 Peh
- - + - - Y1 == 0 + -2-y2 == 0 at s == 1 (94b)
els 2 cl s
and !Cs
in in ( 95)
Y1 == Y1 Y2 == Y2 at t == 0
Equations ( 92) to ( 94) can be rewritten in the following matrix form:
( 96)
with BCs
cly
els +~y_==O at s == 0 (97a)
ely
as+!?y ==0 at s == 1 (97b)
and IC
in (98)
Y.. == Y..
Its solution is given by an infinite series expansion of the form
c .. Y .. (s) exp(A.t) ( 99)
lJ lJ J
where >... are eigenvalues of the associated eigenvalue problem
J
d 2~
>...!!!_ == ~ -2 + ~.'.!!_ (100)
ds
that is, the values of ;\ for which Eq. (100) admits a nontrivial solution.
From Eq. ( 99) it is seen that if all eigenvalues have negative real
parts, the steady state is stable; if one of the eigenvalues has positive
real part, the steady state is unstable. This is a quite straightforward
1016 Morbidelli, Varma, and Aris
conclusion, but its application can be quite difficult, since in general the
number of eigenvalues is infinite, and they can of course be either real or
complex. Therefore, in general it is necessary to resort to suitable num-
erical techniques. The standard procedure is to discretize Eq. (100) along
the space variable s and then compute with a suitable algorithm the eigen-
values associated with the obtained system of algebraic equations. Since
the eigenvalues thus obtained approximate the corresponding largest eigen-
values of the original infinite set, they allow us to identify the stability
character of the steady state under examination. Particularly fortunate is
the case of an adiabatic reactor with Pem = Peh, for it leads to a linearized
system (96) whose linear spatial operator is self-adjoint.
In the following we first analyze this last case, which has received a
great deal of attention in the literature. Then we consider the general
case of a nonadiabatic reactor and discuss some of the stability conditions
which have been obtained using various methods, mainly based on compari-
son theorems and Liapunov direct method. Finally, some numerical tech-
niques for solving the eigenvalue problem (100) are indicated.
Special Case of Adiabatic Reactor: As mentioned above, in the case of
adiabatic axial dispersion model with Pem = Peh and Le = 1, the stability
problem can be greatly simplified. A standard procedure used in the
earlier studies is to introduce the so-called "residual enthalpy," defined as
(101)
By suitably combining Eqs. ( 92) and ( 93), under the assumptions noted
above, it is found that
aw 1 a 2w Pe
at = Pe 2 4
w (102)
as
with BCs
aw Pe
as 2
w =0 at s =0 (102a)
aw Pe
as
+
2
w =0 at s =1 (102b)
which, using the IC
in
w = 0 (103)
admits only the trivial solution w = 0. This implies that if we limit the
analysis to so-called adiabatic perturbations (i.e., win = 0 leads to v +
Su = 0), then during the transient the following relation holds:
v + Su = 1 + S (104)
This allows us to reduce the original system of equations to the single
PDE
Reactor Steady-State Multiplicity /Stability 1017
clv
at =
clv
cl s
+SDar( 1 +: - v,v) (105)
By linearizing Eq, ( 105) and introducing the change of variable ( 91b), a
single linear PDE is obtained whose space operator is self-adjoint. The
stability of the system is then related to the eigenvalues of the problem:
2
Ai/! = - 1 -d t - ( -Pe + Dar - DaSr ) 1/J (106)
Pe ds2 4 u v
with the BCs (102) with w replaced by 1/J. In this case it is known that
the eigenvalues An form an infinite set of real, discrete values.
Using these properties Amundson (1965) derived a necessary and suf-
ficient condition for stability which requires the solution of an initial value
ODE whose coefficients depend only on the steady-state profiles.
The final answer to the stability question was given by Luss and
Amundson ( 1967a), who exploited the possibility of reducing the problem
to a single PDE. Using topological concepts they proved that in the case
of multiple steady states the low- and high-conversion steady states are
asymptotically stable, while the middle one is unstable. Moreover, using
the maximum principle, it was also proved that if a unique steady state
exists, it is always globally stable.
Again using the maximum principle, Luss and Lee (1968) determined
finite regions of stability for each steady state. These allow us a priori
to determine the response of the reactor to large perturbations and even
the final steady state reached from a given initial condition, without per-
forming any transient calculation. In particular, it was found that the
unstable- steady- state profile separates the regions of stability of the two
stable steady states, For cases where the initial profile does not entirely
lie in one or the other of the two stability regions, it is necessary to in-
tegrate the transient model. If at any time during the transient the pro-
file is found to entirely lie inside one stability region, the above-
mentioned criterion can be applied again.
It is worth pointing out that in the particular case under examination
the axial dispersion model is very similar to the catalyst particle model in
the case of Le = 1. Thus the results obtained for one model can be
directly extended to the other. In fact, some of the stability conditions
reported below, as well as for the above-mentioned work by Luss and Lee
(1968), were originally derived for the catalyst particle.
Even though the stability picture for this special case of adiabatic re-
actor is quite clear at this point, there are two reasons for reporting re-
sults obtained with other techniques. The first is that the above-mentioned
stability conditions were obtained considering only adiabatic perturbations,
which gives a character of conditional stability to the final answer. Luss
and Lee (1968) have shown using Eq. (102) that the residual enthalpy
monotonically decreases in time, thus indicating a more general validity of
the stability criteria developed, Nevertheless, other techniques are avail-
able which do not require the use of the residual enthalpy concept at all
(Padmanabhan et al., 1971). The second reason is that since the above-
mentioned methods apply only to a single PDE , they can be used only in
this particular case.
1018 Morbidelli, Varma, and Aris
Wei (1965) was the first to apply the direct method of Liapunov to the
catalyst particle. Berger and Lapidus (1968) and Padmanabhan et al.
(1971) extensively used this method, including more general situations such
as the catalyst particle with Le -j 1. Varma and Amundson ( 1972a) applied
the method of comparison functions. Both these two last approaches do
not require any restriction on the residual enthalpy.
A sufficient condition for stability was first developed by Luss and
Amundson (1967a); it is identical to the uniqueness condition ( 55). This
relation has also been derived by several of the above-mentioned authors
using various methods. For example, Aris (1969) showed that it could be
derived using either the maximum principle or the first or second Liapunov
methods. Finally, this expression was also obtained by Gupalo and
Ryazantsev (1969) using the Sturm-Liouville eigenvalue problem properties,
again limited to adiabatic perturbations.
The issue of the appropriateness of the Danckwerts boundary conditions
( 52) in the transient case has been addressed in detail by Parulekar and
Ramkrishna (1984) for the cases of both zero and nonzero residual enthalpy.
Even though these boundary conditions are valid under transient conditions
only in the case of no mass or heat dispersion outside the reactor, the
stability results were found to be qualitatively quite similar. Besides the
multiplicity characteristics, which are obviously unchanged, Parulekar and
Ramkrishna (1984) have proved again that a unique steady state is globally
asymptotically stable. A sufficient stability condition very similar to Eq.
( 55) was also obtained in this case , the only difference arising from the
effect of the initial state outside the reactor on the reactor transient,
which is obviously nonzero only in the presence of dispersion. A detailed
analysis of the effects of various mixing intensities before and after the
reaction region, as well as of the stability regions, is also presented.
General Nonadiabatic Case
A priori conditions: In the most general case of nonadiabatic tubular
reactor, or adiabatic with either Le -J 1 or Pem -J Peh, the heat and energy
balances cannot be uncoupled. Thus we have to deal with a system of
PDEs which, when linearized, produces a non-self-adjoint space operator.
Under these conditions most of the above-mentioned methods either fail or
become exceedingly complicated, with only the partial exception of the
direct Liapunov method.
One of the very few direct extensions of the results in the preceding
section is in the case of an adiabatic reactor with Pem = Peh and Le -J 1.
Gavalas ( 1968) has shown that if a steady state is unstable for Le = 1, it
is so also for any other Le -J 1.
Nishimura and Matsubara (1969) developed a sufficient condition which
requires the integration of a set of initial value linear ODEs whose coef-
ficients depend on the steady-state profiles under examination. Varma and
Amundson (1972b), using the method for optimizing the Liapunov functional
proposed by Padmanabhan et al. ( 1971) , have shown that the same conditions
which guarantee steady-state uniqueness also guarantee asymptotic stability.
Thus Eqs. ( 58) and ( 59) are sufficient conditions for asymptotic stability
for the nonadiabatic reactor with Pem = Peh , Le = 1 and Pem -J Peh, Le ,f: 1,
respectively (note that for a homogeneous reactor Le = 1 implies that Pem =
Peh).
More conservative sufficient conditions for stability, obtained using
different choices of the Liapunov functional, have been reported by various
Reactor Steady-State Multiplicity /Stability 1019
authors (Clough and Ramirez, 1972; Liou et al. 1972a,b; Varma and
Amundson, 1973a; McGreavy and Soliman, 1973). The effect of recycle on
stability has been studied by Matsuyama ( 1970) for the adiabatic tubular
reactor, and by McGowin and Perlmutter (1971b) and Liou et al. (1974) for
the nonadiabatic case.
Numerical methods: Due to the lack of sharp sufficient conditions for
stability, it is often necessary to resort to numerical techniques. The first
approach is the direct integration of the complete transient model. It was
used in the earliest work of Raymond and Amundson ( 1964) and Hlavacek
et al. (1971). Since then, many sophisticated numerical methods for solving
system of parabolic PDEs have been developed. Some of them have been
used in general computer codes, such as PDEPACK (Madsen and Sincovec,
1975) and PDEL (Cardenas and Karplus, 1970). Most of these techniques
are based on the method of lines, where the space variable is discretized
using a suitable technique such as finite difference or weighted residuals.
The obtained system of ODEs is then integrated in time using a suitable
marching technique. Since the system of ODEs can be stiff for certain
range of parameter values, implicit integration methods (at least partly) are
usually recommended. More detailed information about these numerical
techniques is reported by Finlayson ( 1972) and by Michelsen and Villadsen
( 1978), while a detailed analysis of the application of the orthogonal colloca-
tion method to the particular model under examination has been reported
by Georgakis et al. ( 1977a).
Another approach consists of evaluating the eigenvalues for the linear-
ized system of PDEs (92) to (95) given by the non-self-adjoint eigenvalue
problem ( 100). It should be noted that although Eq. (100) is linear, it
can only be solved numerically, because some of the elements of matrix ~
involve the partial derivatives of the reaction rate at steady state along -
the reactor, which in general do not admit analytical representation.
Usually, a discretization method is used to transform the parabolic PDEs
into a system of ODEs. The most common techniques used for this are:
finite differences (Kirkby and Schmitz, 1966; Heinemann et al., 1979, 1980;
Heinemann and Poore, 1981), Galerkin method (Kuo and Amundson, 1967;
McGowin and Perlmutter, 1971a,b; Varma and Amundson, 1973b; Jensen and
Ray, 1982), and orthogonal collocation (McGowin and Perlmutter, 1971a;
Georgakis et al., 1977a; Jensen and Ray, 1982). The size N of the final
system of ODEs depends on the number of terms in the trial solution in the
Galerkin method, or of collocation points in the orthogonal collocation
method. The final step of the procedure involves evaluation of all the
eigenvalues of the discretized system, which can be accomplished through
standard routines (Michelsen and Villadsen, 1978).
Based on regularity considerations of the solution, it is expected that
by increasing the number of discretization elements, N such that N + oo,
the system of ODEs gives a perfect description of the original system of
PDEs. In particular, the N eigenvalues obtained approximate the first N
largest eigenvalue of the non-self-adjoint problem. This process is illus-
trated by the results reported in Tables 2 and 3. In the first one are shown
the estimates of the largest eigenvalue as a function of the number of trial
functions used in the Galerkin's method (McGowin and Perlmutter, 1971a).
The orthogonal set of trial functions used is based on the solution of the
same model without chemical reaction. This explains why convergence be-
comes slower for increasing values of the outlet conversion. In Table 3
1020 Morbidelli, Varma, and Aris
TABLE 2 Estimate of the Largest Eigenvalue as a
Function of the Number of Trial Functions in
Galerkin's Method, n(Pem = Peh = 10; o = 0.1)
X 0.10 0.35 0.90 0.995
n = 1 -2. 237
n = 2 -2.227 -0.02909 -0. 2498
n = 3 -2. 227
n = 4 -2. 227 0.4212 0.3404 -1. 413
n = 6 0.4537 0.5382 -0. 6879
n =8 0.4553 0.9819 -0.5102
n = 10 0.4554 1. 275 -0.1721
n = 12 0,4554 1. 386 -0.1277
n = 14 0.4554 1. 412 -0.1144
n = 16 1. 415 -0.1002
n = 18 1. 415 -0. 0991
n = 20 -0.0986
n = 22 -0. 0982
n = 24 -0.0982
are shown the first 15 eigenvalues estimated using the orthogonal collocation
methods with 7 (i.e., N = 15) and 15 (i.e., N = 31) collocation points, re-
spectively (Georgakis, et al., 1977b). It appears that while convergence
already seems to have been achieved for the largest eigenvalues (which are
those that determine the reactor dynamics) this is not true yet for the
smaller ones.
About the discretization procedure, Mc Gowin and Perlmutter ( 1971a)
have compared the Galerkin and the orthogonal collocation methods. They
found that the first is more rapidly convergent, and also converges mono-
tonically, while the second converges in a damped oscillatory manner. In
general, they recommended Galerkin's method, unless the model contains
mixed boundary conditions, as in the presence of recycle. These observa-
tions have been confirmed by Jensen and Ray (1982).
Finally, it is worth commenting on the correctness of this entire proce-
dure, since as mentioned above, a rigorous mathematical relation between
the stability of the original nonlinear system and that of the linearized sys-
tem is not available for distributed parameter models. Varma and Amundson
(1973b) successfully checked the stability of the system predicted through
the linearization method in several cases by direct integration of the original
model. Since these results have been analyzed in detail by Varma and Aris
(1977), this argument is not pursued further here. Some of the results
obtained regarding the stability of multiple steady states are discussed in
Reactor Steady-State Multiplicity /Stability 1021
TABLE 3 Estimates of the First 15 Eigenvalues
Using 7 and 15 Collocation Points
7 collocation points 15 collocation points
:\j :\.
J
1 +3.001 +3.007
2 -0.972 - 0. 977
3 -4.273 + 3.322i -4.292 + 3.321i
4 -4.273 - 3.322i -4. 292 - 3. 32li
5 - 6. 793 - 6. 766
6 -11.02 + 1.937i -11.03 + 1.981i
7 -11. 02 - 1. 937i -11. 03 - 1. 981i
8 -19.51 + 2.097i -19. 28 + 1. 857i
9 -19.51-- 2.097i -19.28 - 1.857i
10 - 29. 14 + 1. 210i - 33. 20 + 1. 969i
11 -29.14 - 1. 210i -33. 20 - 1. 969i
12 - 71. 84 + 3. 602i - 50. 95 + 1. 933i
13 -71.84 - 3.602i -50. 95 - 1. 933i
14 -85.42 + 1.352i -72.66 + 1.931i
15 -85.42 - 1.352i -72. 66 - 1. 931i
the next section, where the occurrence of periodic solutions is also taken
into account.
Bifurcation and Dynamic Behavior
As we have noted in the case of a CSTR, the most efficient and sharpest
technique available for investigating multiplicity and dynamic behavior is
bifurcation analysis. A rigorous mathematical treatment of the extension
of this method to distributed systems can be found in Crandall ( 1977) and
Iooss and Joseph ( 1980). From the application point of view, the main
conclusion is that Hopf bifurcation theorem can be extended to the case of
parabolic PDEs, by approximating these with an infinite set of ODEs using
one of the discretization techniques discussed above. In other words, the
bifurcation behavior of the system of Eqs. ( 86), ( 87), ( 52), and ( 89) is
determined by the eigenvalues of the discretized system of linearized ODEs
given by Eqs. (96) to (98) [i.e., the solution of the non-self-adjoint
eigenvalue problem ( 100)]. As in the case of lumped systems, two types
of bifurcation are possible: a static bifurcation, which occurs when one
real eigenvalue is zero, and a Hopf bifurcation, which occurs when a pair
of complex eigenvalues has zero real part (i.e., they are purely imaginary).
Again, in order to have bifurcation to periodic solution it is necessary that
20 xl§n, ·-•.. .....
0
x~ Do """"
x~ I lZIII o x~a:oa
Do
,.--
XLS:_ XL; :Xa
15
Do Do
XLS:_ x~-~
.-····· .X.b
··.
Do en Do
x~ .... Jr
10
X
-
l$'.n Da
Do
X
1
r Ml x~·:t-
.. XII
->1 -.:, , ,- j M2 rs::
~·-·7·,, /l 0
lE Do
z- 'jiJz Do
....- t5'
E:
.. E
x
ts;; Do 5 t ~ S-:-
• ii:: S-,
I/. I
2.Q 2.2 2.4
~=:. <::
Q
~
:.. XDlb fl
xlf=• 0 2 3 4
Xlrf...... ~ §
Do
A..
8 x1 _.:r::o ::i,..
:J.
Cl.>
~Do
Reactor Steady-State Multiplicity /Stability 1023
all the other eigenvalues, besides the pair of purely imaginary ones, have
a negative real part, so that the system actually undergoes a change in
its stability character.
Two different types of numerical techniques are usually employed for
locating such bifurcation points. For static bifurcation points one needs
to solve the steady-state problem and calculate the value of the bifurcation
parameter at which one of the eigenvalues is zero. One way is to solve
the steady state with the usual techniques for any given value of the bi-
furcation parameter, and use the Euler- Newton continuation method to satisfy
the bifurcation condition. To avoid numerical instabilities near the bifurca-
tion points where the Jacobian is singular, it is necessary to adopt the
solution normalization method proposed by Keller (1977). A detailed descrip-
tion of this method, with specific reference to premixed laminar flame
models, is reported by Heinemann et al. (1979).
A different method has been used successfully by Jensen and Ray
(1982) in the bifurcation analysis of tubular reactor models. This method
is based substantially on the same idea proposed previously by Weisz and
Hicks (1962) for one-dimensional problems, and then applied to multi-
dimensional problems by Sorensen et al. ( 1973). It consists of fixing one
value of the unknown solution (e.g., at one collocation point) and taking
in its place the Damkholer number (or Thiele modulus for catalyst particles)
as unknown. The problem so formulated usually admits a unique solution,
and it is then possible to solve it for any given Da, even in the multi-
plicity region.
The Hopf bifurcation points can be obtained by evaluating the eigen-
values corresponding to a given value of the bifurcation parameter through
the method indicated in the preceding section, and then searching for the
bifurcation parameter value that satisfies the bifuraction condition through
standard techniques, such as section, Newton-Raphson, and so on.
Kubicek (19'.79) has suggested including the Hopf bifurcation condition in
the nonlinear system of algebraic equations which solve the steady- state
problem (after discretization) and then solving it all together with a Newton-
Raphson method. Jensen and Ray (1982) have suggested using necessary
conditions for the characteristic polynomial to have purely immaginary roots
to improve the efficiency of the bifurcation point search.
The bifurcation theory has recently been applied to the axial disper-
sion model in the case of a first-order reaction by Heinemann and Poore
(1981) and Jensen and Ray (1982). Some of the above-mentioned numerical
methods have been applied in these two works, and the reported agreement
between the obtained Hopf bifurcation points constitutes a check on their
correctness.
In the first of these two papers the problem of stability of the periodic
solution was also considered. Formulas of the same type as those illus-
trated for the CSTR [see Eq. (79)] were reported. They allow us, on
the basis of only steady-state information, to derive both the direction and
the stability character of the bifurcating periodic solution.
FIGURE 20 Regions in the parameter plane B versus o, surrounded by
the sketches of the corresponding bifurcation diagrams in the x versus Da
plane (parameter values: Pem = Peh = 5, Le = 1, 0 c = 0, y = 20). Ir-
reversible first-order reaction in a tubular reactor with axial dispersion.
1024 Morbidelli, Varma, and Aris
Due to the larger number of parameters involved, a picture of dynamic
behavior as complete as that reported for the CSTR is now unattainable.
We shall therefore be content with examining some of the novel features ex-
hibited by this system. For the special case of adiabatic reactors the
situation is again quite clear. Namely, since the eigenvalue problem in
this case is self-adjoint, the eigenvalues are all real and no bifurcation to
periodic solutions car:, occur. To summarize: this reactor can exhibit at
most three steady states, with alternate stability character (i.e. , stable-
unstable-stable), and can never exhibit self-sustained oscillations.
On the other hand, when the adiabaticity condition is removed, the
dynamic behavior becomes much more complex. Up to seven steady states
with various combinations of stability character can be found, including
the case where all steady states are unstable, which obviously implies the
occurrence of periodic solutions.
In Fig. 20 the same type of representation of the parameter space as in
Fig. 15 for the CSTR has been adopted to illustrate the dynamic behavior
of the axial dispersion model. In particular, the case where Pem = Peh = 5
is examined. This situation is thus intermediate between the two well-known
ideal cases of the CSTR and the plug-flow reactor (Cohen and Poore, 1974):
the latter always admits a unique globally stable steady state, since it is
described by a system of initial value ODEs. In Fig. 20, it appears that
besides curves M1, S1, and S2, which correspond to curves M, S, and SM,
respectively, for the CSTR, one extra multiplicity curve M2 appears to-
gether with three more Hopf bifurcation curves: S3, S:L and S4. Curve
M2 bounds the region where two additional steady states occur- (the fourth
and fifth) and curves S3 and S3 envelope the region where two more Hopf
bifurcation points appear. Curve S4 represents the locus where two Hopf
bifurcation points coalesce. On the whole 14 regions characterized by
qualitatively different bifurcation diagrams of outlet conversion versus Da
are found. The first six of these are the same as those of the CSTR, while
the others are quite different, as is evident from the sketches shown in
the side of Fig. 20. It is noticeable that, besides the occurrence of five
steady states in regions VII and XIII, the bifurcation diagram exhibits
three Hopf bifurcation points. As a consequence, quite different phase
portraits from any of those found for the CSTR (see Fig. 18) are
generated.
A similar analysis has been performed taking the Lewis number as the
bifurcation parameter, in the same manner as Ray and Hastings ( 1980) did
for the CSTR. This leads to the discovery of more exotic bifurcation
diagrams, the most peculiar being perhaps those shown in Fig. 21, which
include for a very small Da range (on the right of the lower Hopf bifurca-
tion point) the possibility of having five unstable steady states surrounded
by a stable limit cycle. More interesting on practical grounds are the re-
ported critical values of the Lewis number (i.e., the Le value above which
no oscillations are possible). Jensen and Ray (1982) have shown that this
value is less than 1 for any Pem = Peh > 14, which indicates that even in
homogeneous reactors (Le ~ 1) oscillations can occur only in very short
reactors. Oscillations in a packed bed, where the Lewis number is of the
order of few hundreds, are then quite unlikely, at least as far as the
phenomena described by the pseudohomogeneou s axial dispersion model
with a simple reaction rate expression are concerned.
Reactor Steady-State Multiplicity /Stability 1025
I .0 ,------r------,-•=.=.-::..-::._-:::::
•::::::::::::: ·:. ·. 6
...
4
·······
X
0.5 CD
t 2
o~--~--~--~ 0
0.14 0.15 0.16 0.17 0.14 0.15 0.16 0.17
Do Do
(a) (b)
FIGURE 21 Bifurcation diagrams (a) x versus Da, and (b) 0 versus Da
characteristic of region XIV (parameter values: Le = 0. 8, 0 = 3, B = 15,
other parameters as in Fig. 20).
COMPLEX TRANSIENTS IN CSTRs
As we have already observed from the steady- state multiplicity point of
view, the complexity of behavior of a CSTR increases significantly for even
a slight increase in the reacting system complexity. This was observed
earlier in the cases of an irreversible first-order reaction in two CSTRs in
series, and of two such reactions occurring in series in a CSTR. The aim
of this section is to indicate some of the exotic dynamic behavior which can
occur in these systems. For completeness, a few comments on the stability
character of the multiple steady states discussed earlier will be made first.
First-Order Reaction in a Series of Two CSTRs
We have already mentioned that a series of N CSTRs, with a first-order
irreversible reaction, can exhibit at most ( 2N +1 - 1) steady states, of
which no more than (N + 1) can be stable. The stability of two reactors
in series has been examined by Kubicek et al. (1980) and Svoronos et al.
( 1982), by applying Liapunov's first method to the transient mass and
energy balances, which can be readily derived from Eqs. (30) and (31).
Since the Jacobian of this system is equal to the product of the Jacobian
of the two single reactors, it follows that a necessary and sufficient condi-
tion for stability is that each of the reactors is itself stable. This conclu-
sion does not hold if a recycle stream is present. Through a detailed
analysis of the eigenvalues of these two Jacobians, Svoronos et al. (1982)
determined the stability character of each possible steady state, as shown
in Fig. 8.
Other novel features have been shown by Kubicek et al. (1980), who
explored different regions of the parameter space and took the reactor
residence time as a bifurcation parameter. As an example, two bifurcation
diagrams (outlet temperature versus residence time) obtained for different
1
set of heat transfer parameter values o and o are shown in Fig. 22.2
The first one (Fig. 22a) exhibits three ignition and three extinction points-
according to the occurrence of five steady states. In the second one
1026 Morbidelli, Varma, and Aris
(a ) ( b)
8? = 8 ~ =0.5 8?=1;8f=2
8 8
I
6 \ 6
\
4 \ 4
"'
Ct) \ "'
Ct)
\ 2
2 \
0 0
(
-2 -2
-4 -4
0.01 01 0.01 0.1
---- T
---- T
FIGURE 22 Characteristic bifurcation diagram (outlet temperature versus
residence time) for two CSTRs in series with a first-order reaction (param-
1 2
eter values: Da = Da = 0.5, y = 20, B = 10, vcl = vc = 0.75).
2
(Fig. 22b) two isolas are present, leading to a total of three· separate
curves on the same bifurcation diagram. Since the smaller isola lies en-
tirely in the shadow of the larger one, it can never be reached from any
of the other two curves simply by changing the reactor residence time.
Svoronos et al. ( 1982) have applied Hopf- Friedrichs bifurcation theory
to this model and reported an analytical relationship for the direction and
stability of the bifurcating periodic orbits. In the case of a single reactor,
this reduces to the same equation [Eq. ( 79)] as that developed by Poore
( 1973) . It has been found that while in this case also, periodic solutions
cannot occur in the adiabatic system, the dynamic behavior is in general
more complex than in a single CSTR. For example, it is possible that
self-sustained oscillations in the first reactor may force oscillations in the
second, which, per se, would have been at a stable steady state.
Two Consecutive Irreversible First-Order Reactions
in a CSTR
The multiplicity pattern of this reacting system was discussed earlier.
Since stability analysis of these steady states can be performed with the
usual methods, we shall concentrate immediately on the dynamic behavior.
First note that the transient model is given by three nonlinear ODEs which
can readily be obtained from the steady-state mass and energy balances
( 40) by adding on the right-hand sides the accumulation terms for the
mass of A, mass of B, and energy, respectively. We have already dis-
cussed the extension of bifurcation theory from two to N dimensions, in
the context of its application to a system of N ODEs arising from the dis-
cretization of one or more parabolic PDEs. From this point of view, the
three-dimensio nal system now under examination can be regarded as the
simplest case (i.e. , N = 3).
Reactor Steady-State Multiplicity /Stability 1027
Hlavac!ek et al. ( 1972) first reported oscillations in a CSTR with two
exothermic first-order reactions, by direct integration of the transient
model. Halbe and Poore ( 1981) applied Hopf-Friedrichs bifurcation theory
and performed an extensive search in the parameter space to identify all
possible shapes of the first reactant conversion versus Damkobler number
bifurcation diagram. Ten qualitatively different bifurcation diagrams were
found, which included situations where up to five steady states and four
Hopf bifurcation points were present simultaneously. Relationships were
also reported for the a priori definition of the direction and stability of
the bifurcating periodic orbits.
The determination of the Hopf bifurcation points is only the first step
toward defining the dynamic behavior of this system, whose detailed under-
standing requires a detailed analysis of each periodic branch. This involves
an identification of the structure of the system dynamics as the bifurcation
parameter changes away from the Hopf bifurcation point. Analysis of this
type usually requires tedious integration of the transient model equations.
Doedel and Heinemann (1983) have applied a continuation method for the
calculation of the entire branch of periodic solutions, both stable and un -
stable. This method is based on a transformation of the original initial
value problem into a boundary value problem, where the period is taken
as unknown and correspondingly the periodicity condition is added. The
final equations are then discretized using orthogonal collocation, and the
resulting system of nonlinear algebraic equations is solved through Newton's
method. This procedure has been implemented by Doedel (1981) on a com-
puter code which also provides the steady-state solution branches using
Keller's (1977) arc-length method for avoiding singularity problems in the
Jacobian at the static bifurcation point, as well as the Hopf bifurcation
points and the bifurcating periodic solution, using the usual perturbation
techniques. This appears to be quite a useful tool for the complete study
of the dynamics of a given system, since it gives the entire bifurcation
diagram (i.e., both steady state and periodic solution branches, both
stable and unstable). The stability character of periodic solutions is de-
termined through the corresponding Floquet multipliers.
Using this program, Doedel and Heinemann (1983) have completed the
10 bifurcation diagrams previously reported by Halbe and Poore ( 1981) by
computing the entire periodic solution branches. One of the most peculiar
bifurcation diagrams so obtained is sketched in Fig. 23a, where four Hopf
bifurcation points occur: in all of them bifurcation occurs to the left; the
first and third are unstable, while the second and fourth are stable. Now,
starting at large Da and decreasing it, the system undergoes a soft bifurca-
tion into a periodic stable orbit and follows this branch until it becomes
unstable. Here a hard bifurcation occurs to another periodic solution,
with smaller oscillations, and eventually the system reaches the lowest
stable steady state through one more hard bifurcation. It may be noted
that in this diagram the classic S-shaped multiplicity pattern is reproduced
with periodic instead of steady-state solutions.
Another interesting and peculiar bifurcation diagram is shown in Fig.
23b. Here the periodic solution branches emanating from the third and
fourth Hopf bifurcation points are not connected, but terminate at an
infinite-period bifurcation point (indicated by the symbol +). Note that
due to the stability character of these two branches and the relative posi-
tion of the respective termination points, there is always a stable steady
state or periodic solution available for the system for any Damk6bler number
value.
1028 Morbidelli, Varma, and Aris
..
(o)
.......
,,,,
....,. ✓•✓ • • •
.... •·00700
X •• I
.. . ,,,,,,
•0 0
00 ••
/'
;0 /
-Do
( b)
/ ---- --:.
l
' .... .:
/~
+•·,
X
...
..
//
•oo /
---Do
FIGURE 23 Qualitative sketches of two bifurcation diagrams (outlet con-
version of the first reactant versus Damkobler number) characteristic of a
CSTR with two consecutive exothermic reactions.
The detailed analysis of periodic solutions does not exhaust all possible
features of the dynamics of the system under examination, because it can
also exhibit nonperiodic solutions (i.e., chaotic behavior). This peculiar
behavior, which according to Poincare-Bendixson theorem cannot occur in
a two-dimensional system (cf. a CSTR with one reaction), is instead quite
common in models of larger dimensionality, just as periodic oscillations are
common in two-dimensional systems. Kahlert et al. (1981) found chaos in
a CSTR with two consecutive reactions: the first exothermic and the
second endothermic. The direct integration of the transient model equa-
tion leads, for a certain set of parameters, to the trajectory in the phase
space shown in Fig. 24. The presence of a well-defined attraction region,
shaped as a folded-over rubber strip, is an indication of the chaotic be-
havior of the system.
The way the system approaches this situation is through a typical
Feigenbaum ( 1979) cascade of periodic solution bifurcations. In particular,
with reference to Fig. 25 and for the parameter values reported in the
caption, it is seen that the system admits two Hopf bifurcation points,
both bifurcating to the right: the first stable and the second unstable.
The periodic solution branch can be constructed through subsequent
Reactor Steady-State Multiplicity /Stability 1029
FIGURE 24 Shape of the attraction region in the chaotic regime in the
case of one exo and one endothermic reaction (parameter values: y = 00
0c = 0, v = 0.5, et= -0.426, \ = 1, Da = 0.26, B = 57.77, 13 = 7.995).
+ +
'-
e
'-
'-
'-,
8*
6.9408 , +82
---o
7.74975
__/'/l
7 .94305
7 95605
7.96205 _J
7.96485
FIGURE 25 Bifurcation diagram: outlet conversion of the first reactant
versus heat transfer parameter, other parameters as in Fig. 24.
1030 Morbidelli, Varma, and Aris
numerical integrations starting from the left Hopf bifurcation point and in-
creasing the value of o . It is found that by increasing o the period of
the stable oscillations changes continuously up to a critical o value where
suddenly a doubling in the oscillation period occurs. In other words, the
periodic orbit becomes unstable and simultaneously a new one, stable and
with doubled period, appears. This new type of bifurcation, which is
often referred to as Poincare bifurcation, occurs again and again at suc-
cessively closer o intervals, up to a new critical o value where chaotic
behavior begins. For a particularly simple one-dimensional case, Feigen-
baum has shown that the o values at which period doubling occurs tend
to approach a convergent geometric series, such that the ratio
8. -
1
8.
1-
l
p := ( 107)
0.l+ l - o.1
is constant and equal to the universal value 4. 6642016.
Chemburkar et al. (in press) have further investigated this system
by analyzing in detail the periodic orbits that branch off from the hard
Hopf bifurcation point o * (all the numerical values reported here are taken
from this last source). The same type of bifurcation pattern has also been
found in this region, again ending in an infinite period termination point,
as qualitatively sketched in Fig. 25. By plotting the number of peaks per
period (which is proportional to the oscillation period) as a function of the
bifurcation parameter, as shown in Fig. 26, it clearly appears that there
exists a window of o values where the system exhibits chaotic behavior.
It should be mentioned that the way this system approaches the chaotic
region is qualitatively similar to that described by Feigenbaum (1979), but
the geometric series of the bifurcation o values is not perfectly reproduced
(at least after the few doublings investigated), and the computed values of
the ratio p [Eq. (107)] are somewhat smaller than the natural Feigenbaum's
constant (ranging from 3 to 3. 5).
"O
0
4
Qi
o_
~
(l)
Q.
8
(/)
~
0
(l)
o_ 16
32
78 7.9 8.0 8.1
3
FIGURE 26 Window of chaotic behavior.
Reactor Steady-State Multiplicity /Stability 1031
Similar behavior has been found by Jorgensen and Aris ( 1983), who
studied the same reacting system, but considering two exothermic reactions.
In this case some more complex dynamic behavior has been identified. A
useful tool for enlightening the bifurcation pattern of the system is offered
by Floquet multipliers. Let us define §_ as the three-dimensional vector aj'
periodic solutions of the transient model characterized by a period value T.
Its stability can be determined by considering the solution of the perturba-
tion problem
d_g
(108)
dt
with the initial condition o = I , the identity matrix, where Q is a 3 x 3 matrix
and J is the Jacobian of the o=riginal system evaluated along the periodic solu-
tion(:. Introducing now the eigenvalues µ of the matrix g, it can be shown
that one of these is equal to unity (this gives a useful check for the accuracy
of the adopted numerical integration technique) and the system is asymptot-
ically stable if and only if all the other eigenvalues are such that
( 109)
In the bifurcation study of periodic solutions it is then quite convenient
also to compute such eigenvalues-the so-called Floquet multipliers. In
the system under examination the doubling of a periodic solution cor-
responds to the situation where one of the multipliers crosses the unit
circle in the complex plane at -1, and then immediately reappears inside
the circle (i.e. , the orbit becomes unstable and a new one stable and with
double period emerges).
Some of the results obtained by Jorgensen and Aris ( 1983) are shown
in Fig. 27, where the heat transfer parameter o is used as a bifurcation
parameter. The various types of dynamic regimes have been indicated by
a capital letter. Regime A corresponds to the case where one unstable
steady state is present together with a stable limit cycle. Regimes B and
C correspond to the case where doubling of the oscillation period occurs
(B) up to the emergence of a chaotic region ( C) . All these features are
quite similar to those described above for the case of one endothermic and
one exothermic reaction. Regimes D, E, and F correspond to interlude
situations separating the occurrence of a chaotic behavior. Even though
some bifurcations of periodic orbits, involving doubling of the period, have
been detected in these regimes, the connection with the Feigenbaum "route
to chaos" appears to be quite weak. Finally, regime G is characterized
by quite complex behavior, where periodic solutions and chaos seem to co-
exist. It should be observed that at this point the numerical accuracy of
the integration technique becomes critical, and only some significant ad-
vances in the theoretical insight can lead to a better understanding of
system behavior. For illustrative purposes, some of the periodic solutions
characteristic of regime B and the attraction region characterizing regime
C are shown in Figs. 28 and 29, respectively.
In conclusion, the dynamic behavior of a CSTR approaching chaos is
not yet well defined, and more research in this area is needed. For
example, considering a different kinetic scheme, constituted by two in-
dependent first-order exothermic reactions:
A+ B C + D
1032 Morbidelli, Varma, and Aris
A A
7.290380
7288 □
FIGURE 27 Bifurcation pattern, with o as a bifurcation parameter, in
the case of two exothermic reactions (parameter values: y == 00 , 0 c == 0,
v == 0. 01, a== 1, ;\ == 1, Da == 0.55, B == 17. 5).
Lynch et al. (1982) have defined the occurrence of chaos, which is reached
by the system through a way different from that discussed so far. More-
over, a useful numerical technique for the identification of the occurrence
of chaos, based on the autocorrelation analysis, has been applied in this
work.
e e
e
(a ) ( b)
( C)
FIGURE 28 Sequence of trajectories in the phase space showing the first
two doubling of the periodic orbit in regime B. (a) o == 6. 94938; (b)
o == 7.28294; (c) o == 7.28665 (other parameters as in Fig. 27).
Reactor Steady-State Multiplicity /Stability 1033
UI
FIGURE 29 Chaotic trajector in regime C; cS = 7. 286670 (other parameters
as in Fig. 27).
PARAMETRIC SENSITIVITY AND RUNAWAY IN
TUBULAR REACTORS
A quite common problem in mathematical modeling, as well as in the experi-
mental analysis of any real-life device, is to establish the effect of each
input parameter on any of the model outputs. Quite often there exists
regions in the parameter space where small variations of the input param-
eters cause large variations of the outputs; these are usually called regions
of parametric sensitivity. This concept was first introduced in the study
of tubular reactors by Bilous and Amundson ( 1956). When a sufficiently
exothermic reaction occurs within nonadiabatic tubular reactors, the
temperature profile at steady state exhibits a maximum, usually called a
hot spot. In the region of parametric sensitivity the magnitude of the hot
spot can undergo very large increases even for very small variations of
one or more of the input parameters; this phenomenon is usually referred
to as temperature runaway. This is illustrated qualitatively in Fig. 30,
where for a particular example (see van Welsenaere and Froment, 1970)
the temperature profile variation as a function of equal changes of the in-
let temperature is shown before and after the runaway boundary.
The prevention of excessive temperature peaks along the reactor is
very important in practical applications not only for safety reasons but also
1034 Morbidelli, Varma, and Aris
800
:,,:
~ To = Tc
I-
LL.I
a:
:::>
I-
<[
a:
LL.I
0.
::;;
LL.I 700
I-
0
:::>
...J
l.L
600'----'----~---~--~
0 0.5 1.0
REACTOR AXIAL LENGTH, Z ( m)
FIGURE 30 Examples of temperature profiles along the reactor axis for
various inlet temperature values inside and outside the runaway region.
because these may adversely affect the conversion of exothermic equilibrium
reactions, selectivity of the process, and in the case of catalytic reactors,
the catalyst activity and durability. Therefore, most of the research in
this area has been devoted to providing graphical or analytical representa-
tions of the region of runaway, so that such behavior could be avoided
immediately at the earlier stage of reaction design. To attain such a repre-
sentation, two problems need to be solved:
1. Formulation of an a priori criterion of parametric sensitivity, which
has to be based on intrinsic reactor behavior with no reference to
any specific situation
2. Implementation of the criterion to produce a simple representation,
either graphical or analytical, of the region of runaway
Most contributions in the literature have examined the case of a plug-flow
reactor with an irreversible nth-order reaction, whose mathematical model
is given by
du
ds = - Dau n exp ( 1 +00 /y ) (110)
d0 n
ds = BDau exp(l /0 /y) - 00 (111)
with IC
u = uo 0 = 00 at s =0 (112)
where in the definition of the quantities 0, Da, y, and B the cooling
temperature Tc has been taken as reference temperature Tr (i.e., 0 =
(T - T )E/RT2, and so on].
C C
Reactor Steady-State Multiplicity /Stability 1035
The first a priori criterion for runaway was proposed by Barkelew
( 1959) as a result of an empirical analysis of a large number of temperature
profiles along the reactor axis. Dente and Collina ( 1964) defined as run-
away the occurrence of a region along the reactor where the second deriva-
tive of temperature with respect to distance is positive. This is physically
sould since it identifies runaway with an "acceleration" in the temperature-
reactor axis plane. According to this criterion, regions in the parameter
space where runaway occurs can be identified, and the boundaries of this
are given by the locus of parameter values where the third derivative of
temperature versus reactor axis is zero. Van Welsenaere and Froment
( 1970) have adopted this same definition of runaway. They produced simple
explicit analytical expressions for the boundaries of the runaway region
by introducing a second criterion, based on the occurrence of a maximum
in the locus of the maxima in the temperature-conversion plane, which
according to them is substantially equivalent to the previous criterion.
Some additional insight into this problem is given by studies reported
earlier in the context of thermal explosion theory. Hlavacek et al. (1969)
pointed out that the lumped mass and heat balances in a symmetrically
heated reactive material are, in fact, identical to Eqs. (110) and (111),
where the reactor length coordinate is replaced by time. The earlier
criteria for ignition or explosion were based on the occurrence of a region
with positive second-order derivative in the temperature versus time pro-
file (see Semenov, 1928), which coincides with the criterion proposed by
Dente and Collina (1964) in the reactor context. Subsequently, Adler
and Enig ( 1964) proposed a somewhat more intrinsic definition of ignition
or explosion based again on the occurrence of a positive second-order
derivative but in the temperature-conversion (instead of temperature-time)
plane. It was also shown that runaway in the temperature-conversion
plane implies runaway in the temperature-time plane, but not vice versa.
The relevant equation, which can easily be derived from Eqs. (110) and
( 112) by introducing the conversion x = 1 - u, is simply given by
d0 = B--_i_ 0 (113)
dx Da n
(1 - x)
with IC
0 = 0 at X = 0 (114)
0
This criterion has been used in the context of tubular reactors by
Morbidelli and Varma (1982), who considered reactions of any positive order
with no limitation on the activation energy or inlet temperature values. The
runaway region was explored using the isocline method, originally intro-
duced by Chambre (1956), which provides quite an efficient procedure for
calculating the region boundaries, avoiding tedious trial and error.
The runaway region in the parameter plane B versus iS /Da (i.e., heat
of reaction versus heat transfer parameter) is shown in Figs. 31 and 32
for various values of the reaction order, activation energy, and inlet
temperature. For parameter values above the line (i.e., large values of
the heat of reaction parameter B and low values of the heat transfer param-
eter iS /Da), the reactor undergoes runaway, while it does not runaway for
parameter values below the line. As expected on physical grounds, it is
....
0
w
0.,
CD
0:
w
I-
~ 401 I I I ~401 I I I 1401 I i I I
[? y= 20,80 =0 (a~ y=I00,80 =0 (b) y=oo,80 =0 ( C)
i:i: 30
z
0
t== 20
<.)
<l'.
w
a: 10
LL
0
0 ~-~~-~-~----'
~ 10 20 30 40 50 10 20 30 40 50 10 20 30 40
w
I
---- HEAT TRANSFER PARAMETER,{ 8100) :e::
0
ti'
FIGURE 31 Effect of the reaction order on the runaway region for three values of 15:
Cll
the activation energy; the runaway region is above the curve. .....
<p
~p
p
;:l
P..
:i,.
"S
s;·
::-,
~
p
....QC
-s
CJ:l
....
~
p
A.
CD
'<
I
cc ....CJ:l
w ....p
1- ~
w
:::;; :s::
<t (a l 6.1 (bl 7.5~ l(c) 10.st 80 =-3
cc s
<t m (Il .....
40~ (Il 40 40
a. ,t;·
z f 5.1 t 6.5
0 §:
301- ___<: c816a J 30 ....
I- '<
(.) y=20,n=0.5 y=20,n = I
<t ~ 3 0 y= 20." = 2
I .......
w CJ:l
20~ -I 20 ,_ 20
cc 0
LL
0
1-
....~
'<
<t
w
I 0~-~-~--~-~-~ o~-~-~-~-~~ o~-~~~~-~--
10 20 30 40 10 20 30 40 10 20 30 40
HEAT TRANSFER PARAMETER,(8/0o)
FIGURE 32 Effect of the inlet temperature on the runaway region for three
reaction orders; the runaway region is above the curve.
1--
0
c...,
-.:i
1038 Morbidelli, Varma, and Aris
also apparent that runaway is more likely for larger values of the activa-
tion energy y and the inlet temperature ei and for smaller reaction order
n.
A detailed comparison between the runaway region predicted by the
latter criterion and those predicted by the earlier criteria proposed by
Barkelew ( 1959) , Dente and Collina ( 1964) , and van Welsenaere and
Froment (1970) has been reported by Morbidelli and Varma (1985).
It was found that in general the criterion based on the temperature-
conversion plane leads to the less conservative results, and that the dis-
crepancy becomes more significant for low values of the activation energy
y and the heat transfer parameter o/Da. This is apparent from Fig. 33,
where the runaway regions calculated by van Welsenaere and Froment
(1970) (dashed line) and Morbidelli and Varma (1982) (solid line) are com-
pared.
On the other hand, this criterion provides estimates of the nonrun-
away region which in fact correspond to safe operating condition for the
reactor. For example, from inspection of the temperature versus conver-
sion profiles shown in Fig. 34 for increasing values of the heat of reaction
parameter, it appears that the critical value Be = 14. 31 indeed represents
a reasonable boundary between safe and runaway operating conditions.
Note that the critical value of Be is defined as the boundary between run-
away and no-runaway, and thus corresponds to the situation where the
third as well as the second derivative of temperature with respect to con -
version vanish. In conclusion, this criterion can be recommended for de-
signing tubular reactors operating outside the runaway region, without
requiring serious limitations on the operating conditions.
50
ID n = I ; 80 = 0
er: 40
w
f-
w
:;;;;
<(
er:
<( 30
a..
z
0
f-
u 20
<(
w
er:
LL
0
f-
10
<(
w
I
HEAT TRANSFER PARAMETER,( 8/Do)
FIGURE 33 Comparison between the runaway region calculated according
to the criterion of Morbidelli and Varma (1982) (solid line), and the one
by van Welsenaere and Froment ( 1970) (dashed line).
Reactor Steady-State Multiplicity /Stability 1039
Cl)
12 12
B = 16 7
w
a: 10 10
:::)
I-
<(
a:
w 8 8
Q.
::i!:
w
I- Cl)
6 6
(/)
(/)
w
_J
z 4 4
2
(/)
z
w 2 2
::i!:
0
0 0
0.2 0.4 0.6 0.8 0.99
C0NVERSI0N,X ~x
FIGURE 34 Temperature versus conversion profiles inside and outside
the runaway region (parameter values: n = 1, y = 20, o /Da = 20, 0 o =
0).
Following a procedure adopted by Gray and Lee ( 1965) and Hlavacek
et al. ( 1969), Morbidelli and Varma (1985) have proposed the following
analytic representation of the runaway region boundaries:
;a a AeB[l -(8:)"'J (115)
where
"= 8.7
°· 6
(116)
7.66 + n
is an empirical factor introduced to improve accuracy. B~ represents the
critical B value in the case of an adiabatic reactor (i.e., o = 0). Using
the isocline method, the following explicit expression can be derived:
n0(1 + 0/y) 2
B0 = 0 - 0 (117)
C 0
o - -
e/y)
2
-
-
e
where 0 is the unique solution of the equation
(n - 1)0 4 + 2y(n - 1)(2 - y)0 3 + [2(n - 1)(3 - y) - y(y - 2)Jy2e2
+ 2[2(n - 1) + y]y 3- 4
0 + (n -- l)y = 0 (118)
1040 Morbidelli, Varma, and Aris
in the internal 0 E [0_,0+1, where 0± = [(y - 2) ± /y(y - 4)]y/2. To
0
facilitate the use of Eq. (115), the values of B 0 , calculated from Eqs.
( 117) and ( 118) as a function of y, are shown in Fig. 35 for various re-
action orders.
In Fig. 36 a comparison between the runaway region predicted by Eq.
( 115) and that numerically calculated by Morbidelli and Varma ( 1982) is
shown. The agreement seems to be quite satisfactorly for any value of the
reaction order and the activation energy. It should be mentioned that less
satisfactory results are obtained for inlet temperature values 0 0 significantly
different from zero. However, since this situation is quite unlikely in in-
dustrial applications, this point has not been pursued further.
Several attempts have been made in the literature to extend this sen-
sitivity analysis to more complex models to account for other phenomena
which may also be of importance in establishing runaway operating condi-
tions of industrial reactors. In particular, Agnew and Potter ( 1966) have
extended Barkelew's ( 1959) criterion to account for heat and mass axial
as well as radial dispersion; Soria Lopez et al. ( 1981) extended van
Welsenaere and Froment (1970) criterion to the case where the cooling fluid
temperature changes along the reactor; finally, the effect of side reactions
on the runaway region has been investigated by Dente et al. (1966a) in
the case of consecutive reactions and by Dente et al. (1966b) and
Westerterp and Ptasinski ( 1984) in the case of parallel reactions. It should
be mentioned that runaway behavior is most likely to occur in catalytic re-
actors, where the intrinsic heterogeneous nature of the reacting system
can play a very important role. However, the effect of inter· and intrapar-
ticle mass and heat transfer resistances on runaway has not received much
attention so far in the literature. McGreavy and Adderley (1973) have
analyzed the effect of transport limitations on a single catalyst particle;
20 0 0 =0
16
12
00
OJ
n =3
8
_ 0-o 5
10 50 100 500 1000 5000
-.. DIMENSIONLESS ACTIVATION ENERGY, y
0
FIGURE 35 Values of the adiabatic critical parameter B0 from Eq. (117)
as a function of y for various orders of reaction and 0 = O.
0
Reactor Steady-State Multiplicity !Stability 1041
ID
(/)
oc
w 40-----~--~--~--~ 40--------~--~--~
( b ) y =oo ; 00 =0
1-
w
::i:
<(
oc 30
<(
a.
z
0
20
~
(..)
<(
w
oc
u. 10
0
I-
o~-~~-~--~--~--~
<(
w
J:
0 10 20 30 40 50
t - HEAT TRANSFER PARAMETER, ( 8100)
FIGURE 36 Comparison of the runaway region predicted by Eq. (115)
(dotted line) and the exact one calculated by Morbidelli and Varma (1982)
( solid line) •
Rajadhyaksha et al. (1975) have extended van Welsenaere and Froment
( 1970) criterion to account for transport limitations in four particular
regimes of reactor operation; finally, the case of multitubular reactors has
been investigated by McGreavy and Dunobbin ( 1984).
APPENDIX: SINGULARITY THEORY
Singularity theory provides a systematic way of tackling the multiplicity
question. It is concerned with three basic ideas about maps or functions
which bear directly on the search for the pattern of solutions of a non-
linear equation. The first of these is stability and we say, that a map is
stable if small perturbations do not really change its character. Thus the
graph of u = x2 is merely shifted up to down by a perturbation u = x2 + a.;
it is distorted by the perturbation u = x2 + 2Sx, but by writing this as
u = (x + S)2 - s2 we see that its qualitative shape is in no way changed.
On the other hand, u = x3 is a monotonic curve which a perturbation
u = x3 - a.x will change into a curve with a maximum and minimum (i.e. ,
qualitatively different) if a. > 0, however small it may be. Singularity
theory provides a way of determining when a map is stable. For example,
the two dimensional mapping u = x3 - xy, v = y is stable, for its cusp-
like character is unchanged by small perturbations such as u = x3 +
3a.x2 - xy, v = y + S, and so on. Now if y =a.is fixed, u = x3 - xa,
and for a.= 0, u = x3. So f(x) = x3 is embedded in F(x,a.) = x3 - a.x
or F is an unfolding of f. The second great topic of singularity theory
is the question of how to unfold an unstable map such as f(x) into a
stable map such as F(x,a.) using the least number of parameters. For exam-
ple, x3 - a. will not do because it is still unstable and x3 + 3f3x2 + a.x is un-
economical, for it may be written as (x + S)3 + (a. - 3S)(x + S) - s3 + 3S2 -
a.S and S is otiose. The third question is one of genericity , that is, of
whether there are enough stable maps to approximate an arbitrary map.
1042 Morbidelli, Varma, and Aris
For multiplicity problems we need a systematic way of finding the
boundaries of parameter space across which the number of roots of a non-
linear equation changes. These are sometimes called catastrophe surfaces
or sets after Rene Thom, a pioneer of singularity theory, classified the
elementary catastrophes and gave their canonical unfoldings. In the litera-
ture there are several terms that it will be helpful to explain first. Sup-
pose that A is a subset of Rn, the Euclidean space of n dimensions, U
an open set in Rn, and V is any set; then if f is a function f: A nu + V
we denote the pair (U ,f) by F. f may be specified further as continuous ,
as differentiable, or in whatever way we wish, but two elements of F
[e.g., (U1,f1) and (U2,f 2)] will be considered equivalent if in some sub-
some subset of U1n U2 they define the same map (i.e., f1 I u = f2 I u) for
some UE::: U1n U2. The equivalence class defined by this relation is called
a germ and this is clearly a way of making precise the fact that we are
going to concentrate on local properties and so do not need to consider
the function outside the immediate neighborhood of a particular point.
Any smooth function can be expanded in a formal power series about a
particular point (say, the origin) and this is called its Taylor series:
r=0
(By formal we mean that we are not saying anything about th~ convergence
of the series. ) If this series is truncated at the kth term we have the
k jet of the function
k
jk f(x) = L
r=0
which is a polynomial that behaves like f "to order k" in the neighborhood
of the origin. Clearly, this may be a local approximation at best and may
not "fit" very well. For example, jl sin x = x quickly diverges from sin x
and it takes j9 to give a decent approximation over the interval (0,1r), or
more generally, j8n+l to approximate over (0,n1r) after which the k jet
goes off to ±00 • [It should be remembered that the formal Taylor series
may not always converge to the function, as, for example, with f(x) =
0,x < 0, f(x) = exp (-1/x), x > 0, whose formal Taylor series is
identically zero.] If the k jet of a function vanishes, it is said to be of
order (k + 1) at the origin and the function f - jkf, which has been
deliberately made of order (k + 1), is sometimes called its Tay!.
The term contact equivalent also occurs frequently and is a precise
way of saying that two functions are locally of essentially the "same shape,"
so that we can learn a lot about the one by studying the other. In particu-
lar, we can rely on a canonical form to give us a correct picture. Formally,
F(x,)..) and G(y,µ) are contact equivalent if there is a smooth and in-
vertible change of coordinates x .>- y given by y = Y(x, )..) , x = X(y, µ), a
reparameterization µ= M(A),).. = L(µ), and a positive scale change S(x,)..)
or T(y,µ) such that
Reactor Steady-State Multiplicity /Stability 1043
G(y,µ) = T(y,µ)F(X(y,µ),L(µ))
or
F(x,l,.) = S(x,l,.)G(Y(x,l,.),M(l,.))
For example, x2 ± ;>,.x is contact equivalent to y2 - µ 2, for we have only
to put X = y ± µ ,L = -2µ, T = 1 to make the transformation.
Golubitsky [in two striking papers, one with Keyfitz ( 1980) and one
with Schaeffer ( 1979)] has given a very useful test for the contact equiv-
alence of an equation F(x,l,.) to one of a number of canonical forms, and
his method has been fruitfully applied by Balakotaiah and Luss (1981,
1982a,b, 1983, 1984) and others. It will be best explained by taking a
concrete example. We will use the autocatalytic scheme that Gray and
Scott ( 1983, 1984) have shown to have many of the features of the single
exothermic reaction without the algebraic complexity that the Arrhenius
temperature dependence induces.
We consider the reactions A + 2B -+ 3B , B -+ C taking place in a
stirred tank and so, with obvious notation, have
With a view to using the residence time 8 as a parameter, we shall want
to vary we set
Then
O'.X = 1 - X - a.f3xy 2
a.y = y - y + a.f3xy2 - a.y
The steady state is obtained when x = y = 0. From x = O we have x =
( 1 + a.f3y2)-1 and substituting this in y = O gives the cubic
F(y; a., f3 ,y) = a.(1 + a.) Sy 3 - a.f3(1 + y)y2 + (1 + a.)y - y = 0
This appears to be the neatest form, although cubics can also be found
for x and z = 1 - x = (1 + a.)y.
Thus the steady states will be the roots of this cubic equation F = O.
Since F( 0) ~ 0 and F -+ + 00 as y -+ 00 , there is always one real root but
there may also be more than one. We shall have two steady states when
there is a double root (i.e., F = Fy = 0), and this represents the
1044 Morbidelli, Varma, and Aris
transition between one and three. There will be a unique triplet root if
F =F =F
y yy
= O. Let us record the derivatives for future use:
F = o:(1 + o:)By3- o:B(l + y)y 2 + (1 + o:)y - Y
F
y
= 30:(1 + o:) By 2 - 2o:B(l + y)y + (1 + o:)
F
yy
= 60:(1 + o:) By - 2o:B(l + y)
F
yyy
= 60:( 1 + o:) B
2
F = (1 + 2o:) By 3 13(1 + y)y + y
0:
2 -
F
o:y = 3(1 + 2o:) By 213(1 + y)y + 1
F
0:0: = 213y 3
3
Fl3 = o:(1 + o:)y - o:(1 + y)y 2
F = -o:By 2 - 1
y
Were we to eliminate y between F = 0 and Fy = 0 we would have a com-
plicated equation between o:, 13, and y representing the surfaces in o:-13-y
space that separate regions of one steady state from regions of three.
Steady-state diagrams giving y as a function of, say, o: could be con-
structed by passing through this space on a line of constant 13 and y.
However, Golubitsky' s method calls for going to the highest-order
singularity we can find. Clearly, we could have F = Fy = Fyy = 0
simultaneously and this would be a line in o:-13-y space. We cannot make
Fyyy = 0 except by putting o: or 13 = 0, and this is pointless. But it is
possible to find a point where F = Fy = Fyy = Fo: = 0, namely o: = 1, 13 =
256/27, y = 1/8, y = 3/16, and we find that although we had no right
to expect it and for reasons which will become clear later, Fo:y also vanishes
here but Fo:o: does not. These are precisely the conditions for the "winged
cusp" singularity, which Golubitsky and Keyfitz found to be the organizing
center for the stirred tank with a single exothermic reaction and this ac-
counts for the similarity of behavior noted by Gray and Scott ( 1984). The
canonical form of the winged cusp is x3 ± >,_2 and Golbuitsky's theorems
imply that there is a contact transformation that will put it in this form.
He also gives the universal unfolding as x3 + (o:2A + o:3)x + o: 1 + A2 . This
canonical form allows us to describe every possible qualitative shape of
the x- A curve. This is shown in Fig. 37, where in the center a surface
in o: 1-o: 2-0: 3 space has been drawn. It really consists of two parts: the
so-called hysteresis variety, H, which is like a trough lying on its side
and pinched into a line, OA, the 0:1 axis in the plane 0:3 = 0; and the
bifurcation surface, B which is like a breaking wave with a cusp line COD.
It is clear that O, the organizing center, is a very singular point, for the
hysteresis trough is pinched down to a cusp, while the cusp of the
Reactor Steady-State Multiplicity /Stability 1045
2 7 6 3
X
FIGURE 37 Qualitative bifurcation diagrams for a winged-cusp
singularity.
bifurcation wave passes through it. The seven regions into which these
surfaces divide the a1-ara3) space correspond to the seven types of bi-
furcation diagrams in the x- .\ plane. The hysteresis variety is the
locus of triples ( a1, a2, a3) for which the x- .\ diagram has a point of in-
flection with vertical tangent, as in the 2/7 and 6/3 diagrams at the bottom.
The bifurcation variety is the locus of ( a1, a2, a3) points for which a third
solution is just being born by the vanishing of the imaginary part of a pair
of complex roots. This is represented by the dot in the 7/6 diagram. The
point E represents a point at which both the 2/7 and the 7/6 transitions
take place at once (i.e., the dot is vertically above the point of vertical
inflection); the locus of points like E might be denoted by 2/7 /6. Notice
that diagrams with one number, such as 2, 7, or 6, belong to a three-
dimensional region of a, space; those like 2 / 7, 7 / 6 are two-dimensional sur-
faces, while those like 2/7 /6 are one-dimensional lines. The organizing
center, 0, is a point.
The strength of the theory is that it exhaustively catalogs the various
bifurcation diagrams that can arise. It is systematic and Golubitsky and
Keyfitz (1980, pp. 326-327) give a useful table of conditions for finding
1046 Morbidelli, Varma, and Aris
the various organizing centers. Its weakness is that it demands consider-
able algebraic labor in most cases, and an excessive amount if the contact
transformation that leads to the canonical form is sought.
In the case of Gray's autocatalytic reaction there are only two addition-
al parameters, for a plays the role of ;\ and this leaves only S and y to
be related to a 1, az, a 3. This implies that the system moves in a two-
dimensional subspace of a1 -az-a3 space and it could be that one or more of
the seven possible diagrams is absent. Gray and Scott (1984) give mush-
roomlike curves such as 3 in the figure, and these seem to be the most
complicated form that their system can attain, for there is an inherent
degeneracy of the hysteresis variety that does not allow one side of the
mushroom to straighten out without the other following suit. Thus there
is never the breaking wave of 4, 5, 6, or 7. An attempt has been made
to use three parameters by taking the order of the autocatalytic reaction
as a further parameter, but aside from the difficulty of regarding it as
continuous, this does not seem to avoid the degeneracy.
In contrast to the autocatalytic scheme, which has two parameters for
its partial unfolding, the stirred tank with the irreversible, first-order
reaction has a universal unfolding through the dimensionless parameters
representing the adiabatic temperature rise, coolant temperature, and heat
transfer coefficient. This is shown by Balakotaiah and Luss (1984), who
give a diagram of the isola and hysteresis varieties in the neighborhood of
the organizing center.
NOTATION
a external heat transfer area
A cross-sectional area of the tubular reactor
-1
~ matrix, ~ ;I
B dimensionless heat transfer coefficient, (-llH)yC 0 /pC T
p C
C concentration
g capacitance matrix defined by Eq. ( 73a)
C specific heat
p
D axial dispersion coefficient of mass
e
Da Damkobler number, V f(C 0 ,Tr)/qC 0 (CSTR) or Lf(C 0 ,Tr)/vC 0
(tubular reactor)
Da/T
E reaction activation energy
f reaction rate
;I Jacobian matrix defined by Eq. ( 73b)
k Arrhenius reaction rate constant
ke axial dispersion coefficient of heat
K reactant adsorption constant
L reactor length
Reactor Steady-State Multiplicity /Stability 1047
Le Lewis number, defined by Eq. (68) (CSTR) or (88) (tubular
reactor)
n reaction order
p perimeter of tubular reactor
Pe Peclet number; Peh = ;LpC /k , Pe = ;L/D
p e m e
q volumetric flow rate
r dimensionless reaction rate, f(C, T) /f(C 0 , Tr)
R universal gas constant
s dimensionless axial coordinate, z /L
t dimensionless time, qt' /V
t' time
T temperature
T reference temperature, defined by Eq. ( 4)
m
T reference temperature: Tm, T O, or Tc
r
u dimensionless concentration, C / C 0
u overall heat transfer coefficient
V dimensionless temperature, T /T
r
V average fluid velocity
V superficial velocity
s
V reactor volume
X conversion, 1 - u
z axial coordinate
z <v - 1) is
Greek Letters
l'IH2/1'1Hl
8 dimensionless heat of reaction, (-l'IH)C 0 /pCPT 0
8 dimensionless heat of reaction, (-l'IH)C 0 /pC T (1 + o)
p m
y dimensionless activation energy, E /RT
r
0 dimensionless heat transfer coefficient, Ua/qpC (CSTR) or
UPL/A;pc (tubular reactor) P
p
o /T
l'IH enthalpy change of reaction
0 dimensionless temperature, (T - T )y /T
r r
>.. E2/El
\) k2(T 0) /kl (T 0)
p density
1048 Morbidelli, Varma, and Aris
cr dimensionless inhibition parameter, KC 0
T reactor residence time, V /q(CSTR) or L/v (tubular reactor)
¢ dimensionless parameter defined by Eq. ( 34)
Subscripts
A reactant
c cooling
0 feed
ACKNOWLEDGEMENT
Massimo Morbidelli was the recipient of a NATO-CNR Fellowship (Bando
number 215.15/3) during the writing of this chapter.
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Index
Absorbance, 211 Aluminum, 923, 924
Absorbed molecules, 152 Ammonia, 214
Absorbed species, 202 decomposition, 186
Absorption/desorption rates, synthesis re actor, 389
calculations of, 700 Anaerobic reactors, 780
Absorption rate, 565 Analysis of reactors, 331
Accuracy of tracer experiments, Angle resolution, 186
86 Angular-dependent SIMS measure-
Activation energy for desorption ments, 186
from TDS, 221 Anionic polymerization, 737, 763
Adiabatic reactors, 380 Anti-Stokes raman lines, 216
Adiabatic perturbations, 1017 Aperiodic solutions, 1001
Adsorbed species on surfaces, Area specific resistance, 945, 949
207-224 Area surface, 151
Adsorbing, 123 Arrhenius number, 988
tracer, 128, 133, 143 Asymptotic stability, 1004, 1014
Adsorption, 129, 928, 939 Auger effect, 176-177
processes, 124 Auger electron spectrometer, 178
Aerobic fermentations, mass Auger electron spectroscopy (AES),
transfer in, 803 169, 176-179
Aerobic reactors, 780 applications, 179
Age distributions, 72 charging, 178
Aggregative fluidization, 452 chemical shifts, 178
Agitation depth profiling, 178
for dispersing gas into liquids, disadvantage, 179
645 electron kinetic energy, 177
speed, 597, 641 focused electron beams, 177
Agitator surface sensitivity, 177
diameter, 640 Auger spectrum, 177
types, 597 Autoacceleration, 765
Airlift Autocatalytic reaction, 120, 1046
columns, 812 Autothermal operation, 386
fermentor, design methodology, Autothermic reactions, 120
825 Available electron balance, 782
Alloys, 186, 222 Average crystallite size, 158-168
1055
1056 Index
Averaging of the steady state Brunauer, Emmett, and Teller (BET)
model, 34 Adsorption Method, 151, 153
Axial dispersion, 36, 943- 945, 947 Iotherm, 153, 156
coefficient, 581, 595, 604 Bubble-cloud, 477
gas phase, 682, 694 Bubble
liquid phase, 682, 692 coalescence, 480
solid phase, 694 columns, 547, 574, 808
Axial dispersion model, 391, 570, columns, design of, 820
973, 993 concentration, 463
approximate solutions of, 614 diameter, 483, 484, 485, 576
Axial thermal conductivity, 633 dynamics, 689
flow, 574
frequency, 471
Backscattering geometry, 197 phase, 477-478, 481
Baffles, 102, 145 rise velocity, 454, 576
Balance of a reacting system, 555 size, 457, 460, 461, 462, 471
Barrett, Joyner, and Halenda velocity, 465, 484, 488
(BJH) method, 155 volume, 463, 485
Basic models, 298 wake, 471, 490
with plug flow, 377 Bubbles, 145
Batch, 923, 924 Bulk density, 444
Batteries, 923, 924, 939, 940, Bulk-flow effects, 315
948-964 Bus, 950, 951, 954, 956, 958--964
Bed voidage, 444 Butler-Volmer equation, 930, 943
Beer-Lamber Law, 211 Butterfly point, 991
Berty reactor, 132, 144 Bypassing, 89
Bifurcation, 1005, 1021 Bypass phenomena, 128
diagram, 1009, 1024
parameter, 1005, 1023
points, 976 Calibration methods, 181
variety, 1045 Capacitance matrix, 1003
Bimetallic clusters, 191, 197 Capacity, 928, 955, 957, 964
Bimolecular second-order reaction, Carbon dioxide, 797
561 Carbon monoxide
Binary, 944, 953, 954 chemisorption, 157, 214
Binding energy, 171 desorption, 222
Biological reactors, design of, 816 hydrogen reactions, 224
Biomass energetic yield, 790 Carbon reaction, 224
Bioreactors, types of, 800- 803 Catalyst
Bipolar, 951 genesis, 197
Bismuth molybdate, 223 particles smaller than diffusion
Blow-off conditions, 390 film thickness, 701
Boiling beds, 452 pellets, reaction and diffusion on,
Boundary value problems, 18 18
Bounding, 143 poisoning, 179, 203
methods for nonlinear reactions, powders, 469
113 surfaces
Bragg's Law, 159 physical characterization, 151
Branching, in step growth physicochemical characterization
polymerization, 744 of, 151
Bright field, 163 Catalysts, 517
Bronsted acid, 214 distribution inside pellets, 207
Index 1057
[Catalysts] Columns
mixed oxide, 223 bubble, 547, 574
oxidation state of active com- cocurrent packed, 592
ponent, 174 countercurrent packed, 585
Catalytic reactors, 123 packed, 547
Catalytic wires, 1011 plate, 548, 574
Catastrophe surfaces, 1042 spray, 548
Cationic polymerization, 764 Combustion, 470
Caustic soda, 923, 924 partial, 502
Cell models, 376 Compartment models, 537
Chain growth polymerization, 742, Complex transients, 1025
752 Composition and structure of sur-
heat transfer effects, 765 faces and solids, 168-203
mass transfer effects, 765 Composition of a surface, 152
Chain stoppers, 744 Concentrated solution theory, 927,
Channel, 924, 925, 931-933 944
flow cells, 924, 925, 931-933 Concentration
Chaotic behavior, 1030 gradients, intraparticle, 384
Charge, 949, 950, 954, 955 overpotential, 929, 930
Charge transfer, 928, 940, 941 programming, 224
Charging, 173 Consecutive reaction, 139, 146,
Chemical microanalysis, 203 226, 988, 1026
Chemical shifts, 201 Conservation equations for heat and
of oxidation state, 173 mass for volume reaction and
Chemisorption particle-pellet models, 306
titration techniques, 157 Constraints
use of carbon monoxide, 157 kinetic, 516
Chlor-alkali, 923-924 process, 516
Chlorination of n-decane, 634 stoichiometric, 512
Chlorine, 923, 924 thermodynamic, 516
Churn turbulent flow , 57 4 Contact equivalent, 991, 1043
Circulation rate, 464 Contact potential, 170-171
Cloud, 456-459, 461, 476-478 Contact-time distribution, 135, 136,
Cloud-dense phase interface, 477 143
Cloud-to-interstitial phase ex- Continuous, 923, 932
change, 487 Continuous-flow stirred-tank reac-
Cluster ions, 184 tor, 973, 974, 1001
Coal, 499 Continuous phase, 143
gasification reactors, 499 Continuously stirred tank reactor
Coalescence, 459, 462, 463, 465, approximate solutions of, 621
477~ 480, 483 liquid phase, 618, 620
Cocurrent packed columns, 592 mass balances for, 572
Coke burning, 42 model, 616
Cold-flow models, 102
Collision cross section, 180 Damkohler number, 988, 997
Collocation, 19 Danckwerts, 63
hyperbolic, 22 boundary conditions, 1014, 1018
one-point, 22 Dark field, 163
spine, 20 Dead end polymerization, 757,
Column height calculation procedure, 770
719 Debye length, 928
1058 Index
Definitions of the residence-time [Diffusion]
distribution age, and future surface, 247
lifetime distribution, 64 in zeolites, 249
Degree of reductance, 782 Diffusional resistances, 132
dehydrochlorination, 637 Diffusivity, 554
Dehydrodesulfurization, 207 effective, 412
Denbigh's rule, 771 in liquids, 553
Dense phase, 477, 481, 488 variations, due to structural
Dense-phase catalytic fluid bed, changes in pellet, 320
145 Dilute, 943
Dense-phase gas, 483 solutions, 927
Density function, 64 systems, 926, 927, 942, 943
Depth profiling, 184 Dimensionless material fluxes, 570
Derivatives, 139 Discharging, 949, 950, 953-- 958,
Design, 923, 925, 926, 932, 935, 936, 961, 964
944, 948, 951, 958, 959, 963, Dispersion, 375, 943- 945, 947
964 models, 334
of heterogeneous reactors, 141 Dispersive versus Fourier transform
of reactor internals, 102 IR, 212
Desorption Distillation columns with chemical
of carbon monoxide, 222 reactions , 636
of hydrogen, 222 Distribution
Detachment, 459 of active catalyst inside pellets,
Determination of rate controlling 207
step in the hydroxylamine of catalytic materials, 20 3- 207
formation, 714 of mate:r;ials, 152
Devolatilization Distributor, 459, 460, 462, 486
Diagnostic tests design, 460
for diffusional limitations, 264 orifice, 459
for temperature gradients, 283 Double layer, 925, 927-929, 934,
Diagonalization of A , 6 939, 940--942, 956
Diaphragm cell, 924 Double limit variety, 991
Diatomic molecule: vibrational Drag coefficient, 446, 449
spectra, 208 Drag force, 443, 446, 449
Differential spectra, 177 Drift dispersion, 770
Diffuse reflectance spectroscopy, Drift profile, 464
(DRS), 213 Dusty-gas model, 243
Diffusion, 925- 927, 943- 945, Dynamic behavior, 1001, 1021
947, 953 Dynamic condition, 1004
coefficient, 943, 953
gaseous, 240 Economy, 923
layer, 931, 932 Efficiencies, 949, 954
limitations, 741 Effective diffusivity, 412
in slow influx, 751 recommended equations, 354
in Ziegler-Natta polymerizations, Effectiveness factor, 253, 414
769 Effective thermal conductivity, 252,
in liquid-filled pores, 251 396
potential, 946 Effects of chemical reactions on
and reaction on catalyst pellets, mass transfer, 557
18 Efficiency, 516
reactor in Ziegler-Natta polymeriza- thermal, 515
tions, 768 Electric vehicle, 949
Index 1059
Electrochemical potential, 927 Equilibrium partition factor, 251
Electrochemical reactor, 923-925, Equivalent model, one-dimensional,
936, 939 398
Electrochemistry, 923- 964 Ergun-type equation, 592
Electrode area, 936- 938, 956, 958-- Escape probability, 90
960, 963, 964 Estimating transport coefficients,
Electrolyte influence on the recommended equations, 356
solubility of gases, 550 Estimation of model parameters, 102
Electron energy loss spectroscopy Ethylene on silver, 220
(eels), 213 Ethylidene, 186
Electron microanalysis of a sample, Exchange coefficients, 479, 481
207 Exchange current density, 930,
Electron microscope resolution, 934, 935, 952, 953
162 Extended electron energy loss fine
Electron probe microanalyzer (EPMA), structure (EXELFS), 189
206 applications, 191-192
Electron spin resonance (ESR), 198 Extended x-ray absorption fine
applications , 199 structure, 184, 187-192
Electroneutrality, 926, 927, 942, Extinction coefficient, 211
944 Exxon donor solvent reactor, 134
Electro-organic synthesis, 931, 940
Electrostatic analyzers, 173 Faraday's Law, 942, 945
Electrostatic ion energy analyzers, Fast bimolecular reaction, 562
182 Fast ion bombardment (FAB), 185
Element map, 178 Fast reaction, 559
Element specific, 187 regime, 613, 618
Elutriation, 449, 471, 472, 474- Felgett's Advantage, 212
476 Fermi Level, 170
Emulsion, 768 Flash desorption spectroscopy, 220
Energy, 923 ,. 949, 961, 963 Film
balances, 512 depth, 557
dispersive spectrometry (EDS), model, approximate solutions of,
204 609
dispersive spectroscopy, ad- theory, 569
vantages of, 205 Fine powders, 468, 469
efficiency, 949 Finite differences, 1019
of mass, 180 Finite-stage models, 334
of scattered primary ion vs. First-order chemical reactions, 136,
mass, 180 138
selection, 186 First order differential equations,
storage, 931, 939, 940, 947, 948 7
Enhancement factor, 556, 558 First-order isothermal reactions,
explicit expressions of, 563 105
implicit expressions of, 562 Fischer-Tropsch, 122
Entrained flow, 525 Fixed- bed catalytic reactors,
gasifier models, 538 models for, 70 8
reactor, 507 Fixed-bed reactors
models, 537 hydrodynamics, mixing, and
Entrainment, 471, 472, 474-476 transport characteristics of,
Enzymatic reactors, 780 674
Equal reactivity assumption, 740 models, 33
Equations, 926-931, 940- 948 unsteady state, 41
1060 Index
Fixed- bed tubular reactor models, Fugacity coefficient, 548
375 Functionality, 751
Flash desorption spectroscopy (FDS), average, 751
220 Future lifetime distribution A(t),
Flash hydrogenation, 74, 76
Floquet multipliers, 1031
Flotsam, 465, 466
Flow-by, 947, 948 Galerkin method, 1019
Flow Galileo number, 445
distribution, 143 Gas
entrained, 525 distribution, 464
permeability, recommended exchange, 477
equations, 355 holdup, 573, 577, 600, 682
regime boundaries, 674, 688 Gaseous diffusion, 240
velocity distribution, 400 Gasification, 502
Flow-redox, 940, 948 Gasifier, 504
Flow-through, 939, 940, 944, 947, fluidized-bed, 510
948 lurgi, 508, 531
Fluid bed, 102, 128 dry ash pressurized, 504
cracking catalyst, 469 moving bed, 50 4
Fluid dynamic instability, 133 ugas, 511
Fluidization minimum gas and Gasifier, Winkler fluid- bed, 510
liquid velocities required, 690 Gas-liquid dispersion, 597
Fluidization, turbulent, 145 Gas-liquid interface temperature,
Fluidized bed, 443 632
equations for basic parameters, Gas- liquid mass transfer, 684, 694
358 Gas-phase axial dispersion, 682,
gasifier, 510 694
models, 539 coefficient, 590
reactors , 343 Gas- side mass transfer coefficient,
Fluidized catalytic cracking, 441 580
Fluid - solid heat transfer co- Gas-solid noncatalytic reactions,
efficient, 403 293
Fluorescence background, 218 Gas-solid reactions
Flux, 925, 926, 941- 945 basic steps, 296
Form drag, 445, 447, 448 examples of, 294
Fouling, 773 Gas sparged versus mechanically
Fourier filter, 189 agitated slurry reactors,
Fourier transform, 78 712
method: crystallite size, 161 Gaussian elimination, 5
13C-NMR, 202 GEGAS reactor, 504
Fraction exposed or dispersion, Gelation, 751
157 Gel effect, 753, 758
Frank-Kamenetskii approximation, Generalized modulus, 415
984 Generating function
Freeboard, 481, 490 transformation, 739
region, 471, 472 use of, 745, 754
Free radical, 753 Geometric distribution, 741, 743, 747
Frequency, 459, 463 Geometries, 923, 924
of bubble formation, 487 Gold distribution, 764
response techniques, Good selectivity, 146
Friction factor correlations, 378 Grain model, 310
Fuel cells, 923, 936- 939, 940 Greek letters for gas-liquid-solid
Fuel gas, 501 reactors, 722
Index 1061
Grid, 950, 951, 956-961, 963, 964 Ideal plug flow, 72
zone, 481 Implicit integration, 9
Group frequencies and identification Implicit methods, 9
of structural groups, 211 Index, 1009
Indirect estimates of f(t) and F(t),
81
G tensor, 100 Industrial reactor, 139
lnealistic electron tunneling
spectroscopy (IETS), 213
Hall-Heroult, 924 Infrared
Harmonic oscillator, 208- 20 9 kinetic studies, 214
Hatta number, 560 spectroscopy, 207-215
Heat applications, 213- 215
of absorption, 631 bulk structures, 214
removal, 773 dispersive versus fourier trans-
transfer, 467, 468, 517, 687, form, 212
698 instruments, 211-213
coefficients, 466, 581, 603 intensities, 211
data, 604 isotopic substitution effect on
fluid-solid, 403 frequency, 209
modified, 35 preparation of the water, 212--
Hengy constant, 549 213
Heterogeneous, 529 selection rules, 209
models, 376 studies of adsorbed molecules,
two-dimensional, 419 214
polymerization, 768 windows, 213
reactors, 12 0 Initial bubble size, 459
Heterogeneously catalyzed polymer- Initiation, 742, 752, 759
izations, 763 Instantaneous number-average
High-conversion, 744 degree of polymerization,
Highly nonlinear , 12 3 759, 762
Holdup, 121 Instantaneous reaction, 560
in multiphase systems, 134 Instantaneous weight-average
Homogeneous, 529 degree of polymerization
isothermal reactor, 106 Intact emission, 184
model, 44 Intensity function or escape
Hopf bifurcation, 1005, 1021, 1027 probability, 68
Horizontal baffles, 102 Interactions between products and
Hot spots, 384 reactants, 120
Hydrazine and ammonia decomposi- Intercell connectors, 951, 961
tion, 224 Interfacial area, 563, 573, 578,
Hydrodesulfurization catalysts, 583, 588, 591, 593, 805
174, 182, 191, 192, 218, Interfacial gradients, in plug-flow
223 model, 402, 412
Hydrodynamic, mixing, and trans- Interfacial polymerization, 744, 750
port characteristics Interfacial temperature gradients,
of fixed-bed reactors, 674 384
of slurry reactors, 687 Internacs in fluid beds, 133
Hydrogen desorption, 222 Interphase exchange, 483
Hydrostatic head, 616 Interphase gas exchange, 442, 478,
Hydrotreater, 124 480, 484
Hyperbolic collocation, 22 Interphase gas transfer, 483
Hysteresis variety, 979, 991, Interphase transfer coefficient, 482
1044 Interstitial flow, 470
1062 Index
Interstitial gas velocity, 453, 457 Laboratory-scale absorbers, 646
Interstitial phase, 477, 478, 479, Langmuir-Hinshelwood kinetics,
484 981, 1000
Intraparticle concentration gradients, Laplace's equation
384 Laplace transform, 79, 81, 134
Intraparticle gradients, in plug- Laquerre polynomials, 749
flow model, 412 Leveque approximation, 932
Invert, 138 Lewis acid, 214
Ion etching, 182 Lewis number, 1002, 1010, 1013,
Ion gun, 185 1024
Ionic mobility, 943 Lewis sites, 220
Ionic reaction, 752 Liapungy method, 1003, 1018
Ionic strength , 553 Limiting-current plateau, 933- 935,
Ion neutralization, 180 940, 944, 946
Ion scattering spectroscopy (ISS), Linear, 86
179-183 Linear algebraic equations, 5
applications, 182-183 Linear polarization, 953, 956
charging, 181-182 Linearized-system, 1003, 1014
instrument, 181 Line scan, 207
surface composition and Liquid film model, 568
calibration, 181 approximate solution of, 605
surface sensitivity, 182 solution, 607
Iron-cobalt alloy catalysts, 197 Liquid holdup, 585, 588, 593,
Isolas, 1026 680
variety, 979, 991, 1046 Liquid mass transfer coefficients,
Isomer shift, 194 579
Isotherm al gas -liquid reactor Liquid-phase axial dispersion, 682,
modeling, 567 692
Isothermal models coefficient, 590
for fixed bed catalytic reactors , Liquid phase continuously stirred
708 tank reactor, 618, 620
for slurry reactors, 709 Liquid-side mass transfer coefficient
591
Liquid-solid mass transfer, 686, 696
Jacobian matrix, 1003, 1023 Lithium-aluminum, iron sulfide, 954,
Jacquinot's advantage, 212 956, 957
Jetsam, 465, 466 Local age distribution Gz, 74
Jumping zone model, 310 Local composition, 184
Local powder voidage, 461
Local structure, 187, 192
Kelvin Equation, 155 Local surface composition, 152
Kinetic constraints, 516 LU decomposition, 6
Kinetics, 915, 916, 932, 934, 943, Lumping approximation, 997
949, 951, 953 Lurgi dry ash pressurized gasifier,
of biological processes, 785 504
Kinetics-free calculations, 521 Lurgi gasifier, 508, 531
Kirchhoff's Law, 957
Knudsen flow, 240
Koppers-Totzek atmospheric reactor, Macrohomogeneous, 940
507 Macropores, 154
Magic angle spinning, 199, 201
Magnetically ordered crystallite,
Laboratory equipment, 648 196
Laboratory models, 647 Magnetic dipole splitting, 194
Index 1063
Magnetic resonance, 198-- 203 Methane production, 526
Maldistribution, 132, 133 Micellar catalysis, 70 0
in industrial reactors, 89 Microbial growth, 781
Markov chain theory, 740 Micropores, 154
Mass balances for the continuously Microreactor, 132, 143
stirred tank reactor model, Migration, 925-927, 943, 944, 953
572 Minimum fluidization value, 471
Mass, energy of, 180 Minimum fluidization velocity, 443,
Mass spectrometer, 222 448, 465
Mass transfer, 468, 924, 925, 932- Minimum gas and liquid velocities
934, 936, 939, 940, 943, 949, required for fluidization, 690
954 Mixed-oxide catalysts, 223
in aerobic fermentations, 803 Mixed oxides, 182
coefficient, 455, 478, 480, 492, Mixed reactor, 133
563, 804, 940, 943, 944 Mixing, 466
effects of chemical reactions on , index, 465
557 processes, 138
gas-liquid, 684, 694 units, 486
liquid-solid, 686, 696 Mobility, 943
parameters, 639 Modeling, 89, 940, 947
Material balances, 926, 927, 941, of isothermal gas-liquid reactors,
943, 944 567
Material utilization efficiency, 949, Models
950 compartment, 537
Maximum bubble size, 463 entrained flow gasifier, 538
Maximum principle, 995, 1017 entrained flow reactor, 537
Mean free path of electrons, 172 for fixed- bed catalytic reactors,
Mean lifetime, 557 708
Mean-square displacement, 191 fluidized-bed, 539
Mean, variance, and moments of multicompartment, 538
f(t) two-dimensional, 538
Measure maldistributions, 124 Model validation, 528
Measurement of Laplace transform Modified heat transfer coefficient ,
from arbitrary inputs, 81 35
Measurement of residence-time Modulus,
distributions, 76 generalized, 415
Mechanically agitated fermentors, Thiele, 254, 414
815 Molecular solids, 185
Mechanically agitated reactors, Moment closure approximation, 750
597 Moment of detachment, 460
Mechanically agitated systems, 815 Moment generating, property of
Medium-BTU, 500 the generating transformation,
Membrane cell, 924 758
Mercury cell, 924 Moments of residence-time distribu-
Mercury porosimetry, 155 tion, 81
Mesopores, 154 Monod model, 786
Metal carbonyl clusters, 191 Monolith converter, 424
Metal deposition processes of Mossbauer
Mo /Al203, 218 applications, 197
Metal-ion removal, 924, 939 experiments, 196
Metal processing, 931, 939 source mode, 196
Metal refining, 931, 939 transmission mode, 196
Metal removal, 939 spectroscopy, 192-198
Methanation, 500 surface sensitivity, 197
1064 Index
Most probable distribution, 743, 747, [Nuclear magnetic resonance]
771 spin echo techniques, 202
Motionless mixers, 813 of zeolites, 201
Moving bed gasifier, 504 Nucleation model, 314
models, 532 Numerical instability, 9
Moving bed reactors, 341, 521 Numerical methods, 1019
models, 529
Multibed adiabatic reactors, 380
Multi.compartment models, 538 Ohmic potential drop, 924-926,
Multiphase system, 76, 86, 120, 929-932, 935, 936, 939, 946,
128 949, 951-954, 959
Multiple reactions, 933- 935 Ohm's Law, 943, 946
Multiple steady states, 393 One-dimensional diffusion model, 72
Multiple tracer experiments, 122 One-dimensional models, fixed-bed
Multiplicity pattern, 977, 998 tubular reactors, 375
Multiplicity, steady-state, 274 One-point collocation, 22
Multistage system, 74 On - line bioreactor monitoring,
Multi.tubular reactors, 384, 1041 On-line control, 771
Multivalue methods, 11 Optimal reactor concepts, 109
Optimization, 735, 769, 935-938,
940, 963-964, 956, 961, 962
Nearest-neighbor distances, 191 Organizing center, 991, 1044
Near plug flow, 72 Orthogonal collocation, 998, 1019
Network of stirred tanks, 112 Ostergaard and Michelsen ( 1969),
Neutron scattering spectroscopy 88
(NSS), 213 Outlet reactant concentration, 481
Newton's method, 6 Overall mass transfer coefficient
Newton's regime, 448 Kgi, 556
Nonadsorbing tracer, 133 Overall rate of exchange, 478
Noncatalytic reactions, gas-solid, Overall transfer coefficients, 479,
293 480
Nonisothermal effects, 317 Oxidation, 500
Nonisothermal gas-liquid reactor, Oxidation-reduction behavior, 197
630, 632 Oxidation state, 152, 193, 194, 223
Nonisothermal models of active component of catalyst,
for fixed-bed catalytic reactors, 174
708 Oxide analysis by secondary ion
for slurry reactors, 710 mass spectroscopy, 186
Nonisothermal reactors, 112 Oxygen absorption into sodium
Nonlinear step growth polymeriza- sulfite, 566
tion, 751
Nonlinear systems, 6, 68
Notation for gas-liquid-solid Packed-bed, 124
reactors, 721 reactors, 333
Not stationary, 124 and trickle-bed reactors, 91
Nuclear hyperfine interactions, Packed columns, 547, 584
194 Packing characteristics, 586
Nuclear magnetic resonance (NMR), Packing, dry area of, 588
198, 199 P and R branches, 210
platinum 195 experiments ( 195 pt) Parallel electrodes, 924, 931-933
202 Parallel plates, 932
shielding effects, 201 Parallel reactions, 265, 988
of solids, 201 Parameter estimation, 360
Index 1065
Parameter fitting, 45 Pore size, 154
Parametric sensitivity, 386, 409, distribution, 151
1033 macropores, 154
Partial combustion, 502 mesopores, 154
Particle density, 444 micropores, 154
Particle mixing, 464 Porosity variations, due to
Particle-pellet model, 310 structural changes in pellet,
conservation equations for heat 320
and mass, 307 Porous electrode, 924, 931, 939-964
Particle size distribution, 167 Posts, 949, 951, 954, 961-964
Particle terminal fall velocity, 491 Potential, 925, 926, 929-932, 936,
Particulate fluidization, 450, 471 938, 940, 946
Partitioning, 15 theory, 926
Peak maximum, 221 Power, 924, 925- 936, 938, 949, 961
Peclet number, 995 963, 964
Penetration depth, 953 absorbed, 599
Penetration model, 557 consumption, 600
Penetration theory, 478, 480 Prater number, 988
Period doubling, 1030 Pressed salt method, 213
Periodic solution, 1005, 1023 Probability theory, 106
Perturbation analysis, 26 Product distribution, 136, 139, 144
Pfaudler agitator scale, 640 Pressure drop, 678
Phase equilibria, 548 equation, 378
Phase holdup, 680, 690 Pressure gradient, 571
Phase shifts, 189 Primary distribution, 932
Phenomenological equation, 132 Prim-mover power, 641
Photoelectron cross section, 1 75 Probe molecule nitric oxide, 199
Photoelectron spectrum, 171 Process constraints, 516
Phthalic anhydride, 490 Processes performed in gas-liquid
Physical characterization of reactors, 546
catalyst surfaces, 151 Product energetic yield, 792
Physicochemical characterization of Product formation, 788
catalyst surfaces, 151 Product inhibition, 789
Plasmon line, 172 Propagation, 742, 752, 759
Plate area, 956, 958-960, 963, 964 Proximity, 184
Plate columns , 5 48, 5 74 Pseudohomogeneous model, 376
Plug flow, 375 basic, with plug flow, 377
model, 973 two-dimensional, 396
with interfacial gradients , 402 Pseudolinear systems, 120
with interfacial and intraparticle Pulse experiments, 77
gradients, 412 Pulse techniques, 157
reactor Pyridine , 214
model with the bimolecular
reaction, 617, 622
Poincare bifurcation, 1030 Quadrupole splitting, 194
Poisson distribution, 764, 771 temperature dependent, 194
Polarizability, 216 Quantitative analysis, 179
Polarization parameters, 957, 958,
961
Polyatomic molecules: vibrations, Radial structure function, 189
210 Raman adsorbed molecules,
Polydispersity, 759 219
Polymer diffusion, 766 Raman applications, 218-220
1066 Index
Raman electrochemical environment , [Reactors]
220 coal gasification, 499
Raman selection rules, 216 enzymatic, 780
Raman spectrometer, 216-218 mechanically agitated, 597
Raman spectroscopy, 215- 220 "Recoil-free" emission and absorp-
Random pore model, 325 tion, 193
Rate of absorption, 565 Recombination, 184
Rate of coalescence, 461 Recovery, 939
Rate controlling step , determination Recursive approach, 740
of in hydroxylamine formation, Redox energy storage, 94 7, 950
714 Reductance, degree of, 782
Rayleigh scattering, 216 Reference electrodes, 928-930, 934,
Reaction 954, 956
and diffusion on catalyst pellets, References for gas-liquid-solid
18 reactors, 723
factor, 558 Reflectance techniques, 213
of hydrogen and ammonium nitrate Regular solutions, 549
on the catalyst surface , 717 Relative concentration, 181
rates, 529 Relaxation times, 201
units, 486 Reliability of the measurement , 87
Reactions Reptation, 767
consecutive, 266 Residence-time distributions (RTD),
parallel, 265 63, 567
scheme of consecutive reactions, Residual enthalpy, 1017
605 Reversibility, 744, 748
simultaneous, 269 Reviews, 924, 939
solid-gas, 529 Reynolds number, 493
with volume change, 315 Riser, 146
Reactor Rotational fine structure, 210
ammonia-synthesis, 389 Runaway, 384, 385, 1033
choice, 638 Runge- Kutta methods, 8
configuration, 736, 771, 924, 947, Rutherford scattering, 179
948, 950
control, 767
design and scaleup, 143 Salting coefficients, 551-552
dynamics, 1001 Same fluid bed, 129
entrained flow , 507 Sample heating, 216
fixed-bed tubular models, 375 Sample preparation, 213
GEGAS, 504 Satellite lines, 172
geometries, 924 Sauter mean diameter, 564
Koppers-Totzek atmospheric, 507 Scale up, 124, 129, 133, 638, 646,
modeling, 96, 528 925, 940, 948, 949, 951,
models, 529 954-956, 961, 962, 964
moving-bed, 529 considerations, 687, 700
moving bed, 521 Scanning auger, 178
selection, 710 microprobe (SAM), 178
Texaco pressurized gasification, Scanning electron microscope (SEM),
508 206
Westinghouse fluid-bed, 511 applications, 207
Reactors, 687 Scattering, 211, 215
aerobic, 780 Scheme of consecutive reactions,
anaerobic, 780 605
classification: examples of indus- Scherrer Formula, 160
trial importance, 667 Schmidt number, 492
Index 1067
Secondary current distribution, 932 [Slurry reactors]
Secondary ion mass spectrometry versus fixed- bed reactors, 711
(SIMS), 183-187 worked example: manufacture of
applications, 186-18 7 hydroxylamine phosphate,
charging, 185 713
classical dynamic calculations, 184 Small-angle x-ray scattering, 154
sample preparation, 185 SNG, 501
spectrometer, 184, 185 Solid-gas reactions, 529
thermodynamic model, 184 Solid particles in the medium
Segregated, 115 insoluble, 705
Segregated flow, 115 sparingly, 703
Segregation, 465, 466 Solid phase axial dispersion, 694
Selective chemisorption, 155 Solubility of gases in water, 550
of gases on metals, 156 Solubility parameter, 549
Semiflow batch model, 630 Source mode, 196
solutions of, 625 Sparged reactors, 573
Semi-implicit method, 10 Specific energy, 949, 961, 963, 964
Sensitivity functions, 12 Specific interfacial area, 564
Sensitivity, parametric, 386, 409 Specific power, 949, 961, 963, 964
Separator, 924, 940, 941, 947, 949- Spine collocation, 20
952, 955, 956, 961 Spray columns, 548
Series of CST Rs, 984, 1025 Stability, 1001, 1013
Series of stirred tanks, 72 diagram, 575
Shadowing, 182 Staged fluidized-bed reactors, 352
"Shake-up" line, 172 Staged reactors, 143
Shallow-bed reactors, 348 Stagewise nonisothermal models, 635
Sharp interface model, 298 Stagnant regions, 72
Sherwood number, 477, 492, 493 Static bifurcation, 1005, 1021
Shinnar and Naor (1967), 74 Statistical arguments, 743
Shinnar et al. ( 1973), 106 Statistical dispersion, 770
Side reaction, 933- 935, 940, 946, Statistical methods, 736, 7 40
950, 951 Steady-state CSTR (anionic poly-
Simulation of industrial units, 646 merization in A), 741
Simultaneous reactions, 269 Steady-state model, averaging of,
Single bubbles in isolation, 453 34
Single crystal studies, 179 Steady-state multiplicity, 274, 634,
Single-particle studies, 296 973, 974, 995
Single-pore model, 325 Steady-states, multiple, 393
Single tracer, 122 Stream gasification rates, 529
Singularity theory, 977, 988, 1041 data, 530
Sintering, 329 Steam reforming, 418
Sinusoidal inputs, 78 Step changes in tracer concentra-
Size of bubble at detachment, 459 tion, 76
Skin friction, 445, 447, 448 Step growth polymerization, 742
Slope condition, 1004 Stirred tank reactors, 546
Slow influx, 750 Stochastic systems, 106
Slow reaction regime, 612, 615 Stoichiometric constrains, 512
Slug flow, 574 Stokes Raman Lines, 216
Slurry reactors Stokes' regime, 447
hydrodynamic, m1xmg, and Strongly adsorbing, 12 3
transport characteristics of, Structural variations, effects of,
687 319
models for, 709 Structure sensitive or demanding
and reactive solids, 703 reactions, 151
1068 Index
Subscripts for gas-liquid-solid Terminal falling velocity, 471, 472
reactors, 723 493
Substrate-inhibited enzyme reac- Termination, 742, 759
tions, 980, 1000 combination, 753
Substrate inhibition, 786 disproportionation, 753
Sulfiding of Mo/Al2O3, 218 Testing, 89
Superparamagnetism, 196 Texaco pressurized gasification
Superscripts for gas-liquid-solid reactor, 508
reactors, 723 Thermal conductivity, effective,
Supported catalysts: TEM IS TEM, 396
164 Thermal desorption spectroscopy,
Supported metals, 174, 191 220
Supporting electrolyte , 944, 946, Thermal efficiency, 515
953 Thermal residence time, 42
Support interactions, 197 Thermal runaway, 766
Surface Thermodynamics, 925, 926, 949
composition, 179 constraints, 516
diffusion, 247 Thiele modulus, 254, 414
enhanced Raman spectroscopy Time-conversion relationships, 322
(SERS), 216 Time scale , 138
enrichment, 182 Tortuosity, 413
overpotential, 925, 926, 930, Total surface area, 153
934 Tracer experiments, 63
reaction studies, 186 Trade-offs, 925, 936
segregation, 192 Transfer, 742, 752, 759
structure, 186 current, 942, 943
Swietering, 115 of hydrogen
Symmetry, 193, 194 from bulk liquid to the catalytic
Synchroton radiation, 187, 189 surface, 715
Syngas, 501 to the bulk liquid, 714
units, 486
Transient response, 536
Tafel approximation, 930, 934- 936, Transient studies, 214, 215
952 Transmission electron microscopy
Tafel kinetics, 936 (TEM), 163
Techniques for solving polymeriza- model catalysts, 167-168
tion rate equations, 738 Transmission mode, 196
Temperature gradients, 271 Transmission vs. reflection and
interfacial, 384 emission, 212
Temperature-programmed desorp- Transport, 927, 943, 944
tion, 220-224 disengaging height, 472
activation energy for desorption, and readsorption problems, 221
221 Trickle beds, 124, 133
and temperature programmed re- Trickle-flow regime, 585
action, experimental Trommsdorff effect, 753, 758, 765
methods, 222 Tubular reactor, 973, 992, 1013
Temperature programmed oxidation, models, fixed-bed, 375
223-224 Turbulent flow, 145
Temperature programmed reaction, Turbulent fluidization, 145
220-224 Two-dimensional bed, 453
Temperature programmed red·uc- Two-dimensional models, 538
tion, 222- 223 fixed-bed tubular reactors,
Temperature-programmed tech- 375
niques, applications of, 222 heterogeneous, 419
Index 1069
[Two-dimensional models] Westinghouse fluid-bed reactor, 511
pseudohomogeneous, 396 Wilke-Change equation, 553
Two-phase theory, 452, 453, 458, "Winged cusp" singularity, 1044
481-482, 485, 490 Winkler fluid-bed gasifier, 510
Worked example: manufacture of
hydroxylamine phosphate in
Ugas gasifier, 511 a slurry reactor, 713
Ultrahigh vacuum, 169 Work function, 170, 185
Ultraviolet photoelectron spectros-
copy (UPS), 170
Unbalanced stoichiometry, in step X-ray
growth polymerization, 748 adsorption cross section, 188
Unsteady-state fixed-bed reactor diffraction, 158
models, 41 line broadening, 160
Upstream counterelectrode, 945, 947 diffractometer, 160
Ultilization, 936- 938, 950--954 emitted, 203
extended absorption fine struc-
ture, 187
Vaporization factor Ki, 548 map, 207
Vibrational-rotational energy, 209 photoelectron spectrometers, 173
Volume change photoelectron spectroscopy, 169,
in radical polymerization, 762 170-176
reactions with, 315 applications, 174-176
Volume reaction model, 302 catalyst: 2% Pd/Na-ZSM-5, 175
conservation equations for heat catalytic activity, 176
and mass, 306 chemical shifts, 172-173
contaminants and promotons,
176
Wake, 463, 464, 466, 471, 476 qualitative analysis, 174
fraction, 455 surface sensitivity, 172
of particles, 454
volume, 455, 485
Waste streams, 924, 939 Zeolites, 191
Water-gas shift, 500 Ziegler-Natta polymerizations,
Wavelength dispersive spectrometry, 768
(WDS), 204 Zone models, 308
Wavelength dispersive spectroscopy, Zinietering's method, 143
advantages of, 205 Zyirin and Shinnar (1975), 74
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