Chemical

Reac/on Engineering II
6. Resistance Analysis
Y.H.Yap

1. Introduction

Todays Topics

Introduc)on

Heterogeneous
Reac)ons

External
Diusion Eects

Diusion &
Reac)on in
Porous Catalyst

Design of
Mul)phase
Cataly)c Reactor

Resistance
Analysis

Data Analysis for

Reactor Design

Catalyst
Deac)va)on

Non-elementary
Reac)on Kine)cs

1. Introduction

Resistance
Analysis

Todays Topics

Areas covered

Introduc)on

Slurry reactor

Trickle bed reactor

1. Introduction

Text

Levenspiel
Chemical Reac/on Engineering
Chapter 19 and 20

Fogler
Chapter 12.8 and 12.9

1. Introduction

1. Introduction

Many real chemical reactors are opera)ng at sub-par

performance. OKen, their performance can be
improved if we take a closer look
There are methods we can employ, such as:
Residence )me distribu)on
Thiele modulus, eec)veness factor etc.
Resistance analysis for heterogeneous reactor
Resistance analysis provides a way to es)mate the
percentage of resistance contributed by each step

1. Introduction

In some cases, resistance analysis will allow us to

select and design a beOer reactor

We consider two examples:
Slurry reactor
Trickle bed reactor

2. Slurry Reactor

Hydrogena)on of methyl linoleate:

Methyl linoleate (l) + Hydrogen (g) --> methyl oleate (l)

H2

Assump)ons:
Liquid phase is well mixed
Solid catalysts are uniformly distributed
Gas phase is in plug ow
Fluid is perfectly mixed in radial direc)on, not axial

2. Slurry Reactor

Resistance involved in G/L reac)on

2. Slurry Reactor

Steps

Five reac)on steps (+ reverse):

1) Absorp)on from gas phase into liquid phase at
the bubble surface

Gas-liquid lm

2) Diusion in the liquid phase from bubble surface

to the bulk liquid
3) Diusion from the bulk liquid to the external
surface of the solid catalyst
4) Internal diusion of the reactant in the porous
catalyst
5) Reac)on within the porous catalyst

2. Slurry Reactor

Steps

Step 1: Rate of H2 absorp)on

(
r = k a (C

r = k g ab p H 2 ,b p H 2 ,i
l

H 2 ,i

C H 2 ,b

)
)

mol mol
m
m

r = 3 3 = 3
s m m m s

kg/l = mass transfer coecient for gas absorp)on (m/s)

ab = bubble surface area (m2/m3 of solu)on)
Ci = H2 concentra)on at oil-H2 bubble interface (mol/m3)
Cb = bulk concentra)on of H2 in solu)on (mol/m3)

2. Slurry Reactor

Steps

Step 2: Transport to the catalyst pellet

Try this
2
m m g cat mol
r =
3 = 3
s g cat m m s

kc = mass transfer coecient for par)cles (m/s)

ap = external surface area (m2/gcat of catalyst)
m = catalyst loading (gcat/m3 of solu)on)
Cs = H2 concentra)on at catalyst external surface (mol/
m3)
Cb = bulk concentra)on of H2 in solu)on (mol/m3)

2. Slurry Reactor

Steps

Step 3: Diusion and reac)on in the catalyst pellet

g cat 1 mol mol

r = 3
= 3
m 1 g cat s m s
= internal eec)veness factor
m = catalyst loading (gcat/m3 of solu)on)
rAs = reac)on rate at the external surface (mol/gcat s)

2. Slurry Reactor

Steps

Step 4: Rate law for surface reac)on

r ' As = kC As
r = m ( r ' As )

m 3 mol mol
r =
3 =

g cat s m g cat s

k = rate constant
CAs = concentra)on at catalyst external surface (mol/m3)

2. Slurry Reactor

Determine the rate limi)ng step

Model as a series of resistance
At steady state, rates are all equal

r = k g ab p H 2 ,b p H 2 ,i

= k g ab H H 2 C H 2 ,b C H 2 ,i

= kl ab C H 2 ,i C H 2 ,b

= k c a p m C H 2 ,b C H 2 , s
= m ( r ' As )

p A = HC A

2. Slurry Reactor

Rearranging:

r
= Cb Ci
k g ab H
r
= Ci Cb
kl ab
r
= Cb C s
kc a p m
r
= Cs
mk

Cb Cb

2. Slurry Reactor

Adding all up:

1
1
1
= Cb
r
+
+
+
k a H k a

k
a
m
mk

l b
c p
g b

Rearrange:

1
Cb
1
1
1

=
+
+
+
k a H k a
r
k
a
m
mk

l b
c p
g b

2. Slurry Reactor

Rearrange:

Cb
1
1
1 1
1
=
+
+
+
r
k g ab H kl ab m kc a p k
Can be thought of as resistance:

Cb
1
= Rg + Rl + (Rc + Rr )
r
m
Gas lm Liquid lm

Transport to
surface

Internal diusion
and reac)on

2. Slurry Reactor

Question

Can you work out the unit of resistance?

2. Slurry Reactor

Becomes a straight line:

Cb
1
= Rg + Rl + (Rc + Rr )
r
m

Bubble lm

Combined
resistance of
external MT
and reac)on

2. Slurry Reactor

Becomes a straight line:

Cb
1
= Rb + (Rcr )
r
m

Total resistance

Cb
r

Rc + Rr

Diusional resistance to
and within pellet and
surface reac)on resistance

Rb

Gas absorp)on
resistance

1
m
Increasing catalyst loading

2. Slurry Reactor

Changing diusion and reac)on resistance:

Cb
r

Rb

Decreasing
par)cle size

Both eec)veness
factor and mass
transfer coecient
increases

1
m

2. Slurry Reactor

Changing gas absorp)on resistance:

Cb
r

Rb

Increasing resistance
to gas absorp)on

To decrease gas
absorp)on resistance,
change the sparger to
produce more gas
bubbles of smaller size

1
m

2. Slurry Reactor

Which step is rate limi)ng ?

Ci
r

Ci
r

Rb

Rb

Gas absorp)on
control

1
m

Diusion and
reac)on control

1
m

So its easy to know whether Rb or Rcr is rate limi)ng

But how do we know whether reac)on, ext di or int di is limi)ng?

2. Slurry Reactor

Varying particle size

So how do we know whether external diusion,

internal diusion or surface reac)on is controlling ?
Overall resistance:

Cb
1
= Rg + Rl + (Rc + Rr )
r
m
Diusion and reac)on resistance:

1
1
Rcr =
+
k a a p k

2. Slurry Reactor

Varying particle size

We can vary the par)cle size

So we want to plot Rcr vs. dp
Small par)cles

1
1
1
Rcr =
+

k a a p k k
1

Moderate-size par)cles

1
Rcr =
1d p
k

For large Thiele modulus

Surface rxn > int diusion

6
=
=
n d p

De

k c S a

1/ 2

2. Slurry Reactor

Varying particle size

But how do we know whether external diusion,

internal diusion or surface reac)on is controlling ?
We can vary the par)cle size
Moderate-size to large par)cles
0

1
1
1
Rcr =
+
=
k a a p k k a a p
External surface area per mass is given by:

ap =

2
p
3
p

( / 6)d c

6
d p c

2. Slurry Reactor

Varying particle size

1
We can vary the par)cle size
Rcr =
kc a p
Moderate-size to large par)cles
We need to know mass transfer coecient
1. No shear stress between par)cles and uid

When par)cle size is small, they move with uid

mo)on with almost zero shear

Sh =

kc d p
DAB

=2

DAB
kc = 2
dp

2. Slurry Reactor

Varying particle size

We need to know mass transfer coecient

1. No shear stress between par)cles and uid

DAB
ka = 2
dp

ap =

1
Rcr =
ka a p
Rcr =

c d

2
p

12 DAB

= 1 d p2

6
d p c

Independent of U,
means increasing
s)rring speed have no
eect on increasing
the overall rate

2. Slurry Reactor

Varying particle size

We need to know mass transfer coecient

2. Shear between par)cles and uid

Can use Frossling correla)on

Sh = 2 + 0.6 Re1/ 2 Sc1/3

Sh Re1/2
kc d p
DAB

d pU

1/ 2

2. Slurry Reactor

Varying particle size

2. Shear between par)cles and uid

Can use Frossling correla)on

kc d p
DAB

d pU

1/ 2

U 1/ 2
k c 1/ 2
dp
U 1/ 2
kc a p 3 / 2
dp
Rcr =

1
= 3 d 1p.5
kc a p

6
ac =
c d p

2. Slurry Reactor

Varying particle size

If we combine everything, the plot (log-log) of Rcr vs. dp:

Rcr =

ln

c d p2

No shear

12 DAB

Rcr 3 d 1p.5 With shear

Rcr

Rcr 1d p
Rcr

Medium to large
External
diusion
limited

Medium par)cle size

Internal diusion limited

1
k Small par)cle size
Reac/on limited

dp

ln

But it does not imply that internal diusion will always occur at
par)cle size smaller than external diusion

2. Slurry Reactor

Summary

General steps to determine the rate limi)ng steps:

Construct a series of Ci/R as a func)on of 1/m for
dierent pellet diameters
Determine the combined resistance from the
slopes of these plots for each corresponding
par)cle diameter
Plot Rcr as a func)on of dp on log-log paper. From
the slope, determine which is rate limi)ng
If the slope is say 0.5, this suggests that more than
one resistance is rate limi)ng

2. Slurry Reactor

Variables aec)ng the observed reac)on rate:

2. Slurry Reactor

Practice

Prac)ce example Cataly)c hydrogena)on of methyl

linoleate:
Determine the controlling resistance
Sizing the reactor

2. Slurry Reactor

Practice

Cataly)c hydrogena)on of methyl linoleate:

Determine the controlling resistance

The cataly)c hydrogena)on of methyl linoleate was carried out in a lab-scale

slurry reactor in which hydrogen gas was bubbled up through the liquid and
catalyst. Unfortunately, the pilot-plant reactor did not live up to lab reactor
expecta)ons. The catalyst par)cle size normally used was between 10 and
100 m. In an eort to deduce the problem, the experiment listed in below
were carried out on the pilot plant slurry reactor at 121C.
Run

H2 par)al
pressure (atm)

H2 solubility
(kmol/m3)

Catalyst
Catalyst
H2 reac)on rate
size (m) charge (kg/m3)
(kmol/m3 s)

0.007

40

5.0

0.0625

0.014

40

0.2

0.0178

0.014

80

0.33

0.0140

0.014

80

0.16

0.0073

2. Slurry Reactor

Practice

Cataly)c hydrogena)on of methyl linoleate:

Determine the controlling resistance

The cataly)c hydrogena)on of methyl linoleate was carried out in a lab-scale

slurry reactor in which hydrogen gas was bubbled up through the liquid and
catalyst. Unfortunately, the pilot-plant reactor did not live up to lab reactor
expecta)ons. The catalyst par)cle size normally used was between 10 and
100 m. In an eort to deduce the problem, the experiment listed in below
were carried out on the pilot plant slurry reactor at 121C

a) What seems to be the major resistance with the pilot plant reactor, and
what steps should be taken to correct the problem? (Support
recommenda)ons with calcula)ons)

b) For the 80 m par)cle size, what are the various percentage resistance to
absorp)on, diusion, and so on, when the catalyst charge is 0.40 kg/m3

2. Slurry Reactor

Practice

We need to plot a graph like this: C

1
b
= Rb + (Rcr )
Total resistance
r
m
Cb
r
Rc + Rr
Diusional resistance to
and within pellet and
surface reac)on resistance

Rb

Gas absorp)on
resistance

1
m
Increasing catalyst loading

2. Slurry Reactor

Practice

To determine the resistance, we plot C/r vs. 1/m:

0.007 /
0.0625

1/40

Run

Cb/r
(min)

1/m
(m3/kg)

0.112

0.20

0.787

5.00

1.00

3.00

1.92

6.25

Cb
r

Rb

80 m

40 m

1
m

2. Slurry Reactor

Practice

Determine the slope

For 40 m

0.787 0.112
min.kg
Rcr =
= 0.14
5.0 0.2
m3

Cb
r

80 m

Rb

For 80 m

40 m
1
m

1.92 1.00
min.kg
Rcr =
= 0.28
6.25 3.00
m3
0.28
ratio =
= 2.0
0.14

Cb
1
= Rb + (Rcr )
r
m

2. Slurry Reactor

Practice

Determine the controlling resistance

Rcr d p
a. Because combined resistance is propor)onal to
the par)cle diameter with power n = 1, internal
diusion is the controlling resistance
b. For 80 m par)cle size with 0.4 kg/m3. the overall
resistance is 1/m = 2.5
From the graph (with scale)

2. Slurry Reactor

Practice

b. For 80 m par)cle size with 0.4 kg/m3. the overall

resistance is 1/m = 2.5
From the graph (with scale)

(min)

Cb
r

80 m

0.84

40 m

Rb
0.08
2.5

1
m

2. Slurry Reactor

Practice

b. For 80 m par)cle size with 0.4 kg/m3. the overall

resistance is 1/m = 2.5
From the graph (with scale)

Percentage gas absorp)on resistance

0.08
=
100 = 9.5%
0.84
Percent internal diusion resistance

0.84 0.08
=
100 = 90.5%
0.84

2. Slurry Reactor

Practice

Prac)ce example Cataly)c hydrogena)on of methyl

linoleate:
Determine the controlling resistance
Sizing the reactor

2. Slurry Reactor

Practice

Cataly)c hydrogena)on of methyl linoleate:

Reactor design catalyst load

Methyl linoleate is to be converted to methyl oleate in a 2m3 slurry reactor.

The molar feed rate of methyl linoleate to the reactor is 0.7 kmol/min. The
par)al pressure of H2 is 6 atm and reactor is considered to be well-mixed.
Calculate the catalyst charge necessary to achieve 30% conversion for a 60
m par)cle size. The reac)on condi)ons are the same.

For a well-mixed reactor, CSTR design equa)on is:

FA0 X
V =
rA

2. Slurry Reactor

Practice

Cataly)c hydrogena)on of methyl linoleate:

Reactor design catalyst load

Ci
VC
=
FA0 X rA
VC
1
= Rb + Rcr
FA0 X
m
From previous example:

Rcr ,80 m

min.kg
= 0.28
m3

min.kg
Rb = 0.08
m3

2. Slurry Reactor

Practice

Cataly)c hydrogena)on of methyl linoleate:

Because it was internal diusion limited

rcr = d p

rcr , 60 m

60
=
0.28 = 0.21 min .kg/m 3
80

Subs)tute the parameter values:

(2m )(0.014kmol/m ) = 0.08 min + 1 0.21kg.min/m

3

(0.7kmol / min )(0.3)

VC
1
= Rb + Rcr
FA0 X
m

2. Slurry Reactor

Practice

Cataly)c hydrogena)on of methyl linoleate:

Therefore

m = 3.9kg / m 3
Slurry reactor typically contain 1 to 5% catalyst by
weight