Topic 7

Catalysts and Catalytic Reactions

AECH 3132 Chemical Reaction Engineering

 Introduction
• Though we have discussed the use of catalyst in a PBR, we have not discussed the process
of catalysis itself.
• An understanding of catalysis, the mechanisms, and catalytic reactor design are the
subject of the next few lectures.

o Catalyst properties
o Steps involved in a catalytic reaction
o Development of a rate law using steps in catalytic reaction
o Different types of catalyst mechanisms
o Design of catalytic reactors

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• A catalyst is a substance that affects the rate of a reaction but emerges from the process
unchanged.
• A catalyst usually changes a reaction rate by promoting a different molecular path
(“mechanism”) for the reaction.
• A catalyst works by providing an alternative pathway for the reaction to occur.
• This alternative pathway has a lower activation energy than the pathway without the
catalyst.

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 Different shapes and sizes of catalyst.

Catalytic packed-bed reactor, schematic.

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 (i) Homogeneous catalytic reactions
• In homogeneous catalysis, the catalyst is in the same phase as the reactant(s).
• The number of collisions between reactants and catalyst is at a maximum because the catalyst is
uniformly dispersed throughout the reaction mixture.
• Many homogeneous catalysts in industry are transition metal compounds but recovering these
expensive catalysts from solution has been a major challenge. Another barrier to their widespread
commercial use, many homogeneous catalysts can be used only at relatively low temperatures.
• Despite these problems, a number of commercially viable processes have been developed in
recent years.
• Acids accelerate (catalyze) the hydrolysis of esters:
CH3CO2CH3 + H2O ⇌ CH3CO2H + CH3OH
At neutral pH, aqueous solutions of most esters do not hydrolyze at practical rates.

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 (ii) Heterogeneous catalytic reactions
• Heterogeneous catalytic process involves more than one phase; usually the catalyst is a solid and
the reactants are in liquid or gaseous form.
• Production of benzene from the dehydration of cyclohexane (obtain from the distillation of crude
petroleum) using platinum-on-alumina as the catalyst.

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Steps in a Heterogeneous Catalytic Reaction

7. Diffusion of B from
1. Mass transfer of external surface to the
A to surface bulk fluid (external
diffusion)

2. Diffusion of A from 6. Diffusion of B

pore mouth to from pellet interior
internal catalytic to pore mouth
surface

3. Adsorption of A 5. Desorption of product

onto catalytic surface B from surface

4. Reaction on surface

This topic assumes steps 1,2,6 & 7 are fast, so only steps 3, 4, and 5 need to be considered 7
 Active Sites
• Reactions are not catalyzed over the entire surface but only at certain active sites or
centers that result from unsaturated atoms in the surface.
• An active site is a point on the surface that can form strong chemical bonds with an
adsorbed atom or molecule.

The bonding from the adsorption of ethylene

on a platinum surface to form chemisorbed
ethylidyne.

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 Adsorption Step
The adsorption of A (gas phase) on an active site S is represented by:
A A
A(g) + S ⇌ A·S I
-S-S-S- -S-S-S-
S: open (vacant) surface site A·S: A bound to a surface site
Rate of adsorption = rate of attachment – rate of detachment
rAD = k APA Cv - k - A CA×S Conc of sites occupied by A
partial pressure of A Molar conc of vacant sites on surface
• Rate is proportional to # of collisions with surface, which is a function of PA
• Rate is proportional to # of vacant (active) sites, Cv, on the surface
• Active site: site on surface that can form a strong bond with adsorbed species
k
In terms of the adsorption equilibrium constant KA where KA = A
k-A
æ k -A ö
rAD = k APA Cv - k - A CA×S ® rAD = k A ç PA Cv - CA×S ÷
è kA ø
æ CA×S ö
® rAD = k A ç PA Cv - ÷ Equation I
è K A ø
 Site Balance
Ct: Total number of active sites per unit mass of catalyst divided by Avogadro’s #
(mol/g cat)
Cv: Number of vacant sites per unit mass of catalyst divided by Avogadro’s #

Active site Active site

Vacant
occupied by A occupied by B
active site
A B

Surface

Cv is not measurable, but the total number of sites Ct can be measured

In the absence of catalyst deactivation, assume the total number of active

sites remains constant:
Site balance:
Ct = Cv + CA·S + CB·S
We will use the site balance equation to put Cv in terms of measurable species
 Langmuir Isotherm Adsorption
Adsorption of carbon monoxide onto a surface: CO + S ⇌ CO·S
æ CCO×S ö kA
rAD = k APCOCv - k - A CCO×S ® rAD = k A ç PCOCv - ÷ KA =
è KA ø k-A
Determine the concentration of CO adsorbed on the surface at equilibrium
æ C ö
At equilibrium, rAD = 0: rAD = 0 = k A ç PCOCv - CO×S ÷
è KA ø
Rearrange & C
® CO×S = PCOCv ® CCO×S = K APCOCv
solve for CCO·S KA
Put Cv in terms of Ct using the site balance; only CO can absorb on the surface:
Ct = Cv + CCO×S ® Ct - CCO×S = Cv Insert into eq for CCO·S from rxn rate
CCO×S = K APCOCv ® CCO×S = K APCO ( Ct - CCO×S ) Solve for CCO·S

® CCO×S = K APCOCt - K APCOCCO×S ® CCO×S + K APCOCCO×S = K APCOCt

K P C
® CCO×S = A CO t Concentration of CO adsorbed on
1 + K APCO surface vs PCO→ Langmuir Isotherm
 K APCOCt Concentration of CO adsorbed on
® CCO×S =
1 + K APCO surface vs PCO→ Langmuir Isotherm

• This equation thus gives the equilibrium concentration of carbon monoxide adsorbed on the surface as a
function of the partial pressure of carbon monoxide and is an equation for the adsorption isotherm.
• This particular type of isotherm equation is called a Langmuir isotherm.

The amount of CO adsorbed per unit mass of The concentration of the atoms C and O
catalyst as a function of the partial pressure of CO. adsorbed per unit mass of catalyst

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 Surface Reaction Step
After the molecule is adsorbed onto the surface, it can react by a few different
mechanisms
1. Singe site mechanism: Only the site to which the reactant is absorbed is involved
in the reaction
A B é CB×S ù kS
A·S ⇌ B·S rS = k C
S ê A ×S - ú where K S =
I ⇌ I ë K S û k -S
-S- -S- Equation IIa
2. Dual site mechanism: Adsorbed reactant interacts with another vacant site to
form the product A·S + S ⇌ S + B·S
A B é CB×SCv ù
I I rS = k S êCA ×SCv - ú Equation IIb
⇌ ë K
-S-S-S -S-S-S- S û
3. Eley-Rideal mechanism: reaction between adsorbed reactant and a molecule in
the gas phase A·S + B(g) ⇌ C·S
B A C é C ù
I I rS = k S êC A ×SPB - C×S ú Equation IIc
⇌ ë KS û
-S-S-S -S-S-S-
 Desorption Step
Products are desorbed into the gas phase

C·S ⇌ C + S
C C é PCCv ù k
I ⇌ rD,C = kD êCC×S - ú where KD,C = D
ë K D,C û k -D
-S-S-S- -S-S-S-
Equation III
Note that the desorption of C is the reverse of the adsorption of C
rD,C = -rAD,C

Also the desorption equilibrium constant KD,C is the reciprocal of the adsorption equilibrium constant KC
1
KD,C =
KC

Substituting 1/KC for KD,C in the rate equation for product desorption gives:
rD,C = kD [CC×S - K CPCCv ]
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 Consider A ⇌ B and assume the following mechanism is correct:
æ CA×S ö
1. Adsorption: A(g) + S ⇌ A·S rAD = k A ç PA Cv - ÷
è K A ø
é C C ù
2. Surface reaction: A·S + S ⇌ S + B·S rS = k S êCA ×SCv - B×S v ú
ë KS û
é PC ù
3. Desorption: B·S ⇌ B + S rD = kD êCB×S - B v ú
ë KD û

We need to select one of these 3 reactions as the rate limiting step, then derive the corresponding
rate equation, and see if this rate eq matches experimental data. Which step is the most logical to
start with?
a) Adsorption
b) Surface reaction
c) Desorption
d) None of the above
e) Any of these would be “logical” - they all have equal probability of being the rate limiting step

The surface reaction step as is rate limiting ~70% of the time

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 The Rate Limiting Step
One particular step in the series is usually found to be rate-limiting or rate-controlling.

• We observe only the total resistance (Rtot).

• It is our task to find which resistance is much
larger (say, 100 Ω ) than the other two resistances
(say, 0.1 Ω ).
• Thus, if we could lower the largest resistance, the
current I (i.e., 𝑟!" ) would be larger for a given
Electrical analog to heterogeneous voltage, E.
reactions. • Analogously, we want to know which step in the
adsorption–reaction–desorption series is limiting
the overall rate of reaction.

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 Industrial Example of Adsorption-Limited Reaction
The synthesis of ammonia from hydrogen and nitrogen over an iron catalyst

The mechanism

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 Industrial Example of Surface-Limited Reaction
The reaction of two noxious automobile exhaust products, CO and NO carried out over a copper
catalyst

The mechanism:

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 Catalyst Deactivation
• Thus far, we assumed the total concentration of active sites on the surface was constant,
which means the catalyst’s activity is constant throughout its lifetime.
• In reality, there is a gradual loss of catalytic activity (active sites on surface of the catalyst)
as the reaction takes place.
•Main types of catalyst deactivation
•Sintering (aging): loss of active surface due to high temperature
•Coking or fouling: carbonaceous material (coke) deposits on surface
•Poisoning: molecules irreversibly bind to the active site
• We will evaluate the kinetics of general catalyst deactivation and these specific types.

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 Catalyst Deactivation Kinetics
Adjustments for catalyst decay need to be made in the design of reactors.
Catalyst activity a(t) is used as a quantitative specification:

-rA' (t) Reaction rate for catalyst used for time t

Catalyst activity at time t: a(t) =
-rA' Reaction rate for fresh, unused catalyst
t =0

0 £ a(t) £ 1

For fresh, unused catalyst, a t =0 = 1

Activity as a function of time.

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Rate of consumption of reactant A on catalyst used for time t is: -r 'A = a ( t ) k ( T ) fn ( C A,CB ,....etc )

a(t): time-dependent catalyst activity k(T): T-dependent specific rate constant

fn(CA, CB…etc): function of gas-phase conc. of reactants, products & contaminants

Function of activity
da
Rate of catalyst decay: rd = - = p éëa ( t ) ùû k d ( T ) h ( CA ,CB ,...,etc )
dt
Temperature-dependent specific decay constant
Functionality of rd on reacting species conc.
h=1: no conc dependence;
h=Cj: linearly dependent on concentration

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 Sintering (Aging)
• Loss of active surface area resulting from the prolonged exposure to high gas-
phase temperatures
• Active surface area is lost by
• Crystal agglomeration and growth of metals deposited on support
• Narrowing or closing of pores inside the catalyst pellet
• Surface recrystallization
• Elimination of surface defects (active sites)
• Sintering is usually negligible at temperatures below 40% of the melting
temperature of the solid
• Second-order decay of reaction rate with respect to present activity:
rd = k da2
1
Catalyst activity at time t: a(t) =
1 + k dt
é Ed æ 1 1 ö ù
Sintering decay constant: k d = k d ( T0 ) exp ê ç - ÷ ú
ë R è T0 T ø û
 Coking (Fouling)
• Common to reactions involving hydrocarbons
• A carbonaceous (coke) material is deposited on surface of catalyst
Concentration of carbon on surface (g/m2): CC = Atn
A & n are fouling parameters
1
Catalyst activity at time t: a(t) =
1 + k ' tm
(one of many different expressions for a(t))
m is a fouling parameter

• Coking can be reduced by running at high pressure & hydrogen-rich feeds

• Catalyst deactivated by coking is often regenerated by burning off the
carbon
 Poisoning
• Poisoning molecule is irreversibly chemisorbed to active sites
• Reduces number of active sites available for reaction
• Catalyst can be poisoned by reactants, products, and impurities

For the overall reaction:

A +S ®B+S
k'd
poisoning by reactant: A + S ¾¾¾
®A ×S
k'd
posioning by product: B + S ¾¾¾
®B × S
k'd
poisoning by impurity: P + S ¾¾¾
®P × S
da
rd = - = a ( t ) k'd CP
dt
a(t): time-dependent catalyst activity
kd: specific decay constant
CP: concentration of the poison
credit to lecture notes :
https://websites.umich.edu/~elements/6e/lectures/index.html 25