CH6610

Chemical Reactor Engineering

Assoc. Prof. Dr. Vu Dinh Tien
Faculty of Chemical Engineering - SCLS
Topic 10 - Theory
Basics of catalysis

Fogler, Chapter 10
• Basics of Catalysis
o Catalyst properties
o Steps involved in a catalytic reaction
o Development of a rate law using steps in catalytic reaction

• Applications
o Chemical Vapor Deposition
o Catalyst deactivation
o Moving bed reactor

Slide 2
Basics of Catalysis & Reaction
Mechanisms
•Although 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 two weeks
•This week:
o Catalyst properties
o Steps involved in a catalytic reaction
o Development of a rate law using steps in catalytic reaction
o Chemical Vapor Deposition
o Catalyst deactivation
o Moving bed reactor

Slide 3
 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 K A = A
k −A
 k 
rAD = k APA Cv − k − A CAS → rAD = k A  PA Cv − − A CAS 
 kA 
 C 
→ rAD = k A  PA Cv − AS  Equation I
 KA 
Slide 6
 Langmuir Isotherm Adsorption
Adsorption of carbon monoxide onto a surface: CO + S ⇌ CO· S
 CCOS  kA
rAD = k APCOCv − k − A CCOS → rAD = k A  PCOCv −  KA =
 KA  k −A
Determine the concentration of CO adsorbed on the surface at equilibrium
 CCOS 
At equilibrium, rAD = 0: rAD = 0 = k A  PCOCv − 
 K A 
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 APCOCt Concentration of CO adsorbed on
→ CCOS =
1 + K APCO surface vs PCO→ Langmuir Isotherm
Slide 8
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  CBS  kS
A· S ⇌ B· S rS = k S C AS −  where K S =
I ⇌ I  K S  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  CBSCv 
I I rS = k C C
S  A S v −  Equation IIb
⇌  K S 
-S-S-S -S-S-S-
3. Eley-Rideal mechanism: reaction between adsorbed reactant and a
molecule in the gas phase A· S + B(g) ⇌ C· S
B A C  C 
I I rS = k S C A SPB − CS  Equation IIc
⇌  KS 
-S-S-S -S-S-S-
Slide 9
Desorption Step
Products are desorbed into the gas phase

C· S ⇌ C + S
C C  PCCv  kD
I ⇌ rD,C = kD CCS −  where KD,C =
 K D,C  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 

Slide 10
Derive a Rate Law for Catalytic
Reaction
• Postulate catalytic mechanism, and then derive the rate law for that mechanism
• Assume pseudo-steady state hypothesis (rate of adsorption = rate of surface
reaction = rate of desorption)
• No accumulation of species on the surface or near interface
• Each species adsorbed on the surface is a reactive intermediate
• Net rate of formation of species i adsorbed on the surface is 0, ri·S=0
• One step is usually rate-limiting
• If the rate-limiting step could be sped up, the entire rxn would be faster
• Although reactions involve all 7 steps, (for this week) only adsorption,
surface reaction, or desorption will be rate limiting
• The surface reaction step is rate limiting ~70% of the time!
• Steps to derive the rate law
• Select among types of adsorption, surface reaction, and desorption
• Write rate laws for each individual step, assuming all are reversible
• Postulate which step is rate limiting
• Use non-rate-limiting steps to eliminate the surface concentration terms that
cannot be measured

Slide 11
Example of Derivation of a Rate
Law for Catalytic Reaction
Consider A ⇌ B and assume the following mechanism is correct:
 C 
1. Adsorption: A(g) + S ⇌ A· S rAD = k A  PA Cv − AS 
 KA 
 CBSCv 
2. Surface reaction: A· S + S ⇌ S + B· S rS = k S C A SCv − 
 K S 
 PBCv 
r = k C
D  BS −
KD 
3. Desorption: B· S ⇌ B + S D


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?

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

Slide 12
 Derivation of a rate law for surface
reaction rate limited case
Consider A ⇌ B and assume the following mechanism is correct:
1. Adsorption 2. Surface reaction 3. Desorption

 CAS   CBSCv   PBCv 

rAD = k A  PA Cv −  rS = k S C A SCv −  rD = kD CBS − 
 K A   K S   K D 
Derive the rate equation for when the surface reaction is rate limiting (true ~70% of
the time)  C C 
−r 'A = rS = k S CA SCv − BS v 
 KS 
1. CA· S, Cv, and CB· S need to be expressed in terms of measurable quantities
• For surface reaction-limited mechanisms, kS is small and kA and kD are relatively
large
• Therefore rAD/kA and rD/kD are very small, and can be approximated as equal to
zero

2. Use this relationship to eliminate CA· S and CB· S from their respective rate
equations and the site balance to eliminate CV

Slide 13
Derivation of a rate law for surface
reaction rate limited case
Derive the rate equation for when −r ' = r = k C C − CBSCv 
S  A S v
the surface reaction is rate limiting A S
 K S 
Use rAD/kA =0 and rD/kD =0 to eliminate CA· S and CB· S from their
respective rate equations and the site balance to eliminate CV
Use rAD/kA =0 & rAD  C 
rAD = k A PA Cv − AS 
equation to solve for CA· S:  KD 
C CAS
r
→ AD = 0 = PA Cv − AS → = PA Cv → CAS = K APA Cv
kA KA KA

Use rD/kD =0 & rD equation  PBCv 

rD = kD CBS − 
to solve for CB· S:  K D 
r PC PC
→ D = 0 = CBS − B v → B v = CBS
kD KD KD

Slide 14
Derivation of a rate law for surface
reaction rate limited case
Derive the rate equation for when the surface reaction is rate limiting
 CBSCv 
−r 'A = rS = k S CA SCv − 
 K S 
PBCv
rAD/kA =0 & rD/kD =0 CAS = K APA Cv = CBS
KD
Use site balance to solve for CV: Ct = Cv + CAS + CBS

→ Cv = Ct − CAS − CBS Make substitutions for CA· S & CB· S, solve for Cv
PC PC
→ Cv = Ct − K APA Cv − B v → Cv + K APA Cv + B v = Ct
KD KD
 P  Ct
→ Cv  1 + K APA + B  = Ct → Cv =
 KD  P
1 + K APA + B
KD

Slide 15
Derivation of a rate law for surface
reaction rate limited case
Derive the rate equation for when the surface reaction is rate limiting
PBCv Ct
CAS = K APA Cv = CBS Cv =
KD 1 + K APA + PB KD

 CBSCv 
−r 'A = rS = k S CA SCv −  Substitute in CA· S, CB· S, &Cv
 K S 
  Ct 
2
PB  Ct  
2
→ −r ' A = rS = k S K APA   −   
  1 + K APA + PB KD  K SKD  1 + K APA + PB KD  

2
 Ct   PB 
→ −r ' A = rS = k S  −
  A A K K 
K P
 1 + K P
A A + PB D 
K S D
This is the rate equation in terms of measurable species and rate
constants for the mechanism given in the problem statement

Slide 16
Evaluating a Catalytic Reaction
Mechanism
• Collect experimental data from test reactor
• See if rate law is consistent with data
• If not, then try other surface mechanism (i.e., dual-site
adsorption or Eley-Rideal) or choose a different rate-limiting
step (adsorption or desorption)

Slide 17
 Derivation of a rate law for
adsorption rate limited case
Consider A ⇌ B and assume the following mechanism is correct:
1. Adsorption 2. Surface reaction 3. Desorption

 CAS   C C   PBCv 
rAD = k A  PA Cv −  rS = k S C A SCv − BS v  rD = kD CBS − 
 K A   KS   K D 

Now derive the rate equation for  CAS 

−r 'A = rAD = k A  PA Cv − 
when adsorption is rate limiting:  K A 
Conc of vacant and occupied sites must be eliminated from the rate equation
If adsorption is rate limiting, kS>>kA, so rS/kS can be approximated as 0.
Then:
 CBS Cv  rS CBS Cv
rS = k S CAS Cv −  → = 0 = C AS Cv −
 KS  k S KS
CBS Cv CBS Need to put CB· S in
→ = C AS Cv → = C AS measureable terms
KS KS
Slide 18
 Derivation of a rate law for
adsorption rate limited case
If adsorption is rate limiting, kD>>kAD, so rD/kD can be approximated as 0. Then
 PB Cv  rD PB Cv PB Cv
rD = kD CBS −  → = 0 = CBS − → = CBS
 KD  kD KD KD
Conc of vacant and occupied sites must be eliminated from the rate eq
CBS PB Cv
= C AS = CBS Solve for Cv using the site balance equation
KS KD
Make substitutions → C = C + CBS + PB Cv
Ct = Cv + CAS + CBS t v
for CA· S & CB· S KS KD
 PB  → Ct
→ Ct = Cv +
PB Cv PB Cv
+ → Ct = Cv  1 +
PB
+ = Cv
 PB PB
K SK D KD  K K
S D K D 1 + +
K SK D K D
Substitute
Cv into the CBS =
PB Ct Substitute PB Ct
C AS =
expression  PB PB  CB· S into  PB PB 
KD  1 + +  CA· S: K SK D  1 + + 
for CB· S:  K K
S D K D  K K
S D K D
Slide 19
Derivation of a rate law for
adsorption rate limited case
PB Ct PB Ct Ct
C AS = CBS = = Cv
 P P   P P  PB PB
K SK D  1 + B + B  KD  1 + B + B  1+ +
 K SK D K D   K SK D K D  K SK D K D

 
Use these eqs  
P C P C
to replace CA·S → rAD = k A  − 
A t B t
 PB PB  PB PB  
& Cv in rAD: 1 +
 K K + K A K SK D  1 + + 
 S D K D  K K
S D K D 
k  
 
Factor P P
→ rAD = k A Ct  A − B 
out Ct:  PB PB  PB PB  
1 +
 K K + K A K SK D  1 + + 
 S D K D  K K
S D K D 

Slide 20
Growth of Germanium Films by
CVD
𝑘𝑑𝑖𝑠
Gas-phase dissociation 𝐺𝑒𝐶𝑙4(𝑔) 𝐺𝑒𝐶𝑙2(𝑔) + 𝐶𝑙2(𝑔)
𝑘−𝑑𝑖𝑠
𝑘𝐴
Adsorption (1) 𝐺𝑒𝐶𝑙2(𝑔) + 𝑆 ֞ 𝐺𝑒𝐶𝑙2 ⋅ 𝑆
𝑘−𝐴
𝑘𝐻
Adsorption (2) 𝐻2(𝑔) + 2𝑆 ֞ 2𝐻 ⋅ 𝑆
𝑘−𝐻

𝑘𝑆
Surface reaction 𝐺𝑒𝐶𝑙2 ⋅ 𝑆 + 2𝐻 ⋅ 𝑆 𝐺𝑒 𝑠 + 2𝐻𝐶𝑙 𝑔 + 2𝑆

Surface reaction is believed to be the rate-limiting step

"
Rate of Ge deposition (nm/s): rDep = k S fGeCl fH2
2
ks: surface specific reaction rate (nm/s)
fGeCl2: fraction of the surface covered by GeCl2
fH2: fraction on the surface occupied by H2
*Surface coverage is in terms of fraction of surface, not conc of active sites
Slide 23
Catalyst Deactivation
Thus far, we assumed the total conc. 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

Slide 24
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
 Ed  1 1  
Sintering decay constant: k d = k d ( T0 ) exp   −  
 R  T0 T  
Slide 26
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

Slide 27
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
′
𝑘𝑑
poisoning by reactant: 𝐴 + 𝑆 𝐴⋅𝑆
′
𝑘𝑑
poisoning by product: 𝐵 + 𝑆 𝐵⋅𝑆
′
𝑘𝑑
poisoning by impurity: 𝑃 + 𝑆 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

Slide 28
Topic 10 – Theory: Summary

• From this lecture you should be able to:

o Understand the steps involved in a catalytic
reaction and develop a rate law based on a rate
limiting step in that reaction;
o Understand how chemical vapor deposition is
related to catalysis
o Understand and analyse catalytic reactions with
catalysts that are deactivated over time
o Perform analysis on moving bed catalytic
reactor designs

Slide 31