Chemical Reaction Engineering

Week 10 (S1-2012)
Fogler Chapter 10
Catalysis and Catalytic Reactors
Lecture 1
Gia Hung Pham
Objectives
- Catalysts and catalytic reactor design
- Steps in a heterogeneous reaction
- Reaction mechanism
- Rate law
- Catalyst decay
- Reactor types
Catalysts
Definition
- Fogler: A substance that affects the rate of a reaction but
emerges from the process unchanged.
- Ostwald (1895): A catalyst accelerates a chemical
reaction without affecting the position of the equilibrium.
Phenomenon
Reaction A P
Catalyst changes reaction pathway.
A
Cat
Cat-A
Chemical bonding
Cat-P
P
- Positive catalyst increases reaction rate.
- Negative catalyst decreases reaction rate.
Importance of catalysis
- About 75% of all chemicals are produced by catalytic process.
Catalyst can be:
- Gas (NO
x
)
- Liquid (H
2
SO
4
)
- Solid (Ni)
Note: In this chapter only solid catalysts will be considered.
Reaction energetic
Energy
A
P
E
a
(without cat)
H
Ea (with cat)
Cat-A
Cat-P
adsorption
reaction
desorption
Reaction progress
Heterogeneous catalyst
PBR
Reactants (gas or liquid)
Solid catalyst
Products
Heterogeneous catalyst
PBR
Catalyst Bed
Heterogeneous catalyst
PBR
Catalyst Bed
Catalyst pellet
Heterogeneous catalyst
PBR
Catalyst Bed
Catalyst pellet
Catalyst pore
Active site
Catalyst surface area
- Specific surface area of silica-alumina cracking catalyst is
300 m
2
/g.
- External surface area of 1mm alumina sphere is
0.0015m
2
/g.
- A catalyst that has large area resulting from pores
(internal surface area) is called a porous catalyst.
Film theory
Fogler. Page 773
Individual steps in heterogeneous catalysis ( A P )
C
Ab
C
As
Cat-A
Cat-P
A
A
A
A
P
P
P
4
Boundary layer

P
Catalyst pellet
Catalyst pore
1
2 3
5
6
7
Individual steps in heterogeneous catalysis (Mass transfer and
chemical reaction)
Step 1. Diffusion of the reactant A from the fluid to the catalyst
surface (External mass transfer).
Step 2. Diffusion of the reactant A from the pore mouth into the
pore (Internal mass transfer or pore diffusion).
Step 3. Adsorption of the reactant onto the surface of the pore
(Reactant adsorption).
Step 4. Chemical reaction on the catalyst surface to form product
P (Surface reaction).
Step 5. Desorption of the product P from the catalyst surface
(Product desorption).
Step 6. Diffusion of the product P out of the pore (Internal mass
transfer or pore diffusion).
Step 7. Diffusion of the product from the pore mouth through the
boundary layer into the bulk fluid (External mass transfer).
Catalytic reaction Kinetics
Mass transfer
and Effective reaction rate r
A,eff
Catalytic reaction
Reaction kinetics without mass transfer effects.
We choose the conditions, under which the mass transfers do not affect the effective
reaction rate.
For example: High feed flow rate and /or small catalyst particle size
No mass transfer limiting C
A,b
= C
A,s
= C
A
Conc.
C
As
Catalyst pore
bulk
C
Ab
C
A
Concentration of A in catalyst pore does NOT change
with pore length L.
L
Assumptions: - Uniform surface
- Active site has the same attraction
Conc.
C
As
Catalyst pore
s
s
s
s
s
bulk
Active site
Catalyst surface
C
Ab
C
A
Steps in a heterogeneous catalytic without mass transfer effects
- Step 3 : Adsorption of reactants
- Step 4 : Surface reaction catalytic chemical reaction
- Step 5 : Desorption of products
Reaction A P
s s s s s
A P
Catalyst surface
3
4
5
Adsorption Isotherms
Concentration of active site
Active site balance: C
t
= C
v
+ C
As
+ C
Ps
s
s
s s
s s
P
A
Occupied sites
Vacant sites
Total active site per gram catalyst (mol/g
cat
)
Vacant site per gram catalyst (mol/g
cat
)
Occupied sites by species A and B (mol/g
cat
)
Two adsorption models
- Model 1: Molecular or nondissociated adsorption.
Example: Adsorption of CO on Ni-catalyst
CO
- Model 2: Dissociative adsorption
Example: Adsorption of CO on Fe-catalyst
s
s
s s
s
C
O
Molecule CO
S = Ni
CO + S
COS
CO
s
s
s s
C O
Atom C and O
S = Fe
CO + 2S C-S +OS
Model 1
Rate law for the reaction
Rate of attachment = k
A
P
CO
C
v
Rate of detachment = k
-A
C
COS
Net rate of adsorption r
AD
= k
A
P
CO
C
v
k
-A
C
COS
or
with (adsorption equilibrium constant)
CO + S COS
k
A
k
-A
A
A
A
k
k
K

=
|
|
.
|

\
|
=
-
A
S CO
v CO A AD
K
C
C P k r
Site balance : C
t
= C
V
+ C
COS
At equilibrium r
AD
= 0 we have C
COS
= K
A
C
V
P
CO
This adsorption isotherm equation is called Langmuir Isotherm.
CO A
t CO A
S CO
P K
C P K
C
+
=
-
1
C
COS
P
CO
Linear
Model 2
CO + 2S CS + OS
Net reaction rate
At equilibrium r
AD
= 0
Site balance C
t
= C
V
+ C
OS
+ C
CS
k
A
K
-A
S C S O A V CO A AD
C C k C P k r
- -
=
2
|
|
.
|

\
|
=
- -
A
S O S C
V CO A AD
K
C C
C P k r
2
( )
( )
2 / 1
2 / 1
2 1
CO A
CO A t
S O
P K
P K C
C
+
=
-
C
OS
P
CO
parabolic
Inverse of both sides and multiply
2 / 1
CO
P
t
CO
A t OS
CO
C
P
K C C
P
2 / 1
2 / 1
2 / 1
2 1
+ =
2 / 1
CO
P
OS
CO
C
P
2 / 1
Adsorption isotherm equation of A in the presence of adsorbate B
s s s
s s
A
B
C
t
= C
V
+ C
AS
+ C
BS
B B A A
t A A
S A
P K P K
C P K
C
+ +
=
-
1
Surface reaction
* Model 1: Single site
A S BS
s
s
A B
k
S
k
-S
|
|
.
|

\
|
=
-
-
S
S B
S A S s
K
C
C k r
k
s
k
-s
* Model 2: Dual site
AS + S BS + S
A
B
|
|
.
|

\
|
=
-
-
S
V S B
V S A S s
K
C C
C C k r
k
s
k
-s
k
s
k
-s
* Model 3: Eley Rideal
AS + B(g) CS
B(g)
A
C
|
|
.
|

\
|
=
-
-
S
S C
B S A S s
K
C
P C k r
s
s
k
s
k
-s
k
s
k
-s
Desorption
CS C + S
With K
DC
= 1/K
C
s
s
C
C
|
|
.
|

\
|
=
-
DC
V C
S C D DC
K
C P
C k r
( )
V C C S C D DC
C P K C k r =
-
k
D
k
-D
k
D
k
-D
Synthesizing a rate law
Mechanism and rate limiting step
Foglers Example (page 671): Reaction
C
6
H
5
CH(CH
3
)
2
C
6
H
6
+ C
3
H
6
Cumene Benzene Propylene
C B P
Reaction mechanism
C + S CS (Adsorption)
CS BS + P(gas) (Surface reaction)
BS B + S (Desorption)
k
A
k
-A
k
S
k
-S
k
D
k
-D
Reaction rate
Adsorption
r
AD
= k
A
P
c
C
v
k
-A
C
CS
Surface reaction
r
S
= k
S
C
CS
k
-S
P
P
C
BS
Desorption
r
D
= k
D
C
BS
k
-D
P
B
C
V
|
|
.
|

\
|
=
-
-
S
S B P
S C S S
K
C P
C k r
( )
V B B S B D D
C P K C k r =
-
|
|
.
|

\
|
=
-
C
S C
V C A AD
K
C
C P k r
Case 1
The reaction rate of three discussed reactions are equal
D S AD C
r r r r = = =
'
Case 2
Reaction rate limiting
One or two of three discussed reactions has/have very slow reaction rate.
We assume the adsorption of cumene is rate limiting (slowest step).
What is the rate law if it is true?
Adsorption rate
We need to express C
v
and C
CS
in terms of P
C
, P
B
and P
P
|
|
.
|

\
|
=
-
C
S C
V C A AD
K
C
C P k r
Unknown
Measurable
k
A
: small
k
S
: large or r
S
/k
S
0
k
D
: large or r
D
/k
D
0
Surface reaction
|
|
.
|

\
|
=
-
-
S
S B P
S C S S
K
C P
C k r
S
P S B
S C
K
P C
C
-
-
=
unknown
Desorption
( )
V B B S B D D
C P K C k r =
-
V B B S B
C P K C =
-
V
S
P B
B S C
C
K
P P
K C =
-
|
|
.
|

\
|
=
C S
V P B B
V C A AD
K K
C P P K
C P k r
Overall reaction C B + P
B
C S
P
K
K K
K =
Site balance C
t
= C
V
+ C
CS
+ C
BS
Solving for C
V
we have
V B B V P B
S
B
V t
C P K C P P
K
K
C C + + =
B B B P
S
B
t
V
P K P P
K
K
C
C
+ +
=
1
Adsorption control rate law
At t = 0 min we have P
c
= P
c,0
P
P
= 0 (no product)
P
B
= 0 (no product)
B P B P
S
B
P
P B
C A t
AD
P K P P
K
K
K
P P
P k C
r
+ +
|
|
.
|

\
|

=
1
Adsorption control rate law at t = 0 min
Plot initial rate versus
.
0 , 0 ,
'
, C C A t AD O C
P k P k C r r = = =
'
,O C
r
0 , C
P
'
,O C
r
0 , C
P
We assume the surface reaction is rate limiting (slowest step).
What is the rate law if it is true?
Surface reaction
* k
S
: small
* k
A
: large or r
AD
/k
A
0
* k
D
: large or r
D
/k
D
0
|
|
.
|

\
|
=
-
-
S
S B P
S C S S
K
C P
C k r
We get these concentrations from
adsorption and desorption reaction.
Adsorption reaction
Desorption reaction
|
|
.
|

\
|
=
-
C
S C
V C A AD
K
C
C P k r
V C C S C
C P K C =
-
( )
V B B S B D D
C P K C k r =
-
V B B S B
C P K C =
-
Surface reaction rate limiting
V
P
B P
C C S S
C
K
P P
P K k r
|
|
.
|

\
|
=
We get this one from site balance
( )
C C B B
t
V
P K P K
C
C
+ +
=
1
C C B B
B
P B
C t C S
S
P K P K
K
P P
P C K k
r
+ +
|
|
.
|

\
|

=
1
At t = 0 min
At low partial pressure of C we have 1 >> K
C
P
C,0
Initial rate increase linearly with the partial pressure of C
0 ,
0 ,
,
0 ,
1
C C
C
S C
P K
P k
r r
+
= =
t C S
C K k k with =
0 ,
,
0 , C S C
P k r r = =
At high initial partial pressure of C we have K
C
P
C,0
>>1
t cons
K
k
r r
C
S C
tan
,
0 ,
= = =
'
,O C
r
0 , C
P
k
We assume the desorption of Benzene reaction is rate limiting (slowest step).
What is the rate law if it is true?
Desorption reaction
* k
D
: small
* k
A
: large or r
AD
/k
A
0
* k
S
: large or r
S
/k
S
0
( )
V B B S B D D
C P K C k r =
-
Not measureable but we can get this one from adsorption and surface reaction.
Surface reaction
Adsorption reaction
Site balance
|
|
.
|

\
|
=
-
P
S C
S S B
P
C
K C
,
V C C S C
C P K C =
-
C C
P
C
S C
t
V
P K
P
P
K K
C
C
+ +
=
1
Desorption limiting
At t= 0 min
|
|
|
|
|
.
|

\
|
+ +

= =
P C C C S C P
B
P B
C
t S C D D C
P P K P K K P
K
P P
P
C K K k r r
,
0 ,
t cons C k r
t D C
tan
,
0 ,
= =
'
,O C
r
0 , C
P
Foglers algorithm for determining reaction mechanism and rate
limiting step.
1. Select a mechanism
2. Assume a rate-limiting step
3. Find the expression for concentration of the
adsorbed species C
i,S
4. Write a site balance
5. Derive the rate law
6. Compare with data
In-class exercise
The following reaction is carried out over a solid catalyst, the reaction
mechanism is believed to be
We assume step 3 is the slowest step, derive the rate law for the
reaction.
S D S D
S C S C
S D S C S B S A
S B S B
S A S A
+ -
+ -
- + - - + -
- +
- +
) 5
) 4
) 3
) 2
) 1