REACTION KINETICS OF

HETEROGENEOUS CATALYSIS
BKF3472
Chemical Reaction Engineering
II
1
TOPIC OUTCOME
Define a catalyst, a catalytic mechanism and a rate limit
step.
Describe the steps in a catalytic mechanism and how one
goes about deriving a rate law and a mechanism and rate
limiting step consistent with the experimental data.
Use Regression to discriminate between reaction rate laws
and mechanisms.
Size isothermal reactors for reactions with Langmuir-
Hinshelwood kinetics.
Discuss the different types of catalyst deactivation and the
reactor types and describe schemes that can help offset the
deactivation.
Analyze catalyst decay and conversion for CSTRs and
PFRs with temperature-time trajectories, moving bed
reactors, and straight through transport reactors.
2
WHAT IS CATALYST?
Definition of catalyst
A substance that affects the rate of a reaction but
comes out from the process unchanged

History
More than 2000 years ago; in wine, cheese and
bread; Berzelius works expanded by Ostwal.

Small amount of catalyst is used.

3
WHAT IS CATALYST?
Efficiency depends on activity, properties & life
of the catalyst
Examples:
Ammonia synthesis Promoted iron
SO
2
oxidation Vanadium Pentaoxide
Cracking Silica, alumina
Dehydrogenation Platinum, Molybdenum


4
Every catalytic reaction is a sequence of elementary steps,
in which reactant molecules bind to the catalyst, where
they react, after which the product detaches from the
catalyst, liberating the latter for the next cycle.
5
Potential energy diagram of a heterogeneous catalytic
reaction, with gaseous reactants and products and a solid
catalyst. Note that the uncatalyzed reaction has to overcome a
substantial energy barrier, whereas the barriers in the catalytic
route are much lower.
6
Classification:
Homogenous catalysis
Heterogeneous catalysis
Catalysts are generally used to:
Speedup reactions
Change the operating temperature level
Influence the product distribution
Catalyst affect yield and selectivity
Changes only the rate of reaction; it does not affect the
equilibrium.

7
Homogeneous:



Catalytic:




At 600K the ratio of catalytic to homogeneous rate is
1.44x10
11
Example: Boudart compared the homogeneous versus
catalytic rates of ethylene hydrogenation.
2
43000
exp 10
27
H
p
RT
r
|
.
|

\
|
=
2
13000
exp 10 2
27
H
p
RT
x r
|
.
|

\
|
=
8
WHAT IS CATALYST?
Alters the rate of reaction
Highly selective
Does it participate in the reaction ??
How does it change the rate ?? Offers an
alternate path with low E.
Does it affect AH
R
, AG
R
, and Eq. constant ??
Does it affect yield & selectivity ??
Does it initiate a reaction ??

9
HETEROGENEOUS CATALYSIS
10
HETEROGENEOUS CATALYTIC PROCESS
Involve more than one phase; usually the
catalyst is a solid and the reactants and
products are in liquid or gaseous form.
Examples:
AlCl
3
used in alkylation and dealkylation.
Pt used in isomerization reactions,
hydrogenation and dehydrogenation reactions.
11
Ostwald Process
Hot Pt wire
over NH
3

solution
Pt-Rh catalysts used
in Ostwald process
4NH
3
(g) + 5O
2
(g) 4NO (g) + 6H
2
O (g)
Pt catalyst
2NO (g) + O
2
(g) 2NO
2
(g)
2NO
2
(g) + H
2
O (l) HNO
2
(aq) + HNO
3
(aq)
13.6
Catalytic Converters
CO + Unburned Hydrocarbons + O
2
CO
2
+ H
2
O
catalytic
converter
2NO + 2NO
2

2N
2
+ 3O
2

catalytic
converter
POROUS STRUCTURE
FINE PORES ---> AREA NEEDED FOR THE HIGH RATE OF
REACTION
e.g SILICA-ALUMINA CRACKING CATALYST HAS A PORE
VOLUME OF 0.6 cm
3
/g (pore radius 4 nm) ---> 300 m
2
/g

MOLECULAR SIEVE --> small pores admit small molecules
but prevent large molecules
e.g Clay, zeolite (natural); aluminosilicates (synthetic)
CATALYST PROPERTIES
14
CATALYST PROPERTIES
SUPPORTED CATALYSTS
active material dispersed over a less active substance

UNSUPPORTED CATALYSTS
mainly promoters that increase activity

DEACTIVATION decline of activity as time progress
Aging (gradual change in surface crystal structure)
Poisoning or Fouling (deposit of foreign material) e.g
coking
15
Promoter: is an additive which has no catalytic
properties of its own but enhances the activity of a
catalyst
Promoter results in:
Increase of available surface area
Stabilization against crystal growth and
sintering
Improvement of mechanical strength

Examples: Alumina, Asbestos
CATALYST PROPERTIES
16
Carrier: principally serve as a framework on which
catalyst is deposited - no catalytic properties of its
own
Carrier results in:
Highly porous nature - increase of available
surface area
Improve stability
Improves the heat transfer characteristics

Examples: Alumina, Asbestos, Carborundum, Iron
oxide, Manganese, Activated carbon, Zinc oxide
CATALYST PROPERTIES
17
Accelerator: are substances which can be added to
a reacting system to maintain the activity of a
catalyst by nullifying the effects of poisons
Poisons: substances which reduce the activity of a
catalyst. They are not deliberately added but are
unavoidably deposited during the reaction.
Examples: Sulfur, Lead, Metal ions such as Hg,
Pd, Bi, Sn, Cu, Fe etc.
CATALYST PROPERTIES
18
Inhibitor: substances added to the catalyst during its
manufacture to reduce its activity.
Coking/Fouling: deposition of carbonaceous material
on the surface of the catalyst - Common to
reactions involving hydrocarbons
CATALYST PROPERTIES
19
Activity: of a catalyst depends on the texture and
electronic structure. Activity of a catalyst can be
explained by:
Active centers on the surface of the catalyst
Geometry of surface
Electronic structure
Formation of surface intermediates
CATALYST PROPERTIES
20
Active site: is a point on the catalyst surface that can
form strong chemical bonds with an adsorbed
atom/molecule. These sites are unsaturated atoms
in the solid resulting from:
Surface irregularities
Dislocations
Edges of crystals
Cracks along grain boundaries
CATALYST PROPERTIES
21
REACTION KINETICS
22
REACTION KINETICS
Chemical Plant
Reactor-the heart of
the chemical plant
Reactor Design
23
REACTION KINETICS
Definition: Study of the rate at which
chemical process occurs and the reaction
mechanism.

Usage: Used to size the reactor; used to
determine the reactor dynamics





25
26
In 2007
REACTION MECHANISM
27
1. Bulk Diffusion of reacting molecules to the surface of the catalyst
2. Pore Diffusion of reacting molecules into the interior pores of the catalyst
3. Adsorption of reactants (chemisorption) on the surface of the catalyst
4. Reaction on the surface of the catalyst between adsorbed molecules
5. Desorption of products
6. Pore Diffusion of product molecules to the surface of the catalyst
7. Bulk Diffusion of product molecules
MECHANISM OF HETEROGENEOUS CATALYSIS
Steps 3,4 and 5 are important
28
Pore and film resistances in a catalyst particle
29
Diffusion:
MECHANISM OF HETEROGENEOUS CATALYSIS
RATE LIMITING STEP (RDS)
30
Rate-Determining Step (rds)
In a kinetics scheme involving more than one step, it may be that
one change occurs much faster or much slower than the others
(as determined by relative magnitudes of rate constants).

In such a case, the overall rate, may be determined almost
entirely by the slowest step, called the rate-determining step (rds).

RDS
31
RDS

32

33
RDS
Type of Limitation Variation of Reaction Rate with:
Velocity Particle Size Temperature
External diffusion / / /
Internal diffusion X / /
Surface reaction X X /
34
/ dependent X independent
- Diffusion controlled reactions are few. Diffusion limitation could be
avoided by adjusting the fluid velocity and catalyst particle size.

- 75% of the reactions which are not controlled by diffusion are
controlled by surface reaction.

- Chemisorption of reactants and desorption of product could also be
rate controlling in a few cases.
SYNTHESIZING A RATE LAW
35
ACTIVE SITE
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.
From the reaction system of AB
SYNTHESIZING A RATE LAW
37
SYNTHESIZING RATE LAW
Example: Decomposition of cumene to form
benzene and propylene

Cumene (C) Benzene (B) + Propylene (P)

What would be the difference in rate law if the
reaction is limited by different step? (refer to
pg. 676 onwards)
38
IRREVERSIBLE SURFACE REACTION LIMITED
RATE LAW
Single site
Dual Site
Eley-Rideal
39
Algorithm to synthesize a rate law
Select a mechanism
Assume a rate-limiting step
Find the expression for concentration of the absorbed
species C
iS
Write a site balance
Derive the rate law
Compare with data
40
SYNTHESIZING A RATE LAW





















Consider,

41
SYNTHESIZING A RATE LAW
From the experimental studies, it was found that the rate law is

I I N N
P
I
N
N
P K P K
K
P
P k
r
+ +
(

=
1
'
What is the mechanism? Please guess..
Adsorption
Surface Reaction
Desorption
Reaction Mechanism
42
SYNTHESIZING A RATE LAW
Is the surface reaction
rate limiting?
43
Assume, surface reaction is a limiting step,
Thus
Then,
(

S
S I
S N S S
K
C
C k r
44
SYNTHESIZING A RATE LAW
Substituting for C
N-S
, C
I-S
, and C
V
into C
T
= C
V
(1 + K
N
P
N
+ K
I
P
I
) :
Site balance:
SYNTHESIZING A RATE LAW
45
Linearizing the Initial Rate:
SYNTHESIZING A RATE LAW
46
SYNTHESIZING A RATE LAW
47
Heterogeneous Data Analysis for Reactor
Design
Steps invloved :
Developing an algebraic rate law consistent with
experimental observations
Find mechanism and rate-limiting step
Analyze the rate law
Design catalytic reactor to achieve desired X


48
DESIGN EQUATION
Catalyst weight W substitute V (reactor
volume)

Batch : N
AO
dX/dt = -r'
A
W

Packed-bed (tubular) F
AO
dX/dW = -r'
A

CSTR : W = F
AO
X / -r'
A
(less frequently used)
49
50
STEP 1: DEDUCE RATE LAW FROM EXPERIMENTAL DATA
51
STEP 2: FINDING THE MECHANISM CONSISTENT
WITH EXPERIMENTAL OBSERVATION
Which
step is the
rate
limiting
step?
52
STEP 3: EVALUATION OF RATE LAW PARAMETERS
USING REGRESSION ANALYSIS (POLYMATH)
Nonlinear least square program
(Example 10.2)
Model



Find k, K
B
and K
T
53
STEP 4: REACTOR DESIGN
Example 10.3
54
REACTOR DESIGN- GROUP WORK
Assuming Benzene and Toluene are weakly adsorbed on the catalyst
surface, determine the catalyst weight required to achieve 68% conversion.
Gro
up
No.
Question 1 Answer Q1 Question 2

1 Pressure drop
parameter, alpha= 2
x 10
-5
kg
-1
429.30 kg
What is the exact catalyst weight if
the assumption is not valid.
2 Pressure drop
parameter, alpha= 4
x 10
-5
kg
-1
431.15 kg
What is the exact catalyst weight if
the assumption is not valid.
3 Pressure drop
parameter, alpha= 6
x 10
-5
kg
-1
433.08kg
What is the exact catalyst weight if
the assumption is not valid.
4 Pressure drop
parameter, alpha=
9.8x10
-5
kg
-1
437
What is the exact catalyst weight if
the assumption is not valid.
55
REACTOR DESIGN- GROUP WORK

56
Assuming Benzene and Toluene are weakly adsorbed on the catalyst surface,
determine the catalyst weight required to achieve 68% conversion.
Gr
ou
p
No.
Question 1 Answer Q1 Question 2

5 Toluene molar flow
rate, F= 30
mol/min

260
What is the exact catalyst weight if the
assumption is not valid.
6 Toluene molar flow
rate, F= 40
mol/min

347.8966kg
What is the exact catalyst weight if the
assumption is not valid.
7 Toluene molar flow
rate, F= 70
mol/min

618
What is the exact catalyst weight if the
assumption is not valid.
REACTOR DESIGN- GROUP WORK

57
Assuming Benzene and Toluene are weakly adsorbed on the catalyst surface,
determine the catalyst weight required to achieve 68% conversion.
Gr
ou
p
No.
Question 1 Answer Q1 Question 2

8 Initial pressure= 30
atm

791
What is the exact catalyst weight if the
assumption is not valid.
9 Initial pressure= 50
atm

277.3415kg
What is the exact catalyst weight if the
assumption is not valid.
10 Initial pressure= 60
atm

192
What is the exact catalyst weight if the
assumption is not valid.
CATALYST DEACTIVATION
Common problem loss of catalytic activity

Catalyst activity defined by a(t)
a(t) = -r'
A
(t) / -r'
A
(t=0)



The rate of catalyst decay, r
d
can be expressed:
) ...... , ( ) ( ) (
) , 0 ( ) (
'
' '
P B A A
A A
C C C fn T k t a r
fresh t r t a r
=
= =
( ) | | ( )
2
decay, order 2nd For
decay, order 1st For
) ...... , (
a p(a)
a p(a)
C C C h T k t a p
dt
da
r
P B A d d
=
=
= =
58

TYPES OF CATALYST DECAY
1.) Sintering
2.) Coking
3.) Poisoning


4.) Slow Decay Temperature-Time Trajectories
5.) Moderate Decay Moving Bed
6.) Rapid Decay
Straight-Through Transport
Reactors (STTR)
Common law/situation
59
DECAY RATE LAW
Refer Table 10-7
60
EXAMPLE
Consider A B
Reaction information,
Isothermal, liquid phase
batch reactor,
catalyst due to decaying 2nd order.
W=20 kg, k=45 liter/kg h, k
d
=180 h
-1
,V=200 liter.
Find the X at t=2 hours
61
Design
Equation
Solution
W r
dt
dX
N
A AO
' =
A A
C t a k r ) ( ' ' =
t k
t a
d
+
=
1
1
) (
) 1 ( ) 1 ( X
V
N
X C C
AO
AO A
= =
Reaction rate
law
Decay Law
Stoichiometry
62
Combining
) 1 )( ( ' X t a k
V
W
dt
dX
=
t k
dt
V
Wk
X
dX
d
+
=
1
'
) 1 (
} }
+
=
t k
dt
V
Wk
X
dX
d
1
'
) 1 (
) 1 ln(
'
1
1
ln t k
Vk
Wk
X
d
d
+ =

Integrate
Solving
136 . 0
) 2 180 1 ln(
180 200
/ 45 20
1
1
ln
1
1
=
+

=

X
h h
h liter
hr kg liter kg
X
63
CATALYST DECAY IN REACTORS
Consider
Example 10-6
Example 10-7
Example 10-8
64
65
66
CATALYST DEACTIVATION- GROUP WORK
G1-G4
Based on the previous group work, assuming that the reaction is performed in a
moving bed reactor with catalyst moving rate of 10 kg/min, there is no pressure
drop, deactivation occurs according to the 1
st
order decay with the kd= 0,007 min
-
1
. Determine the weight of catalyst needed to achieve 68%, Answer: 523kg
G5-G7
Based on the previous group work, assuming that the reaction is performed in a moving
bed reactor with catalyst moving rate of 10 kg/min, there is no pressure drop,
deactivation occurs according to the zero order decay with the kd= 0,007 min
-1
.
Determine the weight of catalyst needed to achieve 68%, A: 282, 391, 775
G8-G10
Based on the previous group work, assuming that the reaction is performed in a moving
bed reactor with catalyst moving rate of 10 kg/min, there is no pressure drop,
deactivation occurs according to the 2
nd
order decay with the kd= 0,007 min
-1
. Determine
the weight of catalyst needed to achieve 68%, A: 1003, 302, 203
67
END
68