REACTION KINETICS OF
HETEROGENEOUS CATALYSIS
BKF3472
Chemical Reaction Engineering II
1
TOPIC OUTCOME
Define catalyst, catalytic mechanism and 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?
• Is a substance that increases the rate at which a chemical rxn
approaches equilibrium without itself undergoing permanent
chemical changes.
• A catalyst cannot change the ultimate equilibrium determined
by thermodynamics; its role is restricted to accelerating the rate
of approach to equilibrium.
• Classification of catalyst homogeneous
heterogeneous
• Eg of rxn that involves catalyst :
The oxidation of a mixture of o-xylene and air to phthalic
anhydride is catalyzed by V205. o-Xylene by itself may
also be oxidized by contacting it alone with V205, in
which case the V205 acts as a reagent and becomes
stoichiometrically reduced to a lower oxide.
WHAT IS CATALYST?
• Efficiency depends on activity, properties & life
of the catalyst
• Examples:
• Ammonia synthesis – Promoted iron
• SO2 oxidation – Vanadium Pentaoxide
• Cracking – Silica, alumina
• Dehydrogenation – Platinum, Molybdenum
5
Every catalytic reaction is a sequence of elementary steps.
6
barrier in the catalytic route
7
Catalysts function by providing an
alternate reaction mechanism that
has a lower activation energy than
would be found in the absence of
the catalyst
This lower activation energy results
in an increase in rate as described
by the Arrhenius equation.
WHAT IS CATALYST?
• Does it participate in the reaction ??
• How does it change the rate ??
• Does it affect HR, GR, and Eq. constant ??
• Does it affect yield & selectivity ??
• Does it initiate a reaction ??
9
Classification:
• Homogenous catalysis
• Heterogeneous catalysis
Example: Boudart compared the homogeneous versus
catalytic rates of ethylene hydrogenation.
Homogeneous:
43000
r 10 exp
27
pH 2
RT
Catalytic:
13000
r 2 x10 exp
27
pH 2
RT
At 600K the ratio of catalytic to homogeneous rate is 1.44x1011
10
HETEROGENEOUS CATALYSIS
11
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:
AlCl3used in alkylation and dealkylation.
Pt used in isomerization reactions, hydrogenation
and dehydrogenation reactions.
12
Ostwald Process
Pt catalyst
4NH3 (g) + 5O2 (g) 4NO (g) + 6H2O (g)
2NO (g) + O2 (g) 2NO2 (g)
2NO2 (g) + H2O (l) HNO2 (aq) + HNO3 (aq)
Hot Pt wire
Pt-Rh catalysts used over NH3
in Ostwald process solution 13.6
Catalytic Converters
catalytic
CO + Unburned Hydrocarbons + O2 converter CO2 + H2O
catalytic
2NO + 2NO2 converter 2N2 + 3O2
TYPES OF CATALYTIC REACTORS
Examples of reactors with fixed catalyst beds (larger particles): (a)
adiabatic packed bed; (b) cooled tubular reactor; (c) cocurrent trickle
bed reactor; (d) packed bubble column.
Common reactor types with moving catalyst beds (fine particles):
(a) fluid-bed reactor; (b) bubble column with suspended catalyst;
(c) sparged stirred tank with suspended catalyst
CATALYST PROPERTIES
SUPPORTED CATALYSTS
active material dispersed over a less active substance
UNSUPPORTED CATALYSTS
DEACTIVATION – decline of activity as time progress
Aging (gradual change in surface crystal structure)
Poisoning or Fouling (deposit of foreign material) e.g
coking
17
CATALYST PROPERTIES
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
18
CATALYST PROPERTIES
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
19
CATALYST PROPERTIES
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
20
CATALYST PROPERTIES
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
21
EXAMPLE
Dehydrocyclization of Diphenylamine to
Carbazole over Platinum-Based Bimetallic
Catalysts (supported by Alumina)
22
EXAMPLE
Preparation and Characterization of Carbon-
Covered Alumina Supported Ni Catalyst and Its
Catalytic Performance for Hydrogenation of 1,4-
Butanediol
23
EXAMPLE
Supported sulfonic acid
24
REACTION KINETICS
25
REACTION KINETICS
Reactor Design
Reactor-the heart of
the chemical plant
Chemical Plant
26
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
28
In 2007
29
REACTION MECHANISM
30
MECHANISM OF HETEROGENEOUS CATALYSIS
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
Steps 3,4 and 5 are important
31
MECHANISM OF HETEROGENEOUS CATALYSIS
Diffusion:
Pore and film resistances in a catalyst particle
32
RATE LIMITING STEP (RDS)
33
RDS
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).
34
RDS
35
36
RDS
Type of Limitation Variation of Reaction Rate with:
Velocity Particle Size Temperature
External diffusion / / /
Internal diffusion X / /
Surface reaction X X /
/ 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.
37
SYNTHESIZING A RATE LAW
38
SYNTHESIZING A RATE LAW
Algorithm to synthesize a rate law
Select a mechanism
Assume a rate-limiting step
Find the expression for concentration of the absorbed
species Ci·S
Write a site balance
Derive the rate law
Compare with data
39
MECHANISM
40
IRREVERSIBLE SURFACE REACTION LIMITED
RATE LAW
Single site
Dual Site
Eley-Rideal
41
RATE LIMITING STEP
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)
42
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: EXAMPLE
Consider,
From the experimental studies, it was found that the rate law is
PI
k PN What is the mechanism? Please guess……..
rN' K P
1 K N PN K I PI
44
SYNTHESIZING A RATE LAW
Reaction Mechanism
Adsorption
Surface Reaction
Desorption
45
Is the surface reaction
rate limiting?
46
SYNTHESIZING A RATE LAW
Assume, surface reaction is a limiting step,
Thus
C I S
rS k S CN S
K S
Then,
47
SYNTHESIZING A RATE LAW
Site balance:
Substituting for CN-S, CI-S, and CV into CT = CV (1 + KN PN + KI PI) :
48
SYNTHESIZING A RATE LAW
Linearizing the Initial Rate:
49
SYNTHESIZING A RATE LAW
50
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
51
DESIGN EQUATION
Catalyst weight W substitute V (reactor volume)
Batch : NAO dX/dt = -r'A W
Packed-bed (tubular) FAO dX/dW = -r'A
CSTR : W = FAOX / -r'A (less frequently used)
52
53
STEP 1: DEDUCE RATE LAW FROM EXPERIMENTAL DATA
54
STEP 2: FINDING THE MECHANISM CONSISTENT
WITH EXPERIMENTAL OBSERVATION
Which
step is the
rate
limiting
step?
55
STEP 3: EVALUATION OF RATE LAW PARAMETERS
USING REGRESSION ANALYSIS (POLYMATH)
Nonlinear least square program
(Example 10.2)
Model
Find k, KB and KT
56
STEP 4: REACTOR DESIGN
Example 10.3
57
REACTOR DESIGN- GROUP WORK
Assuming Benzene and Toluene are weakly adsorbed on the catalyst
surface, determine the catalyst weight required to achieve 68%
conversion.
Gr Question 1 Answer Q1 Question 2
ou
p
No.
429.30 kg
1 Pressure drop What is the exact catalyst weight
parameter, alpha= if the assumption is not valid.
2 x 10-5 kg-1
431.15 kg
2 Pressure drop What is the exact catalyst weight
parameter, alpha= if the assumption is not valid.
4 x 10-5 kg-1
433.08kg
3 Pressure drop What is the exact catalyst weight
parameter, alpha= if the assumption is not valid.
6 x 10-5 kg-1
437
4 Pressure drop What is the exact catalyst weight
parameter, alpha= if the assumption is not valid.
9.8x10-5kg-1 58
REACTOR DESIGN- GROUP WORK
Assuming Benzene and Toluene are weakly adsorbed on the catalyst surface,
determine the catalyst weight required to achieve 68% conversion.
Gr Question 1 Answer Q1 Question 2
ou
p
No.
260
5 Toluene molar flow What is the exact catalyst weight if the
rate, F= 30 assumption is not valid.
mol/min
347.8966kg
6 Toluene molar flow What is the exact catalyst weight if the
rate, F= 40 assumption is not valid.
mol/min
618
7 Toluene molar flow What is the exact catalyst weight if the
rate, F= 70 assumption is not valid.
mol/min
59
REACTOR DESIGN- GROUP WORK
Assuming Benzene and Toluene are weakly adsorbed on the catalyst surface,
determine the catalyst weight required to achieve 68% conversion.
Gr Question 1 Answer Q1 Question 2
ou
p
No.
791
8 Initial pressure= What is the exact catalyst weight if the
30 atm assumption is not valid.
277.3415kg
9 Initial pressure= What is the exact catalyst weight if the
50 atm assumption is not valid.
192
10 Initial pressure= What is the exact catalyst weight if the
60 atm assumption is not valid.
60
READING ASSIGNMENT
Definition of different type of catalyst
deactivation
Type of reactors used to offset the deactivation
Definition of decay law
61
CATALYST DEACTIVATION
Common problem – loss of catalytic activity
Catalyst activity defined by a(t)
a(t) = -r'A (t) / -r'A (t=0)
rA' a(t ) rA' (t 0, fresh)
rA' a(t )k (T ) fn(C A , CB ......CP )
The rate of catalyst decay, rd can be expressed:
pat k d T h(C A , C B ......C P )
da
rd
dt
For 1st order decay, p(a) a
For 2nd order decay, p(a) a 2
62
TYPES OF CATALYST DECAY
Common law/situation
1.) Sintering
2.) Coking
3.) Poisoning
4.) Slow Decay Temperature-Time Trajectories
5.) Moderate Decay Moving Bed
Straight-Through Transport
6.) Rapid Decay
Reactors (STTR)
63
TIME SCALE OF DEACTIVATION
64
DECAY RATE LAW
Refer Table 10-7
65
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, kd=180 h-1,V=200 liter.
Find the X at t=2 hours
66
Solution
Design dX
N AO r ' A W
Equation dt
Reaction rate
law r ' A k ' a(t )CA
1
Decay Law a (t )
1 kd t
Stoichiometry
N AO
C A C AO (1 X ) (1 X )
V
67
Combining
dX W
k ' a (t )(1 X )
dt V
dX Wk ' dt
(1 X ) V 1 k d t
Integrate
dX Wk ' dt
(1 X ) V 1 kd t
Solving
1 Wk '
ln ln( 1 k d t )
1 X Vkd
1 20kg 45liter / kg hr 1
ln 1
ln( 1 180 h 2h)
1 X 200liter180h
X 0.136
68
EXAMPLE
Consider A B
Reaction information,
Isothermal, liquid phase
Moving bed reactor
catalyst due to decaying 2nd order.
W=20 kg, k’=45 liter/kg·h, kd=180 h-1,v0=20liter/h,
Us=10kg/h
Find the X
69
CATALYST DECAY IN REACTORS
Consider
Example 10-6
Example 10-7
Example 10-8
70
71
72
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 1st order decay with the kd= 0,007 min-1.
Determine the weight of catalyst needed to achieve 68%, Answer: 508kg
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, 397, 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 2nd order decay with the kd= 0,007 min-1.
Determine the weight of catalyst needed to achieve 68%, A: 1003, 302, 203
73
END
74
