REACTION KINETICS OF

HETEROGENEOUS CATALYSIS

BKF3472
Chemical Reaction Engineering II

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 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.

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 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.

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 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

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Every catalytic reaction is a sequence of elementary steps.

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barrier in the catalytic route

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 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 ??

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Classification:
• Homogenous catalysis
• Heterogeneous catalysis
Example: Boudart compared the homogeneous versus
catalytic rates of ethylene hydrogenation.
Homogeneous:
 43000 
r  10 exp  
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 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
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HETEROGENEOUS CATALYSIS

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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.

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 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

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 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
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 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

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 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

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 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

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EXAMPLE

 Dehydrocyclization of Diphenylamine to
Carbazole over Platinum-Based Bimetallic
Catalysts (supported by Alumina)

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EXAMPLE

 Preparation and Characterization of Carbon-

Covered Alumina Supported Ni Catalyst and Its
Catalytic Performance for Hydrogenation of 1,4-
Butanediol

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EXAMPLE

 Supported sulfonic acid

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REACTION KINETICS

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REACTION KINETICS

Reactor Design

Reactor-the heart of
the chemical plant

Chemical Plant

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 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
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In 2007

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REACTION MECHANISM

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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

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MECHANISM OF HETEROGENEOUS CATALYSIS
Diffusion:

Pore and film resistances in a catalyst particle

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RATE LIMITING STEP (RDS)

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 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).

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RDS

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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.
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SYNTHESIZING A RATE LAW

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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

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MECHANISM

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IRREVERSIBLE SURFACE REACTION LIMITED
RATE LAW

Single site

Dual Site

Eley-Rideal

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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)

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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 AB
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

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SYNTHESIZING A RATE LAW
Reaction Mechanism
Adsorption

Surface Reaction

Desorption

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Is the surface reaction
rate limiting?

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SYNTHESIZING A RATE LAW
Assume, surface reaction is a limiting step,
Thus
 C I S 
rS  k S CN S  
 K S 

Then,

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SYNTHESIZING A RATE LAW

Site balance:

Substituting for CN-S, CI-S, and CV into CT = CV (1 + KN PN + KI PI) :

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SYNTHESIZING A RATE LAW

Linearizing the Initial Rate:

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SYNTHESIZING A RATE LAW

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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

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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)

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STEP 1: DEDUCE RATE LAW FROM EXPERIMENTAL DATA

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STEP 2: FINDING THE MECHANISM CONSISTENT
WITH EXPERIMENTAL OBSERVATION

Which
step is the
rate
limiting
step?

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STEP 3: EVALUATION OF RATE LAW PARAMETERS
USING REGRESSION ANALYSIS (POLYMATH)

 Nonlinear least square program

(Example 10.2)
 Model

 Find k, KB and KT

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STEP 4: REACTOR DESIGN

 Example 10.3

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 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
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 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.

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READING ASSIGNMENT

 Definition of different type of catalyst

deactivation
 Type of reactors used to offset the deactivation

 Definition of decay law

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 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:

 pat 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

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 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)
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TIME SCALE OF DEACTIVATION

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 DECAY RATE LAW

 Refer Table 10-7

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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

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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
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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
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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

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CATALYST DECAY IN REACTORS

 Consider
 Example 10-6
 Example 10-7

 Example 10-8

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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

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END
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