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Objectives
REACTION ENGINEERING • Define catalyst, catalytic mechanism and rate
CKB 20104 limiting step.
• Describe the steps in a catalytic reaction
• Describe porous catalyst particles
CHAPTER 8 • Describe packed bed catalytic reactor

Heterogeneous Reactions Heterogeneous Reactions

8.1 Catalyst definition and properties
8.2 Steps in a catalytic reaction
Dr. Kelly Yong Tau Len 8.3 Porous catalyst particle
Section of Chemical Engineering Technology UniKL MICET 8.4 Packed bed catalytic reactor
Tel: 06-5512051
Email: kytlen@unikl.edu.my, VLE: CKB20104 – kytlen_MICET
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8.1 Catalyst Definition and Properties

8.1 Catalyst Definition and Properties
• A catalyst is substance that affects the rate of a Catalyst lowers the activation energy for
reaction but emerges from the process both forward and reverse reactions.
UNCHANGED.
• A catalyst usually changes a reaction rate by
promoting a different molecular path
(mechanism) for the reaction
• This new molecular path provides an alternative
reaction pathway of lower activation energy Ea,
compared to the uncatalyzed reaction
• A catalyst changes only the rate of a reaction, it
does not affect the equilibrium
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8.1 Catalyst Definition and Properties 8.1 Catalysts Definition and Properties
The Activation Energy (Ea) determines how fast
a reaction occurs, the higher Activation barrier,
the slower the reaction rate. The lower the
Activation barrier, the faster the reaction

This means the catalyst changes the reaction

path by lowering its activation energy and
consequently the catalyst increases the rate of
reaction. 6
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8.1 Catalysts Definition and Properties

HOMOGENOUS CATALYSIS
• The catalyst and reactants are in the SAME phase
(usually a solution)
• Catalyzed reaction can happen throughout the bulk
of the reaction medium.
• Example: The reaction between persulphate ions
and iodide ions.
Fe 2+ or Fe3+
Catalyst

2- 2-
S2 O 8 + 2I - ® 2SO 4 + I2
7 Reactants

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8.1 Catalysts Definition and Properties 8.1 Catalysts Definition and Properties
HETEROGENOUS CATALYSIS Catalyst Properties

• The catalyst and reactants are in

DIFFERENT phases (usually solid Supported
Monolithic
catalyst and liquid/gaseous reactant)
• Reaction occurs on the catalyst surface Types of
which may be the TRANSITION METAL Catalyst Molecular
or one of its compounds. Unsupported
• The reactants must be adsorbed onto sieves
the catalyst surface at the 'active sites'.
Porous
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8.1 Catalysts Definition and Properties 8.1 Catalysts Definition and Properties
Catalyst Properties Catalyst Properties
2. Molecular Sieves
1. Porous Catalyst Catalyst with small pores. They will only
Catalyst that has large area admit small molecules but prevent large
ones from entering
resulting from pores Derived from natural substances such
Example of these including clays and zeolites or totally synthetic
such as crystalline aluminosilicates
Raney nickel used in the The pores can control the residence
hydrogenation of vegetable time of molecules near the active
surface that essentially allows only the
and animal oils desired molecules to react
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8.1 Catalysts Definition and Properties Major use in

Catalyst Properties catalytic converters
for gasoline fueled
3. Monolithic
vehicles.
An alternative to the use of small particles of Embedded in a
catalysts for very rapid reactions of gases ceramic or metal
Normally encountered for process where support that
pressure drop and heat removal are major consists of square,
consideration. hexagonal,
triangular cells that
It can be either porous or non-porous
are separated by
Catalyst is deposited on the cell walls or thin walls to give a
impregnated into a thin coating or other large number of
porous support. parallel channels.
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8.1 Catalysts Definition and Properties 8.1 Catalysts Definition and Properties
Catalyst Properties Catalyst Properties
4. Supported
The catalyst consists of minute particles of an active material 5. Unsupported
dispersed over a less active substance called a support.
Active material is frequently a pure metal or metal alloy
Catalysts can also have small amounts of active ingredients For unsupported catalysts, the active
added called promoters which increase their activity. ingredients are not dispersed over any
Example such as platinum on alumina catalyst used in
petroleum reforming
support.
Example is the silica-alumina
dehydrogenation catalyst used in
butadiene manufacture

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8.1 Catalysts Definition and Properties 8.1 Catalysts Definition and Properties
Catalyst Deactivation Catalyst Deactivation
1. Most catalysts do not maintain their activities 1. Deactivation By Sintering/Aging
at the same levels for indefinite periods
2. They are subjected to deactivation (the Loss of catalytic activity due to a loss of
decline in a catalyst’s activity as time active surface area resulting from the
progresses.) prolonged exposure to high gas phase
temperatures
Catalyst Deactivation The loss is either by crystal agglomeration
and growth of the metals deposited on the
support or by narrowing or closing of the
Sintering/ Fouling/ pores inside the catalyst pellet.
Poisoning
Aging Coking
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8.1 Catalysts Definition and Properties
Catalyst Deactivation
8.1 Catalysts Definition and Properties
Catalyst Deactivation
2. Deactivation By Coking/Fouling
Common to reactions involving hydrocarbons
It results from a carbonaceous (coke) material
being deposited on the surface of a catalyst

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8.1 Catalysts Definition and Properties

Catalyst Deactivation
3. Deactivation By Poisoning
Occurs when the poisoning molecules become
irreversibly chemisorbed to active sites,
thereby reducing the number of sites available
for the main reaction
The poisoning molecule maybe reactant and/or
product in the main reaction or it maybe an
impurity in the feed stream
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8.2 Steps in a Catalytic Reaction
Step 1: Mass transfer of the reactant
Step 2: Diffusion of the reactant
Step 3: Adsorption of the reactant
Step 4: Reaction on the surface
Step 5: Desorption of the products
Step 6: Diffusion of the products
Step 7: Mass transfer of the products
* Steps 3, 4 & 5 are the MOST important
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8.2 Steps in a Catalytic Reaction

Step 1: Mass transfer of the reactant from the Step 7: Mass transfer of the
bulk fluid to the external surface of the products from the external pellet
catalyst pellet surface to the bulk fluid

A B Step 6:
Diffusion of the
Step 2: External
1 products from
Diffusion of the 7 Diffusion
the
reactant from
interior of the
the pore mouth
pellet to the
through the 2 6
catalyst pores lnternal pore mouth at
Diffusion the external
to the 3 5 surface
immediate
vicinity of the
internal
catalytic
surface 4 Step 5: Desorption of
the product from the
surface
Step 3: Adsorption of reactant A Step 4: Reaction
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onto the catalyst surface on the surface of catalyst 24

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8.2 Steps in a Catalytic Reaction 8.2 Steps in a Catalytic Reaction

Reaction On The Surface Of Catalyst 1. Single Site
1. Only the site on which the reactant is adsorbed is
After a reactant has been adsorbed onto the involved in the reaction
surface, it is capable of reacting in a number of 2. Eg: An adsorbed molecule of A may isomerize directly on
ways to form the reaction product. 3 of these ways the site to which it is attached
are
Ways Of Reaction A.S ⇔ B.S
3. The surface reaction rate law is
CA.S = Concentration of reactant A at adsorbed
Single Eley
" C % active site
Dual rS = kS $ CA.S − B.S ' Cactive= Concentration
B.S of product B at adsorbed
Site Site Rideal # K site
S & K = Surface reaction equilibrium constant
s
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8.2 Steps in a Catalytic Reaction

8.2 Steps in a Catalytic Reaction
2. Dual Site
1. 3 types of dual site mechanism 3. Dual Site
2. Type 1: Adsorbed reactant interacts with another site 1. Type 2: Reaction between 2 adsorbed species
(either occupied or unoccupied) to form the product.
E.g: Adsorbed A may react with adjacent vacant site to
yield a vacant site and a site on which the product is
adsorbed.

A.S + S ⇔ B.S + S A.S + B.S ⇔ C.S + D.S

1. The corresponding surface reaction rate law is
3. The corresponding surface reaction rate law is
" Cv = Concentration of vacant sites " C C %
C C % rS = kS $ CA.S CB.S − C.S D.S '
rS = kS $ CA.S Cv − B.S v ' KS &
# KS & #
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8.2 Steps in a Catalytic Reaction 8.2 Steps in a Catalytic Reaction

2. Dual Site
1. Type 3: Reaction of 2 species adsorbed in different types
of sites, S and S (2 different types of site because
different types of catalyst)
3. Eley Rideal
1. Reaction between an adsorbed molecule and a molecule
in the gas phase, such as the reaction of propylene and
benzene

A.S + B.S' ⇔ C.S' + D.S A.S + B (g) ⇔ C.S + D (g)

1. The corresponding surface reaction rate law is 2. The corresponding surface reaction rate law is
" C 'C % " C P %
rS = kS $ CA.S CB.S ' − C.S D.S ' rS = kS $ CA.S PB − C.S D '
# KS & # KS &
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8.3 Porous Catalyst Particle 8.3 Porous Catalyst Particle

• We want a catalyst with the highest possible Types Of
surface area to attain the highest rate with Porous Catalyst
minimum total reactor volume
• Usually achieved by formulating catalyst as a
powder which is then pressed into porous
pellets that are packed into the packed bed
reactor Amorphous Y-alumina Zeolites
Silica
• These porous pellets can be powder grains
which are compressed into a pellet or a Activated Supported
porous network prepared by drying a Carbon Metals
slurry/gel 32
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8.3 Porous Catalyst Particle
Amorphous Silica (Sio2)
Prepared with very high surface area by
precipitating silica from aqueous silicate
solution (gel) and drying the precipitate
Generally non crystalline
Typically monodisperse (composed of
molecules of the same mass) spheres that
are packed into a pellet with gases migrating
through the voids between the spheres
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8.3 Porous Catalyst Particle
Zeolites (Aluminosilicates)
Crystalline clays that can be either natural
minerals or prepared synthetically by
crystallizing silica and alumina solutions
Can be used as catalysts by themselves as
acidic catalyst by ion exchanging cations that
have catalytic activity or
By depositing salts that decompose to form
metal particles (acts as catalyst) within the
zeolites structure (acts as support).
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8.3 Porous Catalyst Particle
High Area Y-alumina (Al2o3)
Easily prepared by precipitating alumina from
aqueous solution and drying and heating
It is crystalline and the major phase is called
gamma-alumina
Alumina forms a porous network as the water is
removed
A pellet is typically composed of grains of the
porous materials and gases migrate both between
grains and within the porous network inside then
grains
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8.3 Porous Catalyst Particle
Activated Carbon
Prepared by partially burning an organic
material such as wood or coconut shells to
volatilize and pyrolyze the organic components
and leave behind a porous carbon
Cellular structures of the wood fiber are intact
to attain very high surface areas
Widely used as adsorbents and as supports
for catalytically active metals and oxides
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8.3 Porous Catalyst Particle
Supported Noble Metal Catalysts
Depositing noble metals (e.g. palladium,
ruthenium, etc.) on high area oxide supports
(alumina, silica, zeolites) disperses the metal
over the surface so that nearly every metal
atom is on the surface.
High dispersion (fraction of atoms on the
surface) and this is a strong function of
support, method of preparation and treatment
conditions
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8.4 Packed Bed Catalytic Reactor
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8.4 Packed Bed Catalytic Reactor
• Commonly used for heterogeneous catalytic processes
such as gas phase reactions with catalyzed solid
• Used in synthesis, effluent treatment and catalytic
combustion.
• Consists in essence of a container filled with catalyst
particles.
• These particles can be contained within a supporting
structure, like tubes or channels, or they can be packed in
one single compartment in the reactor.
• Advantages: High conversion per unit mass of catalyst,
low operating cost and continuous operations.
• Disadvantages: Undesired thermal gradients may exist,
poor temperature control, and unit maybe difficult to
service and run
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