Catalysis and Catalytic

Reactors
 Catalysis and catalytic
reactors
4.1 Catalyst
4.2 Steps in a catalytic reaction
4.3 Solid catalyzed reaction
4.4 Catalyst deactivation
 Objectives
Upon the completion of this chapter,
students are able to:

•Define a catalyst
•Explain the types of catalysts
•Describe the steps in a catalytic reaction
•Explain the solid catalyzed reaction
•Describe the different types of catalyst
deactivation
 4.1 Catalysts
• A catalyst is substance that affects the rate
of a reaction at which a chemical system
approaches equilibrium , without being
substantially consumed in the process.
• A catalyst usually changes a reaction rate
by promoting a different molecular path
(mechanism) for the reaction
• A catalyst changes only the rate of a
reaction, it does not affect the equilibrium
 4.1 Catalysts
Activation Energy : The energy required to overcome
the reaction barrier. Usually given a symbol Ea

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

5
 4.1 Catalysts
Catalyst lowers the activation energy for both
forward and reverse reactions.

6
 4.1 Catalysts

This means , the catalyst changes the reaction

path by lowering its activation energy and
consequently the catalyst increases the rate of
reaction.
7
4.1 Catalysts

Type of
Catalyst
 4.1 Catalysts
Type of Catalyst
POROUS CATALYST
Catalyst that has large area resulting
from pores
Examples include the Raney nickel
used in the hydrogenation of
vegetable and animal oils
 4.1 Catalysts
Type of Catalyst
MOLECULAR SIEVES
Catalyst with small pores. They will only
admit small molecules but prevent large
ones from entering
Derived from natural substances such clays
and zeolites or totally synthetic such as
crystalline aluminosilicates
The pores can control the residence
time of molecules near the active
surface that essentially allows only
the desired molecules to react
 4.1 Catalysts
Type of Catalyst
MONOLITHIC
An alternative to the use of small particles of
catalysts for very rapid reactions of gases
Normally encountered for process where
pressure drop and heat removal are major
consideration).
It can be either porous or non-porous
Catalyst is deposited on the cell walls or
impregnated into a thin coating or other porous
support.
Major use is in catalytic converters for gasoline
fueled vehicles.
Maybe a ceramic or metal support with
square, hexagonal, triangular cells that are
separated by thin walls to give a large
number of parallel channels.
 4.1 Catalysts
Type of Catalyst
SUPPORTED
Catalyst consists of minute particles
of an active material dispersed over a
less active substance called a
support.
Active material is frequently a pure
metal or metal alloy
Examples is the platinum on alumina
catalyst used in petroleum reforming
 4.1 Catalysts
Type of Catalyst
Highly dispersed metal on metal oxide

Nickel clusters

SiO2
 4.1 Catalysts
Type of Catalyst
UNSUPPORTED
For unsupported catalysts, the active
ingredients are major amounts of
other substances called promoters
which increase the activity
Example is the silica-alumina
dehydrogenation catalyst used in
butadiene manufacture
 4.1 Catalysts
Industrial application
• Almost all chemical industries have one or more
steps employing catalysts
– Petroleum, energy sector, fertiliser, pharmaceutical,
fine chemicals
• Advantages of catalytic processes:
– Achieving better process economics and
productivity:
• Increase reaction rates - fast
• Simplify the reaction steps - low investment cost
• Carry out reaction under mild conditions (e.g.
low T, P) - low energy consumption
 4.1 Catalysts
Industrial application
– Reducing wastes
• Improving selectivity toward desired products -
less raw materials required, less unwanted wastes
• Replacing harmful/toxic materials with readily
available ones
– Producing certain products that may not be possible
without catalysts
– Having better control of process (safety, flexible
etc.)
– Encouraging application and advancement of new
technologies and materials
 4.1 Catalysts
Industrial application
• General requirements for a good catalyst:
– Activity - being able to promote the rate of
desired reactions
– Selective - being to promote only the rate of
desired reaction and also retard the undesired
reactions
Note: The selectivity is sometime considered to
be more important than the activity and
sometime it is more difficult to achieve (e.g.
selective oxidation of NO to NO2 in the presence
of SO2)
 4.1 Catalysts
Industrial application
 Stability - a good catalyst should resist to
deactivation, caused by:
 the presence of impurities in feed
 thermal deterioration, volatility and hydrolysis of
active components
 attrition due to mechanical movement or
pressure shock
– Large surface area - solid catalyst (active
sites). This is usually achieved by making the
solid into a porous structure.
4.1 Catalysts
Type of Catalysis
 4.1 Catalysts
Homogeneous 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
Reactants
 4.1 Catalysts
Heterogeneous Catalysis
• The catalyst and reactants are in
DIFFERENT phases (usually solid
catalyst and liquid/gaseous reactant)

• Reaction occurs on the catalyst surface

which may be the TRANSITION METAL or
one of its compounds.

• The reactants must be adsorbed onto the

catalyst surface at the 'active sites'.
 4.1 Catalysts
Heterogeneous Catalysis
TRANSITION METALS
4.2 Steps in Catalytic Reaction

1. Mass transfer of the reactant

2. Diffusion of the reactant
3. Adsorption
4. Reaction on the surface
5. Desorption
6. Diffusion
7. Mass transfer
* Steps 3, 4 and 5 are MOST important
 4.2 Steps in Catalytic Reaction
1.Mass transfer of the reactant from the 7. Mass transfer of the products
bulk fluid to the external surface of the from the external pellet surface to
catalyst pellet the bulk fluid

6. Diffusion of
the products
from the
2. Diffusion interior of the
of the pellet to the
reactant from pore mouth at
the pore the external
mouth surface
through the
catalyst
pores to the
immediate
vicinity of the
internal
catalytic 5. Desorption of
surface the product from
the surface
3. Adsorption of reactant A 4. Reaction
onto the catalyst surface on the surface of catalyst
4.2 Steps in Catalytic Reaction
porous carrier
(catalyst support)

bed of
catalyst
reactants particles substrate product

reactor reaction desorption

adsorption
products
catalyst support
active
site
4.2 Steps in Catalytic Reaction
REACTION ON THE SURFACE OF
CATALYST
After a reactant has been adsorbed onto the surface, it
is capable of reacting in a number of ways to form
the reaction product. 3 of these ways are
4.2 Steps in Catalytic Reaction

product C
reactant reactant
C B B
A

catalyst surface catalyst surface

4.2 Steps in Catalytic Reaction
SINGLE SITE

1.Only the site on which the reactant is

adsorbed is involved in the reaction
2.Eg: an adsorbed molecule of A may
isomerize directly on the site to which it is
attached
4.2 Steps in Catalytic Reaction
DUAL SITE
1.3 types of dual site mechanism
2.Type 1: the adsorbed reactant interacts with
another site (either occupied or unoccupied)
to form the product
Ex: Adsorbed A may react with adjacent
vacant site to yield a vacant site and a site
on which the product is adsorbed, such as
the dehydration of butanol
4.2 Steps in Catalytic Reaction
DUAL SITE

3. Type 2: Reaction between 2 adsorbed

species
4.2 Steps in Catalytic Reaction
DUAL SITE
4. Type 3: Reaction of 2 species adsorbed in
different types of sites, S and S’
4.2 Steps in Catalytic Reaction
ELEY RIDEAL
Reaction between an adsorbed molecule and a
molecule in the gas phase, such as the reaction
of propylene and benzene
 4.3 Solid Catalyzed Reaction
QUESTION: WHAT IS THE DIFFERENCE BETWEEN
ADSORPTION AND ABSORPTION?
ABSORPTION
Atoms, molecules,
or ions enter some
bulk phase - gas, ADSORPTION
liquid or solid When a gas or
material liquid solute
accumulates on the
surface of a solid
or, forming a
molecular or atomic
film (the adsorbate).
 4.3 Solid Catalyzed Reaction

Physisorption
1. The bond is a van der Waals interaction
2. adsorption energy is typically 5-10 kJ/mol.
(much weaker than a typical chemical bond)
3. many layers of adsorbed molecules may be
formed. 35
 4.3 Solid Catalyzed Reaction

Chemisorption
1. The adsorption energy is comparable to the
energy of a chemical bond.
2. The molecule may chemisorp intact (left) or it
may dissociate (right).
3. The chemisorption energy is 30-70 kJ/mol for
molecules and 100-400 kJ/mol for atoms. 36
 4.4 Catalyst Deactivation
1. Most catalysts do not maintain their
activities at the same levels for
indefinite periods

2. They are subjected to deactivation

(the decline in a catalyst’s activity as
time progresses.)
4.4 Catalyst Deactivation
4.4 Catalyst Deactivation
DEACTIVATION BY SINTERING / AGING

Loss of catalytic activity due to a loss of active

surface area resulting from the prolonged
exposure to high gas phase temperatures

The loss is either by crystal agglomeration and

growth of the metals deposited on the support
or by narrowing or closing of the pores inside
the catalyst pellet.
4.4 Catalyst Deactivation
DEACTIVATION BY SINTERING / AGING
4.4 Catalyst Deactivation
DEACTIVATION BY COKING / FOULING
Common to reactions involving hydrocarbons
It results from a carbonaceous (coke) material
being deposited on the surface of a catalyst
4.4 Catalyst Deactivation
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
 TEST 2
Test 2 will be held in WEEK 14 on:
• Date: 25 October 2018
(Thursday)
• Time: 9.00 – 10.00 am (during
lecture hour)
• Venue: BT4
• Chapter: 2 (flow reactor) - 3