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Catalysis and catalytic

Catalysis and Catalytic reactors
Reactors 4.1 Catalyst
4.2 Steps in a catalytic reaction
4.3 Solid catalyzed reaction
4.4 Catalyst deactivation

Objectives 4.1 Catalysts

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
• 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 4.1 Catalysts

Activation Energy : The energy required to overcome
the reaction barrier. Usually given a symbol Ea Catalyst lowers the activation energy for both
forward and reverse reactions.
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

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4.1 Catalysts 4.1 Catalysts

Supported
Monolithic

Type of
Catalyst
Unsupported Molecular
sieves

This means , the catalyst changes the reaction

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

Type of Catalyst Type of Catalyst
POROUS CATALYST MOLECULAR SIEVES
Catalyst that has large area resulting Catalyst with small pores. They will only
admit small molecules but prevent large
from pores ones from entering
Examples include the Raney nickel Derived from natural substances such clays
used in the hydrogenation of and zeolites or totally synthetic such as
crystalline aluminosilicates
vegetable and animal oils
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 Maybe a ceramic or metal support with
MONOLITHIC square, hexagonal, triangular cells that are
separated by thin walls to give a large
An alternative to the use of small particles of
number of parallel channels.
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.

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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
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
– 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
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4.1 Catalysts
Type of Catalyst
Highly dispersed metal on metal oxide
Nickel clusters
SiO2
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
• 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)
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4.1 Catalysts 4.1 Catalysts

Industrial application Type of Catalysis
 Stability - a good catalyst should resist to
deactivation, caused by:
 the presence of impurities in feed
 thermal deterioration, volatility and hydrolysis Homogeneous
of active components catalysis Heterogeneous
catalysis
 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 4.1 Catalysts

Homogeneous Catalysis Heterogeneous Catalysis
• The catalyst and reactants are in the SAME • The catalyst and reactants are in
phase (usually a solution) DIFFERENT phases (usually solid catalyst
• Catalyzed reaction can happen throughout and liquid/gaseous reactant)
the bulk of the reaction medium.
• Example: The reaction between persulphate
• Reaction occurs on the catalyst surface
ions and iodide ions.
which may be the TRANSITION METAL or
Fe 2+ or Fe3+ one of its compounds.
Catalyst

S2O82  2I   2SO4 2  I 2 • The reactants must be adsorbed onto the

catalyst surface at the 'active sites'.
Reactants

4.1 Catalysts 4.2 Steps in Catalytic Reaction

Heterogeneous Catalysis
TRANSITION METALS
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

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4.2 Steps in Catalytic Reaction

1.Mass transfer of the reactant from the
bulk fluid to the external surface of the
7. Mass transfer of the products
from the external pellet surface to
4.2 Steps in Catalytic Reaction
catalyst pellet the bulk fluid
porous carrier
6. Diffusion of (catalyst support)
the products
from the
2. Diffusion interior of the
of the pellet to the bed of
reactant from pore mouth at catalyst
the pore the external reactants particles substrate product
mouth surface
through the
catalyst
reactor reaction desorption
pores to the
adsorption
immediate
vicinity of the products
catalyst support
internal
catalytic 5. Desorption of
the product from
active
surface
the surface site
3. Adsorption of reactant A 4. Reaction
onto the catalyst surface on the surface of catalyst

4.2 Steps in Catalytic Reaction 4.2 Steps in Catalytic Reaction

REACTION ON THE SURFACE OF
CATALYST
product C
After a reactant has been adsorbed onto the surface, it reactant C
reactant
B
B
is capable of reacting in a number of ways to form A
the reaction product. 3 of these ways are

• Langmuir- A
Single site Hinshelwood
kinetics
catalyst surface catalyst surface
• Langmuir-
Dual site Hinshelwood
kinetics

Eley-Rideal

4.2 Steps in Catalytic Reaction 4.2 Steps in Catalytic Reaction

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

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4.2 Steps in Catalytic Reaction 4.2 Steps in Catalytic Reaction

DUAL SITE DUAL SITE
4. Type 3: Reaction of 2 species adsorbed in
3. Type 2: Reaction between 2 adsorbed different types of sites, S and S’
species

4.2 Steps in Catalytic Reaction 4.3 Solid Catalyzed Reaction

ELEY RIDEAL QUESTION: WHAT IS THE DIFFERENCE BETWEEN
Reaction between an adsorbed molecule and a ADSORPTION AND ABSORPTION?
molecule in the gas phase, such as the reaction of
propylene and benzene 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 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.
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
35 molecules and 100-400 kJ/mol for atoms. 36

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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
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 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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4.4 Catalyst Deactivation
Sintering
/Aging
Coking /
Fouling
Poisoning
4.4 Catalyst Deactivation
DEACTIVATION BY SINTERING / AGING
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
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TEST 2 WEEK DATE ASSESSMENT %

13 26/5/17 Assignment (video 8%
(Friday) presentation)
Test 2 will be held in WEEK 15 on: 14 29/5/17 – Online Discussion 2%
• Date: 7 June 2017 (Wednesday) 2/6/17 (Forum) *VLE
- ‘Catalyst usage in
• Time: 3.00 – 4.00 pm industry’
• Venue: Lestari hall 15 7/6/17 Test 2 10%
(Wednesday)
• Chapter: 2 (continuous reactor) - 3
15 9/6/17 Online Lab Test 5%
(Friday) *20 min
#10.30 am –
3.30 pm
16 16/6/17 Revision class Future
(Friday) 40%