CATALYSIS

SRUJAL RANA

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 Catalysis

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• More than 90 % of industrial processes actually use
catalysts in one form or the other.
• Owing to expanding need of mankind, production in all
sectors is increasing at a fast rate and catalysis
science and technology has a major contribution in
this.
• Thrusts are being given in the areas of catalyst
upgrading to new and more efficient catalysts.
Increasing catalyst life is another area of importance
to maximize catalyst efficiency.

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• Catalysis involves understanding of the
thermodynamics, kinetics, electronic interaction,
crystal structure, reactor design and process
development for a catalytic process.
• It is an interdisciplinary area involving contribution
from chemical engineers, chemists and material
scientists for successful implementation of the entire
process starting from preparation of catalysts to
final utilization in a chemical reactor.

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 Catalytic reactions
• In a thermodynamically feasible chemical reaction,
when addition of a small amount a chemical substance
increases the rate of attainment of chemical
equilibrium but the substance itself does not undergo
any chemical change, then the reaction is called a
catalytic reaction.
• The substance that enhances the reaction rate is
called a catalyst.
• Catalysts work by providing alternative mechanism
involving a different transition state of lower energy.
Thereby, the activation energy of the catalytic
reaction is lowered compared to the uncatalyzed
reaction
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 Types of catalytic reactions
• Heterogeneous catalysis
• Homogeneous catalysis

o In general, it is believed that the entire surface of

the solid catalyst is not responsible for catalyzing any
reaction.
o Only certain sites on the catalyst surface actually
participate in the reaction and these sites are called
active sites on the catalysts.

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o These sites may be the unsaturated atoms resulting
from surface irregularities or atoms with chemical
properties that enable the interaction with the
adsorbed reactant atoms or molecules.
o Activity of the catalyst is directly proportional to
the number of these active sites available on the
surface and is often expressed in terms of turnover
frequency.
o Turnover frequency is defined as the number of
molecules reacting per active site per second at the
condition of experiments.

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• Determination of surface area and pore distribution of
catalysts is important to understand the extent of
dispersion possible for the active metals.
• Higher surface area of support results in higher
dispersion of the active metals. Hence supports of higher
surface area are desirable.
• Pores are usually formed during drying or calcination of
hydroxides precipitates or gel.
• The size and number of pores determines the internal
surface area.
• Pore size also determines the accessibility of reactants to
the active sites and the ability of diffusion of products
back to the bulk fluid.
• Hence pore structure and surface area must be optimized
to provide maximum utilization of active sites for a given
feed stock.

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• The effective industrial catalysts are products, which possess a
special complex of different properties and should be selected
using the following criteria:
(i) high catalytic activity;
(ii) high selectivity;
(iii) proper pore structure;
(iv) long lifetime;
(v) high resistance to deactivation and catalytic poisons;
(vi) easy regeneration;
(vii) low operation and light-off temperature;
(viii) high thermal stability;
(ix) high thermal conductivity;
(x) high mechanical strength;
(xi) high resistance to attrition;
(xii) low price.

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 Characteristics of solid catalyst
• Activity
• Selectivity
 Activity: It is a measure of the accelerating effect
that a catalyst has on the rate of reaction.
 Selectivity: It refers to a property of a catalyst to
speed up the main reaction in the presence of several
side reactions.

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 Catalyst Activity
• The performance of catalyst is characterized by its
activity for reaction and selectivity for a product.
• Catalyst has an ability to increase the rate of
reaction. This ability of catalyst is known as the activity
of catalyst.
• The activity of a catalyst for a reaction at specified
conditions is generally expressed in terms of rate of
reaction at that condition over the catalyst.
• The catalyst that shows higher rate of reaction at the
given conditions is said to have higher activity.
• For solid catalyzed reaction, rate can be defined as, r = g
mol of reacted /s. g of catalyst.
• Here mass of solid is used because amount of catalyst is
important. The reactor volume that contains the catalysts
is of secondary importance.
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• Activity of metal catalyst is often expressed in terms
of turnover frequency or TOF.
• TOF is defined as the number of molecules reacting
per active site per second (s-1).

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 Selectivity
• The selectivity of a product X can be defined
in several ways.

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 Types of Catalyst
• Homogenous catalyst
• – Acid-base catalyst
• – Transition metal compounds

• Heterogeneous catalyst
• -Bulk catalyst
• - Supported catalyst

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Comparison of Homogenous and Heterogeneous Catalyst

Effectivity Homogenous Heterogeneous

Active centres All metal atoms Only surface
atoms
Concentration Low High
Selectivity High Low
Diffusion Absent present
Reaction Mild severe
conditions
Activity loss Cluster formation Sintering and
and poisoning poisoning

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Comparison of Homogenous and Heterogeneous Catalyst

Catalyst Homogenous Heterogeneous

properties
Structure Defined undefined
Modification High Low
possibilities
Thermal stability Low High
Catalyst Difficult Easy
separation

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 Industrial catalysts
• Industrial catalysts can be broadly grouped into three
categories:
1. Bulk catalysts : When the entire catalyst consists of the
catalytically active substance ,then the solid catalyst is
called a bulk catalyst. Examples include silica- alumina
catalysts for catalytic cracking; iron- molybdate for
oxidation of methanol to formaldehyde
2. Supported catalysts: In supported catalysts, the
catalytically active materials are dispersed over the high
surface area support material. For example,
hydrodesulphurization is carried out over molybdenum
oxide supported on alumina.
3. Mixed agglomerates : These catalysts are agglomerated
mixture of active substance and support. These type of
catalysts are used less frequently.

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 Component of Heterogeneous Catalyst

• Active Phase: Metals that provides active sites for

the chemical reaction.
• Support or Carrier: High surface area oxides which
disperse and stabilized the active phase. ( Improves
efficiency, physical strength, selectivity)
• Promoters: Additives which improves the catalyst
properties.

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 Promoters
• Promoters are generally defined as substances added during
preparation of catalysts that improve the activity or selectivity
or stabilize the catalytic agents. The promoter is present in a
small amount and by itself has little or no activity.
• Promoters are termed as physical or chemical promoter
depending on the manner they improve the catalyst
performance.
• The additives that maintain physical integrity of the support
and/or deposited catalytic agents are termed as physical
promoters. For example, addition of small quantities of alumina
to an iron catalyst employed in ammonia synthesis prevents
sintering of the iron crystallites. Thus, for this catalyst, alumina
is a physical promoter.
• The addition of K2O to the same catalyst increases the intrinsic
activity of the iron crystallites and therefore acts as a chemical
promoter.
• The promoter can be added during catalyst preparation or
during reaction.
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 Negative promoters or inhibitors

• Inhibitors act opposite to promoters. When added in

small amounts, these can reduce catalyst activity,
selectivity or stability.
• Inhibitor is particularly useful for reducing the
activity of a catalyst for undesirable side reactions.
• In oxidation of ethylene, ethylene dichloride is added
to inhibit CO2 formation thus acting as an inhibitor.

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 CATALYST DEACTIVATION
• Activity of catalysts normally decreases with time.
The life of any catalyst generally depends on type of
reactions as well as reaction conditions.
• For example, catalysts for catalytic cracking lose
much of their activity within seconds due to carbon
deposition on the surface while promoted iron
catalysts used in ammonia synthesis have a lifetime of
years.
• A catalyst can be deactivated in three ways
I. Poisoning
II. Fouling
III. Sintering or phase transformation

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 POISONING & FOULING
• The decrease in catalyst activity, is due to poisons,
which will be defined as substances, either in the
reactants stream or produced by the reaction, which
lower the activity of catalyst.
• Slow decreased is usually due to chemisorptions of
reactants, products, or impurities. Rapid deactivation
is caused by physically depositing a substance which
block the catalyst is called fouling.
• Deactivation can be caused by a change in the surface
structure of catalyst.

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 Deposited poison:
• Carbon deposition on catalyst used in the petroleum industry
falls into this category.
• The carbon covers the active sites of the catalyst and may also
partially plug the pore entrances.
• This type of poisoning is at least partially reversible, and
regeneration can be accomplished by burning to CO and CO2 with
air and steam.

 Chemisorbed poison:
• Compounds of sulfur and other materials are frequently
chemisorbed on nickel, copper, and platinum catalyst.
• If the strength of the adsorption bond is not great, the activity
will be regained when the poison is removed from the reactants.
• If the adsorbed material is tightly held, the poisoning is more
permanents.

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 Sintering or phase transformation
• Because of local high temperature, support of
catalysts or catalyst itself may undergo structural
modification or sintering causing a reduction in
specific surface area or change in chemical nature of
catalytic agent so that it becomes catalytically
inactive.

• Steps to reduce deactivation: Following steps can

be taken to reduce the possibility of deactivation of
catalysts :
a. Removal of poison material form feed
b. Use of hydrogen which reduces coking
c. Removal of hot spot by proper design of reactor
/process control to prevent any thermal deactivation.
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 Mechanism of solid catalytic reactions
• A solid catalytic reaction A to B goes through the
following steps:
1. Transportation of reactant (A) from bulk fluid to
pore mouth on the external surface of catalysts
pellets
2. Diffusion of the reactant (A) from the pore
mouth through the catalyst pores to the immediate
vicinity of internal catalytic surface
3. Adsorption of reactant (A) onto the catalyst
surface
4. Reaction of (A) on the catalyst surface producing
product (B)
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5. Desorption of the product (B) from the
surface
6. Diffusion of the product (B) from interior
part of the pores to the pore mouth on the
external surface
7. Transfer of the product (B) from pore mouth
on the external surface to the bulk fluid

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• Steps : 1,2,6 and 7 – Diffusion steps
• Steps: 3,4 and 5- Reaction steps
Collectively, steps 3,4 and 5 may be regarded as
surface chemical reaction.

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 Factors affecting rate of reaction

 Surface Kinetics
 Pore diffusion resistance
 Particle temperature gradient
 Film temperature gradient
 Film diffusion resistance

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 Pore diffusion resistance
• This resistance may cause the interior
of the particle to be starved for
reactant.
• Pore diffusion resistance can be reduce
by reducing the catalyst particle size,
which thus shorten the diffusion path.

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 Particle temperature gradient

• Temperature gradient within the

catalyst particle is caused by evolution
or absorption of large amount of heat
during reaction.
• It causes the reaction rate to vary
inside the catalyst.

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 Film temperature gradient

• Film temperature gradient is

temperature difference between the
outer surface of the catalyst particle
and the bulk gas stream.
• Resistance to heat transfer is within
the gas film enveloping the catalyst.

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 Film diffusion resistance

• Film diffusion resistance is external

diffusion resistance and concentration
gradient across the gas film surrounding
the catalyst particle.

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 Preparation of catalyst
1. Bulk preparation process:
• Bulk catalysts and supports are prepared by this
method. Bulk preparation is mainly done by the
following methods :
a. Precipitation process
b. Sol gel process
2. Impregnation process:
• Supports are first prepared by bulk preparation
methods and then impregnated with the catalytically
active material.

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• The active materials can be deposited on the supports
by various methods.
• Most of the methods involve aqueous solutions and
liquid solid interface.
• In some cases, deposition is done from the gas phase
and involves gas- solid interface

3. Physical mixing :
• Mixed agglomerated catalysts are prepared by this
method.
• These catalysts are prepared by physically mixing the
active substances with a powdered support or
precursors of support in ball mill.
• The final mixture is then agglomerated and activated.
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 Precipitation and co-precipitation

 It provides the method of obtaining the solid material

in a porous form. It consists of a adding a
precipitating agent to a desired components.
 The precipitation of hydroxides can be performed
either by starting from an alkaline solution which is
acidified or from acidic solution by raising the pH.
 However, most hydroxides for technical application
are precipitated from an acidic solution by the
addition of an alkaline precipitating agent.

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 Usually, ammonia or sodium bicarbonate is used as the
precipitating agent. Highly soluble inorganic salts such
as nitrates, carbonates or chlorides are generally used
as metal precursors.
 For example, preparation of alumina is done by
precipitating aluminium hydroxide from aluminium
nitrate solution by addition of ammonium hydroxide.
 The precipitates is washed, dried and calcined to get
Alumina.

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• Co-precipitation is used for simultaneous precipitation of more
than one component.
• Catalysts based on more than one component can be prepared
easily by co-precipitation.

Advantages and disadvantages:

 The main advantage of the precipitation process is the
possibility of creating pure and homogenous material.
 However, the major disadvantages include necessity of product
separation after precipitation and generation of the large
volume of salt containing solutions.
 There is also difficulty in maintaining a constant product quality
throughout the whole precipitation process if the precipitation
is carried out discontinuously.

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 Impregnated Catalyst
• One of the Best method for impregnation for porous
catalytic support with solution of active component.
• Impregnation as a means of supported catalyst
preparation is achieved by filling pores of support
with solution of metal salt.
• Especially catalyst with expensive active components
such as Nobel metals are employed as a supported
catalysts.
• A widely use supports are Alumina, Activated Carbon
and Silica Gel.

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• The support is immersed
in a solution of active
component under precisely
defined conditions
(Concentration, mixing,
temperature, time).
• Depending upon the
production conditions,
selective adsorption of
active component occurs
on the surface or interior
of the support.
• The result is non uniform
distribution.

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