CHEMICAL REACTIONS ENGINEERING II (3170501)

Semester – VII (CHEM)

CHAPTER: 4
Chapter Name: Introduction to Catalysis

History of catalyst: [Just for Information]

The science and technology of catalysis is of great significance as it affects our daily life.
Four major sectors of the world economy; petroleum and energy production, chemicals
and polymer production, food industry and pollution control, involve catalytic processes.
Catalysts are also widely used in food processing. 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.
Catalyst technology has been used for many centuries. It ranged from inorganic catalyst to make
soaps to enzyme catalysts for producing wines, cheese and other food and beverages. The
industrial catalyst technology started with the large-scale production of sulfuric acid on platinum
catalyst in 1875. In subsequent years, various major catalytic processes were invented. In 1903,
ammonia oxidation on Pt gauge was developed by Ostwald for nitric acid production. Another
major breakthrough was ammonia synthesis with promoted iron in 1908-1914 by Mittasch, Bosch
and Haber.

4.1 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 as shown in Fig

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 CHEMICAL REACTIONS ENGINEERING II (3170501)
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CHAPTER: 4
Chapter Name: Introduction to Catalysis
A catalyst accelerates both the rates of the forward and reverse reaction. Equilibrium of a
reversible reaction is not altered by the presence of the catalyst. For example, when oxidation of
SO2 is carried out in the presence of three different catalysts, namely Pt, Fe 2O3 and V2O5 , the
equilibrium composition is the same in all three cases. Another important characteristic of catalyst
is its effect on selectivity. The presence of different catalysts can result in different product
distribution from the same starting material. For example, decomposition of ethanol in the
presence of different catalysts results in different products as shown below.

4.2 TYPES OF CATALYTIC REACTIONS

Catalytic reactions can be divided into two main types –
1. Heterogeneous
2. Homogeneous
Heterogeneous catalysis
In heterogeneous catalytic reaction, the catalyst and the reactants are in different phases.
Reactions of liquid or gases in the presence of solid catalysts are the typical examples. An
example is the Contact Process for manufacturing sulphuric acid, in which the sulphur
dioxide and oxygen are passed over a solid vanadium oxide catalyst producing sulphur
trioxide. Several hydrocarbon transformation reactions such as cracking, reforming,
dehydrogenation, isomerization also fall in this category.
Homogeneous catalysis
In a homogeneous catalytic reaction, the catalyst is in the same phase as the reactants.
Typically, all the reactants and catalysts are either in one single liquid phase or gas phase.
Most industrial homogeneous catalytic processes are carried out in liquid phase. Ester
hydrolysis involving general acid-base catalysts, polyethylene production with
organometallic catalysts and enzyme catalyzed processes are some of the important
examples of industrial homogeneous catalytic processes.

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 CHEMICAL REACTIONS ENGINEERING II (3170501)
Semester – VII (CHEM)
CHAPTER: 4
Chapter Name: Introduction to Catalysis

4.3 CATALYST COMPONENTS

A solid catalyst consists of mainly three components :
1. Catalytic agent
2. Support /carrier
3. Promoters and Inhibitors
4.3.1 Catalytic Agent:
These are the catalytically active component in the catalyst. These components generate
the active sites that participate in the chemical reaction. Activity of any catalyst is
proportional to the concentration of these active sites. Though concentration of the active

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 CHEMICAL REACTIONS ENGINEERING II (3170501)
Semester – VII (CHEM)
CHAPTER: 4
Chapter Name: Introduction to Catalysis

sites depends on the amount of catalytically active component, however, it is not always
directly proportional. Availability of active sites depends mainly on the dispersion of
catalytic agent. The dispersion is defined as ratio of total number of exposed
atoms/molecules of catalytic agent available for reaction to total number of
atoms/molecules of catalytic agent present in the catalyst sample.
Catalytic agents may be broadly divided in the following categories:
i. Metallic conductors ( e.g Fe, Pt, Ag, etc.)
ii. Semiconductors (e.g. NiO, ZnO,etc.)
iii. Insulators (e.g. Al2O3, SiO2,MgO etc.)
Metallic conductors: The metals that have strong electronic interaction with the
adsorbates are included in this category. The metals are used in various catalytic reactions
such as methanol synthesis, oxidation , hydrogenation and dehydrogenation processes.
Examples of metal catalysts :
Cu for water gas shift reaction and methanol synthesis ; Ag for oxidation of ethylene to
ethylene oxide, Au for oxidation of methanol to formaldehyde; Fe for ammonia synthesis;
Pd and Pt for hydrogenation of olefins, dienes, aniline or nitriles as well as
dehydrogenation of alkanes, alcohols, cyclohexanes, cyclohexanols etc.
Semiconductors :
The oxides and sulfides of transition metals that have catalytic activity are included in this
category. Similar to conducting metals, they are also capable of electronic interaction with
adsorbed species and catalyze the same type of reactions. Usually the lower valence band
electrons participate in bonding. The upper conduction band separated by band gap energy is
empty unless electrons are promoted by heat or radiation. Semiconductor characteristics may
be intrinsic or induced by addition of foreign ion, creating cationic or anionic vacancies.
Common transition oxides and sulfides such as CuO, AgO, NiO CoO, Fe 2O3 , MnO, Cr2O3,
FeS, V2O5 show conductivity. These materials participate in catalytic reactions and reaction
occurs through acceptation or donation of electrons between the reactant material and
catalysts. Few applications of semiconductor catalysts are : CuO for oxidation of nitric
oxides, NiO for dehydrogenation of alkanes, MnO2 for oxidation of alcohols, and V2O5 for
oxidation of hydrocarbons.
Insulators : Catalytic functions of insulators are different from that of conductor and semi
conductor materials. Insulators have large values of band gap energy and very low
concentration of impurity levels. The electrons remain localized in valence bonds and redox
type reactions involving electronic interaction as observed for metal or semiconductor
catalysts does not occur. However, insulators have sites that generate protons, thereby,

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Chapter Name: Introduction to Catalysis
promote carbonium ion based reactions such as cracking, isomerization or polymerization.
Al2O3, SiO2, SiO2-Al2O3, zeolites, MgO, CaO, MgAl2O4, SiO-MgO are few examples of the
insulators used as catalysts.
4.3.2 Support Or Carrier
Support or carrier provides large surface area for dispersion of small amount of
catalytically active agent. This is particularly important when expensive metals, such as
platinum, ruthenium, palladium or silver are used as the active agent. Supports give the
catalysts its physical form, texture, mechanical resistance and certain activity particularly
for bifunctional catalysts. Area of the support can range from 1 - 1000 m2/gm. Common
supports are alumina, silica, silica-alumina, molecular sieves etc. The surface area of α -
alumina is in the range 1-10 m2/gm whereas the surface area for γ or η - alumina can be
in the range 100 – 300 m2/gm.
Support may be inert or interact with the active component. This interaction may result in
change in surface structure of the active agent and thereby affect the catalyst activity and
selectivity. The support may also exhibit ability to adsorb reactant and contribute to the
reaction process.
4.3.3 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.
4.4.4 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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 CHEMICAL REACTIONS ENGINEERING II (3170501)
Semester – VII (CHEM)
CHAPTER: 4
Chapter Name: Introduction to Catalysis

4.4.5 Catalyst Poison:

It is referred to the partial or total deactivation of a catalyst caused by exposure to a range of
chemical compounds. Poisoning may be desirable when it results in improved selectivity (e.g.
Lindlar's catalyst) but may be undesirable when the catalyst is rendered ineffective (e.g. Lead
in catalytic converters). Poisoning refers specifically to chemical deactivation, rather than
other mechanism of catalyst degradation such as thermal decomposition or physical damage.

4.5 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; iron
doped with alumina and potassium oxide for the synthesis of ammonia.
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.

4.6 PREPARATION OF SOLID CATALYST

The catalyst preparation methods can broadly categorized as follows :
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. 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.

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 CHEMICAL REACTIONS ENGINEERING II (3170501)
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CHAPTER: 4
Chapter Name: Introduction to Catalysis

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.
Basic unit operations involved in preparation of solid catalyst is shown in Fig 1. Each step
is discussed in detail in the following sections.

4.6. 1. BULK (Solid catalyst) 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

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 CHEMICAL REACTIONS ENGINEERING II (3170501)
Semester – VII (CHEM)
CHAPTER: 4
Chapter Name: Introduction to Catalysis

A. PRECIPITATION PROCESS / CO PRECIPITATION METHOD

 In this process, the desired component is precipitated from the solution. 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. The precipitation
process is used for preparation of bulk catalysts and support material such as Al 2O3, SiO2,
TiO2, ZrO2 etc.
Procedures of precipitation method
This method contains various steps as following:
(i) Dissolution step in which the precursors of active components, often in their salt
forms (nitrate is the preferred salt over chloride or sulfate) are first dissolved in water or
suitable medium to form a homogeneous solution.
(ii) Precipitation step in which the solution is subjected to pH adjustment or evaporation
to force those salts to precipitate. During this precipitation, the salts may be hydrolyzed
into hydroxide forms or oxides, so this step can be called hydrothermal process.
During precipitation, several processes occur and the major steps are:
1. Liquid mixing / supersaturation
2. Nucleation
3. Crystal growth to form primary products
4. Aggregation of the primary particles
(iii) Filtration and drying step in which the solid mass is then collected and dried
gradually to about the boiling point of the medium. The dry mass obtained is in a loose
state with irregular shape; therefore, this mass is first ground to powder form. A binder
can be added to help bind together; the binder is chosen so that it is burned into volatile
vapor of steam and carbon dioxide during calcination or activation.
(iv) Calcination step is undertaken to convert the salt or hydroxide form of the active
components into oxides by reacting with air at suitable temperature, for instance, acetate,
carbonate or nitrate decomposes into oxide.
Advantages of the precipitation method:
(i) The homogeneity of component distribution,
(ii) The relatively low reaction temperature,
(iii) The fine and uniform particle size with weakly agglomerated particles, and
(iv) The low cost.
Disadvantages of the precipitation method: Chemical precipitation is generally not a
controlled process in terms of reaction kinetics and the solid phase nucleation and growth

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CHAPTER: 4
Chapter Name: Introduction to Catalysis

processes depending upon the precipitation reactions are highly susceptible to the reaction
conditions. Therefore, the as synthesized solids have a wide particle size distribution,
uncontrolled particle morphology with agglomeration and incomplete precipitation of the
metal ions. However, the control over the stoichiometry of the precursors is rather
difficult to achieve. Thus, this method is insensitive, semi-quantitative and long reaction
time from 18 to 48h.

Parameters affecting the properties of the precipitate

1. Effect of raw materials: The precursors are usually chosen with counter ions that can
easily be decomposed to volatile products during heat treatment steps. Nitrates and
carbonatesalts are preferably used as metal precursors whereas ammonia or sodium
carbonate as the precipitating agent. Chloride and sulphate ions act as poisons in many
catalytic processes. Such ions should be avoided in the precipitation process.
2. Effect of pH : pH directly control the degree of super saturation and hence is expected
to affect the final properties. But the influence of pH is not simple and has to be
investigated experimentally for the specific system.
3. Effect of concentration and composition: It is desirable to precipitate at high
concentration levels of metal ions. This increases the space time yields by decreasing the
vessel volume for the same mass of precipitate. Moreover, higher degree of
supersaturation leads to faster precipitation. Higher concentration levels also results in
smaller particle size and higher surface areas due to increased nucleation rates.
4. Effect of solvent: For preparation of bulk catalysts and supports, water is almost
exclusively used as the solvent for economic reason. Organic solvents are much more

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 CHEMICAL REACTIONS ENGINEERING II (3170501)
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CHAPTER: 4
Chapter Name: Introduction to Catalysis

expensive to use. Furthermore, solubilities of most metal salts used as the precursors are
lower in organic solvents.
5. Effect of temperature : The precipitation temperature is a decisive factor in
controlling precipitate properties such as primary crystallite size , surface area and the
phase formed. Till date it is very difficult to predict the exact nature and extent of effect
of the precipitation temperature on the properties and is generally determined
experimentally.
6. Effect of Additives : Additives are substances which are not necessary ingredients of a
precipitation reaction. The properties of the precipitates can strongly be influenced by
additives. The most widely used additives are organic molecules which are added to the
precipitate in order to control the pore structure. Such organic molecules can later be
removed from the precipitate in the calcination step.
B. SOL GEL METHOD
 In the sol gel process, initially a stable colloidal solution called sol is formed. The sol
is a liquid suspension of solid particles ranging in size from 1 nm to 1 micron. It can
be obtained by hydrolysis and partial condensation of precursors such as an inorganic
salt or a metal alkoxide.
 The further condensation of sol particles into a three dimensional network produces a
gel material. The gel is a diphasic material in which the solids encapsulate the solvent.
The molecular weight of the oxide species produced continuously increases. The
materials are referred to as aqua sol or aqua gels when water is used as a solvent and
aquosol or alcogel when alcohol is used. The general scheme of preparation by sol gel
method is shown in Fig
 The encapsulated liquid can be removed from a gel by either evaporative drying or
with supercritical drying /extraction. The resulting solid products are known as
xerogel and aerogel, respectively. When gels are dried by evaporation, the dried
product is called xerogel. When the gels are dried by supercritical drying, the dried
gel is called aerogels. The aerogel retains high porosity and has very high pore
volume.

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Chapter Name: Introduction to Catalysis

Advantages of sol-gel method:

 Versatile Versatile: better control of the structure, including porosity and particle size;
possibility of incorporating nanoparticles and organic materials into sol-gel-derived
oxides;
 Extended composition ranges Extended composition ranges: it allows the fabrication
of any oxide composition, but also some non-oxides, as well as the production of new
hybrid organic-inorganic materials, which do not exist naturally;
 Better homogeneity Better homogeneity: due to mixing at the molecular level; high
purity high purity;
 Less energy consumption Less energy consumption: there is no need to reach the
melting temperature, since the network structure can be achieved at relatively low
temperatures near T g;
 Coatings and thin films, monoliths, composites, porous membranes, powders and
fibers;
 No need for special or expensive equipment.
Drawbacks of sol-gel method:
 Cost of precursors;
 Shrinkage of a wet gel upon drying, which often leads to fracture due to the
generation of large capillary stresses and, consequently, makes difficult the attainment
of large monolithic pieces;

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Chapter Name: Introduction to Catalysis

 Preferential precipitation of a particular oxide during sol formation (in

multicomponent glasses) due to the different reactivity of the alkoxide precursors;
 Difficult to avoid residual porosity and OH groups.

4.6.2 PREPARATION SUPPORTED CATALYSTS / IMPREGNATION PROCESS

Supported catalysts are prepared by deposition of the active metal on the support
materials. The main purpose of using a support is to achieve an optimal dispersion of the
catalytically active component and to stabilize it against sintering. But in many reactions
the support is not inert and the overall process consists of two catalytic functions both for
active components and support.
Supported catalysts are prepared in two main steps:
1. Deposition of the precursor of the active component on the support.
2. Transformation of this deposited precursor to catalytically active site.
Impregnation Impregnation can be classified in two categories according to the volume of
solution used.
(i) Dry or incipient impregnation
In this method a previously dried support is contacted with volume of solution equal to its
pore volume. The solution contains the required amount of the precursors of the active
phase. As soon as the support is placed in contact with the solution, the solution is drawn
into the pores by capillary suction. In case of proper wetting no excess of solution
remains outside the pore space. Part of the air present in the pores is imprisoned and
compressed under the effect of capillary forces. The pressure developed inside the
imprisoned gas bubbles depend on the radius, r, of the curve of the liquid-gas meniscus
and may reach several MPa when r<100 nm as a result of young Laplace law,

,
where γ is the liquid gas interfacial tension. Considerable forces will thus be exerted on
the portions of the pore walls in contact with these bubbles. The walls that are not strong
enough may break down causing a degradation of the mechanical properties.
Occasionally, even bursting of the catalyst grains occurs. However, the development of
the high pressure is a transitory phenomenon. Under highly compressed conditions, air
dissolves and progressively escapes from the solid.

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Chapter Name: Introduction to Catalysis

(ii) Wet / diffusional impregnation

In this method the pore space of the support is first filled with the same solvent as used in
the impregnating precursor solution. The wetted support is then treated with the
impregnating precursor solution. Here the actual impregnation takes place in diffusional
condition when solvent filled support is dipped in the precursor solution.
The first phase of saturation of the support by solvent involves the characteristics of the
dry impregnation. But in the second phase, when solvent saturated support is added to the
impregnating solution, high pressure is not developed within the pores. The precursor salt
migrates progressively from the solution into the pores of the support. The driving force
at all times is the concentration gradients between the bulk solution and the solution with
in the pores. The impregnation time is much longer than for dry impregnation.
Wet impregnation should be avoided when the interaction between the precursors and the
support is too weak to guarantee the deposition of the former.

4.7 WASHING AND FILTERING

Washing can be done by decantation. This method is time consuming. In this method the
precipitate or gel is added to a large volume of distilled water and the suspension is
thoroughly stirred. Then, the suspension is allowed to settle. The foreign undesirable ions
are desorbed from particles as they settle down slowly at the bottom. When a clear
interface is visible, the water is removed by decantation and the process is repeated. The
number of washings required is determined by checking the impurity level of the
decanted water. After washing, the precipitate or gel is filtered. The process can be
reversed. That is the filtration is done first and the precipitate or gel is washed with
distilled water in the subsequent step. This method takes less time. Impurity level in the
wash water is checked to determine the required number of washings.

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 CHEMICAL REACTIONS ENGINEERING II (3170501)
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CHAPTER: 4
Chapter Name: Introduction to Catalysis

4.8 DRYING
Drying is described as the elimination of water or solvent from the pores of the precipitate
or gel. It can be done in two ways:
 Solvent evaporation
 Super critical drying
Solvent evaporation : This type of drying is done in a conventional oven at 100-200 °C
and is generally accompanied by a contraction of the structure. In case of gel the product
obtained from ordinary drying is known as dry gel or xero gel. Initially drying occurs
through evaporation of moisture from the outside surface of the materials. The rate of
water loss is constant and the mass transfer is controlled by temperature, relative humidity
and flow rate of air over the surface and the size of the filtrate. The process continues
until the moisture content drops to about 50%. Continued moisture loss occurs with a
declining rate in which evaporation is controlled by capillary forces. The saturation point
decreases as the pore become smaller and the evaporation slows until water is forced into
larger pores by concentration gradient. At the moment of drying, as the pore liquid is
evaporated from a gel network, the capillary pressure associated with the liquid vapor
interface within a pore can become very large for small pores. The capillary pressure that

can develop in a pore of radius r is , where P is capillary pressure, γ is

surface tension, r the pore radius and α is the contact angle between liquid and solid.
The capillary pressure with water evaporating from a pore with a radius of 1 nm is in the
order of 1480 atm. Large capillary tension can lead to collapse of internal structure
resulting in loss of pore volume and surface area. This phenomenon is more significant
for a gel having more intricate porous structure compared to ordinary precipitated
material. For a given pore size the capillary pressure can be reduced by
1. Using a solvent with a lower surface tension or with a contact angle close to 90°.
2. Eliminating the liquid vapor interface altogether with either super critical or freeze
drying.
If temperature gradient is high so that evaporation rate is much faster compared to
removal of moisture that is slowed by smaller pores, then large internal pressure of steam
develops and also leads to collapse of structure. Therefore, high temperature gradient in
the sample must be avoided. Drying at a lower temperature gives less surface area loss
since evaporation rates are lower.

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Chapter Name: Introduction to Catalysis

Supercritical drying is aimed at eliminating the liquid vapor interface and the
accompanying capillary pressure responsible for structure collapse during conventional
drying particularly for gels. It is used where retention of original micro structure of the
product is important. This process typically involves displacement of water using an
alcohol followed by removal of this alcohol/water mixture using supercritical carbon
dioxide. In this process the gels are placed in an autoclave filled with ethanol. The system
is pressurized to at least 750-850 psi with CO2 and cooled to 5-10°C. Liquid CO2 is then
flushed through the vessel until all the ethanol has been removed from the vessel and gels.
When the gels are ethanol-free the vessel is heated to a temperature above the critical
temperature of CO2 (31°C). As the vessel is heated the pressure of the system rises.
CO2 is carefully released to maintain a pressure slightly above the critical pressure of
CO2 (1050 psi). The system is held at these conditions for a short time, followed by a
slow, controlled release of CO2 to ambient pressure. As with previous steps, the length of
time required for this process is dependent on the thickness of the gels. The process may
last anywhere from 12 hours to 6 days.

4.9 CALCINATIONS OR SINTERING

After the removal of pore liquid, further heat treatment is necessary to convert the
precipitate or dry gel to catalytically useful form. After drying, the next step of heat
treatment is known as calcination. Often the heating is done in the presence of flowing air
or oxygen to burn any residual organics or to oxidize the sample. Multiple changes occur
during this process including:
1. Active phase generation: The hydroxide form is converted to oxide form.
2. Stabilization of mechanical properties: The catalysts sample is subjected to a more severe
heating treatment than that is likely to encounter in a reactor to ensure the stability of its
textural and structural properties during reaction.
3. Loss of chemically bound water: The chemically bound water is removed at higher
temperature.
4. Changes in pore size distribution and surface area due to sintering: Exposing the sample
to high temperature over an extended period of time leads to some sintering and
consequently decrease in surface area.
5. Change in phase distribution: Higher temperature cause material to crystallize into
different structural forms.

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Chapter Name: Introduction to Catalysis

4.10 CATALYST CHARACTERIZATION

Characterization of heterogeneous catalyst refers to the determination of its physical and
chemical characteristics, which are responsible for its performance in a reaction.
Characteristics of catalysts include:
1. Structural analysis
(a) Surface area
• Widely accepted BET ( Brunauer, Emmet and Teller) method used for
analysing multilayer physisorption isotherms of inert gases to determine
the surface area
(b) pore analysis by
• BJH method
• mercury intrusion method
(c) X-Ray Diffraction (XRD) :
• can detect crystalline materials having crystal domains greater than 3-5
nm.
• Characterization of bulk crystal structure and chemical phase
composition.
2. Chemisorption technique
• determines dispersion of metal in catalysts
• determination of surface metal area
3. Thermal analysis
(a) Temperature programmed reduction (TPR):
• measures the rate of reduction of active metals as function of
temperature.
• can be correlated with activity of catalysts
(b) Temperature programmed desorption (TPD):
• Measurement of rate of desorption of adsorbed molecules as function of
temperature
• Mainly used to of study acid –base property of catalysts
(c) Thermo Gravimetric Analysis (TGA):
• Measurement of weight loss (or gain) as a function of temperature in a
controlled gaseous atmosphere;
• process associated with mass change can be detected and analyzed

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Chapter Name: Introduction to Catalysis

(d) Differential Thermal Analysis (DTA)

• monitoring the temperature difference between sample and reference
• Process associated with latent heat of transition can be detected and
analyzed
4. Spectroscopic techniques
(a) Infra-red spectroscopy
• identify compounds and investigate sample composition
• Study of structure and bonds
(b) Raman spectroscopy:
• Study of oxidation state and interaction of metal oxides
5. Microscopic technique
(a) Scanning electron microscopy (SEM):
• Image the topography of solid surface
• Resolution better than 5 nm.
(b) Transmission electron microscopy (TEM):
• determines the micro –texture and micro structure
• Resolution better than 0.2 nm

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Chapter Name: Introduction to Catalysis

4.11 PHYSICAL PROPERTIES OF CATALYST

 The surface area of sold has pronounced effect on the amount of gas adsorbed and on
its activity as catalyst. For Example, if a fresh sample of fresh Raney Nickel which is
highly porous and large surface area is held in hand, heat can be felt due to oxygen
adsorption which is exothermic in nature. Thus, larger surface are gives higher
Adsorption rate. The dependence of rate of adsorption and catalytic reaction on
surface makes it imperative to develop reliable method for analysis of surface area.
The physical properties like surface area, Pore volume, distribution, void volume,
Solid density are important in any catalytic reaction.
 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.

4.11.1 DETERMINATION OF SURFACE AREA

 BET ( Brunauer, Emmet and Teller) method used for analysing multilayer
physisorption isotherms of inert gases to determine the surface area
 Determination of internal surface area is based on adsorption and condensation of N 2
1. Initially, the sample is evacuated at 293-523 K (120-250 oC) followed by cooling
to 77 K by liquid N2.
2. Then gradually the partial pressure of nitrogen above the sample is increased.
Some quantity of gas will be adsorbed by the sample and removed from the gas
phase.
3. After stabilization the equilibrated pressure is recorded and amount of nitrogen
adsorbed at each equilibrated pressure is noted.
4. The isotherm, volume adsorbed as function of relative pressure p/p o, is plotted
from the data. The pressure over the sample is gradually increased until pressure
reaches near saturation pressure, by when the complete adsorption isotherm is
developed.

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Chapter Name: Introduction to Catalysis

5. The desorption isotherm is measured by a step-wise reduction in pressure until a

low pressure over the sample is achieved.
6. Although the volumes are adsorbed at different conditions, the values are reported
at STP conditions. Fig. shows a typical N2 adsorption and desorption isotherm at
77 K for alumina.

A typical N2 adsorption and desorption isotherm at 77 K for alumina

Basic components of volumetric physical adsorption analyser

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 CHEMICAL REACTIONS ENGINEERING II (3170501)
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CHAPTER: 4
Chapter Name: Introduction to Catalysis

 The BET equation describes the relationship between volume adsorbed at a given
partial pressure and the volume adsorbed at monolayer coverage. BET equation can
be written in the form :

Where,
p = partial pressure of N2;
p0 = saturation pressure at the experimental temperature;
v = volume adsorbed at p;
vm = volume adsorbed at monolayer coverage;
c = constant
 Monolayer coverage is determined using BET equation.

 The is plotted as a function of .

 The plot is linear in the range of relative pressures = 0.05 - 0.3.

 At higher relative pressure p/po, the BET plot deviates from linearity as non-ideality
or pore condensation was not accounted for the derivation of BET equation.
 Slope and intercept of this linear plot is used for determination of monolayer
capacity vm.
 The intercept and slope from the plot is given as

 Then the monolayer volume vm is given as,

 The total number of N2 molecules adsorbed corresponding to monolayer

volume vm can be calculated as

 Now each adsorbed N2 molecule occupies an area of surface comparable to its cross
section area 0.162 nm2.

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CHAPTER: 4
Chapter Name: Introduction to Catalysis

4.11.2 VOID VOLUME AND SOLID DENSITY:

 The void volume, or pore volume, of a catalyst particle can be estimated by boiling a
weighed sample immersed in a liquid such as water. After the air in the pores has
been displaced, the sample is superficially dried and weighed. The increase in weight
divided by the density of the liquid gives the pore volume.
 A more accurate procedure is the helium-mercury method. The volume of helium
displaced by a sample of catalyst is measured; then the helium is removed, and the
volume of mercury displaced is measured. Since mercury will not fill the pores of
most catalysts at atmospheric pressure, the difference in volumes gives the pore
volume of the catalyst sample. The volume of helium displaced is a measure of the
volume occupied by the solid material. From this and the weight of the sample, the
density of the solid phase, Ps, can be obtained. Then the void fraction, or porosity, of
the particle, Ep, may be calculated from the equation

Where mp, is the mass of the particle and Vg, is the void volume per gram of particles. If
the sample of particles is weighed, the mass divided by the mercury volume gives the
density of the porous particles. Note that the porosity is also obtainable from the density
by the expression

From the helium-mercury measurements the pore volume, the solid density, and the
porosity of the catalyst particle can be determined. Values of E, are of the order of 0.5,
indicating that the particle is about half void space and half solid material. Since overall
void fractions in packed beds are about 0.4, a rule of thumb for a fixed-bed catalytic

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reactor is that about 30% of the volume is pore space, 30% is solid catalyst and carrier,
and 40% is void space between catalyst particles.
4.11.3 PORE SIZE DISTRIBUTION
By mercury intrusion
For macropores materials with pore diameter greater than 50 nm, the mercury intrusion
method is preferred. Due to non-wetting nature of mercury on oxide supports, intrusion is
met with resistance and mercury is forced to enter the pores of material under pressure.
The pore radius ‘r' is related to the applied pressure P as

The wetting or contact θ angle between mercury and solid is on average lies in the range
130-1400 and surface tension of mercury is 0.48 N/m2. p is in atm and r in nanometers.
As can be observed from equation smaller the pore radius higher is the pressure needed
for mercury to intrude in the pore.
At low pressure of 0-2 atm, mercury penetrates voids between particles. At moderate
pressure range of 3-500 atm large macro pores are filled. At further higher pressure range
of 500-2000 atm, smaller macro pores and large mesopores are progressively filled. This
technique is satisfactory for pores down to 3-5 nm dia. Maximum diameter that can be
measured is usually 105 nm.
Mercury intrusion method is carried out in the instrument known as mercury porosimeter.
In a typical mercury porosimeter data, volume of mercury penetrating into pores is plotted
as a function of applied pressures.

Intrusion of mercury into pores of various sizes. Here ‘r' represents the radius of
pores.
The pressure required for filling up the pores as a function of pore size is schematically
shown in Fig. As pore radius decreases in the order r1> r2> r3, requried pressure for
filling the pores increases in order of Pressure 1< Pressure 2 < Pressure 3. The available

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 CHEMICAL REACTIONS ENGINEERING II (3170501)
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CHAPTER: 4
Chapter Name: Introduction to Catalysis

instruments can measure pore size up to 2 nm using a maximum operating pressure of

about 400 MPa.
Table: Typical pore volume values of different support and catalyst.

4.12 THE NATURE OF CATALYTIC REACTION

 Although the catalyst remains unchanged at the end of the process, there is no
requirement that the material not take part in the reaction. In fact, present theories of
catalyst activity postulate that the material does actively participate in the reaction.
 From the concept of the energy of activation, the mechanism of catalysis would have
to be such that the free energy of activation is lowered by the presence of the catalytic
material.
 A catalyst is effective in increasing the rate of a reaction because it makes possible an
alternative mechanism, each step of which has a lower free energy of activation than
that for the uncatalyzed process.
 Consider the reaction between hydrogen and oxygen in the presence of spongy
platinum. According to the proposed concept, hydrogen combines with the spongy
platinum to form an intermediate substance, which then reacts with oxygen to provide
the final product and reproduce the catalyst. It is postulated that the steps involving
the platinum surface occur at a faster rate than the homogeneous reaction between
hydrogen and oxygen.
 The combination or complexing of reactant and catalyst is a widely accepted basis for
explaining catalysis. For example, suppose the overall reaction

is catalyzed via two active centers, or catalytic sites, X1 and X2 , which.form

complexes with A and B. The reaction is truly catalytic if the sequence of steps is such
that the centers Xl and X2 are regenerated after they have caused the formation of C.

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Chapter Name: Introduction to Catalysis

 In a general way the process may be written

 Note that whereas X1 and X2 are combined and regenerated a number of times, it
does not necessarily follow that their catalyzing ability and/or number remain
constant forever.
 For example, poisons can intervene to slowly remove X1 and/or X2 from the system,
arresting the catalytic rate. What distinguishes .this decline in catalytic activity from
that of a non- catalytic reaction in which X1 and X2 are not regenerated is that the
complexing- regenerating sequence occurs a great many times before X1 and X2
become inactive. In the noncatalytic sequence no regeneration of X occurs. Hence,
while catalysts can deteriorate, their active lifetime is far greater than the time
required for reaction.

The general characteristics of catalysis may be summarized as follows:

1. A catalyst accelerates reaction by providing alternate paths to products, the activation
energy of each catalytic step being less than that for the homogeneous (noncata1ytic)
reaction.
2. In the reaction cycle active centers of catalysis are combined with at least one reactant
and then freed with the appearance of product. The freed center then recombines with
reactant to produce another cycle, and so on.
3. Comparatively small quantities of catalytic centers are required to produce large
amounts of product.
4. Equilibrium conversion is not altered by catalysis. A catalyst which accelerates the
forward reaction in an equilibrium system is a catalyst for the reverse reaction.
5. The catalyst can radically alter selectivity.

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 CHEMICAL REACTIONS ENGINEERING II (3170501)
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CHAPTER: 4
Chapter Name: Introduction to Catalysis

4.13 THE MECHANISM OF CATALYTIC REACTIONS

 The concept that a catalyst provides an alternate mechanism for accomplishing a
reaction, and that this alternate path is a more rapid one, has been developed in many
individual cases. The basis of this idea is that the catalyst and one or more of the
reactants form an intermediate complex, a loosely bound compound which is
unstable, and that this complex then takes part in subsequent reactions which result in
the final products and the regenerated catalyst. Homogeneol:!:S catalysis can
frequently be explained · in terms of this concept. For example, consider catalysis by
acids and bases.
 In aqueous solutions acids and bases can increase the rate of hydrolysis of ugars,
starches, and esters. The kinetics of the hydrolysis of ethyl acetate catalyzed by
hydrochloric acid can be explained by the following mechanism:

 For this catalytic sequence to be rapid with respect to noncatalytic hydrolysis, .the
free energy of activation of reaction steps 1 and 2 must each be less than the free
energy of activation for the noncatalytic reaction,

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