UNIT-1

Catalysis and Catalytic Reactors

 Catalyst

A catalyst is a substance that Eg. Hydrogen and oxygen

affects the rate of a reaction are inert at room
but emerges from the temperature, but react
process unchanged. rapidly when exposed to
Platinum (Catalyst).

A catalyst changes only the rate of

a reaction; it does not affect the
equilibrium.
 Catalysis

Catalysis is the occurrence, study, and use of catalysts and

catalytic processes

• Heterogeneous Catalysis - A
heterogeneous catalytic process involves
more than one phase; usually the catalyst
There are is a solid and the reactants and products
two types of are in liquid or gaseous form.
catalysis • Homogeneous Catalysis - Homogeneous
catalysis concerns processes in which a
catalyst is in solution with at least one of
the reactants.
Homogenous catalysis: Propylene, CO, H2, Cobalt catalyst gives
Isobutylaldehyde

Heterogenous catalysis: Dehydrogenation of cyclohexane

 Heterogeneous Catalysis

A, heterogeneous catalytic reaction occurs at or very near the

fluid-solid interface.

The principles that govern heterogeneous catalytic reactions

can be applied to both catalytic and non-catalytic fluid-solid
reactions.

These two other types of heterogeneous reactions involve gas-

liquid and gas-liquid-solid systems.

Reactions between gases and liquids are usually mass-transfer

limited.
 Catalyst Types

• Porous Catalysts
• Molecular Sieves
The different types • Monolithic Catalysts
of catalyst are:
• Supported Catalysts
• Unsupported Catalysts
 Porous Catalysts

A catalyst that has a large area resulting from pores is called a

porous catalyst.

• Raney Nickel – used in hydrogenation of

vegetable oils
Examples: • Pt on Al2O3 – used for reforming of
petroleum naphthas
• Fe – used for ammonia synthesis
 Molecular Sieves
Molecular sieves are the catalysts in which the pores are so small
that they will admit small molecules but prevent large ones from
entering.

The diameter of molecular sieves are measured in terms of

angstroms

• Natural catalysts – clays and zeolites

Example: • Synthetic catalysts – crystalline
aluminosilicates
CH4+O❑C2H 3OnometalCH3−
Zeolites help to
22 zeolit
form ethane
molecules
1→ →
→
 Monolithic Catalysts

These types of catalysts are used where pressure drop and heat
removal are major consideration.

They do not need extended surface like porous catalysts.

They can be either porous (honey comb) or non porous (wire

gauze)

• Pt gauze in ammonia oxidation portion of nitric acid

Example • Catalytic converters – used to oxidize pollutants in
: automobile exhausts.
 Unsupported and supported catalysts

Catalysts which consist

of minute particles of • Pt on Al2O3 – used in reforming of
active materials (metal methane
or metal alloys) over a
less active substance • V2O5 on Silica – used to oxidize SO2 in
are called supported the manufacture of H2SO4.
catalysts.

In unsupported catalyst
• Pt guaze – ammonia oxidation
the active materials are • Promoted iron – Ammonia synthesis
other substances • Silica-alumina – for dehydrogenation
known as promoters.
to synthesize butadiene.
Images of different types of catalysts

Porous Catalyst

Molecular Sieves
Monoliths
 Zeolite

Zeolites are microporous, aluminosilicate minerals commonly
used as commercial adsorbents and catalysts.

Zeolites occur naturally but are also produced industrially on a

large scale.

Zeolites have a porous structure that can accommodate a wide

variety of cations, such as Na+, K+, Ca2+, Mg2+ and others.

These positive ions are rather loosely held and can readily be
exchanged for others in a contact solution. Some of the more
common mineral zeolites are analcime, chabazite,
clinoptilolite, heulandite, natrolite, phillipsite, and stilbite.
An example of the mineral formula of a zeolite is:
Na2Al2Si3O10·2H2O, the formula for natrolite.
 Zeolites - Uses
Zeolites are widely used as ion-exchange beds in domestic and
commercial water purification, softening, and other applications.

In chemistry, zeolites are used to separate molecules (only molecules

of certain sizes and shapes can pass through), and as traps for
molecules so they can be analyzed.

Zeolites are also widely used as catalysts and sorbents. Their well-
defined pore structure and adjustable acidity make them highly
active in a large variety of reactions.
Zeolites have the potential of providing precise and specific
separation of gases, including the removal of H2O, CO2 and SO2 from
low-grade natural gas streams. Other separations include noble
gases, N2, O2, freon and formaldehyde.
Zeolite - structure
 Catalyst Properties & Poisoning
A large interfacial area is essential in attaining a significant reaction
rate

Most of the catalysts do not maintain their activity levels for a

long time.

This is known as catalyst deactivation, which refers to decline

in catalyst activity as time progress.

This is due to aging of the catalyst (due to change in

surface crystal structure) or due to deposit of foreign
material (catalyst poisoning or fouling) or due to coking
 Adsorption

For a catalytic reaction to take place, at least one and

frequently all of the reactants must become attached to the
surface.

Adsorption is the adhesion of atoms, ions, or molecules from a

gas, liquid, or dissolved solid to a surface. This process creates
a film of the adsorbate on the surface of the adsorbent.

Adsorption is of two • Physical adsorption

types: • chemisorption
 Physical Adsorption

This is similar to condensation

The process is exothermic and there is generation of heat(1 -15

kcal/g)

The forces of attraction between the gas molecules and the solid
surface are weak. (Weak Van der Waals force of attraction).

The amount of gas that is physically adsorbed decreases with

increasing temperature.
 Chemisorption
Chemisorption is a kind of adsorption which involves a chemical
reaction between the surface and the adsorbate.

New chemical bonds are generated at the adsorbent surface. 

As a result the electronic structure of the chemisorbed
molecule is perturbed significantly, causing to be extremely
reactive.
Chemisorption on active sites is what catalyzes the reaction.

(Ethylene conversion to ethylidyne on Pt)

 Chemisorption – Figure

Ethylidyne as chemisorbed on platinum. (Adapted from G.A.

Somorjai, Introduction to surface chemistry and catalysis, Wiley,
New York, 1994)
 Definitions
• It is a point on the catalyst surface that can
Active
form strong chemical bonds with an
site: adsorbed atom or molecule

• It is a parameter used to quantify the

Turnover activity of a catalyst.
Frequenc • It is the number of molecules reacting per
y (N): active site per second at the conditions of
the experiment.
• The dispersion of the catalyst is the fraction
of the atoms deposited that are on the
Dispersio surface. (or) (Dispersion is the fraction of atoms of a
n (D) material exposed to the surface. Since only atoms that are
exposed to the surface are able to play a role
in catalytic surface reactions.)
S.No. Reaction Type Catalysts
1. Halogenation – Cucl2, AgCl, Pd
Dehalogenation
2. Hydration-dehydration Al2O3, MgO
3. Alkylation-dealkylation AlCl3, Pd
4. Hydrogenation- Co, Pt, Cr2O3, Ni
dehydrogenation
5. Oxidation Cu, Ag, Ni, V2O5
6. Isomerization AlCl3, Pt/Al2O3, Zeolites
 Steps in a catalytic Reaction
1. Mass transfer (diffusion) of the reactant(s) (e.g., species A)
from the bulk fluid to the external surface of the catalyst
pellet
2. Diffusion of the reactant from the pore mouth through the
catalyst pores to the immediate vicinity of the internal
catalytic surface
3. Adsorption of reactant A onto the catalyst surface
4. Reaction on the surface of the catalyst (e.g., A B)
5. Desorption of the products (e.g., B) from the surface
6. Diffusion of the products from the interior of the pellet to
the pore mouth at the external surface
7. Mass transfer of the products from the external pellet
surface to the bulk fluid
 Steps in a heterogeneous catalytic reaction

A reaction takes place on the surface, but the species involved in the
reaction must get to and from the surface
 Adsorption Isotherms
• S is the active site
• A is an atom or molecule
• Adsorption of A on a site S is given as below:

• Total molar concentration(site balance)

https://www.youtube.com/watch?v=_G4AsbVQIng
 Adsorption Isotherms (Contd…)
• Isotherm
– They portray the amount of a gas adsorbed on a solid at different
pressure but at one temperature.

• The isotherms are first modeled and then compared with

experimental data. Then they are compared. If there is a good
correlation, then the behavior of the system is understood or
else the model fails.
• The isotherms are of two types.
– Freundlich Adsorption isotherm
– Langmuir Adsorption isotherm

• The Langmuir isotherm is applied to monolayer adsorption on

homogeneous sites.
• Freundlich isotherm is applied to multilayer adsorption on
heterogeneous sites.
 Freundlich Isotherm
• The Freundlich equation or Freundlich adsorption isotherm, an
adsorption isotherm, is an empirical relation between the
concentration of a solute on the surface of an adsorbent to the
concentration of the solute in the liquid with which it is in contact
• The equation is an expression representing the isothermal variation
of adsorption of a quantity of gas adsorbed by unit mass of solid
adsorbent with pressure.
• The Freundlich adsorption isotherm is mathematically expressed as

x = mass of adsorbate
m = mass of adsorbent
p = Equilibrium pressure of adsorbate
K and n are constants for a given adsorbate and adsorbent at
a particular temperature.
 Freundlich Isotherm contd…

• Experimentally it was determined that the extent of gas adsorption

varies directly with pressure and then it directly varies with
pressure raised to the power 1/n until saturation pressure P s is
reached.

• Beyond that point (saturation pressure), the rate of adsorption

saturates even after applying higher pressure. Thus, the Freundlich
adsorption isotherm fails at higher pressure.
 Langmuir Isotherm
• The Langmuir adsorption model explains adsorption by assuming an
adsorbate behaves as an ideal gas at isothermal conditions. At
these conditions the adsorbate's partial pressure, pA, is related to
the volume of it,V, adsorbed onto a solid adsorbent.
• The adsorbent, is assumed to be an ideal solid surface composed of
series of distinct sites capable of binding the adsorbate.
• The adsorbate binding is treated as a chemical reaction between
the adsorbate molecule Ag and an empty site, S. This reaction yields

an adsorbed complex Aad with an associated equilibrium constant 

Keq
Langmuir Isotherm
 Basic Assumptions
Inherent within this model, the following assumptions are valid
specifically for the simplest case: the adsorption of a single adsorbate
onto a series of equivalent sites on the surface of the solid.
• The surface containing the adsorbing sites is a perfectly flat plane
with no corrugations (assume the surface is homogeneous) .
• The adsorbing gas adsorbs into an immobile state.
• All sites are equivalent.

• Each site can hold at most one molecule of A (mono-layer coverage

only).
• There are no interactions between adsorbate molecules on
adjacent sites.
 Models for adsorption

• Molecular or non-dissociated adsorption

• Dissociative adsorption
 Surface Reaction
After a reactant has been adsorbed onto the surface, it
is capable of reacting in a number of ways to form the
reaction product. Three of these ways are:

• Single Site (Langmuir-Hinshelwood, L-H kinetics)

• Dual Site (Langmuir-Hinshelwood, L-H kinetics)
– Dual site
– Second dual site
– Third dual site
• Eley-Rideal Mechanism (E-R kinetics)
 Single Site
• The surface reaction may be a single-site
mechanism in which only the site on which
the reactant is adsorbed is involved in the
reaction. An absorbed molecule ‘A’ may
isomerize/decompose directly on the site to
which it is attached.
Dual Site Mechanism

The surface reaction may

be a dual-site mechanism
in which the adsorbed
reactant interacts with
another site (either
unoccupied or occupied)
to form the product.
 Second dual-site mechanism
The reaction between two adsorbed species
 Third dual site mechanism
A third dual-site mechanism is the reaction of two species
adsorbed on two different types of sites S and S'.
 Eley-Rideal Mechanism
A third mechanism is the reaction between an
adsorbed molecule and a molecule in the gas phase:
 Desorption
• The products of the surface reaction adsorbed on the
surface are subsequently desorb into the gas phase.

• The rate of desorption of a species ‘C’ is:

Where, KDC = Desorption equilibrium constant; rD =

Rate of desorption
• rD = -rADC & KDC = 1/KAC
 The rate limiting step
 C A S 
Adsorption A S  A S  rA  rAd  k Ad  PACv  
 K A 

 CBS 
Surface Reaction A  S  B  S  rA  rS  k S C A S  
 K S 

Desorption  PB Cv 
BS  B S  rA  rD  k D C B S  
 K DB 

Which step is the Rate Limiting Step (RLS)?

 The rate limiting step

• At steady state the three reaction steps are the same

(adsorption, surface reaction and desorption).
rAD = rS = rD = -rA’
• However one of the steps is the rate limiting or rate
controlling step.
• Assume it is analogous to electrical circuit.
• Driving force or Electromotive force (EMF) / voltage (E) is
analogous to conc. of reactants.
• Here, I (Current, C/s) is analogous to the –rA’ (mol/s.g cat).
• Ri is the resistance associated with the three steps.
 Rate limiting step.
Which step has largest resistance?
 Approach in determining the catalytic reaction

• This technique is termed the Langmuir-Hinshelwood (L-H)

approach.
• It consists of first assuming a sequence of steps in the
reaction. In writing this sequence, one must choose among
such mechanisms as molecular or atomic adsorption, and
single- or dual-site reaction.
• Next, rate laws are written for the individual steps assuming
that all steps are reversible.
• Finally, a rate-limiting step is postulated, and steps that are
not rate-limiting are used to eliminate all coverage-dependent
terms.
 Examples
• Synthesis of ammonia from nitrogen and hydrogen over iron
catalyst- adsorption limited reaction
• The reaction between CO and NO – surface limited reaction

Rapid
Rate Limiting

Rapid

The rate limiting step is believed to be the adsorption of N2

molecule as an N atom
 Example of surface reaction controlled

• The reaction is carried over Cu catalyst to form N2 and CO2.

Rapid

Rate Limiting
Rapid

The reaction between CO and NO – surface limited reaction