HETEROGENOUS CATALYSIS

J. NYIRENDA
INTRODUCTION
CREN -1
 Kinetics: in which estimation of rate of constant and order of the reaction for different forms
 Batch reactor design
 I deal flow reactor design. Particularly that of CSTR and plug flow reactors
 Isothermal cases, adiabatic condition and non isothermal
CREN-II
 Introduction to heterogeneous catalysis
 Residence time distribution
 Fixed bed catalytic reactor design
 Fluidised bed reactors
 Multiphase reactors
 Non-catalytic fluid-solid reactions

The primary purpose of chemical reaction engineering is optimization of chemical reactors, feed composition and
operating conditions
CATALYST
Catalyst are substances which, when added to a reaction, increase the rate
of reaction by providing an alternate reaction pathway with a lower
activation energy.
The substances that alter the rate of a reaction but itself remains
chemically unchanged at the end of the reaction.
They do this buy promoting proper orientation between reacting particles.
CATALYSIS
Catalysis is the increase in the rate of a chemical reaction due to the
participation of an additional substance called catalyst.
With a catalyst, reaction can occur at a faster rate and with less energy
A+ B Products
General Mechanism
A+B C

Step-1 A+x Ax

Step -2 B + x Bx

Step-3 Ax + Bx C + 2x
CATALYST COMPONENTS
A solid catalyst consists of mainly three components :
1. Catalytic agent- (i) Metallic conductors
(ii) Semi conductors
(iii) Insulators
 This are basically those substance which are responsible to provide
catalytic activity in a given reaction
2. Support/carrier
 Are substances which are used to provide a base for catalytic agent
3. Promoters and Inhibitors
 Are substances or chemicals which are added into our catalyst to
either enhance the rate of reaction or to reduce any side reaction
INDUSTRIAL CATALYSTS
Industrial catalysts can be characterized as:
Bulk catalysts : When the entire catalyst consists of the catalytically active
substances, the solid catalyst is called a bulk catalyst
Supported catalysts : In supported catalysts, the catalytically active materials
are dispersed over the high surface area support material.
Mixed agglomerates : These catalysts are agglomerated mixture of active
substance and support.
This refers to the presence of multiple catalyst particles that have fused
or coalesced together, forming larger agglomerates or clusters. These
agglomerates can vary in size, ranging from a few micrometers to
several millimeters, depending on the specific catalyst and its
preparation process.
 PREPARATION OF SOLID
1.CATALYST
Bulk preparation process
(i) Precipitation process
(ii) Sol gel process

2. Impregnation process
 The carrier is immersed in a solution containing active components.
After reaching equilibrium, the remaining liquid is removed and the
catalyst is obtained after drying, calcining and activation.
3. Physical mixing - This is a straightforward and commonly used method for
preparing solid catalysts. In this approach, the catalyst components are mechanically
mixed together to create a homogenous mixture
Basic unit operation in solid catalyst preparation
Precipitation or gel formation from starting materials

Decantation/filtration

Washing

Drying

Crushing and grinding

Forming

Calcination

Impregnation

Final Activation
Precipitation Method
During precipitation, several processes occur and the major steps are:

 Liquid mixing/supersaturation

 Nucleation

 Crystal growth to form primary products

 Aggregation of the primary particles

Disadvantages:
• Product separation after precipitation is quiet difficult
• Generation of the large volume of salt containing solutions
• Difficult in maintaining a constant product quality throughout the whole
precipitation process if the precipitation is carried out discontinuously.
Important parameters in precipitation method.
• Temperature
• PH
• Solvent
• Composition
• Concentration
• Additives
• Raw materials
SOL GEL METHOD
In the similar way to precipitation method we use liquid to form a catalyst
but the only difference between precipitation method and sol-gel method is
in the physical structure of the final product which is obtained.
The sol gel method is distinguished from other routes of material preparation
from solutions or melts such as precipitation and crystallization by two main
characteristics
1. Formation of clear colloidal solution due to primary condensation of
dissolved molecular precursors
2. These colloidal particles merge during subsequent gelation stage into
polymeric chains by chemical bonding between local reactive groups at their
surfaces.
Two main parameters that must be considered;
1. A mount and rate of water addition

2. PH of the solution. The amount of water added is expressed in terms of

When h < 1, there is less possibility of forming infinite network because of the
presence of few M-OH groups for cross linking and gelation
If excess amount of water is present, that is h > 1, extensively cross linked gel
can be formed.
Calcination 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.

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 calcination process
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 heat treatment than that is likely to be encountered in a
reactor. This ensures 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
sintering and consequently decreases the surfaces area.
5. Change in phase distribution: Higher temperature cause material to
crystallize into different structural forms.
 Catalyst Characterization
Characteristics of catalysts include:
• Chemical composition of the bulk and surface of the solids
• Surface are and porosity (micro, meso and macro
• Bulk solid structure, phase composition, crystallite size
• Surface morphology
• Surface chemical properties such as: (i) location and oxidation state of active
metals (ii) acid-base property (iii) reducible – oxidizable property
• Aggregate properties such as aggregate or particle size, density, mechanical
strength and attrition resistance
• Catalytic properties: activity, selectivity, stability