Lecture # 2

Principles of Heterogeneous Catalysis

CHE633A, IIT Kanpur

 Course conduct and content

 Introduction and a bit of history
o Metal
o Type of metal
o Surface of metal
Field of catalysis is multidimensional and multidisciplinary
✓ requires an integrated approach based on different established
practices of engineering and science

✓ “Catalysis” first used by Berzelius in 1800’s. He observed that

several reactions were aided by the presence of certain foreign
substances “Catalytic Force” involved

✓ Several discoveries and patents were made involving catalysis in the

1800s & early 1900s

✓ The progress was limited in scientific understanding and the

discoveries were made by chance → “Black box” technology
Early 1900’s – several theories and postulates were made
Despite this:
• Sabatier → chemical intermediates are formed
• Langmuir → importance of surfaces and reactions happen on them
• Development of relationship between various rates &pressures
Langmuir–Hinshelhwood Eley–Rideal
• Taylor → active sites/centers on catalytic surfaces
Theories:
• Balandin - interpretation of catalytic activity in terms of geometric
arrangement of atoms
• Beck - relationship between lattice spacing and activity
• Schwab - electronic concentration in metal alloys was related to
catalytic activity
Homogeneous catalysis are for those catalytic processes
involving a single phase
 Homogeneous catalysts are attractive for study in research labs
o Mechanism is readily accessible to detailed study – rate data is easier
to interpret
o Species in solution are more easy to characterize
 Advantages of homogeneous catalysis in an industrial scale
o High selectivity
o Ease of heat dissipation from exothermic reactions
 Disadvantages
o Scale-up can be costly, difficult and dangerous
o Separation of catalyst from reactants and products is required
Heterogeneous Catalysts are those when the catalyst is of
a different phase as that of the reactants/products
 Heterogeneous catalysts are more readily used in industry
o Solid catalysts are robust and can be used at high temperatures and
pressures
o No solvents are required
o No separation of catalyst is required

 Only heterogeneous catalysts

considered in this course
VSPARTICLE B.V.. "The Future of Heterogeneous CatalystS".
AZoNano. 20 November 2020.
<https://www.azonano.com/article.aspx?ArticleID=5270>.
Solid catalysts play a key role in the chemical industry

Desired properties of the solid catalysts

 High and stable activity
 Consistently high selectivity
 Controlled surface area and porosity
 Good resistance to poisons
 Good resistance to high temperatures and temperature
fluctuations
 High mechanical strength
Other important factors to consider
 Whether the catalyst should be supported

 What should be the shape of the catalyst

 What should be the void fraction

 Whether diffusional control is necessary

Economic importance of catalysis is reflected in the
following numbers

• More than 85% of all chemical products are manufactured with the
help of catalysts

• 15−20% of the economic activities in industrialized countries depend

directly on catalysis

• The commercial value of the catalysts produced annually amounts to

∼14 billion US$

• In 2005 the value of the goods produced with the help of catalysts
amounted to ∼900 billion US$
 Specific applications of Catalysis
✓ inorganic chemicals (NH3, H2SO4)

✓ organic chemical (hydrogenation, polymerization, oxidation, reduction)

✓ petroleum technology (cracking, reforming, isomerization)

✓ production of synthetic fuels (coal liquefaction, coal gasification)

✓ pollution control (automotive, industrial)

✓ energy conversion (fuel cells)

In India, the chemical industry is the 6th largest in the world and accounts
for about 2.1% of the GDP, employing about 5 million people
Ammonia synthesis is a very important process
Variation of surface area with particle size

Iron
Density = 7.874 g/cm3
Interfacial area
increases
interaction
between solid
and fluid phase

How to
maintain small
size of particles
Metals have different crystal structure and atomic
arrangements at the surface