1.
0 Heterogeneous Catalysis
1.1 Catalysts
• A catalyst is a substance that affects the rate of reaction but emerges from the process
unchanged
• A catalyst acts by lowering the activation energy of the reaction (often by providing an
alternative path that avoids the slow, rate-determining step of the uncatalysed reaction) and
results in a higher reaction rate at the same temperature.
Fig. 1.1 Representation of the action of a catalyst.
• A catalyst changes only the rate of reaction; it does not affect the position of the reaction
equilibrium.
Because the catalyst can speed up (promote) different molecular mechanisms within the overall
reaction scheme, it can influence both yield and selectivity of the reaction to a desired product.
• Activity – a measure of the amount of reactant converted.
• Selectivity – e.g. for the reaction A → B + C + X + P, suppose we want A → P
Selectivity =
[P]
[B] + [C] + [X] + [P]
• Promoter – an additive which improves stability (lifetime), activity and selectivity of a
catalyst.
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1.1.1 Catalysts in Everyday Life
Example 1: Modifying food: margarine production by hydrogenating vegetable oil
Vegetable oil + H2 Ni/SiO2; 420 K, 3 atm
Increase in saturated fat content
[high in unsaturated fat] [Improves spreadability]
Example 2: Pharmaceuticals by asymmetric synthesis
• Nature is usually very specific in the way it makes molecules, especially when a
stereogenic centre is involved (a stereogenic centre is one which is not superimposable on
its mirror image), and it is usually very selective to the isomer which has the required
biological properties.
• A molecule possessing asymmetry leading to optical isomerism is said to be chiral.
• Different chiral versions of the same molecule often have very different properties, e.g., L-
limonene smells of lemons, whereas D-limonene smells of oranges. In the plant, which
produces these fruits, there are natural processes to make only one of the enantiomers with
very high selectivity.
Many drugs are efficacious in only one chiral form and so-called asymmetric catalysis is now
being widely applied in this area:
• Thalidomide: one isomer is sedative, the other causes birth defects
• The drug L-dopa is believed to offer great potential for the treatment of Parkinson’s
disease.
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Example 3: Production of ethylene oxide: precursor to detergents, cosmetics etc.
• USED FOR: Antifreezes, lubricants, detergents, brighteners, cosmetics, fibres, plastics,
solvents, de-emulsifiers, cement additives, pharmaceuticals.
How is ethylene oxide produced?
O2
C2H4 C2H4O [main reaction]
O2
C2H4 CO2 + H2O [side reaction]
Using
• Ag catalyst alone, we get 50% selectivity
• Ag + Alkali oxide, selectivity = 70%
• Ag + Alkali oxide + chloro-organic (ppm level), selectivity = 80%
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1.1.2 Catalysts for the future
Example 1: chemicals from alternative feedstocks
Possibilities exist for the conversion of simple alkanes most of which are currently burned as cheap
fuels or flared off at well heads, to commodity chemicals:
Example 2: catalytic hydrogen production
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1.2 Homogenous and Heterogeneous Catalysis
Homogenous Catalysis
The catalysts and the reactants are both in the same phase, either gas or liquid. The term had been
generalised to include processes in which the catalyst need only be in solution with one of the
reactants.
Example: Industrial Oxo process for manufacturing normal isobutyl-aldehyde using a liquid-phase
cobalt complex.
• highly selective – batch operated
• expensive
• sensitive to process conditions
• difficult (expensive separation at the end) to recover catalyst
Heterogeneous Catalysis
The catalytic process involves more than one phase; usually the catalyst is a solid and the reactants
and the products are in the liquid or gaseous form.
Example:
C 6 H 6 + 3H 2 → C 6 H 12 Ni on support
• low selectivity – continuous with recycle
• cheap
• robust to process conditions
• easy separation of catalyst from product
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Table 1.1 Examples of Heterogeneous Catalysts in Industrial Processes
Reaction Type Reaction Catalyst
butane → butenes Cr 2 O 3 .Al 2 O 3
Butanes → butadiene Fe 2 O 3 promoted with Cr 2 O 3 and
K 2 CO 3
Fe 2 O 3 promoted with Cr 2 O 3 and
Dehydrogenation Ethyl benzene to styrene K 2 CO 3 , in the presence of steam
Steam reforming CH 4 or other Supported Ni
hydrocarbons + H 2 O → CO + H 2
Isopropanol → acetone + hydrogen ZnO
Of edible oils and fats Ni on support
C 6 H 6 + 3H 2 → C 6 H 12 Ni on support
Hydrogenation N 2 + 3H 2 → 2NH 3 Fe promoted with Al 2 O 3 , K 2 O
SO 2 + air → SO 3 V 2 O 5 + K 2 SO 4 on silica
Complete oxidation of CO and Pt or Pd or both on monolith support
Oxidation hydrocarbons for pollution control
Catalytic cracking Zeolite in SiO 2 .Al 2 O 3 matrix
Hydrocracking Pd on zeolite in an amorphous matrix
Acid-Catalysed Paraffin isomerisation Pt on H-mordenite zeolite in alumina
Reactions matrix
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Synthesis gas (“Syn-gas”) is a mixture of carbon monoxide and hydrogen and is produced either
by oxidising coal with steam, or by burning methane. Note how products generated from syn-gas
differ as a function of the catalyst used.
Fig 1.2 Uses of Synthesis gas
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