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Handout2 - Introduction

The document discusses heterogeneous catalysis, explaining that catalysts speed up reactions by lowering activation energy without altering equilibrium. It provides examples of catalysts in everyday life, such as in food production and pharmaceuticals, and contrasts homogeneous and heterogeneous catalysis. The document also lists various industrial processes utilizing different catalysts and highlights the potential future applications of catalysts in producing chemicals from alternative feedstocks.

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Biliat Ligomeka
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5 views

Handout2 - Introduction

The document discusses heterogeneous catalysis, explaining that catalysts speed up reactions by lowering activation energy without altering equilibrium. It provides examples of catalysts in everyday life, such as in food production and pharmaceuticals, and contrasts homogeneous and heterogeneous catalysis. The document also lists various industrial processes utilizing different catalysts and highlights the potential future applications of catalysts in producing chemicals from alternative feedstocks.

Uploaded by

Biliat Ligomeka
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as PDF, TXT or read online on Scribd
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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.

MUST/Reactors II Handout 1 Page 1/7


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.

MUST/Reactors II Handout 1 Page 2/7


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%

MUST/Reactors II Handout 1 Page 3/7


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

MUST/Reactors II Handout 1 Page 4/7


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

MUST/Reactors II Handout 1 Page 5/7


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

MUST/Reactors II Handout 1 Page 6/7


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

MUST/Reactors II Handout 1 Page 7/7

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