OXIDATION

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 Topics to be covered
• Introduction
• Types of Oxidation
• Oxidizing agents
• Liquid-phase oxidation
• Vapor-phase oxidation
• Industrial Applications

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 Introduction
• Oxidation is the addition of oxygen to an organic
compound or, conversely, the removal of hydrogen.

• Reaction control is the major issue during oxidation

reactions. Only partial oxidation is required for
conversion of one organic compound into another or
complete oxidation will ensure the formation of
carbon dioxide and water.

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 Types of Oxidation
• Principle types of oxidation reactions are as follows:

✓ Dehydrogenation
✓ Introduction of oxygen
✓ Addition of oxygen and dehydrogenation
✓ Dehydrogenation by molecular condensation
✓ Oxidation of sulfur compounds

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 Dehydrogenation
• Transformation of a primary alcohol to an aldehyde

• Transformation of a secondary alcohol to ketone

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 Introduction of oxygen
• An atom of oxygen may be introduced into a molecule
e.g. oxidation of an aldehyde into an acid

• From hydrocarbon to alcohol

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 Addition of oxygen and dehydrogenation

• Both of these reactions take place simultaneously as

in the preparation of aldehydes from hydrocarbons.

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 Dehydrogenation by molecular condensation

• Two molecules of benzene react to form biphenyl:

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 Oxidation of sulfur compounds

• These may be oxidized by acid permanganate

(strong), e.g.

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 Applications
• As examples of oxidation processes, two processes
are available for the manufacture of phenol, and
both involve oxidation.

• The major process involves oxidation of cumene to

cumene hydroperoxide, followed by decomposition to
phenol and acetone.

• Phenol is also made by the oxidation of toluene to

benzoic acid, followed by decomposition of the
benzoic acid to phenol.
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 Applications
• Benzoic acid is synthesized by liquid-phase toluene
oxidation over a cobalt naphthenate catalyst with air
as the oxidizing agent.

• Maleic acid and anhydride are recovered as by-

products of the oxidation of xylenes and
naphthalenes to form phthalic acids, and are also
made specifically by the partial oxidation of benzene
over a vanadium pentoxide (V2O5) catalyst.

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 Applications
• Several oxidative routes are available to change
cyclohexane to cyclohexanone, cyclohexanol and
ultimately to adipic acid.

• Acetaldehyde is manufactured by one of the several

possible processes:
✓ The Wacker process, in which ethylene is oxidized directly with air
(or 99% oxygen) in the presence of a catalyst such as palladium
chloride.
✓ A process in which lower molecular weight paraffin hydrocarbons
are oxidized non-catalytically to produce mixed compounds,
among them acetaldehyde and acetic acid.
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 Oxidizing agents
• The most common oxidation agent is air, but oxygen is
frequently used.
• Other chemical oxidizing agents include:
✓ Permanganates
✓ Dichromates
✓ Hypochlorous acid and salts
✓ Sodium chloride and chlorine dioxide
✓ Chlorates
✓ Peroxides
✓ Nitric acid and nitrogen tetraoxide
✓ Copper salt
✓ Ozone

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 Liquid-phase oxidation
• In the case of liquid-phase reactions in which oxygen
is provided by means of air, for example, the
oxidation of liquid hydrocarbons to fatty acids, special
means must be provided to secure adequate mixing
and contact of the two immiscible phases of gaseous
oxidizing agent and the liquid being oxidized.

• As oxidation is exothermic reaction, temperature

must be controlled.

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 Liquid-phase oxidation
• Heat may be removed by circulating the liquid being
oxidized or a special cooling fluid through an external
heat exchanger.

• Mixing may be obtained by the use of special

distributor inlets for the air, designed to spread the
air throughout the liquid.

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 Vapor-phase oxidation
• All the reactants will be in gaseous phase.
• Removal of heat is also essential in this case to
prevent destruction of apparatus, catalyst, or raw
materials, and maintenance of temperature at the
proper level is necessary to ensure the correct rate
and degree of oxidation.

• With plant-scale operation removal of heat

constitutes a major problem because of large
quantities involved.
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 Industrial Applications: Phthalic anhydride
• Phthalic anhydride was first produced by the
oxidation of naphthalene in concentrated sulfuric acid
in the presence of mercury sulphate. This route was
later replaced by the catalytic vapor phase oxidation
of naphthalene in air in the presence of a vanadium
oxide catalyst.
• Today, naphthalene feedstock has been generally
superseded by the use of orthoxylene. In US, all
production is now from orthoxylene
• In Europe, more producers have the capability to use
naphthalene.

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 Industrial Applications: Phthalic anhydride
• In the orthoxylene-based process, an air-orthoxylene
mixture is fed to a reactor containing vanadium
pentoxide with titanium dioxide-antimony trioxide
catalyst. Alternative catalysts include molybdenum
trioxide and calcium oxide, or manganese oxides.

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 Industrial Applications: Phthalic anhydride
Reactions

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 Industrial Applications: Phthalic anhydride
Uses
• Of the current production, 50 percent is used for
plasticizers, 25 percent for alkyd resins, 20 percent for
unsaturated polyester resins and 5 percent for export.

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