Benzoic acid manufacturing process

According to Maki and Takeda , benzoic acid is produced, worldwide, by

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liquid-phase oxidation of toluene with molecular oxygen. Originally the

oxidation reaction was carried out at 140 °C and ca. 0.2 MPa with a cobalt
naphthenate catalyst (0.1%). Other oil-soluble cobalt salts were also used as
catalysts. The purity of toluene is critical because sulphur compounds,
nitrogen compounds, phenols and olefins inhibit the oxidation reaction. The
oxidation reaction is a free-radical chain process. Peroxides are reaction
intermediates. In a typical modern process, the oxidation is conducted at
165 °C and 0.9 MPa. The pressure of the liquid discharged from the reactor
is reduced to atmospheric, and unreacted toluene is recovered. Benzoic acid
is purified by rectification. The bottom residue is extracted to recover the
cobalt catalyst. In the oxidation reaction, several by-products are formed:
benzaldehyde, benzyl alcohol and benzyl benzoate. Other esters, including
benzyl formate and benzyl acetate, are also present. Biphenyl and methyl
biphenyls are formed in smaller amounts. Small amounts of phthalic acid
can also be present. For food and pharmaceutical uses, benzoic acid is
upgraded by further processing. Sublimation, recrystallisation and
neutralization processes have been proposed. To remove phthalic acid,
whose presence is not allowed for food uses, treatment with amines and
rinsing is required.
According to industry, ‘production of benzoic acid is by liquid-phase
oxidation of toluene in the presence of a cobalt catalyst. Air is the source of
oxygen in this free radical reaction. Reaction by-products include
benzaldehyde, acetic acid, formic acid and benzyl alcohol. Crude benzoic
acid is recovered by distillation’ and ‘for sodium benzoate production
sodium hydroxide (caustic soda) is added to benzoic acid’.

Sodium benzoate is produced by the neutralization of benzoic acid with

sodium hydroxide . Potassium benzoate is obtained in high yield by
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reacting an aromatic hydrocarbon solution of benzoic acid, such as that

which is obtained from the toluene oxidation process, with potassium
hydroxide preferably in concentrated aqueous solution, thereby
precipitating solid potassium benzoate . No information was available
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regarding the manufacture of calcium benzoate; the European Food Safety

Authority Panel assumed that it is manufactured similarly, by reaction of
benzoic acid with calcium hydroxide, or other calcium salt. The European
Food Safety Authority Panel noted that if limestone is the source of calcium
carbonate which is used in the production of calcium benzoate, then
calcium benzoate could be contaminated with aluminium. In its opinion on
the re-evaluation of calcium carbonate (E 170) as a food additive , the
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European Food Safety Authority Panel noted that limestone may contain
aluminium at concentrations up to 190 mg/kg. Therefore, specifications for
the maximum level of aluminium in calcium benzoate may be required.