Module:2

Dr. N. K. Patel
Lecture:8 Benzoic acid

Module: 2
Lecture: 8
BENZOIC ACID

INTRODUCTION

Benzoic acid, C6H5COOH or C7H6O2 is a colourless crystalline solid and

a simple aromatic carboxylic acid. The name derived from gum benzoin,
which was the only source for benzoic acid for long time. The dry distillation of
gum benzoin was first described by Nostradamusin1556, and then by Alexius
Pedemontanusin1560 and Blaise de Vigenre in 1596.

In 1830 Pierre Robiquet and Antoine Boutron-Charlard produced

benzaldehyde through a variety of experiences based on amygdalin,
obtained from bitter almonds but they failed in working out a proper
interpretation of the structure of amygdalin that would account for it, and
thus missed the identification of the benzoyl radical C7H5O-. This last step was
achieved by Justus von Liebig and Friedrich Whler in 1832, who determined
the composition of benzoic acid.

Salts of benzoic acid are used as a food preservative. Salkowski

discovered the antifungal abilities of benzoic acid in 1875, which was used for
a long time in the preservation of benzoate-containing cloudberry fruits. The
salts and esters of benzoic acid are known as benzoates.

MANUFACTURE

Raw materials

Basis: 1000kg Benzoic acid from phthalic anhydride

Phthalic anhydride 1350kg
Catalyst 12.5kg

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Lecture:8 Benzoic acid

Reaction

Manufacture process
Caustic soda
Carbon dioxide Benzoic acid

Phthalic
anhydride
Neutralizer

Catalyst Column

Kettle
Steam

Steam
Waste
Figure: Manufacture of Benzoic acid from Phthalic anhydride

Block diagram of manufacturing process

Diagram with process equipment

Animation

The process consist of two steps, first is manufacture of phthalic

anhydride from naphthalene or o-xylene and second is manufacture of
benzoic acid from phthalic anhydride via oxidation.

Phthalic anhydride along with 2 6% catalyst consisting equal parts of

chromium and disodium phthalate were charged into kettle. The charge was
heated to 2000C and introduced 2 20parts of steam/hr below the surface of

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Lecture:8 Benzoic acid

mixture. Water, benzoic acid and phthalic acid was refluxed to the reaction
mass and carbon dioxide vented out. The reaction was continued until the
mixture contain less than 5% phthalic acid. Caustic soda was added to
reaction mixture for complete separation of benzoic acid from the
unreacted phthalic acid before distillation. Benzoic acid is separated from
reaction mixture by distillation. Catalyst was reused for several batches and
finally catalyst was recovered by dissolving the residue in a solution of soda
ash and filtering off the metal precipitate.

Alternative procedure

Benzoic acid may be prepared by passing vapours of phthalic

anhydride mixed with steam over a stationary catalyst maintained at a
temperature 380 4200C. A suitable contact mass mixture consists of an
equal amount of copper carbonate and calcium hydroxide uniformly
coated on pre-size pumice granules.

Raw materials

Basis: 1000kg Benzoic acid from toluene by air oxidation

Toluene 850kg
Air 60000Cu.ft.
Catalyst Small quantity

Reaction

Manufacture process

Toluene was mixed with 0.1 0.3% cobalt naphthenate catalyst and
charged into a reactor. Air was sparged in the reactor until 40% of toluene
oxidized. Reaction mass was maintained at 148.90C temperature and
40 70psi pressure.

The reaction mixture was then sent for distillation after 40% conversion
where unreacted toluene and by-product benzaldehyde was removed. The
toluene was recycled back to process.

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Lecture:8 Benzoic acid

Recycle toluene Vent

gases Hot
water

Water

Water

Scrubber Mixer
Water

Toluene Cooler

Catalyst Water
Distillation column

Air Separator

Reactor

Benzoic acid Filter

Heavy
ends
Figure: Manufacture of Benzoic acid from Toluene by air oxidation

Block diagram of manufacturing process

Diagram with process equipment

Animation

The bottom stream from the column was mixed with hot water to
extract benzoic acid. The aqueous layer was separated and cool to
precipitate benzoic acid, which was filtered and washed to get technical
grade product.

Advantages

It gives chlorine free benzoic acid

To get better yield
Good control of by-products formation

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Lecture:8 Benzoic acid

Engineering problems

Design for efficient gas-liquid contacting and economic recovery of

organics fractions which contains water in the second stage are the two
main design problems.

Engineering aspect

Preparation of catalyst

The catalyst is prepared by the direct addition of equivalent amounts

of chromium hydroxide and caustic soda to the reaction vessel.

PROPERTIES

Molecular formula : C7H6O2

Molecular weight : 122.12gm/mole
Appearance : Colourless crystalline solid
Odour : Pungent
Boiling point : 249.00C
Melting point : 121.70C
Density : 1.316gm/cm3
Flash point : 121.10C
Auto ignition temp : 571.10C
Solubility : Slightly soluble in water, soluble in
alcohol, chloroform, ether, benzene,
carbon disulfide, turpentine

USES

Benzoic acid is used to determine the heat capacity of a bomb

calorimeter
To produce benzoyl chloride and benzyl benzoate
Benzoic acid and its salts are used as a food preservatives
It is a constituent of Whitfields ointment which is used for the treatment
of fungal skin diseases like ringworm, tinea and athletes foot
Major ingredient in both tincture of benzoin and Friars balsam which
are used as antiseptics and inhalant decongestants
As expectorant and analgesic

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Lecture:8 Benzoic acid

As medicinal, industrial preserving foods, fats, alkaloid solutions, fruit

juices, cosmetics, resin preparations, plasticizers, synthetic fibres and
intermediates, dyes as mordant in calico printing
As curing tobacco
As standard in volumetric and calorimetric analysis and pharmaceutics
aid

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