Petrochemical Engineering II

Unit - V

Aromatics-BTX derivatives
 BTX-DERIVATIVES
Isophthalic acid
Benzoic acid
Benzyl chloride, Benzal chloride, Benzotrichloride
Benzaldehyde
Nitrotoluenes
Cresols
Nonyl phenol
Diisopropyl Benzene
Hydroquinone, Anthroquinone
p-diethyl Benzene
 Isophthalic acid
C6H4(COOH)2
It is an important derivative of m-Xylene and is used in the
manufacture of unsaturated and saturated polyesters, alkyl
resins,
Process plasticizers,
Technology: andTwo
in fibres.
step process
Liquid phase oxidation of m-xylene by use of ammonium
sulphate.
(Chevron process) :Temp-320 C pressure is 70-140 atm
 Various process technologies
Chervron process:
It utilizes sulphur based oxidation of m-Xylene in aqueous ammonia at
about 3200C &70-140 atm to produce amide which is then hydrolyzed
with sulphuric acid to produce Isophthalic acid.
Arco chemical process:
Air oxidation of m-xylene in acetic acid, catalyzed by a cobalt salt and
promoted by acetaldehyde at temp. of 100-1500C.
Liquid phase oxidation of m-Xylene in the presence of cobalt salt
activated with bromine in acetic acid at 2000C & 28.2 Kg/cm2 pressure.
Amco chemical process:
The oxidation of mixed xylenes on a cobalt-manganese-bromine catalyst
system
Dupont process:
The oxidation of m-xylene by nitric acid at moderated temperature and
pressure conditions.
USES
Manufacture of unsaturated polyesters which display better
toughness, resistance to abrasion, higher heat distortion
temperature, chemical and weathering resistance.
IPA polymers find application in fibers, films and reinforced
glasses
Manufacture of alkyd coatings which are made by the
reaction of Isophthalic acid and polybasic acids.
Formulation of adhesives, inks, wire enamels (enamels used
for manufacturing of magnet wires. They are coated on the
surface of copper or alumina wires and cured to form
electrical insulation film possessing certain mechanical
strength, thermal resistant and chemical resistant
properties.)
Benzoic Acid(C6H5COOH)
Which is used in the manufacture of caprolactum, phenol and terephthalic acid and used
as mordant.
Process technology:
Liquid phase catalytic oxidation of toluene in the presence of cobalt acetate at 1650C &
11.2 atm pressure.
The major processing steps in the manufacture of benzoic acid consists of:
Catalytic liquid phase air oxidation of toluene
Stripping of unreacted toluene and light end precursors from the benzoic acid for
recycle
Distillation of recover benzoic acid as a pure overhead product.
 Vent gases

Condenser Hot water

Waste water Mixer

Reactor

Distillation
Toluene

Catalyst column
Air Separator Cooler

Heavy ends
Filter

BENZOIC ACID FROM TOLUENE Benzoic Acid

 Benzoic acid is also produced by oxidation of toluene in acetic
acid solution in presence of bromide ions
Uses:
It is used as a Mordant, seasoning of tobacco, in dentifrices
(Dentifrices are agents used along with a toothbrush to clean
and polish natural teeth. ) and medicines.
The growth of Diet soft drinks market has increased the demand
of benzoic acid as sodium and potassium benzoate.
Sodium salt of benzoic acid is used in food and fruit beverages.
It is also used for Manufacture of Diethylene glycol benzoate and
butyl benzoate which are used as plasticizers and perfume
ingredient.
 Benzyl chloride (C6H5CH2Cl)
Benzal chloride (C6H5CHCl2) &
Benzotrichloride(C6H5CCl3)
Process technology:
Toluene can be chlorinated by thermal or photochemical
chlorination to get yield a mixture of Benzyl chloride, Benzal
chloride, Benzotrichloride.
Chlorination is at 65-1000C
In case of Benzyl chloride 1.1 mole of chlorine per mole of
toluene.
In case of Benzal chloride 2-2.2 mole of chlorine per mole of
toluene.
Further chlorination at 100-1400C with UV light yields
benzotri chloride
 Derivatives of commercial importance of benzyl
chloride are benzyl phthalate, benzyl alcohol, benzyl
chloride derived quaternary ammonium
compounds, benzyl acetate, benzyl cyanide, benzyl
silicate and benzyl amine.
Derivatives of Benzal chloride are benzaldehyde,
which is used in the manufacture of perfume, flavor
chemicals, dyes and intermediates.
Derivative of Benzotrichloride are benzoyl chloride,
benzotrifluoride, dyestuff intermediate and UV light
stabilizer.
Benzaldehyde (C6H5CHO)
Various Process technology are:
Benzyl alcohol route
Benzal chloride route
Uses
It is an important chemical used in the manufacture of Perfumes,
dyestuff, drug intermediate
Manufacture of cinnamic acid, benzoic acid, pharmaceuticals and
photographic chemicals.
It is used to produce variety of aldehydes such as cinnamic,
methyl cinnamic, amine cinnamic and hexyl cinnamic.
Other derivatives are benzoin, benzyl alcohol, benzyl amine,
benzyl acetone, and dibenzyl amine.
Benzal chloride route:
This process involves chlorination of toluene to Benzal chloride,
which on hydrolysis yields benzaldehyde and HCl.

Benzyl alcohol route:

This process involves oxidation of benzyl alcohol which is turn, is
oxidized to benzaldehyde.
Further oxidization of benzaldehyde yields benzoic acid.
 NITRO TOLUENES
Mono nitrotoluenes (o-&p-nitrotoluenes) are manufactured by
direct nitration of toluene in the presence of mixture of HNO3
& H2SO4.
They are primarily used in the manufacture of dyes and rubber
chemicals.
During the process about 65% o-Nitrotoluene, 31% p-
Nitrotoluene and 4% m-Nitrotoluene are produced which can be
separated by distillation.
 Toluene diisocyanate is used in the manufacture of polyurethane.
Dinitration of toluene yields 2,4-and 2,6-dinitrotoluene
important feed stock in the production of diisocyanate.
Nitration is carried out in the presence of a mixture of HNO3 &
H2SO4. during the process about 80/20 mixture of 2,4-& 2,6-
Dinitrotoluene is formed.
Typical condition used to achieve high Dinitrotoluene yield and
low TNT formation are: temperature 65-800C using mixed acid
containing 60-70% of H2SO4 & 30-40 % of HNO3.
 Trinitrotoluene which is widely used in both military and
industrial explosives, is manufactured by nitration of
toluene in a mixture of HNO3 & H2SO4.
The Nitration of Toluene to trinitrotoluene takes place
in three steps as follows:
Toluene Mono nitrotoluene Dinitrotoluene
Trinitrotoluene.
It can be produced in batch or continuous process. In
general TNT yield is higher in the batch process.
O-&P-nitrotoluene are used in the manufacture of dyes
and rubber chemicals.
 Cresols - CH3C6H4OH
First stage of the production of cresol is manufacture of
toluene sulphonic acid by sulphonation of toluene.
The second stage involves reacting of molten crude
sulphonation product with molten caustic soda containing 4-
5% of caustic potash at 3500C followed by leaching of sodium
cresylates with water and decomposition with gaseous
sulphur dioxide to give crude cresols which is finally
separated by distillation.

of herbicides, dinitro-o-cresol, 2-methyl 4-chloro phenoxy

acetic acid.
Advantages:
O-Cresol is used in the manufacture of herbicides, dinitro-
o-cresol, 2-methyl-4-chloro phenoxy acetic acid, 2-methyl-
4-chloro phenoxy butyric acid. It also finds application in
the manufacture of plasticizers, antioxidants.
p-Cresol is used in the manufacture of butylated
hydroxytoluene which is used in the manufacture of
antioxidant in edible fats, in plastics, rubber and petroleum
products.
m-Cresol is used in the manufacture of insecticide,
fungicide, industrial bactericide.
 Nonylphenol(C9H19C6H4OH)
Nonylphenol is made by reacting nonylenes, usually propylene trimer,
with phenol using H2SO4, AlCl3 or more commonly BF3 as catalyst.
C6H5OH + C9H18 C9H19C6H4OH
Temperature of 50-1000C

Uses
Nonylphenol is used in the manufacture of detergents where
Nonylphenol is converted either by ethoxidation or sulphonation to a
detergent.
Nonylphenol reacts with ethylene oxide to form polyoxyethylene
derivatives that have surface active properties.
C9H19C6H4OH + n CH2OCH2 C9H19C6H4(OCH2CH2)nOH
Reaction of Nonylphenol with for formaldehyde yields products which is
used as oil additive and synthetic lubricants.
 Hydroquinone (C6H4(OH)2)
The major use of hydroquinone are as an antioxidant, antiozonant in
rubber manufacture and in chemical formulation for the
development of photographic films.
It is also used as a polymerization inhibitor.
It is used as a stabilizer in paints and varnishes, motor fuels and oils.
The major process technologies are:
Hydroxylation of phenol
Bisphenol route
Acetylene route
Electrolytic oxidation of benzene
Anthraquinone(C6H4(CO)2C6H4)
It is an important dye intermediates and pigment.
The major process technologies are
Phthalic anhydride and benzene route:

Styrene route:
Dimerization of styrene to methyl phenylindane which on
oxidation in the vapour phase yields anthraquinone.
 Friedel-Crafts reaction: It is also prepared by the
Friedel-Crafts reaction which involves a reaction
between the organic compounds benzene and
phthalic anhydride in presence of aluminum
chloride. The resulting o-benzoylbenzoic acid, an
organic acid, then undergoes further reactions,
forming anthraquinone. This reaction is useful for
producing substituted anthraquinones.
Diels-Alder reaction: The Diels-Alder reaction of
naphthoquinone (class of natural phenols) and
butadiene (hydrocarbon) followed by oxidative
dehydrogenation (removal of hydrogen) will also
produce anthraquinone.
BASF: Baden Aniline and Soda Factory(BASF), the
largest chemical company in the world and is
 p-Diethyl Benzene(PDEB)
Important high value, low volume, specialty chemically derived
benzene
It is used as desorbent for separating p-xylene from xylene
isomers.
The conventional process involves alkylation of benzene with
ethylene and then dehydrogenation of ethyl benzene, where
styrene and mixed diethyl benzene is formed. PDEB can be
separated from mixed diethyl benzene stream by adsorption