Chlorobenzene

An introduction to manufacturing of
chlorobenzene

Made by:-
Anshumaan Srivastava
131507
HISTORICAL PROFILE

Natural Occurrence and Traditional

Applications

Chlorobenzene (also called

monochlorobenzene or MCB) is a flammable
liquid. It is not found in nature either in pure
form or in mixed form.
Chlorobenzene most high-profile application

has been in the production of the pesticide

DDT
 Chlorobenzene (C6H5Cl) is a colourless, volatile,
water-insoluble, flammable liquid with a
penetrating smell of almonds. Chlorobenzene
belongs to the family of organic halogen
compounds, which is a large class of natural and
synthetic chemicals that contain one or more
halogens (fluorine, chlorine, bromine, or iodine)
combined with carbon and other elements.
Chlorobenzene has been made from the
chlorination of benzene since 1851. It has been
manufactured industrially since the early 20 C.
Early Industrial Applications
Chlorobenzene once was used in the
manufacture of certain pesticides, most
notably DDT by reaction with chloral
(trichloroacetaldehyde).
At one time, chlorobenzene was the main

precursor for the manufacture of phenol:

C6H5Cl + NaOH C6H5OH + NaCl

 The major use of chlorobenzene is as an
intermediate in the production of
commodities such as herbicides, dyestuffs,
and rubber. Chlorobenzene is also used as a
high-boiling solvent in many industrial
applications as well as in the laboratory.
MANUFACTURING PROCESSES
The basic principle behind the manufacture
of Chlorobenzene is the chlorination of
benzene .
Benzene Chlorination in Liquid Phase
Benzene Chlorination in Vapour Phase
Benzene Chlorination in the Vapour Phase

(Loeser and Schmidt Process)

Oxychlorination of Benzene in the Vapour

Phase (Raschig-Hooker Process)

Benzene Chlorination in Liquid
Phase
Catalyst used is ferric chloride.
Temperature is around 40C.
HCl can be recovered by washing with

refrigerated chlorobenzene.
 As the Chlorobenzene is formed, it leaves the
chlorination zone at a speed that allows no
further chlorination to take place. Unreacted
benzene and Chlorobenzene are continuously
separated by fractional distillation, returning
the benzene to the chlorination stage and the
efficiency of this process can be as high as
95%.
Benzene Chlorination in Vapour
Phase

Chlorine react with benzene above 400 0C

and preferably at 500 0C to form a different
series of chlorobenzene. This reaction mainly
takes place at 1 bar, in the presence of
copper chloride.
Benzene Chlorination in the Vapour Phase (Loeser and Schmidt
Process)

In this process, a pre-heated mixture of

benzene vapour, air, steam, and HCl, at
ordinary pressure, is brought into contact at
150 - 300C with a catalyst of copper
hydroxide deposited on alumina support to
form chlorobenzene.
C6 H6 + HCl+ 0.5O2----> C6H5Cl + H2O

Oxychlorination of Benzene in the

Vapour Phase (Raschig-Hooker Process)
In this process, Chlorine react with benzene
above 190 0C and preferably at 230 0C to form a
different series of chlorobenzene. This reaction
mainly takes place at .3-3.1 bar, in the presence
of copper chloride deposited on alumina
support.

C6 H6 + HCl+ 0.5O2---> C6H5Cl + H2O

This Process is mainly used for the production of

phenol from chlorobenzene.
PROCESS SELECTION

 The disadvantages of all these processes

except liquid phase process are low efficiency
and high temperature, which may make the
reaction uncontrollable leading to formation
of higher Chlorobenzene. Based on all the
above considerations, the continuous liquid
phase chlorination of benzene at a
temperature of about 40C is best suited for
production of large amounts of
monochlorobenzene in the industry.
SELECTED PROCESS
Chemical Reaction Involved
The reactions involved in the process are as
follows:
C6H6 + Cl2 ---> C6H5Cl + HCl
C6H5Cl + Cl2 ---> C6H4Cl2 + HCl
Mechanism of reaction
 Catalyst used is Ferric chloride which may be
either in solution form or in the form of
turnings.
Chlorinator conditions-
Pressure- 2.4 bar
Temperature- 40C
 Chlorobenzene may contain 12 to 20 trays
and is operated at a pressure ranging from 3
7 lb/in.2 abs. The temperature in the
chlorobenzene column may be between 100 -
120C. Monochlorobenzene is the overhead
distillate product of a purity of 98%.
Dichlorobenzene is the bottom residue
product of a purity of 97%.
Thank you