Aram Nasih Muhammad

CHLOROBENZENE FROM BENZENE AND CHLORINE

Student name: Aram Nasih Muhammad

Class : 4th stage
Course title: Equipment design
Department : Chemical engineering

Faculty of engineering
Soran university
Academic year 2020-2021

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The project

Design a plant to produce 20,000 tonnes/year of mono chlorobenzene together with not

less than 2000 tonnes/year of dichlorobenzene, by the direct chlorination of benzene.

INTRODUCTION

Chlorobenzene was one of the earliest heavy organic chemicals that is, those chemicals which were

produced industrially in large amounts. The former United Alkali Company first produced

chlorobenzene industrially at Widnes, England, in 1909. Chlorobenzene first acquired importance during

the World War I, when it was required in high tonnage 8 making phenol in picric acid manufacture.

Chlorobenzene is a colorless, mobile liquid with an almond like odor. At ordinary temperature and

pressure chlorobenzene is unaffected by the presence of air, moisture, or light, and upon prolonged

boiling, shows no tendency to split off chlorine. The chlorine atom in chlorobenzene is unreactive at

ordinary temperatures and pressures. At moderate temperatures, chlorobenzene is unaffected by steam,

alkalis, hydrochloric acid, and dilute sulphuric acid. Even boiling for several hours with alcoholic KOH

has no effect on chlorobenzene. It is soluble in all proportions in ether, chloroform, benzene, alcohol and

carbon disulphide. It is insoluble in water. Hydrolysis, with the formation of Phenol takes place at 450°C

to 500°C in the presence of a catalyst or with alcoholic alkalis or with water under pressure at high

temperatures. Aniline may be prepared by reaction with concentrated ammonium hydroxide under

pressure in the presence of copper catalyst. Of technical importance is the preparation of DDT by

condensation of chlorobenzene with chloral in the presence of fuming Sulphuric Acid. Chlorination of

chlorobenzene in the presence of a variety of catalysts produces prominently o and p-Dichlorobenzene

isomers. Chlorobenzene forms both binary and ternary azeotropic mixtures with water and a number of

organic liquids. Chlorobenzene are less toxic than benzene. Liquid chlorobenzene produces mild to

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moderate irritation upon skin contact. Contact with eye tissue at normal temperature cause s pain, mild

to moderate irritation, and possibly some transient corneal injury. Prompt washing with large quantities

of water is extremely helpful. Continued contact may cause roughness or a mild burn. Absorption

through the skin is slow and with short-term exposure over a limited period of time, no significant

amounts will enter the body. Since the monochlorobenzene vapor forms explosive mixtures with air,

open flames and smoking should not be allowed where chlorobenzene is stored or used.

MANUFACTURING PROCESS

The basic principle behind the manufacture of Chlorobenzene is the chlorination of benzene with or
without the presence of a catalyst (Friedel-Craft reaction). The products of such a reaction would be
Chlorobenzene, dichlorobenzene, tri chlorobenzene and the higher chlorinated benzenes. In actual
practice in the industry, only Chlorobenzene and small amounts of dichlorobenzene are formed. The
amounts of dichlorobenzene and higher substituted Chlorobenzene formed can be reduced greatly by
using selective catalysts and modifying reaction conditions. Thus essentially chlorination of benzene can
be considered as taking place in three pairs of two stages each:

(1) Chlorination of benzene to mono chlorobenzene and dichlorobenzene.

(2) Chlorination of dichlorobenzene to tri chlorobenzene and tetra chlorobenzenes.

(3) Chlorination of tetra chlorobenzenes to penta chlorobenzenes and hexa chlorobenzene.

Chlorination can be carried out either batch wise or continuously. When minimum formation of di
chlorobenzenes is required then the latter procedure is followed. In the batch process, benzene is
contained in a deep, iron or steel vessel, fitted with lead cooling coils. The chlorine feed-pipe enters at
the bottom of the chlorinator and the catalyst is ferric chloride. The temperature is maintained at less
than 45°C. HCl produced in the reaction can be recovered after separation from benzene by washing
with a refrigerated solvent. At temperatures below 40°C, the rate of formation of dichlorobenzene is
very low and this fact is used to suppress formation of dichlorobenzene in the continuous process. A
typical continuous process plant consists of a series of small, externally cooled steel vessels containing
the catalyst. Chlorine is supplied to each vessel through suitably placed inlets and the temperature of the
reaction is maintained between 20 - 40°C.
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%.
There are different ways in which the chlorination of benzene can be brought about and these form the
different processes for the manufacture of Chlorobenzene. The first is called the Raschig Process. In this
process, benzene is chlorinated by chlorine that has been produced in situ in the reactor by the catalytic
oxidation of hydrogen chloride. A pre-heated mixture of benzene vapour, air, steam, and HCl, at
ordinary pressure, is brought into contact at 220° - 260°C with a catalyst of copper oxide. 2% of the total
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benzene combusts, giving rise to about one quarter of the total heat output of the process. The
disadvantage of this process is that the high temperature greatly favours high combustion rates of
benzene and the reaction may become uncontrollable. Moreover the high costs of this vapour phase
chlorination process in comparison with other available processes, allows it to be highly uneconomical
for Chlorobenzene manufacture and thus renders it obsolete. In another process, chlorination of benzene
is carried out in a quartz tube at 400 - 500°C. Here the principal product obtained is Chlorobenzene
along with minor amounts of dichlorobenzene. Benzene has also been chlorinated in the gaseous phase
at 425°C by means of nitrosylchloride. The process of Loeser and Schmidt, in which a mixture of
benzene vapour, HCl, and air is reacted at 150 – 300°C in contact with a copper hydroxide-alumina
catalyst (in the form of a fluidised mass), may be regarded as a variant of Raschig’s Process. The
disadvantages of all these processes 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 40°C is
best suited for production of large amounts of monochlorobenzene in the industry. The process is
economically viable too making it the most popular process being used in the industry for the
manufacture of monochlorobenzene all over the world.
As already known, industrial chlorination of benzene is carried out in the liquid phase at moderate
temperature with the help of a catalyst to produce monochlorobenzene and minor amounts of
dichlorobenzene. Chlorobenzene and the o- and p-dichlorobenzene are the principal products. The
reaction is a consecutive, competitive reaction. Liquid benzene is fed to a chlorinator operating at 2.4
bars. The feed enters at 25°C, at atmospheric pressure and also contains some water. Gaseous chlorine is
fed to this tank, also at atmospheric pressure and at 25°C and is considered fully pure. There may be
several chlorinators operating in series or parallel depending upon the degree of chlorination of benzene
required. Ferric chloride is usually the catalyst. This can be added as a solution in benzene, or as iron
turnings, or scrap that provides the ferric chloride in the chlorinator. Since the reaction is exothermic
cooling is required to maintain the temperature at about 40°C. The HCl gas (90% of the HCl formed)
leaving the reactor is first cooled to condense the impurities (benzene and chlorinated products) and then
it is scrubbed in a scrubber using refrigerated Chlorobenzene. The crude chlorobenzene stream leaving
the reactor is washed with NaOH solution (20 wt%; maintained slightly alkaline to protect downstream
equipment from corrosion) in a pre-neutralizer. The product stream is free of HCl. The product is fed to
a Benzene Recovery Column, which is a distillation column. Here the bottoms are almost 100 % pure
chlorobenzene. The tops contain 98 % by weight of benzene and 2% chlorobenzene and all of the
benzene is recycled to the benzene storage via a purifier. From the purifier the monochlorobenzene is
sent to the refrigeration system. The bottoms from the Benzene column contain monochlorobenzene and
dichlorobenzene. This is fed to the chlorobenzene column, which is again a distillation column. This
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 - 120°C. Monochlorobenzene is the overhead distillate
product of a purity of 99%. Dichlorobenzene is the bottom residue product of a purity of 97%. The
reactions involved in the process are as follows:
1. C6 H6 + Cl2 → C6H5Cl + HCl
2. C6H5Cl + Cl2 → C6H4Cl2 + HCl
Dichlorobenzene is assumed to be a para-isomer. Formation of trichloro isomers is neglected. When
concentrations of dissolved chlorine remains essentially constant then reactions are first order.
rb = -k1xb
rm = k1xb – k2xm k1 = 1 x 10-4 s-1 at 55°C
rd = k2xm k2 = 0.15 x 10-4 s-1 at 55°C
Where b = benzene, m = monochlorobenzene, d = dichlorobenzene
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