Industrial Report

Deepak Nitrite
Gsfc University
CONTENTS

 Company Introduction
 Introduction to Chlorobenzene
 Compound Properties
 Process Flow Diagram
 Manufacturing Process
 Process Description
 Material Balance
 Plant Layout Description
Company Introduction

■ Deepak Nitrite Ltd. Is part of DNGL comprising

& Deepak Nitrite Ltd.
■ Starting from a substituent of chemic al
Sodium Nitrite in 1972, Today it has diverse
production of 20 products having turnover of
1174 million ₹.
■ During this period of time it has been
awarded with Sir P.C Ray award for Best
Chemical Manufacturing Unit in INDIA.
■ The Company has been listed among top 500
companies in India in the year 1997-2000 by
their Business Standards.
■ Deepak Nitrite Ltd. take active interest in
responsible care of environment
■ The Research & Development provides
continues support for improving existing
technology with objective of improving safety
environment quality & also overall
competitiveness.
 VISSON

■ To continue to enhance stakeholder value

while adhering to code of response and
ethical values.
■ Be a role model enterprise, respected,
globally for excellence in quality and
innovation.
■ Be an employer of choice and preferred
business partner worldwide.

MISSON
■ The purpose of all human activity is to make
life better .Deepak Nitrite Ltd. Believes in
improving Life through innovative science.
■ Through innovation we constantly endeavor
to create products and process that bring
greater value to society.
Introduction to Chlorobenzene

■ Chlorobenzene was one of the earliest heavy

organic chemicals. Those chemicals which
were produced industrially in large amounts.
■ MCB is colorless liquid with almond like odor.
■ It is unaffected at moderate temp. By steam,
alkalis, HCL, dilute H2SO4. Even after boiling
for several hours with alcoholic KOH. It
becomes more effective.
■ It is soluble in ether, chloroform, benzene,
alcohol and it is insoluble in water.
■ Chlorobenzene is less toxic than benzene.
Compound Properties: -
Product: - MCB
Other/Generic Names: - Chlorobenzene,
Phenyl chloride
Molecular Formula: - C6H5Cl
Molecular Weight: - 112.56 gm/ mol
■ MCB is colorless liquid material that is
insoluble in water.
■ Color :- Colorless Liquid
■ Boiling Point :- 131.6 °C
■ Melting Point :- -45.2 °C
■ Corrosively: - Liquid chlorobenzene will attack
some forms of plastics, rubber, and coatings.
■ Critical Temp. Tc :- 632 K
■ Critical Pressure Cp :- 4.5 Mpa
■ Density :- 1.11 g/cm3
■ Heat Of Combustion :- -3100 kJ/mol at 25 ° C
■ Heat Of Vaporization :- 40.97 kJ/mol at 25 °C
■ Odor :- Almond Like Odor
 Effect on Human Body: -

■ Liquid chlorobenzene produce mild to

moderate irritation upon skin contact.
■ Contact with eye tissue at normal temp.
Causes pain, mild to moderate irritation and
possibly some transient corneal injury. Large
quantity of water always helpful.
■ Continued contact may cause roughness or
mild burn.
■ Since MCB vapor forms explosive mixtures
with air, open flames and smoking should be
not allowed where chlorobenzene is stored.

Product Uses: -
 ■ Used as solvent in Chemical Reaction
■ Manufacturing in phenol, Pignet
intermediate, dyes intermediate.
■ Manufacturing of ONCB, PNCB.
■ Manufacturing of pharmaceutical
intermediates.
■ Manufacturing of Agro chemical
intermediates.
■ Specialty such as Dioctyl Phenol.
■ Aniline can be formed by reacting MCB with
concentrated Ammonium Hydrochloride in
presence of Cu catalyst.
■ DDT is prepared by condensation of MCB with
chloral in presence of fuming H2SO4.
■ Ortho & Para DCB is formed by chlorination of
MCB. Both binary and tertiary azeotropic
mixture with water and number of organic
liquid.

Introduction of Benzene: -
Physical Properties: -
■ Mw:- 78.11
■ Melting Point °C:- 5.533
■ Boiling Point °C :- 80.10
■ Density At -3.77 °C :-873.7 kg/m3
■ Vapor Pressure at 26.075 °C, :-13.33 kPa
■ Refractive Index:- 149792
■ Surface Tension at 25°C, :- 28.16 mN/m
■ Critical temp. :- 289.95 °c
■ Critical pressure :- 492.44 kPa
■ Critical Density :- 300 kg/m3
■ Mw:- 78.11
■ Melting Point °C:- 5.533
■ Boiling Point °C :- 80.10
■ Density At -3.77 °C :-873.7 kg/m3
■ Vapor Pressure at 26.075 °C, :-13.33 kPa
■ Refractive Index:- 149792
■ Surface Tension at 25°C, :- 28.16 mN/m
 ■ Critical temp. :- 289.95 °c
■ Critical pressure :- 492.44 kPa
■ Critical Density :- 300 kg/m3

Chemical Properties: -
■ Substitution:-
 Under suitable conditions, one or more
hydrogen atoms of benzene can be replaced by
atoms such as halogens or by groups such as nitro
& sulfonic acid groups.
■ Electrophilic Substitution :-
When a monosubstitution product of benzene
is subjected to the action of an electrophilic, the
rate of further substitution is increased by some
groups and decreased by some other groups. It
also the direction of second substitution.
■ Nucleophilic Substitution Of Benzene
Derivatives :-
When the benzene ring is substituted with a
sufficient number of highly electronegative
groups, it becomes electrophilic itself & it will
react with nucleophilic substitution reagents.

■ Oxidation:-
 Benzene can be oxidized to a number of
different products. An important reaction is the
Catalytic oxidation benzene to malic anhydride &
byproducts. The oxidation proceeds with air and
oxygen with elevated temperature with a
vanadium pentoxide and molybdenum oxide
catalyst.
■ Reduction:-
Benzene can be reduced to cyclohexene with
help of hydrogen using nickel catalyst at room
temperature and ordinary pressure.
■ Pyrolysis:-
Benzene when passed through red hot tube at
elevated temperature over vanadium compound
formation of biphenyl takes place by
condensation. But over 750°c temperature
Benzene decomposes to Carbon & Hydrogen.
■ Hydrogenation:-
Benzene reacts with Cl2 & Br2 in pressure of
ferric halide to give MCB & DCB.
Uses of Benzene: -
 ■ Styrene monomer is a largest us of benzene
followed by cumene, phenol, cyclohexane and
nitrobenzene.
■ These derivatives are used to produce wide
range of plastic, fibers, resins & films.
■ Benzene is an excellent solvents for waxes,
resins, rubber & various other organic
materials. But toxilogical properties greatly
limit its uses.
■ Benzene has a high octane number & was
valued gasoline blending component until its
use was restricted by pollution control laws.

Chlorine Introduction: -
 ■ Chlorine exits in all three physical states.
Normal ,Temperature, Pressure it is greenish
yellow pungent , Poisonous gas
■ Which can be Liquid, solid chlorine pale
Yellow rhombic crystals.
■ Other important properties of chlorine are
listed below.

Physical Properties: -

■ Atomic Number :-17

■ Molecular Weight :- 35.37 g
■ Melting Point:- 172.17°K
■ Boiling Point:- 239.10°K
■ Critical Temperature Tc :- 417.5°K
■ Critical Pressure Pc :- 7.71x105 N/m2
■ Critical Density :- 3.123 kg/m3
■ Enthalpy Of Hydrogen :- 405.8 KJ/ Kmol
 ■ Density at 0°c:- 3213 kg/m3
■ Density relative to air :- 2.48 kg/m3
■ Enthalpy of Fusion Hf :- 90.33 KJ/kg
■ Enthalpy of vaporization Hv :-287.1 KJ/kg
■ Standard Electrode Potential E°:- 1.359
■ Enthalpy of Dissociation Hd :- 239.44 KJ/kg
■ Electron affinity :- 364.25 KJ/ Kmol

Uses of Chlorine: -
■ During the span of the chlorine industry in the
world the largest single use has been in the
manufacture of pulp & paper.
■ In the early industry the second largest use
was in sanitation for sewage treatment and
purification of water.
■ Later on the demand increase because of the
invention of new compounds.
■ The Major Uses of Chlorine are listed below.
1.Benzene Hexachloride: - Manufacture for
insecticides.
2.Carbon Tetrachloride: - Manufacture for
fluorocarbons for reorients and propellants.
3.Chloral: - Insecticides manufacture.
4.Chloro Paraffin’s:- Lubricant additives and
paints.
5.Dichlorobenzene: - Organic Solvents.
6.Chloroform: - Manufacture for
fluorocarbons.
7.Ethyl Chloride: - Antiknock compounds.
8.Ethylene oxide & glycol: - Antifreeze fluids
and synthetic fibers.
9.Methyl Chloride: - Silicones manufactures,
Solvent & catalyst carrier.
10. Methylene Chloride: - Paint remover
propellants & general solvents.
11. Monochloroacetic Acid: - herbicides,
detergents.
12. Perchloroethylene: - Dry cleaning.
13. Tri chloroethylene: - Metal dereasing.
14. Vinyl Chloride: - Plastic & resin products.
Process Flow Diagram
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,
trichlorobenzene 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
monochlorobenzene and dichlorobenzene.
(2) Chlorination of dichlorobenzene to
dichlorobenzene and tetra chlorobenzenes.
(3) Chlorination of tetra chlorobenzenes to Penta
chlorobenzenes and hex chlorobenzene.
Chlorination can be carried out either batch wise
or continuously.
When minimum formation of dichlorobenzenes 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 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
Process Description: -
■ The process of manufacturing of MCB takes
place within seven important section which
are as follows.
1.Chlorine Expander
2.Benzene Dryer
3.Reactor
4.HCL Adsorption
5.Acid Stripper
6.Benzene Stripper
7.MCB Stripper
 ■ Chlorine Expander :-
In this liquid chlorine is converted to gas form
& continuously fed to reactor.

■ Benzene Dryer:-
Here mixture of benzene from storage tank &
recycle benzene from benzene stripper having
moisture in it. It is sent to benzene dryer known
as aluminum molecular & continuously into
reactor
.
■ Reactor:-
Here dry benzene from benzene dryer is
passed at particular flowrate & pack with M.S
Rasching ring. Cl2 vapor from vaporizer is passed
at a particular flowrate from bottom of the
reactor. The following reaction takes place in
present of Rasching Ring.
C6H6 + Cl2 C6H5Cl + HCl
MCB & HCl product formed along with some
amount of DCB. Reduction is exothermic so
temperature is controlled by circulation of cooling
water.
■ HCl Adsorption :-
In this HCl vapor coming out from the reactor.
It is absorbed in water to form aq. HCl. It is the
controlled by flow indicator to get desired
concentration of liquid HCl.
■ Acid Stripper:-
The liquid reaction is flow to the intermediate
tank by gravity which mainly contains Benzene,
MCB , DCB & dissolved HCl. Dissolved HCl will get
distilled out & is sent to vent gas and adsorbed
where adsorbed HCl gas to converted into
aqueous form.
■ Benzene Stripper:-
In this coloum it is basically controlled by
automatic controller. Where unreacted benzene
will automatically distilled and it will again go to
reactor to again recycle and another part will be
again fed back to intermediate take top as reflux
to control temperature.
 ■ MCB Stripper:-
Now reaction mass from benzene stripper
bottom flow by gravity to intermediate tank.
Where it is pumped to the MCB Stripper at a
controller rate by automatic controller. Where
MCB is distilled from top which is condensed by a
condenser and then flow by gravity to tank where
one part is fed to the top to maintain temperature
and bottom product DCB is taken out to the
intermediate tank.
■ Maintenance :-
Heat Exchanger need to set such that tube
bundles can be easily withdrawn for cleaning and
tube replacement. Vessels that require frequent
replacement of catalyst or patching should be
located on offside of building. Equipment that
requires dismantling for maintenance such as
compressors and large pumps should be placed
under cover.
 ■ Safety:-
Blast walls may be needed to isolate
potentially hazardous equipment and continue
effects of an explosion. At least escape routes for
operator must be provided from each level in
building.

■ Plant Expansion :-
Equipment should be located so that it can be
conveniently tied in which any future expansion
process. Space should be left on pipe alleys for
future needs, service pipes oversized to allow for
future requirements.
Material Balance: -

C6 H6 + Cl2 C6H5Cl + HCl

78 71 112.5 36.5

C6H5Cl + Cl2 C6H4Cl2 + HCl

112.5 71 147 36.5

Basis: -
100 Ton/Day Production of MCB.

Selectivity of MCB = 80% = 100 Ton/Day

Selectivity of DCB = 20% = 25 Ton/Day

Conversion = 100%, 20% Excess Benzene

MCB = 100 Ton/Day = (100*1000/24)

= 4166.67 kg/hr
DCB = 25 Ton/Day = (25*1000/24)
 = 1041.667 kg/hr

C6 H6 + Cl2 C6H5Cl + HCl

78 71 112.5 36.5
2888.9 2629.3 4166.67 1351.85

C6H5Cl + Cl2 C6H4Cl2 + HCl

112.5 71 147 36.5
797.175 1006.212 1041.67
258.645

TOTAL C6 H6 Used = 2888.9 + 552.708

= 3441.608 kg/hr
TOTAL Cl2 Used = 2629.63 + 1006.212
= 1610.495 kg/hr
Here 20% Excess Benzene

TOTAL C6 H6 Used = 3441.608 + 3441.608*0.2

= 4129.9226 kg/hr