Production of

Chlorobenzene
2CH405
Process Calculation
TERM PAPER ASSIGNMENT
CONTENTS:
● INTRODUCTION

● PROPERTIES & USES

● MANUFACTURING PROCESS

● PROCESS FLOW SHEET

● CHEMICAL REACTIONS

● MATERIAL BALANCE

● ENERGY BALANCE
(https://5.imimg.com/data5/JX/KU/MY-71709474/chlorobenzene-chemical-500x500.jpg)
● REFERENCE(S)
INTRODUCTION
● Name: Chlorobenzene

● Formulae: C6H5Cl

● Molecular Weight: 112.56 g/mol

● Density: 1.11 g/cm³ (https://pubchem.ncbi.nlm.nih.gov/image/imgsrv.fcgi?cid=7964&t=l)

● Boiling Point: 132 °C

● Melting Point: −45.58 °C

● Solubility: 0.5 g/l in water at 20 °C (insoluble)

○ Soluble in almost every organic solvents

● Physical State: Colorless, Mobile liquid, Odor: Almond-like

INTRODUCTION
● KEYPOINTS:

○ Unaffected by the presence of air, moisture, or light, and

upon prolonged boiling: shows no tendency to split off Cl at
ordinary temperature & pressure.

○ At moderate temperatures, Unaffected by steam, alkalis,

hydrochloric acid, and dilute sulphuric acid.
USES
● Often used in the manufacture of phenol, aniline & DDT

● Solvent for paints, pesticide formulations

● As a chemical intermediate

● Heat transfer medium

● Dry cleaning industries

● Fiber-swelling agent in textile processing

MANUFACTURING PROCESS
● Generally used: Chlorobenzene from Benzene and Chlorine

● REACTION(S):

i. C6H6 + Cl2 C6H5Cl + HCl

ii. C6H5Cl + Cl2 C6H4Cl2 + HCl

FLOW SHEET
PROCESS DESCRIPTION
● Basic principle: Chlorination of benzene with or without the
presence of a catalyst (Friedel-Craft reaction).

● In actual practice in industry, only Chlorobenzene and small

amounts of dichlorobenzene are formed.

● 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 trichlorobenzene and
tetrachlorobenzenes.
○ (3) Chlorination of tetrachlorobenzenes to
pentachlorobenzenes and hexachlorobenzene.
PROCESS DESCRIPTION
● 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.
PROCESS DESCRIPTION
● 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%.

● 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.
EQUIPMENTS INVOLVED
● Chlorinator

● Neutralizer

● Benzene column

● Recycle Stream

● Chlorobenzene column
MATERIAL BALANCE
● Basis: 330 days/year of operation.

● The plant has to produce 23.3 kmols/hr of monochlorobenzene.

● Assume one hour of operation.

● 1. Balance across Chlorinator

● Assume that 100% chlorination occurs in the chlorinator at 40˚C. It

is also assumed that 10% of the HCl produced in the chlorinator is
entrained as liquid in the product. The rest leaves as vapour along
with benzene, MCB and DCB. Only the p-isomer of DCB is formed
in the chlorinator.
MATERIAL BALANCE
● It is assumed that from the chlorinator, the stream d is led into a
condenser from where we recover the HCl product formed.

○ MCB formed = 24.03 kmols/hr

○ DCB formed = 3.80 kmols/hr
○ HCl formed = 31.63 kmols/hr
○ Benzene remaining = 3.80 kmols/hr

● Input into chlorinator:

○ Benzene present = 31.63 kmols/hr
○ Chlorine present = 31.63 kmols/hr
MATERIAL BALANCE
● Output from chlorinator:
○ In stream d (29.65 kmols/hr):
○ MCB present = 0.44 kmols/hr
○ DCB present = 0.15 kmols/hr
○ HCl present = 28.47 kmols/hr
○ Benzene present = 0.59 kmols/hr

● In stream a (33.46 kmols/hr):

○ MCB present = 23.44 kmols/hr
○ DCB present = 3.65 kmols/hr
○ HCl present = 3.16 kmols/hr
○ Benzene present = 3.21 kmols/h
MATERIAL BALANCE
● 2. Balance across benzene column:

○ It is assumed that all the entering benzene in this column

goes out as distillate as the top product. The Distillate
contains 98 vol% benzene and 2 vol% MCB. Let the distillate
stream be e.

● Input into the benzene recovery column:

○ In Stream c (30.3 kmols/hr):
○ MCB present = 23.44 kmols/hr
○ DCB present = 3.65 kmols/hr
○ Benzene present = 3.21 kmols/hr
MATERIAL BALANCE
● Output from the Benzene recovery column:

○ In stream e (3.26 kmols/hr) :

■ Benzene present = 3.21 kmols/hr
■ MCB present = 0.05 kmols/hr

○ In stream f (27.99 kmols/hr) :

■ MCB present = 24.21 kmols/hr
■ DCB present = 3.78 kmols/hr
MATERIAL BALANCE
● 3. Balance for Recycle stream

● It is assumed that all the benzene from the benzene column goes
to the purifier from which all the benzene is recycled back into the
feed stream.
○ Recycle r into feed stream = 3.21 kmols/hr
○ Fresh feed = 28.42 kmols/hr

● 4. Balance across Chlorobenzene column

○ The purity of the MCB in the distillate is assumed to be 99

mol% .
○ The purity of the MCB in the residue is assumed to be 3 mol%
.
MATERIAL BALANCE
● Input to the chlorobenzene column:

○ In stream f (27.99 kmols/hr) :

■ MCB present = 24.21 kmols/hr
■ DCB present = 3.78 kmols/hr

● Output from the chlorobenzene column:

○ In stream g (24.23 kmols/hr)

■ MCB present = 23.99 kmols/hr
■ DCB present = 0.24 kmols/hr

○ In stream h (3.76 kmols/hr)

■ MCB present = 0.11 kmols/hr
■ DCB present = 3.65 kmols/hr
ENERGY BALANCE
● 1. Chlorinator:

○ Assumption is made that the fresh benzene and chlorine to

the chlorinator are stored at a temperature of 30˚C. The
reaction temperature is 40˚C. The inlet gases are to be
heated to the reaction temperature.

● Thus the heat required for this process is

● By a process of trial and error we find that the outlet temperature

is 345 K.
ENERGY BALANCE
● 1. Benzene Column

○ Assumption is made that no heat losses occur in the column.

○ For such a column the heat balance may be written as

Fhf +Qw =DhD +WhW +Qc

○ F is feed flow rate

○ D is the distillate flow rate
○ W is the underflow flow rate.
○ h indicates the enthalpy of the respective stream
○ Qw and Qc are the reboiler and condenser heat loads.
ENERGY BALANCE

● Tr is refernce temperature taken as 0 K.

● hf = 555.4 kJ/kg
● hd = 615.33 kJ/kg
● hw = 538 kJ/kg

● The condenser heat load may be calculated as

● is the latent heat of vaporization; the values for benzene and

chlorobenzene are 393.3 kJ/kg and 331.1 kJ/kg respectively.
ENERGY BALANCE
● hence QC is obtained as 7.9588 x 103 kJ/hr

● Substituting the values obtained we get

QW = 3.2192 x 106 kJ/hr = 894.22 kW

● 2. Chlorobenzene Column

○ Assumption is made that there are no heat losses.

○ Hence the previous equation holds.

Fhf +Qw = DhD +WhW +Qc

ENERGY BALANCE
● The values for the enthalpies of various streams are
○ hf = 505.7 kJ/kg
○ hd = 508 kJ/kg
○ hw = 497.3 kJ/kg

● The condenser heat load is calculated as

○ Thus QC = 1.3226 x 106 kJ/hr = 367.4 kW

○ Hence QW = 2.8017 x 103 kJ/hr = 778.25 kW
REFERENCES
● 1. Antarim Dutta, Cholorobenzene Production, Page 6-15, 2016.

● 2. S.D. Pravasi, in Encyclopedia of Toxicology (Third Edition), 2014

● 3. Website Resource: National Library of Medicine: PubChem:

Chlorobenzene
Thank
You!
21bch064 – PRATHAM SOLANKI