CHLORINATION PROCESSES

Common Features of Chlorination

1. Basically chlorine is used as chlorinating
agent during chlorination. As chlorine is
stored in liquid form under pressure, it is
need to evaporate before passing it to
reactor.
2. Chlorination reactions are highly exothermic
where Hr ranges between 25 to 30
kcal/gmol.
3. During chlorination, HCl gas is obtained as
the by-product and it is highly corrosive in
nature, hence in environmental and safety
point of view, HCl gas cant be vented
directly in atmosphere. So proper
absorption system for HCl should be
designed.

4. HCl leaving the reactor is saturated with

organics. So after condensation, these
condensed organic contents should be
recovered and recycled back to reactor.
5. The organic phase from reactor contains
traces of HCl. This HCl is stripped off from
reaction mass i.e. HCl stripping is done
using stripper.
6. Recovery of organics from HCl absorption
system is necessary.
 CHOLOROBENZENE

Benzene reacts with chlorine in an

electrophilic substitution reaction, but only in
the presence of a catalyst. The catalyst is
either aluminium chloride or iron chloride.

C6H6 + Cl2 C6H5Cl + HCl

 Although reaction rate of benzene to chlorobenzene is
approximately 8.5 times more than dichlorobenzene but
ortho and para dichlorobenzene is also formed during this
reaction.
Para dichlorobenzene is more valuable (used as insecticide,
moth repellent, deodorant) and is twice as much as ortho
dichlorobenzene in the final product.
The final composition of the charge will vary somewhat
depending upon
temperature,
catalyst and
rate & degree of chlorination,
Approximate composition is usually

Benzene 9%
Monochlorobenzene 70%
p-dichlorobenzene 15%
o-dichlorobenzene 6%

Temperature is kept at 55-60 C. When a sample

shows the required density has reached, benzene
circulation is stopped. The required density is
about 1.280 at 15 C.
The time consumed is about 6 hrs.
 Special type of reactor used for
chlorination
Bubble Column Reactor with external Heat
exchanger.
Bubble column reactors
 Bubble column reactors

Bubble columns are devices in which gas, in

the form of bubbles, comes in contact with
liquid.
The purpose may be simply to mix the liquid
phase.
Substances are transferred from one phase to
the other
 Bubble column reactors
-Simple vertical cylindrical vessels with intense
contact between the two phases.

-The gas phase is dispersed into the liquid phase

using specific gas distributors at the bottom of the
column.

-The net liquid flow may be co-current or counter-

current to the gas flow direction.
Gas is sparged at the bottom of the liquid pool
contained by the column.
(sparging is a technique which involves
bubbling a gas, through a liquid. Sparging
increases the gas-liquid interface.)

Spargers, like porous plates, generate uniform

size bubbles and distribute the gas uniformly at
the bottom of the liquid pool.
 Bubble Column

Co- Counter-
current current
Static Gas Spargers
Dip tube Perforated plate

Perforated ring Porous plate

Bubble column reactors
1. Chlorine from storage tank is passed to chlorine
evaporator to evaporate the chlorine and then
this gaseous chlorine is passed to reactor.
2. Benzene (in liquid form) from Benzene day tank
(DT) is passed to reactor (chlorinator).
3. Reaction between chlorine and benzene takes
place in chlorinator and organic phase mostly
containing mono-chloro-benzene (MCB) along
with few amount of di- and tri- chloro-benzene
(DCB and TCB) is produced; also HCl gas is
produced as by-product.
4. Gaseous phase (mainly containing HCl gas
and few amount of organics saturated with
HCl) from reactor is passed to series of
condensers (2 or 3 condensers), where,
organics get condensed which are recycled
back to chlorinator while HCl gas stream is
further passed to HCl absorption system.
5. Organic phase from chlorinator contains traces
of HCl. Therefore this organic phase before
passing to further separation system, it is
passed to stripper where HCl traces get
stripped off from organic phase.
6. Organic phase now free from HCl is passed to
further purification i.e. to series of distillation
column, where main product MCB gets
separated from traces of DCB, TCB and
unconverted Benzene if any.
 FLOW CHART SHOWING DIFFERENT STEPS
1. Bubble Column Reactor with external Heat
exchanger
To show this bubble column reactor, draw reactor (cylindrical, vertical
arrangement), show the liquid and bubbles inside it. Liquid (Benzene) is fed
from top or from side inlet of reactor.
Here, as it is gas-liquid type reaction, Cl2 gas
(evaporated in Cl2 evaporator) is passed in reactor
from bottom using sparger. Cl2 gas is sparged in
benzene liquid so that it bubbles in liquid and good
contact between gas and liquid takes place for reaction
to occur.
 As reaction is exothermic, we need to
continuously remove this heat of reaction, for
which external heat exchanger is used. The whole
reaction mixture (gas+liquid) is continuously
circulated from reactor to heat exchanger to
reactor. For this circulation, pump is used. Once
the reaction is completed, the reaction mixture
(product) is removed from reactor through
bypass line provided on circulation line
somewhere at the top of reactor.
Draw heat exchanger as vertical shell and tube type heat exchanger
beside the bubble column reactor.
2. HCl Absorption system:
As HCl gas is by-product of chlorination process and
as it is being corrosive in nature, it is needed to
absorb this HCl gas using suitable solvent like water
or any other. The gas free from HCl then further can
be vented in atmosphere.
HCl gas from condensers and stripper, is sent to a
series of towers. The water is passed to these gas
tower, which will absorb HCl.
 After certain time, HCl solution is removed from
its bottom and passed to settler cum separator. In
this settler cum separator, HCl acid gets
separated from traces of organic phase if any. HCl
acid is sent to storage tank (ST).
Tail gases free from HCl gas, are taken out from
top of 1st tower and sent to the top of second
tower.
Tail gases from last tower are absorbed in alkali
solution contained in alkali solution tank to
remove the traces of HCl
3. Separation of Organic Phase from stripper
We need to separate main product MCB from traces
of other by-products like DCB or TCB and
unconverted benzene, from organic phase coming
out from stripper. Three distillation columns are
used to separate different products.
Benzene is separated at the top of first column from other
products and sent to settling tank. Remaining organic phase
is taken out from bottom of 1st column and sent to 2nd
distillation column.
 Second separates MCB from top, which is further sent to
settling tank. Bottoms of second column are sent to 3dr
distillation column.
Traces of DCB gets separated from top of 3rd and sent to ST,
however bottoms of 3rd is residue stream.