MANUFACTURE OF CHLORINECAUSTIC

SODA USING ELECTROLYSIS PROCESS

Introduction

The Chlor-Alkali industry in India forms an important

component of basic chemicals industry ,comprising around
74% of the basic chemicals production in India.

The Chlor-Alkali Industry in the country produces mainly

Caustic Soda, Chlorine and Soda Ash.

The geographic distribution of Chlor-alkali processes worldwide differs appreciably (production capacity of chlorine):
-western Europe, predominance of mercury cell process
(June 2000): 55%
-United States, predominance of diaphragm cell
process: 75%
-Japan, predominance of membrane cell process: >90%

PROPERTIES OF CHLORINE-CAUSTIC SODA-HYROGEN

CAUSTIC SODA
Physical State

Solid.

Appearance

White pellets.

Odor

Odorless.

Vapor Pressure

1 mm Hg @ 739 CO

Boiling Point

1390 CO @ 760 mm Hg

Freezing/Melting Point

318 CO

Solubility

Soluble.

Specific Gravity/Density

2.13 g/cm3.

Molecular Formula

NaOH.

Molecular Weight

40.00

PH

14 (5% aq soln).
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CHLORINE

HYDROGEN

APPEARANCE AND STATE

Colorless gas at normal temperature and

pressure

ODOR

Odorless

MOLECULAR WEIGHT

2.016

BOILING POINT (1 atm)

423.0 _F (-252.8 _C)

SPECIFIC GRAVITY (Air =1)

0.06960

FREEZING POINT/MELTING POINT

-434.5 F (-259.2 _C)

GAS DENSITY (At 70 F (21.1 C) and 1 atm):

0.00521 lb/ft3(0.08342 kg/m3)

SOLUBILITY IN WATER (Vol/Vol at 60 F (15.6

C)

0.019

SPECIFIC VOLUME (At 70 F (21.1 C) and 1 atm

192 ft3/lb (11.99m3/kg)

Competitive Manufacturing
Process
There are 3 types of electrolytic
processes
used
in
the
production of chlorine:
(1) The diaphragm cell process
(2) The mercury cell process
(3) The membrane cell process

A salt solution is electrolyzed

by the action of direct electric
current that converts chloride
ions to elemental chlorine. The
overall process reaction is:

In all 3 methods, the chlorine is

produced
at
the
positive
electrode (anode) and the
caustic soda and hydrogen are
produced, directly or indirectly,
at the negative electrode
(cathode).

The Diaphragm cell

process

FEATURES
DIAPHRAGM CELL

In the diaphragm cell process, there are two

compartments separated by a permeable diaphragm.
Brine is introduced into the anode compartment and
flows into the cathode compartment.
Similarly to the Membrane Cell, chloride ions am
oxidized at the anode to produce chlorine, and at the
cathode, water is split into caustic soda and
hydrogen.
The diaphragm prevents the reaction of the caustic
soda with the chlorine.
A diluted caustic brine leaves the cell.
The caustic soda must usually be concentrated to
50% and the salt removed. This is done using an
evaporative process.

The Mercury cell process

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FEATURES
MERCURY CELL

Electric current flowing through the cell decomposes the brine

passing through the narrow space between the electrodes,
liberating chlorine gas at the anode and metallic sodium at
the cathode
The chlorine gas is accumulated above the anode assembly
and discharged to the purification process.
As it is liberated at the surface of the mercury cathode and
the sodium immediately forms an amalgam (a 'mixture' of two
metals)
The liquid amalgam flows from the electrolytic cell to a
separate reactor, called the decomposer, where it reacts with
water in the presence of a graphite catalyst to form caustic
soda (sodium hydroxide) and hydrogen gas.
The sodium-free mercury is fed back into the electrolyser and
reused.
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The membrane cell

process

12

FEATURES
MEMBRANE CELL

This technology uses water-impermeable ion-conducting

membrane.
The membrane is made of a special resin which permits
cations (positive ions) to pass through.
The anode chamber of a membrane electrolytic cell is filled
with brine, and the cathode chamber with water.
These ions migrate when a current is applied: the positively
charged sodium ions pass through the membrane to the
cathode chamber, while the negatively charged chloride
ions are discharged on the anode surface to form chlorine
gas .
Water in the cathode chamber partly dissociates into
hydrogen and hydroxide ions.
The hydrogen ions capture electrons on the cathode surface
to form hydrogen gas.
The hydroxide ions are attracted to the anode, but blocked
by the membrane, and react with the sodium ions from the
anode chamber to form caustic soda (sodium hydroxide,
NaOH)
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SELECTION OF THE PROCESS

MEMBRANE CELL PROCESS

The membrane cell process has inherent

ecological advantages over the two older
processes, as it does not use mercury or
asbestos.
It is the most energy efficient process.
It is extremely safe to operate it and it
produces a consistently high quality of
caustic
soda.

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15

16

PROCESS FLOW DIAGRAM

17

 DIAPHRAGM CELL TYPE

Anode : Cl - - e

Cl2

Cathode: Na+ H2O + e Na+ + OH- + H2

Overall: NaCl + H2O

NaOH + H2 + Cl2

MERCURY CELL PROCESS

Anode: Cl- - e Cl2
Cathode: Na+ + e Na
: Na + Hg NaHg(amalgam)
Denuding: NaHg + H2O NaOH + H2 + Hg
Overall: NaCl + H2O NaOH + H2 +Cl2
2NaCl + 2H2O 2NaOH + H2 +Cl2

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Factors affecting Plant location

Adequate Supply of Raw materials.
Proximity to the market Minimum supply time. Relative cost low
(one third of caustic plants are attached to paper and rayon mills).
Transport Facilities Good capacity and speedy transportation.
Supply of Labor Cheap Labor Supply.
Power Regular Power Supply for operation machinery at full
capacity.
Supply of Capital Required for Initial promotion and Expansion.
Natural Factors Land, Water, Climate(Agriculture based
Industries).
Political Factors Favorable Development Policies.
Government Subsidies Exemptions, Rebates and Subsidies.
Historical and religious factors.
Need careful analysis of such factors as cheap power and salt sources
coupled with risisng cost of transportation.

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Locations of caustic soda plants

NAME

PROCESS USED

Durgapur Chemicals Ltd

(Durgapur W.B)

Mercury cell

J.K Chemicals Ltd ,thane

(Maharastra)

Mercury cell

Sirpur Paper mills ,sirpur

khaghaz nagar(A.P)

Diaphragm cell

Chemfab Alkalies ltd

(pondicherry)

Membrane cell

Rohtas Industries ltd ( bihar)

Mercury cell
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REFERENCES
1 ) Subrata Basu , Swapan Kumar Mukhopadhyay , Amitava
Gangopadhyay and
Sujata G. Dastidar International
Research Journal of Environment Sciences Characteristic
Change of Effluent from a Chlor-alkali Industry of India due
to Process Modification 2013.
2) S.Koter.A.Warszawski Polish Journal of Environmental
Studies Electro- membrane
Processes in Environment
Protection (2000)
3) Yohannes Kiros and Martin Bursell International Journal
Electrochemistry Science Low Energy Consumption in
Chlor-alkali Cells Using Oxygen Reduction Electrodes
(2008)
4) Rezaee, J. Derayat, S.B. Mortazavi,Y. Yamini and M.T.
Jafarzadeh American Journal of Environmental Sciences
Removal of Mercury from Chlor-alkali Industry Wastewater
using Acetobacter xylinum Cellulose(2005)
5) Drydens outlines of chemical technology (2012)
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