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Chlorine & Caustic Soda Production

The document discusses three industrial processes for producing chlorine and sodium hydroxide through electrolysis of brine. The diaphragm cell process uses a porous diaphragm to separate the anode and cathode compartments, producing chlorine gas and a 10-12% sodium hydroxide solution. The mercury cell process uses a carbon anode, mercury cathode, and brine electrolyte to produce chlorine gas, sodium amalgam, and 50% sodium hydroxide directly from the cell. However, it uses toxic mercury. The document also describes purification of brine and concentration of sodium hydroxide solutions.

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Tejas k
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105 views18 pages

Chlorine & Caustic Soda Production

The document discusses three industrial processes for producing chlorine and sodium hydroxide through electrolysis of brine. The diaphragm cell process uses a porous diaphragm to separate the anode and cathode compartments, producing chlorine gas and a 10-12% sodium hydroxide solution. The mercury cell process uses a carbon anode, mercury cathode, and brine electrolyte to produce chlorine gas, sodium amalgam, and 50% sodium hydroxide directly from the cell. However, it uses toxic mercury. The document also describes purification of brine and concentration of sodium hydroxide solutions.

Uploaded by

Tejas k
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as PDF, TXT or read online on Scribd
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Prof. S. N.

Derle, ChED, KKWIEER


 Chlorine is a chemical element with symbol Cl and atomic
number 17. The element is a yellow-green diatomic gas under
standard conditions.
Chlorine is used:
 to purify water
 as a disinfectant
 in the production of hypochlorous acid (HClO)which is used
to kill bacteria in drinking water
 paper
 antiseptics, insecticides, medicines, textiles, laboratory
chemicals
 paints, petroleum products, solvents, plastics (such as
polyvinyl chloride)
Prof. S. N. Derle, ChED, KKWIEER
Sodium hydroxide (NaOH), also known as lye and
caustic soda & which is available in pellets, flakes,
granular. It is soluble in water, ethanol, and methanol.
Sodium hydroxide is used to:
 make soap and other cleaning agents
 purify bauxite (the ore of aluminium)
 make paper
 make rayon (artificial silk)

Prof. S. N. Derle, ChED, KKWIEER


 Electrolytic process Producing chlorine, sodium
hydroxide and hydrogen as co-products.
 Chlorine process without co-products (HCl Oxidation)
 NaOH process without Cl2 (lime soda Process)

Prof. S. N. Derle, ChED, KKWIEER


 One of the problems of producing chlorine and sodium
hydroxide is that when they are produced together the
chlorine combines with the sodium hydroxide to form
chlorate (ClO−) and chloride (Cl−) ions. This leads to the
production of sodium chlorate, NaClO, a component of
household bleach.

 To overcome this problem the chlorine and sodium


hydroxide must be separated from each other so that
they don't react. There are three industrial processes
that have been designed to overcome this problem.
All three methods involve electrolytic cells

Prof. S. N. Derle, ChED, KKWIEER


 Electrolytic process Producing chlorine, sodium
hydroxide and hydrogen as co-products.
 Chlorine process without co-products (HCl Oxidation)
 NaOH process without Cl2 (lime soda Process)

Prof. S. N. Derle, ChED, KKWIEER


 :

Prof. S. N. Derle, ChED, KKWIEER


Prof. S. N. Derle, ChED, KKWIEER
 A brine solution is purified by using Caustic soda,
soda ash and barium carbonate to remove calcium
magnesium and iron salt.
 This purified brine is heated & electrolyzed in a
diaphragm cell which discharges 10-12% solution of
caustic soda.
 Multiple effect evaporation concentrate the cell liquor
to 50% NaOH solution. The precipitate is separated,
centrifuged, washed and then the slurried with treated
brine.

Prof. S. N. Derle, ChED, KKWIEER


 Salt separator overflow is 50% NaOH product
containing 2% NaCl & 0.1-0.5 % NaClO.
 The comercial grade can be evaporated to produce
73% NaOH liquor or fused to flake, granular or
stick caustic

Prof. S. N. Derle, ChED, KKWIEER


Prof. S. N. Derle, ChED, KKWIEER
In the diaphragm-cell:
 a porous diaphragm divides the electrolytic cell into an
anode compartment and a cathode compartment
 brine is introduced into the anode compartment and
flows through the diaphragm into the cathode
compartment
 an electric current is passed through the brine causing
the salt's chlorine ions and sodium ions to move to the
electrodes

Prof. S. N. Derle, ChED, KKWIEER


 Chlorine gas is produced at the anode
2Cl−(aq) + 2e−→Cl2(g)

 At the cathode, sodium ions react with water forming


caustic soda (NaOH) and hydrogen gas.
2Na+(aq) + 2H2O(ℓ) + e−→2NaOH(aq) + H2(g)
 Some NaCl salt remains in the solution with the
caustic soda and can be removed at a later stage.

Prof. S. N. Derle, ChED, KKWIEER


The advantages of the diaphragm cell are:
 uses less energy than the mercury cell
 does not contain toxic mercury

It also has disadvantages however:


 The sodium hydroxide is much less concentrated and
not as pure
 The chlorine gas often contains oxygen gas as well
 The process is less cost-effective as the sodium
hydroxide solution needs to be concentrated and
purified before it can be used
Prof. S. N. Derle, ChED, KKWIEER
Prof. S. N. Derle, ChED, KKWIEER
 The anode is a carbon electrode suspended from the
top of a chamber.
 The cathode is liquid mercury that flows along the
floor of this chamber.
 The electrolyte is brine (NaCl solution) that is passed
through the chamber.
 When an electric current is applied to the circuit,
chloride ions in the electrolyte are oxidised at the
anode to form chlorine gas.
2Cl−(aq)→Cl2(g) + 2e−

Prof. S. N. Derle, ChED, KKWIEER


 At the same time sodium ions are reduced at the
anode to solid sodium. The solid sodium dissolves in
the mercury making a sodium/mercury amalgam.
Na+(aq) + Hg(ℓ) + e−→Na-Hg

 The amalgam is poured into a separate vessel, where it


decomposes into sodium and mercury.

 The sodium reacts with water in the vessel and


produces sodium hydroxide and hydrogen gas, while
the mercury returns to the electrolytic cell to be used
again.
2Na(Hg) + 2H2O(ℓ)→2NaOH(aq) + H2(g) + Hg(ℓ)

Prof. S. N. Derle, ChED, KKWIEER


It has Some advantages:
 50% NaOH direct from cell
 High Purity Cl2 & H2

it has certain disadvantages:


 mercury is expensive and toxic
 some mercury always escapes with the brine that has been
used
 mercury reacts with the brine to form mercury chloride
 the mercury cell requires a lot of electricity

Prof. S. N. Derle, ChED, KKWIEER

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