CHLOR-ALKALI INDUSTRY Sodium Hydroxide Production

ELECTROLYSIS
Electrolysis is the means of decomposing substances by passing an electric current

through them.
Sodium Chloride in solution, called Brine, during an electrolysis process produces: Sodium Hydroxide, Chlorine and Hydrogen.

ELECTROLYSIS OF BRINE
Brine could be electrolysed by using three (3) different cells:

Diaphragm Cells
Mercury Cells

Membrane Cells.

CHLOR-ALKALI MANUFACTURING PROCESS

HOW SODIUM HYDROXIDE IS GENERALLY PRODUCED

When NaOH is dissolved in water, it decomposes/splits into Na+ cations and Cl- anions. The chloride ions are oxidised at the anode to form chlorine (gaseous form of chloride). Water molecules(H2O) are reduced at the cathode to form hydrogen gas and hydroxide anions(OH-). Sodium Hydroxide is formed when the sodium ions in the solution reacts with the hydroxide produced at the cathode.

DIAPHRAGM CELLS
A diaphragm cell is a rectangular- shaped box. It consists of two electrodes, namely: anode and electrode. The anodes are metallic and are supported from the bottom with copper base plates. The cathodes are metal screens or punch plates connected from one end to the other end of the rectangular tank. Asbestos is dispersed as a slurry in the bath. It is vacuum deposited on the cathodes forming a diaphragm.

DIAPHRAGM CELLS (ANODE)

Brine, in a saturated form, enters the rectangular tank from the anode compartment. During

electrolysis, the chloride ions are attracted to the

anode, where it loses electrons. As a result, chlorine gas is formed and exists from the anode

compartment. The Cl2(aq) is saturated with H2O(aq)

at a partial pressure of water over the anolyte (electrolyte on the anode).

DIAPHRAGM CELLS (CATHODE)

The sodium ions are transported from the anode compartment to cathode compartment. The sodium ions move by a flow of the solution and electromigration (the movement of ions under the influence of p.d). This solution contains the unreacted sodium chloride, the Na+ ions and water. Hydroxide ions and hydrogen

are generated at the cathode when water molecules are

electrolysed. The diaphragm resists the back migration of OHions, which would otherwise react with Cl2 in the anode compartment. The sodium ions combine with the hydroxide ions

and forms sodium hydroxide, aka, caustic soda.

DIAPHRAGM CELLS (REACTIONS)

2Cl- ==> Cl2 + 2e Na+ + e- ==> Na anadoic reaction cathadoic reaction

2H2O + 2e- ==> 2OH- + H2 cathadoic reaction

2Cl- + 2H2O ==> Cl2 + H2 + 2OH- overall ionic reaction 2NaCl + 2H2O ==> Cl2 +2NaOH + H2

overall reaction

DIAPHRAGM CELLS

MERCURY CELLS
A mercury cell consists of steel bottoms with rubbercoated steel sides. There are end boxes for brine

and mercury feed and exit streams with a flexible

rubber or rubber- coated steel cover. The anodes are made of adjustable metal and they are hung

from the top. Mercury forms the cathode flowing on

the inclined bottom. Current therefore flows from the steel bottom to the flowing mercury.

MERCURY CELLS (ANODE)

Saturated brine is fed from the end box and electrolysed at the anode to produce chlorine. The chlorine flows from the top portion of the trough and then exits.

MERCURY CELLS (CATHODE)

The generated sodium ions reacts with the mercury to
form sodium amalgam. The amalgam flows out the end box vertical, cylindrical tank. The decomposer contains water and it is packed with graphite particles. The sodium amalgam reacts with water and produces caustic soda and hydrogen. H2(g) saturated with H2O(aq) and Hg(g) exit from the top. The caustic soda flows out the decomposer.

The unreacted brine flows out the exit end box. The
mercury from the decomposer is pumped back to the cell.

MERCURY CELLS (REACTIONS)

2Cl- ==> Cl2 + 2e- anadoic reaction 2Na+ + 2Hg + 2e- ==> 2Na (in Hg) cathadoic reaction

2Cl- + 2Na+ + 2Hg ==> Cl2 + 2Na (in Hg) reaction

overall cell

2Na (in Hg) + 2H2O ==> H2 +2NaOH + Hg decomposer reaction 2NaCl + 2H2O ==> Cl2 +2NaOH + H2 overall process reaction

MERCURY CELLS

MEMBRANE CELLS
A membrane cell consists of an anode and cathode compartments separated by an ion-

exchange membrane. The separator is

generally a bi-layer membrane (made of perfluorocarboxylic and perfluorosulfonic

acid- based films) sandwiched between the

anode and the cathode.

MEMBRANE CELLS (ANODE)

Saturated brine is fed to the anode compartment. After electrolysis at the anode,

chlorine is produced and released. The

sodium ions and some water migrate through the membrane to the cathode compartment. The unreacted sodium chloride and other inert remain in the anolyte.

MEMBRANE CELLS (CATHODE)

Hydroxide ions at the cathode are produced during the course of hydrogen gas evolution from

water molecules. Sodium ions react with the

hydroxide ions forming caustic soda. H2(g) saturated with H2O(l) exits from the cathode

compartment. Only part of the caustic soda is

withdrawn from the cathode compartment. The remaining caustic is diluted and returned to the cathode compartment.

MEMBRANE CELLS (REACTIONS)

2Cl- ==> Cl2 + 2e Na+ + e- ==> Na anadoic reaction cathadoic reaction

2H2O + 2e- ==> 2OH- + H2 cathadoic reaction 2Cl- + 2H2O ==> Cl2 + H2 + 2OH- overall ionic reaction 2NaCl + 2H2O ==> Cl2 +2NaOH + H2 overall reaction

MEMBRANE CELLS

SUMMARY
All three basic cell technologies generate chlorine at the anode, and hydrogen along with sodium hydroxide in the cathode compartment (or in a separate reactor for mercury cells. The distinguishing difference between the technologies lies in the manner by which the anolyte and the catholyte streams are prevented from mixing with each other, thus to ensure purity of NaOH. Separation is achieved in a diaphragm cell by a separator, and in a membrane cell by an ionexchange membrane. In mercury cells, the cathode itself acts as a separator by forming an alloy of sodium and mercury (sodium amalgam) which is subsequently reacted with water to form sodium hydroxide and hydrogen in a separate reactor.

ANODES AND CATHODES

The anode in all technologies is titanium metal coated with an electrocatalytic layer of

mixed oxides.
The cathode is typically steel in diaphragm cells, nickel in membrane cells, and mercury in mercury cells.

USES OF CAUSTIC SODA

1. Pulp and Paper 2. Textiles
Other small applications for caustic soda include water treatment, cleaners for beverage bottles, cleaning products such as drain and pipe cleaners, oven cleaner and other household

3. Bleach
Manufacturing 4. Petroleum Products

5. Aluminium
Production 6. Chemical

cleaning products and home

soap making.

Processing

CAUSTIC AND ITS USES

ENVIRONMENTAL ISSUES CHLORO -ALKALI INDUSTRY

Chlorine bleaching of wood pulp and Polyvinyl chloride plastic.

dioxin emissions to
the environment. Ozone layer depletion.

Mercury emissions.
Asbestos

This power point was brought to you by students of Form 5 S

Namely:
Simona Broomes, Kimberly Manbodh, Shenelle Khan, Ryan Patiram

END OF CHLOR-ALKALI MANUFACTURING PROCESS