Membrane Cell Process

In the membrane cell, the anode and cathode are separated by an ion-permeable membrane.
Saturated brine is fed to the compartment with the anode (the anolyte). A DC current is passed
through the cell and the NaCl splits into its constituent components. The membrane passes Na +
ions to the cathode compartment (catholyte), where it forms sodium hydroxide in solution. The
membrane allows only positive ions to pass through to prevent the chlorine from mixing with the
sodium hydroxide. The chloride ions are oxidised to chlorine gas at the anode, which is
collected, purified and stored. Hydrogen gas and hydroxide ions are formed at the cathode.

Fig 1.1 Process flow of Membrane cell method

The membrane process is summarised in the diagram below. The cathode and anode
compartments are separated by a water-impermeable membrane. This means that ions can pass,
but water cannot. Concentrated sodium chloride solution (NaCl(aq)) flows though the anode
compartment and water flows though the cathode compartment. The sodium ions and hydroxide
ions combine in the cathode compartment to produce sodium hydroxide.

Fig 1.2 Membrane Cell Compartment.

Mercury Cell Process

The mercury cell process involves two "cells". In the primary electrolyser (or brine cell), purified
and saturated brine containing approximately 25% sodium chloride flows through an elongated
trough that is slightly inclined from the horizontal. In the bottom of this trough a shallow film of
mercury (Hg) flows along the brine cell co-currently with the brine. Closely spaced above the
cathode, an anode assembly is suspended.
Electric current flowing through the cell decomposes the brine passing through the narrow space
between the electrodes, liberating chlorine gas (Cl2) at the anode and metallic sodium (Na) 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, the sodium immediately forms an
amalgam. The liquid amalgam flows from the electrolytic cell to a separate reactor, called the
decomposer or denuder, where it reacts with water in the presence of a graphite catalyst to form
sodium hydroxide and hydrogen gas. The sodium-free mercury is fed back into the electrolyser
and reused.

Fig 1.3 Mercury Cell Flow Process

Fig 1.4 Mercury Cell System

Diaphragm Cell Process

In the diaphragm cell process, a permeable diaphragm, often made of asbestos fibers, separates
the anode and cathode compartments. Brine is introduced into the anode compartment and flows
into the cathode compartment. Similarly to the Membrane Cell, chloride ions are oxidized at the
anode to produce chlorine, and water is split into caustic soda and hydrogen at the cathode. The
diaphragm prevents the reaction of the caustic soda with the chlorine. Diluted caustic brine
leaves the cell. The caustic soda must usually be concentrated to 50% and the salt removed.
Evaporative process is achieved with about three tonnes of steam per tonne of caustic soda. The
salt separated from the caustic brine can be used to saturate diluted brine. The chlorine contains
oxygen and must often be purified by liquefaction and evaporation. When using asbestos
diaphragms, the diaphragm process inherently gives rise to environmental releases of asbestos.

Figure 1.5 Diaphragm Cell System

Figure 1.6 Process Flow of Diaphragm Cell

Diaphragm cells can operate with less pure brine than required by membrane cells and at a lower
voltage than mercury cells. Among the three manufacturing processes, diaphragm cell process is
the most suitable and generally accepted manufacturing processes of caustic soda.