The diaphragm cell process

The diaphragm process was developed in the 1880s in the USA and was the first commercial
process used to produce chlorine and caustic soda from brine. In North America, diaphragm
cells are still the primary technology, accounting for roughly 70% of all USA production. The process differs
from the mercury cell process in that all reactions take place within one cell and the cell effluent contains
both salt and caustic soda. A diaphragm is employed to separate the chlorine liberated at the anode,
and the hydrogen and caustic soda produced directly at the cathode.
Without
the
diaphragm to isolate them, the hydrogen and chlorine would spontaneously ignite and the
caustic soda and chlorine would react to form sodium hypochlorite (NaClO), with further reaction to produce
sodium chlorate (NaClO3) [Kirk-Othmer, 1991].
The diaphragm process uses brine in the production process. The feed brine is mixed with the
Recycle brine in brine saturation tank. The solution is then undergoes precipitation and filtration process to
eliminate unwanted materials. The solution is heated to a certain temperature and after that it is sent to the
electrolysis chamber.
The diaphragm process used inert electrodes a titanium electrode to withstand attack from the chlorine
formed and an iron mesh cathode, which is not affected by the hydroxide solution. The chloride ions
migrate to the anode and are oxidised to chlorine gas. Therefore the reaction at the anode is as follows:
2Cl - (aq) Cl2 (g) + 2e
The sodium ions migrate to the cathode but they are too stable to be reduced: instead water is
reduced to hydrogen gas and hydroxide ions and so a solution of sodium hydroxide is formed. Therefore at
the cathode the reaction that takes place is:
2 H2O (l) + 2e- 2OH- + H2 (g)
The overall reaction of this, including the spectator ions is as follows:
2Na+ + 2Cl- + 2H2O 2Na+ + 2OH- + H2 + Cl2
The complete ionic equation with neutral species is as follows:
2NaCl (aq) + 2H2O (l) 2NaOH (aq) + H2 (g) + Cl2 (g)
The diaphragm is usually made of asbestos and separates the feed brine (anolyte) from the causticcontaining catholyte. Purified brine enters the anode compartment and percolates through the diaphragm
into the cathode chamber. The percolation rate is controlled by maintaining a higher liquid level in the
anode compartment to establish a positive and carefully controlled hydrostatic head. The percolation rate is
determined as a compromise between a low rate that would produce a desirably high concentration of
caustic soda in the catholyte (which provides the cell effluent) and a high rate to limit back-migration of
hydroxyl ions from catholyte to anolyte, which decreases cathode current efficiency [Kirk-Othmer, 1991].
In the diaphragm cell, saturated brine (about 25% NaCl) is decomposed to approximately 50% of its original
concentration in a pass through the electrolyser as compared to a 16% decomposition of salt per pass in
mercury cells. Heating caused by passage of current through the diaphragm cell raises the operating
temperature of the electrolyte to 80-99 C.
All diaphragm cells produce cell liquor that contains ca. 11% caustic soda and 18% sodium chloride. This
solution is evaporated to 50% NaOH by weight at which point all of the salt, except a residual 1.0-1.5% by
weight, precipitates out. The salt generated is very pure and is typically used to make more brine. This high
quality sodium chloride is sometimes used as a raw material for an amalgam or membrane process.