Chapter 8

CHLOR-ALKALI INDUSTRY USING

DIAPHRAGM CELLS

The diaphragm-type chlor-alkali plant consists of the brine treatment yard,

the electrolytic cell room, the caustic evaporation system, and the gas
processing system, both chlorine and hydrogen, as illustrated in Fig. 8.1.,
where the material balance is also shown.
Crude salt is dissolved with water, and the concentrated NaCI solution
is sent to the electrolyzer after purification. The procedure for brine
purification is almost the same as for the amalgam-type chlor-alkali plant,
but the brine is not returned to the brine treatment yard after electrolysis as
in the amalgam cell plant. Instead, salt recovered from the caustic evaporator
is recycled to the brine treatment yard as slurry. In the amalgam cell plant,
the feed brine is acidified with HCI to pH = 3-4 prior to electrolysis. In
contrast, neutralized or alkaline solution is fed to the diaphragm cell in most
plants to protect the asbestos mat from chemical attack.
The catholyte effiuent or the cell liquor, consisting of about 12 %
NaOH and 15 % NaCl, is treated by the evaporator to separate crystallized
salt from caustic soda. A caustic evaporator of double or triple effects is
generally used, but quadruple effect evaporators are being used in very large
plants to minimize steam consumption. (I) Table 8.1 shows an example of the
operating conditions of a triple-effect evaporator. (2) Figure 8.2 illustrates an
example of a triple-effect evaporator in a chlor-alkali plant. Diaphragm-cell
caustic contains NaCI of about 1 % by weight, which is about equal to the
solubility of NaCI in 50% caustic soda solution at room temperature. This
contamination causes certain problems such as insufficient quality for further
processing, local corrosion of equipment, etc. Although there are several
processes for purification of diaphragm-cell caustic, (3,4) they add an extra
cost of ten dollars or more per ton of caustic.
Although the graphite anode resists attack by the chlorine electrode
process, it is gradually corroded by the oxygen electrode reaction, and is
converted into CO and CO 2 , (5,6) Consumption of the graphite anode is also
troublesome in the amalgam cell. Adjustment of the anode-to-cathode gap, or
167
F. Hine, Electrode Processes and Electrochemical Engineering
© Plenum Press, New York 1985
 ......
0-
HYDROGEN 30kg H2 00
99.8"1. 654kg H 20
6~
908kg Cl 2
9~k9 H 2 0
1460kg, dry basis
RECOVERED SALT 1851kg

WATER ACID

CHLORINE

TANKS 37k9 NaCl

1610kg, dry basis
lOOOkg NaOH
at 96% purity
BRINE 965kg H.O
2002kg
HOT CAUSTIC LlOUOR(50-70° C) 19k9 NaCl
• I lOOOkg NaOH
965kg H.O
TRANSFORIoiERS i9a4kg
1496kg NaCl (20-30 4C
POWER l022kg NaOH
l460kg NaC1 60l9kg H.O CELL
19 kg NaOH 8537kg - LIOU OR
669kg H. 0 STORAGE
2148kg RECOVERED SALT (")

~
t;j
'"
!:ti
FIGURE 8.1. Flowsheet of a typical diaphragm-type chlor-alkali plant. 00