2.].

DIAPHRAGM-CELL TECHNOLOGY DEVELOPMENT

During the electrolysis of NaCl brine, chlorine is gcncratcd at the anode and sodium
Hydroxide is produced at the cathode.
At the anode: 2Cl_ -> C1; + 2e
At the cathode: 22110 + 10 ~ H1 + 20H
Overall re-action: zmcl + 21410 J. zmot-1 + ct; + H;
The main difculty during the electrolysis of NaCl solutions was that of achieving
continuous separation of chlorine generated at the anode and sodium hydroxide
produced at 1.he cathode. While il was easy to keep the chlorine and hydrogen gases
in
Ushaped tubes. the sodium hydroxide formed at the cathode reacted with chlorine
lo
form sodium hypochlorite. The British scientist Charles Watt devised the concept of
a current-permeable separator. which allowed the eloclzic current to pass but kept
I11:
anode and cathode products st:parated.Th|.1s, the diaphragm cell was invented in
1851.
The major drawback ho the use of the Watt cell was the lack of electrical generation
capacity. The development of Ihe dynamo around l365 allowed Edison, Sielrvens,
VarIcy. Wlmatsione, and others to invefll generators of electticity with sufeiem
mpacity
and eiciency to make electrolytic production ofchlorine and caustic soda feasible.
Following the breaktluoughx in electricity generation. parallel developrnents in diaphragm cells were made in many coumries. The Credit for the rst commercial cell
for
chlorine production goes to the Griesheim Company in Gerntany. in I883. This
nonpor-

calming diaphragrtt cell. used predorninantly for Cl; production in the early 1900s,
was
based on the use of porous cement diaphragrns. invented by Brauer in 1836 and
rnade by
mixing Portland cement with brine acidied with HCI. followed by setting and
soaking
in water to remove the soluble salts. The cell, termed the Griesheim Elektron cell
[12,
l3| and shown in Fig. 2. I. consists ofan iron box with a steamjacket and is mounted
on
insulation blocks. Each unit contains siit rectangular boxes made ofcernent about 1
cm
thick. The cement boxes act as diaphragms and contain the anodes made of
magnetite
or graphite. The outer box forms the cathodes. and cathode plates are also provided
in
the fomt of iron sheets placed between anode compartments and reach the bottom
of
the cell. The cell was operated at 2.5 ILA. batchwise. with saturated potassium
chloride
solutions for 3 days until a concentration of 7% KOH was obtained. at a current
density
of 100-200 Nml at 8090C: lhe cell voltage is about 4 V and the current efciency
1F08t]%. It is very interesting to not; that the best opcmting conditions for this
ccl! were
found to he: [III anodes preferably of magnetite, ln obtain pure chlorine without any
CO;
in the anode gas. (2) high Concentration of brine, and (3) n temperature of Sl]
9DC, to
reduce the cell voltage. Items (21 and (3) are still lhe desired parameters for
optimal cell
operation.

The rst diaphragm cell developed in Great Britain was lhe HargreavesBird cull.
operated in 3390 by the United Alkali Company. Each cal] consisted nfa rectangular
irnn
box lined with cement. The box was 1[lft]ong,4-Sftdeep. and 2ft wide, divided into
three parts of two separate asbestos sheet diaphragms. Six carbon anodes were
placed in
the anode compartment. and the cathode was a copper gauze attached to the
diapltragrns.
This basic approach of anchoring the diaphragm onto the cathode is still used in
modem
diaphragm cells. The cell design is shown in Fig. 2.2.
The anode compartment was lled with saturated brine. and during electrolysis
chlorine evolved at the anode. The sodium ions. along with sodium chloride and
water.
percolated through the diaphragm into the cathode compartment. Back migration of
hydroxy] ions was suppressed by injecting C0; and steam into the cathode
compartment
to form sod-ium carbonate. The majorcontribution olfliis cell was its venjcal
diaphragm
conguration, which is the basis of modem oells.
Ttvelve cells were run in series at Zlult. which corresponds to a current density of
Z[l].N'm2, at4 t1o4.5 v, when 60% offlte salt isooutvcrtod to sodium carbonate.
The cell, used in France and Italy, was the DI-Ilhtllih-ClIa]andt'e cell [[3]. which
consisted of an irmi box divided into three oornpariments; the outer ones contained
the
carlc liquor, and th.e inner one had the graphite anodes in strong brine. The
diaphragm
was made from cylindrical unglazed porcelain tubes. oemented together into
dividing
walls of the ccll. This cell was more complex than the Griesheim cell and required

considerable attention.
In the United States. LeSoeu.r [I4-I T] developed and operated a cell in I890.
employingapetcolatinghorizouttal diaphragm (Fig. 2.3M.This design perrnitted brine
to
flow from the a.nol)"r.e through the diapluagm oontinuously to achieve a higher
efciency
than lhe contemporary nonpercolating diaphragm cells in Germany and Great
Britain.
LeS|.te|.tr's percolating diaphragm cell, which is the basis for all diaphragm ehlnralkali
cells in use today. shown in Fig. 2.33. is an improved version of the cell depicted
in Fig. 2.3A.
The LeSuel.u' cell was made of iron and divided inlo two compartments separated
by a diaplttagnt. which was depositedon an iron-gauze cathode. The anode was
graphite.
and the anode compartment was sealed to avoid the release ofchlorine. The liquid
level
in the anode companment was higher than the level in the cathode compartment.
and the
caustic flowed out of the cell continuously. This was the rst cell to use the
percolation
method for caustic withdrawal.
Cellcapacitics increased progressively after 1945. from about IURA to 100J-El) ILA.
Suppliers of this technology include De Nora. Hoechst-Uhdc. Krebs.
K1:h:ik0:im0.
Bi-\5F_ Kurcha. Olin-Mathic<son_ So1vay_ To)-0 Soda. and Asahi Glass. The
increased
capacity of U11; mercury ccll depended on lhe Llsc of efficient silicon
mciicrs. which

replaced lhe old rneri::ury-arc rectiers. The distinguishing dierences in

these mercurycell lmhnologies lie in several design factors which include the ma.n.ne!'
by which nleri:ury
is fad I0 the elcclmlyrnr (i:.g.. gnivity ow vs forced ow). dccorn|'msc'r
design. support
structure for lhe anudus and the cathodes. lypcs of ccll lI\'L'T. and
mercury inventory
rc.quir|:rnents. the main motivation being impmvbd economics. These
technologies an:
nutlinod in Chapter 5.
The primary cell technology used for producing chlorine and caustic. in the
world
and in United States. is the diaphragm-cell process_ which had a 3l"Ji\
share of world
chlorine production. In the United States, the diaphragm cell contributed
61% ofchlori no
production [34|. The mercury-cell technology had a dominating share
initially. However.
following the rnercury poisoning cases in Minantala and Niigata. both in
Japan. in I972,
the-re has been adeclining trend away from this tech nology for chlori ne
production. Japan
was the rst country to change from mercury<:e|I technology. and
currently there is no
mercury-well operation in Japan. In Western Europe. rnercurycell
technology is more
widely practiced. The mercury-cell technology still accounts for l8% share
in 2001. in
the world. Mercury cells generate 11% of the chlorine produced in the
United States.
This situation is unlikely to dramatically change in the near iuture. The
environmental

issues and concerns related to the intsneury-cell process are discussed in

Chapter I 6.