Detail of Chlorine-Alkali based industry

Introduction
Chlorine Alkali Industry is the industry that produce chlorine and
caustic(alkali). Chlorine can't be produced without having caustic as
byproduct and Vica Versa. For that reason, chloralkali industry
always have to battle to balance production to the !luctuating
re"uire#ent. chlorine and caustic de#ands never get along.Also the
ti#e it takes !or chlorine to being #anu!actured to being
used$consu#ed is very less co#pared to caustic which #akes #ore
i#balance.
%ne o! &eading co#pany !or ChlorAlkali industry is ''(
)lectrolysis is one o! the acknowledged #eans o! generating che#ical
products !ro# their native state. For e*a#ple, #etallic copper is produced by
electroly+ing an a"ueous solution o! copper sul!ate, prepared by leaching the
copper bearing ores with sul!uric acid. %r, one can prepare chlorine gas and
sodiu# hydro*ide solution by electroly+ing an a"ueous solution o! sodiu#
chloride, which e*ists in nature in a solid !or# as rock salt and also available
as solar or vacuu# evaporated salt. ,he solution o! sodiu# chloride (co##on
table salt) is o!ten called -brine.-
,he pri#ary products o! electrolysis are chlorine gas, hydrogen gas, and
sodiu# hydro*ide solution (co##only called -caustic soda- or si#ply
-caustic-). .owever, i! the electrolyte is #aintained at a p. o! /.0 or 12, one
can !or# chlorate or hypochlorite !ro# the electrogenerated chlorine and
caustic. ,his is the basis !or the electrolytic production o! sodiu# chlorate or
sodiu# hypochlorite (co##only known as -bleach-).
Chlorine and sodium hydroxide end uses
Chlorine and sodiu# hydro*ide are a#ong the top ten che#icals produced in
the world and are involved in the #anu!acturing o! a wide variety o! products
used in daytoday li!e. ,hese include3 phar#aceuticals, detergents,
deodorants, disin!ectants, herbicides, pesticides, and plastics.
,he !irst observation o! a possible application !or chlorine was its bleaching
e!!ect on vegetable #atter. In 1445, Carl 6ilhel# investigated the reactivity o!
the greenishyellow gas generated during the reaction involving the o*idation
o! hydrochloric acid by a #anganese dio*ide ore (pyrolusite). In 1470,
8erthollet tried unsuccess!ully to use ele#ental chlorine !or te*tile bleaching
to replace solar bleaching. )le#ental chlorine caused disco#!ort to the
workers, corroded #etal parts, and so!tened the !abrics. ,he !irst use o!
chlorine in the !or# o! potassiu# hypochlorite was !or bleaching, and dates
back to 1479. It was in 1727 that :avy characteri+ed this greenishyellow gas
as an ele#ent and na#ed it -chlorine.-
,he develop#ent o! che#ical bleaching with chlorine and the discovery o!
calciu# hypochlorite bleaching powder as a practical #ode o! transporting
chlorine was o! great signi!icance. ,hese technologies #ade a #arked i#pact
on the te*tile bleaching operations in (reat 8ritain and )urope, who were in
the #iddle o! the industrial revolution with e*panding production, and hence,
the de#and !or te*tiles. ,he invention o! the power loo# provided the
capability to produce te*tiles on a large scale. .owever, solar bleaching, by
spreading the cloth in open !ields !or #onths, beca#e increasingly e*pensive
in view o! the soaring land values. ,he chlorine bleaching process not only
shortened the operations !ro# #onths to !ew days, but also !reed vast areas o!
land !or #ore productive use. 8ased on the greatly i#proved e!!iciency o!
te*tile bleaching, the pulp and paper industry also began using bleaching
powder. 8etween 140/ and 19;<, the use o! chlorine in the pulp #aking
industry increased. Chlorine, in the !or# o! hypochlorites, re#oved the color
or color producing #aterials !ro# the cellulose !ibers, without undue
degradation o! the !ibers.
,he !irst use o! chlorine !or disin!ection dates back to 17<;, when it was used
in hospitals. Chlorine water was e#ployed in obstetric wards to prevent
puerperal !ever in 17</, and !u#igation with chlorine was practiced during the
great )uropean cholera epide#ic. Following the discovery that bacteria were
responsible !or the trans#ission o! certain diseases, several investigators
studied chlorination o! both sewage and potable water in 1792's in an atte#pt
to destroy these bacteria. 8y 191<, the use o! chlorine !or water treat#ent had
<
beco#e a co##on practice. ,here was signi!icant reduction in the incidence
o! water borne diseases, such as typhoid. For e*a#ple, !ro# %ctober to
:ece#ber 1929, 059 cases o! -winter typhoid- were reported in =ontreal,
Canada. A!ter chlorination o! drinking water was begun in 1912, only 142
cases were reported !or the sa#e 5#onth period. ,hus, virtually all the
chlorine #anu!actured during the 19th century was consu#ed by these two
industries. ,he #a>or turning event !or the growth o! the chlorine industry was
its use in 191< !or water puri!ication during the ?iagara Falls typhoid
epide#ic. It should be noted that bleaching powder was used in 1794 to clean
the polluted #ains during a typhoid break in )ngland.
8etween 19<2 and
1952, several new
applications !or
chlorine were
developed, !or
e*a#ple, in the
#anu!acture o!
ethylene glycol,
chlorinated solvents,
vinyl chloride, and
others. 6orld 6ar II
triggered the
develop#ent o! new
uses !or chlorine !or
#ilitary needs. ,his
trend continued to
produce new products
!or civilian use
!ollowing the war. 'rogress in synthetic organic che#istry in 19th century had
led to the preparation o! substitutes !or natural products and entirely new and
use!ul co#pounds including inter#ediates and !inal products. Chlorine,
because o! its reactivity, uni"ue properties, and low price, was used in #any o!
these, including solvents, phar#aceuticals and dyes. In 1490, dichloroethane
was produced and in 17;1 chloro!or# was synthesi+ed. 8y 1757, the
anesthetic properties o! chloro!or# were recogni+ed and used in surgical
practice.
'resently, the pri#ary uses o! chlorine are in the pulp and paper #anu!acturing
operations !or bleaching to produce a high "uality whitened #aterial and in
Fig. 1. Chlorine end uses.
;
water treat#ent operations as a disin!ectant (Figure 1). ,he other uses o!
chlorine include the production o! organic and inorganic che#icals. ,he
largest volu#e organic che#ical #anu!actured that involves chlorine is
polyvinyl chloride ('VC). 'VC is a very versatile ther#oplastic, used in a
wide variety o! daily products. ,he #a>or use o! chlorine in the production o!
inorganic che#icals is !or titaniu# dio*ide (a widely used pig#ent),
#anu!actured !ro# naturally occurring ores (il#enite or rutile).
,he end uses o!
caustic (sodiu#
hydro*ide) are
diverse
co#pared to the
uses o! chlorine
(Figure <). Its
pri#ary
application are in
the neutrali+ation
reactions and
!or#ing anionic
species such as
alu#inates and
+incates. In the
#anu!acture o!
organic
che#icals,
caustic is
e#ployed !or the
neutrali+ation o! acids, p. control, o!!gas scrubbing, dehydrochlorination,
and as a source o! sodiu# during various che#ical reactions. For e*a#ple, it is
used in the dehydrochlorination stage o! the epo*y resin production and
hydrolysis reactions involving epichlorohydrin in the !or#ation o! glycerin,
used in the phar#aceutical, tobacco and !ood$beverage industries
,he #a>or use o! caustic !or #aking inorganic che#icals is in the production
o! hypochlorite !or household and industrial bleaching purposes. Also, its use
in the pulp and paper industry is in the production o! sodiu# sul!ide and
sodiu# hydrosul!ide !or #echanical pulping. It is also used in the !ood
processing applications, which include skin re#oval o! potatoes, to#atoes etc,
!or !urther processing.
Fig. 2. Caustic soda end uses.
5
Sodium chlorate end uses
,he
electrosynthesis
o! sodiu#
chlorate dates
back to 172<,
when von
.isinger and
8er+elius
prepared sodiu#
chlorate by the
electrolysis o!
sodiu# chloride
solution. ,he !irst
chlorate cell
patent was issued
to 6att in 1701.
,he !irst chlorate
plant was built in
177/ in Villers
@t. @epulchre in @wit+erland, where chlorate was electroche#ically produced
in cells #ade o! wood and e"uipped with a diaphrag#. ,he energy
consu#ption was about 10,222 k6h$ton potassiu# chlorate. ,his #ay be
co#pared to an energy consu#ption !or a crystal product o! about 0,222
/,222 k6h$ton with #odern technologies.
Figure ; describes the enduse pro!ile o! sodiu# chlorate in 1997. About 9;A
o! sodiu# chlorate is used !or production !or bleaching in the pulp and paper
industry. ,he re#ainder is utili+ed in the agricultural industry as a cotton
de!oliant or herbicide (weed killer), as an o*idi+er in uraniu# #illing, and in
the production o! a##oniu# perchlorate used in rocket propulsion. (It is
worth noting that perchlorates are also produced by an electrolytic process,
where chlorate is anodically o*idi+ed to perchlorate.) ,hese uses o! sodiu#
chlorate have re#ained unchanged over the past <2 years, although the relative
de#ands have changed. 6orld capacity o! sodiu# chlorate was esti#ated as
about <.7 #illion short tons during 1997B the ?orth A#erican share was about
1.90 #illion tons.
Chlor/alkali manufacturing process
Fig. 3. Chlorate end uses.
0
,he chloralkali (also
called -chlorine
caustic-) industry is
one o! the largest
electroche#ical
technologies in the
world. It is an energy
intensive process and is
the second largest
consu#er o! electricity
(<522 billion k6h)
a#ong electrolytic
industries. In <22/,
about 75A o! the total
world chlorine capacity
o! about 09 #illion
#etric tons was
produced
electrolytically using
diaphrag# and
#e#brane cells, while
about 1;A was #ade
using #ercury cells (Figure 5).
Chlorine is produced by the electrolysis o! sodiu# chloride (co##on table
salt) solution, o!ten called -brine.- ,hus, when sodiu# chloride is dissolved in
water, it dissociates into sodiu# cations and chloride anions. ,he chloride ions
are o*idi+ed at the anode to !or# chlorine gas and water #olecules are reduced
at the cathode to !or# hydro*yl anions and hydrogen gas. ,he sodiu# ions in
the solution and the hydro*yl ions produced at the cathode constitute the
co#ponents o! sodiu# hydro*ide !or#ed during the electrolysis o! sodiu#
chloride. (,he che#ical reactions occurring in the cell are shown in the
Appendi*.)
Chlorine is produced electrolytically using three types o! electrolytic cells. ,he
#ain di!!erence in these technologies lies in the #anner by which the chlorine
gas and the sodiu# hydro*ide are prevented !ro# #i*ing with each other to
ensure generation o! pure products. ,hus, in diaphrag# cells, brine !ro# the
anode co#part#ent !lows through the separator to the cathode co#part#ent,
the separator #aterial being either asbestos or poly#er#odi!ied asbestos
Fig. 4. Chlorine cell technology in the U.S.
/
co#posite deposited on a !ora#inous cathode. In #e#brane cells, on the other
hand, an ione*change #e#brane is used as a separator. Anolytecatholyte
separation is achieved in the diaphrag# and #e#brane cells using separators
and ione*change #e#branes, respectively, whereas #ercury cells contain no
diaphrag# or #e#brane and the #ercury itsel! acts as a separator. ,he anode
in all technologies is titaniu# #etal coated with an electrocatalytic layer o!
#i*ed o*ides. All #odern cells (since the 1942's) use these socalled
Cdi#ensionally stable anodes- (:@A). )arlier cells used carbon based anodes.
,he cathode is typically steel in diaphrag# cells, nickel in #e#brane cells,
and #ercury in #ercury cells. ,hese cell technologies are sche#atically
depicted in Figures 04 and are described below.
Mercury cells
,he #ercury cell has
steel botto#s with
rubbercoated steel
sides, as well as end
bo*es !or brine and
#ercury !eed and e*it
strea#s with a !le*ible
rubber or rubber
coated steel cover.
Ad>ustable #etal
anodes hang !ro# the
top, and #ercury
(which !or#s the
cathode o! the cell)
!lows on the inclined botto#. ,he current !lows !ro# the steel botto# to the
!lowing #ercury.
@aturated brine !ed !ro# the end bo* is electroly+ed at the anode to produce
the chlorine gas, which !lows !ro# the top portion o! the trough and then e*its.
,he sodiu# ion generated reacts with the #ercury to !or# sodiu# a#alga#
(an alloy o! #ercury and sodiu#), which !lows out o! the end bo* to a vertical
cylindrical tank. About 2.<0A to 2.0A sodiu# a#alga# is produced in the
cell. ,he sodiu# a#alga# reacts with water in the deco#poser, packed with
graphite particles and produces caustic soda and hydrogen. .ydrogen,
saturated with water vapor, e*its !ro# the top along with the #ercury vapors.
,he caustic soda then !lows out o! the deco#poser as 02A caustic. ,he
Fig. 5. Schematic of a mercury cell.
4
unreacted brine !lows out o! the e*it end bo*. @o#e cells are designed with
chlorine and anolyte outlets !ro# the end bo*, which are separated in the
depleted brine tank. ,he #ercury !ro# the deco#poser is pu#ped back to the
cell.
Diaphragm cells
,he diaphrag# cell is a
rectangular bo* with
#etal anodes supported
!ro# the botto# with
copperbase plates,
which carries a
positive current. ,he
cathodes are #etal
screens or punch plates
connected !ro# one
end to the other end o!
the rectangular tank.
Asbestos, dispersed as
a slurry in a bath, is
vacuu# deposited onto the cathodes, !or#ing a diaphrag#. @aturated brine
enters the anode co#part#ent and the chlorine gas liberated at the anode
during electrolysis, e*its !ro# the anode co#part#ent. It is saturated with
water vapor at a partial pressure o! water over the anolyte. ,he sodiu# ions are
transported !ro# the anode co#part#ent to the cathode co#part#ent, by the
!low o! the solution and by electro#igration, where they co#bine with the
hydro*yl ions generated at the cathode during the !or#ation o! the hydrogen
!ro# the water #olecules. ,he diaphrag# resists the back #igration o! the
hydro*yl ions, which would otherwise react with the chlorine in the anode
co#part#ent. In the cathode co#part#ent, the concentration o! the sodiu#
hydro*ide is D1<A, and the salt concentration is D15A. ,here is also so#e
sodiu# chlorate !or#ed in the anode co#part#ent, dependent upon the p. o!
the anolyte.
Membrane cells
Fig. 6. Schematic of a diaphragm cell.
7
In a #e#brane cell, an
ione*change
#e#brane separates
the anode and cathode
co#part#ents. ,he
separator is generally a
bilayer #e#brane
#ade o!
per!luorocarbo*ylic
and per!luorosul!onic
acidbased !il#s,
sandwiched between
the anode and the
cathode. ,he saturated
brine is !ed to the anode co#part#ent where chlorine is liberated at the anode,
and the sodiu# ion #igrates to the cathode co#part#ent. Enlike in the
diaphrag# cells, only the sodiu# ions and so#e water #igrate through the
#e#brane. ,he unreacted sodiu# chloride and other inert ions re#ain in the
anolyte. About ;2;<A caustic soda is !ed to the cathode co#part#ent, where
sodiu# ions react with hydro*yl ions produced during the course o! the
hydrogen gas evolution !ro# the water #olecules. ,his !or#s caustic, which
increases the concentration o! caustic solution to D;0A. ,he hydrogen gas,
saturated with water, e*its !ro# the catholyte co#part#ent. %nly part o! the
caustic soda product is withdrawn !ro# the cathode co#part#ent. ,he
re#aining caustic is diluted to D;<A and returned to the cathode co#part#ent.
,hus, all three basic cell technologies generate chlorine at the anode, and
hydrogen along with sodiu# hydro*ide (caustic soda) in the cathode
co#part#ent (or in a separate reactor !or #ercury cells, see Figure 0). ,he
distinguishing di!!erence between the technologies lies in the #anner by which
the anolyte and the catholyte strea#s are prevented !ro# #i*ing with each
other. @eparation is achieved in a diaphrag# cell by a separator, and in a
#e#brane cell by an ione*change #e#brane. In #ercury cells, the cathode
itsel! acts as a separator by !or#ing an alloy o! sodiu# and #ercury (sodiu#
a#alga#) which is subse"uently reacted with water to !or# sodiu# hydro*ide
and hydrogen in a separate reactor.
A co#parison o! the per!or#ance characteristics o! these three technologies is
presented in the Appendi* together with sche#atic process diagra# !or each o!
the cell technologies. ,he pri#ary technology that is presently being used !or
Fig. . Schematic of a membrane cell.
9
!uture e*pansions or replace#ents o! e*isting circuits is the #e#brane cell
technology. ,he #a>or #e#brane cell technology suppliers, include3 Ehde
(#b., Asahi Che#icals, and Chlorine )ngineers. :e?ora ,ech is the sole
supplier o! diaphrag# cell technology. It is highly unlikely that anyone will
build a new #ercury or diaphrag#cell plant in the !uture. Figures 7 and 9
illustrate cell roo#s with diaphrag# and #e#brane chloralkali cells.
Fig. !. Chlor"al#ali cell room $ith %&"2. membrane
cells 'Courtesy of Uhde (mb)*.
Chlorine processing
,he chlorine gas !ro# the anode co#part#ent contains #oisture, byproduct
o*ygen, and so#e back#igrated hydrogen. In addition, i! the brine is alkaline,
it will contain carbon dio*ide and so#e o*ygen and nitrogen !ro# the air
leakage via the process or pipelines.
Chlorine is !irst cooled to /2
o
F (1/
o
C) and passed through de#isters to re#ove
the water droplets and the particulates o! salt and sodiu# sul!ate. ,he cooled
gas goes to sul!uric acid circulating towers, which are operated in series.
Co##only, three towers are used !or the re#oval o! #oisture. ,he dried
chlorine then goes through de#isters be!ore it is co#pressed and li"ue!ied at
low te#peratures. ,he noncondensed gas, called sni!t gas, is used !or
producing hypochlorite or hydrochloric acid. I! there is no #arket !or
hydrochloric acid, the sni!t gas is neutrali+ed with caustic soda or li#e
12
(calciu# hydro*ide) to !or# hypochlorite. ,he hypochlorite is either sold as
bleach or deco#posed to !or# salt and o*ygen.
Hydrogen processing
,he hydrogen gas !ro# the chloralkali cells is nor#ally used !or the
production o! hydrochloric acid or used as a !uel to produce stea#. .ydrogen
!ro# #ercury cells is !irst cooled to re#ove the #ercury, which is then
returned to the cells. %ccasionally, a secondary treat#ent is used to re#ove the
trace levels o! #ercury in the hydrogen via #olecular sieve colu#ns. ,he
hydrogen gas is then nor#ally co#pressed. I! a custo#er needs nearly pure
hydrogen containing low a#ounts o! o*ygen, so#e plants will heat the
hydrogen over a platinu# catalyst (to re#ove the o*ygen by reacting it with
the hydrogen to !or# water), cool, and co#press the diaphrag# or #e#brane
cell hydrogen, be!ore supplying it to the custo#er. ,he heat value in the
hydrogen cell gas can be recovered in a heat e*changer via heating the brine
!eed to the cells. Although only shown in Figure 1; in the Appendi* !or
diaphrag# cells, the heat recovery !ro# hydrogen is also possible with
#ercury and #e#brane cell processes.
Caustic soda processing
Caustic soda is #arketed as 02A, 4;A, or anhydrous (dry) beads or !lakes.
,he #ercury cell can produce 02A and 4;A caustic directly. ,he caustic !ro#
the deco#poser is cooled and passed once or twice through an activated
carbon !ilter to reduce the #ercury levels in the caustic. A!ter !iltration, the
#ercury concentration is lowered to the partsper#illion (pp#) levels. )ven
these low levels o! #ercury #ay be unacceptable to so#e custo#ers, who then
have to switch to using #e#brane grade caustic soda. ,he #ercury cell caustic
soda has a !ew pp# salt and F0pp# sodiu# chlorate. ,he #ercury cell caustic
is the highest purity caustic that can be #ade electrolytically i! trace
concentrations o! #ercury are tolerable in the end use o! caustic.
,he #e#brane cell caustic is concentrated in a #ultiple e!!ect !alling !il#
evaporator, which increases the caustic soda concentration to 02A with a high
stea# econo#y. Caustic soda !ro# #e#brane cells generally has ;2pp#
sodiu# chloride and 012 pp# sodiu# chlorate.
,he catholyte !ro# the diaphrag# cells contains D1<A sodiu# hydro*ide,
D15A sodiu# chloride, 2.<0A2.;A sodiu# sul!ate, and 122022 pp# sodiu#
11
chlorate. ,he catholyte is evaporated in a #ultie!!ect evaporator. =ost o! the
salt !ro# the catholyte will precipitate during the concentration o! the caustic
soda to 02A sodiu# hydro*ide. ,he 02A caustic soda product will contain
about 1A sodiu# chloride. ,he 02A caustic also has a high chlorate
concentration (D2.1A) co#pared to the caustic !ro# #e#brane or #ercury
cells (D12 pp#). ,he salt, separated !ro# the caustic during evaporation, is
used to resaturate the brine !ed to the cell.
An additional singlee!!ect evaporator is needed to produce 4;A caustic soda.
Anhydrous (dry) caustic soda is produced in a rising !il# evaporator, operating
at 4<0
o
F (;70
o
C) and at a !ew inches (one inch G<.05 c#) o! water vacuu#.
Brine processing
@odiu# chloride is available in the !or# o! solid salt, #ined by e*cavation or
by evaporating seawater. It is also available as a li"uid by solution #ining the
salt do#es. ,he salt has varying concentrations o! i#purities, which should be
re#oved to operate the electrolytic cells at a high current e!!iciency. ,he #a>or
i#purities are calciu#, #agnesiu#, and sul!ates. ,he other #inor i#purities,
which are undesirable, depending upon the type o! chloralkali process
selected, are bariu#, strontiu#, #anganese, alu#inu#, silica, iron, vanadiu#,
chro#iu#, #olybdenu#, titaniu#, etc.
,he solution#ined brine or the solid salt dissolved in the salt dissolver is
treated in a reactor with sodiu# carbonate and caustic soda to precipitate
calciu# carbonate and #agnesiu# hydro*ide (see the Appendi*). ,hese
precipitates are settled in a settler. ,he under!low carries the solid slurry,
which is pu#ped to a !ilter to re#ove it as sludge, or so#eti#es, it is disposed
o!! along with the rest o! the li"uid e!!luent !ro# the plant. ,he calciu#
carbonate precipitates are heavy, and drag with it the hydro*ides o! alu#inu#,
#agnesiu#, strontiu#, etc. ,he over!low !ro# the settler, which carries D12
02 pp# (parts per #illion) o! suspended solids, is !iltered. For the #ercury and
the diaphrag# cell process, this brine is ade"uate, and can be !ed to the
electroly+ers.
In the all cell processes, the !iltered brine is heated and passed through a bed
o! salt in a saturator in order to increase the salt concentration be!ore !eeding it
to the electroly+ers. In so#e plants, the brine !eed is acidi!ied to i#prove the
cell current e!!iciency. ,he acidi!ication reduces the alkalinity, which would
otherwise react with the chlorine in the anolyte co#part#ent !or#ing chlorate.
1<
,he #e#brane cell process brine speci!ications are #ore stringent than that o!
the #ercury and diaphrag# processes, and calls !or i#purities to be at the
partsperbillion (ppb) level. ,his is acco#plished by !iltering the brine in a
precoat type secondary !ilter. An ione*change resin is used to re#ove the
calciu#, #agnesiu#, bariu#, and iron i#purities. It is also possible to re#ove
alu#inu# by ion e*change. %!ten, alu#inu# and silica are re#oved by adding
#agnesiu# chloride in the brine e*iting !ro# the salt dissolver.
,he depleted brine !ro# the #e#brane and #ercury cell processes carries
dissolved chlorine. ,his brine is acidi!ied to reduce the chlorine solubility, and
then dechlorinated in a vacuu# brine dechlorinator. ,he dechlorinated brine is
returned to the brine wells !or solution #ining or to the salt dissolver. I! the
#e#brane and diaphrag# processes coe*ist at a given location, the
dechlorinated brine can be sent to a saturator !or resaturation be!ore being sent
to the diaphrag# cells.
Sodium chlorate manufacturing process
%ne o! the energy intensive electrolytic industries is the production o! sodiu#
chlorate by the electrolysis o! sodiu# chloride solutions in an electrolytic cell
without a separator. ,he products o! the electrode reactions, the chlorine and
the caustic, are allowed to inter#i* and react, producing sodiu# chlorate as
the !inal product (see the Appendi* !or details).
,he #a>or raw #aterial is sodiu# chloride, either very pure, such as solar rock
salt, or partially puri!ied evaporated salt. ,he salt is stored and dissolved in
li*iviators to produce a saturated sodiu# chloride solution. ,his solution is
puri!ied by re#oving calciu#, #agnesiu#, !luoride, sul!ate, and iron as
insoluble co#pounds, through the addition o! sodiu# carbonate, sodiu#
hydro*ide, sodiu# phosphate, and bariu# chloride.
,he i#purities or precipitates are re#oved in a pressure lea! !ilter with
diato#aceous earth as a !ilter precoat and !ilter aid. ,his !ilter cake, containing
appro*i#ately ;0A water, is the only solid waste strea# !ro# the process. A
polishing !iltration stage and an ione*change syste# !ollow pressure lea!
!iltration.
,he che#istry and electroche#istry o! chlorate !or#ation dictates that an
e!!icient and econo#ical cell should e#body several distinct +ones. In the
electrolysis +one, the electrolytic reactions take place along with the hydrolysis
1;
o! chlorine. As the che#ical chlorate !or#ation proceeds very slowly, a
relatively large volu#e o! che#ical reaction +one is needed. A cooling +one is
also re"uired to re#ove the e*cess heat generated !ro# the reaction and
control the operating te#perature. ,he cooling +one #ay be located within the
che#ical reactor or in an e*ternal heat e*changer. .ydrogen gas generated at
the cathode #ust be released !ro# the cell li"uor. ,his hydrogen release takes
place in the electrolysis cell, a separate vessel, or the che#ical reactor.
A continuous strea# o! cell li"uor !lows !ro# the electrolysis syste# to the
-hypo re#oval- syste#, where the sodiu# hypochlorite concentration is
reduced to low levels si#ply by heating the cell li"uor to about 170<22
o
F (70
90
o
C) under care!ul p. control. Final traces o! hypochlorite can be co#pletely
re#oved by treat#ent with a reducing agent (such as sodiu# sul!ite or
hydrogen pero*ide).
@odiu# chlorate is
usually recovered !ro#
cell li"uors by
concentration,
!ollowed by cooling to
!acilitate
crystalli+ation. .ot cell
li"uor, !ollowing hypo
re#oval, is !ed
continuously into the
circulation leg o! a
dra!t tube ba!!le
evaporator$crystalli+er.
Crystal slurry is
withdrawn !ro# the
botto# o! the
crystalli+er section. ,he crystals are separated !ro# the #other li"uor and
washed with water in a pusher centri!uge. ,hey are thoroughly washed to
re#ove sodiu# dichro#ate (an additive to the cell solution to increase current
e!!iciency) !ro# the chlorate crystals. @odiu# dichro#ate contains chro#iu#
in the he*avalent state, which is a recogni+ed hu#an carcinogen. A white
sodiu# chlorate crystal, containing about 1 to 1.0A #oisture, is obtained !ro#
the centri!uge. =other li"uor !ro# the centri!uge is #i*ed with !resh puri!ied
brine and recycled to the electrolytic cells.
Fig. 1+. Chlorate cell room $ith ,25 Chemetics cells
'Courtesy of -#er Chemetics*.
15
Appro*i#ately 97A o! the sodiu# chlorate capacity in ?orth A#erica is
produced directly in sodiu# chlorate cells. ,he re#aining <A is produced
-che#ically- by the reaction o! chlorine and caustic (see the Appendi* !or
details).
In recent years, sodiu# chlorate technology sales have been do#inated by the
!ollowing three suppliers3 ,echnip in France, Che#etics International in
Canada, and .uron ,echnology in Canada. ,here are #any other sodiu#
chlorate technologies in operation, such as :e?ora, )ltech, %*yChe#, %ulu
%y, and Atoche#. ?one o! these are considered to be available !or license.
Figure 12 depicts a chlorate #anu!acturing !acility with =<0 Che#etics cells.
Sodium hypochlorite manufacturing process
Another use!ul product generated by the electrolysis o! weak brine is sodiu#
hypochlorite, otherwise known as -bleach.- @odiu# hypochlorite cells
generally do not re"uire saturated brine, but can utili+e weak brine or even
seawater. 8leach is produced -onsite- !or disin!ection o! drinking water and
wastewater. ,he cells e#ployed !or this purpose are the sa#e as those used !or
chlorate #anu!acture, that is, they consist o! an anode and a cathode without a
separator or diaphrag#. ,he anodic and the cathodic reactions are the sa#e as
in chloralkali and chlorate cells, the di!!erence being the p. o! the electrolyte,
which is #aintained in the range o! 12 to 1<. ,he electrolytically generated
chlorine reacts with sodiu# hydro*ide to !or# sodiu# hypochlorite. .owever,
the hypochlorite ion, !or#ed in the bulk, is easily reduced at the cathode to
re!or# chloride. ,here!ore, only dilute solutions o! bleach can be produced in
the cell. .ypochlorite can also react !urther to !or# chlorate, but this can be
#ini#i+ed by keeping the solution basic and the te#perature low (close to
roo# te#perature).
,here are several #anu!acturers o! seawater electrolysis cells in the #arket.
,he best known cells include @eachlor #ade by :e?ora (producing 1222
<022 pp# active chlorine) or @alinec #ade by )*celtec International
Corporation (generating <22;22 pp# active chlorine).
Growth of the chlor-alkali industry
10
,he #arket de#and,
environ#ental
constraints, and energy
prices have pri#arily
dictated the growth o!
the chloralkali
industry in the E.@.,
with a #a>or ;1A
share o! the world
capacity. ,he industry
en>oyed a strong
growth until about
1942. It !altered in
1942's and peaked
brie!ly in 1949 be!ore
!alling to the lowest
level during 197<.
@ince then, signi!icant rationali+ation has occurred (Figure 11).
:uring the 1902's and 19/2's, the de#and !or chlorine grew at a rate o! 7A$yr
and the plants were operating at greater than 92A capacity. ,he de#and was
!or chlorinated derivatives and inter#ediates such as pesticides (::,) used in
agriculture and solvents, #ainly chlorinated ethanes, which replaced
!la##able hydrocarbons in #any cleaning and degreasing applications. Ese o!
chlorinated #ethanes as inter#ediates increased in the #anu!acture o!
organosilicones, in tetra#ethyl lead gasoline additives and !or !luorocarbons
used as aerosol propellants and re!rigerants. 'olyvinyl chloride ('VC) plastics
grew by 15A$yr as did ethylene and propylene o*ide, which were produced by
processes using chlorinated inter#ediates.
In 1942's, chlorine growth slowed to <A$yr because o! environ#ental concerns
bringing restrictions on the use o! pesticides such as ::,, kepone, dieldrin,
and endrin. Carcinogenic characteristics o! trichloroethylene, polychlorinated
biphenyls ('C8s) and si#ilar co#pounds also contributed to the declined
growth. In 1947, the E.@. )nviron#ental 'rotection Agency banned the use o!
!luorocarbon propellants !or aerosols because o! !ears related to depletion o!
the o+one in the upper at#osphere. ,he passage o! clean water legislation also
had an adverse i#pact on a variety o! enduses. ,hus, the paper industry
started i#ple#enting changes in bleaching technology by increased use o!
sodiu# chlorate, o*ygen, and hydrogen pero*ide as replace#ents !or chlorine
Fig. 11. U.S. chlorine and caustic soda capacity and
production.
1/
bleaching. :uring this period, #any che#ical processes that used chlorine,
particularly ethylene o*ide and propylene o*ide, were also converted to non
chlorine consu#ing processes.
Chloralkali producers, ignoring the potential i#pact o! new nonchlorine
based technologies and the various environ#ental concerns, continuing to
pro>ect growth rates o! 5/A$yr. ,hese pro>ections are based on chlorine
de#and !ro# e*ports, particularly to the Far )ast. Anticipating signi!icant
growth in e*ports, 10,222 tons$day o! new capacity was added through the
early 1972's.
In the 1972's, the environ#ental constraints i#pacted the downstrea# use o!
chlorine and operating costs increased because o! the energy crisis or the cost
o! electricity. In addition, the e*ports declined because o! the new ethylene
dichloride ():C) plants co#ing on strea# overseas. As a result, the de#and
declined and the industry operated at only a /5A capacity. %vercapacity, slow
growth, and high energy costs !orced chloralkali producers to #othball or put
on a standby #ode a large nu#ber o! production !acilities, accounting !or
about 1.< #illion #etric tons (=,). 8y the end o! <22/, restructuring
decreased the operating capacity to 1; #illion =,$yr at an e!!ective operating
rate o! D79A.
,hus, the #a>or !actors that in!luenced the chloralkali industry are the
environ#ental issues related to the use o! products such as ::, or aerosols
and the develop#ent o! nonchlorine based technologies. ,here is yet another
proble# that con!ronts chloralkali producers, that is, the outo!phase de#and
!or chlorine and caustic soda. Chlorine #arkets !ollow the econo#y closely,
since a large portion o! the 'VC #arket (its largest application) is in the
housing and auto#otive industries.
Caustic soda, on the other hand, does not respond as readily to econo#ic
changes because o! the diverse nature o! its #arkets, such as pulp and paper
and che#ical processing. Another advantage !or caustic soda is that it can
#ore easily be stored which helps !latten out variable de#and. ,hese
!luctuating de#ands !or chlorine and caustic soda, resulting !ro# the overall
changes in the econo#y, generally lead to production cut backs and increased
prices !or either chlorine or caustic soda.
In the late 1972's, the chlorine industry recovered !ro# earlier declines in
consu#ption and en>oyed banner production years. In 1974 and 1977, annual
14
increases reached 5 to 0A due to the strong econo#y. ,his was characteri+ed
by the increased de#and !or 'VC and pulp and paper products and by
increased e*ports o! chlorine derivatives.
It should be noted here that #ost o! the chlorine is traded globally as ):C,
vinyl chloride #ono#er (VC=) and pri#ary !or#s o! 'VC and that very little
in its ele#ental !or#. ,he E.@. alone accounted !or al#ost 02A o! this trade in
199<. It is because o! this #arket that chloralkali has seen #oderate growth
rate o! 1<A through 1992's. ,he world de#and !or chlorine is pro>ected to
grow at an annual rate o! <A through the year <211. ,he annual capacity o!
chlorine will grow to 05 #illion =, in <212 !ro# 50 #illion =, in <221.
&ow cost energy regions, such as =iddle )ast, are pro>ected to have higher
annual growth rates o! ; to ;.0A.
Growth of the chlorate industry
,he growth rate in the production o! sodiu# chlorate in ?orth A#erica !ro#
194/ to 1991 was appro*i#ately 12A annually. :uring 19741992, the ?orth
A#erican sodiu# chlorate capacity increased by appro*i#ately ;0A. =ost o!
the increase occurring in Canada as a result o! changes in environ#ental
regulations arising !ro# the !or#ation o! chlorinated organics necessitating the
replace#ent o! chlorine !or bleaching purposes with chlorine dio*ide (which is
produced !ro# chlorate). ,he #a>ority o! pulp and paper #ills were e*pected
to change their bleaching process !ro# chlorine in the !irst stage to partial or
co#plete replace#ent with chlorine dio*ide. I#ple#entation o! o*ygen
bleaching in the pulp and paper industry, increases the use o! chlorine dio*ide,
which re"uires greater production o! sodiu# chlorate. :elays in the conversion
!ro# chlorine to chlorine dio*ide by the pulp #ills decreased the operating
rates in the sodiu# chlorate industry to appro*i#ately 40A o! the rated
capacity in 1991.
@ince 1992's, the use o! ele#ental chlorine !ree ()CF) pulp bleaching
involving chlorine dio*ide !ro# sodiu# chlorate and hydrogen pero*ide has
grown !ro# ;A o! the total bleached pulp production to D00A in 1994. In
contrast, the total chlorine!ree (,CF) bleaching e#ploying a co#bination o!
o+one, hydrogen pero*ide, and o*ygen has decreased D17A in 1994 !ro#
D52A in 1992. It #ay be noted that ,CF uses greater a#ounts o! hydrogen
pero*ide co#pared to that used in )CF technology. Although the current pulp
inventories have declined in 1997, the !inal adoption o! the )nviron#ental
'rotection Agency's cluster rules in April 1997 allowing the substitution o!
17
chlorine dio*ide !or chlorine over total chlorine!ree bleaching, has spurred the
de#and !or sodiu# chlorate which is pro>ected to grow at a rate o! 0A per
year through the ne*t ten years.
Environmental issues within the chlor/alkali industry
,here are several environ#ental concerns that have #ade a signi!icant i#pact
on the growth o! the chloralkali industry over the past twenty years and will
dictate the !uture growth as well. ,hese issues are highly debated, and the
associated -che#ophobia- is likely to adversely a!!ect the chlorine
consu#ption pro!ile in the !uture.
Chlorine bleaching of wood pulp and dioxin emissions to the
environment
'resence o! dio*in, at parts per trillion (ppt) levels, in paper and paper based
products and chlorinated organics in pulp #ill e!!luents led to decreased
chlorine de#and. In the E.@., chlorine consu#ption in the pulp and paper
industry, decreased !ro# 10A in 1974 to 4A in 1997. ,he E.@. )nviron#ental
protection agency pro#ulgated -Cluster Hules- in late 1997, #andating the use
o! ele#ental chlorine!ree bleaching. ,hese rules, which went into e!!ect in
April <221, lowered the chlorine utili+ation in the ?orth A#erican pulp and
paper bleaching operations in !avor o! sodiu# chlorate, hydrogen pero*ide and
o*ygen.
Ozone layer depletion
8ecause o! their contribution to the o+one layer depletion, production o!
chlorinated !luorocarbons (CFC's), carbon tetrachloride (CCl
5
), and 1,1,1
trichloroethane was banned in 1994 !ollowing the =ontreal Accord.
Chlorinated #ethanes and ethanes are under great scrutiny due to the
environ#ental and occupational concerns associated with the#. ?evertheless,
their production will continue because o! their use in the #anu!acture o!
.CFC<<. .CFC<< is less har#!ul than the CFC's towards o+one depletion
and is an inter#ediate in the production o! tetra!luoroethylene !or use in the
production o! ,e!lon and other !luoro poly#ers. .CFC's are currently
substituted !or the CFC's, until they are phased out. .FC's containing no
chlorine are not sub>ect to this restriction.
olyvinyl chloride plastic
19
In 1974, appro*i#ately ;7A o! all E.@. chlorine production was consu#ed in
vinyl chloride #ono#er (VC=) production to satis!y the growing polyvinyl
chloride ('VC) de#and. ,hrough <212, VC= de#and is e*pected to grow
annually because o! the de#and !or 'VC in the construction, packaging, and
other industries. ?early 70A o! all ethylene dichloride ():C) #anu!actured in
the Enited @tates is used to produce VC=, and another 11A is e*ported,
#ostly !or !oreign VC= production. )ven with increasing energy prices in
?orth A#erica, the ):C and VC= capacity is e*pected to keep growing, by
1.1A, through <212. .owever, there are two #a>or environ#ental issues with
'VC, which include their lack o! biodegradability and generation o! dio*ins
when they are incinerated !or energy recovery and !or controlled waste
recycling. .ydrochloric acid !or#ation during the ther#al deco#position o!
'VC is another issue that environ#entalists are strongly invoking !or the
substitution o! chlorine!ree products !or 'VC.
Mercury emissions
8etween 19;2 and 19/2, several tons o! #ercury waste was du#ped in
=ina#ata 8ay in Iapan. ,housands o! people living around the bay developed
#ethyl#ercury poisoning through the consu#ption o! conta#inated !ish. ,he
victi#s su!!ered !ro# severe neurological da#age, which later beca#e known
as =ina#ata :isease. All told, thousands were a!!licted and #ore than 922
died. As o! April 1994, #ore than 14,222 people had applied to the
govern#ent to be certi!ied as =ina#ata victi#s, 1<,/10 have been o!!icially
recogni+ed. @ince then, there was a signi!icant #ove away !ro# #ercurycell
technology to diaphrag# and ione*change#e#branecell operations and
currently only ;0A o! the world capacity (#ostly in western and center )urope
and about 12A o! E.@. production) o! chlorine is produced using the #ercury
cell process. ,here will be no new construction o! #ercurycell plants.
)*isting plants are !ocusing on operating their plants at lower than the
#a*i#u# #ercury loss re"uire#ents o! 1.9 gra#$year$#etric ton o! chlorine
as set by the )urochlor 8est Available ,echnology. ,he )urochlor 8A,
plan !or #ercury e#issions beca#e e!!ective in <224. ,he goal was to reduce
e#issions to 1.2g .g per tonne o! .g cell chlorine capacity. 8y <220, the
e#issions level dropped !ro# 1.29 in <225 to 1.20g .g$t chlorine capacity and
by <224 this goal was achieved.
!sbestos
<2
Asbestos is used as a separator #aterial in diaphrag# cells. .owever, asbestos
is a to*ic #aterial, causing lung cancer, asbestosis, and #esothelio#a. As a
result, in <224, a bill was adopted to ban #ost uses o! asbestos in the Enited
@tates. ChlorAlkali plants were e*e#pt because !ew cost e!!ective alternatives
e*ist !or this technology. .owever, the )'A could revoke this e*e#ption i!
unreasonable risks to health or the environ#ent are !ound. @o#e ways that the
industry has avoided these risks have included surveillance and #onitoring
progra#s !or asbestos related diseases and use o! proper sa!ety e"uip#ent and
!iltration syste#s during ti#es o! unavoidable e*posure. In other countries, the
use o! asbestos in diaphrag# cells had already been banned.
)ven with all these constraints, the chloralkali industry is pro>ected to grow at
a rate o! 1 to ;A depending on pessi#istic or opti#istic reasoning. =uch o!
this will be dictated on how e!!ectively the industry responds to the concerns
o! the environ#entalists and the govern#ent agencies.
Appendix
Chlor"al#ali manufacturing process
Electrochemical and chemical reactions occurring in mercury cells
Electrochemical and chemical reactions occurring in diaphragm
and membrane cells
J1K <Cl

GGL Cl
<
M <e

(anodic reaction)
J<K <?a
M
M <.g M <e

GGL <?a (in .g) (cathodic reaction)

J;K
<Cl

M <?a
M
M <.g GGL Cl
<
M <?a (in
.g)
(overall cell reaction)
J5K
<?a (in .g) M <.
<
% GGL .
<
M<?a%.
M .g
(deco#poser reaction)
J0K <?aCl M <.
<
% GGL Cl
<
M<?a%. M .
<

(overall process
reaction)
<1
Heaction J9K will conta#inate the caustic product with chlorate.
Chemical reactions occurring in brine processing
Comparison of cell technologies
ercury !iaphragm embrane
%perating current density ( kA$#
<
) 7 1; 2.9 <./ ; 0
Cell voltage (V) ;.9 5.< <.9 ;.0 ;.2 ;./
?a%. strength (wtA) 02 1< ;;;0
)nergy consu#ption ( k6h$=, Cl
<
)
at a current density o! (kA$#
<
)
;;/2 (12) <4<2 (1.4) </02 (0)
@tea# consu#ption (k6h$=, Cl
<
)
!or concentration to 02A ?a%.
2 /12 172
"rocess flow sheets
J1K <Cl

GGL Cl
<
M <e

(anodic reaction)
J/K <.
<
% M <e

GGL <%.

M .
<
(cathodic reaction)
J4K <Cl

M <.
<
% GGL Cl
<
M .
<
M <%.

(overall ionic reaction)

J0K <?aCl M <.
<
% GGL Cl
<
M<?a%. M .
<
(overall reaction)
J7K
Cl
<
M <?a%. GGL ?a%Cl M ?aCl M
.
<
%
(side reaction)
J9K ;?a%Cl GGL ?aCl%
;
M <?aCl (side reaction)
J12K Ca@%
5
M ?a
<
C%
;
GGL CaC%
;
M?a@%
5
(CaC%
;
precipitates)
J11K
=gCl
<
M <?a%. GGL =g(%.)
<
M
<?aCl
(=g(%.)
<
precipitates)
<<
Fig. 12. ,ercury cell process flo$ sheet.
<;
<5
Fig. 13. .iaphragm cell process flo$ sheet.
<0
</
Fig. 14. ,embrane cell process flo$ sheet.
$odium hypochlorite"chlorate manufacturing process
Electrochemical and chemical reactions occurring in cells
.ypochlorite !or#ation is pro#oted by the use o! weak brine, basic solution,
and low cell te#peratures.
Chlorate !or#ation is pro#oted by the use o! saturated brine, acidic solution,
and te#peratures close to the boiling point o! the solution.
Chlorate cell process flow sheet
J1K <Cl

GGL Cl
<
M <e

(anodic reaction)
J4K <.
<
% M <e

GGL <%.

M .
<
(cathodic reaction)
J7K Cl
<
M <%.

GGL %Cl

M Cl

M .
<
% (hypochlorite !or#ation)
J9K ;%Cl

GGL Cl%
;

M <Cl

(chlorate !or#ation)
J1<K ?aCl M .
<
% GGL ?a%Cl M .
<

(overall hypochlorite
reaction)
J1;K ?aCl M ;.
<
% GGL ?aCl%
;
M ;.
<

(overall chlorate
reaction)
J15K
;Cl
<
M /?a%. GGL ?aCl%
;
M 0?aCl
M ;.
<
%
(che#ical chlorate
!or#ation)
<4
Fig. 15. Chlorate cell process flo$ sheet.
<7