Gujarat Cleaner Production Centre ENVIS CENTRE

CLEANERPRODUCTION
OPPURTUNITIES
IN

CAUSTICSODA/CHLORALKALI
INDUSTRIES
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IntroductiontoCausticsoda/ChlorAlkaliIndustry

TheChlorAlkaliindustryinIndiaformsanimportantcomponentofbasicchemicalsindustry,
comprisingaround74%ofthebasic chemicals productioninIndia.Caustic soda,soda ash,
chlorine alongside hydrogen and hydrochloric acid comprise the Chloralkali industrys
components.Thesechemicalsfindtheirapplicationsinanumberofindustriessuchastextiles,
chemicals, paper, PVC, water tr eatment, alumina, soaps & detergents, glass, ch lorinated
paraffinwax,amongothers.Thedemandforthetwosubsegmentscausticsoda&sodaash,
hasincreasedsignificantlyregisteringacompoundannualgrowthrate (CAGR)of5.6%and
4.7%respectively,overthepastfiveyears.

TheChlorAlkaliIndustryinthecountryproducesmainlyCausticSoda,ChlorineandSodaAsh.
Theproductsoftheindustryareofvitalimportanceandtheirusesare:

1) CausticSoda
1 SoapsandDetergentIndustry
2 PulpandPaperIndustry
3 TextileProcessingIndustry
4 AluminumSmelting
5 DyesandDyestuffIndustry
6 PlasticPolymers
7 RayonGradePulp
8 Pharmaceuticals
9 Electroplating
10 Adhesives/Additives.

2) Chlorine,ByproductofCausticSodaIndustryisveryimportantformanufacturingofPVC,
one of the five maj or Thermoplastic Commodity Plastics. Besides this, it is used in
disinfectionofdrinkingwater,pharmaceuticalindustryandvariousotherchemicalindustries.
BecauseofthestrongoxidizingpropertiesofChlorine,itiseffectivelyusedto
controlbacteriaandvirusesindrinkingwaterthatcancausedevastatingillnesssuchas
Cholera.UseofChlorineisveryimportantfortheCountrieslikeIndiaespeciallyincase
offloods.85%ofthepharmaceuticalsrelyonChlorineChemistryincludingmedicines
thattreatheartdisease,cancer,AIDSandmanyotherlifethreateningdiseases.Chlorine
tabletsarealsousedbypublichealthworkersinruralareas.

3) SodaAshisusedinGlassIndustry,Soaps&Detergents,Silicatesandvariousother
ChemicalIndustries.
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AsstatedabovethegrowthofCausticSodaandSodaAshIndustryisveryimportantforthe
NationandifcompetitivenessofthisIndustryismaintained,itcancertainlygrowatamuch
fasterrate.

HighlightsofprocessesforChloralkali/causticsoda

The Chloralkali process (also chloralkali and chlor alkali) is an industrial process for the
electrolysis of sodium chloride solution (brine). Depending on the method, several products
besideshydrogencanbeproduced.Iftheproductsareseparated,chlorineandsodiumhydroxide
(caustic soda) are the products; b y mixing, sodium hypochlorite or sodium chlorate are
produced,dependingonthetemperature.

Therearethreebasicprocessesfortheelectrolyticproductionofchlorine,thenatureofthe
cathodereactiondependingonthespecificprocess.Thesethreeprocessesarethediaphragm
cellprocess(Griesheimcell,1885),themercurycellprocess(CastnerKellnercell,1892),and
themembranecellprocess(1970).Eachprocessrepresentsadifferentmethodofkeepingthe

chlorineproducedattheanodeseparatefromthecausticsodaandhydrogenproduced,directly
orindirectly,atthecathode.
Thebasicprincipleintheelectrolysisofasodiumchloridesolutionisthefollowing:
1- Attheanode,chlorideionsareoxidisedandchlorine(Cl2)isformed.
2- At the cathode: In the mercury process a sodium/mercury amalgam is formed and
hydrogen(H2)andhydroxideions (OH)areformedbythereactionofthesodiuminthe
amalgamwithwaterinthedenuder.Inmembrraneanddiaphragmcells,waterdecomposesto
formhydrogen(H2)andhydroxideions(OH)atthecathode.

Forallprocessesthedissolvingofsalt,sodiumchloride,is:

NaClNa++Cl

Theanodereactionforallprocesses

is:2Cl (aq)Cl2(g)+2e

Thecathodereactionis:
+ +
2Na (aq)+2H2O+2e H2(g)+2Na (aq)+2OH (aq)

Theoverallreactionis:
+ +
2Na (aq)+2Cl (aq)+2H2O2Na (aq)+2OH (aq)+Cl2(g)+H2(g)
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(FlowdiagramofthethreemainChloralkaliprocesses)
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(Simplifiedschemeofchlorineelectrolysiscells)

ThemaincharacteristicsofthethreeelectrolysisprocessesarepresentedinTable

Mercury Diaphragm Membrane

Causticquality High,<30ppmNaCl 1.01.5% by weight High,<50ppmNaCl
5150gHg/l(Before NaCl (Before
treatmenttheHglevel treatmenttheNaCl
isbetween2.525mg contentisabout18%)
Hg/l) 0.1%NaClO3 Not
suitable for some
applications

Caustic 50% 12%, requires 33%, requires

concentration concentration to 50% concentration to50%
forsomeapplications forsomeapplications

Chlorinequality Containslowlevelsof Oxygen content Oxygen content

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oxygen(<0.1%)and between1.52.5% between 0.5% and

hydrogen 2%,dependingon
whetheranacidified
electrolyteisused
Brinefeedstock Some purification Some purification
Veryhighpuritybrine
required required butdepends is required as
butdependsonpurity onpurityofsaltor
impuritiesaffect
ofsaltorbrineused brineused Membrane
performance
Variableelectric Good variable Tolerates onlyslight Variable electricity
loadperformance electricityload variationinelectricity load performanceless
performance,downto loadand brineflows thanformercury(40
30%offullload inorder tomaintain 60%depending
possibleforsome diaphragm on design load),
cellrooms,which is performance affects product
very important in quality,and
someEuropean efficiency at lower
countries loads

Auxiliaryprocesses
Therearevariousauxiliaryprocessesattachedtoallthethreetechnologies,whicharelisted
below:
1 saltprocessing;unloading/storage
2 brinepurificationandresaturation
3 chlorineprocessing
4 causticprocessing
5 hydrogenprocessing

CausticProcessing
ProcessforCausticSoda
Sodiumhydroxide(causticsoda)isproducedinafixedratioof1.128tonnes(as100%NaOH)
pertonnechlorineproduced.
Thecausticsodasolutionfromthethreetechnologiesistreatedinslightlydifferentwaysdueto
thedifferenceincompositionandconcentration.
Inthemercurycellprocess,50%causticsodaisobtaineddirectlyfromthedecomposers.Thecaustic
sodaisnormallypumpedthroughacooler,thenthroughamercuryremovalsystemandthentothe
intermediateandfinalstoragesections.Insomecasesthecausticisheatedbeforefiltration.The
mostcommonmethodforremovalofmercuryfromcausticsodaisaplate(orleaf)
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filterwithcarbonprecoat.Undernormaloperatingconditions,mercurycellcausticsoda(as
100%NaOH)contains20100ppmofsodiumchlorideand4060gHg/kgNaH.
Inthecaseofdiaphragmandmembranetechnologiesthecausticsodaisconcentratedby
evaporationbeforefinalstorage.

(Theflowtostorageofcausticsodafromthedifferenttechnologies)

EmissionsinChlorAlkaliIndustry

EmissionfromMercurycellprocess

AirEmission Wateremissions SolidWaste

Releasesofmercuryare theprocess:bleedfrombrinepurification, Solidsfrombrine

specifictotheamalgam
technology.Airemissions
consistofmercuryvapour
comingfrom:
cellroomventilation
processexhausts
brinepurification
condensatefromhydrogendrying, purification
condensatefromcausticsodaconcentration Solidsfrom
units,brineleakage,ionexchangeeluate causticfiltration
fromprocesswater Graphiteand
Treatment. activatedcarbon
thewashwaterfromthecellcleaning fromtreatmentof
operations:inletandoutletboxes gaseousstreams
stackofcausticevaporators therinsingwaterfromtheelectrolysishall:

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hydrogenburntorventedto
atmosphere
mercuryretorting
maintenanceoutsidecell
room
cleaningofthefloors,tanks,pipesand
dismantledapparatus
therinsingwaterfrommaintenanceareas
outsidetheelectrolysishall,iftheyare
cleanedwithwater

EmissionfromDiaphragmcellprocess

AirEmission Wateremissions SolidWaste

Threesourcesofasbestos Wastewaterstreamsfromthediaphragmcell Bagged asbestos

emissioncanbeidentifiedin processmainlyoriginatefrom from scrap
thecellroommaintenance thecondenser diaphragms
area: causticsodaevaporation,
fromtheoffgascompressor, chlorinedrying,
fromtheoffgasdrying brinepurificationofsaltrecovered
oven, from
fromtheoffgasasbestos Theevaporators.
weighingroom

EmissionfromtheMembraneCellProcess

AirEmission Wateremisssions SolidWaste

Wastewaterfromthemembranecellprocess precoatandbodyfeed
originatesfrom materialmadeofcellulose
causticevaporation, Spent membranesand
chlorinedryingand gaskets from membrane
Washwaterfromtheionexchangeresin cells
usedtopurifythebrine.

EnvironmentalIssuesinChloralkali/causticsodaIndustryandCPoptions

1 Implementation of cleaner processes and pollution prevention measures can yield both
economicandenvironmentalbenefits.InMBCP(membraneprocess),thechlorine(atthe
anode)andthehydrogen(atthecathode)arekeptapartbyaselectivepolymermembrane
thatallowssodiumionstopassintothecathodiccompartmentandreactwiththehydroxyl
ionstoformcausticsoda.Thedepletedbrineisdechlorinatedandrecycledtotheinputstage.
ThemajorwastestreamfromtheMBCPconsistsofbrinemudthesludgefromthebrine
purificationstep,whichmaycontainmagnesium,calcium,iron,andothermetalhydroxides,
dependingonthesourceandpurityofthebrine.

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1 Thepollutionemissiontargetnamelywastewatergenerationtargetof0.1m pertonof
1. Having an emergency pr eparedness and response plan for potential unco ntrolled
chlorineandotherreleases.
2. Usingcarbontetrachloridewithlevelsbelow4%toavoidexplosion.
3. UsingmetalratherthangraphiteanodesinDCPtoreduceleadandchlorinatedorganics.
4. Resaturatebrineinclosedvesselstoreducethegenerationofsaltsprays.
5. Usenoncontactcondenserstoreducetheamountofprocesswastewater.
6. Scrubchlorinetailgasestoreducechlorinedischargesandtoproducehypochlorite.
Scrubchlorinetailgasusingsuitablequantityofwaterforpreparationofcausticsolution
forpHmaintenancetoreducechlorinedischargeandtoproducesodiumhypochloride
7. Recyclecondensatesandwasteprocesswatertothebrinesystem,ifpossible.
8. Recyclebrinewastes,ifpossible
9. Preferableuseofsubstitutesforcarbontetrachlorideasthisishazardous
10. chlorineproducedcanbeachievedbyadoptingpreventivemeasuressuchas:
IndianChloralkaliplantshaveachievedhugebenefitsthroughtechnologyshifti.e.
TechnologyshiftfromMercurycelltoMembranecell,whicharetabulatedbelow:
1. Given the fact that Chlo ralkali production relies on energy intensive electrochemical
technology,approximately7075%oftheproductioncostprimarilycomprisesofenergy
costsincaseofmercurycellbasedtechnology.Ontheotherhandincaseofmembranecell
technology,thereisasignificantreductioninenergyconsumptionandthetotalenergycost
onlyconstitutes60%oftheproductioncost.Therefore,immediatereductionofproduction
costofabout24%canbeachievedbytechnologyshifts.
2. Themembranecellplantisanenvironmentfriendlyandenergyefficienttechnology.Any
endproductsorgas,generatedfromthisplantarecompletelyfreeofmercurywithno
chancesofmercurycontaminationtothesoilorwater;
3. Themembranecellbasedplantwouldensurenoemissionofmercuryintotheair;
4. Nochancesofnegativeimpactsonhumansaswellastheenvironmentremainsasthe
mercuryitselfisatoxicelement;
5. Netenergysavingofabout24percent,therebyreducingtheamountofcarbonfootprint
2 Mercury cell Chloralkali plants are subject to special regulations due to the use of
mercury.In
thecaseofmercuryaswellasmembranecellprocess,theinitialinvestmentonpollution
controlmeasuresremainsunchanged;therebytheconversionintechnologydidnotenvisage
anyadditionalinvestment.Convertingtoamercuryfreeprocesswillleadothesavingsof
severalrelevantcosts,whichinapproximateorderofeconomicsignificanceinclude:
1. Avoiding costs of recycl ing, retorting, transporting, inventorying and/or disposing of
mercurywastes;
2. Eliminationofthemercurywastewatertreatmentfacility;
3. Reducedlaborcostsduetoreducedneedformaintenance;
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4. Reduced labor costs du e to reduced need for monitoring mercury emissions and
occupationalexposures,healthtesting,reportingandabatementmeasures;
5. Avoidanceofcostsofstorageofresidualmercury;
6. Eliminationofmercurymonitoringequipment,aswellasequipmentforcleaningmercury
fromproductstreams,flueexhausts,othercleanuprelatedcosts(spillages)etc;
7. Thiscannotbeeasilyquantified;however,atleast5%ofthetotalbenefitslistedabove,
canbeachieved,whichinclude,improvedcommunityrelations,decreasedlegalliability,
improvedpublic/investorimageofthecompany,improvedattractivenessofthecompany
asaplacetowork(employeesatisfaction),reducedenergydemandduringthetimeof
raisedenergyconsciousness,reducedCO2emissionsrelatedtoenergydemandetc.
8. Reduced costs on medical testing of workers and relevant insurances as well as costs
relatedtopotentialneedofrehabilitationincaseworkershadtotaketimeoff.
2 Fundamentalresearchprogrammesrelatedtomercurytechnologyarenotbeingdeveloped
since it is very unlikely th at any new mercury plants will be built. The only recent
improvementsinmercurycellsconcernstheanodegeometrywiththeaimofimprovinggas
release in order to decrease electrical energy usage and increase anode coating life. In
diaphragm technology, with the exception of nonasbestos technology referred earlier,
improvements are minor and related to reducing power consumption in the ce ll. An
interestingexampleisaspecificdevelopmentofactivatedcathodetechnologywhichisthe
precathodeconcept.
3 Oxygendepolarizedcathodesinmembranecellshavethepotentialtosavearound500600
kWh/tonneofchlorineproducedandarenowbeingtestedattheindustrialscale.
Themembraneisbeingdevelopedthatcanproducehighconcentration(50%)causticsoda
andbelievesthatitcouldbeavailableatanacceptablecostwithinafewyears
1 ForMBCP(membranetechnology)thecleaneroptionsinclude:
1. Minimizingthedischargeofchlorateandbromatetowaterbyapplying:acidconditionsin
theanolyte(pH:12)tominimizetheformationofchlorate(ClO3)andbromate(BrO3)
chloratedestructioninthebrinecircuittoremovechloratebeforepurging.
2. Theacidityoftheanolyteisadesignparameterofmembranecellplantandcannotbe
adjustedwithoutaffectingtheoperationofthemembranecell.Ifthisisnotthechosen
option,achloratedecomposermaybenecessarytoremovechloratebeforepurging.
3. ThechloratelevelassociatedwithBATinthebrinecircuitis15g/landtheassociated
bromatelevelis210mg/l(notethatthebromateleveldependsonthebromidelevelinthe
salt).
4. Appropriatehandlingofspentmembranesandgaskets.

EnvironmentalIssuesinCausticSodaManufacturingandCPoptions

Steamisusedasthesourceofevaporativeenergy.Thepresenceofsaltinthediaphragmcell
liquorrequiresthattheevaporatorisequippedwithscraperbladesorotherdevicestodrawoff
theprecipitatedsalt.Thishighqualitysodiumchloridecanthenbeusedtoenrichdepleted
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brine,sometimesitisusedasarawmaterialforanamalgamormembraneprocess.The
residuallevelofsodiumchlorideinsodiumhydroxidefromdiaphragmcellisabout1%and
sodiumchlorate0.1%.Forthisreason,itisunsuitableforcertainendapplicationssuchasthe
manufactureofrayon.
1 Saltandsodiumchlorateinthecausticsodafromdiaphragmcellscanbereducedby
ammoniaextractiontoincreasemarketability,butatincreasedcost.
2 The caustic soda from membrane cells is of high quality, although the caustic soda
produced (usually around 33% NaOH) needs concentration to 50% NaOH for some
applications.Thesaltcontentofthemembranecellcausticsodaliesbetween20100ppm(in
100%NaOH),butisonaverageslightlyhigherthanmercurycellcaustic.
3 Insomeplantsthecausticsodaisfurtherconcentratedtoa73%solutionandto100%as
solidcausticprillsorflakes.
4 SomeChloralkaliproductionfacilitiescancombinethecausticproductionprocess
from
mercuryandmembranecellsinordertominimizeenergycosts.Itispossibletofeed33%
causticfromthemembranecellstothedecomposertoproduce50%causticwithouttheneed
forevaporation.

Bibliography

Books
1. KirkOthmer,Encyclopedia,1991,
2. LindleyEncyclopedia,1997,
3. UllmannsEncyclopedia1996
4. ResearchandMarkets:IndianChlorAlkaliIndustry:causticsoda,sodaash,chlorineand
hydrogenDecember08,201109:28AMEasternStandardTime
5. PreBudgetMemorandum20122013byAlkaliManufacturersofIndia
6. TechnicalEIAguidancemanualforChlorAlkaliIndustryPreparedforTheMinistryof
Environment&ForestsGovernmentofIndiabyIL&FSEcosmartHyderabad,2010
7. ChlorineIndustry:EconomicsOfConversionInIndiaStudyBy:ToxicsLink,New
DelhiSupportedByZeroMercury,2012
8. BREFdocumentonChlorAlkaliManufacturingIndustry.
9. Cost Benefit Analysis for Changeover of HgCell to Membrane Cell tech nology in
ChlorAlkaliIndustry,byCentralPollutionControlBoard(CPCB);
10. The effects of Environm ental Regulation on Technology Diffusion: The Case of
Chlorine Manufacturing, by Lori S nyder, Nolan Miller, Robert Stavins, Aug, 2003:
ResourcesForTheFuture;
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Website
1. http://www.adityabirlachemicals.com/products/chlor_alkali/companies_
producing_chlor_alkalis.html
2. http://www.businesswire .com/news/home/20111208005754/en/Research
MarketsIndianChlorAlkaliIndustrycausticsoda#.UrvzyvtgCho
3. http://www.amaindia.org/
4. http://www.greenbuildin gcongress.com/site/superdirectory/suppliers.jsp?
sector=3&supplier=3
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