2 Applied Processes and Techniques

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2APPLIEDPROCESSESANDTECHNIQUES
2.Appliedprocessesandtechniques
Inthischaptertheappliedprocessesandtechniquesarequalitativelydescribed.Chapter3coversthequantitativeaspectsofconsumptionandemission
levels.
Thechemical,thermodynamicandkineticprinciplesarenotexplained.Forthis,referenceismadetoliteraturerelevanttothesubject[Ullmanns,1996]or
[KirkOthmer,1991].
Thechloralkaliindustryproduceschlorineandcausticsolution(sodiumorpotassiumhydroxide)simultaneouslybymeansofdecompositionofasolution
ofsaltinwater.Alongwiththechlorineandthecausticsolution,hydrogenisproduced.Anindustrialchloralkaliproductionunitcomprisesaseriesof
operations,structuredasshowninFigure2.1.
Inthechloralkalielectrolysisprocess,achloridesaltsolutionisdecomposedelectrolyticallybydirectcurrent.Mostofthetimesodiumchlorideisusedin
theprocessinwesternEuropeandlessfrequentlypotassiumchloride(about34%ofthechlorineproductioncapacity).Otherprocessessuchasthe
electrolysisofhydrochloricacidortheelectrolysisofmoltensodiumchlorideareapplied,buttheseonlyaccountforabout3%oftotalchlorineproduction
capacityinEurope.
TheelectrolysisofmoltensodiumsaltswhichisappliedtoobtainsodiumandforwhichchlorineisonlyacoproductisdescribedintheBATReference
documentonnonferrousmetals,assodiumisanalkalimetal.
Therearethreebasicprocessesfortheelectrolyticproductionofchlorine,thenatureofthecathodereactiondependingonthespecificprocess.These
threeprocessesarethediaphragmcellprocess(Griesheimcell,1885),themercurycellprocess(CastnerKellnercell,1892),andthemembranecell
process(1970).Eachprocessrepresentsadifferentmethodofkeepingthechlorineproducedattheanodeseparatefromthecausticsodaandhydrogen
produced,directlyorindirectly,atthecathode[Ullmanns,1996].
Thebasicprincipleintheelectrolysisofasodiumchloridesolutionisthefollowing:
Attheanode,chlorideionsareoxidisedandchlorine(Cl2)isformed.
At the cathode: In the mercury process a sodium/mercury amalgam is formed and hydrogen (H2) and hydroxide ions (OH ) are formed by the
reactionofthesodiumintheamalgamwithwaterinthedenuder.Inmembraneanddiaphragmcells,waterdecomposestoformhydrogen(H2) and
hydroxideions(OH )atthecathode.
Forallprocessesthedissolvingofsalt,sodiumchloride,is:
NaCl
Na++Cl
Theanodereactionforallprocessesis:
2Cl (aq)
Cl2(g)+2e
Thecathodereactionis:
2Na+(aq)+2H2O+2e
H2(g)+2Na+(aq)+2OH (aq)
Theoverallreactionis:
2Na+(aq)+2Cl (aq)+2H2O
2Na+(aq)+2OH (aq)+Cl2(g)+H2(g)
http://www.ineris.fr/ippc/sites/default/interactive/brefca/bref_gb_ptmo.htm
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Figure2.1:Flowdiagramofthethreemainchloralkaliprocesses
basedon[KirkOthmer,1991],[Ullmanns,1996]
ThemaincharacteristicsofthethreeelectrolysisprocessesarepresentedinTable2.1.
Mercury
Diaphragm
Membrane
Causticquality
High,<30ppmNaCl
1.01.5%byweightNaCl
High,<50ppmNaCl
5150gHg/l
(BeforetreatmenttheNaCl
contentisabout18%)
(BeforetreatmenttheHglevel
isbetween2.525mgHg/l)
0.1%NaClO3
Notsuitableforsomeapplications
Caustic
concentration
50%
12%,requiresconcentrationto
50%forsomeapplications
33%,requiresconcentration
to50%forsomeapplications
Chlorinequality
Containslowlevelsofoxygen
(<0.1%)andhydrogen
Oxygencontentbetween
Oxygencontentbetween
0.5%and2%,dependingon
whetheranacidified
electrolyteisused
1.52.5%
Brinefeedstock
Somepurificationrequiredbut
dependsonpurityofsaltor
brineused
Somepurificationrequiredbut
dependsonpurityofsaltorbrine
used
Veryhighpuritybrineis
requiredasimpuritiesaffect
membraneperformance
Variableelectric
loadperformance
Goodvariableelectricityload
performance,downto30%of
fullloadpossibleforsomecell
rooms,whichisveryimportant
insomeEuropeancountries
Toleratesonlyslightvariationin
electricityloadandbrineflowsin
ordertomaintaindiaphragm
performance
Variableelectricityload
performancelessthanfor
mercury(4060%depending
ondesignload),affects
productquality,andefficiency
atlowerloads
Table2.1:Maincharacteristicsofthedifferentelectrolysisprocesses
after[KirkOthmer,1991],[Lindley,1997],[Ullmanns,1996]andothersources
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Figure2.2:Simplifiedschemeofchlorineelectrolysiscells
after[Dutchreport,1998]
2.1Themercurycellprocess
ThemercurycellprocesshasbeeninuseinEuropesince1892andaccountedin1999for58%oftotalproductioninwesternEurope.AsshowninFigure
2.3,themercurycellprocessinvolvestwo"cells".Intheprimaryelectrolyser(orbrinecell),purifiedandsaturatedbrinecontainingapproximately25%
sodiumchlorideflowsthroughanelongatedtroughthatisslightlyinclinedfromthehorizontal.Inthebottomofthistroughashallowfilmofmercury(Hg)
flowsalongthebrinecellcocurrentlywiththebrine.Closelyspacedabovethecathode,ananodeassemblyissuspended.
Electriccurrentflowingthroughthecelldecomposesthebrinepassingthroughthenarrowspacebetweentheelectrodes,liberatingchlorinegas(Cl2)atthe
anodeandmetallicsodium(Na)atthecathode.Thechlorinegasisaccumulatedabovetheanodeassemblyanddischargedtothepurificationprocess.
Asitisliberatedatthesurfaceofthemercurycathode,thesodiumimmediatelyformsanamalgam[KirkOthmer,1991].Theconcentrationofthe
amalgamismaintainedat0.20.4%Na(byweight)sothattheamalgamflowsfreely,0.3%isthereferencefigurein[Gest93/186,1993].Theliquid
amalgamflowsfromtheelectrolyticcelltoaseparatereactor,calledthedecomposerordenuder,whereitreactswithwaterinthepresenceofagraphite
catalysttoformsodiumhydroxideandhydrogengas.Thesodiumfreemercuryisfedbackintotheelectrolyserandreused.
Thereactionintheelectrolyseris:2Na++2Cl +2Hg
Thereactioninthedecomposeris:2NaHg+2H2O
2NaHg+Cl2(g)
2Na++2OH +H2(g)+2Hg
Thebrineanolyteleavingthecellissaturatedwithchlorineandmustbedechlorinatedbeforebeingreturnedtothedissolvers.
Thesodiumhydroxideisproducedfromthedenuderataconcentrationofabout50%themaximumvaluereportedis73%[Ullmanns,1996].However,
industryreportsstatethatnoplantinEuropeisknowntobeoperatingabove50%.
Thedecomposermayberegardedasashortcircuitedelectricalcellinwhichthegraphitecatalystisthecathodeandsodiumamalgamtheanode.
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Foritsoperation,themercurycelldependsuponthehigheroverpotentialofhydrogenversusmercurytoachievethepreferentialreleaseofsodiumrather
thanhydrogen.However,impuritiesthatcanappearonthemercurysurfacemaylackthisovervoltageprotectionandcancauselocalisedreleaseof
hydrogenintothechlorine(hydrogencanformanexplosivemixture(>4%H2)inchlorineorair).Thepresenceofeventraceamountsofcertainmetals,
suchasvanadium,cancausethereleaseofdangerousamountsofhydrogen.
Mercurycellsareusuallyoperatedtomaintaina2122%(byweight)concentrationofsaltinthespentbrinedischargedfromtheelectrolyser.This
correspondstothedecompositionof1516%ofthesaltduringasinglepass.Furthersaltdecompositiontoalowerconcentrationinthebrinewould
decreasebrineconductivity,withtheattendantlossofelectricalefficiency.
Aportion,orinsomecasesall,ofthedepletedbrineissubsequentlydechlorinated,resaturatedwithsolidsalt,andreturnedtothecellbrinefeed.Some
facilitiespurgesmallamountsofbrinesolutionandusenewbrineasmakeupinordertopreventthebuildupofimpurities,mainlysulphate,inthebrine.
Figure2.3showsaflowdiagramofthemercurycell.
Figure2.3:Flowdiagramofmercurycelltechnology
2.1.1Themercurycathodeelectrolyseranddecomposer
Thecellismadeofanelongated,slightlyinclinedtroughandagastightcover.Thetroughismadeofsteel,anditssidesarelinedwithaprotective,non
conductivecoatingtopreventcontactwiththeanolyte,toconfinebrinecathodecontacttothemercurysurface,andtoavoidthecorrosiveactionofthe
electrolyte.Modernelectrolysersare12.5mwideand1025mlong.Asaresult,thecellareatodaycanbegreaterthan30m2.Thesizeofthecellscan
bevariedoverabroadrangetogivethedesiredchlorineproductionrate.Atthedesignstage,computerprogramscanbeusedtooptimisethecellsize,
numberofcells,andoptimumcurrentdensityasafunctionoftheelectricitycostandcapitalcost[Ullmanns,1996].Thesteelbaseismadeassmoothas
possibletoensuremercuryflowinanunbrokenfilm.Intheeventofabreakinthemercurysurface,causticsodawillbeformedonthebare(steel)
cathode,withsimultaneousreleaseofhydrogen,whichwillmixwiththechlorine.Becausehydrogenandchlorinecanformahighlyexplosivemixture,
greatcareisnecessarytopreventhydrogenformationinthecell.
Characteristicsofthecathode:Thecathodeismadebyashallowlayerofmercurywhichflowsfromoneextremityofthecelltotheotherbecauseofthe
slightinclinationfromthehorizontalofthecell.
Characteristicsoftheanode:Electrolyticcellanodesweremadeofgraphiteuntilthelate1960sinwesternEuropewhenanodesoftitaniumcoatedwith
rutheniumoxide(RuO2)andtitaniumoxide(TiO2)weredeveloped.TheuseofRuO2andTiO2coatedmetalanodesreducesenergyconsumptionbyabout
10%andtheirlifeexpectancyishigher.Inrecentyearstherehavebeencompetitivedevelopmentsindetailedanodegeometry,allwiththeaimof
improvinggasreleaseinordertoreduceohmiclossesandincreasethehomogeneityofthebrinetoimproveanodecoatinglife.
An"endbox"isattachedtoeachendoftheelectrolyser.Theendboxincorporatescompartmentsforcollectingthechlorinegasandweirsforseparating
themercuryandbrinestreams,washingthemercuryandpermittingtheremovalofthickmercury"butter"thatisformedbyimpurities.[KirkOthmer,1991]
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Thewholeelectrolyserisinsulatedfromthefloortopreventstraygroundcurrents.Usually,severalelectrolysersareplacedinseriesbymeansof
electricallyconnectingthecathodeofoneelectrolysertotheanodesofthenextelectrolyser.Individualcellscanbebypassedformaintenanceand
replacement.
Theelectrolyserisoperatedatatemperatureofapproximately7080C.Atthistemperature,theconductivityofthebrinesolutionandthefluidityofthe
mercuryarehighercomparedtooperationatambienttemperature.Thetemperaturecanbeachievedbypreheatingthesaturatedbrinewithsteamandis
increasedintheelectrolyserbytheheatofresistance.
Thedecomposeroperatesatatemperatureofapproximately90130C,whichiscausedbythechemicalreactionsinthedecomposerandtheinputof
warmamalgamfromtheelectrolyser.
2.1.2Decompositionoftheamalgam
Theamalgamisdecomposedinhorizontaldecomposers,alongsideorbeneaththecell(Figure2.4)ormoreoften,sinceca.1960,inverticaldecomposers
(ordenuders),atoneendofthecell(Figure2.5).Industrialdecomposersareessentiallyshortcircuitedelectrochemicalprimarycells.Themostcommon
catalystisgraphite,usuallyactivatedbyoxidesofiron,nickelorcobaltorbycarbidesofmolybdenumortungsten.
Figure2.4:Mercurycellswithhorizontaldecomposer
[LeChlore,1996]
Themercuryprocesshastheadvantageoverdiaphragmandmembranecellsthatitproducesachlorinegaswithnearlynooxygen,anda50%caustic
sodasolution.However,mercurycellsoperateatahighervoltagethandiaphragmandmembranecellsand,therefore,usemoreenergy(causticsoda
concentrationexcluded).Theprocessalsorequiresapurebrinesolutionwithlittleornometalcontaminantstoavoidtheriskofexplosionthrough
hydrogengenerationinthecell.Theamalgamprocessinherentlygivesrisetoenvironmentalreleasesofmercury.
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Figure.5:Mercurycellswithverticaldecomposer
[LeChlore,1996]
2.2Thediaphragmcellprocess
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.InNorthAmerica,diaphragmcellsarestilltheprimarytechnology,accountingforroughly70%ofallUSAproduction.Theprocessdiffersfromthe
mercurycellprocessinthatallreactionstakeplacewithinonecellandthecelleffluentcontainsbothsaltandcausticsoda.Adiaphragmisemployedto
separatethechlorineliberatedattheanode,andthehydrogenandcausticsodaproduceddirectlyatthecathode.Withoutthediaphragmtoisolatethem,
the hydrogen and chlorine would spontaneously ignite and the caustic soda and chlorine would react to form sodium hypochlorite (NaClO), with further
reactiontoproducesodiumchlorate(NaClO3)[KirkOthmer,1991].
Thediaphragmisusuallymadeofasbestosandseparatesthefeedbrine(anolyte)fromthecausticcontaining catholyte. Purified brine enters the anode
compartmentandpercolatesthroughthediaphragmintothecathodechamber.Thepercolationrateiscontrolledbymaintainingahigherliquidlevelinthe
anodecompartmenttoestablishapositiveandcarefullycontrolledhydrostatichead.Thepercolationrate 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
migrationofhydroxylionsfromcatholytetoanolyte,whichdecreasescathodecurrentefficiency[KirkOthmer,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
raisestheoperatingtemperatureoftheelectrolyteto8099C.
When graphite anodes were used, the diaphragm became inoperable after 90100 days due to plugging of the diaphragm by particles of graphite.
Nowadays, all plants in the European Union use metal anodes and the lifetime of the diaphragm is over one year. Their service life has also increased
because their compositions have changed. At the beginning the diaphragms were made of asbestos only and were rapidly clogged by calcium and
magnesium ions coming from the brine. Asbestos was chosen because of its good chemical stability and because it is a relatively inexpensive and
abundantmaterial.Beginningintheearly1970s,asbestosdiaphragmsbegantobereplacedbydiaphragmscontaining75%asbestosand25%offibrous
fluorocarbon polymer of high chemical resistance. These diaphragms, trade named Modified Diaphragms, are more stable. The polymer stabilises the
asbestos,whichinitselflowerscellvoltageandalsoallowsfortheuseoftheexpandableanode[LeChlore,1995][Ullmanns,1996].Chrysotileasbestos
("whiteasbestos")istheonlyformofasbestosusedindiaphragmcells.
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Figure2.6:Typicaldiaphragmelectrolysiscell
[USEPA,1995]
Both diaphragm and membrane cells for the production of chlorine and sodium hydroxide are classified as either monopolar or bipolar. The designation
does not refer to the electrochemical reactions that take place, which of course require two poles or electrodes for all cells, but to the electrolyser
constructionorassembly.Therearemanymorechloralkaliproductionfacilitieswithmonopolarcellsthanwithbipolarcells.Themonopolarelectrolyseris
assembledsothattheanodesandcathodesarearrangedinparallel.Asaresultofthisconfiguration,allcellshavethesamevoltageofaboutthreetofour
voltsupto200cellscanbeconstructedinonecircuit.Bipolarelectrolysershaveunitassembliesoftheanodeofonecellunitdirectlyconnectedtothe
cathodeofthenextcellunit,thusminimisingintercellvoltageloss.Theseunitsareassembledinseries.
Alldiaphragmcellsproducecellliquorthatcontainsca.11%causticsodaand18%sodiumchloride.Thissolutionisevaporatedto50%NaOHbyweight
atwhichpointallofthesalt,exceptaresidual1.01.5%byweight,precipitatesout.Thesaltgenerated 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. A flow diagram of a possible
integratedsiteisshowninFigure2.7onpage*.
Low concentrations of oxygen in chlorine are formed by electrolytic decomposition of water and hypochlorous acid (from the reaction of chlorine with
water).
Precipitationofmagnesiumandcalciumhydroxidesonthecatholytesideofthediaphragmmayalsocreateblockingproblems.Hydrochloricacidisoften
added to the brine to remove CO2 it may also be added to the brine entering the anode compartment to reduce backmigration of hydroxyl ions and to
suppressformationofhypochlorousacid.
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Figure2.7:Flowdiagramofintegrationofmembraneormercuryanddiaphragmprocesses
Diaphragmcellshavetheadvantageof:
operatingatalowervoltagethanmercurycells
operatingwithlesspurebrinethanrequiredbymembranecells
Whenusingasbestosdiaphragms,thediaphragmprocessinherentlygivesrisetoenvironmentalreleasesofasbestos.
2.2.1Diaphragmwithoutasbestos
Duetothepotentialexposureofemployeestoasbestosandemissionsintheenvironment,effortsarebeingexpandedtoreplacetheasbestoswithother
diaphragmmaterials.
Developmentofnonasbestosdiaphragmsstartedinthemiddleofthe1980sandsomecompanieshavenowsucceededinoperatingwiththem.Thebasis
ofthematerialusedisthesameinalldiaphragmsdevelopedfreeofasbestos,i.e.afluorocarbonpolymer,mainlyPTFE(polytetrafluoroethylene).The
differenceslieinthefillersusedandthewaythehydrophobicPTFEfibresaretreatedanddepositedinordertoformapermeableandhydrophilic
diaphragm(seeSection4.3.2.).
2.2.2Activatedcathodes
Manydifferenttypesofactivatedcathodiccoatingareunderdevelopmentinordertoreducethepowerconsumptionofthecell.Thesehavetoberobust
becausethepowerfulwaterjetusedtoremovethediaphragmfromthecathodemeshcanadverselyaffectthecathode.
An industrial application of "integrated precathode" diaphragm has been conducted (full scale) and has been found to contribute to saving energy by
reducingelectricpowerconsumptionandimprovingcurrentefficiency.Thelifetimeofthediaphragmhasalsobeenfoundtobeimprovedbyintroductionof
theprecathode.
2.3Themembranecellprocess
Inthe1970s,thedevelopmentofionexchangemembranesenabledanewtechnologytoproducechlorine:themembraneelectrolysisprocess.Thefirst
ionexchangemembranesweredevelopedatthebeginningofthe1970sbyDuPont(Nafion),followedbyAsahiGlass(Flemion)whichinstalledthefirst
industrialmembraneplantinJapanin1975duetothepressureofJapaneseenvironmentalregulations.Nonchloralkalirelatedmercurypollutionin
MinamatadrovetheauthoritiestoprohibitallmercuryprocessesandJapanwasthefirstcountrytoinstallthemembraneprocessonamassivescalein
themid1980s.
Today,itisthemostpromisingandfastdevelopingtechniquefortheproductionofchloralkalianditwillundoubtedlyreplacetheothertwotechniquesin
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time.Thiscanbededucedfromthefactthatsince1987practically100%ofthenewchloralkaliplantsworldwideapplythemembraneprocess.The
replacementofexistingmercuryanddiaphragmcellcapacitywithmembranecellsistakingplaceatamuchslowerratebecauseofthelonglifetimeofthe
formerandbecauseofthehighcapitalcostsofreplacement.
Inthisprocess,theanodeandcathodeareseparatedbyawaterimpermeableionconductingmembrane.Brinesolutionflowsthroughtheanode
compartmentwherechlorideionsareoxidisedtochlorinegas.Thesodiumionsmigratethroughthemembranetothecathodecompartmentwhichcontains
flowingcausticsodasolution.Thedemineralizedwateraddedtothecatholytecircuitishydrolysed,releasinghydrogengasandhydroxideions.The
sodiumandhydroxideionscombinetoproducecausticsodawhichistypicallybroughttoaconcentrationof3235%byrecirculatingthesolutionbeforeit
isdischargedfromthecell.Themembranepreventsthemigrationofchlorideionsfromtheanodecompartmenttothecathodecompartmenttherefore,the
causticsodasolutionproduceddoesnotcontainsaltasinthediaphragmcellprocess.Depletedbrineisdischargedfromtheanodecompartmentand
resaturatedwithsalt.Ifneeded,toreachaconcentrationof50%causticsoda,thecausticliquorproducedhastobeconcentratedbyevaporation(using
steam).
Thecathodematerialusedinmembranecellsiseitherstainlesssteelornickel.Thecathodesareoftencoatedwithacatalystthatismorestablethanthe
substrateandthatincreasessurfaceareaandreducesovervoltage.CoatingmaterialsincludeNiS,NiAl,andNiNiOmixtures,aswellasmixturesof
nickelandplatinumgroupmetals.Theanodesusedaremetal.
Themembranesusedinthechloralkaliindustryarecommonlymadeofperfluorinatedpolymers.Themembranesmayhavefromoneuptothreelayers,
butgenerallyconsistoftwolayers.Oneoftheselayersconsistsofperfluorinatedpolymerwithsubstitutedcarboxylicgroupsandisadjacenttothe
cathodicside.Theotherlayerconsistsofperfluorinatedpolymerwithsubstitutedsulphonicgroupsandisadjacenttotheanodicside.Togivethe
membranemechanicalstrength,themembraneisgenerallyreinforcedwithPTFEfibres.Themembranesmustremainstablewhilebeingexposedto
chlorineononesideandastrongcausticsolutionontheother.Thegeneraleconomiclifetimeofchloralkalimembranesisapproximatelythreeyears,but
rangesbetween25years[EuroChlorreport,1997].
Membranecellshavetheadvantageofproducingaverypurecausticsodasolutionandofusinglesselectricitythantheotherprocesses.Inaddition,the
membraneprocessdoesnotusehighlytoxicmaterialssuchasmercuryandasbestos.Disadvantagesofthemembraneprocessarethatthecausticsoda
producedmayneedtobeevaporatedtoincreaseconcentrationand,forsomeapplications,thechlorinegasproducedneedstobeprocessedtoremove
oxygen.Furthermore,thebrineenteringamembranecellmustbeofaveryhighpurity,whichoftenrequirescostlyadditionalpurificationstepspriorto
electrolysis(seeparagraphonbrinepurification).
Figure2.8:Diagramofamembraneprocess
Membranescellscanbeconfiguredeitherasmonopolarorbipolar.Asinthecaseofthediaphragmcellprocess,thebipolarcellshavelessvoltageloss
betweenthecellsthanthemonopolarcells.However,thenumberofcellsconnectedtogetherinthesamecircuitislimited.
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Figure2.9:Explodedviewofamonopolarmembraneelectrolyser
[Source:DeNora]
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Figure2.10:Viewofamembranecellroomequippedwithbipolarelectrolysers
(Source:HoechstUhde)
2.4Auxiliaryprocesses
Apart from the cells, which remain the heart of the chlorine production line, there are other processing steps or equipment, common to amalgam,
diaphragmandmembranetechnologies.Theseare:
saltunloadingandstorage
brinepurificationandresaturation
chlorineprocessing
causticprocessing
hydrogenprocessing.
2.4.1Saltunloadingandstorage
Thebrineusedinthemercurycellandmembraneprocessesisnormallysaturatedwithsolidsalt,althoughsomeinstallationsusesolutionminedbrineon
aoncethroughbasis(i.e.nobrinerecirculation).
Brineisgenerallyproducedbythedissolvingoffreshsaltinwaterordepletedbrinefrommercuryandmembraneprocesses.Thebasicrawmaterialis
usuallysolidsalt:rocksalt,solarsalt,orvacuumevaporatedsaltfrompurifyingandevaporatingsolutionminedbrine.
Generallythesaltisstoredinasealedareaequippedwitharoof.Becauseofitshighpuritythevacuumsaltinparticularneedstobeprotected.
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2.4.2Brinepurificationandresaturation
2.4.2.1Brinepurification
As can be seen in Figure 2.1 on page 10, the brine purification process consists of a primary system for mercury and diaphragm technologies and an
additional secondary system for membrane technology. This operation is needed to avoid any undesirable components (sulphate anions, cations of Ca,
Mg, Ba and metals) that can affect the electrolytic process. The quality of the raw material and the brine quality requirements for each of the three
technologiesdeterminethecomplexityofthebrinetreatmentunit.
Primarypurification
Precipitation
The initial stage of purification uses sodium carbonate and sodium hydroxide to precipitate calcium and magnesium ions as calcium carbonate (CaCO3)
and magnesium hydroxide (Mg(OH)2). Metals (iron, titanium, molybdenum, nickel, chromium, vanadium, tungsten) may also precipitate as hydroxide
duringthisoperation.Theusualwaytoavoidmetalsistospecifytheirexclusioninthepurchaseandtransportspecificationforthesalt.Sodiumsulphate
iscontrolledbyaddingcalciumchloride(CaCl2)orbariumsaltstoremovesulphateanionsbyprecipitationofcalciumsulphate(CaSO4)orbariumsulphate
(BaSO4).Precipitationofbariumsulphatecantakeplacesimultaneouslywith the precipitation of calcium carbonate and magnesium hydroxide, whereas
theprecipitationofcalciumsulphaterequiresaseparatevessel.
Filtration
Theprecipitatedimpuritiesareremovedbysedimentation,filtrationoracombinationofboth.Theseparatedfiltercakeisgenerallyconcentratedto5060%
(althoughafigureof6080%isreportedintheliterature)solidscontentinrotarydrumvacuumfiltersorcentrifugesbeforedisposal.[Ullmanns,1996]
Thepurifiedbrineshouldcontainideally[Ullmanns,1996]:
Ca:<2mg/l
Mg:<1mg/l
SO4:<5g/l
Secondarypurification:Membranecircuit
Tomaintainthehighperformanceoftheionexchangemembrane,thefeedbrinemustbepurifiedtoagreaterdegreethanintheconventionalmercuryor
diaphragmprocesses.
The precipitation step alone is not enough to reduce the levels of calcium and magnesium and additional softening is required. Figure 2.11 shows a
possiblelayoutforthebrinepurificationsystemusedinthemembraneprocess.
Figure2.11:Possiblelayoutforthebrinepurificationsystemusedinmembraneprocess
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(Source:AsahiGlassCO)
Thesecondarybrinepurificationconsistsofapolishfiltrationstepandbrinesofteninginanionexchangeunit:
Thesecondaryfiltrationgenerallyconsistsofcandletype,plateframeorpressureleaffilters(eitherwithorwithoutcellulosebasedprecoat)inorder
tosufficientlyreducethesuspensionmatterandprotecttheionexchangeresinfromdamage.
Theionexchangechelatingresintreatmentisdesignedtodecreasethealkalineearthmetalstoppblevel.Table2.2indicatesthespecifications
requiredformetals,SO4andotherimpurities.Thesespecificationscanvaryiftheuserswanttooperateatalowcurrentdensity(<4kA/m2)orata
highcurrentdensity.Thespecificationsaremorestringentforhighdensitycurrent.
Theresinisperiodicallyregeneratedwithhighpurityhydrochloricacidandsodiumhydroxidesolutions.Generally,oneresinexchangecolumnisin
operationwhileanotherresinexchangecolumnisregenerated.
Achelatingresintowermustbeinstalled,butinsomecasesnopolishingfilterisneededinthesecondarybrinetreatment.
GeneralTable
Unit
UpperLimit
Ca+Mg
Impurities
ppb
20
Sr
ppm
0.04
Condition
Influence
Ca:CE,Mg:V
(SiO2 =10ppm)
CE
Remarks
SrandSiO2 seemtobecoprecipitatedwithinthe
membrane.(synergisticeffect)
0.04ppminSrcontentinpurifiedbrineiseasilykept
undernormaloperationofChelatingResinTower.
IfSiO2 contentiskeptlessthan1ppm,thenSris
allowableupto0.1ppm.
SiO2
ppm
10
Ba
ppm
0.5
(Iodine=0.2)
CE,(V)
0.05
(Iodine=0.5)
ppm
0.5
(Ba=0.05)
CE
0.2
(Ba=0.5)
Iodine
CE
BaandIodineseemtobecoprecipitatedwithinthe
membrane.(synergeticeffect)
WhenSO4 contentiskept6g/l,Bacontentshouldbe
0.05ppmorless.
Iodineoriginatesfromundergroundsaltandwater.If
solarsaltandordinarysurfacewaterareused,
Iodinecontentshouldbe0.1ppmorless.
Fe
ppm
Ni
ppm
0.01
Heavy
Metals
ppm
0.1
Al
ppm
0.1
CE,(V)
SO4
g/l
CE
Weareevaluatingtoraisetheupperlimitto8g/l.
ClO3
g/l
20
CE
AdditionalTableforPlantstobeoperatedwithcare
Unit
UpperLimit
Mn
Impurities
ppm
0.1
Condition
Influence
Remarks
Thelimitis0.05ppminsomeplantsduetocausticuser
needs.
Cr
ppm
Mainlyduetocausticuserneeds
Cu
ppm
0.01
Mainlyduetocausticuserneeds
Hg
ppm
10
Mainlyduetocausticuserneedsandriskofcathode
damage
ppm
0.5
SS
ppm
SuspendedSolid
TOC
ppm
TotalOrganicCarbon
CE:CurrentEfficiencyshoulddecrease
V:Cellvoltageshouldincrease
Table2.2:Exampleofbrinespecificationsforthemembraneprocessoperatingatacurrentdensityupto4kA/m 2
(Source:AsahiGlassCo)
Controlofnitrogentrichloride(NCl3)
Apart from sulphates and hardness ions, the brine may contain ammonium ions or organic nitrogen which are converted to nitrogen trichloride in the
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electrolyticcell.Ifconcentratedinliquidformindownstreamprocesses,NCl3mayexplodewithdisastrousresults.
NitrogencompoundsinthebrineisthemainsourceofNCl3.Rocksalt,inparticularsolutionminedsaltusingsurfacewaters,willcontainvaryinglevelsof
ammoniumandnitratesalts,whereastheuseofvacuumsaltinthebrinerecyclecircuitwillgiveverylowlevelsofNCl3,exceptwhereferrocyanidesare
addedtoavoidcaking.Also,thewaterqualitymayvary,inparticularifsurfacewaterisused.Thetotalconcentrationofnitrogencompoundsinthebrine
shouldbecheckedregularly.ChlorinationatapHhigherthan8.5orhypochloritetreatmentofthebrineishowever,capableofdestroyingalargeproportion
oftheammoniumsaltimpurity.[Gest76/55,1990]
MethodstoremoveNCl3fromchlorineafteritisformedaredescribedinSection4.1.6.
Figure2.12:Viewofchelateresintowersinasecondarybrinepurificationsystem
(photographsuppliedbyAsahiGlassCo)
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Figure2.13:Viewofpolishingfiltersinasecondarybrinepurificationsystem
(photographsuppliedbyAsahiGlassCo)
2.4.2.2Brineresaturationanddechlorination
Mercuryandmembranesystemsusuallyoperatewithbrinerecirculationandresaturation.Thereare,however,3wastebrinemercuryplantsand1waste
brinemembraneplantoperatinginwesternEurope.
Somediaphragmcelllineshaveaoncethroughbrinecircuit,whilstothersemploybrinesaturationusingthesaltrecoveredfromthecausticevaporators.
Inrecirculationcircuits,thedepletedbrineleavingtheelectrolysersisfirstdechlorinated:
Partiallyforthemercuryprocess(leavingactivechlorineinthebrinekeepsthemercuryinionicformandreducesthepresenceofmetallicmercury
inthepurificationsludge)
Totallyforthemembraneprocess(necessaryherebecausetheactivechlorinecandamagetheionexchangeresinsofthesecondarybrine
purificationunit).
Forthispurpose,thebrineissenttoanairblownpackedcolumnorissprayedintoavacuumsystemtoextractthemajorpartofthedissolvedchlorine.
Nosuchdechlorinationtreatmentisrequiredforthediaphragmsystemsinceanychlorinepassingthroughthediaphragmreactswithcausticsodainthe
catholytecompartmenttoformhypochloriteorchlorate.
Forthemembrane process, there is a preliminary stage of hydrochloric acid addition (to reach pH 22.5) in order to achieve better chlorine extraction. A
furtherstageisalsonecessarytoeliminatethechlorinecompletelythisisdonebypassingthebrinethroughanactivatedcarbonbedorbyinjectionofa
reducingagent(e.g.sulphite).
Ifthesaturationismadewithimpuresalt(followedbyaprimarypurificationsteponthetotalbrineflow),thepHofthebrineisthenbroughttoanalkaline
valuewithcausticsoda,toreducethesolubilisationofimpuritiesfromthesalt.Ifthesaturationismadewithpuresalt(withsubsequentprimarypurification
onasmallpartoftheflow),thereisnoalkalisationstepatthatlevel(onlyinthepurificationphase).
Depletedbrinefromthemercuryandmembranecells,withaconcentrationof210250g/l,dependingonthetechnology,currentdensityandheatbalance
ofthecell,isresaturatedbycontactwithsolidsalttoachieveasaturatedbrineconcentrationof310315g/l.
Inthecaseofdiaphragmcells,thecatholyteliquor(1012%NaOH,15%NaCl)goesdirectlytothecausticevaporatorswheresolidsaltand50%caustic
arerecoveredtogether.Freshbrinecanbesaturatedwithrecycledsolidsaltfromthecausticevaporatorsbeforeenteringthediaphragmelectrolysers.
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Resaturatorscanbeeitheropenorclosedvessels.
ThepHofthebrinesenttotheelectrolysersmaybeadjustedtoanacidicvalue(pH4)withhydrochloricacidinordertoprotecttheanodecoating,tokeep
the formation of chlorate at a low level and to decrease the oxygen content in the chlorine gas. Hydrochloric acid can also be added in the anodic
compartments of membrane cells to further reduce the content of oxygen in the chlorine, especially for electrolysers with older membranes (poorer
performances)The(bi)carbonatesintroducedwiththesaltaredecomposedbytheseacidadditions,producinggaseouscarbondioxide.
2.4.3Chlorineproduction,storageandhandling
Generally, before the chlorine can be used, it goes through a series of processes for cooling, cleaning, drying, compression and liquefaction. In some
applications,itcanbeusedasadrygaswithoutneedforliquefaction.Veryoccasionallyitcanbeuseddirectlyfromtheelectrolysers.Ageneralflowof
chlorinefromtheelectrolyserstostorageispresentedinFigure2.14.
Figure2.14:Theflowofchlorinefromtheelectrolyserstostorage
[EuroChlorreport,1997]
Thechlorineprocessusuallytakeshot,wetcellgasandconvertsittoacold,drygas.Chlorinegasleavingtheelectrolysersisatapproximately8090C
andsaturatedwithwatervapour.Italsocontainsbrinemist,impuritiessuchasN2,H2,O2,CO2andtracesofchlorinatedhydrocarbons.Electrolysers are
operatedatessentiallyatmosphericpressurewithonlyafewmilliatmospheresdifferentialpressurebetweentheanolyteandthecatholyte.
Cooling
Intheprimarycoolingprocess,thetotalvolumeofgastobehandledisreducedandalargeamountofmoistureiscondensed.Coolingisaccomplishedin
either one stage with chilled water or in two stages with chilled water only in the second stage. Care is taken to avoid excessive cooling because, at
around 10 C, chlorine can combine with water to form a solid material known as chlorine hydrate. Maintaining temperatures above 10 C prevents
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blockagesinprocessequipment.
Twomethodsaremostfrequentlyusedtocoolchlorinegas:
1. Indirectcoolingthroughatitaniumsurface(usuallyinasinglepassverticalshellandtubeexchanger).Theresultantcondensateiseitherfedback
intothebrinesystemofthemercuryprocessordechlorinatedbyevaporationinthecaseofthediaphragmprocess.Thismethodcausesless
chlorinetobecondensedorabsorbedandgenerateslesschlorinesaturatedwaterfordisposal.[BrienWhite,1995]
2. Directcontactwithwater.Thechlorinegasiscooledbypassingitdirectlyintothebottomofatowerinwhichthepackingisdividedintotwo
Sections,for2stagecooling.Waterissprayedintothetopandflowscountercurrenttothechlorine.Thecoolingwatershouldbefreeoftracesof
ammoniumsaltstoavoidtheformationofnitrogentrichloride.Thismethodhastheadvantageofbettermasstransfercharacteristicsandhigher
thermalefficiency.
Closedcircuitdirectcoolingofchlorinecombinestheadvantagesofthetwomethods.Thechlorineladenwaterfromthecoolingtoweriscooledintitanium
platecoolersandrecycled.Thesurpluscondensateistreatedexactlylikethecondensatefromindirectcooling.
Followingprimarycooling,chlorinegasisdemistedofwaterdropletsandbrineimpurities.Impuritiesareremovedmechanicallybyusingspecialfilters,or
bymeansofanelectrostaticprecipitator.Chlorineisthenpassedtothedryingtowers.
Drying
Chlorinefromthecoolingsystemismoreorlesssaturatedwithwatervapour.Thewatercontentistypically13%.Thismustbereducedinordertoavoid
downstreamcorrosionandminimisetheformationofhydrates[BrienWhite,1995].
Dryingofchlorineiscarriedoutalmostexclusivelywithconcentratedsulphuricacid[Ullmanns,1996].Dryingisaccomplishedincountercurrentsulphuric
acidcontacttowerswhichreducethemoisturecontenttolessthan20ppm[Stenhammar].Drychlorineleavingthetopofthedryingtowerpassesthrough
highefficiencydemisterstopreventtheentrainmentofsulphuricaciddroplets.Thespentacidusuallybecomesawasteproductorrequiresreprocessingif
itisreused.Forexample,ithastobedechlorinatedbyairblowingandmaybereconcentratedbeforebeingsoldorusedforeffluenttreatment.
Compression
Afterdrying,chlorinegasmightbescrubbedwithliquidchlorineortreatedwithultravioletirradiationtoreducelevelsofnitrogentrichlorideandthenitmay
becompressedinavarietyofcompressors:
sulphuricacidliquidringcompressorsatlowpressures(~4bar)
monoormultistagecentrifugalcompressors(5barorhigher)
reciprocatingcompressors(>11bar)
screwcompressors(variouspressures)
Because of heat buildup from compression, multistage units with coolers between stages are usually necessary. Compressor seals are generally fitted
withapressurisedpurgetoinhibitleakageofchlorinetotheatmosphere[UKGuidancenote,1993].
Toavoidnoise,whichisquiteimportantevenforlowpressures,chlorinecompressorsshouldbesoundinsulated.
Liquefaction
Liquefaction can be accomplished at different pressure and temperature levels, at ambient temperature and high pressure (for example 18 C and 712
bar),atlowtemperatureandlowpressure(forexample35Cand1bar)oranyotherintermediatecombinationoftemperatureandpressure.
Thechosenliquefactionpressureandtemperatureinfluencethechoiceofcoolingmediaandthesafetyprecautionsnecessarytooperatesafely.However,
theefficiencyofliquefactionislimitedbecausehydrogenisconcentratedintheresidualgas and its concentration needs to be kept below the explosive
limits.
Thechoiceofthecoolingmediuminacertainstageoftheliquefactiondependsonthetemperature of the chlorine. When the temperature is sufficiently
high, water can be used as an indirect cooling medium. When the temperature is relatively low, other cooling media such as HCFCs or HFCs (indirect
cooling),ammonia(indirectcooling)orliquidchlorine(directcooling)areused.
Thetemperatureofthechlorinegasinacertainstagedependsmainlyontheinitialtemperatureandonthepressureincreaseduringcompression.Alarge
pressureincreasegenerallyenableswatercooling,butimpliesanincreasedhazardrisk.Chlorinetemperaturehastobekeptwellbelowthepointwhereit
reactsspontaneouslyanduncontrollablywithiron(approx.120oC).
Constructionmaterialsmustbechosentosuittheconditionsunderwhichchlorineisbeinghandled:
Wetordry
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Gasorliquid
Temperature
Pressure
In terms of safety, it is very important to avoid, during compression and liquefaction, any possibility of mixing chlorine with oils or greases which are
reactiveasregardschlorine.
Table2.3showsthepossibletradeoffbetweendifferenttypesofchlorinegasliquefaction,coolingmethodsappliedandsafetyaspects.
Cooling
medium
Liquefactionsystem
Safetyaspect
Storage
Highpressure(716bar)
andhightemperatures
Water
Highprecautions
Mediumpressure(26
bar)andmedium
temperatures(between
10and20C)
WaterHCFC/
HFCor
ammonia
Moderate
precautions
Normalpressure(~1
bar)andlow
temperatures(below40
C)
Mainly
HCFC/HFCor
ammonia
Precautions1
Lowestenergycostsbut
highmaterialcosts
Moderateenergyand
materialcosts
Cryogenicstorageof
liquidchlorineispossible.
Highenergyandlower
materialcosts
1.Attentionmustbepaidtotheincreasedsolubilityofothergasesatlowtemperatures,especiallycarbondioxide
Table2.3:Possibletradeoffinchlorinegasliquefaction
basedon[Ullmanns,1996],[Dutchreport,1998]
Handlingandstorage
Chlorineisliquefiedandstoredatambientorlowtemperature.Theliquidchlorinefromthebulktankcanbeusedasafeedstockforonsiteprocessesor
loadedintocontainers,roadorrailtankers.Becauseofthehightoxicityofchlorine,thestorageareamustbecarefullymonitoredandspecialcaremustbe
takenduringloadingoperations.
2.4.3.1Dealingwithimpurities
Chlorinegasfromtheelectrolysiscellsmaycontainimpuritiessuchasnitrogentrichloride(NCl3),bromine(Br2),halogenatedhydrocarbons(CXHYXZ),
carbondioxide(CO2),oxygen(O2),nitrogen(N2)andhydrogen(H2).
Nitrogentrichloride,bromineandhalogenatedhydrocarbonspredominantlydissolveintheliquidchlorine,whereasthenoncondensablegases(CO2,O2,
N2,H2)remaininthegasphaseandincreaseinconcentrationduringchlorineliquefaction.Tracesofsulphuricacid,ferricsulphate,ferricchlorideand/or
carbontetrachloridemightalsobepresentinthegasphaseafterdryingandliquefactionofchlorine.
Specialattentionshouldbepaidtothefollowingimpurities:
Water
Allmetalsareattackedbywetchlorinewiththeexceptionoftitaniumandtantalum.Titaniumcanonlybeusedinwetchlorineconditionsitspontaneously
combustsindrychlorine.
Hydrogen
Allthreetechnologiesproducehydrogenwhichcanformanexplosivemixture(>4%H2)inchlorineorair.Light,frictionandgasdepressurisationmaybring
enoughenergytoinitiatethereactionatambienttemperature.Chlorinegasisanalysedregularlytoensuretheabsenceofanexplosivemixture.
Nitrogentrichloride
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Nitrogentrichlorideisformedduringtheelectrolyticproductionofchlorine,duetosidereactionsbetweenthechlorineandvariousnitrogencompoundsin
thebrinesolution.1ppmofNH3inbrineisenoughtogive>50ppmNCl3inliquidchlorine.Inplantswhichusedirectcontactwatercoolingofthechlorine
gasbeforedryingandcompression,NCl3mayalsobeformedifthewaterispollutedwithnitrogencompounds[Gest76/55,1990].
Nitrogentrichlorideischaracterisedbyitsutmostinstability.ExperimentalresultsshowthataconcentrationofNCl3greaterthan3%byweightatambient
temperatureiscapableofaccelerateddecompositionwhichisstronglyexothermic.
NCl3hasahigherboilingpointthanchlorineandanyNCl3presentinthechlorinegaswillconcentrateintheliquidphaseinachlorineliquefactionprocess.
AnyevaporativehandlingofliquidchlorineispotentiallydangerousduetotheselectiveconcentrationofNCl3intheliquidphase.
MethodstoremoveNCl3fromchlorinearedescribedinSection4.1.6.
Bromine
Thequantityofbrominepresentdependsonthequalityofthesaltused.Itsconcentrationisgenerallyhigherifchlorineisobtainedbyelectrolysing
potassiumchloridetoobtainpotassiumhydroxide.Bromine,likewater,canacceleratethecorrosionofthematerials.
Noncondensablegases(CO2,O2,N2,H2)
Thereareseveralwaystodealwiththenoncondensablegases,dependingonthelayoutofthechlorineliquefactionunit.Somearedescribedbelow.
DilutionwithairandproductionofweakNaOCl
Duringchlorinegascompressionandcooling,mostofthechlorinegasiscondensed.However,thenoncondensablegases(H2,CO2,O2,N2)increasein
concentration.Bydilutingtheremainingchlorinegaswithair,theconcentrationofhydrogencanbekeptbelowtheexplosionlimit.Thisallowsadditional
liquefactionofchlorinegas.Theremaininggasesafterliquefaction(socalled"tailgas")havetobepurgedfromthesystem.Thetailgasstillcontainsa
significantamountofchlorine,andthegasisthereforenormallyledtothechlorinedestruction/absorptionunit.
Productionofhydrochloricacid
Insteadofdilutingtheremaininggasesafterpartialcondensationofthechlorinegas,thehydrogencanberemovedfromthesystembymeansofa
reactionwithchlorinegasinacolumn.Thisremovesvirtuallyallthehydrogenandyieldsgaseoushydrochloricacid,whichexistsharmlesslywiththe
chlorinegasandcanberecoveredinahydrochloricacidunit.Theremainingchlorinegascannowsafelybefurthercondensed.Thetailgaseswithsome
chlorinegasandtheremainingnoncondensablegases(CO2,N2,O2)willbepassedthroughahydrochloricacidunit.ThissolutioncanbechosenifHClis
asaleableproductorifitcanbeusedasafeedstockfordownstreamproduction,suchasferricchloride.
2.4.3.2Thechlorineabsorptionunit
Thepurposeofatypicalchlorineabsorptionsystemistwofold:
1. Tocontinuouslyabsorbchlorinegasarisinginstreamssuchastailgasfromliquefaction,airblownfromwastebrineorchlorinecondensate
dechlorinationandalsowetanddrymaintenanceheaders.Upto5%,butnormallylessthan1%,oftheplantproductionisabsorbedinthisway.
2. Toabsorbthefullcellroomproductionduringemergencyforanadequateperiod,usuallynotlessthan15to30minutes,toenablecorrective
measurestobetakenortheplanttobeshutdowninasafemanner.Gravityfedheadtanksorpumpssuppliedwithbackuppowersuppliesmaybe
usedtogiveincreasedreliabilityandoperationunderpowerfailureconditions.
Theabovefunctionscouldbeundertakeninseparatepurposebuiltunits,providingtheintegrityofthesystemsismaintainedbyhavingbackupscrubbers.
All gaseous vents contaminated or potentially contaminated with chlorine thus pass into the atmosphere through caustic scrubbing towers containing
packingirrigatedwithcausticsoda.Heatisgeneratedbytheabsorptionreactionandtemperaturesshouldnotbeallowedtoincreaseaboveabout30Cto
avoid formation of sodium chlorate instead of sodium hypochlorite solution. To avoid overheating during a fullscale relief, the fresh caustic soda feed
solutionshouldnotbestrongerthanabout12%byweight.Highercausticconcentrationscanbeusedprovidingadequatecoolingisinstalled,butthereis
anincreasedriskofsolidsdepositionandblockage.
Tailgasfromthechlorineliquefactionunitcontainsresidualchlorineandcarbondioxide,whichareabsorbedinthecaustic,andhydrogen,whichisdiluted
withairtolessthan4%byvolumetoavoidflammablemixtures.
Optimum design of scrubbing systems must include high reliability, automatic operation in emergencies, and countercurrent flow of liquid and gas to
achievelowexitconcentrations.Ifsaleisnotpossible,efficientdecompositionofthesodiumhypochloriteproducedintosodiumchloridecanbeachieved
usinganickelcatalyst.
2.4.4Causticproduction,storageandhandling
Sodiumhydroxide(causticsoda)isproducedinafixedratioof1.128tonnes(as100%NaOH)pertonnechlorineproduced.
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Figure2.15:Viewofcausticproductionandstorage
[OxyChem,1992]
Thecausticsodasolutionfromthethreetechnologiesistreatedinslightlydifferentwaysduetothedifferenceincompositionandconcentration.
Inthemercurycellprocess,50%causticsodaisobtaineddirectlyfromthedecomposers.Thecausticsodaisnormallypumpedthroughacooler,then
throughamercuryremovalsystemandthentotheintermediateandfinalstoragesections.Insomecasesthecausticisheatedbeforefiltration.Themost
commonmethodforremovalofmercuryfromcausticsodaisaplate(orleaf)filterwithcarbonprecoat.Undernormaloperatingconditions,mercurycell
causticsoda(as100%NaOH)contains20100ppmofsodiumchlorideand4060
gHg/kgNaOH.
Inthecaseofdiaphragmandmembranetechnologiesthecausticsodaisconcentratedbyevaporationbeforefinalstorage.
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Figure.16:Theflowtostorageofcausticsodafromthedifferenttechnologies
Basedon[OxyChem,1992]
Steamisusedasthesourceofevaporativeenergy.Thepresenceofsaltinthediaphragmcellliquorrequiresthattheevaporatorisequippedwithscraper
bladesorotherdevicestodrawofftheprecipitatedsalt.Thishighqualitysodiumchloridecanthenbeusedtoenrichdepletedbrine,sometimesitisused
asarawmaterialforanamalgamormembraneprocess.Theresiduallevelofsodiumchlorideinsodiumhydroxidefromdiaphragmcellisabout1%and
sodiumchlorate0.1%.Forthisreason,itisunsuitableforcertainendapplicationssuchasthemanufactureofrayon.
Saltandsodiumchlorateinthecausticsodafromdiaphragmcellscanbereducedbyammoniaextractiontoincreasemarketability,butatincreasedcost.
Thecausticsodafrommembranecellsisofhighquality,althoughthecausticsodaproduced(usuallyaround33%NaOH)needsconcentrationto50%
NaOHforsomeapplications.Thesaltcontentofthemembranecellcausticsodaliesbetween20100ppm(in100%NaOH),butisonaverageslightly
higherthanmercurycellcaustic(seeTable2.1).
Insomeplantsthecausticsodaisfurtherconcentratedtoa73%solutionandto100%assolidcausticprillsorflakes.
Somechloralkaliproductionfacilitiescancombinethecausticproductionprocessfrommercuryandmembranecellsinordertominimiseenergycosts.It
ispossibletofeed33%causticfromthemembranecellstothedecomposertoproduce50%causticwithouttheneedforevaporation.
Storageandhandling
Becauseofitshighlyreactiveandcorrosiveproperties,causticsodamaycorrodecontainersandhandlingequipment.Constructionmaterialsmustbe
suitedtothecausticsodahandledandstored.
Sodiumhydroxidesolutionsrequiresteamorelectricalheatingwheretemperaturescanfallbelowtheupperfreezingpoint.Frozenpipelinespresentboth
safetyandenvironmentalriskswhenattemptsaremadetounblockthem.SafetymeasuresaresetoutinChapter4.
Storagetanksmaybelinedinordertominimiseironcontaminationoftheproductortoavoidstresscorrosioncrackingthetank.Tanksareusually
includedinprocedurestopreventoverfloworspillageofcausticsoda.Suchproceduresincludecontainmentandmitigation.
Itshouldbenotedthatdissolvedhydrogengascanbereleasedintothevapourspaceabovetheliquidinstoragetanks.Tanksarenormallyventedfrom
thehighestpoint.Testingforanexplosivemixtureofhydrogeninairnormallyprecedesanymaintenanceactivityinthearea.
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2.4.5Hydrogenproduction,storageandhandling
Hydrogen is produced in a fixed ratio of 28 kg per tonne chlorine produced. Hydrogen leaving the cells is highly concentrated (>99.9% by volume) and
normallycooledtoremovewatervapour,sodiumhydroxideandsalt.Thesolutionofcondensedsaltwaterandsodiumhydroxideiseitherrecycledasbrine
makeup or treated with other waste water streams. In the mercury cell process, hydrogen has to be treated to remove mercury. Primary cooling at
ambienttemperatureiscarriedoutattheelectrolyser,allowingmercuryvapourtocondenseintothemainmercurycircuit.Furthercoolingtakesplaceata
laterstageusinglargeheatexchangersandcondensateissentformercuryrecovery.
Hydrogenmaybedistributedtousersusingboosterfansorfedtothemaincompressionplant.Themainhydrogencompressionplantusuallycomprisesa
number of compressors and a gas holder (surge chamber). The hydrogen gas holder is incorporated into the system to minimise fluctuations in the gas
pressurefromtheprimarystage.Thehydrogenproductgasstreamisalwayskeptpressurisedtoavoidingressofair.Allelectricalequipmenttakeninto
thehydrogencompressionplantareamustbe"intrinsicallysafe",i.e.theequipmentwillnotproduceaspark.Areliefvalveisnormallyprovidedwithinthe
systemtorelievehighpressuretoatmosphere.
Hydrogenisnormallyanalysedforoxygencontentthecompressionwillshutdownautomaticallyincriticalsituations[EuroChlorreport,1997].
The hydrogen is in general used for onsite energy production. It is burnt as a fuel, either by the company operating the chlorine plant or by another
company to whom it has been sold as a fuel. Some or all of it can also be used on site in the case of integrated sites or sold to other companies as
chemicalfeedstock(productionofhydroxylamines,hydrochloricacid,hydrogenperoxide,sodiumsulphite,forexample).
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