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US 2020/0399137A1 Dec.24,2020 tionsthatincludemonovalentcations,includinglithium, multivalentcations,monovalentanions,andmultivalent anions. [038]Incertainembodiments,silicamaybepresentin thelithiumchloridecontainingsolutionorgeothermalbrine, andmayberemovedbyavarietyofknownmethods(e.g., U.S.Pat.No.4,016,075),priortouseinthemethods describedherein.Thus,incertainembodiments,themethods forthepreparationoflithiumcarbonatedescribedhereincan includeasilicamanagementstep. forbrinesthatdonotincludesilica,orbrinesthathavea substantialylowinitialsilicaconcentration. [042] Incertainembodiments,silicamanagementstep12 canincludethestepofcontactinglithiumchloridecontain ingsolution10withactivatedaluminatoremoveatleasta portionofthesilicapresent.Aluminathatincludessilica boundtheretocanberegeneratedbycontactingthealumina withsodiumhydroxide.Alternatively,thelithiumchloride containingsolutioncanbecontactedwithaluminumchlo ride,whichisconvertedtoaluminumhydroxide,andcanbe usedtoprecipitatesilicapresentinthelithiumchloride containingstream.Inafurtherembodiment,iron(I)that maybepresentincertainlithiumcontainingbrinescanbe oxidizedwithanoxidant,suchasair,hypochlorite,hydro genperoxide,oxygen,ozone,oralikeoxidizingagent,to generateiron(I)chloride,whichafteradjustmentofthepH toaboveabout5,fromaninitialpHofabout2.5to3.5,wil precipitateferichydroxide.Theferichydroxidecanadsorb 4 [039] ReferingtoFIG.1,providedhereinisamultistep methodfortheisolationoflithiumionsfromabrineorother lithiumcontainingsolutionandthesubsequentproduction oflithiumcarbonatetherefrom.Inafirststepofthemethod, thebrineissupliedtoasilicamanagementstep,wherein silicaisremovedfromthebrinetoproduceasilica-frebrine orlithiumcontainingsolution.Inasecondstepofthe method,lithiumionsareremovedfromthesilica-frebrine orlithiumcontainingsolution.Optionaly,inathirdstep,the silicafromthelithiumcontainingbrine.Inaprefered lithiumioncontainingsolutionfromthesecondstepmaybe concentratedtoproduceaconcentratedlithiumioncontain ingsolution.Inafourthstep,thelithiumcontainingsolution issupliedtoanelectrochemicalceltoproducealithium hydroxidecontainingsolution.Inafifthstep,watercanbe removedfromthelithiumhydroxidecontainingsolution fromstep4tocrystalizeatleastaportionofthelithium hydroxidefromstep4.Inasixthstep,thelithiumhydroxide isisolated,recovered,anddried. [040] ReferingtoFIG.2,providedisamultistepmethod fortheisolationoflithiumionsfromabrineorotherlithium containingsolutionandthesubsequentproductionof lithiumcarbonatetherefrom.Inafirststepofthemethod,a brineissupliedtoasilicamanagementstep,whereinsilica isremovedfromthebrinetoproduceasilica-frebrineor lithiumcontainingsolution.Inasecondstep,lithiumions areremovedfromthesilica-frebrineorlithiumcontaining solution.Inanoptionalthirdstep,thelithiumioncontaining solutioncanbeconcentratedtoproduceaconcentrated lithiumioncontainingsolution.Inafourthstep,thelithium embodiment,thepHisadjustedtobetwenabout5and6to induceprecipitationofsilicaandiron.Inalternateembodi ments,thepHisadjustedtoaboveatleastabout4.5to induceprecipitationofsilicaandiron.Incertainembodi ments,itispreferedthepHisnotincreasedaboveabout6, topreventtheprecipitationofotherionicspeciespresentin thelithiumcontainingbrine.Inyetanotherembodiment, iron(I)canbeadedtothelithiumchloridecontaining solutionandoxidizedbyknownmeanstoiron(I),suchas withbycontactingtheiron(I)withanoxidant,suchasair, oxygen,ozone,hypochlorite,hydrogenperoxide,orother suitableoxidizingagent.Contactingsilicapresentinthe lithiumchloridecontainingsolutionwiththeiron(I) compoundformsaprecipitatewhenthepHisadjustedto betweenabout4.5and6withtheadditionoflimeorsimilar base.Itapreferedembodiment,thepHisadjustedto betweenaboutbetweenabout5and6.Inalternateembodi ments,thepHmustbeadjustedtoaboveatleastabout4.5 forthesilicaandirontoprecipitate.Incertainembodiments, itispreferedthepHisnotincreasedaboveabout6,to preventtheprecipitationofotherionicspecies. containingsolutionissupliedtoanelectrochemicalcelto producelithiumhydroxide.Thelithiumhydroxidecanbe [043]Inadition,silicamanagementstep12caninclude supliedtoafifthstepwherelithiumhydroxideisconverted tolithiumcarbonate.Inasixthstep,lithiumcarbonateis isolatedandrecovered. [041] ReferingtoFIG.3,inoneembodimentofthe presentmethod,lithiumchloridecontainingsolution10is provided.Asnotedabove,lithiumchloridecontainingsolu tion10canbeobtainedfromavarietyofsources,including geothermalbrines.Thelithiumchloridecontainingsolution issupliedtosilicamanagementstep12,whichoperatesto significantlyreducetheamountofsilicathatmaybepresent inlithiumchloridecontainingsolution10,suchthatsilicate precipitate16andsilica-leanlithiumchloridecontaining solution14areproduced.Preferably,afterthesilicaman agementstep,thesiliconconcentrationinsilica-leanlithium chloridecontainingsolution14islesthanabout150ppm, morepreferablytheconcentrationislesthanabout10 ppm,evenmorepreferablytheconcentrationislesthan about50ppm,andevenmorepreferablytheconcentration islesthanabout25ppm.Incertainembodiments,the concentrationofsiliconinsilica-leanlithiumchloridecon tainingsolution14islesthanabout20ppm,lesthanabout 10ppm,orevenlesthanabout5ppm.Itisunderstodthat thesilicamanagementstepmaybeomitedfromtheproces anyknownmeansforremovingaportionofthesilica presentinthefedstream,whileatthesametimemaintain ingtheinitialconcentrationoflithium.Inoneembodiment, lithiumchloridecontainingsolution10canbecontacted withaluminumchloride,ironchloride,aluminumhydrox ide,orthelike,toformaprecipitatewiththesilica. Contactingcanbefacilitatedbyknownmeans,suchasa mixingdevice.Solidsilicaprecipitate16removedfrom lithiumchloridecontainingsolution10canbecolectedand removedfromthemixingorlikedevice,byknownmeans, suchasscreningorfiltering,toyieldlithiumchloride containingstream14thatissubstantialyfreofsilica. [0044] Asknownintheart,variousmembranescanbe used to selectively remove specific undesired ions from lithiumcontainingsolution14. [045) Silica-leanlithiumchloridecontainingstream14, whichisubstantialyfreofsilica(measuredasSiO2),can besupliedtolithiumchlorideisolationstep.Incertain embodiments,silica-leanlithiumchloridecontainingstream 14canbesupliedtoatleastoneintercalatedlithium absorbentcolumn18,whichcanbeconfiguredtoabsorband isolatelithiumchloridefromthesilica-leanlithiumchloride containingsolution,whileatthesametimealowingotherPDF Image | Patent LITHIUM CHLORIDE CONTAINING BRINE
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