elsevierdechemer The metallurgy of antimony Corby G Anderson Kroll Institute for Extractive Metallurgy George S Ansell Department of Metallurgical and Materials Engineering Colorado School of Mines Gold en CO 80401 United States article info Article ID: 56717
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ChemiederErde72(2012)S4,3 8 ContentslistsavailableatSciVerseScienceDirectChemiederErde journalhomepage: ThemetallurgyofantimonyCorbyG.Anderson articleinfo Articlehistory:Received4October2011Accepted10April2012 MineralprocessingExtractivemetallurgy Globally,theprimaryproductionofantimonyisnowisolatedtoafewcountriesandisdominatedbyChina.Assuchitiscurrentlydeemedacriticalandstrategicmaterialformodernsociety.Themetallurgical 1.BackgroundAntimonyisasilvery,white,brittle,crystallinesolidthatexhibitspoorconductivityofelectricityandheat.Ithasanatomicnumberof51,anatomicweightof122andadensityof6.697kg/mat26 Tel.:+13032733580.E-mailaddress:bulletsandarmory.Thestartofmassproductionofautomobilesgaveafurtherboosttoantimony,asitisamajorconstituentoflead-acidbatteries.Themajoruseforantimonyisnowasatrioxideforame-retardants.2.OccurrenceandmineralogyTheabundanceofantimonyintheEarthscrustisapproximately0.2mg/kg.Antimonyisachalcophile,occurringwithsulfurandtheheavymetalscopper,leadandsilver.Morethan100mineralsofantimonyarefoundinnature.Someofthemorecommonones,as C.G.Anderson/ChemiederErde72(2012)S4,3 8Table1Commonprimaryantimonyminerals. HorsforditeCuSbDyscrasiteAgSbStibiodomeykiteCuAurostibiteAuSbBreithauptiteNiSbBreithauptiteNiSbUllmanniteNiSbSGudmunditeFeSbSStibniteSbStibiobismuthine(Bi,Sb)TetrahedriteCuAnniviteCuFreibergite(Cu,Ag)BournonitePbCuSbSStephaniteAgRamdohriteAgAndoriteAgPbSbGeocronitePbZinckenitePbSbJamesonite,PbBoulangeritePbFalkmanitePbMeneghinitePbCylindritePbFranckeitePbLivingstoniteHgSbBerthieriteFeSbFamatiniteCuStibioluzoniteCuBournonitePbCuSbSStibioenargiteCuGerstleyiteNaOKermesiteSbGabrieliteTlStibiocolumbiteSb(Nb,Ta)OSenarmontiteSbRomeite5CaOStibiconiteSbOStenhuggariteCaFeSbAsCervantiteSbStibio-tellurobismutite(Bi,Sb)ValentiniteSb 3.UsesandapplicationsAntimonytrioxide,Sb,isthemostimportantantimonycompoundproduced.Today,antimonytrioxideisproducedbyvolatilizingantimonymetalinanoxidizingfurnace.Itisusedinhalogencompoundameretardingformulationsforplastics,paints,textilesandrubber.Mostcommercialgradesofantimonytrioxidecontainbetween99.2%and99.5%antimonytrioxidewithvaryingamountsofimpuritiessuchasarsenic,ironandlead.Com-mercialsuppliersoffervariousgradesofantimonytrioxidebasedontherelativetintingstrengthoftheirproduct,whichisafunc-tionofparticlesize.AntimonytrioxidealsondsgrowinguseasacatalystforPETproduction.Antimonypentoxideandsodiumanti-monate,NaSb(OH),arealsousedasameretardants.Antimonycompounds,primarilysodiumantimonate,arealsousedindecol-orizingandreningagentsforopticalglassandCRTglass.Intheelectronicsindustry,Sbusegrowsfordiodes.Antimonymetalisalsousedforproductionofantimoniallead,whichisanimpor-tantproductofthesecondaryleadsmelter.Ablastfurnacechargecontainingusedordiscardedbatteryplates,typemetalandbear-ingmetalisreducedtoleadbullion.Thebullionisthenrenedinreverberatoryfurnacestomeetspecications.Lead antimonyalloysareusedinstarting-lighting-ignitionbatteries,ammunition,corrosion-resistantpumpsandpipes,tanklinings,roongsheets,solder,cablesheathsandanti-frictionbearings.Currently,themajorconservationpracticewithintheantimonyindustryistherecyclingofthemetalinusedleadacidstoragebatteries,typemetalandbabbit.Also,antimonialleadandanti-monymetalarerecoveredfromintermediatesmelterproductssuchasslags,drosses,uedustsandresiduesgeneratedatcopperandleadsmelters.Thesupplyofsecondaryantimonysubstantiallyexceedsthatfromprimarysourcesforantimonialleadapplications.Inotherminoruses,antimonyoxidesareusedaswhitepigmentsinpaints,whereasantimonytrisuldeandpentasuldeyieldblack,vermillion,yellowandorangepigments.Camoaugepaintscontainantimonytrisuldewhichreectsinfraredradiation.AntimonytrisuldeisalsousedinthelinersofautomobilebrakesaswellTable2Annualworldmineproductionandreservesbycountry(tonnesofcontained CountryMineproductionReserves 20102011 Bolivia50005000310,000China150,000150,000950,000Russia30003000350,000SouthAfrica3000300021,000Tajikistan2000200050,000Othercountries40006000150,000Worldtotal167,000169,0001,800,000 asinsafetymatchcompositions.Intheproductionofredrubber,antimonypentasuldeisusedasavulcanizingagent.Antimonycompoundsarealsousedincatalysts,pesticides,ammunition,andmedicines.Aswell,avarietyofcompoundscontainingantimonyasthemajorconstituentarealsousedforotherammunitionsuchasdetonators,tracerbulletsandarmory.Also,aspreviouslynoted,antimonywaswidelyusedduringtheFirstWorldWarasitwasfoundtobethebestleadalloymaterialtouseforpenetratingarmorFlameretardantscontinuetodrivegrowthdemandforanti-monytrioxide.ThehistoriccapacityoftheworldsmajorestablishedproducersascompiledbytheauthorislistedinTable3Table4listsarecentcompilationofproductioncapacitiesofglobalminingoperations(Roskill,2011Overall,itisestimatedthatthedistributionofantimonyusesandconsumptionworldwideisameretardants72%,transporta-tionincludingbatteries10%,chemicals10%,ceramicsandglass4%,andother4%.TheUSA,JapanandWesternEuropewhichtogetheraccountforaround70%ofworlddemanddominateworldcon-sumptionofantimony.4.ThemineralprocessingofantimonyOriginallyantimonywasminedandhandsortedtoeffectcon-centration.SincethebulkofprimaryproductionisinChina,wherelaborisplentifulandcheap,surprisingly,handsortingstillndsalargeapplication.However,inrecentyears,manyotherunitoperationsareusedinthemineralprocessingofantimony.Theseincludeprimarilyconventionalcrushingandgrindingfollowedbycombinedgravityconcentrationandotation.First,asstibniteisthepredominantmineralandChinaisthepredominantproducer,theindustrialmineralprocessingofatypicalChinesestibniteorewillbeelucidated.Aswell,thehistoricalotationoperationofalongtermindustrialNorthAmericansilverbearingantimonytetra-hedriteminingoperationwillalsobediscussed.Atypicalstibnitedepositmaycontaintheantimonysuldealongwithpyriteandagangueconsistingofquartz,calcite,barite,kaolinandgypsum.Theoregradingabout2.7%Sbisputtoacombinedtreatmentbyhand-sorting,heavymediumseparationandotation(Xikuangshan,1964;Chen,1964;Huangetal.,1965;Xikuangshan,1979).First,theoreishandsortedonthefeedbelttocrushingforanishedconcentrateofantimonylumps.Crush-ingtakesplaceintwostageclosedcircuitconsistingofajawandconecrusher.Aftercrushingto150mm,atwostagehandsortingiscarriedouttogiveantimonylumpsandtailsthatare150+35mm.The35+10mmfractionisheavymediumsepa-ratedtodiscardaportionofgangue.Thenthehand-selectedlowgradeconcentrateandtheheavyproductfromtheheavymediaseparationaregroundto10mm.Thisiscarriedoutinthreesep-aratesections.Therstandsecondsectionsarecombinedintoa C.G.Anderson/ChemiederErde72(2012)S4,3 8Table3Plantcapacitiesofhistoricleadingproducersofrenedantimony. CompanyLocationTotalcapacityandproducts(Sbtonne/year) HsikwangshanMiningAdministrationChina30,000(metal,trioxide,pentoxide,sodiumantimonate)KadamjaiskAntimonyCombineKyrgystan20,000(metal,trioxide)AmspecChemicalCorp.USA15,000(trioxide)LaurelIndustriesInc.USA12,500(trioxide)SocieteIndustrielleetChimiquedeLAisneFrance12,000(metal,trioxide)DachangMiningAdministrationChina10,000(metal)MinesdelaLucetteFrance9500(metal)EnalBolivia9300(trioxide)GreatLakesChemical(Anzon)USA6000(trioxide)UnionMiniereBelgium6000(sodiumantimonate)GuzhouDushanDongfengChina4000(metal,trioxide)HubeiChongyangChina4000(metal,trioxide)SunshineMiningandReningUSA1000(metal,sodiumantimonate)Totallisted closedcircuitconsistingofballmillsandspiralclassiers.Thethirdsectionhasaballmillinconjunctionwithaspiralclassier,andprovidesthenalorefeedofanenessof60%200mesh.Ore35to+10mmisfedtoadrumH.M.S.separator.Sep-arationdensityisregulatedat2.62 2.56usingferrosilicon.Thelightproductisusedasbackllforthemine.Theheavyproductissenttothegrindingsectionwhereitispreparedforotation.BulkotationisperformedwithnaturalpHontheoregroundto200mesh.Flotationreagentsusedarebutylxanthateasacol-lector(100g/tonne),sodiumdiethyldithiocarbamateasacollector(75g/tonne),shaleoilasacollector(300g/tonne),leadnitrateasanactivator(150g/tonne),pineoilasafrother(100g/tonne)andkerosene(65g/tonne)asacollector.Scavengertailingsarecom-binedanddeliveredtoaseparatebankofcellsfornal,tertiaryscavenging.Rougherconcentrateisthricecleanedtomakeapurestibniteconcentrate.Overall33%oftheoreistreatedbyhandsort-ing,7%byheavymediaseparationand60%byotation.ThetypicalseparationresultsareshowninTable5anddetailedplantow-sheetsandprocessdescriptionsmaybefoundinthereferencedliterature(XikuangshanAdministrationofMines,1979IntheUnitedStates,thelastprimaryproducerofantimonywasSunshineMining&ReningCompany.Theantimonybearingmineralintheminewasargentiferoustetrahedrite,orfreibergite.Asthisisthelongestoperatingprimaryantimonymineralotationcircuitintheworld,adetaileddiscussionows.TheprincipalveinmineralsatSunshinearesiderite,quartz,pyrite,arsenopyrite,tetrahedrite,galena,chalcopyrite,andsphalerite.TheTable4Worldminecapacitybymainproducingcompanies,mid2011. CountryCompanyTotalcapacity(tonne/yearasSb) AustraliaMandalayResources2705BoliviaVarious5460CanadaBeaverBrook6000HsikwangshanTwinklingStar55,000HunanCheznuMining20,000ChinaTinGroup20,000ShenyangHuachengAntimony15,000KazakhstanKazzinc1000KyrgyzstanKadamshai500LaosSRS500MexicoUSAntimony70MyanmarVarious6000RussiaGeoProMining6500SouthAfricaConsolidatedMurchison6000TajikistanAnzob5500ThailandVarious600TurkeyCengiz&OzdemirAntimuanTotallisted143,280 onlymineralofeconomicimportancewastetrahedrite.Histori-cally,tetrahedriteorefeedgradesof1000 1300g/tonnesilverwascommonandcontainingupto1%antimony.Withlittlevariation,sil-vertocopperandantimonyconcentrateratioswere50:1and63:1respectively.Theorewascrushedbystagedgyratorysinclosedcircuittominus2cm.Grindingwasthencarriedoutinthreepri-maryballmillsto60%passing200meshforoptimumliberation.Thecombinedthroughputrateoftheprimarygrindingmillsis45Undertheseconditions,a40,000g/tonnesilverbearingtetra-hedriteconcentratecontaining24%copperand19%antimonywasroutinelyproduced.Overall,recoveriesofthetetrahedriteoreweretypically97%.TheSunshinemillsawitslastmajormodicationinthemid1950swithaddedoorspaceandtheincorporationof30newFagergren56cellsand12GaligherAgitair36cellswhichreplacedoldDenvercells.Additionally,aDenverregrindmillwasinstalled.Thepurposeofthesechangeswastoenhanceproduction,wherebytwoconcentrateswouldbeproduced.Fromthemid1950stheSunshinemillproducedthesetwoconcentratesfromtheotationprocess;thehigh-grade,40,000g/tonnetetrahedritesilverconcen-trateandalow-gradepyriteconcentratewith20,000g/tonnesilverwithverylittlecontainedantimony.Distributionoftherecoveredsilverwas92%tosilverbearingtetrahedriteconcentratesand8%topyriteconcentrateswhiledistributionofantimonywas97%tothetetrahedriteconcentrates.Duringtheperiodbetween1953andearly1989,abulksuldeconcentratewasproducedintherstcircuitutilizingAerooat242astheprimarycollector.Ninety-vepercentofthesilverbearingantimonytetrahedriteorewasrecoveredinthisstep.Thereclean-ingoftherstcircuitcleanerconcentratesasaccomplishedthroughtheadditionofzincsulfateandsodiumsulteasapyriteandgalenadepressantfollowedbyotationtoahigh-gradeproductatcontrolledconditions.Aero3477wasusedinthesecondcircuitwhichscavengedanyremainingrecoverablesilvermineral.Addi-tionally,thetailingsfromtheretreatmentcircuitandthesecondcircuitcleanerconcentratesreportedtotheregrindmillandwereregroundtopassing95%325mesh.ThismaterialwasclassiedthroughaKrebscyclone.ThelowergradeunderowwassubjectedTable5Typicalstibniteoremineralprocessingresults. OperationOregrade(%Sb)Con.grade(%Sb)TailsgradeSbrecovery Handsorting2.257.800.1295.95Heavymedia1.582.650.1895.11Flotation3.1947.580.2193.97Average2.6819.440.1894.11 C.G.Anderson/ChemiederErde72(2012)S4,3 8toroughingandcleaning.Thehighergradeoverowreportedtothepyritecleanerconcentrates.Tailingsfromthepyriteroughersandpyritecleanercellsreportedtothesecondcircuitroughers.Duringearly1995,leadmineralizationasgalenaandasanti-monybearingbournonitebegantoshowupinabundanceinthemillfeed.Hence,tetrahedriteconcentratedilutionwithleadbecameagrowingproblem.Withzincsulfateandsodiumsulteinusetodepresspyriteandgalenaintheretreatmentcircuit,thegalenawouldreporttotheregrindmillandwasrecycledasbefore.Galenaandbournonitethenreoatedasarecirculatingloadinthisarrangementandreportedbacktotherstcircuittoberecoveredagainintherstcircuitcleanerconcentrates.So,therecirculationofleadintherst,second,andretreatmentcircuitsprovidedover-loadedconditionsaswellasdilutedthesilvergradeofoursingleThebankoffourAgitair36cellsremovedfrompyriteclean-ingserviceduringtheinitialsingleconcentratemodicationwerebroughtbackonlinetoserveasanintermediateprocessfortheregroundproduct(namelyretreatmenttailsandsecondcircuitcleanerconcentrates),whichhadpreviouslybeensplitbetweentherstandsecondcircuitroughers.TheKrebscycloneusedtosplittheregroundproductbetweentherstandsecondcircuitrougherswasleftinservicewiththehighergradeoverowcontinuingtoreporttotherstcircuitroughers.ThecycloneunderowbecamefeedtothesefourAgitairotationcells.Tailingsfromthisnewmodica-tionweredirectedtothenewthirdcircuitrougherheadbox.Thedisclterwhichhadpreviouslybeenremovedfromservicewasplacedonline.Asleadvaluesofconcentrateproducedrosetoanacceptablelevelitwasdirectedtothislter.Theleadconcentratesproducedbythismethodprovedtobeanacceptableproductformarketing.Thereferencedliteratureprovidesdetailedowsheetsandprocessdescriptions(Allen,19985.ThepyrometallurgyofantimonyForprimaryproduction,theantimonycontentoftheorehastraditionallydeterminedthepyrometallurgicalmethodofrecov-ery.Ingeneralthelowestgradesofsuldeorescontaining5 25%antimonyarevolatilizedtoantimonytrioxide:25 40%antimonyoresaresmeltedinablastfurnace:and45 60%antimonyoresaretreatedbyliquationorironprecipitation.Adescriptionofeachoftheseaswellasoxidereductionfollows(Motoo,1974;Vladislav,1981;Yong-FuandWei-Tao,1981Oxidevolatilization:Removalofantimonyasthevolatilizedtrioxideistheonlypyrometallurgicalmethodsuitableforlowgradeores.Combustionofthesuldecomponentsoftheoresup-pliessomeoftheheat;hencefuelrequirementsareminor.Therearemanyvariationsofthevolatilizationprocess,theprinciplesemployedbeingthesamebuttheequipmentdiffering.AsshowninEq.,thesulfurisburnedawayatabout1000Candremovedasawastegas,whereasthevolatileantimonytrioxideisrecov-eredinues,condensingpipes,abaghouse,aCottrellprecipitatororacombinationoftheabove.Roastingandvolatilizationareaffectedalmostsimultaneouslybyheatingtheore,mixedwithcokeorcharcoal,undercontrolledconditionsinequipmentsuchasashaftfurnace,rotarykiln,converterorroaster.Ifthevolatilizationconditionsaretoooxidizing,thenonvolatileantimonytetroxide,mayformandtherecoveryofantimony,asantimonytri-oxide,isdiminished.However,specialattentiontothechoiceofcharge,volatilizationconditions,andselectionofproductresultsinahigh-gradeoxidethatissuitableforuseinceramicsandotherapplications.Now,thisisprimarilyaccomplishedbyoxidationofantimonymetalwhichisillustratedinEq.:Antimonysuldeisreadilybutinefcientlysepa-ratedfromthegangueofcomparativelyrichsuldeorebyheatingto550 600Cinperforatedpotsplacedinabrickfurnace.ThisisillustratedinEq..Themoltensuldeiscollectedinlowercontainers.Amoreefcientmethodusesareverberatoryfurnaceandcontinuousliquation,howeverareducingatmospheremustbeprovidedtopreventoxidationofantimonysuldeandlossbyvolatilization.Theoxidevolatilizationprocesstorecoveradditionalantimonyusuallytreatstheresidue,containing12 30%antimony.Theliquatedproduct,calledcrude,liquatedorneedleantimony,issoldassuchforapplicationsrequiringantimonysulde,orisconvertedtometallicantimonybyironprecipitationorcarefulroastingtotheoxidefollowedbyreductioninareverberatoryOxidereduction:Theoxidesofantimonyarereducedtometalwithcharcoalinreverberatoryfurnacesatabout1200C.ThisisillustratedinEqs.(4)and(5).Analkalineuxconsistingofsoda,potashandsodiumsulfate,iscommonlyusedtominimizevolatilizationanddissolveresidualsuldesandgangue.Partoftheslagisfrequentlyreused.Lossofantimonyfromthechargebyvolatilizationishigh(12 20%ormore),evenwiththeuseofampleslagandcarefulcontrol.Thisnecessitatestheuseofeffec-tiveCottrellprecipitatorsorbaghouses,andconsiderablerecyclingofoxide.6CO(5)Ironprecipitation:Richsuldeoreorliquatedantimonysul-de(crudeantimony)isreducedtometalbyironprecipitationThisisillustratedinEq..Thisprocessconsistingofheatingmoltenantimonysuldeincrucibleswithslightlymorethan3FeS(6)theoreticalamountofneironscrap,dependsontheabilityofirontodisplaceantimonyfrommoltenantimonysulde.Sodiumsulfateandcarbonareaddedtoproducesodiumsulde,orslagisaddedtoformalightfusiblemattewithironsuldeandtofacilitateseparationofthemetal.Becausethemetalsoformedcontainsconsiderableironandsomesulfur,asecondfusionwithsomeliquatedantimonysuldeandsaltfollowsforBlastfurnacesmelting:Intermediategradesofoxideorsul-deormixedores,liquationresidues,mattes,richslags,andbriquettednesoruedustsareprocessedinwater-jacketedblastfurnacesat1300 1400C.Theoretically,thisprocessisillus-tratedinEqs.(7)and(8).Ingeneral,thesameblast-furnacepracticeusedforleadisfollowed,employingahighsmeltingcol-umn,comparativelylowairpressure,andaseparationofslagandmetalinaforehearth.Itisthefavoredmodeofsmeltingforallmaterialscontainingfrom25%to40%Sb,whichcanbemixedwithuxestogiveachargesufcientlypoorinmetaltoholddownvolatilization.Aswell,slag,usuallyrunningunder1%antimony,isdesiredbecauseittendstoreducevolatilizationFlowsheetsanddetailedprocessdescriptionsforaprimarypyrometallurgicalproductionMaybefoundintheliterature C.G.Anderson/ChemiederErde72(2012)S4,3 8referenced(Vladislav,1981;XikuangshanAdministrationofMines,1964;Yong-FuandWei-Tao,19816.ThehydrometallurgyofantimonyHydrometallurgicalmethodscanbeemployedforsimpleanti-monymaterialsaswellascomplexonescontaininganynumberofmetals.Normalindustrialantimonyhydrometallurgicalpracticescallforatwostepprocessofleachingfollowedbyelectrodeposition.Inreality,thereareonlytwosolventsystemsutilizedinantimonyhydrometallurgy.Thesearethealkalinesuldesystemandtheacidicchloridesystemandthealkalinesuldesystempredomi-nates.ThealkalinesuldesystemhasbeenemployedindustriallyintheformerSovietUnion,China,AustraliaandtheUnitedStatesAndersonetal.,1992,1994;AndersonandKrys,1993;NordwickandAnderson,1993).Essentially,thelixiviantisamixtureofsodiumsuldeandsodiumhydroxideandwhenitisappliedtostibnite,asolutionofsodiumthioantimoniteisformed.Thiscanbeillustratedas;However,dissolutionofelementalsulfurinsodiumhydroxideisalsousedasalixiviantforalkalinesuldeleachingofantimony.Thecombinationofsodiumhydroxideandelementalsulfurresultsintheformationofspeciesotherthanjustsulde(S).Bothsodiumpolysulde(Na)andsodiumthiosulfate(Na)arecreatedalongwithsulde.ThisisillustratedsimplisticallyinthefollowingO(11)2 5)(12)Duetotheoxidizingpowerofpolysuldeonsodiumthioantimonite,themajorspeciesinsolutionisnormallysodiumthioantimonate(Na).ThiscanbeviewedasS(13)Theelectrodepositionoftheantimonyfromthealkalinesuldesolutiontocathodemetalisnormallycarriedoutviaelectrowin-ningineitherdiaphragmornon-diaphragmcells.Theprimaryanodereactionsare;Theprimarycathodereactionis;Thecathodicmetalantimonyproductmayattainagradeover99.5%pureafterwashing.Thisindustrialalkalinesuldehydrometallurgicalplantransuccessfullyforabout60years.Indus-trialalkalinesuldehydrometallurgicalleachplantowsheetsandmoreprocessdetailsmaybefoundinthereferencedliteratureAckermanetal.,1993;Andersonetal.,1992Theothermethodologyforantimonyhydrometallurgyistheacidicchloridesystem.Whilethealkalinesuldesystempredom-inates,muchresearchandpilotscaleworkhasbeenundertakentoutilizechloride-basedtechnology(KimSooSiketal.,1975;SuGuohi,1981;TangMotangetal.,1981;LiandXu,1984;Thibaultetal.,1997Intheacidicchloridehydrometallurgicalantimonysystem,hydrochloricacid,HCl,ofteninconjunctionwithferricchloride,,iscommonlyusedasthesolventforsuldemineralsuchasstibnite.Thisisillustratedas;S(18)Intheaqueoussolution,FeCldoesthejobofbothanoxidizerandachloridizingagenttoconverttheantimonyofthesuldemineralintoachloridecomplexwhileproducingelementalsulfur.Incaseswheretheantimonyisalreadyoxidized,itmaybeleacheddirectlywithHClwithouttheneedforFeCl.Thisisillus-tratedas;O(19)Aswiththealkalinesuldesystem,thesolubilizedantimonychloridecanbeproducedbyelectrowinningfromsolutionindiaphragmcells.Thisproducescathodeantimonymetal.Theprimarycathodereactionis;Sb(20)Theprimaryanodereactionsare;Alternatively,theantimonychloridesolutioncanbetreatedbyhydrolysisprecipitationoftheantimonyfromsolutionasasolidoxychloride.Then,theprecipitatedsolidistreatedwithammoniatoproduceapureantimonyoxide.Thisisillustratedas;2HCl(23)2HCl(24)O(25)O(26)Insummary,therearetwopredominanthydrometallurgicalsystemsforantimony.Alkalinesuldetechnologyisbyfarthemostutilizedbecauseofitsinherentantimonyselectivityanditseaseoffullscaleapplicationduetominimalcorrosionissuesthatareasso-ciatedwiththechloridesystem.However,thechloridesystemisbeingappliedwithagreaterdegreeofsuccessandcondence.7.AntimonyproductqualityInancienttimes,inextractingantimonyfromsuldeorebytheadditionofiron,astarlikefernshapedcrystallinepatternappearedduringthecourseofsolidication.ThiswasdubbedthePhiloso-phersSignetStarin1610anduntilrecentlytheshapeofthesestarshadcommonlyservedtoindicatethegradeofthemetallicantimony.Indeed,whenantimonymetalcontainsimpuritieslikesulfur,arsenic,leadorirontoanyappreciableextent,itssurfaceshowsthepresenceoftheseforeignelementsbyspecks,byaleadenappearanceorbyapoorlydenedappearanceofthecrystallinepattern.Thisstarringphenomenonisalsoproducedbycoolingantimonymetal,orsocalledregulusundercoverofalayerofaproperlypreparedstarringmixture,orcoverture(Wang,1918whichisaslagthathasameltingpointlowerthanthatofantimonymetal.Whilestarringwastheoriginalindicatorofantimonyqual-ity,withenhancedanalyticaltechniquesavailable,specicationsarenowbetterdened.Tables6 8Yong-FuandWei-Tao,1981indicatethetypicalqualityandspecicationsforvariousantimony C.G.Anderson/ChemiederErde72(2012)S4,3 8Table6Analysisoftypicalimpureantimonyproductionproducts. ImpureSbfromreductionsmeltingImpureSbfromsmelting(%)cathodeSbmetal Sb96 9780 9098 98.5As0.2 0.30.2 0.30.02 0.1Pb0.1 0.250.1 5 C0.001 0.010.03 0.20.004 0.005Fe0.01 0.53 150.005 0.01Na0.02 0.10.02 0.10.1 1.0Sn0.01 0.10.01 0.10.01 0.03S0.1 1.00.2 0.30.15 0.40 Table7Chinesenationalstandardsforantimonymetalpurity. 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