金属钛生产工艺研究进展

41Vol.4No.120042TheChineseJournalofProcessEngineeringFeb.20042003-05-292003-06-27(1976-).(100080)KrollHunterArmstrongTiO2FFC..TF152.2+2A1009-606X(2004)01-0090-07..715001000101h.95%─..3[1-3].5%.2050..1968200~500t.2070.[4-7]...Kroll(1)Kroll191.TiCl4(g)+2Mg(l)→Ti(s)+2MgCl2(l).(1)1(a).MgCl2TiCl4Mg....[8,9].Okabe[10,11].Okabe[12-14].EMRK2TaF7.1(b)EMR.(MgCl2)()EMR.Uda[8,15,16]Dy2+/Dy3+Ti/Ti2+,Ti2+/Ti3+Ti3+/Ti4+Mg/Mg2+EMR(Halidothermicreduction).MgCl2(2)Dy2+(3).Mg2+moltensalt+Dy(s)→Dy2+moltensalt+Mg(l),(2)Tin+moltensalt+nDy2+moltensalt→Ti(s)+nDy3+moltensalt.(3)MgDy3+Mg(4).2Dy3+moltensalt+Mg(l)→2Dy2+moltensalt+Mg2+moltensalt.(4)924.2.Uda[17]TiCl4EMR.(5)(6).TiCl4+4e-→Ti+4Cl-(5)Al→Al3++3e-.(6)TiCl4.KrollEMR.EMRKroll.Hunter()Kroll(7).TiCl4(g)+4Na(l)→Ti(s)+4NaCl(l).(7)RMIHunter.TiCl4200oCTiCl21000oCHunterKroll.Hunter..(InternationalTitaniumPowder,ITP)ArmstrongHunter3[18,19].TiCl4TiCl4.NaCl.2Dy2+/Dy3+Fig.2SchematicdiagramofmagnesiothermicreductionofTin+utilizingDy2+/DymediatedreactioninmoltensaltInmoltensaltTin+Dy2+MgTi(s)Dy3+Mg2+3ArmstrongFig.3FlowchartoftheArmstrongprocessNaClTiO2CokeNaClClTiCl4TiCl4electrolysisreactorNaNasolidorliquidNameltTiCl4storageTiCl4liquidLiquidNastorageTiCl4boilerLiquidNaTiCl4vaporTireactorNa,Ti,NaClslurryCoolerLiquidNaFilterTi,NaCl,residualNaNaCondenserDistillationVaporTi,NaClWashNaClsolutionTiNaClEvaporatorDryerTi1930.15%(50~100)×10-6.-/-.HunterArmstrong:(1)(2)Hunter(3).HunterTiCl4.()TiCl4TiCl4.Tin++ne-→Ti,(n2,3),(8)Cl--e-→Cl2/2.(9)1959Kroll5~10.Hall-HeroultHall-Heroult...TiCl4.2080Dow-HowmetTimet.Ginatta[20-22]TiCl4.2080GTT90...TiCl4..[23,24].Okabe[25,26]-O2-CO2CO(10)~(13)9444.[27,28].[O]inTi+Cainflux=O2-influx+Ca2+influx,(10)+)Ca2+influx+2e-=CaonTicathode→influx,(11)-[O]inTi+2e-=O2-,(12)⊕O2-influx+Ccarbonanode→COgas↑+2e-.(13)Chen[29-31]CaCl2.a.Fray[32,33]TiO25.FFCTiOx(cathode)+2xe-→Ti(s)+xO2-inCaCl2.(14)TiO2Kroll.FFCTiCl4.Fray[32-35]CaCl2TiO2(Double-controlled-electrolysis)(Double-melt-electrolysis).TiCl4[32](1)(2).FFCTiO2TiO2...TiCl4TiO2Kroll.195[1].[J].,2002,5:1-3.[2]FroesFH.TitaniumandOtherLightMetals:Let’sdoSomethingAboutCost[J].JournalofMetals,1998,50(9):15.[3]FallerK,FroesFH.TheUseofTitaniuminFamilyAutomobiles:CurrentTrends[J].JournalofMetals,2001,53(4):27-28.[4].[J].,2000,29(3):1-6.[5].[J].,2002,26(5):391-396.[6].[J].,1999,51(1):92-96.[7].21[J].,2000,11:7-13.[8],,.[J].,2002,7(1):39-45.[9]PoulsenER,HallJA.ExtractiveMetallurgyofTitanium:AReviewoftheStateoftheArtandEvolvingProductionTechniques[J].JournalofMetals,1983,35(6):60-65.[10]OkabeTH,SadowayDR.MetallothermicReductionasanElectronicallyMediatedReaction[J].JournalofMaterialsResearch,1998,13:3372-3377.[11]OkabeTH,WasedaY.ProducingTitaniumThroughanElectronicallyMediatedReaction[J].JournalofMetals,1997,49(6):28-32.[12],,.⋅[J].2000,64(10):940-947.[13]ParkII,OkabeTH,WasedaY.TantalumPowderProductionbyMagnesiothermicReductionofTaCl5ThroughanElectronicallyMediatedReaction(EMR)[J].JournalofAlloysandCompounds,1998,280(1-2):265-272.[14],,.[J].2001,65(8):659-667.[15]UdaT,OkabeTH,WasedaY,etal.PhaseEquilibriaandThermodynamicsoftheSystemDy-Mg-Clat1073K[J].JournalofAlloysandCompounds,1999,284(1-2):282-288.[16],,.[J].,1998,62(1):796-802.[17]UdaT,OkabeTH,WasedaY,etal.ContactlessElectrochemicalReductionofTitanium(II)ChloridebyAluminum[J].Metall.&Mat.Trans.B,2001,31(4):713-721.[18]GerdemannSJ.TitaniumProcessTechnologies[J].AdvancesMaterials&Processes,2001,159(7):41-43.[19]KraftEH.OpportunitiesforLowCostTitaniuminReducedFuelConsumption,ImprovedEmissions,andEnhancedDurabilityHeavy-dutyVehicles[R].Washington:EHKTechnologies,2002.31-38.[20]MajaM,PenazziN,GinattaMV.AlkaliMetalBipolarElectrodeforMoltenSaltElectrolysis[J].J.Electrochem.Soc.,1990,137(11):3498-3504.[21]GinattaMV.ProcessfortheElectrolyticProductionofMetals[P].U.S.Patent:6074545,2000-06-13.[22]GinattaMV.WhyProduceTitaniumbyEW[J].JournalofMetals,2000,52(5):18-20.[23]OkabeTH,OishiT,OnoK.PreparationandCharacterizationofExtra-low-oxygenTitanium[J].JournalAlloysandCompounds,1992,184(1):43-56.[24]OkabeTH,SuzukiRO,OishiT,etal.ThermodynamicPropertiesofDiluteTitanium-OxygenSolidSolutioninBetaPhase[J].Mat.Trans.,1991,32(5):485-488.[25]Fisher,RichardL.DeoxidationofTitaniumandSimilarMetalsUsingaDeoxidantinaMoltenMetalCarrier[P].U.S.Patent:4923531,1990-05-08.[26]OkabeTH,NakamuraM,OishiT,etal.ElectrochemicalDeoxidationofTitanium[J].Metall.Trans.B,1993,24B:449-455.[27]OkabeTH,DeuraTN,OishiT,etal.ThermodynamicPropertiesofOxygeninYttrium-OxygenSolidSolutions[J].Metall.&Mat.Trans.B,1996,27(5):841-847.[28]HirotaK,OkabeTH,SaitoF,etal.ElectrochemicalDeoxidationofRE-O(RE=Gd,Tb,Dy,Er)SolidSolution[J].JournalAlloysandCompounds,1999,282:101-108.[29]ChenGZ,FrayDJ,FarthingTW.DirectElectrochemicalReductionofTitaniumDioxidetoTitaniuminMoltenCalciumChloride[J].Nature,2000,407:361-364.[30]FrayDJ.EmergingMoltenSaltTechnologiesforMetalsProduction[J].JournalofMetals,2001,53(10):26-31.[31]ChenGZ,FrayDJ,FarthingTW.CathodicDeoxygenationoftheAlphaCaseonTitaniumandAlloysinMoltenCalciumChloride[J].Metall.&Mat.Trans.B,2001,32B:1041-10