废旧锂离子电池中钴的生物淋滤机制

2008年第53卷第23期:2881~2887SCIENCEINCHINAPRESS,珅,,,,,,,100081E-mail:[e-mail]2008-06-24,2008-10-24(:2009CB220106),..pH,;pHORP()+,.,.;+Fe3+Fe2+,Fe2+.XPS(X)EDS().,[1].[2][3][4][5].(A.f)(A.t),pH.,[6,7].,;,[8].,,.,[9~14],[9,11].,,,,.75~90[15][10,13][10],60%10%,Fe2+.[13],90%;,.[13].1.2,[13].,[14].,.(NH4)2SO4,2.0g;MgSO4,0.5g;CaCl2,0.25g;KH2PO4,1.0g;FeSO4,0.1g10.0g1000mLpH5.5(NH4)2SO4,2.0g;MgSO4,0.5g;CaCl2,0.25g;KH2PO4,1.0g;FeSO430%pH2.010mL1000mL;pH2.0(NH4)2SO4,2.0g;MgSO4,0.5g;CaCl2,0.25g;KH2PO4,1.0g;FeSO4,0.1g4.0g1000mLpH5.52000mL,2~3pH2.0,.1.3(1).,,100mL/250mL,(5%,).(30,120r/min)pH.10~12d4.0g/L(A)pH1.0,2.0g/L+2.0g/L(B)pH1.5,4.0g/L(C)pH2.0.1mol/LH2SO4BCpHA,pHA,B,C(pH1.0)1g,,.ORPFe3+-Fe2+;pH-,,.3.(2).8000~150001g,pH1.0A,B,C,,.H+Fe3+/Fe2+,,,,.3.3XPSEDS580A,B,CXPSCo2+Co3+EDS1.4(1)Co.4g/L,10~12dpH1.0,pHH2SO4100mL/250mL,1g.,H+,pH;,pH,pH.,H2SO4,pH;.Co.3.(2)Fe2+Co2882.Fe2+Co,pH1.0Fe2+-H2SO4Co.2%()Fe2+H2SO4(pH1.0),100mL/250mL1g,,Co.3.,..2.2Co3CopHORP2.,+Co,Co1280mg/L,998mg/L.,pH,,5pH1.01.54,,5pH1.69.ORP,ORP,ORP,ORP.1.5pH;ORPORP,2min;Co361MC;EDSX(HitachiS-4800,20kV,);XPSX(VGESCALAB,MK-,Alkα=1486.6eV,).2pH,,Co,Co.Co2+Co3+,Co2+,Co3+[17].,H2SO4,Co2+,Co3+,Co,ORP,pH,Co.2.13,Co1.,3Co,Co.,,.Co,Co,.,H2SO4,Co2+.,Fe3+SO42−,Fe3+Fe2+,Co3+.[18,19]:,[16].,,,1,28832008年12月第53卷第23期2pHORP,,FeS2+5O2+4H+=Fe3++2SO42−+2H2O(A.fA.t)FeS2+Fe2(SO4)3=3FeSO4+2S(ΔG0f=−60.3)FeS2+7Fe2(SO4)3+8H2O=15FeSO4+8H2SO4(ΔG0f=−543.02)S+3Fe2(SO4)3+4H2O=4H2SO4+6FeSO4(ΔG0f=−241.36)2FeSO4+2LiCoO2+4H2SO4=Fe2(SO4)3+2CoSO4+Li2SO4+4H2OCo2+Fe3+,ORP;Fe3+,ORP.,Fe3+-Fe2+Co3+-Co2+,ORP;Co2+,Co3+,Co.,H2SO4,Co2+,pHFe3+,Fe2+Co3+Co2+,Co.Co.,H2SO4.+,H2SO4,Fe3+.2.3CopH1.0H2SO41%,CopH3.,,H+,pH;,pH,1.86;H2SO4pH.Co,721mg/L;H2SO4,Co,Co1020mg/L.Co,Co.2.4Fe2+CoFeS2S+FeS2,ORP,pHS,CoS,CoS.,FeS2S+FeS2Co,FeS2Fe3+FeS2Fe2+.Fe2+Co,pH1.0Fe2+Co(4).,Fe2+-pH,Fe2+,24hpH1.02.22;Fe2+pH1.01.99.CoFe2+1.24,619mg/L1388mg/L,Co3+Fe2+Co2+,Co,Fe2+Fe3+ORP.,Fe2+Co28843pH,,4Fe2+-pHORP,Fe2+-.,FeS2S+FeS2Fe3+Fe2+Co3+.2.5XPSXPS.Co3+Co2+780.9780.1eV,,XPSCo3+Co2+,.5,XPSCo,.,H2SO4Co2+,XPSCo3+.H2SO4,Fe3+,Co,Co3+Co2+,.,H2SO4Co2+,Fe3+Co3+,Co3+Co2+,,,EDS.5XPS(a);(b);(c);(d)28852008年12月第53卷第23期2.6LiCoO2,+3;CoO,+2[20].,H2SO4CoOCo2+,Co3+,.,Co3+Co2+,,.,H2SO4Co2+,pHCo3+,,(6).EDS,,,,(7),,.6SEM(a);(b);(c);(d),.[9].[10].[13].,.,7EDS;,,.,;,.,Fe3+;,,[21]..,,,Fe3+;Co2+,Co3+,.,Co2+;,Fe3+Fe2+,Fe2+Co3+,;2886Fe3+,Fe2+..3(1)Co,.(2),Co2+Co.(3)+,Co2+Fe3+Fe2+Co3+,Co.1TormaAE.Biotechnologyappliedtominingofmetals.BiotechnolAdv,1983,1(1):73—80[DOI]2DelvastoP,ValverdeA,BallesterA,etal.Diversityandactivityofphosphatebioleachingbacteriafromahigh-phosphorusironore.Hydrometallurgy,2008,92(3-4):124—129[DOI]3NareshKumarR,NagendranR.Changesinnutrientprofileofsoilsubjectedtobioleachingforremovalofheavymetalsusingacidi-thiobacillusthiooxidans.JHazardMater,2008,156(1-3):102—107[DOI]4LöserC,ZehnsdorfA,HoffmannP,etal.Remediationofheavymetalpollutedsedimentbysuspensionandsolid-bedleaching:Esti-mateofmetalremovalefficiency.Chemosphere,2007,66(9):1699—1705[DOI]5WuHY,TingYP.Metalextractionfrommunicipalsolidwaste(MSW)incineratorflyash:Chemicalleachingandfungalbioleaching.EnzymeMicrobTechnol,2006,38(6):839—847[DOI]6WatlingHR.Thebioleachingofsulphidemineralswithemphasisoncoppersulphides:Areview.Hydrometallurgy,2006,84(1-2):81—1087TyagiRD,BlaisJF,AuclairJC.Bacterialleachingofmetalfromdigestedsewagesludgebyindigenousiron-oxidizing.EnvironPollut,1993,82(1):9—12[DOI]8VeglióF,BeolchiniF,NardiniA,etal.Kineticanalysisofpyrrhotiteorebioleachingbyasulfooxidansstrain:Directandindirectmechanismdiscrimination.ProcessMetall,1999,9(1):607—616[DOI]9ZhaoL,ZhuNW,WangXH.Comparisonofbio-dissolutionofspentNi-Cdbatteriesbysewagesludgeusingferrousionsandele-mentalsulfurassubstrate.Chemosphere,2008,70(6):974—981[DOI]10MishraD,KimDJ,RalphDE,etal.Bioleachingofmetalsfromspentlithiumionsecondarybatteriesusingacidithiobacillusfer-rooxidans.WasteManage,2008,28(2):333—338[DOI]11ZhuNW,ZhangLH,LiCJ,etal.Recyclingofspentnickel-cadmiumbatteriesbasedonbioleachingprocess.WasteManage,2003,23(8):703—708[DOI]12CerrutiC,CurutchetG,DonatiE.Bio-dissolutionofspentnickel-cadmiumbatteriesusingthiobacillusferrooxidans.JBiotechnol,1998,62(3):209—219[DOI]13辛宝平,朱庆荣,李是珅,等.生物淋滤溶出废旧锂离子电池中钴的研究.北京理工大学学报,2007,27(6):551—55514朱庆荣,辛宝平,李是珅,等.生物淋滤直接浸出废旧电池中有毒重金属的实验研究.环境化学,2007,26(5):646—65015FreitasMBJG,GarciaEM.Electrochemicalrecyclingofcobaltfromcathodesofspentlithium-ionbatteries.JPowerSources,2007,171(2):953—959[DOI]16TomonoriI,AkaneN,MasafumiT,etal.Bioleachingofmetalfrommunicipalwasteincinerationflyashusingamixedcultureofsul-fur-oxidizingandiron-oxidizingbacteria.Chemosphere,2005,60(8):1087—1094[DOI]17杨海波,梁辉,黄继承.LiCoO2的化学分解浸取过程.天津大学学报,2006,39(增刊):341—34418欧乐明,何荣权,冯其明.无菌体系下黄铁矿浸出及热力学分析.有色金属,2007,59(4):87—9019武彪,阮仁满,温建康,等.黄铁矿在生物浸矿过程中的电化学氧化行为.金属矿山,2007,10:64—6720袁文辉,邱定蕃,王成彦.还原熔炼失效锂离子电池的研究.有色金属(冶炼部分),2007,4:5—721RohwerderT,GehrkeT,KinzlerK,etal.BioleachingreviewpartA:Progressinbioleaching:fundamentalsandmechanismsofbacte-rialmetalsulfideoxidation.ApplMicrob