废铅酸电池铅膏回收技术的研究进展-杨家宽

废铅酸电池铅膏回收技术的研究进展杨家宽,朱新锋,刘万超,杨海玉,肖　波(华中科技大学环境科学与工程学院,湖北武汉430074):,。,SO2、CO2。,,RSR--。,PbO,。:;;;:TM912　:A　:0253-4320(2009)03-0032-06ReviewofrecoverytechnologyforleadpastefromspentleadacidbatteryYANGJia-kuan,ZHUXin-feng,LIUWan-chao,YANGHai-yu,XIAOBo(CollegeofEnvironmentalScienceandEngineering,HuazhongUniversityofScienceandTechnology,Wuhan430074,China)Abstract:Thecurrentsituationanddevelopmentofleadacidbatteryissummarized,thegenerationprocessofspentleadacidbatteryandtherecoverytechnologywidelyadpotedforleadbypyrometallurgyprocessisintroduced.However,thesmeltingrouteisassociatedwiththeemissionofgreenhousegasCO2,acidraingasSO2,andcriteriapollutantsemissionofvolatileleadparticulates.Therefore,alternativehydrometallurgicalroutesareinvestigatedbymanyresearchers.Asatypicalhydrometallurgicalprocess,thethree-stephydrometallurgical-electrowiningprocessisexpressedasdesulfalization-reduction-electrowinning,suchasRSRprocess.AnovelhydrometallurgicalprocessisproposedtorecoverleadpastewithaqueoussolutionofcitricaciddevelopedinUniversityofCambridge.Moreover,ultrafineleadoxidepowderispreparedfromspentleadbattery,anddirectlyusedasPbOpowderintheproductionofnewbattery.Keywords:spentleadacidbattery;hydrometallurgicalprocess;secondarylead;recoverytechnology　:2008-11-24　:(50804017)　:(1973-),,,,,,027-87792207,[e-mail]。　　、、,4。()()。[1],,25～30。,。、、、、、。,、、。,,,[2]。[3]。19601999,28%73%,100t440t[2]。,209095%～97%,[2]。2000,32t,68%。2010,38t,85%[1]。,。1　1.1　1859,(Plante)。1882,(Glandstone)(Tribe)“”,[4-5]::Pb+HSO-4PbSO4+H++2e(1)　　:·32·Mar.2009现代化工293ModernChemicalIndustry20093PbO2+3H++HSO-4+2ePbSO4+2H2O(2)　　:Pb+PbO2+2H++2HSO-42PbSO4+2H2O(3)　　、、、、,,、、。,,,。、、。,,,[5]。,。1.2　,,。,EngitecCXM.AM.A。4[1]:11%～30%、24%～30%、30%～40%、22%～30%。;;;:PbSO4(50%)、PbO2(28%)、PbO(9%)、Pb(4%)[6],Sb(0.5%)[1]。,,,[7-8]。。1.3　、、。PbSO450%,PbSO4,1000℃,SO2。。1t500～600kg,130～310kg/t,200kg/t[9]。、、,[7-8,10]。Na2CO3、NaOHPbSO4Na2SO4Pb2CO3Pb(OH)2。Na2SO4Na2SO4·10H2O,　　(上接第31页)[21],.[J].,2005,25():16-19.[22],,.[J].,2004,25(5):43-45.[23],,.[J].,2004,20(2):151-154.[24]Sahin.Effectofelectricalfieldandtemperatureonthecrystalgrowthratesofboric[J].AcidCrystResTechnol,2002,37(2/3):183-192.[25],,.-[J].,2005,27(5):524-527.[26],,.[J].:,2006,29(2):83-85.[27].[J].,1999,16(4):245-249.[28],,.[J].,1999,25(2):98-102.[29]YanagiyaS,SazakiG,StephenD,etal.Efectsofamagneticfieldonthegrowthrateoftetragonallysozymecrystals[J].JoumalofCrystalGrowth,2000,208:645-650.[30],,,.--[J].,2007,24(3):218-221.[31],,.[J].,2008(4):194-195.[32],,.[J].,2006,26(4):53-55.[33],,..[J].,1999,20(1):73-75.[34],,,,[J].,2002(11):7-11.[35],,.CdSBi2S3[J].,2003,19(1):107-110.[36].,,,.[J].,2005,20(4):794-800.[37]ZhuH,ZhangC,YinYS.Rapidsynthesisofcoppernanoparticlesbysodiumhypophosphitereductioninethyleneglycolundermicrowaveir-radiation[J].JCrystalGrowth,2004,270(3/4):722-728.[38],,,.、、、[J].,2005,25(5):12-14.□·33·20093:。PbCO3340℃PbO,PbCO3,100～150℃[1]。,5%PbSO4,SO2。[11-12],2007199010。,13,5,5,2,2007200,1。。1　[13-14]　/t·a-1　　、、、。10.0　　　CX--。10.0　　　LMT。10.0　　　MA,。15.0　　　,,,。4.5　　　,,。20.0　2　2.1　,()[15-20]。PrengmannMcDonaldRSR[17]。(NH4)2CO3,SO2PbO2,PbCO3PbO20%H2SiF4HBF4,。,PbO2;。,,H+;O2,Pb2+PbO2。PbO2,,(P、As、Co)。RSR:PbSO4+(NH4)2CO3PbCO3+(NH4)2SO4(4)　　PbO2+Na2SO3PbO+Na2SO4(5)　　PbO+H2SiF4PbSiF4+H2O(6)　　PbCO3+H2SiF4PbSiF4+CO2+H2O(7)　　Pb2++2ePb(8)　　H2O2H++12O2+2e(9)　　RSR--,(NH4)2CO3-Na2SO3-H2SiF4。[18]RSR。NaOH,FeSO4,KNaC4H4O6,NaOH-FeSO4-KNaC4H4O6。CX-EW[19]RSR。Na2CO3,H2O2,HBF4H2SiF4,Na2CO3-H2O2-HBF4/H2SiF4。,--,-,[16,20]。,,SO2。,,,1kg12kWh,。,。·34·现代化工2932.2　PbO2.2.1　传统铅粉活性电极材料的制备。Pb,Pb,。,1。图1　金属铅制备活性物质工艺流程示意图1,PbO,、、、。,-。()(),PbO。,,,PbO。。PbO75%()[3]。,。[21]。(ILZRO),Schrade[22],PbO,。,Karami[23-24],(PVP),Pb(NO3)2PbO,,。,Pb,,PbO。,PbO,,,、。2.2.2　铅与有机物形成的螯合物的研究,,。,-。,,,。Yang[25],3D。EDTA,,Pb。Pellissier[26],,。,,[27]。[28]2,34、5、7。,,,。2.2.3　超细PbO粉体的制备,(CambridgeUniversity),。PbO、PbO2、PbSO4,PbSb。,PbO、PbO2、PbSO43,。:PbO+C6H8O7·H2O[Pb(C6H6O7)]·H2O+H2O(10)PbO2+C6H8O7·H2O+H2O2[Pb(C6H6O7)]·H2O+O2+2H2O(11)3PbSO4+2[Na3C6H5O7·2H2O]C6H8O7·H2O[3Pb·2(C6H5O7)]·3H2O+3Na2SO4+H2O(12)·35·20093:　　:PbO;PbO2,H2O2,Pb(Ⅳ)Pb(Ⅱ),,;PbSO4,,,,Na2SO4(Na2SO4·10H2O)。,,。XRD,ICP。,395%。,(300～500℃),PbOPb。、、-。1。,。-。Pechini[29]。Pechini,,[30]。Verma[31],175℃。-,。Jiang[32],TiO2、SnO2、In2O3PbO。Vivekanandhan[30]LiNi0.5Co0.5VO4。Wolcott[33]WO3。,,,,PbO。2.2.4　柠檬酸湿法处理铅膏新工艺的优点,2。图2　柠檬酸浸出新工艺与传统火法熔炼工艺比较示意流程图　　2,,:①SO2、CO2;②;③PbO,;④PbO,。3　(1),。(2),SO2、CO2。,-()。(3)--,。·36·现代化工293(4),,PbO,“”。[1].[J].,2002,23:157-163.[2]PrengamanRD.Leadproductdevelopmentinthemillennium[C]//JEDutriac.Lead-Zinc2000,ProcoftheLead-Zinc2000Symp.TMSFallExtraction&ProcessMetallurgyMeeting,Pittsburg:TMS,2000:10-22.[3].[M].:,2004.[4].[M].2.:,2002.[5],.-[M].:,1996.[6]FerracinLC,Chcon-SanhuezaAE,DavoglioRA,etal.Leadrecoveryfromatypicalbraziliansludgeofexhaustedlead-acidbatteriesusinganelectrohydrometallurgicalprocess[J].Hydrometallurgy,2002,65:137-144.[7],,,.[J].,2005,24(3):146-149.[8]LyakovNK,AtanasovaDA,VassilevVS.Desulphurizationofdampedbatterypastebysodiumcarbonateandsodiumhydroxide[J].JournalofPowerSources,2007,171:960-965.[9],,,.[J].,2007(4):174-17