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2005,25(2)236~240ChinaEnvironmentalScience,,,(,410082),.,,(0.1mA/cm2,C/N1.07),(TN)98%,1mg/L,pH7,...X703A10006923(2005)02023605Studiesontreatmentofcopperpicklingwastewaterwithelectrode-biomembranetechnique.WUWei-hong,YUANXing-zhong,ZENGGuang-ming,LIWen-wei(DepartmentofEnvironmentalScienceandEngineering,HunanUniversity,Changsha410082,China).ChinaEnviromentalScinence,2005,25(2)236~240AbstractThedirecttreatmentofcopperpicklingwastewaterwascarriedoutinself-designedreactorwithelectrode-biomembranetechnique.Denitrifyingmicroorganismstamedwithgradientadditionofcopperioncouldadapttotheexistenceofcopperionandachieveeffectivelythedenitrificationprocess.Underthebesttechnicalconditionofcurrentdensity0.1mA/cm2andC/N1.07,theremovalrateoftotalnitrogen(TN)intheeffluentwaterreachedabove98%;concentrationofcopperion1mg/L,pHvalueabout7,andnosecondarypollutionexisted.Neutralization,denitrificationandcopperionremovalcouldbeachievedsimultaneouslyandefficientlyusingelectrode-biomembranetechnique.Thefeasibilityofcopperrecoverywithexchangingelectrodeswasprovedinthistest.Keywordsbio-electrodepicklingwastewaterneutralizationdenitrificationcopperion,,.,pH,.,[1].,[2].COD.,Cast[3],,.Watanabe[4],,.,,..,.,,.200408088632001AA644020;70171055,50179011,yxz@hnu.cn223711.1(1),8L,2,,8.350mm,310mm,1246cm2.,(30).,30mL/min.74223115681Fig.1Schematicdiagramofthebio-electrodereactor1.2.3.4.5.6.7.8.1.2CH3COONa·3H2ONO3NNaHCO3K2HPO3CaCl2MgSO4·7H2OCuSO4,0~1700g/L,100,62.5,60,180,300,0~75mg/L.CH3COONa·3H2O,[5].,pH3,NaHCO3.1.31.3.1.2AB,,,,.24h30mg/L,20d(TN)99.1%,,1~2mm,.1.3.2,A(0,1,2,5,8,10,20,30mg/L),24h,24h,.1.3.3,,,,A30mg/L,0.1mA/cm2,20d10hTN98.89%,.1.4,8~10h,,,,.1.5NO3NNO2NDX-120..pHPHS-3CpH.COD(1.08gCOD/g).22.1[6].2(),AB,30mg/L.2,A,8hTN99.01%.A,B8h,24hTN46.78%,A46.88%,[7].,23825(20d),.,,,[8].2Fig.2EffectofacclimatizedwithcopperionondenitrificationmicroorganismsNO3NNO2NTN,,,A.,.2.23:.,,.2.2.1C/NTNC/N,(1.07),,,C/N1.07[9].2.2.23,,,[9].0.1mA/cm2,H2,H2.0.1mA/cm2,H2,,,..3Fig.3Averagedenitrificationrateatdifferentcurrentdensity,0.1mA/cm2,C/N1.07,30mg/L,100mg/L.2.3,1hpH36.8(4).()::2H2O+2eH2+2OH(1)2NO3+5H2N2+4H2O+2OH(2):C+2H2OCO2+4H++4e(3):8NO3+5CH3COOH4N2+10CO2+6H2O+8OH(4)(1)~(4),(1)(2)(4),,,.A0612182430012345678(mg/L)020406080100(%)B0612182430024681012141618202224(h)(mg/L)020406080100(%)3.03.54.04.55.00.000.050.100.150.200.25(mA/cm2)[mg/(L⋅h)]2239,,,(3)(34)NaHCO3,pH.,,pH7.4pHFig.4ChangeofpHinthebio-electrodereactor2.4,.,,.5Fig.5Denitrificationinthebio-electrodereactor5.5,1h,TNNO3NCOD,100,100,286mg/L37.8,26.8,11.7mg/L.,NO2N,11.0mg/L.TN62.2%,.,,.2h,COD,,.11h,,TN98.29%,COD,.2.56,2.1,1h30mg/L3.14mg/L.2,,8h0.71mg/L.,,.,,,,[10].6Fig.6Removalsofcopperion,,.30mg/L8h,0.025mA/cm2,,,..2.6..,,.,,()020406080100012345678910112023(h)(mg/L)345678pHTNpH051015202530012345678(h)Cu2+(mg/L)0408012016020024028001234567891011(h)(mg/L)020406080100(%)CODNO3NNO2N24025,,98%.,.,().,,.33.1,.3.20.1mA/cm2,C/N1.07,.3.3,.HRT11h,TN98%,1mg/L,,.3.4,,.[1]WanNgahWS,EndudCS.Removalofcopperionsfromaqueoussolutionontochitosanandcross-linkedchitosanbeads[J].ReactiveandFunctionalPolymers,2002,50(2):181190.[2]MellorBM,RonnenburgJ,CampbellWH,etal.Reductionofnitrateandnitriteinwaterbyimmobilizedenzymes[J].Nature,1992,355(2):717719.[3]CastK,JosephRVFlora.Anevaluationoftwocathodematerialsandtheimpactofcopperonbio-electro-chemicaldenitrification[J].WaterResearch,1998,32(1):6370.[4]WatanabeT,MotoyamaH,KurodaM.Denitrificationandneutralizationtreatmentbydirectfeedingofanacidicwastewatercontainingcopperionandhigh-strengthnitratetoabio-electrochemicalreactorprocess[J].WaterResearch,2001,35(17):41024110.[5].[J].,1994,15(2):2932.[6]AndersonK,KoopmanB,BittonG.EvaluationofINT-dehydrogenaseassayforheavymetalinhibitionofactivatedsludge[J].WaterResearch,1988,22(3):349353.[7],.[J].,2002,22(6):721725.[8]JiG,SilverS.Bacterialresistancemechanismforheavymetalofenvironmentalconcern[J].J.ofMicrobial,1992,14(1):6175.[9]SakakibaraY,FloraJRV,SuidanMT,etal.Modelingofelectrochemically-activateddenitrifyingbiofilms[J].WaterResearch,1994,28(5):10771086.[10],.[J].,2002,28(1):1821.IGCC200410(GEEnergy)Bechtel(IGCC).IGCC,.IGCC..IGCC.Bechtel,IGCC;GEEnergy,IGCC.,GEIGCC60%,ChevronTexaco.,,IGCC.ChemicalandEngineeringNews,October11,32(2004)