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:2002208201.:,,1975,.:.Tel:(0411)4379133;E2mail:clsun@dicp.ac.cn.:025329837(2003)0520328205:3283321,2,1,1,1(1,116023;2,710000):,XRD,XRFTG2DTG,.,Cu2Al2Zn2O,;,015MPa160220,013mg/L..:,,,,,,,:O643/X7:ATheLeachingandControlofActiveComponentCuinCopper2BasedCatalystsforCatalyticWetAirOxidationDOUHerui1,ZHUJingdong2,CHENYongjun1,WUMing1,SUNChenglin13(1DalianInstituteofChemicalPhysics,TheChineseAcademyofSciences,Dalian116023,Liaoning,China;2PetroChinaChangqingOilfieldCompany,Xian710000,Shaanxi,China)Abstract:Inthispaper,copper2basedcatalystsforthecatalyticwetairoxidationoforganicwastewaterwereprepared.ThecatalystsandtheirprecursorswereanalyzedbyXRD,XRFandTG2DTG.ItwasfoundthatthereisnoorlittleCuleachingforCu2Al2Zncatalystwhoseprecursorpossesseshydrotalcite2likestructure.Inthedegradationofphenol,sodiumdodecyl2benzenesulfonateandsulfosalicylicacidunderthereactionconditionofinitialoxygenpressure015MPaandtemperature160220,Culeachingisbelow013mg/L.Theprelimi2narytheorycalculationandanalysisforthestabilityofthecatalystsweremade.Keywords:hydrotalcite2like,copper2basedcatalyst,wastewatertreatment,catalyticwetairoxidation,phenol,sodiumdodecyl2benzenesulfonate,sulfosalicylicacid,catalyticdegradation(CWAO)(),,CO2H2O,N2,PO3-4SO2-4,COD(),.:,.,,[13].,Cu,.,20mg/L[3,4],.,Cu2Al,,Cu3mg/L[5,6].,Cu2Zn2Al,.245Vol.24No.5ChineseJournalofCatalysis20035May2003©1995-2004TsinghuaTongfangOpticalDiscCo.,Ltd.Allrightsreserved.[7],,Cu2Zn2Al2O,.11.1[8].Cu(NO3)2,Zn(NO3)2,Al(NO3)3,.Na2CO3(110mol/L),,,1224h.,.3mm,11024h,500900812h,.1.2MagixXRF,.D/max2rBX.TG2DTGDT220B,012g,10/min,201000.1.3FDX201.100,018g,40mlH2.,215MPa,015MPa.(120260).2hCOD,COD;,.1Table1Metal2oxidecontentsofcatalystprecursorsPrecursorw(Al2O3)/%w(CuO)/%w(ZnO)/%w(others)/%8.9243.1247.710.2310.0743.3546.460.3222.1,1.,.2.21XRD.[5,6,911]XRD,,Zn2(OH)2CO3,Cu2(OH)2CO3Al(OH)3nH2O..,,.1XRDFig1XRDpatternsofdifferentcatalystprecursors(1)Precursor,(2)Precursor2XRDFig2XRDpatternsofdifferentcatalystsfromdifferentprecursorscalcinedat700(1)2700,(2)27002XRD.2700,,,2700CuOZnO.2700,,.,9235:©1995-2004TsinghuaTongfangOpticalDiscCo.,Ltd.Allrightsreserved.MOx.,Cu,ZnAl.2Table2TheleachingofCucomponentindifferentcatalystsCatalystPrecursorstructure/Reagent(COD,mg/L)pHvalueBeforereactionAfterreactionCODremoval(%)Culeaching(mg/L)2700non2hydrotalcite180PhOH(4710.6)6.406.0089.23.42700hydrotalcite2like180PhOH(4710.6)6.406.8191.30.12700non2hydrotalcite200SSL(3368.8)1.886.0074.021.02700hydrotalcite2like200SSL(3368.8)1.886.6792.40.3Reactiontemperature,SSLsulfosalicylicacid32700Table3TheleachingofCucomponentincatalyst2700/p(O2)/MPat/hReagent(COD,mg/L)pHvalueBeforereactionAfterreactionCODremoval(%)Culeaching(mg/L)2000.52.0SDBS(4368.8)10.009.0050.90.12600.52.0SDBS(4368.8)10.008.8067.70.31600.52.0PhOH(4710.6)6.407.0578.80.11800.52.0PhOH(4710.6)6.406.8189.20.12200.52.0PhOH(4710.6)6.406.9093.302000.52.0SSL(3368.8)1.886.6792.40.3SDBSsodiumdodecyl2benzenesulfonate3TG2DTGFig3TG2DTGprofilesofdifferentcatalystprecursors(a)Precursor,(2)Precursor2.3TG2DTG3TG2DTG.13,1,.1167(Zn2(OH)2CO3)1155(Cu2(OH)2CO3)Al(OH)3;Cu5152Zn5178Al2(OH)26.6CO34H2O.[6],3(a)1Al2(OH)3H2O,3140%,3166%;23Zn2(OH)2CO3Cu22(OH)2CO3H2OCO2,24175%,24182%.3(b)26184%,1H2O,1%;2,34H2O,2218%,2217%.,2,5125%,5130%;34.5CO2,3120%,3114%.,.2.4,2.2700,2700,.2700,,03324©1995-2004TsinghuaTongfangOpticalDiscCo.,Ltd.Allrightsreserved.pH,3.,2700,,013mg/L.[4],(210mg/L).2.5,Mg6Al22(OH)16CO34H2O,.,OH-,CO2-3H2O[9].,Al3+Mg2+,[10,11].[9],Al3+OH-,Cu2+Zn2+,.M2+/M3+,,.,,,,500600,,Al3+,Cu2+Zn2+,MOx,4.4Fig4SchematicdiagramofCu2basedcatalyst,,,.Cu2Al2Zn2O,O2-,Cu2+,Zn2+Al3+O2-,(4)..,Al3+CuO2ZnO,,.,Mg2AlAl,M2O,[9,10].,Al,MOxM2O.,,,.,,.K[12]U=11202105z+z-r++r-1-3415r++r-4.z+z-,r+r-.U(CuO)=31842103kJ/molU(ZnO)=3177103kJ/molU(AlO3/2)=7177103kJ/mol4Table4RadiusofdifferentionsIonCu2+Al3+Zn2+O2-r/pm695074140|z|2322,Cu5152Zn5178Al2(OH)2617CO34H2O,Cu2176Zn2189AlO7115().,U=x1U(CuO)+x2U(ZnO)+x3U(AlO3/2)x1+x2+x3=1016+1019+71776165=4140103kJ/molx1,x2x3CuO,ZnOAlO3/2.,CuO,CuO.2700Cu2+1335:©1995-2004TsinghuaTongfangOpticalDiscCo.,Ltd.Allrightsreserved.,.2700,,CuO,,,.2.6Cu2+,[13].,pH.,[4,13]Cu2+H2.5,,700870.,.5Table5TheleachingofCucomponentinthecatalystcalcinedatdifferenttemperaturesCatalyst/t/hReagent(COD,mg/L)pHvalueBeforereactionAfterreactionCODremoval(%)Culeaching(mg/L)27007002.0H2Acid(8843.1)12.07.2394.016.128708702.0H2Acid(8843.1)12.07.2193.928.65,800,CuO,ZnOCuAl2O4.,,MOx.CuAl2O4,.,CuO,.5XRDFig5XRDpatternsofthecatalystcalcinedatdifferenttemperatures(1)500,(2)600,(3)700,(4)800,(5)8701BoxEOJr,FarhaFJr.US4062772.19772FarhaFJr,BoxEOJr.US4072608.19783AlejandreA,MedinaF,FortunyA,SalagreP,SueirasJE.ApplCatalB,1998,16(1):534,,,,.(BinYJ,ZhuWP,JiangZhP,YinT,YangZhH.ChinJEnvironSci),1999,20(2):425AlejandreA,MedinaF,RodriguezX,SalagreP,CesterosY,SueirasJE.ApplCatalB,2001,30(1/2):1956AlejandreA,MedinaF,RodriguezX,SalagreP,SueirasJE.JCatal,1999,188(2):3117LevecJ.ApplCatal,1990,63(1):L18..:(XiangDH.SolidCatalysts.Beijing:ChemIndPress),1983.3419CavaniF,TrifiroF,VaccariA.CatalToday,1991,11(2):17310PauschI,LohseHH,SchuermannK