电多相催化反应体系对垃圾渗滤液的降解

2008,28(2)131~135ChinaEnvironmentalScience,*,,(,300071)(GAC),,.CuCeγ-Al2O3,GAC,.,SEMXRD.,Cu2%Ce9%,,5.,15.0V,pH3,0.08m3/h,2.0cm.pH.,-Fenton,.X705A10006923(2008)02013105Degradationoflandfillleachatebyelectro-heterogeneouscatalysis.YUELin,WANGQi-shan*,SHIYan,HEShi-zhong(CollegeofEnvironmentalScienceandEngineering,NankaiUniversity,Tianjin300071,China).ChinaEnvironmentalScience,2008,28(2)131~135AbstractUsinggranularactivatedcarbon(GAC)aselectricparticleelectrodeandheterogeneouscatalystloadedmetallicoxidetoreplaceinsulatedparticle,theelectro-heterogeneouscatalyticoxidationsystemwasconstructed.Adoptingimpregnationmethodtoprepareγ-Al2O3supportedcatalystscontainingCu,Ce,itwasevenlymixedwithGACtoconstructpackingmaterials.Landfillleachatewastreatedbyanelectrocatalyticoxidationprocess.Theactivityofcatalystswasexplored,andusingscanningelectronmicroscope(SEM)andX-raydiffraction(XRD),themicrostructureandmorphologywerecharacterized.Whenthemetallicionconcentrationinsoakingsolutionwas2%forCu,9%forCe,theactivityofpreparedcatalystwasthehighest,andthepropertywasstable,evenafterthereactorwasrunfivetimes.Themainparametersofelectrochemicalprocesswerestudiedbyorthogonalexperimentaldesign.Theoptimumreactioncontitionwasobtainedasfollowscellvoltage15.0V,pH3,airflow0.08m3/h,electrodespan2.0cm.CellvoltageandpHvaluehadhighereffectsonthetreatmentoflandfillleachate.Themechanismofelectro-heterogeneouscatalyticoxidationreactionwasdiscussed.Thesynergismofelectro-Fentonandheterogeneacscatalyticoxidationmethodreintorcedthetreatmentoflandfillleachate.Keywordselectro-heterogeneouscatalyticoxidationparticleelectrodewastewatertreatmentlandfillleachatecatalyst,,NH3N.[13].(ECO),ECO[45].(BPBC),·OH[68].,.,,(GAC),γAl2O3,(EHCR),.20070529*,,[e-mail]1322811.1.,,;COD1806.5mg/L,BOD5/COD0.3,;,1637.5mg/L.1.2CuO/γ-Al2O3:,γAl2O3,24h,10510h,4004h,CuCuO/γAl2O3.CuOCeO2/γAl2O3:,CeO2/γAl2O3,10510h,4004h.Cu(NO3)2,24h,10510h,4004h,.wCuO/γAl2O3wCuOw′CeO2/γAl2O3,ww′CuCe.1.34(1).,,6.0cm×12.0cm,5.0cm.100mL1:1GAC(,2~3mm,3~4mm)γAl2O3(,3~4mm,260~300m2/g).789106VA213451Fig.1Schematicdiagramoftheexperimentalapparatus1.2.3.4.5.6.7.8.9.10.,.,,350mL,,,,.,,.1.41.4.1FEIQuanta200,,3.5nm.Rigaku-D/Max-2500X,Cu,0.02,40kV,100mA.:η(ηEHCRηBPBC)/ηBPBC(1):ηEHCRGACE-HCRCOD;ηBPBCGACγAl2O3BPBCCOD.1.4.2(TOC)SHIMADZUTOCVCPH;CODCOD;NH3N;pHMETTLERTOLEDO320;HACHDR/4000U22.19(1).CuO/γAl2O3,2%,.,,;,CuO,M,,M,H2O2,,2133.1*Table1Catalyticactivityofvariouspackingmaterials(%)(%)CODNH3NTOCγAl2O358.214.841.51%CuO/γAl2O370.920.244.021.82%CuO/γAl2O382.836.452.542.33%CuO/γAl2O378.733.951.535.24%CuO/γAl2O373.830.649.226.82%CuO3%CeO2/γAl2O384.045.154.244.32%CuO6%CeO2/γAl2O385.848.257.747.42%CuO9%CeO2/γAl2O389.851.360.354.32%CuO12%CeO2/γAl2O386.149.555.847.9:*:10.0V,pH7,0.04m3/h,180min;2%,Ce,CuOCeO2/γAl2O3CuO/γAl2O3.Ce9%.CeO2,,;CeO2,Ce4+/Ce3+.CeO2,CeO2,CeO2[9].,,2%CuO9%CeO2/γAl2O3,54.3%.2.22.γAl2O3[2(a)],.CuO[2(b)],γAl2O3,,.Ce[2(c)],,,,.(a)γAl2O3(b)2%CuO/γAl2O3(c)2%CuO9%CeO2/γAl2O32(×1000)Fig.2SEMimagesofvariouscatalysts(×1000)X(XRD),3.γAl2O3[3(a)]2θ37.5°45.9°67.4°3γAl2O3.2%CuO/γAl2O3XRD[3(b)],CuO,.CeO2[3(c)],CeO2,2θ28.5°,33.3°,47.6°56.5°CeO2.CuO,CuOCeO2/γAl2O3,CuOCeO2.2.3.2%CuO/γAl2O32%CuO9%CeO2/γAl2O3,2GACEHCR,2.2%CuO/γAl2O3,13428,;,2%CuO9%CeO2/γAl2O3,5,COD70%,NH3N40%,TOC11.8%.,Ce,.1020304050607080(c)(b)(a)Al2O3CeO22θ(°)3XRDFig.3XRDpatternsofvariouscatalysts(a)γ-Al2O3;(b)2%CuO/γ-Al2O3;(c)2%CuO-9%CeO2/γ-Al2O32*Table2Experimentonpackingmaterialsstability(%)CODNH3NTOC2%CuO/γAl2O3182.836.452.5270.238.749.0360.131.247.8453.428.247.2551.623.544.12%CuO9%CeO2/γAl2O3189.851.360.3285.743.758.9379.639.157.5475.338.555.9572.538.053.2:*10.0V,pH7,0.04m3/h,180min;,,,,.,.2.4GAC2%CuO9%CeO2/γAl2O3E-HCR,.pH,,180min,TOC,L9(34).3Table3Orthogonaltestresult(V)pH(m3/h)(cm)TOC(%)110.030.042.058.2210.070.083.055.7310.0110.124.059.3415.030.084.078.7515.070.122.077.4615.0110.043.073.2720.030.123.075.1820.070.044.072.8920.0110.082.073.5m157.770.768.169.7m276.468.669.368.0m373.865.367.366.9R18.75.42.02.83,,TOC75%.,pH.:15.0VpH30.08m3/h2.0cm.3,,.Fenton.::+−→−2Fe2eFe(2):222OH2e2HO→++−+(3):+−+++⋅→+3222FeOHOHOHFe(4)↓→+−+33Fe(OH)3OHFe(5),Fe2+2135H2O2Fenton,·OH(2.8V),.Fe3+OHFe(OH)3,Fe(OH)3,.,,Cu.Cu2+H2O2,·OH,CuO:OHOHCuOOHCuO22⋅++→+−+(6)22OCuOOCuO+→+−+(7)Ce,CeO2,,Ce4+/Ce3+:234222CeO2H2CeHO+++++→+(8)2324OCeOCe+→++−+(9)44.12%CuO9%CeO2/γAl2O3;5,GAC2%CuO9%CeO2/γAl2O3COD70%..Ce,.4.215.0V,pH3,0.08m3/h,2.0cm,pH.4.3EHCRFenton,,Ce,,.[1]OmanC.Identificationoforganiccompoundsinmunicipallandfillleachate[J].EnvironmentalPollution,1993,80(3):265271.[2]WiszniowskiJ,RobertD,Surmacz-GorskaJ,etal.Landfillleachatetreatmentmethods:areview[J].EnvironmentalChemistryLetter,2006,4:5161.[3],,.CODNH3-N[J].,2003,25(4):211214.[4],,,.MnSnSb/γAl2O3[J].,2006,64(3):235239.[5]AnTaicheng,ZhangWenbing,XiaoXianming,etal.Photoelectrocatalyticdegradationofquinolinewithanovelthree-dimensionalelectrode-packedbedphotocatalyticreactor[J].JournalofPhotochemistryandPhotobiologyA:Chemistry,2004,161:233242.[6]KongWuping,WangBo,MaHongzhu,etal.Electrochemicaltreatmentofanionicsurfac