CWO法处理高浓度有机废水中催化剂的研究进展李桂菊

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CWO[]、。,,。,,,,,。[];;[]X703.1[]B[]1005-829X(2009)11-0011-0411211.3004572.300451Abstract:Catalyticwetoxidation(CWO)isanefficientmethodfortreatingorganicwastewaterthatishighlycon-centrated,toxic,anddifficulttobebiodegraded.Thetechnologyofcatalyticwetoxidationissummarized.Em-phasesisplacedontheintroductionofthecategoriesofcatalyticwetoxidation,advantagesanddisadvantagesofdifferentcatalystsandtheirresearchprogressinChinaandabroad,aswellasitsapplicationtowastewatertreat-ment.Itisprospectedthatthecopper-basedcatalystscombiningwithrare-earth-typeelementsaretheresearchdi-rectionofthecatalystsintheCWOtechnology.Onthebasisofkeepinghighactivityofheterogeneouscatalyst,itisnecessarytoreducethedissolutionofactivecomponentsinordertoenhancethestabilityofthecatalyst.Keywords:organicwastewaterwithhighconcentration;catalyticwetoxidation;catalystResearchprogressinthetreatmentofcatalystsinhighlyconcentratedorganicwastewaterbyCWOmethodLiGuiju1,LeiGangxing1,CaiYongkai2,HeYingchun1(1.DepartmentofEnvironmentalScienceandEngineering,TianjinUniversityofScience&Technology,TianjinKeyLaboratoryofMarineResources&Chemistry,Tianjin300457,China;2.HuataiContainerServiceCo.,Ltd.,Tianjin300451,China)〔1-2〕,、、、、、、。、。(CWO)20,。,,。,,。,、、,,,〔3〕。1CWO、。,,。[](2008GC10-04)2911200911IndustrialWaterTreatmentVol.29No.11Nov.,200911——2009-11,29(11)1.1CWO。,。,,,、、,。,Co、Cu、Fe、Ni、V、Mn。S.Imamura〔4〕,235℃,2.19MPa,Cu(NO3)2,Fe(NO3)3,,Zn(NO3)2。Cu(NO3)2CuSO4CuCl2。〔5〕。178~236℃,0.98~2.94MPa,Mn()、Cu()、Fe(),。,、、100%,COD62%~90%,。1.2,。,,,。,,,。、、,,、3〔6-7〕。1.2.1I.I.Ioffe〔8〕,Pt、Pd、RhRe。250℃,30min,2%,0.2mol/L,RePdRhPt。J.Atwater〔9〕5%Ru15%Pt,60℃。1.2.2J.Levec〔10〕,CuO-ZnO,252~286℃,6.70~7.25MPa,,。、,,。〔11〕,Cu,pHKsp;。〔12〕,,Cu2+。600℃,CuO,,,CuO,,,。1.2.3,,Ce。,,。S.Imamura〔13〕、Mn-Ce(7∶3),、、、、,Co-Bi(5∶1)。(ESR)(ESCA),Ce,Mn3+、Mn2+。Ce,Mn(2p3/2),Ce(3d5/2),,。S.Hoc姚ervar〔14〕CuO-CeO2,。Sol-Gel2,:Sol-Gel25%,,Cu5.7mg/L,Cu119mg/L。,,,12——2009-11,29(11)。2CWO,、、、,。、、,、。2.1A.Garg〔15〕60%CuO/40%CeO2,60%CuO/40%MnO25%CuO/95%3,CWO3。5%CuO/95%,8g/L,200℃,0.85MPa,COD96%。D.B.Akolekar〔16〕Cu、Mn、PdCu/Mn、Mn/Pd、Cu/Pd,,463K、P(O2)=0.74MPapH11.3,TOC:Cu/Mn57.8%,Mn/Pd74.1%,Cu/Pd78.8%。2.2,6t/d,TiO2ZrO2,Fe、Co、Ni、Ru、Rh、Pd、Ir、Pt、Au、Tu,,。11000h,,CODNH3-N99.6%〔17〕。〔18〕,,、、,、Ru-Ce/TiO2,COD、NH3-N99.5%99.9%。2.3〔19〕-,H-CWO。CWO。、、、pHCWOH-。,248℃、4.0MPa、2.0h-1、V()∶V()=220∶1,pH=6.0,COD46391mg/L、5600H-,COD95.4%98.2%。,BOD5/COD0.3,。,。3,、,、,,,。,。,:(1)、,,、。(2),、、、。(3),,。,,,。[][1],.[M].:,2001:52-53.[2]MirandaB,DiazE,OrdonezS,etal.Oxidationoftrichloroetheneovermetaloxidecatalysts:Kineticstudiesandcorrelationwithad-sorptionproperties[J].Chemosphere,2007,66(9):1706-1715.[3].[J].,2004,23(2):101-106.[4]ImamuraS,SakaiT,IkuyamaT.Wetoxidationofaceticacidcat-alyzedbycoppersalts[J].JapanPetrol.Inst.,1982,25(2):74.[5],,,.[J].,1988,8(1):98-101.[6],,.[J].,2003,16(4):39-44.[7].[D].:,2006.[8]IoffeII,RubinskayaEV.Reactionofcatalyticoxidationbyliquidwateranditsapplicationtowastewaterpurification[J].Ind.Eng.Chem.Res.,1997,36:2483-2486.,:CWO13——[](1969—),1992,,。:13110049598,E-mail:liguij@tust.edu.cn。[]2009-06-20()[9]AtwaterJ,AkseJR,MckinnisJA,etal.Lowtemperatureaque-ousphasecatalyticoxidationofphenol[J].Chemosphere,1997,34(1):203-212.[10]LevecJ,SmithJ.Oxidationofaceticacidsolutionsinatrickle-bedreactor[J].J.AIchE,1976,22(10):159-168.[11],,,.Cu[J].,2000,21(7):82-85.[12],,,.[J].,2003,4(3):19-22.[13]ImamuraS,NakamuraM,KawabataN,etal.Wetoxidationpoly(ethyleneglycol)catalyzedbymanganese-ceriumcompositeoxide[J].Ind.Eng.Chem.Prod.Res.Dev.,1986,25(1):34-37.[14]HoevarS,KraovecUO,OrelB,etal.CWOofphenolontwodifferentlypreparedCuO-CeO2catalysts[J].Appl.Catal.B:En-vironmental,2000,28(2):113-125.[15]GargA.MishraIM,ChandS.Catalyticwetoxidationofthepre-treatedsyntheticpulpandpapermilleffluentundermoderatecon-ditions[J].Chemosphere,2007,66(9):1799-1805.[16]AkolekarDB,BhargavaSK,ShirgoankarI,etal.Anenviron-mentalsolutionfororganicpollutantremovalfrompaperandpulpindustrialwasteliquor[J].AppliedCatalysisA:General,2002,236(1/2):255-262.[17],.[M].:,2001:179-181.[18],,,.[J].,1996,16(6):11-13.[19],,,.H-[J].,2004,24(9):25-27.[],,,、、pH、、。,COD50%。[];;[]X703.1[]B[]1005-829X(2009)11-0014-041231212121.1000832.1000833.330012Abstract:Suspendedcarriersbiologicalfluidbedisanewstyleofreactor.Itscharacteristicsandexperimentalmethodsareintroduced.Andtheremovalefficiencyoforganiccompoundsincokingwastewaterhasbeenstud-ied.Theeffectsoftheinfluentialfactors,suchashydraulicretentiontime,temperature,pH,aerationamount,andfillingratiooffillersonthetreatmentefficiencyareinvestigated.TheresultsshowthattheaverageremovalrateofCODcouldreach50%.Keywords:suspendedcarriers;biologicalfluidbed;cokingwastewaterStudyonthetreatmentofcokingwastewaterbysuspendedcarriersbio-fluidbedreactorMaLongli1,2,3,LiSuqin1,2,XiongGuohong1,2,CangDaqiang1,2(1.KeyLabofEcologyandCyclingMetallurgy,DepartmentofEducation,Βeijing100083,China;2.DepartmentofEcologicalScienceandEngineering,SchoolofMetallurgicalandEcologicalEngineering,UniversityofScienceandTechnologyBeijing,Beijing100083,China;3.NanchangChangliIronandSteelCo.,Ltd.,Nanchang33001

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