催化剂载体对催化臭氧氧化活性的影响周云瑞

ISSN1000-0054CN11-2223/N()JTsinghuaUniv(Sci&Tech),20074792007,Vol.47,No.921/371481-1484催化剂载体对催化臭氧氧化活性的影响周云瑞1,　祝万鹏1,　刘福东1,　陈　迅2,　董　鑫1(1.,100084;2.,100083):2006-10-08:(50238020):(1980),(),,:,,E-mail:[e-mail]:为了制备高效稳定的催化臭氧氧化催化剂,研究了不同载体负载Ru催化剂催化臭氧氧化降解邻苯二甲酸二甲酯(DMP)的效果。结果表明:以Ru作为活性组分时,不适合采用SiO2载体;以Al2O3为载体的RuO2/Al2O3催化剂对有机物的吸附较少,催化作用明显,但是氧化过程中会产生铝溶出的问题;而以活性炭为载体的Ru/AC催化剂对有机物吸附能力较强,催化作用明显,具有很好的稳定性和较长的使用寿命,且催化过程中没有金属溶出的问题,是一种非常有潜力的催化臭氧氧化催化剂。:催化氧化;臭氧;邻苯二甲酸二甲酯;RuO2/SiO2;RuO2/Al2O3;Ru/AC:X131:A:1000-0054(2007)09-1481-04EffectsofcatalystssupportontheactivityduringcatalyticozonationZHOUYunrui1,ZHUWanpeng1,LIUFudong1,CHENXun2,DONGXin1(1.DepartmentofEnvironmentalScienceandEngineering,TsinghuaUniversity,Beijing100084,China;2.DepartmentofChemicalandEnvironmentalEngineering,ChinaUniversityofMiningandTechnology(Beijing),Beijing100083,China)Abstract:Inordertopreparetheeffectiveandstablecatalysts,thispaperstudiedthedegradationofthedimethylphthalate(DMP)duringcatalyticozonationbythreecatalyticsupports,loadedwithRu.ResultshaveconfirmedthatSiO2isnotadaptedtobethesupportwhenusingRuasactivecomponent.RuO2/Al2O3canenhancethecatalyticozonationefficiencyremarkably;theadsorptionofDMPontheRuO2/Al2O3catalystssurfaceisslightandthecatalyticreactionremovesmuchhigherproportionsofTOC,buttheleachingofaluminumionshouldbecontrolledbeforeapplied.WhileRuO2/ACcanalsoenhancetheefficiencyofmineralizationandtheadsorptionofDMPisnoteworthy.Atthesametime,Ru/ACisastableandeffectivecatalystduringozonationofDMPanddoesnotinvolvemetalleachingproblem,whichindicatesthatRu/ACisapromisingcatalystduringcatalyticozonation.Keywords:catalyticoxidation;ozonation;dimethylphthalate;RuO2/SiO2;RuO2/Al2O3;Ru/AC,O3/H2O2UV/O3UV/H2O2/O3,,[1],,,[2],Al2O3SiO2CeO2[3-6],,SiO2Al2O33Ru(dimethylphthalate,DMP),,(BET)X(XRD),1　材料与方法1.1,DHX-SS-03C(),O2,40kPa,O3118mg/h,()50mm,1200mm,1L300mL/min,Na2S2O3,20;(DMP)5mg/L,(totalorganiccarbon,TOC)4.05mg/L[7]1.2DMP(Shimadzu,LC-10AD,Japan):CH3OH/(20mmol/LKH2PO4)(V/V)=5050,1.0mL/min,40,230nmTOC0.70m,TOC(Shimadzu,TOC-Vwp,Japan)(non-purgeableorganiccarbon,NPOC),30mL,NPOCTOCX(X-raydiffraction,XRD)(Rigaku,D/max-RB,Japan),,BET(Micromeritics,ASAP2010,USA)(inductivelycoupledplasmaemissionspectrome-ter,ICP)(ThermoElectron,IRISIntrepid,USA)1.3,RuCl33H2O,30,100r/min2h,1053hRuO2/SiO2RuO2/Al2O3600()3h,Ru/AC,5003h,1L/min,2　试验结果与讨论2.111,3,13mm,SiO2Al2O3,968.9m2/g1/mm/nmBET/(m2g-1)RuO2/SiO2231.8138.4RuO2/Al2O3235.8165.8Ru/AC136.3968.91XRD1:SiO2SiO2(2=20.542,26.347,49.440)RuO2(2=28.149,35.193,54.453),RuO2/SiO2;Al2O3-Al2O3(2=25.576,35.151,43.363)RuO2,RuO2/Al2O3;C(2=41.924,43.968,47.054)Ru(2=38.180,42.225,43.880),Ru/ACRu,SiO2Al2O3600,,RuO2;,(),,,,Ru,Sherre1,10nm1XRD2.2,DMPTOC2.2.1　催化臭氧氧化对DMP的去除效果2DMP,RuO2/SiO2RuO2/Al2O310g,Ru/AC2g2:DMP,20min,RuO2/SiO21482()2007,47(9),,,,Al2O3,,2DMP2.2.2　催化臭氧氧化对反应体系TOC的去除效果Ru,+Ru435,600,20g/L,120min3TOCTOC:RuO2/SiO28.4%,RuO2/Al2O347.7%,Ru/AC50.6%,2+DMP,,RuO2/SiO2RuO2/Al2O3DMP5%,Ru/ACDMP,120minTOC33.4%(Ru,0.5%)3SiO2(Ru,1.0%)4Al2O3(Ru,2.5%)52.33:,,DMPTOC,,,,60min,60min10min,60min60min,22TOC/%60minTOC/%RuO2/SiO258.35.536.225.4RuO2/Al2O326.09.664.457.0Ru/AC27.537.834.753.92,60min3,RuO2/Al2O3Ru/AC,RuO2/SiO2,21483,:,RuO2/SiO2RuO2/Al2O3,Ru/AC,34.7%,RuO2/Al2O3,Ru/AC,RuO2/SiO2,2.42(RuO2/Al2O3Ru/AC),,20mL/min(50min),300mL/min,118mg/h,40gTOC,6:242h,RuO2/Al2O3TOC45%50%,Ru/ACTOC75%80%ICP,2Ru,RuO2/Al2O3,0.15mg/L,,,,Al2O3,,63　结　论1)RuO2/SiO2,Ru,SiO22)RuO2/Al2O3,120minDMPTOC71.6%,,TOC57%,,RuO2/Al2O3,,,Al2O33)Ru/AC,120minDMPTOC74.5%,42h,,(References)[1]LegubeB,KarpelN.Catalyticozonation:Apromisingadvancedoxidationtechnologyforwatertreatment[J].CatalysisToday,1999,53:61-72.[2],,.[J].,2001,27(6):26-29.LILaisheng,ZHUWanpeng,LIZhonghe.Catalyticozonation:Apromisingadvancedoxidationtechnologyforwatertreatment[J].Water&WastewaterEngineering,2001,27(6):26-29.(inChinese)[3]BeltranFJ,RivasFJ,RamonME,etal.ATiO2/Al2O3catalysttoimprovetheozonationofoxalicacidinwater[J].AppliedCatalysisB:Environmental,2004,47:101-109.[4]FuHX,VelLeitnerNK,LegubeB.CatalyticozonationofchlorinatedcarboxylicacidswithRu/CeO2-TiO2catalystintheaqueoussystem[J].NewJournalofChemistry,2000,26:1662-1666.[5]TongSP,LengWH,ZhangJQ,etal.Catalyticozonationofsulfosalicylicacid[J].OzoneScienceandEngineering,2002,24:117-122.[6]MaJ,SuiMH,ZhangT,GuanCY,etal.EffectofpHonMnOx/GACcatalyzedozonationfordegradationofnitrobenzene[J].WaterResearch,2005,39:779-786.[7],.Al2O3[J].,2006,27(1):51-56.ZHOUYunrui,ZHUWanpeng,Catalyticoxidationofdimethylphthalateinaqueoussolutionbyaluminumoxide[J].EnvironSci,2006,27(1):51-57.(inChinese)1484()2007,47(9)