催化湿式氧化中多相非贵金属催化剂的研究进展闫海生

　2006263　　　　　　　　　　　　　ENVIRONMENTALPROTECTIONOFCHEMICALINDUSTRY[]2005-11-22;[]2005-12-28。[](1973—),,,,,。:024-85869014;:[e-mail]。,　,,,(,110021)[](CWAO)、。。,,。。[];;;[]X703　　　[]A　　　[]1006-1878(2006)03-0213-05ProgressesinResearchofHeterogeneousNon-nobleMetalCatalystsUsedinCatalyticWetAirOxidationProcessYanHaisheng,LiuBo,YuWeifu,XuanYongmei,LiuDongxue(ShenyangResearchInstituteofChemicalIndustry,ShenyangLiaoning110021,China)Abstract:Catalyticwetairoxidation(CWAO)processisanewtechnologyofusingdissolvedoxygentoremovecontaminantswithhightoxicityandlowdegradabilityfromwastewater.Twokindsofcatalysts,noblemetalcatalystsandnon-noblemetalcatalysts,canbeusedinCWAOprocess.Usingnon-noblemetalcatalystsinsteadofnoblemetalcatalystsismoreeconomicalinwastewatertreatmentwithzero-additional-value.Non-noblemetalcatalystsusedinCWAOprocessinrecentyearsaresummarized.Keywords:catalyticwetairoxidation;non-noblemental;heterogeneouscatalyst;wastewatertreatment　　,(CatalyticWetAirOxidation,CWAO)。CWAO()、,、,,CO2H2O,N2,PO3-4SO2-4,COD,[1]。CWAO,()。,,,,,;,,,。CWAO,。,。CWAO。1　多相催化剂载体的选择。CWAO、、、(),CWAO(、[2]),、,·213·　　　　　　ENVIRONMENTALPROTECTIONOFCHEMICALINDUSTRY　　　　　　200626。CWAOAl2O3[3]、SiO2、[4～6]、[7]。Al2O3、SiO2、、、、(),,、、,;,。TiO2、CeO2、ZrO2,、,CWAO[8～12]。、、、、。,,,2～20mm。2　多相非贵金属催化剂,Cu,Ag,Co,Cr,Ni,Mn,Zn,Fe,Mo。,。,CWAO。2.1　,,,。,,。、、、pH。。pH(KSP);[13,14]。,,、。CWAOCo-Bi[15,16]CuMn[3,17]、Fe[17]、Zn[3,13]、Co[3]Ni[3]。Cu,,Cu2+。CWAO,K2O[13,17]Cu/Al2O3,Cu-K/Al2O3,,COD。,Cu2+,K2OCu2+19mg/L,K2OCu2+70mg/L,。,Cu-Al-Zn-O[18～23]Cu-Ni-Al-O[14],,。Cu-Al-Zn-O,、,0.5MPa160～220℃,0.3mg/L。m(CuO)∶m(ZnO)∶m(Al2O3)42∶47∶10。X(XRD)、X(XRF)-(TG-DTA),Cu-Al-Zn-O:CuO,CuO。Cu2+、,。(Cu),,(Cu2+)。,,,。Cu,Co,Cr,Ni,Mn,Zn,Fe,Mo,[24]。CWAO,Cu-Al-Zn-OCu-Ni-Al-O,、。·214·　3.Al2O3,,CWAOCu-Al-Zn-O。2.2　-,,,CWAOCeO2,。[25]:;,;;。1-。1　-[26,27]Cu,Cu-CeH;,,pH,;,,,[28]Cu,Ce,Cd,Co-Bi415HCe-Cu,。pH[23,29]Mn-Ce-O,Co-Ce-O,Ag-Ce-OMn-Ce-O,,[30～36]Mn-Ce-O;Mn-Ce-O[3,37]Cu,Cu-C,Cu-M,Cu-Mn-CeAl2O3Cu-Mn-Ce。CeO2,,。Cu-Mn-Ce3,[11]Ce-Zr-Cu-O,Ce-Zr-Mn-OCe-Zr-Cu-OCe-Zr-Mn-O,。,　　1-,Mn-Ce-O、,,、、。,,。CWAO。Mn-Ce-O,,[30,38,39]。Mn-Ce-O,,[40],-(TPO-MS)、(SEM)、X(XPS/ESCA)[41]。[34,41]。,,,,。Belkacemi[38](ESCA),。Hamoudi[30,39]XPS,,:C2.5%50%,MnCe35%9%1.7%0.5%。,,。,。Mn-Ce-O(K2O[34,36]Cs2O[32])Mn-Ce-O,。3　结语,,。·215·　　　　　　ENVIRONMENTALPROTECTIONOFCHEMICALINDUSTRY　　　　　　200626,、、。,。,,、,,。,Cu-Al-Zn(Ni)-OMn-Ce-O,,。　　　1　DebellefontaineH,FoussardJN.Wetairoxidationforthetreatmentofindustrialwastes.Chemicalaspects,reactordesignandindustrialapplicationsinEurope.WasteMan-agement,2000,20(1):15～252　,,..,2003,24(1):107～1123　.:〔〕.:,20044　StǜberF,FontJ,FortunyA,etal.Carbonmaterialsandcat-alyticwetairoxidationoforganicpollutantsinwastewater.TopCatal,2005,33(1～4):3～505　Suarez-OjedaME,StuberF,FortunyA,etal.Catalyticwetairoxidationofsubstitutedphenolsusingactivatedcar-bonascatalyst.ApplCatalB,2005,58(1,2):105～1146　GarciaJ,GomesHT,SerpP,etal.PlatinumcatalystssupportedonMWNTforcatalyticwetairoxidationofnitrogencontainingcompounds.CatalToday,2005,(102～103):101～1097　GuoJ,Al-DahhanM.Catalyticwetairoxidationofphenolinconcurrentdownflowandupflowpacked-bedreactorsoverpillaredclaycatalyst.ChemEngSci,2005,60(3):735～7468　BessonM,GallezotP.Stabilityofrutheniumcatalystssup-portedonTiO2orZrO2incatalyticwetairoxidation.TopCatal,2005,33(1～4):101～1089　LuckF,RechercheA.Wetairoxidation:past,presentandfuture.CatalToday,1999,53(1):81～9110　RenardB,BarbierJJ,DuprezD,etal.Catalyticwetairoxidationofstearicacidonceriumoxidesupportednoblemetalcatalysts.ApplCatalB,2005,55(1):1～1011　LeitenburgCD,GoiD,PrimaveraA,etal.Wetoxida-tionofaceticacidcatalyzedbydopedceria.ApplCatalB,1996,11(1):29～3512　,,.Ru/ZrO2.,2004,23(6):621～62513　,,.Cu.,2000,21(4):82～8514　AlejandreA,MedinaF,RodriguezX,etal.Cu/Ni/Allayereddoublehydroxidesasprecursorsofcatalystsforthewetairoxidationofphenolaqueoussolutions.AppliedCatalysisB,2001,30(1～2):195～20715　ImamuraS-l,HlranoA,KawabataN.Wetoxidationofaceticacidcatalyzedbyco-bicomplexoxides.IndustrialEngineeringChemistryProductResearchandDevelop-ment,1982,21(4):570～57516　JiangP,ChengT,LiuY,etal.Theeffectofmicro-mor-phologyofBi2O3oncatalyticpropertiesofCo/Bicatalystforwetairoxidationofaceticacid.ReactKinetCatalLett,2004,82(1):49～5617　,,..,2000,20(3):6～1018　MantzavinosD,HellenbrandR,LivingstonAG,etal.Catalyticwetoxidationofp-coumaricacid:Partialoxida-tionintermediates,reactionpathwaysandcatalystleac-hing.ApplCatalB,1996,7(3～4):379～39619　,,..,CN01135047.4,200220　,,..,CN1358567A.200221　.:〔〕.:,200322　,,..,2003,24(5):328～332.23　SilvaAMT,Quinta-FerreiraRM,LevecJ.Catalyticandnoncatalyticwetoxidationofformaldehyde.Anovelkineticmodel.IndEngChemRes,2003,42(21):5099～510824　,,..,1999,17(4):14～2025　,,..,2002,34(4):540～54426　,,..,2004,23(4):361～36527　HocevarS,BatistaJ,LevecJ.WetoxidationofphenolonCe1-xCuxO2-δCatalyst.JCatal,1999,184:39～4828　ZhuW,BinY,LiZ,etal.Applicationofcatalyticwet·216·　3.airoxidationforthetreatmentofH-acidmanufacturingprocesswastewater.WaterRes,2002,36(8):1947～195429　SilvaAMT,Castelo-BrancoIM,Quinta-FerreiraRM,etal.Catalyticstudiesinwetoxidationofeffluentsfromformaldehydeindu