催化湿式氧化BIPB化工废水滴流床反应器系统建立李宁

doi:10.3969/j.issn.1671-7775.2009.06.020BIPB李　宁1,李光明2,陶润先3,赵建夫2,储金宇1(1.,212013;2.,200092;3.,300074):为经济有效地降解高质量浓度化工有机废水,采用连续式固定床反应器进行催化湿式氧化处理,操作运行处于滴流区域.制备的锰铈复合氧化物负载型催化剂具有良好的活性和稳定性,将废水TOC去除率提高20个百分点以上,连续运行50h催化剂仍维持较好的反应活性,其活性组分抗反应溶出性能优异.较小空时(9.43min)时废水已得到较好处理,进一步增大空时对提高废水处理效果并不明显.催化湿式氧化处理不同质量浓度有机废水具有较好的适应性,高质量浓度废水未对反应系统产生明显的抑制.:化工过程废水;废水处理;催化湿式氧化;滴流床反应器;催化剂;锰铈氧化物:X703.1　　:A　　:1671-7775(2009)06-0627-05CatalyticwetairoxidationofBIPBchemicalprocesswastewaterintricklebedreactorLiNing1,LiGuangming2,TaoRunxian3,ZhaoJianfu2,ChuJinyu1(1.SchoolofEnvironment,JiangsuUniversity,Zhenjiang,Jiangsu212013,China;2.StateKeyLaboratoryofPollutionControlandRe-sourceReuse,TongjiUniversity,Shanghai200092,China;3.WaterSupplyWastewaterDrainageResearchDivision,NorthChinaMu-nicipalEngineeringDesignResearchInstitute,Tianjin300074,China)Abstract:Ahigh-strengthorganicwastewater,whichneedstobetreatedcost-effectivelyinChina,wasdisposedbycatalyticwetairoxidation(CWAO)inatricklebedreactor(TBR).Thefixedbedreactorwasoperatedinatrickleflowregimebyadjustingthehydrodynamicparameters.Theloadedcatalystcom-posedofactivecomponents,manganeseandceriumoxides,wasdevelopedandwascharacterizedbyitshighactivityandstability.TOCremovalefficiencywasincreasedby20percentcomparedtowetairoxi-dation(WAO)atthesameconditions.Moreover,thecatalystwaskeptcomparativelystableactivitywith-in50hours.Metalcationleachingoftheactivecomponentswasrelativelylow.Theorganicsinthewastewaterwereeffectivelyremovedevenatshortspacetime(9.43min).Thecontaminantremovaleffi-ciencywasnotsignificantlyenhancedatlongerspacetime.Varioushigh-strengthorganicwastewatershadlittleeffectontheCWAOtreatment.Keywords:chemicalprocesswastewater;wastewatertreatment;CWAO;tricklebedreactor;catalyst;manganeseandceriumoxides:2009-01-06:“863”(2002AA601260);(1283000307):　(1969—),,,,([e-mail]),.(1963—),,,,(,[e-mail]),.()第30卷　　　　　,[1].,,,,,.,,.()(WAO),、、、、[2].(CWAO),.,,,CWAO[3].,　,,CWAO.1　1.1　BIPB“”,,.BIPBTBH、,,.,CODCr17200～62900mg·L-1,TOC4900～17800mg·L-1.1.2　,,1.1　Fig.1　Schematicplanoftricklebedreactor1.3　(AR).CODCr;TOCTOC-500;pHS-25pH;Mn,Ce,AlICP-AES,IRISIntrepid.1.4　,γ-Al2O3,,628第6期　李　宁等:催化湿式氧化BIPB化工废水滴流床反应器系统建立2.0%5.0%,600℃,12h.XRD,.D8-AdvanceX,CuKa,40kV,40～60mA.XXPSESCA,.PHI-5000ESCASystemX,AlKa,1486.6V,1.33×10-7Pa,46.95eV.2　2.1　XRD2.,CeO2Al2O3,(600℃),MnOx,[4-5].,MnOxCeO2,CeO2MnOx,MnOx.ScherrerCeO2γ-Al2O39.8nm15.5nm,.2　XRDFig.2　X-raydiffractionspectrumofcatalyst3Mn2pXPS,MnOx.,Mn2p,(bindingenergy,BE)8eV(Mn2p1/2).,.Mn2p,MnO2,Hamoudi[6].3　XPSFig.3　X-rayphotoelectronspectroscopyspectraofcatalysts2.2　1.Gianetto[7],,,Gianetto4.,,.Larachi[8],0.1558～0.2348,0.6634～0.9002.,,CWAO.1　Tab.1　Experimentaloperationparameters/mm0.60～0.80/℃200,220,240,260,270,280/MPa2.5,3.5,5.0,6.0,6.5,7.0/g20.0pH5.0,7.0,10.0,11.0/(L·h-1)0.045,0.075,0.150,0.360/h-11.91,3.18,6.37,15.3/(kg·m-2·s-1)0.159,0.265,0.531,1.273/(L·h-1)6.0,12.0,18.0/(kg·m-2·s-1)0.0303,0.0606,0.09090.404　Fig.4　Generalizedflowregimemap629()第30卷　　　2.3　CWAO,:CODCr35810～40410mg·L-1;pH13.0～14.0,HNO310.0();0.075L·h-1,(liq-uidhourlyspatialvelocity,LHSV)3.18h-1,(spacetime,ST)18.87min;12.0L·h-1();240℃;3.5MPa.50h,CODCr,5.,50h,2hCWAO.5　Fig.5　StabilityofcatalystsCWAO,.:CODCr=62860mg·L-1,t=260℃,p(O2)=5.0MPa,ST=9.43min.2.,γ-Al2O3,Mn,.,Ce,.Na.2　Tab.2　Concentrationsofmetalionsineffluents　mg·L-1/hρ(Mn)ρ(Ce)ρ(Al)ρ(Na)50.0150.00113.8019.80100.0160.00135.1017.67150.0010.0012.3812.352.4　CWAOγ-Al2O3γ-Al2O3,WAOCWAO,TOC.:TOC=8850～10900mg·L-1,t=240℃260℃,p(O2)=3.5MPa5.0MPa,ST=3.93～31.42min().6.CWAOTOCWAO20,.6　Fig.6　CatalyticactivityinCWAO2.5　CWAO,:TOC=9127～10900mg·L-1,t=200～280℃,p(O2)=2.0～6.5MPa.7.,,,TOC,260℃,.260℃280℃,TOC3%,CWAO.7　CWAOFig.7　EffectofreactiontemperatureonTOCremoval,CWAO,,CWAO,,,.TOC,(ST=9.43min,LHSV=6.37h-1),,,,.ST(LHSV),,630第6期　李　宁等:催化湿式氧化BIPB化工废水滴流床反应器系统建立,.,CWAO,CWAO,,.2.6　BIPB,CWAO,:TOC=4870,941017300mg·L-1,t=260℃,p(O2)=5.0MPa.8.8　CWAOFig.8　EffectoforganicconcentrationininfluentonTOCremoval,TOC,.,CWAO.,CWAOCODCr10000～100000mg·L-1(TOC3000～30000mg·L-1),[1].,,CWAOTOC.,,TOC13;,TOC8.(9.43min),,ST(LHSV),.3　　(1),CWAO,.(2),CWAO.(3)CWAO,TOC,,,.(4)CWAO,CWAO.(References)[1]　LevecJ,PintarA.Catalyticwet-airoxidationprocesses:areview[J].CatalysisToday,2007,124:172-184.[2]　BhargavaSK,TardioJ,PrasadJ,etal.Wetoxidationandcatalyticwetoxidation[J].IndEngChemRes,2006,45:1221-1258.[3]　　,,,.[J].:,2008,29(4):344-347.LiNing,LiGuangming,ZhaoJianfu,etal.Treatmentofhigh-concentrationphenolwastewaterbycatalyticwetairoxidation[J].JournalofJiangsuUniversity:NaturalScienceEdition,2008,29(4):344-347.(inChi-nese)[4]　ImamuraS,AndoA.Oxidationoftristearinonmanga-nese/ceriumcompositeoxide[J].IndEngChemRes,1989,28:1452-1456.[5]　LiNing,LiGuangming,YaoZhenya,etal.Preparationofrare-earthmetalcomplexoxidecatalystsforcatalyticwetairoxidation[J].FrontEnvironSciEnginChina,2007,1(2):190-195.[6]　HamoudiS,LarachiF,AdnotA,etal.CharacterizationofspentMnO2/CeO2wetoxidationcatalystbyTOP-MS,XPS,andS-SIMS[J].JournalofCatalysis,1999,185:333-344.[7]　GianettoA,SecchiaV.Trickle-bedreactors:stateofartandpe