MnCe复合催化剂湿式氧化降解高浓度吡虫啉农药废水的研究

27320073ActaScientiaeCircumstantiaeVo.l27,No.3Mar.,2007:(No.04JK235);(No.2004B28)SupportedbytheSpecialFoundationoftheEducationDivision,ShanpxiProvince(No.04JK235)andNaturalScienceFoundationofShanpxiProvince(No.2004B28):(1964)),,;*(),E-mai:[e-mail]:ZHAOBinxia(1964)),female,associateprofessor;*Correspondingauthor,E-mai:l:[e-mail],,,.2007.Mn/Ce[J].,27(3):408-412ZhaoBX,LiHY,LiuLX,etal.2007.StudyoncatalyticwetairoxidationofpesticidewastewaterofimidaclopridproductionoverMn/Cecatalyst[J].ActaScientiaeCircumstantiae,27(3):408-412Mn/Ce赵彬侠1,2,*,李红亚1,刘林学1,张小里1,韩玉英1,金奇庭21.西北大学化工学院,西安7100692.西安建筑科技大学环境与市政工程学院,西安710055:2006-03-16:2006-11-25:2006-12-30:Mn/Ce,BETXRD,Mn/Ce,.,Mn/Ce,15nm;,,;,,1.6MPa,;,190e1.6MPapH6.21120min,COD93.1%;Mn/Ce.:;Mn/Ce;;:0253-2468(2007)03-0408-05:X703:AStudyoncatalyticwetairoxidationofpesticidewastewaterofimidaclopridproductionoverMn/CecatalystZHAOBinxia1,2,*,LIHongya1,LIULinxue1,ZHANGXiaoli1,HANYuying1,JINQiting21.SchoolofChemicalEngineering,NorthwestUniversity,Xi.an7100692.SchoolofEnvironmentalandMunicipalEngineering,Xi.anUniversityofArchitectureandTechnology,Xi.an710055Received16March2006;receivedinrevisedform25November2006;accepted30December2006Abstract:Mn/Cecatalystwaspreparedwiththeco-precipitationmethodandappliedtothetreatmentofpesticidewastewaterofimidaclopridproductionbycatalyticwetairoxidation.ThecatalystwascharacterizedbymeansofBETspecificsurfaceareameasurementandXRD.Theeffectofthecalcinationstemperatureontheactivityandstabilityofthecatalystwasinvestigated.TheeffectsofcatalyticreactiontemperatureandpartialpressureofoxygenonCODremovalefficiencywerealsostudied.Theresultsshowedthatcrystalsizeofthecatalystislessthan15nm.SpecificsurfaceareaandtheconcentrationofleachedMnandCeincreasedandcrystalsizedecreasedwhendecreasingthecalcinationstemperature.Theactivityandstabilityofthecatalystwerealsoaffectedbythecalcinationstemperature.TheCODremovalefficiencywereobviouslyincreasedwhenincreasingreactiontemperatureofcatalyticreaction,butalmostdidnotchangewhenpartialpressureofoxygenexceeded1.6MPa.UsingMn/Cecatalyst,93.1%CODremovalefficiencywasobtainedattheconditionsoftemperatureof190e,pHof6.21andpartialpressureofoxygenof1.6MPaandtreatmenttime120min.ThisresultindicatedthatMn/Cecatalysthadgoodactivityandstabilityfortreatmentpesticidewastewaterofimidaclopridproduction.Keywords:catalyticwetairoxidation;multipleoxidecatalystofmanganeseandcerium;pesticidewastewater;imidacloprid1(Introduction)(,1997),DMF2,5-,COD1@104mg#L-1,3:Mn/Ce.,.(WAO),(125~320e)(0.5~20MPa),.,,,,,(CWAO)(Mishraetal.,1995)..,3:(1),PtRu(Dobrynkinaetal.,2005;Gomesaetal.,2005);(2),Cu(Levecetal.,1995;,2000);(3),CeO2(Shiowetal.,2003;Changetal.,2003).,,,.Imamura(1986),Mn/Ce,.CeO2-ZrO2-CuOCeO2-ZrO2-MnO2CWAO,,CeO2(Leitenburgetal.,1996).,Ce,(Changetal.,2003).CeMn/Ce,BETXRD;,;,.2(Experiments)2.1废水样品,COD38855~45660mg#L-1,100,SS200~300mg#L-1.2.2催化剂的制备Mn/Ce(,1991).Mn(NO3)2Ce(NO3)3#6H2O2B1(2mol#L-1NaOH),12h..,110e12h,300~500e6h.2.3催化剂的表征BETZXF-06,N2.D/max-3CX.2.4催化剂活性评价与废水处理实验GCF.500mL2.0g,,N2;(150~210e),(4.8MPa,1.2~2.4MPa),.30minCOD,COD.120min.2.5分析方法IRIS,.CODHACH-DR2010COD,pHPHS-3BpH.3(Results)1Mn/CeXRD(a.500e,b.400e,c.300e)Fig.1XRDspectraofMn/Cecatalystatdifferentcalcinedtemperature(a.500e,b.400e,c.300e)3.1Mn/Ce催化剂的表征,,.140927(300e400e500e)Mn/CeXRD.,CeCeO2,,329.20b48.50b57160b,433.70b;CeO2,,;,CeO2,CeO2.XRD,Ce-Mn,.CeO2XRD,Mn/Ce,,MnCeO2,CeO2,CeO2.ScherreCeO21.,Mn/Ce.,.1.,,,.300e500e,31.5%.,.1Table1Thecomparisonofcrystalsizeandspecificsurfaceareaofcatalystspreparedatdifferentcalcinationtemperature/eCeO2/nm/(m2#g-1)E13004127E24008110E35001587,,Mn/Ce,,.3.2焙烧温度对Mn/Ce催化剂活性及稳定性的影响Mn/Ce,190e1.6MPa,COD,2.,Mn/Ce.500e,120min,COD70.3%,14.1%,Mn/Ce.300e,,COD93.1%,COD36.9%.,Mn/Ce,3.1.2Mn/CeCODFig.2InfluenceofcalcinationtemperaturesofMn/CecatalystontheCODremoval,,,.2190e1.6MPa120minMnCe.2,,MnCe,Mn/Ce.:,MnOxCeO2,.,.2Table2TheconcentrationofleachedMnandCeofcatalystspreparedatdifferentcalcinationtemperature/eMn/(mg#L-1)Ce/(mg#L-1)E13000.02990.0316E24000.01820.0285E35000.00510.01193.3氧分压对CWAO反应速率的影响CWAO--.-4103:Mn/Ce,-,-.,,,.,,-,(1):v=G#k[C]m[O]n(1),G,[C][O],k,mn.,G,-.,,,GU1.,,,CWAO().3Mn/Ce.1.21.62.02.4MPa,4.8MPa190e,COD.3,1.2MPa,COD;1.6MPa,COD,.1.6MPa,COD.3Mn/CeCODFig.3InfluenceofoxygenpressuresontheCODremovaloverMn/Cecatalyst3.4温度对CWAO反应速率的影响(1).41.6MPapH=6.21(150e170e190e210e)COD,300e.,COD,210e,60minCOD92.3%;150e120min,COD45.8%.,COD;,,,,,,,190e.4Mn/CeCODFig.4InfluenceofdifferentreactiontemperaturesontheCODremovaloverMn/Cecatalyst2~4,COD,.190e93.1%56.2%,Mn/Ce,,.4(Conclusions)1)Mn/Ce,,.2)Mn/Ce.,CeO2,;.3),1.6MPa,.4),Mn/Ce.,190e4.8MPa1.6MPa,120min41127COD93.1%.5)Mn/Ce,,MnCe.References:ChangDJ,ChenIP,ChenMT,etal.2003.WetairoxidationofareactivedyesolutionusingCoAlPO4-5andCeO2catalysts[J].Chemosphere,52:943)949DobrynkinaNM,BatyginaaMV,NoskovaAS,etal.2005.CatalystsRuCeO2/sibunitforcatalyticwetairoxidationofanilineandphenol[J].TopicsinCatalysis,33(1-4):69)76GaoRJ,BaiJJ,LiuXL,etal.1997.Researchonthesynthesisofimidacloprid[J].Pesticide,36(2):13)14(inChinese)Go