TiO2覆膜沸石光催化剂制备及其降解造纸废水

74Vol.7No.420078TheChineseJournalofProcessEngineeringAug.20072006−09−252006−12−25(20040284)(20063202)(1967−)E-mail:[e-mail].(110142)−(Sol−Gel)TiO2X(XRD)(SEM).−pHTiO2/4.0/0.1/0.15/0.13004.0hpH4.050g/L8.0hCOD81.93%.X703A1009−606X(2007)04−0712−06TiO2[1−3].TiO2.TiO2[4]TiO2...TiO2[5−7]TiO2.−TiO2TiO2.JB5374-91[()]DF-101S()101-2()()()()().100(0.15mm)1055h.(2/3)302h(13.46m2/g)4h1/3.80TiO23004hTiO2(TiO2GB/T19591-2004).BrukerRigaku-D/max-rBX(CuKα)X(XRD)JEOLJSM-6360LV(SEM).4TiO2713500mL400W254nm.(2TiO26.57%)[(ChemicalOxygenDemand,COD)1066.67mg/L]pH15min5min.[8]CODCOD.3.1.1XRD1TiO2XRD.300300.TiO2300TiO2400TiO2850∼950[9,10]TiO2.1XRDFig.1X-raydiffractionpatternsofdifferentsamples3.1.2SEM2(a)300TiO2(b)(c).TiO2..TiO2300TiO2.XRD.TiO2TiO24.(a)Naturalzeolite(b)TiO2-coatedzeolite(c)TiO2-coatedzeoliteafterphotocatalyticdegradation2SEMFig.2ScanningelectronicmicroscopesurfaceimagesTiO2COD1.COD.COD(R2=0.9877)lnCOD=−0.2036t+6.98143CODTable1InfluenceofreactiontimeonremovalofCODTime(h)COD(m/L)CODremovalrate(%)01066.6701806.9424.352701.9834.193608.8642.924515.5251.675418.7760.746328.8569.177252.8076.308192.7581.93204060800306090120150Intensity(CPS)Naturalzeolite2003004005002θ(o)7147−ln(1−P)=kt,(1)PCOD(%),k(h−1)[11].3lnCODFig.3RelationshipbetweenlnCODandreactiontimeTiO2COD4.TiO2300COD.300TiO2COD.4.0hCOD4.0h300.4CODFig.4InfluencesofcalcinationtemperatureandtimeontheCODremovalrate30/0.1/0.15/0.1/3004h./COD5.COD./4.0Ti9(OH)x(OBu)y.4.0COD4.0.5CODFig.5InfluenceofC2H5OHandTiO(C4H9)4ratio(ϕ)ontheCODremovalrate/4.0/COD6.6CODFig.6InfluenceofusedamountofglacialaceticacidontheCODremovalrate34564050607080CODremovalrate(%)Calcinationtime(h)T()200300400500246850607080CODremovalrate(%)C2H5OH/TiO(C4H9)4ratio(ϕ)0.00.10.20.36065707580CODremovalrate(%)CH3COOH/[TiO(C4H9)4]ratio(ϕ)0123456785.25.66.06.46.8lnCODReactiontime(h)4TiO2715CH3COO−Ti.COD./0.1./0.1/COD7./0.1COD/0.1COD81.93%.7CODFig.7InfluenceofusedamountofnitricacidontheCODremovalrate/4.0/0.11.0mL/COD8.8CODFig.8InfluenceofusedamountofwaterontheCODremovalrateofpapermakingwastewater8COD(⎯OR)(⎯OH).TiO2./0.15COD.CODH2SO4NaOHpHpH50mL8.0hCOD9.pH.CODpHpH4.0CODpHCODpH4.0.9pHCODFig.9InfluenceofpHontheCODremovalrateofpapermakingwastewater50mL(pH4.0)8.0hCOD10.TiO2/CODTiO2/−⋅OH.TiO2/50g/L.COD.0.050.100.150.2065707580CODremovalrate(%)HNO3/TiO(C4H6)4ratio(ϕ)0.050.100.150.206065707580CODremovalrate(%)H2O/TiO(C4H9)4ratio(ϕ)234567556065707580CODremovalrate(%)pH716710CODFig.10InfluenceofamountofphotocatalystontheCODremovalrateofpapermakingwastewater2.5g50mL(pH4.0)COD11.COD..TiO2−TiO2(⋅OH).COD.8.0hCOD.8.0h.11CODFig.11InfluenceofradiationtimeontheCODremovalrateofpapermakingwastewaterTiO2TiO2(300)430012.TiO21TiO21.TiO2TiO2TiO2.TiO22,3,4TiO2TiO2TiO2TiO2.4COD73%(COD53.7%∼78.3%[12]68.3%[13])COD.12Fig.12Therecyclingpropertyofphotocatalyst−/4.0/0.1/0.15/0.13004.0hpH4.050g/L8.0hCOD81.93%.TiO24.2468103045607590CODremovalrate(%)Radiationtime(h)1.01.52.02.53.03.54.072757881CODremovalrate(%)Recyclingproperty(times)2.02.53.03.568727680CODremovalrate(%)Amountofphotocatalyst(g)4TiO2717[1].[J].,2002,2(2):183−185.[2]HagfeldtA,GratzelM.Light-inducedRedoxReactionsinNanocrystallineSystems[J].Chem.Rev.,1995,95(1):49−68.[3].TiO2[J].,2006,6(1):108−113.[4]HiroshiY,TsukasaT.TitaniumDioxide/AdsorbentHybridPhotocatalystsofOrganicSubstancesofDiluteConcentration[J].Catal.Today,2000,(1):1−21.[5].TiO2[J].,2005,5(1):20−22.[6].TiO2[J].,2006,(1):13−15.[7].TiO2[J].,2006,37(1):61−63.[8].MnSO4COD[J].,2003,21(5):54−56.[9].[J].,2006,27(2):240−242.[10].[J].,2005,33(1):73−76.[11]HidakaH,ZhaoJC,PelizzettiE,etal.PhotodegradationofSurfactants:8.ComparisonofPhotocatalyticProcessesbetweenAnionicDBSandCationicBDDAContheTitaniaSurface[J].J.Phys.Chem.,1992,96(5):2226−2230.[12].[J].,2002,(6):37−39.[13].WO3/α-Fe2O3/W[J].,2001,19(2):131−138.PreparationandPhotocatalyticPerformanceofTiO2-coatedNaturalZeoliteinDegradationofPapermakingWastewaterYAOShu-hua,HUALi,SHIZhong-liang(DepartmentofAppliedChemistry,ShenyangInstituteofChemicalTechnology,Shenyang,Liaoning110142,China)Abstract:UsingTi(OC4H9)4andC2H5OHasreactionrawmaterials,thephotocatalystofTiO2-coatednaturalzeolitewaspreparedbysol−gelmethod.TheexperimentaltechniquesofXRDandSEMwereusedtocharacterizethepreparedTiO2-coatedphotocatalyst.Theinfluencesofcomponentsofsol−gelsystem,calcinationtemperatureandtime,amountofcatalyst,radiationtimeandpHvalueonthephotocatalyticdegradationofpapermakingwastewaterontheTiO2coatednaturalzeolitewerestudied.Theoptimalexperimentalconditionswereobtained:thevolumeratiosofC2H5OHtoTiO(C4H9)44.0,CH3COOHtoTiO(C4H9)40.1,H2OtoTiO(C4H9)40.15andHNO3toTiO(C4H9)40.1,calcinationtemperature300,calcinationtime4.0h,amountofcatalyst50g/L,pHvalueofpapermakingwastewater4.0,andradiationtime8.0h,theCODremovalrateofpapermakingwastewaterreached81.93%undertheconditions.TheexperimentalresultsshowthatTiO2-coatednaturalzeolitehasagoodphotocatalyticactivitytodegradepapermakingwastewater.Keywords:titaniumdioxide;naturalzeolite;photocatalysis;papermakingwastewater