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:0253-9837(2008)03-0253-06:253～258:2007-09-03. :,,1968,,.:.Tel:(020)39366904;E-mail:gzdxlzl@163.com.:(20466001);(2004ZD01);(62040).SnO2曾玉凤1,3, 刘自力1,2, 刘宏伟4(1广西大学化学化工学院,广西南宁530004;2广州大学化学化工学院,广东广州510006;3玉林师范学院,广西玉林537000;4中化药业(天津)有限公司,天津300380):SnO2,SnO2,.X、(TG-DSC),SnO2.,SnO2,60min,43.04%60.24%.SnO2,SnO2,.723K.SnO2,L.SnO2,L,.:;;:O643 :APreparationandCatalyticOzonationActivityofSnO2ZENGYufeng1,3,LIUZili1,2＊,LIUHongwei4(1SchoolofChemistryandChemicalEngineering,GuangxiUniversity,Nanning530004,Guangxi,China;2CollegeofChemistryandChemicalEngineering,GuangzhouUniversity,Guangzhou510006,Guangdong,China;3YulinNormalUniversity,Yulin537000,Guangxi,China;4SinochemPharmaceutical(Tianjin)Co.,Ltd.,Tianjin300380,China)Abstract:Heterogeneouscatalyticozonationtechnologyisanewozoneoxidationmethodandcandegradeorganiccompoundsthatcannotbeoxidizedordegradedbyozonealoneatroomtemperatureandnormalpressure.ASnO2catalystwaspreparedbytheprecipitationmethodandusedindecolorizationofmolassesfermentationwastewaterthroughozonation.Effectsofprecipitantsandcalcinationtemperatureonthecatalyticozonationac-tivityofSnO2werestudiedbyX-raydiffraction,infraredspectroscopy(IR),andthermalanalysis(TG-DSC).TheresultsshowedthattheSnO2catalystexhibitedconsiderablyhighcatalyticactivityforthecatalyticozonationdecolorizationofmolassesfermentationwastewater.Thedecolorizationrateofthewastewaterwasenhancedfrom43.04%(usingozoneoxidationalone)to60.24%.TheactivityoftheSnO2catalystwassignificantlyaf-fectedbytheprecipitants.SnO2preparedusingammoniaastheprecipitantshowedhigherdegreeofdehydroxy-lationandhighercatalyticactivitythanthosepreparedusingNaOHandNa2CO3precipitants.Theoptimalcalci-nationtemperatureofSnO2was723K.TheIRspectraofadsorbedpyridineshowedthattherewereLewisacidsitesonthesurfaceoftheSnO2catalyst.TheIRspectraofO3adsorbedonSnO2showedthattheterminalOatomofO3wasbondedtothesurfacehydroxylgrouporaLewisacidsitetoformamoreactiveoxygenspeciesthatcanoxidizeanddegradethewastewater.Keywords:tinoxide;catalyticozonation;molassesfermentationwastewater293 20083Vol.29No.3ChineseJournalofCatalysisMarch2008 SnO2n,,.SnO2-、、.,[1],、、,.,(MnO2[2,3],Al2O3[4]TiO2[5,6])、[7～9][10,11]. [12,13].,,.[14,15],,、.SnO2,SnO2,.1 1.1 SnO2 SnCl4()(NH3·H2O,Na2CO3NaOH,).SnCl4,,353K3h,,.383K24h,100,2h,SnO2.1.2 XD-3XXRD,CuKα,2θ=15°～90°,,4°/min,36kV,20mA,. SDTQ600(TA)(TG-DSC),323～1273K,N2,100ml/min,20K/min. ThermoNicoletNEXUS470.473K,,693K1h,,473K,.SnO2.(),KBr.:4cm-1,20,400～4000cm-1,0.6329.,,,15min.1.3 SnO2 ,.OZ-5G,.200ml1035cm,8cm,2.5g/LSnO2.,80L/h,130mg/h.,,TU-1901-(),475nm[14,15]1 SnO2Fig1 Effectofprecipitantsondecolorizationofmolassesfermen-tationwastewaterbySnO2-catalyzedozonation.2 2.1 2.1.1 SnO2,1.1,60min,、Na2CO3NaOHSnO2(723K,2254 29h)60.24%,49.72%44.22%,43.04%.SnO2,,SnO2,NaOHSnO2.15,3045min,SnO2310%.2.1.2 SnO2 2SnO2.2,3XRD,2θ26.7°(110),33.9°(101)52.0°(210),JCPDS(41-1445)SnO2,SnO2.Na2CO3NaOHSnO2XRD2θ31.9°45.6°,NaCl(200)(220),Na2CO3NaOHSnO2NaCl.NaClSnO2,.,SnO2,.2 SnO2XRDFig2 XRDpatternsofSnO2preparedwithdifferentprecipitants(1)NH3·H2O,(2)Na2CO3,(3)NaOH3 SnO2TG-DSCFig3 TG-DSCanalysisofSnO2precursorpreparedbydifferentprecipitants(a)NH3·H2O,(b)Na2CO3,(c)NaOH2.1.3 TG-DSC SnO2,3.TG,NH3·H2OSnO2430～580K:430～536K,529K,41.8%,NH4Cl;536～580K,553K,28.3%,SnO2[16].Sn(OH)4,Sn(OH)4※SnO2+2H2O,19.3%.9%,Sn(OH)4,NH4Cl.,Sn(OH)4618.8K,,[17].3(a),NH3·H2O580K,SnO2.,532556K,,,600K2553:SnO2SnO2.NH3·H2OSnO2,NaOHNa2CO3SnO2,350361K,.423～693K.XRD,SnO2NaCl,NH3·H2O,,,NaClSnO2.2.2 2.2.1 NH3·H2O,1.1,SnO2,60min,723KSnO260.24%,623KSnO256.31%,823,9231023KSnO2.1 SnO2Table1 EffectofcalcinationtemperatureonthedecolorizationrateofmolassesfermentationwastewaterbySnO2-catalyzedozonationCalcinationtemperature(K)Decolorizationrate(%)15min30min45min60min62337.1342.4146.5656.3172329.1145.1251.9960.2482335.2842.9750.5159.2392330.5742.8949.9758.48102334.3642.6250.4156.972.2.2 XNH3·H2OSnO2,4.3(a)TG-DSC,SnO2:600K,SnO2;673～773K,SnO2;873K,SnO2,SnO2.4,623KSnO2XRD,,623K2h,SnO2,SnO2.723KSnO2,JCPDS(41-1445)SnO2,823,9231023KSnO2.,,SnO2,,,723K,.4 SnO2XRDFig4 XRDpatternsofSnO2preparedwithammoniaatdifferentcalcinationtemperatures(1)623K,(2)723K,(3)823K,(4)923K,(5)1023K2.3 SnO2 SnO2,,.SnO2,,5. [18],,473K,,473K.5:30763043cm-1ν(C-H),15871577cm-1(HPY)ν(C-C)ν(C-N)[19],L(Sn4+),1449cm-1[20],1436cm-1.[21,22],256 295 SnO2Fig5 IRspectrumofpyridineadsorbedonSnO214501620cm-1L.5,SnO2L.6 SnO2Fig6 IRspectraofSnO2(1)andozoneadsorbedonSnO2for15min(2)2.4 SnO2 O3SnO2,6.(1)SnO2,3:3354cm-1Sn-OH,1627cm-1,1041cm-1Sn-O-Sn[23].(2)SnO2IR,NOxCO[23～25],.[23～28],,,L.SnO2L,22362213cm-1COO3SnO2L,18091791cm-1C=O,16281599cm-1H-O-HC=C.1364cm-1O2CO,12991273cm-1O3.3 SnO2.SnO2,SnO2,NaOHNa2CO3SnO2Na-Cl,.SnO2,723K.,SnO2L.SnO2,L.1 Kasprzyk-HordernB,ZiolekM,NawrockiJ.ApplCatalB,2003,46(4):6392 AndreozziR,LoCasaleMS,MarottaR,PintoG,PollioA.WaterRes,2000,34(18):44193 TongSP,LiuWP,LengWH,ZhangQQ.Chemo-sphere,2003,50(10):13594 ErnstM,LurotF,SchrotterJC.ApplCatalB,2004,47(1):155 BeltranFJ,RivasFJ,Montero-de-EspinosaR.ApplCatalB,2002,39(3):2216 GilbertE.OzoneSciEng,