Ti凹凸棒石催化剂对染料废水的臭氧氧化降解的影响

　311Vol.31,No.1　20031JOURNALOFTHECHINESECERAMICSOCIETYJanuary,2003Ti-尹　琳1,2,陆现彩1,2,艾　飞3,4(1.,;2.;3.;4.,　210093)　:,。,。,,。pH=11,400mg·L-1,m(TiO2)∶m()1∶20Ti-(COD)21.5%73.8%。(pH=11)(400mg·L-1)。3,TiO2COD。:;-;;:X703　　:A　　:0454-5648(2003)01-0066-04EFFECTSOFTi-ATTAPULGITECATALYSTSFORCATALYTICOZONATIONDEGRADINGPROCESSOFDYEWASTEWATERYINLin1,2,LUXiancai1,2,AIFei3,4(1.StateKeyLaboratoryforMineralDepositsResearch,NanjingUniversity;2.ResearchCenterofAttapulgiteClaysEngineeringandTechnology,Jiangsu;3.DepartmentofChemistry,NanjingUniversity;4.ResearchCenterofSurface&InterfaceChemistryandEngineeringTechnology,Nanjing　210093,China)Abstract:Fornon_biodegradableorganicdyewastewater,ozonationprocessisaneffectivemethodinwatertreatment.However,therearesomeobstaclesoflowefficiencyonoxidizationandhighcostofrunningforozonetechniqueinutilities.Akindofsolidcata-lyst,whichiscomposedofattapulgiteascarrierandTiO2asactivemetaloxide,wasusedtooxygenate(compositecatalysisoxidiza-tion)syntheticdyewastewaterandthegoodeffectispresented.UndertheidealizedconditionofpH=11,theconcentrationofthedyewateris400mg·L-1,ratioofTiO2toattapulgiteis1∶20(inmass),themineralcatalystefficiencyofozonation(expressedas,chemicaloxygendemand,COD,decreasedrate)increasesfrom21.5%,withO3only,to73.8%byusingthecompositecatalyst.Inconditionofalkali(pH=11)andrelativediluentdyewastewater(400mg·L-1),abetterresultcanbeobtained.ThesatisfactorypropertiesforthecatalystinTiO2losingandCODdecreaseratecanbemaintainedafter3timesrepeatedoperation.KeyWords:dyewastewater;titania-mineralcatalyst;attapulgite;compositecatalysisoxidization　　,[1]。,,,:2002-03-11。:2002-06-07。:　(1957～),,,。。,Al2O3、。TiO2。[2,3]Receiveddate:2002-03-11.Approveddate:2002-06-07.Biography:YINLin(1957—),male,doctor,associateprofessor.E-mail:[e-mail],。1　实　　验1.1　　　,:-X3B[4](1)—NN—,。,。,,(chemicaloxygendemand,COD)。,,,。Zn,Ti,Mn,Ni[5～7]。,[8]。、TiO2,。1　-X3BFig.1　Molecularstructuralofmonoazo_dyes(active-bril-liantred)X3B。Bradley[9],2∶1,。350m2/g,5%pH9[2,3]。TiO2。TiO2-。1.2　COD[10]。。MONITOR8810。1.3　TiO2(C.P.)(74μm),PAL,3～5mm,,[11,12]。-X3B,200,400,500,1000mg·L-1。2,1.1L/min,17.2mg/h。900mm,3。30℃。83.3%。2　Fig.2　Diagramofmulti_catalyticaeratingapparatusofozonationexperiment2　结果与讨论2.1　TiO2500mg·L-150mL,TiO2,60minCOD。TiO2(1),,50mLTiO20.1g,0.2%。1　TiO2Table1　InfluencesofdosageofTiO2onthedegradationDosageofTiO2/g00.010.050.10.30.5COD/(mg·L-1)365221199187188189DecreasedrateofCOD/%0　39.5　45.5　48.8　48.5　48.2Colorratio70005003003050250·67·　311　　　　　　　　:Ti-　　　　　　　　　　2.2　,,。200,400mg·L-150mL,TiO20.1g,20,40,60min,2。2　Table2　InfluencesoftimeofaeratingonthedegradationTimeofaerating/minOperation200mg·L-1syntheticdyewaterCOD/(mg·L-1)CODdecreasedrate/%400mg·L-1syntheticdyewaterCOD/(mg·L-1)CODdecreasedrate/%0O3only1380　2560　O3+TiO21380　2560　20O3only11516.722611.7O3+TiO291.633.619125.440O3only10424.620121.5O3+TiO27545.715838.360O3only9828.917830.5O3+TiO269.749.514045.3,,,,,,40min,。2.3　pHpH。400mg·L-150mL,TiO20.1g,40min,pH,(3)。3　pHTable3　InfluencesofpHvalueontheeffectsofcatalysispHvalue2.05.37.011.0COD/(mg·L-1)150158152133CODdecreasedrate/%41.438.340.748.1IncreasedthanonlyO3/%92.678.189.3123.7Note:pHvalueof400mg·L-1syntheticdyewateris5.3.2.4　TiO2,TiO2,TiO2,TiO21∶201∶10。50mL5g,TiO20.238g0.455g。,COD3.4,,(4)。4　Table4　CatalyticozonationeffectsofmineralcatalystsIndexCOD/(mg·L-1)CODdecreasedrate/%ColorratioSynthetic　dyewater＊256—6000　O320121.5500O3+TiO215838.3—1∶10mineral　catalyst+O3＊＊14244.51001∶20mineral　catalyst+O3＊＊　135.847.01001∶20mineral　catalyst+O3＊＊＊6773.8100＊400mg·L-1;＊＊pH=5.3;＊＊＊pH=11.2.5　,,3pH11、40min,。,CODO33.4(5)。,,。5　Table5　DegradingefficienciesofcatalystsviaconcentrationsConcentrationsofsyntheticdyewater/(mg·L-1)4005001000CODofsyntheticdyewater/(mg·L-1)256365530O3onlyCOD/(mg·L-1)201287477CODdecreasedrate/%　21.5　21.3　10.3TiO20.1gascatalyst+O3COD/(mg·L-1)162238455CODdecreasedrate/%　36.7　34.8　14.11∶20mineralcatalyst5g+O3COD/(mg·L-1)67180336CODdecreasedrate/%　73.8　50.7　36.6·68·　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　2003　,40min1000mg·L-1,。2.6　Ti,1∶205g,50mL40min。,(ICP-AES)Ti4+0.0208mg·L-1,0.0007%,Ti。1∶205g400mg·L-150mL,pH11,40min。、、,3。,COD50%(6),。6　Table6　RepeatabilityexperimentsRepeatoperations123COD/(mg·L-1)67112.698CODdecreasedrate/%73.85661.7Massloss/g0.50.2Rare2.7　,TiO2。:5g50mL400mg·L-1,40min,pH711.0。1∶20。,(5g,50mL)COD29.7%(51.2%-21.5%)35.1%(56.6%-21.5%)。17.2%(73.8%-56.6%)22.6%(73.8%-51.2%)(7)。。7　COD　　Table7　ComparisonofadsorptionofattapulgitewithcatalyticozonationIndexAdsorptionofattapulgite(pH=2.0)Adsorptionofattapulgite(pH=7)Adsorptionofattapulgite(pH=11)O3only(pH=5.3)1∶20TiO2mineralcatalystandO3(pH=11)COD/(mg·L-1)15012511120167Decreasedrate/%　41.4　51.2　56.6　21.5　73.83　结　　论(1)TiO2,。(2)TiO20.2%,1∶10(kg)(L)1∶500,。(3)O3,,。。:[1]　(LIJiazhen).、(WastewaterTreatmentofDyesIndustry)[M].:(Beijing:ChemicalIndustryPress),1997.181—221.[2]　(ZHANGPeiyuan).()(In-dustryMineralsandRocks,China,Vol2)[M].:(Beijing:GeologicalPublishingHouse),1987.241—270.[3]　,(ZHAOXingyuan,etal).(ClaysandClaysAnalysis)[M].:(Beijing:ChinaOceanPress),1990.31.[4]　,,(HOUYufen,etal