Fenton试剂氧化降解结晶紫的动力学研究盛勤芳

2011,Vol.28No.9　　　Chemistry&Bioengineering57　　　:2011-07-08:盛勤芳(1965-),女,湖北武汉人,实验师,研究方向:环境分析;通讯作者:葛伊莉,副教授,E-mail:[e-mail]。doi:10.3969/j.issn.1672-5425.2011.09.016Fenton1,　2,2,2(1.湖北轻工职业技术学院,湖北武汉430070;2.湖北大学有机功能分子合成与应用教育部重点实验室,湖北武汉430062)　:探讨了Fenton试剂在光照条件下对结晶紫模拟印染废水进行氧化处理的动力学规律,讨论了H2O2初始浓度、FeSO4初始浓度、反应温度及草酸的络合作用对结晶紫氧化降解的影响,确定了最佳降解条件,建立了Fenton试剂氧化降解结晶紫的动力学方程,为光照条件下利用Fenton试剂处理含结晶紫类的印染废水提供了依据。:结晶紫;Fenton试剂;动力学;分光光度法:O643.12　X703　　　:A　　　:1672-5425(2011)09-0057-05　　70t,80%。,[1]、[2],、,[3]。2080,(OH),Fenton。Fenton,Fe2+H2O2OH,、、[4]。(CrystalViolet,CV),Fenton。Fenton,H2O2、FeSO4、,,Fenton。1　1.1　H2O2、FeSO47H2O、,;C2H2O4,;,。UV2300,;722,。1.2　,50mL,FeSO4、C2H2O4H2O2,H2O2,5min。FeSO4,,。,H2O2C2H2O4。D:D=(1-AA0)×100%:A0;A。2　2.1　0.005mmolL-110mL,,1a,Fenton,,1b～d。　　　:Fenton/2011958　　　(min),a～d:0,2,20,401　Fig.1　TheabsorptioncurvesofCrystalVioletsolutionatdifferentreactiontimes　　1a,0.738,591nm。1b～d,,,,Fenton。2.2　,([CV]),2。CV](mmolL-1),1～6:0.0005,0.001,0.002,0.003,0.004,0.0052　Fig.2　EffectofinitialconcentrationofCrystalVioletonitsdegradation2,,;0.001mmolL-1,;,,Fenton(≥0.001mmolL-1)。,0.001mmolL-1。2.3　H2O2FentonFe2+H2O2OH,H2O2OH,Fenton。,H2O2([H2O2]),3。H2O2](molL-1),1～6:0.097,0.194,0.388,0.582,0.776,0.9703　H2O2Fig.3　EffectofinitialconcentrationofH2O2ondegradationofCrystalViolet3,H2O2,:Fenton/20119　59　　　;H2O20.388molL-1,;H2O2,。,H2O2,H2O2OH,[5]:H2O2+OHH2O+O2HO2H+OHH2O+O2,H2O20.388molL-1。2.4　FeSO4H2O21.70V[6],H2O2Fe2+2.80VOH,,Fe2+Fenton。H2O20.388molL-1,FeSO4([Fe2+]),4。[Fe2+](molL-1),1～6:0.010,0.008,0.006,0.004,0.002,0.0014　FeSO4Fig.4　EffectofinitialconcentrationofFeSO4ondegradationofCrystalViolet4,FeSO4,。,FeSO4OH,Fe2+,OH,,。FeSO40.004molL-1,Fe2+,,FeSO4。,FeSO40.004molL-1。2.5　C2H2O4,Fenton(、),[7]。,FeSO4H2O2,([C2H2O4]),5。5,,C2H2O4[C2H2O4](molL-1),1～6:0.0005,0.001,0.002,0.003,0.004,0.0055　C2H2O4Fig.5　EffectofinitialconcentrationofC2H2O4ondegradationofCrystalViolet,;0.001molL-1,。,C2H2O4,,。,FeSO4,C2H2O4,,H2O2,C2H2O4,。,C2H2O40.001molL-1。,,,6。6　C2H2O4Fig.6　EffectofC2H2O4ondegradationofCrystalViolet6,,,Fenton。2.6　Fenton,(40min),7。7,15～60℃,　　　:Fenton/2011960　　　7　Fig.7　EffectofreactiontemperatureondegradationofCrystalViolet,;35℃。,,OH,OH,;,H2O2O2H2O,OH,[8]。,35℃(308K)。2.7　Fenton,、H2O2Fe2+,[9],:dcdt=-kcP(1):c,P,k,t。,(1):ln(cc0)=-kt(2)Ac,(2):ln(AA0)=-kt(3)D,(3):ln(1-D)=-kt(4)(4),ln(1-D)t,k、[H2O2]、[Fe2+]:k=k0[H2O2]m×[Fe2+]n(5):m、nH2O2Fe2+,;k0。[Fe2+],(5),:lnk=m×ln[H2O2]+C1(6),[H2O2],:lnk=n×ln[Fe2+]+C2(7):C1C2。,ln[H2O2]lnk、ln[Fe2+]lnk,,H2O2mFe2+n。2.7.1　H2O2m[H2O2],[H2O2],ln(1-D)t,kR21。1,(R0.95),,、[H2O2],ln(1-D)=-kt+。1,ln[H2O2]lnk,:y=0.4594x-2.5652,R2=0.9502,H2O2m=0.4594。2.7.2　Fe2+n[Fe2+],[Fe2+],ln(1-D)t,kR21。1Tab.1ThereactionrateconstantofCrystalVioletunderdifferentconditions[H2O2]/molL-1kR2[Fe2+]/molL-1kR2/KkR20.0970.15840.98490.0100.18410.97922880.02710.95580.1490.11070.99660.0080.08650.95122980.02820.97510.3880.13110.99680.0060.06750.96523080.03000.95750.5820.10430.99890.0040.04750.98913180.03110.95890.7760.06850.99230.0020.03620.99443280.03260.94580.9700.04310.98950.0010.02280.98683330.03290.9519:Fenton/20119　61　　　　　1,、[Fe2+],ln(1-D)=-kt+,[Fe2+],[Fe2+],[Fe2+]。0.010molL-1,[Fe2+]()。,Fe2+OH:Fe2++OHFe3++OH-,k=3.0×10-2Lmol-1s-1。1,ln[Fe2+]lnk,:y=0.4594x-7.1399,R2=0.9502,Fe2+n=0.4594。2.7.3　EaAArrhenius():k=Aexp(-Ea/RT)(8)(8),:lnk=lnA-Ea/RT(9)1/Tlnk,,EaA。1,lnk1/T,:y=-0.412x-3.641,R2=0.9741,Ea=3.408kJmol-1,A=0.02623。,,Fenton:-dc/dt=0.02623exp(-3.408/RT)[H2O2]0.4594[Fe2+]0.45943　Fenton,H2O2、FeSO4、,,Fenton,-dc/dt=0.02623exp(-3.408/RT)[H2O2]0.4594[Fe2+]0.4594,Fenton。:[1]　,,,.[J].,2000,26(6):315-319.[2]　,,.PSF[J].,2006,(9):4-6.[3]　,.[J].,2009,(7):62-67.[4]　LoretoL,DoloresS,SoledadR,etal.Identificationofmetoldegra-dationproductsunderFentonreagenttreatmentusingliquidchro-matography-massspectrometry[J].WaterResearch,2000,34(13):3400-3412.[5]　AlatonIA,BalciogluIA,BahnemannDW.Advancedoxidationofareactivedyebatheffluent:ComparisonofO3,H2O2/UV-CandTiO2/UV-Aprocesses[J].WaterResearch,2002,36(5):1143-1154.[6]　,,,.TiO2[J].,2009,26(6):36-39.[7]　NogueiraRFP,GuimaraesJR.Photodegradationofdichloroace-ti-eacidand2,4-dichlorophenolbyferrioxalate/H2O2　system[J].WaterResearch,2000,34(3):895-901.[8]　DurnA,MonteagudoJM,AmoresE.Solarphoto-Fentondegra-dationofReactiveBlue4inaCPCreactor[J].AppliedCatalysisB:Environmental,2008,80(1-2):42-50.[9]　.Fenton[J].,2010,(3):1-4.StudyonKineticsofFentonReagentOxidationDegradationforCrystalVioletSHENGQing-fang1,TIANTao2,GEYi-li2,SONGGong-wu2(1.HubeiLightIndustryTechnologyInstitute,Wuhan430070,China;2.KeyLaboratoryofEducationMinistryfortheSynthesisandApplicationofOrganicFunctionalMolecules,HubeiUniversity,Wuhan430062,China)Abstract:ThekineticsoftheoxidationdegradationofprintinganddyeingwastewaterimitatedwithCrystalVioletbyFentonreagentwasstudied.TheeffectsoftheinitialconcentrationofH2O2andFeSO4,reactiontem-peratureandcomplexactionofoxalicacidonoxidationdegradationofCrystalVioletwerediscussed.Theopti-mumdegradationconditionswereidentified.ThekineticsequationfordegradationofCrystalVioletwassetup.Itprovidesrelevantevidencefortreatmentofprinti