电Fenton法降解青霉素的动力学研究黄昱

26　52007　　9　　　ENVIRONMENTALCHEMISTRYVo.l26,No.5September2007　2006922.　*(50478054);(2004DFA06200);(K051132-72);　(NCET-04-0770)**:E-mail:[e-mail]-Fenton*黄　昱　李小明**　杨　麒　曾光明　张　振(,,410082)　　-Fenton(PenicillinGsodium,PGN),T=20℃,pH=3,0.5gl-1FeSO40.2mll-1H2O2,0.6A(100mgl-1),20min79%,40min95%.:-d[PGN]/dt=2.35×106exp(-32869.4/RT)[Fe2+]0.53[H2O2]0.8[PGN]1.14,,H2O2Fe2+-Fenton.　-Fenton,,.　　,-Fenton,FentonFe2+H2O2、,-Fenton[1—7],.　　Fenton(PenicillinGsodium;PGN),-FentonPGN,,PGN,、.1　1.1　　　(:99.9%,).PGN(RuO2-TiO2,),pH3,,;,.,,.1.2　　　1moll-1NaOHpH7,Fenton.0.45μm,20μl(Agilent1100,Agilent),,PGN.　　LC::ODSC18(250mm×4.6mmi.d.,5μm);:70%(0.1moll-1,1moll-1NaOHpH6)-30%();:30℃;1.0mlmin-1;:225nm;:20μ.l2　　　-Fenton,,,HO,.,,[8],FeSO40.1—0.5gl-1,H2O2　5:-Fenton619　　0.05—0.2mll-1,FentonPGN,-Fenton.:-d[PGN]/dt=k0exp(-Ea/RT)[Fe2+]α[H2O2]β[PGN]γk=k0exp(-Ea/RT),k0:(lmol-1s-1);Ea:(Jmol-1);R:(R=8.314Jmol-1K-1);T:(K);k:(lmol-1s-1);α,β,γ[Fe2+],[H2O2],[PGN].2.1　Fe2+　　1,Fe2+,PGN,.FeSO40.5gl-1,40minPGN90%.　　-Fenton,Fe2+H2O2HO,PGN,;,PGNPGNHO;Fe2+Fe3+,Fe3+PGN,Fe(OH)3,Fe3+Fe2+,Fe3+Fe2+,Fe2+H2O2HO,HO,PGNHO,PGN.　　-d[PGN]/dt=k[Fe2+]α,lg{-[PGN]/dt}=lgk+αlg[Fe2+];d[PGN]/dt—[Fe2+],lg{-d[PGN]/dt}—lg[Fe2+][Fe2+]:-d[PGN]/dt=k[Fe2+]0.53.2.2　H2O2　　2,PGNH2O2,PGN.H2O20.2mll-1,20minPGN74%.　　H2O2HO,H2O2HO,.Fe2+,H2O2HOHO2,PGN,Fe2+HOHO2.,,H2O2PGNFe2+,H2O2(PGN)Fe2+.　　-d[PGN]/dt=k[H2O2]β,lg{-d[PGN]/dt}=lgk+βlg[H2O2];d[PGN]/dt—[H2O2],lg{-d[PGN]/dt}—lg[H2O2][H2O2]:-d[PGN]/dt=k[H2O2]0.8.2.3　PGN　　3,PGN.PGN620　　　　　　　　26;PGNHO,,PGN.,Fenton、PGN,PGN.　　-d[PGN]/dt=k[PGN]γ,lg{-d[PGN]/dt=lgk+γlg[PGN];d[PGN]/dt—[PGN],lg{-d[PGN]/dt}—lg[PGN][PGN]:-d[PGN]/dt=k[PGN]1.14,:-d[PGN]/dt=k[Fe2+]0.53[H2O2]0.8[PGN]1.14.2.4　　　PGN4,15min,,Arrhenius[8].FentonHOPGN,,,,PGN.,,PGN,.40℃,,H2O2,H2OO2,,[1].,40℃,PGNH2O2,HO,,.　　k=k0e(-Ea/RT),lnk=-(Ea/R)(1/T)+lnk0;k-T,lnk-1/TEak0:k=2.35×106exp〔-32869.4/RT〕-Fenton:-d[PGN]/dt=2.35×106exp〔-32869.4/RT〕[Fe2+]0.53[H2O2]0.8[PGN]1.14.　　,;,,Fenton,、,.,H2O20.8,Fe2+0.53,-Fenton,H2O2Fe2+.Fe2+,H2O2,Fe2+Fenton[2],H2O2HO.-Fenton,Fe3+,Fe2+,.,,,,Ea,.,40—400kJmol-1[8].-FentonPGNEa32.87kJmol-1,.k0,,k0,[8].Fenton0.01—109lmol-1s-1[3,4].-FentonPGNk02.35×106lmol-1s-1,,PGN.　5:-Fenton621　　3　　　(1)-FentonPGN:Fe2+0.5gl-1,H2O20.2mll-1,PGN100mgl-1,20℃,PGN:-d[PGN]/dt=2.35×106exp〔-32869.4/RT〕[Fe2+]0.53[H2O2]0.8[PGN]1.14　　(2),-Fenton,H2O2Fe2+.Fe3+,Fe2+,H2O2.　　(3),HO,.　　　[1]　GuedesAnabelaMFM,MadeiraLuisMP,BoaventuraRuiAReta.l,FentonOxidationofCorkCookingWastewater-OverallKineticAnalysis[J].WaterResearch,2003,37(13)∶3061—3069[2]　AnotaiJ,LuMC,ChewpreechaP,KineticsofAnilineDegradationbyFentonandElectro-FentonProcesses[J].WaterResearch,2006,40(9)∶1841—1847[3]　KangN,LeeDS,JeyongY,KineticModelingofFentonOxidationofPhenolandMonochlorophenols[J].Chemosphere,2002,47(9)∶915—924[4]　BurbanoAA,DionysiouDD,SuidanMTeta.l,OxidationKineticsandEffectofpHontheDegradationofMTBEwithFentonReagent[J].WaterResearch,2005,39(1)∶107—108[5]　KangYW,HwangKY,EffectofReactionConditionsontheOxidationEfficiencyintheFentonProcess[J].WaterResearch,1999,34(10)∶2786—2790[6]　AndreozziR,D'ApuzzoA,MarottaRA,KineticModelfortheDegradationofBenzothiazolebyFe3+Photo-AssistedFentonProcessinaCompletelyMixedBatchReactor[J].JournalofHazardousMaterialsB,2000,80(1—3)∶241—257[7]　ContrerasaD,FreeraJ,RodriguezJ,VeratrylAlcoholDegradationbyaCatechol-DrivenFentonReactionasLigninOxidationbyBrown-RotFungiModel[J].InternationalBiodeteriorationBiodegradation,2006,57(1)∶63—68[8]　,[M].:,2002,211—223KINETICSOFPENICILLINGDEGRADATIONBYELECTRO-FENTONPROCESSHUANGYu　　LIXiao-ming　　YANGQi　　ZENGGuang-ming　　ZHANGZhen(CollegeofEnvironmentalScienceandEngineering,HunanUniversity,Changsha,410082,China)ABSTRACT　　ThedegradationofpenicillinGsodium(PGN)simulatewastewaterbyelectro-Fentonhasbeeninvestigated.OperatingatT=20℃,pH=3,Fe2+concentration=0.5gl-1,H2O2concentration=0.2mll-1,PGNconcentration=100mgl-1andelectriccurrent=0.6A,about79%ofPGNwasremovedat20min,and95%ofPGNwasremovedat40min.TheoverallequationforPGNdegradationbyelectro-Fentonprocessis:-d[PGN]/dt=2.35×106exp〔-32869.4/RT〕[Fe2+]0.53[H2O2]0.8[PGN]1.14ThereactionrateconstantandreactionorderindicatethatthereactionrateisveryfastandtheeffectofinitialH2O2concentrationisgreaterthaninitialFe2+concentrationonPGNdegradationbyelectro-Fenton.　　Keywords:electro-Fenton,penicillinGsodium,kinetics.