UVFenton光催化氧化降解对氯苯酚废水反应动力学陈琳

:0253-2468(2004)02-0225-06　　　:X703.1　　　:AUVFenton陈　琳,雷乐成＊,杜瑛　(,()　310027):UVFenton.,、、、pH.,,98%,CODcr80%.,.CODcrUVFenton,,.:UVFenton;;;Kineticstudiesofp-chlorphenolwastewatertreatmentbyUVFentonoxi-dationCHENLin,LEILecheng,DUYingxun　(InstituteofEnvironmentalEngineering,ZhejiangUniversity,Hangzhou(Yuquan)　310027)Abstract:Thephotodegradationofp-chlorphenolinaphoto-Fentonprocesswasinvestigated.Thereactionwasaffectedbyinitialconcentrationofp-chlorphenol,ferrousionandH2O2added,initialpH,aswellascarriergas.Withtheaidofoxygenaeration,theremovalofphenolandCODcrwerereachedabout98%and80%respectivelywheninitialconcentrationofH2O2addedwasaquarterofstoichiometriccalculatedquantities.Akineticmodelwasadoptedtodescribethereactionandtherateequationcouldprovidetheevidenceforthemainreactionpath-way,whichwasfittedverywellwiththeexperimentdata.Keywords:UVFenton;p-chlorphenol;advancedoxidation;kinetics:2003-05-16;:2003-09-01:(20176053):　(1979—),,();＊:[e-mail],20,,[1].,.,UVO3、UVH2O2、UVFentonUVTiO2.,、、,.,,.UVFenton,H2O2,.,UVFenton.24220043　　　　　ACTASCIENTIAECIRCUMSTANTIAEVol.24,No.2Mar.,2004DOI:10.13671/j.hjkxxb.2004.02.0091　1.1　(4-cp),,,.1.2　1.300W(Philips).1　1.　2.　3.4.　5.Fig.1　ExperimentalApparatus1200mm,50mm,40mm,.1L,pH,FeSO4,,.,,H2O2,,5L·h-1,,、.:125mg·L-1;Qth(4-cpH2O2)14,FeSO4120();pH3,(20℃);60min;.,,.1.3　4-[2],H2O2[3],CODcr[2].pHpHS-25pH().2　CODcrFig.2　RemovalefficiencyofphenolandCODcrindifferentsystems2　2.1　2,FentonFentonCODcr.,226　　　　　　　　　　24FentonFenton,,CODcr,.20min,FentonCODcrFenton.60min,FentonCODcr75%,Fenton60%.,UV,CODcr.,,,[4].,UVFenton.2.2　CODcr3.,.3,,,,0.25Qth,2min90%.,5min,0.5Qth1Qth,96%,CODcr,50%.,2QthCODcr,1Qth.3　CODcrFig.3　InfluencesofinitialconcentrationofH2O2addedonthedegradationofphenolandCODcr4　pHFig.4　InfluencesofinitialpHonthedegradationofphenol2.3　pH,pH..pH4.4,pH=3,.pH=10.pH=7pH=3,60min,,,pH,Fe(OH)2+(H2O)5,.,·OH[5],(1).Fe(OH)2++hν[Fe(OH)2+]＊Fe2++·OH(1)pH=8.95,.,pH=10,,UVH2O2,.2272　:UVFenton2.4　Fe2+Fe2+H2O21∶10,1∶20,1∶40,.1∶40,,90%.1∶201∶10,,96%,Fe2+,120.,Fe2+,·OH,[5],(2).Fe(Ⅱ)+OH·Fe(Ⅲ)+OH-(2)k=3.0×108L·mol-1·s-1.,,Fe2+120().2.5　62.5mg·L-1,125mg·L-1,250mg·L-1,,.,,60min,62.5mg·L-198%,250mg·L-185%,.2.6　,.,30min.CODcr5.5,3,,Fenton.5min,3,O2,,N2.,,CODcr.5,,60minCODcr30%,,70%,80%.,,5minCODcr30%,,5min,5min,,,CODcr.,O2,(),CODcr.2.5　CODcrFig.5　InfluencesofcarriergasonthedegradationofphenolandCODcr228　　　　　　　　　　24　　(a)(OH·),[1]:　　　　　　　　R·+O2ROO·(3)　　　　　　　　ROO·+RHROOH+R·(4)(b)H2O2[5],Fenton,4-cp.　　　　　　　　R·+O2RO2·H2OROH+HO2(5)H++HO2·+e-H2O2(6),,,.2.7　2.7.1　　BossmannUV-Fenton[6],2.4CO2H2O.H2O2UV,Fenton,3,,CO2H2O3.:R　k2Sk3　k1PR,S,PCO2、H2O3.k1,k2,k3.3,UVFenton,1Qth,4-cp1min98%,4-cp,CODcr.R、S,、,R、S.-d[R]dt=(k1+k2)[R](7)-d[S]dt=k3[S]-k2[R](8),k=k0e-ERT,k0、、pH、,T,e-ERT.Qth,Fe2+1∶20,,3、4.pH,,k1,k2,k3.(7)(8),[S]0=0,[7]:[R+S][R+S]0=k2k1+k2-k3e-k3t+k1-k3k1+k2-k3e-(k1+k2)t(9)　　CODcr:x=R+S,x0=[R+S]0(10)　　CODcr(9),2292　:UVFentonx=x0k2k1+k2-k3e-k3t+k1-k3k1+k2-k3e-(k1+k2)t(11)2.7.2　　1Qth,COD　　1　UVFentonTable1　ThekineticparametersofUVFentonprocesswithdifferentcarriergasespurgedk1k2k3O20.83970.26000.02180.82940.28590.0229N20.73450.42200.0293,Matlab6.0,1,.　　1k1k2k3,R※P,.R※S※P,k3k2,CO2H2O6　UV-FentonFig.6　Fittingoftheexperimentdataondegra-dationofphenolsbymodelcalcalation,CO2H2O,.,(11),(6).,,.1,k,,k1,.k2、k3,、、k1k23.23,2.90,1.74,.,,.:[1]　,.[M].:,2001[2]　《》.[M].:,1989[3]　SellersRM.SpectrophotometricDeterminationofhydrogenperoxideusingpotassiumtitanium(Ⅳ)Oxalate[J].TheAnalyst,1980,150:950—954[4]　,,　.[J].,1998,17(5):490—492[5]　MontserratPerez,Francesctorrades.RemovaloforganiccontaminantsinpaperpulptreatmenteffluentsunderFentonandphoto-Fen-tonconditions[J].AppliedCatalysisB:Environmental,2002,36:63—74[6]　BossmannSH,OliverosE,etal.Newevidenceagainsthydroxylradicalsasreactiveintermediatesinthethermalandphotochemi-callyenhancedFentonreactions[J].PhysChemA,1998,102:5542—5550[7]　　.UV-Fenton[D].:,2002230　　　　　　　　　　24