Fenton试剂法降解废水中的芳香类化合物曹国民

　　　　　　()JournalofEastChinaUniversityofScienceandTechnology(NaturalScienceEdition)Vol.34No.62008-12:2007-11-13:(B506):(1963-),,,,,。E-mail:[e-mail]　　:1006-3080(2008)06-0830-04Fenton曹国民,　丁　伟,　杨国平,　张大年(华东理工大学环境工程研究所,上海200237)　　:芳香化合物的Fenton氧化性能与其结构密切相关,芳环上取代基位置、数量和种类的不同会对其降解速率产生显著影响。单氯酚3种异构体降解速率大小依次为:3-氯酚4-氯酚2-氯酚;氯酚的反应活性随芳环上Cl取代基数目的增加而下降,2-氯酚、2,4-二氯酚和2,4,6-三氯酚的反应活性遵循下列顺序:2-氯酚2,4-二氯酚2,4,6-三氯酚;芳环上的取代基对芳香化合物的Fenton氧化性能有很大影响,苯胺、氯苯和硝基苯降解速率依次为:苯胺氯苯硝基苯。:Fenton试剂;芳香化合物;结构;废水:X703.1:AAqueousPhaseDegradationofAromaticCompoundsbyFentonOxidationCAOGuo-min,　DINGWei,　YANGGuo-ping,　ZHANGDa-nian(ResearchInstituteofEnvironmentalEngineering,EastChinaUniversityofScienceandTechnology,Shanghai200237,China)Abstract:TheratesofdegradationofaromaticcompoundsbyFentonoxidationareaffectedbyposition,numberandtypeofthesubstitutegroup.Thedegradationrateof3-chlorophenolisfastest,followedby4-chlorophenolandthen2-chlorophenol.Thereactivityofchlorophenolsdecreaseswithmorechlorineonthearomaticring;theoxidationrateofchlorophenolsindecliningorderis2-chlorophenol2,4-dichlorophenol2,4,6-trichlorophenol.TheFentonreactivityofthethreesinglesubstitutedaro-maticcompoundsindecliningorderisanilinechlorobenzenenitrobenzene.Keywords:Fentonoxidation;aromaticcompounds;structure;wastewater　　、、,(、、)EPA[1]。、、、,。1964Eisenhauer[2]Fenton,Fenton、、、,Fenton[3～8],Fenton、Fenton,Fenton。Fenton,Fenton,Fenton。830DOI:10.14135/j.cnki.1006-3080.2008.06.018,,、、、Fenton,Fenton。1　1.1　,,,。。1.2　1.2.1　Fenton氧化实验方法　Fenton1L,、pH、,。,4,25℃。500mL,,FeSO4,1mol/LH2SO42mol/LNaOHpH3.0～3.5,H2O2,10mL,6mol/LNaOHpH,。1.2.2　分析方法　Fenton(HPLC),25cm,V()∶V()=40∶60,1.0mL/min,UV。2　2.1　Fenton2-、3-4-,(c0)3mmol/L,5mmol/L,0.05mmol/LpH3.5,Fenton,1。　　1,3-,4-,2-。Fenton,Fenton。1　Fig.1　Concentrationofmono-chlorophenolsvs.reactiontime◇—2-Chlorophenol;□—3-Chlorophenol;△—4-Chlorophenol　　Fenton,(·OH)(R)(P),:R+·OHkP(1):-dcdt=k′[·OH][c](2):k′,[c][·OH]。,,d[·OH]/dt=0,[·OH]=[·OH]0=([·OH]0)。,:ln(c/c0)=-kt(3):k(min-1),t(min)。ln(c/c0)t,2。2　Fentonln(c/c0)Fig.2　Changeofln(c/c0)withreactiontimeduringmono-chlorophenolsoxidizedbyFenton′sreagent◇—2-Chlorophenol;□—3-Chlorophenol;△—4-Chlorophenol　　2,ln(c/c0)t0.96～0.99,。,2-8316,:Fenton、3-4-0.061、0.1260.082min-1。,Fenton,。Fenton:(1)—OH—Cl、,—OH—Cl[9],3-3—OH—Cl,;(2)4-2-—OH—Cl。,Fenton3-4-2-。,4-2-3-。,2-—OH—Cl4-,2-。,2-4-。:3-4-2-。2.2　Fenton2-、2,4-2,4,6-,(c0)3mmol/L,H2O25mmol/L,Fe2+0.05mmol/LpH3.5,(Cl)Fenton,3。3　Fig.3　Concentrationsofchlorophenolsvs.reactiontime◇—2-Chlorophenol;□—2,4-Dichlorophenol;△—2,4,6-Trichloro-phenol　　3,2-,2,4-,2,4,6-。3ln(c/c0)t,4。　　4,ln(c/c0)～t,Fenton。,2-、2,4-2,4,6-0.061、0.0370.006min-1。,Fenton:2-2,4-2,4,6-。4　Fentonln(c/c0)Fig.4　Changeofln(c/c0)withreactiontimeduringchloro-phenolsoxidizedbyFenton′sreagent◇—2-Chlorophenol;□—2,4-Dichlorophenol;△—2,4,6-Trichloro-phenol　　3:,,(Cl),,,,;,(Cl),,,;,,,。2.3　Fenton3,、、,(c0)1mmol/L,H2O23mmol/L,Fe2+0.1mmol/LpH3.5Fenton,5。　　5,,,。5ln(c/c0)t,6。　　6,、、Fenton,,、、0.038、0.0280.008min-1,、、Fen-ton:。Fenton832()345　Fig.5　Concentrationsofaromaticcompoundsvs.reactiontime◇—Aniline;□—Chlorobenzene;△—Nitrobenzene6　Fentonln(c/c0)Fig.6　Changeofln(c/c0)withreactiontimeduringaro-maticcompoundsoxidizedbyFenton′sreagent◇—Aniline;□—Chlorobenzene;△—Nitrobenzene。　　,,Hammett[10]。Hammett:　　　　lgkk0=σρ(4):x—;y—;k—x;k0—;σ—,;ρ—,,x。Hammettρ25℃,1,σ。σ=lgkk(5)　　,σ,σ,σ,。,,,,σ。、、Hammettσ[11]:-0.66、+0.23、+0.78。,,(σ),Fenton,。。,,,,,。—NH2,。—NO2—Cl[9],。,—NO2,。3　　Fen-ton,、。Fenton:(1)3:3-4-2-。(2),Fenton:2-2,4-2,4,6-。(3)、Fenton:,Fenton。:[1]　W.·.[M].,.:,2004.1-2.[2]　EishenhauerHR.Oxidationofphenolicwastes[J].JWaterPollutContrFed,1964,36:1116-1128.(886)8336,:FentonAWGNMCS、β。,,MCS。,EESMCQI。:[1]　AlouiniMS,GoldsmithAJ.Capacityofrayleighfadingchannelsunderdifferentadaptivetransmissionanddiversity-combiningtechniques[J].IEEETransVehTechnol,1999,48:1165-1181.[2]　CatreuxS,ErcegV,GesbertD,etal.AdaptivemodulationandMIMOcodingforbroadbandwirelessdatanetworks[J].IEEECommunMagazine,2002,40:108-115.[3]　ViswanathP,TseDNC,AnantharamV.Asymptoticallyoptimalwater-fillinginvectormultipleaccesschannels[J].IEEETransInformTheory,2001,47:241-267.[4]　FischerREH,HuberJB.Anewloadingalgorithmfordis-cretemultitonetransmission[A].ProcIEEEGlobecom[C].UK:[s.n.],1996.724-728.[5]　LeiM,HaradaH,WakanaH,etal.Acodedfrequency-domainlinkadaptationschemeforOFDMtransmissioninTDDmode[A].ProcIEEEPIMRC[C].PiscatawayNJ:IEEE,2004.2082-2086.[6]　3GPPTR25.892v6.0.0.FeasibilityStudyforOrthogonalFrequencyDivisionMultiplexing(OFDM)forUTRANenhancement(Release6)[S].[7]　LiuS,ZhangX,WangW.Analysisofmodulationandcod-ingschemeselectioninMIMO-OFDMsystems[A].Proceed-ingsIEEEICCE[C].Hanoi:IEEE,2006.240-245.[8]　ZhengH,ViswanathanH.OptimizingtheARQperformanceindownlinkpacketdatasystemswithscheduling[J].IEEETransWirelessCommun,2005,4:495-506.[9]　YangY,KuangJM,FeiZ.Anovellinkadaptationstrategycombiningtransmitdiversityandspatialmultiplexinginspaceovertime-varyingchannels[A].ProcIEEEWCNC[C].[s.l.]:IEEE,2005.93-96.[10]　ZhouQ,DaiH.JointantennaselectionandlinkadaptationforMIMOsystems[J].IEEETransVehTechnol,2006,55:243-