过氧化氢高级氧化技术去除水中有机污染物张文兵

过氧化氢高级氧化技术去除水中有机污染物张文兵,　肖贤明,　傅家谟,　盛国英,　闵育顺,　刘光汉(中国科学院广州地球化学研究所有机地球化学国家重点实验室,广东广州510640):X703.1;TU991.2　　:D　　:1000-4602(2002)03-0089-04　　:(20003046);　(99B06901G)　　(AdvancedOxi-dationProcesses,AOPs)·OH(2.8V),,。、、,,(Fe2+、UV)(O3),·OH,。,。Fenton、UV/H2O2、H2O2/O3、UV/H2O2/O3。1　Fenton试剂Fenton,pH,Fe2+·OH,。Fenton[1、2]。Fenton,4[3]:,pH=3.5H2O2Fe2+3.7～1.9。3min65%～85%,,。Sheng[4]ABSLAS,90mg/LFeSO4、60mg/LH2O2、pH3,50minABSLAS95%。,Fe(Ⅲ)、Mn(Ⅱ)、、H2O2·OH,[5、6]。(),Fenton()[7、8]。Fe(Ⅲ)Fe(Ⅱ),Fe(Ⅱ),·OHFe(Ⅱ),·OH。(C2O2-4、ED-TA),。MarianneFenton,,;,pH4.1,。,pH,·OH。,FentonFenton,、、、、、、、、、、。FentonpH、、·89·　　　2002Vol.18　　　　　　　　　　CHINAWATER&WASTEWATER　　　　　　　　　　No.3、Fe2+,pH(2～4)。2　UV/H2O2UV/H2O2。[9],290nm、H2O255mg/L,2-、2,4-、2,4,6-,3h100%。,[10],15min99%,HCO-3,·OH,。Liao,UV,;pH、、,。UV/H2O2,Stefan、MTBE[11～14]。Rayox(H2O216mmol/L),、、、、、,。,·OH。MTBE,MTBE,、2--2-、、、、,。1,4-,Stefan、、,、、、、1,2-,TOC。,,。UV/H2O2,76～227μg/L,97.3%～99%,。,3000～4000μg/L0.68～0.83μg/L,。UV/H2O2,H2O2·OH,Fenton—。Fenton、,,。3　H2O2/O3H2O2/O3,。2070,80。,,,。O3pH=2(0.06～3mol/(L·s)[15],O3/H2O2,[(4～5)×109mol/(L·s)]。H2O2/O3,20min95%。Nelieu10L0.46×10-5mol/L[16],、O3/H2O2、pHHCO-3。O3/H2O2。Beltran,O3/H2O2COD[17],pH=6COD86%,。。1986Aeita[18](TCE)(PCE),(1.7),TCE、PCE95%56%～64%。Duguet、、2-、,。UV,O3/H2O2UV,。4　UV/H2O2/O3·90·2002Vol.18　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　No.3UV/H2O2/O3,O3、O3H2O2、H2O2,(pH、UV、)。Zeff1988UV/H2O2/O3[19]。200mg/L30minDOC97%;、、1,1-、1,2-、、、、、,60minTOC98%。,UV/H2O2/O3UV、H2O2、O3。LewisVOC、、、、,O3、H2O2、、UV,VOC98%,。,Ledakowicz[20],,O3/UVUV/H2O2/O3,10%。,。,,COD1290mg/L、TOC378mg/L、TOX1.3mg/L[21]。UV/H2O2/O3TOX,CODTOC83%、69%,。Wenzel、、PAHs[22],UV/H2O2/O3UV/H2O2,TOC10%～20%。5　在饮用水消毒中的应用ClO2、O3,O3,Br-,O3,。,AOPs·OHO3,[23],H2O2(),。,H2O2/O3。O3/H2O2[24、25],CarmimeoH2O2/UVClO2,。6　结语①　、,,。②　,、、、,,。③　,,、,。:[1]　BossmannSH,OliverosE,GobS,etal.Newevidencea-gainsthydroxylradicalsasreactiveintermediatesinthethermalandphotochemicallyenhancedFentonreaction[J].JPhysChemA,1998,102(28):5542-5550.[2]　ZeepRG.Hydroxylradicalformationinaqueousreactions(pH3-8)ofiron(Ⅱ)withhydrogenperoxide:thephoto-Fentonreaction[J].EnvironSciTechnol,1992,26(3):313-319.[3]　WatterZTang,StephanieTassos.OxidationkineticsandmechanismsoftrihalomethanesbyFenton'sreagent[J].WatRes,1997,31(5):1117-1125.[4]　ShengHLin,ChiMLin,HongGLeu.Operatingcharac-teristicsandkineticstudiesofsurfactantwastewatertreat-mentbyFentonoxidation[J].WatRes,1999,33(7):1735-1741.[5]　LuckingF.Ironpowder,graphiteandactivatedcarbonascatalystsfortheoxidationof4-chlorphenolwithhydro-genperoxideinaqueoussolution[J].WatRes,1998,32(9):2607-2614.·91·2002Vol.18　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　No.3[6]　Shu-SungLin,MiratDGurol.Catalyticdecompositionofhydrogenperoxideonironoxide:kinetics,mechanism,andimplications[J].EnvironSciTechnol,1998,32(10):1417-1423.[7]　MarianneEBalmer,BarbaraSulzberger.Atrazinedegra-dationinirradiatediron/oxalatesystems:EffectsofpHandoxalate[J].EnvironSciTechnol,1999,32(14):2418-2424.[8]　NathalicBrand,GillesMailhot,MicheleBolte.Degrada-tionphotoinducedbyFe(Ⅲ):Methodofalkylphenolethoxylatesremovalinwater[J].EnvironSciTechnol,1999,32(18):2715-2720.[9]　MozaPN,FytianosK,SamanidouV,etal.Photodecom-positionofchlorophenolsinaqueousmediuminthepres-enceofhydrogenperoxide[J].BullEnvironContamToxi-col,1988,41(5):671-682.[10]　FernandoJBeltran,JoseMEncinar,JuanFGonzalez.Industrialwastewateradvancedoxidation.Part2.OzonecombinedwithhydrogenperoxideorUVradiation[J].WatRes,1997,31(10):2415-2428.[11]　MihaelaIStefan,JamesBolton.KineticsandmechanismofthedegradationandmineralizationofacetoneindiluteaqueoussolutionsensitizedbytheUVphotolysisofhy-drogenperoxide[J].EnvironSciTechnol,1996,30(7):2382-2390.[12]MihaelaIStefan,JamesBolton.ReinvestigationoftheacetonedegradationmechanismindiluteaqueoussolutionbytheUV/H2O2process[J].EnvrionSciTechnol,1999,33(6):870-873.[13]MihaelaIStefan,JamesRBolton.Degradationpathwaysduringthetreatmentofmethyltert-butyletherbytheUV/H2O2processes[J].EnvironSciTechnol,2000,34(4):650-658.[14]StefanMihaelaI,BoltonJamesR.Mechanismofthedegradationof1,4-dioxaneindiluteaqueoussolutionusingtheUV/hydrogenperoxideprocess[J].EnvironSciTechnol,1998,32(11):1588-1595.[15]　YaoCCD,HaagWR.Rateconstantsfordirectreac-tionsofozonewithseveraldrinkingwatercontaminants[J].WatRes,1991,25(7):761-773.[16]SylvieNelieij,LucienKerhoas,JacquesEinhorn.Degra-dationofatrazineintoammelinebycombinedozone/hy-drogenperoxidetreatmentinwater[J].EnvironSciTechnol,2000,34(3):430-437.[17]FernandoJBeltran,ManuelGonzalez,JuanFGonzalez.Industrialwastewateradvancedoxidation:PartI.UVra-diationinthepresenceandabsenceofhydrogenperoxide[J].WatRes,1997,31(10):2405-2414.[18]　AetiaEM,ReaganKM,LangJS,etal.AdvancedOxi-dationProcessesfortreatinggroundwatercontaminatedwithTCEandPCE.Pilotscaleevaluations[J].JournalAWWA,1998,80(5):64-72.[19]　ZeffJD,LeitisE.Oxidationoforganiccompoindsinwa-ter[P].U.S.Patent4792407,1988.[20]　StanislawLedakowicz,MonikaGonera.Optimizationofoxidantsdoseforcombinedchemicalandbiologicaltreatmentoftextilewastewater[J].WatRes,1999,33(11):2510-2516.[21]　NilsunHInce.Light-enhancedchemicaloxidationfortertiarytr