过硫酸盐活化高级氧化新技术杨世迎

:200710,:200712*(No.2007SR34),(No.200809)**e-mail:[e-mail]过硫酸盐活化高级氧化新技术*杨世迎**陈友媛胥慧真王萍刘玉红王茂东(中国海洋大学环境科学与工程学院海洋环境与生态教育部重点实验室青岛266100)过硫酸盐在热光过渡金属催化等条件激活下产生强氧化性的硫酸根自由基#SO-4基于#SO-4的过硫酸盐活化/高级氧化技术0在环境污染治理领域的应用,是刚刚发展起来的崭新的研究方向,具有广阔的应用前景本文在分析其基本原理的基础上,综述了过硫酸盐活化技术在国内外土壤地下水有机污染原位修复难降解有机废水处理等环境污染治理方面的研究进展,并就存在问题进行了研究展望过硫酸盐活化硫酸根自由基高级氧化技术土壤地下水修复有机污染物:X53;X52:A:1005-281X(2008)09-1433-06ANovelAdvancedOxidationTechnologyBasedonActivatedPersulfateYangShiying*ChenYouyuanXuHuizhenWangPingLiuYuhongWangMaodong(TheKeyLaboratoryofMarineEnvironment&Ecology,MinistryofEducation,CollegeofEnvironmentalScienceandEngineering,OceanUniversityofChina,Qingdao266100,China)AbstractThethermal,photochemicalormetalionsactivateddecompositionofpersulfateanions(S2O2-8)producesapowerfuloxidantknownasthesulfatefreeradical(#SO-4),whichcanpotentiallydestroyorganiccompounds.Activatedpersulfateoxidationchemistryisanemergingadvancedoxidationtechnology(AOT)fororganicpollutantsdegradation.Thispaper,forthefirsttime,providesanup-to-dateoverviewofapplicationofthenoveltechnologyinnotonlysoilandgroundwaterremediation,butalsowastewatertreatment.S2O2-8isarelativelynewformofinsituchemicaloxidation(ISCO)oxidantthathasmainlybeeninvestigatedatbench-scale.However,thetechnologyhasdevelopedrapidlyduetotheconsiderableresearchandapplieduseofthisoxidantatanincreasingnumberoffieldsites.Asforwastewatertreatment,S2O2-8ismostlyusedasanelectron-trappingagenttosuppresshole-electronrecombinationintheTiO2photocatalyticsystem,andonlyaveryfewreportshavediscussedorganicpollutantsdirec-tdegradationbyactivatedpersulfateoxidation.Theprospectsofactivatedpersulfateoxidationtechnologyarealsodiscussed.Keywordsactivatedpersulfate;sulfateradical;advancedoxidationtechnology;soilandgroundwaterremediation;organicpollutants(peroxymonosulfateoxone)(peroxydisulfatepersulfate),()(M2S2O8,M=NaKNH4),,2040,;50;70,,20920089化学进展PROGRESSINCHEMISTRYVol.20No.9Sep.,2008,(activatedpersulfate)/0(advancedoxidationtechnologies,AOTs),,,1S2O2-8,E0+2101V(vs.NHE)[1],(E0=+2107V),(E0=+1168V,)(E0=+1170V)(1)4)()O)O)),S2O2-8Ag+Mn2+MnO-4(5)MnO-4+4H++3e-MnO2+2H2O(1)H2O2+2H++2e-2H2O(2)O3+2H++2e-H2O+O2(3)S2O2-8+2e-2SO2-4(4)2Mn2++5S2O2-8+8H2O=2MnO-4+10SO2-4+16H+(5),,(UV)(Mn+,M=Fe2+Ag+Ce2+Co2+)(6)8),#SO-4[2],O)O3315kcalPmol,Fe2+12kcalPmol[3]S2O2-8heat2#SO-4(6)S2O2-8+Fe2+Fe3++#SO-4+SO2-4(7)S2O2-8hM2#SO-4(8)#SO-4,E0=+216V,S2O2-8(E0=+2101V),#OH(E0=+218V)(9)10)[1],,,CO2[4][2],#SO-4,pH815,#SO-4OH-#OH[5](1112),(13)Couttenye[6](EPR)#SO-4(pH=2)7),#OH(pH12),#SO-4#OH,#SO-4+e-SO2-4(9)2#OH+2H++2e-2H2O(10)#SO-4+H2OHSO-4+#OH(11)#SO-4+OH-SO2-4+#OH(12)#SO-4+CH3OHHSO-4+#CH2OH(13)Fenton(H2O2PFe2+)UVPO3UVPTiO2#OH,,,(AOTs)[7,8],#OH#OH#SO-4,AOTs2,[9)12]TNTP,60e,TOC,(UVP)(100eP),,211,,#1434#化学进展2021111(insituchemicaloxidation,ISCO),,[13](PCBs)(TCE),,,ISCO,,,ISCO33%[14]ISCO(KMnO4)FentonO3[15]ISCO10,,,,[16],KMnO4O3Fenton[15,16],ISCO,21112,(sodiumpersulfate,SPS):(1)SPS(25e100g74g),(25e20gPL110104gPL),SPS,;,[17](2)SPS,O3H2O2[18]SPSNOD(naturaloxidantdemand),(3)O3H2O2,(4),SPSpH,,[19](5)#SO-4#OH(#SO-44s,)[20],,SPS,SPS(TCE)40)60e(TCA)60eSPS[1],20eTCESPS,35hppm(methyltert-butylether,MTEB)8gPLSPS40e1h[18]Cuypers[21]70eSPS14PAHs,16PAHs0)80%Huang[22]59(20e30e40e)SPS,SPSKMnO4,BTEX()FeSPSSPSPFe2+PTCE20P5P1,Fe2+SPS60mgPLTCE47%[23,24],FeSPS:,Fe2+,,;,Fe2+,Fe2+S2O2-8#SO-4,(14)Fenton,pH,Liang[3],TCESPS,30%)50%TCE-1,2-DCE(7)9mgPL)[23]#SO-4+Fe2+Fe3++SO2-4(14)21113,:,,,Fe,,,,(radiofrequencyheating)(steaminjection)(electricalresistanceheating)[15]#1435#9:(1)()()(NAPL),,(1mgPL),,,10)1000ppm(2)MTBE(PCP),PCBs(3),(),SO2-4H+SO2-4250mgPL,,SO2-4(500)1000mgPL)SO2-4400mgPLSO2-4H+,pH53[24]pH,SO2-4Liang[25],SO2-4,,SO2-4,,SO2-4,,,FMC,,KlozuroR35300,MTBEPAHsPCBs1,4-[26]BTEXMTBE(210)3200LgPL),(airsparging)(53)300LgPL);330(1=31785L)818%,4,40h[27]EastlandWoolenMill,1999,1999)2004,100)10000LgPL2003)2006,27000130gPL90%60%[28]2800000LgPL,22177250kg,120694%)99%[29]HobokenTCE(10gPkg)5000,1100)200ppm011ppm[27]7000P,H2O2($1152Pkg)[30]NOD,,,[31]212,,TiO2,21211TiO2,TiO2(38715nm),TiO2,TiO2OH-#OH,,#1436#化学进展20(OÓ-2)[32],,,(),,TiO2[32]TiO2,[33)36]Malato[33]TiO2H2O2PCP,MillsValenzuela[35]Ce4+Fe3+Ag+S2O2-8TiO2:Ce4+Fe3+;Ag+;S2O2-8,2%,#SO-421212#SO-4,,Kronholm[37],013)015mmol#L-12,3-m-(80)400e)(200220310bar),55s110e100%,Maurino[34]TiO2,S2O2-8PUVH2O2PUV[38]S2O2-8PUV,pH=1,8min,5LmolPL100%S2O2-8PAg+[38)40]Gemeay[41]Ag+(sunsetyellow)(ponceau4R),#SO-43,,#SO-4(E=+216V,vs.NHE),#OH(E=+218V),,,,,,,[1]LiangCJ,BruellCJ,MarleyMC,etal.SoilSedimentContam.,2003,12:207)228[2]HouseDA.Chem.Rev.,1962,62(3):185)203[3]LiangCJ,BruellCJ,MarleyMC,etal.Chemosphere,2004,55:1225)1233[4]WangYB,HongCS.WaterRes.,1999,33(9):2031)2036[5]DogliottiL,HayonE.J.Phys.Chem.,1967,71(8):2511)2516[6]CouttenyeRA,HuangKC,HoagGE,etal.Proceedingsofthe19thPetroleumHydrocarbonsandOrganicChemicalsinGroundWater:Prevention,Assessment,andRemediation,ConferenceandExposition,Atlanta,GA.2002.345)350[7]TabriziGB,MehrvarM.J.Environ.Sci.HealthPartA:Tox.Hazard.Subst.Environ.Eng.,2004,39(11P12):3029)3081[8](LiuY),(SunDZ).(IndustrialWaterTreatment),