高级氧化技术在水和废水处理中的应用2

高级氧化技术在水和废水处理中的应用高级氧化处理(AOPs)•Advancedoxidationprocesses(abbreviation:AOPs)referstoasetofchemicaltreatmentproceduresdesignedtoremoveorganicandinorganicmaterialsinwastewaterbyoxidation.Contaminantsareoxidizedbyfourdifferentreagents:ozone,hydrogenperoxide,oxygen,andair,inprecise,pre-programmeddosages,sequences,andcombinations.TheseproceduresmayalsobecombinedwithUVirradiationandspecificcatalysts.Thisresultsinthedevelopmentofhydroxylradicals.TheAOPprocedureisparticularlyusefulforcleaningbiologicallytoxicornon-degradablematerialssuchasaromatics,pesticides,petroleumconstituents,andvolatileorganiccompoundsinwastewater[1].(来源：)高级氧化处理(AOPs)•RuppertandRupert(1994)havedefinedtheAOPsasprocesseswhichinvolvedthegenerationofhydroxylradicalsinsufficientquantity,suchasO3/OH-,O3/H2O2,Fe2+/H2O2,UVC/H2O2,UVC/O3andUVA/TiO2.(RuppertG.,RupertB.G.H.UV-O3,UV-H2O2,UV-TiO2andthephoto-Fentonreactioncomparisonofadvancedoxidationprocessesforwastewatertreatment.Chemosphere1994,28,1447-1454.)Spectrumofelectromagneticradiation高级氧化处理(AOPs)•高级氧化处理是20世纪80年代开始形成的处理有毒污染物技术，它的特点是通过反应产生羟基自由基，该自由基具有极强的氧化性，通过自由基反应能够将有机污染物有效地分解，甚至彻底地转化为无害无机物，如二氧化碳和水等。由于高级氧化工艺具有氧化性强、操作条件易于控制的优点，因此引起世界各国的重视，并相继开展了该方向的研究与开发工作。（来源：《环境工程中的高级氧化技术》）高级氧化处理(AOPs)•Sulfateradical-basedAOPs（1）UV/S2O82-S2O82-+photonsorheat2SO4•-SO4•-+OH-SO42-+HO•SO4•-+H2OHSO4-+HO•（2）Fe2+/S2O82-,Ag+/S2O82-Ag++S2O82-Ag2++SO4•-+SO42-Fe2++S2O82-Fe3++SO42-+SO4•-(3)Co2+/HSO5-,Fe2+/HSO5-Co2++HSO5-Co3++SO4•-+OH-Fe2++HSO5-Fe3++SO4•-+OH-高级氧化处理(AOPs)(4)GranularActivatedCarbon(GAC)/S2O82-GAC-OOH+S2O82-SO4•-+GAC-OO•+HSO4-GAC-OOH+S2O82-SO4•-+GAC-O•+HSO4-Table1.RelativepowerofcommonoxidantsCompoundOxidationpotential(volts)RelativepowerofchlorineFluorine3.062.25Sulfateradical(SO4-)2.5-3.101.84-2.28Hydroxylradical(HO•)2.82.05Atomicoxygen(O•)2.421.78Ferrate(VI)0.7-2.20.52-1.62Ozone2.081.52Perhydroxylradical(HOO•)1.701.25Permanganate1.671.23Chlorinedioxide1.501.10Hypochlorousacid1.491.10Chlorine1.361.0Bromine1.090.80Hydrogenperoxide0.870.64Iodine0.540.40Oxygen0.400.29臭氧(Ozone)•Palebluegas,slightlysolubleinwater•Sharpodor•Harmfuleffectsontherespiratorysystemsofanimals•Powerfuloxidizingagent臭氧技术在水处理中的应用•Removalofinorganicspeciessuchasammonianitrogen(1)(2)inthepresenceofbromide•RemovalofFe2+andMn2+•Oxidationofnaturalorganicmatterlikehumicsubstances(HumicsubstancesareprecursorsofTHMsandfavortheregrowthinthenetwork)3OBrHBrO42HBrONHNBr32323322()OHOOFeFeFeOHMnMnO343ONHNO臭氧技术在水处理中的应用•Increaseinbiodegradability•OxidationofPersistentOrganicPollutants(POPs)•Disinfection----moreeffectivebiocidethanhydroxylradicals(Cankillbacteria,virusandalgaebyreactingwithcytoplasmicsubstancesanddegradingchromosomaldeoxyribonucleicacid)Additionof1μg/LO3leadsto99.99%reductionofE.coliinoneminute.Ozonationhasbeenwidelyusedinthedisinfectionofdrinkingwaterindevelopedcountries.臭氧处理(Ozone)•Onsitegeneration(half-lifeinatmosphericconditionsishalfanhour,2O3→3O2)•HighlypH-dependent(1)O3+OH-→HO2-+O2(2)HO2-+O3→O3-+HO2(3)HO2H++O2-(4)O2-+O3→O3-+O2(5)O3-+H+→HO+O2臭氧处理(Ozone)0.000.020.040.060.080.100.120.140.160.1824681012pHok(min-1)0.00E+002.00E-034.00E-036.00E-038.00E-031.00E-021.20E-021.40E-021.60E-020.002.004.006.008.0010.0012.00pHk,s-1Fig.1bPeudo-first-orderrateconstantof0.1mMlinuron（利谷隆）insole-O3systematvariouspHlevels([O3]=1.7110-5M)(来源：RaoY.F.,ChuW.Chemosphere2009,74,1444-1449)Fig.1aPeudo-first-orderrateconstantof0.2mMCarbofuran(克百威）insole-O3systematvariouspHlevels([O3]=1.810-5M)(来源：LauT.K.,ChuW.,GrahamN.WaterSci.Tech.2007,55,275-280.)臭氧处理(Ozone)•HighlyselectiveTable2.OzonationrateconstantsandOHrateconstantsforsomeorganiccompounds(LegubeB.andLeitnerN.K.V.CatalysisToday,1999,53,61-72)CompoundskO3(M-1s-1)kOH(M-1s-1)Benzene2±0.47.8×109Nitrobenzene0.09±0.023.9×109Toluene14±33.0×109Formicacid5±51.3×108Oxalicacid4×10-21.4×106Aceticacid3×10-51.6×107Succinicacid3×10-23.1×108臭氧处理(Ozone)00.20.40.60.811.21.4020406080100120Time,minC/C0orTOC/TOC0UVOzoneUV/OzoneUV(TOC)Ozone(TOC)UV/Ozone(TOC)Fig.2.Comparisonoflinurondecay(C/C0)andTOCremovalbythedifferenttreatmentprocessesatpH6(C0=0.1mM)(来源：RaoY.F.,ChuW.Chemosphere2009,74,1444-1449)Highlyselective→Lowmineralization臭氧与其他技术联合处理•UV/O3•O3/H2O2O3+H2O2OH+HO2-+O2(k10-2M-1s-1)O3+HO2-OH+2O2[k=(5.5±1.0)×106M-1s-1)]•US/O3•HeterogeneouscatalyticozonationsuchasAC(ActivatedCarbon)/O3,MnO2/O3,Al2O3/O3,TiO2/O3•Homogeneouscatalyticozonationbymetallicions•Ozonation/electrolysisUV/O3•DirectPhotolysis•Directoxidationbyozone•Oxidationbyhydroxylradicals(1)O3+H2O+hvH2O2+O2(2)H2O2+hv2OHUV/OzoneReactorTable3Designdatafora151m3/dayUltroxplantReactorDimensions:LxWxH(m)2.5x4.9x1.5Wetvolume,(L)14,951UVlamps:Numberof65wattlamps378Totalpower,(KW)25OzonegeneratorDimensions:LxWxH(m)1.7x1.8x1.2gmsozone/min5.3Kgozone/d7.7Totalpower,(KW)7.0Totalenergyrequired,(KW/day)768Costsintheabovetablewereconsideredtobecompetitivewithactivatedcarbon.Typicaldesigndatafora150m3/dUV/ozonetreatmentprocessareshownintheabovetable.Theplantisdesignedtor