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：/wiki/Advanced_oxidation_process)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.)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-+photonsorheat2SO4•-

SO4•-+OH-

SO42-+HO•

SO4•-+H2OHSO4-+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.Relativepowerofcommonoxidants

Compound

Oxidationpotential(volts)

Relativepowerofchlorine

Fluorine3.06

2.25Sulfateradical(SO4-)2.5-3.10

1.84-2.28Hydroxylradical(HO•)

2.82.05Atomicoxygen(O•)

2.421.78Ferrate(VI)0.7-2.20.52-1.62Ozone

2.081.52Perhydroxylradical

(HOO•)1.701.25Permanganate1.671.23Chlorinedioxide

1.501.10Hypochlorousacid

1.491.10Chlorine1.361.0Bromine1.090.80Hydrogenperoxide

0.870.64Iodine0.540.40Oxygen0.400.29臭氧(Ozone)Palebluegas,slightlysolubleinwaterSharpodorHarmfuleffectsontherespiratorysystemsofanimalsPowerfuloxidizingagent臭氧技术在水处理中的应用Removalofinorganicspeciessuchasammonianitrogen(1)(2)inthepresenceofbromideRemovalofFe2+andMn2+

Oxidationofnaturalorganicmatterlikehumicsubstances(HumicsubstancesareprecursorsofTHMsandfavortheregrowthinthenetwork)臭氧技术在水处理中的应用IncreaseinbiodegradabilityOxidationofPersistentOrganicPollutants(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)Fig.1bPeudo-first-orderrateconstantof0.1mMlinuron（利谷隆）insole-O3systematvariouspHlevels([O3]=1.7110-5M)(来源：RaoY.F.,ChuW.Chemosphere2009,74,1444-1449)

Fig.1aPeudo-first-orderrateconstantof0.2mMCarbofuran(克百威）insole-O3systematvariouspHlevels([O3]=1.810-5M)(来源：LauT.K.,ChuW.,GrahamN.WaterSci.Tech.2007,55,275-280.)臭氧处理(Ozone)Highlyselective

Table2.OzonationrateconstantsandOHrateconstantsforsomeorganiccompounds(LegubeB.andLeitnerN.K.V.CatalysisToday,1999,53,61-72)CompoundskO3(M-1s-1)kOH(M-1s-1)Benzene2±0.47.8×109Nitrobenzene0.09±0.023.9×109Toluene14±33.0×109Formicacid5±51.3×108Oxalicacid<4×10-21.4×106Aceticacid<3×10-51.6×107Succinicacid<3×10-23.1×108臭氧处理(Ozone)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/H2O2

O3+H2O2

OH+HO2-+O2(k<10-2M-1s-1)

O3+HO2-

OH+2O2[k=(5.5±1.0)×106M-1s-1)]US/O3HeterogeneouscatalyticozonationsuchasAC(ActivatedCarbon)/O3,MnO2/O3,Al2O3/O3,TiO2/O3HomogeneouscatalyticozonationbymetallicionsOzonation/electrolysis

UV/O3DirectPhotolysisDirectoxidationbyozoneOxidationbyhydroxylradicals(1)O3+H2O+hv

H2O2+O2

(2)

H2O2+hv

2OHUV/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.Theplantisdesignedtoreducea50ppmPCBfeedconcentrationtoa1ppmeffluent.UV/OzoneReactor–Ultrox®(Jones,1996)

US/O3PyrolysisOxidationbyozoneOxidationbyhydroxylradicalsO3

+H2O2

OH+HO2-

+O2

(k<10-2M-1s-1)

O3

+HO2-

OH+2O2

[k=(5.5±1.0)×106M-1s-1)]US/O3(来源:HeZ.Q.,SongS.,etal.Chemosphere2007,69,191-199).US/O3(来源:NingB.,GrahamN.J.,LickissP.D.WaterEnvironmentResearch2007,79,2427-2436).HeterogeneousCatalyticOzonationAC(ActivatedCarbon)/Ozone

(1).Generationoffreeradicals:O3+AC→OH

(2).Generationofsuraceradicals:O3+AC→AC-OAC-R+AC-O→PTiO2/OzoneCeramichoneycomb/OzoneAC/OzoneFig.3.EvolutionofthedimensionlessconcentrationofoxalicacidatpH3(C0=1mM,AC=0.5g/L,Ctert-butanol=10mM).(来源：Faria,P.C.C.,Orfao,J.J.M.etal.AppliedcatalysisB:Environmental,2008,79,237-243).TiO2/Ozone(来源:BeltranF.J.,RivasF.J.,EspinosaR.M.AppliedCatalysisB:Environmental2002,39,221-231).Ceramichoneycomb(2MgO–2Al2O3-5SiO2)/Ozone

(来源:ZhaoL.,MaJ.,SunZ.Z..AppliedCatalysisB:Environmental2008,79,244-253).Ceramichoneycomb/Ozone(来源:ZhaoL.,MaJ.,SunZ.Z..AppliedCatalysisB:Environmental2008,79,244-253).HomogeneousCatalyticOzonationbymetallicionsReactionMechanism

Fe2++O3→Fe3++O3-

O3-+H+↔HO3→OH+O2CatalyticozonationbymetallicionsO3alone<Pb2+≈Cu2+≈Zn2+<Fe2+≈Ti2+<Mn2+(来源:NiC.H.,ChenJ.N.,YangP.Y.WaterScienceandTechnolgoy2002,47,77-82).CatalyticozonationbyMn2+(来源:MaJ.,Graham,N.J.D.WaterResearch2000,34,3822-3828).CatalyticozonationbyMn2+(来源:XiaoH.,LiuR.P.,etal.Chemosphere2008,72,1006-1012).Ozonation/electrolysisReactionMechanismO3+e→O3-atcathodesO3-+H2O→OH+O2+OH-Ozonation/electrolysis(来源:KishimotoN.,MoritaY.,etal.WaterResearch2005,39,4661-4672).Ozonation/electrolysis(来源:KishimotoN.,MoritaY.,etal.WaterResearch2005,39,4661-4672).OtherOxidationTechnologySO4•--based

AOPs

UV/Persulfate(S2O82-),heat/S2O82-,Fe2+/S2O82-,Ag+/S2O82-,Co2+/peroxymonosulfate(HSO5-),Fe2+/HSO5-

,AC/PersulfateFerrate(VI)PermanganateSO4•--based

AOPs(来源:YangS.Y.,WangP.,etal.JournalofHazardousMaterials2010,179,552-558).SO4•--based

AOPs(来源:YangS.Y.,WangP.,etal.JournalofHazardousMaterials2010,179,552-558).AC/Persulfate(来源:YangS.Y.,YangX.,etal.JournalofHazardousMaterials2011,186,659-666).Ferrate(VI)Inacidicmedia:FeO42-+8H++3e-

Fe3++4H2OE0=2.2VInbasicmedia:

FeO42-+4H2O+3e-Fe(OH)3+5OH-E0=0.7v高铁酸盐在水处理中应用研究Removalofcyanides(CN-1→NCO-)SimultaneousremovaloforganicpollutantsandphosphateEliminationofsludgeodorDecolorizationOxidationofPOPsCoagulationPermanganate(MnO4-1)Inanacidicsolution,permanganate(VII)isreducedtothecolourless+2oxidationstateofthemanganese(II)(Mn2+)ion.8H++MnO4−+5e−→Mn2++4H2OInastronglybasicsolution,permanganate(VII)isreducedtothegreen+6oxidationstateofthemanganateMnO42−.MnO4−+e−→MnO42−Inaneutralmedium,however,itgetsreducedtothebrown+4oxidationstateofmanganesedioxideMnO2.

2H2O+MnO4−+3e−→MnO2+4OH+Strongoxidizer，apermanganatecanoxidizeanaminetoanitrocompound,[2][3]analcoholtoaketone,[4]analdehydetoacarboxylicacid,[5][6]aterminalalkenetoacarboxylicacid,[7]

oxalicacidtocarbondioxide,[8]andanalkenetoadiol.Permanganate(MnO4-1)InalkeneoxidationsoneintermediateisacyclicMn(V)species:（来源：/wiki/Permanganate）高锰酸钾在水处理中的应用强化预氯化消毒(减少了致癌物三卤甲烷的生成）去除微量重金属离子例如Mn2+，As3+，Pb2+

Mn2++2KMnO4+2H2O=5MnO2+2K++4H+（中性和微酸性）治理染料废水去除难降解有机污染物去除藻类（氧化降解微囊藻毒素MC-LR）消毒去除微量Mn2+（三亚中法供水有限公司-水库）（来源：王菊，潘孝楼，科技资讯，2009，34，115-116.）难降解有机污染物的去除（来源：Hu,L.H.,Martin,H.M.etal.EnvironmentalScience&Technology,2009,43,509-515.）Photocatalysis1、藤岛昭(光触媒之父）和本田健一

（Fujishima,A.andHonda,K.ElectrochemicalPhotolysisofWaterataSemiconductorElectrode.Nature1972,238(5358),37-38.）藤岛昭TiO2-basedPhotocatalysis光催化技术的应用研究高速公路的隔音墙和街道路灯等装置上汽车的喷涂材料光催化剂公路（日本千叶县）医学上消毒以及用来杀死癌细胞保鲜水果利用二氧化钛的亲水性制造不用擦拭的汽车后视镜等产品（东陶公司的渡部俊）脱臭染料电池光催化制氢*水处理（去除金属离子和难降解有机污染物）贵重金属的回收（铂、金）二氧化钛的载体ActivatedCarbon(活性炭）玻璃铝片硅胶陶瓷高分子聚合物ModificationofTiO2CompositePhotocatalysts----TiO2/CdS,TiO2/Cu2O,TiO2/Fe2O3,TiO2/WO3,TiO2/Bi2O3

andsoon.TransitionMetalDoping----Fe,Cr,V,Co,Zretc.Non-metalDoping----N,C,P,S,etc.SurfaceSensitization----Dye,polymerCompositePhotocatalysts（来源：孙德智等，《环境工程中的高级氧化技术》，p241)N-dopedTiO2（来源：Asahi,R.etal.Science,2001,293,269-271）Wavelength,nmSurfaceSensitization（来源：孙德智等，《环境工程中的高级氧化技术》，p243)1.染料容易吸附在半导体表面2.染料激发态（通常是单线态）的电位与半导体导带电位相匹配。H2O2-AidedTiO2PhotocatalysisunderVisibleLight（来源：Li,X.Z.,Chen,C.C.,Zhao,J.C.Langmuir,2001,17,4118-4122.)H2O2-AidedTiO2PhotocatalysisunderVisibleLight（来源：Rao,Y.F.,Chu,W.

EnvironmentalScience&Technology,2009,43,6183-6189.)Figure1.LNRdegradationunderdifferentreactionconditionsH2O2-AidedTiO2PhotocatalysisunderVisibleLight

Theory1:

TitaniumperoxidecomplexformedontheTiO2surfacecouldextendthephotoresponseofTiO2tothevisibleregionandcanbeexcitedbyvisiblelight.TheexcitedsurfacecomplexinjectsanelectrontotheconductionbandofTiO2wheretheelectronsontheconductionbandofTiO2,then,initiatethedecompositionofH2O2toproducehydroxylradicals(Lietal.2001).

H2O2-AidedTiO2PhotocatalysisunderVisibleLight（来源：Li,X.Z.,Chen,C.C.,Zhao,J.C.Langmuir,2001,17,4118-4122.)1.Whetherornotelectronisgeneratedinthissystem?2.Whetherornothydroxylradicalsplayakeyroleinthedegradationoforganiccompoundinthissystem?PhotocatalyticDegradationMechanismofLNRunderVisibleLight

Effectofradicalscavengers

Effectofradicalscavengersonvisible-lightphotocatalysisofLNRwiththeassistanceofH2O2.（来源：Rao,Y.F.,Chu,W.

EnvironmentalScience&Technology,2009,43,6183-6189.)TheGenerationofPhotocurrent(a)(b)Visible-light-inducedcurrent(Iph)generationonaTiO2/ITOelectrodeinwaterwithorwithoutH2O2（来源：Rao,Y.F.,Chu,W.

EnvironmentalScience&Technology,2009,43,6183-6189.)Table7-1:IdentifieddegradationproductsandtheirmainfragmentsdeterminedbyLC/ESI-MSCompoundRetentiontimeMolecularweightMolecularionandmainfragmentsStructuralformulaDetectedinUVVis18.96186185,165,141,119√√29.49278277,250,233,217,119√√310.02262261,156,119,109√410.65200199,42,137,119√√512.62200199,137,119√√613.90230229,37,119,109√√714.61264263,176,119,109√√814.83250249,219,202,176,137,119,109√√9