催化臭氧化一种有前景的水处理高级氧化技术李来胜

　李来胜　祝万鹏　李中和　　　介绍了均相和非均相催化剂增加臭氧氧化去除水溶液中有机物的效率,催化臭氧化能够氧化或降解单独臭氧不能氧化或降解的难降解有机物,减少后续氯化消毒工艺所形成消毒副产物如三氯甲烷等的含量。　催化剂　催化臭氧化　TOC去除率　自由基　水处理　消毒副产物0　,。,,。,,,、。[1～3],,。。O3/H2O2、UV/O3、UV/H2O2、UV/H2O2/O3、TiO2/UVCWAO,()。,106～109M-1s-1[4～6],1。17。:()、。80,。1　、KO3/M-1s-1KOH·/M-1s-12±0.4a7.8×1090.09±0.02a3.9×10994±20a7.5×1095±5a1.3×108100±20b3.2×109(4×10-2)a1.4×106(4×10-2)b7.7×106(3×10-5)a1.6×107(3×10-5)a8.5×107(3×10-2)a3.1×108((3±1)×10-2)b3.1×108174.0×1090.11.7×109　:a;b。1　()1988Abdo[7]、。1992Andreozzi[8]:Mn(Ⅱ),Mn(Ⅱ)pH04.7。pH=0Mn(Ⅱ)Mn(Ⅳ)Mn(Ⅲ),Mn(Ⅱ),MnO226　　　　Vol.27　No.6　2001DOI:10.13789/j.cnki.wwe1964.2001.06.008。pH=4.7,Mn(Ⅲ),,NowellHoigné[9];Mn(Ⅲ)、[10],1。Mn(Ⅱ)+O3+2H+Mn(Ⅳ)+O2+H2OMn(Ⅳ)+Mn(Ⅱ)2Mn(Ⅲ)Mn(Ⅲ)+nAO2-Mn(Ⅲ)(AO2-)nMn(Ⅲ)(AO2-)nMn(Ⅱ)+AO-+(n-1)AO2-AO-+O3+H+2CO2+O2+OH·OH·+AO2-……1　Mn(Ⅱ)[8],Mn(Ⅱ)、[11～12],pH=3.0～4.0MnO2,,。1993Naydenov[13]1995Thompson[14]MnO2,,NaydenovMnO2。1995Gracia[15]、、(=6×10-5mol/L),(TOC=11mg/L,pH=7)Mn(Ⅱ)Ag(Ⅰ),30minTOC62.3%61%,2。2,,TOCmgTOC。3Mn(Ⅱ)TOCCOD。,COD60%～80%。1998Gracia[16],EBRO(TOC=2.95mg/L),。1999MaGraham[17]Mn(Ⅱ),MnO2,,,。,,2　/g/h/mg/LTOC/mg/LTOC/mg/LTOC/%ΔO3/ΔTOC/mg/mgO31.6764.510.63.532.618.7O3/Mn(Ⅱ)1.6747.210.66.662.37.2O3/Fe(Ⅱ)1.6745.610.45.957.37.7O3/Ag(Ⅰ)1.6737.79.45.761.06.6O3/Cd(Ⅱ)1.6740.810.56.158.36.7O3/Fe(Ⅲ)1.6737.710.35.351.07.2O3/Cu(Ⅱ)1.6740.811.06.055.16.8O3/Zn(Ⅱ)1.6740.811.05.752.27.1O3/Co(Ⅱ)1.5034.111.13.430.610.1O3/Cr(Ⅲ)1.5034.111.04.137.88.23　Mn(Ⅱ)TOC/mg/L10.67.14/%32.662.3COD/mg/L2310.15.8/%5675,。,,1mg/L,,2mg/L,。2　,Al2O3,。1989Al-Hayek[18]Al2O3,Fe(Ⅲ)/Al2O3,TOC。TOC40%,Al2O3TOC70%,Fe(Ⅲ)/Al2O3TOC90%。,。1997ChristianVolk[19]O3、O3/H2O2O3/TiO2,(24%)　Vol.27　No.6　200127　　　(15%)(18%),(DOC=2.84mg/L,=5mg/L,=2mg/L,1h),4,。BDOC(),。4　()/mg/LDOC/mg/mg0.320.110.270.100.600.240.180.08　　1999ColinCooper[20]、,5。5、,。5　/min/%/%Al2O3Fe3O3/Al2O3TiO2/Al2O33001585888730012174547302584100100　　1999B.LegubeN.Karpel[21],:TOC(:=250mgCaCO3/L,pH=7.2,TOC=2.5～3.0mg/L,2.2～2.5mg/mgTOC),6。6,TOC12%15%;6　TOC/minTOC/%Cu/aluminaCu/anataseCu/attapulgite10153847323102010124465636037(alumian)(300m2/g,10wt.%Cu)、(anatase)(61m2/g,5wt.%Cu)(attapulgite)(59m2/g,5wt.%Cu),TOC,;TOC。(200m2/g)(=1mM),。,、[22],(TOC=8mg/L),30minTOC60%;()TOC32%12%。2000Gracia[23]EBROTiO2/Al2O3,7。7THMs,THMsTHMs。7　/hmg/LCHCl3/μg/LCHCl2Br/μg/LCHClBr2/μg/LCHBr3/μg/LTHMs/μg/L0.8gO3/gTOC26240.40.30.1152461439612160011331801.6gO3/gTOC26240.50.30.117235113048210011026750.8gO3/gTOC26240.40.30.11225583047210011017771.6gO3/gTOC26240.50.30.112253826261100061662　26240.70.50.21534551627301317230014478108　:TOC=4.46mg/L,2.56mgCl2/L。28　　　　Vol.27　No.6　2001,,。、,,;,,,。3　,:①;②、;③;④。参考文献1　PMFedorak,etal.Theeffectsofphenolandsomealkyphenolicsonbatchanaerobicmethanogenesis.WaterResearch,1984,18(3):361～3672　RBarreiro,etal.Toxiceffectsofchemicalsonmicroorganisms.Wa-terEnvironRes,1992,64(4):632～6413　TReemtsma,etal.Dissolvedorganicsintannerywastewatersandtheiralterationbyacombinedanaerobicandaerobictreatment.Wa-terResearch,(1997),31,(5):1035～10464　JHoigneHBaderRateconstantsofreactionofozonewithorganicandinorganiccompoundsinwaterⅠ:Dissociatingorganiccom-pounds.WaterRes,1983,17:173～1835　JHoigne,HBader.RateconstantsofreactionofozonewithorganicandinorganiccompoundsinwaterⅡ:Dissociatingorganiccom-pounds.WaterRes,1983,17:185～1946　GVBuxton,etal.Criticalreviewofrateconstantsforreactionsofhydratedelectrons,hydrogenatomsandhydroxylradicalsinaqueoussolution.JphysChemRefData,1988,17:513～5947　MSEAbdo,etal.Decolorizationbyozoneofdirectdyesinpresenceofsomecatalysis.JEnvironSciHealthA,1988,23:697～7108　RAndreozzi,etal.ThekineticsofMn(Ⅱ)-catylysedozonationofoxalicacidinaqueoussolution.WaterResearch,1992,26(7):917～9219　LHNowell,etal.Interactionofiron(Ⅱ)andothertransitionmetalswithaqueousozone.8thOzoneWorldCongress.Zurich,198710WibergKB.Oxidationinorganicchemistry,NY:Academicpress,196511RAndreozzi,etal.Manganese-catylysedozonationofglyoxalicacidinaqueoussolution.JournalofChemicalTechnologyandBiotechno-logy,2000,75:59～6512RAndreozzi,etal.Theozonationofpyruvicacidinaqueoussolutionscatalyzedbysuspendedanddissolvedmanganese.WaterResearch,1998,32(5):1492～149613ANaydenov,DMehandjiev.Completeoxidationofbenzeneonman-ganesedioxidebyozone.AppliedCatalysisA:General,1993,97:17～2214PEThompson,etal.Heterogeneouscatalyticoxidationoforganicpollutantsinaqueoussolutions.The1995ICHEMEResearchEvent,1stEuropeanConference,1995,29715RGracia,etal.Studyofcatalyticozonationofhumicsubstancesinwaterandtheirozonationbyproducts.OzoneScience&Engineering,1996,18:195～20816RGracia,etal.Mn(Ⅱ)-catalysedozonationofrawEbroriverwa-teranditsozonationby-products.WaterResearch,1998,32(1):57～6217JMa,NJDGraham.Degradationofatrazinebymanganese-cat-alyzedozonation:influenceofhumicsubstrances.WaterResearch,1999,33(3):785～79318NAl-Hayek,etal.Fe(Ⅲ)/Al2O3-Catalysedozonationofphenolanditsozonationby-products.EnvironTechnolLetters,1989,10:415～42619CVolk,etal.Comparisonoftheettectofozone,ozone-hydrogenperoxidesystemandcatalyticozoneonthebiodegradableorganicmatterofafulvicacidsolution.WaterResearch,1997,31(3):650～65620ColinCooper,etal.Aninvestigationofcatalyti