臭氧氧化技术处理含抗生素废水

22520105PROGRESSINCHEMISTRYVol.22No.5May201020095200912*863No.2007AA06Z345[e-mail]*1211211.1000842.350005、、pH、UV、H2O2。β-、、、、、。X131.2X52A1005-281X201005-1002-08TreatmentofAntibioticWastewaterbyOzonationXuWujun12ZhangGuochen1ZhengMingxia1ChenJian2WangKaijun11.DepartmentofEnvironmentalScienceandEngineeringTsinghuaUniversityBeijing100084China2.FujianNewlandEnTechCo.LtdFuzhou350005ChinaAbstractThebasicprincipleofozonationtechnologyisdescribedindetail.TheeffectsofozonedosagetemperaturepHUVH2O2andcatalystonthetreatmentofantibioticswastewaterbyozonationarediscussed.Therecentdevelopmentsaboutozonationofsixkindsofantibioticwastewaterincludingβ-lactamantibioticsmacrolideantibioticssulfonamideantibioticsquinoloneantibioticstetracyclineantibioticsandchloramphenicolantibioticsarereviewed.Moreoverexistingproblemsanddevelopmenttrendofwastewatertreatmentbyozonationtechnologyarepresented.KeywordsozoneadvancedoxidationprocessesAOPsantibioticdegradationContents1Introduction2Basicprincipleofozonationtechnology2.1Directozonation2.2Freeradicalreactionofindirectozonation3Influencefactorsonthetreatmentofantibioticswastewater3.1O3dosage3.2Temperature3.3pH3.4UV3.5H2O23.6Catalyst4Applicationofozonationinthetreatmentofantibioticswastewater4.1β-lactamantibioticswastewater4.2Macrolideantibioticswastewater4.3Sulfonamideantibioticswastewater4.4Quinolonesantibioticswastewater4.5Tetracyclinesantibioticswastewater4.6Chloramphenicolantibioticswastewater5Conclusion5·1003·1、、1—7。、8—10。1112。。、。13—21。、、、、、、22—28。β-、、、、、6。2、·OHO1.521。。1Table1ComparisonofoxidationabilityofsomeoxidantsoxidantoxidationpotentialVrelativeoxidationability*F23.062.25·OH2.802.05O2.421.78O32.071.52Cl21.361.0H2O20.840.64O20.40.29*calculationbasedonoxidationabilityofCl22.1129301。。—OH、—CH3、—NH2、1a。2。0.55D1b。。1abFig.1Directoxidationmechanismofozonationaelectrophilicsubstitutionreactionbdipolaradditionreaction2.21—531。OH－。·OH、—OH、—NH2232。、TOCCO2H2OCOD。·OH1k106—109M－1·s－12·OH。O3+OH→－·O－2+HO2·1·1004·22O3+OH→－HO－2+O22HO－2+O→3·HO2+·O－33·O－3+H→+HO3·4HO3→·HO·+O252·OHFig.2·OHindirectoxidationmechanismofozonation。pHO333。33.1·OH34—38。。。3.2Arrhenius6。O3。Witte346.0—62.0℃。6.0—35.4℃35.4℃62℃。K=K0·exp－Ea/RT63.3pH283438—42pH12pH。OH－·OH·OH。pHpH12109M－1·s－140。pH=7.0—12.0。3.4UVUV/O3O3310nmH2O2·OH。254nm43。·OH7、8241/3O3+H2O→UVH2O27H2O2→UV2·OH8UV44。UVO3·OHUV/O345—50。UVUV/O3。3.5H2O2H2O2Fenton5152。H2O2/O3H2O2O32253。pHH2O2O3·OH。H2O2O3·OHpH5H2O2HO－2HO－2O3·OH5·1005·54。OH·OHHO－2·OH。HO－21molO31mol·OHOH－0.67mol·OH53。H2O2。AkmehmetBalcioglu55VK20mMH2O2CODH2O270%95%。H2O2VK1hCOD。H2O2/O3H2O2O3。H2O2/O3pHO355—58。H2O2。H2O2H2O29、1024H2O2/O30.5—0.6。H2O2+OH→·HO2·+H2O+O29HO－2+OH→·OH－+HO2·103.65960。。。Cu2+、Mn2+、Fe2+、Ni2+60—64。1O3·OH11、12Fe2+602d、-60。O3·OHTOC。Fe2++O→3FeO2++O211FeO2++H2→OFe3++HO·+OH－12。TiO2、MnO2、Fe2O3/Ru/CeO2、Cu/Al2O3596065—68。5960。Lewis·OH。。/·OH。。TOC59—71。Yang67Al2O3MnOx、。MnOx/Al2O3TOCFT-IRMnOx—OH。TiO682Mn2+/MnO6771x。44.1β-β-、VK。β-。4.1.1Arslan-Alaton33O3/OH－、H2O2/UV、Fe2+/H2O2、Fe3+/H2O2、Fe2+/H2O2/UV、Fe3+/H2O2/UV6VKCOD=1395mg/L。O3/OH－VK·1006·22pH=11.52.75g/LVKCOD86%。Andreozzi40pH。pH274×103M－1·s－16×106M－1·s－1pH。S。Spry72SS、R。Andreozzi402--2---。。4.1.2AkmehmetBalcioglu55。pH=7.0、2.96g/L1.0hCODTOC74%50%。pHH2O2。UV254nm90%。。4.212—16。、、。Huber25、。3.5mg/LO3。Qiang73stopped-flowpH2.43×106M－1·s－13.26×105M－1·s－1。N2573—75。S。SN。N73。4.3“”。7677。。、、、。Huber253.5mg/L0.5—5.0μg/L、、。Dantas26。O30.4g/L15min200mg/L。60minTOC18%。60min30min。。Beltrán65TiO2UV/TiO2。10minTiO2/O3、UV/TiO2/O370%85%100%。120minTOC10%TiO2/O3、UV/TiO2/O3TOC43%93%。N。NN。S—N5·1007·2733。4.4、、。15%—50%。700。。Andreozzi37、H2O2/UV、TiO2。H2O2/UV560mg/LTiO2。AkmehmetBalcioglu55COD、pH、H2O2。COD。pHH2O2。4.5、。、。。Dalmázio78O3。120min200mg/L5%。Uslu。71Mn2+/MnO2115mg/L。Mn2+/MnO2。60min44.5%93.6%。Uslu795—10mg/LCOD465.8mg/L5min97%。4.6。、。TiO28081。pH。。pH4.0—8.53。3pHFig.3EffectofpHontheozonationdegradationofchloramphenicol5、。600。。《》O3。COD。·1008·22。1LafiWKAl-QodahZ.J.Hazard.Mater.2006B137489—4972HuangYLiXMYangQ.IndustrialWaterTreatment20062613—173KummererKAl-AhmadAMerschV.Chemosphere200040701—7104SapkotaASapkotaARKucharskiMetal.Environ.Int.2008341215—12265BarnesKKKolpinDWFurlongETetal.Sci.TotalEnviron.2008402192—2006HongADPhamNHNguyenHTetal.Chemosphere200872968—9737BaqueroFMartínezJLCantónR.Curr.Opin.Biotech.200819260—2658RomanHThomasTKlausHetal.Sci.TotalEnviron.1999225109—1189JonesOVoulvoulisNLesterJ.WaterRes.2005365013—502210BenWQiangZAdamsCetal.J.Chromatogr.A20081202173—18011BrittanAWValHSFrankDetal.Environ.Sci.Technol.2003371713—171912ChristaSMEvaMMarcJFSetal.Environ.Sci.Technol.2003375479—548613ParkJHChoIHChangSW.J.Environ.Sci.HealthPartB200641109—12014KurbusTMarechalAMLVoncinaDB.DyesPigments200358245—25215WangXJSongYMaiJS.J.Hazard.Mater.2008160344—34816AnTChenJLiGetal.Catal.Today200813969—7617Méndez-ArriagaFTorres-PalmaRAPétrierCetal.WaterRes.2008424243—424818PimentelMOturanNDezottiMetal.Appl.Catal.B-Environ.200883140—14919IkehataKEl-DinMGSnyderSA.Ozone-Sci.Eng.20083021—2620LiMLiJTSunHW.ProgressinChemistry2008201187