FeOOH催化臭氧氧化滤后水的醛酮副产物生成情况

FeOOH、鲁金凤1,　王　群2,3,　马　军2,3,　郭晓燕1,　王启山1(1.南开大学环境科学与工程学院,天津300071;2.哈尔滨工业大学市政环境工程学院,黑龙江哈尔滨150090;3.城市水资源开发利用北方国家工程研究中心,黑龙江哈尔滨150090)　　　:　在连续流条件下采用羟基氧化铁催化臭氧氧化(FeOOH/O3)工艺处理滤后水,考察了小分子醛、酮副产物的生成情况。结果表明,FeOOH/O3明显提高了对DOC和SUVA的去除率,而醛、酮副产物的产量比单独臭氧氧化的增加了12.23%。经催化氧化后,出水中醛、酮产量的顺序为:甲醛乙醛乙二醛甲基乙二醛丙酮。在不同的反应条件下,随着O3投量的升高和接触氧化时间的延长,催化氧化出水的醛、酮总量均是先升高后降低,但都高于单独臭氧氧化的生成量。FeOOH/O3明显增加醛、酮总量的趋势表明,其能够进一步提高滤后水的可生化性。　　:　羟基氧化铁;　催化臭氧氧化;　滤后水;　醛;　酮;　可生化性:TU991　　:A　　:1000-4602(2010)01-0032-04FormationofAldehydesandKetonesinFilteredWaterwithFerricOxyhydroxide-catalyzedOzonationLUJin-feng1,　WANGQun2,3,　MAJun2,3,　GUOXiao-yan1,　WANGQi-shan1(1.CollegeofEnvironmentalScienceandEngineering,NankaiUniversity,Tianjin300071,China;2.SchoolofMunicipalandEnvironmentalEngineering,HarbinInstituteofTechnology,Harbin150090,China;3.NationalEngineeringResearchCenterofUrbanWaterResources,Harbin150090,China)　　Abstract:　Theformationofaldehydesandketonesinfilteredwaterwithferricoxyhydroxide-cata-lyzedozonation(FeOOH/O3)inacontinuousflowreactorwasinvestigated.TheresultsshowthatFeOOH/O3improvestheremovalratesofDOCandSUVAsignificantly,andtheformationofaldehydesandketonesisincreasedby12.23%comparedwithozonationalone.Thesequenceofaldehydesandke-tonesformationafterFeOOH/O3isformaldehydeacetaldehydeglyoxalmethylglyoxalace-tone.Theyieldsofaldehydesandketonesinthefinishedwaterinitiallyincreaseandthendecreaseaso-zonedosageincreasesandcontacttimelengthensunderthedifferentreactionconditions.Incomparisontoozonationalone,FeOOH/O3significantlyincreasestheconcentrationsofaldehydesandketones,whichindicatesthatFeOOH/O3canfurtherimprovethebiodegradabilityoffilteredwater.　　Keywords:　ferricoxyhydroxide;　catalyticozonation;　filteredwater;　aldehyde;　ketone;　biodegradability　　:(2009ZX07424-005)·32·第26卷　第1期2010年1月　　　　　　　　　　　　中国给水排水CHINAWATERWASTEWATER　　　　　　　　　　　　　Vol.26No.1Jan.2010　　,,。(NOM),TOC,NOM、,。[1],,,。,、。,6NOM(FeOOH/O3),、NOM[2]。,FeOOH,FeOOH/O3、,、,。1　试验材料与方法1.1　FeOOH/O31。,40mm,550mm,50mm。,,。O3。,,KI。5h,0.5、1、35h。DOC,,UV254。1μm(TOCDOC)。1　Fig.1　Schematicdiagramofreactor1.2　。:、。1μm。1。1　Tab.1　Characteristicsoffilteredwater/NTUTOC/(mg·L-1)UV254/cm-1SUVA/(L·m-1·mg-1)pHBr-/(mg·L-1)/℃0.4～0.63.75～3.870.070～0.0761.87～1.967.7～7.90.0517～180.503.810.0731.927.80.0517.5　　FeOOH:24h,pH,60℃2d,FeOOH。1.3　、USEPAMethod556.1。O-(2,3,4,5,6-pentafluorobenzyl)hydroxylaminehydrochloride(),(EI)GC/MS、[3],、。TOCTOC,UV254752/。2　结果与讨论2.1　DOCSUVADOCSUVA[4]。,O3、FeOOH/O3FeOOHDOCSUVA2。2,O3,DOC10.76%～13.12%。O3·33·鲁金凤,等:FeOOH催化臭氧氧化滤后水的醛、酮副产物生成情况第26卷　第1期,O3SUVA。FeOOH/O3O3DOC。FeOOH/O328.08%～31.23%DOC,SUVAO310.92%～21.05%。,,,。,FeOOHDOCSUVA,5%。,FeOOH/O3·OHDOC。2　DOCSUVATab.2　RemovalofDOCandSUVAinfilteredwaterbydifferentprocesses/hDOC/(mg·L-1)SUVA/(L·m-1·mg-1)O3FeOOH/O3O3FeOOH/O303.813.813.811.921.921.920.53.312.623.691.261.101.9013.262.693.721.311.131.9133.362.653.671.191.061.8853.402.743.631.331.051.902.2　、,GC/MS、:、、、、、、、。,、、(1μg/L),GC/ECD,、、、5、。(3.50±0.25)mg/L、9.8min、T=18℃2。2　、Fig.2　Formationofaldehydesandketonesafterozonationandcatalyticozonation,(0.5、1、3、5h),。2,FeOOH、:;。,、。Swietlik[5]。、NOM,CanGurol[6]NOM,。,、,NOM,SUVA,。O3,FeOOH/O3、,12.23%。,,4、O3。,FeOOH/O3·OHNOM、,CanGurol[6]:·OH、。、[7]。、,FeOOH/O3。,。2.3　DOC3.81mg/L、9.8min、18℃,3、(3)。3O3/DOC0.18、0.921.31。O3,、;、O3/DOC=0.92。、O3/DOC[8]。O3NOM,DOC,O3,·34·第26卷　第1期　　　　　　　　　　　　　　中国给水排水　　　　　　　　　　　　[8]。3　、Fig.3　EffectofozonedosageonformationofaldehydesandketonesO3,FeOOH/O3、。O3,、15.65%;O33.5mg/L,FeOOH/O3、。3,FeOOH,O3,。,O3,,。,FeOOH,。2.4　、,。,(3.3、6.3、9.8min),O3FeOOH/O3、。,、,、。,FeOOH/O3、O3,FeOOH/O3·OH,,NOM,。3　结论①　FeOOH/O3DOCSUVA。②　、,。,FeOOH/O3、,,。③　O30.7～5mg/L,FeOOH/O3、,O3。O3/DOC≈1,FeOOH/O3、,、。④　,FeOOH/O3、,,FeOOH/O3、。:[1]　,.[J].,1998,64(2):10-14.[2]　,,,.FeOOHNOM[J].,2009,30(3):765-770.[3]　HuangWJ,FangGC,WangCC.Thedeterminationandfateofdisinfectionby-productsfromozonationofpollutedrawwater[J].SciTotalEnviron,2005,345(1-3):261-272.[4]　ChinYP,AikenG,O'loughlinE.Molecularweight,polydispersity,andspectroscopicpropertiesofaquatichu-micsubstances[J].EnvironSciTechnol,1994,28(11):1853-1858.[5]　SwietlikJ,DabrowskaA,NawrockiJ,etal.Reactivityofnaturalorganicmatterfractionswithchlorinedioxideandozone[J].WaterRes,2004,38(3):547-558.[6]　CanZS,GurolM.Formaldehydeformationduringozona-tionofdrinkingwater[J].OzoneSciEng,2003,25(1):41-51.[7]　WeinbergHS,GlazeWH,KranserSW,etal.Formationandremovalofaldehydesinplantsthatuseozonation[J].JAWWA,1993,85(5):72-85.[8]　NawrockiJ,KalkowskaI.Humicandfulvicacidsaspre-cursorsofaldehydes-ozonationby-products[J].ToxicolEnvironChem,1999,68(34):297-306.:(1980-　),　,　,　,　,　。E-mail:[e-mail]::2009-08-24·35·鲁金凤,等:FeOOH催化臭氧氧化滤后水的醛、酮副产物生成情况第26卷　第1期