催化湿式氧化技术处理焦化废水袁金磊

25420097WATERRESOURCESPROTECTIONVol.25No.4Jul.2009　　:(1972—),,,,。E-mail:[e-mail]1,1,1,2(1.,　050026;2.,　050018):以非贵金属氧化物CuO、Co3O4、La2O3为主要活性成分,以TiO2-ZrO2为载体,制备了CuO-Co3O4-La2O3/TiO2-ZrO2复合负载型催化剂,用该催化剂采用催化湿式氧化技术处理焦化企业在生产过程中产生的焦化废水。系统考察了工艺条件如催化剂加入量、反应温度、反应时间和氧气分压等对催化湿式氧化反应的影响,得到最佳的工艺条件为:催化剂加入量10g/L,反应温度220℃,氧气分压3.5MPa。在此条件下反应2h,COD去除率达到98.7%,NH3-N去除率达到97.9%。反应15次COD和NH3-N去除率分别维持在90%和88%左右,表明使用该催化剂在处理焦化废水时显示出良好的催化活性和稳定性。:催化湿式氧化;焦化废水;废水处理:X703.1　　　:B　　　:1004-6933(2009)04-0051-04CatalyticwetoxidationofcokingwastewaterYUANJin-lei1,YANGXue-lin1,HUANGYong-mao1,DONGWen-geng2(1.HebeiChemicalandPharmaceuticalVocationalTechnologyCollege,Shijiazhuang050026,China;2.CollegeofEnvironmentalScienceandEngineering,HebeiUniversityofScienceandTechnology,Shijiazhuang050018,China)Abstract:Containingnon-noblemetalsCuO,Co3O4,andLa2O3asthemainactivatedcomponentsandTiO2-ZrO2asthecarrier,aCuO-Co3O4-La2O3/TiO2-ZrO2compoundcatalystwaspreparedtotreatthecokingwastewaterfromacokingfactorywiththecatalyticwetoxidationtechnique.Aftersystematicinvestigationofthefactorsinfluencingthecatalyticwetoxidationprocess,suchascatalystdosage,reactiontemperature,reactiontimeandoxygenpartialpressure,theoptimalreactionconditionswerefoundtobeacatalystdosageof10g/L,areactiontemperatureof220℃andanoxygenpartialpressureof3.5MPa.Theremovalratereached98.7%forCODand97.9%forNH+4-Naftertwohours'reactiontimeundertheoptimalreactionconditions.Theremovalrateremainedatabout90%and88%forCODandNH+4-N,respectively,after15reactions.ThisshowedthatthecompoundcatalystCuO-Co3O4-La2O3/TiO2-ZrO2hashigherefficacyandstabilityintreatingcokingwastewater.Keywords:catalyticwetoxidation;cokingwastewater;wastewatertreatment　　、,。、、、,。,。,,CODNH3-N[1-3]。,、,、,[4-7]。,、、[8-9]。·51·,、,,TiO2-ZrO2CuO-Co3O4-La2O3/TiO2-ZrO2,。1　1.1　。、、,,,70℃12h,,110℃12h,。1.2　GCF,2.0kW,2L;400℃,40MPa,600r/min。,COD7860mg/L,NH3-N3483mg/L,pH9.6。1000mL,,,,,“”,CODNH3-N,CODNH3-N。1.3　GB11914—1989《》,COD;GB7479—1987《》,NH3-N;Cu2+IRIS;pHPHS-3B;BET。2　2.1　CuO,γ-Al2O3、TiO2、TiO2-ZrO2,,Cu3%,200℃、8g/L、3.0MPa、2h,,,1。1　%CODNH3-NCuO/γ-Al2O342.640.3CuO/TiO251.748.7CuO/TiO2-ZrO268.954.6WAO()21.617.31,,CuOCODNH3-N,TiO2-ZrO2,CuO,TiO2-ZrO2。2.2　　　,TiO2-ZrO2,CuO,Co3O4,La2O3,,Cu3%、Co2%、La1%,200℃、8g/L、3.0MPa、2h,Co3O4La2O3COD、NH3-NCu2+,2。2　Co3O4La2O3COD/%NH3-N/%ρ(Cu2+)/(mg·L-1)CuO/TiO2-ZrO268.954.616.8CuO-Co3O4/TiO2-ZrO275.467.39.7CuO-La2O3/TiO2-ZrO273.672.11.6CuO-Co3O4-La2O3/TiO2-ZrO284.379.61.82,Co3O4La2O3;La2O3,CuO/TiO2-ZrO2Cu2+1.6mg/L,CuO-Co3O4/TiO2-ZrO2Cu2+1.8mg/L,La2O3Cu2+,。2.3　CuO-Co3O4-La2O3/TiO2-ZrO2,200℃、8g/L、3.0MPa、2h,、Cu2+、CODNH3-N,3。3,,CODNH3-N,600℃,,CODNH3-N;Cu2+·52·。,,,;,,,。600℃。3　/℃COD/%NH3-N/%/(m2·g-1)ρ(Cu2+)/(mg·L-1)40038.743.6189.618.645058.954.3180.214.650068.462.8175.89.255079.873.6165.62.160084.379.6168.71.865080.275.3143.61.570072.163.5119.61.375053.258.695.61.02.4　2.4.1　催化剂加入量200℃、3.0MPa、2h,CuO-Co3O4-La2O3/TiO2-ZrO2CODNH3-N,1。1　CODNH3-N1,CODNH3-N。010g/L,COD21.6%88.7%,NH3-N17.3%85.4%。10g/L,CODNH3-N。,10g/L。2.4.2　反应温度。10g/L、3.0MPa、2h,CODNH3-N,2。,,CODNH3-N。2,140℃220℃,COD40.3%95.9%,NH3-N30.1%94.3%。,,220℃。2　CODNH3-N2.4.3　氧气分压,,CODNH3-N。10g/L、220℃、2h,CODNH3-N,3。3　CODNH3-N3,1.0MPa3.5MPa,COD56.7%98.7%,NH3-N51.4%97.9%。CODNH3-N,3.5MPa。2.4.4　反应时间10g/L、220℃、3.5MPa,CODNH3-N,4。4　CODNH3-N4,0.5h2h,COD60.8%98.7%,NH3-N·53·54.3%97.9%,CODNH3-N。2h。2.5　10g/L、220℃、3.5MPa、2h,,CODNH3-N,5。5　5,CODNH3-N98.7%97.9%,,CODNH3-N90%88%;Cu2+,Cu2+1.8mg/L,Cu2+,0.2mg/L。,CuO-Co3O4-La2O3/TiO2-ZrO2。3　　a.CuO、Co3O4、La2O3,TiO2-ZrO2,CuO-Co3O4-La2O3/TiO2-ZrO2。b.,:10g/L,220℃,3.5MPa,2h。COD98.7%,NH3-N97.9%。c.,15,COD90%,NH3-N88%,。:[1],.[J].,2008,28(5):35-37.[2],,.COD[J].,2008,31(1):62-64.[3],,.[J].,2008,18(3):72-74.[4],.[J].,1993,15(5):88-91.[5]LUCKF.Wetairoxidation:past,presentandfuture[J].CatalysisToday,1999,53(1):81-91.[6],,,.[J].EnviromentalScience,1999,20(2):42-44.[7]ZHUWang-peng,BINYue-jing,LIZhong-he,etal.ApplicationofcatalyticwetoxidationforthetreatmentofH-acidmanufacturingprocesswastewater[J].WaterResearch,2002,36(8):1947-1954.[8].[D].:,2006.[9],,.[J].,2006,26(9):41-44.(:2008-12-08　:)(上接第50页):[1]BEUNJJ,HENDRIKSA,VanLOOSDRECHTMCM,etal.Aerobicgranulationinasequencingbatchreactor[J].WaterRes,1999,33(10):2283-2290.[2]LIUYong-qiang,TAYJH,MOYBYP.Characteristicsofaerobicgranularsludgeinasequencingbatchreactorwithvariableaeration[J].ApplMicrobiolBiotechnol,2006,71:761-766.[3]IVANOVV,WANGXiao-hui,TAYSTL,etal.Bioaugmentationandenhancedformationofmicrobialgranulesusedinaerobicwastewatertreatment[J].ApplMicrobiolBiotechnol,2006,70:374-381.[4]JIANGHe-long,TAYJH,LIUYu,etal.Ca2+augmentationforenhancementofaerobicallygrownmicrobialgranulesinsludgeblanketreactors[J].BiotechnologyLetters,2003,25:95-99.[5],,,.[J].,2006,27(9):1858-1861.[6]HULSHOFFPOLLW,deCASTROLOPESSI,LETTINGAG,etal.Anaerobicsludgegranulation[J].WaterRes,2004,38:1376-1389.(:2008-05-02　:)·54·