臭氧催化氧化降解苯胺的机理宁军

72Vol．7No．220132ChineseJournalofEnvironmentalEngineeringFeb．2013*210095。MnO2-CuO-CeO2/200mg/L20min75%89%LC-MS、、。MnO2-CuO-CeO2/X703A1673-9108201302-0551-06DegradationmechanismofanilinebyozonationcatalysisNingJunChenLiweiCaiTianmingDepartmentofEnvironmentalEngineeringCollegeofResourcesandEnvironmentalSciencesNanjingAgriculturalUniversityNanjing210095ChinaAbstractWecomparedthedegradationefficiencyofanilinebyozonationaloneandcatalyzedozonationandananylzedthechangeofproductsinoxidationprocessbyLC-MS．TheresultsshowedthatMnO2-CuO-CeO2/zeolitecatalystcouldeffectivelyimprovethedegradationrateofanilinebyozonationandwhenoriginalanilineconcentrationwas200mg/Ltheremovalefficiencyofanilineincreasedfrom75%to89%after20minLC-MSanalysisshowedthatthedegradationproductsofanilinebycatalyzedozonationaresuccessivelyp-benzoquinoni-minep-benzoquinonemaleicacidandoxalicacidandaccordingtothatthedegradationpathwayofanilinebyozonationisinferred．KeywordsanilineMnO2-CuO-CeO2/zeolitecatalysisozonationdegradationpathway20100052011－12－072012－02－271985～。[e-mail]*[e-mail]、、、、1。、、“”、23。、、、、、。4。5。Jiang6。Deiber7。8。GitiEmtiazi9。MnO2-CuO-CeO2/MnO2-CuO-CeO2/。11．1、。CHYF-12A、UV-24507、Agilent6410、FL2200、DELTA320pH。1．2、1。。5L。1Fig．1Experimentalset-upofanilinewastewaterbyaloneozoneoxidationandozonecatalyticoxidation10g/h。10min。5L。5minpH、COD、、。KI。1．3pHpHCOD1011LC-MS12。ultimateC182．0μm4．6mm×250mm1．0mL/min30℃∶=20∶80V/V240nm20μL。AgilentC181．8μm2．1mm×50mm0．25mL/min30℃∶=20∶80V/V50μL。ESI4．0kV30nA350℃10．0L/min。1．412hpH7．0～8．0105～110℃13。5．0g500mL5%MnNO32、CuNO32、CeNO331∶3∶130℃160r/min3h30min238mL1．5mol/LpH10．5～11．0105～110℃。MnO2-CuO-CeO2/560℃4h14-16。、。22．1200mg/LpH7．03。2。2Fig．2Changesofconcentrationofanilineinanilinewastewaterbyaloneozoneoxidationandozonecatalyticoxidation2MnO2-CuO-CeO2/2552。20min21．14mg/L89%49．71mg/L75%。40min。MnO2-CuO-CeO2/5%。MnO2-CuO-CeO2/·OH1718。2．2COD200mg/LpH7．03COD490．12mg/L。COD3。3CODFig．3ChangeofCODinanilinewastewaterbyaloneozoneoxidationandozonecatalyticoxidation3MnO2-CuO-CeO2/。COD490．12mg/L261．87mg/L、230．63mg/L。90minCOD172．99mg/L·h150min91．30mg/L·h。MnO2-CuO-CeO2/COD8%COD。CODMnO2-CuO-CeO2/·OHCOD。COD50%。2．3pH7．032．001-----。。1pHTable1pHchangeinprocessofdegradationofanilinewastewaterunderdifferentconditionsminpHO3O3+MnO2-CuO-CeO2/07．037．0356．516．48105．986．09156．016．01205．935．55255．524．97305．494．54355．004．02405．014．00454．543．57604．063．03753．522．52903．552．011103．031302．481502．02LC-MS。4。4a0min2m/z=94．10M+H+m/z=116．10M+Na+。93。4b5min2。m/z=130．10M+Na+m/z=147．10M+K+。107、108、。—NH2C—HMnO2-CuO-CeO2/·OHN—HC—H35574MnO2-CuO-CeO2/Fig．4MassspectrogramsofintermediateofanilinebyozonecatalyticoxidationwithMnO2-CuO-CeO2/zeolitecatalystatdifferenttimes。。4c15min4。m/z=94．10M+H+m/z=131．10M+Na+m/z=139．20M+Na+m/z=147．30M+K+。93、108、116108、、。。。4d35min3。m/z=89．10M－H－m/z=107．20M－H－m/z=115．10M－H－。90、108116、。。。4e75min3。m/z=89．20M－H－m/z=107．10M－H－m/z=115．20M－H－。90、108116、。、。。2．45Fig．5Degradationpathwayofanilinebyaloneozoneoxidationandozonecatalyticoxidation1920。LC-MS、、45。44552、。5。31MnO2-CuO-CeO2/。200mg/L20min89%75%。2COD490．12mg/LCOD261．87mg/L、230．63mg/LMnO2-CuO-CeO2/150min90min。3—————pH7．032．00LC-MS2。、。。1．SBR．2009298844-845ShanDanMaFangWangJinshengetal．Bioaugmenta-tionwithaniline-degradingbacteriainSBRtreatinganilinewastewateratlowtemperature．ChinaEnvironmentalSci-ence2009298844-845inChinese2．、．20042110772-774784FuDongmeiChenJipingLiangXinmiao．Wetairoxida-tionofphenolnitrobenzeneandanilineinwasterwater．FineChemicals20042110772-774784inChinese3．、-．200427264-6575GengChunxiangZhangXiuxia．Degradationofwastewatercontaininganilineandnitrobenzeneusingadsorption-bica-talysishydrogenperoxide．EnvironmentalScience＆Tech-nology200427264-6575inChinese4．．200329223-25DuHuilingYaoLili．Studyonremovinganilinefromwastewaterbymeansofextraction．EnvironmentalProtec-tionScience200329223-25inChinese5．．2001213125-131ZhangWeimingXuZhongyanChenJinlongetal．StudyontreatmentofwastewaterfromproductionofN-phenylPeriacid．EnvironmentalProtectionofChemicalIndustry2001213125-131inChinese6JiangY．PetrierC．WaiteT．D．EffectofpHontheul-trasonicdegradationofionicaromaticcompoundsinaqueoussolution．UltrasonicSonochemistry200293163-1687DeiberG．FoussardJ．N．DebellefoniaineH．RemovalofnitrogenouscompoundsbycatalyticwetairoxidationKinet-icstudy．EnvironmentalPollution1997963311-3198．DSA．20012724-6SongWeifengMaQianLiYijiuetal．Studyondegra-dationanilinewithdifferentDSAanodecatalyticsystem．EnvironmentalProtectionScience20012724-6inChinese9GitiEmtiaziMohamadSatariiFatemehMazaherion．Theutilizationofanilinechlorinatedanilineandanilineblueastheonlysourceofnitrogenbyfungiinwater．WaterRe-search20013551219-222410．4．200211．．201026192197-2198QinXiaobinZhaoJiangboChangJinlingetal．Deter-minationofanilineinwaterwithHPLC．OccupationandHealth201026192197-2198inChinese12．-．2011235649-651ZouYulinChenYongLvGuibinetal．Determinationofanilineinwaterbyliquidchromatography-massspec-trometry．ChemicalResearchandApplication2011235649-651inChinese13．．2010321259-605557ShaoQinJinLahuaLiuYubingetal．Preparationofzeolitecatalystsfor