OzonebasedtreatmentofMunicipalWastewaters:MicropollutantsRemovalAndOrganicMatterOxidation臭氧在市政污水中的应用:去除痕量污染物、氧化有机物Dr.SylvieBAIGIOAPresident国际臭氧协会主席挑战及目标Waterqualityandavailabilityaretwocriticalissues水质恶化,水资源紧缺Whyadvancedtreatmentofwastewaters?为什么需要对废水进行深度处理?–Resourcesmanagement:Improvementofdischargequality–水资源管理:提高排放水的水质–Alternativeresource:Wastewaterreuse–资源化利用:废水回用Approachforsustainableuseofwater水资源的可持续发展–Answertowatershortage解决水资源紧缺问题–Controlofenvironmentalandhealthrisks控制环境污染和健康风险Newchallenge:Emergingmicropollutantsremoval新挑战:痕量污染物的去除–Persistenceafterconventionaltreatments传统处理不能去除–Widespreadoccurrenceintheenvironment在环境中普遍存在–Potentialorprovenenvironmentalandhealthrisks已被证实有危害或潜在危害–Currenttrends当前趋势-应用臭氧或高级氧化PrimaryTreatmentScreening,settling初级处理格栅,沉淀SecondaryTreatmentBiological二级处理生物AdvancedTreatment深度处理DischargeReuse排放或回用SewageSystem排水系统Ozone,AOPs臭氧,高级氧化MunicipalWasteWaterTreatment市政污水处理Ozonation,AOPs(AfterROinadvancedtreatment)TertiaryTreatment三级处理–Useofphysical,chemicalorbiologicalmeanstoimprovesecondarywastewaterquality.采用物理、化学或生物法对二级出水进行处理提高水质–Mostcommonmethodsincludevariousfiltrationmediaanddisinfection.–现有工艺中多数包括过滤和消毒技术QuaternaryTreatment四级处理–Useofspecialprocessesforre-purificationofthewater.采用特殊工艺重新制备净水–Includesadvancedoxidation,ionexchange,electro-dialysis,electro-deionization,reverseosmosis,nanofiltration,MF/UF,evaporation/crystallization.包含高级氧化,离子交换,电渗析,电去离子,反渗透,纳滤,微/超滤,蒸馏/结晶–Multi-barrierapproach,RO+oxidation多重过滤,RO+氧化Themostpowerfuloxidantavailable可制得的最强的氧化剂Chemistrywithtwopathways两种反应途径–Accordingtomediumconditions(pH,temperature,alkalinity…)–视反应条件(pH,温度,碱度……)–Onorganics,inorganicsandlivingorganisms与无机物,有机物,生物体反应O2ClO2Cl2MnO4-H2O2O3HO°E°(V)1,231,271,361,671,772,072,80Ozonechemistry臭氧化学性质+MO3+IMoxHO°+MM'oxDirectreaction直接反应Highlyselective高选择性FastandunselectivereactionsInhibitionbyscavengers反应速度快,无选择性,会被清除剂终止Indirectreaction:AOP间接反应:高级氧化Decompositionuponinitiation引发剂基于臭氧的高级氧化工艺Reactionrateconstants(k,M–1s–1)of,with反应速率常数O3HO°Chlorinatedalkenes氯代烃Phenols酚N-containingorganics含N有机物Aromatics芳香化合物Ketones酮Alcohols醇103-10410310-1021-102110-2-1109-1011109-1010108-1010108-1010109-1010108-109AdvancedOxidationProcess高级氧化工艺Involvinginsituproductionofsecondaryoxidantmorepowerfulthantheprimaryone结合另一种氧化剂,获取比两种氧化剂更强的氧化性–MainlyHO°主要是羟基自由基Operatingnearambientpressureandtemperature常温常压下操作Kineticbenefit反应速率快O3/H2O22O3+H2O22HO•+3O2rO3=2k.[O3].[HO2-](k=2,98.106M-1.s-1)[HO2-]=[H2O2].10(pH-11,7)O3/UV–O3O2+O(1D)O(1D)+H2O2HO°–O3+H2OH2O2+O2hh废水处理中的常见应用Fullscaletertiarytreatment三级处理Ozone臭氧UVAOPs高级氧化工艺Colour脱色Surfaceactiveagents除表面活性剂COD除CODToxics&Micropollutants毒性和痕量污染物Disinfection消毒None暂无应用Disinfection消毒Relatedozoneuse:sludgereduction,airtreatment其它应用:污泥减量,空气净化O3vsAOPO3ttCOD(Ozone)COD(AOP)WithnoscavengingeffectCODpossiblyBOD市场增长趋势Thewastewatertreatmentmarketisoneofthefastestgrowingsectorsofthewaterindustry(USDm)污水处理是目前增长最快的领域(以百万美元计)In2010.theglobalozonemarketisclosetoUSD361million.ItisexpectedtoexceedUS$597millionby2016,reflectingagrowthrateof9.6%.2010,全球臭氧市场将达到3.61亿美元,到2016年将超过5.97亿美元,增长9.6%Source:GWI研究背景及目标Fewdatapublishedonadvancedtreatmentofmunicipalbiotreatedeffluentsbyozoneoxidation生物处理后的市政废水被臭氧氧化后的相关数据发布较少–Ozone:CODremoval/Disinfectionsince1970s–OzoneactivationbyHydrogenPeroxideandUV–Persistentpollutants/CODObjectives目标–Advancedremovaloforganics进一步去除有机污染物DCODover30%–AssessthebenefitsofAOPs评估高级氧化工艺的价值O3/H2O2asAOPImpactofwaterquality对水质的影响–MicropollutantswhileCODoxidation氧化COD的同时去除痕污染物DCOD30%010203040506070800255075100125150TransferredOzoneDosemg/LDCODmg/LPersistentpollutants顽固污染物Pharmaceuticals&PersonalCareProducts(PPCPs)医药和个人护理产品Pesticides杀虫剂DomesticandIndustrialchemicalsandtheirby-products工业和家用化学品的副产物:Ozoneapplication臭氧应用-去除有机污染物OutletCODmg/LBOD5mg/LUV254cm-1TOCmg/LpHTICmg/LN-NH4+mg/LN-NO3-mg/LGSEMBR24.91.40.116.27.318.10.013.4CSEASSF44.25.60.2811.57.845.826.18.60.00.10.20.30.40.50.60.70.80.91.00102030405060708090100Time(min)COD/CODo020406080100120140TOD(mg/L)COD_CSECOD_GSECOD_Gongetal.2008TOD_CSETOD_GSE0.00.10.20.30.40.50.60.70.80.91.00102030405060708090100Time(min)COD/CODo020406080100120140TOD(mg/L)COD_CSECOD_GSECOD_Gongetal.2008TOD_CSETOD_GSECODremovalkineticsandozonetransferdependonwaterqualityi-epretreatmentperformancesanddesign对COD的去除效果和臭氧的传质效率取决于被处理水的水质,例如预处理的设计和效果CSECODremoval44%Ozonedose122mg/LTOCremoval12%GSECODremoval55%Ozonedose77mg/LTOCremoval48%DCOD30%achievableCOD去除率30%