高温湿式空气氧化工艺处理炼油废碱渣试验研究邓德刚1

113001、210230250270℃6090120minS2－COD、。。270℃、9．0MPa、120minS2－COD83．5%99．4%TOC71．9%95．6%B/C0．320．69。、。。、、、、。COD、40%～50%1、。、2。WAO3。4WAO、、S2－COD、、。。11．1、COD800450g/L20%～35%。COD120g/L。2∶35WAO。6%。1。1Table1Analysisresultsofspentcausticg/LCOD787～814398～462≤120288～50456～257≤40S2－14～1660～677～1019．8～20．219．8～20．8BOD5487．048．637．4～55．2≤0．16－≤0．160．02～0．1618．102．90～3．20SO2－40．17～0．35S2O2－3≤21．4TOC33．9～36．70．02mg/L。2014－10－082014－11－05。1991。[e-mail]。—51—1．2100%～120%41～4210230250270℃4．06．56．59．0MPa6090120min。WAO1。1WAOFig．1Bench-scaletestingflowofhigh-temperatureWAOprocess1。pH。、。22．1S2－210℃、1hWAOS2－0．4mg/L100%。S2－210℃。WAOS2－。S2－2S2O2－31。=ρS2O2－3ρS2O2－3+11264ρS2－×100%12S2－Table2ConversionformofS2－atdifferentreactiontemperaturesmg/L/minρS2－ρS2O2－3%ρSO2－4%1608300299014308．162851700098．32908300641014006．692681590098．431207400647012006．182471710098．67260751037004402．612882170098．7790778086303401．532062040099．101207780199002000．602061980099．04360778039503702．113502270098．5790781038202401．372262050098．98120778019900－02061320098．90460846086304241．812061650099．0890776011100－02061440098．8612079303700－02881799098．75—61—2210℃S2－SO2－4SO2－498%S2－S2O2－3250℃S2O2－3SO2－4S2O2－3。S2－。2．22。2Fig．2Ｒeactiontemperatureandresidencetimeversusphenolremovalrate2。230℃90．0%250℃C—CCO2。270℃99．4%。2．3CODCOD3。3COD。210℃S2－S2O2－3S2－S2O2－3SO2－4COD。、C—CCOD。270℃、120minCOD83．5%。COD。3CODFig．3ＲeactiontemperatureandresidencetimeversusCODremovalrate2．4TOCTOC4。4TOCCODTOC。120minTOC。250～270℃、90～120minTOC。270℃、120minTOC71．9%。—71—2．5。。4TOCFig．4ＲeactiontemperatureandresidencetimeversusTOCremovalrateWAO53。5Fig．5Ｒeactiontemperatureandresidencetimeversusorganicnitrogenremovalrate53。270℃、120min95．6%。。3Table3Ｒeactiontemperatureandresidencetimeonammonianitrogengeneration/minρ/g·L－1160－0．350．2590－0．310．26120－0．320．31260－0．970．9390－1．411．29120－1．541．483600．161．291．20900．090．141．38120－2．222．034600．101．45900．032．16120－2．59CODTOC。2．6BOD5/CODCrB/C。。6。6B/C。210～230℃B/C。230℃B/C—81—270℃60～120min、B/C270℃、120minB/C0．69。6Fig．6Ｒeactiontemperatureandresidencetimeversusbiodegradabilityofspentcaustic31270℃9．0MPa、120minS2－COD83．5%99．4%TOC71．9%B/C0．320．69。。2270℃、120min95．6%WAO。1KolhatkarASubletteK．BiotreatmentofrefineryspentsulfidiccausticbyspecializedculturesandacclimatedactivatedsludgeJ．AppliedBiochemistryandBiotechnology19965857945-946．2．J．20111126-29．3MishraVSMahajaniVVJoshiJB．WetAirOxidationJ．IndEngChemＲes19953412-48．4．CN98121081．3P．2000-06-21．Laboratorytestofhigh-temperaturewetairoxidationtechnologyfortreatingrefineryspentcausticsludgeDengDegangZhouTongQinLijiaoSINOPECFushunＲesearchInstituteofPetroleumandPetrochemicalsFushunLiaoning113001AbstractBaseduponthecharacteristicsofhighcontaminantsanddifficultbiodegradabilityofrefineryspentcausticsludgetestsofhigh-temperaturewetairoxidationprocesswerecarriedouttostudytheimpactsofreactiontemperature210230250and270℃．respectivelyandresidencetime6090and120minrespectivelyontheremovalrateofcontaminantssuchasS2－CODphenolandorganicnitrogenaswellaswastewaterbiodegradability．Theresultsshowthattheremovalrateofvariouscontaminantsinthespentcausticsludgeincreaseswiththeincreasingreactiontemperatureandextendedresidencetimeandreactiontempera-tureisthemainimpactfactor．Undertheprocessconditionsofreactiontemperature270℃9．0MPaandresidencetimenotlessthan120mintheS2－isnotfoundintreatedeffluentandtheremovalratesofCODphenolTOCandorganicnitrogenare83．5%99．4%71．9%and95．6%respectivelyAlmostallorganicnitrogeniscompletelyconvertedtoammonianitrogen．B/Cvalueisincreasedto0．69from0．32．Thefoulodourofthespentcausticcanbecompletelyremovedanditsbiodegradabilitycanbegreatlyimproved．Thereactionproductsaremainlylow-molecularorganicacidssuchasformicacidandaceticacid．AstheWAOprocessispoorinremovalofammonianitrogenthespentcausticsludgeshouldberemovedbeforegoingintowastewatertreatmentplantforfurthertreatment．KeyWordsspentcausticsludgehigh-temperaturewetairoxidationreactiontemperatureresidencetimeremovalratebiodegradability—91—