搜索
40120061JOURNALOFXIANJIAOTONGUNIVERSITYVol.401Jan.2006,,,,(,710049,):(COD),,,.:,COD90%;COD,,COD;1162,0122,(9212919)kJmol-1(31533.33)103,10%.,.:;;;:X703:A:0253O987X(2006)01O0115O05ReactionMechanismandKineticsofOil2BearingSewageDisposalbySupercriticalWaterOxidationWangLiang,WangShuzhong,ZhangQinming,ShenLinhua,DuanBaiqi(StateKeyLaboratoryofMultiphaseFlowinPowerEngineering,XianJiaotongUniversity,Xian710049,China)Abstract:Theconventionaltreatmentsareunabletoeffectivelyremovethechemicaloxygendemand(COD)ofwastewaterproducedduringoilextraction,andthus,ithasseriouslythreatenedtheenvironmentandthenormalproductionofoil2field.AnadvancedmethodforoilObearingsewagetreatment,supercriticalwateroxidation(SCWO),wasproposed.TheoxidativedegradationwasinvestigatedandtheprocessofSCWOwasexplainedwithmechanismoffreeradicalreaction.TheexperimentalresultsshowthatSCWOisahigh2efficiencytreatmentanddisposaltechniquefororganicwastes.TemperatureandresidencetimeserveasthemaininfluencefactorsinremovingCODofoil2bearingsewage,withwhichtheCODremovalrateobviouslyincreases.ThereactionofSCWOis1162orderinsewageCODand0.22orderinoxygen,thefrequencyfactorandactivationenergyare(31533133)103and(92.2919)kJmol-1under26MPa,respectively.Thedeviationbetweenthemodelandexperimentaldataisrangedwithin10%.TheexistingproblemsintheprocessofSCWOandthepossiblesolutionsarediscussed.Keywords:supercriticalwateroxidation;oil2bearingsewage;reactionmechanism;kinetics.[1],,(COD)350mgL-1,,,,,.2080,Modell[2]:2005O05O24.:(1981),,;(),,,.:(2003CB214500).(SCWO),.,,N2H2OCO2,..Tc=374115,Pc=2211MPa.,:(1/3);;,08717230,;,10100;,.,,O2CO2,O2CO2,,.,.1111[3].,Tpt(H2O2).COD12001300mgL-1,COD128018mgL-1.13.,,,CODXCOD90%.COD,,.112,,,SCWO.[4],,1COD2COD3COD.,O2C-HRH+O2R+HOO(1)(R;RH)RH+HOOR+H2O2(2)H2O2+M2HO(3)M.,.,RH+HOR+H2O(4)R,61140R+O2ROO(5)ROO+RHROOH+R(6),,CO2,.[5],,,H2O2OO2,.6O2H2O2.,.113,,1,,COD.,,COD,,,,.,.,,,,410450.2,COD,COD.3[6]:,,;,;,,,COD.,COD.,,,,,,2428MPa.COD,1,90s,COD90%.,,COD,,,COD.,,,,,60100s.[7],(10%),O2,(O2)(10).,265%375%,COD,.SCWO,H2O2,,.,,,,COD,COD.114SCWO,,CODTOC.CODr=-d(1-XCOD)dt=k[COD]0(a-1)(1-XCOD)a[O]b[H2O]c(7)XCOD=[COD]0-[COD][COD]0=1-[COD][COD]0(8):r,mgL-1s-1;k,abc;[COD]0,mgL-1;[COD],mgL-1;[O],mgL-1,[O]=[O]0-XCOD[COD]0,,[O]=[O]0;[H2O],mgL-1.,,99%,,7111,:.[H2O]ck,(7)r=-d(1-XCOD)dt=k[COD]0(a-1)(1-XCOD)a[O]0b(9)a1,,XCOD=1-{1+(a-1)k[COD]0(a-1)[O]0bt}1/(1-a)(10),Gauss2Newton,26MPa,1.1T/klnkab390615510-5-91634181157750117415410917910-5-91231951162410121571430117110-4-81679711166620124096Arrheniusk=k0exp-EaRT(11):k0,k;Ea,Jmol-1;R,Jmol-1K-1.,T-1lnk=-Ea1RT+lnk0(12)lnk1/(RT),,2.226MPaSCWOabk0Ea/kJmol-111620122(31533133)103(9212919)0198364SCWOCODr=-d[COD]dt=(31533133)103exp[-(91220199)104/(RT)][COD]1162[O]00122(13)4,.(10)COD,XcXe5.,,10%,(13).4COD52SCWO,.300,,.400,,[8].[9],SCWO.,,Cr6+.,,(H2O2),.SCWO,.[10]:,,LOSALAMOS110MPa;,,;81140,,.,,SCWO,.SCWO,,,,SCWO.3(1)SCWO,,COD90%,.(2),.(3).(4)(13).(5)SCWO,.:[1].[M].:,200215O8.[2]ModellM.Treatmentforoxidationoforganicmaterialinsupercriticalwater[P].USPatent,433819911982O07O06.[3],,.[J].,2004,20(9):9O12.[4]LiLixiong,ChenPeishi,GloynaEF.Generalizedki2neticmodelforwetoxidationoforganiccompounds[J].AIChEJ,1991,37(11):1687O1697.[5],,.[J].,2003,54(1):80O85.[6],,,.e2[J].,2000,14(5):480O483.[7],,,.[J].,2000,20(4):305O308.[8]KronholmJ,HuhtalaS.Oxidationof42chloro232methylphenolinpressurizedhotwaterinliquidandva2porphases[J].AdvancesinEnvironmentalResearch,2002(6):199O206.[9].[J].,1999,11(1):53O56.[10]KritzerP,DinjusE.Anassessmentofsupercriticalwateroxidation(SCWO)existingproblems,possiblesolutionsandnewreactorconcepts[J].ChemicalEngi2neeringJournal,2001(83):207O214.()(52)(3),.:[1].[D].:,2003.[2],.[J].,1999(10):11O14.[3]EkdungeP.Asimplifiedmodelofthelead/acidbatter2y[J].JournalofPowerSources,1993,46(2):251O262.[4]WangLX.Adaptivefuzzysystemsandcontrol:de2signandstabilityanalysis[M].EnglewoodCliffs,NJ:PTRPrentice2Hall,1994.96O110()9111,: