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7654Ind.Eng.Chem.Res.2008,47,7654–7662ComprehensiveKineticModelfortheDegradationofMethyltert-ButylEtherbyanOzone/UVProcessTemesgenGaroma*andMiratD.GurolCiVil,Construction,andEnVironmentalEngineeringDepartment,CollegeofEngineering,SanDiegoStateUniVersity,5500CampanileDriVe,SanDiego,California92182Thepaperpresentsacomprehensivekineticmodelthatdescribesthedegradationofmethyltert-butylether(MTBE)inanozone/UVprocess.First,thedegradationpathwaysforMTBEwereproposedonthebasisofmajorreactionintermediatesidentifiedduringtheoxidationofMTBE.Theyieldforeachmajorreactionintermediatewasdeterminedbyfittingexperimentaldatatothemodelprediction.Accordingly,43,20,15,11,and6%ofMTBEoxidizedresultedinthegenerationofTBF,MMP,TBA,acetone,andmethylacetate,respectively.TBFoxidationresultedinthegenerationofHiBA,acetone,andTBAasprimaryintermediatesat47,24,and20%,respectively.DuringtheoxidationofTBA,66%resultedinthegenerationofHiBAand34%inacetone.ThekineticmodelwasverifiedusingdifferentsetsofexperimentaldatabyvaryingtheinitialconcentrationofMTBE,influentozonegasconcentration,andincidentUVlightintensity.ThemodelpredictedwellthedegradationofMTBEbyanozone/UVprocess.Inaddition,themodelpredictedtheaccumulationanddecayofprimaryintermediates(TBF,TBA,MMP,methylacetate,andacetone)withslightvariations.IntroductionThedegradationofMTBEbyanozone/UVprocesshasbeeninvestigatedbytheauthors.21Methyltert-butylether(MTBE)wasintroducedinthelate1970sandearly1980sasanantiknockingagentwhenleadwasphasedoutofgasoline.Since1990,ithasbeenusedtofulfillApproachthefueloxygenaterequirementssetbytheU.S.CongressinToestablishthedegradationpathwaysforMTBE,firstMTBEtheCleanAirActAmendment(CAAA).TheCAAAmandatedwasoxidizedinanozone/UVprocessandmajorreactioncompoundsthatincreaseoxygenbeaddedeitherinthewinterintermediateswereidentified.ThemajorreactionintermediatesorallyeartogasolineinspecificpartsoftheUnitedStateswhereidentifiedwerealsooxidizedbyanozone/UVprocessunderconcentrationsofcarbonmonoxideinthewinterorozon
