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1,Chapter9Oxidation-ReductionReactionsandtheirIndustrialPossibilities,9.1GeneralIntroductionofoxidation,1.Thereactiontypes,+Oinorganiccompounds,both-Hand+Oinorganiccompounds,organiccompoundsoxidationanddecomposition,organiccompoundsammoniac-oxidized,Epoxy-ethane,Cyano-compound,2,2.canbemadebytheoxidationreactions,ROH,Epoxy-compound,Cyano-compound,3,3.Thegeneralfeaturesoftheoxidationreactions,1）Theoxidizingagents,ThegasphaseoxygenO2cheaper,withouttheinstrumentdamage,butloweroxidizingabilityneedcatalytic.,OxygenatomOgeneratedfromthechemicaloxidizingagents,highoxidizing-abilities,highselection,mildreactionconditions,buthighcost.,4,2)Strongheatreleasingreactions,3)Unconvertedreaction,4)Multi-reactionwaysandwithby-reactions,Inordertoobtainedthetargetoxidizedcompound,thesuitablewaymustbeselected,5,Theairisflowedintotheorganiccompoundinliquidphaseundertheactionofcatalytic,thenthecompoundisoxidized,thiskindofreactionhasbeencalledtheairliquidphaseoxidationreaction,9.2Airliquidphaseoxidationreactions,Definitionforthereaction,requirement,A:specialreactor：air-flowing-stylereactorB:catalytic(solubleintheorganicliquid),6,9.2.1Thereactionprocess,Someorganiccompounds,O2,Automaticreact,Thereactionveryslow,Increasingthereaction,Catalyticorinitiationagent,7,Theautomaticoxidation,Typicalfreeradicalchain-stylereaction,B:Chaintransfer,C:Chaintermination,A:Chaininitiation,8,1.Thechaininitiation,9,2.TheChaintransfer,10,3.Thechaintermination,11,9.2.2Theelementsofinfluencetheautomaticoxidation,1.Initiationagentsandcatalytic,1)+initiationagenttheorganiccompoundtobeoxidizedeasy,2)+catalytic(thetransitionalmetalion,suchas:Co2+,Mn2+,Fe3+,V5+etc.)theactivationenergyoftheorganiccompoundtobereduced,12,2.Theinfluenceoftheoxidizedorganiccompoundsstructure,TheorganiccompoundsC-Hbondstobebrokenarerelativetotheenergyofthesebonds,Theenergyorderasfollows:ThethirdC-HthesecondC-HthefirstC-H,thus,theoxidationfirstoccuratthethirdCatom.,13,3.Theinfluenceoftheanti-reactive（阻化）agents,Theanti-reactiveagentscanreactwiththefreeradicalstoformthestablecompounds,andtoresultthechaintermination;andfewquantityoftheagentscanalsomaketheoxidationprocessslowingdown.,14,Thestrongeranti-reactiveagentsincluding:,a:phenolic;,b:amine;,c:quinone;,d:alkene,suchas:,15,4.Theinfluenceofthedegreeoftheoxidation（氧化深度）,Formostoftheautomaticoxidation,particularlytosynthesizeorganicperoxides,aldehydesandketones:,Inordertoovercomethisproblem,theconversationrateshouldbekeptatlowerlevel,astheresulttheoxidationcouldbewithahigherreactionspeedandahigherselective.,withtheconversationrate（转化率）increasingtheby-products（containingtheanti-reactiveagents)increasedtheoxidationspeedssloweddowntheby-reactioncanalsocausetheoxidizedcompoundtobedecomposedfurther.,16,Althoughtheconversationrateon-one-wayisunlikelyhigher,butthehigherselectivecouldbekept,andtheunreactedrawmaterialcouldalsotobere-usedcircularly,therefore,thegeneralproductivityishigher.onspecialsituation,fortheoxidationwithsomestableoxidizedproducts,suchas:carboxylicacid(羧酸),17,Benzoicacidasthefoodadditive,intermediateofdyes,drugsandperfumesetcpayaveryimportantroleinthefinechemicalindustry,thecommonwaytosynthesisthiscompoundtoemploytolueneandair:,9.3.2Industrialexample,18,Theindustrialchemicalprocessofsynthesisbenzoicacid,19,1),1Theoxidationreactor,pre-heated,2)Air,Tobepressed,3)Co(Ac)2,from7,Theoxidationliq.From3,Theoxidationliquid,thegasphaseto2,20,4)Theoxidationliquid,21,2gas/liq.separator,
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