铜配合物催化剂制备及其羰基合成碳酸二甲酯性能的研究

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1、南京理工大学博士学位论文铜配合物催化剂制备及其羰基合成碳酸二甲酯性能的研究姓名：刘定华申请学位级别：博士专业：化学工程与技术指导教师：钟秦;刘晓勤20100601AbstractDimethylcarbonate(DMC)isagreenchemicalattractedhil曲attention．TheearbonylationofmethanoltoDMCishighlypromisingforindustrialapplicationduetotheinexpensivesubstrates，simpleprocess，a

2、ndlowpollution．ThecatalystCuCIiswidelyusedfortheliquidphasecarbonylationofmethanoltoDMC；however,theapplicationofCuCIishinderedbytheshortcomingsoflowstability,strongcorrosiveness，anddifficultseparationofreactionmixture．Asaresult，theimprovementofcatalyticperformancebec

3、omesahotresearchtopic．WechooseCuBr2insteadofCuClasresearchdirectionbecauseofthebetterstabilityandsolubilityaSwellaslowercorrosivenessofCuBr2thanCuCI，whilethecatalyticactivityofCu(II)isrelativelylow．Takingaccountofthespecialcrystallinestructureandcoordinationpropertyo

4、fmetalcomplexes，weemployedtransitionmetalcomplexes弱catalystsandsystematicallyinvestigatedtheircatalyticperformance，whichincludesthepreparationandcharacterizationofcomplexes，thermodynamics，mechanism，andprocesssimulation．Firstly,wechoosequaternaryammoniumsaltsandphosph

5、oniumsaltsaSligandstoformcomplexeswithCuBr2．InteractionbetweenR4N+or(R4P+)inligandandBr"havebeenchangedtoenhancetheactivationdegreeofBr-inCuBr2，whicharefavorableforthegenerationofreactionintermediatesandtheinsertionofCO，02andmethanol，andsubsequentlyenhancethereaction

6、activity．1heeffectofligandquaternaryammoniumsaltsisobviousthanphosphoniumsalts，whichiSconsistent、Ⅳiththeshieldextentofnitrogenandphosphoratoms．Amongthem，theligand(C3H7)4NBrinquaternaryammoniumsaltsshowedthebestpromotingeffect．N-methyl-imidazoleand2，2-bipyridinecailre

7、actwithCuBr2toformstablecoppercomplexes，whichiSnotbeneficialtotheadditionofreactantmolecules．Hence，thepromotioneffectsareworsethanthoseof(C3HT)4NBrand(C6Hs)4PBr．Secondly,onthebaSisoftheresultsofFTIR,XRD，EA，ICP_AES，andXPS，thestructureofcoppercomplexesis[Cu2Br6]2-rathe

8、rthanthecolnm011structure【CuX4]z-．Thechemicalformulaofcoppercomplexesis【(C3HT)4N]2Cu2Br6．田leoptimalpreparationconditionswerethemola