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1、镍基均相络合催化剂异辛烯加氢反应动力学喻惠利1,罗文国2,俞芳1,温朗友1(1.中国石化石油化工科学研究院,北京100083;2.中国石化荆门分公司,湖北荆门448002)摘要:采用Ziegler2Natta型镍基均相加氢催化剂和半连续操作的釜式反应器,研究了异辛烯(2,4,42三甲基戊烯21(TMP21)和2,4,42三甲基戊烯22(TMP22))液相加氢制异辛烷的反应动力学。结果表明,反应开始阶段,因存在反应诱导期和TMP21与TMP22的异构化反应,致使加氢反应动力学十分复杂而难于用简单的数学方程式来描述
2、;在反应诱导期结束后,异辛烯加氢反应可以采用幂函数型动力学模型描述。通过对动力学数据的线性回归,得到TMP21加氢反应的级次对烯烃为1级、对氢分压为1.5级,反应活化能为25.6kJ/mol;TMP22加氢反应的级次对烯烃为1.2级、对氢分压为1.6级,反应活化能为46.5kJ/mol。经检验,TMP21、TMP22加氢反应模型的计算值与实验结果的平均偏差分别为6.5%、7.6%,具有较高的可信度,可用于反应过程模拟和反应器设计。关键词:异辛烯;加氢;异辛烷;Ziegler2Natta催化剂;反应动力学中图分类
3、号:TE621文献标识码:AHYDROGENATIONKINETICSOFISOOCTENESWITHHOMOGENEOUSNi2BASEDCOMPLEXASCATALYSTYUHuili1,LUOWenguo2,YUFang1,WENLangyou1(1.ResearchInstituteofPetroleumProcessing,SINOPEC,Beijing100083,China;2.JingmenBranchCo.,SINOPEC,Jingmen448002,China)Abstract:Thekin
4、eticsforliquid2phasehydrogenationofisooctenes(2,4,42trimethylpentene21(TMP21)and2,4,42trimethylpentene22(TMP22))toisooctanewerestudiedwithZiegler2NattatypeNi2basedhomogeneouscomplexascatalystinasemi2batchreactor.Experimentalresultsrevealedthatthehydrogenatio
5、nreactionwastoocomplicatedtodescribewithsimplemathematicsequationsduetotheformationof"reactioninduceperiod"andtheisomerizationbetweenTMP21andTMP22atthebeginningofthereaction.Afterthe"reactioninduceperiod",theempiricalpower2lawmodelcouldbeusedtodescribethekin
6、eticsofthehydrogenationreaction.Themodelparameterswereestimatedbylinearregressionofthekineticexperimentaldata,fromwhichitwasknownthatTMP21hydrogenationwasfirstorderreactiontoTMP21and1.5orderreactiontohydrogenpartialpressure,theapparentactivationenergywas25.6
7、kJ/mol;whileTMP22hydrogenationwas1.2orderreactiontoTMP22and1.6orderreactiontohydrogenpartialpressure,theapparentactivationenergywas46.5kJ/mol.Theanalysisofverificationofvarianceandtheaveragedeviationshowedthatthekineticequationswereacceptablewithahighcredibi
8、lity,therefore,couldbeusedinprocesssimulationandreactordesign.Keywords:isooctene;hydrogenation;isooctane;Ziegler2Nattacatalyst;reactionkinetics收稿日期:2009202228基金项目:国家自然科学基金项目(NS220736009)资助通讯联系人:
