Co-Mo/Al2O3催化剂上裂解汽油中单烯烃加氢宏观动力学

Co-Mo/Al2O3催化剂上裂解汽油中单烯烃加氢宏观动力学

  • 摘要: 采用绝热管式固定床积分反应器,在2.0MPa~4.0MPa、524K~644K、氢/裂解汽油摩尔比1.5~3.5和反应器入口环戊烯、3乙基1戊烯、苯乙烯和1己烯的分压分别为0.87kPa~5.60kPa、1.09kPa~7.01kPa、1.14kPa~7.35kPa和0.25kPa~0.97kPa下,对CoMo/Al2O3催化剂上裂解汽油中单烯烃催化加氢的宏观动力学特性进行了系统研究。以Powell优化法和Merson迭代法对动力学实验数据进行非线性参数估值,建立了与实验数据吻合良好、裂解汽油中单烯烃催化加氢的幂函数型宏观动力学模型。其中,环戊烯、3乙基1戊烯、苯乙烯和1己烯的反应级数分别为1.725、0.685、0.7和0.655,对应的加氢反应宏观活化能依次为63455 J·mol-1, 61781 J·mol-1, 52105 J·mol-1和54181 J·mol-1。实验所用CoMo/Al2O3催化剂对环戊烯、3乙基1戊烯和苯乙烯加氢具有明显的催化作用,对1己烯加氢具有一定的催化作用,但对1庚烯加氢基本无催化活性。加氢反应压力控制在3.5MPa左右更为适宜。

     

    Abstract: The macrokinetic experiments of olefin hydrogenation in pyrolysis gasoline over an industrial CoMo/Al2O3 catalyst were carried out in an integral tubular fixedbed reactor under the following conditions: 2.0MPa~4.0MPa, 524K~644K, H2/pyrolysisgasoline molar ratio 1.5~3.5 and the partial pressure at reactor inlet for cyclopentene, 3ethyl1pentene, styrene and 1hexene 0.87kPa~5.60kPa, 1.09kPa~7.01kPa, 1.14kPa~7.35kPa and 0.25kPa~0.97kPa, respectively. By means of Powell optimal method and Merson integral method, the powerlaw type macrokinetic models of catalytic hydrogenation of olefin in pyrolysis gasoline were developed, and a good agreement with experimental data and those calculated by the kinetic models estimated was obtained. The reaction orders of cyclopentene, 1hexene, styrene and 3ethyl1pentene were 1.725, 0.685, 0.7 and 0.655, respectively. And the activation energies of hydrogenation reaction of theirs were 63455J·mol-1, 61781J·mol-1, 52105J·mol-1 and 54181J·mol-1, respectively. The CoMo/Al2O3 catalyst here shows a good catalytic activity for 1hexene hydrogenation, a better activity for the hydrogenation of cyclopentene, 3ethyl1pentene and styrene, but a poor activity for 1heptene hydrogenation. The favorable operating pressure is about 3.5MPa for this catalyst.

     

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