Co-Mo/Al_2O_3催化剂上裂解汽油中单烯烃加氢宏观动力学  

Macrokinetics of olefin hydrogenation in pyrolysis gasoline over Co-Mo/Al_2O_3 catalyst

作　　者：李建伟[1] 李英霞[1] 陈标华[1] 李成岳[1] 张小工 

机构地区：[1]北京化工大学化工资源有效利用国家重点实验室,北京100029 [2]中国石油兰州石化研究院催化所,甘肃兰州730060

出　　处：《燃料化学学报》2006年第2期170-174,共5页Journal of Fuel Chemistry and Technology

基　　金：教育部新世纪优秀人才支持计划(NCET-04-0117);中国石油天然气集团公司资助(990813-19)

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/A l2O3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M erson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/A l2O3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。The macrokinetic experiments of olefin hydrogenation in pyrolysis gasoline over an industrial Co-Mo/ Al2O3 catalyst were carded out in an integral tubular fixed-bed reactor under the following conditions： 2.0 MPa 4.0 MPa, 524 K - 644 K, H2/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-l-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/Al2O3 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.

关 键 词：催化加氢 动力学 裂解汽油 单烯烃 

分 类 号：O643[理学—物理化学] TQ53[理学—化学]