裂解汽油加氢脱硫脱烯烃的本征动力学

INTRINSIC KINETICS OF HYDRODESULFURIZATION AND OLEFIN HYDROGENATION FOR PYROLYSIS GASOLINE

采用微型等温积分反应器,在2.4～4.0MPa,220～400℃,氢/裂解汽油摩尔比为1.8～3.5,裂解汽油中噻吩、单甲基噻吩、双甲基噻吩、环戊烯、1己烯和苯乙烯的质量分数分别为260～580μg/g、300～650μg/g、200～320μg/g、1.7%～4.0%、0.25%～1.5%和0.7%～4.0%的条件下,系统地研究了裂解汽油在国产CoMo/Al2O3催化剂上加氢脱硫和单烯烃催化加氢饱和的本征动力学特性。根据幂函数型速率方程,以SimplexPowell复合优化法和Merson迭代法对动力学实验数据进行搜索、选优,建立了与实验数据相符的裂解汽油加氢脱硫脱烯烃的本征动力学模型。其中,噻吩、单甲基噻吩、双甲基噻吩、环戊烯、1己烯和苯乙烯的反应级数分别为0.73、0.83、0.87、0.724、0.764和0.775,对应的加氢反应活化能依次为71855、75955、64855、64845、59845和65545J/mol。

The intrinsic kinetic experiments of hydrodelsulfurization and olefin hydrogenation of pyrolysis gasoline over Co-Mo/Al2O3 catalyst were carried out in an integral micro-reactor under the conditions of 2.4-4.0 MPa, 220-400°C, H2/pyrolysis-gasoline molar ratio 1.8-3.5, and the mass fraction of thiophene, methylthiophene, diomethylthiophene, cyclopentene, 1-hexene and styrene in feed pyrolysis-gasoline, 260-580 μg/g, 300-650 μg/g, 200-320 μg/g, 1.7%-4.0%, 0.25%-1.5% and 0.7%-4.0%, respectively. Based on the power-law type kinetic equation and using Simplex-Powell optimal method and Merson integral method, the intrinsic kinetic models were established, which were consistent with the experimental data of hydrodelsulfurization and olefin hydrogenation of pyrolysis gasoline. The reaction orders of thiophene, methylthiophene, diomethylthiophene, cyclopentene, 1-hexene and styrene were 0.73, 0.83, 0.87, 0.724, 0.764 and 0.775, respectively. The activation energies of hydrogenation reaction of theirs were 71855, 75955, 64855, 64845, 59845 and 65545 J/mol, respectively.