中国炼油与石油化工

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沥青质加氢热裂解和催化加氢裂解反应动力学与选择性

赵迎宪,李达   

  1. 浙江大学宁波理工学院
  • 收稿日期:2010-07-20 修回日期:2010-09-26 出版日期:2011-03-31
  • 通讯作者: 赵迎宪

Kinetics and Selectivity of Asphaltene Thermal Hydrocracking and Catalytic Hydrocracking

ZHAO Ying-Xian,Da Li   

  • Received:2010-07-20 Revised:2010-09-26 Online:2011-03-31
  • Contact: ZHAO Ying-Xian

摘要: 用微型间歇反应器考察了一种戊烷不溶的沥青质,在430ºC下的加氢热裂解和NiMo/γ-Al2O3反应。实验获得的反应物转化率数据较好地拟合二级反应动力学方程,求得表观速率常数分别为2.435x10-2 和9.360 x10-2, wt frac-1min-1。一个三集总的反应动力学模型被建立并求解估算沥青质转化为液体油反应的速率常数(k1)和与它平行的沥青质转化为焦炭+气体反应的速率常数(k3),以及与它连续的液体油转化为焦炭+气体反应的速率常数(k2)。沥青质在无或有催化剂存在条件下加氢热裂解,速率常数k1分别为2.430x10-2和9.355x10-2 wt frac-1min-1,k2分别为2.426x10-2和6.347x10-3 min-1,k3分别为5.416x10-5和4.803x10-5 wt frac-1min-1。选择性分析显示催化加氢裂解过程有效地促进液体产物的生产,并抑制焦炭的生成。

Abstract: A pentane-insoluble asphaltene was processed by thermal hydrocracking and catalytic hydrocracking over Ni-Mo/γ-Al2O3 in a microbatch reactor at 430ºC. The experimental data of asphaltene conversion fit second-order kinetics adequately, to give the apparent rate constants of 2.435 x10-2 and 9.360 x10-2 wt frac-1min-1for the two processes respectively. A three-lump kinetic model is proposed to evaluate rate constants of parallel reactions of asphaltenes to produce liquid oil (k1) and gas + coke (k3), and consecutive reaction from liquid to gas + coke (k2). The evaluated k1 is 2.430Х10-2 and 9.355Х10-2 wt frac-1min-1, k2 is 2.426Х10-2 and 6.347Х10-3 min-1 , and k3 is 5.416Х10-5 and 4.803Х10-5 wt frac-1min-1 for asphaltenes hydrocracking in the presence or absence of the catalyst, respectively. Analysis of selectivity shows that the catalytic hydrocracking process promotes liquid production and inhibits coke formation effectively.