全硅MCM-41担载的Ni-W催化剂上二苯并噻吩加氢脱硫反应动力学研究

以二苯并噻吩(DBT)的质量分数为0．2％～0．8％的十氢萘溶液为模型化合物，在中压固定床反应器上，研究了全硅MCM-41担载的Ni—W硫化物催化剂上的加氢脱硫反应(HDS)动力学。理论分析和实验结果都表明，常用的Langmiur—Hinshelwood方程不适用于气—液—固三相滴流床积分反应器。应用假1级平推流反应模型，分别得到了各催化剂作用下的该反应的速率常数和表观活化能。催化剂的Ni俐摩尔比(nNi／nW)为0．25、0．5、0．75和1．0时，该催化HDS反应的表观活化能分别为117．3、96．7、64．4和72．9kJ／mol。其中，nNi／nW=0．75的反应表观活化能最低。将催化剂的HDS活性与表观活化能相关联可以发现，表观活化能和催化剂活性之间有对应关系，表观活化能越低，催化剂活性越高。

STUDY ON HYDRODESULFURIZATION KINETICS OF DIBENZOTHIOPHENE OVER Ni-W SULFIDES SUPPORTED BY SILICEOUS MCM-41

The kinetics of hydrodesulfrization (HDS) of dibenzothiophene (DBT) catalyzed by Ni W/Si MCM 41 catalyst was studied.Both the theoretical analysis and the experimental results indicated that the Langmiur Hinshelwood model was not suitable for the kinetics of trickle bed integrated reactor,involving transportation among gas liquid solid three phases.The rate constants of HDS were well correlated to a pseudo first order plug flow reaction model.The apparent activation energy of HDS was calculated by the Arrhenius equation and changed with the Ni/W atomic ratio in catalyst.The apparent activation energy were 117.3,96.7,64.4 and 72.9?kJ/mol corresponding to the Ni/W atomic ratio of 0.25,0.50,0.75 and 1.0,respectively.HDS reaction showed the lowest apparent activation energy on the catalyst with the Ni/W atomic ratio of 0.75 .The correlation between apparent activation energy and HDS reactivity revealed that the catalyst with low apparent activation energy exhibited high performance in HDS of DBT.