工业NiW/Al_2O_3催化剂上二苯并噻吩的加氢脱硫动力学  

Kinetics of the hydrodesulfurization of dibenzothiophene over a commercial NiW/Al_2O_3 catalyst

作　　者：余夕志[1] 任晓乾[1] 董振国[1] 王军[1] 王延儒[1] 

机构地区：[1]南京工业大学化学化工学院,江苏南京210009

出　　处：《燃料化学学报》2005年第4期483-486,共4页Journal of Fuel Chemistry and Technology

摘　　要：以二苯并噻吩(DBT)为含硫模型化合物,在高压滴流床反应装置中,考察了工业NiW/Al2O3催化剂(RN10)的加氢脱硫(HDS)动力学规律,研究了氢分压(1.5MPa～4.5MPa)、氢油体积比(150～700)、液体质量空速(15h-1～60h-1)、反应温度(280℃～380℃)等对DBT的HDS反应结果的影响。结果表明,当氢分压和氢油体积比较大时,两者变化对DBT的转化率基本无影响;温度对DBT的转化率影响较大,提高温度可有效提高DBT的转化率,随着温度的升高,DBT转化率的增加逐渐变缓。采用2级平推流反应动力学模型对不同温度实验数据进行了拟合,求得了不同温度的表观反应速率常数,模型的相关系数>0.989。活化能计算结果表明,RN10催化剂在高反应温度区(>330℃)的DBT的HDS活化能明显低于较低温度时的活化能,分别为13.4kJ/mol和121.4kJ/mol。对于RN10催化剂,不可单纯地通过提高反应温度来大幅度提高HDS转化率。The kinetics of the hydrodesulfurization （HDS） reaction of dibenzothiophene （ DBT）, as the model compound for S-bearing organics in middle distillates, were studied over the commercial NiW/Al2O3 catalyst RN-10 in a high-pressure trickle-bed reactor. The effect of reaction conditions on the catalytic behavior was studied at the hydrogen pressure of 1.5 MPa - 4.5 MPa, volume ratio of hydrogen/oil of 150 - 700, weight hourly space velocity of 15 h^-1 -60 h^-1 and reaction temperature of 280 ℃ to 380 ℃. The hydrogen pressure and volume ratio of hydrogen/oil exert little influence on the conversion of DBT at the high hydrogen pressures and volume ratios of hydrogen/oil. At low reaction temperatures, the conversion of DBT increases drastically with the increase of reaction temperature up to 330 ℃, while it increases slowly at high reaction temperatures. A kinetic model of HDS is established according to a second-order kinetics model at various reaction temperatures.The parameters of the model are calculated. The model correlation coefficient is above 0. 989. The apparent activated energy at high reaction temperature region （ ≥ 330℃ ） is less than that at low temperature region, which are 13.4 kJ/mol and 121.4 kJ/mol respectively. Therefore, the HDS performance of the RN-10 catalyst could not be improved by just increasing the reaction temperature.

关 键 词：加氢脱硫 反应动力学 二苯并噻吩 NiW/Al2O3催化剂 

分 类 号：O643.3[理学—物理化学]