工业NiW/Al2O3催化剂上二苯并噻吩的加氢脱硫动力学

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（RN-10）的加氢脱硫(HDS)动力学规律，研究了氢分压（1.5 MPa～4.5 MPa）、氢油体积比（150~700）、液体质量空速(15 h-1~60 h-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，RN-10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13.4 kJ/mol和121.4 kJ/mol。对于RN-10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。

Kinetics of the hydrodesulfurization of dibenzothiophene over a commercial NiW/Al2O3 catalyst

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.