NiW/Al2O3上喹啉对二苯并噻吩 加氢脱硫的抑制作用及反应动力学

 以二苯并噻吩(DBT)为含硫模型化合物，在中压滴流床反应装置中研究了工业NiW/Al₂O₃催化剂(RN-10)上喹啉对DBT加氢脱硫(HDS)的抑制作用，考察了喹啉质量分数(0.5%~1.5%)、反应温度(290~380℃)、反应压力(4.0~5.6MPa)对DBT的HDS的影响。结果表明，喹啉的存在对于DBT的HDS反应有很强的抑制作用，且喹啉浓度越高，抑制作用越大；对DBT的先加氢饱和再脱硫路径(HYD)的抑制作用比对直接脱硫路径(DDS)更大；提高反应温度对DDS和HYD路径的脱硫活性均有提升，但由DDS路径生成联苯的选择性降低；较高反应压力有利于提高HYD路径产物的选择性。采用带有氮化物吸附(中毒项)的拟一级反应动力学模型对实验数据进行拟合，得到不同喹啉质量分数下DBT的HDS表观反应速率常数。经检验，模型计算结果与实验结果吻合。

INHIBITION EFFECTS OF QUINOLINE ON THE HYDRODESULFURIZATION OF DIBENZOTHIOPHENE AND ITS REACTION KINETICS OVER NiW/Al2O3 CATALYST

The inhibition of nitrogen compound quinoline for the hydrodesulfurization (HDS) reaction of dibenzothiophene (DBT), the model compound of S-bearing aromatics in diesel, was studied in a pressured trickle bed reactor over a commercial NiMo/Al₂O₃ catalyst (RN-10). The effects of the reaction conditions and the concentration of quinoline in the feed on the HDS of DBT were investigated, at the quinoline mass fraction of 0.5%-1.5%, total pressure of 4.0-5.6 MPa and temperature of 290-380℃. It was found that quinoline strongly inhibited the HDS of DBT, and with the increase of concentration of quinoline, the inhibition effect increased significantly. In the HDS of DBT, the inhibition of quinoline for hydrogenation (HYD) route was more severe than for direct desulfurization (DDS) route. High temperature was favorable to both HYD and DDS, but could cause the decrease of biphenyl (BP) selectivity via DDS route. High pressure could improve the selectivity of HYD products. The inhibition effect of quinoline for HDS of DBT was quantitatively described in a proposed modified pseudo first-order kinetic model, into which an adsorption equilibrium constant of quinoline was introduced, and the apparent reaction rate constants of DBT HDS were obtained at different mass fractions of quinoline. The kinetic model was well fitted with the experimental data.