Abstract:

Al-FDU-12 mesoporous materials with different silicon-to-aluminum atomic ratios (Si/Al=50, 40, 30, 20 and 10) were synthesized by in-situ synthesis, and the catalysts NiMo/Al-FDU-12 were prepared by further impregnating nickel and molybdenum active metals. The Al-FDU-12 and catalysts were characterized by means of small-angle XRD, wide-angle XRD, N₂ adsorption and desorption, SEM, TEM, UV and other characterization means. The hydrodesulfurization (HDS) performances of the NiMo/Al-FDU-12 with different Si and Al ratios were also evaluated. It showed that FDU-12 with high pore size, volume and surface area would lead to the high dispersion degree of active metals. The hydrodesulfurization and denitrification performances of NiMo/Al-FDU-12 catalyst were improved after Al modification. As the reaction conditions were: temperature of 350℃, hydrogen and oil volume ratio of 600, pressure of 5.0MPa, WHSV of 1.0h^-1, Si and Al atomic ratio of 20, the catalyst showed the highest hydrodesulfurization and denitrification activity. The desulfurization and denitrification rate could reach 98.9% and 95.3%, respectively. Under similar reaction conditions, the industrial catalyst presented lower hydrodesulfurization and denitrification activity than the NiMo/AF-20 and NiMo/AF-10 catalysts. Therefore, the FDU-12 materials after Al modification possessed good prospect of industrial application.

Key words: catalyst, synthesis, activity, petroleum, deactivation

摘要：

采用原位合成法合成了不同硅铝原子比（Si/Al=50、40、30、20、10）的Al-FDU-12介孔材料，进一步浸渍镍钼活性金属制备了催化剂。通过小角X射线衍射（XRD）、广角XRD、N₂吸附-脱附、扫描电镜（SEM）、透射电镜（TEM）和紫外等表征手段对材料及催化剂做了相应的表征，并且考察了不同硅铝比的NiMo/Al-FDU-12催化剂在催化裂化柴油中的加氢脱硫脱氮性能。结果表明，FDU-12介孔材料孔径、孔容以及比表面积大，活性金属分散度高。铝改性后的NiMo/Al-FDU-12催化剂加氢脱硫、脱氮活性得到显著提高。当反应条件为温度350℃、氢油体积比600、压力5.0MPa、质量空速（WHSV）1.0h^-1、硅铝比20时，催化剂的加氢脱硫脱氮活性最高，脱硫率可达98.9%，脱氮率可达95.3%。在相同反应条件下，工业催化剂催化柴油加氢脱硫、脱氮率低于NiMo/AF-20以及NiMo/AF-10催化剂。因此，铝改性后的FDU-12材料具有良好的工业应用前景。

关键词: 催化剂, 合成, 活性, 石油, 失活