有序介孔材料Al-FDU-12的合成及其加氢精制应用

Synthesis of well ordered Al-FDU-12 mesoporous materials and their application in hydrogenation

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、N_(2)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。

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,N_(2)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.