机械化学法制备的Al/Ce复合氧化物负载NiMo催化剂的加氢脱硫活性

doi:10.1016/S1872-2067(15)61016-6

摘要/Abstract

摘要：

将Al和/或Ce的硝酸盐与NH₄HCO₃球磨混合, 采用机械化学法制备了Al₂O₃-CeO₂载体(其中Ce含量为1-10 wt%), 再以杂多钼酸盐(NH₄)₄NiMo₆O₂₄为活性金属Ni和Mo的前驱体, 通过浸渍法制备NiMo₆/Al₂O₃-CeO₂催化剂, 并将其用于1-苯并噻吩(BT)的加氢脱硫(HDS)反应中. 运用化学分析、X射线衍射、N₂吸附-脱附法、H₂程序升温还原、NH₃程序升温脱附和X射线光电子能谱对催化剂的物化性质进行了表征. 结果表明, 催化剂的酸性随着载体中Ce含量的增加而下降. Ce修饰的Al₂O₃载体表面的NiS/MoS原子比下降了2倍. NiMo₆/Al₂O₃催化剂表现出最高的HDS活性(以单位重量催化剂计), 其酸性和表面MoO_xS_y物种的浓度(Mo⁵⁺浓度)也最高; 当催化剂中Ce含量逐渐增加到10 wt%以上时, 其活性逐渐将为0. 与浸渍法制得的参比催化剂相比, 前驱体和催化剂组成相同的情况下, 采用机械化学法制得的所有催化剂活性明显提高.

关键词: 镍, 钼, 氧化铝, 氧化铈, Anderson型杂多钼酸盐, 1-苯并噻吩, 加氢脱硫, 机械化学法

Abstract:

Al₂O₃-CeO₂ supports containing 1-10 wt% Ce were prepared mechanochemically by milling aluminum and/or cerium nitrates with NH₄HCO₃. Heteropolymolybdate, (NH₄)₄NiMo₆O₂₄, was used as the precursor of the Ni and Mo to prepare NiMo₆/Al₂O₃-CeO₂ components in catalysts by impregnation method. The physicochemical properties of the catalysts were determined using chemical analysis, X-ray diffraction, temperature-programmed H₂ reduction, temperature-programmed NH₃ desorption, X-ray photoelectron spectroscopy (XPS), and the Brunauer-Emmett-Teller method. The catalyst acidity decreased with increasing Ce concentration in the support. XPS showed that the NiS/MoS ratio decreased two-fold for the Ce-modified alumina support. NiMo₆/Al₂O₃, which had the highest acidity, showed the highest activity in hydrodesulfurization of 1-benzothiophene (normalized per weight of catalyst). The concentration of surface MoO_xS_y species (which is equal to the concentration of Mo⁵⁺) gradually decreased to zero for catalysts with Ce concentrations ≥ 10 wt%. However, the activities of all the catalysts prepared mechanochemically from Al₂O₃ and Al₂O₃-CeO₂ supports significantly exceeded that of a reference NiMo₆/Al₂O₃ catalyst prepared by impregnation method using the same precursor and with the same composition.

Key words: Nickel, Molybdenum, Alumina, Ceria, Anderson heteropolymolybdate, 1-Benzothiophene, Hydrodesulfurization, Mechanochemical method

Květa Jirátová, Alla Spojakina, Luděk Kaluža, Radostina Palcheva, Jana Balabánová, Georgi Tyuliev. 机械化学法制备的Al/Ce复合氧化物负载NiMo催化剂的加氢脱硫活性[J]. 催化学报, 2016, 37(2): 258-267.

Květa Jirátová, Alla Spojakina, Luděk Kaluža, Radostina Palcheva, Jana Balabánová, Georgi Tyuliev. Hydrodesulfurization activities of NiMo catalysts supported on mechanochemically prepared Al-Ce mixed oxides[J]. Chinese Journal of Catalysis, 2016, 37(2): 258-267.

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