摘要
Al2O3-CeO2 supports containing 1-10 wt%Ce were prepared mechanochemically by milling aluminum and/or cerium nitrates with NH4HCO3.Heteropolymolybdate,（NH4）4NiMo6O（24）,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 MoOxSy species（which is equal to the concentration of Mo^（5＋）） gradually decreased to zero for catalysts with Ce concentrations 10 wt%.However,the activities of all the catalysts prepared mechanochemically from Al2O3 and Al2O3-CeO2supports significantly exceeded that of a reference NiMo6/Al2O3 catalyst prepared by impregnation method using the same precursor and with the same composition.
将Al和/或Ce的硝酸盐与NH_4HCO_3球磨混合,采用机械化学法制备了Al_2O_3-CeO_2载体(其中Ce含量为1-10 wt%),再以杂多钼酸盐(NH_4)_4NiMo_6O_(24)为活性金属Ni和Mo的前驱体,通过浸渍法制备NiMo_6/Al_2O_3-CeO_2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、N_2吸附-脱附法、H_2程序升温还原、NH_3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Al_2O_3载体表面的NiS/MoS原子比下降了2倍.NiMo_6/Al_2O_3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(Mo^(5+)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.
基金
Czech Science Foundation(Project P106/11/0902) for financial support
