Progress in application of binary composite oxides as supports for hydrodesulfurization catalysts
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摘要: 加氢脱硫技术对实现劣质油品清洁化、低碳化与多元化高效利用至关重要,其关键是高性能催化剂的开发,核心之一是适宜催化剂载体材料的创新。本工作分别总结了向Al2O3及TiO2中引入第二组元后作为加氢脱硫催化剂载体的研究进展。第二组元氧化物的引入克服了Al2O3载体酸类型单一及商用催化剂金属与载体间相互作用过强等缺点,同时保持了较大的比表面积;第二组元氧化物能够有效提升TiO2载体材料的热稳定性及比表面积的同时调节了载体材料表面酸性等。究其原因在于第二组元的引入可显著改变Al2O3或TiO2表面羟基环境,进而促进了活性金属前驱体在载体表面的锚定和分散,有利于更多NiMo(W)S活性相的形成,提升了催化剂的加氢脱硫性能。Abstract: Hydrodesulfurization (HDS) technique has been considered to play a crucial role in the clean, low-carbon, and diverse effective utilization of inferior crude distillates. The key to this technology is the development of catalyst with excellent catalytic performance. After decades of development, although the HDS performances for most sulfides of the non-noble metal supported catalysts have been greatly improved, but their catalytic activities for highly refractory sulfides are still limited due to the over-strong metal and support interaction (MSI), insufficient acidity, poor textural properties and damnable surface environments. Researches across the world made a lot of efforts to solve the above problems and the developing of novel support candidates is considered as the most efficient solution. In this review, we summarized the developments for the applications of binary Al2O3 based composite oxides and binary TiO2 based composite oxides as support for hydrodesulfurization catalyst and systematically analyzed the effect of the second component on both the properties of the catalyst, mainly focused on the acidity property, MSI, pore structures and the catalytic performances, and the applications of the corresponding catalysts in thiophene, dibenzoethiophene, 4,6-dimethyldibenzothiophene and inferior diesel fuels. It was concluded that both the MSI and the acidity can be effectively modulated after incorporation of appropriate amount of SiO2 into Al2O3 support, which can be attributed to the successful formation of Al−OH−Si linkages over the support surface and thus prevented the formation of excessive Mo−O−Al bonds, resulted in the enhanced hydrogenation activity of the corresponding catalyst which further contributed to the excellent HDS performance. The introduction of ZrO2 into Al2O3 support can also modulate the MSI and the acidity due to the similar reasons, except for that, researchers also found that the reducibility of the active phase precursors can be effectively enhanced, which is favorable for the formation of more active phases. Introducing small amounts of MgO into Al2O3 can effectively enhance the dispersion of active metals over the support surface and promote the formation of Ni(Co)−O−Mo(W) precursors, then acquiring more Ni(Co)Mo(W)S active phases. The introducing of B2O3 can effectively lower the density of hydroxyls and promote the formation of octahedral coordinated Mo species which can be easily sulfided. In summary, the introduction of the second component into Al2O3 successfully overcame the disadvantages such as the solely acid type and the strong interaction between the metal and the support materials over Al2O3 based hydrodesulfurization catalyst, and the advantage of high specific surface area remained. The addition of SiO2 into TiO2 support can effectively improve both the acidity property and the stability of the catalyst, moreover, the specific surface area of the catalyst can also be enlarged after SiO2 addition. After introduction of ZrO2 into TiO2, the density of hydroxyl groups over the support surface decreased, the dispersion of active metals improved and the high stacking Mo(W)S2 slabs formed, thus enhanced the direct desulfurization pathway selectivity. Addition of basic MgO into TiO2 support can enhance the MSI and thus improve the dispersion of active metals over the support surface due to the strong interaction between the basic-acidic pairs. In summary, the introduction of the second component not only improved the thermal stability and the specific surface area, but also modulated the acidity properties. The main factor causing these changes is that the introduction of the second component profoundly changed the hydroxyl environments. Which further improved the anchorage and dispersion of the precursors over the support surface and promoted the formation of more NiMo(W)S active phase, resulted in the enhanced hydrodesulfurization performances of the corresponding catalysts.
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表 1 不同氧化物的特点
Table 1 Characteristics of different oxides
Oxide Advantage Disadvantage Al2O3 high specific surface area, good thermal stability, etc MSI is too strong, only L acid without B acid, etc TiO2 the electronic structure is adjustable, both B acid and
L acid, etcsmall specific surface area, poor thermal stability, etc SiO2 stable chemical properties, large specific surface area, etc the mechanical strength is not high, MSI is weak ZrO2 the chemical properties are stable, oxidizing and reducing, acid-alkaline and so on small specific surface area, expensive, etc MgO high specific surface area, high fire insulation, etc it is unstable in aqueous solution, which makes it difficult to prepare the catalyst based on it B2O3 high melting point and high thermal stability as a catalyst, it is easy to deactivate Catalyst Acid content/(mmol·g−1) L B B+L B/(B+L) NiW/CTS-1 1.7 0.8 2.5 0.32 NiW/CTS-4 2.3 1.1 3.4 0.32 表 3 TiO2-Al2O3复合氧化物的孔结构特性[59]
Table 3 Pore structure characteristics of TiO2-Al2O3 composite oxides[59]
Sample BET surface area
/(m2·g−1)BJH pore volume
/(cm3·g−1)Average pore
size/nmAl2O3 296 0.80 8.01 TiO2 145 0.38 4.40 TiO2-Al2O3(ME) 169 0.63 11.34 TiO2-Al2O3(SG) 242 0.88 12.24 TiO2-Al2O3(PR) 180 0.71 11.89 TiO2-Al2O3(CP) 291 0.26 3.08 -
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