Insight into the Physicochemical Properties of Co-Based Catalysts in Fischer–Tropsch Synthesis

Reactions Pub Date : 2023-08-04 DOI:10.3390/reactions4030025
Nothando C. Shiba, Xinying Liu, Yali Yao
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Abstract

The effect of the different supports and catalyst-reducing agents on the Fischer–Tropsch (FT) reaction was investigated. The large surface area SiO2 support with a smaller pore volume deposited fine, evenly distributed Co3O4. Cubic-shaped Co3O4 appeared in clusters on the TiO2 support, whereas Co3O4 existed as single large particles on the Al2O3 support. The activity data obtained were discussed in terms of cluster size, particle size, particle shape, and mass transport limitations. The SiO2-supported catalysts showed a higher activity for the formation of paraffinic products when reduced in H2 at 250 °C. This is attributed to the formation of the CoO-Co active bond, which enhanced the activation of CO and the hydrogenation reactions. A higher activity was observed for the TiO2-supported catalyst at a higher reduction temperature (350 °C) when the mass of Co metal was higher. It afforded more paraffinic products due to enhanced secondary hydrogenation of olefins at higher reaction rates. The large Co3O4 supported on Al2O3 showed the least activity at both reduction temperatures due to strong metal-support interactions. The H2-reduced catalysts exhibited superior activity compared to all the syngas-reduced catalysts. Syngas reduction led to surface carbon deposition and the formation of surface carbides which suppressed the hydrogenation reactions and are selective to olefinic products.
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费托合成中co基催化剂的物理化学性质研究
研究了不同载体和还原剂对费托反应的影响。孔隙体积小、表面积大的SiO2载体沉积了细小、均匀的Co3O4。Co3O4在TiO2载体上呈立方状簇状存在,而在Al2O3载体上呈单个大颗粒存在。得到的活性数据从簇大小、颗粒大小、颗粒形状和质量输运限制等方面进行了讨论。sio2负载型催化剂在250℃的H2还原条件下,具有较高的石蜡产物生成活性。这是由于CO - CO活性键的形成,增强了CO的活化和加氢反应。在较高的还原温度(350℃)下,tio2负载型催化剂的活性越高,Co金属质量越高。在较高的反应速率下,烯烃的二次加氢反应增强,从而产生更多的石蜡产物。在两种还原温度下,由Al2O3支撑的大Co3O4表现出最低的活性,这是由于强的金属-载体相互作用。h2还原催化剂的活性优于所有合成气还原催化剂。合成气还原导致表面碳沉积和表面碳化物的形成,抑制了加氢反应,对烯烃产物有选择性。
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