No abstract

No abstract

No abstract

We investigated the effect of pre-treatment conditions on the activity and selectivity of cobalt catalysts for Fischer–Tropsch synthesis (FTS) by varying both the reduction atmosphere and the reduction temperature. Catalysts supported on SiO2, Al2O3, and TiO2, prepared via incipient wetness impregnation, were evaluated, and activation temperatures in the range 250–350 °C were considered. Activation with syngas led to a better product selectivity (low CH4, high selectivity to liquid hydrocarbons, and low paraffin to olefin ratio (P/O)) than the catalysts reduced in H2 at lower activation temperatures. The CoxC species suppressed the hydrogenation reaction, and it is hypothesised that this resulted in the high selectivity of olefins observed for the syngas pre-treated catalysts. On the basis of the experimental results, we postulated that a synergistic effect between Co0 and CoxC promotes the production of the long chain hydrocarbons and suppresses the formation of CH4. In addition, for systems aimed at producing lower olefins, syngas activation is recommended, and for the FTS plants that focus on maximising the production of higher molecular weight products, H2 activation might be considered. These results provide insights for the future FTS catalyst design and for target product-driven operations.

No abstract

No abstract

Stringent environmental regulations and energy insecurity necessitate the development of an integrated process to produce high-quality fuels from renewable resources and to reduce dependency on fossil fuels, in this case Fischer–Tropsch synthesis (FTS). The FT activity and selectivity are significantly influenced by the pretreatment of the catalyst. This article reviews traditional and developing processes for pretreatment of cobalt catalysts with reference to their application in FTS. The activation atmosphere, drying, calcination, reduction conditions and type of support are critical factors that govern the reducibility, dispersion and crystallite size of the active phase. Compared to traditional high temperature H2 activation, both hydrogenation–carbidisation–hydrogenation and reduction–oxidation–reduction pretreatment cycles result in improved metal dispersion and exhibit much higher FTS activity. Cobalt carbide (Co2C) formed by CO treatment has the potential to provide a simpler and more effective way of producing lower olefins, and higher alcohols directly from syngas. Syngas activation or direct synthesis of the metallic cobalt catalyst has the potential to remove the expensive H2 pretreatment procedure, and consequently simplify the pretreatment process, which would make it more economical and thus more attractive to industry.

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.