The formation of Co2C species in activated carbon supported cobalt-based catalysts and its impact on Fischer-Tropsch reaction

The cobalt carbide (Co2C) species was formed in some activated carbon supported cobalt-based (Co/AC) catalysts during the activation of catalysts. It was found that the activity of Fischer-Tropsch reaction over Co-based catalysts decreased due to the formation of cobalt carbide species. Some promoters and pretreatment of activated carbon with steam could restrain the formation of cobalt carbide.

A DFT study of the chain growth probability in Fischer-Tropsch synthesis

The chain growth probability (alpha value) is one of the most significant parameters in Fischer-Tropsch (FT) synthesis. To gain insight into the chain growth probability, we systematically studied the hydrogenation and C-C coupling reactions with different chain lengths on the stepped Co(0001) surface using density functional theory calculations. Our findings elucidate the relationship between the barriers of these elementary reactions and the chain length. Moreover, we derived a general expression of the chain growth probability and investigated the behavior of the alpha value observed experimentally. The high methane yield results from the lower chain growth rate for C-1 + C-1 coupling compared with the other coupling reactions. After C-1, the deviation of product distribution in FT synthesis from the Anderson-Schulz-Flory distribution is due to the chain length-dependent paraffin/olefin ratio. (C) 2008 Elsevier Inc. All rights reserved.

A quantitative determination of reaction mechanisms from density functional theory calculations: Fischer-Tropsch synthesis on flat and stepped cobalt surfaces

We systematically investigated the mechanism of the C-1 + C-1 coupling reactions using density functional theory. The activation energies of C-1 + C-1 coupling and carbon hydrogenation reactions on both flat and stepped surfaces were calculated and analyzed. Moreover, the coverages of adsorbed C-1 species were estimated, and the reaction rates of all possible C-1 + C-1 coupling pathways were quantitatively evaluated. The results suggest that the reactions of CH2 + CH2 and CH3 + C at steps are most likely to be the key C-1 + C-1 coupling steps in FT synthesis on Co catalysts. The reactions of C-2 + C-1 and C-3 + C-1 coupling also were studied; the results demonstrate that in addition to the pathways of RCH + CH2 and RCH2 + C, the coupling of RC + C and RC + CH also may contribute to the chain growth after C-1. (C) 2008 Elsevier Inc. All rights reserved.