Fischer-Tropsch synthesis: Anchoring of cobalt particles in phosphorus modified cobalt/silica catalysts

Abstract

The effect of phosphorus addition on silica-supported cobalt catalyst was investigated for Fischer-Tropsch synthesis (FTS). As shown by STEM images and chemisorption, the addition of phosphorus to cobalt of up to 1wt% increased the dispersion of cobalt. Further addition of phosphorus (e.g., 3 and 5wt.%), as demonstrated by TPR, pulse reoxidation, and XANES, significantly hindered the reduction of cobalt oxides. The cobalt FTS catalysts containing 0.5 and 1.0wt% P exhibited greater stability in comparison with undoped and 3.0wt% P containing cobalt catalysts. Analysis of XANES spectra at the P and Co K-edges, along with DRIFTS results of H2-activated cobalt catalysts, suggest that cobalt particles interact with PO43− ions, indicating a role played by P in anchoring Co particles to the support, thus hindering the cobalt sintering rate. The initial selectivity to methane was slightly higher for 0.5%P-20%Co/SiO2 and 1.0%P-20%Co/SiO2 catalysts compared to the undoped catalyst, but at longer times differences were small. At higher loadings of P (3wt.%), FT activity and selectivity were adversely and irreversibly affected.