Fischer–Tropsch synthesis in slurry-phase reactors over Mn- and Zr-modified Co/SiO2 catalysts

Abstract: Fischer–Tropsch (F–T) synthesis was carried out in a gas-flowed slurry-phase reaction system over Mn- and Zr-modified Co/SiO2 catalysts. A 0.5 L stirred tank slurry reactor (STSR) was used for catalyst screening and a 12.5 L slurry bubble column reactor (SBCR) was used for trial pilot operation. While using the 0.5 L reactor for catalyst screening, Co supported on the SiO2 with an average pore size of 10 nm showed a high catalytic performance for the F–T synthesis due to the suitable Co particle size in the catalyst. Zr promoter improved the activity and Mn promoter improved the stability of Co/SiO2 catalyst for the F–T synthesis. H2-TPR profiles indicated that Zr and Mn promoters improved the reduction degree of Co3O4 particles (on SiO2 surface) to Co0 active species in H2 flow at low temperature. While using the 12.5 L reactor for trial pilot operation over Mn–Zr–Co/SiO2 catalyst, the space-time yield (STY) of C5+ hydrocarbons (liquid fuel) showed almost the same values when various solvents (n-C16H34, n-C14H30, diesel from petrol station, F–T crude oil) were used. Diesel and F–T crude oil are suitable for using in a large-scaled F–T synthesis plant owing to the low prices. Mn–Zr–Co/SiO2 catalyst achieved a STY of C5+ hydrocarbons larger than 1000 g-C5+ kg-cat−1 h−1 in the 12.5 L reactor. The production capacity of liquid fuel from the 12.5 L reactor reached to 15.6 L per day (assumed for 24 h continuous operation). The stirring was very important for the F–T synthesis both reaction in the 0.5 L reactor and reaction in the 12.5 L reactor. The shape of slurry reactor also influenced the CO conversion for the F–T synthesis: reaction in the 12.5 L SBCR gave a higher CO conversion than that of reaction in the 0.5 L STSR (at the same W/F value under the same stirring speed) because the slender column reactor (SBCR) extended the residue time of reaction gas in the slurry-phase containing catalyst. [Copyright &y& Elsevier]