Effect of H2S in syngas on the Fischer–Tropsch synthesis performance of a precipitated iron catalyst

Abstract

The sulfur limit, the relationship between the sulfur added and the surface Fe atoms lost (Fe/S), and mechanism of sulfur poisoning were studied using an iron Fischer–Tropsch synthesis (FTS) catalyst (100 Fe/5.1 Si/2.0Cu/3.0K). The FTS reaction was carried out at 230–270°C, 1.3MPa, H2/CO=0.67–0.77 and 30–70% CO conversion using a 1-L slurry phase reactor. The used Fe catalysts were characterized by XRD, Mössbauer spectroscopy and XANES spectroscopy to understand the deactivation mechanism of the Fe based catalyst after adding up to 1ppm H2S in the feed. Co-feeding of 0.1ppm H2S in syngas for 70h caused a very small change in the activity of the Fe catalyst, but increasing the H2S level to 0.2ppm or above resulted in measurable deactivation of the Fe catalyst over a similar time period. The limit of sulfur level in the syngas feed (sensitivity) was determined to be 50ppb. The added sulfur improved the selectivities of the secondary reactions of olefins and the WGS reaction even though the rates for these declined. The addition of H2S decreased CH4 selectivity and increased C5+ selectivities of the Fe catalyst. The Fe/S ratio, which can be used to define the poisoning ability of sulfur for the iron catalyst, was quantified based on the deactivation data obtained. The Fe/S ratio strongly depended on temperature and decreased remarkably with increasing temperature. At 270°C one sulfur atom was found to eliminate ∼6 surface Fe atoms, and the ratio increased to 7.2 at 260°C and increased further to 13.5 at 230°C. The Fe/S relationship with increasing temperature is in good agreement with sulfur sorption theory. The changes in FTS and WGS rates of the Fe catalyst by sulfur were also studied. The decreases in rates of the two reactions were nearly the same. The results of XRD and Mössbauer spectroscopy indicated that the online addition of sulfur did not greatly alter the distributions of iron carbide and magnetite. Both data sets consistently suggest an adsorption mechanism, in line with the results of reaction testing. XANES results at the S K-edge further confirmed sulfur adsorption, and some sulfide and sulfate species, likely confined to the surface zone, were detected. In this study, the sulfur tolerances of the precipitated Fe and a supported Co catalyst were compared at an identical temperature (i.e., 230°C), and similar M/S ratios (13.5–15.0) were obtained.