An Auger Electron Spectroscopy Study of the Activation of Iron Fischer-Tropsch Catalysts

Abstract

Activation procedures can have a dramatic effect on the activity of iron-based catalysts for Fischer-Tropsch (F-T) synthesis. CO conversion over a 100 Fe/3 Cu/0.2 K catalyst (parts by weight) can vary by nearly a factor of 3, depending on activation treatment. In contrast, a 100 Fe/5 Cu/4.2 K/25 SiO2 catalyst displays little dependence of F-T activity on activation treatment. An ultra-high vacuum surface analysis chamber coupled to an atmospheric reactor has been used to measure the surface composition of these catalysts following activation in carbon monoxide at 280°C, while transmission electron microscopy (TEM) and BET surface area measurements have been used to investigate catalyst morphology. CO activation of the 100 Fe/5 Cu/4.2 K/25 SiO2 catalyst at 280°C results in partial reduction of iron to a mixture of FexO and Fe3O4, and an overall surface composition very similar to that obtained following hydrogen activation at 220 or 280°C, consistent with the invariance of F-T activity with activation treatment for this catalyst. Activation of the 100 Fe/3 Cu/0.2 K catalyst in CO at 280°C results in the formation of iron carbide particles, growth of graphitic carbon (Cg) filaments, and formation of a thick, porous, Cg layer covering the carbide particles. Differences in F-T activity between the hydrogen- and CO-activated 100 Fe/3 Cu/O.2 K catalyst are discussed in terms of surface composition and catalyst morphology. The difference in sensitivity of the two catalysts to activation conditions is related to differences in the extent of reduction of the catalysts.