The removal of carbon deposits from carburized Fe-based Fischer–Tropsch catalysts is a critical aspect of their performance. In this study, a method is presented to remove carbon deposits from freshly prepared χ-Fe5C2. The method involves successive passivation and reduction steps, which do not affect the bulk structure of the χ-Fe5C2 catalyst. The passivation step transforms the carbonaceous deposits from a graphitic structure to a disordered oxygen-functionalized structure, facilitating its removal by a reduction step in hydrogen. This results in a higher initial activity of the catalyst and substantially shortens the induction period observed without such pretreatment. The findings underscore the possibility of improving catalytic performance of Fe-carbides by changing the structure and reactivity of carbonaceous deposits.

The kinetics of the transformation of metallic Fe to the active Fe carbide phase at the start of the Fischer-Tropsch (FT) reaction were studied. The diffusion rates of C atoms going in or out of the lattice were determined using 13C-labeled synthesis gas in combination with measurements of the transient 12C and 13C contents in the carbide by temperature-programmed hydrogenation. In the initial 20 min, C diffuses rapidly into the lattice occupying thermodynamically very stable interstitial sites. The FT reaction starts already during these early stages of carburization. When reaching steady state, the diffusion rates of C in and out of the lattice converge and the FT reaction continues via two parallel reaction mechanisms. It appears that the two outer layers of the Fe carbide are involved in hydrocarbon formation via a slow Mars-Van Krevelen-like reaction contributing to ∼10% of the total activity, while the remainder of the activity stems from a fast Langmuir-Hinshelwood reaction occurring over a minor part of the catalyst surface.

The formation of Fe-carbide phases is relevant to the synthesis of Fischer-Tropsch synthesis catalysts. We investigated the carburization of Raney Fe as a model catalyst using spectroscopic and temperature-programmed techniques. IR spectroscopy shows that CO dissociation already occurs at −150 °C, while C diffusion into metallic Fe requires much higher temperature (~180 °C). The carburization rate increases with increasing H₂/CO ratio, which can be attributed to the lower overall barrier for O removal as H₂O as compared to CO₂. O removal frees vacancies that are needed for CO dissociation. The resulting higher C coverage increases the driving force for Fe-carbide formation. A higher driving force leads to predominant formation of the more carbon-rich ε(́)-carbide, while χ-Fe₅C₂ is formed at lower H₂/CO ratio. The removal of surface O appears to be the rate-limiting step under all conditions. Initially, most of deposited C is used for Fe-carbide formation with a small contribution to hydrocarbons formation.