Oil has long been the dominant feedstock for producing fuels and chemicals, but coal, natural gas and biomass are increasingly explored alternatives. Their conversion first generates syngas, a mixture of CO and H2, which is then processed further using Fischer–Tropsch (FT) chemistry. However, although commercial FT technology for fuel production is established, using it to access valuable chemicals remains challenging. A case in point is linear α-olefins (LAOs), which are important chemical intermediates obtained by ethylene oligomerization at present. The commercial high-temperature FT process and the FT-to-olefin process under development at present both convert syngas directly to LAOs, but also generate much CO2 waste that leads to a low carbon utilization efficiency. The efficiency is further compromised by substantially fewer of the converted carbon atoms ending up as valuable C5–C10 LAOs than are found in the C2–C4 olefins that dominate the product mixtures. Here we show that the use of the original phase-pure χ-iron carbide can minimize these syngas conversion problems: tailored and optimized for the process of FT to LAOs, this catalyst exhibits an activity at 290 °C that is 1–2 orders higher than dedicated FT-to-olefin catalysts can achieve above 320 °C, is stable for 200 h, and produces desired C2–C10 LAOs and unwanted CO2 with carbon-based selectivities of 51% and 9% under industrially relevant conditions. This higher catalytic performance, persisting over a wide temperature range (250–320 °C), demonstrates the potential of the system for developing a practically relevant technology.@en

The Fe-catalyzed Fischer-Tropsch (FT) synthesis reaction is the core of the coal-to-liquids (CTL) process, which is an efficient route to convert coal into liquid fuels via synthesis gas (a mixture of CO and H₂). Conventional Fe-based FT catalysts convert typically 30% of the feed CO to undesirable CO₂during the FT step. A decrease of CO₂production in FT units can reduce the profitability of the overall CTL process. In this context, we synthesized phase-pure ϵ-Fe-carbide FT catalysts by careful control of the pretreatment and carburization conditions starting from Raney Fe. The resulting phase-pure Fe-carbide exhibits a low CO₂selectivity during the Fischer-Tropsch reaction. The developed preparation method can be applied to supported Fe catalysts and does not require expensive starting chemicals. The purity and durability of as-synthesized phase-pure ϵ-Fe-carbide catalyst under FT conditions were characterized in detail by in situ characterization techniques. A bulk phase-pure ϵ-Fe-carbide catalyst operated at 23 bar, 235 °C and a H₂/CO ratio of 1.5 shows stable performance with no deactivation during a 150 h pilot test. The catalyst is free of primary CO₂formation and presents reduced secondary CO₂formation compared to conventional Fe-based FT catalysts. These findings contribute to the development of new Fe-based FT catalysts for CTL processes.

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