Cobalt‐Iron‐Manganese Catalysts for the Conversion of End‐of‐Life‐Tire‐Derived Syngas into Light Terminal Olefins

Co‐Fe‐Mn/γ‐Al2O3 Fischer–Tropsch synthesis (FTS) catalysts were synthesized, characterized and tested for CO hydrogenation, mimicking end‐of‐life‐tire (ELT)‐derived syngas. It was found that an increase of C2‐C4 olefin selectivities to 49 % could be reached for 5 wt % Co, 5 wt % Fe, 2.5 wt % Mn/γ‐Al2O3 with Na at ambient pressure. Furthermore, by using a 5 wt % Co, 5 wt % Fe, 2.5 wt % Mn, 1.2 wt % Na, 0.03 wt % S/γ‐Al2O3 catalyst the selectivity towards the fractions of C5+ and CH4 could be reduced, whereas the selectivity towards the fraction of C4 olefins could be improved to 12.6 % at 10 bar. Moreover, the Na/S ratio influences the ratio of terminal to internal olefins observed as products, that is, a high Na loading prevents the isomerization of primary olefins, which is unwanted if 1,3‐butadiene is the target product. Thus, by fine‐tuning the addition of promoter elements the volume of waste streams that need to be recycled, treated or upgraded during ELT syngas processing could be reduced. The most promising catalyst (5 wt % Co, 5 wt % Fe, 2.5 wt % Mn, 1.2 wt % Na, 0.03 wt % S/γ‐Al2O3) has been investigated using operando transmission X‐ray microscopy (TXM) and X‐ray diffraction (XRD). It was found that a cobalt‐iron alloy was formed, whereas manganese remained in its oxidic phase. Na and S can be used as additives to improve the selectivity towards C2–C4 olefins for the Fischer–Tropsch‐to‐olefins reaction over Mn‐promoted Co‐Fe/γ‐Al2O3 catalysts. It was found that Na prevents the isomerization of primary olefins, such as 1‐butene. Operando transmission X‐ray microscopy and X‐ray diffraction indicates the formation of a Co‐Fe‐alloy, whereas Mn stayed in its oxidic phase.