Effect of pretreatment conditions on a benchmark iron catalyst for CO2 hydrogenation to light olefins

To improve the CO₂-to-light olefin process in terms of economics, efficient catalysts are essential to maximize the yield. Our research was carried out on FeAlCuK, which is still considered as a benchmark for olefin formation via CO₂ Fischer-Tropsch synthesis (FTS). Nevertheless, the effect of various activation conditions on the formation of desired active species and final activity of this catalyst has not been described in literature to date. We studied the pretreatment by varying both the reduction gas and temperature. The catalyst was pretreated with pure H₂ or synthesis gas (H₂/CO = 3) to identify the bulk and surface species formed in each case. We demonstrate that the FeCuAlK catalyst should be activated in a H₂/CO atmosphere at 250 °C for 4 h before the test at typical FTS reaction conditions to reach maximum productivity. The reduction with H₂/CO led to the formation of active Fe₅C₂ and Fe₃O₄ phases producing a high fraction of light olefins at higher CO₂ conversion. The role of promoters K and Cu was also investigated. Selectivity for desired C₂-C₄ olefins increased by 10 % compared to catalysts which were used directly in FTS without preliminary activation. Characterization with ex and in situ powder X-ray diffraction, Raman spectroscopy, and XPS after each activation treatment as well as Mössbauer spectroscopy revealed a strong impact of gas nature on the phase composition which was correlated with the performance.