Selective Conversion of Syngas to Olefins via Novel Cu-Promoted Fe/RGO and Fe-Mn/RGO Fischer-Tropsch Catalysts: Fixed-Bed Reactor vs Slurry-Bed Reactor.

Abstract

Fischer–Tropsch has become an indispensable choice in the gas-to-liquid conversion reactions to produce a wide range of petrochemicals using recently emerging biomass or other types of feedstock such as coal or natural gas. Herein we report the incorporation of novel Cu nanoparticles with two Fischer–Tropsch synthesis (FTS) catalytic systems, Fe/reduced graphene oxide (rGO) and Fe–Mn/rGO, to evaluate their FTS performance and olefin productivity in two types of reactors: slurry-bed reactor (SBR) and fixed-bed reactor (FBR). Four catalysts were compared and investigated, namely Fe, FeCu7, FeMn10Cu7, and FeMn16, which were highly dispersed over reduced graphene oxide nanosheets. The catalysts were first characterized by transmission electron microscopy (TEM), nitrogen physisorption, X-ray fluorescence (XRF), X-ray diffraction (XRD), and H-TPR techniques. In the SBR, Cu enhanced olefinity only when used alone in FeCu7 without Mn promotion. When used with Mn, the olefin yield was not changed, but light olefins decreased slightly at the expense of heavier olefins. In the FBR system, Cu as a reduction promoter improved the catalyst activity. It increased the olefin yield mainly due to increased activity, even if the CO2 decreased by the action of Cu promoters. The olefinity of the product was improved by Cu promotion but it did not exceed the landmark made by FeMn16 at 320 °C. The paraffinity was also enhanced by Cu promotion especially in the presence of Mn, indicating a strong synergistic effect. Cu was found to be better than Mn in enhancing the paraffin yield, while Mn is a better olefin yield enhancer. Finally, Cu promotion was found to enhance the selectivity towards light olefins C2–4. This study gives a deep insight into the effect of different highly dispersed FTS catalyst systems on the olefin hydrocarbon productivity and selectivity in two major types of FTS reactors.