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.

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.

Mn-Fe nanoparticles on a reduced graphene oxide catalyst for enhanced olefin production from syngas in a slurry reactor.

Fe nanoparticles (NPs) supported on reduced graphene oxide (rGO) nano-sheets were promoted with Mn and used for the production of light olefins in Fischer-Tropsch reactions carried out in a slurry bed reactor (SBR). The prepared catalysts were characterized by X-ray fluorescence (XRF), X-ray diffraction (XRD), transmission electron microscope (TEM), Raman spectroscopy, N2 physisorption, temperature programmed reduction (TPR) and X-ray photoelectron spectroscopic (XPS) methods. Mn was shown to preferentially migrate to the Fe NP surface, forming a Mn-rich shell encapsulating a core rich in Fe. The Mn shell regulated the diffusion of molecules to and from the catalyst core, and preserved the metallic Fe phase by lowering magnetite formation and carburization, so decreasing water gas shift reaction (WGSR) activity and CO conversion, respectively. Furthermore, the Mn shell reduced H2 adsorption and increased CO dissociative adsorption which enhanced olefin selectivity by limiting hydrogenation reactions. Modification of the Mn shell thickness regulated the catalytic activity and olefin selectivity. Simultaneously the weak metal-support interaction further increased the migration ability owing to the utilization of a graphene-based support. Space velocities, pressures and operating temperatures were also tested in the reactor to further enhance light olefin production. A balanced Mn shell thickness produced with a Mn concentration of 16 mol Mn/100 mol Fe was found to give a good olefin yield of 19% with an olefin/paraffin (O/P) ratio of 0.77. Higher Mn concentrations shielded the active sites and reduced the conversion dramatically, causing a fall in olefin production. The optimum operating conditions were found to be 300 °C, 2 MPa and 4.2 L g-1 h-1 of 1 : 1 H2 : CO syngas flow; these gave the olefin yield of 19%.

Utilizing FBR to produce olefins from CO reduction using Fe-Mn nanoparticles on reduced graphene oxide catalysts and comparing the performance with SBR.

Mn was used as a promoter for Fe nanoparticles (NPs) loaded on reduced graphene oxide (rGO). The prepared catalysts were the unpromoted Fe/rGO catalysts along with two Mn promoted catalysts FeMn16 and FeMn29. These catalysts were used as Fischer-Tropsch catalysts in a Fixed Bed Reactor (FBR). The operating conditions of the reactor, namely temperature, pressure and space velocity, were varied to evaluate the catalyst performance and the olefin productivity. The olefins were produced in maximum yields of 34.5% and 31.3% with FeMn29 at 320 and 340 °C respectively. The ratio of light to heavy olefins was three times higher at 340 °C. The catalysts showed good stability up to 50 h of interrupted operation while varying the conditions at each interruption. The performance of the catalysts in the FBR was compared with a previous investigation carried out in an SBR under identical conditions with the same catalysts. The FBR was found to be more Mn tolerant than the SBR, giving very high conversion activity with high Mn concentrations (FeMn29). The FBR produced olefins in much higher yields than the SBR. The SBR was more selective to light olefins at low temperatures and high Mn loading levels, while the FBR produced light olefins at higher selectivities at high temperatures and high Mn concentrations.