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

Abstract

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%.