The use of carbide catalysts in Fischer–Tropsch synthesis (FTS) is an active area of research, as carbide phases have been shown to improve the stability and performance of catalysts in this reaction. This study compared the catalytic activity and product selectivity of cobalt and iron catalysts supported on SBA-15, with and without a carbide phase and reduction treatment before the reaction. Results showed that the presence of the carbide phase had a noticeable influence on the catalytic behavior of the catalysts, and the reduction of the catalyst with hydrogen also affected the product selectivity. The presence of the carbide phase in non-reduced cobalt catalysts resulted in increased selectivity to liquid phase products, as evidenced by a CO conversion of 37% with 68% selectivity to the products in the liquid phase. The catalytic activity of the iron carbide catalyst for CO dissociation was found to be 38% after reducing the catalyst with hydrogen, leading to the formation of more active sites. The presence of metal carbides and formation of metallic cobalt and iron during the FT reaction and reduction step was found to have a significant effect on the catalytic performance and product selectivity. The findings of this research provide new insights into the role of carbide in the performance of cobalt and iron catalysts in Fischer–Tropsch synthesis.

The determination of the catalyst’s active phase helps improve the catalytic performance of the Fischer–Tropsch (FT) synthesis. Different phases of cobalt, including cobalt oxide, carbide, and metal, exist during the reaction. The content of each phase can affect the catalytic performance and product distribution. In this study, a series of cobalt carbide catalysts were synthesized by exposure of Co/Al2O3 catalyst to CH4 at different temperatures from 300 °C to 800 °C. The physicochemical properties of the carbide catalysts (CoCx/Al2O3) were evaluated by different characterization methods. The catalytic performances of the catalysts were investigated in an autoclave reactor to determine the role of cobalt carbides on the CO conversion and product distribution during the reaction. XRD and XPS analysis confirmed the presence of Co2C in the prepared catalysts. The higher carbidation temperature resulted in the decomposition of methane into hydrogen and carbon, and the presence of graphitic carbon was confirmed by XRD, XPS, SEM, and Raman analysis. The Co2C also decomposed to metallic cobalt and carbon, and the content of cobalt carbide decreased at higher carbidation temperatures. Higher content of Co2C resulted in a lower CO conversion and higher selectivity to light alkanes, mainly methane. The higher carbidation temperature resulted in the decomposition of Co2C to metallic cobalt with higher activity in the FT reaction. The CO conversion increased by increasing the carbidation temperature from 300 °C to 800 °C, due to the higher content of metallic cobalt. In the presence of pure hydrogen, the Co2C could be converted mainly into hexagonal, close-packed (hcp) Co with higher activity for dissociative adsorption of CO, which resulted in higher catalyst activity and selectivity to heavier hydrocarbons.