Transition metal nitrides, carbides and phosphides have the potential to replace the expensive and hazardous catalysts typically used for the conversion of fatty acids. However, there has been little research on the influence of treatment conditions and precursor nature on the properties of such catalytic systems. To better understand these dependencies, we synthesized a number of Mo catalysts by temperature‐programmed reduction (700‐900 °C; CH4/N2, N2/H2) using ammonium heptamolybdate, diammonium phosphate and hexamethylenetetramine (HMT) as Mo, C, N and P sources. The presence of HMT in the precursor mixtures ensured the synthesis of pure phase Mo2C, Mo2N and MoP. Catalytic activity in the (hydro)deoxygenation of stearic acid (240 min; 360 °C; 50 bar of H2) decreased in the following order: Mo2C>Mo2N>MoP. However, all of the studied Mo‐based catalysts showed good deoxygenation efficiency and, thus, represent excellent alternatives to traditional noble and sulfur‐containing catalysts.
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.
This study focuses on a comparison of alkali-activated materials based on natural zeolites without and with the addition of blast furnace slag and their subsequent modification by acid leaching. The addition of slag to alkali-activated mixtures is generally used to increase the strength. The subsequent modification of its chemical, textural and mechanical properties by acid leaching makes this material usable in other industries, especially in the chemical industry. This study aimed to examine the influence of the addition of blast furnace slag to alkali-activated mixtures based on natural zeolites and observe the effect of subsequent acid leaching on the chemical, textural and mechanical properties and CO2 adsorption capacity of these materials. The modification of alkali-activated materials was carried out by acid leaching using 0.1 M HCl and then using 3 M HCl. The properties of these materials were determined using N2 physisorption, Hg porosimetry, XRF, XRD, DRIFT, TGA and strength measurements. The results showed that the addition of blast furnace slag significantly increased the cutting-edge strength of the obtained materials and affected the textural properties, especially in leached samples. The presence of blast furnace slag generated a higher proportion of mesopores, which are attributed to the presence of the calcium silicate hydrate (C–S–H) phase and are easily removed by leaching, as shown by the XRF results. The obtained data showed an improvement in properties and extension of the potential applicability of these materials in the chemical industry, especially for catalytic and adsorption applications.
Owing to the increased use of secondary materials for diesel production, refineries must confront bad quality parameters. Therefore, catalysts with certain capabilities (to remove heteroatoms and improve quality parameters at low hydrogen consumption) and their lifetimes are required. An important parameter that influences the quality of the products and the economy of the unit is the activity of the catalyst. Prior to industrial use, the catalyst is typically tested in a pilot unit. This is necessary to obtain a considerable amount of data on the lifetime of the catalyst in the shortest feasible time. Here, deactivation steps were used to test the catalyst. Two experiments were performed to evaluate the effect of two types of accelerated deactivations on the catalyst activity and product properties. The first type of deactivation proceeded for 6 h and comprised a tripling of the amount of incoming feedstock, and the second type proceeded for 18 h without an increase in the amount of feedstock. For both cases, the pressure and hydrogen flow were minimised. Both types of accelerated deactivations had similar effects on the quality of the final products and catalyst. The only difference was in the duration of catalyst recovery after deactivation. The results were compared with those of a test in which the spontaneous deactivation of the catalyst was studied.
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.
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