CO2 Reforming of CH4 Using Coke Oven Gas over Ni/MgO-Al2O3 Catalysts: Effect of the MgO:Al2O3 Ratio

Research is being actively conducted to improve the carbon deposition and sintering resistance of Ni-based catalysts. Among them, the Al2O3-supported Ni catalyst has been broadly studied for the dry reforming reaction due to its high CH4 activity at the beginning of the reaction. However, there is a problem of deactivation due to carbon deposition of Ni/Al2O3 catalyst and sintering of Ni, which is a catalytically active material. Supplementing MgO in Ni/Al2O3 catalyst can result in an improved MgAl2O4 spinel structure and basicity, which can be helpful for the activation of methane and carbon dioxide molecules. In order to confirm the optimal supports’ ratio in Ni/MgO-Al2O3 catalysts, the catalysts were prepared by supporting Ni after controlling the MgO:Al2O3 ratio stepwise, and the prepared catalysts were used for CO2 reforming of CH4 (CDR) using coke oven gas (COG). The catalytic reaction was conducted at 800 °C and at a high gas hourly space velocity (GHSV = 1,500,000 h−1) to screen the catalytic performance. The Ni/MgO-Al2O3 (MgO:Al2O3 = 3:7) catalyst showed the best catalytic performance between prepared catalysts. From this study, the ratio of MgO:Al2O3 was confirmed to affect not only the basicity of the catalyst but also the dispersion of the catalyst and the reducing property of the catalyst surface.

The Synthesis of Renewable Hydrocarbons from Different Vegetable Oils and Soapstock by Hydrotreatment over High Metal Loading Supported Ni Catalyst

The catalytic hydrotreatment of sunflower (SO), linseed (LO), coconut (CO), rapeseed (RO), and its soapstock derived acid oil (RS) over commercial Ni65%/SiO2-Al2O3 catalyst was investigated to evaluate utilization feasibility of various vegetable oil feedstocks with different fatty acid content, composition, and saturation for marketable hydrocarbon production. The active metal loading of catalyst was characterized by XRF and its textural properties by N2 sorption analysis. The hydrotreatment tests of different vegetable oils were carried out in solvent free medium, under initial H2 pressure 10 MPa, at operating temperature 340 oC, and residence time 15 min using catalyst amount 5%. GC-FID and GC-MS analysis were used for estimation of dominant n-pentadecane, n-hexadecane, n-heptadecane, n-octadecane, and other hydrocarbon contents in obtained samples. Under studied hydrotreatment conditions complete conversion of different vegetable oils into marketable liquid renewable hydrocarbons without presence of oxygen containing substances was achieved. Highly active Ni65%/SiO2-Al2O3 has remarkable selectivity to hydrocarbons produced by reaction pathways, where elimination of carbonyl groups occurs. The saturation of fatty acids in feedstock determines H2 consumption, but influence on produced hydrocarbon production is insignificant. Depending on the fatty acid composition different saturated linear hydrocarbons with wide range of carbon chain length C5-C19 and similar calorific value 47.16-47.34 MJ/kg were produced in process. Overall liquid hydrocarbon yields were from 44.6 % to 78.1 %. The highest overall liquid saturated linear hydrocarbon yield was observed for feedstock with high amount of long chain fatty acids – SO, LO, RO and RS. Pure hydrocarbons obtained from vegetable oils depending on hydrocarbon composition can be used in various areas.

Optimizing MgO Content for Boosting g-Al2O3-Supported Ni Catalyst in Dry Reforming of Methane

The dry reforming of methane (DRM) process has attracted research interest because of its ability to mitigate the detrimental impacts of greenhouse gases such as methane (CH4) and carbon dioxide (CO2) and produce alcohols and clean fuel. In view of this importance of DRM, we disclosed the efficiency of a new nickel-based catalyst, which was promoted with magnesia (MgO) and supported over gamma-alumina (g-Al2O3) doped with silica (SiO2), toward DRM. The synthesized catalysts were characterized by H2 temperature-programmed reduction (H2-TPR), X-ray diffraction (XRD), X-ray Photoelectron Spectroscopy (XPS), Thermogravimetric analysis (TGA), and Transmission electron microscopy (TEM) techniques. The effect of MgO weight percent loading (0.0, 1.0, 2.0, and 3.0 wt. %) was examined because the catalytic performance was found to be a function of this parameter. An optimum loading of 2.0 wt. % of MgO was obtained, where the conversion of CH4 and CO2 at 800 °C were 86% and 91%, respectively, while the syngas (H2/CO) ratios relied on temperature and were in the range of 0.85 to 0.95. The TGA measurement of the best catalyst, which was operated over a 15-hour reaction time, displayed negligible weight loss (<9.0 wt. %) due to carbon deposition, indicating the good resistance of our catalyst system to the deposition of carbon owing to the dopant and the modifier. TEM images showed the presence of multiwalled carbon nanotubes, confirming the TGA.

Well-Dispersed MgAl2O4 Supported Ni Catalyst with Enhanced Catalytic Performance and the Reason of Its Deactivation for Long-Term Dry Methanation Reaction

Dry methanation of syngas is a promising route for synthetic natural gas production because of its water and cost saving characteristics, as we reported previously. Here, we report a simple soaking process for the preparation of well-dispersed Ni/MgAl2O4-E catalyst with an average Ni size of 6.4 nm. The catalytic test results showed that the Ni/MgAl2O4-E catalyst exhibited considerably higher activity and better stability than Ni/MgAl2O4-W catalyst prepared by conventional incipient wetness impregnation method in dry methanation reaction. The long-term stability test result of 335 h has demonstrated that the deactivation of the Ni/MgAl2O4-E catalyst is inevitable. With multiple characterization techniques including ICP, EDS, XRD, STEM, TEM, SEM and TG, we reveal that the graphitic carbon encapsulating Ni nanoparticles are the major reasons responsible for catalyst deactivation, and the rate of carbon deposition decreases with reaction time.