Application of liquid organic hydrogen carriers, such as “methylcyclohexane (MCH)–toluene” chemical couple, is one of the promising approaches for hydrogen storage and transportation. In the present study, copper-modified nickel catalysts with high metal loading of 75 wt% were synthesized via heterophase sol–gel technique, and investigated in the dehydrogenation of MCH. Two approaches towards the copper introduction were applied. The catalyst samples prepared via wetness impregnation of the nickel sol–gel catalyst are characterized by more effective Ni-Cu interaction compared to those where two metals were introduced simultaneously by the mixing of their solid precursors. As a result, the “impregnated” catalysts revealed higher selectivity towards toluene. The addition of copper up to 30 wt% of total metal content was shown to increase significantly toluene selectivity and yield without a noticeable decrease in MCH conversion. The catalyst with the active component including 80 wt% of Ni and 20 wt% of Cu demonstrated 96% and 89% toluene selectivity at 40% and 80% MCH conversion, respectively. Based on the obtained data, this non-noble catalytic system appears quite promising for the MCH dehydrogenation.
The high-energy potential of wastewater sewage sludge (SS) produced in large amounts around the world makes it an attractive feedstock for fuels and energy sectors. Thermochemical valorization relying on pyrolysis of SS followed by hydrotreatment of pyrolysis oil (Py-SS) might even allow the integration of SS into existing oil refineries. In the present study, catalytic hydrotreatment of Py-SS was performed over a NiCuMo-P-SiO2 catalyst in a batch reactor at temperatures in the range of 200–390 °C. Due to sulfur presence in the feed, the increasing reaction temperature induced in situ transformation of metallic Ni into Ni3S2 in the catalyst. In contrast, the Ni3P active phase possessed remarkable stability even at the harshest reaction conditions. The oxygen content in the reaction products was decreased by 59%, while up to 52% of N and 89% of S were removed at 390 °C. The content of free fatty acids was greatly reduced by their conversion to n-alkanes, while the larger amount of volatile aromatics was generated from high molecular mass compounds. The quality of oil-derived products greatly changed at elevated temperatures, providing strong evidence of effective upgrading via decarboxy(ny)lation, hydrogenation, and hydrocracking transformations.
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