Mineral Montmorillonite Valorization by Developing Ni and Mo-Ni Catalysts for Third-Generation Green Diesel Production.

Four Ni catalysts and one Mo-Ni catalyst supported on montmorillonite were synthesized, characterized by various techniques and evaluated, under solvent-free conditions, for the production of green diesel from waste cooking oil. The optimum Ni content was found to be 20 wt.%. The addition of 2 wt.% Mo to the catalyst resulted in a considerable increase in the amount of green diesel hydrocarbons. The Mo species, moreover, led to a decrease in the (C15 + C17)/(C16 + C18) ratio, which is beneficial from the viewpoint of carbon atom economy. The promoting action of Mo was mainly attributed to the synergy between the oxygen vacancies on the surface of the well-dispersed Mo(V) and Mo(VI) oxides and the neighboring Ni sites. The optimum reaction conditions, for achieving a proportion of liquid product in the green diesel hydrocarbons (C15-18) equal to 96 wt.%, were found to be 350 °C, 3 g of catalyst per 100 mL of waste cooking oil and 13 h reaction time. These conditions correspond to an LHSV of 2.5 h, a value that is considered quite reliable from the viewpoint of industrial applications. Thus, the cheap and abundant mineral montmorillonite is proved a promising support for developing efficient Ni-Mo catalysts for green diesel production.