Acetonitrile Synthesis via Ammoxidation: Mo/zeolites Catalysts Screening

Abstract

Mo/zeolites catalysts were investigated in ethane and ethylene ammoxidation into acetonitrile. The catalysts were prepared either in solid‒solid or liquid‒solid interface after varying different parameters. The stabilization of Mo species upon the exchange is dependent on the hydrophilic/hydrophobic character of the zeolite and the type of Mo precursor. In fact, zeolites with low Si/Al molar ratios should be avoided due to their higher dehydration enthalpy values (Δdehyd.H). On the other hand, the use of MoOCl4, Mo(CO)6 and MoCl3 precursors and zeolites with high Si/Al ratios led to inefficient [Mo7O24]6‒ species and amorphous MoO3 which catalyzes the combustion reaction. Nevertheless, the use of MoCl5, MoO3 and MoO2(C5H7O2)2 led to promising activities. In catalysis, [MoO4]2‒ species are required to activate C2H6 into C2H4, while [MoxO3x+1]2‒ (x =1, 2) species catalyze the ammoniation of C2H4 and the ethylamine dehydrogenation into CH3CN. Interestingly, active catalysts could be obtained by humid impregnation and a simultaneous oxidative treatment. Such a treatment improves the dispersion state of crystalline MoO3, which activate ethane molecules. It is judicious to perform C2H6 oxidative dehydrogenation before ammoxidation since the interference between the different investigated parameters could be noted.