An Fe19.2K0.2/gamma-Al2O3 catalyst for the catalytic amination of glycerol to propionitrile was prepared. Acetonitrile as a major product was obtained over this catalyst from the amination of glycerol. Additionally, propionitrile, ethylene and propylene were also obtained. The parameters influencing the catalyst performance were studied thoroughly, and an optimised process for the amination of glycerol to acetonitrile and propionitrile over the catalyst was obtained. Under the optimised conditions, which were a reaction temperature of 525 degrees C, an atmospheric pressure with an ammonia/glycerol molar ratio of 8:1 and GHSV of 1338 h(-1), the total yield of acetonitrile and propionitrile was 58.4%, and the converted amount of glycerol over one gram of catalyst reached 0.42 g h(-1). The catalyst was characterised by XRD, XPS, TEM and IR of the adsorbed pyridine. The characterisation results indicated that the dehydration reaction in the tandem reaction mainly occurred on the Lewis acid sites and revealed that both Fe2O3 and Fe3O4 are active species for the dehydrogenation of imines to nitriles, but the former is more active than the latter. It also revealed that the catalyst deactivation was due to carbon deposits, the transformation of Fe2O3 to the Fe3O4 phase, as well as agglomeration of the Fe2O3 or Fe3O4 phase during the catalytic run and regeneration process. (C) 2014 Elsevier Inc. All rights reserved.