Published online by Cambridge University Press: 10 February 2011
A series of γ-Al2O3 and SiO2 supported tungsten carbides was synthesized by the temperature programmed reaction of supported tungstates with CH4/H2 mixtures. The three known phases, W2C, WC and WC1−x, were evaluated as butane dehydrogenation catalysts. The microstructure and composition of the supported carbides depended on the loading and final synthesis temperature. The low and medium loaded materials were x-ray amorphous suggesting highly dispersed carbide domains on the support. The high loaded materials possessed small crystallites of W2C, WC or WC1-x. The supported carbides were as active as a commercial dehydrogenation catalyst with comparable selectivities in several cases. The butane conversion activity decreased in the following order: W2C > WC > WC1-x. The dehydrogenation selectivity decreased as the activity increased. The results suggest that there were two different types of sites, those catalyzing the selective dehydrogenation of butane and those capable of butane hydrogenolysis. The activity of these latter sites declined significantly with time on stream. We believe the hydrogenolysis activity was due to acid sites on the supported carbides.