Trapping AsPh3 via reaction with NiS/gamma-Al2O3 in the presence of H-2: Reaction mechanism and kinetics

Removal of As from petroleum feedstocks is an important process which can be realized using As trapping mass containing supported nickel sulfide. In order to understand the mechanism of the trapping we studied the reaction of AsPh3 with NiS/gamma-Al2O3 in the presence of H-2 in a batch reactor in toluene solution at 230 degrees C. This reaction results in formation of NiAs, benzene and H2S. Also, the intermediate species, thiophenol and diphenylsulfide, were observed. Despite formation of NiAs layer in the course of reaction, the rate of AsPh3 decomposition is not affected by the solid state diffusion up to similar to 50 % of nickel conversion. The rate determining step in these conditions appears to be the hydrogenolysis of As-C bonds. It was found that the reaction order changes in the course of reaction from zero to one. This trend is described by a kinetic model assuming adsorption of AsPh3 molecules followed by decomposition.