Catalyst Deactivation and Reactor Fouling during Hydrogenation of Conjugated Cyclic Olefins over a Commercial Ni–Mo–S/γ-Al2O3 Catalyst

The dimerization of conjugated cyclic olefins during hydrogenation at low temperatures (≤250 °C) on a spent commercial Ni–Mo–S/γ-Al2O3 catalyst is reported. Hydrogenation of 4-methylstyrene versus α-methylstyrene showed that the methyl group attached to the vinyl group of α-methylstyrene decreased the dimer yield as a result of steric hindrance, while the yield of hydrogenated products remained high. The addition of 20 wt % cyclohexene to 4-methylstyrene and reaction at a lower temperature (200 versus 250 °C) decreased the 4-methylstyrene hydrogenation rate. An increased concentration of 4-methylstyrene and a lower reaction temperature increased dimer and gum yields. The data indicate that dimers are precursors to gum formation and that catalyst deactivation is linked to gum formation that results in an increased carbon content and a decreased Brunauer–Emmett–Teller surface area of the used catalyst. Furthermore, an increase in pressure drop across the fixed-bed reactor with time on stream (TOS) observed with 4-methylstyrene as the reactant but not with α-methylstyrene is consistent with cumulative gum deposition in the catalyst bed. The pressure drop is well-described by the Ergun equation, assuming that gum deposition reduces bed voidage with TOS.