Poisoning and Reuse of Supported Precious Metal Catalysts in the Hydrogenation of <i>N</i>-Heterocycles, Part II: Hydrogenation of 1-Methylpyrrole over Rhodium

Abstract

Poisoning effect of nitrogen on heterogeneous, supported precious metal catalysts, along with their recycling, was further examined in the liquid-phase hydrogenation of 1-methylpyrrole (MP) to 1-methylpyrrolidine (MPD) over rhodium on carbon or γ-alumina, in methanol, under non-acidic conditions, at 25–50 °C and 10 bar. Reusing a spent, unregenerated 5% Rh/C or 5% Rh/γ-Al2O3 catalyst, it was found that the conversion of this model substrate and the activity of the catalyst were strongly dependent on the amount of catalyst, the type of support, the catalyst pre- or after-treatment, the temperature, and the number of recycling, respectively. An unexpected catalytic behaviour of rhodium was observed when it was used in a prehydrogenated form, because no complete conversion of MP was achieved over even the fresh Rh/C or Rh/γ-Al2O3, contrary to the untreated one. In addition, there was a significant difference in the reusability and activity of these rhodium catalysts, depending on their supports (activated carbon, γ-alumina). These diversions were elucidated by applying dispersion (O2- and H2-titration), temperature-programmed desorption of ammonia (NH3-TPD), and transmission electron microscopy (TEM) measurements.

Keywords

• hydrogenation
• poisoning
• reusing
• rhodium
• pyrroles
• pyrrolidines