Journal of Catalysis, Vol.150, No.1, 199-211, 1994
Direct Oxidation of L-Sorbose to 2-Keto-L-Gulonic Acid with Molecular-Oxygen on Platinum-Based and Palladium-Based Catalysts
The selective oxidation of the C1 hydroxyl group of L-sorbose to a carboxylic group without protection of the four other hydroxyl functions was investigated. The reactions were performed in slightly alkaline aqueous solutions with molecular oxygen over various alumina- and carbon-supported Pt and Pd catalysts. Optimum reaction conditions were 50 degrees C, pH 7.3, and a catalyst:reactant ratio of 1:4 (wt/wt). The lower the pH and the temperature, the higher the selectivity toward 2-keto-L-gulonic acid. Catalyst deactivation was also found to increase with lower pH and temperature. A 5 wt% Pt/alumina catalyst showed the best catalytic performance (67% selectivity at 58% conversion). Promotion with Pi or Pb had a detrimental effect on selectivity for 2-keto-L-gulonic acid. Electrochemical measurements indicated that the reaction occurs in a rather narrow potential range, which corresponds to a moderate oxygen coverage of Pt or Pd. Four types of catalyst deactivation processes were identified, based on XPS and ICP-AES analysis and on the in situ determination of the oxidation state by monitoring the catalyst potential during reaction. A significant chemical poisoning of the active noble metal sites occurred during the initial, destructive adsorption of L-sorbose and during the oxidation reaction. The successive contamination of active sites resulted in overoxidation (too high oxygen coverage of Pt or Pd). The partially oxidized promoters and noble metals were corroded and dissolved in the presence of 2-keto-L-gulonic acid, resulting in an irreversible deactivation.
Keywords:LIQUID-PHASE OXIDATION;LEAD-MODIFIED PLATINUM;D-GLUCONIC ACID;SELECTIVE OXIDATION;SUPPORTED PLATINUM;ORGANIC-MOLECULES;CARBON CATALYSTS;ALDONIC ACIDS;DEACTIVATION;ELECTRODES