Influence of pH on the wet oxidation of phenol with copper catalyst

This work reports the influence of pH on the catalytic wet oxidation (CWO) of phenol performed with a commercial copper-based catalyst. The results obtained show that pH is a critical parameter able to modify the chemical stability of the catalyst, the significance of the oxidation reaction in the liquid phase, the reaction mechanism and, consequently, the oxidation route of phenol. Experiments have been carried out to study the mentioned aspects. Stirred basket and fixed bed reactors (FBRs) have been employed, at 140 °C and at 16 bar of oxygen pressure. Three initial pH values have been used: 6 (the pH of the phenol solution), 3.5 (adjusted by H2SO4) and 8 (by addition of Na2CO3). Furthermore, some phenol oxidation runs without solid catalyst but with different concentrations of copper in solution have been accomplish at pHo=3.5. At acid pH, important leaching of copper from the catalyst to the solution was achieved, finding this negligible at pH 8. It was found that the major contribution to the phenol conversion reached at acid pH by using the solid catalyst was due to the catalytic activity of the leached copper. Both oxidation mechanisms at acid and basic conditions have been elucidated to explain the differences in the type and distribution of the intermediates obtained. The catalytic phenol oxidation route found at pH=8 comprises intermediates less toxic than phenol while at acid pH the cyclic intermediates formed as first oxidation intermediates are far more toxic than phenol.