Copper- and iron-pillared clay catalysts for the WHPCO of model and real wastewater streams from olive oil milling production

The properties of copper-based pillared clays (Cu-PILC) have been studied and compared with those of the analogous iron-based clays (Fe-PILC) in the wet hydrogen peroxide catalytic oxidation (WHPCO) of model phenolic compounds (p-coumaric and p-hydroxybenzoic acids) and real olive oil milling wastewater (OMW). These two catalysts show comparable performances in all these reactions, although they show some differences in the rates of the various steps of reaction. In particular, Cu-PILC shows a lower formation of oxalic acid (main reaction intermediate) with respect to Fe-PILC. Both catalysts show no leaching of the transition metal differently from other copper-based catalysts prepared by wetness impregnation on oxides (alumina, zirconia) or ion-exchange of clays (bentonite) or zeolite ZSM-5. No relationship was observed between copper reducibility in the catalyst and the performance in WHPCO, as well as between the rate of copper leaching and catalytic behavior. Cu-PILC shows a comparable activity to dissolved Cu2+ ions, although the turnover number is lower assuming that all copper ions in Cu-PILC are active. Cu-PILC shows a high resistance to leaching and a good catalytic performance, which was attributed to the presence of copper essentially in the pillars of the clay. A high efficiency in H2O2 use in the first hour of reaction with the participation of dissolved O2 in solution was also shown. For longer reaction times, however, the efficiency of H2O2 use considerably decreases.