Reaction pathways for the HDO of guaiacol over supported Pd catalysts: Effect of support type in the deoxygenation of hydroxyl and methoxy groups

The effect of support type (SiO2, CeO2, ZrO2, TiO2, Nb2O5) on the removal of the different oxygenated functional groups (hydroxyl and methoxy) was investigated in the hydrodeoxygenation (HDO) of guaiacol over supported Pd catalysts at 573 K and atmospheric pressure. The product distribution depended on the support type, and three main reaction pathways were proposed: demethoxylation, demethylation and dehydroxylation. Demethoxylation yielding phenol was the dominant reaction pathway over all catalysts with only a minor contribution from the demethylation reaction taking place. However, significant dehydroxylation reaction was still observed for the catalysts having Pd supported on ZrO2, TiO2 and Nb2O5. Further conversion of phenol to cylohexanone was favored over SiO2 and CeO2-based catalysts, while benzene was only detected over ZrO2, TiO2 and Nb2O5, which is due to the presence of oxophilic cations. DRIFTS measurements were carried out to evaluate the adsorption mode and strength of guaiacol on the catalyst surface. The functional groups involved in adsorption of guaiacol included both hydroxyl and methoxy groups. At the reaction conditions, the hydroxyl group is strongly adsorbed to the catalyst surface and may block the catalytic sites, thus inhibiting further conversion of phenol and resulting in lower deoxygenation rates.