Hydroconversion of Lignin-Derived Platform Compound Guaiacol to Fuel Additives and Value-Added Chemicals over Alumina-Supported Ni Catalysts

Hydroconversion of guaiacol (GUA) over gamma-Al2O3 and phosphatized-gamma-Al2O3 (gamma-Al2O3(P)) supported Ni catalysts was initiated by Lewis-sites and active Ni sites. Conversion proceeded via transmethylation and hydrodemethylation/hydrodemethoxylation as major and minor pathways, respectively, resulting in mainly catechol and methylcatechols, and via series of consecutive hydrodehydroxylation (HDHY) and ring hydrogenation (HYD) reactions leading to partially and fully deoxygenated, saturated, and unsaturated products. High Ni-loading and high H2 pressure promoted the formation of cyclohexane and methyl-substituted cyclohexanes; however, above 300 degrees C the hydrogenation-dehydrogenation equilibrium favored the formation of benzene and methylsubstituted benzenes. Ni/gamma-Al2O3(P) showed suppressed HYD/HDHY activity resulting in pronounced formation of catechol and/or phenol and their methyl-substituted derivatives. Surface phenolate species were substantiated as surface intermediates of hydrodeoxygenation. Phosphatizing reduced the concentration of both basic OH and Lewis acid (Al+) - Lewis base (O-) pair surface sites of the gamma-Al2O3 support and, thereby, suppressed phenolate formation and hydrodeoxgenation.