Sulfur-Tolerant Molybdenum Carbide Catalysts Enabling Low-Temperature Stabilization of Fast Pyrolysis Bio-oil

Low-temperature hydrogenation of carbonyl compounds can greatly improve the thermal stability of fast pyrolysis bio-oil, thereby enabling long-term operation of upgrading reactors which generally require high temperatures to achieve deep deoxygenation. The state-of-the-art hydrogenation catalysts, precious metals such as ruthenium, although effective in carbonyl hydrogenation, deactivate due to high sulfur sensitivity. In the present work, we showed that molybdenum carbides were active and sulfur-tolerant in low-temperature conversion of carbonyl compounds. Furthermore, due to surface bifunctionality (i.e., both metallic and acid sites present), carbides catalyzed both Cî»O bond hydrogenation and C-C coupling reactions. Combined, these reactions transformed carbonyl compounds to more stable and higher molecular weight oligomeric compounds while consuming less hydrogen than pure hydrogenation. The carbides proved to be resistant to other deactivation mechanisms including hydrothermal aging, oxidation, coking, and leaching. These properties enabled carbides to achieve and maintain good catalytic performance in both aqueous-phase furfural conversion and real bio-oil stabilization in the presence of sulfur. This finding strongly suggests that molybdenum carbides can provide a catalyst solution necessary for the development of practical bio-oil stabilization technology.