Catalytic hydrodeoxygenation (HDO) of phenol over supported molybdenum carbide, nitride, phosphide and oxide catalysts

• Synthesis of TiO2 supported carbide, nitride and phosphide catalysts.
• Catalysts were active for phenol HDO with promising selectivity.
• The 15 wt% Mo2C/TiO2 showed the highest activity (crystals 10–30 nm).
• Moderate deactivation was observed (15 wt% Mo2C/TiO2 during 400 min.).
• Supported MoP showed the highest hydrogenation activity.

The performance of titania-supported molybdenum carbide, nitride, phosphide and oxide catalysts was compared for catalytic hydrodeoxygenation (HDO) of phenol. Phenol was selected as a stable model component for lignin degradation products in fast pyrolysis bio-oil. The synthesis and formation path of the materials was evaluated by the use of complementary characterization techniques (XRD, TPR and TGA–MS). All the catalysts showed promising catalytic performance during testing in a fixed-bed reactor set-up at a temperature of 350 °C and total pressure of 25 bar, and the highest activity was achieved with 15 wt% Mo2C/TiO2. A high selectivity towards benzene was observed with all catalysts. MoP supported on TiO2 showed the strongest tendency to aromatic ring hydrogenation and also a significant selectivity (10% level) towards methylcyclopentane, indicating contributions of acidic surface chemistry. Thus, Mo based materials are active and promising materials for establishing selectivity control in HDO of bio-oils.

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