Fast pyrolysis bio-oil is very difficult to be used because of its acidity, instability, high degree of unsaturation, etc. Processes for property upgrading are necessary and required. In this study, three kinds of Raney Ni catalysts were prepared and used to investigate two-step esterification–hydrogenation (TEH) to upgrade the light fraction of bio-oil. The results show that the first step in esterification markedly decreased the content of active compounds such as acids and ketones and aldehydes and increased the content of alcohols and esters (from 10.53% to 47.55%), which improved the bio-oil stability and was favorable for the following hydrogenation reaction. The second step of TEH (hydrogenation) further improved the quality of the bio-oil over Raney Ni and metal-modified Raney Ni catalysts at 140 °C. In particular, the Mo-RN catalyst displayed the best hydrogenation effect, with only 5.44% of acid content, and the stable component content reached 90.16%. This may be attributed to the higher hydrogenation activity from Raney Ni combined with acid MoOx species and the thermal stability of the catalyst. Moreover, the obtained upgraded bio-oil mixture could be used as a solvent for raw bio-oil’s esterification. Therefore, it has the potential to reduce methanol solvent usage and energy consumption for solvent separation during the two-step treatment of raw bio-oil in this context. Compared with the OHE (one-step esterification-hydrogenation) process, THE showed a better performance for raw bio-oil upgrading with higher alcohols and stable compounds, which is more favorable for the saturation and stability of bio-oil’s complex components step by step.
Two-Step Esterification–Hydrogenation of Bio-Oil to Alcohols and Esters over Raney Ni Catalysts