Ni-Based Catalysts for the Hydrotreatment of Fast Pyrolysis Oil

• Published in: Energy & fuels 2016-03, Vol.30 (3), p.1544-1554
• Main Authors: Ardiyanti, A. R, Bykova, M. V, Khromova, S. A, Yin, W, Venderbosch, R. H, Yakovlev, V. A, Heeres, H. J
• Format: Article
• Language: English
• ISSN: 0887-0624; 1520-5029
• DOI: 10.1021/acs.energyfuels.5b02223

Catalytic hydrotreatment is an attractive technology to convert fast pyrolysis oil to stabilized oil products for co-processing in conventional crude oil refinery units. We report here the use of novel bimetallic NiCu- and NiPd-based (Picula) catalysts characterized by a high Ni content (29–58 wt %) and prepared using a sol–gel method with SiO2, La2O3, kaolin, ZrO2, and combinations thereof as the support, for the catalytic hydrotreatment of fast pyrolysis oil. The experiments were performed in a batch autoclave (1 h at 150 °C, 3 h at 350 °C, and 200 bar initial pressure at 350 °C). The catalyst with the highest nickel loading (58 wt % Ni) promoted with Pd (0.7 wt %) was the most active, yielding oil products with improved properties compared to the crude pyrolysis oil (lower oxygen content, higher solubility in hydrocarbons, and less tendency for coke formation). For all Picula catalysts, except the ZrO2-based catalysts, methane formation was considerably lower than for Ru/C, the benchmark catalyst in catalytic hydrotreatment of fast pyrolysis oil. To anticipate possible catalyst deactivation at very long times on stream, catalyst regeneration studies were performed using thermogravimetric analysis. Analyses of the regenerated catalysts (X-ray diffraction, high-resolution transmission electron microscopy, and Brunauer–Emmett–Teller surface area) showed the occurrence of active metal agglomeration.