Catalytic hydrotreatment of fast-pyrolysis oil using non-sulfided bimetallic Ni-Cu catalysts on a 未-Al₂O₃ support

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• 作者：A.R. Ardiyanti^a ; S.A. Khromova^b ; R.H. Venderbosch^c ; V.A. Yakovlev^b ; H.J. Heeres^a ; ^{h.j.heeres@rug.nl}
• 关键词：Hydrotreatment ; Hydrodeoxygenation ; Fast pyrolysis oil ; Bio-oil ; Anisole ; Nickel catalyst ; Characterization ; Bimetallic nickel-copper catalysts
• 刊名：Applied Catalysis B ; Environmental
• 出版年：2012
• 期刊代码：4_09263373
• 类别：ce
• 出版时间：18 May, 2012
• 卷：117-118
• 期：Complete
• 页码：105-117
• 文件大小：1707 K

摘要

Fast pyrolysis oil from lignocellulosic biomass is an attractive energy carrier. However, to improve the product characteristics such as a reduced polarity and higher thermal stability, upgrading is required. We here report activities on the catalytic hydrotreatment of fast pyrolysis oil using bimetallic NiCu/未-Al₂O₃ catalysts with various Ni/Cu ratios (0.32 to 8.1 w/w) at a fixed total metal intake of about 20 wt%with the objective to improve product properties for co-feeding applications in conventional oil refineries. Hydrotreatment reactions were initially carried out for a model compound (anisole, continuous set-up, 300 掳C, 10 bar) and subsequently for fast pyrolysis oil (batch autoclave, 1 h at 150 掳C followed by 3 h at 350 掳C, at 100 bar initial pressure). Best results, i.e. the highest hydrodeoxygenation yield for experiments with anisole (75 mol%), and an upgraded oil with the most favorable properties for fast pyrolysis oil (high H/C ratio, low M_w of 500 g/mol, low thermogravimetric residue of 6.8 wt%), were obtained for a catalyst with a Ni to Cu wt%ratio of eight (16Ni2Cu). For this catalyst, hydrogen consumption was the highest (146 NL/kg_PO). The findings were rationalized using a reaction network model earlier developed for Ru/C. Analysis of catalyst (ICP, HRTEM, XRD and TGA) before and after reaction showed the occurrence of leaching of both active metals (Ni and Cu) and support, as well as coke deposition on the support. The most active catalyst in the series (16Ni2Cu) also gave lowest leaching and coking levels in the series.