Study of the Hydrodeoxygenation of Carbonyl, Carboxylic and Guaiacyl Groups Over Sulfided Como/gamma-al2o3 and Nimo/gamma-al2o3 Catalysts .1. Catalytic Reaction Schemes
Study of the Hydrodeoxygenation of Carbonyl, Carboxylic and Guaiacyl Groups Over Sulfided Como/gamma-al2o3 and Nimo/gamma-al2o3 Catalysts .1. Catalytic Reaction Schemes
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DOI：
10.1016/0926-860x(94)85004-6
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发表时间：
1994-02
影响因子：
5.5
通讯作者：
E. Laurent;B. Delmon
中科院分区：
文献类型：
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作者：
E. Laurent;B. Delmon
消除生物质衍生的热解油（生物油）的特定含氧基团对于提高其稳定性是必要的。这些主要是不饱和基团，如烯烃、羰基和羧基官能团，以及愈创木基基团。对于实际应用，希望选择性地进行反应以避免过量的氢气消耗。该反应必须在相对较低的温度下进行，以限制竞争性热缩合反应。在这项研究中，使用了模型含氧化合物，即 4-甲基苯乙酮、癸二酸二乙酯和愈创木酚。在间歇系统中，在γ-氧化铝催化剂负载的硫化钴-钼和镍-钼存在下，在一项反应测试中同时对它们进行了测试。确定了它们的反应性和转化方案。酮基在高于200℃的温度下容易且选择性地氢化成亚甲基。羧基也被氢化为甲基，但平行的脱羧反应以相当的速率发生。芳基基团的转化以及愈创木基基团的转化需要约 300°C 的温度。愈创木酚的主要反应方案是转化为羟基苯酚，随后再转化为苯酚。但在间歇式反应器条件下，愈创木酚产生高比例的重产物。 CoMo 和 NiMo 催化剂具有相当的活性和选择性。然而，NiMo 催化剂具有比 CoMo 更高的脱羧活性，并且在愈创木酚转化过程中也会导致更高比例的重产物。
The elimination of specific oxygenated groups of biomass-derived pyrolysis oils (bio-oils) is necessary for improving their stability. These are mainly unsaturated groups like alkene, carbonyl and car☐ylic functions, as well as guaiacyl groups. For practical applications, it is desirable that the reactions are performed selectively in order to avoid excessive hydrogen consumption. The reactions must be done at relatively low temperature in order to limit competitive thermal condensation reactions. In this study, model oxygenated compounds were used, namely 4-methylacetophenone, diethyldecanedioate and guaiacol. They were tested simultaneously in one reaction test in the presence of sulfided cobalt-molybdenum and nickel-molybdenum supported on γ-alumina catalysts in a batch system. Their reactivity and conversion scheme were determined. The ketonic group is easily and selectively hydrogenated into a methylene group at temperatures higher than 200°C. Car☐ylic groups are also hydrogenated to methyl groups, but a parallel decar☐ylation occurs at comparable rates. A temperature around 300°C is required for the conversion of car☐ylic groups as well as for the conversion of the guaiacyl groups. The main reaction scheme of guaiacol is its transformation in hydroxyphenol which is subsequently converted to phenol. But in batch reactor conditions, guaiacol gives a high proportion of heavy products. CoMo and NiMo catalysts have comparable activities and selectivities. However, the NiMo catalyst has a higher decar☐ylating activity than CoMo and also leads to a higher proportion of heavy products during the conversion of guaiacol.