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双金属铜-钯催化剂催化糠醛转移加氢制备 2-甲基呋喃和 2-甲基四氢呋喃。

Catalytic Transfer Hydrogenation of Furfural to 2-Methylfuran and 2-Methyltetrahydrofuran over Bimetallic Copper-Palladium Catalysts.

机构信息

Department of Chemical Engineering, Nanjing Forestry University, Longpan Road, Nanjing, China.

出版信息

ChemSusChem. 2016 Dec 8;9(23):3330-3337. doi: 10.1002/cssc.201601122. Epub 2016 Nov 9.

Abstract

The catalytic transfer hydrogenation of furfural to the fuel additives 2-methylfuran (2-MF) and 2-methyltetrahydrofuran (2-MTHF) was investigated over various bimetallic catalysts in the presence of the hydrogen donor 2-propanol. Of all the as-prepared catalysts, bimetallic Cu-Pd catalysts showed the highest catalytic activities towards the formation of 2-MF and 2-MTHF with a total yield of up to 83.9 % yield at 220 °C in 4 h. By modifying the Pd ratios in the Cu-Pd catalyst, 2-MF or 2-MTHF could be obtained selectively as the prevailing product. The other reaction conditions also had a great influence on the product distribution. Mechanistic studies by reaction monitoring and intermediate conversion revealed that the reaction proceeded mainly through the hydrogenation of furfural to furfuryl alcohol, which was followed by deoxygenation to 2-MF in parallel to deoxygenation/ring hydrogenation to 2-MTHF. Finally, the catalyst showed a high reactivity and stability in five catalyst recycling runs, which represents a significant step forward toward the catalytic transfer hydrogenation of furfural.

摘要

研究了在氢气供体 2-丙醇存在下,各种双金属催化剂对糠醛催化转移氢化生成燃料添加剂 2-甲基呋喃(2-MF)和 2-甲基四氢呋喃(2-MTHF)的催化性能。在所制备的所有催化剂中,双金属 Cu-Pd 催化剂在 220°C 下 4 h 内对 2-MF 和 2-MTHF 的总收率高达 83.9%,表现出最高的催化活性。通过改变 Cu-Pd 催化剂中的 Pd 比例,可以选择性地得到 2-MF 或 2-MTHF 作为主要产物。其他反应条件对产物分布也有很大影响。通过反应监测和中间转化的机理研究表明,反应主要通过糠醛加氢生成糠醇进行,同时平行进行脱氧生成 2-MF,以及脱氧/环加氢生成 2-MTHF。最后,该催化剂在五次催化剂循环回收实验中表现出高的反应活性和稳定性,这是糠醛催化转移氢化的一个重要进展。

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