酚类衍生物制备液体燃料的研究

傅尧 肖睿 黄耀兵

摘 要：生物质酚类衍生物经过催化加氢生成饱和烷基醇类化合物含氧燃料或者继续进行增碳后再加氢脱氧制备饱和烷烃液体燃料。该研究从木质素酚类衍生物出发，发展了两类非均相钌系金属催化剂，实现了酚类加氢饱和和选择性断裂C-O键的过程。主要研究工作如下：（1）发展了钌系金属催化的氢转移体系，采用异丙醇作为氢转移溶剂，在较为温和的条件下实现了酚类混合物全组分转化为饱和醇类化合物。研究了金属中心、氢转移溶剂和反应温度等参数对反应的影响，掌握了氢转移反应的特点和规律；（2）以苯酚和愈创木酚为模型物，采用复合碱性载体负载的钌催化剂实现了酚类化合物C-O选择性断裂，获得一系列饱和烷基醇类底物。通过对催化剂的表征和反应中间体的捕捉，证实了反应经历芳环加氢——甲氧基脱除的反应历程。此外，采用碱催化的缩合反应实现了从烷基醇的自身偶联增碳反应，提高了底物的碳原子数，获得高碳液体燃料的前体，经过进一步加氢脱氧获得了C12以上的烷烃，从而实现了从酚类衍生物到高碳数燃料的转化。

关键词：酚类衍生物 钌 含氧燃料 烷烃燃料 C-O断键

Study on the Conversion of phenolic Compounds into Liquid Fuels

Fu Yao1 Xiao Rui2 Huang Yaobing1

（1.University of Science and Technology of China；2.Southeast University）

Abstract：Biomass derived phenolic compounds can be converted into saturated alkyl alcohols， a kind of oxygenated fuels， through catalytic hydrogenation or liquid fuels after carburization and hydrodeoxygenation. In this study， two heterogeneous catalysts based on the Ru metal were developed and used in the conversion of phenolic compounds into liquid fuels. The main research work is as follows：（1）the development of catalytic transfer hydrogenation system based on ruthenium catalyst under relatively mild conditions， using isopropanol as the hydrogen donor. The phenolic mixture was converted into saturated alcohols. The active sites， different solvents and different reaction conditions were also studied The catalyst can be recycled for times. The characterization of the used catalyst gave insightful information about the factors that led to the loss in the catalytic actvity；（2）A new Ru catalyst with dopant material as support was developed and used in the conversion of model compounds， phenol and guaiacol. A series of daturated alkyl alcohols were obtained though hydrogenation and selective C-O bond cleavage. Characterization of the catalyst and capturing the reaction intermediates helped to explore the reaction mechanism-through hydrogenation of aromatic rings and followed by methoxy removal. Furthermore， the alcohols can go self-condensation by a base-catalyzed reaction achieving a liquid precursor with more carbons. It was further hydrodeoxygenated into C12 alkanes.

Key Words：Phenolics； Ruthenium； Oxygenated fuels； Alkane fuels； C-O cleavage

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