酚類衍生物制備液體燃料的研究

傅堯 肖睿 黃耀兵

摘 要：生物質(zhì)酚類衍生物經(jīng)過催化加氫生成飽和烷基醇類化合物含氧燃料或者繼續(xù)進(jìn)行增碳后再加氫脫氧制備飽和烷烴液體燃料。該研究從木質(zhì)素酚類衍生物出發(fā)，發(fā)展了兩類非均相釕系金屬催化劑，實(shí)現(xiàn)了酚類加氫飽和和選擇性斷裂C-O鍵的過程。主要研究工作如下：（1）發(fā)展了釕系金屬催化的氫轉(zhuǎn)移體系，采用異丙醇作為氫轉(zhuǎn)移溶劑，在較為溫和的條件下實(shí)現(xiàn)了酚類混合物全組分轉(zhuǎn)化為飽和醇類化合物。研究了金屬中心、氫轉(zhuǎn)移溶劑和反應(yīng)溫度等參數(shù)對(duì)反應(yīng)的影響，掌握了氫轉(zhuǎn)移反應(yīng)的特點(diǎn)和規(guī)律；（2）以苯酚和愈創(chuàng)木酚為模型物，采用復(fù)合堿性載體負(fù)載的釕催化劑實(shí)現(xiàn)了酚類化合物C-O選擇性斷裂，獲得一系列飽和烷基醇類底物。通過對(duì)催化劑的表征和反應(yīng)中間體的捕捉，證實(shí)了反應(yīng)經(jīng)歷芳環(huán)加氫——甲氧基脫除的反應(yīng)歷程。此外，采用堿催化的縮合反應(yīng)實(shí)現(xiàn)了從烷基醇的自身偶聯(lián)增碳反應(yīng)，提高了底物的碳原子數(shù)，獲得高碳液體燃料的前體，經(jīng)過進(jìn)一步加氫脫氧獲得了C12以上的烷烴，從而實(shí)現(xiàn)了從酚類衍生物到高碳數(shù)燃料的轉(zhuǎn)化。

關(guān)鍵詞：酚類衍生物 釕 含氧燃料 烷烴燃料 C-O斷鍵

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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