生物质衍生芳香族含氧化合物中C—O键断裂研究进展  

Cleavage of C—O bonds in biomass-derived aromatic oxygenates

作　　者：邱泽刚[1] 石亚斐 李志勤[1] QIU Zegang;SHI Yafei;LI Zhiqin(College of Chemistry and Chemical Engineering,Xi’an Shiyou University,Xi’an 710065,Shaanxi,China)

机构地区：[1]西安石油大学化学化工学院,陕西西安710065

出　　处：《化工进展》2025年第3期1183-1193,共11页Chemical Industry and Engineering Progress

基　　金：国家自然科学基金(22378324);陕西省教育厅服务地方专项计划(24JC075);陕西省重点研发计划(2022GY-153);西安石油大学研究生创新与实践能力培养项目(YCS22111011)。

摘　　要：木质生物质含有芳香环结构,但是其含氧量高。生物质衍生芳香族含氧化合物高值化利用的关键问题是其C—O键的活化断裂。生物质衍生芳香族含氧化合物中的C—O键有多种类型,主要包括连接芳环碳与羟基氧的C_(aryl)—O(H)键、醚键C_(aryl)—O—CH_(3)、芳环侧链中的C==O键等。通过催化加氢脱氧(HDO)使芳香族含氧化合物C—O键活化断裂。本文综述了生物质衍生芳香族含氧化合物的C—O键完全断裂,以及C—O键选择性断裂的研究现状;阐述了苯酚、甲基酚、苯甲醚、愈创木酚、丁香酚和香兰素等典型芳香族含氧化合物的C—O键催化断裂机理;分析了催化剂的加氢能力、亲氧性、酸位点、电子结构和金属位点等性质和结构对芳香族含氧化合物C—O键催化断裂的作用;进而提出了芳香族含氧化合物C—O键催化断裂的一些关键问题和研究重点。Lignocellulosic biomasses contain aromatic ring structures but have high oxygen contents.The key issue for the high value utilization of biomass-derived aromatic oxygenates is the activation and breaking of C—O bonds.There are various types of C—O bonds in biomass-derived aromatic oxygenated compounds,mainly including C_(aryl)—O(H)bonds connecting the carbon of the aromatic ring with the hydroxy-oxygen,ether bonds C_(aryl)—O—CH_(3),and C==O bonds in the side chain of the aromatic ring.Catalytic hydrodeoxygenation(HDO)is an effective way for cleavage of C—O bonds of aromatic oxygenated compounds.This paper reviews the current research status of complete C—O bond cleavage and selective C—O bond cleavage of biomass-derived aromatic oxygenates,and describes the catalytic cleavage mechanism of C—O bond for typical aromatic oxygenates such as phenol,methylphenol,anisole,guaiacol,eugenol and vanillin.The roles of catalyst properties and structures such as hydrogenation ability,oxophilicity,acid sites,electronic structure and metal sites on C—O bond cleavage of aromatic oxygenated compounds are analyzed.Furthermore,some key issues and research focuses on the C—O bond breaking of aromatic oxygenated compounds are proposed.

关 键 词：生物质 芳香含氧化合物 C—O键 加氢脱氧 催化机理 

分 类 号：TK6[动力工程及工程热物理—生物能]