芳香多元羧酸,如对苯二甲酸、邻苯二甲酸、偏苯三甲酸、均苯三甲酸、均苯四甲酸等是重要的大宗化学品,可以制备各种聚合物材料,在日常生活的各个领域应用广泛。工业上,这些芳香多元羧酸是以石油基衍生的芳香烃为原料进行高温高压催化氧化获得。在双碳背景下,开发利用可再生生物质替代传统化石能源生产芳香多元羧酸具有重要的现实意义。生物质转化过程是首先在化学或生物催化下,将生物质降解到一系列C1~C6的平台化合物,然后再通过这些化合物之间的耦合转化制备工业化学品。详细总结了生物质平台化合物催化转化制备芳香多元羧酸的研究进展。这些工作的创新点是开拓新的生物质基合成工艺来生产芳香多元羧酸,关键挑战步骤是芳环的构建。针对该难点,成功开发了两种策略:①呋喃类分子与烯烃的Diels-Alder反应与后续脱水芳构化反应;②醇脱水生成共轭二烯烃,再与烯烃进行Diels-Alder反应以及后续的脱氢芳构化反应。按所生产芳香多元羧酸的种类进行分类,包括对苯二甲酸、苯酐/邻苯二甲酸、苯三甲酸以及均苯四甲酸。研究为生物质催化转化新体系的研发与工艺过程优化提供借鉴。

Aromatic polycarboxylic acids, such as terephthalic acid, phthalic acid, trimellitic acid, trimesic acid and pyromellitic acid,are important bulk chemicals in modern industry. They can be used to prepare diverse polymers that have been widely applied in variousaspects of our daily life. Industrially, these compounds are obtained by catalytic oxidation of petroleum-derived aromatic hydrocarbons atelevated temperature and pressure. In the context of dual carbon strategy, using renewable biomass to replace traditional fossil energy toproduce chemicals is of great significance. The process for biomass conversion included catalytic degradation of biomass into a series ofC1-C6 platform molecules, and subsequent carbon-carbon couplings of these compounds. This review carefully summarized the advancesin catalytic conversion of biomass-based compounds into aromatic polycarboxylic acids. The novelty of these works is the establishment ofnew biomass-based synthetic process towards aromatic polycarboxylic acids, and the key challenging step is the construction of aromaticrings. To address this issue, two strategies have been developed: ① Diels-Alder reaction of furans with olefins and subsequent aromatization via dehydration. ② Alcohol dehydration to dienes and subsequent Diels-Alder reaction, followed by aromatization via dehydrogenation. This review is categorized by the types of aromatic polycarboxylic acids, including terephthalic acid, phthalic anhydride/ acid,benzenetricarboxylic acid, and pyromellitic acid. This review provides important guidance for the development of new biomass conversionsystem and process optimization.

0 引言

1 生物质催化转化制备对苯二甲酸

   1.1 呋喃衍生物制备对苯二甲酸

   1.2 己二烯二酸制备对苯二甲酸

   1.3 山梨酸制备对苯二甲酸

   1.4 异戊二烯制备对苯二甲酸

   1.4 香豆灵酸（酯）制备对苯二甲酸

   1.5 木质素制备对苯二甲酸

   1.6 蒎烯制备对苯二甲酸

   1.7 丙烯酸酯制备对苯二甲酸

2 生物质催化转化制备苯酐/邻苯二甲酸

3 生物质催化转化制备苯三甲酸

4 生物质催化转化制备均苯四甲酸

5 结论与展望