School of Chemical Engineering and Technology, Taiyuan University of Technology
School of Chemical Engineering, China University of Mining and Technology

燃烧化石燃料是目前获取能源的有效途径，但由此排放的CO2严重影响了地球的生态环境。同时CO2本身是一种低毒、不易燃、储量丰富且廉价易得的碳一资源，通过化学方法实现CO2的资源化利用不仅为CO2的固定提供有益的思路，同时还能得到高附加值产品。其中CO2直接羧基化因其在步骤经济和原子经济方面的优点而备受关注，此类反应中常用催化剂包括金属配合物、路易斯酸和碱等，其中金属配合物大多合成步骤复杂且价格昂贵。芳烃和杂环化合物是煤化工行业的重要产品，拓宽煤基化学品的下游利用是促进煤化工产业转型升级的重要途径。芳酸是一类非常重要的化工产品，目前大多数芳酸的生产过程需要多步反应且原子利用率低、成本高。综述了在路易斯酸或碱的催化下，以煤基芳香族化合物为底物，利用廉价易得的CO2作为羧基化原料合成芳酸的研究进展。相比于芳酸的传统合成方法，CO2羧基化法反应流程短，合成产品成本低，产物选择性和收率较高，是一种绿色、经济的合成方法。以煤基芳香族化合物为原料，通过与CO2羧基化制芳酸技术具有着广阔的发展前景。通过对比，负载型碳酸盐催化剂安全性和稳定性较好，且可以再生，但所得目标化合物收率及选择性都较低，在后续发展中需不断改进催化剂的性能以及安全性，促进该反应应用到大规模的工业生产中。

Burning fossil fuels is an effective way to obtain energy at present, but the emitted carbon dioxide has seriously affected the earth’s ecological environment. Meanwhile, CO2 itself is a low toxicity, nonflammable, abundant and cheap carbon resource. The resource utilization of CO2 through chemical methods not only provides some useful ideas for the fixation of CO2, but also obtains some high value-added products. Among them, the direct carboxylation of CO2 has attracted much attention because of its advantages in the step economy and the atom economy. The commonly used catalysts in such reactions include metal complexes, Lewis acids and bases, while most of the metal complexes face complex synthesis steps and high price. Aromatics and heterocyclic compounds are important products of coal chemical industry. Expanding the downstream utilization of coal-based chemicals is an important way to promote the transformation and upgrading of coal chemical industry. Aromatic acid is a kind of very important chemical products. At present, the production process of most aromatic acids involves multi-step reaction, with low atomic utilization and high cost. This paper reviews the research progress in the synthesis of aromatic acids catalyzed over Lewis acid or base, using coal-based aromatic compounds as substrates and cheap and easily available CO2 as carboxylation raw materials. Compared with the traditional synthesis method of aromatic acid, the CO2 carboxylation method is a green and economic synthesis method with short reaction process, low cost, high product selectivity and yield. Taking coal-based aromatic compounds as raw materials, the technology of preparing aromatic acids by carboxylation with CO2 has broad development prospects. Through comparison, the supported carbonate catalyst has good safety and stability, and can be regenerated, but the yield and selectivity of the target compound are low. In the subsequent development, the performance and safety of the catalyst need to be continuously improved for promoting the application of the reaction in a large-scale industrial production.

国家自然科学基金青年基金资助项目(21706172); 山西省基础研究计划资助项目(202203021221069); 省部共建煤炭高效利用与绿色化工国家重点实验室开放课题资助项目(2021-K79)

赵宇鹏，王玉高，申峻，等. 煤基芳香族化合物与CO2羧基化反应研究进展[J]. 煤炭学报，2023，48(8)：3263−3276.

ZHAO Yupeng，WANG Yugao，SHEN Jun，et al. Research progress in carboxylation of coal-based aromatic compounds with CO2[J]. Journal of China Coal Society，2023，48(8)：3263−3276.