boehmite负载CuO催化5-羟甲基糠醛转移加氢制备2,5-双(羟甲基)呋喃的研究

IF 4.3 3区 工程技术 Q2 ENGINEERING, CHEMICAL Frontiers of Chemical Science and Engineering Pub Date : 2023-01-14 DOI:10.1007/s11705-022-2225-4
Zexing Huang, Zhijuan Zeng, Xiaoting Zhu, Wenguang Zhao, Jing Lei, Qiong Xu, Yongjun Yang, Xianxiang Liu
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引用次数: 2

摘要

2,5-二(羟甲基)呋喃(BHMF)是聚酯的重要单体。其含氧刚性环结构和对称的二醇官能团,使其成为替代石油基单体生产可降解生物基聚酯材料的独特优势。在此,我们制备了一种薄铝石负载的氧化铜催化剂,用于通过催化转移加氢(CTH)将5-羟甲基糠醛选择性加氢成BHMF。此外,乙醇成功地取代了传统的高压氢作为氢供体,在合适的条件下,BHMF的选择性高达96.9%。通过表征和因素研究,发现CuO对高BHMF选择性至关重要。此外,动力学研究表明,副产物活化能高于BHMF,这解释了反应温度对产物分布的影响。为了建立催化剂的构效关系,提出了一种可能的机理。铜氧化物催化剂在CTH后失活,因为乙醇降低了CuO,从而降低了活性位点。最后,催化剂在空气中煅烧恢复其活性。这些结果将对生物质工业的加氢过程产生积极影响。
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Boehmite-supported CuO as a catalyst for catalytic transfer hydrogenation of 5-hydroxymethylfurfural to 2,5-bis(hydroxymethyl)furan

2,5-bis(hydroxymethyl)furan (BHMF) is an important monomer of polyester. Its oxygen-containing rigid ring structure and symmetrical diol functional group establish it as an alternative to petroleum-based monomer with unique advantages for the prodution of the degradable bio-based polyester materials. Herein, we prepared a boehmite-supported copper-oxide catalyst for the selective hydrogenation of 5-hydroxymethylfurfural into BHMF via catalytic transfer hydrogenation (CTH). Further, ethanol successfully replaced conventional high-pressure hydrogen as the hydrogen donor, with up to 96.9% BHMF selectivity achieved under suitable conditions. Through characterization and factor investigations, it was noted that CuO is crucial for high BHMF selectivity. Furthermore, kinetic studies revealed a higher by-product activation energy compared to that of BHMF, which explained the influence of reaction temperature on product distribution. To establish the catalyst structure-activity correlation, a possible mechanism was proposed. The copper-oxide catalyst deactivated following CTH because ethanol reduced the CuO, which consequently decreased the active sites. Finally, calcination of the catalyst in air recovered its activity. These results will have a positive impact on hydrogenation processes in the biomass industry.

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来源期刊
CiteScore
7.60
自引率
6.70%
发文量
868
审稿时长
1 months
期刊介绍: Frontiers of Chemical Science and Engineering presents the latest developments in chemical science and engineering, emphasizing emerging and multidisciplinary fields and international trends in research and development. The journal promotes communication and exchange between scientists all over the world. The contents include original reviews, research papers and short communications. Coverage includes catalysis and reaction engineering, clean energy, functional material, nanotechnology and nanoscience, biomaterials and biotechnology, particle technology and multiphase processing, separation science and technology, sustainable technologies and green processing.
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