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果糖一步法制备MMF及树脂催化剂再生方法探究

鞠嘉浩a,b, 徐吉磊b,*, 王康军a,*, 黄家辉b   

  1. a沈阳化工大学化学工程学院 沈阳 110142;
    b中国科学院大连化学物理研究所 大连洁净能源国家实验室 大连 116023
  • 投稿日期:2024-08-21
  • 基金资助:
    辽宁振兴人才计划(XLYC1907029).

One-step preparation of MMF from fructose and regeneration of resin catalyst

Jiahao Jua,b, Jilei Xub,*, Kangjun Wanga,*, Jiahui Huangb   

  1. aCollege of Chemical Engineering, Shenyang University of Chemical Technology, Shenyang 110142, China;
    bDalian National Laboratory for Clean Energy, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China
  • Received:2024-08-21
  • Contact: * E-mail: wangkj_dut@syuct.edu.cn; xujilei@dicp.ac.cn; Tel.: 18840968483
  • Supported by:
    Liaoning Revitalization Talents Program (XLYC1907029).

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With the excessive use of fossil energy, energy and environmental problems have become increasingly prominent, and the search for new energy sources is imminent. Biomass is renewable, widely distributed, carbon neutral, and can be used to produce a variety of chemicals, so it has attracted wide attention from the scientific community and the business community. 5-Hydroxymethylfurfural (HMF) is an important biomass-based platform molecule that can be used to synthesize a variety of chemicals and fuels. It is a key intermediate for the synthesis of bio-based polyester monomer 2,5-Furandicarboxylicacid (FDCA). However, HMF is very active and heat-sensitive, and can self-polymerize at room temperature to form by-products such as humin. 5-Methoxymethyl-2-furan (MMF) is a new bio-based platform molecule. Its structure is similar with HMF, but its properties are more stable. It can be separated from the reaction system by simple distillation, and the separation cost is much lower than that of HMF, which is expected to replace HMF as a key platform compound for the product of bio-based furan chemicals. Therefore, the direct conversion of bio-based raw materials into MMF has very important research value and industrial significance. In this paper, a series of resin catalysts were used to realize the one-step conversion from fructose to MMF using ionic liquids and methanol as cosolvent. Under the best conditions, about 67.7% yield of MMF was obtained in the present of DA-330, which is higher than related research. However, the activity of DA-330 resin decreases very quickly in the reaction system. The yield of MMF was about 10% during the second experiment,which was much lower than that of the first time. After a series of characterizations, such as BET, FTIR, acid base titration and elemental analysis, it was determined that the deactivation of the resin catalyst was due to the coverage of humin, ion exchange between the resin and ionic liquid, and the loss of acid sites of resin. After hydrogen peroxide oxidation, H+ ion exchange, the activity of the resin catalyst was restored to the level of the new catalyst, and the yield of MMF did not significantly decrease after recycled four times.

Key words: Etherification reaction, Resin, Ionic liquid, HMF, MMF, Biomass energy