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糠醛一锅法制备γ-戊内酯的多相催化研究进展

Research Progress on Heterogenous Catalytic Conversion of Furfural to γ-Valerolactone by One-pot Reaction

  • 摘要: γ-戊内酯(GVL)是一种重要的生物质平台化合物, 可以用作绿色溶剂、聚合物前体、燃料和燃料添加剂等, 催化转化生物质制备GVL是资源化利用生物质和缓解资源、能源危机的重要途径之一。糠醛经麦尓外因-彭多夫-沃莱(MPV)还原一锅制备GVL具有操作简单、经济环保、安全可靠等优点, 是GVL合成研究领域极具工业化潜质的路线, 受到学术界和工业界的广泛关注。本文阐述了糠醛转化为GVL各步所需Brønsted酸(B酸)和Lewis酸(L酸)催化活性中心, 从催化剂构筑方法、载体结构等方面总结了糠醛一锅法制备GVL的高效固体催化剂。发现水热稳定且具有良好传质效果的分子筛(如beta分子筛、ZSM-5分子筛等)是该反应中常用的载体, 以及通过分子筛脱Al改性, 或引入具有L酸位的Zr、Hf化合物、具有B酸位的磷钨酸(HPW)等活性中心是构筑该反应的高效双功能催化剂的常用手段。并对催化剂失活的原因和再生方法进行了总结, 分析了溶剂、温度等催化反应条件对反应活性的影响, 同时还对设计该反应的新型高效催化提出了建议。

     

    Abstract: As a important biomass platform compound, γ-valerolactone(GVL) could be used as green solvent, polymer precursor, fuel, and fuel additive, etc. Therefore, catalytic conversion of biomass to GVL was one of the important ways to utilize resource-based bio material and alleviate the resource and energy crisis. Furfural underwent Meerwein-Ponndorf-Verley(MPV) transfer hydrogenation reaction to prepare GVL in one pot had the advantages of simple operation, economy, environmental protection, safety and reliability. It was a route with great industrialization potential in the field of GVL synthesis research, therefore, it had received extensive attention from academia and industry. This paper described the catalytic activity centers of Brønsted acid(B acid) and Lewis acid(L acid) required for each step of the conversion of furfural to GVL. The efficient solid catalysts for the preparation of GVL by the one-pot method from furfural were summarized in terms of catalyst construction methods and the structure of the carrier. Molecular sieves with hydrothermal stability and good mass transfer effect(e.g. beta molecular sieve, ZSM-5 molecular sieve, etc.) were found to be the commonly used carriers in this reaction. In addition, modification by molecular sieves with de-Al, or introducing active centers such as Zr and Hf compounds with L acid sites, and phosphotungstic acid with B acid sites are common means to construct efficient bifunctional catalysts for the this reaction. The causes of catalyst deactivation and regeneration methods were also summarized in this paper, and the effects of catalytic reaction conditions such as solvent and temperature on the reaction activity were analyzed. At the same time, some suggestions were provided for the design of new and efficient catalysts for this reaction.

     

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