甲醛乙炔化反应铜基催化剂研究进展

Research progress of Cu-based catalysts for ethynylation of formaldehyde

1,4-丁二醇(BDO)因可作为重要的精细化工原料、高分子聚合物原料和可降解塑料原料而备受关注。甲醛乙炔化反应由铜基催化剂催化进行,首先原位生成乙炔亚铜,然后与甲醛发生亲核加成反应生成1,4-丁炔二醇,1,4-丁炔二醇可被催化氢化还原为BDO。铜基催化剂能够催化甲醛乙炔化反应合成1,4-丁炔二醇,且其结构影响该反应的活性与稳定性。综述了甲醛乙炔化反应铜基催化剂的研究现状,结合甲醛乙炔化反应机理,重点探讨了铜基催化剂的制备方法和载体与助剂对催化剂结构和甲醛乙炔化性能的影响,发现中间体乙炔亚铜的高度分散及稳定存在是铜基催化剂具有较好活性和稳定性的关键,铜基催化剂所采用的制备方法和载体与助剂的种类决定了铜物种的分散性、价态变化及电子协同作用。结合绿色环保理念,合理设计铜基催化剂,并对甲醛乙炔化反应后催化剂进行活性恢复,将是未来铜基催化剂甲醛乙炔化合成1,4-丁炔二醇的发展趋势。

1,4-butanediol(BDO) attracts extensive attention as important fine chemical raw materials, polymer raw materials and degradable plastic raw materials. The ethynylation of formaldehyde is catalyzed by Cu-based catalysts. Firstly, cuprous acetylide is generated in situ, and then nucleophilic addition reaction with formaldehyde is carried out to generate 1,4-butynediol. 1,4-butynediol can be reduced to BDO by catalytic hydrogenation. Cu-based catalysts can catalyze the ethynylation of formaldehyde reaction to synthesize 1,4-butynediol and its structure affects the activity and stability of the reaction. The research status of Cu-based catalysts for ethynylation of formaldehyde was reviewed. Combined with the ethynylation of formaldehyde reaction mechanism, the effects of the preparation methods of Cu-based catalysts and the catalyst supports and additives on the structure and performance of catalysts were discussed. It is found that the high dispersion and stable existence of intermediate cuprous acetylide is the key to the good activity and stability of Cu-based catalysts. The preparation method of Cu-based catalysts and the types of catalyst supports and additives determine the dispersion, valence change and electronic synergy of copper specie. Combined with the concept of green environmental protection, the rational design of Cu-based catalysts and the activity recovery of the catalysts after ethynylation of formaldehyde reaction will be the development trend of Cu-based catalysts for formaldehyde acetylene synthesis of 1,4-butynediol in the future.