由甲醇向下游衍生合成甲酸甲酯、甲缩醛和聚甲醛二甲醚等反应过程,不仅可以有效延伸甲醇产业链,消化业已形成的甲醇过剩产能,而且还可以带来巨大的经济和环境保护方面的效益,近年来受到研究者的广泛关注,与之相关的催化研究和开发也已取得长足的进步和发展。述评概述了近年来由甲醇出发制备甲酸甲酯、甲缩醛以及聚甲醛二甲醚等过程在催化剂制备和反应机理探索方面的研究进展,侧重介绍了贵金属催化剂上甲醇选择氧化制甲酸甲酯、钒基催化剂上甲醇选择氧化制甲缩醛以及分子筛催化剂上甲醇或甲缩醛与三聚甲醛合成聚甲醛二甲醚等催化反应过程。最后,对甲醇催化转化利用的未来发展方向进行了展望。
The synthesis of methyl formate ( MF), dimethoxymethane (DMM) and polyoxymethylene dimethyl ethers (PODEn) from methanol can not only extend the methanol industry chain and digest the large surplus production capacity of methanol, but also bring on enormous benefits in respects of economic development and environmental protection. As a result, it has attracted extensive attention in recent years and great progresses have also been made in the research and development of efficient catalysts and production processes. This paper attempts to make a review on the recent research progresses in the catalytic synthesis of MF, DMM and PODEn from methanol, in the aspects of developing efficient catalysts and exploring the catalytic reaction mechanism. Especially, the review focuses on the selective oxidation of methanol to MF over noble metal catalysts, the selective oxidation of methanol to DMM over vanadium-based catalysts, and the synthesis of PODEn from trioxymethylene (TOM) with methanol or DMM over acidic zeolite catalysts. Lastly, an outlook is given on the possible trends in the development of new efficient catalysts and processes to acquire methanol-down-stream oroducts with high value.