甲缩醛歧化制甲酸甲酯的全新路线研究  

A new route for the production of methyl formate by dimethylmethane disproportionation

作　　者：杨磊磊 陈之旸 倪友明[1] 刘红超[1] 朱文良[1] YANG Leilei;CHEN Zhiyang;NI Youming;LIU Hongchao;ZHU Wenliang(Dalian Institute of Chemical Physics,Chinese Academy of Sciences,Dalian 116023,China;University of Chinese Academy of Sciences,Beijing 100049,China)

机构地区：[1]中国科学院大连化学物理研究所,辽宁大连116023 [2]中国科学院大学,北京100049

出　　处：《应用化工》2025年第1期1-6,11,共7页Applied Chemical Industry

基　　金：国家自然科学基金(22378388);中国科学院“变革性洁净能源关键技术与示范”战略先导课题专项(XDA29030401)。

摘　　要：提出了一个负载型杂多酸催化甲缩醛歧化制甲酸甲酯的新策略,并通过系统研究载体、杂多酸类型以及酸量对甲缩醛歧化性能的影响,验证了新策略具有可行性。研究发现,杂多酸在载体表面的分散性是影响催化剂性能的重要因素。其中SiO_(2)和HPW分别是实现甲缩醛高效转化的优良载体以及活性物种。更为重要的是,酸性质特别是酸量对甲缩醛的转化具有重要影响,在保证良好分散性的前提下,通过提高杂多酸负载量进而增加酸量有利于甲缩醛转化。在P=0.1 MPa,T=373 K,WHSV_(DMM)=2 g/(g_(cat)·h)的条件下,30%HPW/SiO_(2)催化剂表现出最佳的反应性能,甲缩醛的转化率以及甲酸甲酯的时空产率分别为93.9%以及0.71 g/(g_(cat)·h)。为替代传统工业生产方法,开发绿色、高效甲酸甲酯合成新路线提供了重要的理论支撑,具有重要的工业应用前景。A new strategy for methyl formate production from methylal disproportionation catalyzed by supported heteropoly acid was proposed,the feasibility of the new strategy was verified by systematically studying the effect of carrier,heteropoly acid type and amount on the disproportionation performance.The results show the dispersion of heteropolyacid over the supports is a critical factor affecting the performance of catalysts.Among them,SiO_(2)and HPW are excellent support and active species to realize the efficient conversion of DMM,respectively.In addition,the acid properties,especially the strong acid center and the amount of acidic sites also have an important effect on the transformation of DMM.Up to nearly 93.9%DMM conversion and 0.71 g/(g_(cat)·h)of MF space time yield(STY)was achieved over 30%HPW/SiO_(2)under moderate conditions of WHSV_(DMM)=2 g/(g_(cat)·h),0.1 MPa and 373 K.This study provides a new way to produce methyl formate under mild conditions.

关 键 词：杂多酸 甲缩醛 甲酸甲酯 歧化 

分 类 号：TQ225[化学工程—有机化工] TQ426