水在甲缩醛与三聚甲醛合成聚甲氧基二甲醚中的作用研究  

Synthesis of Polyoxymethylene Dimethyl Ethers from Methylal and Paraformaldehyde under Different Amounts of Water

作　　者：雷森 邓聪迩[1] 雷骞[1] 张小明[1] 陈洪林[1] LEI Sen;DENG Cong-er;LEI Qian;ZHANG Xiao-ming;CHEN Hong-lin(Chengdu Institute of Organic Chemistry, Chinese Academy of Sciences, No. 9, Section 4, Renmin South Road, Chengdu 610041, Sichuan, People’s Republic of China;University of Chinese Academy of Sciences, Beijing 100049, People’s Republic of China)

机构地区：[1]中国科学院成都有机化学研究所,四川成都610041 [2]中国科学院大学,北京100049

出　　处：《合成化学》2021年第4期332-336,共5页Chinese Journal of Synthetic Chemistry

基　　金：国家重点研发计划项目(2018YFB0604900)。

摘　　要：聚甲醛二甲醚(PODE)添加到柴油中,可以减少不完全燃烧造成的空气污染。在不同温度下,以HZSM-5为催化剂,三聚甲醛(TOX)和甲缩醛(DMM)为原料,加入不同含量的水以模拟甲醛原料水含量(0~10 wt%)对PODE合成的影响。结果表明:在相同的甲醛/甲缩醛摩尔比的条件下,随着TOX中水含量的增加,TOX和DMM的转化率变化不明显,而产物中PODE3-8的含量则明显降低,从无水时的39.55%减少到3 wt%水时的32.09%,10 wt%水时的23.66%。同时,发现MeOH等的含量随着含水量的增加明显增加,由无水时的0.53%增加至3 wt%水时的2.82%和10 wt%时的4.42%。进一步研究表明:反应体系中的水与MeOH的生成密切相关。通过物料衡算证实PODE合成过程中的水主要与DMM反应生成MeOH。Polyoxymethylene dimethyl ethers(PODE)can be added to diesel to reduce air pollution caused by incomplete combustion.In this work,PODE were formed from methylal(DMM)and trioxane(TOX)over HZSM-5 catalyst at different temperatures,and different amounts of water were added to simulate the water content of the formaldehyde raw materials(0 wt%,3 wt%And 10 wt%)on the synthesis of PODE.Studies have shown that under the same formaldehyde/formal molar ratio,as the water content in TOX gradually increases from no water,the conversion rate of TOX and DMM does not change significantly,while the content of PODE3-8 in the product Significantly reduced,from 39.55%without water to 32.09%with 3 wt%water and 23.66%with 10 wt%water.At the same time,it was found that the content of MeOH,etc.increased significantly with the increase of water content,from 0.53%in the absence of water to 2.82%in 3 wt%water and 4.42%at 10 wt%water.Further research shows that the water in the reaction system is closely related to the formation of MeOH.Through material balance calculation,it was confirmed that water mainly reacted with DMM to form MeOH during PODE synthesis.

关 键 词：柴油添加剂 聚甲氧基二甲醚 甲醇 HZSM-5 三聚甲醛 甲缩醛 合成 催化 

分 类 号：O62[理学—有机化学]