Formation kinetics of polyoxymethylene dimethyl ethers from methylal and trioxane with little water  

作　　者：Xiaofei Qin Sen Lei Xubin Zhang Chen Cao Feng Xin Honglin Chen Xiaoming Zhang Yachen Yin Guilian Wu 

机构地区：[1]School of Chemical Engineering and Technology,Tianjin University,Tianjin 300350,China [2]Chengdu Institute of Organic Chemistry,Chinese Academy of Sciences,Chengdu 610041,China

出　　处：《Chinese Journal of Chemical Engineering》2021年第5期139-146,共8页中国化学工程学报（英文版）

基　　金：This research was supported by the National Key R&D Program of China(2018YFB0604900).

摘　　要：Polyoxymethylene dimethyl ethers(CH_(3)-O-(CH_(2)O)_(n)-CH_(3),PODE_(n),n>1)can be added to diesel to reduce air pollution caused by incomplete combustion.Driven by this need,a cost-effective and efficient synthetic route is presented and investigated by this work for the production of PODE_(n),which are formed from methylal and trioxane with low water content(<10%(mass))over HZSM-5 catalyst in a batch slurry autoclave at the temperature from 353.15 K to 393.15 K.The reaction rate laws including the PODE_(n) and byproducts of polyoxymethylene hemiformals(HF_(n)),polyoxymethylene glycols(MG),methanol(MeOH)and methyl formate(MF)are developed.The rate constants of propagation step(k_(6))and depolymerization step(k_(-6))are assumed independent on polymerization degree of PODE_(n).The rate of reaction is proportional to the content of the catalyst(Wcat)for the catalytic reaction within the scope of the study.All kinetic parameters were estimated by combining genetic algorithm and least square regression to fit experimental data well.This work is valuable for process optimization and reactor design.

关 键 词：Fuel additive POLYOXYMETHYLENE DIMETHYL ETHERS KINETICS HZSM-5 

分 类 号：TE624.81[石油与天然气工程—油气加工工程]