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

doi:10.1016/j.cjche.2020.06.011

中国化学工程学报 ›› 2021, Vol. 33 ›› Issue (5): 139-146.DOI: 10.1016/j.cjche.2020.06.011

• Catalysis, Kinetics and Reaction Engineering • 上一篇下一篇

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

Xiaofei Qin¹, Sen Lei², Xubin Zhang¹, Chen Cao¹, Feng Xin¹, Honglin Chen², Xiaoming Zhang², Yachen Yin¹, Guilian Wu¹

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

收稿日期:2020-04-09 修回日期:2020-05-12 出版日期:2021-05-28 发布日期:2021-08-19
通讯作者: Xubin Zhang, Feng Xin
基金资助:
This research was supported by the National Key R&D Program of China (2018YFB0604900).

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

Xiaofei Qin¹, Sen Lei², Xubin Zhang¹, Chen Cao¹, Feng Xin¹, Honglin Chen², Xiaoming Zhang², Yachen Yin¹, Guilian Wu¹

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

Received:2020-04-09 Revised:2020-05-12 Online:2021-05-28 Published:2021-08-19
Contact: Xubin Zhang, Feng Xin
Supported by:
This research was supported by the National Key R&D Program of China (2018YFB0604900).

摘要/Abstract

摘要： Polyoxymethylene dimethyl ethers (CH₃-O-(CH₂O)_n-CH₃, 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 (b10 %(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 (k₆) 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 (W_cat) 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

Abstract: Polyoxymethylene dimethyl ethers (CH₃-O-(CH₂O)_n-CH₃, 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 (b10 %(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 (k₆) 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 (W_cat) 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.

Key words: Fuel additive, Polyoxymethylene dimethyl ethers, Kinetics, HZSM-5

Xiaofei Qin, Sen Lei, Xubin Zhang, Chen Cao, Feng Xin, Honglin Chen, Xiaoming Zhang, Yachen Yin, Guilian Wu. Formation kinetics of polyoxymethylene dimethyl ethers from methylal and trioxane with little water[J]. 中国化学工程学报, 2021, 33(5): 139-146.

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

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

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