Investigation on Reaction Kinetics of Polyoxymethylene Dimethyl Ethers and Influence Mechanism of Polymerization Degree

ZHOU Zijie; YANG Yajing; CUI Wang; WEI Yanju; LIU He; LIU Shenghua

doi:10.7652/xjtuxb202508012

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Investigation on Reaction Kinetics of Polyoxymethylene Dimethyl Ethers and Influence Mechanism of Polymerization Degree

更新时间：2025-07-30

- Investigation on Reaction Kinetics of Polyoxymethylene Dimethyl Ethers and Influence Mechanism of Polymerization Degree
- Journal of Xi’an Jiaotong University Vol. 59, Issue 8, Pages: 122-133(2025)
- 作者机构：
  
  1.西安交通大学能源与动力工程学院， 710049，西安
  2.西安交通大学航天航空学院， 710049，西安
- 作者简介：
- 基金信息：
- DOI：10.7652/xjtuxb202508012
  CLC： TK46+4
- Received：04 December 2024，
  
  Online First：17 March 2025，
  
  Published：10 August 2025
- 稿件说明：
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ZHOU Zijie, YANG Yajing, CUI Wang, et al. Investigation on Reaction Kinetics of Polyoxymethylene Dimethyl Ethers and Influence Mechanism of Polymerization Degree[J]. Journal of Xi’an Jiaotong University, 2025, 59(8): 122-133.
DOI：

ZHOU Zijie, YANG Yajing, CUI Wang, et al. Investigation on Reaction Kinetics of Polyoxymethylene Dimethyl Ethers and Influence Mechanism of Polymerization Degree[J]. Journal of Xi’an Jiaotong University, 2025, 59(8): 122-133. DOI： 10.7652/xjtuxb202508012.

摘要

为揭示不同聚合度的聚甲氧基二甲醚（PODE）各组分反应活性随聚合度变化的规律及动力学机理，构建了适用于广泛工况的反应路径框架，对比分析了PODE多组分反应动力学行为。基于二甲氧基甲烷（PODE

）的反应机理，构建了PODE

、PODE

的反应机理，并对该反应机理进行了验证。根据各基元反应的反应动力学作用，提出PODE反应路径统一框架，阐明了PODE反应活性的3个来源通道：伯碳脱氢后通过两次加氧发生的典型链分支反应，部分氢过氧燃料自由基分解为羰基氢过氧化物的链分支反应，仲碳脱氢分解为低聚合度燃料自由基后发生的链分支反应。PODE在第一阶段点火延迟时间的敏感性分析结果表明，构建的PODE

、PODE

的反应动力学机理能够预测实验测量的点火延迟时间，可以对PODE的反应动力学行为作出解释。通道1和通道2是所有PODE分子所共有的链分支反应通道，而通道3是高聚合度PODE所特有的反应路径，是重要的反应活性贡献来源。

Abstract

To reveal the variation law of reaction activity of polyoxymethylene dimethyl ethers (PODE) components with different polymerization degrees and the underlying kinetic mechanisms

a reaction pathway framework applicable to a

wide range of conditions is constructed to comparatively analyze the multi-component reaction kinetic behaviors of PODE. Based on the reaction mechanism of dimethoxymethane (PODE

)

the reaction mechanisms of PODE

and PODE

are developed and validated. According to the role of each elementary reaction in reaction kinetics

a unified framework for PODE reaction pathways is proposed

elucidating three source channels of PODE reactivity: the typical chain-branching reaction via primary carbon dehydrogenation followed by two oxygen additions; the chain-branching reaction resulting from the decomposition of some hydroperoxy fuel radicals into carbonyl hydroperoxides; the chain-branching reaction triggered by secondary carbon dehydrogenation and decomposition into lower-polymerization-degree fuel radicals. Sensitivity analysis of the first-stage ignition delay time of PODE demonstrates that the constructed reaction kinetic mechanism of PODE

and PODE

can predict experimentally measured ignition delay times and explain the reaction kinetic behaviors of PODE. Channels 1 and 2 are common chain-branching reaction pathways for all PODE molecules

while channel 3 is unique to higher-polymerization-degree PODE and serves as an important contributor to reactivity.

关键词

Keywords

references

LAUTENSCHÜTZ L , OESTREICH D , SEIDENSPINNER P , et al . Physico-chemical properties and fuel characteristics of oxymethylene dialkyl ethers [J ] . Fuel , 2016 , 173 : 129 - 137 .

BARTHOLET D L , ARELLANO-TREVIÑO M A , CHAN Fanliang , et al . Property predictions demonstrate that structural diversity can improve the performance of polyoxymethylene ethers as potential bio-based diesel fuels [J ] . Fuel , 2021 , 295 : 120509 .

KANG Meirong , SONG Heyuan , JIN Fuxiang , et al . Synthesis and physicochemical characterization of polyoxymethylene dimethyl ethers [J ] . Journal of Fuel Chemistry and Technology , 2017 , 45 ( 7 ): 837 - 845 .

刘军恒 , 杨军 , 周海磊 , 等 . 聚甲氧基二甲醚-甲醇混合燃料的燃烧与排放特性研究 [J ] . 内燃机工程 , 2021 , 42 ( 2 ): 16 - 22 .

LIU Junheng , YANG Jun , ZHOU Hailei , et al . Investigation on combustion and emission characteristics of polyoxymethylene dimethyl ethers-methanol blends [J ] . Chinese Internal Combustion Engine Engineering , 2021 , 42 ( 2 ): 16 - 22 .

刘浩业 , 王志 , 王建昕 . 聚甲氧基二甲醚火(PODE n )引燃时刻对HCII燃烧与排放的影响 [J ] . 汽车安全与节能学报 , 2016 , 7 ( 1 ): 94 - 99 .

LIU Haoye , WANG Zhi , WANG Jianxin . Effects of induced injection-timing on combustion and emission performances inhomogeneous-charge-induced-ignition (HCII) combustion by using polyoxymethylene dimethyl ethers (PODE n ) [J ] . Journal of Automotive Safety and Energy , 2016 , 7 ( 1 ): 94 - 99 .

CHEN Hao , WANG Hui , CHEN Zhaoyang , et al . Research progress on the spray, combustion and emission of polyoxymethylene dimethyl ethers as a diesel blend fuel: a review [J ] . Fuel , 2022 , 324 ( Part C ): 124731 .

BURGER J , SIEGERT M , STRÖFER E , et al . Poly (oxymethylene) dimethyl ethers as components of tailored diesel fuel: properties, synthesis and purification concepts [J ] . Fuel , 2010 , 89 ( 11 ): 3315 - 3319 .

QI Jianguang , HU Yufeng , NIU Jiangge , et al . Evaluation of polyoxymethylene dimethyl ethers as a new type of diesel additives [J ] . Fuel , 2018 , 234 : 135 - 141 .

HAN D Y , CAO Z B , SHI W W , et al . Influence of polyoxymethylene dimethyl ethers on diesel fuel properties [J ] . Energy Sources: Part A Recovery, Utilization, and Environmental Effects , 2016 , 38 ( 18 ): 2687 - 2692 .

TAN Yongren , BOTERO M L , SHENG Yuan , et al . Sooting characteristics of polyoxymethylene dimethyl ether blends with diesel in a diffusion flame [J ] . Fuel , 2018 , 224 : 499 - 506 .

UECKERDT F , BAUER C , DIRNAICHNER A , et al . Potential and risks of hydrogen-based e-fuels in climate change mitigation [J ] . Nature Climate Change , 2021 , 11 ( 5 ): 384 - 393 .

HUANG Zhen , ZHU Lei , LI Ang , et al . Renewable synthetic fuel: turning carbon dioxide back into fuel [J ] . Frontiers in Energy , 2022 , 16 ( 2 ): 145 - 149 .

杨斌 , 张英佳 , 李玉阳 , 等 . 面向碳中和的燃烧反应动力学研究进展与展望 [J ] . 工程热物理学报 , 2022 , 43 ( 8 ): 1993 - 2008 .

YANG Bin , ZHANG Yingjia , LI Yuyang , et al . Research progress and prospect of combustion reaction kinetics for carbon neutrality [J ] . Journal of Engineering Thermophysics , 2022 , 43 ( 8 ): 1993 - 2008 .

VERMEIRE F H , CARSTENSEN H H , HERBINET O , et al . Experimental and modeling study of the pyrolysis and combustion of dimethoxymethane [J ] . Combustion and Flame , 2018 , 190 : 270 - 283 .

HE Tanjin , WANG Zhi , YOU Xiaoqing , et al . A chemical kinetic mechanism for the low-and intermediate-temperature combustion of polyoxymethylene dimethyl ether 3 (PODE 3 ) [J ] . Fuel , 2018 , 212 : 223 - 235 .

KOPP W A , KRÖGER L C , DÖNTGEN M , et al . Detailed kinetic modeling of dimethoxymethane: Part Ⅰ Ab initio thermochemistry and kinetics predictions for key reactions [J ] . Combustion and Flame , 2018 , 189 : 433 - 442 .

JACOBS S , DÖNTGEN M , ALQUAITY A B S , et al . Detailed kinetic modeling of dimethoxymethane: Part Ⅱ experimental and theoretical study of the kinetics and reaction mechanism [J ] . Combustion and Flame , 2019 , 205 : 522 - 533 .

SUN Wenyu , LIU Zhongkai , ZHANG Yan , et al . Comparing the pyrolysis kinetics of dimethoxymethane and 1,2-dimethoxyethane: an experimental and kinetic modeling study [J ] . Combustion and Flame , 2021 , 226 : 260 - 273 .

GOLKA L , WEBER I , OLZMANN M . Pyrolysis of dimethoxymethane and the reaction of dimethoxymethane with H atoms: a shock-tube/ARAS/TOF-MS and modeling study [J ] . Proceedings of the Combustion Institute , 2019 , 37 ( 1 ): 179 - 187 .

YU Tongpo , WU Xiangkun , ZHOU Xiaoguo , et al . Hydrogen migration as a potential driving force in the thermal decomposition of dimethoxymethane: new insights from pyrolysis imaging photoelectron photoion coincidence spectroscopy and computations [J ] . Combustion and Flame , 2020 , 222 : 123 - 132 .

PEUKERT S , SELA P , NATIVEL D , et al . Direct measurement of high-temperature rate constants of the thermal decomposition of dimethoxymethane, a shock tube and modeling study [J ] . The Journal of Physical Chemistry: A , 2018 , 122 ( 38 ): 7559 - 7571 .

GOLKA L , GRATZFELD D , WEBER I , et al . Temperature-and pressure-dependent kinetics of the competing C—O bond fission reactions of dimethoxymethane [J ] . Physical Chemistry Chemical Physics , 2020 , 22 ( 10 ): 5523 - 5530 .

CAI Liming , JACOBS S , LANGER R , et al . Auto-ignition of oxymethylene ethers (OME n , n =2－4) as promising synthetic e-fuels from renewable electricity: shock tube experiments and automatic mechanism generation [J ] . Fuel , 2020 , 264 : 116711 .

WANG Hu , YAO Zhifeng , ZHONG Xin , et al . Experimental and kinetic modeling studies on low-temperature oxidation of polyoxymethylene dimethyl ether (DMM 1-3 ) in a jet-stirred reactor [J ] . Combustion and Flame , 2022 , 245 : 112332 .

SHRESTHA K P , ECKART S , DROST S , et al . A comprehensive kinetic modeling of oxymethylene ethers (OME n , n =1－3) oxidation-laminar flame speed and ignition delay time measurements [J ] . Combustion and Flame , 2022 , 246 : 112426 .

LI Wei , FANG Qilong , ZHANG Jianguo , et al . Role of CH 2 O moiety on laminar burning velocities of oxymethylene ethers (OME n ): a case study of dimethyl ether, OME 1 and OME 2 [J ] . Proceedings of the Combustion Institute , 2023 , 39 ( 1 ): 795 - 804 .

DE RAS K , KUSENBERG M , VANHOVE G , et al . A detailed experimental and kinetic modeling study on pyrolysis and oxidation of oxymethylene ether-2 (OME-2) [J ] . Combustion and Flame , 2022 , 238 : 111914 .

LI Ning , GIRHE S , ZHANG Mingzhi , et al . A machine learning method to predict rate constants for various reactions in combustion kinetic models [J ] . Combustion and Flame , 2024 , 263 : 113375 .

SUN Wenyu , WANG Guoqing , LI Shuang , et al . Speciation and the laminar burning velocities of poly (oxymethylene) dimethyl ether 3 (POMDME 3 ) flames: an experimental and modeling study [J ] . Proceedings of the Combustion Institute , 2017 , 36 ( 1 ): 1269 - 1278 .

REN Shuojin , WANG Zhi , LI Bowen , et al . Development of a reduced polyoxymethylene dimethyl ethers (PODE n ) mechanism for engine applications [J ] . Fuel , 2019 , 238 : 208 - 224 .

DROST S , SCHIEßL R , WERLER M , et al . Ignition delay times of polyoxymethylene dimethyl ether fuels (OME 2 and OME 3 ) and air: measurements in a rapid compression machine [J ] . Fuel , 2019 , 258 : 116070 .

李宁 , 赵玉伟 , 魏衍举 , 等 . 聚甲氧基二甲醚-2燃烧动力学模型及试验研究 [J ] . 内燃机工程 , 2024 , 45 ( 1 ): 98 - 108 .

YANG Zhenbin , REN Chunxiao , JIANG Siqi , et al . Theoretical predictions of compatibility of polyoxymethylene dimethyl ethers with diesel fuels and diesel additives [J ] . Fuel , 2022 , 307 : 121797 .

FENARD Y , VANHOVE G . A mini-review on the advances in the kinetic understanding of the combustion of linear and cyclic oxymethylene ethers [J ] . Energy & Fuels , 2021 , 35 ( 18 ): 14325 - 14342 .

CURRAN H J . Developing detailed chemical kinetic mechanisms for fuel combustion [J ] . Proceedings of the Combustion Institute , 2019 , 37 ( 1 ): 57 - 81 .

ZHONG Xin , WANG Hu , ZUO Qingming , et al . Experimental and kinetic modeling studies of polyoxymethylene dimethyl ether (PODE) pyrolysis in jet stirred reactor [J ] . Journal of Analytical and Applied Pyrolysis , 2021 , 159 : 105332 .

QIU Zeyan , ZHONG Anhao , HUANG Zhen , et al . An experimental and modeling study on polyoxymethylene dimethyl ether 3 (PODE 3 ) oxidation in a jet stirred reactor [J ] . Fundamental Research , 2022 , 2 ( 5 ): 738 - 747 .

WANG Zhandong , HERBINET O , HANSEN N , et al . Exploring hydroperoxides in combustion: history, recent advances and perspectives [J ] . Progress in Energy and Combustion Science , 2019 , 73 : 132 - 181 .

ROTAVERA B , TAATJES C A . Influence of functional groups on low-temperature combustion chemistry of biofuels [J ] . Progress in Energy and Combustion Science , 2021 , 86 : 100925 .

CONIGLIO L , BENNADJI H , GLAUDE P A , et al . Combustion chemical kinetics of biodiesel and related compounds (methyl and ethyl esters): experiments and modeling-advances and future refinements [J ] . Progress in Energy and Combustion Science , 2013 , 39 ( 4 ): 340 - 382 .

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