1</sub> )的反應(yīng)機(jī)理，構(gòu)建了 PODE<sub>2</sub> 、 PODE<sub>3</sub> 的反應(yīng)機(jī)理，并對(duì)該反應(yīng)機(jī)理進(jìn)行了驗(yàn)證。根據(jù)各基元反應(yīng)的反應(yīng)動(dòng)力學(xué)作用，提出PODE反應(yīng)路徑統(tǒng)一框架，闡明了PODE反應(yīng)活性的3個(gè)來(lái)源通道：伯碳脫氫后通過(guò)兩次加氧發(fā)生的典型鏈分支反應(yīng)，部分氫過(guò)氧燃料自由基分解為羰基氫過(guò)氧化物的鏈分支反應(yīng)，仲碳脫氫分解為低聚合度燃料自由基后發(fā)生的鏈分支反應(yīng)。PODE在第一階段點(diǎn)火延遲時(shí)間的敏感性分析結(jié)果表明，構(gòu)建的 PODE<sub>2</sub> 、 PODE<sub>3</sub> 的反應(yīng)動(dòng)力學(xué)機(jī)理能夠預(yù)測(cè)實(shí)驗(yàn)測(cè)量的點(diǎn)火延遲時(shí)間，可以對(duì)PODE的反應(yīng)動(dòng)力學(xué)行為作出解釋。通道1和通道2是所有PODE分子所共有的鏈分支反應(yīng)通道，而通道3是高聚合度PODE所特有的反應(yīng)路徑，是重要的反應(yīng)活性貢獻(xiàn)來(lái)源。-龍?jiān)雌诳W(wǎng)" />

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聚甲氧基二甲醚反應(yīng)動(dòng)力學(xué)及聚合度影響機(jī)理探究

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中圖分類號(hào)： TK46+4 文獻(xiàn)標(biāo)志碼：ADOI：10.7652/xjtuxb202508012 文章編號(hào)：0253-987X（2025）08-0122-12

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

ZHOU Zijie1，YANG Yajing2，CUI Wangl，WEI Yanju1，LIU He1 ，LIU Shenghual （1. School of Energy and Power Engineering，Xi'an Jiaotong University，Xi'an 71o049，China; 2.School of Astronautics，Xi'an JiaotongUniversity，Xi'an 7lo049，China）

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 （ PODE1 ），the reaction mechanisms of PODE2 and PODE3 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 chainbranching reaction triggered by secondary carbon dehydrogenation and decomposition into lowerpolymerization-degree fuel radicals. Sensitivity analysis of the first-stage ignition delay time of PODE demonstrates that the constructed reaction kinetic mechanism of PODE2 and PODE3 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.

Keywords： polyoxymethylene dimethyl ethers； reaction kinetics；degree of polymerization； elementary reaction

在可再生合成燃料中，醚類燃料聚甲氧基二甲醚（polyoxymethylene dimethyl ethers，PODE）分子通式為 CH3O（CH2O）nCH3 （記為 PODEn ），具有十六烷值高、含氧量高、污染物排放少的特點(diǎn)[1-3]，并且能較好地適配壓燃式內(nèi)燃機(jī)，應(yīng)用前景良好[4-6]為了在實(shí)際內(nèi)燃機(jī)中有效應(yīng)用PODE這類新型燃料，需要構(gòu)建一種貼合發(fā)動(dòng)機(jī)實(shí)際運(yùn)行工況的燃燒反應(yīng)動(dòng)力學(xué)模型。（剩余21218字）

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