Exploration of the oxidation chemistry of dimethoxymethane: Jet-stirred reactor experiments and kinetic modeling
Exploration of the oxidation chemistry of dimethoxymethane: Jet-stirred reactor experiments and kinetic modeling
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二甲氧基甲烷氧化化学的探索：喷射搅拌反应器实验和动力学建模
DOI：
10.1016/j.combustflame.2018.04.008
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发表时间：
2018-07
影响因子：
4.4
通讯作者：
Philippe Dagaut
中科院分区：
文献类型：
--
作者：
Wenyu Sun;Tao Tao;Maxence Lailliau;Nils Hansen;Bin Yang;Philippe Dagaut
二甲氧基甲烷（DMM，CH_3 OCH_2 OCH_3）是一种实用的柴油添加剂，也是一种简单的聚甲醛二甲醚（POMDME）同系物，被认为是有前途的替代燃料。为了获得DMM氧化动力学的深入知识，在近大气压（750 Torr）下操作的喷射搅拌反应器（JSR）中研究了外部加热的贫燃料（Xe = 0.5）DMM/O2/Ar混合物的化学。采用同步辐射光电离的分子束质谱仪（MBMS）被用来探测活性中间体。高压（10个大气压）氧化实验，涵盖不同的当量比（0.2，0.5和1.5）进行了使用另一个JSR设施配备气相色谱（GC）和傅里叶变换红外光谱（FTIR）的形态测量。构建了一个新的动力学模型，并对当前的测量以及文献报道的那些进行了验证。在所研究的条件下，DMM没有观察到明显的低温反应性，尽管DMM具有足够长的链以允许内部氢转移导致链支化。动力学模型表明，从中央（单键OCH 2 O单键）部分的氢提取的青睐，生产占主导地位的CH 3 OCH 3燃料自由基，然后迅速分解，而不是导致链支化通过O2加成。相反，次要燃料自由基CH 3 OCH 2 OCH 2可以通过O2加成和随后的异构化步骤，如环醚物种的检测所证实的。CH 3 O2 HOCH 3 β-断裂快速产生CH 3的另一个影响是CH 3 O2 H作为重要的OH提供者，促进了中温下的燃料消耗。主要的燃料破坏模式也可能适用于较大的POMDME化合物。
Dimethoxymethane (DMM, CH3OCH2OCH3) is a practical diesel additive, as well as a simple homologue in the class of polyoxymethylene dimethyl ethers (POMDMEs) which are considered as promising alternative fuels. To acquire an in-depth knowledge of DMM oxidation kinetics, the chemistry of an externally heated fuel-lean (ϕ= 0.5) DMM/O2/Ar mixture was investigated in a jet-stirred reactor (JSR) operated at near-atmospheric pressure (750 Torr). A molecular-beam mass spectrometer (MBMS) employing synchrotron photoionization was used to probe reactive intermediates. High-pressure (10 atm) oxidation experiments covering different equivalence ratios (0.2, 0.5 and 1.5) were carried out using another JSR facility equipped with gas chromatography (GC) and Fourier transform infrared spectrometry (FTIR) for speciation measurements. A new kinetic model was constructed and validated against the current measurements as well as those reported in literature. No obvious low-temperature reactivity was observed for DMM under the investigated conditions, though DMM has a long enough chain to allow internal hydrogen transfers leading to chain-branching. The kinetic modeling showed that hydrogen abstractions from the central (single bondOCH2Osingle bond) moiety are favored, producing dominantly the CH3OĊHOCH3fuel radical, which then rapidly decomposes instead of leading to chain-branching via O2addition. In contrast, the minor fuel radical CH3OCH2OĊH2can go through the O2addition and the subsequent isomerization steps, as confirmed by the detection of cyclic ether species. Another impact of the fast CH3production from CH3OĊHOCH3β-scission is that CH3O2H serves as an important OH provider, facilitating the fuel consumption at medium temperatures. Major fuel destruction patterns could also apply to larger POMDME compounds.
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影响因子：
4.4
作者：
Shengkai Wang;D. Davidson;R. Hanson
通讯作者：
Shengkai Wang;D. Davidson;R. Hanson
聚甲醛二甲醚 3 (POMDME3) 火焰的形态和层流燃烧速度：实验和建模研究
影响因子：
3.4
作者：
Wenyu Sun;Guoqing Wang;Shuang Li;Ruzheng Zhang;Bin Yang;Jiuzhong Yang;Yuyang Li;Charles K. Westbrook;Chung K. Law
通讯作者：
Chung K. Law
DOI：
10.1021/j100147a027
发表时间：
1993-11
期刊：
The Journal of Physical Chemistry
影响因子：
--
作者：
M. Jenkin;G. Hayman;T. Wallington;M. D. Hurley;J. C. Ball;O. Nielsen;T. Ellermann
通讯作者：
M. Jenkin;G. Hayman;T. Wallington;M. D. Hurley;J. C. Ball;O. Nielsen;T. Ellermann
DOI：
10.1016/j.proci.2016.06.088
发表时间：
2017
期刊：
The journal of physical chemistry. A
影响因子：
--
作者：
M. Döntgen;Leif C. Kröger;K. Leonhard
通讯作者：
M. Döntgen;Leif C. Kröger;K. Leonhard
DOI：
10.1021/acs.jpca.5b01801
发表时间：
2015-06
期刊：
The journal of physical chemistry. A
影响因子：
--
作者：
A. Alquaity;B. Giri;J. Lo;A. Farooq
通讯作者：
A. Alquaity;B. Giri;J. Lo;A. Farooq