Insights into the interaction kinetics between propene and NOx at moderate temperatures with experimental and modeling methods
Insights into the interaction kinetics between propene and NOx at moderate temperatures with experimental and modeling methods
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DOI：
10.1016/j.proci.2020.07.041
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发表时间：
2020-09
期刊：
影响因子：
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通讯作者：
Wenhao Yuan;L. Ruwe;S. Schwarz;Chuangchuang Cao;Jiuzhong Yang;O. Deutschmann;K. Kohse-Höinghaus
中科院分区：
文献类型：
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作者：
Wenhao Yuan;L. Ruwe;S. Schwarz;Chuangchuang Cao;Jiuzhong Yang;O. Deutschmann;K. Kohse-Höinghaus
这项工作旨在从实验和动力学建模的角度深入了解丙烯与氮氧化物的相互作用。在常压、725-1250K温度范围内的层流反应器中研究了贫燃料（Φ=0.23）条件下丙烯的氧化以及掺杂NOxat的丙烯贫燃料（Φ=0.23）和富燃料（Φ=1.35）条件下的氧化。采用同步加速器真空紫外光电离质谱（SVUV-PIMS）实现了全面的异构体解析主要产品和关键含氮、羰基和烃类中间体的鉴定。为了补充实验，从广泛使用的核心机制开始，开发了一个详细的动力学模型。进行生产率分析和敏感性分析来解释实验观察结果。结果表明,NOx对丙烯氧化反应活性的促进作用是由烯丙基自由基与NO2在低温下发生反应引发的,即C3H5单键A+NO2双键C3H5O+NO。对于富含燃料的丙烯/NOx混合物的氧化，丙烯、O2和产物的温度依赖性摩尔分数分布显示出几个不同的区域，反映了通过C3H5单键A+NO2双键C3H5O+NO的链增长和通过C3H5单键A+NO双键C3H5NO的链终止之间的竞争。还分析和讨论了 NOx 存在下羰基和烃中间体的形成和消耗化学。
This work aims to provide insight into the interaction of propene with NOxfrom both experimental and kinetic modeling perspectives. The oxidation of propene at fuel-lean (ϕ=0.23) condition and the oxidation of propene doped with NOxat fuel-lean (ϕ=0.23) and fuel-rich (ϕ=1.35) conditions have been investigated in a laminar flow reactor at atmospheric pressure in the temperature range of 725-1250 K. Synchrotron vacuum ultraviolet photoionization mass spectrometry (SVUV-PIMS) was used to achieve comprehensive, isomer-resolved identification of major products and critical nitrogenous, carbonyl and hydrocarbon intermediates. To complement the experiments, a detailed kinetic model, starting from widely used core mechanisms, was developed. Rate of production analyses and sensitivity analyses were performed to interpret the experimental observations. The results show that the promoting effects of NOxon the oxidation reactivity of propene are initiated by the reactions of allyl radical with NO2at low temperature,i.e.C3H5single bondA+NO2double bondC3H5O+NO. For the oxidation of the fuel-rich propene/NOxmixture, temperature-dependent mole fraction profiles of propene, O2and products show several distinct regions reflecting a competition between chain propagationviaC3H5single bondA+NO2double bondC3H5O+NO and chain terminationviaC3H5single bondA+NOdouble bondC3H5NO. The formation and consumption chemistry of carbonyl and hydrocarbon intermediates in the presence of NOxwas also analyzed and discussed.