Serinyel Zeynep, Herbinet Olivier, Frottier Ophélie, Dirrenberger Patricia, Warth Valérie, Glaude Pierre Alexandre, Battin-Leclerc Frédérique
Laboratoire Réactions et Génie des Procédés, UMR 7274 CNRS, Université de Lorraine, 1 rue Grandville, 54001 Nancy, France.
Combust Flame. 2013 Nov;160(11):2319-2332. doi: 10.1016/j.combustflame.2013.05.016.
The experimental study of the oxidation of cyclohexane has been performed in a jet-stirred reactor at temperatures ranging from 500 to 1100 K (low- and intermediate temperature zones including the negative temperature-coefficient area), at a residence time of 2 s and for dilute mixtures with equivalence ratios of 0.5, 1, and 2. Experiments were carried out at quasi-atmospheric pressure (1.07 bar). The fuel and reaction product mole fractions were measured using online gas chromatography. A total of 34 reaction products have been detected and quantified in this study. Typical reaction products formed in the low-temperature oxidation of cyclohexane include cyclic ethers (1,2-epoxycyclohexane and 1,4-epoxycyclohexane), 5-hexenal (formed from the rapid decomposition of 1,3-epoxycyclohexane), cyclohexanone, and cyclohexene, as well as benzene and phenol. Cyclohexane displays high low-temperature reactivity with well-marked negative temperature-coefficient (NTC) behavior at equivalence ratios 0.5 and 1. The fuel-rich system (ϕ = 2) is much less reactive in the same region and exhibits no NTC. To the best of our knowledge, this is the first jet-stirred reactor study to report NTC in cyclohexane oxidation. Laminar burning velocities were also measured by the heated burner method at initial gas temperatures of 298, 358, and 398 K and at 1 atm. The laminar burning velocity values peak at ϕ = 1.1 and are measured as 40 and 63.1 cm/s for T = 298 and 398 K, respectively. An updated detailed chemical kinetic model including low-temperature pathways was used to simulate the present (jet-stirred reactor and laminar burning velocity) and literature experimental (laminar burning velocity, rapid compression machine, and shock tube ignition delay times) data. Reasonable agreement is observed with most of the products observed in our reactor, as well as the literature experimental data considered in this paper.
在喷射搅拌反应器中，于500至1100K的温度范围内（包括负温度系数区域的低温和中温区）、停留时间为2秒且当量比为0.5、1和2的稀释混合物条件下，开展了环己烷氧化的实验研究。实验在准大气压（1.07巴）下进行。使用在线气相色谱法测量燃料和反应产物的摩尔分数。本研究共检测并定量了34种反应产物。环己烷低温氧化过程中形成的典型反应产物包括环醚（1,2 - 环氧环己烷和1,4 - 环氧环己烷）、5 - 己烯醛（由1,3 - 环氧环己烷快速分解形成）、环己酮和环己烯，以及苯和苯酚。环己烷在当量比为0.5和1时表现出高低温反应活性以及明显的负温度系数（NTC）行为。富燃料系统（ϕ = 2）在同一区域的反应活性要低得多，且未表现出NTC。据我们所知，这是首次在喷射搅拌反应器研究中报道环己烷氧化中的NTC。还通过加热燃烧器法在初始气体温度为298、358和398K以及1个大气压下测量了层流燃烧速度。层流燃烧速度值在ϕ = 1.1时达到峰值，对于T = 298K和398K，分别测得为40和63.1厘米/秒。使用包含低温路径的更新详细化学动力学模型来模拟当前（喷射搅拌反应器和层流燃烧速度）以及文献中的实验（层流燃烧速度、快速压缩机和激波管点火延迟时间）数据。与我们反应器中观察到的大多数产物以及本文所考虑的文献实验数据观察到了合理的一致性。
