Sivaramakrishnan Raghu, Brezinsky Kenneth, Dayma Guillaume, Dagaut Philippe
Department of Mechanical & Industrial Engineering, University of Illinois at Chicago, Chicago, IL, USA.
Phys Chem Chem Phys. 2007 Aug 21;9(31):4230-44. doi: 10.1039/b703379f. Epub 2007 Jul 17.
The mutual sensitization of the oxidation of NO and a CH(4)-C(2)H(6) (10 : 1) simulated natural gas (NG) blend was studied under fuel lean conditions (Phi = 0.5) at 50 atm and 1000-1500 K in the UIC high pressure shock tube (HPST). New experimental results were also obtained for the mutual sensitization of methane and the NG blend in the CNRS jet stirred reactor (JSR) at 10 atm. A detailed chemical kinetic model was assembled to describe the observed changes in reactivity in the CH(4) and NG blends, with and without NO, in the HPST and the JSR. The data and the validated model (tested against a variety of targets) show a reduced difference of reactivity between methane and NG blends in the presence of NO at characteristic reaction times for the JSR (250-1000 micros). However the HPST data and subsequent simulations using the validated model have revealed that at higher pressures and in the millisecond time scale regime representative of the HPST experiments (and practical combustion devices) there still persists a significant difference in reactivity between methane and NG blends in the presence of NO. The experimental data, the model development and validations and its predictions and utility as a tool to probe the NO-hydrocarbon sensitization effects under practical combustion conditions is discussed.
在伊利诺伊大学芝加哥分校的高压激波管(HPST)中,于50个大气压和1000 - 1500K的贫燃条件(Phi = 0.5)下,研究了NO氧化与CH(4)-C(2)H(6)(10 : 1)模拟天然气(NG)混合气之间的相互敏化作用。在法国国家科学研究中心的喷射搅拌反应器(JSR)中,于10个大气压下,也获得了甲烷与NG混合气相互敏化作用的新实验结果。构建了一个详细的化学动力学模型,以描述在HPST和JSR中,有和没有NO存在时,CH(4)和NG混合气中观察到的反应活性变化。数据和经过验证的模型(针对各种目标进行了测试)表明,在JSR的特征反应时间(250 - 1000微秒)下,存在NO时甲烷与NG混合气之间的反应活性差异减小。然而,HPST数据以及随后使用经过验证的模型进行的模拟表明,在更高压力和代表HPST实验(以及实际燃烧装置)的毫秒时间尺度范围内,存在NO时甲烷与NG混合气之间的反应活性仍存在显著差异。讨论了实验数据、模型开发与验证及其预测,以及作为在实际燃烧条件下探测NO - 碳氢化合物敏化效应工具的实用性。