Laboratoire Réactions et Génie des Procédés (LRGP), Université de Lorraine, CNRS, BP 20451, 1 rue Grandville, 54001 Nancy, France.
J Phys Chem A. 2013 Feb 21;117(7):1371-92. doi: 10.1021/jp308901q. Epub 2013 Jan 31.
A detailed kinetic model describing the oxidation of 2,5-dimethylfuran (DMF), a potential second-generation biofuel, is proposed. The kinetic model is based upon quantum chemical calculations for the initial DMF consumption reactions and important reactions of intermediates. The model is validated by comparison to new DMF shock tube ignition delay time measurements (over the temperature range 1300-1831 K and at nominal pressures of 1 and 4 bar) and the DMF pyrolysis speciation measurements of Lifshitz et al. [ J. Phys. Chem. A 1998 , 102 ( 52 ), 10655 - 10670 ]. Globally, modeling predictions are in good agreement with the considered experimental targets. In particular, ignition delay times are predicted well by the new model, with model-experiment deviations of at most a factor of 2, and DMF pyrolysis conversion is predicted well, to within experimental scatter of the Lifshitz et al. data. Additionally, comparisons of measured and model predicted pyrolysis speciation provides validation of theoretically calculated channels for the oxidation of DMF. Sensitivity and reaction flux analyses highlight important reactions as well as the primary reaction pathways responsible for the decomposition of DMF and formation and destruction of key intermediate and product species.
提出了一个详细的动力学模型，用于描述 2,5-二甲基呋喃（DMF）的氧化，DMF 是一种有潜力的第二代生物燃料。该动力学模型基于量子化学计算，用于描述初始 DMF 消耗反应和重要中间体反应。通过与新的 DMF 激波管点火延迟时间测量（温度范围为 1300-1831 K，名义压力为 1 和 4 巴）以及 Lifshitz 等人的 DMF 热解谱测量进行比较，对模型进行了验证。[J. Phys. Chem. A 1998, 102 (52), 10655-10670]。总体而言，模型预测与考虑的实验目标非常吻合。特别是，新模型很好地预测了点火延迟时间，模型与实验的偏差最大不超过 2 倍，并且很好地预测了 DMF 热解转化率，与 Lifshitz 等人的数据的实验分散度一致。此外，对测量和模型预测的热解谱的比较验证了 DMF 氧化的理论计算通道。敏感性和反应通量分析突出了重要的反应以及负责 DMF 分解以及关键中间体和产物形成和破坏的主要反应途径。
