Herbinet Olivier, Husson Benoit, Ferrari Maude, Glaude Pierre-Alexandre, Battin-Leclerc Frédérique
Laboratoire Réactions et Génie des Procédés, CNRS, Université de Lorraine, 1 rue Grandville, 54000 Nancy, France.
Proc Combust Inst. 2013 Jan;34(1):297-305. doi: 10.1016/j.proci.2012.06.005.
The oxidation of two blends, benzene/-decane and toluene/-decane, was studied in a jet-stirred reactor with gas chromatography analysis (temperatures from 500 to 1100 K, atmospheric pressure, stoichiometric mixtures). The studied hydrocarbon mixtures contained 75% of aromatics in order to highlight the chemistry of the low-temperature oxidation of these two aromatic compounds which have a very low reactivity compared to large alkanes. The difference of behavior between the two aromatic reactants is highly pronounced concerning the formation of derived aromatic products below 800 K. In the case of benzene, only phenol could be quantified. In the case of toluene, significant amounts of benzaldehyde, benzene, and cresols were also formed, as well as several heavy aromatic products such as bibenzyl, phenylbenzylether, methylphenylbenzylether, and ethylphenylphenol. A comparison with results obtained with neat -decane showed that the reactivity of the alkane is inhibited by the presence of benzene and, to a larger extent, toluene. An improved model for the oxidation of toluene was developed based on recent theoretical studies of the elementary steps involved in the low-temperature chemistry of this molecule. Simulations using this model were successfully compared with the obtained experimental results.
在配有气相色谱分析的喷射搅拌反应器中（温度范围为500至1100K，大气压，化学计量混合物）研究了两种混合物（苯/正癸烷和甲苯/正癸烷）的氧化反应。所研究的烃类混合物含有75%的芳烃，以便突出这两种芳烃化合物低温氧化的化学过程，与大型烷烃相比，它们的反应活性非常低。在低于800K时，两种芳烃反应物在衍生芳烃产物形成方面的行为差异非常明显。就苯而言，只有苯酚可以定量。就甲苯而言，还形成了大量的苯甲醛、苯和甲酚，以及几种重质芳烃产物，如联苄、苯基苄基醚、甲基苯基苄基醚和乙基苯基苯酚。与纯正癸烷的结果比较表明，烷烃的反应活性受到苯的存在的抑制，并且在更大程度上受到甲苯的抑制。基于对该分子低温化学中涉及的基本步骤的最新理论研究，开发了一种改进的甲苯氧化模型。使用该模型进行的模拟成功地与获得的实验结果进行了比较。
