Experimental and kinetic modeling study of the oxidation of benzene
Experimental and kinetic modeling study of the oxidation of benzene
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DOI：
10.1002/1097-4601(2000)32:8
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发表时间：
2000
影响因子：
1.5
通讯作者：
M. Alzueta;P. Glarborg;K. Dam‐Johansen
中科院分区：
文献类型：
--
作者：
M. Alzueta;P. Glarborg;K. Dam‐Johansen
已经通过实验和详细的化学动力学模型研究了流动反应器条件下苯的氧化。实验是在活塞流条件下进行的，过量空气比范围从接近化学计量到非常稀薄。温度范围为 900–1450 K，停留时间约为 150 ms。通过改变水蒸气的浓度和添加NO来扰动自由基池。此外，还对苯酚的热解和氧化进行了一些实验。苯氧化在~1000 K 时开始；完全氧化的温度取决于化学计量，范围从 1100 K（非常稀薄的条件）到 1300 K（接近化学计量）。水蒸气水平和 NO 的存在对氧化温度范围只有很小的影响。通过与现有实验数据以及文献中的流动反应器和混合反应器数据进行比较，验证了所提出的化学动力学模型。该模型对苯在研究条件范围内的整体氧化行为提供了相当好的描述。然而，在令人满意地预测氧化行为的细节之前，需要解决许多动力学问题。这些包括苯基和环戊二烯基与分子氧反应的产物通道和速率，以及氧化过程中作为中间体形成的含氧环状化合物的反应化学。 © 2000 John Wiley & Sons, Inc. Int J Chem Kinet 32: 498–522, 2000
The oxidation of benzene under flow-reactor conditions has been studied experimentally and in terms of a detailed chemical kinetic model. The experiments were performed under plug-flow conditions, at excess air ratios ranging from close to stoichiometric to very lean. The temperature range was 900–1450 K and the residence time of the order of 150 ms. The radical pool was perturbed by means of varying the concentration of water vapor and by adding NO. Furthermore, a few experiments were conducted on pyrolysis and oxidation of phenol. Benzene oxidation is initiated at ∼1000 K; the temperature for complete oxidation depends on stoichiometry, ranging from 1100 K (very lean conditions) to 1300 K (close to stoichiometric). The water vapor level and the presence of NO have only a minor impact on the temperature regime for oxidation. The proposed chemical kinetic model was validated by comparison with the present experimental data as well as flow reactor and mixed reactor data from literature. The model provides a reasonably good description of the overall oxidation behavior of benzene over the range of conditions investigated. However, before details of the oxidation behavior can be predicted satisfactorily, a number of kinetic issues need to be resolved. These include product channels and rates for the reactions of phenyl and cyclopentadienyl with molecular oxygen as well as reaction chemistry for the oxygenated cyclic compounds formed as intermediates in the oxidation process. © 2000 John Wiley & Sons, Inc. Int J Chem Kinet 32: 498–522, 2000