Modeling of two- and three-ring aromatics formation in the pyrolysis of toluene
Modeling of two- and three-ring aromatics formation in the pyrolysis of toluene
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DOI：
10.1016/j.proci.2012.06.032
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发表时间：
2013-01-01
影响因子：
3.4
通讯作者：
Miyoshi, Akira
中科院分区：
文献类型：
--
作者：
Matsugi, Akira;Miyoshi, Akira
在Shukla等人的低压(约10Torr)实验条件下，建立了甲苯热解和随后生成多环芳烃(PAHs)的详细化学动力学模型。作者声明：[J.Phys.化学。A 11 1(2007)8308-8324；J.Phys.化学。A 112(2008)2362-2369]。Richter等人提出的预混火焰中多环芳烃生成动力学模型。[程序。燃烧。安装30(2005)1397-1405]被用作起点模型，并对若干反应进行了修订。对涉及共振稳定烃自由基的重要反应的速率常数进行了计算和经验估算。生成的模型由289个物种和947个反应组成。用该模型进行的数值模拟较好地再现了Shukla等人在1136-1507K下甲苯、甲苯/乙炔和甲苯/苯混合物低压流动反应裂解过程中观察到的二环和三环芳香烃的形成。灵敏度和通量分析表明，苯基、富文烯基和炔丙基等共振稳定自由基的反应对多环芳烃的形成过程具有重要意义。(C)2012年，燃烧研究所。爱思唯尔公司出版，版权所有。
A detailed chemical kinetic model for the pyrolysis of toluene and subsequent formation of polycyclic aromatic hydrocarbons (PAHs) was constructed for the low pressure (similar to 10 Torr) experimental condition of Shukla et al. [J. Phys. Chem. A 11 1 (2007) 8308-8324; J. Phys. Chem. A 112 (2008) 2362-2369]. The kinetic model for PAHs formation in premixed flames proposed by Richter et al. [Proc. Combust. Inst. 30 (2005) 1397-1405] was used as a starting-point model and was revised for a number of reactions. Computational and empirical estimates of the rate constants were performed for important reactions involving resonance stabilized hydrocarbon radicals. The resultant model consists of 289 species and 947 reactions. The numerical simulation with the proposed model satisfactory reproduced the formation of two-and three-ring aromatic hydrocarbons observed in the mass spectrometric experiments for the low-pressure flow-reactor pyrolysis of toluene and toluene/acetylene and toluene/benzene mixtures at temperatures 1136-1507 K by Shukla et al. The sensitivity and flux analyses indicated the importance of the reactions of resonance stabilized radicals such as benzyl, fulvenallenyl and propargyl radicals for the PAHs formation processes. (C) 2012 The Combustion Institute. Published by Elsevier Inc. All rights reserved.