1,3-丁二烯热裂解的动力学计算与模型研究

引用本文: 杜鸟锋, 甯红波, 李泽荣, 张其翼, 李象远. 1,3-丁二烯热裂解的动力学计算与模型研究[J]. 物理化学学报, 2016, 32(2): 453-464. doi: 10.3866/PKU.WHXB201512071 shu

Citation: DU Niao-Feng, NING Hong-Bo, LI Ze-Rong, ZHANG Qi-Yi, LI Xiang-Yuan. Kinetic Calculation and Modeling Study of 1,3-Butadiene Pyrolysis[J]. Acta Physico-Chimica Sinica, 2016, 32(2): 453-464. doi: 10.3866/PKU.WHXB201512071 shu

1,3-丁二烯热裂解的动力学计算与模型研究

杜鸟锋 ^1, ,
甯红波 ^2, ,
李泽荣 ^{3,
,} ,
张其翼 ^{2,
,} ,
李象远 ^2,

1.
1 四川大学空天科学与工程学院, 成都 610065;
2.
2 四川大学化学工程学院, 成都 610065;
3.
3 四川大学化学学院, 成都 610064

通讯作者: 李泽荣, 张其翼; 李泽荣, 张其翼

基金项目:
国家自然科学基金(91441114,91441132)资助项目 (91441114,91441132)

摘要: 1,3-丁二烯是碳氢燃料燃烧和裂解过程中生成的一种重要产物,也是形成多环芳烃(PAHs)的一种重要前驱体。目前,关于1,3-丁二烯燃烧实验以及机理的研究较多,但是其热裂解机理的研究较少。本文在B3LYP/CBSB7 水平下对1,3-丁二烯裂解过程中相关反应的反应物、产物以及过渡态进行了几何结构优化和频率计算,并通过组合方法CBS-QB3 计算得到了单点能和热力学参数。对于紧致过渡态的反应和无能垒反应,分别采用过渡态理论(TST)和可变反应坐标过渡态理论(VRC-TST)计算其高压极限条件下的反应速率常数。计算得到的反应速率常数与已有文献报导的结果吻合较好。通过量子化学计算,对Hidaka等人提出1,3-丁二烯的热裂解机理模型进行了更新和改进:更新后的机理模型包含45 个物种和224 步反应,并对更新后的机理模型进行了模拟验证。结果表明,更新的机理模型能更好地预测1,3-丁二烯激波管裂解实验过程中C₂H₂、1-丁烯-3-炔(C₄H₄)以及苯(C₆H₆)主要产物的浓度分布,为进一步完善核心机理(C₀-C₄)模型提供了可靠的热、动力学参数。

关键词:

English

Kinetic Calculation and Modeling Study of 1,3-Butadiene Pyrolysis

1.
1 School of Aeronautics & Astronautics, Sichuan University, Chengdu 610065, P. R. China;
2.
2 School of Chemical Engineering, Sichuan University, Chengdu 610065, P. R. China;
3.
3 College of Chemistry, Sichuan University, Chengdu 610064, P. R. China

Corresponding author: 李泽荣, 张其翼; 李泽荣, 张其翼

Received Date: 24 August 2015
Fund Project:
国家自然科学基金(91441114,91441132)资助项目

Abstract: 1,3-Butadiene is an important product in combustion and pyrolysis of hydrocarbon fuels and it is also an important precursor to formpolycyclic aromatic hydrocarbons (PAHs). Currently, a variety of experimental and mechanism studies have been performed on 1,3-butadiene oxidation. However, few studies about pyrolysis mechanism of 1,3-butadiene have been done. In this work, the optimization of the geometries and the vibrational frequencies for the reactants, products, and transition states of the relevant reactions in 1,3-butadiene pyrolysis have been performed at the B3LYP/CBSB7 level. Their single point energies and the thermodynamic parameters are also calculated by using the composite CBS-QB3 method. The high-pressure limit rate constants for tight transition state reactions and barrierless reactions are obtained by transition state theory and variable reaction coordinate transition state theory, respectively. The calculated rate constants in this work are in good agreement with those available from literature. Furthermore, the mechanism of Hidaka et al. is updated with replacing the calculated rate constants of reactions in this work to simulate the shock tube experiment results of 1,3-butadiene pyrolysisand the updated mechanism consists of 45 species and 224 reactions. It can be seen that the updated mechanism can improve the concentration profiles of the main products, ethylene, 1-butylene-3-acetylene, and benzene in 1,3-butadiene pyrolysis. It can also provide reliable kinetic and thermodynamic parameters to further improve the core mechanism of C₀-C₄ species.

Key words:

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1.
沈阳化工大学材料科学与工程学院沈阳 110142

1,3-丁二烯热裂解的动力学计算与模型研究

通讯作者: 李泽荣, 张其翼; 李泽荣, 张其翼

English

Kinetic Calculation and Modeling Study of 1,3-Butadiene Pyrolysis

Corresponding author: 李泽荣, 张其翼; 李泽荣, 张其翼

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通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

1,3-丁二烯热裂解的动力学计算与模型研究

通讯作者: 李泽荣, 张其翼; 李泽荣, 张其翼

English

Kinetic Calculation and Modeling Study of 1,3-Butadiene Pyrolysis

Corresponding author: 李泽荣, 张其翼; 李泽荣, 张其翼

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南： 你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

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