物理化学学报 >> 2016, Vol. 32 >> Issue (3): 595-604.doi: 10.3866/PKU.WHXB201512211

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基于直接关系图方法的丁酸甲酯燃烧反应机理的框架简化

王全德*()   

  • 收稿日期:2015-10-15 发布日期:2016-03-04
  • 通讯作者: 王全德 E-mail:wqd198686@126.com
  • 基金资助:
    中央高校基本科研业务费专项资金(2013QNA08);国家自然科学基金(21403296)

Skeletal Mechanism Generation for Methyl Butanoate Combustion via Directed Relation Graph Based Methods

Quan-De WANG*()   

  • Received:2015-10-15 Published:2016-03-04
  • Contact: Quan-De WANG E-mail:wqd198686@126.com
  • Supported by:
    the Fundamental Research Funds for the Central Universities of China(2013QNA08);National Natural Science Foundation of China(21403296)

摘要:

由于直接关系图(DRG)方法的概念简单和计算量较小,使得DRG方法目前已经成为详细燃烧反应机理框架简化的主流方法。DRG方法中评价物种之间依赖关系的相互作用系数和关系图连接权重的计算方法控制着DRG方法的简化效果。采用四种不同形式的相互作用系数的定义方法,分别与标准的DRG搜索算法和基于误差传播的搜索算法结合,构建了丁酸甲酯的框架燃烧反应机理。通过系统的误差分析比较了不同简化方法构建的框架机理的模拟可靠性。重点采用基于元素流量分析的反应路径分析方法研究了框架机理的化学动力学。最后,通过交集的思想构建了一个只包含96个物种的丁酸甲酯框架燃烧反应机理,并且反应路径分析结果表明丙烯的燃烧化学动力学在丁酸甲酯燃烧过程中占有重要地位。本文通过对不同DRG方法的系统比较研究表明了反应路径分析在框架机理可靠性验证中的重要性,对进一步发展更为有效的框架简化方法提供重要依据。

关键词: 燃烧反应机理, 直接关系图方法, 框架简化, 丁酸甲酯

Abstract:

Directed relation graph (DRG) based skeletal reduction methods have become the mainstream approach for skeletal mechanism generation because of their simple concept and low computational cost. Within the DRG framework, the definitions of the interaction coefficients and the connection weights in different DRG methods control the resulting skeletal mechanisms. In this work, based on DRG methods, four contemporary definitions of the interaction coefficients in conjunction with both standard DRG and error propagation (EP) graph search methods are used to derive skeletal mechanisms for methyl butanoate (MB) combustion. Detailed comparisons of contemporary DRG based methods are performed by systematic error analysis. To further evaluate the performance of the different DRG-based methods, reaction paths are investigated via element flux analysis to check the chemical kinetics of the resulting skeletal mechanisms. Furthermore, a 96-species skeletal mechanism for MB combustion is proposed. Reaction path analysis highlights the importance of propene chemistry during MB oxidation. This work reveals the applicability of reaction path analysis in skeletal reduction using different DRG-based methods, and also provides critical information for further development of skeletal reduction methods.

Key words: Combustionmechanism, Directed relation graphmethod, Skeletal reduction, Methyl butanoate

MSC2000: 

  • O643