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2-糠酸甲酯与羟基反应动力学的理论研究

Theoretical Studies on the Reaction Kinetics of Methyl 2-Furoate with Hydroxyl Radical

  • 摘要: 糠酸甲酯是随着2,5-呋喃二甲酸二甲酯新合成方法的发展而发展起来的一种新型可再生生物燃料. 本文用CCSD(T)/CBS//M062X/cc-pVTZ方法研究了糠酸甲酯与羟基自由基之间的势能面,包括夺氢反应和加成反应. 确定了异构化和分解反应生成的初级自由基. 结果表明,支链甲基上的夺氢反应是主要的反应通道,呋喃环上的OH加成具有明显的压力依赖性. 本文提出的速率系数为糠酸甲酯燃烧机理的改进提供了重要的动力学数据,为进一步研究实际燃料的燃烧过程奠定了良好的基础.

     

    Abstract: Methyl 2-furoate (FAME2) is a model for the potential renewable biofuel of dimethyl furan-2, 5-dicarboxylate, with the development of its new synthesis method. The potential energy surfaces of H-abstractions and OH-additions between FAME2 and hydroxyl radical (OH) were studied using CCSD(T)/CBS//M062X/cc-pVTZ. The subsequent isomerization and decomposition reactions were also determined for the primary radicals produced. The results showed that H-abstraction on the branched methyl group was the dominant channel and that the OH-addition reactions on the furan ring had a significant pressure dependency. The rate coefficients presented here provide important kinetic data to support future improvement of the combustion mechanism of FAME2, and present a sound basis for further research into practical fuels.

     

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