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Theoretical study of sensitive reactions in phenol decomposition
Reaction Chemistry & Engineering ( IF 3.4 ) Pub Date : 2019/12/12 , DOI: 10.1039/c9re00418a Luna Pratali Maffei 1, 2, 3, 4 , Matteo Pelucchi 1, 2, 3, 4 , Tiziano Faravelli 1, 2, 3, 4 , Carlo Cavallotti 1, 2, 3, 4
Reaction Chemistry & Engineering ( IF 3.4 ) Pub Date : 2019/12/12 , DOI: 10.1039/c9re00418a Luna Pratali Maffei 1, 2, 3, 4 , Matteo Pelucchi 1, 2, 3, 4 , Tiziano Faravelli 1, 2, 3, 4 , Carlo Cavallotti 1, 2, 3, 4
Affiliation
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The reactivity of phenol is of utmost importance in combustion systems. In fact, phenol is the simplest phenolic compound, abundant in bio-oils derived from biomass fast pyrolysis and therefore included as a reference component in bio-oil surrogate mixtures. Phenol is also relevant to the mechanism of oxidation of benzene, a building block in the growth of polycyclic aromatic hydrocarbons (PAHs), precursors of soot formation. Hence, in a modular and hierarchical approach to combustion chemistry, the knowledge of the pyrolysis and combustion kinetics of phenol is essential to characterize the reactivity and the combustion properties of bio-oils and mono aromatic hydrocarbons (MAHs), as well as to improve the understanding of PAHs and soot formation. Although the reaction pathways of phenol decomposition are well defined in the literature, the rate constants still require more accurate assessment, and a validation of the reaction mechanism of phenol pyrolysis against the full set of experimental data available is still missing. In this work, we compute with the ab initio transition state theory based master equation (AI-TST-ME) method the rate constants of the main reaction pathways of phenol decomposition, also relevant to benzene oxidation. In particular, we investigate phenol molecular decomposition to C5H6 + CO and its competition with the O–H bond fission and H-atom abstraction reactions by H to form the phenoxy radical (C6H5O). We also investigate the successive decomposition of C6H5O to C5H5 + CO and the H-atom abstraction reaction on C5H6 by H, which plays a pivotal role in controlling the H concentration in phenol pyrolysis and combustion. The calculated rate constants are found to be in good agreement with experimental values. The CRECK kinetic model is updated with the new rate constants and validated against the available experimental data of phenol pyrolysis providing, to our knowledge, the first comprehensive validation of phenol decomposition kinetics. However, discrepancies are still present in the profiles of products formed from secondary reactivity. Our analysis suggests that further investigation of the reactivity of C5H6 is required, providing guidelines for a more accurate characterization of the decomposition to smaller species.
中文翻译：
苯酚分解中敏感反应的理论研究
苯酚的反应性在燃烧系统中至关重要。实际上，苯酚是最简单的酚类化合物，在源自生物质快速热解的生物油中含量丰富，因此作为参考成分包含在生物油替代混合物中。苯酚还与苯的氧化机理有关，苯是烟灰形成的前体多环芳烃（PAHs）生长的基础。因此，在模块化的燃烧化学分级方法中，对苯酚的热解和燃烧动力学的了解对于表征生物油和单芳烃（MAH）的反应性和燃烧特性以及改善燃烧效率至关重要。了解多环芳烃和烟灰的形成。尽管在文献中已明确定义了苯酚分解的反应途径，速率常数仍然需要更准确的评估，并且仍然缺少对酚热解反应机理的完整实验数据的验证。在这项工作中，我们使用从头算基于过渡态理论的主方程（AI-TST-ME）方法，苯酚分解的主要反应途径的速率常数也与苯氧化有关。特别是，我们研究了苯酚分子分解为C 5 H 6 + CO及其与O–H键裂变和H形成H原子抽象反应的竞争，从而形成苯氧基（C 6 H 5 O）。我们还研究了C 6 H 5 O到C 5 H 5 + CO的连续分解以及在C 5 H 6上的H原子抽象反应H在酚热解和燃烧中控制H浓度起着关键作用。发现计算出的速率常数与实验值非常吻合。CRECK动力学模型已使用新的速率常数进行了更新，并根据现有的苯酚热解实验数据进行了验证，据我们所知，这是对苯酚分解动力学的首次全面验证。但是，由二次反应形成的产物的谱图中仍然存在差异。我们的分析表明，需要对C 5 H 6的反应性进行进一步研究，为更准确地表征分解为较小物种提供指导。
更新日期：2020-03-03
中文翻译：
苯酚分解中敏感反应的理论研究
苯酚的反应性在燃烧系统中至关重要。实际上，苯酚是最简单的酚类化合物，在源自生物质快速热解的生物油中含量丰富，因此作为参考成分包含在生物油替代混合物中。苯酚还与苯的氧化机理有关，苯是烟灰形成的前体多环芳烃（PAHs）生长的基础。因此，在模块化的燃烧化学分级方法中，对苯酚的热解和燃烧动力学的了解对于表征生物油和单芳烃（MAH）的反应性和燃烧特性以及改善燃烧效率至关重要。了解多环芳烃和烟灰的形成。尽管在文献中已明确定义了苯酚分解的反应途径，速率常数仍然需要更准确的评估，并且仍然缺少对酚热解反应机理的完整实验数据的验证。在这项工作中，我们使用从头算基于过渡态理论的主方程（AI-TST-ME）方法，苯酚分解的主要反应途径的速率常数也与苯氧化有关。特别是，我们研究了苯酚分子分解为C 5 H 6 + CO及其与O–H键裂变和H形成H原子抽象反应的竞争，从而形成苯氧基（C 6 H 5 O）。我们还研究了C 6 H 5 O到C 5 H 5 + CO的连续分解以及在C 5 H 6上的H原子抽象反应H在酚热解和燃烧中控制H浓度起着关键作用。发现计算出的速率常数与实验值非常吻合。CRECK动力学模型已使用新的速率常数进行了更新，并根据现有的苯酚热解实验数据进行了验证，据我们所知，这是对苯酚分解动力学的首次全面验证。但是，由二次反应形成的产物的谱图中仍然存在差异。我们的分析表明，需要对C 5 H 6的反应性进行进一步研究，为更准确地表征分解为较小物种提供指导。
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