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C2链烃在热解/气化中的碳链裂解机理及速率常数计算研究

朱中旭 唐烽 金余其 陈思雨 马家瑜

朱中旭, 唐烽, 金余其, 陈思雨, 马家瑜. C2链烃在热解/气化中的碳链裂解机理及速率常数计算研究[J]. 燃料化学学报. doi: 10.19906/j.cnki.JFCT.2022048
引用本文: 朱中旭, 唐烽, 金余其, 陈思雨, 马家瑜. C2链烃在热解/气化中的碳链裂解机理及速率常数计算研究[J]. 燃料化学学报. doi: 10.19906/j.cnki.JFCT.2022048
ZHU Zhong-xu, TANG Feng, JIN Yu-qi, CHEN Si-yu, MA Jia-yu. Computational study on the chain cracking mechanisms and rate constants of C2 chain hydrocarbons during pyrolysis/gasification[J]. Journal of Fuel Chemistry and Technology. doi: 10.19906/j.cnki.JFCT.2022048
Citation: ZHU Zhong-xu, TANG Feng, JIN Yu-qi, CHEN Si-yu, MA Jia-yu. Computational study on the chain cracking mechanisms and rate constants of C2 chain hydrocarbons during pyrolysis/gasification[J]. Journal of Fuel Chemistry and Technology. doi: 10.19906/j.cnki.JFCT.2022048

C2链烃在热解/气化中的碳链裂解机理及速率常数计算研究

doi: 10.19906/j.cnki.JFCT.2022048
基金项目: 国家重点研发计划(2018YFD1100602)资助
详细信息
    通讯作者:

    金余其, 男, 博士, 主要从事废弃物焚烧、热解气化和资源化利用研究. E-mail: jinyuqi@zju.edu.cn

  • 中图分类号: O643.12

Computational study on the chain cracking mechanisms and rate constants of C2 chain hydrocarbons during pyrolysis/gasification

Funds: Supported by National Key R&D Program of China (2018YFD1100602)
  • 摘要: 链烃裂解在热解/气化过程中大量存在,其中轻质链烃反应时间短并且存在多种反应路径,难以通过试验的方式对单一演变路径进行准确的检测和分析。本文选用Gaussian及其配套软件对C2系列链烃(包括乙烷、乙烯和乙炔)的反应位点进行了预测,并对上述链烃在H/OH/O自由基及水分子作用下的碳链裂解机理进行研究。结果表明,自由基对乙烷的C原子及H原子均可发起进攻,而对于乙烯和乙炔的进攻则主要集中在C原子。在上述三种自由基中,OH自由基对不饱和烃的裂解效果最佳,而H自由基对于饱和烃的裂解效果更好,该结果反映了实际过程中水蒸气对于C2系列链烃化合物的碳链断裂具有积极作用。此外,对比乙烯和乙炔与OH自由基作用的最优路径可以发现CH2CH2OH在低于1200 K的环境中比CH2CHO更容易裂解,而在高于1200 K的环境中则是CH2CHO裂解更易,从中可以推断出醛类基团对于温度变化的响应速度优于醇类基团。
  • 图  1  C2链烃化合物在电子密度为0.001a.u.等值面上的静电势(ESP)及平均局部离子化能(ALIE)分布图((a)、 (b)、 (c)为ESP分布;(d)、 (e)、 (f)为ALIE分布)

    Figure  1  The distribution of electrostatic potential and average local ionization energy of C2 chain hydrocarbons on the isosurface of electron density of 0.001a.u. ((a), (b), (c) are ESP;(d), (e), (f) are ALIE)

    图  2  乙烷在不同路径下的反应能垒变化图

    Figure  2  The change of reaction energy barrier of ethane under different paths

    图  3  乙烯在不同路径下的反应能垒变化图

    Figure  3  The change of reaction energy barrier of ethylene under different paths

    图  4  乙炔在不同路径下的反应能垒变化图

    Figure  4  The change of reaction energy barrier of acetylene under different paths

    图  5  乙烷在不同路径下的反应速率常数

    Figure  5  Reaction rate constants of ethane under different reaction paths

    图  6  乙烯在不同路径下的反应速率常数

    Figure  6  Reaction rate constants of ethylene under different reaction paths

    图  7  乙炔在不同路径下的反应速率常数

    Figure  7  Reaction rate constants of acetylene under different reaction paths

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  • 收稿日期:  2022-03-14
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