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吸热型碳氢燃料正癸烷热裂解机理、热沉及产物分布的理论研究

李国娜 ,  李春迎 ,  王渭娜 ,  沈文 ,  吕剑 ,  王文亮

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引用本文: 李国娜, 李春迎, 王渭娜, 沈文, 吕剑, 王文亮. 吸热型碳氢燃料正癸烷热裂解机理、热沉及产物分布的理论研究[J]. 燃料化学学报, 2013, 41(9): 1136-1145. shu
Citation:  LI Guo-na, LI Chun-ying, WANG Wei-na, SHEN Wen, LÜ Jian, WANG Wen-liang. Theoretical study on the mechanism, heat sink and product distribution for thermal decomposition of endothermic hydrocarbon fuel n-decane[J]. Journal of Fuel Chemistry and Technology, 2013, 41(9): 1136-1145. shu

吸热型碳氢燃料正癸烷热裂解机理、热沉及产物分布的理论研究

    通讯作者: 王文亮, Tel: 029-81530815, Fax: +86-29-81530727, E-mail: wlwang@snnu.edu.cn。
  • 基金项目:

    国家自然科学基金(21173139)。 (21173139)

摘要: 采用密度泛函理论(DFT)的B3LYP方法在6-311G(d,p)基组水平上对正癸烷裂解过程中涉及的反应物、产物及过渡态进行了几何构型优化和振动频率计算,运用B3LYP/aug-cc-pVTZ方法计算单点能并构建势能剖面图。利用TheRate程序包及Eckart校正模型计算了各反应速率常数k。采用统计热力学原理求得不同温度下的热容Cp,mθ及熵S298 Kθ,并通过设计等键反应获得了各物种的标准生成焓△fH298 Kθ。用Chemkin II程序模拟预测了产物分布,理论计算了热沉值,并讨论了温度、压力对产物分布和热沉的影响。结果表明,C-C键断裂过程是反应的初始步骤,且抽氢反应较β键断裂反应更易进行。裂解起始温度为500 ℃,反应主要发生在600~700 ℃,其主要产物为氢气、甲烷、乙烯、乙烷、丙烯和1,3-丁二烯,且产物分布随温度不同而变化。模拟计算获得正癸烷在温度600 ℃、压力2.5 MPa条件下的总热沉值为2.334 MJ/kg,对应的热裂解转化率为25.9%,该热沉值可以满足速率为5~6马赫数的飞行器的冷却要求。

English

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  • 收稿日期:  2013-02-19
  • 网络出版日期:  2013-05-04
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