首页|基于量子化学计算的正己烷热解反应动力学模拟

基于量子化学计算的正己烷热解反应动力学模拟

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  • 国家科技期刊平台
  • NETL
  • NSTL
  • 万方数据
为研究正己烷(n-C6H14)的常压热解特性，提出了正己烷热解(NHP)模型，该模型使用基于误差传播的直接关系图(DRGEP)简化方法和色散校正密度泛函理论的B2PLYP/def2-tzvp方法，得到了一个包含33种物种和134个基元反应的简化机理。利用该模型计算了n-C6H14在不同温度下主要热解产物乙烯(C2H4)、丙烯(C3H6)和丁炔(C4H6)的相对摩尔分数，并对n-C6H14的热解过程进行了反应路径分析。利用同步辐射真空紫外光电离质谱法(SVUV-PIMS)结合射流搅拌反应器(JSR)在温度为673～1103K、压力为1atm条件下对n-C6H14进行了热解实验，并与NHP模型进行了对比分析。结果表明:n-C6H14热解过程中最主要的产物是C2H4，促使C2H4生成较为重要的两个反应的指前因子分别为6。01×1013s-1和2。18×1013s-1。在673～1023K温度范围内，结合量子化学计算得到的NHP模型对n-C6H14主要热解产物的相对摩尔分数进行了预测，与JetSurF 2。0模型相比，C2H4和C4H6的最大误差分别减小了27。9%和47。9%。反应路径分析表明，C2H4主要来源于己基的一系列β位断裂。
Kinetic simulation of n-hexane pyrolysis reaction based on quantitative calculations
To study the atmospheric pressure pyrolysis properties of n-hexane(n-C6H14),an n-hexane pyrolysis(NHP)model was proposed,which used the error propagation-based direct relation graph(DRGEP)simplification method and the B2PLYP/def2-tzvp method employing dispersion-corrected density-functional theory to obtain a model with 33 components and 134 primitive reactions in a simplified mechanism.The model was utilized to calculate the relative mole fractions of the major pyrolysis products of n-C6H14,ethylene(C2H4),propylene(C3H6)and butyne(C4H6),at different temperatures,and the reaction pathways were analyzed for the pyrolysis process of n-C6H14.The pyrolysis of n-C6H14 was tested using synchrotron radiation vacuum ultraviolet photoionization mass spectrometry(SVUV-PIMS)coupled with a jet-stirred reactor(JSR)at temperatures ranging from 673K to 1103K and pressures up to 1atm,and was analyzed in comparison with the NHP model.The results showed that the finger-forward factors for the two reactions,which were more important for promoting the generation of C2H4,were 6.01×1013s-1 and 2.18×1013s-1,respectively.n-C6H14 was mainly analyzed by the NHP model combined with the NHP model obtained from quantum chemical calculations in the temperature range of 673-1023K.The relative molar fractions of the main n-C6H14 pyrolysis products were predicted in terms of their relative molar fractions.Compared with the JetSurF 2.0 model,the maximum errors for C2H4 and C4H6 were reduced by 27.9%and 47.9%,respectively.The reaction path analysis indicated that the most dominant product during the pyrolysis of n-C6H14 was C2H4,which mainly originated from a series of β-breaks of the hexyl group.

n-hexanepyrolysiscomputational chemistryreaction kineticssynchrotron-base vacuum ultraviolet photoionization mass spectrometry(SVUV-PIMS)jet-stirred reactor(JSR)

殷晨阳、刘永峰、陈睿哲、张璐、宋金瓯、刘海峰

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北京建筑大学北京市建筑安全监测工程技术研究中心,北京 102627

天津大学先进内燃动力全国重点实验室,天津 300072

正己烷 热解 计算化学 反应动力学 同步辐射真空紫外光电离质谱法 射流搅拌反应器

国家自然科学基金先进内燃动力全国重点实验室开放基金

51976007K2023-04

2024

10.16085/j.issn.1000-6613.2023-1268

化工进展
中国化工学会,化学工业出版社

化工进展

CSTPCD北大核心
影响因子：1.062
ISSN：1000-6613
年,卷(期)：2024.43(8)