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Product Identification and Mass Spectrometric Analysis of n-Butane and i-Butane Pyrolysis at Low Pressure
Yi-jun Zhang,Wen-hao Yuan,Jiang-huai Cai,Li-dong Zhang,Fei Qi,Yu-yang Li*
Author NameAffiliationE-mail
Yi-jun Zhang National Synchrotron Radiation Laboratory, University of Science and Technology of China, Hefei 230029, ChinaState Key Laboratory of Fire Science, University of Science and Technology of China, Hefei 230026, China  
Wen-hao Yuan State Key Laboratory of Fire Science, University of Science and Technology of China, Hefei 230026, China  
Jiang-huai Cai National Synchrotron Radiation Laboratory, University of Science and Technology of China, Hefei 230029, China  
Li-dong Zhang National Synchrotron Radiation Laboratory, University of Science and Technology of China, Hefei 230029, China  
Fei Qi National Synchrotron Radiation Laboratory, University of Science and Technology of China, Hefei 230029, ChinaState Key Laboratory of Fire Science, University of Science and Technology of China, Hefei 230026, China  
Yu-yang Li* State Key Laboratory of Fire Science, University of Science and Technology of China, Hefei 230026, China yuygli@ustc.edu.cn 
Abstract:
The pyrolysis of n-butane and i-butane at low pressure was investigated from 823-1823 K in an electrically heated flow reactor using synchrotron vacuum ultraviolet photoionization mass spectrometry. More than 20 species, especially several radicals and isomers, were detected and identified from the measurements of photoionization efficiency (PIE) spectra. Based on the mass spectrometric analysis, the characteristics of n-butane and i-butane pyrolysis were discussed, which provided experimental evidences for the discussion of decomposition pathways of butane isomers. It is concluded that the isomeric structures of n-butane and i-butane have strong influence on their main decomposition pathways, and lead to dramatic differences in their mass spectra and PIE spectra such as the different dominant products and isomeric structures of butene products. Furthermore, compared with n-butane, i-butane can produce strong signals of benzene at low temperature in its pyrolysis due to the enhanced formation of benzene precursors like propargyl and C4 species, which provides experimental clues to explain the higher sooting tendencies of iso-alkanes than n-alkanes.
Key words:  n-Butane, i-Butane, Flow reactor pyrolysis, Synchrotron vacuum ultraviolet photoionization mass spectrometry, Product identification, Mass spectrometric analysis
FundProject:
正丁烷和异丁烷低压热解的产物鉴定及质谱分析
张义军,苑文浩,蔡江淮,张李东,齐飞,李玉阳*
摘要:
利用同步辐射真空紫外光电离质谱技术研究了正丁烷和异丁烷在流动反应器中的低压热解,实验温度为823~1823 K. 通过扫描光电离效率(PIE)谱探测并鉴定了20多种热解产物,特别是多种自由基和同分异构体. 在质谱分析的基础上讨论了正丁烷和异丁烷热解的不同特性,从而为丁烷同分异构体分解路径的讨论提供了实验依据. 通过讨论可以发现,丁烷的同分异构体结构对它们的主要分解路径具有强烈的影响,从而导致了它们质谱和PIE谱的差异,如不同的主要产物和丁烯产物结构等. 此外与正丁烷热解相比,异丁烷热解在较低的温度下即可生成苯,这与后者中炔丙基和C4物种等苯前驱体的生成得到了加强是密切相关的,也为解释支链烷烃碳烟生成趋势高于直链烷烃的现象提供了实验线索.
关键词:  正丁烷和异丁烷,流动反应器热解,同步辐射真空紫外光电离质谱,产物鉴定,质谱分析
DOI:10.1063/1674-0068/26/02/151-156
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