利用不同质谱技术分析鉴定金刚烷类化合物

黄凌; 翁娜; 魏彩云; 苏劲; 张斌; 张文龙; 胡国艺

doi:10.11781/sysydz2020061024

利用不同质谱技术分析鉴定金刚烷类化合物

doi: 10.11781/sysydz2020061024

黄凌^{1, 2,},
翁娜²,
魏彩云²,
苏劲²,
张斌²,
张文龙²,
胡国艺²

1.
中国石油学会学术交流部, 北京 100724
2.
中国石油天然气集团公司油气地球化学重点实验室, 北京 100083

基金项目:

国家自然科学基金项目 41473020

国家自然科学基金项目 40903026

中国石油天然气股份有限公司重点项目 2016A-0205

详细信息

作者简介:
黄凌(1979-), 男, 博士, 高级工程师, 从事油气地球化学研究。E-mail: linghuang@petrochina.com.cn

中图分类号: TE135
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- 被引次数: 0
出版历程
- 收稿日期: 2019-10-10
- 修回日期: 2020-10-19
- 刊出日期: 2020-11-28

Analysis and identification of diamondoids by different mass spectrometry techniques

1.
Academic Exchange Department, Chinese Petroleum Society, Beijing 100724, China
2.
Key Laboratory of Petroleum Geochemistry, CNPC, Beijing 100083, China

摘要

摘要: 金刚烷类化合物因在油气勘探领域具有重要的应用价值受到研究人员的广泛关注。由于具有复杂的分子结构和数量众多的同分异构体，目前对于某些金刚烷类化合物的定性结果还存在争议。通过气相色谱—质谱联用法、气相色谱—三重四极杆质谱联用法和全二维气相色谱—飞行时间质谱联用法，开展了烷基取代单金刚烷衍生物的定性研究，对3-甲基-1-乙基单金刚烷和3，5，7-三甲基-1-乙基单金刚烷在不同类型质谱色谱图中的出峰位置进行了确认。此外，利用MASS FRONTIER软件推断了3，5，7-三甲基-1-乙基单金刚烷在电子轰击离子源作用下的碎裂机理以及产生的特征离子。
- 金刚烷类化合物 /
- 质谱 /
- 定性分析 /
- 碎裂机理
Abstract: Diamondoids have attracted extensive attention from researchers because of their important application value in oil and gas exploration. Since diamondoids have complex molecular structures and a large number of isomers, the identification of certain diamondoids is still controversial. In this paper, a qualitative study of adamantane derivatives, such as 1-ethyl-3-methyladamantane and 1-ethyl-3,5,7-trimethyladamantane, was carried out using gas chromatography-mass spectrometry, gas chromatography-triple quadrupole mass spectrometry and two dimensional gas chromatography-time-of-flight mass spectrometry. The chromatography peak position of these compounds in different mass spectrograms was confirmed. In addition, with the help of MASS FRONTIER software, the fragmentation mechanism and the characteristic ions formed during electron ionization was interpreted for 1-ethyl-3,5,7-trimethyladamantane in the ion source.
- diamondoids /
- mass spectrometer /
- qualitative analysis /
- fragmentation mechanism

HTML全文

图 1 塔里木盆地中深-1C井原油饱和烃样品的单金刚烷类化合物GC-MS色谱图

各峰峰号所代表的化合物见表 1。

Figure 1. GC-MS chromatogram of adamantane derivatives in saturated hydrocarbon of crude oil samples from well Zhongshen-1C in Tarim Basin

下载: 全尺寸图片幻灯片

图 2 塔里木盆地中深-1C井原油饱和烃样品的部分单金刚烷类化合物GC-MS色谱图

各峰峰号所代表的化合物见表 1。

Figure 2. GC-MS chromatogram of partial adamantane derivatives in saturated hydrocarbon of crude oil samples from well Zhongshen-1C in Tarim Basin

下载: 全尺寸图片幻灯片

图 3 3-甲基-1-乙基单金刚烷的标准质谱图(来源于NIST库)

Figure 3. Standard mass spectrum of 1-ethyl-3-methyladamantane (from NIST library)

下载: 全尺寸图片幻灯片

图 4 GC-MS全扫描模式下峰号分别为11^a和11^b色谱峰的质谱图

Figure 4. Mass spectra of peaks with the peak numbers of 11a and 11b in full scan mode of GC-MS

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图 5 塔里木盆地中深-1C井原油饱和烃样品的单金刚烷类化合物GC-MS-MS色谱图

各峰峰号所代表的化合物见表 1。

Figure 5. GC-MS-MS chromatogram of adamantane derivatives in saturated hydrocarbon of crude oil samples from well Zhongshen-1C in Tarim Basin

下载: 全尺寸图片幻灯片

图 6 塔里木盆地中深-1C井原油饱和烃样品的单金刚烷类化合物GC×GC-TOFMS色谱图

各峰峰号所代表的化合物见表 1。

Figure 6. GC×GC-TOFMS chromatogram of adamantane derivatives in saturated hydrocarbon of crude oil samples from well Zhongshen-1C in Tarim Basin

下载: 全尺寸图片幻灯片

图 7 峰号为22^a的色谱峰GC×GC-TOFMS质谱图

Figure 7. GC×GC-TOFMS mass spectra of peak 22^a

下载: 全尺寸图片幻灯片

图 8 3,5,7-三甲基-1-乙基单金刚烷的质谱碎裂机理

Figure 8. Fragmentation mechanism of 1-ethyl-3,5,7-trimethyladamantane in a mass spectrometer

下载: 全尺寸图片幻灯片

表 1 单金刚烷类化合物分子信息

Table 1. Molecular information of adamantane derivatives

峰号	化合物名称	简写	分子式	基峰(m/z)	分子离子峰(m/z)
1	1-甲基单金刚烷	1-MA	C₁₁H₁₈	135	150
2	2-甲基单金刚烷	2-MA	C₁₁H₁₈	135	150
3	1-乙基单金刚烷	1-EA	C₁₂H₂₀	135	164
4	2-乙基单金刚烷	2-EA	C₁₂H₂₀	135	164
5	单金刚烷	A	C₁₀H₁₆	136	136
6	1,3-二甲基单金刚烷	1,3-DMA	C₁₂H₂₀	149	164
7	1,4-二甲基单金刚烷(顺式)	1,4-DMA (cis)	C₁₂H₂₀	149	164
8	1,4-二甲基单金刚烷(反式)	1,4-DMA (trans)	C₁₂H₂₀	149	164
9	1,2-二甲基单金刚烷	1,2-DMA	C₁₂H₂₀	149	164
10	2,6-+2,4-二甲基单金刚烷	2,6-+2,4-DMA	C₁₂H₂₀	149	164
11^{a, b}	3-甲基-1-乙基单金刚烷	1-E-3-MA	C₁₃H₂₂	149	178
12	1,3,5-三甲基单金刚烷	1,3,5-TMA	C₁₃H₂₂	163	178
13	1,3,6-三甲基单金刚烷	1,3,6-TMA	C₁₃H₂₂	163	178
14	1,3,4-三甲基单金刚烷(顺式)	1,3,4-TMA (cis)	C₁₃H₂₂	163	178
15	1,3,4-三甲基单金刚烷(反式)	1,3,4-TMA (trans)	C₁₃H₂₂	163	178
16	1,2,3-三甲基单金刚烷	1,2,3-TMA	C₁₃H₂₂	163	178
17	3,5-二甲基-1-乙基单金刚烷	1-E-3,5-DMA	C₁₄H₂₄	163	192
18	1,3,5,7-四甲基单金刚烷	1,3,5,7-TeMA	C₁₄H₂₄	177	192
19	1,2,5,7-四甲基单金刚烷	1,2,5,7-TeMA	C₁₄H₂₄	177	192
20	1,3,5,6-四甲基单金刚烷	1,3,5,6-TeMA	C₁₄H₂₄	177	192
21	1,2,3,5-四甲基单金刚烷	1,2,3,5-TeMA	C₁₄H₂₄	177	192
22	3,5,7-三甲基-1-乙基单金刚烷	1-E-3,5,7-TMA	C₁₅H₂₆	177	206
注：11^{a, b}表示11号峰在文献中存在11^a和11^b两个峰位的争议。

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