石油中不同环数芳烃化合物的精细分离和制备

刘雪; 李美俊; 唐友军; 何大祥; KONAN N'Guessan Francois De Sales; 师生宝; 朱雷

doi:10.11781/sysydz202103524

石油中不同环数芳烃化合物的精细分离和制备

doi: 10.11781/sysydz202103524

刘雪^{1, 2,},
李美俊^{1, 2, 3, 4, ,},
唐友军^{1, 2},
何大祥^{1, 2, 3, 4},
KONAN N'Guessan Francois De Sales^{3, 4},
师生宝^{3, 4},
朱雷^{3, 4}

1.
长江大学油气资源与勘探技术教育部重点实验室, 武汉 430100
2.
长江大学资源与环境学院, 武汉 430100
3.
中国石油大学(北京)油气资源与勘探国家重点实验室, 北京 102249
4.
中国石油大学(北京) 地球科学学院, 北京 102249

基金项目:

国家自然科学基金项目 41972148

国家重点研发计划 2017YFC0603102

详细信息

作者简介:
刘雪(1993-), 女, 硕士研究生, 从事油气地球化学研究。E-mail: 201872271@yangtzeu.edu.cn

通讯作者:
李美俊(1972-), 男, 教授, 从事油气地球化学、油气成藏研究。E-mail: meijunli@cup.edu.cn

中图分类号: TE135
计量
- 文章访问数: 820
- HTML全文浏览量: 209
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- 被引次数: 0
出版历程
- 收稿日期: 2020-09-03
- 修回日期: 2021-03-10
- 刊出日期: 2021-05-28

An improved column-chromatographic separation for polycyclic aromatic compounds in petroleum

LIU Xue^{1, 2
,},
LI Meijun^{1, 2, 3, 4
, ,},
TANG Youjun^{1, 2},
HE Daxiang^{1, 2, 3, 4},
KONAN N'Guessan Francois De Sales^{3, 4},
SHI Shengbao^{3, 4},
ZHU Lei^{3, 4}

1.
Key Laboratory of Exploration Technologies for Oil and Gas Resources of Ministry of Education, Yangtze University, Wuhan, Hubei 430100, China
2.
College of Resources and Environment, Yangtze University, Wuhan, Hubei 430100, China
3.
State Key Laboratory of Petroleum Resources and Prospecting, China University of Petroleum(Beijing), Beijing 102249, China
4.
College of Geosciences, China University of Petroleum(Beijing), Beijing 102249, China

摘要

摘要: 石油族组分的分离和制备过程是后续分子组成、同位素分析的基础。由于同分异构体多，传统技术制备的芳烃化合物组分仍然无法满足单体化合物的同位素分析要求。采用两种不同的分离方案对原油中的多环芳烃进行精细的分离和制备，其中“一步法”是直接将脱沥青质的原油样品经过一次氧化铝/硅胶层析柱，用不同体积比的石油醚/二氯甲烷混合溶剂进行洗脱；“两步法”先将原油采用常规的族组分分离方法得到芳烃馏分，再将芳烃馏分经氧化铝层析柱，用不同比例的石油醚/二氯甲烷混合溶剂进行洗脱，可得到不同环数芳烃的组分。对洗脱出来的不同组分进行色谱—质谱分析（GC-MS），与“一步法”相比，“两步法”可以更好地实现单环、双环与三环芳烃化合物的分离制备，其中，石油醚/二氯甲烷（99/1，V/V）的混合溶剂可以制备单环芳烃化合物；石油醚/二氯甲烷（9/1，V/V）混合溶剂可制备得到以双环芳烃化合物占绝对优势的组分；石油醚/二氯甲烷（8/2，V/V）混合溶剂则可制备得到三环芳烃化合物组分。
- 石油 /
- 柱层析 /
- 分离 /
- 多环芳烃
Abstract: The separation and preparation process of petroleum group components is the basis for the subsequent molecular composition and isotopic analysis. Due to the complex composition of isomers, the components of aromatic compounds prepared by traditional techniques still cannot meet the isotopic analysis requirements of specific compounds. Two different separating methods were used to finely separate and prepare polycyclic aromatic hydrocarbons in crude oils. The "one-step method" was to directly pass the de-asphalted crude oil samples through an alumina/silica gel chromatography column, and elute them with different ratios of petroleum ether/dichloromethane mixed solvent. The "two-step method" firstly used conventional separation methods to obtain aromatic fraction from crude oils, and then applied the aromatic fraction to a column filled with alumina and sub-fractions with different ring numbers then eluted with mixed solvent with different ratios of petroleum ether/dichloromethane. Gas chromatography-mass spectrometry (GC-MS) analysis for the sub-fractions were carried out for the comparison between the two separation methods. Results show that the "two-step method" can better realize the separation and preparation of monocyclic, bicyclic and tricyclic aromatic compounds. The mixed solvents of petroleum ether/dichloromethane of V/V: 99/1, 9/1 and 8/2 can obtain monocyclic, bicyclic and tricyclic aromatic compounds respectively.
- petroleum /
- column chromatography /
- separation /
- polycyclic aromatic

HTML全文

图 1 “一步法”和“两步法”层析柱分离实验的分离流程

Figure 1. Separating procedures of "one-step" and "two-step" methods

下载: 全尺寸图片幻灯片

图 2 Termit盆地原油样品“一步法”中使用石油醚/二氯甲烷试剂洗脱出的化合物总离子流图

峰上的数值代表取代基的位置

Figure 2. Total ion flow diagram of compounds eluted with petroleum ether/dichloromethane solvents in "one-step" process of crude oil samples from Termit Basin

下载: 全尺寸图片幻灯片

图 3 Termit盆地原油样品“两步法”中使用石油醚/二氯甲烷试剂洗脱出的化合物总离子流图

峰上的数值代表取代基的位置

Figure 3. Total ion flow diagram of compounds eluted with petroleum ether/dichloromethanesolvents in "two-step" process of crude oil samples from Termit Basin

下载: 全尺寸图片幻灯片

图 4 盆地原油样品芳烃总馏分与“两步法”中使用石油醚/二氯甲烷试剂洗脱出的化合物总离子流图

Figure 4. Total aromatic fractions and total ion flow diagrams of compounds eluted with petroleum ether/dichloromethane solvent in "two-step" process of crude oil samples from Termit Basin

下载: 全尺寸图片幻灯片

表 1 Termit盆地原油样品中芳烃化合物亚组分“一步法”检测结果

Table 1. Results of "one-step" separation for aromatic sub-fractions in crude oil samples from Termit Basin

化合物系列	烷基侧链	m/z	石油醚/二氯甲烷(V/V)
化合物系列	烷基侧链	m/z	99/1	95/5	9/1	1/2
烷基苯	C_nH₂_n₊₁	92	有
萘系物	萘	128
	甲基萘	142		有	有
	乙基或二甲基萘	156		有	有
	三甲基萘	170		有	有	有
	四甲基萘	184		有	有	有
菲系物	菲	178				有
	甲基菲	192				有
	乙基或二甲基菲	206				有
	三甲基菲	220				有
	C₄-菲	234

下载: 导出CSV

表 2 Termit盆地原油样品中芳烃化合物亚组分“两步法”检测结果

Table 2. Results of "two-step" separation for aromatic sub-fractions in crude oil samples from Termit Basin

化合物系列	烷基侧链	m/z	石油醚/二氯甲烷(V/V)
化合物系列	烷基侧链	m/z	99/1	95/5	9/1	8/2	0/100
烷基苯	C_nH₂_n₊₁	92	有
萘系物	萘	128
	甲基萘	142		有	有
	乙基或二甲基萘	156		有	有
	三甲基萘	170		有	有
	四甲基萘	184		有	有
菲系物	菲	178				有
	甲基菲	192				有
	乙基或二甲基菲	206				有
	三甲基菲	220				有
	C₄-菲	234

下载: 导出CSV

参考文献(33)

[1]	LI Meijun, WANG Tieguan, LIU Ju, et al. Total alkyl dibenzothiophenes content tracing the filling pathway of condensate reservoir in the Fushan Depression, South China Sea[J]. Science in China Series D(Earth Sciences), 2008, 51(S2): 138-145. doi: 10.1007/s11430-008-6025-6
[2]	侯读杰, 张林晔. 实用油气地球化学图鉴[M]. 北京: 石油工业出版社, 2003. HOU Dujie, ZHANG Linye. Practical oil and gas geochemistry illustrated book[M]. Beijing: Petroleum Industry Press, 2003.
[3]	CHEN Yongxin, TIAN Chuntao, LI Kangning, et al. Influence of thermal maturity on carbon isotopic composition of individual aromatic hydrocarbons during anhydrous closed-system pyrolysis[J]. Fuel, 2016, 186: 466-475. doi: 10.1016/j.fuel.2016.08.102
[4]	JIA Wanglu, WANG Qiuling, PENG Ping'an, et al. Isotopic compositions and biomarkers in crude oils from the Tarim Basin: oil maturity and oil mixing[J]. Organic Geochemistry, 2013, 57: 95-106. doi: 10.1016/j.orggeochem.2013.01.002
[5]	HAYES J M, TAKIGIKU R, OCAMPO R, et al. Isotopic compositions and probable origins of organic molecules in the Eocene Messel shale[J]. Nature, 1987, 329(6134): 48-51. doi: 10.1038/329048a0
[6]	GRICE K, SCHAEFFER P, SCHWARK L, et al. Changes in palaeoenvironmental conditions during deposition of the Permian Kupferschiefer (Lower Rhine Basin, northwest Germany) inferred from molecular and isotopic compositions of biomarker components[J]. Organic Geochemistry, 1997, 26(11/12): 677-690.
[7]	李美俊, 王延山, 王铁玲, 等. 辽河盆地东部凹陷原油的碳同位素组成特征[J]. 现代地质, 2003, 17(2): 217-221. https://www.cnki.com.cn/Article/CJFDTOTAL-XDDZ200302019.htm LI Meijun, WANG Yanshan, WANG Tieling, et al. The characteristics of carbon isotopic composition of the Dongbu Depression in the Liaohe Basin[J]. Geoscience, 2003, 17(2): 217-221. https://www.cnki.com.cn/Article/CJFDTOTAL-XDDZ200302019.htm
[8]	刘美美, 凌媛, 谢曼曼, 等. 多环芳烃单体同位素分析进展[J]. 岩矿测试, 2010, 29(1): 64-70. https://www.cnki.com.cn/Article/CJFDTOTAL-YKCS201001021.htm LIU Meimei, LING Yuan, XIE Manman, et al. Advances in compound specific isotope analysis of polycyclic aromatic hydrocarbons[J]. Rock and Mineral Analysis, 2010, 29(1): 64-70. https://www.cnki.com.cn/Article/CJFDTOTAL-YKCS201001021.htm
[9]	ASIF M, NAZIR A, FAZEELAT T, et al. Applications of polycyclic aromatic hydrocarbons to assess the source and thermal maturity of the crude oils from the Lower Indus Basin, Pakistan[J]. Petroleum Science and Technology, 2011, 29(21): 2234-2246. doi: 10.1080/10916461003699226
[10]	BUDZINSKI H, GARRIGUES P, CONNAN J, et al. Alkylated phenanthrene distributions as maturity and origin indicators in crude oils and rock extracts[J]. Geochimica et Cosmochimica Acta, 1995, 59(10): 2043-2056. doi: 10.1016/0016-7037(95)00125-5
[11]	RADKE M. Application of aromatic compounds as maturity indicators in source rocks and crude oils[J]. Marine and Petroleum Geology, 1988, 5(3): 224-236. doi: 10.1016/0264-8172(88)90003-7
[12]	张敏, 赵红静, 洪艳春, 等. 塔里木盆地海相烃源岩与原油芳烃单体烃碳同位素分布特征及其意义[J]. 中国科学(地球科学), 2014, 44(8): 1723-1730. https://www.cnki.com.cn/Article/CJFDTOTAL-JDXK201408012.htm ZHANG Min, ZHAO Hongjing, HONG Yanchun, et al. The distribution characteristic and its significance of compound specific isotopic composition of aromatic hydrocarbon from marine source rock and oil in the Tarim Basin, Northwest China[J]. Science China Earth Sciences, 2014, 57(11): 2791-2798. https://www.cnki.com.cn/Article/CJFDTOTAL-JDXK201408012.htm
[13]	张敏, 陈祖林, 程熊, 等. 不同沉积环境烃源岩芳烃馏分单体烃碳同位素分布特征及其意义[J]. 石油天然气学报, 2013, 35(12): 13-17. https://www.cnki.com.cn/Article/CJFDTOTAL-JHSX201312002.htm ZHANG Min, CHEN Zulin, CHENG Xiong, et al. Distribution characteristics and significance of individual hydrocarbon carbon isotopes in aromatic fractions of source rocks in different sedimentary environments[J]. Journal of Oil and Gas Technology, 2013, 35(12): 13-17. https://www.cnki.com.cn/Article/CJFDTOTAL-JHSX201312002.htm
[14]	何大祥, 唐友军, 郑彬, 等. 生排烃热模拟中页岩生物标志化合物的变化及其地质意义[J]. 断块油气田, 2020, 27(6): 689-694. https://www.cnki.com.cn/Article/CJFDTOTAL-DKYT202006004.htm HE Daxiang, TANG Youjun, ZHENG Bin, et al. Changes of shale biomarkers in thermal simulation of hydrocarbon generation and expulsion and its geological significance[J]. Fault-Block Oil and Gas Field, 2020, 27(6): 689-694. https://www.cnki.com.cn/Article/CJFDTOTAL-DKYT202006004.htm
[15]	马晓潇, 黎茂稳, 刘鹏, 等. 江汉盆地盐间页岩中芳基类异戊间二烯烷烃特征及对页岩油勘探的意义[J]. 石油实验地质, 2020, 42(4): 575-585. doi: 10.11781/sysydz202004575 MA Xiaoxiao, LI Maowen, LIU Peng, et al. Aryl isoprenoids and their significance for inter-salt shale oil exploration in the Jianghan Basin[J]. Petroleum Geology & Experiment, 2020, 42(4): 575-585. doi: 10.11781/sysydz202004575
[16]	王传远, 杜建国, 段毅, 等. 芳香烃地球化学特征及地质意义[J]. 新疆石油地质, 2007, 28(1): 29-32. https://www.cnki.com.cn/Article/CJFDTOTAL-XJSD200701007.htm WANG Chuanyuan, DU Jianguo, DUAN Yi, et al. Geochemical characteristics and significance of aromatic hydrocarbon in oil and gas[J]. Xinjiang Petroleum Geology, 2007, 28(1): 29-32. https://www.cnki.com.cn/Article/CJFDTOTAL-XJSD200701007.htm
[17]	徐世平, 孙永革. 一种适用于沉积有机质族组分分离的微型柱色谱法[J]. 地球化学, 2006, 35(6): 681-688. https://www.cnki.com.cn/Article/CJFDTOTAL-DQHX200606015.htm XU Shiping, SUN Yongge. Micro-column chromatography for the separation of compound-grouped fractions of sedimentary organic matter[J]. Geochimica, 2006, 35(6): 681-688. https://www.cnki.com.cn/Article/CJFDTOTAL-DQHX200606015.htm
[18]	王汇彤, 魏彩云, 宋孚庆, 等. 细硅胶层析柱对饱和烃和芳烃的分离[J]. 石油实验地质, 2009, 31(3): 312-314. doi: 10.11781/sysydz200903312 WANG Huitong, WEI Caiyun, SONG Fuqing, et al. Separation of saturated and aromatic hydrocarbon using fine silica gel[J]. Petroleum Geology and Experiment, 2009, 31(3): 312-314. doi: 10.11781/sysydz200903312
[19]	JIANG Aizhu, ZHOU Peiyu, SUN Yongge, et al. Rapid column chromatography separation of alkylnaphthalenes from aromatic components in sedimentary organic matter for compound specific stable isotope analysis[J]. Organic Geochemistry, 2013, 60: 1-8. doi: 10.1016/j.orggeochem.2013.04.007
[20]	綦艳丽. 正构烷烃单体烃的氢同位素分析方法及应用[J]. 石油实验地质, 2020, 42(2): 319-324. doi: 10.11781/sysydz202002319 QI Yanli. Method and application of hydrogen isotope analysis of n-alkanes[J]. Petroleum Geology & Experiment, 2020, 42(2): 319-324. doi: 10.11781/sysydz202002319
[21]	陈祖林, 彭相林, 王细超, 等. 中性氧化铝对原油链状烷烃和芳烃组分吸附行为[J]. 地质科技情报, 2010, 29(2): 68-70. https://www.cnki.com.cn/Article/CJFDTOTAL-DZKQ201002014.htm CHEN Zulin, PENG Xianglin, WANG Xichao, et al. Adsorptive behavior of paraffin and aromatic hydrocarbons on neutral alumina[J]. Geological Science and Technology Information, 2010, 29(2): 68-70. https://www.cnki.com.cn/Article/CJFDTOTAL-DZKQ201002014.htm
[22]	熊永强, 耿安松, 廖玉宏, 等. 原油中烷基萘和烷基菲的碳同位素组成研究[J]. 新疆石油地质, 2004, 25(4): 355-357. https://www.cnki.com.cn/Article/CJFDTOTAL-XJSD200404001.htm XIONG Yongqiang, GENG Ansong, LIAO Yuhong, et al. Carbon isotopic composition of alkylnaphthalenes and alkylphenanthrenes in crude oils[J]. Xinjiang Petroleum Geology, 2004, 25(4): 355-357. https://www.cnki.com.cn/Article/CJFDTOTAL-XJSD200404001.htm
[23]	周佩瑜, 孙永革. 原油中萘系物柱色谱快速分离技术及其初步应用[J]. 地球化学, 2008, 37(5): 512-518. https://www.cnki.com.cn/Article/CJFDTOTAL-DQHX200805011.htm ZHOU Peiyu, SUN Yongge. Rapid separation of alkylated naphthalenes in crude oils by column chromatography and its elementary application[J]. Geochimica, 2008, 37(5): 512-518. https://www.cnki.com.cn/Article/CJFDTOTAL-DQHX200805011.htm
[24]	陈祖林, 赵红静, 张敏, 等. 一种快速分离和富集萘系和菲系化合物的小型氧化铝柱层析法[J]. 石油天然气学报, 2012, 34(12): 42-44. https://www.cnki.com.cn/Article/CJFDTOTAL-JHSX201212010.htm CHEN Zulin, ZHAO Hongjing, ZHANG Min, et al. A rapid separation and enrichment of naphthalene and phenanthrene compounds by small alumina column chromatography[J]. Journal of Oil and Gas Technology, 2012, 34(12): 42-44. https://www.cnki.com.cn/Article/CJFDTOTAL-JHSX201212010.htm
[25]	陈祖林, 张敏, 刘海钰. 芳烃单体烃GC/IRMS分析分离的便捷柱色谱法[J]. 石油实验地质, 2013, 35(3): 347-350. doi: 10.11781/sysydz201303347 CHEN Zulin, ZHANG Min, LIU Haiyu. Micro-column convenient chromatography for separation of aromatic hydrocarbon compound and GC/IRMS analysis[J]. Petroleum Geology and Experiment, 2013, 35(3): 347-350. doi: 10.11781/sysydz201303347
[26]	WAN Lunkun, LIU Jiguo, MAO Fengjun, et al. The petroleum geochemistry of the Termit Basin, Eastern Niger[J]. Marine and Petroleum Geology, 2014, 51: 167-183.
[27]	LIU J, ZHANG G, LI Z, et al. Oil charge history of Paleogene-Eocene reservoir in the Termit Basin (Niger)[J]. Australian Journal of Earth Sciences, 2019, 66(4): 597-606.
[28]	XIAO Hong, WANG T G, LI Meijun, et al. Geochemical characteristics of Cretaceous Yogou Formation source rocks and oil-source correlation within a sequence stratigraphic framework in the Termit Basin, Niger[J]. Journal of Petroleum Science and Engineering, 2019, 172: 360-372.
[29]	李美俊, 赖洪飞, 毛凤军, 等. 层序地层格架下烃源岩地球化学研究: 以尼日尔Termit盆地为例[J]. 地球科学, 2018, 43(10): 3603-3615. https://www.cnki.com.cn/Article/CJFDTOTAL-DQKX201810021.htm LI Meijun, LAI Hongfei, MAO Fengjun, et al. Geochemical assessment of source rock within a stratigraphic geochemical framework: taking Termit Basin (Niger) as an example[J]. Earth Science, 2018, 43(10): 3603-3615. https://www.cnki.com.cn/Article/CJFDTOTAL-DQKX201810021.htm
[30]	KILLOPS S D, READMAN J W. HPLC fractionation and GC-MS determination of aromatic hydrocarbons from oils and sediments[J]. Organic Geochemistry, 1985, 8(4): 247-257.
[31]	王培荣. 生物标志物质量色谱图集[M]. 北京: 石油工业出版社, 1993. WANG Peirong. The biomarker quality chromatographic atlas[M]. Beijing: Petroleum Industry Press, 1993.
[32]	李美俊, 师生宝, 王铁冠, 等. 石油和沉积有机质中C_3^-、C_4^-烷基取代二苯并噻吩的鉴定[J]. 地球化学, 2014, 43(2): 157-165. https://www.cnki.com.cn/Article/CJFDTOTAL-DQHX201402007.htm LI Meijun, SHI Shengbao, WANG Tieguan, et al. The identification of C_3^- and C_4^- alkylated dibenzothiophenes in petroleum and sedimentary organic matter[J]. Geochimica, 2014, 43(2): 157-165. https://www.cnki.com.cn/Article/CJFDTOTAL-DQHX201402007.htm
[33]	VAN KAAM-PETERS H M E, KÖSTER J, DE LEEUW J W, et al. Occurrence of two novel benzothiophene hopanoid families in sediments[J]. Organic Geochemistry, 1995, 23(7): 607-616.