在线裂解色谱—同位素比值质谱测定天然气丙烷位碳同位素及其初步应用

马媛媛; 陶成; 把立强; 王杰; 李吉鹏; 李璐赟; 孙永革

doi:10.11781/sysydz202202350

在线裂解色谱—同位素比值质谱测定天然气丙烷位碳同位素及其初步应用

doi: 10.11781/sysydz202202350

马媛媛^{1, 2,},
陶成^{1, 2},
把立强^{1, 2},
王杰^{1, 2},
李吉鹏^{1, 2},
李璐赟^{1, 2},
孙永革^{1, 2, 3, ,}

1.
中国石化石油勘探开发研究院无锡石油地质研究所, 江苏无锡 214126
2.
中国石化油气成藏重点实验室, 江苏无锡 214126
3.
浙江大学地球科学学院有机地球化学研究组, 杭州 31002

基金项目:

国家自然科学基金 42030803

中国石化科技部项目 P21035-1

详细信息

作者简介:
马媛媛(1983—)，女，高级工程师，从事油气地球化学研究。E-mail: mayuanyuan.syky@sinopec.com

通讯作者:
孙永革(1969—)，男，教授，从事有机地球化学研究。E-mail：ygsun@zju.edu.cn

中图分类号: TE135
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- 文章访问数: 628
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- 被引次数: 0
出版历程
- 收稿日期: 2021-12-20
- 修回日期: 2022-02-10
- 刊出日期: 2022-03-28

Measurements of position-specific carbon isotopic compositions in propane by on-line Gas Chromatography-Pyrolysis-Gas Chromatography-Isotope Ratio Mass Spectrometer (GC-Py-GC-IRMS) and its preliminary application

MA Yuanyuan^{1, 2
,},
TAO Cheng^{1, 2},
BA Liqiang^{1, 2},
WANG Jie^{1, 2},
LI Jipeng^{1, 2},
LI Luyun^{1, 2},
SUN Yongge^{1, 2, 3
, ,}

1.
Wuxi Research Institute of Petroleum Geology, SINOPEC, Wuxi, Jiangsu 214126, China
2.
SINOPEC Key Laboratory of Petroleum Accumulation Mechanisms, Wuxi, Jiangsu 214126, China
3.
Organic Geochemistry Unit, School of Earth Sciences, Zhejiang University, Hangzhou, Zhejiang 310027, China

摘要

摘要: 遵循富集、色谱分离、瞬时裂解、同位素比值测试原则，搭建了气相色谱—裂解—气相色谱同位素比值质谱(GC-Py-GC-IRMS)在线位碳同位素测试系统用以测定特定化合物位碳同位素组成。由于丙烷瞬时裂解严格受控于动力学过程，因此，以丙烷为例，考察不同温度下丙烷裂解转化率以及裂解产物碳同位素组成，获得该测试系统丙烷的最佳裂解温度为780~820 ℃，并根据丙烷裂解动力学分馏模型，计算获得丙烷位碳同位素组成。对鄂尔多斯盆地大牛地气田已知上古生界煤系成因两件天然气样品丙烷位碳同位素进行了测定，结果表明，奥陶系马家沟组五段气藏和石炭—二叠系气藏天然气丙烷中心碳相同的碳同位素组成可能指示二者具有相同的气源，而石炭—二叠系气藏天然气丙烷端元碳同位素显著富集¹³C，则指示了其高演化阶段成因特征。研究成果初步展示了丙烷位碳同位素组成在天然气成因研究中具有广阔应用前景。
- 稳定同位素 /
- 位碳同位素 /
- 丙烷 /
- 天然气 /
- 鄂尔多斯盆地
Abstract: In this study, an on-line Gas Chromatography-Pyrolysis-Gas Chromatography-Isotope Ratio Mass Spectrometer (GC-Py-GC-IRMS) was established to conduct position-specific isotope analysis (PSIA) by enrichment of compound interested, chromatographic separation, instantaneous pyrolysis and isotope ratio measurement. Propane, as its instantaneous pyrolysis can be kinetically controlled, was selected for tests. The molar conversion (mol%) of propane during pyrolysis and the carbon isotopic compositions of pyrolysis products upon temperature sequence show that the optimal pyrolysis temperature of propane is 780-820 ℃ for its position-specific carbon isotope analysis. Integrated with carbon isotopic fractionation during the propane pyrolysis, the carbon isotopes of central and terminal carbon were successfully calculated. Two natural gas samples from the Daniudi Gas Field, Ordos Basin were collected for central and terminal carbon isotope measurements in propane. Similar δ¹³C values of central carbon of propane in natural gas from the Ordovician and Carboniferous-Permian reservoirs could be indicative of the same source strata. While ¹³C-enrichment in the terminal C-atom of propane in natural gas from the Carboniferous-Permian reservoirs probably indicates that natural gas accumulated in the Carboniferous-Permian reservoir maybe have experienced a higher thermal maturation compared to that from the Ordovician reservoirs. The results suggest that the PSIA in propane can be a potentially powerful tool to probe the mechanisms on natural gas generation.
- stable isotope /
- position-specific carbon isotope /
- propane /
- natural gas /
- Ordos Basin

HTML全文

图 1 气相色谱—裂解—气相色谱同位素比值质谱(GC-Py-GC-IRMS)在线位碳同位素测试系统示意

Figure 1. On-line determination using Gas Chromatography-Pyrolysis-Gas Chromatography-Isotope Ratio Mass Spectrometer (GC-Py-GC-IRMS)

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图 2 天然气样品G中丙烷在不同裂解温度下产物及残余丙烷的相对摩尔含量

Figure 2. Relative molar concentration (mol%) of fragments and residual propane from propane pyrolysis of natural gas sample G at different temperatures

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图 3 天然气样品G中丙烷在820 ℃裂解产物的气相色谱图

Figure 3. Gas chromatogram of pyrolysis products from propane in natural gas sample G at 820 ℃

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图 4 丙烷瞬时裂解反应过程与产物特征^[24-25]

Figure 4. Process and product characteristics of propane instantaneous pyrolytic reactions

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图 5 丙烷在不同裂解温度下产物及残余丙烷的碳同位素值

Figure 5. δ¹³C values of residual propane and its pyrolytic fragments at different temperatures

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图 6 鄂尔多斯盆地大牛地气田奥陶系马五段与石炭—二叠系储集层天然气成因判识图^[39]

Figure 6. Genetic identification of natural gas in 5th member of Ordovician Majiagou Formation and Carboniferous-Permian reservoirs, Daniudi Gas Field, Ordos Basin

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表 1 天然气样品基础数据

Table 1. Basic data of natural gas samples

样品	层位	天然气组分含量/%										碳同位素δ¹³C_VPDB/‰
样品	层位	H₂	N₂	CO₂	CH₄	C₂H₆	C₃H₈	iC₄H₁₀	nC₄H₁₀	iC₅H₁₂	nC₅H₁₂	C₁	C₂	C₃
G		12.89	2.82	0.84	73.64	4.03	2.35	0.58	1.77	0.36	0.71	-44.3	-40.5	-34.3
DPF-305	O₁m⁵	0.13	0.01	4.48	92.78	2.15	0.37		0.08			-37.5	-27.4	-27.5
D12-8	P₁s¹- P₁x¹	0.33	0.14	2.18	87.81	6.72	1.92	0.30	0.45		0.15	-37.2	-25.6	-25.5

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表 2 标准天然气样G中丙烷裂解分馏因子及位碳同位素组成

Table 2. Enrichment factors and absolute δ¹³C values of position-specific carbons of propane pyrolysis in standard natural gas G ‰

裂解温度/℃	ε₁	ε₂	ε₃	δ¹³C_a	δ¹³C_b	计算值δ¹³C_丙烷	实测值δ¹³C_丙烷	偏差
740	-5.3	-0.1	-6.7	-36.5	-30.1	-34.4	-34.3	0.1
760	-5.7	0.3	-4.1	-37.5	-28.2	-34.4	-34.3	0.1
780	-5.9	0.2	-5.9	-36.9	-29.6	-34.4	-34.3	0.1
800	-6.3	0.9	-4.2	-37.7	-28.1	-34.3	-34.3	0.2
820	-6.9	1.4	-4.6	-37.1	-29.3	-34.5	-34.3	0.2
840	-6.1	2.8	-4.3	-37.0	-29.6	-34.5	-34.3	0.2
860	-4.2	5.7	-4.0	-36.6	-30.5	-34.5	-34.3	0.2
880	-2.8	7.5	-4.1	-36.3	-31.0	-34.6	-34.3	0.3
900	-1.2	9.3	-4.6	-37.1	-29.8	-34.7	-34.3	0.4
注：ε₁、ε₂、ε₃分别为丙烷瞬时裂解的3个主要反应的分馏因子(见图 4)；δ¹³C_a为丙烷端位碳同位素值；δ¹³C_b为丙烷中间位碳同位素值。

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表 3 鄂尔多斯盆地大牛地气田天然气样品丙烷位碳同位素组成

Table 3. Absolute δ¹³C values of position-specific carbons of propane in Daniudi Gas Field, Ordos Basin ‰

样品号	层位	δ¹³C_a	δ¹³C_b	δ¹³C_a-δ¹³C_b	计算值δ¹³C_丙烷	实测值δ¹³C_丙烷
DPF-305	O₁m⁵	-27.1	-28.9	1.8	-27.7	-27.5
D12-8	P₁s¹- P₁x¹	-23.4	-29.6	6.2	-25.4	-25.5

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