四川盆地二叠系大隆组页岩芳烃热演化规律及成熟度意义

张存杨; 张小涛; 刘岩; 杨佳佳; 孙玮琳; 沈斌; 徐学敏; 许智超; 田涛

doi:10.11781/sysydz2025030580

四川盆地二叠系大隆组页岩芳烃热演化规律及成熟度意义

doi: 10.11781/sysydz2025030580

张存杨^{1, 2,},
张小涛^2, ,,
刘岩¹,
杨佳佳²,
孙玮琳²,
沈斌²,
徐学敏²,
许智超²,
田涛³

1.
长江大学资源与环境学院, 武汉 430100
2.
国家地质实验测试中心, 北京 100083
3.
陕西省煤田地质集团有限公司自然资源部煤炭资源勘查与综合利用重点实验室, 西安 710021

基金项目:

中国地质调查局项目 DD20230265

陕西省2023年创新能力支撑计划 2023KJXX-122

中国地质科学院基本科研业务费项目 CSJ-2022-06

详细信息

作者简介:
张存杨(1997—)，男，博士生，地质学专业，油气地球化学方向。E-mail: appletuqu@163.com

通讯作者:
张小涛(1982-), 男, 高级工程师, 从事油气地球化学及油气成藏研究。E-mail: zxt347@foxmail.com

中图分类号: TE121.11
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- 被引次数: 0
出版历程
- 收稿日期: 2024-01-07
- 修回日期: 2025-04-08
- 刊出日期: 2025-05-28

Thermal evolution trend of aromatic hydrocarbons in shales from Permian Dalong Formation in Sichuan Basin and its significance in thermal maturity

1.
College of Resources and Environment, Yangtze University, Wuhan, Hubei 430100, China
2.
National Research Center for Geoanalysis, Beijing 100083, China
3.
Key Laboratory of Coal Resources Exploration and Comprehensive Utilization of Ministry of Natural Resources, Shaanxi Coal Geology Group CO., LTD., Xi'an, Shaanxi 710021, China

摘要

摘要: 中国南方古生代海相页岩具有重要的油气勘探意义，然而，由于海相沉积中普遍缺乏高等植物来源的有机质(镜质体)，导致其成熟度厘定存在明显的不确定性。对四川盆地广元地区二叠系大隆组页岩进行了生排烃热模拟实验，探索芳烃成熟度参数在高—过成熟阶段的适用性，通过气相色谱—质谱法(GC-MS)对热模拟后固体样品的芳烃萃取物进行分析。结果显示，四川广元上寺地区大隆组页岩热模拟残留油含有萘、菲、屈、苯并(a)蒽、硫芴、联苯、氧芴、芴、萤蒽、芘、蒽、三芳甾烷等丰富的芳烃化合物。大多数芳烃成熟度参数随模拟温度在升高过程中出现了拐点，且参数值在拐点前后显示不同的变化趋势，表明这些芳烃成熟度参数具有特定的适用范围。其中，芳烃成熟度参数(如MNR、DNR、MPI3、DPR、F1、F2、MDR、DBDBT2)可用于评价成熟—高成熟阶段(0.8% < Easy R_o < 2.5%)页岩的成熟度，而PMNr则更加适用于评价高—过成熟阶段(2.5% < Easy R_o < 4.5%)的页岩。研究发现，C-2 DBF-1/MDBF-1和C-2 DBF-2/MDBF-1这两个参数对评价成熟—过成熟阶段(0.8% < Easy R_o < 4.5%)的页岩有很好的效果，尤其在高温演化阶段与温度的相关性更强，这表明它们在评价高—过成熟页岩方面具有潜力。
- 页岩 /
- 生排烃热模拟实验 /
- 芳烃成熟度参数 /
- 拐点温度 /
- 二苯并呋喃 /
- 大隆组 /
- 四川盆地
Abstract: The Paleozoic marine shales in southern China hold great significance for hydrocarbon exploration. However, the lack of organic matter (vitrinite) derived from higher plants in marine sediments leads to considerable uncertainties in maturity assessment. In this paper, an thermal simulation experiment of hydrocarbon generation and expulsion for the Permian Dalong Formation shales in Guangyuan, Sichuan Basin was conducted to explore the applicability of aromatic maturity parameters in highly mature to over-mature stages. Analysis of the aromatic hydrocarbon extracts from the solid samples after thermal simulation was performed using gas chromatography-mass spectrometry (GC-MS). The results revealed that the thermal simulation residual oil from Dalong Formation shales in Shangsi section, Guangyuan area, Sichuan, contained abundant aromatic hydrocarbon compounds, including naphthalene, phenanthrene, chrysene, benzo(a)anthracene, dibenzothiophene, biphenyl, dibenzofuran, fluorene, fluoranthene, pyrene, anthracene, and triaromatic steranes. Most aromatic maturity parameters exhibited turning points with increasing thermal simulation temperatures, and the parameter values showed different trends before and after the turning points, indicating that these parameters have specific applicable ranges. Among them, aromatic maturity parameters (such as MNR, DNR, MPI3, DPR, F1, F2, MDR and DBDBT2) can be used to evaluate the maturity of shales at mature to highly mature stages (0.8% < Easy R_o < 2.5%), while PMNr is more suitable for evaluating high to over-mature shales (2.5% < Easy R_o < 4.5%). It was found that the parameters of C-2 DBF-1/MDBF-1 and C-2 DBF-2/MDBF-1 are effective for evaluating shales at mature to over-mature stages (0.8% < Easy R_o < 4.5%), showing a stronger correlation with temperature in the high-temperature evolution stages. This suggests their potential for assessing high to over-mature shales.
- shale /
- thermal simulation experiment of hydrocarbon generation and expulsion /
- aromatic maturity parameters /
- turning point temperature /
- dibenzofuran (DBF) /
- Dalong Formation /
- Sichuan Basin
注释:

利益冲突声明/Conflict of Interests

所有作者声明不存在利益冲突。

All authors declare no relevant conflict of interests.

作者贡献/Authors’Contributions

张小涛、沈斌、徐学敏、田涛参与实验设计；张存杨、杨佳佳、孙玮琳、许智超完成实验操作；张存杨、张小涛、刘岩参与论文写作和修改。所有作者均阅读并同意最终稿件的提交。

The experiment was designed by ZHANG Xiaotao, SHEN Bin, XU Xuemin, and TIAN Tao. The experimental operation was completed by ZHANG Cunyang, YANG Jiajia, SUN Weilin and XU Zhichao. The manuscript was drafted and revised by ZHANG Cunyang, ZHANG Xiaotao, and LIU Yan. All authors have read the final version of the paper and consented to its submission.

HTML全文

图 1 四川盆地广元地区地质构造概况据参考文献[13]修改。

Figure 1. Geological structure map of Guangyuan area, Sichuan Basin

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图 2 四川盆地上寺剖面二叠系大隆组页岩芳烃化合物系列相对含量

Figure 2. Relative content of aromatic hydrocarbon compound series in Permian Dalong Formation shales of Shangsi section, Sichuan Basin

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图 3 四川盆地上寺剖面二叠系大隆组页岩不同热模拟温度下Easy R_o热演化阶段

Figure 3. Thermal evolution stages of Easy R_o at different thermal simulation temperatures in Permian Dalong Formation shales of Shangsi section, Sichuan Basin

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图 4 四川盆地上寺剖面二叠系大隆组页岩奈系列化合物部分质量色质图

Figure 4. Partial mass chromatograms of naphthalene compound series in Permian Dalong Formation shales of Shangsi section, Sichuan Basin

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图 5 四川盆地上寺剖面二叠系大隆组页岩芳烃部分质量色质图

Figure 5. Partial mass chromatograms of aromatic hydrocarbons in Permian Dalong Formation shales of Shangsi section, Sichuan Basin

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图 6 四川盆地上寺剖面二叠系大隆组页岩萘系列主要成熟度参数变化趋势

Figure 6. Variation trends in maturity parameters of naphthalene compound series in Permian Dalong Formation shales in Shangsi section, Sichuan Basin

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图 7 四川盆地上寺剖面二叠系大隆组页岩菲系列主要成熟度参数变化趋势

Figure 7. Variation trends in maturity parameters of phenanthrene compound series in Permian Dalong Formation shales of Shangsi section, Sichuan Basin

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图 8 四川盆地上寺剖面二叠系大隆组页岩二苯并噻吩、三芳甾烷、二苯并呋喃部分成熟度参数变化趋势

Figure 8. Variation trends in selected maturity parameters of dibenzothiophene, triaromatic steranes, and dibenzofuran in Permian Dalong Formation shales of Shangsi section, Sichuan Basin

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图 9 有水、无水模拟实验芳烃成熟度参数拐点温度差异无水古近系沙三段、无水青白口系下马岭组数据引自文献[5, 36]。

Figure 9. Differences of turning point temperatures for aromatic maturity parameters in aqueous and anhydrous simulation experiments

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表 1 四川盆地广元地区上寺剖面二叠系大隆组页岩热模拟实验相关参数

Table 1. Parameters related to thermal simulation experiment of hydrocarbon generation and expulsion in Permian Dalong Formation shales of Shangsi section, Guangyuan area, Sichuan Basin

样品编号	模拟温度/℃	静岩压力/MPa	排烃流体压力/MPa
SSR1-300	300	77.0	36.0
SSR1-325	325	96.0	44.4
SSR1-350	350	121.0	55.2
SSR1-375	375	128.0	58.8
SSR1-400	400	136.0	62.4
SSR1-425	425	142.0	64.8
SSR1-450	450	158.0	72.0
SSR1-500	500	171.0	78.0
SSR1-550	550	184.0	84.0
SSR1-590	590	198.0	90.0
SSR1-650	650	213.0	96.6

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表 2 芳烃成熟度参数表达式

Table 2. Expressions of parameters about aromatic hydrocarbon maturity

参数代号	表达式
MNR	2-MN/1-MN
DNR	(2, 6-DMN+2, 7-DMN)/1, 5-DMN
TNR1	2, 3, 6-TMN/(1, 4, 6-TMN+1, 3, 5-TMN)
TMNr3	1, 3, 7-/(1, 3, 7-+1, 2, 5-)TMN
TeMNr	1, 3, 6, 7-/(1, 3, 6, 7-+1, 2, 5, 6-+1, 2, 3, 5-)TeMN
PMNr	1, 2, 4, 6, 7-/(1, 2, 4, 6, 7-+1, 2, 3, 5, 6-)PMN
MPR1	1-MP/P
MPI3	(2-+3-)MP/(1-+9-) MP
DPR	(2, 6-+2, 7-)DMP/(1, 6-+2, 10-)DMP
F1	(2-+3-)MP/(2-+3-+9-+1-)MP
F2	2-MP/(2-+3-+9-+1-)MP
MDR	4-MDBT/1-MDBT
DBDBT2	2, 4-DMDBT/1, 4-DMDBT
C₂₆/C₂₈20S-TAS	C₂₆, 20S-TAS /C₂₈, 20S-TAS
C₂₇/C₂₈20R-TAS	C₂₇, 20R-TAS /C₂₈, 20R-TAS

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表 3 四川盆地广元地区上寺剖面二叠系大隆组页岩芳烃成熟度参数数据

Table 3. Summary of parameters about aromatic hydrocarbon maturity in Permian Dalong Formation shales of Shangsi section, Guangyuan area, Sichuan Basin

温度/℃	Easy R_o/%	MNR	DNR	TNR1	TMNr3	TeMNr	PMNr	P	MPR1	MPI3	DPR	F1	F2	MDR	DBDBT2	A	B	C	D
300	0.8	0.69	1.22	0.72	0.44	0.55	0.33	14.91	0.53	0.58	0.17	0.37	0.19	2.38	0.53	1.84	0.81	0.07	0.13
325	1.0	1.09	2.89	0.94	0.44	0.61	0.24	21.81	0.27	1.36	0.42	0.58	0.31	2.76	0.56	3.89	0.72	0.22	0.09
350	1.3	1.36	2.36	0.94	0.34	0.60	0.18	14.57	0.42	0.76	0.24	0.43	0.23	2.30	0.44	3.25	0.57
375	1.5	1.26	5.56	1.33	0.62	0.73	0.07	15.10	0.39	1.15	0.42	0.54	0.30	2.56	0.49			0.15	0.04
400	1.8	2.10	8.68	1.82	0.81	0.83	0.03	21.30	0.27	1.96	0.70	0.66	0.37	3.55	0.67			0.31	0.13
425	2.1	4.79	32.07	3.75	0.81	0.81	0.01	42.09	0.08	7.16	2.54	0.88	0.47	11.76	3.15			0.19	0.10
450	2.5	7.12	47.82	0.59	0.76	0.71	0.02	69.32	0.02	10.59	3.18	0.91	0.51	36.65	10.06	9.42	1.08	0.33	0.17
500	3.1	1.18	4.01	0.88	0.54	0.66	0.12	94.71	0.01	3.06	0.60	0.75	0.42	7.13	0.68	5.47	0.82	0.22	0.11
550	3.6	0.98	2.51	0.83	0.49	0.62	0.32	67.15	0.04	2.19	0.50	0.69	0.35	2.66	0.73	3.60	0.79	0.69	0.27
590	4.0	1.24	0.57	1.12	0.38	0.62	0.36	13.00	0.44	0.77	0.22	0.43	0.23	1.16	0.75	0.68	0.61	1.09	0.55
650	4.5	0.94	1.94	0.60	0.37	0.55	0.45	17.98	0.28	0.90	0.19	0.47	0.26	1.13	1.02	3.43	0.67	1.20	0.58
原样	0.8	0.49	1.91	0.61	0.52	0.65	0.48	15.24	0.52	0.59	0.16	0.37	0.19	2.16	0.62	0.17	0.48	0.17	0.65
注：P为菲，A=C₂₆/C₂₈20S-TAS，B=C₂₇/C₂₈20R-TAS，C=C-2 DBF-1/MDBF-1，D=C-2 DBF-2/MDBF-1。

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表 4 四川盆地上寺剖面二叠系大隆组页岩部分芳烃成熟度参数适用范围

Table 4. Application ranges of selected aromatic maturity parameters in Permian Dalong Formation shales of Shangsi section, Sichuan Basin

芳烃化合物	参数代号	适用范围	相关性(R²)	拐点温度/℃	拐点Easy R_o/%
萘系列	MNR	成熟—高熟阶段后期	0.88，正相关	450	2.5
	DNR	成熟—高熟阶段后期	0.84，正相关	450	2.5
	TNR1	成熟—高熟阶段	0.96，正相关	425	2.1
	TMNr3	高熟—过熟阶段	0.95，负相关	400	2.1
	TeMNr	高熟—过熟阶段	0.97，负相关	400	1.8
	PMNr	成熟—高熟阶段	0.97，负相关	425	2.1
	PMNr	高熟—过熟阶段	0.97，正相关	425	2.1
菲系列	MPR1	成熟—过熟阶段初期	0.82，负相关	500	3.1
	MPI3	成熟—高熟阶段后期	0.76，正相关	450	2.5
	MPI3	过熟阶段	0.82，负相关	450	2.5
	DPR	成熟—高熟阶段后期	0.79，正相关	450	2.5
	DPR	过熟阶段	0.87，负相关	450	2.5
	F1	成熟—高熟阶段后期	0.83，正相关	450	2.5
	F2	成熟—高熟阶段后期	0.87，正相关	450	2.5
三芳甾烷系列	MDR	成熟—高熟阶段后期	0.71，正相关	450	2.5
二苯并呋喃系列	C-2 DBF-1/ MDBF-1	成熟—过熟阶段	0.82，正相关
二苯并呋喃系列	C-2 DBF-2/ MDBF-1	成熟—过熟阶段	0.72，正相关

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