碳酸盐岩烃源岩不同热模拟方式下气体碳同位素演变特征

陈磊; 郑伦举; 黄海平; 宁传祥

doi:10.11781/sysydz202201121

碳酸盐岩烃源岩不同热模拟方式下气体碳同位素演变特征

doi: 10.11781/sysydz202201121

陈磊^1,,
郑伦举^{2, 3, 4, ,},
黄海平¹,
宁传祥^{2, 3, 4}

1.
中国地质大学(北京) 能源学院, 北京 100083
2.
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
3.
页岩油气富集机理与有效开发国家重点实验室, 江苏无锡 214126
4.
国家能源页岩油研发中心, 江苏无锡 214126

基金项目:

国家自然科学基金 42072156

国家自然科学基金企业创新发展联合基金 U19B6003

详细信息

作者简介:
陈磊(1993-), 男, 硕士研究生, 从事油气地球化学研究。E-mail: 1291521919@qq.com

通讯作者:
郑伦举(1966-), 男, 博士, 研究员, 从事油气地球化学与非常规油气地质等相关研究。E-mail: 292002418@qq.com

中图分类号: TE122.113
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出版历程
- 收稿日期: 2021-02-08
- 修回日期: 2021-11-29
- 刊出日期: 2022-01-28

Carbon isotopic evolution of hydrocarbon gases generated from carbonate source rocks via different thermal simulation methods

CHEN Lei^1
,,
ZHENG Lunju^{2, 3, 4
, ,},
HUANG Haiping¹,
NING Chuanxiang^{2, 3, 4}

1.
School of Energy, China University of Geosciences (Beijing), Beijing 100083, China
2.
Wuxi Research Institute of Petroleum Geology, SINOPEC, Wuxi, Jiangsu 214126, China
3.
State Key Laboratory of Shale Oil and Gas Enrichment Mechanisms and Effective Development, Wuxi, Jiangsu 214126, China
4.
National Energy Shale Oil Research and Development Center, Wuxi, Jiangsu 214126, China

摘要

摘要: 我国海相烃源岩普遍处于高—过成熟阶段，现有的烃气碳同位素指标不能直接应用于判识海相碳酸盐岩天然气成因类型以及进行油气源对比。利用云南禄劝Ⅱ₁型低成熟海相碳酸盐岩烃源岩，开展了不同热模拟方式下的系列热解生烃实验，对收集的气体产物进行碳同位素分析。结果表明：①在整个热演化阶段，干酪根碳同位素值随成熟度变化不大，而甲、乙烷碳同位素值均随成熟度增加先变轻再变重，具有相似的演变特征，在油气生成的主要阶段，明显小于其母质干酪根碳同位素值，在过成熟阶段，乙烷碳同位素变重的趋势明显加快，甚至大于其母质干酪根的碳同位素值，呈现出“煤型气”特征，故单纯地采用甲、乙烷碳同位素值来判识天然气类型时需要慎重；②在成熟度相同时，半封闭—半开放体系模拟实验所得气体碳同位素值相比封闭体系模拟实验的要轻，这指示同一烃源岩排出烃气所形成的常规天然气藏，其烃气碳同位素值与滞留在源内的页岩气碳同位素值存在一定的差异，显示出似乎“不同源”的特征，在利用碳同位素模版或回归公式开展气源对比时也需要注意；③两种热模拟方式下、同一种烃源岩在全演化阶段，甲烷碳同位素值总是比乙烷的要小，这表明由单一烃源岩直接供气形成的常规天然气藏，不会发生甲、乙烷碳同位素的“倒转现象”。
- 热压生排烃模拟 /
- 天然气碳同位素 /
- 天然气判识 /
- 油气源对比 /
- 烃源岩 /
- 碳酸盐岩
Abstract: Chinese marine source rocks are generally at the stage of high- to over-mature, there are still some uncertainties about whether the existing hydrocarbon isotopic indexes can be directly employed to distinguish the genetic types of marine carbonate natural gas and consequently, gas-oil source correlation can be carried out. In this paper, a series of pyrolysis experiments for hydrocarbon generation with different conditions were carried out using the low-maturity marine carbonate source rocks of Luquan Ⅱ₁ type in Yunnan province to analyze the carbon isotope of the collected gas products. The results showed that: ①During the entire thermal evolution stage, the carbon isotope values of kerogen did not vary significantly with the increasing of maturity, while the carbon isotope values of methane and ethane both decreased and then increased with the increase of maturity, showing similar evolution characteristics. In the main oil and gas generation stage, it is significantly smaller than the isotope value of its parent material kerogen. In the over-mature stage (VR_o ≥2.2%), the tendency of carbon isotope of ethane to become heavier is obviously accelerated, even greater than the carbon isotope value of its parent material kerogen, showing the characteristics of "coal-type gas". This suggested that we need to be cautious when simply using the carbon isotope values of methane and ethane to identify the type of natural gas. ②At the same maturity, the carbon isotope values obtained from the pyrolysis experiment of semi-closed and semi-open system are lighter than those obtained from the pyrolysis experiment of closed system. This indicates that conventional natural gas reservoirs formed by the discharge of hydrocarbon gas from the same source rock have a certain difference between the carbon isotope values of hydrocarbon gas and the carbon isotope values of shale gas retained in the source, showing the characteristics of "different sources". Attention should also be exercised to the use of carbon isotope templates or regression formulas to carry out gas-source comparisons. ③With the two pyrolysis methods, the carbon isotope value of methane is always lighter than that of ethane in the full evolution stage of the same source rock. This indicated that conventional natural gas reservoirs formed by direct gas supply from single set of source rock do not have "inversion" phenomenon of methane and ethane carbon isotopes.
- pyrolysis simulation of hydrocarbon generation and expulsion /
- carbon isotope of natural gas /
- natural gas identification /
- hydrocarbon-source correlation /
- source rock /
- carbonate rock

HTML全文

图 1 云南禄劝泥盆系华宁组海相碳酸盐岩烃源岩碳同位素随成熟度的演变特征

样品DK-LQ-2为半封闭—半开放体系实验；其他样品为封闭体系实验。

Figure 1. Evolution of carbon isotopes with maturity of marine carbonate source rocks in Devonian Huaning Formation, Luquan area, Yunnan province

下载: 全尺寸图片幻灯片

图 2 云南禄劝泥盆系华宁组海相碳酸盐岩2种热模拟方式下甲烷、乙烷碳同位素演变特征对比

DK-LQ-2为半封闭—半开放体系实验；LQ-2为封闭体系实验。

Figure 2. Comparison of carbon isotopic evolution of methane and ethane with two thermal modeling methods in marine carbonate rocks of Devonian Huaning Formation, Luquan area, Yunnan province

下载: 全尺寸图片幻灯片

图 3 云南禄劝泥盆系华宁组海相碳酸盐岩烃源岩不同演化阶段热模拟天然气δ¹³C₁—δ¹³C₂的关系

底图来源于文献[30]。

Figure 3. Relationship between δ¹³C₁ and δ¹³C₂ values of thermally simulated natural gas in different evolution stages of marine carbonate source rocks in Devonian Huaning Formation, Luquan area, Yunnan province

下载: 全尺寸图片幻灯片

图 4 云南禄劝海相碳酸盐岩烃源岩不同热模拟演化阶段天然气δ¹³C₂与δ¹³C₂－δ¹³C₁的关系

底图据戴金星等^[6]修改。

Figure 4. Relationship between δ¹³C₂ and δ¹³C₂-δ¹³C₁ of natural gas in different thermal simulation stages of marine carbonate source rocks in Devonian Huaning Formation, Luquan area, Yunnan province

下载: 全尺寸图片幻灯片

表 1 云南禄劝泥盆系华宁组泥灰岩基本油气地球化学特征

Table 1. Basic geochemical characteristics of marl in Devonian Huaning Formation, Luquan area, Yunnan province

样品编号	ω(TOC)/%	VR_o/%	沥青“A”/%	I_H/(mg·g^-1)	碳酸盐矿物/%	显微组分/%				类型指数	干酪根类型
样品编号	ω(TOC)/%	VR_o/%	沥青“A”/%	I_H/(mg·g^-1)	碳酸盐矿物/%	腐泥组	壳质组	镜质组	惰质组	类型指数	干酪根类型
LQ-2	3.45	0.58	0.145 2	425	40.04	78	12	4	6	75	Ⅱ₁
LQ-4	4.55	0.58	0.204 7	429	35.95	74	15	6	5	75	Ⅱ₁
LQ-5-2	5.33	0.58	0.278 6	356	33.15	72	16	5	7	75	Ⅱ₁

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表 2 云南禄劝泥盆系华宁组海相泥灰岩生烃模拟实验条件

Table 2. Simulation experiment conditions for hydrocarbon generation in marine marl in Devonian Huaning Formation, Luquan area, Yunnan province

序号	模拟温度/℃	恒温时间/h	上覆静岩压力/MPa			流体压力/MPa				等效镜质体反射率/%
序号	模拟温度/℃	恒温时间/h	DK-LQ-2	LQ-2	LQ-4	DK-LQ-2	LQ-2	LQ-4	LQ-5-2	DK-LQ-2	LQ-2	LQ-4	LQ-5-2
1	250	48					3.5	2.8	3.2		0.62	0.61	0.65
2	300	48	94			48.8	5.8	6.2	6.9	0.71	0.78	0.75	0.78
3	350	48	108			56.3	10.2	11.4	12.3	1.05	1.12	1.18	1.15
4	400	48	121			63.1	23.5	24.6	26.8	1.57	1.68	1.66	1.70
5	450	48	139			72.5	26.4	28.6	29.2	1.96	2.25	2.11	2.17
6	500	48	163			85.0	32.2	35.1	35.9	2.79	2.75	2.67	2.71
7	550	48	173			90.0				3.22
注：DK-LQ-2为半封闭—半开放体系实验；其他样品为封闭体系实验。

下载: 导出CSV

表 3 云南禄劝泥盆系华宁组泥灰岩在不同热模拟方式下干酪根和气体碳同位素值

Table 3. Carbon isotopic values of kerogen and gas generated from marl in Devonian Huaning Formation, Luquan area, Yunnan province with different thermal modeling methods

热模拟方式	样品号	模拟温度/℃	δ¹³C_PDB/‰				碳同位素差值/‰
热模拟方式	样品号	模拟温度/℃	干酪根	甲烷	乙烷	丙烷	Δδ¹³C_{PDB(干酪根-甲烷)}	Δδ¹³C_{PDB(乙烷-甲烷)}
封闭体系	LQ-2		-32.55
	LQ-2	250	-32.72	-42.14	-36.32	-34.40	9.42	5.82
	LQ-2	300	-32.61	-43.66	-38.4	-36.33	11.05	5.26
	LQ-2	350	-32.53	-45.11	-37.60	-35.96	12.59	7.51
	LQ-2	400	-32.35	-44.40	-36.59	-34.19	11.65	7.81
	LQ-2	450	-32.17	-40.96	-34.03	-26.65	8.79	6.93
	LQ-2	500	-32.38	-38.15	-26.32		5.77	11.83
半封闭—半开放体系	DK-LQ-2	300	-32.25	-40.41	-36.84	-36.17	8.16	3.57
	DK-LQ-2	350	-32.43	-47.92	-39.30	-36.56	15.49	8.62
	DK-LQ-2	400	-32.78	-47.10	-37.57	-34.91	14.32	9.53
	DK-LQ-2	450	-32.36	-45.10	-36.42	-34.2	12.74	8.68
	DK-LQ-2	500	-31.74	-41.44	-31.65	-22.36	9.70	9.79
	DK-LQ-2	550	-31.93	-38.63	-23.97	-20.53	6.70	14.66
封闭体系	LQ-4		-32.96
	LQ-4	250	-32.64	-41.44	-37.52	-35.18	0.89	3.92
	LQ-4	300	-32.89	-42.18	-38.09	-36.53	9.29	4.09
	LQ-4	350	-32.8	-45.95	-37.56	-36.10	13.15	8.39
	LQ-4	400	-32.75	-45.36	-36.49	-34.73	12.61	8.87
	LQ-4	450	-32.21	-41.72	-33.62	-26.30	9.51	8.10
	LQ-4	500	-32.66	-38.54	-26.41		5.88	12.13
	LQ-5-2		-33.28
	LQ-5-2	250	-33.40	-40.78	-38.46	-36.53	2.30	2.32
	LQ-5-2	300	-33.40	-41.21	-38.70	-37.21	7.81	2.51
	LQ-5-2	350	-33.19	-46.49	-37.56	-36.06	13.30	8.93
	LQ-5-2	400	-33.2	-45.58	-36.20	-34.27	12.38	9.38
	LQ-5-2	450	-33.07	-41.67	-33.12	-26.20	8.60	8.55
	LQ-5-2	500	-33.11	-38.59	-26.08		5.48	12.51
注：Δδ¹³C_{PDB(干酪根-甲烷)}与Δδ¹³C_{PDB(乙烷-甲烷)}表示括号内两者之间的差值。

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