页岩孔隙中气—水赋存特征研究——以川东南地区下志留统龙马溪组为例

俞凌杰; 刘可禹; 范明; 刘友祥

doi:10.11781/sysydz2021061089

页岩孔隙中气—水赋存特征研究——以川东南地区下志留统龙马溪组为例

doi: 10.11781/sysydz2021061089

俞凌杰^{1, 2, 3,},
刘可禹¹,
范明^{2, 3},
刘友祥^{2, 3}

1.
中国石油大学(华东), 山东青岛 266580
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.
中国石化油气成藏重点实验室, 江苏无锡 214126

基金项目:

国家自然科学基金“页岩气改造散失途径与保存条件” 41690133

详细信息

作者简介:
俞凌杰(1982-), 男, 博士研究生, 高级工程师, 从事页岩油气实验技术研究。E-mail: yulj.syky@sinopec.com

中图分类号: TE122.23
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出版历程
- 收稿日期: 2021-08-09
- 修回日期: 2021-10-12
- 刊出日期: 2021-11-28

Co-occurring characteristics of pore gas and water in shales: a case study of the Lower Silurian Longmaxi Formation in the southeastern Sichuan Basin

YU Lingjie^{1, 2, 3
,},
LIU Keyu¹,
FAN Ming^{2, 3},
LIU Youxiang^{2, 3}

1.
School of Geosciences, China University of Petroleum (East China), Qingdao, Shandong 266580, China
2.
Wuxi Research Institute of Petroleum Geology, SINOPEC, Wuxi, Jiangsu 214126, China
3.
SINOPEC Key Laboratory of Petroleum Accumulation Mechanisms, Wuxi, Jiangsu 214126, China

摘要

摘要: 以川东南地区下志留统龙马溪组页岩为研究对象，借助重量法水蒸气吸附仪、重量法甲烷等温吸附仪以及页岩组成和孔隙结构等分析手段，开展束缚水、吸附气赋存定量研究，并探讨了微纳米孔隙中气—水赋存特征及主要影响因素。研究表明，不同类型页岩束缚水赋存能力差异较明显，可以利用水蒸气吸附—脱附和GAB模型比较准确地定量描述束缚水特征。页岩最大单层水分子吸附量与黏土矿物含量呈显著的正相关，表明黏土矿物为水分子提供了主要的活性吸附位。页岩对水分子的吸附能力要整体高于甲烷分子，而甲烷分子则主要以单层吸附形式在孔隙中赋存。不同页岩中束缚水、吸附气和游离气赋存的孔隙空间存在差异。2 nm以下孔隙均被吸附气和孔隙水所占据；有机碳（TOC）含量小于2.5%的页岩中游离气主体赋存空间约为5 nm以上孔隙，而TOC含量大于2.5%的页岩中游离气赋存空间主体约为3 nm以上孔隙；有机碳含量越高，游离气赋存的空间占比越高。
- 束缚水 /
- 水蒸气吸附 /
- 单层吸附 /
- 赋存特征 /
- 页岩 /
- 龙马溪组 /
- 下志留统 /
- 川东南地区
Abstract: In this paper, the co-occurring characteristics of pore gas and water in the Longmaxi Formation shales in the Sichuan Basin, South China were investigated. Water vapor and methane adsorption by the means of gravimetric methods were carried out to quantitatively determine the behavior of gas and bounding water in micro-nano pores. The impact of the shale compositions and pore structures on the occurring characteristics were discussed. Results showed that the storage capacity of bound water in different types of shales varied dramatically, and the characteristics of bound water could be described by the water vapor adsorption curve and the GAB model. There is an apaprent positive correlation between the maximum monolayer water molecule adsorption capacity and the clay mineral content in shales, indicating that clay minerals provide the main active adsorption sites for water molecules. The adsorption capacity of shale to water molecule is higher than that of methane molecule overall, and methane molecule mainly exist in pores with the form of monolayer adsorption. Bound water, adsorbed gas and free gas could be stored in different pore ranges of different shales. Pores with diameters lower than 2 nm are occupied by bounding water and adsorbed gas. For shales with TOC < 2.5%, free gas would be stored in pores with diameters larger than 5 nm approximately, while for the shales with TOC>2.5%, free gas would be stored in pores with diameters larger than 3 nm approximately. The higher the TOC content, the higher the proportion of the free-gas storage space.
- bounding water /
- water vapor adsorption /
- monolayer adsorption /
- occurrence characteristics /
- shale /
- Longmaxi Formation /
- Lower Silurian /
- southeastern Sichuan Basin

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图 1 川东南地区三口井中龙马溪组页岩样品水蒸气吸附—脱附曲线

Figure 1. Water vapor adsorption-desorption curves of shales selected from three wells in Lower Silurian Longmaxi Formation shale in southeastern Sichuan Basin

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图 2 川东南地区龙马溪组两个典型页岩样品实测水蒸气吸附曲线与GAB模型拟合的吸附曲线

Figure 2. Experimental and GAB model fitting water vapor adsorption curves for two typical shales from Lower Silurian Longmaxi Formation in southeastern Sichuan Basin

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图 3 川东南地区龙马溪组中黏土及TOC含量对页岩最大单层水分子吸附量的影响

Figure 3. Impacts of clay mineral content and TOC on the maximum capacity of monolayer water molecule adsorption of shale in Lower Silurian Longmaxi Formation in southeastern Sichuan Basin

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图 4 不同页岩对应的实验所得最大吸附量与理论单层吸附量的比值

Figure 4. Ratios between experimental maximum adsorption capacity and theoretical monolayer adsorption capacity of different shales

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图 5 川东南地区龙马溪组页岩TOC对甲烷分子单层吸附量和水分子单层吸附量的影响

Figure 5. Impact of TOC on monolayer adsorption capacity of water and methane molecules, Longmaxi Formation, southeastern Sichuan

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表 1 川东南地区下志留统龙马溪组页岩X衍射矿物组成与水蒸气吸附结果

Table 1. X-diffraction mineral composition and water vapor adsorption results of Lower Silurian Longmaxi Formation shale in southeastern Sichuan Basin

样品名称	井号	井深/m	ω(TOC)/%	X衍射分析结果			单位岩石水蒸气吸附结果
样品名称	井号	井深/m	ω(TOC)/%	黏土含量/%	石英含量/%	碳酸盐矿物含量/%	W_m/%	W_m/(mmol·g^-1)	K	C
Sw-1	JY11-4	2 271.8	1.02	53.3	40.4	2.0	0.76	0.42	0.60	5.72
Sw-4		2 286.4	2.83	47.5	37.1	6.5	0.70	0.39	0.68	4.83
Sw-5		2 289.8	2.93	40.9	45.8	6.3	0.62	0.34	0.71	4.75
Sw-9		2 308.3	2.06	35.0	51.7	8.5	0.51	0.28	0.7	5.49
Sw-10		2 311.6	1.91	34.1	53.8	5.6	0.49	0.27	0.69	5.73
Sw-14		2 329.5	3.58	35.1	53.9	6.3	0.55	0.31	0.74	5.1
Sw-17		2 342.3	3.54	26.3	58.5	10.6	0.42	0.23	0.78	5.54
Sw-18		2 347.1	4.16	26.1	61.2	6.4	0.43	0.24	0.77	5.81
Sw-20		2 355.9	6.20	25.2	65.9	2.8	0.45	0.25	0.83	6.48
JY2-1	JY2	2 572.5	5.69	18.4	58.3	20.0	0.30	0.17	0.79	2.78
JY2-2		2 566.8	4.40	25.3	63.8	7.4	0.47	0.26	0.71	2.18
JY2-3		2 470.9	0.80	64.3	31.6	1.4	1.83	1.02	0.27	2.41
JY2-4		2 460.3	2.98	44.5	46.3	4.9	0.77	0.43	0.59	2.32
HD-2	PY1	2 130.4	1.49	52.1	35.8	7.3	1.15	0.64	0.42	2.54
HD-5		2 138.1	2.36	41.4	43.0	9.9	0.62	0.34	0.56	3.36
HD-6		2 142.9	2.78	46.4	48.6	2.2	0.64	0.36	0.63	3.95
注：W_m为水分子最大单层吸附量；K为多层吸附势常数；C为单层吸附热常数。

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表 2 川东南地区龙马溪组页岩全孔径分布与甲烷等温吸附结果

Table 2. Full diameter distribution and methane isotherm adsorption results of Longmaxi Formation shale in southeastern Sichuan Basin

样品名称	井号	井深/m	全孔径分布结果		甲烷等温吸附结果
样品名称	井号	井深/m	比表面积/(m²·g^-1)	总孔容/(mL·g^-1)	V_L/(m³·t^-1)	P_L/MPa	甲烷V_L/(mmol·g^-1)	理论单层吸附量/(m³·t^-1)
Sw-1	JY11-4	2 271.8	9.8	0.014 25	1.80	3.93	0.08	3.22
Sw-4		2 286.4	18.4	0.024 54	3.14	4.16	0.14	6.04
Sw-5		2 289.8	18.5	0.024 40	3.00	3.66	0.13	6.07
Sw-9		2 308.3	12.4	0.019 86	2.37	4.37	0.11	4.07
Sw-10		2 311.6	11.3	0.018 36	2.32	5.86	0.10	3.71
Sw-14		2 329.5	20.0	0.026 97	3.08	3.66	0.14	6.57
Sw-17		2 342.3	15.4	0.022 95	2.94	3.48	0.13	5.06
Sw-18		2 347.1	19.2	0.026 71	3.24	3.32	0.14	6.30
Sw-20		2 355.9	26.7	0.034 44	4.07	2.76	0.18	8.76
JY2-1	JY2	2 572.5	24.6	0.035 20	3.86	1.16	0.17	8.08
JY2-2		2 566.8	17.3	0.030 00	3.52	1.55	0.16	5.68
JY2-3		2 470.9	9.4	0.007 39	1.68	3.67	0.08	3.09
JY2-4		2 460.3	17.3	0.019 81	-	-	-	5.58
HD-2	PY1	2 130.4	11.4	0.017 40	2.40	2.57	0.11	3.74
HD-5		2 138.1	11.8	0.023 90	2.14	2.78	0.10	3.87
HD-6		2 142.9	15.6	0.020 60	3.13	2.01	0.14	5.12

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表 3 川东南地区龙马溪组不同页岩孔隙中束缚水、吸附气和游离气赋存空间特征

Table 3. Illustration of pores occupied by bound water, adsorbed gas and free gas in different shales in Lower Silurian Longmaxi Formation, southeastern Sichuan Basin

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