高压条件下CO<sub>2</sub>对页岩微观孔隙结构影响及其在页岩中的吸附特征

张臣; 周世新; 陈科; 李靖; 陈克非; 张玉红; 李朋朋; 孙泽祥; 付德亮

doi:10.3799/dqkx.2019.107

高压条件下CO₂对页岩微观孔隙结构影响及其在页岩中的吸附特征

doi: 10.3799/dqkx.2019.107

张臣^1,2,3, ,,
周世新^1,2, ,,
陈科⁴,
李靖^1,2,
陈克非^1,2,3,
张玉红^1,2,3,
李朋朋^1,2,3,
孙泽祥^1,2,3,
付德亮⁵

1.
中国科学院西北生态环境资源研究院, 甘肃兰州 730000
2.
甘肃省油气资源研究重点实验室, 甘肃兰州 730000
3.
中国科学院大学, 北京 100049
4.
中国地质调查局油气资源调查中心, 北京 100083
5.
自然资源部煤炭资源勘查与综合利用重点实验室, 陕西西安 710016

基金项目:

国家重大专项 2016ZX05003002-004

国家重大专项 2016B-0502

国家重大专项 2017ZX05036003-007

中国科学院先导专项 XDB10010103

国家自然科学基金项目 41072105

国家自然科学基金项目 41872147

详细信息

作者简介:
张臣(1992-), 女, 博士, 主要从事非常规油气勘探开发、二氧化碳地质存储相关研究

通讯作者:
周世新

中图分类号: P618
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- 被引次数: 0
出版历程
- 收稿日期: 2019-05-23
- 刊出日期: 2019-11-15

Impact on Microscopic Pore Structure and Adsorption Behavior of Carbon Dioxide on Shale under High Pressure Condition

Zhang Chen^{1,2,3
,
,},
Zhou Shixin^{1,2
, ,},
Chen Ke⁴,
Li Jing^1,2,
Chen Kefei^1,2,3,
Zhang Yuhong^1,2,3,
Li Pengpeng^1,2,3,
Sun Zexiang^1,2,3,
Fu Deliang⁵

1.
Northwest Institute of Eco-Environment and Resources, Chinese Academy of Sciences, Lanzhou 730000, China
2.
Key Laboratory of Petroleum Resources of Gansu Province, Lanzhou 730000, China
3.
University of Chinese Academy of Sciences, Beijing 100049, China
4.
Oil & Gas Survey, China Geological Survey, Beijing 100083, China
5.
Key Laboratory of Coal Exploration and Comprehensive Utilization, Ministry of Natural Resources, Xi'an 710016, China

摘要

摘要: 为了解高压条件下二氧化碳（CO₂）对页岩微观孔隙结构改造及吸附行为，以四川盆地焦页6井页岩为研究对象，通过低温N₂吸附和重量法等温吸附实验，研究了不同温压条件下CO₂处理前后的页岩微观结构特征及CO₂在页岩中的吸附行为.研究表明随处理温度升高，CO₂作用后的页岩比表面积呈下降趋势，平均孔径和孔体积呈上升趋势，微孔、中孔比例减少，宏孔比例增大.CO₂会改变页岩孔隙结构，改变程度与温度呈正相关关系.研究同时表明页岩对CO₂的过剩吸附量随压力增大而增加直至达到最大值，后随压力增大而减小；绝对吸附量随压力增大而增加，在40 MPa之后，吸附量趋于稳定.页岩对CO₂的吸附行为与温度压力有关，在高压条件下，Langmuir模型依然能较好地拟合CO₂在页岩中的吸附.
- 页岩气 /
- 超临界CO₂ /
- 微观结构 /
- 吸附 /
- 油气地质
Abstract: In order to understand the transformation of microscopic pore structure and adsorption behavior of carbon dioxide (CO₂) on shale under high pressure condition, using low-pressure N₂ adsorption analysis and isothermal adsorption instrument based on gravimetric method, the microstructural characteristics before and after CO₂ treatment, and the adsorption behavior of CO₂ in Jiaoye 6 shale from Jiaoshiba area of Sichuan basin were studied. The results show that the shale specific surface area decreased, and the average pore size and pore volume increased with increasing CO₂ treatment temperature. Besides, the proportions of micropore and mesopore decreased, and the proportion of macropore increased with increasing temperature. CO₂ could change the pore structure of shale, and the degree of change is positively correlated with temperature. The results also show that the excess adsorption amount of CO₂ increased with increasing pressure, reached a maximum value, and then decreased. The absolute adsorption amount of CO₂ increased with increasing pressure, and then tended to be stable after 40 MPa. The adsorption behavior of CO₂ on shale is related to temperature and pressure. Langmuir model can still fit CO₂ adsorption on shale well under high pressure.
- shale gas /
- supercritical carbon dioxide /
- microscopic pore structure /
- adsorption /
- petroleum geology

HTML全文

图 1 页岩孔体积（a）和比表面积（b）分布特征

Fig. 1. Pore size distribution (a) and pore specific surface distribution (b) of shale

下载: 全尺寸图片幻灯片

图 2 页岩原始样品N₂吸附-脱附曲线

Fig. 2. N₂ adsorption-desorption isotherms of original shale

下载: 全尺寸图片幻灯片

图 3 页岩扫描电镜图和能谱图

Fig. 3. The SEM and EDS images of shale

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图 4 不同温度条件下超临界CO₂作用后页岩的N₂吸附-脱附曲线

Fig. 4. N₂ adsorption-desorption isotherms of shale samples after supercritical CO₂ treatment at different temperatures

下载: 全尺寸图片幻灯片

图 5 不同温度条件下超临界CO₂作用后页岩孔隙结构参数

Fig. 5. Pore structure parameters of shale samples after supercritical CO₂ treatment at different temperatures

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图 6 页岩的CO₂过剩吸附曲线(a)和绝对吸附曲线(b)

Fig. 6. Excess adsorption isotherms (a) and absolute adsorption isotherms (b) of CO₂ on shale

下载: 全尺寸图片幻灯片

表 1 四川盆地焦石坝地区焦页6井页岩矿物组分

Table 1. Mineral compositions of Jiaoye 6 shale in Jiaoshiba area of Sichuan basin

井名	深度（m）	全岩矿物组分（%）							粘土矿物组成（%）
井名	深度（m）	石英	斜长石	钾长石	方解石	白云石	黄铁矿	粘土矿物	绿泥石	伊利石	伊/蒙混层
焦页6	2 770.0	53.6	7.7	1.3	2.7	3.5	3.0	22.0	29.0	42.0	29.0

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表 2 页岩孔隙结构特征和CO₂吸附特征

Table 2. Pore structure and CO₂ adsorption characteristics of shale samples

样品	微孔比例（%）	中孔比例（%）	宏孔比例（%）	DFT孔体积(10^-3cm³·g^-1)	BET比表面积(m²·g^-1)	平均孔径（nm）	Langmuir吸附量(mg·g^-1)	P_L (MPa)	R²
原始	30	49	21	9.64	13.57	6.35	-	-	-
T=40 ℃	23	43	34	14.21	11.40	6.51	9.29	1.47	0.992
T=60 ℃	21	44	35	10.24	12.17	7.42	6.94	1.05	0.994
T=80 ℃	18	46	36	11.08	10.59	7.82	6.88	0.94	0.997
T=100 ℃	20	42	38	12.93	10.45	7.39	4.31	0.99	0.998

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