The influences of composition and pore structure on the adsorption behavior of CH<sub>4</sub> and CO<sub>2</sub> on shale

doi:10.1007/s11707-021-0879-8

Front. Earth Sci.

2021, Vol. 15

Issue (2) : 283-300 https://doi.org/10.1007/s11707-021-0879-8

RESEARCH ARTICLE

The influences of composition and pore structure on the adsorption behavior of CH₄ and CO₂ on shale

Xiangzeng WANG¹, Junping ZHOU^2,³(

), Xiao SUN¹(

), Shifeng TIAN^2,³, Jiren TANG^2,³, Feng SHEN¹, Jinqiao WU¹

¹. Research Institute of Yanchang Petroleum (Group) Co. Ltd, Xi’an 710052, China
². State Key Laboratory of Coal Mine Disaster Dynamics and Control, Chongqing University, Chongqing 400044, China
³. School of Resources and Safety Engineering, Chongqing University, Chongqing 400044, China

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Abstract

CO₂ enhanced shale gas recovery (CO₂-ESGR) has attracted extensive attention as it can improve the shale gas recovery efficiency and sequestrate CO₂ simultaneously. In this study, the relationship between mineral composition, pore structure, CH₄ and CO₂ adsorption behavior as well as selective adsorption coefficient of CO₂ over CH₄ ( $α C O 2 / C H 4$ ) in marine and continental shales at different temperatures was investigated. The results illustrated that shale with higher total organic carbon (TOC), higher clay minerals and lower brittle mineral contents has a larger micropores and mesopores volume and specific surface area. TOC content was positively correlated with fractal dimension D_f. Both CH₄ and CO₂ adsorption capacity in shale have positive correlations with TOC and clay mineral content. CO₂ adsorption capacity of the all the tested shale samples were greater than CH₄, and the $α C O 2 / C H 4$ of shale were larger than 1.00, which indicated that using CO₂-ESGR technology to improve the gas recovery is feasible in these shale gas reservoirs. A higher TOC content and in shale corresponding to a lower $α C O 2 / C H 4$ due to the organic matters show stronger affinity on CH₄ than that on CO₂. Shale with a higher brittle mineral content corresponding to a higher $α C O 2 / C H 4$ , and no obvious correlation between $α C O 2 / C H 4$ and clay mineral content in shale was observed due to the complexity of the clay minerals. The $α C O 2 / C H 4$ of shale were decreased with increasing temperature for most cases, which indicated that a lower temperature is more favorable for the application of CO₂-ESGR technique.

Keywords shale gas carbon dioxide sequestration pore structure selective adsorption fractal dimensions

Corresponding Author(s): Junping ZHOU,Xiao SUN

Online First Date: 27 May 2021 Issue Date: 26 October 2021

Cite this article:

Xiangzeng WANG,Junping ZHOU,Xiao SUN, et al. The influences of composition and pore structure on the adsorption behavior of CH₄ and CO₂ on shale[J]. Front. Earth Sci., 2021, 15(2): 283-300.

URL:

https://academic.hep.com.cn/fesci/EN/10.1007/s11707-021-0879-8
https://academic.hep.com.cn/fesci/EN/Y2021/V15/I2/283

Fig.1 Shale samples for different tests.

Fig.2 PCTPro Full-automatic gas adsorption/desorption instrument of Setaram.

Tab.1 Main element content (%) of shale samples

Tab.2 R_o (%), TOC (%) and mineral composition content (%) of shale samples

Fig.3 N₂ adsorption-desorption isotherms of shale samples.

Tab.3 Pore structure parameters of shale samples

Fig.4 Fitting plot of ln(ln(p₀/p))-ln(V) based on N₂ adsorption data in shale samples.

Tab.4 FFH fractal dimensions D_f, fractal fitting equation and R²

Fig.5 Relationship between R_o, TOC and pore structure parameters.

Fig.6 Relationship between clay minerals, brittle minerals and pore structure parameters.

Fig.7 Langmuir model fitting of CH₄, CO₂ adsorption isotherms at different temperatures.

Tab.5 Fitting parameters of Langmuir model for CH₄, CO₂ adsorption isotherms　

Fig.8 Relationship between R_o, TOC and maximum adsorption capacity V_L.

Fig.9 Relationship between component characteristics and maximum adsorption capacity V_L.

Fig.10 Relationship between PV_total and V_L.

Fig.11 Relationship between pore specific surface area and V_L.

Tab.6 α_CO2/CH4 of shale samples at different temperatures

Fig.12 Relationship between mineral compositions and α_CO2/CH4.

Fig.13 Relationship between pore structure parameters and α_CO2/CH4.

1	H Bi, Z Jiang, J Li, P Li, L Chen, Q Pan, Y Wu (2016). The Ono–Kondo model and an experimental study on supercritical adsorption of shale gas: a case study on Longmaxi shale in southeastern Chongqing, China. J Nat Gas Sci Eng, 35: 114–121
2	S Brunauer, P H Emmett, E Teller (1938). Adsorption of gases in multi-molecular layers. J Am Chem Soc, 60(2): 309–319
3	Y Cai, D Liu, Z Pan, Y Yao, J Li, Y Qiu (2013). Pore structure and its impact on CH4 adsorption capacity and flow capability of bituminous and subbituminous coals from Northeast China. Fuel, 103: 258–268
4	P Charoensuppanimit, S A Mohammad, K A M Gasem (2016). Measurements and modeling of gas adsorption on shales. Energy Fuels, 30: 2309–2319
5	J Cui, R Zhu, Z Mao, S Li (2019). Accumulation of unconventional petroleum resources and their coexistence characteristics in Chang7 shale formations of Ordos Basin in central China. Front Earth Sci, 13(3): 575–587
6	A M Dayal (2017). Chapter 10-role of nonconventional shale gas energy in the next century. Shale Gas Explor Environ Econ Imp, 157–164
7	X Du, M Gu, Z Hou, Z Liu, T Wu (2019). Experimental study on the kinetics of adsorption of CO2 and CH4 in gas-bearing shale reservoirs. Energy Fuels, 33(12): 12587–12600
8	S Duan, M Gu, X Du, X Xian (2016). Adsorption equilibrium of CO2 and CH4 and their mixture on Sichuan Basin shale. Energy Fuels, 30(3): 2248–2256
9	G Feng, Y Zhu, G G X Wang, S Chen, Y Wang, W Ju (2019). Supercritical methane adsorption on overmature shale: effect of pore structure and fractal characteristics. Energy Fuels, 33(9): 8323–8337
10	M Gasparik, P Bertier, Y Gensterblum, A Ghanizadeh, B M Krooss, R Littke (2014). Geological controls on the methane storage capacity in organic-rich shales. Int J Coal Geol, 123: 34–51
11	Y Gensterblum, A Merkel, A Busch, B M Krooss (2013). High-pressure CH4 and CO2 sorption isotherms as a function of coal maturity and the influence of moisture. Int J Coal Geol, 118: 45–57
12	M Gu, X Xian, S Duan, X Du (2017). Influences of the composition and pore structure of a shale on its selective adsorption of CO2 over CH4. J Nat Gas Sci Eng, 46: 296–306
13	R Heller, M Zoback (2014). Adsorption of methane and carbon dioxide on gas shale and pure mineral samples. J Unconv Oil Gas Resour, 8: 14–24
14	L Hong, J Jain, V Romanov, C Lopano, C Disenhof, A Goodman, S Hedges, D Soeder, S Sanguinito, R Dilmore (2016). An investigation of factors affecting the interaction of CO2 and CH4 on shale in Appalachian Basin. J Unconv Oil Gas Resour, 14: 99–112
15	H Hou, L Shao, Y Li, Z Li, W Zhang, H Wen (2018). The pore structure and fractal characteristics of shales with low thermal maturity from the Yuqia Coalfield, northern Qaidam Basin, northwestern China. Front Earth Sci, 12(1): 148–159
16	Y Hou, S He, J Yi, B Zhang, X Chen, Y Wang, J Zhang, C Cheng (2014). Effect of pore structure on methane sorption potential of shales. Pet Explor Dev, 41: 272–281
17	R Iddphonce, J Wang, L Zhao (2020). Review of CO2 injection techniques for enhanced shale gas recovery: prospect and challenges. J Nat Gas Sci Eng, 77: 103240
18	M Jaroniec (1995). Evaluation of the fractal dimension from a single adsorption isotherm. Langmuir, 11: 2316–2317
19	L Ji, J Qiu, Y Xia, T Zhang (2012a). Micro-pore characteristics and methane adsorption properties of common clay minerals by electron microscopy canning. Acta Petrol Sin, 33(2): 249–256 (in Chinese)
20	F Jiao (2019). Theoretical insights, core technologies and practices concerning “volume development” of shale gas in China. Nat Gas Ind B, 6(6): 525–538
21	A Keshavarz, R Sakurovs, M Grigore, M Sayyafzadeh (2017). Effect of maceral composition and coal rank on gas diffusion in Australian coals. Int J Coal Geol, 173: 65–75
22	I Klewiah, D S Berawala, H C Alexander Walker, P Ø Andersen, P H Nadeau (2020). Review of experimental sorption studies of CO2 and CH4 in shales. J Nat Gas Sci Eng, 73: 103045
23	L Kuang, D Dong, W He, S Wen, S Sun, S Li, Z Qiu, X Liao, Y Li, J Wu, L Zhang, Z Shi, W Guo, S Zhang (2020). Geological characteristics and development potential of transitional shale gas in the east margin of the Ordos Basin, NW China. Pet Explor Dev, 47(3): 471–482
24	I Langmuir (1918). The adsorption of gases on plane surfaces of glass, mica and platinum. J Am Chem Soc, 40(9): 1361–1403
25	A Li, W Ding, J He, P Dai, S Yin, F Xie (2016). Investigation of pore structure and fractal characteristics of organic-rich shale reservoirs: a case study of lower Cambrian Qiongzhusi formation in Malong block of eastern Yunnan Province, South China. Mar Pet Geol, 70: 46–57
26	X Li, D Elsworth (2015). Geomechanics of CO2 enhanced shale gas recovery. J Nat Gas Sci Eng, 26: 1607–1619
27	Z Li, X Shen, Z Qi, R Hu (2018). Study on the pore structure and fractal characteristics of marine and continental shale based on mercury porosimetry, N2 adsorption and NMR methods. J Nat Gas Sci Eng, 53: 12–21
28	Y Li, Z Wang, Z Pan, X Niu, Y Yu, S Meng (2019). Pore structure and its fractal dimensions of transitional shale: a cross section from east margin of the Ordos Basin, China. Fuel, 241: 417–431
29	Y Li, J Yang, Z Pan, W Tong (2020b). Nanoscale pore structure and mechanical property analysis of coal: an insight combining AFM and SEM images. Fuel, 260: 116352
30	J Liu, X Hui Xie, Q Wang, S Chen, Z Hu (2020). Influence of pore structure on shale gas recovery with CO2 sequestration: insight into molecular mechanisms. Energy Fuels, 34: 1240–1250
31	J Liu, L Xie, D Elsworth, Q Gan (2019). CO2/CH4 competitive adsorption in shale: implications for enhancement in gas production and reduction in carbon emissions. Environ Sci Technol, 53(15): 9328–9336 PMID:31318200
32	Y Liu, J Hou (2020). Selective adsorption of CO2/CH4 mixture on clay-rich shale using molecular simulations. J CO2 Util, 39: 101143
33	X Lu, F Li, A T Watson (1995). Adsorption studies of natural gas storage in Devonian shales. SPE Form Eval, 10(2): 109–113
34	X Ma, S Guo (2020). Study on pore evolution and diagenesis division of a Permian Longtan transitional shale in Southwest Guizhou, China. Energy Sci Eng, 00: 1–22
35	F Pang, Z Zhang, J Zhang, K Chen, D Shi, S Bao, S Li, T Guo (2020). Progress and prospect on exploration and development of shale gas in the Yangtze River economic belt. J China Univ Geosci, 45(6): 2152–2159
36	Q R Passey, K M Bohacs, W L Esch, R Klimentidis (2010). From oil-prone source rock to gas-producing shale reservoir—geologic and petrophysical characterization of unconventional shale-gas reservoirs. Soc Petrol Engi, 13150: 1–29
37	P Pei, K Ling, J He, Z Liu (2016). Shale gas reservoir treatment by a CO2-based technology. J Nat Gas Sci Eng, 26: 1595–1606
38	P J Pomonis, E T Tsaousi (2009). Frenkel-Halsey-Hill equation, dimensionality of adsorption, and pore anisotropy. Langmuir, 25(17): 9986–9994 pmid: 19705894
39	R Qi, Z Ning, Q Wang, Y Zeng, L Huang, S Zhang, H Du (2018). Sorption of methane, carbon dioxide, and their mixtures on shales from Sichuan Basin, China. Energ Fuels, 32: 2926–2940
40	C Qin, Y Jiang, Y Luo, J Zhou, H Liu, X Song, D Li, F Zhou, Y Xie (2020). Effect of supercritical CO2 saturation pressures and temperatures on the methane adsorption behaviours of Longmaxi shale. Energy, 206: 118150
41	D J K Ross, R M Bustin (2009). The importance of shale composition and pore structure upon gas storage potential of shale gas reservoirs. Mar Pet Geol, 26: 916–927
42	C Shan, T Zhang, Y Wei, Z Zhang (2017). Shale gas reservoir characteristics of Ordovician-Silurian formations in the central Yangtze area, China. Front Earth Sci, 11(1): 184–201
43	V A Shcherba, A P Butolin, A Zieliński (2019). Current state and prospects of shale gas production. In: IOP Conference Series: Earth Env Sci, 272
44	K S W Sing (1982). Reporting physisorption data for gas/solid systems with special reference to the determination of surface area and porosity (Provisional). Pure Appl Chem, 54(11): 2201–2218
45	R M Slatt, N R O’Brien (2011). Pore types in the Barnett and Woodford gas shales: contribution to understanding gas storage and migration pathways in fine-grained rocks geohorizon. AAPG Bull, 95(12): 2017–2030
46	M Thommes, K Kaneko, A V Neimark, J P Olivier, F Rodriguez-Reinoso, J Rouquerol, K S Sing (2015). Physisorption of gases, with special reference to the evaluation of surface area and pore size distribution (IUPAC Technical Report). Pure Appl Chem, 87(9−10): 1051–1069
47	J Wang, S Guo (2020). Comparison of geochemical characteristics of marine facies, marine-continental transitional facies and continental facies shale in typical areas of China and their control over organic-rich shale. Energ Source Part A: 1–13
48	M Wang, Z Guo, C Jiao, S Lu, J Li, H Xue, J Li, J Li, G Chen (2019a). Exploration progress and geochemical features of lacustrine shale oils in China. J Petrol Sci Eng, 178: 975–986
49	S Wang, Z Song, T Cao, X Song (2013). The methane sorption capacity of Paleozoic shales from the Sichuan Basin, China. Mar Pet Geol, 44: 112–119
50	Y Wang, D Dong, H Yang, L He, S Wang, J Huang, B Pu, S Wang (2014). Quantitative characterization of reservoir space in the Lower Silurian Longmaxi Shale, southern Sichuan, China. Sci China Earth Sci, 57(2): 312–322
51	Y Wang, Y Zhu, S Liu, R Zhang (2016). Methane adsorption measurements and modeling for organic-rich marine shale samples. Fuel, 172: 301–309
52	C Yang, J Zhang, X Tang, J Ding, Q Zhao, W Dang, H Chen, Y Su, B Li, D Lu (2017). Comparative study on micro-pore structure of marine, terrestrial, and transitional shales in key areas, China. Int J Coal Geol, 171: 76–92
53	S Zeng, J Gu, S Yang, H Zhou, Y Qian (2019). Comparison of techno-economic performance and environmental impacts between shale gas and coal-based synthetic natural gas (SNG) in China. J Clean Prod, 215: 544–556
54	J Zhang, Y Tang, D He, P Sun, X Zou (2020). Full-scale nanopore system and fractal characteristics of clay-rich lacustrine shale combining FE-SEM, nano-CT, gas adsorption and mercury intrusion porosimetry. Appl Clay Sci, 196: 105748
55	Q Zhang, R H Liu, Z L Pang, W Lin, W H Bai, H Y Wang (2016). Characterization of microscopic pore structures in Lower Silurian black shale (S11), southeastern Chongqing, China. Mar Pet Geol, 71: 250–259
56	J Zhou, N Hu, X Xian, L Zhou, J Tang, Y Kang, H Wang (2019a). Supercritical CO2 fracking for enhanced shale gas recovery and CO2 sequestration: results, status and future challenges. Adv Geo-Energ Res, 3(2): 207–224
57	J Zhou, Z Jin, K H Luo (2019b). Effects of moisture contents on shale gas recovery and CO2 sequestration. Langmuir, 35(26): 8716–8725 pmid: 31244260
58	J Zhou, M Liu, X Xian, Y Jiang, Q Liu, X Wang (2019c). Measurements and modelling of CH4 and CO2 adsorption behaviors on shales: implication for CO2 enhanced shale gas recovery. Fuel, 251: 293–306
59	J Zhou, Q Liu, J Tan, Y Jiang, X Xian, H Yin, Y Ju (2017). Pore structure and adsorption characteristics of marine and continental shale in China. J Nanosci Nanotechnol, 17(9): 6356–6366
60	J Zhou, S Xie, Y Jiang, X Xian, Q Liu, Z Lu, Q Lyu (2018). Influence of supercritical CO2 exposure on CH4 and CO2 adsorption behaviors of shale: implications for CO2 sequestration. Energ Fuels, 32: 6073–6089
61	J Zhou, S Tian, L Zhou, X Xian, K Yang, Y Jiang, C Zhang, Y Guo (2020). Experimental investigation on the influence of sub- and super-critical CO2 saturation time on the permeability of fractured shale. Energ, 191: 116574
62	C Zou, D Dong, S Wang, J Li, X Li, Y Wang, D Li, K Cheng (2010). Geological characteristics, formation mechanism and resource potential of shale gas in China. Pet Explor Dev, 37(6): 641–653

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