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

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 ({\alpha }_{{CO}_2/{CH}_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 {\alpha }_{{CO}_2/{CH}_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 {\alpha }_{{CO}_2/{CH}_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 {\alpha }_{{CO}_2/{CH}_4}, and no obvious correlation between {\alpha }_{{CO}_2/{CH}_4} and clay mineral content in shale was observed due to the complexity of the clay minerals. The {\alpha }_{{CO}_2/{CH}_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.

Graphical abstract

Keywords

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

References

[1] Bi H, Jiang Z, Li J, Li P, Chen L, Pan Q, Wu Y (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] Brunauer S, Emmett P H, Teller E (1938). Adsorption of gases in multi-molecular layers. J Am Chem Soc, 60(2): 309–319

[3] Cai Y, Liu D, Pan Z, Yao Y, Li J, Qiu Y (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] Charoensuppanimit P, Mohammad S A, Gasem K A M (2016). Measurements and modeling of gas adsorption on shales. Energy Fuels, 30: 2309–2319

[5] Cui J, Zhu R, Mao Z, Li S (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] Dayal A M (2017). Chapter 10-role of nonconventional shale gas energy in the next century. Shale Gas Explor Environ Econ Imp, 157–164

[7] Du X, Gu M, Hou Z, Liu Z, Wu T (2019). Experimental study on the kinetics of adsorption of CO₂ and CH₄ in gas-bearing shale reservoirs. Energy Fuels, 33(12): 12587–12600

[8] Duan S, Gu M, Du X, Xian X (2016). Adsorption equilibrium of CO₂ and CH₄ and their mixture on Sichuan Basin shale. Energy Fuels, 30(3): 2248–2256

[9] Feng G, Zhu Y, Wang G G X, Chen S, Wang Y, Ju W (2019). Supercritical methane adsorption on overmature shale: effect of pore structure and fractal characteristics. Energy Fuels, 33(9): 8323–8337

[10] Gasparik M, Bertier P, Gensterblum Y, Ghanizadeh A, Krooss B M, Littke R (2014). Geological controls on the methane storage capacity in organic-rich shales. Int J Coal Geol, 123: 34–51

[11] Gensterblum Y, Merkel A, Busch A, Krooss B M (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] Gu M, Xian X, Duan S, Du X (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] Heller R, Zoback M (2014). Adsorption of methane and carbon dioxide on gas shale and pure mineral samples. J Unconv Oil Gas Resour, 8: 14–24

[14] Hong L, Jain J, Romanov V, Lopano C, Disenhof C, Goodman A, Hedges S, Soeder D, Sanguinito S, Dilmore R (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] Hou H, Shao L, Li Y, Li Z, Zhang W, Wen H (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] Hou Y, He S, Yi J, Zhang B, Chen X, Wang Y, Zhang J, Cheng C (2014). Effect of pore structure on methane sorption potential of shales. Pet Explor Dev, 41: 272–281

[17] Iddphonce R, Wang J, Zhao L (2020). Review of CO₂ injection techniques for enhanced shale gas recovery: prospect and challenges. J Nat Gas Sci Eng, 77: 103240

[18] Jaroniec M (1995). Evaluation of the fractal dimension from a single adsorption isotherm. Langmuir, 11: 2316–2317

[19] Ji L, Qiu J, Xia Y, Zhang T (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] Jiao F (2019). Theoretical insights, core technologies and practices concerning “volume development” of shale gas in China. Nat Gas Ind B, 6(6): 525–538

[21] Keshavarz A, Sakurovs R, Grigore M, Sayyafzadeh M (2017). Effect of maceral composition and coal rank on gas diffusion in Australian coals. Int J Coal Geol, 173: 65–75

[22] Klewiah I, Berawala D S, Alexander Walker H C, Andersen P Ø, Nadeau P H (2020). Review of experimental sorption studies of CO₂ and CH₄ in shales. J Nat Gas Sci Eng, 73: 103045

[23] Kuang L, Dong D, He W, Wen S, Sun S, Li S, Qiu Z, Liao X, Li Y, Wu J, Zhang L, Shi Z, Guo W, Zhang S (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] Langmuir I (1918). The adsorption of gases on plane surfaces of glass, mica and platinum. J Am Chem Soc, 40(9): 1361–1403

[25] Li A, Ding W, He J, Dai P, Yin S, Xie F (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] Li X, Elsworth D (2015). Geomechanics of CO₂ enhanced shale gas recovery. J Nat Gas Sci Eng, 26: 1607–1619

[27] Li Z, Shen X, Qi Z, Hu R (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] Li Y, Wang Z, Pan Z, Niu X, Yu Y, Meng S (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] Li Y, Yang J, Pan Z, Tong W (2020b). Nanoscale pore structure and mechanical property analysis of coal: an insight combining AFM and SEM images. Fuel, 260: 116352

[30] Liu J, Hui Xie X, Wang Q, Chen S, Hu Z (2020). Influence of pore structure on shale gas recovery with CO₂ sequestration: insight into molecular mechanisms. Energy Fuels, 34: 1240–1250

[31] Liu J, Xie L, Elsworth D, Gan Q (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] Liu Y, Hou J (2020). Selective adsorption of CO₂/CH₄ mixture on clay-rich shale using molecular simulations. J CO₂ Util, 39: 101143

[33] Lu X, Li F, Watson A T (1995). Adsorption studies of natural gas storage in Devonian shales. SPE Form Eval, 10(2): 109–113

[34] Ma X, Guo S (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] Pang F, Zhang Z, Zhang J, Chen K, Shi D, Bao S, Li S, Guo T (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] Passey Q R, Bohacs K M, Esch W L, Klimentidis R (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] Pei P, Ling K, He J, Liu Z (2016). Shale gas reservoir treatment by a CO₂-based technology. J Nat Gas Sci Eng, 26: 1595–1606

[38] Pomonis P J, Tsaousi E T (2009). Frenkel-Halsey-Hill equation, dimensionality of adsorption, and pore anisotropy. Langmuir, 25(17): 9986–9994

[39] Qi R, Ning Z, Wang Q, Zeng Y, Huang L, Zhang S, Du H (2018). Sorption of methane, carbon dioxide, and their mixtures on shales from Sichuan Basin, China. Energ Fuels, 32: 2926–2940

[40] Qin C, Jiang Y, Luo Y, Zhou J, Liu H, Song X, Li D, Zhou F, Xie Y (2020). Effect of supercritical CO₂ saturation pressures and temperatures on the methane adsorption behaviours of Longmaxi shale. Energy, 206: 118150

[41] Ross D J K, Bustin R M (2009). The importance of shale composition and pore structure upon gas storage potential of shale gas reservoirs. Mar Pet Geol, 26: 916–927

[42] Shan C, Zhang T, Wei Y, Zhang Z (2017). Shale gas reservoir characteristics of Ordovician-Silurian formations in the central Yangtze area, China. Front Earth Sci, 11(1): 184–201

[43] Shcherba V A, Butolin A P, Zieliński A (2019). Current state and prospects of shale gas production. In: IOP Conference Series: Earth Env Sci, 272

[44] Sing K S W (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] Slatt R M, O’Brien N R (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] Thommes M, Kaneko K, Neimark A V, Olivier J P, Rodriguez-Reinoso F, Rouquerol J, Sing K S (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] Wang J, Guo S (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] Wang M, Guo Z, Jiao C, Lu S, Li J, Xue H, Li J, Li J, Chen G (2019a). Exploration progress and geochemical features of lacustrine shale oils in China. J Petrol Sci Eng, 178: 975–986

[49] Wang S, Song Z, Cao T, Song X (2013). The methane sorption capacity of Paleozoic shales from the Sichuan Basin, China. Mar Pet Geol, 44: 112–119

[50] Wang Y, Dong D, Yang H, He L, Wang S, Huang J, Pu B, Wang S (2014). Quantitative characterization of reservoir space in the Lower Silurian Longmaxi Shale, southern Sichuan, China. Sci China Earth Sci, 57(2): 312–322

[51] Wang Y, Zhu Y, Liu S, Zhang R (2016). Methane adsorption measurements and modeling for organic-rich marine shale samples. Fuel, 172: 301–309

[52] Yang C, Zhang J, Tang X, Ding J, Zhao Q, Dang W, Chen H, Su Y, Li B, Lu D (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] Zeng S, Gu J, Yang S, Zhou H, Qian Y (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] Zhang J, Tang Y, He D, Sun P, Zou X (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] Zhang Q, Liu R H, Pang Z L, Lin W, Bai W H, Wang H Y (2016). Characterization of microscopic pore structures in Lower Silurian black shale (S11), southeastern Chongqing, China. Mar Pet Geol, 71: 250–259

[56] Zhou J, Hu N, Xian X, Zhou L, Tang J, Kang Y, Wang H (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] Zhou J, Jin Z, Luo K H (2019b). Effects of moisture contents on shale gas recovery and CO₂ sequestration. Langmuir, 35(26): 8716–8725

[58] Zhou J, Liu M, Xian X, Jiang Y, Liu Q, Wang X (2019c). Measurements and modelling of CH₄ and CO₂ adsorption behaviors on shales: implication for CO₂ enhanced shale gas recovery. Fuel, 251: 293–306

[59] Zhou J, Liu Q, Tan J, Jiang Y, Xian X, Yin H, Ju Y (2017). Pore structure and adsorption characteristics of marine and continental shale in China. J Nanosci Nanotechnol, 17(9): 6356–6366

[60] Zhou J, Xie S, Jiang Y, Xian X, Liu Q, Lu Z, Lyu Q (2018). Influence of supercritical CO₂ exposure on CH₄ and CO₂ adsorption behaviors of shale: implications for CO₂ sequestration. Energ Fuels, 32: 6073–6089

[61] Zhou J, Tian S, Zhou L, Xian X, Yang K, Jiang Y, Zhang C, Guo Y (2020). Experimental investigation on the influence of sub- and super-critical CO₂ saturation time on the permeability of fractured shale. Energ, 191: 116574

[62] Zou C, Dong D, Wang S, Li J, Li X, Wang Y, Li D, Cheng K (2010). Geological characteristics, formation mechanism and resource potential of shale gas in China. Pet Explor Dev, 37(6): 641–653

Acknowledgments

This study was financially supported by the National Natural Science Foundation of China (Grant Nos. 51774060, U19B2009), the Program for Changjiang Scholars and Innovative Research Team in University (IRT_17R112), the Basic Research and Frontier Exploration Projects in Chongqing (cstc2019jcyj-msxmX0053, cstc2019yszx-jcyjX0007), Shaanxi innovation capability support plan (2019KJXX-023).

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