CO2 Sequestration in Shale with Enhanced Gas Recovery

  • Danqing Liu
  • Sen Yang
  • Yilian Li
  • Ramesh AgarwalEmail author
Part of the Energy, Environment, and Sustainability book series (ENENSU)


Shale is an important geological media for carbon capture utilization and storage. On one hand it can be regarded as impermeable caprock to prevent CO2 migration from reservoir, and on the other hand it can also treated as both natural gas and CO2 storage reservoir. CO2-shale reactions within caprock can interfere with the integrity of the rock integrity and compromise the long-term carbon storage safety and stability; however this interaction can also improve the conductivity of the rock to enhance the shale gas recovery from the organic-rich shale. This chapter presents a review of the current state of knowledge regarding CO2 and shale interactions and their potential impacts on shale properties and groundwater quality in the context of CO2 enhanced shale gas recovery. The characterization of shale and CO2 which is critical to the understanding of various interactions between CO2 and shale is first summarized. The major interaction mechanisms between CO2 and shale including CO2-shale-water geochemical reactions, CO2 adsorption induced clay swelling and organic matter extraction with supercritical CO2 and their impact on rock porosity and permeability, and mechanical properties, gas adsorption capacity and groundwater quality are surveyed. Finally, the open questions in this field are emphasized and new research needs are highlighted.


CO2 enhanced shale gas recovery CO2-shale interaction Porosity and permeability Mechanical properties Adsorption capacity Groundwater quality 



This work has been supported by the National Natural Science Foundation of China (NSFC, No. 41572233), and the China Postdoctoral Science Foundation funded project (No. 2018M632943) has also provided partial support for this study.


  1. Akinlua A, Torto N, Ajayi TR et al (2008) Supercritical fluid extraction of aliphatic hydrocarbons from Niger Delta sedimentary rock. J Supercrit Fluids 45:57–63. Scholar
  2. Akob D, Cozzarelli I, Dunlap D et al (2015) Organic and inorganic composition and microbiology of produced waters from Pennsylvania shale gas wells. Appl Geochem 60:116–125. Scholar
  3. Alemu BL, Aagaard P, Munz IA et al (2011) Caprock interaction with CO2: a laboratory study of reactivity of shale with supercritical CO2 and brine. Appl Geochem 26:1975–1989. Scholar
  4. Allawzi M, Al-Otoom A, Allaboun H et al (2011) CO2 supercritical fluid extraction of Jordanian oil shale utilizing different co-solvents. Fuel Process Technol 92:2016–2023. Scholar
  5. Anderson R, Ratcliffe I, Greenwell H et al (2010) Clay swelling—a challenge in the oilfield. Earth-Sci Rev 98:201–216. Scholar
  6. Ao X, Lu Y, Tang J, Chen Y, Li H (2017) Investigation on the physics structure and chemical properties of the shale treated by supercritical CO2. J CO2 Utilization 20:274–281. Scholar
  7. Bakhshian S, Hosseini SA (2019) Prediction of CO2 adsorption-induced deformation in shale nanopores. Fuel 241:767–776. Scholar
  8. Bondar E, Koel M (1998) Application of supercritical fluid extraction to organic geochemical studies of oil shales. Fuel 77:211–213. Scholar
  9. Busch A, Alles S, Gensterblum Y et al (2008) Carbon dioxide storage potential of shales. Int J Greenh Gas Control 2:297–308. Scholar
  10. Chareonsuppanimit P, Mohammad SA, Jr RLR et al (2012) High-pressure adsorption of gases on shales: measurements and modeling. Int J Coal Geol 95:34–46. Scholar
  11. Chen B, Evans JRG, Greenwell HC et al (2008) A critical appraisal of polymer–clay nanocomposites. Chem Soc Rev 37:568–594. Scholar
  12. Chen T, Feng X, Pan Z (2018) Experimental study on kinetic swelling of organic-rich shale in CO2, CH4 and N2. J Nat Gas Sci Eng 55:406–417. Scholar
  13. Cluff MA, Hartsock A, MacRae JD et al (2014) Temporal changes in microbial ecology and geochemistry in produced water from hydraulically fractured marcellus shale gas wells. Environ Sci Technol 48:6508–6517. Scholar
  14. Cui G, Ren S, Rui Z et al (2018) The influence of complicated fluid-rock interactions on the geothermal exploitation in the CO2, plume geothermal system. Appl Energy 227:49–63. Scholar
  15. Deng H, Fitts JP, Crandall D et al (2015) Alterations of fractures in carbonate rocks by CO2-acidified brines. Environ Sci Technol 49:10226–10234. Scholar
  16. Duan S, Gu M, Du X et al (2016) Adsorption equilibrium of CO2 and CH4, and their mixture on sichuan Basin shale. Energy Fuels 30:2248–2256. Scholar
  17. Dustin M, Bargar J, Jew A et al (2018) Shale kerogen: hydraulic fracturing fluid interactions and contaminant release. Energy Fuels 32:8966–8977. Scholar
  18. Feng G, Kang Y, Sun Z et al (2019) Effects of supercritical CO2 adsorption on the mechanical characteristics and failure mechanisms of shale. Fuel 173:870–882. Scholar
  19. Giesting P, Guggenheim S, Af KVG et al (2012) X-ray diffraction study of K- and Ca-exchanged montmorillonites in CO2 atmospheres. Environ Sci Technol 46:5623–5630. Scholar
  20. Glikson M, Chappell BW, Freeman RS et al (1985) Trace elements in oil shales, their source and organic association with particular reference to Australian deposits. Chem Geol 53:155–174. Scholar
  21. Goodman A, Sanguinito S, Tkach M et al (2019) Investigating the role of water on CO2-utica shale interactions for carbon storage and shale gas extraction activities—evidence for pore scale alterations. Fuel 242:744–755. Scholar
  22. Griffith CA, Dzombak DA, Lowry GV (2011) Physical and chemical characteristics of potential seal strata in regions considered for demonstrating geological saline CO2 sequestration. Env Earth Sci 64:925–948. Scholar
  23. He Y, Cheng J, Dou X et al (2017) Research on shale gas transportation and apparent permeability in nanopores. J Nat Gas Sci Eng 38:450–457. Scholar
  24. 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. Scholar
  25. Hui D, Pan Y, Luo P et al (2019) Effect of supercritical CO2 exposure on the high-pressure CO2 adsorption performance of shales. Fuel 247:57–66. Scholar
  26. Huo P, Zhang D, Yang Z et al (2017) CO2 geological sequestration: displacement behavior of shale gas methane by carbon dioxide injection. Int J Greenhouse Gas Control 66:48–59. Scholar
  27. Ilgen A, Aman M, Espinoza D et al (2018) Shale-brine-CO2 interactions and the long-term stability of carbonate-rich shale caprock. Int J Greenh Gas Control 78:244–253. Scholar
  28. Jarboe PJ, Candela PA, Zhu W et al (2015) Extraction of hydrocarbons from high maturity marcellus shale using supercritical carbon dioxide. Energy Fuels 29:7897–7909. Scholar
  29. Jean JS, Wang CL, Hsiang HI et al (2015) Experimental investigation of trace element dissolution in formation water in the presence of supercritical CO2 fluid for a potential geological storage site of CO2 in Taiwan. J Nat Gas Sci Eng 23:304–314. Scholar
  30. Jiang F, Chen D, Chen J, Li Q, Liu Y, Shao X (2016) Fractal analysis of shale pore structure of continental gas shale reservoir in the Ordos Basin, NW China. Energy Fuels 30:4676–4689. Scholar
  31. Jin L, Hawthorne S, Sorensen J et al (2017) Advancing CO2, enhanced oil recovery and storage in unconventional oil play—experimental studies on bakken shales. Appl Energy 208:171–183. Scholar
  32. Jones TA, Detwiler RL (2016) Fracture sealing by mineral precipitation: the role of small-scale mineral heterogeneity. Geophys Res Lett 43:7564–7571. Scholar
  33. Kolak JJ, Burruss RC (2006) Geochemical investigation of the potential for mobilizing non-methane hydrocarbons during carbon dioxide storage in deep coal beds. Energy Fuels 20:566–574. Scholar
  34. Lahann R, Mastalerz M, Rupp JA et al (2013) Influence of CO2 on new albany shale composition and pore structure. Int J Coal Geol 108:2–9. Scholar
  35. Li Y, Li X, Wang Y et al (2015) Effects of composition and pore structure on the reservoir gas capacity of carboniferous shale from Qaidam Basin, China. Mar Pet Geol 62:44–57. Scholar
  36. Liang C, Jiang Z, Zhang C et al (2014) The shale characteristics and shale gas exploration prospects of the lower silurian longmaxi shale, Sichuan Basin, South China. J Nat Gas Sci Eng 21:636–648. Scholar
  37. Liu F, Lu P, Griffith C et al (2012) CO2–brine–caprock interaction: reactivity experiments on Eau Claire shale and a review of relevant literature. Int J Greenh Gas Control 7:153–167. Scholar
  38. Liu D, Li Y, Agarwal RK (2016) Numerical simulation of long-term storage of CO2 in Yanchang shale reservoir of the Ordos Basin in China. Chem Geol 440:288–305. Scholar
  39. Liu Q, Tao L, Zhu H (2017) Macroscale mechanical and microscale structural changes in Chinese wufeng shale with supercritical carbon dioxide fracturing. SPE J 23:691–703. Scholar
  40. Lu Y, Ao X, Tang J et al (2016) Swelling of shale in supercritical carbon dioxide. J Nat Gas Sci Eng 30:268–275. Scholar
  41. Lu Y, Chen X, Tang J (2019) Relationship between pore structure and mechanical properties of shale on supercritical carbon dioxide saturation. Energy 172:270–285. Scholar
  42. Luo X, Ren X, Wang S (2019) Supercritical CO2-water-shale interactions and their effects on element mobilization and shale pore structure during stimulation. Int J Coal Geol 202:109–127. Scholar
  43. Lyu Q, Ranjith PG, Long X et al (2016) Experimental investigation of mechanical properties of black shales after CO2-water-rock interaction. Mater 9:663–678. Scholar
  44. Lyu Q, Long X, Ranjith PG et al (2018) Experimental investigation on the mechanical properties of a low-clay shale with different adsorption times in sub-/super-critical CO2. Energy 147:1288–1298. Scholar
  45. Marcon V, Kaszuba JP (2015) Carbon dioxide–brine–rock interactions in a carbonate reservoir capped by shale: experimental insights regarding the evolution of trace metals. Geochim Cosmochim Acta 168:22–42. Scholar
  46. Mokhtari M, Tutuncu AN (2015) Characterization of anisotropy in the permeability of organic-rich shales. J Pet Sci Eng 133:496–506. Scholar
  47. Naik SN, Lentz H, Maheshawari RC (1989) Extraction of perfumes and flavors from plant materials with liquid carbon dioxide under liquid–vapor equilibrium conditions. Fluid Phase Equilib 49:115–126. Scholar
  48. Nuttall BC, Eble CF, Drahovzal JA, Bustin RM (2005) Analysis of Devonian black shales in kentucky for potential carbon dioxide sequestration and enhanced natural gas production. Report Kentucky Geological Survey/University of Kentucky (DE-FC26-02NT41442). Scholar
  49. Okamoto I, Li X, Ohsumi T (2005) Effect of supercritical CO2 as the organic solvent on cap rock sealing performance for underground storage. Energy 30:2344–2351. Scholar
  50. Pan Y, Hui D, Luo P, Zhang Y, Zhang L, Sun L (2018a) Influences of subcritical and supercritical CO2 treatment on the pore structure characteristics of marine and terrestrial shales. J CO2 Utilization 28:152–167. Scholar
  51. Pan Y, Dong H, Luo P et al (2018b) Experimental investigation of the geochemical interactions between supercritical CO2 and shale: implications for CO2 storage in gas-bearing shale formations. Energy Fuels 32:1963–1978. Scholar
  52. Phan TT, Capo RC, Stewart BW et al (2015) Trace metal distribution and mobility in drill cuttings and produced waters from marcellus shale gas extraction: uranium, arsenic, barium. Appl Geochem 60:89–103. Scholar
  53. Rathnaweera TD, Ranjith PG, Perera MSA et al (2016) Experimental investigation of geochemical and mineralogical effects of CO2 sequestration on flow characteristics of reservoir rock in deep saline aquifers. Sci Rep 6:19362. Scholar
  54. Rezaee R, Saeedi A, Iglauer S et al (2017) Shale alteration after exposure to supercritical CO2. Int J Greenh Gas Control 62:91–99. Scholar
  55. Rillard J, Gombert P, Toulhoat P et al (2014) Geochemical assessment of CO2 perturbation in a shallow aquifer evaluated by a push–pull field experiment. Int J Greenhouse Gas Control 21:23–32. Scholar
  56. Ripley EM, Shaffer NR, Gilstrap MS (1990) Distribution and geochemical characteristics of metal enrichment in the new albany shale (Devonian-Mississippian), Indiana. Econ Geol 85:1790–1807. Scholar
  57. Romanak KD, Smyth RC, Yang C et al (2012) Sensitivity of groundwater systems to CO2: application of a site-specific analysis of carbonate monitoring parameters at the SACROC CO2-enhanced oil field. Int J Greenhouse Gas Control 6:142–152. Scholar
  58. Ross DJK, Bustin RM (2009) The importance of shale composition and pore structure upon gas storage potential of shale gas reservoirs. Mar Pet Geol 26:916–927. Scholar
  59. Sanguinito S, Goodman A, Tkach M et al (2018) Quantifying dry supercritical CO2-induced changes of the utica shale. Fuel 226:54–64. Scholar
  60. Schaef H, Loring J, Glezakou V et al (2015) Competitive sorption of CO2 and H2O in 2:1 layer phyllosilicates. Geochim Cosmochim Acta 161:248–257. Scholar
  61. Scherf AK, Zetzl C, Smirnova I et al (2011) Mobilisation of organic compounds from reservoir rocks through the injection of CO2-Comparison of baseline characterization and laboratory experiments. Energy Procedia 4:4524–4531. Scholar
  62. Shen Z, Sheng JJ (2017) Experimental study of permeability reduction and pore size distribution change due to asphaltene deposition during CO2 huff and puff injection in eagle ford shale. Asia-Pac J Chem Eng 12:380–381. Scholar
  63. Shen Z, Sheng JJ (2018) Experimental and numerical study of permeability reduction caused by asphaltene precipitation and deposition during CO2 huff and puff injection in Eagle Ford shale. Fuel 211:432–445. Scholar
  64. Shukla R, Ranjith P, Haque A et al (2010) A review of studies on CO2 sequestration and caprock integrity. Fuel 89:2651–2664. Scholar
  65. Soong Y, Crandall D, Howard BH et al (2017) Permeability and mineral composition evolution of primary seal and reservoir rocks in geologic carbon storage conditions. Environ Eng Sci 35:391–400. Scholar
  66. Span R, Wagner W (1996) A new equation of state for carbon dioxide covering the fluid region from the triple-point temperature to 1100 K at pressures up to 800 MPa. J Phys Chem Ref Data 25:1509. Scholar
  67. Strong L, Gould T, Kasinkas L, Sadowsky MJ, Aksan A, Wackett LP (2013) Biodegradation in waters from hydraulic fracturing: chemistry, microbiology, and engineering. J Environ Eng B4013001-1-6.
  68. Tan J, Weniger P, Krooss B et al (2014) Shale gas potential of the major marine shale formations in the Upper Yangtze platform, South China, Part II: methane sorption capacity. Fuel 129:204–218. Scholar
  69. Thomas MM, Clouse JA (1990) Primary migration by diffusion through kerogen: II. Hydrocarbon diffusivities in kerogen. Geochim Cosmochim Acta 54:2781–2792. Scholar
  70. Viswanathan H, Dai Z, Lopano C et al (2012) Developing a robust geochemical and reactive transport model to evaluate possible sources of arsenic at the CO2 sequestration natural analog site in Chimayo, New Mexico. Int J Greenhouse Gas Control 10:199–214. Scholar
  71. Wu T, Xue Q, Li X et al (2015) Extraction of kerogen from oil shale with supercritical carbon dioxide: molecular dynamics simulations. J Supercrit Fluids 107:499–506. Scholar
  72. Xiong J, Liu X, Liang L et al (2017) Adsorption of methane in organic-rich shale nanopores: an experimental and molecular simulation study. Fuel 200:299–315. Scholar
  73. Yang F, Ning Z, Zhang R et al (2015) Investigations on the methane sorption capacity of marine shales from Sichuan Basin, China. Int J Coal Geol 146:104–117. Scholar
  74. Yang Z, Dong Z, Wang L et al (2018) Experimental study on selective adsorption/desorption of CO2 and CH4 behaviors on shale under a high-pressure condition. Energy Fuels 32:9255–9262. Scholar
  75. Yin H, Zhou J, Jiang Y et al (2016) Physical and structural changes in shale associated with supercritical CO2 exposure. Fuel 184:289–303. Scholar
  76. Yin H, Zhou J, Xian X et al (2017) Experimental study of the effects of sub- and super-critical CO2 saturation on the mechanical characteristics of organic-rich shales. Energy 132:84–95. Scholar
  77. Yu Z, Liu L, Yang S et al (2012) An experimental study of CO2–brine–rock interaction at in situ pressure–temperature reservoir conditions. Chem Geol 326–327:88–101. Scholar
  78. Zhang K, Cheng Y, Li W et al (2017a) Influence of supercritical CO2, on pore structure and functional groups of coal: implications for CO2, sequestration. J Nat Gas Sci Eng, 40:288–298. Scholar
  79. Zhang S, Xian X, Zhou J et al (2017b) Mechanical behaviour of longmaxi black shale saturated with different fluids: an experimental study. RSC Adv 7:42946–42955. Scholar
  80. Zhao T, Li X, Zhao H et al (2017) Molecular simulation of adsorption and thermodynamic properties on type II kerogen: influence of maturity and moisture content. Fuel 190:198–207. Scholar
  81. Zhou L, Bai SP, Su W (2003) Comparative study of the excess versus absolute adsorption of CO2 on super-activated carbon for the near-critical region. Langmuir 19:97–100. Scholar
  82. Zhou J, Xie S, Jiang Y et al (2018) Influence of supercritical CO2 exposure on CH4 and CO2 adsorption behaviors of shale: implications for CO2 sequestration. Energy Fuels 32:6073–6089. Scholar
  83. Ziemkiewicz PF (2013) Characterization of liquid waste streams from shale gas development. AGH Drill, Oil, Gas 30:297–309. Scholar
  84. Zou Y, Li S, Ma X et al (2018) Effects of CO2–brine–rock interaction on porosity/permeability and mechanical properties during supercritical-CO2 fracturing in shale reservoirs. J Nat Gas Sci Eng 49:157–168. Scholar

Copyright information

© Springer Nature Singapore Pte Ltd. 2020

Authors and Affiliations

  • Danqing Liu
    • 1
    • 2
  • Sen Yang
    • 2
  • Yilian Li
    • 2
  • Ramesh Agarwal
    • 3
    Email author
  1. 1.State Key Laboratory of Biogeology and Environmental GeologyChina University of GeosciencesWuhanChina
  2. 2.School of Environmental StudiesChina University of GeosciencesWuhanChina
  3. 3.Washington University in St. LouisSt. LouisUSA

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