Experimental investigation of methane adsorption and desorption in water-bearing shale

Aifen Li, Wencheng Han, Qi Fang, Asadullah Memon, Min Ma

Abstract view|498|times       PDF download|181|times Supplementary download|39|times



Methane adsorption and desorption in shale can significantly be affected by water due to the water-bearing depositional environment of shale and the application of hydraulic fracturing technology in shale gas production. The characteristics of shale gas adsorption and desorption are comprehensively affected by the temperature, pressure, and especially, the water content in the reservoir. To further explore the impact of water on shale gas adsorption and desorption, the adsorption-desorption experiments of methane in water-bearing shale at different temperatures and different pressures are performed. Afterward, the adsorption behavior and desorption hysteresis are characterized by employing the Langmuir model and Langmuir+λ model. Finally, the ways of the pressure, temperature, and water combinedly affect shale gas adsorption behavior and desorption hysteresis are analyzed. The results show that adsorption and desorption of methane in the water-bearing shale are irreversible, which are consistent with the Langmuir model and the Langmuir+λ model, respectively. An increase in temperature will reduce adsorption and promote desorption, as an increase in temperature essentially enhances the thermal movement of methane molecules. Water lowers the adsorption and desorption of methane in shale, as the water molecules occupy the adsorption sites in organic pores and clay mineral pores in different ways. However, the effect of temperature and water content on adsorption is closely related to the pressure. The lower the pressure, the more significant the effect of temperature and water content. The combined effect analysis demonstrates that the impact of water on methane adsorption in shale is much more significant than that of the temperature. Still, desorption is simultaneously affected by both temperature and water content. As the pressure decreases in the desorption process, the desorption rate is dominantly affected by water when the pressure is lower than 8 MPa, and the desorption rate is aggressively affected by temperature when the pressure is at above 8 MPa.

Cited as: Li, A., Han, W., Fang, Q., Memon, A., Ma, M. Experimental investigation of methane adsorption and desorption in water-bearing shale. Capillarity, 2020, 3(3), 45-55, doi: 10.46690/capi.2020.03.02


Water-bearing shale, methane, water content, adsorption, desorption

Full Text:

PDF Supplementary


Ahmad, M., Haghighi, M. Water saturation evaluation of Murteree and Roseneath shale gas reservoirs cooper basin Australia using wire-line logs focused ion beam milling and scanning electron microscopy. Paper SPE 167080 Presented at SPE Unconventional Resources Conference and Exhibition-Asia Pacif, Brisbane, Australia, 11-13 November, 2013.

Al-Mutarreb, A., Jufar, S.R., Abdulelah, H., et al. Influence of water immersion on pore system and methane desorption of shales: A case study of Batu Gajah and Kroh shale formations in Malaysia. Energies 2018, 11(6): 1511-1526.

Battistutta, E., van Hemert, P., Lutynski, M., et al. Swelling and sorption experiments on methane, nitrogen and carbon dioxide on dry selar Cornish coal. Int. J. Coal Geol. 2010, 84(1): 39-48.

Billemont, P., Coasne, B., De Weireld, G. An experimental and molecular simulation study of the adsorption of carbon dioxide and methane in nanoporous carbons in the presence of water. Langmuir 2011, 27(3): 1015-1024.

Busch, A., Gensterblum, Y. CBM and CO2 -ECBM related sorption processes in coal: A review. Int. J. Coal Geol. 2011, 87(2): 49-71.

Cai, J., Lin, D., Singh, H., et al. A simple permeability model for shale gas and key insights on relative importance of various transport mechanisms. Fuel 2019, 252: 210-219.

Chalmers, G.R.L., Bustin, R.M. On the effects of petrographic composition on coalbed methane sorption. Int. J. Coal Geol. 2007a, 69(4): 288-304.

Chalmers, G.R.L., Bustin, R.M. The organic matter distribu-tion and methane capacity of the lower cretaceous strata of northeastern British Columbia, Canada. Int. J. Coal Geol. 2007b, 70(1-3): 223-239.

Dicker, A., Smits, R. A practical approach for determining permeability from laboratory pressure-pulse decay measurements. Paper SPE 17578 Presented at SPE International Meeting on Petroleum Engineering, Tianjin, China, 1-4 November, 1988.

Dutta, P., Bhowmik, S., Das, S. Methane and carbon dioxide sorption on a set of coals from India. Int. J. Coal Geol. 2011, 85(3-4): 289-299.

Fan, E., Tang, S., Zhang, C., et al. Methane sorption capacity of organics and clays in high-over matured shale-gas systems. Energy Explor. Exploit. 2014, 32(6): 927-942.

Fan, K., Li, Y., Elsworth, D., et al. Three stages of methane adsorption capacity affected by moisture content. Fuel 2018, 231: 352-360.

Fang, C., Huang, Z., Wang, Q., et al. Cause and significance of the ultra-low water saturation in gas-enriched shale reservoir. Nat. Gas Geosci. 2014, 25(3): 471-476.

Fitzgerald, J.E., Sudibandriyo, M., Pan, Z., et al. Modeling the adsorption of pure gases on coals with the SLD model. Carbon 2003, 41(12): 2203-2216.

Gasparik, M., Bertier, P., Gensterblum, Y., et al. Geological controls on the methane storage capacity in organic-rich shales. Int. J. Coal Geol. 2014a, 123: 34-51.

Gasparik, M., Ghanizadeh, A., Bertier, P., et al. High-pressure methane sorption isotherms of black shales from the Netherlands. Energy Fuels 2012, 26(8): 4995-5004.

Gasparik, M., Rexer, T.F.T., Aplin, A.C., et al. First international inter-laboratory comparison of high-pressure CH4 , CO2 and C2H6 sorption isotherms on carbonaceous shales. Int. J. Coal Geol. 2014b, 132: 131-146.

Ghanbari, E., Dehghanpour, H. The fate of fracturing water: A field and simulation study. Fuel 2016, 163: 282-294.

Guo, S. Experimental study on isothermal adsorption of methane gas on three shale samples from upper Paleozoic strata of the Ordos basin. J. Pet. Sci. Eng. 2013, 110: 132-138.

Herrle, J.O., Pross, J., Friedrich, O., et al. Forcing mechanisms for mid-cretaceous black shale formation: Evidence from the upper Aptian and lower Albian of the vocontian basin (SE France). Palaeogeogr. Palaeoclimatol. Palaeoecol. 2003, 190: 399-426.

Hill, D.G., Nelson, C.R. Gas productive fractured shales: An overview and update. Gas Tips 2000, 6(3): 4-13.

Hu, Y., Devegowda, D., Striolo, A., et al. Microscopic dynamics of water and hydrocarbon in shale-kerogen pores of potentially mixed-wettability. SPE J. 2014, 20(1): 112-124.

Huang, L., Ning, Z., Wang, Q., et al. Effect of organic type and moisture on CO2 /CH4 competitive adsorption in kerogen with implications for CO2 sequestration and enhanced CH4 recovery. Appl. Energy 2018a, 210: 28-43.

Huang, L., Ning, Z., Wang, Q., et al. Molecular simulation of adsorption behaviors of methane, carbon dioxide and their mixtures on kerogen: Effect of kerogen maturity and moisture content. Fuel 2018b, 211: 159-172.

Jarvie, D.M., Hill, R.J., Ruble, T.E., et al. Unconventional shale-gas systems: The mississippian Barnett shale of north-central Texas as one model for thermogenic shale-gas assessment. AAPG Bull. 2007, 91(4): 475-499.

Jiao, B., Ding, W., Gu, Y., et al. The reservoir characteristics of marine shale and its effect on the adsorption of methane in northern Guizhou. Pet. Sci. Technol. 2019, 37(21): 2199-2206.

Joubert, J.I., Grein, C.T., Bienstock, D. Sorption of methane in moist coal. Fuel 1973, 52(3): 181-185.

Kim, H.J., Shi, Y., He, J., et al. Adsorption characteristics of CO2 and CH4 on dry and wet coal from subcritical to supercritical conditions. Chem. Eng. J. 2011, 171(1): 45-53.

Krooss, B.M., van Bergen, F., Gensterblum, Y., et al. High-pressure methane and carbon dioxide adsorption on dry and moisture-equilibrated Pennsylvanian coals. Int. J. Coal Geol. 2002, 51(2): 69-92.

Li, J., Li, X., Wang, X., et al. Water distribution characteristic and effect on methane adsorption capacity in shale clay. Int. J. Coal Geol. 2016, 159: 135-154.

Li, Y., Li, X., Wang, Y., et al. Effects of composition and pore structure on the reservoir gas capacity of carboniferous shale from Qaidam basin, China. Mar. Pet. Geol. 2015, 62: 44-57.

Liu, H., Wang, H. Ultra-low water saturation characteristics and the identification of over-pressured play fairways of marine shales in south China. Nat. Gas Ind. 2013, 33(7): 140-144.

Lu, X., Li, F., Watson, A.T. Adsorption measurements in Devonian shales. Fuel 1995, 74(4): 599-603.

Ma, D., Zhang, S., Lin, Y. Isothermal adsorption and desorption experiment of coal and experimental results accuracy fitting. Journal of China Coal Society 2011, 36(3): 477-480. (in Chinese)

Mcglade, C., Speirs, J., Sorrell, S. Unconventional gas-a review of regional and global resource estimates. Energy 2013, 55: 571-584.

Merkel, A., Fink, R., Littke, R. The role of pre-adsorbed water on methane sorption capacity of Bossier and Haynesville shales. Int. J. Coal Geol. 2015, 147-148: 1-8.

Rexer, T.F., Mathia, E.J., Aplin, A.C., et al. High-pressure methane adsorption and characterization of pores in Posidonia shales and isolated kerogens. Energy Fuels 2014, 28(5): 2886-2901.

Ross, D.J.K., Bustin, R.M. Shale gas potential of the lower Jurassic Gordondale member, northeastern British Columbia, Canada. Bull. Can. Pet. Geol. 2007, 55(1): 51-75.

Sakurovs, R., Day, S., Weir, S. Causes and consequences of errors in determining sorption capacity of coals for carbon dioxide at high pressure. Int. J. Coal Geol. 2009, 77(1-2): 16-22.

Sandoval, D.R., Yan, W., Michelsen, M.L., et al. Modeling of shale gas adsorption and its influence on phase equilibrium. Ind. Eng. Chem. Res. 2017, 57(17): 5736-5747.

Tan, J., Weniger, P., Krooss, B., et al. Shale gas potential of the major marine shale formations in the upper Yangtze platform, south China, part II: Methane sorption capacity. Fuel 2014, 129: 204-218.

Thommes, M., Kaneko, K., Neimark, A.V., et al. Physisorption of gases, with special reference to the evaluation of surface area and pore size distribution (IUPAC technical report). Pure Appl. Chem. 2015, 87(9-10): 1051-1069.

Wang, G., Ren, T., Wang, K., et al. Influence of maximum pressure on the path of CO2 desorption isotherm on coal. Energy Fuels 2014a, 28(11): 7093-7096.

Wang, H., Ajao, O., Economides, M.J. Conceptual study of thermal stimulation in shale gas formations. J. Nat. Gas Sci. Eng. 2014b, 21: 874-885.

Wang, L., Liu, M., Altazhanov, A., et al. Data driven machine learning models for shale gas adsorption estimation. Paper SPE 200621 Presented at SPE Europe featured at 82nd EAGE Conference and Exhibition, Amsterdam, Netherlands, 8-11 December, 2020.

Wang, L., Yu, Q. The effect of moisture on the methane adsorption capacity of shales: A study case in the eastern Qaidam basin in China. J. Hydrol. 2016, 542: 487-505.

Wang, S., Feng, Q., Javadpour, F., et al. Oil adsorption in shale nanopores and its effect on recoverable oil-in-place. Int. J. Coal Geol. 2015, 147-148: 9-24.

Wang, S., Javadpour, F., Feng, Q. Fast mass transport of oil and supercritical carbon dioxide through organic nanopores in shale. Fuel 2016, 181: 741-758.

Wang, S., Song, Z., Cao, T., et al. The methane sorption capacity of Paleozoic shales from the Sichuan basin, China. Mar. Pet. Geol. 2013, 44: 112-119.

Wattenbarger, R.A., Alkouh, A.B. New advances in shale reservoir analysis using flowback data. Paper SPE 165721 Presented at SPE Eastern Reginal Meeting, Pittsburgh, Pennsylvania, USA, 20-22 August, 2013.

Weniger, P., Kalkreuth, W., Busch, A., et al. High-pressure methane and carbon dioxide sorption on coal and shale samples from the Paran ´a basin, Brazil. Int. J. Coal Geol. 2010, 84(3-4): 190-205.

Xing, Y., Wang, Y., Wang, D. Numerical simulation of enhancing desorption of shale gas by electrical heating. Xi’an Shiyou University (Natural Science Edition) 2014, 29(6): 74-78. (in Chinese)

Xiong, J., Liu, X., Liang, L., et al. Investigation of methane adsorption on chlorite by grand Canonical Monte Carlo simulations. Pet. Sci. 2017, 14(1): 37-49.

Yang, F., Xie, C., Ning, Z., et al. High-pressure methane sorption on dry and moisture-equilibrated shales. Energy Fuels 2017, 31(1): 482-492.

Yang, R., Jia, A., Hu, Q., et al. Particle size effect on water vapor sorption measurement of organic shale: One example from Dongyuemiao member of lower Jurassic Ziliujing formation in Jiannan area of China. Adv. Geo-Energy Res. 2020, 4(2): 207-218.

Yuan, W., Pan, Z., Li, X., et al. Experimental study and modeling of methane adsorption and diffusion in shale. Fuel 2014, 117: 509-519.

Zeng, F., Zhang, Q., Guo, J., et al. Capillary imbibition of confined water in nanopores. Capillarity 2020, 3(1): 8-15.

Zhang, J., Tang, Y., Chen, D. Prediction of methane adsorption content in continental coal-bearing shale reservoir using SLD model. Pet. Sci. Technol. 2019, 37(15): 1839-1845.

Zhang, K., Cheng, Y., Wang, L., et al. Pore morphology characterization and its effect on methane desorption in water-containing coal: An exploratory study on the mechanism of gas migration in water-injected coal seam. J. Nat. Gas Sci. Eng. 2020, 75: 103152.

Zhang, L., Aziz, N., Ren, T., et al. Influence of coal particle size on coal adsorption and desorption characteristics. Arch. Min. Sci. 2014, 59(3): 807-820.

Zhang, R., Liu, S. Experimental and theoretical characteri-zation of methane and CO2 sorption hysteresis in coals based on Langmuir desorption. Int. J. Coal Geol. 2017, 171: 49-60.

Zhang, T., Ellis, G.S., Ruppel, S.C., et al. Effect of organic-matter type and thermal maturity on methane adsorption in shale-gas systems. Org. Geochem. 2012, 47: 120-131.

Zhao, T., Li, X., Ning, Z., et al. Molecular simulation of methane adsorption on type II kerogen with the impact of water content. J. Pet. Sci. Eng. 2018, 161: 302-310.

Zhao, T., Li, X., Zhao, H., et al. Molecular simulation of adsorption and thermodynamic properties on type II kerogen: Influence of maturity and moisture content. Fuel 2017, 190: 198-207.

Zhu, G., Yao, J., Sun, H., et al. The numerical simulation of thermal recovery based on hydraulic fracture heating technology in shale gas reservoir. J. Nat. Gas Sci. Eng. 2016, 28: 305-316.


  • There are currently no refbacks.

Copyright (c) 2020 The Author(s)

Creative Commons License
This work is licensed under a Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International License.

Copyright ©2018. All Rights Reserved