Investigation of methane adsorption mechanism on Longmaxi shale by combining the micropore filling and monolayer coverage theories

Shangwen Zhou, Yang Ning, Hongyan Wang, Honglin Liu, Huaqing Xue

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Abstract


Understanding the methane adsorption mechanism is critical for studying shale gas storage and transport in shale nanopores. In this work, we conducted low-pressure nitrogen adsorption (LPNA), scanning electron microscopy (SEM), and high-pressure methane adsorption experiments on seven shale samples from the Longmaxi formation in Sichuan basin. LPNA and SEM results show that pores in the shale samples are mainly nanometer-sized and have a broad size distribution. We have also shown that methane should be not only adsorbed in micropores (< 2 nm) but also in mesopores (2-50 nm) by two hypotheses. Therefore, we established a novel DA-LF model by combining the micropore filling and monolayer coverage theories to describe the methane adsorption process in shale. This new model can fit the high-pressure isotherms quite well, and the fitting error of this new model is slightly smaller than the commonly used D-A and L-F models. The absolute adsorption isotherms and the capacities for micropores and mesopores can be calculated using this new model separately, showing that 77% to 97% of methane molecules are adsorbed in micropores. In addition, we conclude that the methane adsorption mechanism in shale is: the majority of methane molecules are filled in micropores, and the remainder are monolayer-adsorbed in mesopores. It is anticipated that our results provide a more accurate explanation of the shale gas adsorption mechanism in shale formations.

Cited as: Zhou, S., Ning, Y., Wang, H., Liu, H., Xue, H. Investigation of methane adsorption mechanism on Longmaxi shale by combining the micropore filling and monolayer coverage theories. Advances in Geo-Energy Research, 2018, 2(3): 269-281, doi: 10.26804/ager.2018.03.05


Keywords


Shale gas, adsorption mechanism, micropore filling, monolayer adsorption, nanopores, adsorption model

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References


Amankwah, K.A.G., Schwarz, J.A. A modified approach for estimating pseudo-vapor pressures in the application of the Dubinin-Astakhov equation. Carbon 1995, 33(9): 1313-1319.

Ambrose, R.J., Hartman, R.C., Diaz-Campos, M., et al. New pore-scale considerations for shale gas in place calculations. Paper SPE 131772 present at the SPE Un-conventional Gas Conference, Pittsburgh, Pennsylvania, USA, 23-25 February, 2010.

Ambrose, R.J., Hartman, R.C., Diaz-Campos, M., et al. Shale gas-in-place calculations part I: new pore-scale considerations. SPE J. 2012, 17(1): 219-229.

Aranovich, G.L., Donohue, M.D. Adsorption of supercritical fluids. J. Colloid Interface Sci. 1996, 180(2): 537-541.

Bi, H., Jiang, Z., Li, J., et al. 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. 2016, 35: 114-121.

Brunauer, S., Deming. L.S., Deming, W.E., et al. On a theory of the van der Waals adsorption of gases. J. Am. Chem. Soc. 1940, 62(7): 1723-1732.

Brunauer, S., Emmett, P.H., Teller, E. Adsorption of gases in multimolecular layers. J. Am. Chem. Soc. 1938, 60(2): 309-319.

Chareonsuppanimit, P., Mohammad, S.A., Robinson, Jr.R.L., et al. High-pressure adsorption of gases on shales: Measurements and modeling. Int. J. Coal Geol. 2012, 95: 34-46.

Chen, G., Lu, S., Zhang, J., et al. Keys to linking GCMC simulations and shale gas adsorption experiments. Fuel 2017, 199: 14-21.

Clarkson, C.R., Bustin, R.M., Levy, J.H. Application of the mono/multilayer and adsorption potential theories to coal methane adsorption isotherms at elevated temperature and pressure. Carbon 1997, 35(12): 1689-1705.

Clarkson, C.R., Haghshenas, B. Modeling of supercritical fluid adsorption on organic-rich shales and coal. Paper SPE 164532 present at the SPE Unconventional Resources Conference, The Woodlands, Texas, USA, 10-12 April, 2013.

Curtis, J.B. Fractured shale-gas systems. AAPG Bull. 2002, 86(11): 1921-1938.

Curtis, M.E., Cardott, B.J., Sondergeld, C.H., et al. Devel-opment of organic porosity in the Woodford Shale with increasing thermal maturity. Int. J. Coal Geol. 2012, 103: 26-31.

Do, D.D. Adsorption analysis: equilibria and kinetics. London, UK, Imperial college press, 1998.

Do, D.D., Do, H.D. Adsorption of supercritical fluids in non-porous and porous carbons: analysis of adsorbed phase volume and density. Carbon 2003, 41(9): 1777-1791.

Dubinin, M.M. Adsorption in micropores. J. Colloid Interface Sci. 1967, 23(4): 487-499.

Dubinin, M.M., Astakhov, V.A. Development of the concepts of volume filling of micropores in the adsorption of gases and vapors by microporous adsorbents. Russ. J. Phys. Chem. B 1971, 20(1): 3-7.

Findnegg, G.H. High pressure physical adsorption of gases on homogeneous surfaces, in Fundamentals of Adsorption, edited by A. L. Myers, G. Belfort, A.I.O.C. Engineers,et al., American Institute of Chemical Engineers, New York, pp. 207-219, 1983.

Foo, K.Y., Hameed, B.H. Insights into the modeling of adsorption isotherm systems. Chem. Eng. J. 2010, 156(1): 2-10.

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.

Hao, S., Chu, W., Jiang, Q., et al. Methane adsorption characteristics on coal surface above critical temperature through Dubinin-Astakhov model and Langmuir model. Colloid Surf. A 2014, 444: 104-113.

He, S., Ning, Y., Chen, T., et al. Transport properties of natural gas in shale organic and inorganic nanopores using non-equilibrium molecular dynamics simulation. Paper IPTC 18875 Present at the International Petroleum Technology Conference, Bangkok, Thailand, 14-16 November, 2016.

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 2018, 211: 159-172.

Ji, W., Song, Y., Jiang, Z., et al. Estimation of marine shale methane adsorption capacity based on experimental investigations of Lower Silurian Longmaxi formation in the Upper Yangtze Platform, south China. Mar. Pet. Geol. 2015, 68: 94-106.

Jiao, K., Yao, S., Liu, C., et al. The characterization and quantitative analysis of nanopores in unconventional gas reservoirs utilizing FESEM-FIB and image processing: an example from the lower Silurian Longmaxi Shale, upper Yangtze region, China. Int. J. Coal Geol. 2014, 128: 1-11.

Langmuir, I. The adsorption of gases on plane surfaces of glass, mica and platinum. J. Am. Chem. Soc. 1918, 40(9): 1361-1403.

Li, A., Ding, W., Zhou, X., et al. Investigation of the methane adsorption characteristics of marine shale: A case study of lower cambrian qiongzhusi shale in eastern Yunnan Province, South China. Energy Fuels 2017, 31(3): 2625-2635.

Li, Z., Min, T., Kang, Q., et al. Investigation of methane adsorption and its effect on gas transport in shale matrix through microscale and mesoscale simulations. Int. J. Heat Mass Transf. 2016, 98: 675-686.

Liang, F., Bai, W., Zou, C., et al. Shale gas enrichment pattern and exploration significance of Well WuXi-2 in northeast Chongqing, NE Sichuan Basin. Pet. Explor. Dev. 2016, 43(3): 386-394.

Mastalerz, M., Schimmelmann, A., Drobniak, A., et al. Porosity of devonian and mississippian new albany shale across a maturation gradient: Insights from organic petrology, gas adsorption, and mercury intrusion. AAPG Bull. 2013, 97(10): 1621-1643.

Mikhail, R.S., Brunauer, S., Bodor, E.E. Investigations of a complete pore structure analysis: I. Analysis of micropores. J. Colloid Interface Sci. 1968, 26(1): 45-53.

Milliken, K.L., Rudnicki, M., Awwiller, D.N., et al. Organic matter-hosted pore system, Marcellus formation (Devo-nian), Pennsylvania. AAPG Bull. 2013, 97(2): 177-200.

Montgomery, S.L., Jarvie, D.M., Bowker, K.A., et al. Mississippian barnett shale, fort worth basin, north-central Texas: Gas-shale play with multi-trillion cubic foot potential. AAPG Bull. 2005, 89(2): 155-175.

Mosher, K., He, J., Liu, Y., et al. Molecular simulation of methane adsorption in micro-and mesoporous carbons with applications to coal and gas shale systems. Int. J. Coal Geol. 2013, 109: 36-44.

Pini, R., Ottiger, S., Burlini, L., et al. Sorption of carbon dioxide, methane and nitrogen in dry coals at high pressure and moderate temperature. Int. J. Greenhouse Gas Control 2010, 4(1): 90-101.

Rexer, T.F., Benham, M.J., Aplin, A.C., et al. Methane ad-sorption on shale under simulated geological temperature and pressure conditions. Energy Fuels 2013, 27(6): 3099-3109.

Ross, D.J.K., Bustin, R.M. The importance of shale composi-tion and pore structure upon gas storage potential of shale gas reservoirs. Mar. Pet. Geol. 2009, 26(6): 916-927.

Sakurovs, R., Day, S., Weir, S., et al. Application of a modified Dubinin Radushkevich equation to adsorption of gases by coals under supercritical conditions. Energy Fuels 2007, 21(2): 992-997.

Sing, K.S. Reporting physisorption data for gas/solid systems with special reference to the determination of surface area and porosity (Recommendations 1984). Pure. Appl. Chem. 1985, 57(4): 603-619.

Sips, R. On the structure of a catalyst surface. J. Chem. Phys. 1948, 16(5): 490-495.

Tang, X., Ripepi, N., Luxbacher, K., et al. Adsorption models for methane in shales: Review, comparison, and application. Energy Fuels 2017, 31(10): 10787-10801.

Tang, X., Ripepi, N., Stadie, N.P., et al. A dual-site Langmuir equation for accurate estimation of high pressure deep shale gas resources. Fuel 2016, 185: 10-17.

Tian, H., Li, T., Zhang, T., et al. Characterization of methane adsorption on overmature Lower Silurian-Upper Ordovician shales in Sichuan Basin, southwest China: Experimental results and geological implications. Int. J. Coal Geol. 2016, 156: 36-49.

Tian, H., Pan, L., Xiao, X., et al. A preliminary study on the pore characterization of Lower Silurian black shales in the Chuandong Thrust Fold Belt, southwestern China using low pressure N2 adsorption and FE-SEM methods. Mar. Pet. Geol. 2013, 48: 8-19.

Ushiki, I., Ota, M., Sato, Y., et al. Measurements and Dubinin-Astakhov correlation of adsorption equilibria of toluene, acetone, n-hexane, n-decane and methanol solutes in supercritical carbon dioxide on activated carbon at temperature from 313 to 353 K and at pressure from 4.2 to 15.0 MPa. Fluid Phase Equilib. 2013, 344: 101-107.

Wang, Y., Zhu, Y., Liu, S., et al. Methane adsorption measurements and modeling for organic-rich marine shale samples. Fuel 2016a, 172: 301-309.

Wang, Y., Zhu, Y., Liu, S., et al. Pore characterization and its impact on methane adsorption capacity for organic-rich marine shales. Fuel 2016b, 181: 227-237.

Wang, Z., Li, Y., Guo, P., et al. Analyzing the adaption of different adsorption models for describing the shale gas adsorption law. Chem. Eng. Technol. 2016c, 39(10): 1921-1932.

Weniger, P., Kalkreuth, W., Busch, A., et al. High-pressure methane and carbon dioxide sorption on coal and shale samples from the Paran Basin, Brazil. Chem. Eng. Technol. 2010, 84(3-4): 190-205.

Xiong, J., Liu, X., Liang, L., et al. Adsorption of methane in organic-rich shale nanopores: An experimental and molecular simulation study. Fuel 2017, 200: 299-315.

Yang, R. Gas Separation by Adsorption Processes. London, UK, Imperial College Press, 2013.

Yang, R., He, S., Yi, J., et al. Nano-scale pore structure and fractal dimension of organic-rich Wufeng-Longmaxi shale from Jiaoshiba area, Sichuan Basin: Investigations using FE-SEM, gas adsorption and helium pycnometry. Mar. Pet. Geol. 2016, 70: 27-45.

Yu, W., Sepehrnoori, K., Patzek, T.W. Modeling gas adsorption in Marcellus shale with Langmuir and bet isotherms. SPE J. 2016, 21(2): 589-600.

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, P., Cai, J., Huang, Z., et al. Estimating permeability of shale gas reservoirs from porosity and rock compositions. Geophysics 2018a, 83(5): 1-36.

Zhao, P., Ma, H., Rasouli, V., et al. An improved model for estimating the TOC in shale formations. Mar. Pet. Geol. 2017, 83: 174-183.

Zhou, L., Bai, S., Su, W., et al. Comparative study of the excess versus absolute adsorption of CO2 on superacti-vated carbon for the near-critical region. Langmuir 2003, 19(7): 2683-2690.

Zhou, S., Xue, H., Ning, Y., et al. Experimental study of supercritical methane adsorption in Longmaxi shale: Insights into the density of adsorbed methane. Fuel 2018b, 211: 140-148.

Zhou, S., Yan, G., Xue, H., et al. 2D and 3D nanopore characterization of gas shale in Longmaxi formation based on FIB-SEM. Mar. Pet. Geol. 2016, 73: 174-180.

Zou, C., Dong, D., Wang, Y., et al. Shale gas in China: Characteristics, challenges and prospects (II). Pet. Explor. Dev. 2016, 43(2): 182-196.


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