Absolute Adsorption of CH4 on Shale with the Simplified Local-Density Theory
- Yueliang Liu (China University of Petroleum (East China)) | Jian Hou (China University of Petroleum (East China)) | Chen Wang (Xi’an Shiyou University and State Key Laboratory of Oil and Gas Reservoir Geology and Exploitation (Chengdu University of Technology))
- Document ID
- Society of Petroleum Engineers
- SPE Journal
- Publication Date
- February 2020
- Document Type
- Journal Paper
- 212 - 225
- 2020.Society of Petroleum Engineers
- excess adsorption isotherm, simplified local density theory, shale, nanopore, adsorption-phase density
- 4 in the last 30 days
- 244 since 2007
- Show more detail
- View rights & permissions
|SPE Member Price:||USD 5.00|
|SPE Non-Member Price:||USD 35.00|
Using a thermogravimetric (TGA) method, the excess methane (CH4) adsorption of four organic shale samples is measured at temperatures of 303.15 to 383.15 K and pressures of 0 to 15.0 MPa. Simplified-local-density (SLD) theory is used to calculate the density distribution of CH4 in nanopores, which is then used to obtain the adsorbed CH4 density on four shale samples. Such density is applied to obtain the absolute CH4 adsorption by correcting the measured excess CH4 adsorption. SLD theory shows that the adsorbed CH4 density is strongly affected by temperature and pressure, as well as the pore size, which is in line with the previous findings from molecular simulations. SLD theory captures the density of the adsorbed phase of CH4 in the presence of CH4/pore-wall interactions. However, the SLD theory is more efficient than molecular simulation methods in determining the adsorbed CH4 density considering that only two parameters in the SLD model are adjusted to match the excess adsorption of CH4 on shale. It is observed that the corresponding absolute adsorption of CH4 is higher than the excess adsorption; this suggests that it is not reasonable to use the measured excess adsorption to estimate the storage of CH4 on shale. This study applies the SLD theory to investigate the adsorption behavior of CH4 in organic pores at different pressure/temperature conditions, and, more importantly, it yields a more-efficient approach (i.e., SLD theory) in determining the absolute adsorption than the sophisticated molecular simulations tools.
|File Size||1 MB||Number of Pages||14|
Ambrose, R. J., Hartman, R. C., Diaz-Campos, M. et al. 2012. Shale Gas-In-Place Calculations Part I: New Pore-Scale Considerations. SPE J. 17 (1): 219–229. SPE-131772-PA. https://doi.org/10.2118/131772-PA.
Chen, G., Zhang, J., Lu, S. et al. 2016. Adsorption Behavior of Hydrocarbon on Illite. Energy Fuels 30 (11): 9114–9121. https://doi.org/10.1021/acs.energyfuels.6b01777.
Chen, J. H., Wong, D. S. H., Tan, C. S. et al. 1997. Adsorption and Desorption of Carbon Dioxide onto and from Activated Carbon at High Pressures. Ind Eng Chem Res 36 (7): 2808–2815. https://doi.org/10.1021/ie960227w.
Clarkson, C. R. and Haghshenas, B. 2013. Modeling of Supercritical Fluid Adsorption on Organic Rich Shales and Coal. Paper presented at the SPE Unconventional Resources Conference, Woodlands, Texas, USA, 10–12 April. SPE-164532-MS. https://doi.org/10.2118/164532-MS.
Cristancho-Albarracin, D., Akkutlu, I. Y., Criscenti, L. J. et al. 2017. Shale Gas Storage in Kerogen Nanopores with Surface Heterogeneities. Appl Geochem 84: 1–10. https://doi.org/10.1016/j.apgeochem.2017.04.012.
Dasani, D., Wang, Y., Tsotsis, T. T. et al. 2017. Laboratory-Scale Investigation of Sorption Kinetics of Methane/Ethane Mixtures in Shale. Ind Eng Chem Res 56: 9953–9963. https://doi.org/10.1021/acs.iecr.7b02431.
de Boer, J. H. and Lippens, B. C. 1964. Studies on Pore Systems in Catalysts II. The Shapes of Pores in Aluminum Oxide Systems. J Catal 3 (1): 38–43. https://doi.org/10.1016/0021-9517(64)90090-9.
Didar, B. R. and Akkutlu, I. Y. 2013. Pore-Size Dependence of Fluid Phase Behavior and Properties in Organic-Rich Shale Reservoirs. Paper presented at the SPE International Symposium on Oilfield Chemistry, Woodlands, Texas, USA, 8–10 April. SPE-164099-MS. https://doi.org/10.2118/164099-MS.
Dobrzanski, C. D., Maximov, M. A., and Gor, G. Y. 2018. Effect of Pore Geometry on the Compressibility of a Confined Simple Fluid. J Chem Phys 148: 054503. https://doi.org/10.1063/1.5008490.
Dong, X., Liu, H., Hou, J. et al. 2016. Phase Equilibria of Confined Fluids in Nanopores of Tight and Shale Rocks Considering the Effect of Capillary Pressure and Adsorption Film. Ind Eng Chem Res 55 (3): 798–811. https://doi.org/10.1021/acs.iecr.5b04276.
Dubinin, M. M. 1960. The Potential Theory of Adsorption of Gases and Vapors for Adsorbents with Energetically Nonuniform Surfaces. Chem Rev 60 (2): 235–241. https://doi.org/10.1021/cr60204a006.
Fan, C., Do, D. D., and Nicholson, D. 2011. On the Cavitation and Pore Blocking in Slit-Shaped Ink-Bottle Pores. Langmuir 27 (7): 3511–3526. https://doi.org/10.1021/la104279v.
Fitzgerald, J. E. 2005. Adsorption of Pure and Multi-Component Gases of Importance to Enhanced Coalbed Methane Recovery: Measurements and Simplified Local Density Model. PhD dissertation, Oklahoma State University, Stillwater, Oklahoma, USA (July 2005).
Gasem, K. A. M., Gao, W., Pan, Z. et al. 2001. A Modified Temperature for the Peng-Robinson Equation of State. Fluid Phase Equilib 181 (1): 113–125. https://doi.org/10.1016/S0378-3812(01)00488-5.
Gasparik, M. Ghanizadeh, A., Bertier, P. et al. 2012. High-Pressure Methane Sorption Isotherms of Black Shales from The Netherlands. Energy Fuels 26 (8): 4995–5004. https://doi.org/10.1021/ef300405g.
Gensterblum, Y., van Hemert, P., Billemont, P. et al. 2009. European Inter-Laboratory Comparison of High Pressure CO2 Sorption Isotherms. I: Activated Carbon. Carbon 47 (13): 2958–2969. https://doi.org/10.1016/j.carbon.2009.06.046.
Gregg, S. J. and Sing, K. S. W. 1982. Adsorption, Surface Area and Porosity. London, UK: Academic Press.
Groen, J. C., Peffer, L. A. A., and Pérez-Ramírez, J. 2003. Pore Size Determination in Modified Micro- and Mesoporous Materials. Pitfalls and Limitations in Gas Adsorption Data Analysis. Microporous Mesoporous Mater. 60: 1–17. https://doi.org/10.1016/S1387-1811(03)00339-1.
Heller, R. and Zoback, M. 2014. Adsorption of Methane and Carbon Dioxide on Gas Shale and Pure Mineral Samples. J Unconventional Oil Gas Resour 8: 14–24. https://doi.org/10.1016/j.juogr.2014.06.001.
Huang, X., Li, T., Gao, H. et al. 2019. Comparison of SO2 with CO2 for Recovering Shale Resources Using Low-Field Nuclear Magnetic Resonance. Fuel 245: 563–569. https://doi.org/10.1016/j.fuel.2019.01.135.
Jiang, W. and Lin, M. 2018. Molecular Dynamics Investigation of Conversion Methods for Excess Adsorption Amount of Shale Gas. J Nat Gas Sci Eng 49: 241–249. https://doi.org/10.1016/j.jngse.2017.11.006.
Jin, Z. and Firoozabadi, A. 2013. Methane and Carbon Dioxide Adsorption in Clay-Like Slit Pores by Monte Carlo Simulations. Fluid Phase Equilib 360: 456–465. https://doi.org/10.1016/j.fluid.2013.09.047.
Keffer, D., Davis, H. T., and McCormick, A. 1996. The Effect of Nanopore Shape on the Structure and Isotherms of Adsorbed Fluids. Adsorption 2: 9–21. https://doi.org/10.1007/BF00127094.
Klomkliang, N., Do, D. D., and Nicholson, D. 2013. On the Hysteresis Loop and Equilibrium Transition in Slit-Shaped Ink-Bottle Pores. Adsorption 19 (6): 1273–1290. https://doi.org/10.1007/s10450-013-9569-5.
Lee, L. L. 1988. Molecular Thermodynamics of Non-Ideal Fluids. Stoneham, Massachusetts, USA: Butterworths.
Lemmon, E. W., McLinden, M. O., and Friend, D. G. 2009. NIST Standard Reference Database Number 69: Thermophysical Properties of Fluid Systems, NIST Chemistry WebBook. Gaithersburg, Maryland, USA: National Institute of Standards and Technology.
Li, Z., Jin, Z., and Firoozabadi, A. 2014. Phase Behavior and Adsorption of Pure Substances and Mixtures and Characterization in Nanopore Structures by Density Functional Theory. SPE J. 19 (6): 1096–1109. SPE-169819-PA. https://doi.org/10.2118/169819-PA.
Liu, Y., Jin, Z., and Li, H. A. 2018a. Comparison of Peng-Robinson Equation of State with Capillary Pressure Model with Engineering Density-Functional Theory in Describing the Phase Behavior of Confined Hydrocarbons. SPE J. 23 (5): 1784–1797. SPE-187405-PA. https://doi.org/10.2118/187405-PA.
Liu, Y., Li, H., Tian, Y. et al. 2018b. Determination of the Absolute Adsorption/Desorption Isotherms of CH4 and n-C4H10 on Shale from a Nano-Scale Perspective. Fuel 218: 67–77. https://doi.org/10.1016/j.fuel.2018.01.012.
Liu, Y. and Wilcox, J. 2012. Molecular Simulations of CO2 Adsorption in Micro- and Mesoporous Carbons with Surface Heterogeneity. Int J Coal Geol 104: 83–95. https://doi.org/10.1016/j.coal.2012.04.007.
Lu, X. C., Li, F. C., and Watson, A. T. 1995. Adsorption Measurements in Devonian Shales. Fuel 74 (4): 599–603. https://doi.org/10.1016/0016-2361(95)98364-K.
Mohammad, S. A., Arumugam, A., Robinson, R. L. Jr. et al. 2011. High-Pressure Adsorption of Pure Gases on Coals and Activated Carbon: Measurements and Modeling. Energy Fuels 26 (1): 536–548. https://doi.org/10.1021/ef201393p.
Mohammad, S. A., Chen, J. S., Robinson, R. L. Jr. et al. 2009. Generalized Simplified Local-Density/Peng-Robinson Model for Adsorption of Pure and Mixed Gases on Coals. Energy Fuels 23: 6259–6271. https://doi.org/10.1021/ef900642j.
Pang, Y., Mohamed, Y. S., and Sheng, J. 2018. Investigating Gas-Adsorption, Stress-Dependence, and Non-Darcy-Flow Effects on Gas Storage and Transfer in Nanopores by Use of Simplified Local Density Model. SPE Res Eval & Eng 21 (1): 73–95. SPE-187961-PA. https://doi.org/10.2118/187961-PA.
Rangarajan, B., Lira, C. T., and Subramanian, R. 1995. Simplified Local Density Model for Adsorption Over Large Pressure Ranges. AIChE J 41 (4): 838–845. https://doi.org/10.1002/aic.690410411.
Rexer, T. F. T., Benham, M. J., Aplin, A. C. et al. 2013. Methane Adsorption on Shale under Simulated Geological Temperature and Pressure Conditions. Energy Fuels 27 (6): 3099–3109. https://doi.org/10.1021/ef400381v.
Riewchotisakul, S. and Akkutlu, I. Y. 2016. Adsorption-Enhanced Transport of Hydrocarbons in Organic Nanopores. SPE J. 21 (6): 1960–1969. SPE-175107-PA. https://doi.org/10.2118/175107-PA.
Ross, D. J. K. and Bustin, R. M. 2009. The Importance of Shale Composition and Pore Structure upon Gas Storage Potential of Shale Gas Reservoirs. Mar Pet Geol 26 (6): 916–927. https://doi.org/10.1016/j.marpetgeo.2008.06.004.
Santos, J. M. and Akkutlu, I. Y. 2013. Laboratory Measurement of Sorption Isotherm under Confining Stress with Pore-Volume Effects. SPE J. 18 (5): 924–931. SPE-162595-PA. https://doi.org/10.2118/162595-PA.
Sing, K. S. W., Everett, D. H., Haul, R. A. W. et al. 2008. Reporting Physisorption Data for Gas/Solid Systems. In Handbook of Heterogeneous Catalysis. Weinheim, Germany: Wiley-VCH Verlag GmbH & Co. KGaA.
Tarazona, P., Marconi, U., and Evans, R. 1987. Phase Equilibria of Fluid Interfaces and Confined Fluids. Mol Phys 60 (3): 573–595. https://doi.org/10.1080/00268978700100381.
Tian, Y., Yan, C., and Jin, Z. 2017. Characterization of Methan Excess and Absolute Adsorption in Various Clay Nanopores from Molecular Simulation. Sci Rep 7, Article Number 12040. https://doi.org/10.1038/s41598-017-12123-x.
Wang, Y., Tsotsis, T. T., and Jessen, K. 2015. Competitive Adsorption of Methane/Ethane Mixtures on Shale: Measurements and Modeling. Ind Eng Chem Res 54 (48): 12187–12195. https://doi.org/10.1021/acs.iecr.5b02850.
Wang, Y., Zhu, Y., Liu, S. et al. 2016. Methane Adsorption Measurements and Modeling for Organic-Rich Marine Shale Samples. Fuel 172: 301–309. https://doi.org/10.1016/j.fuel.2015.12.074.
Wu, Y., Fan, T., Jiang, S. et al. 2015. Methane Adsorption Capacities of the Lower Paleozoic Marine Shales in the Yangtze Platform, South China. Energy Fuels 29 (7): 4160–4167. https://doi.org/10.1021/acs.energyfuels.5b00286.
Xiong, F., Wang, X., Amooie, M. A. et al. 2017. The Shale Gas Sorption Capacity of Transitional Shales in the Ordos Basin, NW China. Fuel 208: 236–246. https://doi.org/10.1016/j.fuel.2017.07.030.
Zhou, S., Wang, H., Xue, H. et al. 2016. Difference Between Excess and Absolute Adsorption Capacity of Shale and a New Shale Gas Reserve Calculation Method. Nat Gas Ind 36: 12–20. https://doi.org/10.3787/j.issn.1000-0976.2016.11.002.