Reduced methane recovery at high pressure due to methane trapping in shale nanopores

Neil, Chelsea W.; Mehana, Mohamed Zakaria Saad; Hjelm Jr., Rex P.; Hawley, Marilyn E.; Watkins, Erik B.; Mao, Yimin; Viswanathan, Hari S.; Kang, Qinjun; Xu, Hongwu

doi:10.1038/s43247-020-00047-w

Reduced methane recovery at high pressure due to methane trapping in shale nanopores

Journal Article · Tue Nov 10 00:00:00 EST 2020 · Communications Earth & Environment

DOI:https://doi.org/10.1038/s43247-020-00047-w· OSTI ID:1756822

^[1]; ^[1]; ^[2]; Hawley, Marilyn E. ^[1]; ^[1]; Mao, Yimin ^[3]; ^[1]; ^[1]; ^[1]

Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Los Alamos National Lab. (LANL), Los Alamos, NM (United States); The New Mexico Consortium, Los Alamos, NM (United States)
Univ. of Maryland, College Park, MD (United States); National Inst. of Standards and Technology (NIST), Gaithersburg, MD (United States). Center for Neutron Research

By 2050, shale gas production is expected to exceed three-quarters of total US natural gas production. However, current unconventional hydrocarbon gas recovery rates are only around 20%. Maximizing production of this natural resource thus necessitates improved understanding of the fundamental mechanisms underlying hydrocarbon retention within the nanoporous shale matrix. In this study, we integrated molecular simulation with high-pressure small-angle neutron scattering (SANS), an experimental technique uniquely capable of characterizing methane behavior in situ within shale nanopores at elevated pressures. Samples were created using Marcellus shale, a gas-generative formation comprising the largest natural gas field in the United States. Our results demonstrate that, contrary to the conventional wisdom that elevated drawdown pressure increases methane recovery, a higher peak pressure led to the trapping of dense, liquid-like methane in sub-2 nm radius nanopores, which comprise more than 90% of the measured nanopore volume, due to irreversible deformation of the kerogen matrix. These findings have critical implications for pressure management strategies to maximize hydrocarbon recovery, as well as broad implications for fluid behavior under confinement.

View Accepted Manuscript (DOE)

Research Organization:: Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)

Sponsoring Organization:: USDOE Laboratory Directed Research and Development (LDRD) Program; USDOE National Nuclear Security Administration (NNSA); USDOE Office of Fossil Energy (FE)

Grant/Contract Number:: 89233218CNA000001

OSTI ID:: 1756822

Report Number(s):: LA-UR--20-22897

Journal Information:: Communications Earth & Environment, Journal Name: Communications Earth & Environment Journal Issue: 1 Vol. 1; ISSN 2662-4435

Publisher:: Springer NatureCopyright Statement

Country of Publication:: United States

Language:: English

References (68)

Methane solubility in liquid hydrocarbons at high pressure Pribylov, A. A.; Skibitskaya, N. A.; Zekel´, L. A. Russian Chemical Bulletin, Vol. 64, Issue 4 https://doi.org/10.1007/s11172-015-0942-2	journal	April 2015
Gas transport in shale matrix coupling multilayer adsorption and pore confinement effect Chai, Di; Yang, Gang; Fan, Zhaoqi Chemical Engineering Journal, Vol. 370 https://doi.org/10.1016/j.cej.2019.03.276	journal	August 2019
Apparent permeability for gas transport in nanopores of organic shale reservoirs including multiple effects Wang, Jing; Liu, Huiqing; Wang, Lei International Journal of Coal Geology, Vol. 152 https://doi.org/10.1016/j.coal.2015.10.004	journal	December 2015
Pore characteristics of Longmaxi shale gas reservoir in the Northwest of Guizhou, China: Investigations using small-angle neutron scattering (SANS), helium pycnometry, and gas sorption isotherm Sun, Mengdi; Yu, Bingsong; Hu, Qinhong International Journal of Coal Geology, Vol. 171 https://doi.org/10.1016/j.coal.2016.12.004	journal	February 2017
Porosity of the Marcellus Shale: A contrast matching small-angle neutron scattering study Bahadur, Jitendra; Ruppert, Leslie F.; Pipich, Vitaliy International Journal of Coal Geology, Vol. 188 https://doi.org/10.1016/j.coal.2018.02.002	journal	March 2018
Characterization of tight gas reservoir pore structure using USANS/SANS and gas adsorption analysis Clarkson, C. R.; Freeman, M.; He, L. Fuel, Vol. 95 https://doi.org/10.1016/j.fuel.2011.12.010	journal	May 2012
Pore structure characterization of North American shale gas reservoirs using USANS/SANS, gas adsorption, and mercury intrusion Clarkson, C. R.; Solano, N.; Bustin, R. M. Fuel, Vol. 103 https://doi.org/10.1016/j.fuel.2012.06.119	journal	January 2013
Porosity evolution in oil-prone source rocks Zargari, Saeed; Canter, Karen Lyn; Prasad, Manika Fuel, Vol. 153 https://doi.org/10.1016/j.fuel.2015.02.072	journal	August 2015
Applying SANS technique to characterize nano-scale pore structure of Longmaxi shale, Sichuan Basin (China) Yang, Rui; He, Sheng; Hu, Qinhong Fuel, Vol. 197 https://doi.org/10.1016/j.fuel.2017.02.005	journal	June 2017
Adsorption of methane in organic-rich shale nanopores: An experimental and molecular simulation study Xiong, Jian; Liu, Xiangjun; Liang, Lixi Fuel, Vol. 200 https://doi.org/10.1016/j.fuel.2017.03.083	journal	July 2017
Porosity and storage capacity of Middle Devonian shale: A function of thermal maturity, total organic carbon, and clay content Song, Liaosha; Martin, Keithan; Carr, Timothy R. Fuel, Vol. 241 https://doi.org/10.1016/j.fuel.2018.12.106	journal	April 2019
Numerical investigation of gas flow rate in shale gas reservoirs with nanoporous media Song, Hongqing; Yu, Mingxu; Zhu, Weiyao International Journal of Heat and Mass Transfer, Vol. 80 https://doi.org/10.1016/j.ijheatmasstransfer.2014.09.039	journal	January 2015
A model for multiple transport mechanisms through nanopores of shale gas reservoirs with real gas effect–adsorption-mechanic coupling Wu, Keliu; Chen, Zhangxin; Li, Xiangfang International Journal of Heat and Mass Transfer, Vol. 93 https://doi.org/10.1016/j.ijheatmasstransfer.2015.10.003	journal	February 2016
Pressure-dependent transport characteristic of methane gas in slit nanopores Yu, Hao; Fan, JingCun; Chen, Jie International Journal of Heat and Mass Transfer, Vol. 123 https://doi.org/10.1016/j.ijheatmasstransfer.2018.03.003	journal	August 2018
Molecular dynamics simulation of methane transport in confined organic nanopores with high relative roughness He, Jian; Ju, Yang; Kulasinski, Karol Journal of Natural Gas Science and Engineering, Vol. 62 https://doi.org/10.1016/j.jngse.2018.12.010	journal	February 2019
Injection of mixture of shale gases in a nanoscale pore of graphite and their displacement by CO2/N2 gases using molecular dynamics study Akbarzadeh, Hamed; Abbaspour, Mohsen; Salemi, Sirous Journal of Molecular Liquids, Vol. 248 https://doi.org/10.1016/j.molliq.2017.10.089	journal	December 2017
Shale characteristics impact on Nuclear Magnetic Resonance (NMR) fluid typing methods and correlations Mehana, Mohamed; El-monier, Ilham Petroleum, Vol. 2, Issue 2 https://doi.org/10.1016/j.petlm.2016.02.002	journal	June 2016
Differentiating Defect and Basal Plane Contributions to the Surface Energy of Graphite Using Inverse Gas Chromatography Ferguson, Auren; Caffrey, Ivan T.; Backes, Claudia Chemistry of Materials, Vol. 28, Issue 17 https://doi.org/10.1021/acs.chemmater.6b02721	journal	August 2016
Small-angle Neutron Scattering (SANS) Characterization of Clay- and Carbonate-rich Shale at Elevated Pressures Neil, Chelsea W.; Hjelm, Rex P.; Hawley, Marilyn E. Energy & Fuels, Vol. 34, Issue 7 https://doi.org/10.1021/acs.energyfuels.0c01009	journal	June 2020
Nanoconfined Transport Characteristic of Methane in Organic Shale Nanopores: The Applicability of the Continuous Model Yu, Hao; Xu, HengYu; Xia, Jun Energy & Fuels, Vol. 34, Issue 8 https://doi.org/10.1021/acs.energyfuels.0c01789	journal	June 2020
Pores in Marcellus Shale: A Neutron Scattering and FIB-SEM Study Gu, Xin; Cole, David R.; Rother, Gernot Energy & Fuels, Vol. 29, Issue 3 https://doi.org/10.1021/acs.energyfuels.5b00033	journal	February 2015
Methane Adsorption on Carbon Models of the Organic Matter of Organic-Rich Shales Xiong, Jian; Liu, Xiangjun; Liang, Lixi Energy & Fuels, Vol. 31, Issue 2 https://doi.org/10.1021/acs.energyfuels.6b03144	journal	February 2017
Supercritical Methane Diffusion in Shale Nanopores: Effects of Pressure, Mineral Types, and Moisture Content Wang, Sen; Feng, Qihong; Zha, Ming Energy & Fuels, Vol. 32, Issue 1 https://doi.org/10.1021/acs.energyfuels.7b02892	journal	December 2017
Roughness Factor-Dependent Transport Characteristic of Shale Gas through Amorphous Kerogen Nanopores Yu, Hao; Xu, HengYu; Fan, JingCun The Journal of Physical Chemistry C, Vol. 124, Issue 23 https://doi.org/10.1021/acs.jpcc.0c02456	journal	May 2020
Deformation and Swelling of Kerogen Matrix in Light Hydrocarbons and Carbon Dioxide Tesson, Stéphane; Firoozabadi, Abbas The Journal of Physical Chemistry C, Vol. 123, Issue 48 https://doi.org/10.1021/acs.jpcc.9b04592	journal	November 2019
A USANS/SANS Study of the Accessibility of Pores in the Barnett Shale to Methane and Water Ruppert, Leslie F.; Sakurovs, Richard; Blach, Tomasz P. Energy & Fuels, Vol. 27, Issue 2 https://doi.org/10.1021/ef301859s	journal	February 2013
Methane Adsorption on Shale under Simulated Geological Temperature and Pressure Conditions Rexer, Thomas F. T.; Benham, Michael J.; Aplin, Andrew C. Energy & Fuels, Vol. 27, Issue 6 https://doi.org/10.1021/ef400381v	journal	May 2013
Small-Angle and Ultrasmall-Angle Neutron Scattering (SANS/USANS) Study of New Albany Shale: A Treatise on Microporosity Bahadur, Jitendra; Radlinski, Andrzej P.; Melnichenko, Yuri B. Energy & Fuels, Vol. 29, Issue 2 https://doi.org/10.1021/ef502211w	journal	January 2015
Transferable Potentials for Phase Equilibria. 1. United-Atom Description of n-Alkanes Martin, Marcus G.; Siepmann, J. Ilja https://doi.org/10.1021/jp972543+		March 1998
Self-Diffusion of Methane in Single-Walled Carbon Nanotubes at Sub- and Supercritical Conditions Cao, Dapeng; Wu, Jianzhong Langmuir, Vol. 20, Issue 9 https://doi.org/10.1021/la036375q	journal	April 2004
Thermodynamics of Water Confined in Porous Calcium-Silicate-Hydrates Bonnaud, P. A.; Ji, Q.; Coasne, B. Langmuir, Vol. 28, Issue 31 https://doi.org/10.1021/la301738p	journal	July 2012
Porous Ice Phases with VI and Distorted VII Structures Constrained in Nanoporous Silica Zhu, Jinlong; Quan, Zewei; Lin, Yu-Shen Nano Letters, Vol. 14, Issue 11 https://doi.org/10.1021/nl503165n	journal	October 2014
Water conduction through the hydrophobic channel of a carbon nanotube Hummer, G.; Rasaiah, J. C.; Noworyta, J. P. Nature, Vol. 414, Issue 6860 https://doi.org/10.1038/35102535	journal	November 2001
Enhanced flow in carbon nanotubes Majumder, Mainak; Chopra, Nitin; Andrews, Rodney Nature, Vol. 438, Issue 7064 https://doi.org/10.1038/438044a	journal	November 2005
Giant osmotic energy conversion measured in a single transmembrane boron nitride nanotube Siria, Alessandro; Poncharal, Philippe; Biance, Anne-Laure Nature, Vol. 494, Issue 7438 https://doi.org/10.1038/nature11876	journal	February 2013
Seven challenges for nanomedicine Sanhai, Wendy R.; Sakamoto, Jason H.; Canady, Richard Nature Nanotechnology, Vol. 3, Issue 5 https://doi.org/10.1038/nnano.2008.114	journal	May 2008
Observation of extreme phase transition temperatures of water confined inside isolated carbon nanotubes Agrawal, Kumar Varoon; Shimizu, Steven; Drahushuk, Lee W. Nature Nanotechnology, Vol. 12, Issue 3 https://doi.org/10.1038/nnano.2016.254	journal	November 2016
Molecular dynamics simulations of propane in slit shaped silica nano-pores: direct comparison with quasielastic neutron scattering experiments Gautam, Siddharth; Le, Thu; Striolo, Alberto Physical Chemistry Chemical Physics, Vol. 19, Issue 48 https://doi.org/10.1039/C7CP05715F	journal	January 2017
Size matters: why nanomaterials are different Roduner, Emil Chemical Society Reviews, Vol. 35, Issue 7 https://doi.org/10.1039/b502142c	journal	January 2006
Melting and freezing of water in cylindrical silica nanopores Jähnert, S.; Vaca Chávez, F.; Schaumann, G. E. Physical Chemistry Chemical Physics, Vol. 10, Issue 39 https://doi.org/10.1039/b809438c	journal	January 2008
Rheo–small-angle neutron scattering at the National Institute of Standards and Technology Center for Neutron Research Porcar, L.; Pozzo, D.; Langenbucher, G. Review of Scientific Instruments, Vol. 82, Issue 8, Article No. 083902 https://doi.org/10.1063/1.3609863	journal	August 2011
Chemistry in noninteger dimensions between two and three. I. Fractal theory of heterogeneous surfaces Pfeifer, Peter; Avnir, David The Journal of Chemical Physics, Vol. 79, Issue 7 https://doi.org/10.1063/1.446210	journal	October 1983
Flow of methane in shale nanopores at low and high pressure by molecular dynamics simulations Jin, Zhehui; Firoozabadi, Abbas The Journal of Chemical Physics, Vol. 143, Issue 10 https://doi.org/10.1063/1.4930006	journal	September 2015
Channel-width dependent pressure-driven flow characteristics of shale gas in nanopores Chen, Jie; Yu, Hao; Fan, Jingcun AIP Advances, Vol. 7, Issue 4 https://doi.org/10.1063/1.4982729	journal	April 2017
Structure and dynamics of ethane confined in silica nanopores in the presence of CO ₂ Liu, Tingting; Gautam, Siddharth; Cole, David R. The Journal of Chemical Physics, Vol. 152, Issue 8 https://doi.org/10.1063/1.5134451	journal	February 2020
Geochemical evidence for possible natural migration of Marcellus Formation brine to shallow aquifers in Pennsylvania Warner, Nathaniel R.; Jackson, Robert B.; Darrah, Thomas H. Proceedings of the National Academy of Sciences, Vol. 109, Issue 30 https://doi.org/10.1073/pnas.1121181109	journal	July 2012
Direct observation of stick-slip movements of water nanodroplets induced by an electron beam Mirsaidov, U. M.; Zheng, H.; Bhattacharya, D. Proceedings of the National Academy of Sciences, Vol. 109, Issue 19 https://doi.org/10.1073/pnas.1200457109	journal	April 2012
Phase separation in confined systems Gelb, Lev D.; Gubbins, K. E.; Radhakrishnan, R. Reports on Progress in Physics, Vol. 62, Issue 12 https://doi.org/10.1088/0034-4885/62/12/201	journal	December 1999
Bridging scales from molecular simulations to classical thermodynamics: density functional theory of capillary condensation in nanopores Neimark, Alexander V.; Ravikovitch, Peter I.; Vishnyakov, Aleksey Journal of Physics: Condensed Matter, Vol. 15, Issue 3 https://doi.org/10.1088/0953-8984/15/3/303	journal	January 2003
Computer Simulation of Liquids Allen, Michael P.; Tildesley, Dominic J. https://doi.org/10.1093/oso/9780198803195.001.0001	book	June 2017
Understanding hydraulic fracturing: a multi-scale problem Hyman, J. D.; Jiménez-Martínez, J.; Viswanathan, H. S. Philosophical Transactions of the Royal Society A: Mathematical, Physical and Engineering Sciences, Vol. 374, Issue 2078 https://doi.org/10.1098/rsta.2015.0426	journal	October 2016
Multilevel structure of reinforcing silica and carbon Schaefer, D. W.; Rieker, T.; Agamalian, M. Journal of Applied Crystallography, Vol. 33, Issue 3 https://doi.org/10.1107/S0021889800001199	journal	June 2000
Small-angle scattering in materials science - a short review of applications in alloys, ceramics and composite materials Fratzl, Peter Journal of Applied Crystallography, Vol. 36, Issue 3 https://doi.org/10.1107/S0021889803000335	journal	April 2003
Reduction and analysis of SANS and USANS data using IGOR Pro Kline, Steven R. Journal of Applied Crystallography, Vol. 39, Issue 6, p. 895-900 https://doi.org/10.1107/S0021889806035059	journal	November 2006
The 30 m Small-Angle Neutron Scattering Instruments at the National Institute of Standards and Technology Glinka, C. J.; Barker, J. G.; Hammouda, B. Journal of Applied Crystallography, Vol. 31, Issue 3, p. 430-445 https://doi.org/10.1107/S0021889897017020	journal	June 1998
Factors Affecting Hydraulically Fractured Well Performance in the Marcellus Shale Gas Reservoirs Osholake, Tunde; Yilin Wang, John; Ertekin, Turgay Journal of Energy Resources Technology, Vol. 135, Issue 1 https://doi.org/10.1115/1.4007766	journal	December 2012
Why Fracking Works Bažant, Zdeněk P.; Salviato, Marco; Chau, Viet T. Journal of Applied Mechanics, Vol. 81, Issue 10 https://doi.org/10.1115/1.4028192	journal	August 2014
Fast Mass Transport Through Sub-2-Nanometer Carbon Nanotubes Holt, J. K. Science, Vol. 312, Issue 5776 https://doi.org/10.1126/science.1126298	journal	May 2006
Surface Energy of North American Shales and its Role in Interaction of Shale with Surfactants and Microemulsions Zelenev, Andrei S. SPE International Symposium on Oilfield Chemistry https://doi.org/10.2118/141459-MS	conference	April 2013
Resource Evaluation for Shale Gas Reservoirs Dong, Zhenzhen; Holditch, Stephen; McVay, Duane SPE Economics & Management, Vol. 5, Issue 01 https://doi.org/10.2118/152066-PA	journal	January 2013
Microscopic Dynamics of Water and Hydrocarbon in Shale-Kerogen Pores of Potentially Mixed Wettability Hu, Yinan; Devegowda, Deepak; Striolo, Alberto SPE Journal, Vol. 20, Issue 01 https://doi.org/10.2118/167234-PA	journal	February 2014
Effect of Confinement on Pressure/Volume/Temperature Properties of Hydrocarbons in Shale Reservoirs Pitakbunkate, Termpan; Balbuena, Perla B.; Moridis, George J. SPE Journal, Vol. 21, Issue 02 https://doi.org/10.2118/170685-PA	journal	April 2016
Evaluation of Gas Adsorption in Marcellus Shale Yu, Wei; Sepehrnoori, Kamy; Patzek, Tadeusz Wiktor SPE Annual Technical Conference and Exhibition https://doi.org/10.2118/170801-MS	conference	October 2014
Modeling Gas Adsorption in Marcellus Shale With Langmuir and BET Isotherms Yu, Wei; Sepehrnoori, Kamy; Patzek, Tadeusz W. SPE Journal, Vol. 21, Issue 02 https://doi.org/10.2118/170801-PA	journal	April 2016
Thermodynamic Modeling of Phase Behavior in Shale Media Jin, Zhehui; Firoozabadi, Abbas SPE Journal, Vol. 21, Issue 01 https://doi.org/10.2118/176015-PA	journal	February 2016
What Factors Control Shale-Gas Production and Production-Decline Trend in Fractured Systems: A Comprehensive Analysis and Investigation Wang, HanYi SPE Journal, Vol. 22, Issue 02 https://doi.org/10.2118/179967-PA	journal	August 2016
Marcellus Wells' Ultimate Production Accurately Predicted from Initial Production Male, Frank; Marder, Michael P.; Browning, John SPE Low Perm Symposium https://doi.org/10.2118/180234-MS	conference	May 2016
Fast parallel algorithms for short-range molecular dynamics Plimpton, S. https://doi.org/10.2172/10176421	report	May 1993

Similar Records

Fundamental Study of Disposition and Release of Methane in a Shale Gas Reservoir

Technical Report · Thu Sep 01 00:00:00 EDT 2016 · OSTI ID:1431467

Nanostructural control of methane release in kerogen and its implications to wellbore production decline

Journal Article · Wed Jun 15 20:00:00 EDT 2016 · Scientific Reports · OSTI ID:1257808

Related Subjects

58 GEOSCIENCES
geophysics
petrology

Reduced methane recovery at high pressure due to methane trapping in shale nanopores

Citation Formats

References (68)

Similar Records

Related Subjects