Search Menu
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information
Search Scholarly Publications

Title: Differential retention and release of CO2 and CH4 in kerogen nanopores: Implications for gas extraction and carbon sequestration

Abstract

Methane (CH4) and carbon dioxide (CO2), the two major components generated from kerogen maturation, are stored dominantly in nanometer-sized pores in shale matrix as (1) a compressed gas, (2) an adsorbed surface species and/or (3) a species dissolved in pore water (H2O). In addition, supercritical CO2 has been proposed as a fracturing fluid for simultaneous enhanced oil/gas recovery (EOR) and carbon sequestration. A mechanistic understanding of CH4-CO2-H2O interactions in shale nanopores is critical for designing effective operational processes. Using molecular simulations, we show that kerogen preferentially retains CO2 over CH4 and that the majority of CO2 either generated during kerogen maturation or injected in EOR will remain trapped in the kerogen matrix. The trapped CO2 may be released only if the reservoir pressure drops below the supercritical CO2 pressure. When water is present in the kerogen matrix, it may block CH4 release. Furthermore, the addition of CO2 may enhance CH4 release because CO2 can diffuse through water and exchange for adsorbed methane in the kerogen nanopores.

Authors:
 [1];  [1];  [2];  [1]
+ Show Author Affiliations
  1. Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
  2. Sandia National Lab. (SNL-NM), Carlsbad, NM (United States)
Publication Date:
Research Org.:
Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
Sponsoring Org.:
USDOE National Nuclear Security Administration (NNSA)
OSTI Identifier:
1421764
Report Number(s):
SAND-2018-1044J
Journal ID: ISSN 0016-2361; 660339
Grant/Contract Number:  
AC04-94AL85000
Resource Type:
Accepted Manuscript
Journal Name:
Fuel
Additional Journal Information:
Journal Volume: 220; Journal Issue: C; Journal ID: ISSN 0016-2361
Publisher:
Elsevier
Country of Publication:
United States
Language:
English
Subject:
03 NATURAL GAS; Organic matter; Kerogen; Nanoscale transport; Shale gas; Carbon sequestration

Citation Formats

Ho, Tuan Anh, Wang, Yifeng, Xiong, Yongliang, and Criscenti, Louise J. Differential retention and release of CO2 and CH4 in kerogen nanopores: Implications for gas extraction and carbon sequestration. United States: N. p., 2018. Web. doi:10.1016/j.fuel.2018.01.106.
Copy to clipboard
Ho, Tuan Anh, Wang, Yifeng, Xiong, Yongliang, & Criscenti, Louise J. Differential retention and release of CO2 and CH4 in kerogen nanopores: Implications for gas extraction and carbon sequestration. United States. https://doi.org/10.1016/j.fuel.2018.01.106
Copy to clipboard
Ho, Tuan Anh, Wang, Yifeng, Xiong, Yongliang, and Criscenti, Louise J. Tue . "Differential retention and release of CO2 and CH4 in kerogen nanopores: Implications for gas extraction and carbon sequestration". United States. https://doi.org/10.1016/j.fuel.2018.01.106. https://www.osti.gov/servlets/purl/1421764.
Copy to clipboard
@article{osti_1421764,
title = {Differential retention and release of CO2 and CH4 in kerogen nanopores: Implications for gas extraction and carbon sequestration},
author = {Ho, Tuan Anh and Wang, Yifeng and Xiong, Yongliang and Criscenti, Louise J.},
abstractNote = {Methane (CH4) and carbon dioxide (CO2), the two major components generated from kerogen maturation, are stored dominantly in nanometer-sized pores in shale matrix as (1) a compressed gas, (2) an adsorbed surface species and/or (3) a species dissolved in pore water (H2O). In addition, supercritical CO2 has been proposed as a fracturing fluid for simultaneous enhanced oil/gas recovery (EOR) and carbon sequestration. A mechanistic understanding of CH4-CO2-H2O interactions in shale nanopores is critical for designing effective operational processes. Using molecular simulations, we show that kerogen preferentially retains CO2 over CH4 and that the majority of CO2 either generated during kerogen maturation or injected in EOR will remain trapped in the kerogen matrix. The trapped CO2 may be released only if the reservoir pressure drops below the supercritical CO2 pressure. When water is present in the kerogen matrix, it may block CH4 release. Furthermore, the addition of CO2 may enhance CH4 release because CO2 can diffuse through water and exchange for adsorbed methane in the kerogen nanopores.},
doi = {10.1016/j.fuel.2018.01.106},
journal = {Fuel},
number = C,
volume = 220,
place = {United States},
year = {Tue Feb 06 00:00:00 EST 2018},
month = {Tue Feb 06 00:00:00 EST 2018}
}
Copy to clipboard
Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1016/j.fuel.2018.01.106
Copyright Statement
Other availability
Search WorldCat Search WorldCat to find libraries that may hold this journal
Citation Metrics:
Cited by: 49 works
Citation information provided by
Web of Science

Figures / Tables:

Fig. 1 Fig. 1: (A) Over-mature nanoporous kerogen structure. Red, blue, yellow, gray, and white spheres represent oxygen, nitrogen, sulfur, carbon, and hydrogen atoms, respectively. Pore-volume and kerogen interface is outlined in blue (i.e., surface side facing the pore volume) and in gray (i.e., surface side facing the kerogen atoms). (B) Cylindricalmore » carbon nanotube (CNT) connecting with a reservoir defined in between two flat graphene sheets. The pore size effect was investigated by changing CNT diameter from 0.814 nm to 1.085 nm. (C) Graphene slit-pore connecting with a reservoir. The pore shape effect was studied by comparing the results obtained for cylindrical pore (0.814 nm CNT – Fig. 1B) and for 0.814 nm graphene slit-pore (Fig. 1C). (D) Initial configuration to study the invasion of CO2 (cyan-red) into the methane (green)-filled CNT. (E) Simulation snapshot represents the water (red-white spheres) blocking at the opening of CNT filled with methane molecules (green spheres). The temperature is 338K for all simulations. Note that half of the CNT is removed to visualize the methane molecules inside. See SM for more simulation details regarding the number of molecules simulated and force field implemented. (For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article.)« less
All figures and tables (5 total)
Save / Share:
Export Metadata
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.

Works referenced in this record:

Investigation of Methane Desorption and Its Effect on the Gas Production Process from Shale: Experimental and Mathematical Study
journal, December 2016

Understanding Shale Gas: Recent Progress and Remaining Challenges
journal, September 2017

Shale gas and non-aqueous fracturing fluids: Opportunities and challenges for supercritical CO2
journal, June 2015

Organic–inorganic interactions in petroleum-producing sedimentary basins
journal, November 2003

Nanostructural control of methane release in kerogen and its implications to wellbore production decline
journal, June 2016

  • Ho, Tuan Anh; Criscenti, Louise J.; Wang, Yifeng
  • Scientific Reports, Vol. 6, Issue 1
  • DOI: 10.1038/srep28053

Model representations of kerogen structures: An insight from density functional theory calculations and spectroscopic measurements
journal, August 2017

Direct Characterization of Kerogen by X-ray and Solid-State 13 C Nuclear Magnetic Resonance Methods
journal, May 2007

  • Kelemen, S. R.; Afeworki, M.; Gorbaty, M. L.
  • Energy & Fuels, Vol. 21, Issue 3
  • DOI: 10.1021/ef060321h

Molecular Modeling of the Volumetric and Thermodynamic Properties of Kerogen: Influence of Organic Type and Maturity
journal, December 2014

  • Ungerer, Philippe; Collell, Julien; Yiannourakou, Marianna
  • Energy & Fuels, Vol. 29, Issue 1
  • DOI: 10.1021/ef502154k

Consistent force field studies of intermolecular forces in hydrogen-bonded crystals. 2. A benchmark for the objective comparison of alternative force fields
journal, August 1979

  • Hagler, A. T.; Lifson, S.; Dauber, P.
  • Journal of the American Chemical Society, Vol. 101, Issue 18
  • DOI: 10.1021/ja00512a002

Fast Parallel Algorithms for Short-Range Molecular Dynamics
journal, March 1995

MCCCS Towhee: a tool for Monte Carlo molecular simulation
journal, December 2013

Vapor–liquid equilibria of mixtures containing alkanes, carbon dioxide, and nitrogen
journal, July 2001

  • Potoff, Jeffrey J.; Siepmann, J. Ilja
  • AIChE Journal, Vol. 47, Issue 7, p. 1676-1682
  • DOI: 10.1002/aic.690470719

Computer simulation of ammonia on graphite. I. Low temperature structure of monolayer and bilayer films
journal, March 1990

  • Cheng, Ailan; Steele, W. A.
  • The Journal of Chemical Physics, Vol. 92, Issue 6
  • DOI: 10.1063/1.458562

Simulation Insights for Graphene-Based Water Desalination Membranes
journal, July 2013

  • Konatham, Deepthi; Yu, Jing; Ho, Tuan A.
  • Langmuir, Vol. 29, Issue 38
  • DOI: 10.1021/la4018695

Thermal Maturation of Gas Shale Systems
journal, May 2014

Characterization of oil shale, isolated kerogen, and postpyrolysis residues using advanced 13C solid-state nuclear magnetic resonance spectroscopy
journal, March 2013

  • Cao, Xiaoyan; Birdwell, Justin E.; Chappell, Mark A.
  • AAPG Bulletin, Vol. 97, Issue 3
  • DOI: 10.1306/09101211189

Activated desorption at heterogeneous interfaces and long-time kinetics of hydrocarbon recovery from nanoporous media
journal, June 2016

  • Lee, Thomas; Bocquet, Lydéric; Coasne, Benoit
  • Nature Communications, Vol. 7, Issue 1
  • DOI: 10.1038/ncomms11890

Molecular simulation of methane adsorption in micro- and mesoporous carbons with applications to coal and gas shale systems
journal, April 2013

Adsorption of methane and carbon dioxide on gas shale and pure mineral samples
journal, December 2014

The missing term in effective pair potentials
journal, November 1987

  • Berendsen, H. J. C.; Grigera, J. R.; Straatsma, T. P.
  • The Journal of Physical Chemistry, Vol. 91, Issue 24
  • DOI: 10.1021/j100308a038

Numerical integration of the cartesian equations of motion of a system with constraints: molecular dynamics of n-alkanes
journal, March 1977

  • Ryckaert, Jean-Paul; Ciccotti, Giovanni; Berendsen, Herman J. C.
  • Journal of Computational Physics, Vol. 23, Issue 3
  • DOI: 10.1016/0021-9991(77)90098-5

A molecular dynamics method for simulations in the canonical ensemble
journal, June 1984

Constant pressure molecular dynamics algorithms
journal, September 1994

  • Martyna, Glenn J.; Tobias, Douglas J.; Klein, Michael L.
  • The Journal of Chemical Physics, Vol. 101, Issue 5
  • DOI: 10.1063/1.467468

Time reversible and symplectic integrators for molecular dynamics simulations of rigid molecules
journal, June 2005

  • Kamberaj, H.; Low, R. J.; Neal, M. P.
  • The Journal of Chemical Physics, Vol. 122, Issue 22
  • DOI: 10.1063/1.1906216

Rapid Transport of Gases in Carbon Nanotubes
journal, October 2002

Adsorption and diffusion of carbon dioxide and nitrogen through single-walled carbon nanotube membranes
journal, February 2006

  • Skoulidas, Anastasios I.; Sholl, David S.; Johnson, J. Karl
  • The Journal of Chemical Physics, Vol. 124, Issue 5
  • DOI: 10.1063/1.2151173

Prediction of carbon dioxide permeability in carbon slit pores
journal, June 2010

Effect of pore wall model on prediction of diffusion coefficients for graphitic slit pores
journal, January 2008

  • Cai, Qiong; Biggs, Mark J.; Seaton, Nigel A.
  • Physical Chemistry Chemical Physics, Vol. 10, Issue 18
  • DOI: 10.1039/b716648f

Simulations of Binary Mixture Adsorption of Carbon Dioxide and Methane in Carbon Nanotubes:  Temperature, Pressure, and Pore Size Effects
journal, July 2007

  • Huang, Liangliang; Zhang, Luzheng; Shao, Qing
  • The Journal of Physical Chemistry C, Vol. 111, Issue 32
  • DOI: 10.1021/jp067226u

Enhanced flow in carbon nanotubes
journal, November 2005

  • Majumder, Mainak; Chopra, Nitin; Andrews, Rodney
  • Nature, Vol. 438, Issue 7064
  • DOI: 10.1038/438044a

Water conduction through the hydrophobic channel of a carbon nanotube
journal, November 2001

  • Hummer, G.; Rasaiah, J. C.; Noworyta, J. P.
  • Nature, Vol. 414, Issue 6860
  • DOI: 10.1038/35102535

Fluid flow in carbon nanotubes and nanopipes
journal, February 2007

Enhanced Fluid Flow through Nanoscale Carbon Pipes
journal, September 2008

  • Whitby, Max; Cagnon, Laurent; Thanou, Maya
  • Nano Letters, Vol. 8, Issue 9
  • DOI: 10.1021/nl080705f

Characterization of MCM-41 Using Molecular Simulation:  Heterogeneity Effects
journal, March 1997

  • Maddox, M. W.; Olivier, J. P.; Gubbins, K. E.
  • Langmuir, Vol. 13, Issue 6
  • DOI: 10.1021/la961068o

Thirty Years of Gas Shale Fracturing: What Have We Learned?
conference, April 2013

  • King, George Everette
  • SPE Annual Technical Conference and Exhibition
  • DOI: 10.2118/133456-MS

Geological controls on the methane storage capacity in organic-rich shales
journal, March 2014

  • Gasparik, Matus; Bertier, Pieter; Gensterblum, Yves
  • International Journal of Coal Geology, Vol. 123
  • DOI: 10.1016/j.coal.2013.06.010

Pore Networks and Fluid Flow in Gas Shales
conference, April 2013

  • Wang, Fred P.; Reed, Rob M.
  • SPE Annual Technical Conference and Exhibition
  • DOI: 10.2118/124253-MS

The impact of kerogen properties on shale gas production: A reservoir simulation sensitivity analysis
journal, December 2017

  • Wang, Shihao; Pomerantz, Andrew E.; Xu, Wenyue
  • Journal of Natural Gas Science and Engineering, Vol. 48
  • DOI: 10.1016/j.jngse.2017.06.009

Pore-throat sizes in sandstones, tight sandstones, and shales
journal, March 2009

Unconventional shale-gas systems: The Mississippian Barnett Shale of north-central Texas as one model for thermogenic shale-gas assessment
journal, April 2007

  • Jarvie, Daniel M.; Hill, Ronald J.; Ruble, Tim E.
  • AAPG Bulletin, Vol. 91, Issue 4
  • DOI: 10.1306/12190606068

A reality check on the shale revolution
journal, February 2013

Unconventional gas – A review of regional and global resource estimates
journal, June 2013

Impact of Shale Gas Development on Regional Water Quality
journal, May 2013

Shale gas development impacts on surface water quality in Pennsylvania
journal, March 2013

  • Olmstead, S. M.; Muehlenbachs, L. A.; Shih, J. -S.
  • Proceedings of the National Academy of Sciences, Vol. 110, Issue 13
  • DOI: 10.1073/pnas.1213871110

Non-hydrocarbons of significance in petroleum exploration: volatile fatty acids and non-hydrocarbon gases
journal, October 1987

Late Generation of Methane from Mature Kerogens
journal, January 2002

  • Lorant, François; Behar, Françoise
  • Energy & Fuels, Vol. 16, Issue 2
  • DOI: 10.1021/ef010126x

pH buffering by metastable mineral-fluid equilibria and evolution of carbon dioxide fugacity during burial diagenesis
journal, March 1993

  • Hutcheon, Ian; Shevalier, Maurice; Abercrombie, Hugh J.
  • Geochimica et Cosmochimica Acta, Vol. 57, Issue 5
  • DOI: 10.1016/0016-7037(93)90037-W
    Sort by:
    [ × clear filter / sort ]

    Works referencing / citing this record:

    Enhancement of oil flow in shale nanopores by manipulating friction and viscosity
    journal, January 2019

    • Ho, Tuan A.; Wang, Yifeng
    • Physical Chemistry Chemical Physics, Vol. 21, Issue 24
    • DOI: 10.1039/c9cp01960j

    Molecular Investigation of CO2/CH4 Competitive Adsorption and Confinement in Realistic Shale Kerogen
    journal, November 2019

    • Zhou, Wenning; Zhang, Zhe; Wang, Haobo
    • Nanomaterials, Vol. 9, Issue 12
    • DOI: 10.3390/nano9121646
      Sort by:
      [ × clear filter / sort ]

      Figures / Tables found in this record:

      Fig. 1 (p. 2)figure
      Fig. 2 (p. 3)figure
      Fig. 3 (p. 4)figure
      Table 1 (p. 4)table
      Fig. 4 (p. 5)figure
        [ × clear filter / sort ]
        Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.

        Similar Records in DOE PAGES and OSTI.GOV collections: