DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Insights into Controls of Mineralogy and Pore Structure on the Density of Methane Adsorption Phase in Shales under Supercritical Conditions

Abstract

With gradually increasing enhancing population and industrialization, exploitation of shale gas is enhancing in the world to satisfy the growing demand for energy worldwide. To exploit shale gas efficiently, accurate assessment of shale gas in place (GIP) is necessary for determining production strategies. Unlike free and dissolved gas, adsorbed gas contributes to the shale GIP up to 85% due to the well-developed surface area and micropores. Measured excess adsorption of methane (up to over 95% of subsurface shale gas) is often corrected to absolute adsorption to obtain the actual amount of adsorption under supercritical (or geological) conditions. During the correction, adsorption phase density (APD) is critical. However, the APD of subsurface shale gas and the effects of shale properties (e.g., mineralogy and pore structure) on APD remain poorly understood. A series of high-pressure methane adsorption isotherms (HPMAI) on Caney Shales were collected and analyzed in conjunction with other United States and Chinese shales from the literature at 35–125 °C and up to 15 MPa. Here, a three-layer Ono–Kondo (OK3) model is utilized to derive the temperature- and pressure-dependent APD coupling low-pressure nitrogen adsorption isotherms (LPNAI) and HPMAI. X-ray diffraction and organic geochemistry are combined to reveal the mineralogy. Brunauer–Emmett–Teller, Barrett–Joyner–Halenda,more » and Horvath–Kawazoe analyses via LPNAI are used to investigate the pore structures. Results show that APD increases with organic matter (OM) proxied by total organic carbon and decreases with clay minerals and the sum of quartz and feldspar. OM dramatically contributes to the APD as multiple-layer adsorption exists, and the APD for OM could be 1.4–8.5 times that for clay minerals. Other inorganic minerals contribute less to APD. The properties and constitution of the surface area instead of the volume fraction contribute to the APD in shales. APD does not show an obvious correlation with micropore volume, likely related to the ratio of micropore volume to the total pore volume. Here, we provide a significant and comprehensive study of petrological factors that impact the APD of subsurface shale gas, which will improve the estimation of supercritical adsorption and shale GIP under reservoir conditions. Also, the findings in this work can provide applications for subsurface carbon dioxide adsorption and storage.« less

Authors:
ORCiD logo [1]; ORCiD logo [2];  [1]
  1. Oklahoma State Univ., Stillwater, OK (United States)
  2. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Publication Date:
Research Org.:
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division; USDOE Office of Fossil Energy (FE)
OSTI Identifier:
1883778
Grant/Contract Number:  
AC05-00OR22725; FE0031776
Resource Type:
Accepted Manuscript
Journal Name:
Energy and Fuels
Additional Journal Information:
Journal Volume: 36; Journal Issue: 17; Journal ID: ISSN 0887-0624
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
58 GEOSCIENCES; methane adsorption; adsorption phase density; geological control; supercritical shale gas; BET surface area; clay; hydrocarbons; minerals; shale

Citation Formats

Xiong, Fengyang, Rother, Gernot, and Radonjic, Mileva. Insights into Controls of Mineralogy and Pore Structure on the Density of Methane Adsorption Phase in Shales under Supercritical Conditions. United States: N. p., 2022. Web. doi:10.1021/acs.energyfuels.2c01847.
Xiong, Fengyang, Rother, Gernot, & Radonjic, Mileva. Insights into Controls of Mineralogy and Pore Structure on the Density of Methane Adsorption Phase in Shales under Supercritical Conditions. United States. https://doi.org/10.1021/acs.energyfuels.2c01847
Xiong, Fengyang, Rother, Gernot, and Radonjic, Mileva. Mon . "Insights into Controls of Mineralogy and Pore Structure on the Density of Methane Adsorption Phase in Shales under Supercritical Conditions". United States. https://doi.org/10.1021/acs.energyfuels.2c01847. https://www.osti.gov/servlets/purl/1883778.
@article{osti_1883778,
title = {Insights into Controls of Mineralogy and Pore Structure on the Density of Methane Adsorption Phase in Shales under Supercritical Conditions},
author = {Xiong, Fengyang and Rother, Gernot and Radonjic, Mileva},
abstractNote = {With gradually increasing enhancing population and industrialization, exploitation of shale gas is enhancing in the world to satisfy the growing demand for energy worldwide. To exploit shale gas efficiently, accurate assessment of shale gas in place (GIP) is necessary for determining production strategies. Unlike free and dissolved gas, adsorbed gas contributes to the shale GIP up to 85% due to the well-developed surface area and micropores. Measured excess adsorption of methane (up to over 95% of subsurface shale gas) is often corrected to absolute adsorption to obtain the actual amount of adsorption under supercritical (or geological) conditions. During the correction, adsorption phase density (APD) is critical. However, the APD of subsurface shale gas and the effects of shale properties (e.g., mineralogy and pore structure) on APD remain poorly understood. A series of high-pressure methane adsorption isotherms (HPMAI) on Caney Shales were collected and analyzed in conjunction with other United States and Chinese shales from the literature at 35–125 °C and up to 15 MPa. Here, a three-layer Ono–Kondo (OK3) model is utilized to derive the temperature- and pressure-dependent APD coupling low-pressure nitrogen adsorption isotherms (LPNAI) and HPMAI. X-ray diffraction and organic geochemistry are combined to reveal the mineralogy. Brunauer–Emmett–Teller, Barrett–Joyner–Halenda, and Horvath–Kawazoe analyses via LPNAI are used to investigate the pore structures. Results show that APD increases with organic matter (OM) proxied by total organic carbon and decreases with clay minerals and the sum of quartz and feldspar. OM dramatically contributes to the APD as multiple-layer adsorption exists, and the APD for OM could be 1.4–8.5 times that for clay minerals. Other inorganic minerals contribute less to APD. The properties and constitution of the surface area instead of the volume fraction contribute to the APD in shales. APD does not show an obvious correlation with micropore volume, likely related to the ratio of micropore volume to the total pore volume. Here, we provide a significant and comprehensive study of petrological factors that impact the APD of subsurface shale gas, which will improve the estimation of supercritical adsorption and shale GIP under reservoir conditions. Also, the findings in this work can provide applications for subsurface carbon dioxide adsorption and storage.},
doi = {10.1021/acs.energyfuels.2c01847},
journal = {Energy and Fuels},
number = 17,
volume = 36,
place = {United States},
year = {Mon Aug 22 00:00:00 EDT 2022},
month = {Mon Aug 22 00:00:00 EDT 2022}
}

Works referenced in this record:

Kerogen nanoscale structure and CO2 adsorption in shale micropores
journal, February 2021


SEM petrography of dispersed organic matter in black shales: A review
journal, January 2022


Supercritical Methane Adsorption on Shale over Wide Pressure and Temperature Ranges: Implications for Gas-in-Place Estimation
journal, February 2020


Methane Adsorption on Shale under Simulated Geological Temperature and Pressure Conditions
journal, May 2013

  • Rexer, Thomas F. T.; Benham, Michael J.; Aplin, Andrew C.
  • Energy & Fuels, Vol. 27, Issue 6
  • DOI: 10.1021/ef400381v

Fractal characteristics of bulk-mudrock, washed, and kerogen samples of Chang 7 member mudrocks from the Ordos Basin, China
journal, November 2018


Methane and CO 2 Adsorption Capacities of Kerogen in the Eagle Ford Shale from Molecular Simulation
journal, July 2017


Direct Measure of the Dense Methane Phase in Gas Shale Organic Porosity by Neutron Scattering
journal, October 2016


A comparative study of the specific surface area and pore structure of different shales and their kerogens
journal, January 2015


Machine Learning for Estimating Rock Mechanical Properties beyond Traditional Considerations
conference, January 2019

  • Gong, Yiwen; Mehana, Mohamed; El-Monier, Ilham
  • Proceedings of the 7th Unconventional Resources Technology Conference
  • DOI: 10.15530/urtec-2019-897

Organic pore heterogeneity and its formation mechanisms: Insights from the Lower Cretaceous lacustrine Shahezi shale in the Songliao Basin, NE China
journal, November 2021


From excess to absolute adsorption isotherm: The effect of the adsorbed density
journal, December 2021


Effect of water on methane and carbon dioxide sorption in clay minerals by Monte Carlo simulations
journal, November 2014


Mississippian Barnett Shale, Fort Worth basin, north-central Texas: Gas-shale play with multi–trillion cubic foot potential
journal, February 2005

  • Montgomery, Scott L.; Jarvie, Daniel M.; Bowker, Kent A.
  • AAPG Bulletin, Vol. 89, Issue 2
  • DOI: 10.1306/09170404042

On the pressure and temperature dependence of adsorption densities and other thermodynamic properties in gas shales
journal, September 2020


A new determination method of absolute adsorption isotherm of supercritical gases under high pressure with a special relevance to density-functional theory study
journal, March 2001

  • Murata, Katsuyuki; El-Merraoui, Mustapha; Kaneko, Katsumi
  • The Journal of Chemical Physics, Vol. 114, Issue 9
  • DOI: 10.1063/1.1344926

Mineralogy and Gas Content of Upper Paleozoic Shanxi and Benxi Shale Formations in the Ordos Basin
journal, January 2019


Shale Gas-in-Place Calculations Part I: New Pore-Scale Considerations
journal, March 2012

  • Ambrose, Raymond J.; Hartman, Robert C.; Diaz-Campos, Mery
  • SPE Journal, Vol. 17, Issue 01
  • DOI: 10.2118/131772-PA

Controls on methane sorption capacity of Mesoproterozoic gas shales from the Beetaloo Sub-basin, Australia and global shales
journal, November 2018


Determination of CH4, C2H6 and CO2 adsorption in shale kerogens coupling sorption-induced swelling
journal, April 2021


Convergence of micro-geochemistry and micro-geomechanics towards understanding proppant shale rock interaction: A Caney shale case study in southern Oklahoma, USA
journal, December 2021

  • Katende, Allan; Rutqvist, Jonny; Benge, Margaret
  • Journal of Natural Gas Science and Engineering, Vol. 96
  • DOI: 10.1016/j.jngse.2021.104296

Adsorption measurements in Devonian shales
journal, April 1995


Spectrum of pore types and networks in mudrocks and a descriptive classification for matrix-related mudrock pores
journal, June 2012

  • Loucks, Robert G.; Reed, Robert M.; Ruppel, Stephen C.
  • AAPG Bulletin, Vol. 96, Issue 6
  • DOI: 10.1306/08171111061

Pore structure and heterogeneity of shale gas reservoirs and its effect on gas storage capacity in the Qiongzhusi Formation
journal, November 2021


A multi-site model to determine supercritical methane adsorption in energetically heterogeneous shales
journal, October 2018


Predictions of Multilayer Adsorption Using Lattice Theory
journal, May 1997

  • Aranovich, G. L.; Donohue, M. D.
  • Journal of Colloid and Interface Science, Vol. 189, Issue 1
  • DOI: 10.1006/jcis.1997.4796

High-pressure adsorption of methane on montmorillonite, kaolinite and illite
journal, November 2013


Experimental investigation of changes in methane adsorption of bitumen-free Woodford Shale with thermal maturation induced by hydrous pyrolysis
journal, January 2015


Specific surface area and pore-size distribution in clays and shales
journal, January 2013


Changes in the pore characteristics of shale during comminution
journal, July 2016


Connecting Geomechanical Properties with Potential for Proppant Embedment and Production Decline for the Emerging Caney Shale, Oklahoma
conference, January 2021

  • Benge, Margaret; Lu, Yunxing; Katende, Allan
  • Proceedings of the 9th Unconventional Resources Technology Conference
  • DOI: 10.15530/urtec-2021-5084

Application of a Modified Dubinin−Radushkevich Equation to Adsorption of Gases by Coals under Supercritical Conditions
journal, March 2007

  • Sakurovs, Richard; Day, Stuart; Weir, Steve
  • Energy & Fuels, Vol. 21, Issue 2
  • DOI: 10.1021/ef0600614

Investigation of gas content of organic-rich shale: A case study from Lower Permian shale in southern North China Basin, central China
journal, March 2018


The importance of shale composition and pore structure upon gas storage potential of shale gas reservoirs
journal, June 2009


Characteristics and origin of the heterogeneity of the Lower Silurian Longmaxi marine shale in southeastern Chongqing, SW China
journal, November 2015

  • Xiong, Fengyang; Jiang, Zhenxue; Tang, Xianglu
  • Journal of Natural Gas Science and Engineering, Vol. 27
  • DOI: 10.1016/j.jngse.2015.10.003

The Paleoclimate Significance of the δ13C Composition of Individual Hydrocarbon Compounds in the Maoming Oil Shales, China
journal, March 2021


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

Comprehensive Review about Methane Adsorption in Shale Nanoporous Media
journal, April 2021


Multiscale Characterization of the Caney Shale — An Emerging Play in Oklahoma
journal, September 2021


ABSTRACT: Oil and Shale Gas from the Barnett Shale, Ft. Worth Basin, Texas
journal, January 2001


Effect of adsorbed phase density on the correction of methane excess adsorption to absolute adsorption in shale
journal, September 2021


Bituminous coal seams from underground mines in the Zonguldak Basin (NW Turkey): Insights from mineralogy, coal petrography, Rock-Eval pyrolysis, and meso-and microporosity
journal, November 2018

  • Karayiğit, Ali İhsan; Mastalerz, Maria; Oskay, Rıza Görkem
  • International Journal of Coal Geology, Vol. 199
  • DOI: 10.1016/j.coal.2018.09.020

Dissolution Trapping of Carbon Dioxide in Heterogeneous Aquifers
journal, June 2017

  • Soltanian, Mohamad Reza; Amooie, Mohammad Amin; Gershenzon, Naum
  • Environmental Science & Technology, Vol. 51, Issue 13
  • DOI: 10.1021/acs.est.7b01540

High-Pressure Methane Adsorption and Characterization of Pores in Posidonia Shales and Isolated Kerogens
journal, April 2014

  • Rexer, Thomas F.; Mathia, Eliza J.; Aplin, Andrew C.
  • Energy & Fuels, Vol. 28, Issue 5
  • DOI: 10.1021/ef402466m

Reexamining supercritical gas adsorption theories in nano-porous shales under geological conditions
journal, March 2021


Development of organic porosity in the Woodford Shale with increasing thermal maturity
journal, December 2012

  • Curtis, Mark E.; Cardott, Brian J.; Sondergeld, Carl H.
  • International Journal of Coal Geology, Vol. 103
  • DOI: 10.1016/j.coal.2012.08.004

Effect of organic-matter type and thermal maturity on methane adsorption in shale-gas systems
journal, June 2012


Pore characterization of isolated organic matter from high matured gas shale reservoir
journal, April 2017


A dual-site Langmuir equation for accurate estimation of high pressure deep shale gas resources
journal, December 2016


Microstructural Characterization of Adsorption and Depletion Regimes of Supercritical Fluids in Nanopores
journal, November 2007

  • Rother, Gernot; Melnichenko, Yuri B.; Cole, David R.
  • The Journal of Physical Chemistry C, Vol. 111, Issue 43
  • DOI: 10.1021/jp073698c

Experimental investigation of main controls to methane adsorption in clay-rich rocks
journal, December 2012


Shale’s Pore Structure and Sorption-Diffusion Characteristics: Effect of Analyzing Methods and Particle Size
journal, June 2022


Adsorption of Gases in Multimolecular Layers
journal, February 1938

  • Brunauer, Stephen; Emmett, P. H.; Teller, Edward
  • Journal of the American Chemical Society, Vol. 60, Issue 2, p. 309-319
  • DOI: 10.1021/ja01269a023

Adsorption Models for Methane in Shales: Review, Comparison, and Application
journal, September 2017


Physical adsorption of gases at high pressure. IV. An improvement of the Dubinin—Astakhov adsorption equation
journal, July 1976

  • Ozawa, Sentaro; Kusumi, Seiichiro; Ogino, Yoshisada
  • Journal of Colloid and Interface Science, Vol. 56, Issue 1
  • DOI: 10.1016/0021-9797(76)90149-1

Prediction model for gas adsorption capacity of the Lower Ganchaigou Formation in the Qaidam Basin, China
journal, April 2016


Characterization of Methane Excess and Absolute Adsorption in Various Clay Nanopores from Molecular Simulation
journal, September 2017


High-pressure CH4 and CO2 sorption isotherms as a function of coal maturity and the influence of moisture
journal, October 2013

  • Gensterblum, Yves; Merkel, Alexej; Busch, Andreas
  • International Journal of Coal Geology, Vol. 118
  • DOI: 10.1016/j.coal.2013.07.024