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Title: Interaction of Hydrocarbons with Clays under Reservoir Conditions: In Situ Infrared and Nuclear Magnetic Resonance Spectroscopy and X-ray Diffraction for Expandable Clays with Variably Wet Supercritical Methane

Abstract

The results from novel in situ high-pressure nuclear magnetic resonance (NMR) spectroscopy, infrared (IR) spectroscopy, and X-ray diffraction (XRD) investigation of the interaction of the smectite hectorite with variably wet supercritical methane (scCH4) at 90 bar and 323 K (hydrostatic conditions equivalent to ~1 km depth) show that CH4 occurs in the clay interlayers, in pores external to the individual clay particles, and as bulk fluid. The occupancy of each environment depends on the relative humidity (RH) of the CH4-rich fluid and the hydration energy and size of the charge-balancing cation. As RH increases, the fraction of interlayer and interparticle CH4 decreases, although with Cs+, addition of a small amount of H2O initially increases CH4 uptake. Maximum interlayer CH4 adsorption occurs when the mean basal spacing just permits methane intercalation (~11.5 Å) and never below this basal spacing. It is also higher with divalent cations than with monovalent cations. The data show that CH4 adsorption occurs predominantly via a weak dispersion interaction with the clay and that its intercalation occurs via a passive space-filling hydrophobic mechanism. The results suggest that, under reservoir conditions, smectite interlayers may provide a reservoir for CH4 under low-water conditions.

Authors:
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [2]; ORCiD logo [2];  [2]; ORCiD logo [2];  [1]; ORCiD logo [3];  [3]
+ Show Author Affiliations
  1. St. Mary’s College of Maryland, St. Mary’s City, MD (United States)
  2. Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
  3. Michigan State Univ., East Lansing, MI (United States)
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC); Battelle Memorial Institute, Columbus, OH (United States); Michigan State Univ., East Lansing, MI (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Science (SC), Workforce Development for Teachers and Scientists (WDTS); USDOE Office of Fossil Energy (FE)
OSTI Identifier:
1543713
Grant/Contract Number:  
AC05-76RL01830; FG02-08ER15929
Resource Type:
Accepted Manuscript
Journal Name:
ACS Earth and Space Chemistry
Additional Journal Information:
Journal Volume: 2; Journal Issue: 7; Journal ID: ISSN 2472-3452
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Chemistry; Geochemistry & Geophysics

Citation Formats

Bowers, Geoffrey M., Loring, John S., Schaef, H. Todd, Walter, Eric D., Burton, Sarah D., Hoyt, David W., Cunniff, Sydney S., Loganathan, Narasimhan, and Kirkpatrick, R. James. Interaction of Hydrocarbons with Clays under Reservoir Conditions: In Situ Infrared and Nuclear Magnetic Resonance Spectroscopy and X-ray Diffraction for Expandable Clays with Variably Wet Supercritical Methane. United States: N. p., 2018. Web. doi:10.1021/acsearthspacechem.8b00039.
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Bowers, Geoffrey M., Loring, John S., Schaef, H. Todd, Walter, Eric D., Burton, Sarah D., Hoyt, David W., Cunniff, Sydney S., Loganathan, Narasimhan, & Kirkpatrick, R. James. Interaction of Hydrocarbons with Clays under Reservoir Conditions: In Situ Infrared and Nuclear Magnetic Resonance Spectroscopy and X-ray Diffraction for Expandable Clays with Variably Wet Supercritical Methane. United States. https://doi.org/10.1021/acsearthspacechem.8b00039
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Bowers, Geoffrey M., Loring, John S., Schaef, H. Todd, Walter, Eric D., Burton, Sarah D., Hoyt, David W., Cunniff, Sydney S., Loganathan, Narasimhan, and Kirkpatrick, R. James. Mon . "Interaction of Hydrocarbons with Clays under Reservoir Conditions: In Situ Infrared and Nuclear Magnetic Resonance Spectroscopy and X-ray Diffraction for Expandable Clays with Variably Wet Supercritical Methane". United States. https://doi.org/10.1021/acsearthspacechem.8b00039. https://www.osti.gov/servlets/purl/1543713.
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@article{osti_1543713,
title = {Interaction of Hydrocarbons with Clays under Reservoir Conditions: In Situ Infrared and Nuclear Magnetic Resonance Spectroscopy and X-ray Diffraction for Expandable Clays with Variably Wet Supercritical Methane},
author = {Bowers, Geoffrey M. and Loring, John S. and Schaef, H. Todd and Walter, Eric D. and Burton, Sarah D. and Hoyt, David W. and Cunniff, Sydney S. and Loganathan, Narasimhan and Kirkpatrick, R. James},
abstractNote = {The results from novel in situ high-pressure nuclear magnetic resonance (NMR) spectroscopy, infrared (IR) spectroscopy, and X-ray diffraction (XRD) investigation of the interaction of the smectite hectorite with variably wet supercritical methane (scCH4) at 90 bar and 323 K (hydrostatic conditions equivalent to ~1 km depth) show that CH4 occurs in the clay interlayers, in pores external to the individual clay particles, and as bulk fluid. The occupancy of each environment depends on the relative humidity (RH) of the CH4-rich fluid and the hydration energy and size of the charge-balancing cation. As RH increases, the fraction of interlayer and interparticle CH4 decreases, although with Cs+, addition of a small amount of H2O initially increases CH4 uptake. Maximum interlayer CH4 adsorption occurs when the mean basal spacing just permits methane intercalation (~11.5 Å) and never below this basal spacing. It is also higher with divalent cations than with monovalent cations. The data show that CH4 adsorption occurs predominantly via a weak dispersion interaction with the clay and that its intercalation occurs via a passive space-filling hydrophobic mechanism. The results suggest that, under reservoir conditions, smectite interlayers may provide a reservoir for CH4 under low-water conditions.},
doi = {10.1021/acsearthspacechem.8b00039},
journal = {ACS Earth and Space Chemistry},
number = 7,
volume = 2,
place = {United States},
year = {Mon May 07 00:00:00 EDT 2018},
month = {Mon May 07 00:00:00 EDT 2018}
}
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https://doi.org/10.1021/acsearthspacechem.8b00039
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    Works referencing / citing this record:

    Understanding methane/carbon dioxide partitioning in clay nano- and meso-pores with constant reservoir composition molecular dynamics modeling
    journal, January 2019

    • Loganathan, Narasimhan; Bowers, Geoffrey M.; Ngouana Wakou, Brice F.
    • Physical Chemistry Chemical Physics, Vol. 21, Issue 13
    • DOI: 10.1039/c9cp00851a
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