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Title: Clay Swelling in Dry Supercritical Carbon Dioxide: Effects of Interlayer Cations on the Structure, Dynamics, and Energetics of CO2 Intercalation Probed by XRD, NMR, and GCMD Simulations

Abstract

In situ X-ray diffraction (XRD) and nuclear magnetic resonance (NMR) experiments combined with molecular dynamics simulations using the grand canonical ensemble [grand canonical molecular dynamics (GCMD)] show that the cation size, charge, and solvation energy play critical roles in determining the interlayer expansion of smectite clay minerals when exposed to dry supercritical scCO2 (scCO2) under conditions relevant to petroleum reservoirs and geological CO2 sequestration conditions. The GCMD results show that the smectite mineral, hectorite, containing interlayer alkali and alkaline earth cations with small ionic radii and high solvation energies (e.g., Na+ and Ca2+) does not intercalate CO2 and that the fully collapsed interlayer structure is the most energetically stable configuration. With Cs+ and Ba2+, the monolayer structure is the stable configuration, and CO2 should spontaneously enter the interlayer. With Cs+, there is not even an energy barrier for CO2 intercalation, in agreement with the XRD and NMR results. 13C NMR and simulations show that the average orientation of the intercalated CO2 is with their O–C–O axes parallel to the basal clay surface and that they undergo a rapid rotation about an axis perpendicular to the main molecular axis. The simulations show that the strength of the interaction between the exchangeablemore » cation and the clay structure dominates the intercalation energetics in dry scCO2.« less

Authors:
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [3]; ORCiD logo [4];  [4]; ORCiD logo [5];  [6]
  1. Michigan State Univ., East Lansing, MI (United States). Dept. of Chemistry
  2. St. Mary's College of Maryland, St. Mary's City, MD (United States). Dept. of Chemistry and Biochemistry
  3. Michigan State Univ., East Lansing, MI (United States). Dept. of Chemistry; Univ. College London (United Kingdom). Dept. of Chemical Engineering
  4. Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
  5. Laboratoire SUBATECH, Nantes (France)
  6. Michigan State Univ., East Lansing, MI (United States). College of Natural Science
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Fossil Energy (FE)
OSTI Identifier:
1483686
Grant/Contract Number:  
FG02-08ER15929; FG02-10ER16128
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. C
Additional Journal Information:
Journal Volume: 122; Journal Issue: 8; Journal ID: ISSN 1932-7447
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Loganathan, Narasimhan, Bowers, Geoffrey M., Yazaydin, A. Ozgur, Schaef, H. Todd, Loring, John S., Kalinichev, Andrey G., and Kirkpatrick, R. James. Clay Swelling in Dry Supercritical Carbon Dioxide: Effects of Interlayer Cations on the Structure, Dynamics, and Energetics of CO2 Intercalation Probed by XRD, NMR, and GCMD Simulations. United States: N. p., 2018. Web. https://doi.org/10.1021/acs.jpcc.7b12270.
Loganathan, Narasimhan, Bowers, Geoffrey M., Yazaydin, A. Ozgur, Schaef, H. Todd, Loring, John S., Kalinichev, Andrey G., & Kirkpatrick, R. James. Clay Swelling in Dry Supercritical Carbon Dioxide: Effects of Interlayer Cations on the Structure, Dynamics, and Energetics of CO2 Intercalation Probed by XRD, NMR, and GCMD Simulations. United States. https://doi.org/10.1021/acs.jpcc.7b12270
Loganathan, Narasimhan, Bowers, Geoffrey M., Yazaydin, A. Ozgur, Schaef, H. Todd, Loring, John S., Kalinichev, Andrey G., and Kirkpatrick, R. James. Thu . "Clay Swelling in Dry Supercritical Carbon Dioxide: Effects of Interlayer Cations on the Structure, Dynamics, and Energetics of CO2 Intercalation Probed by XRD, NMR, and GCMD Simulations". United States. https://doi.org/10.1021/acs.jpcc.7b12270. https://www.osti.gov/servlets/purl/1483686.
@article{osti_1483686,
title = {Clay Swelling in Dry Supercritical Carbon Dioxide: Effects of Interlayer Cations on the Structure, Dynamics, and Energetics of CO2 Intercalation Probed by XRD, NMR, and GCMD Simulations},
author = {Loganathan, Narasimhan and Bowers, Geoffrey M. and Yazaydin, A. Ozgur and Schaef, H. Todd and Loring, John S. and Kalinichev, Andrey G. and Kirkpatrick, R. James},
abstractNote = {In situ X-ray diffraction (XRD) and nuclear magnetic resonance (NMR) experiments combined with molecular dynamics simulations using the grand canonical ensemble [grand canonical molecular dynamics (GCMD)] show that the cation size, charge, and solvation energy play critical roles in determining the interlayer expansion of smectite clay minerals when exposed to dry supercritical scCO2 (scCO2) under conditions relevant to petroleum reservoirs and geological CO2 sequestration conditions. The GCMD results show that the smectite mineral, hectorite, containing interlayer alkali and alkaline earth cations with small ionic radii and high solvation energies (e.g., Na+ and Ca2+) does not intercalate CO2 and that the fully collapsed interlayer structure is the most energetically stable configuration. With Cs+ and Ba2+, the monolayer structure is the stable configuration, and CO2 should spontaneously enter the interlayer. With Cs+, there is not even an energy barrier for CO2 intercalation, in agreement with the XRD and NMR results. 13C NMR and simulations show that the average orientation of the intercalated CO2 is with their O–C–O axes parallel to the basal clay surface and that they undergo a rapid rotation about an axis perpendicular to the main molecular axis. The simulations show that the strength of the interaction between the exchangeable cation and the clay structure dominates the intercalation energetics in dry scCO2.},
doi = {10.1021/acs.jpcc.7b12270},
journal = {Journal of Physical Chemistry. C},
number = 8,
volume = 122,
place = {United States},
year = {2018},
month = {2}
}

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Figures / Tables:

Table 1 Table 1: Calculated intermittent c(t) and continuous C(t) residence times (ns) for different atomic pairs for monolayer basal spacing (12.4 Å) in the interlayers of hectorite with different charge compensating cations at 323 K and 90 bar.

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    Review of Molecular Simulation Method for Gas Adsorption/desorption and Diffusion in Shale Matrix
    journal, September 2018


    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