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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

Journal Article · · ACS Earth and Space Chemistry
 [1];  [2];  [2];  [2];  [2];  [2];  [1];  [3];  [3]
  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)
+ Show Author Affiliations
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.
Research Organization:
Battelle Memorial Institute, Columbus, OH (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC); Michigan State Univ., East Lansing, MI (United States)
Sponsoring Organization:
USDOE Office of Fossil Energy (FE); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); USDOE Office of Science (SC), Workforce Development for Teachers and Scientists (WDTS) (SC-27)
Grant/Contract Number:
AC05-76RL01830; FG02-08ER15929
OSTI ID:
1543713
Alternate ID(s):
OSTI ID: 1560148
Journal Information:
ACS Earth and Space Chemistry, Journal Name: ACS Earth and Space Chemistry Journal Issue: 7 Vol. 2; ISSN 2472-3452
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English

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