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Title: Microscopic diffusion of pure and mixed methane and carbon dioxide in ZIF-11 by high field diffusion NMR

Authors:
; ; ; ; ORCiD logo
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Center for Understanding and Control of Acid Gas-induced Evolution of Materials for Energy (UNCAGE-ME)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1388093
DOE Contract Number:
SC0012577
Resource Type:
Journal Article
Resource Relation:
Journal Name: Microporous and Mesoporous Materials; Journal Volume: 248; Journal Issue: C; Related Information: UNCAGE-ME partners with Georgia Institute of Technology (lead); Lehigh University; Oak Ridge National Laboratory; University of Alabama; University of Florida; University of Wisconsin; Washington University in St. Louis
Country of Publication:
United States
Language:
English
Subject:
catalysis (heterogeneous), defects, membrane, carbon capture, materials and chemistry by design, synthesis (novel materials), synthesis (self-assembly), synthesis (scalable processing)

Citation Formats

Forman, Evan M., Pimentel, Brian R., Ziegler, Kirk J., Lively, Ryan P., and Vasenkov, Sergey. Microscopic diffusion of pure and mixed methane and carbon dioxide in ZIF-11 by high field diffusion NMR. United States: N. p., 2017. Web. doi:10.1016/j.micromeso.2017.04.041.
Forman, Evan M., Pimentel, Brian R., Ziegler, Kirk J., Lively, Ryan P., & Vasenkov, Sergey. Microscopic diffusion of pure and mixed methane and carbon dioxide in ZIF-11 by high field diffusion NMR. United States. doi:10.1016/j.micromeso.2017.04.041.
Forman, Evan M., Pimentel, Brian R., Ziegler, Kirk J., Lively, Ryan P., and Vasenkov, Sergey. 2017. "Microscopic diffusion of pure and mixed methane and carbon dioxide in ZIF-11 by high field diffusion NMR". United States. doi:10.1016/j.micromeso.2017.04.041.
@article{osti_1388093,
title = {Microscopic diffusion of pure and mixed methane and carbon dioxide in ZIF-11 by high field diffusion NMR},
author = {Forman, Evan M. and Pimentel, Brian R. and Ziegler, Kirk J. and Lively, Ryan P. and Vasenkov, Sergey},
abstractNote = {},
doi = {10.1016/j.micromeso.2017.04.041},
journal = {Microporous and Mesoporous Materials},
number = C,
volume = 248,
place = {United States},
year = 2017,
month = 8
}
  • This paper reports an experiment conducted on isothermal vapor-liquid equilibrium data for binary systems at high pressure. Carbon dioxide-methanol, carbon dioxide-ethanol, carbon dioxide-1-propanol, methane-ethanol, methane-1-propanol, ethane-ethanol, and ethane-1-propanol were measured by a new static phase equilibrium apparatus at 313.4 and 333,4 K.
  • We introduce a simple correction to the calculation of the lattice constants of fully occupied structure sI methane or carbon dioxide pure hydrates that are obtained from classical molecular dynamics simulations using the TIP4PQ/2005 water force field. The obtained corrected lattice constants are subsequently used in order to obtain isobaric thermal expansion coefficients of the pure gas hydrates that exhibit a trend that is significantly closer to the experimental behavior than previously reported classical molecular dynamics studies.
  • Replacement of methane with carbon dioxide in hydrate has been proposed as a strategy for geologic sequestration of carbon dioxide (CO{sub 2}) and/or production of methane (CH{sub 4}) from natural hydrate deposits. This replacement strategy requires a better understanding of the thermodynamic characteristics of binary mixtures of CH{sub 4} and CO{sub 2} hydrate (CH{sub 4}-CO{sub 2} mixed hydrates), as well as thermophysical property changes during gas exchange. This study explores the thermal dissociation behavior and dissociation enthalpies of CH{sub 4}-CO{sub 2} mixed hydrates. We prepared CH{sub 4}-CO{sub 2} mixed hydrate samples from two different, well-defined gas mixtures. During thermal dissociationmore » of a CH{sub 4}-CO{sub 2} mixed hydrate sample, gas samples from the head space were periodically collected and analyzed using gas chromatography. The changes in CH{sub 4}-CO{sub 2} compositions in both the vapor phase and hydrate phase during dissociation were estimated based on the gas chromatography measurements. It was found that the CO{sub 2} concentration in the vapor phase became richer during dissociation because the initial hydrate composition contained relatively more CO{sub 2} than the vapor phase. The composition change in the vapor phase during hydrate dissociation affected the dissociation pressure and temperature; the richer CO{sub 2} in the vapor phase led to a lower dissociation pressure. Furthermore, the increase in CO{sub 2} concentration in the vapor phase enriched the hydrate in CO{sub 2}. The dissociation enthalpy of the CH{sub 4}-CO{sub 2} mixed hydrate was computed by fitting the Clausius-Clapeyron equation to the pressure-temperature (PT) trace of a dissociation test. It was observed that the dissociation enthalpy of the CH{sub 4}-CO{sub 2} mixed hydrate lays between the limiting values of pure CH{sub 4} hydrate and CO{sub 2} hydrate, increasing with the CO{sub 2} fraction in the hydrate phase.« less