Insights into the structure of mixed CO2/CH4 in gas hydrates

Everett, S. Michelle; Rawn, Claudia J.; Chakoumakos, Bryan C.; Keffer, David J.; Huq, Ashfia; Phelps, Tommy J.

doi:10.2138/am-2015-4929

Title: Insights into the structure of mixed CO₂/CH₄ in gas hydrates

Abstract

The exchange of carbon dioxide for methane in natural gas hydrates is an attractive approach to harvesting CH₄ for energy production while simultaneously sequestering CO₂. In addition to the energy and environmental implications, the solid solution of clathrate hydrate (CH₄)_1-x(CO₂)_x·5.75H₂O provides a model system to study how the distinct bonding and shapes of CH₄ and CO₂ influence the structure and properties of the compound. In this paper, high-resolution neutron diffraction was used to examine mixed CO₂/CH₄ gas hydrates. CO₂-rich hydrates had smaller lattice parameters, which were attributed to the higher affinity of the CO₂ molecule interacting with H₂O molecules that form the surrounding cages, and resulted in a reduction in the unit-cell volume. Experimental nuclear scattering densities illustrate how the cage occupants and energy landscape change with composition. Finally, these results provide important insights on the impact and mechanisms for the structure of mixed CH₄/CO₂ gas hydrate.

Authors:

Everett, S. Michelle ^[1]; Rawn, Claudia J. ^[2]; Chakoumakos, Bryan C. ^[3]; Keffer, David J. ^[1]; Huq, Ashfia ^[4]; Phelps, Tommy J. ^[5]

Univ. of Tennessee, Knoxville, TN (United States). Dept. of Materials Science and Engineering
Univ. of Tennessee, Knoxville, TN (United States). Dept. of Materials Science and Engineering; Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Materials Science and Technology Division
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Quantum Condensed Matter Division
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemistry and Engineering Materials Division
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Biosciences Division

Publication Date:: Tue May 12 00:00:00 EDT 2015

Research Org.:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Org.:: USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF); USDOE Office of Fossil Energy (FE)

OSTI Identifier:: 1185328

Grant/Contract Number:: AC05-00OR22725; DGE0801470

Resource Type:: Accepted Manuscript

Journal Name:: American Mineralogist

Additional Journal Information:: Journal Volume: 100; Journal Issue: 5-6; Journal ID: ISSN 0003-004X

Publisher:: Mineralogical Society of America

Country of Publication:: United States

Language:: English

Subject:: 58 GEOSCIENCES; 54 ENVIRONMENTAL SCIENCES; neutron diffraction; methane hydrate; carbon dioxide/methane exchange; Fourier density maps

Citation Formats


                    Everett, S. Michelle, Rawn, Claudia J., Chakoumakos, Bryan C., Keffer, David J., Huq, Ashfia, and Phelps, Tommy J. Insights into the structure of mixed CO2/CH4 in gas hydrates.  United States: N. p., 2015. 
Web.  doi:10.2138/am-2015-4929.

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                    Everett, S. Michelle, Rawn, Claudia J., Chakoumakos, Bryan C., Keffer, David J., Huq, Ashfia, & Phelps, Tommy J. Insights into the structure of mixed CO2/CH4 in gas hydrates.  United States.  https://doi.org/10.2138/am-2015-4929

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                    Everett, S. Michelle, Rawn, Claudia J., Chakoumakos, Bryan C., Keffer, David J., Huq, Ashfia, and Phelps, Tommy J. Tue .  
"Insights into the structure of mixed CO2/CH4 in gas hydrates".  United States.  https://doi.org/10.2138/am-2015-4929.  https://www.osti.gov/servlets/purl/1185328.

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@article{osti_1185328,

  title        = {Insights into the structure of mixed CO2/CH4 in gas hydrates},

  author       = {Everett, S. Michelle and Rawn, Claudia J. and Chakoumakos, Bryan C. and Keffer, David J. and Huq, Ashfia and Phelps, Tommy J.},

  abstractNote = {The exchange of carbon dioxide for methane in natural gas hydrates is an attractive approach to harvesting CH4 for energy production while simultaneously sequestering CO2. In addition to the energy and environmental implications, the solid solution of clathrate hydrate (CH4)1-x(CO2)x·5.75H2O provides a model system to study how the distinct bonding and shapes of CH4 and CO2 influence the structure and properties of the compound. In this paper, high-resolution neutron diffraction was used to examine mixed CO2/CH4 gas hydrates. CO2-rich hydrates had smaller lattice parameters, which were attributed to the higher affinity of the CO2 molecule interacting with H2O molecules that form the surrounding cages, and resulted in a reduction in the unit-cell volume. Experimental nuclear scattering densities illustrate how the cage occupants and energy landscape change with composition. Finally, these results provide important insights on the impact and mechanisms for the structure of mixed CH4/CO2 gas hydrate.},

  doi          = {10.2138/am-2015-4929},

  journal      = {American Mineralogist},

  number       = 5-6,

  volume       = 100,

  place        = {United States},

  year         = {Tue May 12 00:00:00 EDT 2015},

  month        = {Tue May 12 00:00:00 EDT 2015}

}

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Works referencing / citing this record:

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Title: Insights into the structure of mixed CO2/CH4 in gas hydrates

Abstract

Citation Formats

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Clathrate Hydrates of Greenhouse Gases in the Presence of Natural Amino Acids: Storage, Transportation and Separation Applications journal, June 2018

Title: Insights into the structure of mixed CO₂/CH₄ in gas hydrates

Monte Carlo simulations of the separation of a binary gas mixture (CH ₄ + CO ₂ ) using hydrates
journal, January 2018

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journal, June 2018