In situ inelastic neutron scattering of mixed CH4–CO2 hydrates

Bernadette R. Cladek; A. J. Ramirez-Cuesta; S. Michelle Everett; Marshall T. McDonnell; Luke Daemen; Yongqiang Cheng; Paulo H.B. Brant Carvalho; Christopher Tulk; Matthew G. Tucker; David J. Keffer; Claudia J. Rawn

doi:10.1016/j.fuel.2022.125197

In situ inelastic neutron scattering of mixed CH₄–CO₂ hydrates

Bernadette R. Cladek, A. J. Ramirez-Cuesta, S. Michelle Everett, Marshall T. McDonnell, Luke Daemen, Yongqiang Cheng, Paulo H.B. Brant Carvalho, Christopher Tulk, Matthew G. Tucker, David J. Keffer, Claudia J. Rawn

Research output: Contribution to journal › Article › peer-review

3 Scopus citations

Abstract

An abundant source of CH₄ can be found in natural hydrate deposits. Recent demonstration of CH₄ recovery from hydrates via CO₂ exchange has revealed the potential as a fuel source that also provides a medium for carbon sequestration. It is vital to understand the structural and dynamic impacts of guest variation in CH₄, CO₂, and mixed hydrates and link the results to the stability of various deposits in nature, harvesting methane, and sequestering CO₂. Molecular vibrations are examined in CH₄, CO₂, and mixed CH₄-CO₂ hydrates at 5 and 190 K and Xe hydrates for comparison. Inelastic neutron scattering (INS) is an ideal spectroscopy technique to observe the dynamic modes in the hydrate structure and enclathrated CH₄, as it is extremely sensitive to ¹H. The presence of CO₂ in hydrates tightens the lattice. It introduces more active librational modes to the host lattice, while hindering the motion of CH₄ in mixed CH₄-CO₂ hydrate at 5 K. At 190 K, a large broadening of the CH₄ librational modes indicates disorder in the structure leading to dissociation.

Original language	English
Article number	125197
Journal	Fuel
Volume	327
DOIs	https://doi.org/10.1016/j.fuel.2022.125197
State	Published - Nov 1 2022

Funding

This research used resources at the Spallation Neutron Source (SNS), a US Department of Energy (DOE) Office of Science User Facility operated by Oak Ridge National Laboratory (ORNL). BRC has been partially supported by the Center for Materials Processing, a Tennessee Higher Education Commission Center of Excellence located at the University of Tennessee, Knoxville, a University of Tennessee Chancellor's Fellowship, and the Office of Science Graduate Student Research (SCGSR) program. The SCGSR program is administered by the Oak Ridge Institute for Science and Education for DOE. Research at SNS was sponsored by the DOE Office of Basic Energy Sciences. The computing resources were made available through the VirtuES and the ICE-MAN projects, funded by Laboratory Directed Research and Development program and Compute and Data Environment for Science (CADES) at ORNL. Code availability, The codes used in this study are primarily cited. OCLIMAX is available upon request. MD simulations were performed with LAMMPS, documented at https://lammps.sandia.gov/doc/Manual.html. This research used resources at the Spallation Neutron Source (SNS), a US Department of Energy (DOE) Office of Science User Facility operated by Oak Ridge National Laboratory (ORNL). BRC has been partially supported by the Center for Materials Processing, a Tennessee Higher Education Commission Center of Excellence located at the University of Tennessee, Knoxville, a University of Tennessee Chancellor’s Fellowship, and the Office of Science Graduate Student Research (SCGSR) program. The SCGSR program is administered by the Oak Ridge Institute for Science and Education for DOE. Research at SNS was sponsored by the DOE Office of Basic Energy Sciences. The computing resources were made available through the VirtuES and the ICE-MAN projects, funded by Laboratory Directed Research and Development program and Compute and Data Environment for Science (CADES) at ORNL.

Funders	Funder number
Compute and Data Environment for Science
Office of Science Graduate Student Research
SCGSR
U.S. Department of Energy
Office of Science
Basic Energy Sciences
Oak Ridge National Laboratory
Oak Ridge Institute for Science and Education
Laboratory Directed Research and Development
University of Tennessee
Tennessee Higher Education Commission

Keywords

CO2 Sequestration
Molecular dynamics simulations
Natural gas hydrates
Neutron scattering
methane-CO2 exchange

UN SDGs

This output contributes to the following UN Sustainable Development Goals (SDGs)

Access to Document

10.1016/j.fuel.2022.125197

Cite this

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title = "In situ inelastic neutron scattering of mixed CH4–CO2 hydrates",

abstract = "An abundant source of CH4 can be found in natural hydrate deposits. Recent demonstration of CH4 recovery from hydrates via CO2 exchange has revealed the potential as a fuel source that also provides a medium for carbon sequestration. It is vital to understand the structural and dynamic impacts of guest variation in CH4, CO2, and mixed hydrates and link the results to the stability of various deposits in nature, harvesting methane, and sequestering CO2. Molecular vibrations are examined in CH4, CO2, and mixed CH4-CO2 hydrates at 5 and 190 K and Xe hydrates for comparison. Inelastic neutron scattering (INS) is an ideal spectroscopy technique to observe the dynamic modes in the hydrate structure and enclathrated CH4, as it is extremely sensitive to 1H. The presence of CO2 in hydrates tightens the lattice. It introduces more active librational modes to the host lattice, while hindering the motion of CH4 in mixed CH4-CO2 hydrate at 5 K. At 190 K, a large broadening of the CH4 librational modes indicates disorder in the structure leading to dissociation.",

keywords = "CO2 Sequestration, Molecular dynamics simulations, Natural gas hydrates, Neutron scattering, methane-CO2 exchange",

author = "Cladek, {Bernadette R.} and Ramirez-Cuesta, {A. J.} and Everett, {S. Michelle} and McDonnell, {Marshall T.} and Luke Daemen and Yongqiang Cheng and {Brant Carvalho}, {Paulo H.B.} and Christopher Tulk and Tucker, {Matthew G.} and Keffer, {David J.} and Rawn, {Claudia J.}",

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doi = "10.1016/j.fuel.2022.125197",

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AU - Cladek, Bernadette R.

AU - Ramirez-Cuesta, A. J.

AU - Everett, S. Michelle

AU - McDonnell, Marshall T.

AU - Daemen, Luke

AU - Cheng, Yongqiang

AU - Brant Carvalho, Paulo H.B.

AU - Tulk, Christopher

AU - Tucker, Matthew G.

AU - Keffer, David J.

AU - Rawn, Claudia J.

PY - 2022/11/1

Y1 - 2022/11/1

N2 - An abundant source of CH4 can be found in natural hydrate deposits. Recent demonstration of CH4 recovery from hydrates via CO2 exchange has revealed the potential as a fuel source that also provides a medium for carbon sequestration. It is vital to understand the structural and dynamic impacts of guest variation in CH4, CO2, and mixed hydrates and link the results to the stability of various deposits in nature, harvesting methane, and sequestering CO2. Molecular vibrations are examined in CH4, CO2, and mixed CH4-CO2 hydrates at 5 and 190 K and Xe hydrates for comparison. Inelastic neutron scattering (INS) is an ideal spectroscopy technique to observe the dynamic modes in the hydrate structure and enclathrated CH4, as it is extremely sensitive to 1H. The presence of CO2 in hydrates tightens the lattice. It introduces more active librational modes to the host lattice, while hindering the motion of CH4 in mixed CH4-CO2 hydrate at 5 K. At 190 K, a large broadening of the CH4 librational modes indicates disorder in the structure leading to dissociation.

AB - An abundant source of CH4 can be found in natural hydrate deposits. Recent demonstration of CH4 recovery from hydrates via CO2 exchange has revealed the potential as a fuel source that also provides a medium for carbon sequestration. It is vital to understand the structural and dynamic impacts of guest variation in CH4, CO2, and mixed hydrates and link the results to the stability of various deposits in nature, harvesting methane, and sequestering CO2. Molecular vibrations are examined in CH4, CO2, and mixed CH4-CO2 hydrates at 5 and 190 K and Xe hydrates for comparison. Inelastic neutron scattering (INS) is an ideal spectroscopy technique to observe the dynamic modes in the hydrate structure and enclathrated CH4, as it is extremely sensitive to 1H. The presence of CO2 in hydrates tightens the lattice. It introduces more active librational modes to the host lattice, while hindering the motion of CH4 in mixed CH4-CO2 hydrate at 5 K. At 190 K, a large broadening of the CH4 librational modes indicates disorder in the structure leading to dissociation.

KW - CO2 Sequestration

KW - Molecular dynamics simulations

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