Review of CO2–CH4 clathrate hydrate replacement reaction laboratory studies – Properties and kinetics

•Replacement reaction studies on CO2–CH4 gas hydrates are reviewed.•Dissociation enthalpies, thermal conductivities and thermal diffusivities are tabulated for CO2 hydrate and CH4 hydrate.•Experimental methods for measuring the kinetics are reviewed.•New analytical methods such as thermo-Raman shoul...

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Published inJournal of the Taiwan Institute of Chemical Engineers Vol. 44; no. 4; pp. 517 - 537
Main Authors Komatsu, Hiroyuki, Ota, Masaki, Smith, Richard L., Inomata, Hiroshi
Format Journal Article
LanguageEnglish
Published Elsevier B.V 01.07.2013
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Abstract •Replacement reaction studies on CO2–CH4 gas hydrates are reviewed.•Dissociation enthalpies, thermal conductivities and thermal diffusivities are tabulated for CO2 hydrate and CH4 hydrate.•Experimental methods for measuring the kinetics are reviewed.•New analytical methods such as thermo-Raman should be explored to develop a localized picture. Replacement reactions in clathrate hydrates, for which CO2 is used to replace methane gas trapped in inclusion compounds in the deep sea or permafrost areas, have gained growing attention as a possible method to sequester CO2 and recover natural gas. This review examines research progress in the replacement reactions and analytical methods with special focus on laboratory studies. Methane hydrate dissociation enthalpies, carbon dioxide hydrate dissociation enthalpies, methane hydrate thermal conductivities and thermal diffusivities are tabulated. Methods used to study the CH4–CO2 replacement reaction include material balance (MB), MB with particle size analyzer, MB and Raman, NMR, and magnetic resonance imaging. New analytical methods such as thermo-Raman should be explored in the future to develop a localized picture of the microscopic replacement mechanism including water molecule movement. Combination of these data with molecular simulations will allow new macroscopic models to be developed for use with practical processes for unconventional natural gas.
AbstractList •Replacement reaction studies on CO2–CH4 gas hydrates are reviewed.•Dissociation enthalpies, thermal conductivities and thermal diffusivities are tabulated for CO2 hydrate and CH4 hydrate.•Experimental methods for measuring the kinetics are reviewed.•New analytical methods such as thermo-Raman should be explored to develop a localized picture. Replacement reactions in clathrate hydrates, for which CO2 is used to replace methane gas trapped in inclusion compounds in the deep sea or permafrost areas, have gained growing attention as a possible method to sequester CO2 and recover natural gas. This review examines research progress in the replacement reactions and analytical methods with special focus on laboratory studies. Methane hydrate dissociation enthalpies, carbon dioxide hydrate dissociation enthalpies, methane hydrate thermal conductivities and thermal diffusivities are tabulated. Methods used to study the CH4–CO2 replacement reaction include material balance (MB), MB with particle size analyzer, MB and Raman, NMR, and magnetic resonance imaging. New analytical methods such as thermo-Raman should be explored in the future to develop a localized picture of the microscopic replacement mechanism including water molecule movement. Combination of these data with molecular simulations will allow new macroscopic models to be developed for use with practical processes for unconventional natural gas.
Author Komatsu, Hiroyuki
Ota, Masaki
Smith, Richard L.
Inomata, Hiroshi
Author_xml – sequence: 1
  givenname: Hiroyuki
  surname: Komatsu
  fullname: Komatsu, Hiroyuki
  organization: Graduate School of Environmental Studies, Tohoku University, Aramaki Aza Aoba-6-6-11, Aoba-ku, Sendai 980-8579, Japan
– sequence: 2
  givenname: Masaki
  surname: Ota
  fullname: Ota, Masaki
  email: masa@scf.che.tohoku.ac.jp
  organization: Research Center of Supercritical Fluid Technology, Tohoku University, Aramaki Aza Aoba-6-6-11, Aoba-ku, Sendai 980-8579, Japan
– sequence: 3
  givenname: Richard L.
  surname: Smith
  fullname: Smith, Richard L.
  email: smith@scf.che.tohoku.ac.jp
  organization: Graduate School of Environmental Studies, Tohoku University, Aramaki Aza Aoba-6-6-11, Aoba-ku, Sendai 980-8579, Japan
– sequence: 4
  givenname: Hiroshi
  surname: Inomata
  fullname: Inomata, Hiroshi
  organization: Research Center of Supercritical Fluid Technology, Tohoku University, Aramaki Aza Aoba-6-6-11, Aoba-ku, Sendai 980-8579, Japan
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Snippet •Replacement reaction studies on CO2–CH4 gas hydrates are reviewed.•Dissociation enthalpies, thermal conductivities and thermal diffusivities are tabulated for...
SourceID crossref
elsevier
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Publisher
StartPage 517
SubjectTerms Activation energy
CO2 hydrate
Exchange
Kinetics
Methane hydrate
Phase equilibria
Raman
Title Review of CO2–CH4 clathrate hydrate replacement reaction laboratory studies – Properties and kinetics
URI https://dx.doi.org/10.1016/j.jtice.2013.03.010
Volume 44
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