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

Hiroyuki Komatsu, Masaki Ota, Richard L. Smith, Hiroshi Inomata

Research output: Contribution to journalReview articlepeer-review

89 Citations (Scopus)


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.

Original languageEnglish
Pages (from-to)517-537
Number of pages21
JournalJournal of the Taiwan Institute of Chemical Engineers
Issue number4
Publication statusPublished - 2013 Jul


  • Activation energy
  • CO hydrate
  • Exchange
  • Kinetics
  • Methane hydrate
  • Phase equilibria
  • Raman

ASJC Scopus subject areas

  • Chemistry(all)
  • Chemical Engineering(all)


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