Phase equilibrium measurements and crystallographic analyses on structure-H type gas hydrate formed from the CH4-CO2-neohexane-water system

Tsutomu Uchida, Ryo Ohmura, Ikuko Y. Ikeda, Jiro Nagao, Satoshi Takeya, Akira Hori

Research output: Contribution to journalArticle

28 Citations (Scopus)

Abstract

Phase equilibrium conditions and the crystallographic properties of structure-H type gas hydrates containing various amounts of methane (CH 4), carbon dioxide (CO2), neohexane (2,2-dimethylbutane; NH), and liquid water were investigated. When the CH4 concentration was as high as approximately 70%, the phase equilibrium pressure of the structure-H hydrate, which included NH, was about 1 MPa lower at a given temperature than that of the structure-I hydrate with the same composition (except for a lack of NH). However, as the CO2 concentration increased, the pressure difference between the structures became smaller and, at CO2 concentrations below 50%, the phase equilibrium line for the structure-H hydrate crossed that for the structure I. This cross point occurred at a lower temperature at higher CO2 concentration. Extrapolating this relation between the cross point and the CO2 concentration to 100% CO2 suggests that the cross-point temperature would be far below 273.2 K. It is then difficult to form structure-H hydrates in the CO 2-NH-liquid water system. To examine the structure, guest composition, and formation process of structure-H hydrates at various CH 4-CO2 compositions, we used the methods of Raman spectroscopy, X-ray diffraction, and gas chromatography. Raman spectroscopic analyses indicated that the CH4 molecules were found to occupy both 512 and 435663 cages, but they preferably occupied only the 512 cages. On the other hand, the CO2 molecules appeared to be trapped only in the 435 663 cages. Thus, the CO2 molecules aided the formation of structure-H hydrates even though they reduced the stability of that structure. This encaged condition of guest molecules was also compared with the theoretical calculations. In the batch-type reactor, this process may cause the fractionation of the remaining vapor composition in the opposite sense as that for CH4-CO2 hydrate (structure-I), and thus may result in an alternating formation of structure-H hydrates and structure-I in the same batch-type reactor.

Original languageEnglish
Pages (from-to)4583-4588
Number of pages6
JournalJournal of Physical Chemistry B
Volume110
Issue number10
DOIs
Publication statusPublished - 2006 Mar 16
Externally publishedYes

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Gas hydrates
Hydrates
Phase equilibria
hydrates
Water
gases
water
Molecules
Chemical analysis
molecules
reactors
methylidyne
Methane
Liquids
Carbon Monoxide
Fractionation
Carbon Dioxide
Gas chromatography
Temperature
gas chromatography

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

Phase equilibrium measurements and crystallographic analyses on structure-H type gas hydrate formed from the CH4-CO2-neohexane-water system. / Uchida, Tsutomu; Ohmura, Ryo; Ikeda, Ikuko Y.; Nagao, Jiro; Takeya, Satoshi; Hori, Akira.

In: Journal of Physical Chemistry B, Vol. 110, No. 10, 16.03.2006, p. 4583-4588.

Research output: Contribution to journalArticle

Uchida, Tsutomu ; Ohmura, Ryo ; Ikeda, Ikuko Y. ; Nagao, Jiro ; Takeya, Satoshi ; Hori, Akira. / Phase equilibrium measurements and crystallographic analyses on structure-H type gas hydrate formed from the CH4-CO2-neohexane-water system. In: Journal of Physical Chemistry B. 2006 ; Vol. 110, No. 10. pp. 4583-4588.
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abstract = "Phase equilibrium conditions and the crystallographic properties of structure-H type gas hydrates containing various amounts of methane (CH 4), carbon dioxide (CO2), neohexane (2,2-dimethylbutane; NH), and liquid water were investigated. When the CH4 concentration was as high as approximately 70{\%}, the phase equilibrium pressure of the structure-H hydrate, which included NH, was about 1 MPa lower at a given temperature than that of the structure-I hydrate with the same composition (except for a lack of NH). However, as the CO2 concentration increased, the pressure difference between the structures became smaller and, at CO2 concentrations below 50{\%}, the phase equilibrium line for the structure-H hydrate crossed that for the structure I. This cross point occurred at a lower temperature at higher CO2 concentration. Extrapolating this relation between the cross point and the CO2 concentration to 100{\%} CO2 suggests that the cross-point temperature would be far below 273.2 K. It is then difficult to form structure-H hydrates in the CO 2-NH-liquid water system. To examine the structure, guest composition, and formation process of structure-H hydrates at various CH 4-CO2 compositions, we used the methods of Raman spectroscopy, X-ray diffraction, and gas chromatography. Raman spectroscopic analyses indicated that the CH4 molecules were found to occupy both 512 and 435663 cages, but they preferably occupied only the 512 cages. On the other hand, the CO2 molecules appeared to be trapped only in the 435 663 cages. Thus, the CO2 molecules aided the formation of structure-H hydrates even though they reduced the stability of that structure. This encaged condition of guest molecules was also compared with the theoretical calculations. In the batch-type reactor, this process may cause the fractionation of the remaining vapor composition in the opposite sense as that for CH4-CO2 hydrate (structure-I), and thus may result in an alternating formation of structure-H hydrates and structure-I in the same batch-type reactor.",
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AU - Takeya, Satoshi

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