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Modeling the properties of methane + ethane (Propane) binary hydrates, depending on the composition of gas phase state in equilibrium with hydrate


The properties of methane + ethane and methane + propane hydrates of cubic structures sI and sII are theoretically investigated. It is shown that the composition of the formed binary hydrate strongly depends on the percentage of a heavier guest in gas phase. For instance, for a 1% molar ethane concentration in gas phase, even at a low pressure, ethane occupies 60% large cavities in the hydrate sII, and as the pressure grows to 100 atm, it occupies 80% large cavities at a low temperature. The tendency remains the same at a temperature of higher than the ice melting point, but the methane concentration in the hydrate decreases to 30%. In the structure sI, the influence of the component composition of the gas mixture on that of the formed hydrate is less evident. However, in this case, calculation showed also that for a 1% molar ethane concentration in gas phase, ethane molecules occupy from 8 to 10% large hydrate cavities, depending on the pressure. This work is concerned with modeling phase transitions between cubic structures sI and sII of methane + ethane binary hydrates in view of incomplete occupation of cavities in the hydrate by guest molecules. For an ethane concentration under 2% in the gas mixture, the structure sII becomes more thermodynamically stable than the structure sI. However, as the ethane concentration grows to 20% in the equilibrium ice-gas-hydrate and to 40% in the equilibrium water-gas-hydrate, the structure sI becomes more thermodynamically stable. Hence, for low ethane concentrations in a gas mixture, the structure sI can be formed only as a metastable phase. Phase equilibria of methane hydrate sI and mixed methane + propane hydrate sII are considered, depending on the gas phase composition. Similar results are obtained for this equilibrium; this can evidence simultaneous formation of hydrates sI and sII at low propane concentrations.

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Zhdanov, R.K., Adamova, T.P., Subbotin, O.S. et al. Modeling the properties of methane + ethane (Propane) binary hydrates, depending on the composition of gas phase state in equilibrium with hydrate. J. Engin. Thermophys. 19, 282–288 (2010).

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  • Ethane
  • Guest Molecule
  • Hydrate Formation
  • Ethane Concentration