Thermodynamic and Molecular Properties of Gas Hydrates from Mixtures Containing Methane, Argon, and Krypton

Holder, Gerald D.; Corbin, G.; Papadopoulos, Kyriakos

doi:10.1021/i160075a008

Cited by 348 publications

(284 citation statements)

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“…The equilibrium pressure at 283.5 K is 7.20 MPa with pure water (Sloan, 1998). For the krypton hydrate, Holder et al (1980) experimentally determined the equilibrium pressure at 273.2 K is 1.47 MPa with pure water. The equilibrium pressure of krypton hydrate at the formation temperature of 273.5 K used in this work is suggested to be slightly higher than that at 273.2 K. The solution was intermittently sampled through the outlet before the gas pressure reached the equilibrium pressure.…”

Section: Methodsmentioning

confidence: 99%

Experimental study on isotopic fractionation in water during gas hydrate formation

Maekawa

2004

Geochem. J.

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Isotopic fractionation of oxygen and hydrogen in water caused by gas hydrate formation was investigated experimentally. Two different gas hydrates in structures, Structure I hydrate and Structure II hydrate, were formed with methane and krypton gases in a NaCl solution. Isotopic fractionation during gas hydrate formation was observed by measuring oxygen and hydrogen isotopic compositions in the solutions sampled before and after gas hydrate formation. Heavy isotopes of oxygen and hydrogen in water were depleted in the solution resulting from that those isotopes were concentrated in the gas hydrate. The isotopic fractionation was larger as increasing amounts of gas hydrates that were calculated from both the decrease of gas pressure and increase of NaCl concentration in solution. The isotopic fractionation factors of oxygen and hydrogen in water between gas hydrate and liquid water were determined to be 1.0023-1.0032 and 1.014-1.022, respectively. The significant difference of the gas hydrate structures was not observed beyond the analytical errors. These factors are similar to those between ice and liquid water.

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Section: Methodsmentioning

confidence: 99%

Experimental study on isotopic fractionation in water during gas hydrate formation

Maekawa

2004

Geochem. J.

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“…Δh w β-I/L and Δv w β-I/L are the molar enthalpy and molar volume differences between an empty hydrate lattice and ice or liquid water. Δh w β-I/L is given by the following equation (Anderson and Prausnitz, 1986;Holder et al, 1980): (17) where C' and subscript P refer to molar heat capacity and pressure, respectively. Δh w 0 is the enthalpy difference between the empty hydrate lattice and pure water, at the triple point.…”

Section: Tablementioning

confidence: 99%

“…Δh w 0 is the enthalpy difference between the empty hydrate lattice and pure water, at the triple point. The heat capacity difference between the empty hydrate lattice and the pure liquid water phase, ΔC' Pw is also temperature dependent and the equation recommended by Holder et al (1980) is used: (18) where ΔC' Pw is in J.mol -1 K -1 . Furthermore, the heat capacity difference between hydrate structures and ice is set to zero.…”

Section: Tablementioning

confidence: 99%

Methane and Water Phase Equilibria in the Presence of Single and Mixed Electrolyte Solutions Using the Cubic-Plus-Association Equation of State

Haghighi

Chapoy

Tohidi

2008

Oil & Gas Science and Technology - Rev. IFP

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Résumé -Application de l'équation d'état Cubic-Plus-Association pour la prédiction des équilibres entre phases pour les systèmes contenant du méthane et de l'eau en présence d'électrolyte(s) -Les hydrates de méthane ont été largement présentés comme une potentielle nouvelle source d'énergie. Les hydrates à l'état naturel peuvent se former dans diverses roches ou sédiments si les conditions appropriées de pression et température en présence d'eau et de méthane sont réunies. Toutefois, la salinité des eaux de formation peut connaître d'importantes variations, et ces changements modifient la zone de stabilité des hydrates. En outre, l'eau de gisement produite avec les fluides de réservoir peut contenir diverses quantités de sels, pouvant prévenir la formation d'hydrates. Par conséquent, il est essentiel d'obtenir une meilleure compréhension de l'effet des sels sur la stabilité des hydrates. Dans cette communication, de nouvelles données expérimentales de dissociation d'hydrates de méthane en présence de solutions aqueuses contenant différentes concentrations de NaCl, KCl et de MgCl 2 ont été réalisées. Les nouvelles données ont été mesurées en utilisant une méthode à volume constant. La précision et la fiabilité des mesures expérimentales ont été démontrées en comparant les mesures avec les données de la littérature. Une approche thermodynamique dans lequel l'équation d'état CPA est combinée avec une modification du terme électrostatique proposé par Debye-Hückel a été employée pour modéliser les équilibres entre phases. Les conditions de formation d'hydrates sont modélisées par la théorie développée par van der Waals et Platteeuw. Pour modéliser en milieux poreux les équilibres entre phases d'hydrate, l'effet de la pression capillaire a été pris en compte. Les prédictions du modèle développé ont été validées par rapport à des données expérimentales indépendantes et les données obtenues dans ce travail. Un bon accord entre les prédictions et les données expérimentales a été observé, confirmant la fiabilité du modèle développé. Abstract -Methane and Water Phase Equilibria in the Presence of Single and Mixed Electrolyte

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“…The hydrate phase is modeled using the solid solution theory of van der Waals and Platteeuw, 25 as developed by Parrish and Prausnitz. 26 The equation recommended by Holder et al 28 is used to calculate the heat capacity difference between the empty hydrate lattice and pure liquid water. The Kihara 29 model for spherical molecules is applied to calculate the potential function for compounds forming hydrate phases.…”

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confidence: 99%

Carbon monoxide clathrate hydrates: Equilibrium data and thermodynamic modeling

2005

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in Wiley InterScience (www.interscience.wiley.com). 2 and CH 4 hydrates. Data for Carbon monoxide occurs in abundance throughout the cosmos, potentially in clathrate form, whereas on Earth, it forms a notable constituent of industrial flue gases. It has been proposed that hydrate technology could be used in CO 2 separation from flue gases, and in subsea flue gas CO 2 disposal. This-and the likely widespread occurrence of CO clathrates in the cosmos-means it is important that the phase behavior of CO hydrates is known. Here, we present experimental H-L-V (hydrate-liquid-vapor) equilibrium data for CO, CO-CO 2 , and CO-C 3 H 8 (propane) clathrate hydrates. Data were generated by a reliable step-heating technique validated using measured data for CO IntroductionGas hydrates, or clathrate hydrates, are a group of nonstoichiometric, icelike crystalline compounds formed through a combination of water and suitably sized "guest " molecules under low-temperature and elevated pressure conditions. In the clathrate lattice, water molecules form hydrogen-bonded cagelike structures, encapsulating the guest molecules, which generally consist of low molecular diameter gases and organic compounds. A concise review of gas hydrates is given by Sloan. 1 Alongside molecular hydrogen and water, carbon monoxide is one of the most abundant molecules in the cosmos. It is found in solid, gaseous, and potentially clathrate hydrate forms throughout the galaxy, either in interstellar gas clouds, or as a component of comets and planetary bodies. [2][3][4] In the terrestrial environment, CO forms a notable constituent of flue and other exhaust gases resulting from the combustion of organic materials.Recently, hydrate technology has been proposed as a means for CO 2 separation from industrial flue gases. 5 Carbon monoxide is a common component of such gases, and thus its effects on hydrate equilibria should be considered in process design. Similarly, any CO present in CO 2 destined for proposed hydrate sequestration schemes 6,7 will also influence the phase behavior. These factors, and the potential widespread abundance of CO clathrates in the cosmos, warrant an improved understanding of CO clathrate hydrate equilibria.Currently, only very limited data are available in the literature concerning CO hydrates. Carbon monoxide is similar in molecular size to oxygen and nitrogen. Given that both O 2 and N 2 can form simple (single guest) gas hydrates, it was proposed in the 1960s that carbon monoxide should also form clathrates. 2,8,9 In the absence of experimental data, Miller 3 and 4 however, using the classical Lennard-Jones-Devonshire (LJD) cell model (with cell parameters apparently modified from those of nitrogen hydrates), concluded that structure I would be the more stable structure for carbon monoxide, giving a dissociation pressure around 20% lower than that for structure II at the same temperature. Davidson et al. 10 subsequently resolved this issue through low-temperature X-ray powder diffraction studies, which demonstrated that ...

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Thermodynamic and Molecular Properties of Gas Hydrates from Mixtures Containing Methane, Argon, and Krypton

Cited by 348 publications

References 10 publications

Experimental study on isotopic fractionation in water during gas hydrate formation

Experimental study on isotopic fractionation in water during gas hydrate formation

Methane and Water Phase Equilibria in the Presence of Single and Mixed Electrolyte Solutions Using the Cubic-Plus-Association Equation of State

Carbon monoxide clathrate hydrates: Equilibrium data and thermodynamic modeling

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