High‐pressure phase‐equilibrium studies by gas‐liquid partition chromatography

Stalkup, F.I.; Kobayashi, Riki

doi:10.1002/aic.690090127

Cited by 52 publications

(34 citation statements)

References 9 publications

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“…In practice, when the concentration step is not large, one can neglect the second terms in Eqs (14) and (15) and Eqs (21) and (22) can be used to calculate the concentrations in the stationary phase. …”

Section: Methodsmentioning

confidence: 99%

An alternative theoretical approach for the determination of competitive isotherms by frontal-velocity analysis

Yang

1999

Chromatographia

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Section: Methodsmentioning

confidence: 99%

An alternative theoretical approach for the determination of competitive isotherms by frontal-velocity analysis

Yang

1999

Chromatographia

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“…Vapor-liquid distribution ratio of light hydrocarbons between a gas phase made of methane and a liquid phase composed of heavy hydrocarbons are needed in industrial applications, for instance pipe line design or tertiary oil recovery using a miscible gas. For infinitely diluted light hydrocarbons, determination of partition coefficients, KT, can be performed using a static apparatus (Reamer et al, 1949) or retention time in gas-liquid chromatography using CHI as carrier gas and the heavy component as stationary phase (Stalkup and Kobayashi, 1963a; Koonce and Kobayashi, 1964).…”

Section: Scopementioning

confidence: 99%

Vapor‐liquid equilibrium constants at infinite dilution determined by a gas stripping method: Ethane, propane, n‐butane, n‐pentane in the methane‐n‐decane system

Legret¹,

Desteve²,

Richon³

et al. 1983

AIChE Journal

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A new apparatus to measure partition coefficients K: at infinite dilution up to 200 lo5 Pa and 423 K is described. Measurements of the systems: (1) methane-ethane-ndecane and methane-propane-n-decane at 294.25 K; and (2) methane-n-butane-ndecane at 344.25 K illustrate the reproducibility and good agreement with literature data. In addition, new data were obtained for the system methane-n- SCOPEVapor-liquid distribution ratio of light hydrocarbons between a gas phase made of methane and a liquid phase composed of heavy hydrocarbons are needed in industrial applications, for instance pipe line design or tertiary oil recovery using a miscible gas. For infinitely diluted light hydrocarbons, determination of partition coefficients, KT, can be performed using a static apparatus (Reamer et al., 1949) or retention time in gas-liquid chromatography using CHI as carrier gas and the heavy component as stationary phase (Stalkup and Kobayashi, 1963a; Koonce and Kobayashi, 1964).The new method introduced in this paper consists of stripping the solute by a constant flow of gas from a solution contained in one vessel. The solution (mainly heavy hydrocarbons) and the gas (mostly CHI in this paper) have the composition corresponding to the equilibrium in the conditions of pressure and temperature of the measurement. The distribution ratio of the very diluted solute is related to the decrease in time of the concentration of the solute in the gas phase after stripping as determined by gas chromatography. This new technique is an extension to higher pressures of the method described by Leroi et al. (1977) and . It uses a saturator for the gas stream entering the stripping cell. CONCLUSIONS AND SIGNIFICANCEA new apparatus for measuring partition coefficients of infinitely diluted solutes in mixed solvent (gas dissolved in heavy components) has been designed, constructed and tested. Tests mixtures have been used to check the reliability of measurements. The results show a good agreement with the literature data. The experimental error on KT measurements is estimated at less than 2%.The method is fast and may be used for studying several solutes simultaneously if all solute chromatographic peaks can be resolved. Accurate measurements are possible even for volatile solvents. Such measurements are impossible with a retention time chromatographic method. The accuracy is better than in the static methods.

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“…The high value a t infinite dilution was attributed to a high value of the activity coefficient predicted by the Scatchard-Hildebrand equation. (22,9,23). Accordingly 6, -= liquid mixture solubility parameter evaluated from the liquid composition with component I a t infinite dilution.…”

Section: Development Of a Correlation For The Intermediate Componentsmentioning

confidence: 99%

The correlation of vapor‐liquid equilibria of light hydrocarbons in paraffinic and in aromatic solvents at low temperatures and elevated pressures

Horn

Kobayashi

1968

AIChE Journal

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Rice U n i v e r s i t y , H o u s t o n , TexasA correlational procedure was developed to predict the vapor-liquid equilibrium behavior of light hydrocarbons in heavier hydrocorbon solvents at low temperatures and elevated pressures. T h e method i s applicable to paraffinic a s well a s aromatic solvents. The method employed the Benedict-Webb-Rubin equation of state to predict the vapor phase fugacities. Methane liquid fugacities in the various hydrocarbon solvents were based upon Henry's law which included terms to account for compositional and pressure effects. The liquid fugacities for ethane and propane were calculoted using infinite dilution data to modify empirically the Scatchord-Hildebrond equation. Excellent agreement between the correlated and low-temperature data available on this class of systems was obtained.The literature abounds with correlations for vapor-liquid equilibria at elevated pressures. Of particular note are the Chao-Seader correlation ( 4 , correlations in light hydrocarbon systems based on equations of state (11, and convergence pressure correlations such a s those appearing in the NGSMA Data Book (12). The strength of the Chao-Seader correlation lies in i t s generality; that i s , in i t s ability to predict vapor-liquid phase behavior in systems composed of paraffins, napthenes and aromatics, including gases such a s hydrogen, nitrogen, carbon dioxide, and hydrogen sulfide a t low concentrations. T h e application of equations of state and the corresponding s t a t e s methods is usually limited to systems composed of paraffins and nonpolar substances. The purpose of this paper i s to develop a method of predicting phase behavior in systems containing a supercritical component, methane, with intermediates, ethane and propane, and a relatively heavy paraffin or aromatic component, such as heptane or toluene, using basic data which are functions of pressure and temperature only. Temperatures of interest range from 70' to -100OF. and pressures up to 1,500 Ib./sq. in. abs. Other correlations have not been successful for this type of system under these conditions. By definition, the vapor-liquid equilibrium constant, or K value, is the ratio of mole fractions of the component in the vapor and in the liquid. Since the fugacities for components are equal among the equilibrium phases (1) Chao and Seader (4) chose to separate the liquid fugacity

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High‐pressure phase‐equilibrium studies by gas‐liquid partition chromatography

Cited by 52 publications

References 9 publications

An alternative theoretical approach for the determination of competitive isotherms by frontal-velocity analysis

An alternative theoretical approach for the determination of competitive isotherms by frontal-velocity analysis

Vapor‐liquid equilibrium constants at infinite dilution determined by a gas stripping method: Ethane, propane, n‐butane, n‐pentane in the methane‐n‐decane system

The correlation of vapor‐liquid equilibria of light hydrocarbons in paraffinic and in aromatic solvents at low temperatures and elevated pressures

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