A thermodynamic model to predict the aqueous solubility of hydrocarbon mixtures at two-phase hydrate-liquid water equilibrium

Velaga, Srinath C.; Levine, Jonathan S.; Warzinski, Robert P.; Anderson, Brian J.

doi:10.1016/j.fluid.2015.12.049

A thermodynamic model to predict the aqueous solubility of hydrocarbon mixtures at two-phase hydrate-liquid water equilibrium

Journal Article · Thu Dec 31 00:00:00 EST 2015 · Fluid Phase Equilibria

DOI:https://doi.org/10.1016/j.fluid.2015.12.049· OSTI ID:1399471

^[1]; Levine, Jonathan S. ^[2]; Warzinski, Robert P. ^[2]; Anderson, Brian J. ^[1]

West Virginia University, Morgantown, WV (United States); National Energy Technology Laboratory (NETL), Pittsburgh, PA (United States)
National Energy Technology Laboratory (NETL), Pittsburgh, PA (United States)

In order to understand the fate and transport of hydrocarbons and hydrocarbon mixtures in the deep sea and underlying sediments it requires an accurate determination of the two-phase hydrate (H)-liquid water (L_w) thermodynamic equilibrium in the absence of a free gas phase. In addition to controlling hydrate formation directly from the aqueous phase, the H-L_w equilibrium provides the aqueous solubility of dissolving hydrate. The aqueous solubility of hydrocarbon mixture at H-L_w equilibrium was calculated based on the van der Waals and Platteeuw statistical thermodynamic model and the Holder model. Langmuir constants were calculated from cell potential parameters obtained from ab initio intermolecular potentials and thus the model contains no fitting parameters. The model accurately predicts pure methane, ethane, and propane experimental H-L_w equilibrium solubility data, including new data provided here for methane. Here, we present hydrocarbon solubilities in water and seawater at H-L_w equilibrium at deep sea conditions for both methane and a thermogenic mixture based on the methane–ethane–propane ratio from the 2010 Macondo oil spill. We also present model predictions of the proportion of occupied large and small cages at H-L_w equilibrium for both systems, as well as hydrocarbon ratios in the hydrate phase for the thermogenic mixture.

View Accepted Manuscript (DOE)

Research Organization:: National Energy Technology Laboratory (NETL), Pittsburgh, PA, and Morgantown, WV (United States). In-house Research

Sponsoring Organization:: USDOE

OSTI ID:: 1399471

Alternate ID(s):: OSTI ID: 1252029

Report Number(s):: NETL-PUB--20193; PII: S0378381215302910

Journal Information:: Fluid Phase Equilibria, Journal Name: Fluid Phase Equilibria Journal Issue: C Vol. 414; ISSN 0378-3812

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

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A thermodynamic model to predict the aqueous solubility of hydrocarbon mixtures at two-phase hydrate-liquid water equilibrium

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