Water Solubility in Supercritical Methane, Nitrogen, and Carbon Dioxide: Measurement and Modeling from 422 to 483 K and Pressures from 3.6 to 134 MPa

Abstract

A series of experiments to measure the water solubility in supercritical nitrogen and carbon dioxide have been conducted at experimental conditions up to 483 K and 134 MPa. The accuracy of the experimental procedure is verified by comparing the water content data of methane in the literature and our experimental data for the methane−water system. In addition, a fugacity−fugacity approach including the cubic-plus-association equation of state (CPA EoS) and a fugacity−activity approach based on the Peng−Robinson EoS and the Henry’s law model are incorporated to predict the water content data of methane, nitrogen, and carbon dioxide. A comparison between our experimental data, literature data, and the results of the fugacity−activity approach shows the reliability of the PR-Henry’s law model for the phase behavior studies of the nitrogen−water system over a wide range of pressure and temperature conditions. However, the CPA equation is not capable of reproducing the high pressure vapor and liquid phase compositions of the water−nitrogen system. The concept of cross-association satisfactorily improves the performance of the CPA equation of state in predicting the water content data of supercritical methane. On the basis of the literature and new measured data in this study, it has been found that the CPA equation better represents the phase behavior of the water−carbon dioxide system if carbon dioxide is considered as a self- and cross-associating molecule.

Mathematical-thermodynamic solubility model developed by the application of discrete Volterra functional series theory

“…For calculations of coefficients of all models, a sample data set (30% of the all-available data including maximum and minimum points) was used, which covers all materials of study with the maximum and minimum data point to ensure consistency of calculations [47]. For a comprehensive and depth comparison between the proposed and previously published models in literature, four statistical Table 1 Details of studied systems [27,33,[48][49][50][51][52].…”

A Geochemical Model of Fluids and Mineral Interactions for Deep Hydrocarbon Reservoirs

“…For CO 2 -H 2 O-NaCl systems, the experimental studies [17][18][19] are sufficient, which cover temperature from 0 ∘ C to more than 250 ∘ C and pressure from 1 bar to more than 1500 bar. From our comparison, the average absolute derivations for most of the data points are less than 10%.…”

Thermophysical Properties, Hydrate and Phase Behaviour Modelling in Acid Gas‐Rich Systems

“…The developed model can predict accurately the distribution of water in the CO 2 or H 2 S-rich phase and solubility of CO 2 or H 2 S in the aqueous phase below and above the critical point of pure CO 2 as shown in Wiebe and Gaddy (1941); () Experimental data from Gillepsie and Wilson (1982) ; () Experimental data from Nakayama et al (1987) ; () Experimental data from King et al (1992) ; (): Experimental data from Hou et al (2013) ; (): Experimental data from Valtz et al (2004). Right figure: (): Experimental data from Takenouchi and Kennedy (1964); () Experimental data from Gillepsie and Wilson (1982); (): Experimental data from Tabasinejad et al (2011) at 422.98 K ;(): Experimental data from Hou et al (2013). (): calculated data Duan and Sun (2003) Figure 6.…”