Thermodynamics of gas mixtures in nanoporous materials: Extension to non-ideal systems at high pressures
https://doi.org/10.17586/2220-8054-2024-15-6-950-958
Abstract
In this work, we developed a phenomenological approach to describe the equilibrium adsorption of nonideal gas mixtures in nanoporous adsorbents over a wide pressure range. The key point of the developed approach is an observation that the Gibbs free energy of a gas mixture is close to its ideal term. This feature, being more general than the empirical Raoult’s law in the ideal adsorbed solution theory (IAST), was combined with the distribution of elements of the adsorption volume (EAV) of the porous material over potentials in the spirit of Polanyi’s theory. We applied this approach to the adsorption of individual and binary gas mixtures of CO2, CH4, and N2 on an activated carbon in a wide pressure range up to 13 MPa. The approach provides high accuracy in predicting the adsorption of gas mixtures based on individual adsorption isotherms and obeys the Gibbs-Duhem equation, which confirms its thermodynamic consistency
Keywords
high-pressure adsorption,
supercritical gases,
nanoporous carbons,
mixture adsorption,
adsorbed phase thermodynamics,
equation of state
Supporting agencies: The research was carried out within the framework of the state assignment on topic No. 121031300090-2 (TAK) and No. 0081-2022-0008 (EAU)
About the Authors
T. A. Kuznetsova
Lomonosov Moscow State University
Russian Federation
Russian Federation
Tatiana A. Kuznetsova, Chemistry Department
GSP-1, Leninskie Gory, Moscow, 119991
E. A. Ustinov
Ioffe Institute
Russian Federation
Russian Federation
Eugene A. Ustinov
26 Polytechnicheskaya, St. Petersburg, 194021
References
1. Myers A.L., Prausnitz J.M. Thermodynamics of mixed-gas adsorption. AIChE J., 1965, 11, P. 121–127.
2. Rios R.B., Stragliotto F.M., Peixoto H.S., Torres A.E.B., Bastos-Neto A.M., Azevedo D.C.S., Cavalcante C.L. Studies on the adsorption behavior of CO2-CH4 mixtures using activated carbon. Braz. J. Chem. Eng., 2013, 30, P. 939–951.
3. Pino D., Plantier F., Bessieres D. Experimental determination of the adsorption isoterms in gas mixtures under extended pressure and temperature range. J. Term. Anal. Calorim., 2014, 117, P. 1469–1477.
4. Pino D., Bessieres D. CH4/CO2 Mixture adsorption on a characterized activated carbon. J. Chem. Eng. Data., 2017, 62, P. 1475–1480.
5. Dreisbach F., Staudt R., Keller J.U. High pressure adsorption data of methane, nitrogen, carbon dioxide and their binary and ternary mixture on activated carbon. Adsorption, 1999, 5, P. 215–227.
6. Sudibandriyo M., Pan Zh., Fitzgerald J.E., Robinson R.L., Gasem K.A.M. Adsorption of methane, nitrogen, carbon dioxide, and their binary mixtures on dry activated carbon at 318.2 K and pressures up to 13.6 MPa. Langmuir, 2003, 19, P. 5323–5331.
7. Rufford T.E.,Watson G.C.Y., Saleman T.L., Hofman P.S. Adsorption equilibria and kinetics of methane + nitrogen mixtures on the activated carbon Norit RB3. Ind. Chem. Eng. Res., 2013, 52, P. 14270–14281.
8. Fitzgerald J.E., Pan Z., Sudibandriyo M., Robinson R.L., Gasem K.A.M., Reeves S. Adsorption of methane, nitrogen, carbon dioxide and their mixtures on wet Tiffany coal. Fuel, 2005, 84, P. 2351–2363.
9. Vaart R. van der Huiskes C., Bosch H., Reith T. Single and mixed gas adsorption equilibria of carbon dioxide/methane on activate carbon. Adsorption, 2000, 6, P. 311–323.
10. Valenzuela D.P., Myers A.L., Talu O., Zwiebel I. Adsorption of gas mixtures: Effect of energetic heterogeneity. AIChE J., 1988, 34, P. 397–402.
11. Jensen C.R.C., Seaton N.A., Gusev V., O’Brien J.A. Prediction of multicomponent adsorption equilibrium using a new model of adsorbed phase nonuniformity. Langmuir, 1997, 13, P. 1205–1210.
12. Goetz V., Pupier O., Guillot A. Carbon dioxide-methane mixture adsorption on activated carbon. Adsorption, 2006, 12, P. 55–63.
13. Dubinin M.M. Fundamentals of the theory of adsorption in micropores of carbon adsorbents: Characteristics of their adsorption properties and microporous structures. Carbon, 1989, 27, P. 457–467.
14. Hoory S.E., Prausnitz J.M. Monolayer adsorption of gas mixtures on homogeneous and heterogeneous solids. Chem. Eng. Sci., 1967, 22, P. 1025–1033.
15. DeGance A.E. Multicomponent high-pressure adsorption equilibria on carbon substrates: Theory and data. Fluid Phase Equilibria, 1992, 78, P. 99–137.
16. Ustinov E.A., Do D.D., Herbst A., Staudt R., Harting P. Multicomponent adsorption on activated carbons under supercritical conditions. J. Colloid Interface Sci., 2004, 275, P. 376–385.
17. Shapiro A.A., Stenby E.H. Potential theory of multicomponent adsorption. J. Colloid Interface Sci. 1998, 201, P. 146–157.
18. Dundar E., Zacharia R., Chahine R., B´enard, P. Potential theory for prediction of high-pressure gas-mixture adsorption on activate carbons and MOFs. Sep. Purif. Technol., 2014, 135, P. 229–242.
19. Polanyi M. The potential theory of adsorption. Science, 1963, 141, P. 1010–1013.
20. Ustinov E.A., Do D.D., Herbst A., Staudt R., Harting P. Modeling of gas adsorption equilibrium over a wide range of pressure: A thermodynamic approach based on equation of state. J. Colloid Interface Sci., 2002, 250, P. 49–62.
21. Platzer B., Maurer G. Application of a generalized Bender equation of state to the description of vapour-liquid equilibria in binary systems. Fluid Phase Equilibria, 1993, 84, P. 79–110.
22. Ustinov E.A. Thermodynamics of liquid and fluid mixtures from kinetic Monte Carlo viewpoint. Phys. Chem. Chem. Phys., 2023, 25, P. 27321–27330.
Review
For citations:
Kuznetsova T.A., Ustinov E.A. Thermodynamics of gas mixtures in nanoporous materials: Extension to non-ideal systems at high pressures. Nanosystems: Physics, Chemistry, Mathematics. 2024;15(6):950-958. https://doi.org/10.17586/2220-8054-2024-15-6-950-958
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