Hydrate Formation in Mesoporous Materials: Thermodynamic Modeling and Experimental Investigations
Full article
Journal |
Fuel
ISSN: 0016-2361
, E-ISSN: 1873-7153
|
Output data |
Year: 2023,
Volume: 331,
Number: 1,
Article number
: 125722,
Pages count
: 12
DOI:
10.1016/j.fuel.2022.125722
|
Tags |
Gas hydrate; Carbon dioxide; Mesoporous sorbents; Confinement; Phase transition; Equilibrium conditions |
Authors |
Smirnov Vyacheslav G.
1
,
Manakov Andrey Y.
2
,
Ismagilov Zinfer R.
1,3
|
Affiliations |
1 |
Federal Research Center of Coal and Coal-Chemistry SB RAS, Sovetskiy ave., 18, Kemerovo 650000, Russian Federation
|
2 |
Nikolaev Institute of Inorganic Chemistry SB RAS, Acad. Lavrentiev ave., 3, Novosibirsk 630090, Russian Federation
|
3 |
Boreskov Institute of Catalysis SB RAS, Acad. Lavrentiev ave., 5, Novosibirsk 630090, Russian Federation
|
|
Funding (2)
1
|
Ministry of Science and Higher Education of the Russian Federation
|
FWUZ-2021-0001 (121031700321-3)
|
2
|
Ministry of Science and Higher Education of the Russian Federation
|
075-00485-21-00 (121031500512-7) (0286-2021-0004)
|
Until recently, analysis and interpretation of the equilibrium conditions of hydrate formation from water adsorbed in mesoporous materials have been carried out with the use of the Gibbs-Thomson equation. For this purpose, only the shift of equilibrium conditions due to the small size of hydrate particles formed in the confining pores was taken into account. A distribution of equilibrium temperatures of the hydrate formed in mesoporous materials was interpreted as a consequence of the existence of hydrate particles differing from each other in size. A new equation describing the equilibrium conditions for gas hydrate in thin pores of mesoporous materials is proposed in this work. This equation takes into account the size of hydrate particles together with the chemical potential of pore water in equilibrium with the hydrate. Thus, an increase in the temperature shift from the equilibrium curve causes simultaneous formation of hydrate in smaller and smaller pores, and an increase in the size of gas hydrate particles that have been previously formed in larger pores. The latter occurs due to gradual transformation into hydrate of the layer of bound water, located between the pore wall and hydrate particle being formed in the pore center. Modeling results are compared with the data obtained previously on the equilibrium conditions for the hydrate of carbon dioxide in mesoporous Al2O3 samples. It is demonstrated that experimental results are in reasonable qualitative agreement with the proposed model. © 2022 Elsevier Ltd