Skip to Main content Skip to Navigation
Theses

Thermodynamics and kinetics of methane hydrate formation in nanoporous media : theory and molecular simulation

Abstract : Methane hydrate is a non-stoichiometric crystal in which water molecules form hydrogen-bonded cages that entrap methane molecules. Abundant methane hydrate resources can be found on Earth, especially trapped in mineral porous rocks (e.g., clay, permafrost, seafloor, etc.). For this reason, understanding the thermodynamics and formation kinetics of methane hydrate confined in porous media is receiving a great deal of attention. In this thesis, we combine computer modeling and theoretical approaches to determine the thermodynamics and formation kinetics of methane hydrate confined in porous media. First, the state-of-the-art on the thermodynamics and formation kinetics of methane hydrate is presented. Second, different molecular simulation strategies, including free energy calculations using the Einstein molecule approach, the direct coexistence method, and the hyperparallel tempering technique, are used to assess the phase stability of bulk methane hydrate at various temperatures and pressures. Third, among these strategies, the direct coexistence method is chosen to determine the shift in melting point upon confinement in pores, ∆Tm=Tm^{pore}-Tm^{bulk} where Tm^{pore} and Tm^{bulk} are the melting temperatures of bulk and confined methane hydrate. We found that confinement decreases the melting temperature, Tm^{pore}≺Tm^{bulk}. The shift in melting temperature using the direct coexistence method is consistent with the Gibbs-Thompson equation which predicts that the shift in melting temperature linearly depends on the reciprocal of pore width, i.e., ∆Tm/Tm^{bulk}∼k{GB}/Dp. The quantitative validity of this classical thermodynamic equation to describe such confinement and surface effects is also addressed. The surface tensions of methane hydrate-substrate and liquid water-substrate interfaces are determined using molecular dynamics to quantitatively validate the Gibbs-Thompson equation. Molecular dynamics simulations are also performed to determine important thermodynamic properties of bulk and confined methane hydrate: (a) thermal conductivity λ using the Green-Kubo formalism and the autocorrelation function of the heat-flux and (b) the thermal expansion αP and isothermal compressibility κT. Finally, some conclusions and perspectives for future work are given.
Complete list of metadatas

Cited literature [250 references]  Display  Hide  Download

https://tel.archives-ouvertes.fr/tel-02181782
Contributor : Abes Star :  Contact
Submitted on : Friday, July 12, 2019 - 1:43:07 PM
Last modification on : Friday, November 6, 2020 - 3:02:14 PM

File

JIN_2018_diffusion.pdf
Version validated by the jury (STAR)

Identifiers

  • HAL Id : tel-02181782, version 1

Collections

Citation

Dongliang Jin. Thermodynamics and kinetics of methane hydrate formation in nanoporous media : theory and molecular simulation. Other [cond-mat.other]. Université Grenoble Alpes, 2018. English. ⟨NNT : 2018GREAY076⟩. ⟨tel-02181782⟩

Share

Metrics

Record views

138

Files downloads

257