Methane hydrate nucleation and growth in porous model carbon materials illuminates the way towards the design of an optimized solid-based methane storage technology. High-pressure methane adsorption studies on pre-humidified carbons with well-defined and uniform porosity show that methane hydrate formation in confined nanospace can take place at relatively low pressures, even below 3 MPa CH4, depending on the pore size and the adsorption temperature. The methane hydrate nucleation and growth is highly promoted at temperatures below the water freezing point, due to the lower activation energy in ice vs. liquid water. The methane storage capacity via hydrate formation increases with an increase in the pore size up to an optimum value for the 25 nm pore size model-carbon, with a 173% improvement in the adsorption capacity as compared to the dry sample. Synchrotron X-ray powder diffraction measurements (SXRPD) confirm the formation of methane hydrates with a sI structure, in close agreement with natural hydrates. Furthermore, SXRPD data anticipate a certain contraction of the unit cell parameter for methane hydrates grown in small pores.

Methane hydrate nucleation and growth in porous model carbon materials illuminates the way towards the design of an optimized solid-based methane storage technology. High-pressure methane adsorption studies on pre-humidified carbons with well-defined and uniform porosity show that methane hydrate formation in confined nanospace can take place at relatively low pressures, even below 3 MPa CH4, depending on the pore size and the adsorption temperature. The methane hydrate nucleation and growth is highly promoted at temperatures below the water freezing point, due to the lower activation energy in ice vs. liquid water. The methane storage capacity via hydrate formation increases with an increase in the pore size up to an optimum value for the 25 nm pore size model-carbon, with a 173% improvement in the adsorption capacity as compared to the dry sample. Synchrotron X-ray powder diffraction measurements (SXRPD) confirm the formation of methane hydrates with a sI structure, in close agreement with natural hydrates. Furthermore, SXRPD data anticipate a certain contraction of the unit cell parameter for methane hydrates grown in small pores.

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / O objetivo do presente trabalho é apresentar um estudo sobre o equilíbrio de fases sólido-líquido-vapor para hidratos de metano. A análise do equilíbrio trifásico sólido-líquido-vapor tem encontrado diversas aplicações para sistemas hidrocarboneto-água, uma vez que permite, por exemplo, a determinação da região de estabilidade de hidratos de metano e hidratos de gás natural. Inicialmente foi feita uma pesquisa sobre o estado da arte no que diz respeito ao comportamento termodinâmico e equilíbrio de fases de hidratos. Foram implementados os modelos apresentados por Ballard (2002) e Zhang et al. (2005). A proposta de Zhang et al. (2005) é aplicável para equilíbrios de fases a temperaturas abaixo de 300 K. Sua abordagem combinou a teoria de van der Waals e Platteeuw para a fase hidrato com a equação do estado de Peng-Robinson (1976) modificada por Stryjek e Vera (1986) para ambas as fases fluidas (fase vapor e fase aquosa). A abordagem de Ballard (2000) considerou a distorção do hidrato do seu estado padrão, o que fornece uma exata composição do hidrato e melhora a previsão da formação dos hidratos a altas pressões. Ao esclarecer a mudança de volume no hidrato, o raio da gaiola do hidrato é uma função do seu volume. Com isso, Ballard propôs uma nova abordagem considerando tal variação de volume e gerou um equilíbrio de fases em uma rotina de flash multifásico através da minimização da energia livre de Gibbs. Assim, o presente trabalho apresenta as abordagens de Zhang et al. (2005) e Ballard (2002) para o comportamento termodinâmico de hidratos e faz uma análise e comparação entre eles. Para resolver o problema do flash computacionalmente, foi utilizada a ferramenta lsqnonlin (built-in do software MATLAB). O lsqnonlin é um algoritmo baseado no método de Levenberg-Marquadt. / The objective of the present work is to present a study of solid-vapor-liquid three-phase equilibrium for methane hydrates. The analysis of three-phase equilibrium has several applications for water-hydrocarbon systems, since it permits, for example, determination of stability region for methane hydrates and natural gas hydrates. We have started seeking in literature about the state-of-art for thermodynamic behaviour and phase equilibrium for hydrates. And then the models proposed by Ballard (2002) and Zhang et al. (2005) were implemented. Zhang et al. (2005) have proposed a phase equilibrium for single-guest gas hydrates at temperatures below 300 K. Their approach has combined the van der WaalsPlatteeuw theory for the hydrate phase and the PengRobinson equation of state for both fluid phases (vapor and aqueous phase) (1976) modified by Stryjek and Vera (1986). Ballards (2000) approach has allowed the hydrate distortion from its standard state and has gave a more accurate composition of the hydrate and has improved hydrate formation predictions at high pressures. As a direct result of accounting for a changing hydrate volume, the cage radii were functions of the hydrate volume. Thus, Ballard have proposed the hydrate phase equilibrium by Gibbs energy minimization in a multi-phase flash routine. Thus, this work presents the Zhang et al. (2005) and Ballards (2002) approaches for hydrate thermodynamic behavior and makes an analysis and comparison of them. To compute the flash problem, we use the tool lsqnonlin (built-in of MATLAB software). The algorithm lsqnonlin is based on the Levenberg-Marquadt method.

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / O objetivo do presente trabalho é apresentar um estudo sobre o equilíbrio de fases sólido-líquido-vapor para hidratos de metano. A análise do equilíbrio trifásico sólido-líquido-vapor tem encontrado diversas aplicações para sistemas hidrocarboneto-água, uma vez que permite, por exemplo, a determinação da região de estabilidade de hidratos de metano e hidratos de gás natural. Inicialmente foi feita uma pesquisa sobre o estado da arte no que diz respeito ao comportamento termodinâmico e equilíbrio de fases de hidratos. Foram implementados os modelos apresentados por Ballard (2002) e Zhang et al. (2005). A proposta de Zhang et al. (2005) é aplicável para equilíbrios de fases a temperaturas abaixo de 300 K. Sua abordagem combinou a teoria de van der Waals e Platteeuw para a fase hidrato com a equação do estado de Peng-Robinson (1976) modificada por Stryjek e Vera (1986) para ambas as fases fluidas (fase vapor e fase aquosa). A abordagem de Ballard (2000) considerou a distorção do hidrato do seu estado padrão, o que fornece uma exata composição do hidrato e melhora a previsão da formação dos hidratos a altas pressões. Ao esclarecer a mudança de volume no hidrato, o raio da gaiola do hidrato é uma função do seu volume. Com isso, Ballard propôs uma nova abordagem considerando tal variação de volume e gerou um equilíbrio de fases em uma rotina de flash multifásico através da minimização da energia livre de Gibbs. Assim, o presente trabalho apresenta as abordagens de Zhang et al. (2005) e Ballard (2002) para o comportamento termodinâmico de hidratos e faz uma análise e comparação entre eles. Para resolver o problema do flash computacionalmente, foi utilizada a ferramenta lsqnonlin (built-in do software MATLAB). O lsqnonlin é um algoritmo baseado no método de Levenberg-Marquadt. / The objective of the present work is to present a study of solid-vapor-liquid three-phase equilibrium for methane hydrates. The analysis of three-phase equilibrium has several applications for water-hydrocarbon systems, since it permits, for example, determination of stability region for methane hydrates and natural gas hydrates. We have started seeking in literature about the state-of-art for thermodynamic behaviour and phase equilibrium for hydrates. And then the models proposed by Ballard (2002) and Zhang et al. (2005) were implemented. Zhang et al. (2005) have proposed a phase equilibrium for single-guest gas hydrates at temperatures below 300 K. Their approach has combined the van der WaalsPlatteeuw theory for the hydrate phase and the PengRobinson equation of state for both fluid phases (vapor and aqueous phase) (1976) modified by Stryjek and Vera (1986). Ballards (2000) approach has allowed the hydrate distortion from its standard state and has gave a more accurate composition of the hydrate and has improved hydrate formation predictions at high pressures. As a direct result of accounting for a changing hydrate volume, the cage radii were functions of the hydrate volume. Thus, Ballard have proposed the hydrate phase equilibrium by Gibbs energy minimization in a multi-phase flash routine. Thus, this work presents the Zhang et al. (2005) and Ballards (2002) approaches for hydrate thermodynamic behavior and makes an analysis and comparison of them. To compute the flash problem, we use the tool lsqnonlin (built-in of MATLAB software). The algorithm lsqnonlin is based on the Levenberg-Marquadt method.

Formation of gas hydrates is an important feature of water systems. It occurs undesirably in natural gas pipelines, but also in deep-sea deposits and unfreezing permafrost. However, the natural occurrence is of particular interest because methane hydrates have one of the highest energy densities of all naturally occurring forms of methane. Therefore, an accurate description of its thermodynamic properties is required. In this work, we demonstrate how the material properties of methane hydrate can be more easily calculated compared to ab initio methods. Furthermore, it is shown how the material properties depend on the cage occupancy by using the comparably fast self-consistent-charge density-functional tight-binding (SCC-DFTB) method. The cell potential is calculated and compared to a numerical as well as an ab initio model, and is in good agreement with the literature.