Thesis (M.S. in E.A.S.)--School of Earth and Atmospheric Sciences, Georgia Institute of Technology, 2004. Directed by Daniel Lizarralde. / Includes bibliographical references (leaves 69-73).

No description available.

Gas hydrates are a topic of great interest and intense investigation. Traditionally, these compounds have been seen as a nuisance to the oil and gas industry, which can plug pipelines and cause hours of costly downtime. More recently, gas hydrates have been viewed as a possible energy source due to the vast amount of methane trapped in the form of gas hydrate. Many researchers have also proposed the possibility of transporting natural gas in the form of gas hydrate may be safer and more economical than using liquid or compressed natural gas. Gas hydrate may also offer the possibility of reducing greenhouse gas emissions via the sequestration of carbon dioxide. / Surfactants have been found to act as both promoters and inhibitors of hydrate formation. In the present study, the formation rate, solubility and mass transfer conductance of methane in the presence of Gemini surfactant, a new class of surfactants, was studied with varying concentration of Gemini surfactant. The experiments to determine the formation rates of methane hydrate were conducted at 4°C and 6500 kPa. While the experiments to determine solubility and mass conductance were carried out at 4°C and 3800 kPa. The resulting values were used to determine experimental accuracy and reproducibility by comparing the values obtained with literature values and by analyzing the distribution of the data obtained. Solubility measurements were extremely close to literature values with only a 1.4% difference. The distribution of solubility values and formation rates did not deviate significantly between replicates indicating a high degree of reproducibility; however, a lot of variability was observed in mass transfer conductance. This may be attributed to the fact that mass transfer was not determined experimentally by regressing a coefficient to fit a curve, which may be less accurate than other experimentally determined parameters. / In the second part of the study, the formation rate, solubility and mass transfer conductance of methane were determined using aqueous Gemini surfactant solutions. The experiments to determine the formation rates of methane hydrate were conducted at 4°C and 6500 kPa. While the experiments to determine solubility and mass transfer conductance were carried out at 4°C and 3800 kPa. The resulting values were used to determine the effect of Gemini surfactant on the properties of interest by comparing the values obtained with aqueous Gemini surfactant with the values previously obtained for pure water. The results obtained showed that solubility increased with increasing concentrations of Gemini surfactant with solubility increasing by up to 18% for higher concentration of Gemini surfactant. The mass transfer conductance was also found to increase by up to 49%; however other than the existence of an increase, no conclusive relationship could be determined between the concentration of Gemini surfactant and mass transfer conductance. / Finally, the formation rate of gas hydrates was found to decrease slightly, relative to water, at low concentrations, increased linearly at subsequently higher concentrations and ultimately plateau at a maximum. This trend was in agreement with similar experiments found in literature and the increase in formation rate may be attributed to the increase in both solubility and mass transfer conductance when using aqueous Gemini surfactant.

No description available.

Gas hydrates are crystalline compounds made of gas and water molecules. Methane hydrates are found in marine sediments and permafrost regions; extensive amounts of methane are trapped in the form of hydrates. The unique behavior of hydrate-bearing sediments requires the development of special research tools, including new numerical algorithms (tube- and pore-network models) and experimental devices (high pressure chambers and micromodels). Hydraulic conductivity decreases with increasing variance in pore size distribution; while spatial correlation in pore size reduces this trend, both variability and spatial correlation promote flow focusing. Invading gas forms a percolating path while nucleating gas forms isolated gas bubbles; as a result, relative gas conductivity is lower for gas nucleation than for gas invasion processes, and constitutive models must be properly adapted for reservoir simulations. Physical properties such as gas solubility, salinity, pore size, and mixed gas conditions affect hydrate formation and dissociation; implications include oscillatory transient hydrate formation, dissolution within the hydrate stability field, initial hydrate lens formation, and phase boundary changes in real field situations. High initial hydrate saturation and high depressurization favor gas recovery efficiency during gas production from hydrate-bearing sediments. Even a small fraction of fines in otherwise clean sand sediments can cause fines migration and concentration, vuggy structure formation, and gas-driven fracture formation during gas production by depressurization.

Thesis (Ph. D.)--Chemistry and Biochemistry, Georgia Institute of Technology, 2008. / Committee Chair: Dr. Boris Mizaikoff; Committee Member: Dr. Andrew Lyon; Committee Member: Dr. Donald R. Webster; Committee Member: Dr. Facundo M. Fernandez; Committee Member: Dr. Joseph Montoya. Part of the SMARTech Electronic Thesis and Dissertation Collection.

Natural gas hydrates store a substantial portion of the Earth's organic carbon, although their occurrence is restricted by thermobaric boundaries and the availability of methane-rich fluids. The complexity of geological systems and the multiphase flow processes promoting hydrate formation can result in a mismatch between the predicted and the observed hydrate distribution. The purpose of this research is to achieve a better comprehension of the factors that influence the distribution of gas hydrates and the mechanism of fluid movements beneath and across the gas hydrate stability zone (GHSZ). Therefore, this study integrates seismic, petrophysical and geochemical data from different gas hydrate provinces. This work provides evidence that hydrates can occur below bottom-simulating reflectors, in the presence of sourcing thermogenic hydrocarbons. The relationship between fluid-escape pipes and gas hydrates is further explored, and pipe-like features are suggested to host a significant volume of hydrates. The host lithology also represents a critical factor influencing hydrate and free gas distribution and, in evaluating a natural gas hydrate system, needs to be considered in conjunction with the spatial variability in the methane supply. The three-dimensional distribution of gas hydrate deposits in coarse-grained sediments, representing the current target for hydrate exploration, is shown to be correlated with that of the underlying free gas zone, reflecting sourcing mechanisms dominated by a long-range advection. In such systems, the free gas invasion into the GHSZ appears controlled by the competition between overpressure and sealing capacity of the gas hydrate-bearing sediments. Globally, the thickness of the free gas zones is regulated by the methane supply and by different multi-phase flow processes, including fracturing, capillary invasion and possibly diffusion. In conclusion, this research indicates that geological, fluid flow and stability factors interweave at multiple scales in natural gas hydrate systems.

Recently, carbon dioxide injection into deep sea sediments has become one of the carbon dioxide mitigation methods since carbon dioxide hydrates are stable at the prevailing pressure and temperature conditions. The Black Sea, which is one of the major identified natural methane hydrate regions of the world, can be a good candidate for carbon dioxide storage in hydrate form. Injected carbon dioxide under the methane hydrate stability region will be in contact with methane hydrate which should be analyzed thoroughly in order to increase our understanding on the gaseous carbon dioxide and methane hydrate interaction. For the storage of huge amounts of CO2, geological structure must contain an impermeable barrier. In general such a barrier may consist of clay or salt. In this study, sealing efficiency of methane hydrate and long term fate of the CO2 disposal under the methane hydrate zone is investigated. In order to determine the interaction of CO2 and CH4 hydrate and the sealing efficiency of CH4 hydrate, experimental setup is prepared and various tests are performed including the CH4 hydrate formation in both bulk conditions and within sand particles, measurement of the permeability of unconsolidated sand particles that includes 30% and 50% methane hydrate saturations and injection of CO2 into the CH4 hydrate. Results of the experiments indicate that, presence of hydrate sharply decreases the permeability of the unconsolidated sand system and systems with hydrate saturations greater than 50% may act as an impermeable layer. Also, CO2-CH4 swap within the hydrate cages is observed at different experimental conditions. As a result of this study, it can be concluded that methane hydrate stability region in deep sea sediments would be a good alternative for the safe storage of CO2. Therefore, methane hydrate stability region in the Black Sea sediments can be considered for the disposal of CO2.

Gas hydrate consists of guest gas molecules encaged in water molecules. Methane is the most common guest molecule in natural hydrates. Methane hydrate forms under high fluid pressure and low temperature and is found in marine sediments or in permafrost region. Methane hydrate can be an energy resource (world reserves are estimated in 20,000 trillion m3 of CH4), contribute to global warming, or cause seafloor instability. Research documented in this thesis starts with an investigation of hydrate formation and growth in the pores, and the assessment of formation rate, tensile/adhesive strength and their impact on sediment-scale properties, including volume change during hydrate formation and dissociation. Then, emphasis is placed on identifying the advantages and limitations of different gas production strategies with emphasis on a detailed study of CH4-CO2 exchange as a unique alternative to recover CH4 gas while sequestering CO2. The research methodology combines experimental studies, particle-scale numerical simulations, and macro-scale analyses of coupled processes.

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.