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Sediments collected from various cores in Mississippi Canyon 118 were tested to evaluate the abilities to promote natural gas hydrate formation. Memory effects for hydrate formation of sediments with in-situ seawater were of a major concern. The possible mechanisms of memory effects were combined to give an overall hypothesis on the bioproducts-mineral-microorganism system. Unique permanent memory effects in the sediment were found. Temperatures from 50 to 65°C dissipated all memory effects by disrupting microbial cell wall material. Bacillus subtilis is known to produce several types of biosurfactants, including surfactin. The catalytic effect of purified surfactin from B. subtilis on hydrate formation was studied in the presence of smectite clays. The interlayer spacings of clay minerals measured by X-ray powder diffraction indicated that hydrate formation and surfactin adsorption on the smectite clays have impacts on their structures. Laboratory gas mixture sequestering was also conducted by hydrate formation to study the various factors that may affect the separation of its hydrateorming gases. The effects of agitation, temperature, initial pressure and thermal conductors were explored.

This study presents a two-step desalination process, in which produced water is cleaned by forming gas hydrate in it and subsequently dewatering the hydrate to remove the residual produced water trapped in between the hydrate crystals. All experiments were performed with pressure in the range of 450 to 800psi and temperature in the range of -1 to 1°C using CO? as guest molecule for the hydrate crystals. The experiments were conducted using artificial produced waters containing different amounts of NaCl, CaCl₂ and MgCl₂ at varying temperature (T) and pressure (P). The results are presented as functions of %Reduction of difference chemical elements, CO? requirements and applied T and P conditions. The impact of dewatering techniques, including centrifuge and filtration process, on gas hydrate solid product is studied. The results showed that over 99% of dissolved NaCl and MgCl2 can be removed from artificial saline water in laboratory experiments. This was achieved in a process involving a single-stage hydrate formation step, followed by a single-step solid-liquid separation (or dewatering). The results also show that the %Reduction (percentage of the concentration decrease) of artificial produced water increases with centrifugation time and rotational speed (rpm). The %Reduction was increased considerably after hydrate crystals were crushed and filtered, indicating that the artificial process water was entrapped in between the hydrate crystals. It was found also that the finer the particle size, the higher the extent of salt removal. In general, filtration was a better than centrifugation for the removal of TDS (Total Dissolved Solids). / Master of Science

Natural gas hydrate, a type of inclusion compound or clathrate, are composed of gas molecules trapped within a cage of water molecules. The presence of gas hydrate has been confirmed by core samples recovered from boreholes. Interests in the distribution of natural gas hydrate stem from its potential as a future energy source, geohazard to drilling activities and their possible impact on climate change. However the current geophysical investigations of gas hydrate reservoirs are still too limited to fully resolve the location and the total amount of gas hydrate due to its complex nature of distribution. The goal of this thesis is twofold, i.e., to model (1) the heterogeneous gas hydrate reservoirs and (2) seismic wave propagation in the presence of heterogeneities in order to address the fundamental questions: where are the location and occurrence of gas hydrate and how much is stored in the sediments. Seismic scattering studies predict that certain heterogeneity scales and velocity contrasts will generate strong scattering and wave mode conversion. Vertical Seismic Profile (VSP) techniques can be used to calibrate seismic characterization of gas hydrate expressions on surface seismograms. To further explore the potential of VSP in detecting the heterogeneities, a wave equation based approach for P- and S-wave separation is developed. Tests on synthetic data as well as applications to field data suggest alternative acquisition geometries for VSP to enable wave mode separation. A new reservoir modeling technique based on random medium theory is developed to construct heterogeneous multi-variable models that mimic heterogeneities of hydrate-bearing sediments at the level of detail provided by borehole logging data. Using this new technique, I modeled the density, and P- and S-wave velocities in combination with a modified Biot-Gassmann theory and provided a first order estimate of the in situ volume of gas hydrate near the Mallik 5L-38 borehole. Our results suggest a range of 528 to 768×10^6 m^3/km^2 of natural gas trapped within hydrate, nearly an order of magnitude lower than earlier estimates which excluded effects of small-scale heterogeneities. Further, the petrophysical models are combined with a 3-D Finite Difference method to study seismic attenuation. Thus a framework is built to further tune the models of gas hydrate reservoirs with constraints from well logs other disciplinary data.

Natural gas hydrate, a type of inclusion compound or clathrate, are composed of gas molecules trapped within a cage of water molecules. The presence of gas hydrate has been confirmed by core samples recovered from boreholes. Interests in the distribution of natural gas hydrate stem from its potential as a future energy source, geohazard to drilling activities and their possible impact on climate change. However the current geophysical investigations of gas hydrate reservoirs are still too limited to fully resolve the location and the total amount of gas hydrate due to its complex nature of distribution. The goal of this thesis is twofold, i.e., to model (1) the heterogeneous gas hydrate reservoirs and (2) seismic wave propagation in the presence of heterogeneities in order to address the fundamental questions: where are the location and occurrence of gas hydrate and how much is stored in the sediments. Seismic scattering studies predict that certain heterogeneity scales and velocity contrasts will generate strong scattering and wave mode conversion. Vertical Seismic Profile (VSP) techniques can be used to calibrate seismic characterization of gas hydrate expressions on surface seismograms. To further explore the potential of VSP in detecting the heterogeneities, a wave equation based approach for P- and S-wave separation is developed. Tests on synthetic data as well as applications to field data suggest alternative acquisition geometries for VSP to enable wave mode separation. A new reservoir modeling technique based on random medium theory is developed to construct heterogeneous multi-variable models that mimic heterogeneities of hydrate-bearing sediments at the level of detail provided by borehole logging data. Using this new technique, I modeled the density, and P- and S-wave velocities in combination with a modified Biot-Gassmann theory and provided a first order estimate of the in situ volume of gas hydrate near the Mallik 5L-38 borehole. Our results suggest a range of 528 to 768×10^6 m^3/km^2 of natural gas trapped within hydrate, nearly an order of magnitude lower than earlier estimates which excluded effects of small-scale heterogeneities. Further, the petrophysical models are combined with a 3-D Finite Difference method to study seismic attenuation. Thus a framework is built to further tune the models of gas hydrate reservoirs with constraints from well logs other disciplinary data.

Gas hydrates are a well-known problem in the oil and gas industry and cost millions of dollars in production and transmission pipelines. To prevent this problem, it is important to predict the temperature and pressure under which gas hydrates will form. Of the thermodynamic models in the literature, only a couple can predict the hydrate-formation temperature or pressure for complex systems including inhibitors. I developed two simple correlations for calculating the hydrate-formation pressure or temperature for single components or gas mixtures. These correlations are based on over 1,100 published data points of gas-hydrate formation temperatures and pressures with and without inhibitors. The data include samples ranging from pure-hydrate formers such as methane, ethane, propane, carbon dioxide and hydrogen sulfide to binary, ternary, and natural gas mixtures. I used the Statistical Analysis Software (SAS) to find the best correlations among variables such as specific gravity and pseudoreduced pressure and temperature of gas mixtures, vapor pressure and liquid viscosity of water, and concentrations of electrolytes and thermodynamic inhibitors. These correlations are applicable to temperatures up to 90ºF and pressures up to 12,000 psi. I tested the capability of the correlations for aqueous solutions containing electrolytes such as sodium, potassium, and calcium chlorides less than 20 wt% and inhibitors such as methanol less than 20 wt%, ethylene glycol, triethylene glycol, and glycerol less than 40 wt%. The results show an average absolute percentage deviation of 15.93 in pressure and an average absolute temperature difference of 2.97ºF. Portability and simplicity are other advantages of these correlations since they are applicable even with a simple calculator. The results are in excellent agreement with the experimental data in most cases and even better than the results from commercial simulators in some cases. These correlations provide guidelines to help users forecast gas-hydrate forming conditions for most systems of hydrate formers with and without inhibitors and to design remediation schemes such as: · Increasing the operating temperature by insulating the pipelines or applying heat. · Decreasing the operating pressure when possible. · Adding a required amount of appropriate inhibitor to reduce the hydrateformation temperature and/or increase the hydrate-formation pressure.

Bacillus subtilis capable of producing surfactin was cultured to evaluate effects of microbial cell mass on natural gas hydrate formation, dissociation, and stability characteristics. The direct molecular influences of microbial cell wall polymers inhibited gas hydrate formation significantly, decreased hydrate formation rates, and increased dissociation rates. Upon the introduction of bentonite, significant synergy was observed in the system in the form of a catalytic effect. Microbes cultured from seafloor seawater-saturated sediments collected from Mississippi Canyon 118 (MC-118) produced similar effects and generalized the observed trends. MC-118 cultures also produced biosurfactant in several culture media, which was shown to catalyze natural gas hydrate formation in porous media. Microorganisms inhabit gas hydrate macrostructures and consume hydrocarbons and other substrates from within. Sulfate reduction and anaerobic hydrocarbon oxidation occurred within gas hydrate during incubations with MC-118 indigenous consortia. A mathematical model was developed to explore the diffusion-reaction implications in massive seafloor gas hydrates.

No description available.

Gas hydrate formation was studied in Gulf of Mexico (GOM) sediments. Sediments studied were from six-meter long cores from Mississippi Canyon Block 118 and a 27-meter core from a cruise in 2002 of the Marion Dufresne. These sediments retained their in situ seawater before testing. Hydrate formation rate and induction times were measured. The hydrate memory effect was studied in GOM sediments with and without in situ seawater. Hydrate induction time was short when in situ seawater was present. Bioproducts adsorbed on particles in the sediments are postulated to shorten the induction times by maintaining seawater structuring around coated particles. Hydrate nucleation was studied by Dynamic Light Scattering and Scanning Electron Microscopy. Particles around 50 to 100 nm nucleated hydrate formation. These small nucleating particles appeared to be clays or surfactant molecules and interactions thereof. Hydrate capillaries were studied and found to be at least 100 nm in diameter because the sediment nucleating particles with bioproducts diffused through the hydrate capillaries. Large complexes of nontronite smectite clay and Emulsan, an anionic biosurfactant, were found to facilitate hydrate formation. It was determined that Emulsan entered the interlayer of nontronite. The clay contents of the GOM sediments were determined. All sediments contained smectite, illite, chlorite, and kaolinite in different proportions. The study gave new insight into the gas hydrate formation mechanism in seafloor sediments.

The ability of marine controlled-source electromagnetic (MCSEM) methods to help image electrical conductivity contrasts below the Earth’s surface makes them useful for both initial reconnaissance surveying for hydrocarbons and for delineating prospective regions of high resistivity in development drilling. A 3-D finite-element MCSEM Fortran algorithm used for forward modeling was developed by Badea. Additional code was written and used for this thesis, with the goal of enforcing more realistic electromagnetic (EM) Dirichlet boundary value conditions. The results of the new boundary conditions on a MCSEM survey model, with a hydrocarbon-saturated region in the subsurface, show that the method does not work as hoped. Constant boundary values were applied to gauge the transmitter-receiver (TXRX) range at which results are not boundary influenced, using a hydrate/hydrocarbon model of the subsurface, at each of the three transmitter frequencies used in this study (1 Hz, 3 Hz, and 10 Hz). Results showed that electric field data were reliable to roughly 5000 m of TX-RX offset for the 1 Hz and 3 Hz cases, and to 6500 m offset for 10 Hz. The gas hydrate/hydrocarbon model was then run with zero-value boundary conditions. The goal was to determine what effect changing parameters of the gas hydrate, including hydrate radius, thickness, and depth, have on the EXEXS (xcomponent of secondary electric field inline with the transmitter dipole axis) curves at various offset, particularly in relation to a hydrocarbon-only model of the subsurface response, so as to evaluate the EM masking effect the hydrate has on the hydrocarbon. The results showed that the x-component of electric field in an inline survey is dominated by the hydrate response, in all cases studied, with a couple of exceptions. One exception is 1 Hz transmitter frequency at 2500 m to 3000 m offset when depth to top of the massive gas hydrate zone was greater or equal to 250 m. Receivers at these offsets would successfully detect the hydrocarbon target.