Mathematical model, which depicts on macroscopic scale the physical phenomena occurring during the decomposition of gas hydrate, was set up and applied to the spherical methane hydrate pellet decomposing into ice. Initially, porous hydrate pellet is at uniform temperature and pressure within hydrate stable region. The pressure starts to decrease at t=0 with a fixed rate down to the final pressure and is kept constant afterwards. The bounding surface of pellet is heated by convection. Governing equations are based on the conservation principles, the phase equilibrium relation, equation of gas state and phase change kinetics. The single-domain approach and volume average formulation are employed to take into account transient change of local pressure, volumetric liberation of latent enthalpy, and convective heat and mass transfer accompanied by the decomposed gas flow through hydrate/ice solid matrix. The algorithm called “enthalpy method” is extended to deal with non-equilibrium phase change and utilized to determine local phase volume fractions. Predicted results suggest that the present numerical implementation is capable of predicting essential features of heat and mass transfer during non-equilibrium decomposition of hydrate pellet.

It is becoming increasingly recognized that the flood of anthropogenic CO2 into the atmosphere should be reduced in order to mitigate the Earth’s atmospheric greenhouse and slow climate change. If immediate action is required, then a number of greenhouse gas reduction strategies may need to be implemented even before complete study of their impacts can be fully understood. Energy production through combustion produces large amounts of CO2 in a relatively small number of locations at which CO2 capture and compression to a liquid, transportable form can be achieved. Physical disposal offers the best option for sequestering this waste CO2. Because of the costs of transportation, geological sequestration will be most applicable for one set of power plants, deep ocean sequestration may be most applicable for some others. In both cases, the sequestration processes can provide some economic benefits. Ocean CO2 disposal can produce desalinated, treated water as a byproduct.

Understanding when hydrates will nucleate has notable importance in the area of flow assurance. Attempts to model hydrate formation in subsea pipelines currently requires an arbitrary assignment of a nucleation subcooling. Previous studies showed that sII hydrate containing a model water-soluble former, tetrahydrofuran, would nucleate over a narrow temperature range of a few degrees with constant cooling. It is desirable to know if gas phase hydrate formers, which are typically more hydrophobic and hence have a very low solubility in water, also exhibit this nucleation behavior. In this study, differential scanning calorimetry has been applied to determine the hydrate nucleation point for gas phase hydrate formers. Constant cooling ramps and isothermal approaches were combined to explore the probability of hydrate nucleation. In the temperature ramping experiments, methane and xenon were used at various pressures and cooling rates. In both systems, hydrate nucleation occurred over a narrow temperature range (2-3°C). Using methane at lower pressures, ice nucleated before hydrate; whereas at higher pressures, hydrate formed first. A subcooling driving force of around 30°C was necessary for hydrate nucleation from both guest molecules. The cooling rates (0.5-3°C/min) did not show any statistically significant effect on the nucleation temperature for a given pressure. The isothermal method was used for a methane system with pure water and a water-in-West African crude emulsion. Two isotherms (-5 and -10°C) were used to determine nucleation time. In both systems, the time required for nucleation decreased with increased subcooling.

Here, we present a dissolution study of exposed hydrate from outcrops at Barkley Canyon. Previously, a field experiment on synthetic methane hydrate samples showed that mass transfer controlled dissolution in under-saturated seawater. However, seafloor hydrate outcrops have been shown to have significant longevity compared to expected dissolution rates based upon convective boundary layer diffusion calculations. To help resolve this apparent disconnect between the dissolution rates of synthetic and natural hydrate, an in situ dissolution experiment was performed on two distinct natural hydrate fabrics. A hydrate mound at Barkley Canyon was observed to contain a “yellow” hydrate fabric overlying a “white” hydrate fabric. The yellow hydrate fabric was associated with a light condensate phase and was hard to core. The white hydrate fabric was more porous and relatively easier to core. Cores from both fabrics were inserted to a mesh chamber within a few meters of the hydrate mound. Time-lapse photography monitored the dissolution of the hydrate cores over a two day period. The diameter shrinkage rate for the yellow hydrate was 45.5 nm/s corresponding to a retreat rate of 0.7 m/yr for an exposed surface. The white hydrate dissolved faster at 67.7 nm/s yielding a retreat rate of 1.1 m/yr. It is possible these hydrate mounds were exposed due to the fishing trawler incident in 2001. If these dissolution experiments give a correct simulation, then the exposed faces should have retreated ~ 3.5 m and 5.5 m, respectively, from 2001 to this expedition in August 2006. While the appearance of the hydrate mounds appeared quite similar to photographs taken in 2002, these dissolution experiments show natural hydrate dissolves rapidly in ambient seawater. The natural hydrate dissolution rate is on the same order as the synthetic dissolution experiment strongly implying another control for the dissolution rates of natural hydrate outcrops. Several factors could contribute to the apparent longevity of these exposed mounds from upward flux of methane-rich fluid to protective bacterial coatings.

The dissociation behavior of the CH4+CO2 binary gas hydrate has been investigated using Nuclear Magnetic Resonance (NMR) spectroscopy. This technique allows us to distinguish the hydrate structure present, as well as to quantify phase concentrations. Single-pulse excitation was used in combination with magic-angle spinning (MAS). Time-resolved in situ decomposition experiments were carried out at different compositions in sealed, pressurized samples. The decomposition profiles of the CH4+CO2 binary gas hydrate system obtained at various compositions suggest that the decomposition rate is a strong function of the fractional cage occupancy and temperature. An unexpected CH4 hydrate reformation was observed during our decomposition experiments when the temperature reached the ice melting point. A decrease on the CO2 content in the hydrate phase was found during the decomposition experiment, as the pressure and temperature of the system increases.

Hydrate plugging of hydrocarbon production conduits can cause large operational problems resulting in considerable economical losses. Modeling capabilities to predict hydrate plugging occurrences would help to improve facility design and operation in order to reduce the extent of such events. It would also contribute to a more effective and safer remediation process. This paper systematically describes different operational scenarios where hydrate plugging might occur and how a hydrate plug formation prediction tool would be beneficial. The current understanding of the mechanisms for hydrate formation, agglomeration and plugging of a pipeline are also presented. The results from this survey combined with the identified industrial needs are then used as a basis for the assessment of the capabilities of an existing hydrate plug formation model, called CSMHyK (The Colorado School of Mines Hydrate Kinetic Model). This has recently been implemented in the transient multiphase flow simulator OLGA as a separate module. Finally, examples using the current model in several operational scenarios are shown to illustrate some of its important capabilities. The results from these examples and the operational scenarios analysis are then used to discuss the future development needs of the CSMHyK model.

This thesis studies methane hydrate crystal formation and decomposition at 1.0, 4.0 and 7.0°C in a new apparatus. Hydrate was formed in the interstitial space of a variable volume bed of silica sand particles with an average diameter equal to 329μm (150 to 630μm range). The initial pressure inside the reactor was 8.0MPa for all the formation experiments. Three bed sizes were employed in order to observe the effects of the silica sand bed size on the rate of methane consumption (formation) and release (decomposition). The temperature at various locations inside the silica sand bed was measured with thermocouples during formation and decomposition experiments. For the decomposition experiments, two different methods were employed to dissociate the hydrate: thermal stimulation and depressurization. It was found that more than 74.0% of water conversion to hydrates was achieved in all hydrate formation experiments at 4.0°C and 1.0°C starting with a pressure of 8.0MPa. The dissociation of hydrate was found to occur in two stages when thermal stimulation was employed whereas three stages were found during depressurization. In both cases, the first stage was strongly affected by the changing bed size whereas it was not found to depend on the bed size afterwards.

Carbon dioxide CO₂capture through hydrate formation is a novel technology under consideration as an efficient means of separating CO₂from flue/fuel gas mixtures for sequestration and enhanced oil recovery operations. This thesis examines post-combustion capture of CO₂from fossil-fuel power plant flue-gas streams through hydrate formation in a silica gel column. Power plant flue-gas contains essentially CO₂and nitrogen (N2) after suitable pre-treatment steps, thus a model flue-gas comprising 17% co₂and 83% N2 was used in the study. Previous studies employed a stirred-tank reactor to achieve water-gas contact for formation of hydrates; recent microscopic studies involved using water dispersed in silica gel to react with gas, showing potential for improved hydrate formation rates without the need for agitation. This study focuses on macroscopic kinetics of hydrate formation in silica gel to evaluate hydrate formation rates, CO₂separation efficiency and determining optimal silica gel properties as a basis for a CO2 capture process. Spherical silica gels with 30.0 and 100.0 nm pore sizes and 40-75 and 75-200 μm particle sizes were studied to determine pore size and particle size effects on hydrate formation. 100.0 nm pores achieved higher gas uptake and CO₂recovery over the 30.0 nm case. Improved CO₂separation was obtained when 75-200 μm particles with 100.0 nm pores were used. The two effects observed are due to improved gas diffusion occurring with larger pore and particle size, favouring increased hydrate formation. Compared to stirred-tank experiments, results in this study show a near four-fold increase in moles of gas incorporated in the hydrate per mole of water, showing that improved water-to-hydrate conversion is obtained with pore-dispersed water. At similar experimental conditions, CO₂recovery improved from 42% for stirred-tank studies to 51% for the optimum silica (100.0 nm 75-200 μm) determined in this study. Finally, effects of tetrahydrofuran (THF) - an additive that reduces operating pressure were evaluated. Experiments with 1 mol% THF, the optimum determined from previous stirred tank studies, showed improved gas consumption in silica but reduced CO₂recovery, indicating that the optimum concentration for use in silica is different from that in stirred-tank experiments.

Hydrochloric acid leaching of saprolite nickel ores has been proposed as an effective means of recovering nickel and cobalt. However, the leach produces a concentrated brine of magnesium chloride which must be hydrolyzed to recover the HCl lixiviant. The processing of carnallite similarly produces a concentrated MgCl2 brine; converting this brine into HCl and MgO provides an attractive way of adding value while effectively disposing of this waste product. Direct pyrohydrolysis of magnesium chloride brines by the reaction, MgCl2,a + H2Oa  MgOs + 2HClg is energy-intensive as large volumes of water must be evaporated. The energy cost is high, and the HCl stream produced is limited to approximately 20 wt% HCl. This thesis explores alternative methods of obtaining HCl from aqueous magnesium chloride solutions. Two methods are considered: the hydrolysis, under autogenous pressure, of concentrated MgCl2 molten salt hydrates; and the precipitation of magnesium hydroxychloride compounds such as 2MgO·MgCl2·6H2O and 3MgO·MgCl2·11H2O, which are subsequently decomposed at high temperature. Considerable experimental difficulties were encountered in studying pressure hydrolysis of molten salt hydrates, despite extensive equipment modifications. Ultimately, the work moved on to precipitation and decomposition of hydroxychlorides. This was found to bear promise, and conceptual flowsheets based on these reactions are presented. A phase stability diagram giving the areas of predominance of the different hydroxychloride phases is presented, and fundamental thermochemical data are derived. The results of a kinetic study on magnesium hydroxychloride thermal decomposition are also presented. / Thesis (Ph.D, Mining Engineering) -- Queen's University, 2011-03-11 10:14:53.455

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