As the oil industry moves from a heuristic of avoidance of hydrates to a heuristic of risk management time dependent phenomena of hydrate formation and plugging must be known. One of the key parameters to this process is the aggregation of hydrate particles, the fractal networks they form, and the effect these two parameters have on flow. Unfortunately the aggregation and fractal structure information is extremely difficult to acquire experimentally, for this reason a three-dimension discrete element method (3D-DEM) model has been implemented. The 3D-DEM model calculates detailed solutions to Newton's equations of motion for individual particles. In addition these particles are coupled with the surrounding fluid through computational fluid dynamics (CFD). This coupled 3D-DEM can be used to investigate what the effects of shear, suspending viscosity, attractive forces, and other relevant variables have on the structure, stresses, and positions of the hydrate particles over time. In addition, the effect on viscosity has been calculated using CFD and compared back to basic hard sphere theory.

A number of notable studies on pure ionic clathrate hydrates have utilized their unique ionic characteristics for electric applications, including their use as an electrolyte for nickel-metal hydride batteries. Although quaternary ammonium salt hydrates have recently been applied to gas separation and storage areas with the expectation of the small co-guest occupancy in empty cages, most of the researches have been oriented to macroscopic approaches based on hydrate phase equilibria and many other process variables. On the other hand, spectroscopic analyses for identifying the structure transition of ionic clathrate hydrates together with a comprehensive consideration of their complex phase patterns have not yet been reported in spite of their importance to the energy and environmental fields. Accordingly, in this study, we present the report of an extraordinary structural transition accompanying the occurrence of more than two coexisting clathrate hydrate phases and channel-induced tuning pattern in ionic double hydrate systems. In particular, the tuning observation uniquely occurring in the ionic clathrate hydrates is quite surprising, even though the tuning behavior is more commonly observed in the non-ionic hydrate systems. The remarkable feature of this work is that the icy ionic hydrate materials can be effectively used in energy devices. Moreover, the microscopic analyses of ionic clathrate hydrates for identifying the physicochemical characteristics are expected to provide new insights into a variety of inclusion chemistry fields.

L’utilisation des coulis d’hydrates comme Fluides Frigoporteurs Diphasiques (FFD) permet de réduire l’impact environnemental des systèmes frigorifiques car ces fluides possèdent une densité énergétique élevée. Leur application pour le stockage d’énergie thermique serait une réponse à une problématique industrielle de distribution de froid (climatisation, procédés de refroidissement). Un montage expérimental constitué d’une boucle de circulation et d’un réacteur de formation a été utilisé afin d’évaluer les caractéristiques thermo-hydrauliques des coulis d’hydrates de CO2 et a permis de déterminer les viscosités et les coefficients d’échange convectif des coulis. A l’aide de ces paramètres, une étude énergétique et exergétique a été réalisée sur le système. Cette étude a permis de développer un modèle numérique capable d’évaluer la distribution de l’énergie dans différents éléments du montage expérimental (réacteur de formation des hydrates et échangeur de chaleur pour la dissociation des hydrates), ainsi que de déterminer les pertes exergétiques engendrées par ces éléments. Un bon accord entre les données expérimentales et le modèle numérique pour le suivi en température du coulis lors de sa formation et dissociation a été montré. L’étude a confirmé que les fluides diphasiques présentent une plus grande efficacité énergétique et moins de pertes exergétiques que les fluides monophasiques. / Hydrates slurries as two-phase secondary refrigerants (FFD) reduces the environmental impact of refrigeration systems because these fluids have a high energy density. Their use for cold storage could be a solution to an industrial cold distribution at various temperature levels (air-conditioning, cooling process or preservation temperature). An experimental device composed of a circulation loop and a formation tank enables to characterize the thermal-hydraulic properties of CO2 hydrates slurries in order to determine the viscosities and the convective heat transfer coefficients of hydrates slurries. With these hydraulic and thermal parameters, an energy study was carried out on the system. Within this study a numerical model was developed to evaluate the energy distribution in different experimental elements (hydrate formation tank and hydrates dissociation heat exchanger) and to determine the exergetic losses created by these components. A good agreement between the experimental data and the numerical model for the temperature evolution of the slurry has been shown. The study has confirmed that multi-phases fluids provide higher energy efficiency and less exergetic losses than one-phase fluids.

The concept which led to the establishment of the research in natural gas hydrate production, was born by Dr. Robert Amin (currently Professor of Petroleum Engineering at Curtin University and Chair of the Woodside Research Foundation) and Alan Jackson of Woodside Energy. The intended research in this field is to establish the viability of utilizing a synthesised natural gas hydrate as a means to allow a cheaper form of transportation of natural gas from the wellhead to the customer in direct competition with liquefied natural gas (LNG). Natural gas exists in ice-like formations called hydrates found on or under sea-beds and under permafrost. Hydrates trap methane molecules inside a cage of frozen water, where the amount of hydrates trapped is dependent on surrounding formation pressure. The amount of natural gas trapped in hydrates is largely unknown, but it is very large. A number of scientists believe that hydrates contain more than twice as much energy as all the world's coal, oil, and natural gas combined, hence making it a viable option of fuel in the 21st century, in a world constantly seeking cleaner sources of energy. The feasibility of production of natural gas hydrates on offshore installations and onshore facilities makes this development a viable option. As such this technology requires detailed research and development in a laboratory environment coupled with a pilot plant construction for commercial operation. Current estimates for onshore based facilities for the production of hydrates show a cost reduction of approximately 25% compared with LNG plants of the same energy capacity. / There are two major issues which require detailed research and development in order to progress this technology. First is the enhancement of the hydrates production by the use of other additives, and second, the continuous production at near atmospheric pressures. Other research related to transport methodology and re-gasification will be essential for the overall success of this technology, however, this work is outside the scope of this research.

The interaction between sunlight and our atmosphere is one of the most fundamental processes affecting weather and climate. The majority of the Sun�s radiation is produced in the ultraviolet, visible and near-infrared regions of the electromagnetic spectrum. These spectral regions correspond to the energies of vibrational overtone and electronic transitions. The composition of our atmosphere is complex, and many trace species have a large influence on its chemistry and dynamics. Hydrogen bound hydrated complexes are trace species that could play an important role in the Earth�s atmosphere. However, before this role can be quantified, spectral identification and characterisation of these complexes is essential. We have developed vibrational local mode Hamiltonians to simulate the absorption spectra of hydrated complexes. To test the approximations made in the vibrational model, we have peformed calculations on the diatomics OH, HF and CO, which can be considered to act as pure local modes. When highly correlated ab initio methods and large basis sets are used to calculate the potential energy and dipole moment curve, the simulated vibrational transitions of the diatomics are in excellent agreement with experiment. We have derived approximate vibrational Hamiltonians which describe the OH-stretching and HOH-bending modes of vibration in the complexes H₂O�H₂O, H₂O�HO₂ and H₂O�HO. The calculated spectrum of H₂O�H₂O has been used to assess its atmospheric importance, and to succesfully guide experimental efforts to detect H₂O�H₂O in the laboratory and the Earth�s atmosphere. The calculated transition energies and intensities of H₂O�H₂O and H₂O�HO are in good agreement with experimental matrix isolation and gas-phase studies. To investigate the effect of low frequency modes on OH-stretching overtone spectra we have simulated the spectrum of HOONO. We have derived a Hamiltonian that couples the NOOH-torsional mode to the high frequency OH-stretching and OOH-bending modes. The simulated spectrum is in good agreement with the experimentally observed spectrum. We find that the OH-stretching spectra are perturbed strongly only if the barrier to torsion is low. We have also investigated changes in the electronic spectrum of hydrated complexes and the corresponding parent monomers. Upon complex formation, the lowest-lying electronic transition in the hydroxyl radical is strongly redshifted outside the region of monomeric absorption.

A gas hydrate refers to the state in which hydrogen-bonded water molecules form a rigid lattice structure of so-called "cages", wherein "guest" molecules of natural gas are entrapped. Not unlike ice, gas hydrates are prone to form at low temperatures and high pressures; however, their crystalline structure allows them to remain stable at temperatures and pressures under which the phase limits of ice would otherwise be exceeded. To date, a number of instances of gas hydrates forming in the subsurface of Arctic climates below layers of permafrost have been identified, however the challenge of identifying past occurrences of methane hydrates during episodes of global cooling and glacial advance remains relatively unmet. During these periods of glacial/permafrost cover, the presence of hydrates could have a significant impact on the groundwater flow system due to the significant reduction of the porosity and permeability of hydrate saturated sediments. The purpose of this study is to investigate whether there is evidence to suggest that methane hydrates could have formed in the sedimentary units of the Michigan Basin at the Bruce nuclear site near Kincardine, Ontario, particularly when subjected to the impacts of glacial ice sheet loading. This study aims to provide insight into whether the potential impact of gas hydrates should be considered in the design of the proposed deep-geologic repository (DGR) for low- and intermediate-level nuclear waste. This study presents a framework employing regional-scale numerical modelling to estimate the evolution of temperature, pressure and salinity profiles across the study area, combined with thermodynamic predictive modelling to identify potential paleo-methane hydrate stability zones in the subsurface at the Bruce nuclear site. This study represents the first step to ultimately assess the extent of paleo-methane hydrates and their impact on subsurface conditions at the site. Transient subsurface conditions at the Bruce nuclear site were modelled over a period of 120,000 years (120 ka), encompassing episodes of glacial advance and retreat during the Pleistocene epoch. The spatial and transient outputs from numerical modelling of the study area were then used as inputs to thermodynamic predictive modelling of methane hydrate stability. The results of this study show that, based upon the subsurface temperature, pressure and salinity histories determined using a three-dimensional regional-scale numerical modelling approach, paleo-conditions at the Bruce nuclear site become conducive with methane hydrate stability during the study period. Two separate episodes of methane hydrate stability were identified - lasting from 62.5 to 56 thousand years before present (kaBP) and from 23 to 13.5 kaBP, respectively - which were found to correspond to periods of glacial advance across the study area. The vertical extent of the estimated hydrate stability zones varied across the site, however it generally followed the limits of the Upper Silurian units, penetrating to deeper elevations towards the south west end of the study area.

The thermal properties of hydrate bearing sediments remain poorly studied, in part due to measurement difficulties inside the hydrate stability envelope. In particular, there is a dearth of experimental data on hydrate-bearing sediments, and most available measurements and models correspond to bulk gas hydrates. However, hydrates in nature largely occur in porous media, e.g. sand, silt and clay. The purpose of this research is to determine the thermal properties of hydrate-bearing sediments under laboratory conditions, for a wide range of soils from coarse-grained sand to fine-grained silica flour and kaolinite. The thermal conductivity is measured before and after hydrate formation, at effective confining stress in the range from 0.03 MPa to 1 MPa. Results show the complex interplay between soil grain size, effective confinement and the amount of the pore space filled with hydrate on the thermal conductivity of hydrate-bearing sediments.

Thesis (M.S.)--West Virginia University, 2001. / Title from document title page. Document formatted into pages; contains xi, 59 p. : ill. Includes abstract. Includes bibliographical references (p. 57-59).

Thesis (M. Phil.)--University of Hong Kong, 1999. / Title from title frame. Includes bibliographical references (leaves 154-159).

published_or_final_version / abstract / toc / Dentistry / Master / Master of Philosophy