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.

Many Arctic gas hydrate reservoirs such as those of the Prudhoe Bay and Kuparuk River area on the Alaska North Slope (ANS) are believed originally to be natural gas accumulations converted to hydrate after being placed in the gas hydrate stability zone (GHSZ) in response to ancient climate cooling. A mechanistic model is proposed to predict/explain hydrate saturation distribution in “converted free gas” hydrate reservoirs in sub-permafrost formations in the Arctic. This 1-D model assumes that a gas column accumulates and subsequently is converted to hydrate. The processes considered are the volume change during hydrate formation and consequent fluid phase transport within the column, the descent of the base of gas hydrate stability zone through the column, and sedimentological variations with depth. Crucially, the latter enable disconnection of the gas column during hydrate formation, which leads to substantial variation in hydrate saturation distribution. One form of variation observed in Arctic hydrate reservoirs is that zones of very low hydrate saturations are interspersed abruptly between zones of large hydrate saturations. The model was applied on data from Mount Elbert well, a gas hydrate stratigraphic test well drilled in the Milne Point area of the ANS. The model is consistent with observations from the well log and interpretations of seismic anomalies in the area. The model also predicts that a considerable amount of fluid (of order one pore volume of gaseous and/or aqueous phases) must migrate within or into the gas column during hydrate formation. This work offers the first explanatory model of its kind that addresses "converted free gas reservoirs" from a new angle: the effect of volume change during hydrate formation combined with capillary entry pressure variation versus depth. Mechanisms by which the fluid movement, associated with the hydrate formation, could have occurred are also analyzed. As the base of the GHSZ descends through the sediment, hydrate forms within the GHSZ. The net volume reduction associated with hydrate formation creates a “sink” which drives flow of gaseous and aqueous phases to the hydrate formation zone. Flow driven by saturation gradients plays a key role in creating reservoirs of large hydrate saturations, as observed in Mount Elbert. Viscous-dominated pressure-driven flow of gaseous and aqueous phases cannot explain large hydrate saturations originated from large-saturation gas accumulations. The mode of hydrate formation for a wide range of rate of hydrate formation, rate of descent of the BGHSZ and host sediments characteristics are analyzed and characterized based on dimensionless groups. The proposed transport model is also consistent with field data from hydrate-bearing sand units in Mount Elbert well. Results show that not only the petrophysical properties of the host sediment but also the rate of hydrate formation and the rate of temperature cooling at the surface contribute greatly to the final hydrate saturation profiles. / text

Replacement of the traditional thermodynamic hydrate inhibitors (methanol and glycols) in multiphase applications is highly desirable for Health, Safety & Environment (HSE) considerations and for investment costs savings. Low Dose Hydrate Inhibitors (LDHI) are good candidates to achieve this objective and their interest is growing in the E&P industry. There are two types of LDHI: the Kinetic Hydrate Inhibitors (KHI) and the Anti-Agglomerants (AA) also called dispersant additives. The main challenge with LDHIs is that they require the unprocessed effluents to be produced inside the hydrate stability zone. It is then of the utmost importance to select, qualify and implement properly LDHIs, so that their field deployment is performed with success. But due to the very stochastic nature of the nucleation step, the hydrate crystallisation process leads to very large discrepancies between performances results carried out at lab or pilot scales. In order to overcome this difficulty, we have developed an in-house special protocol which is implemented prior to each qualification tests series. This in-house 15 years old protocol consists in conducting each tests series with a fluids system having previously formed hydrates in a first step but followed by a dissociation step at moderate temperature for a few hours. This paper presents results selected from several field cases studies and obtained from our 80 bara and 165 bara flow loops. They show the very good reproducibility obtained with and without LDHIs. In the case of KHI, where the stochastic nature of the nucleation step is very critical, the results show that the deviation on the “hold time” for a given subcooling is less than 15%. (Revised version of ICGH paper 5499_1)

Dans les applications industrielles et lors des opérations de transport du gaz naturel, la présence d'eau sous forme liquide ou en phase vapeur peut entraîner la formation d'hydrates provoquant le colmatage des unités industrielles et des lignes de conduites et il est indispensable de définir précisément les seuils de déshydratation à réaliser, afin d'éviter la formation d'hydrates. Cela est réalisé à l'aide d'un modèle thermodynamique qui prédit la stabilité des hydrates, en fonction de la température, de la pression et de la composition du gaz.Les modèles thermodynamiques classiques, développés uniquement sur la base de données expérimentales de formation d'hydrates en présence d'eau liquide, surestiment fortement la température de dissociation des hydrates en l'absence d'une phase aqueuse.Dans le but de définir un modèle thermodynamique capable de représenter convenablement les équilibres de phases vapeur-hydrate et prédire ainsi la température de dissociation des hydrates que l'on soit en présence ou en l'absence d'eau liquide, nous avons mis au point une méthodologie originale pour la détermination de la température de dissociation des hydrates de corps purs et de mélanges en l'absence d'eau liquide. Cette méthodologie, basée sur le suivi de la teneur en eau de phase vapeur, en fonction de la température par coulométrie Karl Fischer, a permis la détermination de la température de dissociation de plusieurs hydrates simples et mixtes à des teneurs en eau et pressions différentes ainsi que les quantités d'hydrates formées dans ces conditions.Sur la base de ces nouvelles données, nous avons défini un modèle thermodynamique basé sur l'utilisation de l'approche de Dharmawardhana pour le calcul de la fugacité de l'eau dans l'hydrate vide,le potentiel de Kihara pour le calcul de la constante de Langmuir et l'équation d'état CPA (Cubic Plus Association) pour la modélisation des phases fluides. Nous avons montré que l'utilisation de l'équation d'état CPA, capable de prendre en compte l'auto association de l'eau apporte une amélioration très significative.Le développement d'un flash biphasique hydrate-fluide nous a permis de calculer les quantités d'hydrates mixtes formées et de les comparer à nos données expérimentales. / In industrial applications and during natural gas transport, the presence of water under liquid form or within a vapour phase can lead to gas hydrate formation causing the blockage of industrial units and transport lines. Hence, in order to avoid such situation, it is very important to well determine its formation conditions. It is occurred by using a rigorous thermodynamic model. Due to the lack of data in the literature concerning gas hydrates formation in the absence of an aqueous phase,usual thermodynamic models predict correctly gas hydrate dissociation temperature only in the presence of aqueous water. Our purpose is to propose a thermodynamic model with hydrate phase that can predict gas hydrate dissociation temperature in both cases: with and without water liquid phase.At first, using an existing apparatus, we have developed a new experimental protocol in order tomeasure gas hydrate dissociation temperature in the absence of liquid water. It consists in measuring the water content in the vapour phase as a function of the temperature by using a Karl Fischer coulometer. We have measured the dissociation temperature of many simple and mixture hydrates.We have also developed a thermodynamic model that is able to predict correctly gas hydrate dissociation temperature, in the absence and in the presence of liquid water. This model is based onthe use of Dharmawardhana's approach for the calculation of hydrate fugacity in the empty hypothetical hydrate, Kihara potential for the calculation of the Langmuir constant and CPA EoS forfluid phases modelling. We have shown that the use of CPA EoS improves the prediction of gas hydrate dissociation temperature. We have also developed a biphasic flash (hydrate-fluid) allowing the calculation of the formed mixture hydrate amounts. The calculated amounts are in agreement with the experimental ones.

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.

This thesis examines the prospect of structure H (sH) hydrate to be exploited for methane storage. The methane content in the hydrate, hydrate kinetics and conversion rates are areas of particular importance. Experiments and theory are employed at the macroscopic and molecular levels to study the relevant phenomena. sH hydrate was successfully synthesized from ice particles with full conversion achieved within a day when thermal ramping above the ice melting point was applied. It was found that a polar guest (tert-butyl methyl ether / TBME) wets ice more extensively compared to two hydrophobic guests (neo-hexane / NH and methyl-cyclohexane / MCH). TBME also has much higher solubility in water. Consequently, the system with TBME was found to exhibit the highest initial hydrate formation rate from ice particles or in water in a well stirred vessel. However, the rate with the hydrophobic guests was the fastest when the temperature exceeded the ice point. Thus, the applied temperature ramping compensated the slow kinetics below the ice point for the hydrophobic guests and allowed faster overall conversion than the polar guest. Structure, cage occupancy, composition and methane content in the hydrate were also determined by employing different techniques and the results were found to be consistent. It was found that the methane content in structure H hydrate with TBME was the smallest (103-125 v/v) whereas that with NH was 130-139 (v/v) and that with MCH was 132-142 (v/v). The methane content in structure II hydrate by using propane (C₃H₈) and tetrahydrofuran (THF) as the large guest molecule were also estimated. Optimal methane content was found at approximately 100 (v/v) for both C₃H₈ and THF systems with the large guest concentrations at 1% for C₃H₈ (10°C) and 1% for THF (room temperature). The gas content is of course lower than that for structure I hydrate (170 v/v) but one should consider the fact that the hydrate formation conditions are much lower (less than 1 MPa). Finally, MD simulations revealed for the first time the formation of defects in the cavities for the TBME/methane/water (sH hydrate) system which may affect hydrate stability and kinetics.

In this thesis seafloor cold vents are examined using autonomous underwater vehicle (AUV) and remotely operated vehicle (ROV) data on the Northern Cascadia margin. These data were collected in a 2009 joint cruise between the Monterey Bay Aquarium Research Institute (MBARI) and Natural Resources Canada (NRCan). High- resolution bathymetry data, acoustic reflectivity (backscatter) data, and 3.5 kHz sub bottom profiler data were examined for cold-vent-related features that include pockmarks, chemosynthetic biological communities (CBC), and authigenic carbonate. Additionally subsequent ROV observations, sediments from push cores and seafloor video/photos were used to ground truth AUV data. Numerous prolific venting sites were examined in detail and a model for the evolution of venting was generated. Vents are categorized as juvenile, intermediate, or mature depending on the presence and or absence of cold-vent-features. High near-surface reflection amplitudes are coincident with an anomalous area of seafloor backscatter. In June of 2012, NEPTUNE (North East Pacific Time-series Underwater Networked Experiment) collected a near-surface push core with their ROV ROPOS (Remotely Operated Platform for Ocean Sciences) in the high reflective area. The retrieved core showed stacked turbidites in the top 0.5 meters of the sediment column. Closely spaced high-velocity turbidite sands are highly reflective and inhibit acoustic penetration to depth. The presence of high-density, high-velocity sands in the near surface is linked to steady ocean bottom currents. These bottom currents progress northeast to southwest over the study area and differentially erode the surface sediments by removing muds and leaving heavy sands over the exposed area. / Graduate / 0373 / 0374 / jonfurlong@hotmail.com

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Pulverised fuel ash (PFA) is a reactive silica source used in the manufacture of autoclaved aerated concrete (AAC). Experiments studied the hydrothermal reactions of PFA samples from two UK power stations with calcium hydroxide at 457 K, for periods up to 21 h. These conditions are comparable to those used in the manufacture of AAC. The process is characterised by the rapid consumption of ash particles. Associated with this is the solubilisation of large amounts of silica, alumina and alkalis. The formation of a semi-crystalline calcium silicate hydrate and a hydrogarnet phase occurs during the early stages of autoclaving. The hydrogarnet phase persists under the conditions studied, but conversion of the calcium silicate hydrate into tobermorite occurs with prolonged autoclaving. Differences in the hydrothermal performance of the two PFA samples are evident, which cannot be explained by the bulk elemental composition. Ash fractions obtained from a centrifugal air classifier have different reactivities during autoclaving and can result in specimens with different compressive strengths. Quantitative x-ray diffractometry showed that high levels of aluminosilicate glass are associated with the fine ash fractions, whereas most quartz, haematite and magnetite is associated with the coarse fractions. Significant differences exist in the mineralogical analyses of the two sets of ash fractions obtained from the bulk ash samples. The coarse ash fractions have the most varied morphology and composition.