The question of when gas hydrate will become a commercially viable resource most concerns those nations with the most severe energy deficiencies. With the vast potential attributed to gas hydrate as a new gas play, the interest is understandable. Yet the resource potential of gas hydrate has persistently remained just over the horizon. Technical and economic hurdles have pushed back the timeline for development, yet considerable progress has been made in the past five years. An important lesson learned is that an analysis of the factors that control the formation of high grade hydrate deposits must be carried out so that both exploration and recovery scenarios can be modeled and engineered. Commercial hydrate development requires high concentrations of hydrate in porous, permeable reservoirs. It is only from such deposits that gas may be recovered in commercial quantities. While it is unrealistic to consider the global potential of gas hydrate to be in the hundreds of thousands of tcfs, there is a strong potential in the hundreds of tcfs or thousands of tcfs. Press releases from several National gas hydrate research programs have reported gas hydrate “discoveries”. These are, in fact, hydrate shows that provide proof of the presence of hydrate where it may previously only have been predicted. Except in a few isolated areas, valid resource assessments remain to be accomplished through the identification of suitable hosts for hydrate concentrations such as sandstone reservoirs. A focused exploration effort based on geological and depositional characteristics is needed that addresses hydrate as part of a larger petroleum system. Simply drilling in areas that have identifiable bottom simulating reflectors (BSRs) is unlikely to be a viable exploration tool. It is very likely that with drilling on properly identified targets, commercial development could become a reality in less than a decade.

The experimental formation of natural gas hydrate on pendant water droplet exposed to natural gas was conducted and visually observed under the pressures from 3.86MPa to 6.05MPa. The temperature was set at 274.75K and 273.35K. The diameter of the pendant water droplet was around 4mm. The nucleation and growth of hydrate film on the pendant water drop exhibited a generalized trend. The film initially generated at the boundary between the water drop and suspension tube, and afterwards grew laterally and longitudinally on the surface of the water drop. The phenomenon of the two layers of hydrate films growing on the pendant water drop distinguished from the experiments on the sessile water drop. The effect of the driving force that resulted from the overpressure from the three equilibrium pressure on the hydrate nucleation and growth was investigated. It was found that the elevation of the driving force reduced the nucleation time and shortened the process of the hydrate growth on the pendant water drop. The crystals on the hydrate shell became coarser with the increase of the driving force. The mechanism for the hydrate film formation and growth on static pedant water droplet included four stages, such as nucleation, generation of the hydrate film, growth of the hydrate film, and hydration below the hydrate shell.

After reviewing the documents about the studies of hydrate formation kinetics in the world, this paper analyzed the process of hydrate formation on a suspended water droplet, which was based on the hydrate formation with water spay method, proposed a corresponding mathematical model, and solved it. Afterwards, the discussion about this model was presented. The results indicated that equilibrium time diminished with the decrease of the water droplet radius, and prolonged with the increase of sub-cooling degree, the reaction time for the second period reduced with the increase of subcooling degree, but was free from the effect of the variation of the water droplet size. The first period of the hydration on the water droplet was quite short, while the second period was considerably longer. Therefore, shortening the duration time of the second period of hydration was obviously able to accelerate the hydrate formation on the water droplet.

Gas hydrates are found worldwide and many studies have been carried out to develop an efficient method to identify and quantify them using various geophysical as well as other anomalies. In this study, various seismic anomalies related to gas hydrates and the underlying gas are analysed, and correlated them to rock physics properties. Observations of velocities in sediments containing gas hydrates show that the rigidity, and hence the velocity of sediments increases with increase of hydrate saturation. The increase of velocity due to the presence of gas hydrate can be explained in terms of gradual cementation of the sediment matrix. In the case of seismic attenuation, gas hydrate bearing sediments are quite different from common sedimentary rock behaviour of low seismic attenuation with high rigidity. In contrary gas hydrate bearing sediments is observed to have increased seismic attenuation of higher frequencies with increase of hydrate saturation. This strange phenomenon can be explained in terms of differential fluid flow within sediment and hydrate matrix. Also it is observed that the presence of large amount of gas hydrate can result in an increase of seismic amplitudes, a signature similar to the presence of small amount of gas. Hence misinterpretation of these enhanced amplitudes could result in the under estimation of gas present not only as shallow drilling hazard but also on the resource potential of the region. The increase of seismic reflection amplitude results from the formation of gas hydrates in selective intervals causing strong positive and negative impedance contrasts across the formations with and without gas hydrates.

The Scotian margin of the east coast of Canada has a large theoretical gas hydrate stability zone (GHSZ) yet review of extensive industry seismic data reveals a prominent BSR at only one location. 3D seismic reflection and long offset (9 km) pre-stack 2D multichannel seismic data were used to study the velocity structure and geophysical characteristics of the hydrate zone and surrounding regions. The Mohican Channel study area shows a unique double BSR at 300 to 450 m below the seafloor in the western section of the study area immediately adjacent to the Mohican Channel in a water depth range of 1500- 1930m. The topmost BSR (BSR 1) is the more extensive of the two covering an area of 150 km2 in the 3D volume and a calculated area of 280 km2 using 2D industry and single-channel seismic profiles outside of the study area. BSR 2 covers an area of ~50 km2 and occurs approximately 80m below BSR 1. A system of polygonal faults is prominent in the area and some faults appear as conduits for gas leakage into the GHSZ. Fluid escape features are common on the surface of BSR 1 but rare on the seafloor suggesting that fluid flux is at lower levels than in the past.

Design and construction of long term gas hydrate production facilities will require assessment of the in situ formation response to production at a field scale. Key parameters such as temperature and pressure are critical for the determination of phase conditions, others such as formation resistivity, formation acoustic properties and fluid mobility support the inference of gas hydrate saturation, permeability and porosity. An ability to continuously monitor the response of these parameters during the course of a production test would facilitate tracking of the dissociation front and yield valuable information for engineering design and verification of numerical reservoir simulators. Such a monitoring system has been designed, developed and introduced as a part of the Japan Oil, Gas and Metals National Corporation and Natural Resources Canada gas hydrate production testing program carried out in the winter of 2007 in the Mackenzie Delta, Canada. While the deployment of some sensors and the acquisition of some data sets were limited due to operational problems encountered during the field program, considerable experience has been gained during all phases of the research program. In particular, the acquisition and interpretation of downhole temperature profiles and changes in formation electrical potentials during testing provide insight into the production response of the reservoir and may assist in the understanding of operational conditions and related decision-making processes.

Stable isotope of natural gas hydrates provides useful information of their gas sources. We investigated the isotopic fractionation of gas molecules during the formation of synthetic gas hydrates composed of methane and ethane. The gas hydrate samples were experimentally prepared in a pressure cell and isotopic compositions (δ13C and δD) of both residual and hydratebound gases were measured. δD of hydrate-bound molecules of methane and ethane hydrates was several per mil lower than that of residual gas molecules in the formation processes, while there was no difference in the case of δ13C. Effect of temperature on the isotopic fractionation was also investigated and it was found that the fractionation was effective at low temperature.

Ice-associating proteins (IAPs) are proteins that interact directly with ice crystals, either by offering a site for nucleation, i.e. ice nucleating proteins (INPs), or by binding to nascent crystals to prevent addition of more water molecules, i.e. antifreeze proteins (AFPs). AFPs have been found to inhibit the formation of clathrate-hydrates, ice-like crystalline solids composed of water-encaged guest molecules. Study of AFP-hydrate interaction is leading to a greater understanding of AFP adsorption and of the mechanism behind the “memory effect” in hydrates, wherein previously frozen crystals reform more quickly after a brief melt. AFP is currently the only known memory inhibitor. Such a low-dosage hydrate inhibitor (LDHI) is of great interest to the oil and gas industry, as hydrate formation and reformation in the field is a huge problem. Bacterial AFPs, though largely uncharacterized, may be the best candidates for large-scale production of hydrate inhibitors, given the difficulties in obtaining AFP from other sources. The popular kinetic inhibitors (KIs) polyvinylpyrrolidone (PVP) and polyvinylcaprolactam (PVCap) were used for points of comparison in experiments exploring the hydrate-inhibition activity of several ice-associating bacteria and proteins. The addition of the soil microbe, Chryseobacterium, increased the average lag-time to tetrahydrofuran (THF) hydrate formation by 14-fold, comparable to PVP or PVCap. Samples containing Pseudomonas putida, a bacterium having both ice-nucleation protein (INP) and AFP activity, had lag-times double that of the control. Solutions with P. putida and Chryseobacterium sometimes formed hydrate slurries of stunted crystal nuclei instead of solid crystals. No inhibition of memory or nucleation was noted in bacterial assays, however bacteria with INP activity was linked to unusually rapid memory reformation. Quartz crystal microbalance experiments with dissipation (QCM-D) showed that a tight adsorption to SiO2 and resistance to rinsing are correlated with a molecule’s inhibition of hydrate formation and reformation. These results support a heterogeneous nucleation model of the memory effect, and point to the affinity of AFP for heterogeneous nucleating particles as an important component of memory inhibition. / Thesis (Master, Biology) -- Queen's University, 2008-05-30 15:20:38.749

This thesis examines the sensitivity of the marine controlled source electromagnetic (CSEM) method to sub-seafloor resistivity structure, with a focus on gas hydrate and free gas occurrences. Different analysis techniques are applied with progressive sophistication to a series of studies based on simulated and measured data sets. CSEM data are modelled in time domain for one-dimensional models with gas hydrate, free gas and/or permafrost occurrences. Linearized and non-linear inversion methods are considered to infer subsurface models from CSEM data. One study applies forward modelling and singular value decomposition to estimate uncertainties for permafrost models of the Beaufort Sea. This simulation study analyzes the resolution of the CSEM data for shallow water depth which is a challenging case because the electromagnetic signature of the air-water boundary may mask the sub-seafloor response. The results reveal a blind window as a function of water depth in which the CSEM data are insensitive to the sub-seafloor structure. However, the CSEM data are sensitive to the top and the bottom of the permafrost with increasing uncertainties with depth. The next study applies non-linear Bayesian inversion to CSEM data acquired in 2005/2006 on the Northern Cascadia margin to investigate sub-seafloor resistivity structure related to gas hydrate deposits and cold vents. Bayesian inversion provides a rigorous approach to estimate model parameters and uncertainties by probabilistically sampling of the parameter space. The resulting probability density function is interpreted here in terms of posterior median models, marginal and joint marginal probability densities for model parameters and credibility intervals. The Bayesian information criterion is applied to determine the amount of structure (number of layers) that can be resolved by the data. The parameter space is sampled with the Metropolis-Hastings algorithm in principal-component space. Non-linear, probabilistic inversion allows the analysis of unknown acquisition parameters such as time delays between receiver and transmitter clocks or unknown source amplitude. The estimated posterior median models and credibility intervals from Bayesian CSEM inversion are compared to reflection seismic data to provide a more complete geological interpretation. The CSEM data on the Northern Cascadia margin generally reveal a 1 to 3 layer sediment structure. Inversion results at the landward edge of the gas hydrate stability zone indicate a sediment unconformity as well as several potential cold vents which were previously unknown. The resistivities generally increase upslope due to sediment erosion along the slope. Inversion results on the middle slope infer several vent systems close to well-known Bullseye vent in agreement with ongoing interdisciplinary observations. Finally, a trans-dimensional (trans-D) Bayesian inversion is applied to CSEM data acquired in 2012 in the German North Sea to investigate possible free gas occurrences. Trans-D inversion treats the number of layers as an additional unknown sampled probabilistically in the inversion. %over the parameter space by evaluating probabilistically the transition to a higher or lower number of interfaces. Parallel tempering is applied to increase sampling efficiency and completeness. Inversion results for the German North Sea yield resistivities at the seafloor which are typical for marine deposits, while resistivities at greater depth increase slightly and can be correlated with a transition from fine-grained marine deposits (Holocene age) to coarse-grained, glacial sediments (Pleistocene age), which is observed in a sediment core. The depths of layer interfaces estimated from CSEM inversion match the seismic reflector related to the contrast between the two depositional environments. The CSEM survey targeted a strong, phase-reversed, inclined seismic reflector within the glacial sediments, potentially indicating free gas. While interface-depth estimates from CSEM inversion do not correlate closely with this reflector, resistivities are generally elevated above the strong seismic amplitudes and the thickness of the resistive layer follows the trend of the inclined reflector. However, the uncertainties of deeper interface depth estimates increase significantly and overlap with the targeted reflector at some of the measurement sites. Relatively low resistivities of a third layer correlate with sediments of late-Miocene origin with a high gamma-ray count indicating an increased amount of fine-grained sediments with organic material. The interface at the bottom of the third layer has wide uncertainties which relates to the penetration limit of the CSEM array. / Graduate

Gas hydrates are a solid, ice-like mixture of water and low molecular weight hydrocarbons. They are found under the permafrost and to a far greater extent under the ocean, usually at water depths greater than 300m. Hydrates are a potential energy resource, a possible factor in climate change, and a geohazard. For these reasons, it is critical that gas hydrate deposits are quantitatively assessed so that their concentrations, locations and distributions may be established. Due to their ice-like nature, hydrates are electrically insulating. Consequently, a method which remotely detects changes in seafloor electrical conductivity, such as marine controlled source electromagnetics (CSEM), is a useful geophysical tool for marine gas hydrate exploration. Hydrates are geometrically complex structures. Advanced electromagnetic modelling and imaging techniques are crucial for proper survey design and data interpretation. I develop a method to model thin resistive structures in conductive host media which may be useful in building approximate geological models of gas hydrate deposits using arrangements of multiple, bent sheets. I also investigate the possibility of interpreting diffusive electromagnetic data using seismic imaging techniques. To be processed in this way, such data must first be transformed into its non-diffusive, seismic-like counterpart. I examine such a transform from both an analytical and a numerical point of view, focusing on methods to overcome inherent numerical instabilities. This is the first step to applying seismic processing techniques to CSEM data to rapidly and efficiently image resistive gas hydrate structures. The University of Toronto marine electromagnetics group has deployed a permanent marine CSEM array offshore Vancouver Island, in the framework of the NEPTUNE Canada cabled observatory, for the purposes of monitoring gas hydrate deposits. In this thesis I also propose and examine a new CSEM survey technique for gas hydrate which would make use of the stationary seafloor transmitter already on the seafloor, along with a cabled receiver array, towed from a ship. I furthermore develop a modelling algorithm to examine the electromagnetic effects of conductive borehole casings which have been proposed to be placed in the vicinity of this permanent marine CSEM array, and make preliminary recommendations about their locations.