The statistics of liquid-to-crystal nucleation are measured for clathrate-forming mixtures of tetrahydrofuran and water using an automatic lag time apparatus (ALTA). We measure the nucleation temperature where a single sample is repeatedly cooled, nucleated and thawed. This is done for a series of tetrahydrofuran concentrations and in several different sample tubes since the nucleation is heterogeneous and occurring on the tube wall. The measurements are also done at the same concentrations and tubes but with an added catalyst, a single crystal of silver iodide. We discuss the need for this type of measurement if the true nucleation temperature of the clathrate is to be found. Comparisons are also made with our high pressure data on real-world clathrate formers.

Hundreds of pockmarks and mounds, which seismic reflection sections show to be underlain by chimney-like structures, exist in southeast part of the Vøring plateau, Norwegian continental margin. These chimneys may be representative of a class of feature of global importance for the escape of methane from beneath continental margins and for the provision of a habitat for the communities of chemosynthetic biota. Thinning of the time intervals between reflectors in the flanks of chimneys, observed on several high-resolution seismic sections, could be caused by the presence of higher velocity material such as hydrate or authigenic carbonate, which is abundant at the seabed in pockmarks in this area. Evidence for the presence of hydrate was obtained from cores at five locations visited by the Professor Logachev during TTR Cruise 16, Leg 3 in 2006. Two of these pockmarks, each about 300-m wide with active seeps within them, were the sites of high-resolution seismic experiments employing arrays of 4-component OBS (Ocean-Bottom Seismic recorders) with approximately 100-m separation to investigate the 3D variation in their structure and properties. Shot lines at 50-m spacing, run with mini-GI guns fired at 8-m intervals, provided dense seismic coverage of the sub-seabed structure. These were supplemented by MAK deep-tow 5-kHz profiles to provide very high-resolution detail of features within the top 1-40 m sub-seabed. Travel-time tomography has been used to detail the variation in Vp and Vs within and around the chimneys. Locally high-amplitude reflectors of negative polarity in the flanks of chimneys and scattering and attenuation within the interiors of the chimneys may be caused by the presence of free gas within the hydrate stability field. A large zone of free gas beneath the hydrate stability field, apparently feeding several pockmarks, is indicated by attenuation and velocity pull-down of reflectors.

While alternative natural gas transportation technologies against currently available pipeline or liquefied natural gas (LNG) are expected to develop to be suitable for small and medium or remote gas fields, Mitsui Engineering & Shipbuilding Co., Ltd. (MES) has been studying natural gas hydrate (NGH) transportation chain and advocated at ICGH2005 the NGH chain was economical compared with conventional LNG system under some conditions. Meanwhile, MES has been carrying out research and development on the relevant technology development including construction of 600 kg/day class NGH production and pelletizing plants and a re-gasification facility and the process technology resulted from this R&D leads to the forthcoming demonstration plant of 5 ton/day production (under construction) to be dedicated to the demonstration project of small-lot NGH land transportation in western Japan. As the latest achievement, MES and Mitsui & Co., Ltd. (Mitsui) established NGH Japan Co., Ltd. (NGHJ) in April 2007, in order to study in detail on actual viability of NGH ocean transportation chain. NGHJ, MES and Mitsui have been conducting a practical feasibility study on certain cases in Southeast Asia in cooperation with 6 Japanese leading companies related to natural gas businesses. The study suggests that NGH chain was appropriate as a media for transportation from Southeast Asia to Japan and regional transportation within Southeast Asia in view of economics.

This work deals with the problem of pipeline plugging by gas hydrates during oil production. Gas hydrates are crystals resulting from water and gas molecules association under high pressure and low temperature conditions. Such thermodynamical conditions are generally encountered during oil production and transport, particularly in deep offshore fields or in cold areas. Due to an agglomeration process which is still debated, hydrate occurrence can lead to plug formation. This study aims at improving the understanding in this mechanism process, in the case of water-in-oil emulsions. Therefore, ice or hydrate particle agglomeration is compared. Ice or trichlorofluoromethane (CCl3F) hydrate particles dispersed in xylene with asphaltenes as surfactant is chosen as a model system. As CCl3F hydrates are stable under atmospheric pressure, it allows us to apply different techniques without being limited by high pressure conditions. The Nuclear Magnetic Resonance (NMR) technique is used. The very different relaxation rate for solids or liquids is used to monitor in situ the ratio between solid and total hydrogen or fluorine as a function of time with controlled shearing conditions. Thus, a kinetic study is realized, that enabled to know the amount of ice formed. The apparent viscosity of the system, during crystallization and plugging, is also followed with rheometry in order to characterize agglomeration. This experimental approach allows us to highlight that physico-chemistry of interface water/oil has an important role in agglomeration. It enables us to discuss different mechanisms of agglomeration of ice and hydrate particles in a hydrocarbon phase.

A one-kilometer-diameter carbonate/hydrate mound in Mississippi Canyon Block 118 has been chosen to be the site of a multi-sensor, multi-discipline sea-floor observatory. Several surveys have been carried out in preparation for installing the observatory. The resulting data set permits discussing the mound’s structure in some detail. Samples from the water column and intact hydrate outcrops show gas associated with the mound to be thermogenic. Lithologic and bio-geochemical studies have been done on sediment samples from gravity and box cores. Pore-fluid analyses carried out on these cores reveal that microbial sulfate reduction, anaerobic methane oxidation, and methanogenesis are important processes in the upper sediment. These microbial processes control the diffusive flux of methane into the overlying water column. The activity of microbes is also focused within patches near active vents. This is primarily dependent upon an active flux of hydrocarbon-rich fluids. The geochemical evidence suggests that the fluid flux waxes and wanes over time and that the microbial activity is sensitive to such change. Swath bathymetry by AUV combined with sea-floor video provides sub-meter resolution of features on the surface of the mound. Seismic reflection profiling with source-signature processing resolves layer thicknesses within the upper 200-300m of sediment to about a meter. Exploration-scale 3-D seismic imaging shows that a network of faults connects the mound to a salt diapir a few hundred meters below. Analyses of gases from fluid vents and hydrate outcrops imply that the faults act as migration conduits for hydrocarbons from a deep, hot reservoir. Source-signature-processed seismic traces provide normal-incidence reflection coefficients at 30,000 locations over the mound. Picking reflection horizons at each location allows a 3-D model of the mound’s interior to be constructed. This model provides a basis for understanding the movement of fluids within the mound.

The use of Kinetic Hydrate Inhibitors (KHI) is one of the optimum methods employed to control gas hydrate formation issues and provide flow assurance in oil and gas production systems. The application of this technology has several advantages to operators, including significant cost savings and extended life of oil and gas systems. This paper will highlight a specific case where a Major operator in the North Sea (UK sector) significantly reduced the cost of well intervention operations by applying a KHI in a subsea gas lift line. Considerable cost savings were realized by reducing volume of chemical required and this enabled the application to be performed from the FPSO eliminating the need for a dedicated Diving Support Vessel (DSV). Furthermore, the application of KHI also reduced manual handling and chemical logistics usually associated with this particular treatment. In order to prevent mineral scale deposition occurring in downhole tubing and near well bore and in the formation; scale inhibitor squeeze applications are standard practice. For subsea wells the fluids can be pumped down in to the well via gas lift lines. However, upon completion of previous scale squeeze operations at this particular location, hydrate formation was observed when a mixture of MEG and water was used following interventions via the gas lift line. By applying 1% KHI with a mixture of MEG and Water, the well was brought back into production following scale squeeze operations without hydrate formation occurring.

Formation condition data for methane hydrate in ammonia + water and ammonia + water + tetrahydrofunan (THF) systems are very important for the process development and the determination of operation condition for recycling the vent gas of ammonia synthesis using hydrates. This paper focused on the formation conditions of methane hydrate in the presence of NH3 + H2O and NH3 + H2O + THF system. Equilibrium data of methane hydrate in the temperature, pressure and concentration ranges from 277 to 291 K, 0 to 8 MPa, 1 to 5 % ammonia, were obtained. The experimental results indicate that ammonia has an inhibitive effect on hydrate formation. The higher the concentration of ammonia is, the higher the formation pressure for methane hydrate will be.

In this paper, the effect of additives on COB2B hydrate formation is investigated in a high-pressure test cell surrounded by a thermostated coolant bath. An agitator is configured inside the cell. The characteristics of COB2B gas hydrate formation with additives SDS, THF and mixture of both were discussed. It was found that, in a quiescent system with single SDS，hydrate could form rapidly and the induction time of hydrates formation was reduced, while THF shows no improvement effect on COB2B hydrate formation. However, the mixture of SDS and THF can promote the hydrate formation rate considerably, and large amount of hydrates formed. In a stirring system with mixture additives, hydrates can form completely about 100 minutes early than that in the quiescent system.

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.

13C NMR spectroscopic analysis was carried out to clarify the formed hydrate structure in specific conditions on hydrate phase diagram of ternary methane, neohexane, and water system. The obtained NMR spectra at three different conditions suggested that both structure I and H were formed simultaneously and coexisted at 273.6 K and 50 bar. But, for both conditions of 273.6 K, 25 bar and 283.1 K, 50 bar the formed hydrate was identified as structure H only. These results showed that the pure CH4 hydrate of structure I was formed and coexisted with mixed CH4+neohexane hydrate of structure H in low temperature and high pressure region after passing through the phase boundary of pure CH4 hydrate. We have examined the structure coexistence at 273.6 K and 50 bar with other structure H formers of isopentane, methylcyclopentane, and methylcyclohexane. In case of isopentane, the obtained NMR spectrum showed that structure I and H coexisted and the amount of methane molecules in structure I was two times as many as in cages of structure H. However, there were no resonance lines of structure I when methylcyclohexane formed structure H with methane molecules.