The reformation of methane-ethane hydrate was observed in situ using 13C MAS NMR spectroscopy. In all reformation experiments, structure I (stable state for the reformation conditions) reformed, and the hydrate cage occupancy ratios were found to be almost the same as those predicted by a statistical thermodynamics program CSMGem, suggesting that there is no preferential formation of large or small cages on the relatively long time scale of this NMR experiment. It was also found that the reformation rate of the sample with PVCap is several times faster compared with the pure system, indicating that the presence of PVCap promotes the hydrate reformation at a high subcooling though this chemical is well-known as a good hydrate inhibitor.

Hydrate film growth has been examined at the hydrocarbon/water interface for cyclopentane and methane hydrate. Video microscopy was used to measure hydrate film thickness, propagation rate across the hydrocarbon/water interface and gas consumption measurements characterized the hydrate formation mechanism. Cyclopentane and methane hydrate film formation were measured over the temperature range of 260–279K and pressure range of atmospheric to 8.3MPa. Hydrate formation was initiated by the propagation of a thin, porous film across the hydrocarbon/water interface. The propagation rate and thickening of the hydrate film was strongly dependent on the hydrate former solubility in the aqueous phase, in the absence and presence of hydrate. Cyclopentane hydrate film thickness began at ~12 μm and grew to a final thickness (15–40 μm) which increased with subcooling. Methane hydrate film thickness began at ~ 5 μm and grew to a final thickness (20–100 μm) which also increased with subcooling. The hydrate film grew into the water phase. Gas consumption measurements indicated that the aqueous phase supplied hydrate former during the initial hydrate growth, and the free gas supplied the hydrate former for film thickening and development. Hydrate film formation at the hydrocarbon/water interface was proposed to consist of three consecutive stages: propagation, development and bulk conversion.

Fundamental understanding of the structural changes occurring during hydrate formation and inhibition is important in the development of new strategies to control hydrates in flowlines and in inhibitor design. Neutron diffraction coupled with Empirical Potential Structure Refinement (EPSR) simulation has been used to determine the hydration structure around propane molecules before and during sII hydrate formation. The EPSR simulation results were generated by fitting neutron data (with H/D isotopic substitution) obtained from the SANDALS diffractometer at ISIS. Using this combination of techniques, the structural transformations of water around propane can be studied during propane (sII) hydrate formation. The hydration structure was found to be different in the liquid phases of the partially formed propane hydrate compared to that before any hydrate formation. The effect of a kinetic hydrate inhibitor, poly-N-pyrrolidone on the hydration structure was also examined. No significant effect was observed on the water structure in the presence of this inhibitor.

Economic studies on simulated natural gas hydrate reservoirs have been compiled to estimate the price of natural gas that may lead to economically viable production from the most promising gas hydrate accumulations. As a first estimate, large-scale production of natural gas from North American arctic region Class 1 and Class 2 hydrate deposits will be economically acceptable at gas prices over $CDN2005 10/Mscf and $CDN2005 17/Mscf, respectively, provided the cost of building a pipeline to the nearest distribution point is not prohibitively expensive. These estimates should be seen as rough lower bounds, with positive error bars of $5 and $10, respectively. While these prices represent the best available estimate, the economic evaluation of a specific project is highly dependent on the producibility of the target zone, the amount of gas in place, the associated geologic and depositional environment, existing pipeline infrastructure, and local tariffs and taxes. Class 1 hydrate deposits may be economically viable at a lower natural gas price due largely to the existing free gas, which can be produced early in project lifetimes. Of the deposit types for which hydrates are the sole source of hydrocarbons (i.e. Class 2, 3, and 4 deposits), theoretical simulation studies imply that Class 2 deposits may be the most likely to be economically viable (with all else equal) due to assistance that removal of the underlying free water will provide to depressurization; thus $CDN2005 17/Mscf can be seen as a lower bound on the natural gas price that may render hydrate deposits economically acceptable in the absence of free gas. Results from a recent analysis of the production of gas from marine hydrate deposits are also considered in this report [6]. On a rate-or-return (ROR) basis, it is approximately $2008 3/Mscf more expensive to produce from a Class 3 marine hydrates than a conventional marine gas reservoir of similar size.

Raman spectroscopic measurements of various hydrogen bearing clathrate hydrates have been performed under high (< 1cm-1) and low resolution (>2 cm-1) conditions. Raman bands for hydrogen in most common clathrate hydrate cavities have been assigned. Unlike most clathrate hydrate guests, the general observation is no longer valid that the larger the clathrate cavity in which a guest resides, the lower the vibrational frequency. This is rationalized by the multiple hydrogen occupancies in larger clathrate cavities. Both the roton and vibron bands for hydrogen clathrates illuminate interesting quantum dynamics of the enclathrated hydrogen molecules. At 77K, the progression from ortho to para H2 occurs over a relatively slow time period (days). The para contribution to the roton region of the spectrum exhibits the triplet splitting also observed in solid para H2. The complex vibron region of the Raman spectrum has been interpreted by observing the change in population of these bands with temperature and with isotopic substitution by deuterium. Raman spectra from H2 and D2 hydrates suggest that the occupancy patterns between the two hydrates are analogous. The Raman measurements demonstrate that this is an effective and convenient method to determine the relative occupancy of hydrogen molecules in different clathrate cavities.

The inter-conversion of methane-ethane hydrate from metastable to stable structures was studied using Raman spectroscopy. To investigate factors controlling the inter-conversion, the rate of structural transition was measured at 59% and 93% methane in ethane. The observed slower structural conversion rate in the lower methane concentration atmosphere can be explained in terms of the differences in kinetics (mass transfer of gas and water rearrangement). Also, the effect of kinetic hydrate inhibitors, poly-N-vinylpyrrolidone (PVP) and polyethylene-oxide (PEO), on the hydrate metastability was investigated at 65% and 93% methane in ethane. PVP increased the conversion rate at 65% methane in ethane (sI is thermodynamically stable), but retarded the rate at 93% methane in ethane (sII is thermodynamically stable), indicating that the function of PVP depends on hydrate structure. PEO did not affect the structural transition considerably for either methane-ethane compositions.

Gas Hydrates Markup Language (GHML) has been under development since 2003 by the CODATA Task Group “Data for Natural Gas Hydrates” as an international standard for data storage and transfer in the gas hydrates community. We describe the development of this evolving communication protocol and show examples of its implementation. In describing this protocol, we concentrate on the most recent updates that have enabled us to include ThermoML, the widely used IUPAC XML communication standard for thermodynamic data, into the GHML schema for the representation of all gas hydrate thermodynamic data. In addition, a new GHML element for the description of crystal structures is described. We then demonstrate a new tool - Guided Data Capture for Gas Hydrates - for the rapid capture of large amounts of data into GHML format. This tool is freely available and publicly licensed for use by any gas hydrate data producer or collector interested in using the GHML format. An effort will be made to achieve a consensus between scientific journals publishing thermophysical and structural data for gas hydrates to recommend their authors use this new software tool in order to generate GHML data files at the time of the submission of scientific articles. Finally, we will demonstrate how this format can be used to advantage when accessing data from a web-based resource by showing on-line access to GHML files for gas hydrates through a web service.

Large amounts of CH4 in the form of solid hydrates are stored on continental margins and in permafrost regions. If these CH4 hydrates could be converted into CO2 hydrates, they would serve double duty as CH4 sources and CO2 storage sites. Herein, we report the swapping phenomena between global warming gas and various structures of natural gas hydrate including sI, sII, and sH through 13C solid-state nuclear magnetic resonance, and FT-Raman spectrometer. The present outcome of 85% CH4 recovery rate in sI CH4 hydrate achieved by the direct use of binary N2 + CO2 guests is quite surprising when compared with the rate of 64 % for a pure CO2 guest attained in the previous approach. The direct use of a mixture of N2 + CO2 eliminates the requirement of a CO2 separation/purification process. In addition, the simultaneously-occurring dual mechanism of CO2 sequestration and CH4 recovery is expected to provide the physicochemical background required for developing a promising large-scale approach with economic feasibility. In the case of sII and sH CH4 hydrates, we observe a spontaneous structure transition to sI during the replacement and a cage-specific distribution of guest molecules. A significant change of the lattice dimension due to structure transformation induces a relative number of small cage sites to reduce, resulting in the considerable increase of CH4 recovery rate. The mutually interactive pattern of targeted guest-cage conjugates possesses important implications on the diverse hydratebased inclusion phenomena as clearly illustrated in the swapping process between CO2 stream and complex CH4 hydrate structure.

The chloride anion is known to be the most abundant salt ion in sea water. At the regions such as ODP Sites 1249 and 1250 the highly enriched chloride concentration is observed in a zone extended from near the sediment surface (~1 mbsf) to depths about 25 mbsf. Here, we designed the in-situ electric circuit system for measuring chloride concentration within reliable accuracy. In the cylindrical cell the 5-10 tubes having holes on the wall and electrodes were equipped around clay mixture. The open holes were made to regulate to a certain degree the interface area between methane gas and clay sample. As may be anticipated, the chloride concentration abnormally increased under fast rate condition for forming methane hydrate, but no noticeable concentration change was detected under relatively low rate. In fact, the present experiment seems to be a lot deficient to investigate the ion diffusion and moreover does not fully reflect the real deep-sea floor condition, but the meaningful results for describing the abnormal salinity enrichment might be drawn. The physical effects of chloride anions on surface morphologies of methane hydrate formed in the sediments were additionally examined with the Field Emission-Scanning Electronic Microscope (FE-SEM).

Evaluation of host geologic sediment interactions with carbon dioxide is very important in sequestration strategies. The objective of the study is to experimentally investigate the effects of different soil mineral types on carbon dioxide hydrate formation. At isothermal, isochoric, and isobaric conditions, batch experiments were conducted with different types of solids (bentonite, kaolinite, nontronite, pyrite, and soil) and electrolytes (NaCl, KCl, CaCl2, and MgCl2) to measure carbon dioxide hydrate formation times. A 50 mL pressurized vessel was used for the experiment by bubbling gaseous CO2 into the solid suspension. We observed that the formation time of carbon dioxide hydrate was dependent on the reactor temperature (273.4 K and 277.1 K) and types of solid and electrolyte. A clear peak was observed in the temperature profile of each experimental run and determined as the hydrate formation time. This is due to the initiation of the hydrate crystallization and latent heat release at the hydrate formation time. The temperature profiles vary significantly with respect to the types of solids and electrolytes. As crystallization initiates, peaks were observed at higher temperatures in pyrite and soil suspensions. The results showed that hydrate formation times for clay minerals in water were approximately twice and 10 times faster than that for pyrite and soil, respectively. The rates of gas consumption were able to be determined by the pressure monitoring. The kaolinite appeared to have the fastest gas consumption rate among the clay mineral suspensions, which was 2.4 times and 7.4 times faster than nontronite and bentonite, respectively. Results from these experiments seem to provide an insight on the formation and growth of carbon dioxide hydrate, once sequestered into the sea bed sediments under the deep sea environment.