For a number of years the NRC group has been working on a laboratory protocol for the analysis of gas hydrate that has been recovered from various natural sites. The expectation was that a comprehensive set of techniques would become available for the general use of hydrate researchers around the world. With the current set of available techniques a good picture of natural gas hydrates can be obtained, although the emerging complexity of the hydrate-mineral system still demands additional work. Here we present a suite of techniques that will take a researcher from preservation techniques to hydrate occurrence, gas/water/sediment ratios, gas and isotope analysis, P-T behaviour, structure, composition, degree of water conversion to hydrate, hydrate homogeneity and decomposition behaviour. As more detailed studies become possible a variety of more subtle features are revealed, for instance the role of minor gas components in hydrate stability, decomposition behaviour and heterogeneity in structure and composition.

In this paper we report a low symmetry version of structure H hydrate that results from the hexagonal form on cooling below 167 K. Phase changes with temperature in the common clathrate hydrates structural families I, II and H have not been observed before, except in doped systems where ordering transitions take place or in the structure I hydrate of trimethylene oxide where the guest molecule dipoles are known to order. Since there is an inverse relationship between the effect of temperature and pressure on ices, it may well be that the low symmetry form reported at low temperature can also be reached by applying high pressure, and that in fact some of the observed high pressure phases are lower symmetry versions of hexagonal sH.

Previously we have suggested the concept of tuning hydrate compositions which makes it possible to increase the gas storage capacity of binary hydrates. Herein, we report for the first time the existence of a critical guest concentration (CGC) and establish the complete tuning pattern that appears to exist in binary hydrates, including the water-soluble hydrate formers (promoters) and water insoluble guests,. The first attempt to verify the new features of clathrate hydrate compositions is executed on the binary hydrate of CH4 + THF and involves a detailed examination of the guest distribution by spectroscopic methods. THF molecules by themselves form sII hydrate from a completely miscible aqueous solution, and in this structure, because of their size, THF molecules occupy only the large 51264 cages. The CGC value appears to depend largely on the chemical nature of the liquid guest component participating in the binary hydrate formation. The present experimental findings on the existence of critical guest concentration and the complete tuning phenomenon can be expected to make a meaningful contribution to both inclusion chemistry and a variety of hydrate-based fields.

Solid State NMR spectroscopy has taken a very prominent place among the many spectroscopic techniques employed for the characterization of clathrate hydrates. Exceptionally high sensitivity of the spectra to the molecular environment and dynamic processes, together with the ability to provide accurate and quantitative data make NMR spectroscopy a highly desirable and versatile approach for studying hydrates. Application of the method to its full capacity, however, requires some extensive instrumental developments to adapt it to the specific experimental requirements of hydrate studies, for example, very low temperatures and high pressures. In this presentation we will give an overview of recent Solid State NMR advances in various areas of hydrate research. Examples will include analysis of the composition and structure of mixed gas hydrates prepared from multi-component mixtures of hydrocarbons, characterization of the natural gas hydrates from different sources, and evaluation of formation conditions and properties of mixed hydrogen hydrates. 13C NMR with Magic Angle Spinning (MAS) at -100C has been the main approach in the first two examples. We will discuss the requirements and the necessary instrumental developments to make the experiments of this type successful. The detailed characterization of mixed hydrogen hydrates required low temperature 1H MAS. Problems of quantification in these experiments will be discussed. We expect that all these recent experimental developments will prompt wider application of Solid State NMR in hydrate research.

Clathrate hydrates can be reasonable choices for high-density hydrogen storage into compact host media, which is an essential task for hydrogen-based future society. However, conventional storage scheme where aqueous solution is frozen with hydrogen gas was impractically slow for practical use. Here we propose a much faster scheme where hydrogen gas was directly charged into hydrogen-free, crystalline hydrate powders. The storage kinetics was observed in situ by nuclear magnetic resonance (NMR) spectroscopy in a pressurized tube cell. At pressures up to 20 MPa the storage was complete within 80 minutes, as observed by growth of stored-hydrogen peak into the hydrate. Since the rate-determining step of current storage scheme is body diffusion of hydrogen within the crystalline hydrate media, we have measured the diffusion coefficient of hydrogen molecules using the pulsed field gradient NMR method. The results show that at temperatures down to 250 K the stored hydrogen is highly mobile, so that the powdered hydrate media should work well even in cold environments. Compared with more prevailing hydrogen storage media such as metal hydrides, the clathrate hydrate could offer even more advantages: It is free from hydrogen embrittlement, more chemically durable, more environmentally benign, as well as economically quite affordable.

Electronic structure calculations are performed to determine the barriers to migration of molecular hydrogen in clathrate cages. The barriers are used in a chemical reaction rate expression to determine the rate of H2 migration and the diffusion coefficient for the hydrogen guest molecules. Calculations are performed for migration of hydrogen guests through pentagonal and hexagonal clathrate cage faces. Cage faces where the water molecules obey the water rules and cage faces with Bjerrum L and D defects are considered. The migration barriers were calculated to be ≈25 kcal/mol from the pentagonal faces and between 5 to 6 kcal/mol for the hexagonal faces, depending on the orientation of the hydrogen molecule.

A series of studies have been carried out to elucidate the sediment effect on the saturation level of methane hydrate in sediments. The specimens tested covered most of the natural sediment types, with various combinations of particle size and mineral composition. The results obtained indicate that particle size and clay contents are the two key factors determining the saturation level of gas hydrate in sediments: the finer the particle size and/or the higher the clay content, the lower the hydrate saturation. The observed particle size effect and clay effect on hydrate saturation can be accredited to the specific surface area of a sediment.

The dedicated gas hydrate coring/drilling program was carried out under National Gas Hydrate Program (NGHP) in four Indian offshore areas (Kerala-Konkan, Krishna- Godavari, Mahanadi and Andman) during 28th April to 19th August, 2006. During NGHP Expedition 01, 2006, total of 39 holes were drilled/cored at 21 sites in these areas. The gas hydrates have been found to be present in large quantities in Indian offshore areas particularly in KG basin. More than 130 confirmed solid gas hydrate samples were recovered during this hydrate coring/drilling program. The laboratory analysis was carried out on the 34 natural gas hydrate samples recovered from offshore India. The gas hydrate characterization was carried out using the microscopic techniques such as Raman, 13C NMR and XRD for its structure, cavity occupancy and hydration number. The gas hydrates occur in grayish green fine sediments, gray medium sands and white volcanic ash as pore-filling hydrate and massive hydrates in fractured shale/clay. The visible massive gas hydrates developed especially at Site NGHP 1-10B, 10C, 10D and 21A in K G area. The structures of the gas hydrates in the studied samples are all sI, with methane as the dominant guest molecule. The occupancy of methane in large cage is almost complete, while it is variable in the small cage (0.75 to 0.99). The hydration number is 6.10 ± 0.15 for most of the hydrates in the samples studied. This paper presents the results of the laboratory analysis on the structural characterization of natural gas hydrates in core samples from offshore India.

Shallow marine gas hydrates occurring above the Sulfate-Methane-Interface (SMI) often contain small amounts of H2S beside methane and other hydrocarbons, but the distribution of H2S in these natural samples is not always homogeneous. To learn more about the formation of H2Scontaining hydrates, gas hydrates with different ratios of H2S/CH4 were synthesized under various conditions. The samples were synthesized from ice and water phases, with constant feed gas compositions or controlled changes in feed gas compositions. It turns out that the detailed nature of the synthetic hydrate samples depends on the method of sample preparation. The sample prepared with gas containing small amounts of H2S (1% H2S and 99% CH4) appeared homogeneous in composition, while that prepared in a water-H2S-CH4 system with higher H2S contents was heterogeneous. The samples were analysed with Raman spectroscopy, and differential scanning calorimetry (DSC).

Recently, clathrate hydrate has attracted much attention because of its energy gas enclathration phenomenon. Since energy gas such as methane, ethane, and hydrogen could be stored in solid hydrate form, clathrate hydrate research has been considerably focused on energy gas storage and transportation medium. Especially, methane hydrate, which is crystalline compound that are formed by physical interaction between water and relatively small sized guest molecules, can contain about as much as 180 volumes of gas at standard pressure and temperature condition. To utilize gas hydrate as energy storage and transportation medium, two important key features: storage capacity and storage condition must be considered. Herein, we report the inclusion phenomena of methane occurred on tert-butyl alcohol hydrate through thermodynamic measurement and spectroscopic analysis by using powder X-ray diffractometer, and 13C solidstate NMR. From spectroscopic analysis, we found the formation of sII type (cubic, Fd3m) clathrate hydrate by introducing methane gas into tert-butyl alcohol hydrate whereas tert-butyl alcohol hydrate alone does not form clathrate hydrate structure. Under equilibrium condition, pressure-lowering effect of methane + tert-butyl alcohol double hydrate was also observed. The present results give us several key features for better understanding of inclusion phenomena occurring in the complex hydrate systems and further developing methane or other gas storage and transportation technique.