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.

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).

This contribution aims to publicize the efforts made in the identification of gas hydrates in the Uruguayan continental shelf, analyze the most outstanding aspects related to its energy potential, as well as include this topic in other areas of knowledge for a comprehensive understanding of the subject. The hydrates, crystalline solid formed mainly by water and natural gas, are reservoirs of carbon that occur naturally in the continents in permafrost areas, and at sea, in the offshore basins of continental margins. They contain more than twice the total carbon in the world, surpassing the conventional hydrocarbon reserves. Principal energy programs foresee its commercial exploitation by 2015. International research programs include not only the energy aspect, but studying such systems considering their participation in the global carbon cycle, climate change and benthic communities associated with them. In our country, several seismic surveys showed evidence of the presence of gas hydrates in continental shelf and the surrounding area. The first survey was carried out by Brazil in the south of the Brazilian continental shelf, ANCAP then showed the continuity of the hydrate layer on the Uruguayan continental shelf and estimated the gas potential of the mineralized layer (87 TCF). Finally, the BGR survey verified the existence of seismic evidence of gas hydrates layer and the presence of free gas below these. The typical seismic response of gas hydrate and free gas is the BSR (Bottom Simulating Reflector) and is interpreted as a positive intensity reflection, followed by a negative intensity, showing the wave passage from a high acoustic impedance zone to a low acoustic impedance zone.

Using a combination of micromechanical force and flowloop measurements, hydrate deposition on a pipe wall surface was investigated for ‘dry’ hydrates formed in the bulk phase and for hydrates growing on the pipe surface. Cyclopentane ‘dry’ hydrates (without a free water phase) were used to predict whether hydrates, formed in a bulk condensate phase, would adhere to a pipe wall. Adhesion forces between cyclopentane hydrates and steel were measured using a micro-mechanical force apparatus. The average force of adhesion was measured to be very small, less than 0.01 N/m. This force was used in a particle force balance, predicting that hydrates formed in the bulk phase would not deposit on the pipe wall. It was hypothesized than in the presence of a water saturated hydrocarbon, hydrates would grow on the pipe wall as the fluid cooled below its equilibrium temperature. This hypothesis was confirmed using a single pass condensate flowloop. Water was continuously dissolved into the flowloop inlet stream as water deposited in the flowloop test section, resulting in both a pressure drop and fluid temperature increase. This work illustrates the need for a hydrate wall growth model.

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.

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.