The storage of large quantities of hydrogen at safe pressures is a key factor in establishing a hydrogen-based economy. Previous strategies--where hydrogen has been bound chemically, adsorbed in materials with permanent void space or stored in hybrid materials that combine these elements--have problems arising from either technical considerations or materials cost. A recently reported clathrate hydrate of hydrogen exhibiting two different-sized cages does seem to meet the necessary storage requirements; however, the extreme pressures (approximately 2 kbar) required to produce the material make it impractical. The synthesis pressure can be decreased by filling the larger cavity with tetrahydrofuran (THF) to stabilize the material, but the potential storage capacity of the material is compromised with this approach. Here we report that hydrogen storage capacities in THF-containing binary-clathrate hydrates can be increased to approximately 4 wt% at modest pressures by tuning their composition to allow the hydrogen guests to enter both the larger and the smaller cages, while retaining low-pressure stability. The tuning mechanism is quite general and convenient, using water-soluble hydrate promoters and various small gaseous guests.

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Natural gas hydrates are a potential source of energy and may play a role in climate change and geological hazards. Most natural gas hydrate appears to be in the form of 'structure I', with methane as the trapped guest molecule, although 'structure II' hydrate has also been identified, with guest molecules such as isobutane and propane, as well as lighter hydrocarbons. A third hydrate structure, 'structure H', which is capable of trapping larger guest molecules, has been produced in the laboratory, but it has not been confirmed that it occurs in the natural environment. Here we characterize the structure, gas content and composition, and distribution of guest molecules in a complex natural hydrate sample recovered from Barkley canyon, on the northern Cascadia margin. We show that the sample contains structure H hydrate, and thus provides direct evidence for the natural occurrence of this hydrate structure. The structure H hydrate is intimately associated with structure II hydrate, and the two structures contain more than 13 different hydrocarbon guest molecules. We also demonstrate that the stability field of the complex gas hydrate lies between those of structure II and structure H hydrates, indicating that this form of hydrate is more stable than structure I and may thus potentially be found in a wider pressure-temperature regime than can methane hydrate deposits.

/npsi/ctrl?action=rtdoc&an=12337993&lang=en http://nparc.cisti-icist.nrc-cnrc.gc.ca/npsi/ctrl?action=rtdoc&an=12337993&lang=fr READ THESE TERMS AND CONDITIONS CAREFULLY BEFORE USING THIS WEBSITE.http://nparc.cisti-icist.nrc-cnrc.gc.ca/npsi/jsp/nparc_cp.jsp?lang=en Vous avez des questions? Nous pouvons vous aider. Pour communiquer directement avec un auteur, consultez la première page de la revue dans laquelle son article a été publié afin de trouver ses coordonnées. Si vous n'arrivez pas à les repérer, communiquez avec nous à PublicationsArchive-ArchivesPublications@nrc-cnrc.gc.ca. Questions?Contact the NRC Publications Archive team at PublicationsArchive-ArchivesPublications@nrc-cnrc.gc.ca. If you wish to email the authors directly, please see the first page of the publication for their contact information. NRC Publications Archive Archives des publications du CNRCThis publication could be one of several versions: author's original, accepted manuscript or the publisher's version. / La version de cette publication peut être l'une des suivantes : la version prépublication de l'auteur, la version acceptée du manuscrit ou la version de l'éditeur. For the publisher's version, please access the DOI link below./ Pour consulter la version de l'éditeur, utilisez le lien DOI ci-dessous.http://doi.org/10.1021/es049269zEnvironmental Science & Technology, 39, 7, pp. 2315-2319, 2005 Thermodynamic measurements and NMR spectroscopic analysis were used to show that it is possible to recover CO 2 from flue gas by forming a mixed hydrate that removes CO 2 preferentially from CO 2 /N 2 gas mixtures using water dispersed in the pores of silica gel. Kinetic studies with 1 H NMR microimaging showed that the dispersed water in the silica gel pore system reacts readily with the gas, thus obviating the need for a stirred reactor and excess water. Hydrate phase equilibria for the ternary CO 2 -N 2 -water system in silica gel pores were measured, which show that the three-phase hydrate-water-rich liquid-vapor equilibrium curves were shifted to higher pressures at a specific temperature when the concentration of CO 2 in the vapor phase decreased. 13 C cross-polarization NMR spectral analysis and direct measurement of the CO 2 content in the hydrate phase suggested that the mixed hydrate is structure I at gas compositions of more than 10 mol % CO 2 , and that the CO 2 molecules occupy mainly the more abundant 5 12 6 2 cages. This makes it possible to achieve concentrations of more than 96 mol % CO 2 gas in the product after three cycles of hydrate formation and dissociation. 1 H NMR microimaging showed that hydrate yields of better than 85%, based on the amount of water, could be obtained in 1 h when a steady state was reached, although ∼90% of this yield was achieved after ∼20 min of reaction time.

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Gas hydrates are becoming an attractive way of storing and transporting large quantities of natural gas, although there has been little effort to understand the preferential occupation of heavy hydrocarbon molecules in hydrate cages. In this work, we present the formation kinetics of mixed hydrate based on a gas uptake measurement during hydrate formation, and how the compositions of the hydrate phase are varied under corresponding formation conditions. We also examine the effect of silica gel pores on the physical properties of mixed hydrate, including thermodynamic equilibrium, formation kinetics, and hydrate compositions. It is expected that the enclathration of ethane and propane is faster than that of methane early stage hydrate formation, and later methane becomes the dominant component to be enclathrated due to depletion of heavy hydrocarbons in the vapor phase. The composition of the hydrate phase seems to be affected by the consumed amount of natural gas, which results in a variation of heating value of retrieved gas from mixed hydrates as a function of formation temperature. 13C NMR experiments were used to measure the distribution of hydrocarbon molecules over the cages of hydrate structure when it forms either from bulk water or water in silica gel pores. We confirm that 70% of large cages of mixed hydrate are occupied by methane molecules when it forms from bulk water; however, only 19% of large cages of mixed hydrate are occupied by methane molecules when it forms from water in silica gel pores. This result indicates that the fractionation of the hydrate phase with heavy hydrocarbon molecules is enhanced in silica gel pores. In addition when heavy hydrocarbon molecules are depleted in the vapor phase during the formation of mixed hydrate, structure I methane hydrate forms instead of structure II mixed hydrate and both structures coexist together, which is also confirmed by 13C NMR spectroscopic analysis.