A study of the xenon effect in type-II clathrate hydrate synthesis; Commencing with hydrogen, argon and xenon uptake into a propane clathrate hydrate

It has been proposed that clathrate hydrates can be a possible storage medium for alternative fuels, such as hydrogen. The type-II propane gas hydrate is a viable choice because there are twice as many small cages as large cages and the small cavities are available for hydrogen storage. However, propane hydrate formation is a kinetically slow process which makes it commercially unattractive. Our objectives were twofold; (1) to quantify hydrogen, argon and xenon sorption into a preformed type-II propane hydrate at near-ambient conditions and (2) to investigate the effect of xenon on the rate of type-II propane hydrate formation.;The propane hydrate is synthesized from 250 mum ice grains, and is estimated to have a porosity of 65 %. Hydrogen is rapidly absorbed by the hydrate sample and approaches the equilibrium vapor pressure in an hour before a very slow residual absorption process ensues. For an initial hydrogen pressure of 1.5 MPa, about 4.5 % of the available 512 cages are occupied by hydrogen after one hour, and 4.9 % after 18 hours. In contrast, for both argon and xenon significantly more gas is absorbed by the hydrate, but at a much slower rate: about 5% as fast for xenon and 1% as fast for argon. We conclude that hydrogen readily diffuses through the propane hydrate microcrystal structure, while argon and xenon are probably absorbed by growing new double hydrate while consuming the propane hydrate. Thus, although considerably higher pressures would be required to store significant quantities of hydrogen in propane hydrate, it appears that the crystal can be loaded and emptied in relatively short amounts of time.;Experimental results show that propane is incorporated into clathrate hydrate cages more rapidly using propane-xenon mixtures than for pure propane gas. For a 0.92 xenon: propane mix, 60% of the theoretical yield of propane enclathration is achieved in 20 minutes, versus several days for pure propane. It appears that xenon serves to nucleate the dodecahedral 512 cages, and that the presence of propane results in type-II structure growth rather than the native xenon type-I structure. The type-II xenon-propane structure is more thermodynamically stable than either pure hydrate.