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Clathrate Hydrates for Production of Potable Water

  • Robert W. Bradshaw (a1), Blake A. Simmons (a2), Eric H Majzoub (a3), W. Miles Clift (a4) and Daniel E. Dedrick (a5)...

Abstract

Clathrate hydrates are crystalline inclusion compounds of water and a guest molecule (e.g., methane) that form at temperatures below ambient but above the freezing point of water. There are three known crystalline structures of hydrates (structure I, II, and H) in which cavities within the hydrogen bonded water molecule lattice trap the hydrate-forming species. The clathrate structure excludes dissolved solutes, such as sodium chloride, from the aqueous phase and thereby offers a possible means to produce potable water from seawater or brackish water. The concept of using clathrate hydrates for desalination is not new. However, before clathrate hydrate desalination becomes a viable technology, fundamental issues of controlled hydrate formation, hydrate size and morphology, agglomeration, amount of entrapped salt, and the efficient recovery of hydrates must be understood. This paper will report structural characterization of hydrates formed with several guest molecules over a wide range of conditions in an attempt to further the physicochemical insight needed to address these issues.

Clathrate hydrate formation experiments were performed using a variety of host molecules, including R141b, a commercial refrigerant, C2FCl2H3. Hydrates of R141b were formed at temperatures from 2°C to 6°C and atmospheric pressure from deionized water and 2% - 7% NaCl solutions. Samples of the hydrates were characterized by cold-stage x-ray diffraction and Raman spectroscopy and determined to be structure II. Additional experiments were conducted with a gaseous hydrate former, ethylene, which readily formed hydrates with deionized or saline water at 2°C and several atmospheres of pressure. Experiments with several other hydrate forming molecules were conducted and the results obtained from their structural characterization will be reported. We will also present proof-of-concept experiments demonstrating a novel technique of desalination using these hydrate formers.

Sandia National Laboratories is a multiprogram laboratory operated by Sandia Corporation, a Lockheed Martin company, for the United States Department of Energy under contract DE-AC04-94AL85000.

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References

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1. Sloan, E. D. Jr , Clathrate hydrates of natural gas, 2nd ed., (Marcel Dekker, New York, 1998) pp. 3347.
2. Knox, W. G., Hess, M., Jones, G. E., and Smith, H. B., Chem. Engg. Prog., 57 (2), 66 (1961)
3. Barduhn, A. J., Towlson, H. E. and Hu, Y. C., Ch, A.I.. E. J., 8 (2), 176 (1962)
4. McCormack, R. A. and Niblock, G. A., Investigation of High Freezing Temperature, Zero Ozone, and Zero Global Warming Potential Clathrate Formers for Desalination, Bureau of Reclamation Water Desalination report No. 59, June 2000.
5. Yousuf, M., et al, Applied Physics A, 78, 925 (2004).

Keywords

Clathrate Hydrates for Production of Potable Water

  • Robert W. Bradshaw (a1), Blake A. Simmons (a2), Eric H Majzoub (a3), W. Miles Clift (a4) and Daniel E. Dedrick (a5)...

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