The study of methane hydrate growth kinetics by NMR method

Authors: V.D. Skirda, A.A. Ivanov, V.E. Kosarev, D.K. Nurgaliev (Kazan (Volga Region) Federal University, RF, Kazan), S.S. Safonov, I.V. Nicolin (Schlumberger, RF, Moscow)
Key words: methane hydrate, nuclear magnetic resonance (NMR), kinetics, diffusion, relaxation.
The nuclear magnetic resonance method conducted researches of long-term kinetics of growth of methane of hydrate on limit of the section gas - liquid (water). The amount of the formed methane of hydrate was registered according to the analysis of a signal of recession of a free induction. To methane to hydrate that part of a signal which was characterized by small time of a cross relaxation belonged. The analysis of kinetic curves of growth of thickness of a film of methane of hydrate on limit of the section gas-liquid showed that they aren't described within the assumption of normal diffusion of molecules of methane through a film of methane of hydrate. The detailed analysis of dependence of a share of a signal of methane of hydrate from time allows to suggest about abnormal diffusive process.

References

1. Solov'ev B.A., Rossiyskiy khimicheskiy zhurnal – Russian Journal of General

Chemistry, 2003, V. XLVII, no. 3, pp. 59-69.

2. Kleinberg R.L., Flaum C., Straley C., Griffin D.D., Seafloor NMR assay of

methane hydrate in sediments and rock, Journal of geophysical research,

2003, V. 108, pp. 1-13.

3. Lin W., Chen G.-J., Sun C.-Y., Guo X.-Q. et al., Effect of surfactant on the formation

and dissociation kinetic behavior of methane hydrate, Chemical Engineering

Science, 2004, V. 59, pp. 4449-4455.

4. Powles J.G., Mansfield P., Double-pulse nuclear-resonance transients in

solids, Phys. Letters, 1962, V 2, pp. 58-60.

5. Kimmich R., NMR: Tomography, Diffusometry, Relaxometry, Berlin, Heidelberg,

New York: Springer-Verlag, 1997, 524 p.

6. Chapoy A., Mohammadi H.A., Dominique R., Bahman T., Gas solubility

measurement and modeling for methane–water and methane–ethane–nbutane–

water systems at low temperature conditions, Fluid Phase Equilibria

220, 2004, V. 220, pp. 113–121.

7. Makogon Yu.F., Khol'sti Dzh. S., Rossiyskiy khimicheskiy zhurnal – Russian Journal

of General Chemistry, 2003, V. XLVII, no. 3, pp. 43-48.

8. Skirda, V.D., The features of PFG NMR technique and some methodical aspects

of its application, NATO science series II. Mathematics, Physics and

Chemistry, Netherlands: Springer, 2002, V. 76, pp. 245 – 254.

9. Kortunov P.V., Skirda V.D., Kolloidnyy zhurnal - Colloid Journal, 2005, V. 67, pp.

633-640.

10. Karger J., Ruthven M., Diffusion in Zeolites, New York: Wiley, 1992.

Key words: methane hydrate, nuclear magnetic resonance (NMR), kinetics, diffusion, relaxation.
The nuclear magnetic resonance method conducted researches of long-term kinetics of growth of methane of hydrate on limit of the section gas - liquid (water). The amount of the formed methane of hydrate was registered according to the analysis of a signal of recession of a free induction. To methane to hydrate that part of a signal which was characterized by small time of a cross relaxation belonged. The analysis of kinetic curves of growth of thickness of a film of methane of hydrate on limit of the section gas-liquid showed that they aren't described within the assumption of normal diffusion of molecules of methane through a film of methane of hydrate. The detailed analysis of dependence of a share of a signal of methane of hydrate from time allows to suggest about abnormal diffusive process.

References

1. Solov'ev B.A., Rossiyskiy khimicheskiy zhurnal – Russian Journal of General

Chemistry, 2003, V. XLVII, no. 3, pp. 59-69.

2. Kleinberg R.L., Flaum C., Straley C., Griffin D.D., Seafloor NMR assay of

methane hydrate in sediments and rock, Journal of geophysical research,

2003, V. 108, pp. 1-13.

3. Lin W., Chen G.-J., Sun C.-Y., Guo X.-Q. et al., Effect of surfactant on the formation

and dissociation kinetic behavior of methane hydrate, Chemical Engineering

Science, 2004, V. 59, pp. 4449-4455.

4. Powles J.G., Mansfield P., Double-pulse nuclear-resonance transients in

solids, Phys. Letters, 1962, V 2, pp. 58-60.

5. Kimmich R., NMR: Tomography, Diffusometry, Relaxometry, Berlin, Heidelberg,

New York: Springer-Verlag, 1997, 524 p.

6. Chapoy A., Mohammadi H.A., Dominique R., Bahman T., Gas solubility

measurement and modeling for methane–water and methane–ethane–nbutane–

water systems at low temperature conditions, Fluid Phase Equilibria

220, 2004, V. 220, pp. 113–121.

7. Makogon Yu.F., Khol'sti Dzh. S., Rossiyskiy khimicheskiy zhurnal – Russian Journal

of General Chemistry, 2003, V. XLVII, no. 3, pp. 43-48.

8. Skirda, V.D., The features of PFG NMR technique and some methodical aspects

of its application, NATO science series II. Mathematics, Physics and

Chemistry, Netherlands: Springer, 2002, V. 76, pp. 245 – 254.

9. Kortunov P.V., Skirda V.D., Kolloidnyy zhurnal - Colloid Journal, 2005, V. 67, pp.

633-640.

10. Karger J., Ruthven M., Diffusion in Zeolites, New York: Wiley, 1992.



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