Metastable Dry Water Methane Hydrate Stability below 0°C

Tyumen State University Herald. Physical and Mathematical Modeling. Oil, Gas, Energy


Release:

2017, Vol. 3. №1

Title: 
Metastable Dry Water Methane Hydrate Stability below 0°C


For citation: Kislitsyn A. A., Drachuk A. O., Podenko L. S., Molokitina N. S. 2017. “Metastable Dry Water Methane Hydrate Stability below 0°C”. Tyumen State University Herald. Physical and Mathematical Modeling. Oil, Gas, Energy, vol. 3, no 1, pp. 10-21. DOI: 10.21684/2411-7978-2017-3-1-10-21

About the authors:

Anatoliy A. Kislitsin, Dr. Sci. (Phys.-Math.), Professor, Department of Experimental Physics and Nanotechnology, University of Tyumen; akislicyn@utmn.ru

Andrey O. Drachuk, Postgraduate Student, Department of Experimental Physics and Nanotechnologies, Institute of Physics and Technology, Tyumen State University; andrey0410@mail.ru

Lev S. Podenko, Cand. Sci. (Phys.-Math.), Leading Researcher, Institute of the Earth Cryosphere of the Siberian Branch of the RAS (Tyumen); lpodenko@yandex.ru

Nadezhda S. Molokitina, Cand. Sci. (Tech.), Researcher, Institute of the Earth Cryosphere of the Siberian Branch of the RAS (Tyumen); molokitina.nadya@yandex.ru

Abstract:

In this work stability of metastable dry water methane hydrate contained residual unreacted water at a supercooled state below 0°C and supercooled unreacted water stability was studied. Gas hydrates which did not contain unreacted water could exist at a temperature below 0°C as a metastable phase at the pressure range that meant the field between the ice-hydrate-gas and supercooled liquid-hydrate-gas equilibrium lines. The experiments were carried out in the high pressure reactor. Phase transformations in the reactor were observed by the pressure and temperature monitoring and using differential thermal analysis (DTA). It was established dissociation probability of dry water methane hydrate contained in the metastable field at temperature below 0°C might be significantly higher than probability of ice nucleation in unreacted supercooled water contained in the gas hydrate samples. Thus wise, the induction time of methane hydrate dissociation was even more than one-tenth of the average existence time of supercooled unreacted water at the temperature of –5°C and at pressure less than the equilibrium pressure 15%. It was observed that the increase of fumed silica nanoparticle concentration in “dry water” used for its preparing led to decrease of metastable dry water gas hydrate stability contained unreacted supercooled water. It was shown that at a temperature below 0°C the increase of fumed silica nanoparticle concentration from 5 to 10 wt% led to rapidly decrease of the induction time of metastable gas hydrate dissociation. Specifically, the decrease of the induction time almost 20 times was noticed at the temperature of –5°C and the pressure of 2000 kPa.

References:

  1. Landau L. D., Lifshits E. M. 1964. Statisticheskaya fizika [Statistical Physics]. Moscow: Nauka, 568 p.
  2. Lifshits E. M., Pitaevskiy L. P. 1979. Fizicheskaya kinetika [Physical Kinetics]. Moscow: Nauka, 528 p.
  3. Melnikov V. P., Podenko L. S., Nesterov A. N., Drachuk A. O., Molokitina N. S., Reshetnikov A. M. 2015. “Dissociation of Gas Hydrates Produced from Methane and "Dry Water" at Temperatures below 273 K”. Doklady Physical Chemistry, vol. 461, no 1, pp. 49-52. DOI: 10.1134/S001250161503001X
  4. Melnikov V. P., Nesterov A. N., Reshetnikov A. M. 2003. “Mechanism of Gas Hydrate Decomposition at a Pressure of 0.1 MPa”. Doklady Earth Sciences, vol. 389, no 3, pp. 455-458.
  5. Melnikov V. P., Podenko L. S., Nesterov A. N., Drachuk A. O., Molokitina N. S., Reshetnikov A. M. 2016. “Self-Preservation of Methane Hydrates Produced in "Dry Water"”. Doklady Chemistry, vol. 466, no 2, pp. 53-56. DOI: 10.1134/S0012500816020038
  6. Podenko L. S., Nesterov A. N., Drachuk A. O., Molokitina N. S., Reshetnikov A. M. 2014. “Mekhanizmy dissotsiatsii gazovykh gidratov, poluchennykh iz "sukhoy vody", pri temperaturakh nizhe 273 K” [Mechanisms of the Dissociation of Gas Hydrates Obtained from "Dry Water" at Temperatures below 273 K]. Zhurnal fizicheskoy khimii, vol. 88, no 7-8, pp. 1257-1263. DOI: 10.7868/S0044453714060260
  7. Podenko L. S., Nesterov A. N., Molokitina N. S., Shalamov V. V., Reshetnikov A. M., Larionov E. G. 2011. “Proton Magnetic Relaxation in a Disperse "Dry Water" Nanosystem”. Journal of Applied Spectroscopy, vol. 87, no 2, pp. 260-265. DOI: 10.1007/s10812-011-9456-3
  8. Skripov V. P., Koverda V. P. 1984. Spontannaya kristallizatsiya pereokhlazhdennykh zhidkostey [Spontaneous crystallization of supercooled liquids]. Moscow: Nauka.
  9. Binks B. P., Murakami R. 2006. “Phase inversion of particle-stabilized materials from foams to dry water”. Nature Mater, vol. 5, pp. 865-869. DOI: 10.1038/nmat1757
  10. Istomin V. A., Yakushev V. S., Makhonina N. A., Kwon V. G., Chuvilin E. M. 2006. “Self-preservation phenomenon of gas hydrates”. Gas Industry of Russia (Digest), no 4, pp. 16-27.
  11. Melnikov V. P., Nesterov A. N., Reshetnikov A. M., Zavodovsky A. G. 2009. “Evidence of liquid water formation during methane hydrates dissociation below the ice point”. Chemical Engineering Science, vol. 64, no 6, pp. 1160-1166. DOI: 10.1016/j.ces.2008.10.067
  12. Sloan E. D., C. A. Koh. 2008. Clathrate Hydrates of Natural Gases 3rd ed. CRC Press, Boca Raton.
  13. Wang W. X., Bray C. L., Adams D. J., Cooper A. I. 2008. “Methane storage in dry water gas hydrates”. Journal of the American Chemical Society, vol. 130, no 35, pp. 11608-1609. DOI: 10.1021/ja8048173