Heat and Mass Transfer

, Volume 55, Issue 12, pp 3537–3545 | Cite as

Diffusion-kinetic model of gas hydrate film growth along the gas–water interface

  • Valeriy A. VlasovEmail author


An analytic model that describes the kinetics of the process of gas hydrate film growth along the gas–water interface is presented. This model is based on the assumption that this process is controlled only by the mass transfer of gas molecules dissolved in water to the moving front of the gas hydrate film. In the presented model, the driving force of the process of gas hydrate film growth along the gas–water interface is the concentration driving force. The calculated data obtained in the framework of the presented model are compared with the available experimental data on the kinetics of methane hydrate film growth on a planar water surface and on the surface of a methane bubble suspended in water. Moreover, the calculated data obtained in the framework of the presented model are compared with the available experimental data on the kinetics of carbon dioxide hydrate film growth on the surface of a carbon dioxide bubble suspended in water. As a result of this comparison, the dependence of the thickness of carbon dioxide hydrate film on the concentration driving force was determined.



This work was supported by the Basic Research Program of the Russian Academy of Sciences (project No. IX.135.2.3).

Compliance with ethical standards

Conflict of interest

The author declares that he has no conflict of interest.


  1. 1.
    Chong ZR, Yang SHB, Babu P, Linga P, Li X-S (2016) Review of natural gas hydrates as an energy resource: prospects and challenges. Appl Energy 162:1633–1652CrossRefGoogle Scholar
  2. 2.
    Vorotyntsev VM, Malyshev VM (2011) Gas hydrates: nanosized phases in the separation and purification of substances by crystallization. Russ Chem Rev 80:971–991CrossRefGoogle Scholar
  3. 3.
    Rehder G, Eckl R, Elfgen M, Falenty A, Hamann R, Kähler N, Kuhs WF, Osterkamp H, Windmeier C (2012) Methane hydrate pellet transport using the self-preservation effect: a techno-economic analysis. Energies 5:2499–2523CrossRefGoogle Scholar
  4. 4.
    Shagapov VS, Musakaev NG, Khasanov MK (2015) Formation of gas hydrates in a porous medium during an injection of cold gas. Int J Heat Mass Transf 84:1030–1039CrossRefGoogle Scholar
  5. 5.
    Shagapov VS, Chiglintseva AS, Belova SV (2017) On the theory of formation of a gas hydrate in a heat-insulated space compacted with methane. J Eng Phys Thermophys 90:1147–1161CrossRefGoogle Scholar
  6. 6.
    Veluswamy HP, Kumar A, Seo Y, Lee JD, Linga P (2018) A review of solidified natural gas (SNG) technology for gas storage via clathrate hydrates. Appl Energy 216:262–285CrossRefGoogle Scholar
  7. 7.
    Sloan ED (ed) (2010) Natural gas hydrates in flow assurance. Gulf Professional Publishing, BurlingtonGoogle Scholar
  8. 8.
    Taylor CJ, Miller KT, Koh CA, Sloan ED (2007) Macroscopic investigation of hydrate film growth at the hydrocarbon/water interface. Chem Eng Sci 62:6524–6533CrossRefGoogle Scholar
  9. 9.
    Molokitina NS, Nesterov AN, Podenko LS, Reshetnikov AM (2019) Carbon dioxide hydrate formation with SDS: further insights into mechanism of gas hydrate growth in the presence of surfactant. Fuel 235:1400–1411CrossRefGoogle Scholar
  10. 10.
    Li S-L, Sun C-Y, Liu B, Feng X-J, Li F-G, Chen L-T, Chen G-J (2013) Initial thickness measurements and insights into crystal growth of methane hydrate film. AIChE J 59:2145–2154CrossRefGoogle Scholar
  11. 11.
    Freer EM, Selim MS, Sloan ED (2001) Methane hydrate film growth kinetics. Fluid Phase Equilib 185:65–75CrossRefGoogle Scholar
  12. 12.
    Sun C-Y, Chen G-J, Ma C-F, Huang Q, Luo H, Li Q-P (2007) The growth kinetics of hydrate film on the surface of gas bubble suspended in water or aqueous surfactant solution. J Cryst Growth 306:491–499CrossRefGoogle Scholar
  13. 13.
    Peng BZ, Dandekar A, Sun CY, Luo H, Ma QL, Pang WX, Chen GJ (2007) Hydrate film growth on the surface of a gas bubble suspended in water. J Phys Chem B 111:12485–12493CrossRefGoogle Scholar
  14. 14.
    Tanaka R, Sakemoto R, Ohmura R (2009) Crystal growth of clathrate hydrates formed at the interface of liquid water and gaseous methane, ethane, or propane: variations in crystal morphology. Cryst Growth Des 9:2529–2536CrossRefGoogle Scholar
  15. 15.
    Beltrán JG, Servio P (2010) Morphological investigations of methane-hydrate films formed on a glass surface. Cryst Growth Des 10:4339–4347CrossRefGoogle Scholar
  16. 16.
    Melnikov VP, Nesterov AN, Reshetnikov AM, Istomin VA, Kwon VG (2010) Stability and growth of gas hydrates below the ice–hydrate–gas equilibrium line on the PT phase diagram. Chem Eng Sci 65:906–914CrossRefGoogle Scholar
  17. 17.
    Melnikov VP, Nesterov AN, Reshetnikov AM, Istomin VA (2011) Metastable states during dissociation of carbon dioxide hydrates below 273 K. Chem Eng Sci 66:73–77CrossRefGoogle Scholar
  18. 18.
    Saito K, Kishimoto M, Tanaka R, Ohmura R (2011) Crystal growth of clathrate hydrate at the interface between hydrocarbon gas mixture and liquid water. Cryst Growth Des 11:295–301CrossRefGoogle Scholar
  19. 19.
    Wu R, Kozielski KA, Hartley PG, May EF, Boxall J, Maeda N (2013) Methane–propane mixed gas hydrate film growth on the surface of water and Luvicap EG solutions. Energy Fuels 27:2548–2554CrossRefGoogle Scholar
  20. 20.
    Kitamura M, Mori YH (2013) Clathrate-hydrate film growth along water/methane phase boundaries–an observational study. Cryst Res Technol 48:511–519CrossRefGoogle Scholar
  21. 21.
    Li S-L, Sun C-Y, Liu B, Li Z-Y, Chen G-J, Sum AK (2014) New observations and insights into the morphology and growth kinetics of hydrate films. Sci Rep 4:4129CrossRefGoogle Scholar
  22. 22.
    Daniel-David D, Guerton F, Dicharry C, Torré J-P, Broseta D (2015) Hydrate growth at the interface between water and pure or mixed CO2/CH4 gases: influence of pressure, temperature, gas composition and water-soluble surfactants. Chem Eng Sci 132:118–127CrossRefGoogle Scholar
  23. 23.
    Liu Z, Li H, Chen L, Sun B (2018) A new model of and insight into hydrate film lateral growth along the gas–liquid interface considering natural convection heat transfer. Energy Fuels 32:2053–2063CrossRefGoogle Scholar
  24. 24.
    Mori YH (2001) Estimating the thickness of hydrate films from their lateral growth rates: application of a simplified heat transfer model. J Cryst Growth 223:206–212CrossRefGoogle Scholar
  25. 25.
    Mochizuki T, Mori YH (2006) Clathrate-hydrate film growth along water/hydrate-former phase boundaries–numerical heat-transfer study. J Cryst Growth 290:642–652CrossRefGoogle Scholar
  26. 26.
    Saito K, Sum AK, Ohmura R (2010) Correlation of hydrate-film growth rate at the guest/liquid-water interface to mass transfer resistance. Ind Eng Chem Res 49:7102–7103CrossRefGoogle Scholar
  27. 27.
    Kishimoto M, Ohmura R (2012) Correlation of the growth rate of the hydrate layer at a guest/liquid-water interface to mass transfer resistance. Energies 5:92–100CrossRefGoogle Scholar
  28. 28.
    Mochizuki T, Mori YH (2017) Simultaneous mass and heat transfer to/from the edge of a clathrate-hydrate film causing its growth along a water/guest-fluid phase boundary. Chem Eng Sci 171:61–75CrossRefGoogle Scholar
  29. 29.
    Vlasov VA (2013) Formation and dissociation of gas hydrate in terms of chemical kinetics. React Kinet Mech Catal 110:5–13CrossRefGoogle Scholar
  30. 30.
    Frank-Kamenetskii DA (1969) Diffusion and heat transfer in chemical kinetics, 2nd edn. Plenum Press, New YorkGoogle Scholar
  31. 31.
    Fogler HS (2016) Elements of chemical reaction engineering, 5th edn. Prentice Hall, KendallvilleGoogle Scholar
  32. 32.
    Bergman TL, Lavine AS, Incropera FP, DeWitt DP (2011) Fundamentals of heat and mass transfer, 7th edn. Wiley, New YorkGoogle Scholar
  33. 33.
    Lide DR (ed) (2009) CRC handbook of chemistry and physics, 90th edn. Boca Raton, CRC PressGoogle Scholar
  34. 34.
    Moore JC, Battino R, Rettich TR, Handa YP, Wilhelm E (1982) Partial molar volumes of “gases” at infinite dilution in water at 298.15 K. J Chem Eng Data 27:22–24CrossRefGoogle Scholar
  35. 35.
    Ricaurte M, Torré J-P, Asbai A, Broseta D, Dicharry C (2012) Experimental data, modeling, and correlation of carbon dioxide solubility in aqueous solutions containing low concentrations of clathrate hydrate promoters: application to CO2–CH4 gas mixtures. Ind Eng Chem Res 51:3157–3169CrossRefGoogle Scholar
  36. 36.
    Lu W, Guo H, Chou IM, Burruss RC, Li L (2013) Determination of diffusion coefficients of carbon dioxide in water between 268 and 473 K in a high-pressure capillary optical cell with in situ Raman spectroscopic measurements. Geochim Cosmochim Acta 115:183–204CrossRefGoogle Scholar
  37. 37.
    Takeya S, Udachin KA, Moudrakovski IL, Susilo R, Ripmeester JA (2010) Direct space methods for powder X-ray diffraction for guest–host materials: applications to cage occupancies and guest distributions in clathrate hydrates. J Am Chem Soc 132:524–531CrossRefGoogle Scholar
  38. 38.
    Sloan ED, Koh CA (2008) Clathrate hydrates of natural gases, 3rd edn. CRS Press, Boca RatonGoogle Scholar
  39. 39.
    Rettich TR, Handa YP, Battino R, Wilhelm E (1981) Solubility of gases in liquids. 13. High-precision determination of Henry’s constants for methane and ethane in liquid water at 275 to 328 K. J Phys Chem 85:3230–3237CrossRefGoogle Scholar
  40. 40.
    Klauda JB, Sandler SI (2000) A fugacity model for gas hydrate phase equilibria. Ind Eng Chem Res 39:3377–3386CrossRefGoogle Scholar
  41. 41.
    Guo H, Chen Y, Lu W, Li L, Wang M (2013) In situ Raman spectroscopic study of diffusion coefficients of methane in liquid water under high pressure and wide temperatures. Fluid Phase Equilib 360:274–278CrossRefGoogle Scholar
  42. 42.
    Wagner W, Pruβ A (2002) The IAPWS formulation 1995 for the thermodynamic properties of ordinary water substance for general and scientific use. J Phys Chem Ref Data 31:387–535CrossRefGoogle Scholar
  43. 43.
    Pátek J, Hrubý J, Klomfar J, Součková M, Harvey AH (2009) Reference correlations for thermophysical properties of liquid water at 0.1 MPa. J Phys Chem Ref Data 38:21–29CrossRefGoogle Scholar

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© Springer-Verlag GmbH Germany, part of Springer Nature 2019

Authors and Affiliations

  1. 1.Institute of the Earth Cryosphere, Tyumen Scientific CenterSiberian Branch of the Russian Academy of SciencesTyumenRussia

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