Equilibrium conditions and kinetics of natural gas hydrate formation in the clay soils of the Markhinskiy deposit

Subpermafrost aquifers are distinguished by their low stratum temperatures and pressures that approximate conventional hydrostatic pressures, rendering them suitable geological formations for the organization of underground gas storage facilities in a hydrate state. The design of such facilities requires the execution of experimental studies focused on hydrate formation within porous media. This paper examines the subpermafrost aquifers located in the Vilyui syneclise, where the hydrate stability zone covers Cretaceous and Jurassic deposits, specifically terrigenous-clayey strata. The mineralogical and granulometric composition, density, porosity, and moisture content, along with the presence of clays in the porous medium, influence the conditions conducive to hydrate formation. Therefore, the investigation of hydrate formation in clayey soils is a critical component that will support the development of underground gas storage facilities. To analyze the thermobaric conditions associated with hydrate formation, the method of differential thermal analysis was employed. The samples of porous media comprised clayey soils with varying moisture content, ranging from 15% to 40%. The results indicate that in soils with a moisture content of 20% or greater, a mechanical mixture of hydrates consisting of nearly pure methane and gases with higher molecular weights is produced. Additionally, it was observed that an increase in the moisture content of clay soils correlates with a decrease in the kinetic characteristics of hydrate formation. Based on the conducted research, it can be concluded that porous media characterized by clay layers with minimal moisture content are optimal for the establishment of underground gas storage facilities in a hydrated state.  

1. Malagar B.R.C., Lijith K.P., Singh D.N. Formation & dissociation of methane gas hydrates in sediments: A critical review. Journal of Natural Gas Science and Engineering. 2019;65:168–184. http://doi.org/10.1016/j.jngse.2019.03.005

2. Kalacheva L.P., Ivanova I.K., Portnyagin A.S., et al. Determination of the lower boundaries of the natural gas hydrates stability zone in the subpermafrost horizons of the Yakut arch of the Vilyui syneclise, saturated with bicarbonate-sodium type waters. SOCAR Proceedings, Special. 2021;(2):1–11. http://doi.org/10.5510/OGP2021SI200549

3. Safronov A.F. Geology of Oil and Gas. Yakutsk: Yakut Branch of the Publishing House SB RAS; 2000. 166 p. (In Russ.)

4. Zheleznyak M.N., Semenov V.P. Geotemperature Field and Cryolithozone of the Vilyui Syneclise. Novosibirsk: Publishing House SB RAS; 2020. 123 p. (In Russ.)

5. Saw V.K., Udayabhanu G., Mandal A., Laik S. Methane hydrate formation and dissociation in the presence of silica sand and bentonite clay. Oil & Gas Science and Technology – Rev. IFP Energies nouvelles. 2015; 70(6):1087–1099. http://doi.org/10.2516/ogst/2013200

6. Yan K., Li X., Chen Z., et al. Methane hydrate formation and dissociation behaviors in montmorillonite. Chinese Journal of Chemical Engineering. 2019;27(5):1212–1218. http://doi.org/10.1016/j.cjche.2018.11.025

7. Davletshina D.A., Chuvilin E.M. Estimation of potential gas hydrate formation in finely dispersed soils at negative temperatures: Experimental modeling. Earth’s Cryosphere. 2020;24(4):25–33. http://doi.org/10.21782/KZ1560-7496-2020-4(25-33 (In Russ.)

8. Wu Z., Li Y., Sun X., et al. Experimental study on the effect of methane hydrate decomposition on gas phase permeability of clayey sediments. Applied Energy. 2018;230:1304–1310. http://doi.org/10.1016/j.apenergy.2018.09.053

9. Gur’eva O.M. Hydrate formation processes during CO2 burial in the cryolithozone: Abstr. … Diss. Cand. Sci., Moscow; 2011. 173 p. (In Russ.)

10. Chuvilin E.M., Gur’eva O.M. Experimental investigation of CO2 gas hydrate formation in porous media of frozen and freezing sediments. Earth’s Cryosphere. 2009;13(3):70–79. (In Russ.)

11. Yu C., Sun B., Hasan M., et al. Experimental investigation and modeling on the dissociation kinetics of methane hydrate in clayey silt cores in depressurization. Chemical Engineering Journal. 2024;486(4):150325. http://doi.org/10.1016/j.cej.2024.150325

12. Li Y., Chen M., Song H., et al. Effect of cations (Na+, K+, and Ca2+) on methane hydrate formation on the external surface of montmorillonite: insights from molecular dynamics simulation. ACS Earth and Space Chemistry. 2020;4(4):572–582. https://doi.org/10.1021/acsearthspacechem.9b00323

13. Chen C., Zhang Y., Li X., et al. Experimental investigation into gas production from methane hydrate in sediments with different contents of illite clay by depressurization. Energy. 2024;296:131181. https://doi.org/10.1016/j.energy.2024.131181

14. Ren J., Liu X., Niu M., Yin Z. Effect of sodium montmorillonite clay on the kinetics of CH4 hydrate-implication for energy recovery. Chemical Engineering Journal. 2022;437:135368. https://doi.org/10.1016/j.cej.2022.135368

15. Ren J., Yin Z., Chen G., et al. Effect of marine clay minerals on the thermodynamics of CH4 hydrate: Evidence for the inhibition effect with implications. Chemical Engineering Journal. 2024;488:151148. https://doi.org/10.1016/j.cej.2024.151148

16. Explanatory note to the overview map of the deposits of building materials of the Yakut ASSR on a scale of 1:2,500 0000. In two volumes. Ministry of Geology of the USSR, Soyuzgeolfond association, 1 volume. Moscow; 1988. 422 p. (In Russ.)

17. GOST 25584-2016 Soils. Methods of laboratory determination of the filtration coefficient. Instead of GOST 25584-90; introduced. 01.05.2017. Moscow: Standartinform; 2019. 25 p. (In Russ.)

18. Kalacheva L.P., Ivanova I.K., Portnyagin A.S., et al. Determination of the lower boundaries of the natural gas hydrates stability zone in the subpermafrost horizons of the Yakut arch of the Vilyui syneclise, saturated with bicarbonate-sodium type waters. SOCAR Proceedings, Special. 2021;(2):1–11. http://doi.org/10.5510/OGP2021SI200549

19. Linga P., Daraboina N., Ripmeester J.A., Englezos P. Enhanced rate of gas hydrate formation in a fixed bed column filled with sand compared to a stirred vessel. Chemical Engineering Science. 2012;68(1):617−623. https://doi.org/10.1016/j.ces.2011.10.030

20. Istomin V.A., Yakushev V.S. Gas Hydrates in Natural Conditions. Moscow: Nedra; 1992. 236 p. (In Russ.)

21. Ivanova I.K., Kalacheva L.P., Portnyagin A.S., et al. Experimental study of natural gas hydrate formation in a porous medium in the presence of aqueous solutions of sodium chloride and sodium bicarbonate. Chemistry and Technology of Fuels and Oils. 2023;59(4):679–685. http://doi.org/10.1007/s10553-023-01570-0

22. Makogon YU.F. Natural Gas Hydrates. Moscow: Nedra; 1974. 208 p. (In Russ.)

23. Bulejko V.M., Vovchuk G.A., Grigor’ev B.A., et al. Phase behavior of hydrocarbon systems in a water-saturated sand reservoir under hydrate formation conditions. Vesti Gazovoy Nauki. 2014;20(4):156–163. (In Russ.)

24. Kang S.P., Lee J.W. Formation characteristics of synthesized natural gas hydrates in meso-and macroporous silica gels. The Journal of Physical Chemistry B. 2010; 114(20):6973–6978. http://doi.org/10.1021/jp100812p

25. Zaripova Y., Yarkovoi V., Varfolomeev M., et al. Influence of water saturation, grain size of quartz sand and hydrate-former on the gas hydrate formation. Energies. 2021;14(5):1272. https://doi.org/10.3390/en14051272