The Effect of Dynamics and Mass Transfer Limitation on the Kinetic Growth Rate of Methane Gas Hydrates

Open Access

Year : 2026 | Volume : 16 | Issue : 01 | Page : 76 84
    By

    Alamezie Chinedu*,

  1. Research Scholar, School of Engineering, University of Aberdeen, Aberdeen AB24 3UE, Scotland, UK

Abstract

Hydrate management aims to prevent impediments to fluid flow in pipes caused by hydrate deposition. To achieve this goal effectively, a comprehensive understanding of the thermodynamics and kinetics of hydrate formation is essential for predicting their equilibrium conditions, quantifying the amount of deposition, and estimating the associated risk. Hydrate growth studies are a relatively new field, and independent laboratory experiments have shown that hydrate growth is controlled by heat transfer, mass transfer, and its intrinsic kinetic property. At the commencement of growth, the intrinsic kinetics control the growth rate, and this mechanism gradually fades with the inclusion of mass transfer as growth progresses. This phase of transmission from intrinsic kinetic mechanism to mass transfer is not adequately explored in previous literature, and a common diffusivity constant that controls the mass transfer mechanism of gas hydrates is vital. Addressing these issues is crucial for estimating the growth rate of hydrants, which justifies this paper. Experimental data from the published literature were analyzed, and regression analysis was applied to model the behavior of methane gas consumption rates and stirring speeds during hydrate growth. Additionally, we examined how the diffusivity coefficient of methane hydrates depends on system temperature. R-squared values of 97.05% and 70.39% indicate good model fitness. The relationship between flow dynamics and intrinsic kinetics as a driving force is discussed, and threshold speeds in rpm for negligible mass transfer inclusion are presented for further methane hydrate growth studies. This paper seeks to advance the currently available knowledge in hydrate growth studies and, in a broader sense, flow assurance: risk analysis and management.

Keywords: Diffusivity, flow assurance, intrinsic kinetics, mass transfer, methane hydrates

[This article belongs to Journal of Petroleum Engineering & Technology ]

How to cite this article:
Alamezie Chinedu*. The Effect of Dynamics and Mass Transfer Limitation on the Kinetic Growth Rate of Methane Gas Hydrates. Journal of Petroleum Engineering & Technology. 2026; 16(01):76-84.
How to cite this URL:
Alamezie Chinedu*. The Effect of Dynamics and Mass Transfer Limitation on the Kinetic Growth Rate of Methane Gas Hydrates. Journal of Petroleum Engineering & Technology. 2026; 16(01):76-84. Available from: https://journals.stmjournals.com/jopet/article=2026/view=239310


References

  1. Bollavaram P, Devarakonda S, Selim MS, Sloan ED Jr. Growth kinetics of single crystal sII hydrates: elimination of mass and heat transfer effects. Ann N Y Acad Sci. 2000;912(1):533–543. doi:10.1111/j.1749-6632.2000.tb06808.x.
  2. Brumby PE, Yuhara D, Wu DT, Sum AK, Yasuoka K. Cage occupancy of methane hydrates from Gibbs ensemble Monte Carlo simulations. Fluid Phase Equilib. 2016;413:242–248. doi:10.1016/j.fluid.2015.10.005.
  3. Chaudhari RV, Gholap RV, Emig G, Hofmann H. Gas-liquid mass transfer in ‘dead-end’ autoclave reactors. Can J Chem Eng. 1987;65(5):744–751. doi:10.1002/cjce.5450650506.
  4. Chicco D, Warrens MJ, Jurman G. The coefficient of determination R-squared is more informative than SMAPE, MAE, MAPE, MSE and RMSE in regression analysis evaluation. PeerJ Comput Sci. 2021;7:e623. doi:10.7717/peerj-cs.623.
  5. Clarke MA, Bishnoi PR. Determination of the intrinsic kinetics of CO₂ gas hydrate formation using in situ particle size analysis. Chem Eng Sci. 2005;60(3):695–709. doi:10.1016/j.ces.2004.08.040.
  6. Davies SR, Lachance JW, Sloan ED, Koh CA. A novel approach to measuring methane diffusivity through a hydrate film using differential scanning calorimetry. In: Proceedings of the 6th International Conference on Gas Hydrates (ICGH 2008); 2008 Jul 6–10; Vancouver, BC, Canada. Vancouver: University of British Columbia; 2008. doi:10.14288/1.0041018.
  7. Englezos P, Kalogerakis N, Dholabhai PD, Bishnoi PR. Kinetics of formation of methane and ethane gas hydrates. Chem Eng Sci. 1987;42(11):2647–2658. doi:10.1016/0009-2509(87)87015-X.
  8. Filarsky F, Hagelstein M, Schultz HJ. Influence of different stirring setups on mass transport, gas hydrate formation, and scale transfer concepts for technical gas hydrate applications. Appl Res. 2023;2(1):e202200050. doi:10.1002/appl.202200050.
  9. Garcia-Ochoa F, Gomez E. Theoretical prediction of gas–liquid mass transfer coefficient, specific area and hold-up in sparged stirred tanks. Chem Eng Sci. 2004;59(12):2489–2501. doi:10.1016/j.ces.2004.02.009.
  10. Hassanpouryouzband A, Joonaki E, Vasheghani Farahani MV, Takeya S, Ruppel C, Yang J, et al. Gas hydrates in sustainable chemistry. Chem Soc Rev. 2020;49(15):5225–5309. doi:10.1039/C8CS00989A.
  11. Ijomah AM. On the misconception of r² for (r)² in a regression model. Int J Res Sci Innov. 2019;6(12):2321–2705.
  12. Jensen L, Thomsen K, von Solms N, Wierzchowski S, Walsh MR, Koh CA, et al. Calculation of liquid water-hydrate-methane vapor phase equilibria from molecular simulations. J Phys Chem B. 2010;114(17):5775–5782. doi:10.1021/jp911032q.
  13. Ke W, Svartaas TM. Effects of stirring and cooling on methane hydrate formation in a high pressure isochoric cell. J Mater Sci Eng B. 2013;3:436–444. doi:10.17265/2161-6221/2013.07.005.
  14. Ke W, Svartaas TM, Chen D. A review of gas hydrate nucleation theories and growth models. J Nat Gas Sci Eng. 2019;61:169–196. doi:10.1016/j.jngse.2018.10.021.
  15. Kuhs WF, Staykova DK, Salamatin AN. Formation of methane hydrate from polydisperse ice powders. J Phys Chem B. 2006;110(26):13283–13295. doi:10.1021/jp061060f.
  16. Liu B, Pang W, Peng B, Sun C, Chen G. Heat transfer related to gas hydrate formation/dissociation. In: Bernardes MAS, editor. Developments in Heat Transfer. London: IntechOpen; 2011. p. 477–502. doi:10.5772/19711.
  17. Lo H, Lee MT, Lin ST. Water vacancy driven diffusion in clathrate hydrates: molecular dynamics simulation study. J Phys Chem C. 2017;121:8280–8289. doi:10.1021/acs.jpcc.7b00853.
  18. Meindinyo RET. Gas hydrate growth kinetics: experimental study related to effects of heat transfer [dissertation]. Stavanger: University of Stavanger, Faculty of Science and Technology, Department of Petroleum Engineering; 2017.
  19. Mork M. Formation rate of natural gas hydrate – reactor experiments and models [dissertation]. Trondheim: Norwegian University of Science and Technology, Faculty of Engineering; 2002. 186 p. Available from: https://hdl.handle.net/11250/231310
  20. Neto ET, Rahman MA, Imtiaz S, Pereira TDS, Sousa FSD. Coupled heat and mass transfer CFD model for methane hydrate. In: Proceedings of the ASME 2015 34th International Conference on Ocean, Offshore and Arctic Engineering (OMAE2015); 2015 May 31–Jun 5; St. John’s, Newfoundland, Canada. New York: American Society of Mechanical Engineers; 2015. p. V010T11A033. doi:10.1115/OMAE2015-42258.
  21. Odukoya A, Naterer GF. Heat transfer and multiphase flow with hydrate formation in subsea pipelines. Heat Mass Transfer. 2015;51(7):901–909. doi:10.1007/s00231-014-1457-3.
  22. Ozili PK. The acceptable R-square in empirical modelling for social science research. In: Saliya CA, editor. Social Research Methodology and Publishing Results: A Guide to Non-Native English Speakers. Hershey (PA): IGI Global; 2023. p. 134–143. doi:10.4018/978-1-6684-6859-3.ch009.
  23. Peters B, Zimmermann NER, Beckham GT, Tester JW, Trout BL. Path sampling calculation of methane diffusivity in natural gas hydrates from a water-vacancy assisted mechanism. J Am Chem Soc. 2008;130(51):17342–17350. doi:10.1021/ja802014m.
  24. Ranieri U, Koza MM, Kuhs WF, Klotz S, Falenty A, Gillet P, et al. Fast methane diffusion at the interface of two clathrate structures. Nat Commun. 2017;8(1):1076. doi:10.1038/s41467-017-01167-2.
  25. Roosta H, Khosharay S, Varaminian F. Experimental study of methane hydrate formation kinetics with or without additives and modeling based on chemical affinity. Energy Convers Manag. 2013;76:499–505. doi:10.1016/j.enconman.2013.05.024.
  26. Shi BH, Gong J, Sun CY, Zhao JK, Ding Y, Chen GJ. An inward and outward natural gas hydrates growth shell model considering intrinsic kinetics, mass and heat transfer. Chem Eng J. 2011;171(3):1308–1316. doi:10.1016/j.cej.2011.05.029.
  27. Skovborg P, Rasmussen P. A mass transport limited model for the growth of methane and ethane gas hydrates. Chem Eng Sci. 1994;49(8):1131–1143. doi:10.1016/0009-2509(94)85085-2.
  28. Sloan ED Jr, Koh CA. Clathrate Hydrates of Natural Gases. Boca Raton (FL): CRC Press; 2007.
  29. Takahata M, Kashiwaya Y, Ishii K. Kinetics of methane hydrate formation catalyzed by iron oxide and carbon under intense stirring conditions. Mater Trans. 2010;51:727–734. doi:10.2320/matertrans.M2009369.
  30. Vysniauskas A, Bishnoi PR. A kinetic study of methane hydrate formation. Chem Eng Sci. 1983;38(7):1061–1072. doi:10.1016/0009-2509(83)80027-X.
  31. Yang S, Li X, Yang C, Ma B, Mao ZS. Computational fluid dynamics simulation and experimental measurement of gas and solid holdup distributions in a gas–liquid–solid stirred reactor. Ind Eng Chem Res. 2016;55(12):3276–3286. doi:10.1021/acs.iecr.5b03163.
  32. Yin Z, Chong ZR, Tan HK, Linga P. Review of gas hydrate dissociation kinetic models for energy recovery. J Nat Gas Sci Eng. 2016;35:1362–1387. doi:10.1016/j.jngse.2016.04.050.
  33. Yin Z, Khurana M, Tan HK, Linga P. A review of gas hydrate growth kinetic models. Chem Eng J. 2018;342:9–29. doi:10.1016/j.cej.2018.01.120.
Regular Issue Open Access Original Research
Volume 16
Issue 01
Received 10/02/2026
Accepted 20/02/2026
Published 27/03/2026
Publication Time 45 Days
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