Prediction of Gas and Refrigerant Hydrate Equilibrium Conditions With and Without Thermodynamic Inhibitors Using Simple Empirical Correlations

Document Type : Research Paper


Department of Chemical Engineering, Faculty of Engineering, University of Science and Technology of Mazandaran, Behshahr, Mazandaran, Iran


Clathrate hydrates (gas hydrates) are solid crystalline compounds formed from water molecules as host molecules and gas molecules as guest molecules. Due to the hydrogen bonds, water constructs a framework that entraps some small nonpolar molecules (typically gases) and in suitable conditions (i. e. low temperature and high pressure) gas hydrate forms. The objective of this research is to estimate the gas and refrigerant hydrate dissociation conditions with and without alcohols and sodium chloride aqueous solutions using simple empirical correlations. Generally, the empirical suggested correlations to estimate the equilibrium clathrate hydrate pressure of CH4, C2H6, C3H8, CO2, N2, H2S, R22, R23, R134a, R116, R125a, R152a, R141b, R410a, R407c, R507c, CH4 + methanol, CH4 + ethylene glycol, CH4 + triethylene glycol, CH4 + ethanol, CH4 + sodium chloride, CO2 + methanol, CO2 + glycerol, CO2 + sodium chloride, R134a + sodium chloride, R507c + sodium chloride and R410a + sodium chloride systems are a function of equilibrium hydrate temperature and concentration. A genetic algorithm was employed as an optimization method to determine correlation coefficients, and the mean squared error was selected as its fitness function. Due to the low values of the calculated absolute average deviations (between 0.00 and 7.65), except for H2S + pure water with the highest amount of the absolute average deviation percent (AAD% equal to 11.51), these correlations are capable of predicting the studied hydrate dissociation conditions.


  1. Sloan ED, Koh CA (2008) Clathrate hydrates of natural gases, 3rd ed., CRC Press/ Taylor & Francis, 386-513.##
  2. Javanmardi J, Nasrifar Kh, Najibi SH, Moshfeghian M (2005) Economic evaluation of natural gas hydrate as an alternative for natural gas transformation, Applied Thermal Journal of Engineering, 25: 1708-1728. ##
  3. Demirbas A (2010) Methane hydrates as potential energy resource: part 2- methane production processes from gas hydrates, Energy Conversion and Management, 51: 1562-1571. ##
  4. Veluswamy HP, Kumar R, Linga P (2014) Hydrogen storage in clathrate hydrates: current state of the art and future directions, Applied Energy, 122: 112-132. ##
  5. Park K, Hong SY, Lee JW, Kang KC, Lee YC, Ha MG, Lee JD (2011) A new apparatus for seawater desalination by gas hydrate process and removal characteristics of dissolved minerals (Na+, Mg2+, Ca2+, K+, B3+), Desalination, 274: 91-96. ##
  6. Babu P, Linga P, Kumar R, Englezos P (2015) A review of the hydrate-based gas separation (HBGS) process for carbon dioxide pre-combustion capture, Energy, 85: 261-279. ##
  7. Wang X, Dennis M, Hou L (2014) Clathrate hydrate technology for cold storage in air conditioning systems, Renewable and Sustainable Energy Reviews, 36: 34-51. ##
  8. Koh JH, Zakaria Z, Veerasamy D (2017) Hydrocarbons as refrigerants-a review, ASEAN Journal on Science and Technology for Development, 34:35-50. ##
  9. Dreepaul RK (2017) A study of alternative refrigerants for the refrigeration and air conditioning sector in Mauritius, IOP Conf. Series: Earth and environmental science 93. ##
  10. Carbajo JJ (1985) A direct-contact charged direct-contact discharged cool storage system using gas hydrate, ASHRAE Trans, 91:258-266. ##
  11. Karamoddin M, Varaminian F (2013) Experimental measurement of phase equilibrium for gas hydrates of refrigerants, and thermodynamic modeling by SRK, VPT and CPA EoSs, The Journal of Chemical Thermodynamics, 65:213- 219. ##
  12. Haghtalab A, Mohammadi M. (2014) Thermodynamic modeling of refrigerants hydrates dissociation by two-step hydrates formation theory of Chen-Guo, The 8th International Chemical Engineering Congress and Exhibition (IChEC 2014), Kish , Iran , 24-27 February. ##
  13. Ngema PTh, Petticrew C, Naidoo P, Mohammadi AH, Ramjugernath D (2014) Experimental measurements and thermodynamic modeling of the dissociation conditions of clathrate hydrates for (Refrigerant + NaCl + Water) systems, Journal of Chemical and Engineering Data, 59: 466-475. ##
  14. Nikbakht F, Izadpanah AA, Varaminian F, Mohammadi AH  (2012) Thermodynamic modeling of hydrate dissociation conditions for refrigerants R-134a, R-141b and R-152a, International Journal of Refrigerants, 35: 145-151. ##
  15. Hashemi H, Babaee S, Mohammadi AH, Naidoo P, Ramjugernath D (2015) Clathrate hydrates dissociation conditions of refrigerants R-404a, R-406a, R-408a and R-427a: experimental measurement and thermodynamic modeling, The Journal of Chemical and Thermodynamics, 90: 193-198. ##
  16. Hashemi H, Babaee S, Naidoo P,  Mohammadi AH, Ramjugernath D (2014) Experimental measurements and thermodynamic modeling of clathrate hydrate dissociation conditions for refrigerants R116, R23 and their mixtures R508b, Journal of Chemical and Engineering Data, 59:3907-3911. ##
  17. Izadpanah AA, Nikbakht F, Varaminian F (1392) Modeling of hydrate formation in some refrigerant hydrates using CPA equation of state for calculating Kihara parameters, Oil Research Journal, 57:68-77. ##
  18. Ghanbari MJ,  Moradi Gh (1395) Thermodynamic modeling for phase equilibrium refrigerant hydrates with PRSV2 equation of state, Chemistry and Chemical Engineering of Iran, 135: 125-132. ##
  19. Wang Z, Li F, Fan T, Xiong W, Yang B (2015) Research on the application of gas hydrate in cool storage air conditioning, Procedia Engineering, 121: 1118-1125. ##
  20. Salehy Y, Clain P, Boufares A, Osswald V, Delahaye A, Fournaison L (2017) Rheological study on CO2 hydrate slurries for secondary refrigeration, Energetica, 122: 105-112. ##
  21. Hashemi H, Babaee S, Mohammadi AH, Naidoo P, Ramjugernath D (2015) Experimental measurements and thermodynamic modeling of refrigerant hydrates dissociation conditions, Journal of Chemical Thermodynamics, 80: 30-40. ##
  22. Liang D, Guo K, Wang R, Fan Sh (2001) Hydrate equilibrium data of 1,1,1,2-tetrafluoroethane (HFC-134a), 1,1-dichloro-1-fluoroethane (HCFC-141b) and 1,1-difluoroethane (HFC-152a), Fluid Phase Equilibria, 187-188: 61-70. ##
  23. van der Waals JH, Platteeuw JC (1959) Clathrate solutions, Advanced Chemistry and Physics, 2: 1-57. ##
  24. Parrish WR, Prausnitz JM (1972) Dissociation pressures of gas hydrate formed by gas mixture, Industrial Engineering Chemistry Process Design and Development, 11: 26-34. ##
  25. Chen JH, Guo TM (1998) A new approach to gas hydrate modeling, Chemical Engineering Journal, 71: 145-151. ##
  26. Chen GJ, Guo TM (1996) Thermodynamic modeling of hydrate formation based on new concepts, Fluid Phase Equilibria, 122: 43-65. ##
  27. Abolala M, Karamoddin M, Varaminian F (2014) Thermodynamic modeling of phase equilibrium for gas hydrate in single and mixed refrigerants by using SPC-SAFT equation of state, Fluid Phase Equilibria, 370: 69-74. ##
  28. Heydari A, Shayesteh K, Kamalzadeh L  (2006) Prediction of hydrate formation temperature for natural gas using artificial neural network, Oil and Gas Business, 2: 1-10. ##
  29. Zahedi Gh, Karami Z, Yaghoobi H (2009) Prediction of hydrate formation temperature by both statistical models and artificial neural network approaches, Energy Conversion and Management, 50: 2052-2059. ##
  30. Elgibaly A, Elkamel A (1999) Optimal hydrate inhibition policies with the aid of neural network, Energy and Fuels, 13: 105-113. ##
  31. Zeinali N, Saber M, Ameri A (2012) Comparative analysis of hydrate formation pressure applying Cubic Equations of State (EoS), Artificial neural network (ANN) and Adaptive Neuro-Fuzzy Inference System (ANFIS), International Journal of Thermodynamics (IJoT), 15: 91-101. ##
  32. Hashim FM, Abbasi A (2016) Empirical modeling of hydrate formation prediction in deepwater pipelines, ARPN Journal of Engineering and Applied Science, 11: 12212-12216. ##
  33. Rebai N, Hadjadj A, Benmounah A, Berrouk AS, Boualleg SM (2019) Prediction of natural gas hydrates formation using a combination of thermodynamic and neural network modeling,  Journal of Petroleum Science and Engineering, 182: 1-19. ##
  34. Hammerschmidt EG (1934) Formation of gas hydrates in natural gas transmission lines, Industrial and Engineering Chemistry, 26, 851. ##
  35. Makogon Y (1981) Hydrates of Natural Gas, Penn Well Publishing Company, Tulsa, 1- 237. ##
  36. Kobayashi R, Song K, Sloan E (1987) Phase behavior of water/hydrocarbon systems. In: Bradley, H.B., Gipson Fred, W. (Eds.), Petroleum Engineering Handbook, Society of Petroleum Engineers, Richardson, TX, USA. ##
  37. Sangtam B T, Majumder SK. (2018) A new empirical correlation for prediction of gas hydrate dissociation equilibrium, Journal of Petroleum science and technology, 36: 1432-1438. ##
  38. Chavoshi S, Safamirzaei M, Pajoum Shariati F (2018) Evaluation of empirical correlations for predicting gas hydrate formation temperature, Gas Processing Journal, 6: 15-36. ##
  39. Aregbe AG (2019) A generalized correlation for predicting ethane, propane, and isobutane hydrates equilibrium data in pure water and aqueous salt solutions, Global Challenges, 3: 1-10. ##
  40. Bahadori A, Vuthaluru HB (2009) A novel correlation for estimation of hydrate forming condition of natural gases, Journal of Natural Chemistry, 18: 453-457. ##
  41. Sayyad Amin J, Bahadori M, Bahadori A, Abbasi Souraki B, Rafiee S (2016) Modeing of CO2 capture and separation from different gas mixtures using semiclathrate hydrates, Petroleum Science and Technology, 34: 406-414. ##
  42. Maekawa T, Itoh S, Sakata S, Igari SI, Imai N (1995) Pressure and temperature conditions for methane hydrate dissociation in sodium chloride solutions, Geochemical Journal, 29, 5: 325–9. ##
  43. Jager MD, Sloan ED (2001) The effect of pressure on methane hydration in pure water and sodium chloride solutions, Fluid Phase Equilibria, 185: 89–99. ##
  44. Maekawa T (2008) Equilibrium conditions of propane hydrates in aqueous solutions of alcohols, glycols, and glycerol, Journal of Chemical and Engineering Data, 53: 2838–43. ##
  45. Maekawa T (2012) Equilibrium conditions of ethane hydrates in the presence of aqueous solutions of alcohols, glycols, and glycerol, Journal of Chemical and Engineering Data, 57: 526–31. ##
  46. Mesbah M, Habibnia S, Ahmadi Sh, Dehghani AH, Bayat S (2020) Developing a robust correlation for prediction of sweet and sour gas hydrate formation temperature, Journal of Petroleum. ##
  47. Ikoku CU (1984) Natural gas production engineering, New York: John Wiley and Sons Inc., 1-516. ##
  48. Goldberg DE (1989) Genetic algorithms in search, optimization, and machine learning Addison Wesley Publication Company. ##
  49. Back T (1996) Evolutionary algorithms in theory and practice: evolution strategies, evolutionary programming, genetic algorithms, 1st ed., New York, Oxford University Press. ##
  50. Deep K, Das KN (2008) Quadratic approximation based hybrid genetic algorithm for function optimization, Applied Mathematics and Computation, 203 : 86-98. ##
  51. Gen M, Cheng R (1997) Genetic algorithms and enginerring design, John Wiley and Sons. ##
  52. Javanmardi J, Ayatollahi Sh, Motealleh R, Moshfeghian M (2004) Experimental measurement and modeling of R22 ((CHClF2) hydrates in mixtures of Acetone + water , Journal of Chemical and Engineering Data, 49: 886-889. ##
  53. Kubota H, Shimizu K, Tanaka Y, Makita T (1984) Thermodynamic properties of R13 (CClF3), R23 (CHF3), R152a (C2H4F2), and Propane hydrates for desalination of sea water, Journal of Chemical Engineering Of Japan, 17: 423-429. ##
  54. Kim E, Shin E, Ko G, Kim SH, Han OH, Kwak SK, Seo Y (2016) Enclathration of CHF3 and C2F6 molecules in gas hydrates for potential application in fluorinated gas (F-gas) separation, Journal of Chemical Engineering, 306: 298-305. ##
  55. Hashimoto Sh, Makino T, Inoue Y, Ohgaki K (2010) Three- phase equilibrium relations and hydrate dissociation enthalpies for hydrofluorocarbon hydrate systems: HFC-134a, -125, and -143a hydrates, Journal of Chemical and Engineering Data, 55: 4951-4955. ##