Thermodynamics Modeling of Refrigerant Gases Hydrates by Using PSRV2 Equation of State

Document Type : Research Note


Catalyst Research Center, Department of Chemical Engineering, Faculty of Engineering, Razi University, Kermanshah, I.R. IRAN


In this study, a thermodynamic model is presented for the study of the phase equilibria of clathrate hydrates of refrigerants namely Chlorodifluoromethane (R22), Trifluoromethane (R23), difluoromethane) R32), Pentafluoroethane (R125), 1,1,1,2-tetrafluoroethane (R134a), 1,1-difluoroethane  (R152a), and carbon dioxide  (R744). For the modeling of the vapor and liquid phases, the Peng-Robinson equation of state modified by Stryjek and Vera (PRSV2) and the Margules-type mixing rule were employed. To achieve more accurate results, binary interaction parameters are adjusted as a function of temperature. The model is based on equality of water fugacity in the liquid water and hydrate phases. Equation of Du and Guo has been used for the calculation of the Langmuir constant. Also, the parameters was fitted by Nedler–Mead non-linear regression method. The experimental and predicted values show good agreement. The average absolute deviation values of models for R22, R23, R32, R125, R134a, R152a, and R744 refrigerants hydrates are about 1.33%, 0.24%, 0.71%, 1.34%, 0.84%, 0.99%, and 0.97% respectively.


Main Subjects

[1] کرم‌الدین، مریم؛ ورامینیان، فرشاد؛، فرایند شیرین­سازی آب با استفاده از هیدرات گازی، نشریه مهندسی شیمی ایران، سال دوازدهم، 71: 90 تا 98 (1392).
[2] Sloan, E.D., Koh, C.A., "Clathrate Hydrates of Natural Gases", Third Edition, CRC Press, Taylor & Francis Group, (2008).
[3] Karamoddin, Maryam., Varaminian, Farshad., Solubility of R22, R23, R32, R134a, R152a, R125 and R744 Refrigerants in Water by Using Equations of State, International Journal of Refrigeration, 36: 1681-1688 (2013).
[4] Fatemeh Nikbakht, Amir A. Izadpanah, Farshad Varaminian, Amir H. Mohammadi, Thermodynamic Modeling of Hydrate Dissociation Conditions for Refrigerants R-134a, R-141b and R-152a, International Journal of Refrigeration, 35, 1914- 920 (2012).
[5] ایزدپناه، امیر عباس؛ نیکبخت، فاطمه؛ ورامینیان، فرشاد؛، مدل‌سازی تشکیل هیدرات در برخی مبردها با استفاده از معادله حالت CPA جهت تعیین پارامترهای کیهارا، پژوهش نفت، سال بیست و سوم 57 :68 تا 77 (1392).
[6] Fialho P.S., Nieto de Castro C.A., Prediction of Halocarbon Liquid Densities by a Modified Hard SphereeDe Santis Equation of State, Fluid Phase Equilibria, 118: 103-114 (1996).
[7] Miguel A.F., Ferreira G.M., Fonseca M.A., Solubilities of Some New Refrigerants in Water, Fluid Phase Equilibria, 173: 97-107 (2000).
[9] Yaho Du., Tian-Min Guo., Prediction of Hydrate Formation for Systems Containing Methanol, Chemical Engineering Science, 45: 893-900 (1990).
[10] Stryjek R., Vera J.H., PRSV2: A Cubic Equation of State for Accurate Vapor-Liquid Equilibria Calculations, Can. J. Chem. Eng., 64: 820-826 (1986c ).
[12] Klauda J.B., Sandler S.I., A Fugacity Model for Gas Hydrate Phase Equilibria, Industrial & Engineering Chemistry Research, 39: 3377-3386(2000).
[13] Mohammadi A.H., Richon D., Thermodynamic Model for Predicting Liquid Water-Hydrate Equilibrium of the Water-Hydrocarbon System, Ind. Eng. Chem. Res., 47: 1346-1350 (2008).
[14] Jafar Javanmardi, Shahabedin Ayatollahi, Razieh Motealleh, Mahmood Moshfeghian, Experimental Measurement and Modeling of R22 (CHClF2) Hydrates in Mixtures of Acetone + Water, J. Chem. Eng. Data, 49: 886-889 (2004).
[15] Hironobu Kubota, Kunihiko Shimizu, Yoshiyuki Tanaka, Tadashi MakIta, Thermodynamic Properties of R13 (CIF3), R23 (HF3), R152a (C2H4F2), and Propane Hydrates for Desalination of Sea Water, J. Chem. Eng. Jpn., 17: 423-429 (1984). 
[16] Shunsuke Hashimoto, Hiroshi Miyauchi, Yoshiro Inoue, Kazunari Ohgaki, Thermodynamic and Raman Spectroscopic Studies on Difluoromethane (HFC32) + Water Binary System, J. Chem. Eng. Data, 55: 2764-2768(2010).
[17] Shunsuke Hashimoto, Takashi Makino, Yoshiro Inoue, Kazunari Ohgaki, Three-Phase Equilibrium Relations and Hydrate Dissociation Enthalpies for Hydrofluorocarbon Hydrate Systems: HFC-134a, -125, and -143a Hydrates, J. Chem. Eng. Data, 55: 4951-4955 (2010).
[18] Sugahara T., Endo A., Miyauchi H., An Choi S., Matsumoto Y., Yasuda K., Hashimoto S., Ohgaki K., High-Pressure Phase Equilibrium and Raman Spectroscopic Studies on the 1,1-Difluoroethane (HFC-152a) Hydrate System, J.Chem.Eng.Data, 56: 4592-4596 (2011).
[19] Hashemi H., Babaee S., Mohammadi A.H., Naidoo P., Ramjugernath D., Experimental Measurements and Thermodynamic Modeling of Refrigerant Hydrates Dissociation Conditions Conditions., J. Chem. Thermodynamics, 80: 30–40 (2015).