Skip to main content
SpringerLink
Log in

Four phase hydrate equilibria of methane and carbon dioxide with heavy hydrate former compounds: Experimental measurements and thermodynamic modeling

  • Separation Technology, Thermodynamics
  • Published:
Korean Journal of Chemical Engineering Aims and scope Submit manuscript

Abstract

We experimentally investigated the hydrate dissociation condition for four phase hydrate (H)-aqueous liquid (LAq)-hydrocarbon rich liquid (LHC)-vapor (V) for the ternary systems of help gas-heavy hydrate former-water. Methane and carbon dioxide are known as help gases and benzene and cyclohexane are considered as heavy hydrate formers. The experimental data were generated using an isochoric pressure-search method. Two different equations of state (EOS) were employed to study the equilibrium phase behavior of ternary four phase systems. The EOSs considered are Valderama-Patel-Teja EOS combined with non-density dependent mixing rule (VPT+NDD) and Statistical Associating Fluid Theory EOS proposed by Huang and Radosz (SAFT-HR). The required binary interaction parameters (BIP) were obtained using vapor-liquid equilibrium (VLE) and liquid-liquid equilibrium (LLE) data. The hydrate phase was modeled by the modification of the solid solution theory of van der Waals and Platteeuw. To obtain reliable results, distortion of cages due to occupation of large molecules was considered. The Kihara parameters of cyclohexane were adjusted to hydrate dissociation data. Model calculations for hydrate forming conditions were found to be in satisfactory agreement with the newly reported data in this work and literature data.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Similar content being viewed by others

References

  1. E.D. Sloan and C. Koh, Clathrate Hydrates of Natural Gases, Third Edition, CRC Press (2007).

    Book  Google Scholar 

  2. K.K. Ostergaard, A. Danesh, A.C. Todd and R.W. Burgass, Trans IChemE, 78, 731 (2000).

    Article  CAS  Google Scholar 

  3. A. Danesh, B. Tohidi, R.W. Burgass and A. C. Todd, Trans IChemE, 71, 457 (1993).

    CAS  Google Scholar 

  4. B. Tohidi, A. Danesh, R.W. Burgass and A. C. Todd, Effect of Heavy Hydrate Formers on the Hydrate Free Zone of Real Reservoir Fluids, in, Society of Petroleum Engineers (1996).

    Book  Google Scholar 

  5. B. Tohidi, A. Danesh, A.R. Tabatabaei and A. C. Todd, Ind. Eng. Chem. Res., 36, 2871 (1997).

    Article  CAS  Google Scholar 

  6. B. Tohidi, A. Danesh, A. C. Todd, R.W. Burgass and K. K. Østergaard, Fluid Phase Equilib., 138, 241 (1997).

    Article  CAS  Google Scholar 

  7. K. A. Udachin, C. I. Ratcliffe and J. A. Ripmeester, Hydrate structure and composition from single crystal X-ray diffraction: Examples of Str. I, II and H hydrates, in: Fourth International Conference on Gas Hydrates, Domestic Organaizing Committee, ICGH-4, 2002, Yokohama, Japan, 604 (2002).

    Google Scholar 

  8. G.D. Holder, S. Zele and R. Enick, Annals of the New York Academy of Sciences, 715, 344 (1994).

    Article  CAS  Google Scholar 

  9. J. S. Tse, W.R. McKinnon and M. Marchi, J. Phys. Chem., 91, 4188 (1987).

    Article  CAS  Google Scholar 

  10. S.R. Zele, S.Y. Lee and G.D. Holder, J. Phys. Chem. B, 103, 10250 (1999).

    Article  CAS  Google Scholar 

  11. R.A. Kini, Z. Huo, M.D. Jager, P. Bollavaram, A. L. Ballad, S. F. Dec and E.D. Sloan, Importance of Hydrate Phase Measurements in Flow Assurance and Energy, in: Fourth International Conference on Gas Hydrates, Domestic Organaizing Committee, ICGH-4, Yokohama, Japan, 867 (2002).

    Google Scholar 

  12. H. Tavasoli and F. Feyzi, J. Natural Gas Sci. Eng., 24, 473 (2015).

    Article  CAS  Google Scholar 

  13. J.H. v. d. Waals and J.C. Platteeuw, Clathrate Solutions, in: Advances in Chemical Physics, John Wiley & Sons, Inc., 1 (1959).

    Google Scholar 

  14. A. L. Ballard and E.D. Sloan, Hydrate Separation Processes for Close-Boiling Compounds, in: Fourth International Conference on Gas Hydrates, Domestic Organaizing Committee, ICGH-4, Yokohama, Japan, 1007 (2002).

    Google Scholar 

  15. A.H. Mohammadi and D. Richon, Chem. Eng. Sci., 66, 4936 (2011).

    Article  CAS  Google Scholar 

  16. P. J. Herslund, K. Thomsen, J. Abildskov, N. von Solms, A. Galfré, P. Brântuas, M. Kwaterski and J.-M. Herri, International J. Greenhouse Gas Control, 17, 397 (2013).

    Article  CAS  Google Scholar 

  17. J.A. Ripmeester, C. I. Ratcliffe and G.E. McLaurin, The role of heavier hydrocarbons in hydrate formation, in: AIChE. Spring Meeting, Session 44, Hydrates in the Gas Industry, Houston, TX (1991).

    Google Scholar 

  18. J.A. Ripmeester, S.T. John, C. I. Ratcliffe and B. M. Powell, Nature, 325, 135 (1987).

    Article  CAS  Google Scholar 

  19. A. H. Mohammadi, V. Belandria and D. Richon, Ind. Eng. Chem. Res., 48, 5916 (2009).

    Article  CAS  Google Scholar 

  20. M.M. Mooijer-van den Heuvel, C. J. Peters and J. de Swaan Arons, Fluid Phase Equilib., 172, 73 (2000).

    Article  CAS  Google Scholar 

  21. Z.-G. Sun, S.-S. Fan, K.-H. Guo, L. Shi, Y.-K. Guo and R.-Z. Wang, J. Chem. Eng. Data, 47, 313 (2002).

    Article  CAS  Google Scholar 

  22. B. Tohidi, A. Danesh, R.W. Burgass and A. C. Todd, Chem. Eng. Sci., 51, 159 (1996).

    Article  Google Scholar 

  23. A.H. Mohammadi and D. Richon, Chem. Eng. Sci., 64, 5319 (2009).

    Article  CAS  Google Scholar 

  24. M.M. Mooijer-van den Heuvel, R. Witteman and C. J. Peters, Fluid Phase Equilib., 182, 97 (2001).

    Article  CAS  Google Scholar 

  25. M. Mohammad-Taheri, A. Zarringhalam Moghaddam, K. Nazari and N. Gholipour Zanjani, Fluid Phase Equilib., 338, 257 (2013).

    Article  CAS  Google Scholar 

  26. R. Ohmura, S. Takeya, T. Uchida and T. Ebinuma, Ind. Eng. Chem. Res., 43, 4964 (2004).

    Article  CAS  Google Scholar 

  27. B. Tohidi, R.W. Burgass, A. Danesh, K. K. ØStergaard and A.C. Todd, Annals of the New York Academy of Sciences, 912, 924 (2000).

    Article  CAS  Google Scholar 

  28. J. Valderrama, J. Chem. Eng. Japan, 23, 87 (1990).

    Article  CAS  Google Scholar 

  29. D. Avlonitis, A. Danesh and A.C. Todd, Fluid Phase Equilib., 94, 181 (1994).

    Article  CAS  Google Scholar 

  30. S.H. Huang and M. Radosz, Ind. Eng. Chem. Res., 29, 2284 (1990).

    Article  CAS  Google Scholar 

  31. S.H. Huang and M. Radosz, Ind. Eng. Chem. Res., 30, 1994 (1991).

    Article  CAS  Google Scholar 

  32. S. Babaee, H. Hashemi, J. Javanmardi, A. Eslamimanesh and A.H. Mohammadi, Fluid Phase Equilib., 336, 71 (2012).

    Article  CAS  Google Scholar 

  33. A. Chapoy, I. Alsiyabi, J. Gholinezhad, R. Burgass and B. Tohidi, Fluid Phase Equilib., 337, 150 (2013).

    Article  CAS  Google Scholar 

  34. D. Avlonitis, Thermodynamics of gas hydrate equilibria, in: Petroleum Engineering, Heriot-Watt University, Edinburgh, Scotland (1992).

    Google Scholar 

  35. A. Chapoy, Phase Behavior in Water/hydrocarbon Mixtures Involved in Gas Production Systems, in, Ecole Des Mines Paris Tech., Paris, France (2004).

    Google Scholar 

  36. M.W. Barrick, J.M. Anderson and R. L. Robinson, J. Chem. Eng. Data, 31, 172 (1986).

    Article  CAS  Google Scholar 

  37. J. J. Carroll, F.-Y. Jou, A. E. Mather and F.D. Otto, Can._J. Chem. Eng., 76, 945 (1998).

    Article  CAS  Google Scholar 

  38. H. Chen and J. Wagner, J. Chem. Eng. Data, 39, 470 (1994).

    Article  CAS  Google Scholar 

  39. N.A. Darwish, K. A. M. Gasem and R. L. Robinson, Jr., J, Chem. Eng. Data, 39, 781 (1994).

    Article  CAS  Google Scholar 

  40. N.A. Darwish, K.A.M. Gasem and R.L. Robinson, J. Chem. Eng. Data, 43, 238 (1998).

    Article  CAS  Google Scholar 

  41. I. Gainar, The solubility of CO2 and N2O in some C6 hydrocarbons at high pressures, Analele Universitatii Bucuresti: Chimie (2003).

    Google Scholar 

  42. A. Chapoy, A.H. Mohammadi, A. Chareton, B. Tohidi and D. Richon, Ind. Eng. Chem. Res., 43, 1794 (2004).

    Article  CAS  Google Scholar 

  43. W.B. Kay and R. E. Albert, Ind. Eng. Chem., 48, 422 (1956).

    Article  CAS  Google Scholar 

  44. C.-H. Kim, P. Vimalchand and M.D. Donohue, Fluid Phase Equilib., 31, 299 (1986).

    Article  CAS  Google Scholar 

  45. Y. S. Kim, S. K. Ryu, S.O. Yang and C. S. Lee, Ind. Eng. Chem. Res., 42, 2409 (2003).

    Article  CAS  Google Scholar 

  46. A. P. Kudchadker and J. J. McKetta, AIChE J., 7, 707 (1961).

    Article  CAS  Google Scholar 

  47. E.N. Lay, V. Taghikhani and C. Ghotbi, J. Chem. Eng. Data, 51, 2197 (2006).

    Article  CAS  Google Scholar 

  48. D. Legret, D. Richon and H. Renon, J. Chem. Eng. Data, 27, 165 (1982).

    Article  CAS  Google Scholar 

  49. K. Lekvam and P.R. Bishnoi, Fluid Phase Equilib., 131, 297 (1997).

    Article  CAS  Google Scholar 

  50. H.-M. Lin, H. M. Sebastian, J. J. Simnick and K.-C. Chao, J. Chem. Eng. Data, 24, 146 (1979).

    Article  CAS  Google Scholar 

  51. A. Maczynski, D.G. Shaw, M. Goral, B. Wisniewska-Goclowska, A. Skrzecz, I. Owczarek, K. Blazej, M.-C. Haulait-Pirson, G.T. Hefter, Z. Maczynska, A. Szafranski and C.L. Young, J. Phys. Chem. Reference Data, 34, 657 (2005).

    Article  CAS  Google Scholar 

  52. T. Merker, N. Franke, R. Gläser, T. Schleid and H. Hasse, J. Chem. Eng. Data, 56, 2477 (2011).

    Article  CAS  Google Scholar 

  53. D. J. Miller and S.B. Hawthorne, J. Chem. Eng. Data, 45, 78 (2000).

    Article  CAS  Google Scholar 

  54. A. H. Mohammadi, A. Chapoy, B. Tohidi and D. Richon, Ind. Eng. Chem. Res., 45, 4825 (2006).

    Article  CAS  Google Scholar 

  55. B. J. Neely, J. Wagner, R. L. Robinson and K.A. M. Gasem, J. Chem. Eng. Data, 53, 165 (2008).

    Article  CAS  Google Scholar 

  56. M. P.W.M. Rijkers, M. Malais and C. J. Peters, J. de Swaan Arons, Fluid Phase Equilib., 77, 327 (1992).

    Article  CAS  Google Scholar 

  57. E. P. Schoch, A. E. Hoffmann and F.D. Mayfield, Ind. Eng. Chem., 32, 1351 (1940).

    Article  CAS  Google Scholar 

  58. P. Servio and P. Englezos, Fluid Phase Equilib., 190, 127 (2001).

    Article  CAS  Google Scholar 

  59. K.Y. Song, G. Feneyrou, F. Fleyfel, R. Martin, J. Lievois and R. Kobayashi, Fluid Phase Equilib., 128, 249 (1997).

    Article  CAS  Google Scholar 

  60. C. Tsonopoulos and G. M. Wilson, AIChE J., 29, 990 (1983).

    Article  CAS  Google Scholar 

  61. A. Valtz, A. Chapoy, C. Coquelet, P. Paricaud and D. Richon, Fluid Phase Equilib., 226, 333 (2004).

    Article  CAS  Google Scholar 

  62. L.-K. Wang, G.-J. Chen, G.-H. Han, X.-Q. Guo and T.-M. Guo, Fluid Phase Equilib., 207, 143 (2003).

    Article  CAS  Google Scholar 

  63. Y. Wang, B. Han, H. Yan and R. Liu, Thermochim. Acta, 253, 327 (1995).

    Article  CAS  Google Scholar 

  64. J. B. Klauda and S. I. Sandler, Ind. Eng. Chem. Res., 39, 3377 (2000).

    Article  CAS  Google Scholar 

  65. A. L. Ballard, A non-ideal hydrate solid solution model for a multiphase equilibria program, in, Colorado School of Mines (2002).

    Google Scholar 

  66. V.R. Belosludov, T. M. Inerbaev, O. S. Subbotin, R.V. Belosludov, J.-i. Kudoh and Y. Kawazoe, J. Supramolecular Chem., 2, 453 (2002).

    Article  CAS  Google Scholar 

  67. B.C. Chakoumakos, C. J. Rawn, A. J. Rondinone, L.A. Stern, S. Circone, S. H. Kirby, Y. Ishii, C.Y. Jones and B. H. Toby, Canadian J. Phys., 81, 183 (2003).

    Article  CAS  Google Scholar 

  68. T. Ikeda, S. Mae, O. Yamamuro, T. Matsuo, S. Ikeda and R.M. Ibberson, J. Phys. Chem. A, 104, 10623 (2000).

    Article  CAS  Google Scholar 

  69. S. Takeya, H. Fujihisa, A. Hachikubo, H. Sakagami and Y. Gotoh, Chem. -A European J., 20, 17207 (2014).

    Article  CAS  Google Scholar 

  70. T.A. Strobel, C. A. Koh and E.D. Sloan, Fluid Phase Equilib., 280, 61 (2009).

    Article  CAS  Google Scholar 

  71. E.D. Sloan, K. A. Sparks and J. J. Johnson, Ind. Eng. Chem. Res., 26, 1173 (1987).

    Article  CAS  Google Scholar 

  72. S. Saito, D. R. Marshall and R. Kobayashi, AIChE J., 10, 734 (1964).

    Article  CAS  Google Scholar 

  73. W.R. Parrish and J. M. Prausnitz, Ind. Eng. Chem. Process Design Development, 11, 26 (1972).

    Article  CAS  Google Scholar 

  74. G.D. Holder and J. H. Hand, AIChE J., 28, 440 (1982).

    Article  CAS  Google Scholar 

  75. L. Lundgaard and J. Mollerup, Fluid Phase Equilib., 76, 141 (1992).

    Article  CAS  Google Scholar 

  76. D. Avlonitis, Chem. Eng. Sci., 49, 1161 (1994).

    Article  CAS  Google Scholar 

  77. A. P. Mehta and E.D. Sloan, AIChE J., 42, 2036 (1996).

    Article  CAS  Google Scholar 

  78. E.D. Sloan, Clathrate Hydrates of Natural Gases, Second Edition, Revised and Expanded, Taylor & Francis (1998).

    Google Scholar 

  79. M.M. Mooijer-van den Heuvel, phase behavior and structural aspects of ternary clathrate hydrate systems. The role of additives, in, Technical universiteit Delf (2004).

    Google Scholar 

  80. I.B.A. Sfaxi, V. Belandria, A.H. Mohammadi, R. Lugo and D. Richon, Chem. Eng. Sci., 84, 602 (2012).

    Article  CAS  Google Scholar 

  81. F. E. Anderson and J.M. Prausnitz, AIChE J., 32, 1321 (1986).

    Article  CAS  Google Scholar 

  82. M. Illbeigi, A. Fazlali and A. H. Mohammadi, Ind. Eng. Chem. Res., 50, 9437 (2011).

    Article  CAS  Google Scholar 

  83. J.A. Ripmeester and C. I. Ratcliffe, J. Phys. Chem., 94, 8773 (1990).

    Article  CAS  Google Scholar 

  84. T. Nakamura, T. Makino, T. Sugahara and K. Ohgaki, Chem. Eng. Sci., 58, 269 (2003).

    Article  CAS  Google Scholar 

  85. T. Maekawa, Fluid Phase Equilib., 267, 1 (2008).

    Article  CAS  Google Scholar 

  86. K. Tumba, P. Reddy, P. Naidoo, D. Ramjugernath, A. Eslamimanesh, A. H. Mohammadi and D. Richon, J. Chem. Eng. Data, 56, 3620 (2011).

    Article  CAS  Google Scholar 

Download references

Author information

Authors and Affiliations

  1. Thermodynamic Research Laboratory, School of Chemical Engineering, Iran University of Science and Technology, Tehran, 16846-13114, Iran

    Hamed Tavasoli & Farzaneh Feyzi

Authors
  1. Hamed Tavasoli
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Farzaneh Feyzi
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Farzaneh Feyzi.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Tavasoli, H., Feyzi, F. Four phase hydrate equilibria of methane and carbon dioxide with heavy hydrate former compounds: Experimental measurements and thermodynamic modeling. Korean J. Chem. Eng. 33, 2426–2438 (2016). https://doi.org/10.1007/s11814-016-0110-x

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s11814-016-0110-x

Keywords

Search

Navigation