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Thermodynamic Modeling Study on Phase Equilibrium of Gas Hydrate Systems for CO2 Capture

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Abstract

A thermodynamic model is introduced to describe equilibrium conditions of gas hydrates formed from mixtures of CO2, N2 and H2O. The model employs the van der Waals and Platteeuw (vdW–P) solid solution theory and a modified version of cubic-plus-association equation of state that uses the Peng–Robinson equation of state for physical interactions (PR–CPA) to describe hydrate and fluid phases, respectively. When not available elsewhere, the model parameters are determined as part of this work. Pure component parameters for N2 were calculated by fitting of the PR–CPA parameters to vapor pressures and saturated liquid densities. Moreover, solubility data for N2 in pure water are used to fit the binary interaction parameter for the N2–H2O system. Finally, Kihara cell potential parameters are obtained by regressing the model to the hydrate dissociation pressures of mixed hydrates. The model is validated with available experimental data in terms of equilibrium dissociation pressure and hydrate composition. Results reveal that the model is capable of describing equilibrium conditions with high accuracy. In addition to the equilibrium dissociation pressure, the model is able to predict hydrate compositions with satisfactory accuracy compared to other models, although such data were not utilized as reference data in the fitting procedure. Due to disparity amongst various data sets for the studied system, it is difficult to find unequivocally a model that perform better for all data sets. However, the introduced model shows more accurate results for most data sets and obtains satisfactory agreement in the rest. Additionally, the presented model predicts the structural transition boundary better than other similar models.

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Abbreviations

a :

Attractive parameter of a cubic EoS

b :

Co-volume parameter of a cubic EoS

g :

Radial distribution function

k ij :

Binary interaction parameter

l ij :

Binary interaction parameter

P :

Pressure

R :

Universal ideal gas constant

T :

Absolute temperature

v :

Molar volume

Z :

Compressibility factor

\(T^{\prime}_{c}\) :

Rescaled critical temperature

\(P^{\prime}_{c}\) :

Rescaled critical pressure

f :

Fugacity of gas species

y j :

The mole fraction of component j in the vapor phase

xi :

The mole fraction of the component i in the liquid/vapor phase

\(X^{{A_{i} }}\) :

The mole fraction of the molecule i not bonded at site A

\(w(r)_{m,j}\) :

The spherical core cell potential of component j in a cavity of type m

r :

The linear distance from the center of the cell

z m :

The coordination number for the guest in a cavity of type m

R m :

The radius of cavity type m

C m,j :

The Langmuir coefficient of component j in a cavity of type m

k B :

The Boltzmann constant

NDP:

Number of data points

Y j :

The composition of hydrate former j in the hydrate phase on a water-free basis

\(\varepsilon^{{A_{i} B_{j} }}\) :

Association energy between site A of molecule i and site B on molecule j

\(\beta^{{A_{i} B_{j} }}\) :

Association volume between site A of molecule i and site B on molecule j

ω′:

Rescaled acentric factor

ρ :

The molar density of the mixture

μ :

The chemical potential

ν m :

The number of cavities of type m per water molecule in the unit cell

θ m,j :

The fractional occupancy of component j in a cavity of type m

\(\Delta^{{A_{i} B_{j} }}\) :

Association strength

α :

The activity of water in the non-ideal liquid phase

\(\Delta \mu \left( {T, P} \right)_{w}^{L}\) :

Chemical potential difference for water between the meta-stable β-phase and liquid phase

\(\Delta \mu \left( {T_{0} , P_{0} } \right)_{w}^{\beta - L}\) :

The chemical potential difference for water between the β-phase and liquid phase at reference temperature T0 and reference pressure P0

\(\Delta \mu \left( {T, P_{R} } \right)_{w}^{{L,{\text{ref}}}}\) :

The chemical potential difference for water at temperature T and the dissociation pressure of the reference pressure PR

\(\Delta H\left( {T_{0} , P_{0} } \right)_{w}^{{\beta - {\text{ice}}}}\) :

The differences in molar enthalpy for water between the meta-stable β-phase measured for the reference hydrate and ice

\(\Delta H\left( T \right)_{w}^{{{\text{ice}} - L}}\) :

The differences in molar enthalpy for water between ice and liquid water

\(\Delta V_{w}^{{\beta - {\text{ice}}}}\) :

The differences in molar volume for water between the β-phase measured for the reference hydrate and ice

\(\Delta V_{w}^{{{\text{ice}} - L}}\) :

The differences in molar volume for water between ice and liquid water

\(\Delta C_{P}\) :

The isobaric heat capacity difference for water from the reference temperature to the actual temperature

L :

The liquid phase

H :

The hydrate phase

V :

The vapor phase

β :

The meta-stable phase with the same structure of water in the hydrate as in the reference state

φ j :

The fugacity coefficient of component j in the vapor phase

c :

Critical property

r :

Reduced property

i :

The component i

j :

The component j

w :

Water

0:

The reference situation

References

  1. Eslamimanesh, A., Mohammadi, A.H., Richon, D., Naidoo, P., Ramjugernath, D.: Application of gas hydrate formation in separation processes: a review of experimental studies. J. Chem. Thermodyn. 46, 62–71 (2012). https://doi.org/10.1016/j.jct.2011.10.006

    Article  CAS  Google Scholar 

  2. Tzirakis, F., Stringari, P., von Solms, N., Coquelet, C., Kontogeorgis, G.: Hydrate equilibrium data for the CO2+N2 system with the use of tetra-n-butylammonium bromide (TBAB), cyclopentane (CP) and their mixture. Fluid Phase Equilib. 408, 240–247 (2016). https://doi.org/10.1016/j.fluid.2015.09.021

    Article  CAS  Google Scholar 

  3. Hajizadeh, A., Mohamadi-Baghmolaei, M., Azin, R., Osfouri, S., Heydari, I.: Technical and economic evaluation of flare gas recovery in a giant gas refinery. Chem. Eng. Res. Des. 131, 506–519 (2018)

    Article  CAS  Google Scholar 

  4. Mustafa, J., Farhan, M.: CO separation from flue gses using different types of membranes. J. Membr. Sci. Technol. (2016). https://doi.org/10.4172/2155-9589.1000153

    Article  Google Scholar 

  5. Chazallon, B., Pirim, C.: Selectivity and CO2 capture efficiency in CO2–N2 clathrate hydrates investigated by in situ Raman spectroscopy. Chem. Eng. J. 342, 171–183 (2018). https://doi.org/10.1016/j.cej.2018.01.116

    Article  CAS  Google Scholar 

  6. Herslund, P.J.: Thermodynamic and Process Modelling of Gas Hydrate Systems in CO2 Capture Processes. Technical University of Denmark, Department of Chemical and Biochemical Engineering, Lyngby (2013)

    Google Scholar 

  7. Sloan, E.D., Koh, C.A.: Clathrate Hydrates of Natural Gases, 3rd edn. Chemical Industries. CRC Press, Boca Raton (2008)

    Google Scholar 

  8. Belandria, V., Eslamimanesh, A., Mohammadi, A.H., Richon, D.: Gas hydrate formation in carbon dioxide+nitrogen+water system: compositional analysis of equilibrium phases. Ind. Eng. Chem. Res. 50(8), 4722–4730 (2011). https://doi.org/10.1021/ie101635k

    Article  CAS  Google Scholar 

  9. Li, L., Zhu, L., Fan, J.: The application of CPA-vdWP to the phase equilibrium modeling of methane-rich sour natural gas hydrates. Fluid Phase Equilib. 409, 291–300 (2016). https://doi.org/10.1016/j.fluid.2015.10.017

    Article  CAS  Google Scholar 

  10. Kontogeorgis, G.M., Voutsas, E.C., Yakoumis, I.V., Tassios, D.P.: An equation of state for associating fluids. Ind. Eng. Chem. Res. 35(11), 4310–4318 (1996). https://doi.org/10.1021/ie9600203

    Article  CAS  Google Scholar 

  11. Herslund, P.J., Thomsen, K., Abildskov, J., von Solms, N.: Phase equilibrium modeling of gas hydrate systems for CO2 capture. J. Chem. Thermodyn. 48, 13–27 (2012). https://doi.org/10.1016/j.jct.2011.12.039

    Article  CAS  Google Scholar 

  12. Sfaxi, I.B.A., Belandria, V., Mohammadi, A.H., Lugo, R., Richon, D.: Phase equilibria of CO2+N2 and CO2+CH4 clathrate hydrates: experimental measurements and thermodynamic modelling. Chem. Eng. Sci. 84, 602–611 (2012). https://doi.org/10.1016/j.ces.2012.08.041

    Article  CAS  Google Scholar 

  13. Tsivintzelis, I., Kontogeorgis, G.M., Michelsen, M.L., Stenby, E.H.: Modeling phase equilibria for acid gas mixtures using the CPA equation of state. Part II: binary mixtures with CO2. Fluid Phase Equilib. 306(1), 38–56 (2011). https://doi.org/10.1016/j.fluid.2011.02.006

    Article  CAS  Google Scholar 

  14. Tabasinejad, F., Moore, R.G., Mehta, S.A., Van Fraassen, K.C., Barzin, Y., Rushing, J.A., Newsham, K.E.: Water solubility in supercritical methane, nitrogen, and carbon dioxide: measurement and modeling from 422 to 483 K and pressures from 3.6 to 134 MPa. Ind. Eng. Chem. Res. 50(7), 4029–4041 (2011)

    Article  CAS  Google Scholar 

  15. Perakis, C., Voutsas, E., Magoulas, K., Tassios, D.: Thermodynamic modeling of the vapor–liquid equilibrium of the water/ethanol/CO2 system. Fluid Phase Equilib. 243(1), 142–150 (2006). https://doi.org/10.1016/j.fluid.2006.02.018

    Article  CAS  Google Scholar 

  16. Voutsas, E., Perakis, C., Pappa, G., Tassios, D.: An evaluation of the performance of the cubic-plus-association equation of state in mixtures of non-polar, polar and associating compounds: towards a single model for non-polymeric systems. Fluid Phase Equilib. 261(1), 343–350 (2007). https://doi.org/10.1016/j.fluid.2007.07.051

    Article  CAS  Google Scholar 

  17. Pappa, G.D., Perakis, C., Tsimpanogiannis, I.N., Voutsas, E.C.: Thermodynamic modeling of the vapor–liquid equilibrium of the CO2/H2O mixture. Fluid Phase Equilib. 284(1), 56–63 (2009). https://doi.org/10.1016/j.fluid.2009.06.011

    Article  CAS  Google Scholar 

  18. Aasen, A., Hammer, M., Skaugen, G., Jakobsen, J.P., Wilhelmsen, Ø.: Thermodynamic models to accurately describe the PVTxy-behavior of water/carbon dioxide mixtures. Fluid Phase Equilib. 442, 125–139 (2017). https://doi.org/10.1016/j.fluid.2017.02.006

    Article  CAS  Google Scholar 

  19. Peng, D.-Y., Robinson, D.B.: A new two-constant equation of state. Ind. Eng. Chem. Fundam. 15(1), 59–64 (1976). https://doi.org/10.1021/i160057a011

    Article  CAS  Google Scholar 

  20. Pfohl, O., Giese, T., Dohrn, R., Brunner, G.: 1. Comparison of 12 equations of state with respect to gas-extraction processes: reproduction of pure-component properties when enforcing the correct critical temperature and pressure. Ind. Eng. Chem. Res. 37(8), 2957–2965 (1998). https://doi.org/10.1021/ie970524g

    Article  CAS  Google Scholar 

  21. Pfohl, O., Pagel, A., Brunner, G.: Phase equilibria in systems containing o-cresol, p-cresol, carbon dioxide, and ethanol at 323.15–473.15 K and 10–35 MPa. Fluid Phase Equilib. 157(1), 53–79 (1999). https://doi.org/10.1016/S0378-3812(99)00019-9

    Article  CAS  Google Scholar 

  22. Platteeuw, J.C., van der Waals, J.H.: Thermodynamic properties of gas hydrates. Mol. Phys. 1(1), 91–96 (1958). https://doi.org/10.1080/00268975800100111

    Article  CAS  Google Scholar 

  23. Chen, G.-J., Guo, T.-M.: A new approach to gas hydrate modelling. Chem. Eng. J. 71(2), 145–151 (1998). https://doi.org/10.1016/S1385-8947(98)00126-0

    Article  CAS  Google Scholar 

  24. Bhawangirkar, D.R., Adhikari, J., Sangwai, J.S.: Thermodynamic modeling of phase equilibria of clathrate hydrates formed from CH4, CO2, C2H6, N2 and C3H8, with different equations of state. J. Chem. Thermodyn. 117, 180–192 (2017). https://doi.org/10.1016/j.jct.2017.09.024

    Article  CAS  Google Scholar 

  25. Parrish, W.R., Prausnitz, J.M.: Dissociation pressures of gas hydrates formed by gas mixtures. Ind. Eng. Chem. Process. Des. Dev. 11(1), 26–35 (1972). https://doi.org/10.1021/i260041a006

    Article  CAS  Google Scholar 

  26. Chen, G.-J., Guo, T.-M.: Thermodynamic modeling of hydrate formation based on new concepts. Fluid Phase Equilib. 122(1), 43–65 (1996). https://doi.org/10.1016/0378-3812(96)03032-4

    Article  CAS  Google Scholar 

  27. Klauda, J.B., Sandler, S.I.: A fugacity model for gas hydrate phase equilibria. Ind. Eng. Chem. Res. 39(9), 3377–3386 (2000). https://doi.org/10.1021/ie000322b

    Article  CAS  Google Scholar 

  28. Klauda, J.B., Sandler, S.I.: Phase behavior of clathrate hydrates: a model for single and multiple gas component hydrates. Chem. Eng. Sci. 58(1), 27–41 (2003). https://doi.org/10.1016/S0009-2509(02)00435-9

    Article  CAS  Google Scholar 

  29. Kontogeorgis, G.M., Michelsen, M.L., Folas, G.K., Derawi, S., von Solms, N., Stenby, E.H.: Ten years with the CPA (cubic-plus-association) equation of state. Part 1 Pure compounds and self-associating systems. Ind. Eng. Chem. Res. 45(14), 4855–4868 (2006). https://doi.org/10.1021/ie051305v

    Article  CAS  Google Scholar 

  30. Mohamadi-Baghmolaei, M., Hajizadeh, A., Azin, R., Izadpanah, A.A.: Assessing thermodynamic models and introducing novel method for prediction of methane hydrate formation. J. Pet. Explor. Prod. Technol. 8, 1401–1412 (2018)

    Article  CAS  Google Scholar 

  31. Boston, J.F., Mathias, P.: Phase equilibria in a third-generation process simulator. In: Paper presented at the Proceedings of the 2nd International Conference on Phase Equilibria and Fluid Properties in the Chemical Processing Industry. Berlin, March 17–21, 1980

  32. Mathias, P.M.: A versatile phase equilibrium equation of state. Ind. Eng. Chem. Process. Des. Dev. 22(3), 385–391 (1983). https://doi.org/10.1021/i200022a008

    Article  CAS  Google Scholar 

  33. McKoy, V., Sinanoğlu, O.: Theory of dissocation pressures of some gas hydrates. J. Chem. Phys. 38, 2946–2956 (1963). https://doi.org/10.1063/1.1733625

    Article  CAS  Google Scholar 

  34. Herri, J.M., Bouchemoua, A., Kwaterski, M., Fezoua, A., Ouabbas, Y., Cameirao, A.: Gas hydrate equilibria for CO2–N2 and CO2–CH4 gas mixtures—experimental studies and thermodynamic modelling. Fluid Phase Equilib. 301(2), 171–190 (2011). https://doi.org/10.1016/j.fluid.2010.09.041

    Article  CAS  Google Scholar 

  35. Mooijer-van den Heuvel, M.M., Peters, C.J., Swaan Arons, J.: Influence of water-insoluble organic components on the gas hydrate equilibrium conditions of methane. Fluid Phase Equilib. 172(1), 73–91 (2000). https://doi.org/10.1016/S0378-3812(00)00367-8

    Article  Google Scholar 

  36. Holder, G.D., Corbin, G., Papadopoulos, K.D.: Thermodynamic and molecular properties of gas hydrates from mixtures containing methane, argon, and krypton. Ind. Eng. Chem. Fundam. 19(3), 282–286 (1980). https://doi.org/10.1021/i160075a008

    Article  CAS  Google Scholar 

  37. Huang, S.H., Radosz, M.: Equation of state for small, large, polydisperse, and associating molecules. Ind. Eng. Chem. Res. 29(11), 2284–2294 (1990). https://doi.org/10.1021/ie00107a014

    Article  CAS  Google Scholar 

  38. Dharmawardhana, P.B., Parrish, W.R., Sloan, E.D.: Experimental thermodynamic parameters for the prediction of natural gas hydrate dissociation conditions. Ind. Eng. Chem. Fundam. 19(4), 410–414 (1980). https://doi.org/10.1021/i160076a015

    Article  CAS  Google Scholar 

  39. Design Institute for Physical Property, D.: DIPPR Project 801, Full Version: Evaluated Standard Thermophysical Property Values (2011)

  40. Chapoy, A., Mohammadi, A.H., Tohidi, B., Richon, D.: Gas solubility measurement and modeling for the nitrogen+water system from 274.18 K to 363.02 K. J. Chem. Eng. Data 49(4), 1110–1115 (2004). https://doi.org/10.1021/je049869d

    Article  CAS  Google Scholar 

  41. Baranenko, V.I., Sysoev, V.S., Fal’kovskii, L.N., Kirov, V.S., Piontkovskii, A.I., Musienko, A.N.: The solubility of nitrogen in water. Soviet At. Energy 68, 162–165 (1990). https://doi.org/10.1007/BF02069879

    Article  Google Scholar 

  42. Herslund, P.J., Thomsen, K., Abildskov, J., von Solms, N.: Modelling of tetrahydrofuran promoted gas hydrate systems for carbon dioxide capture processes. Fluid Phase Equilib. 375, 45–65 (2014). https://doi.org/10.1016/j.fluid.2014.04.031

    Article  CAS  Google Scholar 

  43. Kang, S.-P., Lee, H., Lee, C.S., Sung, W.M.: Hydrate phase equilibria of the guest mixtures containing CO2, N2 and tetrahydrofuran. Fluid Phase Equilib. 185, 1 (2001). https://doi.org/10.1016/S0378-3812(01)00460-5

    Article  Google Scholar 

  44. Fan, S.-S., Guo, T.-M.: Hydrate formation of CO2-rich binary and quaternary gas mixtures in aqueous sodium chloride solutions. J. Chem. Eng. Data 44(4), 829–832 (1999). https://doi.org/10.1021/je990011b

    Article  CAS  Google Scholar 

  45. Sun, S.-C., Liu, C.-L., Meng, Q.-G.: Hydrate phase equilibrium of binary guest-mixtures containing CO2 and N2 in various systems. J. Chem. Thermodyn. 84, 1–6 (2015). https://doi.org/10.1016/j.jct.2014.12.018

    Article  CAS  Google Scholar 

  46. Sadeq, D., Iglauer, S., Lebedev, M., Smith, C., Barifcani, A.: Experimental determination of hydrate phase equilibrium for different gas mixtures containing methane, carbon dioxide and nitrogen with motor current measurements. J. Nat. Gas Sci. Eng. 38, 59–73 (2017). https://doi.org/10.1016/j.jngse.2016.12.025

    Article  CAS  Google Scholar 

  47. Olsen, M.B., Majumdar, A., Bishnoi, P.R.: Experimental studies on hydrate equilibrium–carbon dioxide and its systems. Int. J. Soc. Mater. Engi. Res. 7(1), 17–23 (1999). https://doi.org/10.5188/ijsmer.7.17

    Article  CAS  Google Scholar 

  48. Lee, Y., Lee, S., Lee, J., Seo, Y.: Structure identification and dissociation enthalpy measurements of the CO2+N2 hydrates for their application to CO2 capture and storage. Chem. Eng. J. 246, 20–26 (2014). https://doi.org/10.1016/j.cej.2014.02.045

    Article  CAS  Google Scholar 

  49. Bruusgaard, H., Beltrán, J.G., Servio, P.: Vapor − liquid water − hydrate equilibrium data for the system N2+CO2+H2O. J. Chem. Eng. Data 53(11), 2594–2597 (2008). https://doi.org/10.1021/je800445x

    Article  CAS  Google Scholar 

  50. Linga, P., Kumar, R., Englezos, P.: The clathrate hydrate process for post and pre-combustion capture of carbon dioxide. J. Hazard. Mater. 149(3), 625–629 (2007). https://doi.org/10.1016/j.jhazmat.2007.06.086

    Article  CAS  PubMed  Google Scholar 

  51. Linga, P., Kumar, R., Englezos, P.: Gas hydrate formation from hydrogen/carbon dioxide and nitrogen/carbon dioxide gas mixtures. Chem. Eng. Sci. 62(16), 4268–4276 (2007). https://doi.org/10.1016/j.ces.2007.04.033

    Article  CAS  Google Scholar 

  52. Garapati, N., Anderson, B.J.: Statistical thermodynamics model and empirical correlations for predicting mixed hydrate phase equilibria. Fluid Phase Equilib. 373, 20–28 (2014). https://doi.org/10.1016/j.fluid.2014.03.010

    Article  CAS  Google Scholar 

  53. Diamond, L.W.: Salinity of multivolatile fluid inclusions determined from clathrate hydrate stability. Geochim. Cosmochim. Acta 58(1), 19–41 (1994). https://doi.org/10.1016/0016-7037(94)90443-X

    Article  CAS  Google Scholar 

  54. Seo, Y., Lee, H.: Structure and guest distribution of the mixed carbon dioxide and nitrogen hydrates as revealed by X-ray diffraction and 13C NMR spectroscopy. J. Phys. Chem. B 108, 530–534 (2004)

    Article  CAS  Google Scholar 

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Authors and Affiliations

  1. Iranian Gas Transmission Company, District 10, Bushehr, Iran

    Ahmad Banafi

  2. Department of Chemical Engineering, Faculty of Petroleum, Gas and Petrochemical Engineering, Persian Gulf University, Bushehr, Iran

    Mohamad Mohamadi-Baghmolaei, Abdollah Hajizadeh & Amir Abbas Izadpanah

  3. Department of Petroleum Engineering, Faculty of Petroleum, Gas and Petrochemical Engineering, Persian Gulf University, Bushehr, Iran

    Reza Azin

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Banafi, A., Mohamadi-Baghmolaei, M., Hajizadeh, A. et al. Thermodynamic Modeling Study on Phase Equilibrium of Gas Hydrate Systems for CO2 Capture. J Solution Chem 48, 1461–1487 (2019). https://doi.org/10.1007/s10953-019-00909-8

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