Thermodynamics Analysis on Methane Hydrate Formation in Porous Carbon

Wibiana W. Nandari(1*), Imam Prasetyo(2), Moh. Fahrurrozi(3)

(1) Chemical Engineering Department, UPN “Veteran” Yogyakarta, Jl. SWK 104 (Lingkar Utara), Condongcatur, Yogyakarta
(2) Chemical Engineering Department, Universitas Gadjah Mada, Jl. Grafika no.2 Kampus UGM Yogyakarta
(3) Chemical Engineering Department, Universitas Gadjah Mada, Jl. Grafika no.2 Kampus UGM Yogyakarta
(*) Corresponding Author


Methane is a potential alternative energy source which is abundant and produces lower CO2 emissions when it is used as fuel due to the content of C in the methane molecule is much lesser than its H content. Besides in a form of gas, methane in nature can also be in the form of methane hydrates. The formation process of methane hydrates in nature can be adopted as a method of storage of methane. In this study, a thermodynamics review will be studied related to temperature and pressure in a phase equilibrium system of methane hydrate . Thermodynamic model aims to predict the stability of methane hydrates for effective storage of methane. Each volume of methane hydrate contains as 164 volumes of methane gas under standard conditions ( STP ). The study was conducted by adsorbing methane on a wet porous carbon with the method of static volumetric.. The experimental results show that at the temperature of 274 K methane hydrates was formed at a pressure of 2.75 MPa; at a temperature of 275 K, pressure of 3.16 MPa; at a temperature of 276 K, pressure of 3.44 MPa, while at a temperature of 277 K, pressure of 3.67 MPa. Temperatures and pressures data are used to calculate the parameters of Langmuir equation constants modeled by the Van der Waals - Platteeuw for the chemical potential of water in the hydrate phase, Holder et al for the chemical potential of water in the liquid phase, as well as for the Gibbs-Thomson effect of porous carbon media.


methane hydrate , modeling thermodynamics , Langmuir constants, porous carbon, mechanism of hydrate formation, methane storage

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1. Aladko. E.Y., Dyadin, Y.A., Fenelonov, V.B., Larionov, E.G., Mel’gunov, M.S., Manakov, A.Y., Nesterov, A.N., Zhurko, F.V. (2004). Dissociation conditions of methane hyydrate in mesoporous silica gels in wide ranges of pressure and water content, J. Phys. Chem., B 108, 16540-16547. [Journal article]
2. Anderson, R., Llamedo, M., Tohidi, B., Burgass, R.W. (2003). Characteristic of chlathrate hydrate equilibria in mesopores and interpretation of experimental data, J.Phys.Chem., B 107, 3500-3506. [Journal article]
3. Baker, F. S. (1980). Activated Carbon Adsorption Handbook Second Edition, Michigan : Ann Arbor Science Pub Inc. [Books]
4. Benedict, W.S., Gailar, N., Plyler, E.K., J. (1956). Chemical Physis. [Books]
5. Bugge, T., Benderson, R.H., Kenyon, N.H. (1988). Phil Trans Roy Soc Lond. [Books]
6. Carroll, John (2009). Natural Gas Hydrates, Elsevier’s Science and Technology Rights Departement in Oxford. [Books]
7. Celzard, A., Mareche, J. F. (2005). Optimal Wetting of Active Carbons for Methane Hydrate Formation, Universite Henry Poincare-Nancy, France. [Journal article]
8. Clarke, M.A., Pooladi-Darvish, M., Bishnoi, P.R. (1999). A Method to Predict Equilibrium Conditions of Gas Hydrates Formation in Porous Media, Ind. Eng. Chem. Res., 38, 2485-2490. [Journal article]

9. Clennell, M.B., Hovland, M., Booth, J.S., Henry, P., Winters, W.J. (1999). Formation of Natural Gas Hydrates in Marine Sediments, Conceptual Model of Gas Hydrate Growth Conditioned by Host Sediment Properties, J., Geophys, Res., 104(B10), 22985-23003. [Journal article]
10. Dai, X.D., Liu, X.M., Xing, W., Qian, L., Qiao, K., Yan, Z.F. (2009). Natural Gas Storage on Activated Carbon Nodified by Metal Oxides, J Porous Mater, vol.16, pp.27-32. [Books]
11. Davidson, D. W. (1983). Natural Gas Hydrate, Butterworths, London. [Books]
12. Dicharry, C., Gayet, P., Marion, G., Graciaa,A., Nesterov, A. N. (2005). Modeling Heating Curve for Gas Hydrate Dissociation in Porous Media, J. Phys. Chem., B109, 17205-17211.
[Journal article]
13. Do, D. D. (1998). Adsoprtion Analysis:Equilibria and Kinetics, Imperial College Press, 203 Electrical Engineering Building, Imperial College, London SW 72 BT, pp.13-17; 50-59. [Books]
14. Fauzi, A. A. (2012). Adsorpsi Gas CO2 Menggunakan Karbon Mesopori dari Pirolisis Resin Resorcinol-Phenol- Formaldehyde dengan Penambahan Etylen Glycol, Laporan Penelitian, Universitas Gadjah Mada, Yogyakarta. [Journal article]

15. Handa, Y. P., Stupin, D. (1992). Thermodynamic properties and dissociation characteristics of methane and propane hydrates in 70-A-Radius silica gel pores, J. Phys. Chem 96, 8599- 8603. [Journal article]

16. Henry, P., Thomas, M., Clennell, M. B. (1999). Formation of Natural Gas Hydrates in Marine Sediments, J Geophys. [Journal article]
17. Klauda, J. B., Sandler, S.I. (2001). Modeling Gas Hydrate Phase Equilibria in Laboratory and Natural Porous Media, Ind. Eng. Chem. Res., 40, 4197- 4280. [Journal article]
18. Klauda, J.B., Sandler, S.I. (2003). Predictions of Gas Hydrate Phase Equilibria and Amounts in Natural Sediment Porous Media, Mar Pet Geol,
20, 459-470. [Journal article] 19. Legget,J. (1990). Global Warming : The Greenpeace Report, Oxford University Press, Oxford. [Books]
20. Lysne, D. (1995). An Experimentall Study of Hydrate Plug Dissociation by Pressure Reduction, D.Ing, Thesis, Norwegian Institute of Technology. [Thesis]
21. Makogon, Y. F., Holditch, S.A. and Makogon, T.Y. (2007). Natural gas Hydrate-A Potential Energy Source for 21th Century, Journal Petrolleum Science and Engineering. [Journal
22. Manocha, S.M. (2003). Porous Carbons, Sadhana volume 28 part 1&2 pp 335- 348, India. [Books]
23. McCelland, A. L. (1963). Dipole Moment, San Fransisco. [Books]
24. Mutiara, T. (2013). Tinjauan Termodinamika Pembetukan Hidrat Metana pada Media Glass Beads, Laporan Thesis, Universitas Gadjah Mada, Yogyakarta. [Thesis]
25. Penelitian tim BPPT
26. Pople, J.A. (1951). Proc Royal Society. [Books]

27. Ponnivalavan, Yee, D., Linga, P., Palmer, A., Cheong, B., Soon, T., Rangsunvigit, P. (2013). Morphology of Methane Hydrate Formation in Porous Media. [Journal article]
28. Prasetya, I., Budhijanto, Rochmadi, Yunanto, R., Ariyanto, T. (2011). Methane Storage by Methane Hydrate Formation Within Water-Saturated Porous Carbon, The Effect of Mesoporosity. [Journal article]
29. Qiu Jun-hong, Guo Tian-min, (2002). Kinetics of Methane Hydrate Formation in Pure Water and Inhibitor Containing Systems, Chin. J. Chem. Eng., 2002, V10(3):316-322. [Journal article]
30. Riestenberg, D., West, O., Lee, S.C., McCallum, S., Phelps, T.J. (2003). Sediment surface effect of methane hydrate formation and dissociation, Mar. Geol, 198,181-190. [Journal
31. Roadifer, R. D., Godbole, S.P., Kamath, V.A. (1987). SPE California Regional Meeting, Ventura. [Journal article]
32. Rodrigues, A.E., Leva, D., dan Tondeur, D. (1989). Adsorption: Science and Technology, Kluver, Dordrect. [Books]
33. Ruppel, C. (1997). Anomalously cold temperatures observed at the base of the gas hydrate stability zone on the U.S. Atlantic passive margin, Geology 25, 699-702. [Journal article]

34. Schmuck, E.A, Paull, C.K. (1993). Geo- Mar.Lett. [Journal article]

35. Seo. Y., Lee, H. (2003). Hydrate phase equilibria of the ternary mixture in silica gel pores, J. Phys. Chem., B 107, 889-894. [Journal article]
36. Seshandri, K., Wilder, J.W., Smith, D.H. (2001). Measurement of Equilibrium Pressures and temperatures for propane Hydrate in Silica Gels with Different Pore-Size Distributions, J. Phys. Chem., B 105, 2627-2631. [Journal article]

37. Sing, K. S. W., Everett, D. H., Haul, R. A. W., Moscoul, L., Pierotti, R.A., Rouqerol,
J., Siemieniewska, T. (1985). Reporting Physisorption Data for Gas/Solid Systems with Special Reference to the Determination of Source Area and Porosity, Pure Appl, Chem., 57, pp. 603-619. [Journal article]
38. Sloan, E. D., Koh, C. A. (2008). Chlatrate Hydrates of Nautral Gases, 3rd Edition, Taylor and Francis Group, USA. [Books]
39. Smith, D.H., Wilder, J. W., Seshandri, K. (2002). Methane Hydrate Equilibria in Silica Gels with Broad Pore-Size Distribution, AIChE.J.48, 393-400. [Journal article]
40. Soesilo, (2008). Gas Hidrat Metan (methane hydrate) Sumber Energi Alternatif Masa Depan Pengganti BBM, [Journal article]
41. Sudibandriyo, M. (2003). A Generalized Ono-Kondo Lattice Model for High Pressure on Carbon Adsorben, Ph.D Disertation, Oklahoma State University. [Disertation]
42. Sun, R., Duan, Z. (2007). Prediction of CH4 and CO2 Hydrate Phase Equilibrium and Cage Occupancy From ab Initio Intermolecular Potential, Geochim Cosmochim. [Journal article]
43. Sung Chan Nam, Lingga, P., Haligva, C., Ripmeester, J.A., Englezos, P. (2008). Kinetics of Hydrate Formation and Decomposition of Methane in Silica  Sand, Proceedings of the 6th International Conference on Gas Hydrates, British Columbia, Canada. [Conference papers]

44. Talu, O. (1992). An Overview of Adsorptive Storage of Natural Gas, Fundamentals of Adsorption, Proc. 4th Int. Conf. On Fundamentals of Adsorption, Kyoto, May 17-22, pp.655- 662. [Journal article]
45. Traufetter, Gerald, (2008). Methane Hydrate China and India Exploit Icy Energy Reserves, [Journal article]
46. Trehu, M. A., Bohrmann, G., Rack, R.F., Torres, M. E., Bargs, N. L., et al. (2006). in Proc.ODP (Ocean Drilling Program), Initial Repts. 204, Texas A & M University, College Station. [Journal article]
47. Uchida, T., Takeya, S., Chuvilin, E.M., Ohmura. R.,Nagao, J., Yakushev, V.S., Istomin, V.A., Minagawa, H., Ebinuma, T., Narita, H. (2004). Decomposition of methane hydrates in sand, a=sandstone, clays, and glass beads, J., Geophys. Res. 109, B05206. [Journal article]
48. Van der Waals, J. H., Platteeuw, J. C. (1959). Clathrate Solution, In : Prigogine, I. (Ed), Advances in Chemical Physics, Interscience. [Journal article]

49. Waldeza, R. (2012). Pengaruh Suhu Terhadap Pembuatan Karbon Aktif dari Proses Pirolisis Ploimer RPF dengan Aktivasi CO2 Serta Pengaruhnya Terhadap Adsorpsi Butana, Laporan Penelitian, Universitas Gadjah Mada, Yogyakarta. [Journal article]
50. Wilder, J. W., Seshandri, K., Smith, D. H. (2001). Modeling Hydrate Formation in Media with Broad Pore Size Distribution, Langmuir 17,6729-6735. [Journal article]
51., (2012).
52., (2012).
53. Yang, R. T. (2003). Adsorbent Fundamentals and Applications, University of Michigan, Michigan. [Journal article]
54. Yunanto, R. (2012). Penjerapan Gas Rumah Kaca dengan Menggunakan
Berbagai Karbon Berpori, Laporan Thesis, Universitas Gadjah Mada, Yogyakarta. [ Thesis ]
55. Zhang. W., Wilder, J.W., Smith, D. H. (2002). Interpretation of methane hydrate equilibrium data for porous media involving hydrate-ice euilibria, AIChE.J.48, 2324-2331. [Journal article]
56. Zhou, Y.P., Dai, M., Zhou, L. (2004). Storage of Methane on wet activated carbon: Influence of pore size distribution. [Journal article]


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