Formation of the structure-II gas hydrate from low-concentration propane mixed with methane

doi:10.1016/j.cjche.2022.10.014

中国化学工程学报 ›› 2023, Vol. 58 ›› Issue (6): 306-314.DOI: 10.1016/j.cjche.2022.10.014

• Full Length Article • 上一篇下一篇

Formation of the structure-II gas hydrate from low-concentration propane mixed with methane

Sanya Du^1,2, Xiaomin Han¹, Wenjiu Cai^3,4, Jinlong Zhu^5,6, Xiaobai Ma⁷, Songbai Han⁸, Dongfeng Chen⁷, Yusheng Zhao^5,6, Hui Li¹, Hailong Lu⁴, Xiaohui Yu^2,9

1. Beijing Advanced Innovation Center for Soft Matter Science and Engineering, Beijing University of Chemical Technology, Beijing 100029, China;
2. National Laboratory for Condensed Matter Physics, Institute of Physics, Chinese Academy of Sciences, Beijing 100190, China;
3. College of Engineering, Peking University, Beijing 100871, China;
4. Beijing International Center for Gas Hydrate, School of Earth and Space Sciences, Peking University, Beijing 100871, China;
5. Department of Physics, Southern University of Science and Technology (SUSTech), Shenzhen 518055, China;
6. Southern Marine Science and Engineering Guangdong Laboratory (Guangzhou), Guangzhou 511458, China;
7. Department of Nuclear Physics, China Institute of Atomic Energy, Beijing 102413, China;
8. Academy for Advanced Interdisciplinary Studies, Southern University of Science and Technology (SUSTech), Shenzhen 518055, China;
9. Songshan Lake Materials Laboratory, Dongguan 523808, China

收稿日期:2022-04-06 修回日期:2022-10-03 出版日期:2023-06-28 发布日期:2023-08-31
通讯作者: Hui Li,E-mail:hli@buct.edu.cn;Hailong Lu,E-mail:hlu@pku.edu.cn;Xiaohui Yu,E-mail:yuxh@iphy.ac.cn
基金资助:
This work is supported by the National Key Research and Development Program of China (2016YFA0401503 and 2018YFA0305700), the National Natural Science Foundation of China (11575288, 91934303, 21935001 and 11775011), the Strategic Priority Research Program and Key Research Program of Frontier Sciences of the Chinese Academy of Sciences (XDB33000000, XDB25000000 and QYZDBSSW-SLH013), the Youth Innovation Promotion Association of the Chinese Academy of Sciences (Y202003), the China Geological Survey (DD20190234), and the Scientific Instrument Developing Project (ZDKYYQ20170001) of the Chinese Academy of Sciences.

Formation of the structure-II gas hydrate from low-concentration propane mixed with methane

Sanya Du^1,2, Xiaomin Han¹, Wenjiu Cai^3,4, Jinlong Zhu^5,6, Xiaobai Ma⁷, Songbai Han⁸, Dongfeng Chen⁷, Yusheng Zhao^5,6, Hui Li¹, Hailong Lu⁴, Xiaohui Yu^2,9

1. Beijing Advanced Innovation Center for Soft Matter Science and Engineering, Beijing University of Chemical Technology, Beijing 100029, China;
2. National Laboratory for Condensed Matter Physics, Institute of Physics, Chinese Academy of Sciences, Beijing 100190, China;
3. College of Engineering, Peking University, Beijing 100871, China;
4. Beijing International Center for Gas Hydrate, School of Earth and Space Sciences, Peking University, Beijing 100871, China;
5. Department of Physics, Southern University of Science and Technology (SUSTech), Shenzhen 518055, China;
6. Southern Marine Science and Engineering Guangdong Laboratory (Guangzhou), Guangzhou 511458, China;
7. Department of Nuclear Physics, China Institute of Atomic Energy, Beijing 102413, China;
8. Academy for Advanced Interdisciplinary Studies, Southern University of Science and Technology (SUSTech), Shenzhen 518055, China;
9. Songshan Lake Materials Laboratory, Dongguan 523808, China

Received:2022-04-06 Revised:2022-10-03 Online:2023-06-28 Published:2023-08-31
Contact: Hui Li,E-mail:hli@buct.edu.cn;Hailong Lu,E-mail:hlu@pku.edu.cn;Xiaohui Yu,E-mail:yuxh@iphy.ac.cn
Supported by:
This work is supported by the National Key Research and Development Program of China (2016YFA0401503 and 2018YFA0305700), the National Natural Science Foundation of China (11575288, 91934303, 21935001 and 11775011), the Strategic Priority Research Program and Key Research Program of Frontier Sciences of the Chinese Academy of Sciences (XDB33000000, XDB25000000 and QYZDBSSW-SLH013), the Youth Innovation Promotion Association of the Chinese Academy of Sciences (Y202003), the China Geological Survey (DD20190234), and the Scientific Instrument Developing Project (ZDKYYQ20170001) of the Chinese Academy of Sciences.

摘要/Abstract

摘要： It has been recognized that a small amount of propane mixed with methane can change greatly in not only the thermodynamics but also the structural properties of gas hydrate. However, its mechanism is still not well understood yet. In this research, structure-II (sII) hydrate is synthesized using a methane-propane gas mixture with an initial mole ratio of 99:1, and it is found that large (5¹²6⁴) cages are co-occupied by multiple gases based on the rigid structure analysis of neutron diffraction data. The first principles calculation and molecular dynamics simulation are conducted to uncover the molecular mechanism for sII methane-propane hydrate formation, revealing that the presence of propane inhibits the formation of structure-I (sI) hydrate but promotes sII hydrate formation. The results help to understand the accumulation mechanism of natural gas hydrate and benefit to optimize the condition for gas storage and transportation in hydrate form.

关键词: Multiple guest molecules, Clathrates, Neutron powder diffraction, Structural transformation, Molecular mechanism

Abstract: It has been recognized that a small amount of propane mixed with methane can change greatly in not only the thermodynamics but also the structural properties of gas hydrate. However, its mechanism is still not well understood yet. In this research, structure-II (sII) hydrate is synthesized using a methane-propane gas mixture with an initial mole ratio of 99:1, and it is found that large (5¹²6⁴) cages are co-occupied by multiple gases based on the rigid structure analysis of neutron diffraction data. The first principles calculation and molecular dynamics simulation are conducted to uncover the molecular mechanism for sII methane-propane hydrate formation, revealing that the presence of propane inhibits the formation of structure-I (sI) hydrate but promotes sII hydrate formation. The results help to understand the accumulation mechanism of natural gas hydrate and benefit to optimize the condition for gas storage and transportation in hydrate form.

Key words: Multiple guest molecules, Clathrates, Neutron powder diffraction, Structural transformation, Molecular mechanism

Sanya Du, Xiaomin Han, Wenjiu Cai, Jinlong Zhu, Xiaobai Ma, Songbai Han, Dongfeng Chen, Yusheng Zhao, Hui Li, Hailong Lu, Xiaohui Yu. Formation of the structure-II gas hydrate from low-concentration propane mixed with methane[J]. 中国化学工程学报, 2023, 58(6): 306-314.

参考文献

[1] E.D. Sloan, C.A. Koh, Clathrate Hydrates of Natural Gases, third ed., CRC Press, Boca Raton, 2008
[2] K. Wallmann, E. Pinero, E. Burwicz, M. Haeckel, C. Hensen, A. Dale, L. Ruepke, The global inventory of methane hydrate in marine sediments: a theoretical approach, Energies 5 (7) (2012) 2449-2498
[3] A.A. Swaranjit Singh, Techniques for exploitation of gas hydrate (clathrates) an untapped resource of methane gas, J. Microb. Biochem. Technol. 7 (2) (2015) 108-111.
[4] K.A. Kvenvolden, Gas hydrates-geological perspective and global change, Rev. Geophys. 31 (2) (1993) 173-187.
[5] Z.R. Chong, S.H.B. Yang, P. Babu, P. Linga, X.S. Li, Review of natural gas hydrates as an energy resource: prospects and challenges, Appl. Energy 162 (2016) 1633-1652.
[6] Y.D. Cui, C. Lu, M.T. Wu, Y. Peng, Y.B. Yao, W.J. Luo, Review of exploration and production technology of natural gas hydrate, Adv. Geo-Energy Res. 2 (1) (2018) 53-62.
[7] P. Englezos, J.D. Lee, Gas hydrates: a cleaner source of energy and opportunity for innovative technologies, Korean J. Chem. Eng. 22 (5) (2005) 671-681
[8] H. Liu, S.Y. Zhan, P. Guo, S.S. Fan, S.L. Zhang, Understanding the characteristic of methane hydrate equilibrium in materials and its potential application, Chem. Eng. J. 349 (2018) 775-781.
[9] D.L. Katz, D. Cornell, R. Kobayashi, F.H. Poettmann, J.A. Vary, J.R. Elenblass, C.F. Weinaug, Handbook of Natural Gas Engineering, McGraw-Hill, New York, 1959
[10] E.M. Hendriks, B. Edmonds, R.A.S. Moorwood, R. Szczepanski, Hydrate structure stability in simple and mixed hydrates, Fluid Phase Equilibria 117 (1-2) (1996) 193-200.
[11] S. Subramanian, R.A. Kini, S.F. Dec, E.D. Sloan, Evidence of structure II hydrate formation from methane + ethane mixtures, Chem. Eng. Sci. 55(11) (2000) 1981-1999.
[12] J.L. Thakore, G.D. Holder, Solid vapor azeotropes in hydrate-forming systems, Ind. Eng. Chem. Res. 26 (3) (1987) 462-469
[13] C.A. Koh, E.D. Sloan, A.K. Sum, D.T. Wu, Fundamentals and applications of gas hydrates, Annu. Rev. Chem. Biomol. Eng. 2 (2011) 237-257
[14] K.C. Hester, Z. Huo, A.L. Ballard, C.A. Koh, K.T. Miller, E.D. Sloan, Thermal expansivity for sI and sII clathrate hydrates, J. Phys. Chem. B 111 (30) (2007) 8830-8835.
[15] H.S. Truong-Lam, S. Seo, S. Kim, Y. Seo, J.D. Lee, In situ Raman study of the formation and dissociation kinetics of methane and methane/propane hydrates, Energy Fuels 34 (5) (2020) 6288-6297.
[16] Y. Liu, L. Ojamäe, C-C stretching Raman spectra and stabilities of hydrocarbon molecules in natural gas hydrates: a quantum chemical study, J. Phys. Chem. A 118 (49) (2014) 11641-11651.
[17] T. Uchida, I.Y. Ikeda, S. Takeya, Y. Kamata, R. Ohmura, J. Nagao, O.Y. Zatsepina, B.A. Buffett, Kinetics and stability of CH₄-CO₂ mixed gas hydrates during formation and long-term storage, ChemPhysChem 6 (4) (2005) 646-654.
[18] S.Y. Lee, E. McGregor, G.D. Holder, Experimental study of hydrate crystal growth from methane, carbon dioxide, and methane + propane mixtures, Energy Fuels 12 (2) (1998) 212-215.
[19] J. Hutter, M. Iannuzzi, F. Schiffmann, J. VandeVondele, cp2k: atomistic simulations of condensed matter systems, Wiley Interdiscip. Rev. Comput. Mol. Sci. 4 (1) (2014) 15-25.
[20] C. Lee, W. Yang, R.G. Parr, Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density, Phys. Rev. B Condens. Matter 37 (2) (1988) 785-789.
[21] A.D. Becke, Density-functional exchange-energy approximation with correct asymptotic behavior, Phys. Rev. A Gen. Phys. 38 (6) (1988) 3098-3100.
[22] S. Grimme, J. Antony, S. Ehrlich, H. Krieg, A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu, J Chem Phys 132 (15) (2010) 154104.
[23] S. Goedecker, M. Teter, J. Hutter, Separable dual-space Gaussian pseudopotentials, Phys Rev B Condens Matter 54 (3) (1996) 1703-1710.
[24] C. Hartwigsen, S. Goedecker, J. Hutter, Relativistic separable dual-space Gaussian pseudopotentials from H to Rn, Phys. Rev. B 58 (7) (1998) 3641-3662.
[25] H.J.C. Berendsen, D. van der Spoel, R. van Drunen, GROMACS: a message-passing parallel molecular dynamics implementation, Comput. Phys. Commun. 91 (1-3) (1995) 43-56.
[26] H.W. Horn, W.C. Swope, J.W. Pitera, J.D. Madura, T.J. Dick, G.L. Hura, T. Head-Gordon, Development of an improved four-site water model for biomolecular simulations: TIP4P-Ew, J. Chem. Phys. 120 (20) (2004) 9665-9678.
[27] W.L. Jorgensen, D.S. Maxwell, J. Tirado-Rives, Development and testing of the OPLS all-atom force field on conformational energetics and properties of organic liquids, J. Am. Chem. Soc. 118 (45) (1996) 11225-11236.
[28] D.J. Evans, B.L. Holian, The nose-hoover thermostat, J. Chem. Phys. 83 (8) (1985) 4069-4074.
[29] S. Melchionna, G. Ciccotti, B.L. Holian, Hoover NPT dynamics for systems varying in shape and size, Mol. Phys. 78 (3) (1993) 533-544.
[30] R.K. McMullan, G.A. Jeffrey, Polyhedral clathrate hydrates. IX. structure of ethylene oxide hydrate, J. Chem. Phys. 42 (8) (1965) 2725-2732.
[31] A. Falenty, T.C. Hansen, W.F. Kuhs, Formation and properties of ice XVI obtained by emptying a type sII clathrate hydrate, Nature 516 (7530) (2014) 231-233.
[32] W. Cai, H. Lu, X. Huang, Experimental investigations about the effect of trace amount of propane on the formation of mixed hydrates of methane and propane, AGU Fall Meeting Abstracts, (2016)
[33] T. Uchida, M. Moriwaki, S. Takeya, I.Y. Ikeda, R. Ohmura, J. Nagao, H. Minagawa, T. Ebinuma, H. Narita, K. Gohara, S. Mae, Two-step formation of methane-propane mixed gas hydrates in a batch-type reactor, AIChE J. 50 (2) (2004) 518-523.
[34] J.M. Schicks, R. Naumann, J. Erzinger, K.C. Hester, C.A. Koh, E.D. Sloan, Phase transitions in mixed gas hydrates: experimental observations versus calculated data, J. Phys. Chem. B 110 (23) (2006) 11468-11474.
[35] C.J. Rawn, A.J. Rondinone, B.C. Chakoumakos, S. Circone, L.A. Stern, S.H. Kirby, Y. Ishii, Neutron powder diffraction studies as a function of temperature of structure II hydrate formed from propane, Can. J. Phys. 81 (1-2) (2003) 431-438.
[36] A. Hoshikawa, T. Matsukawa, T. Ishigaki, Evaluation of filling rate of methane in methane-propane hydrate by neutron powder diffraction, Phys. B Condens. Matter 551 (2018) 274-277.
[37] R. Susilo, S. Alavi, J. Ripmeester, P. Englezos, Tuning methane content in gas hydrates via thermodynamic modeling and molecular dynamics simulation, Fluid Phase Equilibria 263 (1) (2008) 6-17.
[38] J.A. Ripmeester, C.I. Ratcliffe, Low-temperature cross-polarization/magic angle spinning carbon-13 NMR of solid methane hydrates: structure, cage occupancy, and hydration number, J. Phys. Chem. 92 (2) (1988) 337-339.
[39] A.K. Sum, R.C. Burruss, E.D. Sloan, Measurement of clathrate hydrates via Raman spectroscopy, J. Phys. Chem. B 101 (38) (1997) 7371-7377.
[40] H.L. Lu, Y.T. Seo, J.W. Lee, I. Moudrakovski, J.A. Ripmeester, N.R. Chapman, R.B. Coffin, G. Gardner, J. Pohlman, Complex gas hydrate from the Cascadia margin, Nature 445 (7125) (2007) 303-306.
[41] C.L. Liu, Q.G. Meng, X.L. He, C.F. Li, Y.G. Ye, Z.Q. Lu, Y.H. Zhu, Y.H. Li, J.Q. Liang, Comparison of the characteristics for natural gas hydrate recovered from marine and terrestrial areas in China, J. Geochem. Explor. 152 (2015) 67-74.
[42] A.G. Aregbe, Gas hydrate—properties, formation and benefits, Open Journal of Yangtze Oil and Gas 2 (1) (2017) 27-44.
[43] Z.X. Huo, K. Hester, E.D. Sloan, K.T. Miller, Methane hydrate nonstoichiometry and phase diagram, AIChE J. 49 (5) (2003) 1300-1306.
[44] T. Uchida, T. Hirano, T. Ebinuma, H. Narita, K. Gohara, S. Mae, R. Matsumoto, Raman spectroscopic determination of hydration number of methane hydrates, AIChE J. 45 (12) (1999) 2641-2645.
[45] J. Vatamanu, P.G. Kusalik, Molecular insights into the heterogeneous crystal growth of si methane hydrate, J. Phys. Chem. B 110 (32) (2006) 15896-15904.
[46] V.I. Medvedev, P.A. Gushchin, V.S. Yakushev, A.P. Semenov, Study of the effect of the degree of overcooling during the formation of hydrates of a methane-propane gas mixture on the equilibrium conditions of their decomposition, Chem. Tech. Fuels Oil, 51 (5) (2015) 470-479.
[47] T. Nakamura, T. Makino, T. Sugahara, K. Ohgaki, Stability boundaries of gas hydrates helped by methane—structure-H hydrates of methylcyclohexane and cis-1, 2-dimethylcyclohexane, Chem. Eng. Sci. 58 (2) (2003) 269-273.
[48] E. Frost, W.M. Deaton, Gas hydrate composition and equilibrium data [Direct and calculated measurements are in close agreement; CO₂, CH₄, C₂H₆, C₃H₈ used], Oil Gas J, United States, 1946.
[49] C. Smith, D. Pack, A. Barifcani, Propane, n-butane and i-butane stabilization effects on methane gas hydrates, J. Chem. Thermodyn. 115 (2017) 293-301.
[50] G.D. Holder, P.F. Angert, V.T. John, S. Yen, A thermodynamic evaluation of thermal recovery of gas from hydrates in the earth (includes associated papers 11863 and 11924), J. Pet. Technol. 34 (05) (1982) 1127-1132.
[51] R. García Fernández, J.L. Abascal, C. Vega, The melting point of ice Ih for common water models calculated from direct coexistence of the solid-liquid interface, J. Chem. Phys. 124 (14) (2006) 144506.

Formation of the structure-II gas hydrate from low-concentration propane mixed with methane

Formation of the structure-II gas hydrate from low-concentration propane mixed with methane

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