Microscopic experimental study on the effects of NaCl concentration on the self-preservation effect of methane hydrates under 268.15 K

doi:10.1016/j.cjche.2024.04.022

Chinese Journal of Chemical Engineering ›› 2024, Vol. 73 ›› Issue (9): 1-14.DOI: 10.1016/j.cjche.2024.04.022

Microscopic experimental study on the effects of NaCl concentration on the self-preservation effect of methane hydrates under 268.15 K

Yu-Jie Zhu¹, Yu-Zhou Chen¹, Yan Xie², Jin-Rong Zhong³, Xiao-Hui Wang¹, Peng Xiao¹, Yi-Fei Sun¹, Chang-Yu Sun¹, Guang-Jin Chen¹

1. State Key Laboratory of Heavy Oil Processing, China University of Petroleum, Beijing 102249, China;
2. Research Centre of Ecology &Environment for Coastal Area and Deep Sea, Guangdong University of Technology, Guangzhou 510006, China;
3. School of Chemistry and Food Engineering, Changsha University of Science and Technology, Changsha 410114, China

Received:2023-12-22 Revised:2024-04-10 Accepted:2024-04-15 Online:2024-05-28 Published:2024-11-21
Contact: Xiao-Hui Wang,E-mail:xh.wang@cup.edu.cn;Chang-Yu Sun,E-mail:cysun@cup.edu.cn
Supported by:
The financial support received from the Basic Research Program of Qinghai Province (2023-ZJ-703), the National Natural Science Foundation of China (22178379, 42206223), and the National Key Research and Development Program of China (2021YFC2800902) is gratefully acknowledged.

Microscopic experimental study on the effects of NaCl concentration on the self-preservation effect of methane hydrates under 268.15 K

Yu-Jie Zhu¹, Yu-Zhou Chen¹, Yan Xie², Jin-Rong Zhong³, Xiao-Hui Wang¹, Peng Xiao¹, Yi-Fei Sun¹, Chang-Yu Sun¹, Guang-Jin Chen¹

1. State Key Laboratory of Heavy Oil Processing, China University of Petroleum, Beijing 102249, China;
2. Research Centre of Ecology &Environment for Coastal Area and Deep Sea, Guangdong University of Technology, Guangzhou 510006, China;
3. School of Chemistry and Food Engineering, Changsha University of Science and Technology, Changsha 410114, China

通讯作者: Xiao-Hui Wang,E-mail:xh.wang@cup.edu.cn;Chang-Yu Sun,E-mail:cysun@cup.edu.cn
基金资助:
The financial support received from the Basic Research Program of Qinghai Province (2023-ZJ-703), the National Natural Science Foundation of China (22178379, 42206223), and the National Key Research and Development Program of China (2021YFC2800902) is gratefully acknowledged.

Abstract

Abstract: It is known that salt ions are abundant in the natural environment where natural gas hydrates are located; thus, it is essential to investigate the self-preservation effect of salt ions on methane hydrates. The dissociation behaviors of gas hydrates formed from various NaCl concentration solutions in a quartz sand system at 268.15 K were investigated to reveal the microscopic mechanism of the self-preservation effect under different salt concentrations. Results showed that as the salt concentration rises, the initial rate of hydrate decomposition quickens. Methane hydrate hardly shows self-preservation ability in the 3.35% (mass) NaCl and seawater systems at 268.15 K. Combined the morphology of hydrate observed by the confocal microscope with results obtained from in situ Raman spectroscopy, it was found that during the initial decomposition stage of gas hydrate below the ice point, gas hydrate firstly converts into liquid water and gas molecules, then turns from water to solid ice rather than directly transforming into solid ice and gas molecules. The presence of salt ions interferes with the ability of liquid water to condense into solid ice. The results of this study provide an important guide for the mechanism and application of the self-preservation effect on the storage and transport of gas and the exploitation of natural gas hydrates.

Key words: Gas hydrate, Self-preservation, Salinity, In situ Raman spectroscopy, Endothermic behavior, Dissociation

摘要： It is known that salt ions are abundant in the natural environment where natural gas hydrates are located; thus, it is essential to investigate the self-preservation effect of salt ions on methane hydrates. The dissociation behaviors of gas hydrates formed from various NaCl concentration solutions in a quartz sand system at 268.15 K were investigated to reveal the microscopic mechanism of the self-preservation effect under different salt concentrations. Results showed that as the salt concentration rises, the initial rate of hydrate decomposition quickens. Methane hydrate hardly shows self-preservation ability in the 3.35% (mass) NaCl and seawater systems at 268.15 K. Combined the morphology of hydrate observed by the confocal microscope with results obtained from in situ Raman spectroscopy, it was found that during the initial decomposition stage of gas hydrate below the ice point, gas hydrate firstly converts into liquid water and gas molecules, then turns from water to solid ice rather than directly transforming into solid ice and gas molecules. The presence of salt ions interferes with the ability of liquid water to condense into solid ice. The results of this study provide an important guide for the mechanism and application of the self-preservation effect on the storage and transport of gas and the exploitation of natural gas hydrates.

关键词: Gas hydrate, Self-preservation, Salinity, In situ Raman spectroscopy, Endothermic behavior, Dissociation

Yu-Jie Zhu, Yu-Zhou Chen, Yan Xie, Jin-Rong Zhong, Xiao-Hui Wang, Peng Xiao, Yi-Fei Sun, Chang-Yu Sun, Guang-Jin Chen. Microscopic experimental study on the effects of NaCl concentration on the self-preservation effect of methane hydrates under 268.15 K[J]. Chinese Journal of Chemical Engineering, 2024, 73(9): 1-14.

References

[1] E. D. Sloan, C. A. Koh, Clathrate hydrates of natural gases, 3rd ed CRC Press, 2008.
[2] E.D. Sloan Jr, Fundamental principles and applications of natural gas hydrates, Nature 426 (6964) (2003) 353-363.
[3] E. Kim, S. Lee, J.D. Lee, Y. Seo, Influences of large molecular alcohols on gas hydrates and their potential role in gas storage and CO₂ sequestration, Chem. Eng. J. 267 (2015) 117-123.
[4] R. Boswell, T.S. Collett, Current perspectives on gas hydrate resources, Energy Environ. Sci. 4 (4) (2011) 1206-1215.
[5] Y. Xie, R. Li, X.H. Wang, T. Zheng, J.L. Cui, Q. Yuan, H.B. Qin, C.Y. Sun, G.J. Chen, Review on the accumulation behavior of natural gas hydrates in porous sediments, J. Nat. Gas Sci. Eng. 83 (2020) 103520.
[6] C.G. Xu, X.S. Li, K.F. Yan, X.K. Ruan, Z.Y. Chen, Z.M. Xia, Research progress in hydrate-based technologies and processes in China: A review, Chin. J. Chem. Eng. 27 (9) (2019) 1998-2013.
[7] E. Chaturvedi, S. Laik, A. Mandal, A comprehensive review of the effect of different kinetic promoters on methane hydrate formation, Chin. J. Chem. Eng. 32 (2021) 1-16.
[8] B.Y. Zhang, Y.P. Cheng, Q. Wu, Sponge effect on coal mine methane separation based on clathrate hydrate method, Chin. J. Chem. Eng. 19 (4) (2011) 610-614.
[9] C.Y. Sun, W.Z. Li, X. Yang, F.G. Li, Q. Yuan, L. Mu, J. Chen, B. Liu, G.J. Chen, Progress in research of gas hydrate, Chin. J. Chem. Eng. 19 (1) (2011) 151-162.
[10] J.N. Zheng, F.B. Cheng, Y.P. Li, X. Lu, M.J. Yang, Progress and trends in hydrate based desalination (HBD) technology: A review, Chin. J. Chem. Eng. 27 (9) (2019) 2037-2043.
[11] J.L. Zhang, X. Liu, S. Liu, Y.X. Li, Q.H. Hu, W.C. Wang, Microscopic morphology evolution of the crystal structure of tetrahydrofuran hydrate under flowing condition, Chin. J. Chem. Eng. 45 (2022) 103-110.
[12] W. Ke, D.Y. Chen, A short review on natural gas hydrate, kinetic hydrate inhibitors and inhibitor synergists, Chin. J. Chem. Eng. 27 (9) (2019) 2049-2061.
[13] G. Bhattacharjee, H.P. Veluswamy, A. Kumar, P. Linga, Stability analysis of methane hydrates for gas storage application, Chem. Eng. J. 415 (2021) 128927.
[14] L. Stern, S. Circone, S. Kirby, W. Durham, Anomalous preservation of pure methane hydrate at 1 atm, J. Phys. Chem. B 105 (2001) 1756-1762.
[15] S. Takeya, W. Shimada, Y. Kamata, T. Ebinuma, T. Uchida, J. Nagao, H. Narita, In situ X-ray diffraction measurements of the self-preservation effect of CH₄ hydrate, J. Phys. Chem. A 105 (42) (2001) 9756-9759.
[16] L.A. Stern, S. Circone, S.H. Kirby, W.B. Durham, Temperature, pressure, and compositional effects on anomalous or “self” preservation of gas hydrates, Can. J. Phys. 81 (1-2) (2003) 271-283.
[17] S. Takeya, T. Ebinuma, T. Uchida, J. Nagao, H. Narita, Self-preservation effect and dissociation rates of CH₄ hydrate, J. Cryst. Growth 237 (2002) 379-382.
[18] X.L. Wang, G.J. Chen, C.Y. Sun, L.Y. Yang, Q.L. Ma, J. Chen, P. Liu, X.L. Tang, H.W. Zhao, W.D. Chen, The dependence of the dissociation rate of methane-SDS hydrate below ice point on its manners of forming and processing, Chin. J. Chem. Eng. 17 (1) (2009) 128-135.
[19] Y. Xie, T. Zheng, J.R. Zhong, Y.J. Zhu, Y.F. Wang, Y. Zhang, R. Li, Q. Yuan, C.Y. Sun, G.J. Chen, Experimental research on self-preservation effect of methane hydrate in porous sediments, Appl. Energy 268 (2020) 115008.
[20] Y. Zhang, T. Wang, X.S. Li, K.F. Yan, Y. Wang, Z.Y. Chen, Decomposition behaviors of methane hydrate in porous media below the ice melting point by depressurization, Chin. J. Chem. Eng. 27 (9) (2019) 2207-2212.
[21] S.Y. Misyura, I.G. Donskoy, Dissociation of gas hydrate for a single particle and for a thick layer of particles: The effect of self-preservation on the dissociation kinetics of the gas hydrate layer, Fuel 314 (2022) 122759.
[22] X.B. Zhou, Q. Zhang, Z. Long, D.Q. Liang, In situ PXRD analysis on the kinetic effect of PVP-K90 and PVCap on methane hydrate dissociation below ice point, Fuel 286 (2021) 119491.
[23] S Takeya, A Yoneyama, K Ueda, H Mimachi, M Takahashi, K Sano, Anomalously Preserved Clathrate Hydrate of Natural Gas in Pellet Form at 253 K, J Phys Chem C. 2012;116(26): 13842-13848.
[24] S. Takeya, H. Mimachi, T. Murayama, Methane storage in water frameworks: Self-preservation of methane hydrate pellets formed from NaCl solutions, Appl. Energy 230 (2018) 86-93.
[25] Y.P. Handa, Calorimetric determinations of the compositions, enthalpies of dissociation, and heat capacities in the range 85 to 270 K for clathrate hydrates of xenon and krypton, J. Chem. Thermodyn. 18 (9) (1986) 891-902.
[26] Q Zhang, The hydrates dissociation rate measurement for natural gas recovery from hydrates sediment, In: Conference the Hydrates Dissociation Rate Measurement for Natural Gas Recovery from Hydrates Sediment. IEEE, p. 1-4.
[27] H. Mimachi, S. Takeya, A. Yoneyama, K. Hyodo, T. Takeda, Y. Gotoh, T. Murayama, Natural gas storage and transportation within gas hydrate of smaller particle: Size dependence of self-preservation phenomenon of natural gas hydrate, Chem. Eng. Sci. 118 (2014) 208-213.
[28] A.G. Ogienko, A.V. Kurnosov, A.Y. Manakov, E.G. Larionov, A.I. Ancharov, M.A. Sheromov, A.N. Nesterov, Gas hydrates of argon and methane synthesized at high pressures: Composition, thermal expansion, and self-preservation, J. Phys. Chem. B 110 (6) (2006) 2840-2846.
[29] W. Shimada, S. Takeya, Y. Kamata, T. Uchida, J. Nagao, T. Ebinuma, H. Narita, Texture change of ice on anomalously preserved methane clathrate hydrate, J. Phys. Chem. B 109 (12) (2005) 5802-5807.
[30] L.Y. Ding, C.Y. Geng, Y.H. Zhao, X.F. He, H. Wen, Molecular dynamics simulation for surface melting and self-preservation effect of methane hydrate, Sci. China Ser. B Chem. 51 (7) (2008) 651-660.
[31] S. Takeya, J.A. Ripmeester, Dissociation behavior of clathrate hydrates to ice and dependence on guest molecules, Angew. Chem. Int. Ed Engl. 47 (7) (2008) 1276-1279.
[32] S. Takeya, A. Yoneyama, K. Ueda, K. Hyodo, T. Takeda, H. Mimachi, M. Takahashi, T. Iwasaki, K. Sano, H. Yamawaki, Y. Gotoh, Nondestructive imaging of anomalously preserved methane clathrate hydrate by phase contrast X-ray imaging, J. Phys. Chem. C 115 (32) (2011) 16193-16199.
[33] H. Ohno, I. Oyabu, Y. Iizuka, T. Hondoh, H. Narita, J. Nagao, Dissociation behavior of C₂H₆ hydrate at temperatures below the ice point: Melting to liquid water followed by ice nucleation, J. Phys. Chem. A 115 (32) (2011) 8889-8894.
[34] V.P. Mel’nikov, A.N. Nesterov, A.M. Reshetnikov, Formation of supercooled water upon dissociation of propane hydrates at T < 270 K, Dokl. Phys. Chem. 417 (1) (2007) 304-307.
[35] V.P. Melnikov, A.N. Nesterov, A.M. Reshetnikov, A.G. Zavodovsky, Evidence of liquid water formation during methane hydrates dissociation below the ice point, Chem. Eng. Sci. 64 (6) (2009) 1160-1166.
[36] C Y Sun, G J Chen. Methane hydrate dissociation above 0 ℃ and below 0 ℃. Fluid Phase Equilib. 2006; 242(2): 123-128.
[37] P.Y. Zhang, Y. Wang, R. Jia, J. Lei, Y.M. Li, W. Guo, Dissociation characteristic of methane hydrate in clayey silt below the ice point, J. Nat. Gas Sci. Eng. 100 (2022) 104443.
[38] G.C. Zhang, R.E. Rogers, Ultra-stability of gas hydrates at 1atm and 268.2K, Chem. Eng. Sci. 63 (8) (2008) 2066-2074.
[39] S.Y. Misyura, The influence of porosity and structural parameters on different kinds of gas hydrate dissociation, Sci. Rep. 6 (2016) 30324.
[40] E. Chuvilin, B. Bukhanov, D. Davletshina, S. Grebenkin, V. Istomin, Dissociation and self-preservation of gas hydrates in permafrost, Geosciences 8 (12) (2018) 431.
[41] S. Takeya, T. Uchida, J. Nagao, R. Ohmura, W. Shimada, Y. Kamata, T. Ebinuma, H. Narita, Particle size effect of CH 4 hydrate for self-preservation, Chem. Eng. Sci. 60 (5) (2005) 1383-1387.
[42] V.E. Nakoryakov, S.Y. Misyura, The features of self-preservation for hydrate systems with methane, Chem. Eng. Sci. 104 (2013) 1-9.
[43] T. Uchida, M. Kida, J. Nagao, Dissociation termination of methane-ethane hydrates in temperature-ramping tests at atmospheric pressure below the melting point of ice, Chemphyschem 12 (9) (2011) 1652-1656.
[44] J. Chen, J.J. Wu, Y.S. Zeng, Z.K. Liang, G.J. Chen, B. Liu, Z. Li, B. Deng, Self-preservation effect exceeding 273.2 K by introducing deuteriumoxide to form methane hydrate, Chem. Eng. J. 433 (2022) 134591.
[45] R.H. Sun, M.J. Yang, Y.C. Song, Effect of NaCl concentration on depressurization-induced methane hydrate dissociation near ice-freezing point: Associated with metastable phases, J. Nat. Gas Sci. Eng. 96 (2021) 104304.
[46] P.S.R. Prasad, B.S. Kiran, Self-preservation and stability of methane hydrates in the presence of NaCl, Sci. Rep. 9 (1) (2019) 5860.
[47] H. Mimachi, S. Takeya, Y. Gotoh, A. Yoneyama, K. Hyodo, T. Takeda, T. Murayama, Dissociation behaviors of methane hydrate formed from NaCl solutions, Fluid Phase Equilib. 413 (2016) 22-27.
[48] D. Shin, M.J. Cha, Y. Yang, S. Choi, Y. Woo, J. Lee, D. Ahn, J. Im, Y. Lee, O. H. Han, J. Yoon, Temperature- and pressure-dependent structural transformation of methane hydrates in salt environments. Geophys Res Lett. 2017, 44 (5) 2129-2137.
[49] H. Sato, T. Tsuji, T. Nakamura, K. Uesugi, T. Kinoshita, M. Takahashi, H. Mimachi, T. Iwasaki, K. Ohgaki, Preservation of methane hydrates prepared from dilute electrolyte solutions, Int. J. Chem. Eng. 2009 (2009) 843274.
[50] H. Sato, H. Sakamoto, S. Ogino, H. Mimachi, T. Kinoshita, T. Iwasaki, K. Sano, K. Ohgaki, Self-preservation of methane hydrate revealed immediately below the eutectic temperature of the mother electrolyte solution, Chem. Eng. Sci. 91 (2013) 86-89.
[51] Y. Xie, Y.J. Zhu, L.W. Cheng, T. Zheng, J.R. Zhong, P. Xiao, C.Y. Sun, G.J. Chen, J.C. Feng, The coexistence of multiple hydrates triggered by varied H₂ molecule occupancy during CO₂/H₂ hydrate dissociation, Energy 262 (2023) 125461.
[52] Y.J. Zhu, Y. Xie, J.R. Zhong, Y.J. Zhu, X.H. Wang, P. Xiao, Y.F. Sun, X.X. Li, C.Y. Sun, G.J. Chen, In situ investigation on the morphology and formation kinetics of a CO₂/N₂ mixed hydrate film, ACS Sustainable Chem. Eng. 11 (12) (2023) 4678-4689.
[53] D.L. Li, D.Q. Liang, S.S. Fan, H. Peng, Estimation of ultra-stability of methane hydrate at 1 atm by thermal conductivity measurement, J. Nat. Gas Chem. 19 (3) (2010) 229-233.
[54] Y. Xie, Y.J. Zhu, T. Zheng, Q. Yuan, C.Y. Sun, L.Y. Yang, G.J. Chen, Replacement in CH₄-CO₂ hydrate below freezing point based on abnormal self-preservation differences of CH₄ hydrate, Chem. Eng. J. 403 (2021) 126283.
[55] W.F. Kuhs, G. Genov, D.K. Staykova, T. Hansen, Ice perfection and onset of anomalous preservation of gas hydrates, Phys. Chem. Chem. Phys. 6 (21) (2004) 4917-4920.
[56] X. Xue, Z.Z. He, J. Liu, Detection of water-ice phase transition based on Raman spectrum, J. Raman Spectrosc. 44 (7) (2013) 1045-1048.
[57] Y.J. Zhu, Y. Xie, J.R. Zhong, X.H. Wang, P. Xiao, C.Y. Sun, G.J. Chen, Mini review on application and outlook of In situ Raman spectrometry in gas hydrate research, Energy Fuels 36 (18) (2022) 10430-10443.
[58] H.S. Truong-Lam, S. Lee, C.J. Jeon, S. Seo, K. Kang, J.D. Lee, Effects of salinity on hydrate phase equilibrium and kinetics of SF₆, HFC134a, and their mixture, J. Chem. Eng. Data 66 (5) (2021) 2295-2302.
[59] A. Kumar, H.P. Veluswamy, S. Kumar, R. Kumar, P. Linga, In situ characterization of mixed CH₄-THF hydrates formed from seawater: High-pressure calorimetric and spectroscopic analysis, J. Phys. Chem. C 125 (30) (2021) 16435-16443.
[60] M.J. Cha, Y. Hu, A.K. Sum, Methane hydrate phase equilibria for systems containing NaCl, KCl, and NH₄Cl, Fluid Phase Equilib. 413 (2016) 2-9.
[61] V.K. Saw, I. Ahmad, A. Mandal, G. Udayabhanu, S. Laik, Methane hydrate formation and dissociation in synthetic seawater, J. Nat. Gas Chem. 21 (6) (2012) 625-632.
[62] P.D. Dholabhai, N. Kalogerakis, P.R. Bishnoi, Equilibrium conditions for carbon dioxide hydrate formation in aqueous electrolyte solutions, J. Chem. Eng. Data 38 (4) (1993) 650-654.
[63] X.Y. Li, D.L. Zhong, P. Englezos, Y.Y. Lu, J. Yan, S.L. Qing, Insights into the self-preservation effect of methane hydrate at atmospheric pressure using high pressure DSC, J. Nat. Gas Sci. Eng. 86 (2021) 103738.

Microscopic experimental study on the effects of NaCl concentration on the self-preservation effect of methane hydrates under 268.15 K

Microscopic experimental study on the effects of NaCl concentration on the self-preservation effect of methane hydrates under 268.15 K

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