Baoyong Zhang1,2, Yue Yu  1,2, Xia Gao3, Qiang Wu1,2, and Chuanhai Liu1,2

1Department of Safety Engineering, Heilongjiang University of Science and Technology, Harbin 150022, Heilongjiang China
2National Professional Center Lab of Safety Basic Research for Hydrocarbon Gas Pipeline Transportation Network, Harbin 150022, Heilongjiang, China
3Department of Architectural and Civil Engineering, Heilongjiang University of Science of Technology, Harbin 150022, China


 

Received: September 2, 2021
Accepted: October 18, 2021
Publication Date: November 1, 2021

 Copyright The Author(s). This is an open access article distributed under the terms of the Creative Commons Attribution License (CC BY 4.0), which permits unrestricted use, distribution, and reproduction in any medium, provided the original author and source are cited.


Download Citation: ||https://doi.org/10.6180/jase.202208_25(4).0006  


ABSTRACT


The research on the micro crystal structure of coal mine gas (CMG) hydrate is especially significant for the technology of gas hydrate separation. Raman spectroscopy is an effective method for on-line analysis of gas hydrate microstructure. Using Raman spectroscopy to observe the microstructure of mixed-gas hydrate crystals formed by three kinds of gas samples under two driving forces, which contain a high concentration of carbon dioxide. This experiment obtained information about the hydrate crystals, including large and small cage occupancy, and obtained the hydration number indirectly based on the statistical thermodynamic model of van der Waals and Platteeuw. The results show that the large cages of hydrate phases are nearly fully occupied by carbon dioxide and methane molecules together, with the occupancy ratios between 97.70% and 98.70%. Most of the guest molecules in large cages are carbon dioxide (75.82% ∼ 94.00%) and only a few are filled with methane (4.70% ∼ 31.50%). However, the small cage occupancy ratios are generally low, in the range from 18.28% to 66.06%, and the guest molecules are all methane. The cage occupancy, both large and small, which methane occupied, increased as the methane concentration in the gas sample increased. However, the large cage occupancy, which methane occupied, is lower than the small cage. In addition, the hydration number of three kinds of gas samples in different systems is from 6.38 to 7.32. The occupancy of small cavities increased as the methane concentration in the coal mine gas sample increased, while the hydration number decreased.


Keywords: Gas hydrate; Raman spectrum; Cage occupancy; Hydration numbe


REFERENCES


  1. [1] A. Sum, R. Burruss, and E. Sloan Jr., (1997) “Measurement of clathrate hydrates via Raman spectroscopy" Journal of Physical Chemistry B 101(38): 7371–7377. DOI: 10.1021/jp970768e.
  2. [2] L. Huai-yan, G. Bao-cong, L. Jian-hui, and L. Zhen, (2005) “Coupled relationship among hydrate structure, hydration number, and Raman spectrum" Geoscience 19(1): 83.
  3. [3] S. Subramanian, R. Kini, S. Dec, and E. Sloan Jr., (2000) “Evidence of structure II hydrate formation from methane + ethane mixtures" Chemical Engineering Science 55(11): 1981–1999. DOI: 10.1016/S0009-2509(99)00389-9.
  4. [4] P. Prasad and B. Kiran, (2020) “Stability and exchange of guest molecules in gas hydrates under the influence of CH4, CO2, N2 and CO2+N2 gases at low-pressures" Journal of Natural Gas Science and Engineering 78: DOI: 10.1016/j.jngse.2020.103311.
  5. [5] P. Prasad, Y. Sowjanya, and K. Shiva Prasad, (2009) “Micro-Raman investigations of mixed gas hydrates" Vibrational Spectroscopy 50(2): 319–323. DOI: 10.1016/j.vibspec.2009.02.003.
  6. [6] B. Samset, J. Fuglestvedt, and M. Lund, (2020) “Delayed emergence of a global temperature response after emission mitigation" Nature Communications 11(1): DOI: 10.1038/s41467-020-17001-1.
  7. [7] C. Zheng, B. Jiang, S. Xue, Z. Chen, and H. Li, (2019) “Coalbed methane emissions and drainage methods in underground mining for mining safety and environmental benefits: A review" Process Safety and Environmental Protection 127: 103–124. DOI:10.1016/j.psep.2019.05.010.
  8. [8] W. Wang, H. Li, Y. Liu, M. Liu, H. Wang, and W. Li, (2020) “Addressing the gas emission problem of the world’s largest coal producer and consumer: Lessons from the Sihe Coalfield, China" Energy Reports 6: 3264–3277. DOI: 10.1016/j.egyr.2020.11.199.
  9. [9] N. Gaikwad, J. Sangwai, P. Linga, and R. Kumar, (2021) “Separation of coal mine methane gas mixture via sII and sH hydrate formation" Fuel 305: DOI: 10.1016/j.fuel.2021.121467.
  10. [10] S. Daghash, P. Servio, and A. Rey, (2020) “Elastic properties and anisotropic behavior of structure-H (sH) gas hydrate from first principles" Chemical Engineering Science 227: DOI: 10.1016/j.ces.2020.115948.
  11. [11] X.-Y. Zeng, J.-R. Zhong, Y.-F. Sun, S.-L. Li, G.-J. Chen, and C.-Y. Sun, (2017) “Investigating the partial structure of the hydrate film formed at the gas/water interface by Raman spectra" Chemical Engineering Science 160: 183–190. DOI: 10.1016/j.ces.2016.11.012.
  12. [12] P. Chattaraj, S. Bandaru, and S. Mondal, (2011) “Hydrogen storage in clathrate hydrates" Journal of Physical Chemistry A 115(2): 187–193. DOI: 10.1021/jp109515a.
  13. [13] T. Uchida, T. Hirano, T. Ebinuma, H. Narita, K. Gohara, S. Mae, and R. Matsumoto, (1999) “Raman spectroscopic determination of hydration number of methane hydrates" AIChE Journal 45(12): 2641–2645. DOI: 10.1002/aic.690451220.
  14. [14] M. Gborigi, D. Riestenberg, M. Lance, S. McCallum, Y. Atallah, and C. Tsouris, (2007) “Raman spectroscopy of a hydrated CO2/water composite" Journal of Petroleum Science and Engineering 56(1-3): 65–74. DOI: 10.1016/j.petrol.2005.09.005.
  15. [15] H. Truong-Lam, S. Cho, and J. Lee, (2019) “Simultaneous in-situ macro and microscopic observation of CH4 hydrate formation/decomposition and solubility behavior using Raman spectroscopy" Applied Energy 255: DOI: 10.1016/j.apenergy.2019.113834.
  16. [16] Y. Hiraga, T. Sasagawa, S. Yamamoto, H. Komatsu, M. Ota, T. Tsukada, and J. Smith R.L., (2020) “A precise deconvolution method to derive methane hydrate cage occupancy ratios using Raman spectroscopy" Chemical Engineering Science 214: DOI: 10.1016/j.ces.2019.115361.
  17. [17] Q. Lv and X. Li. “Raman Spectroscopic Studies on Microscopic Mechanism of CP - CH4 Mixture Hydrate”. In: 142. 2017, 3264–3269. DOI: 10.1016/j.egypro.2017.12.501.
  18. [18] T. Makino, Y. Ogura, Y. Matsui, T. Sugahara, and K. Ohgaki, (2009) “Isothermal phase equilibria and structural phase transition in the carbon dioxide + cyclopropane mixed-gas hydrate system" Fluid Phase Equilibria 284(1): 19–25. DOI: 10.1016/j.fluid.2009.05.020.
  19. [19] H. Joon Shin, Y.-J. Lee, J.-H. Im, K. Won Han, J.-W. Lee, Y. Lee, J. Dong Lee, W.-Y. Jang, and J.-H. Yoon, (2009) “Thermodynamic stability, spectroscopic identification and cage occupation of binary CO2 clathrate hydrates" Chemical Engineering Science 64(24): 5125–5130. DOI: 10.1016/j.ces.2009.08.019.
  20. [20] C. Liu, Y. Ye, Q. Meng, Z. Lu, Y. Zhu, J. Liu, and S. Yang, (2010) “Raman spectroscopic characteristics of natural gas hydrate recovered from Shenhu Area in South China Sea and Qilian mountain permafrost" Acta Chimica Sinica 68(18): 1881–1886.
  21. [21] S.-P. Kang and J.-W. Lee, (2013) “Hydrate-phase equilibria and 13C NMR Studies of Binary (CH4+ C2H4) and (C2H6+ C2H4) hydrates" Industrial & Engineering Chemistry Research 52(1): 303–308.
  22. [22] C.-L. Liu, Y.-G. Ye, and Q.-G. Meng, (2010) “Determination of hydration number of methane hydrates using micro-laser Raman spectroscopy" Guang Pu Xue Yu Guang Pu Fen Xi/Spectroscopy and Spectral Analysis 30(4): 963–966. DOI: 10.3964/j.issn.1000-0593(2010)04-0963-04.
  23. [23] Y. Garrabos, V. Chandrasekharan, M. Echargui, and F. Marsault-Herail, (1989) “Density effect on the raman fermi resonance in the fluid phases of CO2" Chemical Physics Letters 160(3): 250–256. DOI: 10.1016/0009-2614(89)87591-8.
  24. [24] Y. Garrabos, M. Echargui, and F. Marsault-Herail, (1989) “Comparison between the density effects on the levels of the Raman spectra of the Fermi resonance doublet of the 12C16O2 and 13C16O2 molecules" The Journal of Chemical Physics 91(10): 5869–5881. DOI: 10.1063/1.457455.
  25. [25] C. Ratcliffe and J. Ripmeester, (1986) “Proton and carbon-13 NMR studies on carbon dioxide hydrate" The Journal of Physical Chemistry 90(7): 1259–1263.
  26. [26] S. Subramanian and E. Sloan Jr., (2002) “Trends in vibrational frequencies of guests trapped in clathrate hydrate cages" Journal of Physical Chemistry B 106(17): 4348–4355. DOI: 10.1021/jp013644h.


    
 

0.9
2021CiteScore
 
 
42nd percentile
Powered by  Scopus

SCImago Journal & Country Rank

Enter your name and email below to receive latest published articles in Journal of Applied Science and Engineering.