Characterization of Binary Hydrates Containing Methane by X-ray Diffraction and Microscopic Laser Raman Spectroscopy

MENG Qing-guo; LIU Chang-ling; LI Cheng-feng; HAO Xi-luo

doi:10.15898/j.cnki.11-2131/td.202005290077

2021 Vol. 40, No. 1

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MENG Qing-guo, LIU Chang-ling, LI Cheng-feng, HAO Xi-luo. Characterization of Binary Hydrates Containing Methane by X-ray Diffraction and Microscopic Laser Raman Spectroscopy[J]. Rock and Mineral Analysis, 2021, 40(1): 85-94. doi: 10.15898/j.cnki.11-2131/td.202005290077

Citation:

MENG Qing-guo, LIU Chang-ling, LI Cheng-feng, HAO Xi-luo. Characterization of Binary Hydrates Containing Methane by X-ray Diffraction and Microscopic Laser Raman Spectroscopy[J]. Rock and Mineral Analysis, 2021, 40(1): 85-94. doi: 10.15898/j.cnki.11-2131/td.202005290077

Characterization of Binary Hydrates Containing Methane by X-ray Diffraction and Microscopic Laser Raman Spectroscopy

1.
Key Laboratory of Gas Hydrate, Ministry of Natural Resources, Qingdao Institute of Marine Geology, Qingdao 266071, China
2.
Laboratory for Marine Mineral Resources, Pilot National Laboratory for Marine Science and Technology of Qingdao, Qingdao 266237, China

More Information

Corresponding author: LIU Chang-ling, qdliuchangling@163.com

Received Date: 29 May 2020

Revised Date: 18 August 2020

Accepted Date: 19 September 2020

Publish Date: 28 January 2021

Abstract

Abstract

BACKGROUND
The crystal structure of natural gas hydrate mainly depends on the species and composition of guest molecules. At present, the structure and spectral characteristics of single-component hydrate are relatively clear, but the studies of multi-component hydrates are relatively scarce.
OBJECTIVES
To solve the problem of structure identification of multi-component hydrate, and understand its spectral characteristics.
METHODS
Methane-propane (CH₄-C₃H₈) and methane-tetrahydrofuran (CH₄-THF) binary hydrates, as well as CH₄, C₃H₈ and THF (molar ratio 1:17) single-component hydrate samples were synthesized and characterized by low-temperature X-ray powder diffraction (PXRD) and Raman spectroscopy.
RESULTS
Both of the binary hydrates were typical structure Ⅱ hydrates, which were the same as those of C₃H₈ and THF hydrate. The crystal cell parameters a for CH₄-C₃H₈ and CH₄-THF binary hydrates were 17.2312×10^-10 m and 17.2241×10^-10 m, respectively. For CH₄-C₃H₈ hydrate, CH₄ was distributed in both large and small cages, showing two characteristic Raman peaks (2900cm^-1 and 2911cm^-1); C₃H₈ was only distributed in the large cage. Compared with C₃H₈ hydrate, the C-H stretching vibration peak was almost unchanged while the C-C stretching vibration peak (873cm^-1) shifted by 3cm^-1 to low frequency. For CH₄-THF hydrate, the large cage was occupied by THF and CH₄ was only filled in the small cage (2910cm^-1). The peak positions of C-C and C-H stretching vibrations of THF in CH₄-THF hydrate were consistent with those of THF hydrate.
CONCLUSIONS
The structure types of binary hydrates are consistent with those of single component hydrates. Molecules with larger sizes play a key role in the crystal structure of binary hydrates containing CH₄. Moreover, the distribution of CH₄ molecules in the cages are also influenced by larger molecules, and the Raman spectral characteristics of binary hydrates are significantly different. The conclusion of this study has important guiding significance for identifying the microstructure of multi-component hydrate based on spectral characteristics.
- binary hydrate containing methane /
- crystal structure /
- spectrum characteristics /
- guest molecule /
- X-ray powder diffraction /
- microscopic laser Raman spectroscopy

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