Determination of Hydration Number of Methane Hydrates Using Micro-Laser Raman Spectroscopy
LIU Chang-ling1，2，YE Yu-guang1，2，MENG Qing-guo1，3
1. Key Laboratory of Marine Hydrocarbon Resources and Environmental Geology, Ministry of Land and Resources, Qingdao 266071, China 2. Qingdao Institute of Marine Geology, Qingdao 266071, China 3. College of Chemistry and Chemical Engineering, Qingdao University, Qingdao 266071, China
Abstract：Methane hydrates are clathrate compounds that are formed by methane molecules and water molecules under low temperature and high pressure conditions. It was found that methane hydrates exist widely in sea-shelf floor and permafrost, and are considered as a potential energy resource. In the crystal lattice of clathrate hydrate, the water molecules form both large cages (51262) and small cages (512) under the interaction of the hydrogen-hydrogen bond. In this paper, the authors designed a set of experimental apparatus for methane hydrates formation. Based on this equipment, the authors synthesized a series of methane hydrates in various systems in laboratory, including SDS solution (3% Wt) and methane, powdered ice and methane, and powdered ice and methane and natural sand with various sizes (i. e. 250-350, 180-250, 125-180 and 63-90 μm), under different temperature and pressure. The authors also designed a small device which was proved to be convenient for Raman determination of the methane hydrates. Raman spectroscopy was used to analyze the methane hydrates and to measure the structural parameters such as hydration numbers and cage occupancies. The results show that the methane hydrate samples are all in structure Ⅰ type, and hydration numbers and cage occupancies are almost independent of the sediment sizes. In the three systems, the large cages of methane hydrate samples are nearly full occupied, with the occupancy ratios larger than 97%, whereas the small cages between 80% and 86%. The hydration numbers of these methane hydrate samples are between 6.05 and 6.15.
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