A Solid-State 13C NMR and Laser Raman Spectroscopy Study on Synthesized Methane Hydrates

doi:10.11938/cjmr20170203

Chinese Journal of Magnetic Resonance ›› 2017, Vol. 34 ›› Issue (2): 148-155.doi: 10.11938/cjmr20170203

Previous Articles Next Articles

A Solid-State ¹³C NMR and Laser Raman Spectroscopy Study on Synthesized Methane Hydrates

FU Juan^1,2,5, WU Neng-you^3,4, WU Dai-dai², SU Qiu-cheng²

1. Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou 510640, China;
2. Key Laboratory of Gas Hydrate, Guangzhou Institute of Energy Conversion, Chinese Academy of Sciences, Guangzhou 510650, China;
3. Key Laboratory of Natural Gas Hydrate, Ministry of Land and Resources, Qingdao Institute of Marine Geology, Qingdao 266071, China;
4. Laboratory for Marine Mineral Resources, Qingdao National Laboratory for Marine Science and Technology, Qingdao 266071, China;
5. University of Chinese Academy of Sciences, Beijing 100049, China

Received:2016-09-05 Revised:2017-04-18 Online:2017-06-05 Published:2017-06-05

Abstract

Abstract: Methane hydrates (CH₄·nH₂O) mainly composed of methane and water are ice-like crystalline clathrate compounds. They form a large natural gas reservoir due to their abundance. Solid-state NMR and laser Raman spectroscopy are two techniques which can be used for microscopic analysis for methane hydrates. In this paper, a low temperature solid-state ¹³C NMR technology was used to study the structures of synthesized methane hydrates. It was shown that ¹H high power decoupling (¹H HPDEC) had a better performance than ¹³C cross polarization (¹³C CP) for quantitative analysis for methane hydrates. The NMR results indicated that the methane hydrates synthesized by mixing methane gas with ice powder had a type-I structure, with large and small cage occupancies of 0.988 and 0.824, respectively, and a hydrate number of 6.07. Methane hydrates synthesized by mixing the methane gas with the continental slope of the South China Sea site SH2 sediments and ice powder also had a type-I structure, with large and small cage occupancies of 0.987 and 0.887, respectively, and a hydrate number of 5.98. The result showed that addition of site SH2 sediments could reduce hydrate number of methane hydrates, and make small cage occupancy and hydrate saturation higher, which were verified by laser Raman spectroscopy.

Key words: solid-state ¹³C NMR, laser Raman spectroscopy, methane hydrates

CLC Number:

O482.53

FU Juan, WU Neng-you, WU Dai-dai, SU Qiu-cheng. A Solid-State ¹³C NMR and Laser Raman Spectroscopy Study on Synthesized Methane Hydrates[J]. Chinese Journal of Magnetic Resonance, 2017, 34(2): 148-155.

References

[1] PAULL C K, DILLON W P, et al. Natural gas hydrates:occurrence, distribution, and detection[M]. Washington DC:American Geophysical Union, 2001:131-143.
[2] KIDA M, HACHIKUBO A, SAKAGAMI H, et al. Natural gas hydrates with locally different cage occupancies and hydration numbers in Lake Baikal[J]. Geochem Geophy Geosy, 2009, 10(5):1-8.
[3] UCHIDA T, HIRANO T, EBINUMA T, et al. Raman spectroscopic determination of hydration number of methane hydrates[J]. AIChE J, 1999, 45(12):2641-2645.
[4] LU H L, LORENSON T D, MOUDRAKOVSKI I L, et al. The characteristics of gas hydrates recovered from the Mount Elbert Gas Hydrate stratigraphic test well, Alaska North Slope[J]. Mar Petrol Geol, 2011, 28(2):411-418.
[5] HANDA Y P. A Calorimetric study of naturally occurring gas hydrated[J]. Ind Eng Chem Res, 1988, 27(5):872-874.
[6] RIPMEESTER J A, RATCLIFFEA C I. Low-temperature cross-polarizatlon/magic angle spinning ¹³C NMR of solid methane hydrates:structure, cage occupancy, and hydration number[J]. J Phys Chem, 1988, 92(2):337-339.
[7] XIA N, LIU C L, YE Y G, et al. Study on determination method of natural gas hydrates by micro-laser raman spectroscopy[J]. Rock and Mineral Analysis, 2011, 30(4):416-422. 夏宁, 刘昌岭, 业渝光, 等. 显微激光拉曼光谱测定天然气水合物的方法研究[J]. 岩矿测试, 2011, 30(4):416-422.
[8] OHNO H, TIMOTHY A S, STEVEN F D, et al. Raman studies of methane-ethane hydrate metastability[J]. J Phys Chem A, 2009, 113:1711-1716.
[9] MENG Q G, LIU C L, YE Y G, et al. Measurement of micro-struc ture features of binary CH₄-THF clathrate hydrate based on the ¹³C solid state NMR[J]. Natural Gas Industry, 2015, 35(3):1-6. 孟庆国, 刘昌岭, 业渝光, 等. ¹³C固体核磁共振法测定CH₄-THF二元水合物的微观结构特征[J]. 天然气工业, 2015, 35(3):1-6.
[10] LIU C L, MENG Q G, YE Y G. Applications of solid state NMR in the studies of gas hydrate[J]. Chinese J Magn Reson, 2012, 29(3):465-474. 刘昌岭, 孟庆国, 业渝光. 固体核磁共振技术在气体水合物研究中的应用[J]. 波谱学杂志, 2012, 29(3):465-474.
[11] MOUDRAKOVSHI I, LU H L, RIPMEESTER J A. Experimental solid state NMR of gas hydrates:problems and solutions[C]//Vancouver:Proceedings of the 6th International Conference on Gas Hydrates, 2008.
[12] WU N Y, ZHANG H Q, YANG S X, et al. Preliminary discussion on natural gas hydrate(NGH) reservoir system of Shenhu Area, North Slope of South China Sea[J]. Natural Gas Industry, 2007, 27(9):1-6. 吴能友, 张海啟, 杨胜雄, 等. 南海神狐海域天然气水合物成藏系统初探[J]. 天然气工业, 2007, 27(9):1-6.
[13] WU N Y, ZHANG H Q, YANG S X, et al. Gas hydrate system of Shenhu area, Northern South China Sea:Geochemical results[J]. Journal of Geological Research, 2011:370298.
[14] SUBRAMANIAN S, SLOAN E D. Trends in vibrational frequencies of guests trapped in clathrate hydrate cages[J]. J Phys Chem B, 2002, 106(17):4348-4355.
[15] KIDA M, SUZUKI K, KAWAMURA T, et al. Characteristics of natural gas hydrates occurring in pore-spaces of marine sediments collected from the eastern Nankai Trough, off Japan[J]. Energy Fuels, 2009, 23(11):5580-5586.
[16] DAVDSON D W, HANDA Y P, RIPMEESTER J A. Xenon¹²⁹ NMR and the thermodynamic parameters of xenon hydrate[J]. J Phys Chem, 1986, 90:6549-6552.
[17] SUSILO R, RIPMEESTER J A, ENGLEZOS P. Characterization of gas hydrates with PXRD, DSC, NMR, and Raman spectroscopy[J]. Chem Eng Sci, 2007, 62(15):3930-3939.
[18] LEE J W, LEE J, KANG S P. ¹³C NMR spectroscopies and formation kinetics of gas hydrates in the presence of monoethylene glycol as an inhibitor[J]. Chem Eng Sci, 2013, 104:755-759.
[19] RIPMEESTER J A, LU H, MOUDRAKOVSKI I L, et al. Structure and composition of gas hydrate in sediment recovered from the JAPEX/JNOC/GSC et al. Mallik 5L-38 gas hydrate production research well, determined by X-ray diffraction and Raman and solid-state nuclear magnetic resonance spectroscopy[J]. Geological Survey of Canada Bulletin. 2005, 585:106.
[20] KIM D Y, UHM T W, LEE H, et al. Compositional and structural identification of natural gas hydrates collected at Site 1249 on Ocean DrillingProgram Leg 204[J]. Korean J Chem Eng, 2005, 22(4):569-572.
[21] KLAPPROTH A, GORESHNIK E, STAKOVA D, et al. Structural studies of gas hydrates[J]. Can J Phys, 2003, 81(1, 2):503-518.
[22] TANG X Q, ZHANG Z F, YANG J. Heating of biological samples in studies of MAS solid-state NMR[J]. Chinese J Magn Reson, 2015, 32(1):123-140. 唐新启, 张正逢, 杨俊. 生物固体核磁共振中样品发热的研究进展[J]. 波谱学杂志, 2015, 32(1):123-140.
[23] LIU C L, YE Y G, MENG Q G, et al. The characteristics of gas hydrates recovered from Shenhu Area in the South China Sea[J]. Mar Geol, 2012, 307-310:22-27.

A Solid-State ¹³C NMR and Laser Raman Spectroscopy Study on Synthesized Methane Hydrates

Knowledge

Abstract

Cite this article

share this article

References

Related Articles 1

Recommended Articles

Metrics

Comments