Parameter Optimization and Analysis Method for Determination of Natural Gas Hydrate by Powder X-ray Diffraction
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摘要: 天然气水合物是由烃类气体和水在低温高压下形成的一种非化学计量的笼型晶体水合物,在常温常压下极易分解,需要在低温条件下对其进行测试。本文针对天然气水合物这一特殊样品,重点研究其粉晶X射线衍射测试条件,系统地探讨了步长、扫描速度、累加次数及测试温度等因素对测试结果的影响,优化了仪器参数,建立了粉晶X射线衍射测试天然气水合物晶体结构的方法,并应用到实验合成的甲烷水合物和我国南海珠江口盆地钻获的天然气水合物样品的晶体结构测试中。结果表明,我国南海珠江口盆地的天然气水合物样品与实验合成的甲烷水合物结构相同,均属立方晶系,为典型的Ⅰ型水合物,晶胞参数分别为11.9309×10-10 m和11.9135×10-10 m。该技术可准确获得天然气水合物的结构信息,为我国天然气水合物的深入研究提供技术支撑。Abstract: Gas hydrate is a form of non-stoichiometric clathrate compound which is produced by hydrocarbon gas molecules and water molecules at high pressure and low temperature. Usually under atmospheric pressure and room temperature, the hydrate sample is easy to decompose and thus the analysis must be carried out at low temperature. The analysis conditions of powder X-ray Diffraction for natural gas hydrate is the focus of this study. The influencing factors (i.e., increment, scan speed, cumulative number, and the temperature) were systematically studied to optimize the analytical parameters. As a result, a powder X-ray Diffraction method to measure the crystal structure of gas hydrate is proposed. This method has been used successfully to measure the crystal structure of the hydrate samples from both the laboratory and the Pearl River Mouth basin in the South China Sea. The results show that the hydrate samples have a similar cubic crystal structure. Both the gas hydrate from the Pearl River Mouth basin in the South China Sea and the synthetic methane hydrate in the laboratory belong to the type I hydrate and have unit cell parameters of 11.9309×10-10 m and 11.9135×10-10 m, respectively. This method can be used to obtain the structural information of gas hydrate, and will provide a technical support for further research of gas hydrate in China.
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Key words:
- natural gas hydrate /
- powder X-ray Diffraction /
- methane hydrate /
- lattice parameter /
- crystal structure
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[1] 刘昌岭, 孟庆国.天然气水合物实验测试技术[M].北京:科学出版社, 2016:32-45.
Liu C L, Meng Q G.Gas Hydrates Experiment and Testing Technologies[M].Beijing:Science Press, 2016:32-45.
[2] 业渝光.天然气水合物实验探测和测试技术[J].海洋地质前沿, 2011, 27(6):37-43. http://youxian.cnki.com.cn/yxdetail.aspx?filename=YKCS2017092700I&dbname=CAPJ2015
Ye Y G.Detection and testing techniques in gas hydrate experiments[J].Marine Geology Frontiers, 2011, 27(6):37-43. http://youxian.cnki.com.cn/yxdetail.aspx?filename=YKCS2017092700I&dbname=CAPJ2015
[3] Takeya S, Kamata Y, Uchida T, et al.Coexistence of structure Ⅰ and Ⅱ hydrates formed from a mixture of methane and ethane gases[J].Canadian Journal of Physics, 2003, 81(1-2):479-484. doi: 10.1139/p03-038
[4] Takeya S, Hori A, Uchida T, et al.Crystal lattice size and stability of type H clathrate hydrates with various large-molecule guest substances[J].Journal of Physical Chemistry B, 2006, 110(26):12943-12947. doi: 10.1021/jp060198v
[5] Sloan E D.Fundamental principles and applications of natural gas hydrates[J].Nature, 2003, 426(6964):353-363. doi: 10.1038/nature02135
[6] Kim D Y, Uhm T W, Lee H, et al.Compositional and structural identification of natural gas hydrates collected at site 1249 on ocean drilling program leg 204[J].Korean Journal of Chemical Engineering, 2005, 22(4):569-572. doi: 10.1007/BF02706645
[7] 刘昌岭, 孟庆国.X射线衍射法在天然气水合物研究中的应用[J].岩矿测试, 2014, 33(4):468-479. http://www.ykcs.ac.cn/article/id/6282aa83-d939-4005-abb8-50932afbb35c
Liu C L, Meng Q G.Applications of X-ray diffraction in natural gas hydrate research[J].Rock and Mineral Analysis, 2014, 33(4):468-479. http://www.ykcs.ac.cn/article/id/6282aa83-d939-4005-abb8-50932afbb35c
[8] Khlystov O, Batist M D, Shoji H, et al.Gas hydrate of Lake Baikal:Discovery and varieties[J].Journal of Asian Earth Sciences, 2013, 62:162-166. doi: 10.1016/j.jseaes.2012.03.009
[9] 张妮, 林春明.X射线衍射技术应用于宝石鉴定-合成及晶体结构研究进展[J].岩矿测试, 2016, 35(3):217-228. http://www.ykcs.ac.cn/article/doi/10.15898/j.cnki.11-2131/td.2016.03.002
Zhang N, Lin C M.Review on the application of X-ray diffraction in gem identification, synthesis and crystal structure research[J].Rock and Mineral Analysis, 2016, 35(3):217-228. http://www.ykcs.ac.cn/article/doi/10.15898/j.cnki.11-2131/td.2016.03.002
[10] 刘昌岭, 业渝光.海洋天然气水合物实验分析技术[J].海洋地质动态, 2008, 24(11):13-16. doi: 10.3969/j.issn.1009-2722.2008.11.003
Liu C L, Ye Y G.Experimental and analytical techniques for marine gas hydrate[J].Marine Geology Letters, 2008, 24(11):13-16. doi: 10.3969/j.issn.1009-2722.2008.11.003
[11] 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. http://www.cnki.com.cn/Article/CJFDTOTAL-PPXZ201203017.htm
Liu C L, Meng Q G, Ye Y G.Applications of solid state NMR in studies of gas hydrate[J].Chinese Journal of Magnetic Resonance, 2012, 29(3):465-474. http://www.cnki.com.cn/Article/CJFDTOTAL-PPXZ201203017.htm
[12] 孟庆国, 刘昌岭, 业渝光.13C固体核磁共振测定气体水合物结构实验研究[J].分析化学, 2011, 39(9):1447-1450. http://kns.cnki.net/KCMS/detail/detail.aspx?filename=fxhx201109029&dbname=CJFD&dbcode=CJFQ
Meng Q G, Liu C L, Ye Y G.13C solid-state nuclear magnetic resonance investigations of gas hydrate structure[J].Chinese Journal of Analytical Chemistry, 2011, 39(9):1447-1450. http://kns.cnki.net/KCMS/detail/detail.aspx?filename=fxhx201109029&dbname=CJFD&dbcode=CJFQ
[13] 刘昌岭, 业渝光, 孟庆国.显微激光拉曼光谱测定甲烷水合物的水合指数[J].光谱学与光谱分析, 2010, 30(4):963-966. http://kns.cnki.net/KCMS/detail/detail.aspx?filename=guan201004024&dbname=CJFD&dbcode=CJFQ
Liu C L, Ye Y G, Meng Q G.Determination of hydration number of methane hydrates using micro-laser raman spectroscopy[J].Spectroscopy and Spectral Analysis, 2010, 30(4):963-966. http://kns.cnki.net/KCMS/detail/detail.aspx?filename=guan201004024&dbname=CJFD&dbcode=CJFQ
[14] Luzi M, Schicks J M, Naumann R, et al.Systematic kinetic studies on mixed gas hydrates by Raman spectroscopy and powder X-ray diffraction[J].Journal of Chemical Thermodynamics, 2012, 48(5):28-35. http://linkinghub.elsevier.com/retrieve/pii/S002196141100437X
[15] 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. http://www.ykcs.ac.cn/article/id/ykcs_20110406
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. http://www.ykcs.ac.cn/article/id/ykcs_20110406
[16] Luzi M, Girod M, Naumann R, et al.A high-pressure cell for kinetic studies on gas hydrates by powder X-ray diffraction[J].Review of Scientific Instruments, 2010, 81(12):105-125. http://aip.scitation.org/doi/abs/10.1063/1.3520465
[17] Fucke K, Steed J W.X-ray and neutron diffraction in the study of organic crystalline hydrates[J].Cheminform, 2010, 41(39):333-350. http://www.mdpi.com/2073-4441/2/3/333
[18] Rojas Y, Lou X.Instrumental analysis of gas hydrates properties[J].Asia-Pacific Journal of Chemical Engineering, 2010, 5(2):310-323. doi: 10.1002/apj.v5:2
[19] Takeya S, Udachin K A, Moudrakovski I L, et al.Direct space methods for powder X-ray diffraction for guest-host materials:Applications to cage occupancies and guest distributions in clathrate hydrates[J].Journal of the American Chemical Society, 2010, 132(2):524-531. doi: 10.1021/ja905426e
[20] Sum A K, Koh C A, Sloan E D.Clathrate hydrates:From laboratory science to engineering practice[J].Industrial & Engineering Chemistry Research, 2009, 48(16):7457-7465. http://pubs.acs.org/doi/full/10.1021/ie900679m
[21] 房俊卓, 张霞, 徐崇福.实验条件对X射线衍射物相定量分析结果的影响[J].岩矿测试, 2008, 27(1):60-62. http://www.ykcs.ac.cn/article/id/ykcs_20080120
Fang J Z, Zhang X, Xu C F.Effect of experimental conditions on X-ray diffractometric quantitative phase analysis[J].Rock and Mineral Analysis, 2008, 27(1):60-62. http://www.ykcs.ac.cn/article/id/ykcs_20080120
[22] 周健, 王河锦.X射线衍射峰五基本要素的物理学意义与应用[J].矿物学报, 2002, 22(2):95-100. http://www.cnki.com.cn/Article/CJFDTOTAL-KWXB200202000.htm
Zhou J, Wang H J.The physical meanings of five basic parameters of an X-ray diffraction peak and their application[J].Acta Mineralogica Sinica, 2002, 22(2):95-100. http://www.cnki.com.cn/Article/CJFDTOTAL-KWXB200202000.htm
[23] 吴斗峰, 尹辛波, 张丽娟.获得高质量X射线衍射谱的测试条件优化[J].分析仪器, 2012(3):65-68. http://www.cnki.com.cn/Article/CJFDTOTAL-FXYQ201203015.htm
Wu D F, Yin X B, Zhang L J.Parametrical optimization for high quality X-ray diffraction spectrum[J].Analytical Instrumentation, 2012(3):65-68. http://www.cnki.com.cn/Article/CJFDTOTAL-FXYQ201203015.htm
[24] 汤云晖.介孔材料的小角度X射线衍射实验条件研究[J].分析测试学报, 2009, 28(3):365-367. http://www.cnki.com.cn/Article/CJFDTOTAL-TEST200903027.htm
Tang Y H.Study on experimental conditions of small-angle X-ray diffraction on mesoporous materials[J].Journal of Instrumental Analysis, 2009, 28(3):365-367. http://www.cnki.com.cn/Article/CJFDTOTAL-TEST200903027.htm
[25] 肖利, 张斯淇, 刘晓静, 等.关于X射线在晶体中衍射的理论研究[J].核电子学与探测技术, 2012, 32(1):83-86. http://www.cnki.com.cn/Article/CJFDTOTAL-HERE201201019.htm
Xiao L, Zhang S Q, Liu X J, et al.Research on X-ray diffraction in crystal[J].Nuclear Electronics & Detection Technology, 2012, 32(1):83-86. http://www.cnki.com.cn/Article/CJFDTOTAL-HERE201201019.htm
[26] 杨有利, 田中青, 孟范成.应用X射线衍射法的阿莫西林的参数测量[J].重庆理工大学学报(自然科学版), 2013, 27(6):33-36. http://www.cnki.com.cn/Article/CJFDTOTAL-CGGL201306008.htm
Yang Y L, Tian Z Q, Meng F C.Parameter studies of X-ray diffraction measuring amoxicillin[J].Journal of Chongqing University of Technology (Natural Science), 2013, 27(6):33-36. http://www.cnki.com.cn/Article/CJFDTOTAL-CGGL201306008.htm
[27] 吴建鹏, 朱振峰.XRD中扫描速度对物相分析的影响[J].热加工工艺, 2003(4):53-54. http://www.cnki.com.cn/Article/CJFDTOTAL-SJGY200304025.htm
Wu J P, Zhu Z F.Influences of scanning speed on phase analyze in XRD[J].Hot Working Technology, 2003(4):53-54. http://www.cnki.com.cn/Article/CJFDTOTAL-SJGY200304025.htm
[28] 孙士文, 隋淞印, 何力, 等.X射线衍射形貌术在碲锌镉晶体中的应用[J].激光与红外, 2014(11):1216-1219. doi: 10.3969/j.issn.1001-5078.2014.11.008
Sun S W, Sui S Y, He L, et al.Application of X-ray diffraction topography in the CdZnTe single crystals[J].Laser and Infrared, 2014(11):1216-1219. doi: 10.3969/j.issn.1001-5078.2014.11.008
[29] Hirai H, Tanaka T, Matsuoka T, et al.Phase changes induced by guest orientational ordering of filled ice Ih methane hydrate under high pressure and low temperature[J].Journal of Physics:Conference Series, 2014, 500(19):192-206. http://iopscience.iop.org/1742-6596/500/19/192006?recenthistorytab=viewed
[30] 李青海, 何荔, 姚燕, 等.LiCl、CaCl2和NaCl-CaCl2水溶液体系低温相变过程的X射线衍射法研究[J].无机化学学报, 2010, 26(10):1804-1809. http://kns.cnki.net/KCMS/detail/detail.aspx?filename=wjhx201010015&dbname=CJFD&dbcode=CJFQ
Li Q H, He L, Yao Y, et al.Processes of the phase changes for LiCl, CaCl2 and NaCl-CaCl2 aqueous solutions at the subzero-temperature with X-ray diffraction method[J].Chinese Journal of Inorganic Chemistry, 2010, 26(10):1804-1809. http://kns.cnki.net/KCMS/detail/detail.aspx?filename=wjhx201010015&dbname=CJFD&dbcode=CJFQ
[31] 王海震, 王秀峰, 于成龙, 等.温度对溶胶-凝胶法制备Bi0.5Na0.5TiO3粉体X射线衍射特征的影响[J].硅酸盐通报, 2010, 29(1):142-146. http://kns.cnki.net/KCMS/detail/detail.aspx?filename=gsyt201001033&dbname=CJFD&dbcode=CJFQ
Wang H Z, Wang X F, Yu C L, et al.Effect of temperature on the X-ray diffraction characteristics of Bi0.5Na0.5TiO3 powders by sol-gel method[J].Bulletin of the Chinese Ceramic Society, 2010, 29(1):142-146. http://kns.cnki.net/KCMS/detail/detail.aspx?filename=gsyt201001033&dbname=CJFD&dbcode=CJFQ
[32] Susilo R, Ripmeester J A, Englezos P.Characterization of gas hydrates with PXRD, DSC, NMR, and Raman spectroscopy[J].Chemical Engineering Science, 2007, 62(15):3930-3939. doi: 10.1016/j.ces.2007.03.045
[33] Takeya S, Kida M, Minami H, et al.Structure and thermal expansion of natural gas clathrate hydrates[J].Chemical Engineering Science, 2006, 61(8):2670-2674. doi: 10.1016/j.ces.2005.11.049
[34] Liu C L, Meng Q G, He X L, et al.Characterization of natural gas hydrate recovered from Pearl River Mouth basin in South China Sea[J].Marine and Petroleum Geology, 2015, 61(61):14-21. http://www.sciencedirect.com/science/article/pii/S0264817214003687
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