1. National Engineering Research Center for Coal & Gas Control, China University of Mining & Technology, Xuzhou 221008, China 2. Department of Safety Engineering, Heilongjiang University of Science and Technology, Harbin 150022, China 3. National Central Laboratory of Hydrocarbon Gas Transportation Pipeline Safety, Harbin 150022, China 4. School of Architecture and Civil Engineering Heilongjiang University of Science and Technology, Harbin 150022, China
摘要： 抽采瓦斯气分离产物特性精确获取是水合分离新技术应用关键。针对两种浓度构成的瓦斯混合气(CO2—CH4—N2)，利用瓦斯水合分离产物Raman测试装置，原位合成两种水合物样品并观测Raman光谱。基于客体分子振动模式、“松笼-紧笼”模型及Raman谱带面积比，结合van der Waals-Platteeuw模型，确定出水合物晶体结构，计算出晶体孔穴占有率、水合指数等结构参数。结果表明，两种瓦斯水合物样品均为Ⅰ型结构，其大孔穴占有率分别为98.57%和98.52%，小孔穴占有率分别为29.93%和33.87%，小孔穴不易被客体分子填充;两种分离产物水合指数比较接近，分别为7.14和6.98，均大于Ⅰ型水合物水合指数理论值。
关键词：瓦斯水合物;拉曼光谱;晶体结构;孔穴占有率;水合指数
Abstract：Accurate determination of coal mine gas separation product characteristics is the key for gas separation application based on hydrate technology. Gas hydrate was synthesized from two types of gas compositions (CO2—CH4—N2). The separation products were measured by in situ Raman spectroscopy. The crystal structure of mixed-gas hydrate was determined, and the cavity occupancy and hydration index were calculated, based on the object molecular various vibrational mode, “loose cage-tight cage” model and the Raman bands area ratio, combined with the model of van der Waals-Platteeuw. The results show that the mixed-gas hydrates are both structureⅠ for the two gas samples; Large cages of mixed-gas hydrate are nearly occupied by guest molecules, and the large cavity occupancies are 98.57% and 98.52%, respectively; but small cages are not easy to be occupied, and the small cavity occupancies are 29.93% and 33.87%, respectively; hydration index of the two gas samples hydrate is 7.14 and 6.98, respectively, which is greater than the theoretical value of structure Ⅰ.
Key words：Gas hydrate;Raman spectra;Crystal structure;Cavity occupancy;Hydration index
[1] LI Wei, CHENG Yuan-ping, YANG Yun-feng(李 伟, 程远平, 杨云峰). Journal of China University of Mining & Technology(中国矿业大学学报), 2011, 40(2): 190. [2] WANG Lian-jie, SUN Dong-sheng, ZHANG Li-rong(王连捷, 孙东生, 张利容). Journal of China Coal Society(煤炭学报), 2009, 34(1): 28. [3] LI Shu-gang, CHANG Xin-tan, XU Jing-cai(李树刚, 常心坦, 徐精彩). Journal of Xi’an University of Science and Technology(西安科技大学学报), 2000, 20(1): 1. [4] WU Qiang, ZHANG Bao-yong, SUN Deng-lin(吴 强, 张保勇, 孙登林). Journal of China Coal Society(煤炭学报), 2009, 34(3): 361. [5] WU Qiang, ZHANG Bao-yong(吴 强, 张保勇). Journal of China University of Mining & Technology(中国矿业大学学报), 2010, 39(4): 484. [6] WU Qiang, ZHU Yu-mei, ZHANG Bao-yong(吴 强, 朱玉梅, 张保勇). CIESC Journal(化工学报), 2009, 60(5): 1193. [7] Sloan E D, Koh C H. Clatrate Hydrates of Natural Gases. 3rd ed. USA: CRC Press，2008. [8] Ripmeester J A, Tse J S, Ratcliffe C I. Journal de Physique, 1987, 114: 2173. [9] Li Dongliang, Du Jianwei, He Song. Science China(Chemistry), 2012, 55(3): 373. [10] Li X S, Zhang Y, Li G. J. Chem. Thermodyn., 2008, 40: 1464. [11] Uchida T, Takeya S, Wilson L D. Canadian Journal of Physics, 2003, 81: 351. [12] Yoon J H, Kawamura T, Yamamoto Y, et al. Journal of Physical Chemistry A, 2004, 108: 5057. [13] Lu H, Seo Y T, Lee J W. Nature, 2007, 445(18): 303. [14] YAO Lin-tao, LIU Mu-hua, LIU Dao-jin, et al(药林桃, 刘木华, 刘道金, 等). Acta Laser Biology Sinica(激光生物学报), 2007, 16(3): 370. [15] QIN Chao-jian, QIU Yu-zhuo, ZHOU Guo-fu, et al(秦朝建, 裘愉卓, 周国富, 等). Acta Minalogica Sinica(矿物学报), 2007, 27(3/4): 400. [16] Burke E A J. Lithos, 2001, 55: 139. [17] FAN Hong-rui, TAO Ke-jie, XIE Yi-han, et al(范宏瑞, 陶克捷, 谢奕汉, 等). Acta Petrologioa Sinica(岩石学报), 2003, 19(1): 169. [18] QIN Chao-jian, QIU Yu-zhuo, ZHOU Guo-fu, et al(秦朝建，裘愉卓，周国富，等). Acta Petrologioa Sinica(岩石学报), 2007, 23(1): 161. [19] WANG Yi-lin, YANG Qun(王怡林, 杨 群). Chinese Journal of Light Scattering(光散射学报), 2007, 19(2): 128. [20] LIU Wen-han, YANG Mo, WU Xiao-qiong, et al(刘文涵, 杨 末, 吴小琼, 等). Chinese Journal of Analytical Chemistry(分析化学), 2007, 35(3): 416. [21] LIU Wen-han, YANG Mo, WU Xiao-qiong, et al(刘文涵, 杨 末, 吴小琼, 等). Chinese Journal of Analytical Chemistry(分析化学), 2007, 35(10): 1503. [22] Robin Susilo, John A Ripmeester, Peter Englezos. Chemical Engineering Science, 2007, (62): 3930. [23] Manja Luzi, Judith M Schicks, Rudolf Naumann. J. Chem. Thermodynamics, 2012, 48: 28. [24] Sum A K, Burruss R C, Sloan E D. Journal of Physics and Chemistry, 1997, 101: 7371. [25] Uchida T, Takagi A, Hirano T, et al. Proceedings of the Second International Conference on NGH. Toulouse, France. 1996: 335. [26] Alondra Torres Trueba, Ivona R Radovic, John F Zevenbergen, et al. International Journal of Hydrogen Energy, 2012, 37: 5790. [27] Subramanian S，Sloan E D. J. Phys. Chem. B，2002, 106：4348. [28] Uchida T, Moriwaki M, Takeya S, et al. AICHE Journal, 2004, 50(2): 518. [29] Ripmeester J A, Ratcliffe C I J. Phys. Chem., 1988, 92: 337. [30] Lu H, Moudrakovski I, Riedel M, et al. J. Geophys. Res., 2005, 110: B10204. [31] Hester K C, Dunk R M, White S N, et al. Geochimica et Cosmochimica Acta, 2007, 71: 2947. [32] Lu H, Seo Y T, Lee J W, et al. Nature, 2007, 445(18): 303.
