季铵盐半笼型甲烷水合物激光拉曼光谱研究
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摘要
四丁基铵盐生成的半笼型水合物以其独有的高稳定性、不易挥发性等优点,成为一种有吸引力的水合物法工业应用的新方法。实验制备了不同浓度的四丁基溴化铵和四丁基氯化铵溶液中生成的半笼型甲烷水合物样品,并使用激光拉曼光谱仪进行了光谱实验和结构分析。结果表明,半笼型水合物中的512小笼可以将CH_4分子包络其中;且当添加剂浓度较低时,CH_4分子对半笼型结构产生HS结构诱导作用,当添加剂浓度较高时,添加剂对半笼型结构的影响占主导作用。
Semiclathrate hydrate, formed with tetrabutylammonium salts, became an attractive method for hydrate based industrial applications, due to its unique advantages of strong stability and non-volatility. In this work, semiclathrate hydrate samples were formed with aqueous solutions of tetrabutylammonium bromide or tetrabutylammonium chloride at different mass fractions. A lase Raman spectrometer was employed to analyze their structures. The results showed that the small 512 cage of semiclathrate hydrate could trap CH_4 molecules. In addition, the CH_4 molecules showed a great influence on semiclathrate hydrate structures of HS formation at low salt concentrations. While at high salt concentrations, the salt played a dominant role in semiclathrate hydrate structures.
Semiclathrate hydrate, formed with tetrabutylammonium salts, became an attractive method for hydrate based industrial applications, due to its unique advantages of strong stability and non-volatility. In this work, semiclathrate hydrate samples were formed with aqueous solutions of tetrabutylammonium bromide or tetrabutylammonium chloride at different mass fractions. A lase Raman spectrometer was employed to analyze their structures. The results showed that the small 512 cage of semiclathrate hydrate could trap CH_4 molecules. In addition, the CH_4 molecules showed a great influence on semiclathrate hydrate structures of HS formation at low salt concentrations. While at high salt concentrations, the salt played a dominant role in semiclathrate hydrate structures.
引文
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[21]Hashimoto S, Sugahara T, Moritoki M, et al. Thermodynamic Stability of Hydrogen Plus Tetra-n-butyl Ammonium Bromide Mixed Gas Hydrate in Nonstoichiometric Aqueous Solutions[J]. Chemical Engineering Science,2008, 63(4):1092-1097
[22]Oshima M, Kida M, Nagao J. Thermal and Crystallographic Properties of Tetra-n-butylammonium Bromide+Tetra-n-butylammonium Chloride Mixed Semiclathrate Hydrates[J]. Journal of Chemical and Engineering Data,2016, 61(9):3334-3340
[2]Makogon Y F, Holditch S A, Makogon T Y. Natural Gashydrates-a Potential Energy Source for the 21st Century[J]. Journal of Petroleum Science and Engineering,2007, 56(1-3):14-31
[3]Eslamimanesh A, Mohammadi A H, Richon D, et al. Application of Gas Hydrate Formation in Separation Processes:a Review of Experimental Studies[J]. Journal of Chemical Thermodynamics, 2012, 46:62-71
[4]Babu P, Linga P, Kumar R, et al. A Review of the Hydrate Based Gas Separation(HBGS)Process for Carbon Dioxide Pre-combustion Capture[J]. Energy, 2015, 85:261-279
[5]Dashti H, Zhehao Yew L,Lou X. Recent Advances in Gas Hydrate-Based CO_2 Capture[J]. Journal of Natural Gas Science and Engineering, 2015, 23:195-207
[6]Javanmardi J, Moshfeghian M. Energy Consumption and Economic Evaluation of Water Desalination by Hydrate Phenomenon[J]. Applied Thermal Engineering, 2003,23(7):845-857
[7]Ngema P T, Petticrew C, Naidoo P, et al. Experimental Measurements and Thermodynamic Modeling of the Dissociation Conditions of Clathrate Hydrates for(Refrigerant Plus Nacl Plus Water)Systems[J]. Journal of Chemical and Engineering Data, 2014, 59(2):466-475
[8]Ngema P T, Naidoo P, Mohammadi A H, et al. Thermodynamic Stability Conditions of Clathrate Hydrates for Refrigerant(R134a or R410a or R507)With MgCl2 Aqueous Solution[J]. Fluid Phase Equilibria, 2016, 413:92-98
[9]Ngema P T, Naidoo P, Mohammadi A H, et al. Experimental Clathrate Hydrate Dissociation Data for Systems Comprising Refrigerant+CaCl_2 Aqueous Solutions[J].Journal of Chemical and Engineering Data, 2016, 61(2):827-836
[10]Lv Y N, Wang S S, Sun C Y, et al. Desalination by Forming Hydrate From Brine in Cyclopentane Dispersion System[J]. Desalination, 2017, 413:217-222
[11]Tanii T. Energy storage:Low Temperature Heat Storage(Use of Clathrate)[J]. Journal of the Japan Society ofMechanical Engineers, 1994, 97(912):925-927
[12]Li G, Hwang Y H, Radermacher R. Review of Cold Storage Materials for Air Conditioning Application[J]. International Journal of Refrigeration-Revue Internationale Du Froid, 2012, 35(8):2053-2077
[13]Wang X, Dennis M, Hou L. Clathrate Hydrate Technology for Cold Storage in Air Conditioning Systems[J]. Renewable and Sustainable Energy Reviews, 2014, 36:34-51
[14]Mohammadi A H, Eslamimanesh A, Belandria V, et al.Phase Equilibria of Semiclathrate Hydrates of CO_2, N2,CH4, or H_2+Tetra-n-Butylammonium Bromide Aqueous Solution[J]. Journal of Chemical and Engineering Data,2011, 56(10):3855-3865
[15]Shi L L, Liang D Q, Wu N Y. Phase Equilibrium Data of the Double Tetrabutylammonium Chloride Plus Carbon Dioxide or Nitrogen Semiclathrate Hydrate[J]. Journal of Chemical and Engineering Data, 2014, 59(7):2320-2323
[16]Li S, Fan S, Wang J, et al. Semiclathrate Hydrate Phase Equilibria for CO_2 in the Presence of Tetra-n-Butyl Ammonium Halide(Bromide, Chloride, or Fluoride)[J]. Journal of Chemical and Engineering Data, 2010, 55(9):3212-3215
[17]Shimada W, Shiro M, Kondo H, et al. TetranButylammonium Bromide-water(1/38)[J]. Acta Crystallographica Section C-Crystal Structure Communications,2005, 61:065-066
[18]Rodionova T V, Komarov V Y, Villevald G V, et al.Calorimetric and Structural Studies of Tetrabutylammonium Bromide Ionic Clathrate Hydrates[J]. Journal of Physical Chemistry B, 2013, 117(36):10677-10685
[19]Rodionova T, Komarov V, Villevald G, et al. Calorimetric and Structural Studies of Tetrabutylammonium Chloride Ionic Clathrate Hydrates[J]. Journal of Physical Chemistry B, 2010, 114(36):11838-11846
[20]Komarov V Y, Rodionova T V, Terekhova I S, et al. The Cubic Superstructure-I of Tetrabutylammonium Fluoride(C4H9)4NF-29.7H_2O Clathrate Hydrate[J]. Journal of Inclusion Phenomena and Macrocyclic Chemistry, 2007,59(1/2):11-15
[21]Hashimoto S, Sugahara T, Moritoki M, et al. Thermodynamic Stability of Hydrogen Plus Tetra-n-butyl Ammonium Bromide Mixed Gas Hydrate in Nonstoichiometric Aqueous Solutions[J]. Chemical Engineering Science,2008, 63(4):1092-1097
[22]Oshima M, Kida M, Nagao J. Thermal and Crystallographic Properties of Tetra-n-butylammonium Bromide+Tetra-n-butylammonium Chloride Mixed Semiclathrate Hydrates[J]. Journal of Chemical and Engineering Data,2016, 61(9):3334-3340