†Department of Energy and Resources Engineering, Korea Maritime and Ocean University, Busan 606-791, Korea.
§Department of Environmental Engineering, Kongju National University, Chungnam 330-717, Korea.
Environ Sci Technol. 2015 May 19;49(10):6045-50. doi: 10.1021/acs.est.5b00866. Epub 2015 Apr 30.
Many studies have focused on desalination via hydrate formation; however, for their potential application, knowledge pertaining to thermodynamic stability, formation kinetics, and guest occupation behavior in clathrate hydrates needs to be determined. Herein, the phase equilibria of SF6 hydrates in the presence of NaCl solutions (0, 2, 4, and 10 wt %) were monitored in the temperature range of 277-286 K and under pressures of up to 1.4 MPa. The formation kinetics of SF6 hydrates in the presence of NaCl solutions (0, 2, and 4 wt %) was also investigated. Gas consumption curves of SF6 hydrates showed that a pure SF6 hydrate system allowed fast hydrate growth as well as high conversion yield, whereas SF6 hydrate in the presence of NaCl solutions showed retarded hydrate growth rate as well as low conversion yield. In addition, structural identification of SF6 hydrates with and without NaCl solutions was performed using spectroscopic tools such as Raman spectroscopy and X-ray diffraction. The Raman spectrometer was also used to evaluate the temperature-dependent release behavior of guest molecules in SF6 and SF6 + 4 wt % NaCl hydrates. The results indicate that whereas SF6 hydrate starts to decompose at around 240 K, the escape of SF6 molecules in SF6 + 4 wt % NaCl hydrate is initiated rapidly at around 205 K. The results of this study can provide a better understanding of guest-host interaction in electrolyte-containing systems.
许多研究都集中在通过水合物形成进行海水淡化上;然而,为了潜在的应用,需要确定关于热力学稳定性、形成动力学以及笼形水合物中客体占据行为的知识。在此,监测了在温度范围为 277-286 K 和压力高达 1.4 MPa 的条件下,SF6 水合物在 NaCl 溶液(0、2、4 和 10wt%)中的相平衡。还研究了 NaCl 溶液(0、2 和 4wt%)存在下 SF6 水合物的形成动力学。SF6 水合物的气体消耗曲线表明,纯 SF6 水合物体系允许快速水合生长以及高转化率,而 NaCl 溶液存在下的 SF6 水合物则表现出较慢的水合生长速率和较低的转化率。此外,使用拉曼光谱和 X 射线衍射等光谱工具对含有和不含有 NaCl 溶液的 SF6 水合物进行了结构鉴定。还使用拉曼光谱仪评估了 SF6 和 SF6+4wt%NaCl 水合物中客体分子的温度依赖性释放行为。结果表明,SF6 水合物在约 240 K 开始分解,而 SF6+4wt%NaCl 水合物中 SF6 分子的逸出则在约 205 K 迅速开始。本研究的结果可以更好地理解含电解质体系中的客体-主体相互作用。