Ⅱ型二元氢气水合物相边界条件测定及分解焓计算

Measurement of Phase Boundary Conditions and Calculation of Dissociation Enthalpy of sⅡ Binary Hydrogen Hydrate

针对水合物法储氢存在相平衡数据较少及其分解焓直接实验测定非常困难的问题,在已有的高压可视蓝宝石反应釜中测定了环戊烷/丙酮/叔丁胺/四氢呋喃-水-氢气三组分体系中的水合物相边界条件,并结合Clausius-Clapeyron方程计算确定了4种Ⅱ型二元氢气水合物的分解焓.结果表明:含环戊烷/丙酮/叔丁胺/四氢呋喃的Ⅱ型二元氢气水合物的相平衡压力可降低至纯氢气水合物同温度下相平衡压力的1/10甚至更多.二元氢气水合物的分解焓与添加剂和相平衡温度有关,对于同一种添加剂,随着相平衡温度的升高,所得到的二元氢气水合物分解焓增加.二元氢气水合物相平衡边界和分解焓的测定对进一步研究和开发水合物法储氢技术具有重要价值.

Experiments on sII binary hydrogen hydrate phase boundary conditions of the cyclo- pentane/tetrahydrofuran/tert-butylamine/acetone-hydrogen-water system were conducted in a high pressure visual sapphire reactor to obtain the phase equilibrium data for hydrogen hydrate. On the basis of the experimental data, the dissociation enthalpy of sII binary hydrogen hydrate was calculated with the Clausius-Clapeyron equation. The results show that the phase equilibrium pressure of sII binary hydrogen hydrate is one-tenth or even more lower that of hydrogen hydrate without additives. The dissociation enthalpy of sII binary hydrogen hydrate is related to the additives and the phase equilibrium temperature, and with the same kind of additives the dissociation enthalpy of the binary hydrogen hydrate increases with the phase equilibrium temperature. The results of this study may lead to the development of hydrogen storage by hydrate technique.