Chemical Engineering Department, Center for Hydrate Research, Colorado School of Mines, Golden, Colorado 80401, USA.
J Phys Chem A. 2009 Oct 22;113(42):11311-5. doi: 10.1021/jp906492j.
Binary clathrate hydrates with methane (CH(4), 4.36 A) and tert-butylamine (t-BuNH(2), 6.72 A) as guest molecules were synthesized at different molar concentrations of t-BuNH(2) (1.00-9.31 mol %) with methane at 7.0 MPa and 250 K, and were characterized by powder X-ray diffraction (PXRD) and Raman microscopy. A structural transformation from sVI to sII of t-BuNH(2) hydrate was clearly observed on pressurizing with methane. The PXRD showed sII signatures and the remnant sVI signatures were insignificant, implying the metastable nature of sVI binary hydrates. Raman spectroscopic data on these binary hydrates suggest that the methane molecules occupy the small cages and vacant large cages. The methane storage capacity in this system was nearly doubled to approximately 6.86 wt % for 5.56 mol % > t-BuNH(2) > 1.0 mol %.
具有甲烷（CH(4)，4.36 A）和叔丁胺（t-BuNH(2)，6.72 A）作为客体分子的二元笼形水合物在不同摩尔浓度的 t-BuNH(2)（1.00-9.31 mol %）与甲烷在 7.0 MPa 和 250 K 下合成，并通过粉末 X 射线衍射（PXRD）和拉曼显微镜进行了表征。在加压甲烷时，明显观察到 t-BuNH(2)水合物从 sVI 到 sII 的结构转变。PXRD 显示 sII 特征，残余 sVI 特征不明显，表明 sVI 二元水合物具有亚稳性。这些二元水合物的拉曼光谱数据表明，甲烷分子占据小笼和空位大笼。在该体系中，甲烷的储存容量几乎增加了一倍，约为 6.86wt%，对于 5.56mol%>t-BuNH(2)>1.0mol%。
