In this study, stability conditions and characterization of guest gas (CH₄ and N₂) + CP hydrates were investigated with a primary focus on phase equilibria and microscopic analyses. Four-phase (H-L_W-L_CP-V) equilibria of the CH₄ + CP and N₂ + CP hydrates measured at the pressure range of 0–11 MPa demonstrated that CP could significantly reduce hydrate equilibrium pressure at any given temperature and, thus, could be used as a powerful thermodynamic promoter for gas hydrates containing CH₄ and N₂. Powder X-ray diffraction revealed that guest gas (CH₄ and N₂) + CP hydrates are indexed using a cubic sII unit cell (space group Fd3m) and that the inclusion of guest gases does not affect the original structure of CP hydrates. It was confirmed from ¹³C NMR spectra that CH₄ molecules are enclathrated only in the small 5¹² cages of sII CH₄ + CP hydrates and that the cage occupancy of CH₄ molecules in the small 5¹² cages of sII CH₄ + CP hydrates is relatively lower than that of sI CH₄ hydrate. Time-dependent in situ Raman spectra also indicated the occupation of guest gases in the CP hydrate and an absence of structural transformation caused by the inclusion of guest gases. The findings of this study can broaden our understanding of cage-specific occupation of guest molecules in gas hydrates and, thus, provide important information on the application of CP hydrates to gas storage and separation.

在这项研究中，研究了客气（CH ₄和N ₂）+ CP水合物的稳定性条件和表征，主要着眼于相平衡和微观分析。 在0-11 MPa压力范围内测得的CH ₄  + CP和N ₂ + CP水合物的四相（HL _W -L _CP -V）平衡表明，在任何给定温度下，CP均可显着降低水合物平衡压力，并且，因此，可以用作含有CH ₄和N _2的气体水合物的强大热力学促进剂。粉末X射线衍射表明，客气（CH ₄和N ₂）+ CP水合物使用立方sII晶胞（空间群Fd3m）进行索引，并且客气的夹杂不会影响CP水合物的原始结构。从¹³ C NMR光谱证实，CH ₄分子仅被包封在5^个12个sII CH ₄  + CP水合物的笼中，并且CH ₄分子在5^个12个小笼中的sII CH ₄  + CP水合物中占据了CH ₄分子。相对低于sCH ₄水合物。时间相关的原位拉曼光谱还表明，CP水合物中的客气已被占用，并且由于客气的夹杂而没有发生结构转变。这项研究的发现可以拓宽我们对气体水合物中客体分子的笼特定占据的了解，从而为CP水合物在气体存储和分离中的应用提供重要信息。