蒙脱石层间阳离子类型对甲烷水合物生长特性的影响研究

  天然气水合物因其储量大、能量密度高、分布范围广、产物清洁等优点被认为是最具开发潜力的替代能源之一。天然气水合物中约80%分布在海底沉积物中，蒙脱石是沉积物的重要组成部分，其为片层状矿物，具有高比表面积，层间含有可交换阳离子，这种特性使得蒙脱石影响水分子的活度和有序排列，进而可能对水合物的结构及其动力学产生影响。此外，由于天然气水合物包含的客体分子中甲烷比例达到99.9%，又称其为甲烷水合物（Methane Hydrate，MH）。因此，研究蒙脱石对MH生长特性的影响规律，将为海底沉积物中天然气水合物的赋存和开采提供一定理论参考。

  本文分别基于水合物动力学装置和拉曼成像装置开展了蒙脱石悬浮液中MH生成的宏观及微观动力学实验，总结了蒙脱石层间阳离子类型对MH生成动力学的影响规律；又基于低温X射线衍射、红外光谱和拉曼光谱表征了冻结过程中含水蒙脱石结构变化和其中生成的MH的微观结构，得到了蒙脱石层间阳离子类型对冰和MH结构的影响规律。研究结果如下：

  （1）钠基蒙脱石和钙基蒙脱石对MH的成核和生长具有抑制作用，而钾基蒙脱石对其无明显影响。含水钙基蒙脱石和钠基蒙脱石中冰在-20 ℃以下开始明显生成，而在含水钾基蒙脱石中冰在0 ℃以下开始生成，表明在蒙脱石层间，Ca²⁺和Na⁺抑制了冰的形成，而K⁺对冰的形成无明显影响。

  （2）含水蒙脱石中冰和MH的形成导致蒙脱石片层间脱水和片层结构局部坍塌，进而形成微孔结构，且此种结构破坏不可恢复。冰晶和MH主要形成于微孔中，并受微孔壁的限制致使晶面间距偏小。

  （3）CH₄分子在含水蒙脱石中生成的MH大小笼中的占据率比值低于纯MH样品中，且层间阳离子电荷密度越高，笼占比越低；此外，在含水蒙脱石中生成的MH小笼中，CH₄的C-H振动拉曼峰位高于在纯MH样品中，且层间阳离子电荷密度越高，峰位越高。

  本文开展了不同层间阳离子类型的蒙脱石对MH生成动力学及晶体结构的实验研究，得到了蒙脱石对MH生长特性的影响规律，为海底沉积物中天然气水合物的赋存和开发提供一定理论参考。

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