Applications of X-ray Diffraction in Natural Gas Hydrate Research
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摘要: 天然气水合物是一种由气体分子（包括烃类和CO2、H2S等非烃类气体）和水分子在高压低温环境中形成的笼型水合物，主要有Ⅰ型（立方晶体结构）、Ⅱ型（菱形晶体结构）和H型（六方晶体结构）三种晶体结构。研究水合物的结构特征及变化规律，对于认识水合物形成机理、微观动力学、相态转化及水合物样品鉴定等具有重要意义。X射线衍射（XRD）是一种利用X射线照射晶体（或某些非晶态物质）时产生的衍射来研究晶体内部结构（即内部原子排布）的分析技术。该技术应用于天然气水合物研究，不仅能准确获取水合物的结构类型及晶格参数等重要信息，还能观测水合物生成分解的微观动力学过程。本文阐述了XRD技术应用于水合物结构特征研究、水合物生成/分解动力学过程原位观测以及野外水合物样品鉴定等方面的研究进展。已知结构Ⅰ型和Ⅱ型水合物立方晶体的边长分别约为12.0×10-10 m和17.3×10-10 m，而结构H型水合物六方晶体a轴和c轴的边长分别约为12.2×10-10 m和10.0×10-10 m，因此，通过XRD技术准确测量水合物晶体的晶格参数，即可判定水合物晶体的结构类型，该技术在国外已应用于海洋和冻土区钻获的天然气水合物样品鉴定并获得结构信息。此外，通过测定不同条件下生成的水合物晶体参数的变化，可研究水合物的结构转换及其影响规律，研究表明混合气体的组成、客体分子体积及直径大小、温度等都对水合物晶体参数及结构产生影响。通过在高压环境下的XRD原位技术，可测定水合物的生成与分解过程中衍射峰的变化，研究水合物生成/分解动力学过程，研究表明水合物生成/分解主要分两个阶段，即在气液（固）表面的快速生成/分解过程及气体分子在液（固）体内部的扩散过程，后一个阶段控制着反应速度。目前，国外在水合物研究中应用XRD技术已相对成熟，而我国才刚刚起步。本文认为，将XRD技术应用到天然气水合物的研究中，可解决水合物的结构类型鉴别及晶格参数测量等基本的科学问题，而且XRD技术与核磁共振、红外光谱、X-CT等分析技术的联用，尚有很大的发展空间，将为天然气水合物相关的理论研究提供强有力的技术支撑。Abstract: Natural gas hydrates are clathrate hydrates formed from gas molecules (e.g. hydrocarbon gases and non-hydrocarbon gases such as CO2 and H2S) and water molecules under high pressure and low temperature, with three types of crystal structure, such as cubic (Ⅰ), rhombus (Ⅱ) and hexagonal (H). The structural characteristics and variation rule of clathrate hydrate is significant for understanding the formation mechanism, micro-kinetic, phase transformation and identification of gas hydrate. X-ray Diffraction (XRD) is an analytical technique that is used to analyze the crystal micro-structure (i.e. atom orientation) based on the diffraction pattern produced by X-ray irradiating the crystal or some non-crystal substances. When XRD is applied in gas hydrate research, not only can it provide the important information such as structure type and lattice parameter of gas hydrate, but it can also be used to observe the micro-kinetic process of hydrate formation and dissociation. Several applications of XRD in natural gas hydrates research, such as structural characteristics, in situ observation of gas hydrates formation/dissociation, and hydrate sample identification on field are reviewed in this paper. It is well known that the crystal lattice of structure Ⅰ and Ⅱ is approximately 12.0×10-10 m and 17.3×10-10 m, respectively, and approximately 12.2×10-10 m and 10.0×10-10 m along a and c axis for structure H. Therefore, the crystal structure type can be easily identified with the accurate lattice parameters measured by XRD. Now, the XRD technique has been already conducted in identifying and obtaining the structural information of gas hydrate samples recovered from marine and permafrost region overseas. In addition, the structure transformation and influencing factors of gas hydrate can be investigated based on the lattice parameter variation of gas hydrate, which was measured under different conditions. The experimental results show that all the mixture composition, the volume and diameter of guest molecules as well as the temperature can affect the lattice parameter and structure of gas hydrate. In situ XRD technique under high pressure is also used to measure the variation of diffraction peaks during gas hydrate formation/dissociation, and eventually to investigate the kinetic processes of gas hydrate formation and dissociation. The results show that two stages were observed during gas hydrate formation/dissociation, the fast process of hydrate formation/dissociation on the gas-liquid (solid) surface and the gas molecules diffusion process in the liquid (solid). The last stage controls the whole reaction speed. At present, although the XRD technique is widely used in gas hydrate research abroad, it is just beginning in China. It is believed that the XRD technique can be used in gas hydrate research to resolve the basic scientific problems such as structure type identification and lattice parameter measurement, and will provide a powerful technological support for gas hydrate relevant theory research once it combines with other analytical techniques like NMR, IR and X-CT.
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Key words:
- X-ray diffraction /
- natural gas hydrate /
- structure type /
- lattice parameter /
- in-situ observation
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表 1 三种类型天然气水合物晶体结构参数[33]
Table 1. The crystal structure parameters of three types of gas hydrate [33]
孔穴规格 Ⅰ型天然气水合物 Ⅱ型天然气 水合物 H型天然气 水合物 小 大 小 大 小 中 大 孔穴结构 512 51262 512 51264 512 435663 51268 孔穴数目 2 6 16 8 3 2 1 孔穴半径(10-10 m) 3.91 4.33 3.91 0.473 3.91 4.06 5.71 晶格大小(10-10 m) a≈12.0 a≈17.3 a≈12.2,c≈10.0 空间群 Pm3n Fd3m P6/mmm 晶体 立方体 菱形 六面体 
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表 2 客体分子的大小和体积及在-100℃形成的Ⅱ型水合物晶胞参数 [10]
Table 2. Sizes and volumes of the guests and the lattice parameters of structure Ⅱ hydrate at -100℃ [10]
Ⅱ型水合物的 客体分子 分子直径 Dmax (×10-10 m) 分子体积 (×10-10 m) 单位晶胞参数 (×10-10 m) 环氧丙烷 6.01 56 17.182 1,3-二氧戊烷 6.19 63 17.157 丙酮 6.26 59 17.181 三氯甲烷 6.50 69 17.236 四氯化碳 6.50 82 17.330 四氢呋喃 6.95 82 17.316 苯+氙 7.07 76 17.363
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