气体水合物生成微观机理及分析方法研究进展

doi:10.11949/0438-1157.20220304

摘要/Abstract

摘要：

水合物技术在能源和气候领域有着广阔的应用前景，有望成为应对能源挑战和气候变化的关键技术。但目前该技术存在着水合物生成速率慢、气体消耗量低的缺点，限制了水合物技术的工业化发展。从微观机理的角度，梳理和总结了关于气体水合物生成机制的理论观点，简述了驱动力和气体溶解度在水合物成核过程中的影响，介绍了表面活性剂和纳米粒子对水合物形成的影响机理以及常用的微观分析技术。分析发现，气体水合物的形成机制时至今日仍未有统一定论，对于促进剂作用机理的研究也不够充分，现有的微观分析手段难以捕捉水合物形成过程中的分子行为。这些问题限制了水合物技术向更快、更高效方面发展。探究水合物技术的相关机理，了解各类影响因素的作用原理，探索新的分析手段，将有助于突破水合物技术的瓶颈，为寻找更佳性能的促进剂、更高效地合成水合物探明道路。

关键词: 水合物技术, 微观机理, 水合物成核, 促进剂, 纳米粒子

Abstract:

Hydrate technology has broad application prospects in the fields of energy and climate, and is expected to become a key technology for addressing energy challenges and climate change. However, the current technology has the disadvantages of slow hydrate formation rate and low gas consumption, which limits the industrial development of hydrate technology. In this paper, from the perspective of microscopic mechanism, the theoretical viewpoints on the formation mechanism of gas hydrates are reviewed and summarized, and the effects of driving force and gas solubility on the nucleation process of hydrates are briefly described. The influence mechanism of surfactants and nanoparticles on hydrate formation and the commonly used microscopic analysis techniques are introduced. It is found that the formation mechanism of gas hydrate is not yet unified, and the research on the action mechanism of accelerator is not enough. It is difficult to capture the molecular behavior of gas hydrate in micro-state by the existing micro-analysis methods. These problems limit the development of hydrate technology to be faster and more efficient. Exploring the relevant mechanism of hydrate technology, understanding the working principles of various influencing factors and exploring new analytical means will be helpful to break through the bottleneck of hydrate technology and search for an accelerator with better performance, a way to synthesize hydrates more efficiently.

Key words: hydrate technology, microscopic mechanism, hydrate nucleation, promoter, nanoparticles

中图分类号:

O 643.1

张炜, 李昊阳, 徐纯刚, 李小森. 气体水合物生成微观机理及分析方法研究进展[J]. 化工学报, 2022, 73(9): 3815-3827.

Wei ZHANG, Haoyang LI, Chungang XU, Xiaosen LI. Research progress on the microscopic mechanism and analytical methods of gas hydrate formation[J]. CIESC Journal, 2022, 73(9): 3815-3827.

图/表 6

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文献	微观分析技术手段	研究课题
[108]	激光拉曼	CH₄水合物动力学分析
[109]	激光拉曼	新的笼占有率的计算方法
[110]	X射线衍射	真空中水合物形成原位观测
[111]	激光拉曼+X射线衍射	CH₄水合物高压相变过程观测
[112]	激光拉曼+X射线衍射	客体分子分布情况
[113]	中子衍射	CO水合物亚稳态研究
[114]	中子衍射	客体分子填充率
[115]	中子衍射	鉴定1-丙醇+甲烷水合物的结构
[116]	固体核磁共振	计算笼占有率与置换效率
[117]	固体核磁共振	验证水合物结构转变
[118]	激光拉曼+固体核磁共振	水合物置换机理与结构研究
[119]	激光拉曼+ X射线衍射+固体核磁共振	晶体结构、气体分布与笼占有率
[120]	低温扫描电镜	sⅠ型与sⅡ型水合物表面观测
[121]	低温扫描电镜	CH₄和CO₂水合物形态观测
[122]	磁共振成像	沉积物中CH₄水合物形成分解观测
[123]	磁共振成像	气液界面CO₂水合物膜形成观测
[124]	X射线成像	煤介质中甲烷水合物形成原位成像
[125]	X射线成像	砂质沉积物中甲烷水合物形态观测
[126]	X射线成像	新的反应速率常数的计算方法

文献	微观分析技术手段	研究课题
[108]	激光拉曼	CH₄水合物动力学分析
[109]	激光拉曼	新的笼占有率的计算方法
[110]	X射线衍射	真空中水合物形成原位观测
[111]	激光拉曼+X射线衍射	CH₄水合物高压相变过程观测
[112]	激光拉曼+X射线衍射	客体分子分布情况
[113]	中子衍射	CO水合物亚稳态研究
[114]	中子衍射	客体分子填充率
[115]	中子衍射	鉴定1-丙醇+甲烷水合物的结构
[116]	固体核磁共振	计算笼占有率与置换效率
[117]	固体核磁共振	验证水合物结构转变
[118]	激光拉曼+固体核磁共振	水合物置换机理与结构研究
[119]	激光拉曼+ X射线衍射+固体核磁共振	晶体结构、气体分布与笼占有率
[120]	低温扫描电镜	sⅠ型与sⅡ型水合物表面观测
[121]	低温扫描电镜	CH₄和CO₂水合物形态观测
[122]	磁共振成像	沉积物中CH₄水合物形成分解观测
[123]	磁共振成像	气液界面CO₂水合物膜形成观测
[124]	X射线成像	煤介质中甲烷水合物形成原位成像
[125]	X射线成像	砂质沉积物中甲烷水合物形态观测
[126]	X射线成像	新的反应速率常数的计算方法

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