南海海泥中甲烷水合物的形貌及赋存特性

doi:10.16085/j.issn.1000-6613.2022-1623

化工进展 ›› 2023, Vol. 42 ›› Issue (7): 3865-3874.DOI: 10.16085/j.issn.1000-6613.2022-1623

南海海泥中甲烷水合物的形貌及赋存特性

张凯¹^,²^,³(), 吕秋楠¹^,²^,³(), 李刚¹^,²^,³, 李小森¹^,²^,³(), 莫家媚¹^,²^,³

^1.中国科学院天然气水合物重点实验室，中国科学院广州能源研究所，广东广州 510640
^2.广东省新能源和可再生能源研究开发与应用重点实验室，广东广州 510640
^3.中国科学院大学，北京 100049

收稿日期:2022-09-05 修回日期:2022-10-09 出版日期:2023-07-15 发布日期:2023-08-14
通讯作者: 吕秋楠,李小森
作者简介:张凯（1996—），男，硕士研究生，研究方向为天然气水合物。E-mail：zhangkai@ms.giec.ac.cn。
基金资助:
国家自然科学基金(51976228);国家自然科学基金重点项目(51736009);中国科学院前沿科学重点研究项目(QYZDJ-SSW-JSC033);广东省促进经济发展专项资金（海洋经济发展用途）(粤自然资合[2020]044号);广州市科技计划(202002030334)

Morphology and occurrence characteristics of methane hydrates in the mud of the South China Sea

ZHANG Kai¹^,²^,³(), LYU Qiunan¹^,²^,³(), LI Gang¹^,²^,³, LI Xiaosen¹^,²^,³(), MO Jiamei¹^,²^,³

^1.Key Laboratory of Gas Hydrate, Guangzhou Institute of Energy Conversion, Chinese Academy of Sciences, Guangzhou 510640, Guangdong, China
^2.Guangdong Provincial Key Laboratory of New and Renewable Energy Research and Development, Guangzhou 510640, Guangdong, China
^3.University of Chinese Academy of Sciences, Beijing 100049, China

Received:2022-09-05 Revised:2022-10-09 Online:2023-07-15 Published:2023-08-14
Contact: LYU Qiunan, LI Xiaosen

摘要/Abstract

摘要：

水合物表观形貌受水合物的生长方式影响，能够反映水合物在沉积物中的分布以及与沉积物的空间关系，进而对含水合物沉积物的物理特性产生影响。本文通过在实际钻采的南海神狐海域水深2713m的海泥中生成甲烷水合物，利用冷冻扫描电子显微镜（Cryo-SEM）和能谱仪（EDS）对合成水合物的微观形貌、元素组成进行表征。结果表明，与冰相比，纯水体系下的甲烷水合物形貌单一且容易分解。纯水体系生成的水合物与海泥体系生成的水合物形貌相似，均呈颗粒胶结状，微量纳米级别的颗粒冰分布在表面。元素分析表明相较于纯水体系，海泥中生成的水合物C元素含量更高，水合物笼子占有率也越高。海泥中含有微量的C元素，通过C元素含量增加及C、Si比提高确定了表面颗粒胶结状为水合物。本研究为辨别沉积物中的水合物提供了新思路，为研究水合物的表观形貌及赋存提供了重要方法。

关键词: 海泥, 甲烷, 水合物, 表面形貌, 扫描电镜和能谱仪

Abstract:

Hydrate surface morphology was affected by hydrate growth patterns, as well as can reflect distribution in sediments and the spatial relationship with sediments, thereby affecting the physical properties of hydrate-bearing sediments. Methane hydrate was synthesized in the device by using the actual drilled marine mud in the Shenhu sea of South China Sea at a depth of 2713m as sediment. Cryo-scanning electron microscopy (Cryo-SEM) and energy spectrometry (EDS) were used to characterize the microscopic morphology and elemental composition of the synthesized hydrates. The results showed that the methane hydrate in the pure water system was homogeneous and easily decomposed compared to ice. The hydrates formed in the pure water system and in the marine mud were similar in morphology, both of which were in the form of granular colloid, with trace amounts of nanoscale particle ice distributed on the surface. The element analysis showed that the content of carbon element in marine mud was higher than that in pure water, and hence the hydrate cage occupancy was higher. The content of carbon element in marine mud was negligible, and the cement structure on the surface of the marine mud was proved to be hydrate by the increase of the content of carbon element and the ratio of carbon to silicon elements. The research provided a new idea to identify hydrate from sediments and an important way to investigate the surface morphology and occurrence of hydrate in sediments.

Key words: marine mud, methane, hydrate, surface morphology, scanning electron microscopy and energy dispersive spectrometer

中图分类号:

张凯, 吕秋楠, 李刚, 李小森, 莫家媚. 南海海泥中甲烷水合物的形貌及赋存特性[J]. 化工进展, 2023, 42(7): 3865-3874.

ZHANG Kai, LYU Qiunan, LI Gang, LI Xiaosen, MO Jiamei. Morphology and occurrence characteristics of methane hydrates in the mud of the South China Sea[J]. Chemical Industry and Engineering Progress, 2023, 42(7): 3865-3874.

图/表 11

参考文献 26

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探测手段	技术原理	技术特点
显微镜	光学放大特性	二维观测。放大倍数较小，无法观察水合物微观结构
核磁共振成像（MRI）	质子在不同物质中的核磁共振信号不同	可实现内部成像，易区分水合物和水，但成像分辨率有限
X射线断层扫描成像（X-CT）	X射线穿过被测物质时，不同物质的吸收能力存在差异	三维观测。水合物与水的灰度相近不易区分，水合物含量较低时成像分辨率有限
扫描电子显微镜（SEM）	电子束激发表面信息	二维观测。高分辨率、高景深，不易区分水合物与冰，可捕捉水合物分解过程

探测手段	技术原理	技术特点
显微镜	光学放大特性	二维观测。放大倍数较小，无法观察水合物微观结构
核磁共振成像（MRI）	质子在不同物质中的核磁共振信号不同	可实现内部成像，易区分水合物和水，但成像分辨率有限
X射线断层扫描成像（X-CT）	X射线穿过被测物质时，不同物质的吸收能力存在差异	三维观测。水合物与水的灰度相近不易区分，水合物含量较低时成像分辨率有限
扫描电子显微镜（SEM）	电子束激发表面信息	二维观测。高分辨率、高景深，不易区分水合物与冰，可捕捉水合物分解过程

扫描区域	C元素质量分数 /%	O元素质量分数 /%	Si元素质量分数 /%
A	0	91.7	8.3
B	9.95	89.99	0.06
D	5.57	94.27	0.16
E	7.11	92.85	0.04

扫描区域	C元素质量分数 /%	O元素质量分数 /%	Si元素质量分数 /%
A	0	91.7	8.3
B	9.95	89.99	0.06
D	5.57	94.27	0.16
E	7.11	92.85	0.04

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南海海泥中甲烷水合物的形貌及赋存特性

Morphology and occurrence characteristics of methane hydrates in the mud of the South China Sea

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