量热法多孔沉积物内CH4水合物生成过程中的放热行为

doi:10.16085/j.issn.1000-6613.2020-2134

摘要/Abstract

摘要：

掌握天然气水合物在多孔沉积物生成过程中的放热规律对于天然气水合物的资源开发和了解水合物的成藏规律都具有重要意义。本研究通过高压微量热仪考察了石英砂粒径、初始含水率、温度及含盐条件对CH₄水合物在多孔沉积物内生成过程中放热行为的影响。实验结果表明，随着石英砂粒径的减小，水合物生成的放热速率随之增加。随着初始含水率的降低，水合物的放热峰明显增大，但在实验考察时间内，最终的累积放热量和含水率并没有呈现出明显的相关性。当温度在263.15K时，CH₄水合物生成过程中不存在明显的放热。对于在3.35% NaCl盐溶液体系中进行的甲烷水合物生长放热实验，发现其放热规律与在纯水体系下的放热规律具有较高的一致性，但其总体放热速率和累积放热量较纯水体系更低。实验结果呈现了良好的规律性，对进一步开发量热仪在水合物生成动力学方面的应用具有一定的参考价值。

关键词: CH₄水合物, 放热行为, 沉积物, 高压微量热仪

Abstract:

Comprehending the heat-release behaviors of natural gas hydrate during their formation in porous sediments is of great significance to the development of natural gas hydrate resources and the understanding of hydrate accumulation. In this study, the influence of quartz sand particle size, initial water content, temperature and salt conditions on the heat release behaviors during CH₄ hydrate formation in porous sediments was investigated by using a high-pressure micro differential scanning calorimeter. The experimental results show that, as the particle size of the quartz sand decreases, the heat release rate for CH₄ hydrate formation increases. The exothermic peak for CH₄ hydrate formation increases obviously with the initial water content decreased. However, there is not a significant correlation between the final cumulative heat and initial water content in the experimental time. When the temperature is 263.15K, there is no obvious exothermic peak during the CH₄ hydrate formation. The exothermic law during CH₄ hydrate formation in 3.35% NaCl solution is consistent with that in deionized water system, but their overall heat release rate and cumulative heat are lower. The experimental results by micro calorimeter show good regularities, which also has certain reference value for the further development of the calorimeter in hydrate formation kinetics.

Key words: CH₄ hydrate, exothermic behavior, sediment, micro differential scanning calorimeter

中图分类号:

TE122

朱玉洁, 谢炎, 钟瑾荣, 孙长宇, 陈光进, 王晓辉. 量热法多孔沉积物内CH₄水合物生成过程中的放热行为[J]. 化工进展, 2021, 40(10): 5506-5513.

ZHU Yujie, XIE Yan, ZHONG Jinrong, SUN Changyu, CHEN Guangjin, WANG Xiaohui. Heat-release behaviors during CH₄ hydrate formation in porous sediments by differential scanning calorimeter[J]. Chemical Industry and Engineering Progress, 2021, 40(10): 5506-5513.

图/表 11

参考文献 25

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实验编号	目数/目	粒径/μm	含水率^①/%	温度/K	压力/MPa	最终放热量/mJ	水转化率/%
A1	20～40	380～830	50	274.15	10.172	2585.9	11.32
A2	100～120	120～150	50	274.15	10.172	5013.1	21.30
A3	140～180	80～109	50	274.15	10.172	9971.5	43.48
A4	400～500	25～38	50	274.15	10.172	17245.3	72.48
B1	20～40	380～830	10	274.15	10.172	3462.4	75.82
B2	100～120	120～150	10	274.15	10.172	4384.9	93.14
B3	140～180	80～109	10	274.15	10.172	3777.7	82.36
B4	400～500	25～38	10	274.15	10.172	3621.7	76.11
C1	400～500	25～38	70	274.15	10.172	6095.0	18.30
C2	400～500	25～38	100	274.15	10.172	457.7	0.96
G1	400～500	25～38	10	263.15	10.172	4211.5	88.51
G2	400～500	25～38	50	263.15	10.172	18601.7	78.18
G3	400～500	25～38	70	263.15	10.172	5786.6	17.37
G4	400～500	25～38	100	263.15	10.172	840.2	1.77
F1^②	400～500	25～38	10	274.15	10.172	3847.2	80.85
F2	400～500	25～38	50	274.15	10.172	11089.6	46.61
F3	400～500	25～38	70	274.15	10.172	2281.3	6.85
F4	400～500	25～38	100	274.15	10.172	1497.9	3.15

实验编号	目数/目	粒径/μm	含水率^①/%	温度/K	压力/MPa	最终放热量/mJ	水转化率/%
A1	20～40	380～830	50	274.15	10.172	2585.9	11.32
A2	100～120	120～150	50	274.15	10.172	5013.1	21.30
A3	140～180	80～109	50	274.15	10.172	9971.5	43.48
A4	400～500	25～38	50	274.15	10.172	17245.3	72.48
B1	20～40	380～830	10	274.15	10.172	3462.4	75.82
B2	100～120	120～150	10	274.15	10.172	4384.9	93.14
B3	140～180	80～109	10	274.15	10.172	3777.7	82.36
B4	400～500	25～38	10	274.15	10.172	3621.7	76.11
C1	400～500	25～38	70	274.15	10.172	6095.0	18.30
C2	400～500	25～38	100	274.15	10.172	457.7	0.96
G1	400～500	25～38	10	263.15	10.172	4211.5	88.51
G2	400～500	25～38	50	263.15	10.172	18601.7	78.18
G3	400～500	25～38	70	263.15	10.172	5786.6	17.37
G4	400～500	25～38	100	263.15	10.172	840.2	1.77
F1^②	400～500	25～38	10	274.15	10.172	3847.2	80.85
F2	400～500	25～38	50	274.15	10.172	11089.6	46.61
F3	400～500	25～38	70	274.15	10.172	2281.3	6.85
F4	400～500	25～38	100	274.15	10.172	1497.9	3.15

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量热法多孔沉积物内CH₄水合物生成过程中的放热行为

Heat-release behaviors during CH₄ hydrate formation in porous sediments by differential scanning calorimeter

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