Basic research progress on marine CO2 hydrate sequestration

doi:10.11949/0438-1157.20240554

Abstract

Abstract:

This review aims to explore the thermodynamic and kinetic characteristics of CO₂ hydrates in seawater, with a focus on the influence of salinity on hydrate formation and stability. By comprehensively analyzing the existing literature, the effects of temperature, pressure and salinity in seawater on the formation and stability of CO₂ hydrates are discussed. Several common equilibrium condition models for CO₂ hydrates in saltwater systems were elaborated, followed by a summary of the effects of seawater systems on the formation rate and stability of CO₂ hydrates, as well as the inhibitory effects of different salt ions on CO₂ hydrate formation. Finally, through the evaluation and summary of seawater CO₂ hydrate storage in recent years, the main problem at present is that the research on CO₂ hydrates in seawater and marine mud systems is not sufficient. Future research directions mainly focus on marine mud as a porous medium that can replace hydrate formation promoters, in order to provide reference for the industrial application of CO₂ hydrate marine storage technology and the study of CO₂ hydrates.

Key words: CO₂ sequestration, hydrate, carbon emission reduction, thermodynamics, dynamics

摘要：

系统探讨了CO₂水合物在海水环境中的热力学和动力学，特别关注盐度对水合物形成和稳定性的影响。通过综合分析现有文献，讨论了海水的温度、压力、盐度等因素对CO₂水合物的形成和稳定性的影响。阐述了几种常见的盐水体系下CO₂水合物的相平衡条件模型，总结了海水环境CO₂水合物形成速率与稳定性的影响，归纳出不同盐离子对CO₂水合物形成的抑制作用。最后，对近年来海水CO₂水合物封存进行评估与总结，指出目前主要问题在于海水海泥体系中CO₂水合物研究还不够充分，未来研究方向应主要围绕海泥作为多孔介质可以替代水合物形成促进剂展开，以期为CO₂水合物海洋封存技术的工业化应用和CO₂水合物的研究提供参考。

关键词: CO₂封存, 水合物, 碳减排, 热力学, 动力学

CLC Number:

O 643.1

Yunhao LI, Chungang XU, Xiaosen LI, Zhaoyang CHEN. Basic research progress on marine CO₂ hydrate sequestration[J]. CIESC Journal, 2024, 75(12): 4403-4412.

李云昊, 徐纯刚, 李小森, 陈朝阳. 海洋CO₂水合物封存基础性研究进展[J]. 化工学报, 2024, 75(12): 4403-4412.

Figures/Tables 7

Fig.1 Hydrate phase equilibrium of CP+CO2+NaCl+water system[29]

Fig.2 Three phase equilibrium of CO2 (20%)+N2 (80%)+NaCl (3.5%(mass))+water mixture[30]

Fig.3 Temperature pressure curve of CO2/CP (7%(mass) MgCl2)[31]（1bar=0.1 MPa）

Fig.4 Changes of hydrate relaxation time in 3%(mass) NaCl-0.5%(mass) CSOM solution (a) and 3%(mass) CaCl2-0.5%(mass) solution (b)[54]

Fig.5 Predict nucleation rate of CO2 hydrates in different systems and variation of experimental temperature over time[56]

Table 1 Measured CO2 hydrate formation kinetic data at 0.2%（mass） of L-meth， L-iso， L-threo， and SDS in 3.3%（mass） brine solution at 4 MPa and 274.15 K in quartz sand［57］

System	Introduction time/h	CO₂ gas consumed /mol	CO₂ gas uptake/ (mol·mmol^-1)	Hydrate formation rate /(mmol·h^-1)	C_gh/%	C_wh/%
L-methionine	100	0.6568	90.89	2.173	93.29	53.99
L-isoleucine	112	0.2623	36.30	0.376	38.27	21.56
L-threonine	16.6	0.4587	56.41	5.427	70.54	33.84
SDS	150	0.5349	66.69	1.422	80.75	40.01
brine	28	0.4270	57.11	7.494	68.38	34.26

Fig.6 Gas absorption rates during hydrate formation in different aqueous solutions at a constant concentration of 1000 mg/L[65]

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Basic research progress on marine CO₂ hydrate sequestration

海洋CO₂水合物封存基础性研究进展

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