不同分解压力下L-Met浓度对CO2水合物稳定性影响研究

doi:10.13745/j.esf.sf.2025.2.8

摘要/Abstract

摘要： 在当前能源需求和“双碳”的大背景下,利用添加促进剂的水合物法储存CO₂受到广泛关注,而促进剂的使用对CO₂水合物的各项性能影响不同。因此本文以硅胶为多孔介质,以3.0 MPa、274.15 K为初始生成条件,对比分析了分解温度为275.15 K条件下,分解压力分别为0、0.5、1 MPa时纯水体系和不同浓度(0.8、0.9、1.0、1.1、1.2 g/L)的L-蛋氨酸(L-Met)体系对CO₂水合物稳定性的影响。结果表明:在0 MPa分解压力下1.1 g/L L-Met体系中的CO₂水合物稳定性最好,分解压力为0.5 MPa和1 MPa时,0.9 g/L L-Met体系中水合物均表现出最好的稳定性,有利于水合物的稳定储存。除了研究L-Met浓度对稳定性的影响外,还分析了分解压力对水合物分解的影响。研究发现在纯水体系中,分解压力为0 MPa时水合物分解速率表现为先增大后减小,而其余分解压力条件下均在初始时刻具有最大分解速率,呈现单调递减趋势;同时发现除0.8 g/L L-Met体系外,其他体系在常压下分解初期时水合物分解速率均是先增大后减小,具有水合物的“自保护”效应,而在0.5 MPa和1 MPa压力下,只在初始时刻具有最大的分解速率,呈现单调减小的趋势,对上述效应具有破坏作用。通过上述研究,为CO₂水合物的长距离运输和长时间储存提供数据及理论支撑。

关键词: CO₂水合物, 硅胶, L-Met, 分解压力, 稳定性

Abstract:

The storage of carbon dioxide (CO₂) hydrate using promoters has garnered significant attention in the context of increasing energy demand and the “dual carbon” goals. However, different promoters exhibit varying effects on the properties of CO₂ hydrate. This study investigates the formation and stability of CO₂ hydrate using silica gel as a porous medium under initial formation conditions of 3.0 MPa and 274.15 K, followed by decomposition at 275.15 K. The effects of decomposition pressures (0, 0.5, and 1 MPa) on the stability of CO₂ hydrate were analyzed in systems containing pure water and L-Met (L-methionine) solutions at concentrations of 0.8, 0.9, 1.0, 1.1, and 1.2 g/L. The results show that the CO₂ hydrate in the 1.1 g/L L-Met solution exhibits the highest stability at a decomposition pressure of 0 MPa. The 0.9 g/L L-Met solution provides the best hydrate stability at decomposition pressures of 0.5 MPa and 1 MPa, which is favorable for stable hydrate storage. In addition to analyzing the influence of L-Met concentrations on hydrate stability, the effect of decomposition pressure on hydrate dissociation rates was also studied. In the pure water system, the dissociation rate initially increases and then decreases under a decomposition pressure of 0 MPa. For all other decomposition pressures, the maximum dissociation rate occurs at the initial stage, followed by a monotonic decrease. Furthermore, in L-Met systems, except for the 0.8 g/L concentration, the dissociation rate of hydrate under atmospheric pressure (0 MPa) initially increases and then decreases, demonstrating the “self-protection” effect of hydrate. However, the dissociation rate reaches its maximum at the initial moment and monotonically decreases at decomposition pressures of 0.5 MPa and 1 MPa, indicating that higher pressures undermine the self-protection effect. This study provides insights into the effects of promoter concentration and decomposition pressure on the stability and dissociation behavior of CO₂ hydrate, contributing to advancements in hydrate-based CO₂ storage technologies.

Key words: carbon dioxide hydrate, silica gel, L-Methionine, dissociation pressure, stability

中图分类号:

P744.4
P599

王英梅, 王立瑾, 滕亚栋, 姜雪晨, 张鹏. 不同分解压力下L-Met浓度对CO₂水合物稳定性影响研究[J]. 地学前缘, 2025, 32(2): 195-205.

WANG Yingmei, WANG Lijin, TENG Yadong, JIANG Xuechen, ZHANG Peng. Study on the influence of L-methionine concentrations on carbon dioxide hydrate stability under different decomposition pressures[J]. Earth Science Frontiers, 2025, 32(2): 195-205.

图/表 8

图1 CO2水合物形成与稳定性分析实验装置图 1—CO2气瓶;2、5、6、8、13—单向阀门;3—预冷罐;4、10—循环冷浴;7—压力表;9—真空泵;11—温度传感器;12—反应釜;14—气体流量计;15—数据采集仪;16—电脑。

Fig.1 The experimental device for the analysis of CO2 hydrate formation and stability

表1 实验材料

Table 1 Experiment materials

材料	参数	厂家
二氧化碳(CO₂)	纯度:99.99%	兰州中科凯特有限公司
酒精(C₂H₅OH)	纯度:95.0%	兰州中科凯特有限公司
去离子水(H₂O)	电导率: 18.25 MΩ·cm	自制
L-蛋氨酸(L-Met)	纯度:98.0%	上海湘泓生物科技有限公司
硅胶	粒径:0.5~1 mm, 合格率:≥99%	青岛宸容新材料有限公司

图2 不同浓度的L-Met体系在3种分解压力下CO2水合物降压分解过程温压变化曲线 a—0 MPa;b—0.5 MPa;c—1 MPa;d—0 MPa分解压力下纯水体系温压曲线。

Fig.2 Temperature and pressure variation curves of CO2 hydrate decomposition under different concentrations of LMet system and decomposition pressures

图3 3种分解压力下不同浓度的L-Met体系中CO2水合物分解速率随时间变化曲线

Fig.3 Variation curves of CO2 hydrate decomposition rate with time in LMet system with different concentrations under three decomposition pressures

图4 不同分解压力及L-Met体系中CO2水合物平均分解速率

Fig.4 Average decomposition rate of CO2 hydrate in LMet system under different decomposition pressures

图5 3种分解压力下不同浓度L-Met体系中CO2水合物分解百分比随时间变化曲线

Fig.5 Percentage decomposition of CO2 hydrate in LMet system with different concentrations under three decomposition pressures as a function of time

图6 不同浓度L-Met体系中CO2水合物分解速率与分解压力关系曲线

Fig.6 Relationship curves of CO2 hydrate decomposition rate and decomposition pressure in different concentrations of LMet system

图7 不同浓度L-Met体系中CO2水合物分解百分比变化曲线

Fig.7 Percentage decomposition curves of CO2 hydrate in different concentrations of LMet system

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不同分解压力下L-Met浓度对CO₂水合物稳定性影响研究

Study on the influence of L-methionine concentrations on carbon dioxide hydrate stability under different decomposition pressures

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