CO2-海水水合物生成强化方法研究

doi:10.11949/0438-1157.20240506

摘要/Abstract

摘要：

海水中的盐离子成分阻碍水合物成核进程，使得水合物法海洋碳封存耗时长、封存比率低。结合水合物非均相成核特征考虑，认为在局部区域内实现水合物优先成核，进而带动大片海域内水合物扩展生成的封存方法极具工业可行性。因而，开展海水水合物强化生成方法基础研究是推进水合物法海洋碳封存应用落地的基础。基于此，以高效、高转化率生成水合物为目标，在实验室尺度分别探究了高过冷度、添加剂四丁基溴化铵（TBAB）以及变温速率对海水水合物生成特性的影响。结果表明，受到盐离子抑制作用，400 m深度海水中水合物自然生成难度极大，而提高生成过程的过冷度可增强水合物生成驱动力；热力学添加剂TBAB难以显著改善海水水合物的生成条件，但可使生成速率有所提高；0.3 K/min降温速率下的水合物转化率分别是过冷度作用和添加剂作用下的1.28倍和1.19倍。在后续研究中，应考虑多种强化生成方法的耦合作用效果，开发更能缓解海水水合物生成难题的技术手段。

关键词: 二氧化碳, 水合物, 成核, 相平衡

Abstract:

The salt ion components in seawater hinder the hydrate nucleation process, making the hydrate method for marine carbon sequestration take a long time and have a low sequestration rate. Considering the non-homogeneous nucleation characteristics of hydrates, it is feasible to implement a storage method that achieves preferential hydrate nucleation in local areas, leading to the extended generation of hydrates across large sea areas. Therefore, fundamental research on the enhanced generation of seawater hydrate is essential for promoting the application of the hydrate method for ocean carbon sequestration. Based on this premise, laboratory-scale investigations were conducted to study the effects of high subcooling, additives (TBAB), and variable temperature rates on the seawater hydrate generation characteristics, aiming for efficient and high conversion rate hydrate generation. The results indicated that the natural generation of hydrates in seawater at a depth of 400 m is extremely difficult due to the inhibitory effects of salt ions. However, increasing the supercooling degree of the generation process can enhance the driving force for hydrate formation. Although the thermodynamic additive TBAB did not significantly improve the conditions for seawater hydrate generation in the present experiments, it did increase the rate of generation. Furthermore, the study found that the hydrate conversion rate at a cooling rate of 0.3 K/min was enhanced by 1.28 and 1.19 times compared to the effects of subcooling degree and additives, respectively. In conclusion, future studies should consider the coupling effects of various enhanced generation methods to develop technical means that can better mitigate the challenges of seawater hydrate generation.

Key words: carbon dioxide, hydrate, nucleation, phase equilibria

中图分类号:

TQ 95

杨明军, 宋维, 张磊, 凌铮, 陈兵兵, 宋永臣. CO₂-海水水合物生成强化方法研究[J]. 化工学报, 2024, 75(8): 2939-2948.

Mingjun YANG, Wei SONG, Lei ZHANG, Zheng LING, Bingbing CHEN, Yongchen SONG. Research on the enhanced method of CO₂-seawater hydrate generation[J]. CIESC Journal, 2024, 75(8): 2939-2948.

图/表 12

图1 实验装置图

Fig.1 Diagram of experimental setup

表1 常规生成组实验信息汇总

Table 1 Summary of experimental information for routine generation group

组别	是否生成	实验过程	恒温时间/min
1	否	4.02 MPa恒压、4℃恒温诱导	600
2	否	4.06 MPa恒压、1℃恒温诱导	500

图2 不同恒定诱导温度下的温度及热流曲线

Fig.2 Temperature and heat flow curves at different constant induction temperatures

表2 高过冷度作用组实验信息汇总

Table 2 Summary of experimental information on the high subcooling action group

组别	实验过程	生成时刻/min	生成温度/℃	过冷度/℃	水转化率/%	生成速率/(10^-6 mol/min)
3	4.09 MPa恒压、-15℃恒温诱导	283.4	-9.84	18.95	7.95	7.54
4	4.06 MPa恒压、-15℃恒温诱导	273.4	-8.85	17.96	9.35	3.77
5	4.05 MPa恒压、-15℃恒温诱导	274.1	-8.92	18.03	5.38	3.68

图3 高过冷度下的温度及热流曲线

Fig.3 Temperature and heat flow profiles at high degree of subcooling

图4 高过冷度作用下水合物生成特性

Fig.4 Characterisation of hydrate generation under high subcooling conditions

图5 CO2水合物在不同体系下的相平衡曲线

Fig.5 Phase equilibrium conditions for CO2 hydrate in different systems

表3 添加剂作用组实验信息汇总

Table 3 Summary of experimental information on additive action group

组别	促进剂浓度/%（质量分数）	生成时刻/min	生成温度/℃	水转化率/%	生成速率/(10^-6 mol/min)
6	2	296.18	-11.11	9.074	5.486
7	3	372.08	-14.72	8.079	11.827
8	4	285.37	-10.04	9.359	4.933

图6 不同浓度添加剂作用下的热流曲线及水合物生成特性参数

Fig.6 Heat flow curves and parameters of hydrate generation characteristics in the presence of different concentrations of additives

表4 变温速率组实验信息汇总

Table 4 Summary of experimental information for the variable temperature rate group

组别	变温速率/(K/min)	生成时刻/min	生成温度/℃	水转化率/%	生成速率/(10^-6 mol/min)
9	0.1	273.38	-8.85	9.351	3.768
10	0.2	165.33	-11.30	9.313	5.791
11	0.3	134.55	-14.73	9.647	7.146

图7 不同变温速率下的热流曲线及水合物生成特性参数

Fig.7 Heat flow curves and hydrate generation characteristic parameters at different temperature change rates

图8 三种影响因素下的水合物生成特性参数对比

Fig.8 Comparison of hydrate generation characteristic parameters under three influence factors

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CO₂-海水水合物生成强化方法研究

Research on the enhanced method of CO₂-seawater hydrate generation

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