海洋CO2水合物封存基础性研究进展

doi:10.11949/0438-1157.20240554

摘要/Abstract

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

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

中图分类号:

O 643.1

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.

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

图/表 7

图1 CP + CO2 + NaCl +水体系的水合物相平衡[29]

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

图2 CO2 (20%) + N2 (80%) + NaCl[3.5%（质量分数）] +水混合物的三相平衡[30]

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

图3 CO2/CP[7%（质量分数） MgCl2]的温度-压力曲线[31]

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

图4 3%（质量分数）NaCl-0.5%（质量分数）CSOM溶液中水合物弛豫时间变化（a）和3%（质量分数） CaCl2-0.5%（质量分数）溶液中水合物弛豫时间变化（b）[54]

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]

图5 预测不同体系的CO2水合物成核速率和实验温度随时间的变化[56]

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

表1　在3.3%（质量分数）的石英砂-盐水溶液中（4 MPa， 274.15 K），在0.2%（质量分数）的L-蛋氨酸、L-异亮氨酸、L-苏氨酸和SDS下测量的CO2水合物形成动力学数据[57]

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

图6 恒定浓度为1000 mg/L时不同水溶液中水合物形成过程中的气体吸收速率[65]

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

参考文献 70

1	Amstrup S C, Deweaver E T, Douglas D C, et al. Greenhouse gas mitigation can reduce sea-ice loss and increase polar bear persistence[J]. Nature, 2010, 468(7326): 955-958.
2	Stainforth D A, Aina T, Christensen C, et al. Uncertainty in predictions of the climate response to rising levels of greenhouse gases[J]. Nature, 2005, 433(7024): 403-406.
3	Ajayi T, Gomes J S, Bera A. A review of CO₂ storage in geological formations emphasizing modeling, monitoring and capacity estimation approaches[J]. Petroleum Science, 2019, 16(5): 1028-1063.
4	Orr J C, Fabry V J, Aumont O, et al. Anthropogenic ocean acidification over the twenty-first century and its impact on calcifying organisms[J]. Nature, 2005, 437(7059): 681-686.
5	Ricke K L, Orr J C, Schneider K, et al. Risks to coral reefs from ocean carbonate chemistry changes in recent earth system model projections[J]. Environmental Research Letters, 2013, 8(3): 034003.
6	Siegel D A, DeVries T, Doney S C, et al. Assessing the sequestration time scales of some ocean-based carbon dioxide reduction strategies[J]. Environmental Research Letters, 2021, 16(10): 104003.
7	Kumar Y, Sangwai J S. A perspective on the effect of physicochemical parameters, macroscopic environment, additives, and economics to harness the large-scale hydrate-based CO₂ sequestration potential in oceans[J]. ACS Sustainable Chemistry & Engineering, 2023, 11(30): 10950-10979.
8	Zulqarnain M, Mohd Yusoff M H, Keong L K, et al. Recent development of integrating CO₂ hydrogenation into methanol with ocean thermal energy conversion (OTEC) as potential source of green energy[J]. Green Chemistry Letters and Reviews, 2023, 16(1): 2152740.
9	Sun X, Shang A R, Wu P, et al. A review of CO₂ marine geological sequestration[J]. Processes, 2023, 11(7): 2206.
10	Chong Z R, Yang S H B, Babu P, et al. Review of natural gas hydrates as an energy resource: Prospects and challenges[J]. Applied Energy, 2016, 162: 1633-1652.
11	Englezos P. Clathrate hydrates[J]. Industrial & Engineering Chemistry Research, 1993, 32(7): 1251-1274.
12	Zheng J J, Chong Z R, Qureshi M F, et al. Carbon dioxide sequestration via gas hydrates: a potential pathway toward decarbonization[J]. Energy & Fuels, 2020, 34(9): 10529-10546.
13	Nesterov A N, Reshetnikov A M. New combination of thermodynamic and kinetic promoters to enhance carbon dioxide hydrate formation under static conditions[J]. Chemical Engineering Journal, 2019, 378: 122165.
14	Qureshi M F, Khandelwal H, Usadi A, et al. CO₂ hydrate stability in oceanic sediments under brine conditions[J]. Energy, 2022, 256: 124625.
15	Park S, Koh D Y, Kang H, et al. Effect of molecular nitrogen on multiple hydrogen occupancy in clathrate hydrates[J]. The Journal of Physical Chemistry C, 2014, 118(35):20203-20208.
16	Zatsepina O Y, Buffett B A. Phase equilibrium of gas hydrate: implications for the formation of hydrate in the deep sea floor[J]. Geophysical Research Letters, 1997, 24(13): 1567-1570.
17	Duan Z H, Sun R. An improved model calculating CO₂ solubility in pure water and aqueous NaCl solutions from 273 to 533 K and from 0 to 2000 bar[J]. Chemical Geology, 2003, 193(3/4): 257-271.
18	House K Z, Schrag D P, Harvey C F, et al. Permanent carbon dioxide storage in deep-sea sediments[J]. Proceedings of the National Academy of Sciences of the United States of America, 2006, 103(33): 12291-12295.
19	Chong Z R, Koh J W, Linga P. Effect of KCl and MgCl₂ on the kinetics of methane hydrate formation and dissociation in sandy sediments[J]. Energy, 2017, 137: 518-529.
20	Jacobson L C, Hujo W, Molinero V. Amorphous precursors in the nucleation of clathrate hydrates[J]. Journal of the American Chemical Society, 2010, 132(33): 11806-11811.
21	Khurana M, Yin Z Y, Linga P. A review of clathrate hydrate nucleation[J]. ACS Sustainable Chemistry & Engineering, 2017, 5(12): 11176-11203.
22	Ke W, Svartaas T M, Chen D Y. A review of gas hydrate nucleation theories and growth models[J]. Journal of Natural Gas Science and Engineering, 2019, 61: 169-196.
23	Liang R D, Xu H J, Shen Y N, et al. Nucleation and dissociation of methane clathrate embryo at the gas-water interface[J]. Proceedings of the National Academy of Sciences of the United States of America, 2019, 116(47): 23410-23415.
24	Kiran B S, Prasad P S R. Storage of methane gas in the form of clathrates in the presence of natural bioadditives[J]. ACS Omega, 2018, 3(12): 18984-18989.
25	Fakharian H, Ganji H, Naderifar A. Desalination of high salinity produced water using natural gas hydrate[J]. Journal of the Taiwan Institute of Chemical Engineers, 2017, 72: 157-162.
26	Chong Z R, Chan A H M, Babu P, et al. Effect of NaCl on methane hydrate formation and dissociation in porous media[J]. Journal of Natural Gas Science and Engineering, 2015, 27: 178-189.
27	Tse C W, Bishnoi P R. Prediction of carbon dioxide gas hydrate formation conditions in aqueous electrolyte solutions[J]. The Canadian Journal of Chemical Engineering, 1994, 72(1): 119-124.
28	van der Waals J H, Platteeuw J C. Clathrate Solutions[M]. NYSE: John Wiley & Sons, Ltd.,2007.
29	Lee J, Kim K S, Seo Y. Thermodynamic, structural, and kinetic studies of cyclopentane + CO₂ hydrates: applications for desalination and CO₂ capture[J]. Chemical Engineering Journal, 2019, 375: 121974.
30	Mok J, Choi W, Kim S, et al. NaCl-induced enhancement of thermodynamic and kinetic CO₂ selectivity in CO₂ + N₂ hydrate formation and its significance for CO₂ sequestration[J]. Chemical Engineering Journal, 2023, 451: 138633.
31	Serikkali A, Van H N, Pham T K, et al. Phase equilibrium and dissociation enthalpies of CO₂/cyclopentane hydrates in presence of salts for water treatment and CO₂ capture: new experimental data and modeling[J]. Fluid Phase Equilibria, 2022, 556: 113410.
32	Zeng S Y, Yin Z Y, Ren J J, et al. Effect of MgCl₂ on CO₂ sequestration as hydrates in marine environment: a thermodynamic and kinetic investigation with morphology insights[J]. Energy, 2024, 286: 129616.
33	Naullage P M, Bertolazzo A A, Molinero V. How do surfactants control the agglomeration of clathrate hydrates?[J]. ACS Central Science, 2019, 5(3): 428-439.
34	Lv X F, Lu D Y, Liu Y, et al. Study on methane hydrate formation in gas-water systems with a new compound promoter[J]. RSC Advances, 2019, 9(57): 33506-33518.
35	Wang F, Liu G Q, Meng H L, et al. Improved methane hydrate formation and dissociation with nanosphere-based fixed surfactants as promoters[J]. ACS Sustainable Chemistry & Engineering, 2016, 4(4): 2107-2113.
36	Kumar A, Bhattacharjee G, Kulkarni B D, et al. Role of surfactants in promoting gas hydrate formation[J]. Industrial & Engineering Chemistry Research, 2015, 54(49): 12217-12232.
37	Sa J H, Sum A K. Promoting gas hydrate formation with ice-nucleating additives for hydrate-based applications[J]. Applied Energy, 2019, 251: 113352.
38	Zhong Y, Rogers R E. Surfactant effects on gas hydrate formation[J]. Chemical Engineering Science, 2000, 55(19): 4175-4187.
39	Heydari A, Peyvandi K. Study of biosurfactant effects on methane recovery from gas hydrate by CO₂ replacement and depressurization[J]. Fuel, 2020, 272: 117681.
40	Hayama H, Mitarai M, Mori H, et al. Surfactant effects on crystal growth dynamics and crystal morphology of methane hydrate formed at gas/liquid interface[J]. Crystal Growth & Design, 2016, 16(10): 6084-6088.
41	Dicharry C, Diaz J, Torré J P, et al. Influence of the carbon chain length of a sulfate-based surfactant on the formation of CO₂, CH₄ and CO₂-CH₄ gas hydrates[J]. Chemical Engineering Science, 2016, 152: 736-745.
42	Okutani K, Kuwabara Y, Mori Y H. Surfactant effects on hydrate formation in an unstirred gas/liquid system: an experimental study using methane and sodium alkyl sulfates[J]. Chemical Engineering Science, 2008, 63(1): 183-194.
43	Tian L Q, Wu G Z. Cyclodextrins as promoter or inhibitor for methane hydrate formation?[J]. Fuel, 2020, 264: 116828.
44	Wang F, Jia Z Z, Luo S J, et al. Effects of different anionic surfactants on methane hydrate formation[J]. Chemical Engineering Science, 2015, 137: 896-903.
45	Kwon Y A, Park J M, Jeong K E, et al. Synthesis of anionic multichain type surfactant and its effect on methane gas hydrate formation[J]. Journal of Industrial and Engineering Chemistry, 2011, 17(1): 120-124.
46	Kumar A, Sakpal T, Linga P, et al. Influence of contact medium and surfactants on carbon dioxide clathrate hydrate kinetics[J]. Fuel, 2013, 105: 664-671.
47	Molokitina N S, Nesterov A N, Podenko L S, et al. Carbon dioxide hydrate formation with SDS: further insights into mechanism of gas hydrate growth in the presence of surfactant[J]. Fuel, 2019, 235: 1400-1411.
48	Naeiji P, Varaminian F. Kinetic study of carbon dioxide hydrate formation by thermal analysis in the presence of two surfactants: sodium dodecyl sulfate (SDS) and lauryl alcohol ethoxylate (LAE)[J]. Journal of Molecular Liquids, 2018, 254: 120-129.
49	Du J W, Li H J, Wang L G. Effects of ionic surfactants on methane hydrate formation kinetics in a static system[J]. Advanced Powder Technology, 2014, 25(4): 1227-1233.
50	Darbouret M, Cournil M, Herri J M. Rheological study of TBAB hydrate slurries as secondary two-phase refrigerants[J]. International Journal of Refrigeration, 2005, 28(5): 663-671.
51	David F, Vokhmin V, Ionova G. Water characteristics depend on the ionic environment. Thermodynamics and modelisation of the aquo ions[J]. Journal of Molecular Liquids, 2001, 90(1/2/3): 45-62.
52	Dichicco M C, Laurita S, Paternoster M, et al. Serpentinite carbonation for CO₂ sequestration in the southern Apennines: preliminary study[J]. Energy Procedia, 2015, 76: 477-486.
53	Emerson W W, Chi C L. Exchangeable calcium, magnesium and sodium and the dispersion of illites in water(Ⅱ): Dispersion of illites in water[J]. Soil Research, 1977, 15(3): 255.
54	Liu Y Z, Qi H P, Liang H Y, et al. Influence mechanism of interfacial organic matter and salt system on carbon dioxide hydrate nucleation in porous media[J]. Energy, 2024, 290: 130179.
55	Farhang F, Nguyen A V, Hampton M A. Influence of sodium halides on the kinetics of CO₂ hydrate formation[J]. Energy & Fuels, 2014, 28(2): 1220-1229.
56	Rehman A N, Pendyala R, Lal B. Effect of brine on the kinetics of carbon dioxide hydrate formation and dissociation in porous media[J]. Materials Today: Proceedings, 2021, 47: 1366-1370.
57	Rehman A N, Bavoh C B, Khan M Y, et al. Amino acid-assisted effect on hydrate-based CO₂ storage in porous media with brine[J]. RSC Advances, 2024, 14(13): 9339-9350.
58	Claussen W F. A second water structure for inert gas hydrates[J]. The Journal of Chemical Physics, 1951, 19(11): 1425-1426.
59	Asadi F, Ejtemaei M, Birkett G, et al. The link between the kinetics of gas hydrate formation and surface ion distribution in the low salt concentration regime[J]. Fuel, 2019, 240: 309-316.
60	Karamoddin M, Varaminian F. Performance of hydrate inhibitors in tetrahydrofuran hydrate formation by using measurement of electrical conductivity[J]. Journal of Industrial and Engineering Chemistry, 2014, 20(5): 3815-3820.
61	Yang S H B, Babu P, Chua S F S, et al. Carbon dioxide hydrate kinetics in porous media with and without salts[J]. Applied Energy, 2016, 162: 1131-1140.
62	Li F, Chen Z J, Dong H S, et al. Promotion effect of graphite on cyclopentane hydrate based desalination[J]. Desalination, 2018, 445: 197-203.
63	Moeini H, Bonyadi M, Esmaeilzadeh F, et al. Experimental study of sodium chloride aqueous solution effect on the kinetic parameters of carbon dioxide hydrate formation in the presence/absence of magnetic field[J]. Journal of Natural Gas Science and Engineering, 2018, 50: 231-239.
64	Ling Z, Shi C R, Li F, et al. Desalination and Li⁺ enrichment via formation of cyclopentane hydrate[J]. Separation and Purification Technology, 2020, 231: 115921.
65	Maniavi Falahieh M, Bonyadi M, Lashanizadegan A. A new hybrid desalination method based on the CO₂ gas hydrate and capacitive deionization processes[J]. Desalination, 2021, 502: 114932.
66	Sun Z G, Wang R Z, Ma R S, et al. Natural gas storage in hydrates with the presence of promoters[J]. Energy Conversion and Management, 2003, 44(17): 2733-2742.
67	Riesco N, Trusler J P M. Novel optical flow cell for measurements of fluid phase behaviour[J]. Fluid Phase Equilibria, 2005, 228: 233-238.
68	Babu P, Kumar R, Linga P. Pre-combustion capture of carbon dioxide in a fixed bed reactor using the clathrate hydrate process[J]. Energy, 2013, 50: 364-373.
69	Arjang S, Manteghian M, Mohammadi A. Effect of synthesized silver nanoparticles in promoting methane hydrate formation at 4.7MPa and 5.7MPa[J]. Chemical Engineering Research and Design, 2013, 91(6): 1050-1054.
70	da Silva Lirio C F, Pessoa F L P, Uller A M C. Storage capacity of carbon dioxide hydrates in the presence of sodium dodecyl sulfate (SDS) and tetrahydrofuran (THF)[J]. Chemical Engineering Science, 2013, 96: 118-123.

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海洋CO₂水合物封存基础性研究进展

Basic research progress on marine CO₂ hydrate sequestration

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