Gas Production and Storage Using Hydrates Through the Replacement of Multicomponent Gases: A Critical Review
Abstract
:1. Introduction
1.1. Natural Gas Hydrate
1.2. Natural Gas Hydrate Extraction
1.2.1. Traditional Natural Gas Hydrate Extraction Methods
1.2.2. CO2 and CH4 Displacement Method
2. Structure and Properties of Hydrates
2.1. Crystal Structure of Hydrates
2.2. Thermodynamic Study
2.2.1. Thermodynamic Characteristics of Replacement Reactions
2.2.2. Stability of Hydrates and Gas Distribution Behavior
2.3. Kinetic Studies
2.3.1. Gas Diffusion and Exchange Rate
2.3.2. Reaction Mechanisms in the Displacement Process
2.3.3. Kinetic Characteristics of the Displacement Reaction
3. Combined Enhancement of Displacement Method and Traditional Methods
3.1. Combined Extraction of Displacement Method and Depressurization Method
3.2. Combined Extraction of Displacement and Thermal Stimulation Methods
3.3. Combined Extraction of Displacement and Chemical Inhibitor Methods
4. Multicomponent Gas Displacement Process
4.1. CO2-H2 Mixture Replacement to Improve CH4 Recovery Rate
4.2. CO2 and N2 Mixture Displacement to Improve CH4 Recovery Rate
4.3. The Displacement of CH4 Recovery Is Improved by Using CO2 Mixed with N2 and H2
5. Conclusions
Author Contributions
Funding
Conflicts of Interest
References
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Method | Advantages | Disadvantages |
---|---|---|
Depressurization Method | Technologically mature; simple to operate; no chemical additives; no negative impact on the environment | Requires prolonged depressurization, leading to increased extraction costs; relatively low extraction rate; rapid pressure changes may cause well leakage or collapse |
Thermal Stimulation Method | Increase the decomposition rate of hydrates; applicable to low-temperature areas | High energy consumption; damages wellbore and reservoir; using thermal fluids may require treatment of the injected water; otherwise, it could introduce environmental contaminants |
Chemical Inhibitor Injection Method | Low energy demand; adaptable to various reservoir conditions | High chemical costs; requires precise control of injection volume |
Method | Advantages | Disadvantages |
---|---|---|
Thermal fluid injection method | Increase recovery rate; widely applicable; high heat transfer efficiency | High energy consumption; significant heat loss; complex equipment maintenance |
Electric heating method | High energy efficiency; precise control; minimal equipment requirements | High equipment cost; high power consumption; poor adaptability |
Geothermal heating method | Low energy consumption; minimal heat loss; wide applicability | Slow heating effect; limited improvement in yield; less effective than high-temperature heating |
Inhibitor | Type | Advantages | Disadvantages |
---|---|---|---|
Thermodynamic Hydrate Inhibitors | Alcohols and electrolytes | Effectively reduce the formation temperature of hydrates, thereby preventing their formation | It usually requires a high dosage, leading to increased costs and environmental impact |
Kinetic Hydrate Inhibitors | Polymeric compound | Effectively inhibit hydrate formation at a lower dosage, suitable for long-term flow assurance | In some cases, it may not be stable enough, and its effectiveness varies with different gas compositions |
Anti-agglomerants | Compounds with various chemical structures | Prevent the agglomeration of hydrate particles, thereby reducing the risk of blockage | It needs to be used in combination with other inhibitors to enhance effectiveness |
Dual-function Hydrate Inhibitors | Amino acids, ionic liquids, and nanoparticles | Combining the advantages of thermodynamic and kinetic inhibition provides a more comprehensive inhibitory effect | Relatively novel, and it requires further research to determine its long-term effects and cost-effectiveness |
Extraction Method Combination | Advantages | Disadvantages | Suitable Geological Conditions | Key Factors Affecting Extraction |
---|---|---|---|---|
Displacement Method Combined with Pressure Reduction Method | Increase extraction rate; sustainable gas release; reduce the risk of hydrate re-crystallization | High cost of gas injection; extraction efficiency limited by reservoir characteristics | Higher bottom pressure, better permeability, and porosity | Reservoir temperature and pressure; gas injection rate and gas selection |
Displacement Method Combined with Thermal Stimulation Method | Thermal energy promotes hydrate dissociation, enhancing displacement effectiveness | Thermal stimulation method may cause potential damage to the reservoir; high energy consumption and relatively high cost | The hydrate layer at a lower temperature (0 °C to 10 °C) is relatively thick and evenly distributed | Reservoir temperature and thermal response characteristics; heat injection methods and temperature control; thermal stability and structure of the reservoir |
Displacement Method Combined with Chemical Inhibitor Method | Improve the long-term stability of natural gas production; prevent hydrate recrystallization | Inhibitors may increase environmental risks; chemical inhibitors are expensive and could negatively impact extraction costs | Mid- to high-saturation hydrate reservoirs under low-temperature and high-pressure conditions | Selection and injection concentration of chemical inhibitors; cost and environmental friendliness of inhibitors; synergistic effect of inhibitors and displacement gases |
Method | Experimental Conditions | Advantages | CH4 Recovery Rate | Literature Source |
---|---|---|---|---|
Combined Pressure Reduction and Substitution Method | Experiments conducted using a customized high-pressure flow-through apparatus at different methane hydrate dissociation levels (0%, 20%, 40%, 60%, 80%, 100%) | The mechanical properties of methane hydrate-bearing sediments were considered to provide a basis for economically safe extraction; experimental studies were conducted to investigate the effects of various factors on mechanical properties and methane recovery rate | 35.4–63.3% | Lee et al. [57] |
Pressure Reduction-Assisted CO2 Substitution Method | Design of a one-dimensional experimental setup to simulate the interface between horizontal wells, investigating the impact of different pressures (inlet pressure, outlet pressure) on CO2 substitution behavior. The experimental temperature is 275 K, and the methane hydrate saturation is 32% | By combining the advantages of CO2 substitution and pressure reduction, production efficiency is improved, and risks are reduced; the impact of pressure parameters on natural gas extraction was studied, providing theoretical support for further research and application | 27.2–46.6% | Chen et al. [58] |
Pressure Reduction-Assisted CO2 Substitution Method | Study of the depressurization-assisted CO2 substitution process by varying initial hydrate dissociation ratio (0%, 50%, 100%), substitution period (1, 4, 7 days), and CO2 injection flow rate | The issues of weakened geomechanical strength of methane hydrate-bearing sediments caused by pressure reduction alone and the slow production rate during substitution were addressed; methane production and CO2 sequestration efficiency were improved | Through depressurization-assisted substitution, the amount of CO2 stored in the sediment can be greater than the amount of CH4 produced, with approximately 92% of the initial methane being replaced by CO2 | Choi et al. [68] |
Combined CH4/CO2 Substitution and Thermal Stimulation Method | Experiments conducted under different methane hydrate saturations, substitution zones, and freezing point conditions | The diffusion rate of CO2 was increased through thermal stimulation, overcoming the diffusion limitation in the CO2 substitution process alone; the methane substitution percentage, CO2 storage efficiency, and energy efficiency under different conditions were analyzed and discussed | 64.63% | Zhang et al. [62] |
Combined CH4/CO2 Substitution and Thermal Stimulation Method | Experiments conducted in a large-scale hydrate vessel (LSHV) with heating rates of 20, 50, and 100 W | The effect of temperature on N2 capture was studied, and it was found that N2 is selectively captured in hydrate cages at temperatures below 12 °C | At a heating rate of 100 W, the mole number of methane during thermal stimulation is 8.5; during thermal stimulation with CO2 substitution, it is 16; and during thermal stimulation with CO2 + N2 substitution, it is 20 | Tupsakhare et al. [63] |
Combined Thermal Stimulation and CH4/CO2 Substitution Method with Nanoparticle Addition | Experiments conducted in a high-pressure stainless steel reactor under different pressures (40 bar, 45 bar) and temperatures (5.5 °C, 8 °C, 10 °C) | Without the need for vacuum extraction, this method can effectively increase methane recovery and CO2 storage efficiency; the optimal experimental conditions (45 bar and 8 °C) were determined | The recovery rate of CH4 increased from 19.8% to 51.9% | Adibi et al. [69] |
Inhibitor-Assisted Substitution Method (Using Methanol Solution) | Using an automated core flooding system to simulate and monitor fluid flow and studying the effects of different inhibitors on CH4 hydrate dissociation and CO2 substitution by varying the injected fluid | The CO2 substitution method and thermodynamic hydrate inhibitor technology were combined to replace the simple CH4 hydrate substitution process | Under the experimental conditions, the methane recovery rate exceeds 92% | Khlebnikov et al. [66] |
Bio-Surfactant-Assisted Method (Using Rhamnolipid) | Studying the effect of different concentrations of rhamnolipids on the kinetics of methane hydrate formation and comparing it with the chemical surfactant SDS | Compared to the chemical surfactant SDS, it significantly reduces the induction time and total time; improves gas consumption and increases the kinetic growth rate of the hydrate; it can enhance the substitution rate and CO2 storage capacity | Injecting rhamnolipid increased the substitution percentage by approximately 72.6% | Heydari et al. [67] |
Mixed Gas Ratio (CO2/H2) | Hydrate Medium | Temperature | Pressure | CH4 Recovery Rate | Literature Source |
---|---|---|---|---|---|
0.72/0.28 | Sandstone + brine | 275.6 K | 5.0 MPa | 28.0% | Wang et al. [28] |
0.55/0.45 | 47.0% | ||||
0.36/0.64 | 25.0% | ||||
0.18/0.82 | 70.0% | Xu et al. [75] | |||
0.4/0.6 | Pure water | 274.0 K | 4.5 MPa | 78% | |
0.601/0.399 | 274.2 K | 6.0 MPa | 32% | Sun et al. [73] | |
0.74/0.26 | Quartzite + brine | 276.0 K | 3.6 MPa | 41.4~52.4% | |
0.74/0.26 | Quartz sand + brine | 276.0 K | 3.7 MPa | 30.0~50.0% | |
0.4/0.6 | Quartz sand + brine | 276.0 K | 3.7 MPa | 40.0~75.0% | Sun et al. [73] |
0.22/0.78 | 276.0 K | 3.7 MPa | 12.0~88.0% |
Gas Mixture Ratio (CO2/N2) | Hydrate Medium | Temperature | Pressure | CH4 Recovery Rate | Literature Source |
---|---|---|---|---|---|
0.1/0.9 | Porous silica + water | 274.0 K | 11.5/14.6/18.6 MPa | 77%/80%/79% | Lee et al. [79] |
0.2/0.8 | 13.7 MPa | 80% | |||
0.6/0.4 | Pure water | 4.5 MPa | 73.4% | Xu et al. [75] | |
0.146/0.854 | Silica sand + water | 273.3 K | 4.2 MPa | 53.3% | Yang et al. [59] |
0.28/0.72 | Pure water + SDS solution | 284.3K | 9.0 MPa | 13.2% | Niu et al. [80] |
0.5/0.5 | Pure water | 273.9 K | 5.0/6.7 MPa | 8.3%/17.7% | Zhou et al. [81] |
0.75/0.25 | 274.0 K | 2.6/3.2/3.5 MPa | 9.5%/12.6%/17.9% |
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Zhu, Z.; Zhao, X.; Wang, S.; Jiang, L.; Dong, H.; Lv, P. Gas Production and Storage Using Hydrates Through the Replacement of Multicomponent Gases: A Critical Review. Energies 2025, 18, 975. https://doi.org/10.3390/en18040975
Zhu Z, Zhao X, Wang S, Jiang L, Dong H, Lv P. Gas Production and Storage Using Hydrates Through the Replacement of Multicomponent Gases: A Critical Review. Energies. 2025; 18(4):975. https://doi.org/10.3390/en18040975
Chicago/Turabian StyleZhu, Zhiyuan, Xiaoya Zhao, Sijia Wang, Lanlan Jiang, Hongsheng Dong, and Pengfei Lv. 2025. "Gas Production and Storage Using Hydrates Through the Replacement of Multicomponent Gases: A Critical Review" Energies 18, no. 4: 975. https://doi.org/10.3390/en18040975
APA StyleZhu, Z., Zhao, X., Wang, S., Jiang, L., Dong, H., & Lv, P. (2025). Gas Production and Storage Using Hydrates Through the Replacement of Multicomponent Gases: A Critical Review. Energies, 18(4), 975. https://doi.org/10.3390/en18040975