Natural gas hydrate (NGH) is considered as an alternative energy resource in the future as it is proven to contain about 2 times carbon resources of those contained in the fossil energy on Earth. Gas hydrate technology is a new technology which can be extensively used in methane production from NGH, gas separation and purification, gas transportation, sea-water desalination, pipeline safety and phase change energy storage, etc. Since the 1980s, the gas hydrate technology has become a research hotspot worldwide because of its relatively economic and environmental friendly characteristics. China is a big energy consuming country with coal as a dominant energy. With the development of the society, energy shortage and environmental pollution are becoming great obstacles to the progress of the country. Therefore, in order to ensure the sustainable development of the society, it is of great significance to develop and utilize NGH and vigorously develop the gas hydrate technology. In this paper, the research advances in hydrate-based processes in China are comprehensively reviewed from different aspects, mainly including gas separation and purification, hydrate formation inhibition, sea-water desalination and methane exploitation from NGH by CH₄-CO₂ replacement. We are trying to show the relevant research in China, and at the same time, summarize the characteristics of the research and put forward the corresponding problems in a technical way.

Insights into the mechanism of hydrate nucleation are of great significance for the development of hydrate-based technologies, hydrate relevant flow assurance, and the exploration of in situ natural gas hydrates. Compared with the thermodynamics of hydrate formation, understanding the nucleation mechanism is challenging and has drawn substantial attention in recent decades. In this paper, we attempt to give a comprehensive review of the recent progress of studies of clathrate hydrate nucleation. First, the existing hypotheses on the hydrate nucleation mechanism are introduced and discussed. Then, we summarize recent experimental studies on induction time, a key parameter evaluating the velocity of the nucleation process. Subsequently, the memory effect is particularly discussed, followed by the suggestion of several promising research perspectives.

Natural gas has been considered as the best transition fuel into the future carbon constraint world. The ever-increasing demand for natural gas has prompted expanding research and development activities worldwide for exploring methane hydrates as a future energy resource. With its vast global resource volume (~3000 trillion cubic meter CH₄) and high energy storage capacity (170 CH₄ v/v methane hydrate), recovering energy from naturally-occurring methane hydrate has attracted both academic and industry interests to demonstrate the technical feasibility and economic viability. In this review paper, we highlight the recent advances in fundamental researches, seminal discoveries and implications from ongoing drilling programs and field production tests, the impending knowledge gaps and the future perspectives of recovering energy from methane hydrates. We further emphasize the current scientific, technological and economic challenges in realizing long-term commercial gas production from methane hydrate reservoir. The continuous growth of the corresponding experimental studies in China should target these specific challenges to narrow the knowledge gaps between laboratory-scale investigations and reservoir-scale applications. Furthermore, we briefly discuss both the environmental and geomechanical issues related to exploiting methane hydrate as the future energy resource and believe that they should be of paramount importance in the future development of novel gas production technologies.

The shortage of freshwater boosts the development of seawater desalination technology. As a novel method, the hydrate based desalination technology has been put forward for decades and achieved considerable development in the past years. This review focuses on the experimental progress at the aspects of the hydrate former choice, formation promotion and ion removal efficiency and conceptive innovation of hydrate separation and energy utilization. It should be noted that gaseous hydrate former with low formation pressure and insoluble liquid hydrate former are worthy for further study. Besides, the water migration caused by propane deserves to be investigated much more deeply for the potential value of wide application. Moreover, the utilization proposal of LNG cold energy brings more possibility of commercial application. In a word, the hydrate based desalination technology is hopefully an environment friendly, low-cost and widely used desalination technology in the near future.

Significant effort including field work has been devoted to develop a natural gas extraction technology from natural gas hydrate reservoirs through the injection of carbon dioxide. Natural gas hydrate is practically methane hydrate. The hypothesis is that carbon dioxide will be stored as hydrate owing to its favorable stability conditions compared to methane hydrate. Although the dynamics of the CO₂/CH₄ exchange process are not entirely understood it is established that the exchange process is feasible. The extent is limited but even if the CH₄ recovery is optimized there is a need for a CH₄/CO₂ separation plant to enable a complete cyclic sequence of CO₂ capture, injection and CH₄ recovery. In this paper we propose an alternative paradigm to the Inject (CO₂)/Exchange with (CH₄)/Recover (CH₄) one namely Recover (CH₄) first and then Inject (CO₂) for Storage.

Gas hydrate-caused pipeline plugging is an industrial nuisance for petroleum flow assurance that calls for technological innovations. Traditional thermodynamic inhibitors such as glycols and inorganic salts suffer from high dosing, environmental unfriendliness, corrosiveness, and economical burden. The development and use of kinetic hydrate inhibitors (KHIs), mostly polymeric compounds, with their inhibiting effects on hydrate nucleation and growth are considered an effective and economically viable chemical treatment for hydrate prevention. However, the actual performance of a KHI candidate is dependent on various factors including its chemical structure, molecular weight, spatial configuration, effective concentration, pressure and temperature, evaluation methods, use of other additives, etc. This review provides a short but systematic overview of the fundamentals of natural gas hydrates, the prevailing categories of polymeric kinetic hydrate inhibitors with proposed inhibition mechanisms, and the various synergists studied for boosting the KHI performance. Further research endeavors are in need to unveil the KHI working modes under different conditions. The conjunctive use of KHIs and synergists may facilitate the commercial application of effective KHIs to tackle the hydrate plugging problem in the oil and gas flow assurance practices.

Natural gas hydrate (NGH) is a highly efficient and clean energy, with huge reserves and widespread distribution in permafrost and marine areas. Researches all over the world are committed to developing an effective exploring technology for NGH reservoirs. In this paper, four conventional in-situ hydrate production methods, such as depressurization, thermal stimulation, inhibitor injection and CO₂ replacement, are briefly introduced. Due to the limitations of each method, there has been no significantly breakthrough in hydrate exploring technology. Inspired by the development of unconventional oil and gas fields, researchers have put forward some new hydrate production methods. We summarize the enhanced hydrate exploiting methods, such as CO₂/N₂-CH₄ replacement, CO₂/H₂-CH₄ replacement, hydraulic fracturing treatment, and solid exploration; and potential hydrate mining techniques, such as self-generating heat fluid injection, geothermal stimulation, the well pattern optimization of hydrate exploring. The importance of reservoir stimulation technology for hydrate exploitation is emphasized, and it is believed that hydrate reservoir modification technology is a key to open hydrate resources exploitation, and the major challenges in the process of hydrate exploitation are pointed out. The combination of multiple hydrate exploring technologies and their complementary advantages will be the development trend in the future so as to promote the process of hydrate industrialization.

In the current work, molecular dynamics simulation is employed to understand the intrinsic growth of carbon dioxide and methane hydrate starting from a seed crystal of methane and carbon dioxide respectively. This comparison was carried out because it has relevance to the recovery of methane gas from natural gas hydrate reservoirs by simultaneously sequestering a greenhouse gas like CO₂. The seed crystal of carbon dioxide and methane hydrate was allowed to grow from a super-saturated mixture of carbon dioxide or methane molecules in water respectively. Two different concentrations (1:6 and 1:8.5) of CO₂/CH₄ molecules per water molecule were chosen based on gas-water composition in hydrate phase. The molecular level growth as a function of time was investigated by all atomistic molecular dynamics simulation under suitable temperature and pressure range which was well above the hydrate stability zone to ensure significantly faster growth kinetics. The concentration of CO₂ molecules in water played a significant role in growth kinetics, and it was observed that maximizing the CO₂ concentration in the aqueous phase may not result in faster growth of CO₂ hydrate. On the contrary, methane hydrate growth was independent of methane molecule concentration in the aqueous phase. We have validated our results by performing experimental work on carbon dioxide hydrate where it was seen that under conditions appropriate for liquid CO₂, the growth for carbon dioxide hydrate was very slow in the beginning.

To provide an evidence of natural gas hydrate occurrence state, a series of experiments on multiple growth and dissociation of 90.0% methane/10.0% propane hydrates at 1.3 MPa and 270.15 K were carried out in two sediments for morphology observation via a visible jacketed-reactor. The gas hydrate crystals were observed to form and grow on the surface of sediments at the initial growth. During the thermal decomposition, gas and liquid products had an unceasingly impact on the sediments, then gas/liquid-solid migration occurred, and a large number of cavitation appeared. In the later growth and dissociation experiments, the gas hydrate particles were in suspension or supporting states in the interstitial pore space between the sediment particles, indicating that the gas hydrate displayed a pore-filling characteristics. Through analyzing the distribution of gas hydrates and bubbles, it was found that the amount of gas hydrates distributed in the sediments was improved with multiple growth-dissociation cycle proceedings. Gas migration enhanced the sediment movement, which led to the appearance of the increasing quantity of gas bubbles in the sediments during cycles. Salts affected the growth of the gas hydrates and the migration of sediment grains, which also restricted the accumulation of gas bubbles in the sediments. According to the Raman analysis, the results showed that sII hydrates were formed for CH₄ and C₃H₈ gas mixtures in different sediments and solutions with hydration number of 5.84-6.53. The Salt restricted the access of gas into the hydrate cages.

Methane hydrate is considered as a potential energy source in the future due to its abundant reserves and high energy density. To investigate the influence of initial hydrate saturation, production pressure, and the temperature of thermal stimulation on gas production rate and cumulative gas production percentage, we conducted the methane hydrate dissociation experiments using depressurization, thermal stimulation and a combination of two methods in this study. It is found that when the gas production pressures are the same, the higher the hydrate initial saturation, the greater change in hydrate reservoir temperature. Therefore, it is easier to appear the phenomenon of icing and hydrate reformation when the hydrate saturation is higher. For example, the reservoir temperature dropped to below zero in depressurization process when the hydrate saturation was about 37%. However, the same phenomenon didn't appear as the saturation was about 12%. This may be due to more free gas in the reservoir with hydrate saturated of 37%. We also find that the temperature variation of reservoir can be reduced effectively by combination of depressurization and thermal stimulation method. And the average gas production rate is highest with combined method in the experiments. When the pressure of gas production is 2 MPa, compared with depressurization, the average of gas production can increase 54% when the combined method is used. The efficiency of gas production is very low when thermal stimulation was used alone. When the temperature of thermal stimulation is 11℃, the average rate of gas production in the experiment of thermal stimulation is less than 1/3 of that in the experiment of the combined method.

Gas hydrate is regarded as a promising energy owing to the large carbon reserve and high energy density. However, due to the particularity of the formation and the complexity of exploitation process, the commercial exploitation of gas hydrate has not been realized. This paper reviews the physical properties of gas hydratebearing sediments and focuses on the geomechanical response during the exploitation. The exploitation of gas hydrate is a strong thermal-hydrological-mechanical-chemical (THMC) coupling process:decomposition of hydrate into water and gas produces multi-physical processes including heat transfer, multi-fluid flow and deformation in the reservoir. These physical processes lead to a potential of geomechanical issues during the production process. Frequent occurrence of sand production is the major limitation of the commercial exploitation of gas hydrate. The potential landslide and subsidence will lead to the cessation of the production and even serious accidents. Preliminary researches have been conducted to investigate the geomechanical properties of gas hydrate-bearing sediments and to assess the wellbore integrity during the exploitation. The physical properties of hydrate have been fully studied, and some models have been established to describe the physical processes during the exploitation of gas hydrate. But the reproduction of actual conditions of hydrate reservoir in the laboratory is still a huge challenge, which will inevitably lead to a bias of experiment. In addition, because of the effect of microscopic mechanisms in porous media, the coupling mechanism of the existing models should be further investigated. Great efforts, however, are still required for a comprehensive understanding of this strong coupling process that is extremely different from the geomechanics involved in the conventional reservoirs.

Natural gas hydrates easily form in pipelines, causing potential safety issues during oil and gas production and transportation. Injecting gas hydrate inhibitors is one of the most effective methods for preventing gas hydrate formation or aggregation. However, some thermodynamic hydrate inhibitors are toxic and harmful to the environment, whereas degradation of kinetic inhibitors is difficult. Therefore, environmentally friendly and easily biodegradable novel green inhibitors have been proposed and investigated. This paper provides a short but systematic review of the inhibitory performance of amino acids, antifreeze proteins, and ionic liquids. For different hydrate formation systems, the influences of the inhibitor type, structure, and concentration on the inhibitory effects are summarized. The mechanism of green inhibitors as kinetic inhibitors is also discussed. The

During the development and application of natural gas, hydrate plugging the pipelines is a very important issue to solve. Currently, adding thermodynamic hydrate inhibitors (THIs) and kinetic hydrate inhibitors (KHIs) in gas-dominated pipelines is a main way to prevent hydrate plugging of flow lines. This paper mainly reviews the efforts to develop THIs and KHIs in the past 20 years, compare the role of various THIs, such as methanol, ethylene glycol and electrolyte, and give the tips in using. The direction of KHIs is toward high efficiency, low toxicity, low pollution and low cost. More than a hundred inhibitors, including polymers, natural products and ionic liquids, have been synthesized in the past decade. Some of them have better performance than the current commercial KHIs. However, there are still few problems, such as the complex synthesis process, high cost and low solubility, impeding the commercialization of these inhibitors. The review also summarized some application of KHIs in China. Research of KHIs in China began late. There are no KHIs used in gas pipelines. Only a few field tests have been carried out. In the end of this paper, the field test of self-developed KHIs by China is summarized, and the guidance is given according to the application results.

Natural gas hydrate (NGH) has been widely considered as an alternative form of energy with huge potential, due to its tremendous reserves, cleanness and high energy density. Several countries involving Japan, Canada, India and China have launched national projects on the exploration and exploitation of gas hydrate resources. At the beginning of this century, an early trial production of hydrate resources was carried out in Mallik permafrost region, Canada. Japan has conducted the first field test from marine hydrates in 2013, followed by another trial in 2017. China also made its first trial production from marine hydrate sediments in 2017. Yet the low production efficiency, ice/hydrate regeneration, and sand problems are still commonly encountered; the worldwide progress is far before commercialization. Up to now, many gas production techniques have been proposed, and a few of them have been adopted in the field production tests. Nevertheless, hardly any method appears really promising; each of them shows limitations at certain conditions. Therefore, further efforts should be made on the economic efficiency as well as sustainability and environmental impacts. In this paper, the investigations on NGH exploitation techniques are comprehensively reviewed, involving depressurization, thermal stimulation, chemical inhibitor injection, CO₂-CH₄ exchange, their combinations, and some novel techniques. The behavior of each method and its further potential in the field test are discussed. The advantages and limitations of laboratory studies are also analyzed. The work could give some guidance in the future formulation of exploitation scheme and evaluation of gas production behavior from hydrate reservoirs.

Gas hydrate reserves are potential source of clean energy having low molecular weight hydrocarbons trapped in water cages. In this work, we report how organic compounds of different chain lengths and hydrophilicities when used in small concentration may modify hydrate growth and either act as hydrate inhibitors or promoters. Hydrate promoters foster the hydrate growth kinetics and are used in novel applications such as methane storage as solidified natural gas, desalination of sea water and gas separation. On the other hand, gas hydrate inhibitors are used in oil and gas pipelines to alter the rate at which gas hydrate nucleates and grows. Inhibitors such as methanol and ethanol which form strong hydrogen bond with water have been traditionally used as hydrate inhibitors. However, due to relatively high volatility a significant portion of these inhibitors ends up in gas stream and brings further complexity to the safe transportation of natural gas. In this study, organic additives such as oxalic acid, succinic acid and L-aspartic acid (all three) having—COOH group(s) with aspartic acid having an additional—NH₂ group, are investigated for gas hydrate promotion/inhibition behavior. These compounds are polar in nature and thus have significant solubility in liquid water; the presence of weak acidic and water loving (carboxylic/amine groups) moieties makes these organic acids an excellent candidate for further study. This study would pave ways to identify a novel(read better) promoter/inhibitor for gas hydrate formation. Suitable thermodynamic conditions were generated in a stirred tank reactor coupled with cooling system; comparison of gas hydrate formation kinetics with and without additives were carried out to identify the effect of these acids on the formation and growth of hydrates. The possible mechanisms by which these additives inhibit or promote the hydrate growth are also discussed.

To obtain the fundamental data of CO₂/N₂ gas mixture hydrate formation kinetics and CO₂ separation and sequestration mechanisms, the gas hydrate formation process by a binary CO₂/N₂ gas mixture (50:50) in fine sediments (150-250 μm) was investigated in a semibatch vessel at variable temperatures(273, 275, and 277 K)and pressures (5.8-7.8 MPa). During the gas hydrate reaction process, the changes in the gaseous phase composition were determined by gas chromatography. The results indicate that the gas hydrate formation process of the binary CO₂/N₂ gas mixture in fine sediments can be reduced to two stages. Firstly, the dissolved gas containing a large amount of CO₂ formed gas hydrates, and then gaseous N₂ participated in the gas hydrate formation. In the second stage, all the dissolved gas was consumed. Thus, both gaseous CO₂ and N₂ diffused into sediment. The first stage in different experiments lasted for 5-15 h, and >60% of the gas was consumed in this period. The gas consumption rate was greater in the first stage than in the second stage. After the completion of gas hydrate formation, the CO₂ content in the gas hydrate was more than that in the gas phase. This indicates that CO₂ formed hydrate easily than N₂ in the binary mixture. Higher operating pressures and lower temperatures increased the gas consumption rate of the binary gas mixture in gas hydrate formation.

Gas hydrates have drawn global attentions in the past decades as potential energy resources. It should be noted that there are a variety of possible applications of hydrate-based technologies, including natural gas storage, gas transportation, separation of gas mixture, and seawater desalination. These applications have been critically challenged by insufficient understanding of hydrate formation kinetics. In this work, the literatures on growth kinetic behaviors of hydrate formation from water-hydrocarbon were systematically reviewed. The hydrate crystal growth, hydrate film growth and macroscopic hydrate formation in water system were reviewed, respectively. Firstly, the hydrate crystal growth was analyzed with respect to different positions, such as gas/liquid interface, liquid-liquid interface and gas-liquid-liquid system. Secondly, experimental and modeling studies on the growth of hydrate film at the interfaces between guest phase and water phase were categorized into two groups of lateral growth and thickening growth considering the differences in growth rates. Thirdly, we summarized the promoters and inhibitors reported (biological or chemical, liquid or solid and hydrophobic or hydrophilic) and analyzed the mechanisms affecting hydrate formation in bulk water system. Knowledge gaps and suggestions for further studies on hydrate formation kinetic behaviors are presented.

Molecular-dynamics (MD) simulations have been performed for the growth of a spherical methane-hydrate nano-crystallite, surrounded by a supersaturated water-methane liquid phase, using both a hybrid and globalsystem thermostatting approach. It was found that hybrid thermostatting led to more sluggish growth and the establishment of a radial temperature profile about the spherical hydrate crystallite, in which the growing crystal phase is at a higher temperature than the surrounding liquid phase in the interfacial region, owing to latent-heat dissipation. In addition, Onsager's-hypothesis fluctuation-dissipation analysis of fluctuations in the number of crystal-state water molecules at the interface shows slower growth.

Study on the microscopic structure of clathrate hydrate has made significant progress in the past decades. This review aims to summarize the state of the art of the experimental characterization of guest molecular occupancy in clathrate hydrate cages, which is an important area of the microscopic structures. The characterizing method and features of different guest molecular, such as hydrocarbon, carbon dioxide, hydrogen and inhibitor/promoter, in different hydrate cages have been extensively reviewed. A comprehensive use of advanced technologies such as X-ray diffraction, Raman spectroscopy and nuclear magnetic resonance may provide better understanding on the compositions and microscopic mechanisms of clathrate hydrate.

The decomposition behaviors of methane hydrate below the ice melting point in porous media with different particle size and different pore size were studied. The silica gels with the particle size of 105-150 μm, 150-200 μm and 300-450 μm, and the mean pore diameters of 12.95 nm, 17.96 nm and 33.20 nm were used in the experiments. Methane recovery and temperature change curves were determined for each experiment. The hydrate decomposition process in the experiments can be divided into the depressurization period and the isobaric period. The temperature in the system decreases quickly in the depressurization process with the hydrate decomposition and reaches the lowest point in the isobaric period. The hydrate decomposition in porous media below ice-melting point is very fast and no self-perseveration effect is observed. The hydrate decomposition is influenced both by the driving force and the initial hydrate saturation. In the experiments with the high hydrate saturation, the hydrate decomposition will stop when the pressure reaches the equilibrium dissociation pressure. The stable pressure in the experiment with high hydrate saturation exceeds the equilibrium dissociation pressure of bulk hydrate and increases with the decrease of the pore size.

China has entered the area of new normal economy which requires the harmonious development of energy consumption, environmental protection and economic development. Natural gas hydrate is a potential clean energy with tremendous reserve in China. The successful field test of marine hydrate exploitation in South China Sea created a new record of the longest continuous gas production from natural gas hydrate. However, the corresponding fundamental research is still urgently needed in order to narrow the gap between field test and commercial production. This paper reviewed the latest advances of experimental study on gas production from hydrate reservoir in China. The experimental apparatus for investigating the performance of hydrate dissociation in China has developed from one dimensional to two dimensional and three dimensional. In addition, well configuration developed from one tube to complicated multi-well networks to satisfy the demand of different production models. Besides, diverse testing methods have been established. The reviewed papers preliminary discussed the mechanical properties and the sediment deformation situation during the process of hydrate dissociation. However, most reported articles only consider the physical factor, the coupled mechanism of physical and chemical factor for the mechanical properties of the sediment and the sand production problem should be studied further.