Technology readiness level of gas hydrate technologies

Gas or clathrate hydrates are non-stoichiometric crystalline materials known primarily for the operational and safety problems they pose during hydrocarbon processing as well as a potential source of unconventional natural gas. Gas hydrates also have a variety of other applications, mostly representing opportunities for technology development such as gas separations and seawater desalination. This dual nature of gas hydrates is best represented by the two faces of a Janus particle. Although the research on the various gas hydrate-based technologies has been reviewed, the focus has been on the phase equilibrium and kinetic data needed for process design. On the other hand, the status of the technologies in terms of their commercialization has not been methodically assessed. In this work, we employ the nine-level technology readiness level (TRL) tool to classify the various technologies that are based on gas hydrate crystallization. A brief review of the current status of the technologies is presented first, followed by the status of each one on the TRL scale.     

Phase behavior and structure transition of the mixed methane and nitrogen hydrates

Pure methane and nitrogen form structure I and II hydrate, respectively, and therefore the structure type of mixed gas hydrate was found to largely depend on their relative gas composition. In addition to the structural difference of size and shape, each hydrate structure shows different capacity to store the guest molecules. In this study, we investigated phase and structural behaviors according to the composition of methane+nitrogen gas mixture. Three-phase (H-Lw-V) equilibria of solid hydrate, water-rich liquid and vapor phase containing 25.24 mol%, 28.51 mol%, 31.23 mol% and 40.39 mol% of methane were determined at various temperatures (in the range from 273.30 K to 285.05 K) and pressures (from 8.325 MPa to 20.700 MPa). 13C solid-state NMR spectroscopy and powder XRD method were performed to identify the formed structure of hydrate samples. The experimental results showed that gas hydrate of the methane+nitrogen mixture changes its structure from sI to sII between 25.24 mol% and 28.51 mol% of methane concentration. These results of phase behavior and structure identification for the mixed gas hydrates are expected to be very helpful in evaluating the feasibility of exploitation of methane gas from natural gas hydrate and the separation process using gas hydrate as a storage-media     

天然气水合物生成与流动特性研究进展

随着石油天然气工业不断向深海、极地等极端开采环境发展,天然气水合物已经成为油气开采和输送安全的主要威胁之一。在水合物生成和分解机理、浆液流变特性以及流动压降特性三个方面分别综述了目前的相关研究进展,同时对天然气水合物今后的研究方向提出了几条建议。     

Compositional and structural identification of natural gas hydrates collected at site 1249 on ocean drilling program leg 204

In contrast to the structural studies of laboratory-grown gas hydrate, this study has been performed on naturally grown clathrate hydrates from the sea floor. The PXRD pattern of natural gas hydrate shows that the sample had a structure I hydrate. The¹³C NMR spectrum was obtained for the natural gas hydrate sample in order to identify the cage occupancy of guest molecules and determine the hydration number. The NMR spectrum reveal that the natural gas hydrates used in this study contain only methane with no noticeable amount of other hydrocarbons. The existence of two peaks at different chemical shifts indicates that methane molecules are encapsulated in both large and small cages. In addition, Raman spectroscopic analysis is also carried out to identify natural hydrates and compared with the NMR results. Investigating the composition and structure of natural gas hydrates is essential for applying natural gas hydrates as a novel energy source.     

CO2 sequestration from coal fired power plants

The paper takes into consideration a new approach for CO₂ capture and transport, based on the formation of solid CO₂ hydrates.Carbon dioxide sequestration from power plants can take advantage of the properties of gas hydrates. The formation and decomposition of hydrates from various N₂-CO₂ mixtures has been studied experimentally in a 2 l reactor, to determine the CO₂ separation in terms of hydrate composition and residual CO₂ content in the reacted gas.Carbon dioxide acts as a co-former for the production of hydrates containing nitrogen, besides CO₂. The mixed hydrates that are obtained are less stable than simple CO₂ hydrates. When CO₂ content in the flue gas is higher than 30% by volume, the hydrates formed at 5 MPa are sufficiently concentrated (about 70% CO₂) and carbon dioxide reduction in the reacted gas is acceptable.The application of a process based on hydrate formation could be especially interesting (for CO₂ capture and transport) when connected to an oxy-coal combustion process; in this case the CO₂ content in the flue gas is very high and the hydrate formation is greatly facilitated.     

Evidence for pore-filling gas hydrates in the sediments through morphology observation

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.     

多孔介质中天然气水合物相平衡条件研究进展

天然气水合物主要赋存于各种沉积物孔隙之中,只有6%左右以块状纯水合物的形式存在。现在对于天然气水合物相平衡条件的研究主要集中在对多孔介质各因素的考察。就目前研究成果来看,理论预测自然条件中水合物稳定条件的准确性仍然较差,其主要原因：水合物稳定存在的天然条件影响因素远比实验室中（大多预测模型基于实验室建立）的影响因素复杂得多;实际中的介质微孔孔径并不恒定,呈分布状态,且分布比较复杂;自然条件下的多孔介质的成分、结构都非常复杂。     

Proposing ab initio assisted lattice distortion theory for phase equilibrium: Pure and mixed refrigerant gas hydrates

With promising applications in cold storage and seawater desalination, various refrigerant gas hydrates are experimentally studied for their phase equilibrium behavior; however, the theoretical modeling to predict their formation conditions is under development. Although a high degree of lattice distortion is expected in these gas hydrates due to highly polar and nonspherical molecules of refrigerants, this issue is not addressed in the van der Waals–Platteeuw theory. With this research gap, we formulate a lattice distortion theory for both pure and mixed refrigerant hydrates. For the first time, ab initio methodology comprising the spin-component scaled MP2 method with Dunning's basis set is implemented for estimating cavity potential of refrigerant hydrates. The extent of lattice distortion is documented in terms of reference chemical potential and enthalpy differences, which are obtained by regressing the Holder's equation with the experimental data of refrigerant hydrate formation. A critical observation is made that the reference properties linearly vary with the “Boltzmann weighted energy-well depth” of the guest. Analyzing the accuracy of the model using average absolute relative deviation between experimental and predicted pressure of hydrate formation, the proposed lattice distortion model outperforms the existing thermodynamic models for variety of pure and mixed refrigerant hydrates.     

气体水合物生成微观机理及分析方法研究进展

水合物技术在能源和气候领域有着广阔的应用前景,有望成为应对能源挑战和气候变化的关键技术。但目前该技术存在着水合物生成速率慢、气体消耗量低的缺点,限制了水合物技术的工业化发展。从微观机理的角度,梳理和总结了关于气体水合物生成机制的理论观点,简述了驱动力和气体溶解度在水合物成核过程中的影响,介绍了表面活性剂和纳米粒子对水合物形成的影响机理以及常用的微观分析技术。分析发现,气体水合物的形成机制时至今日仍未有统一定论,对于促进剂作用机理的研究也不够充分,现有的微观分析手段难以捕捉水合物形成过程中的分子行为。这些问题限制了水合物技术向更快、更高效方面发展。探究水合物技术的相关机理,了解各类影响因素的作用原理,探索新的分析手段,将有助于突破水合物技术的瓶颈,为寻找更佳性能的促进剂、更高效地合成水合物探明道路。     

气体水合物生成微观机理及分析方法研究进展

水合物技术在能源和气候领域有着广阔的应用前景,有望成为应对能源挑战和气候变化的关键技术。但目前该技术存在着水合物生成速率慢、气体消耗量低的缺点,限制了水合物技术的工业化发展。从微观机理的角度,梳理和总结了关于气体水合物生成机制的理论观点,简述了驱动力和气体溶解度在水合物成核过程中的影响,介绍了表面活性剂和纳米粒子对水合物形成的影响机理以及常用的微观分析技术。分析发现,气体水合物的形成机制时至今日仍未有统一定论,对于促进剂作用机理的研究也不够充分,现有的微观分析手段难以捕捉水合物形成过程中的分子行为。这些问题限制了水合物技术向更快、更高效方面发展。探究水合物技术的相关机理,了解各类影响因素的作用原理,探索新的分析手段,将有助于突破水合物技术的瓶颈,为寻找更佳性能的促进剂、更高效地合成水合物探明道路。     

Gas hydrates: A cleaner source of energy and opportunity for innovative technologies

The global energy system is characterized by a gradual de-carbonization and move to cleaner burning technologies: from wood to coal to oil and to natural gas. A final destination characterized by the term“hydrogen economy” is desired. Gas hydrate found in the earth’s crust is considered a source of natural gas that is essentially 100% methane (CH₄) gas. Natural gas hydrate estimates worldwide range from 10,000 to 40,000 trillion cubic meters (TCM). Efforts are underway to exploit this resource. These methane hydrates in the earth’s crust also have the potential to be a significant factor in global climate change. Moreover, gas hydrates offer opportunities for the development of innovative technologies (separation of CO₂ from CO₂/N₂ and CO₂/H₂ mixtures, CO₂ sequestration, natural gas transportation and storage and H₂ storage). In this work we assess the progress towards exploitation of gas hydrates as a resource for methane (cleaner energy) and summarize the state of the art with respect to the role of gas hydrates in the development of innovative technologies.     

油藏流体中H型水合物生成条件的计算

1 INTRODUCTION Gas hydrates are serious problems in the petroleum and petrochemical industries since it may cause the plugging of production facilities and trans- portation pipelines during gas and oil production. It is known to all that gas hydrates have three poten- tial hydrate formation structures: structure- structure- and structure-H (SH). The two for- mer structures have been studied extensively and their phase equilibrium conditions are well characterized. For a long time, molecu…     

地面集输管线中水合物堵塞预测研究

天然气水合物一旦在地面集输管线中形成就会造成阀门堵塞、管道停输等严重事故,造成重大的经济损失。气流组成、温度、压力和含水量是影响地面集输管线中水合物形成的主要因素,此外,气井产量、管线长度、油管直径等对水合物的形成也有一定的影响。本文综合国内外有关水合物研究成果,并结合长庆气田某气藏生产过程中天然气水合物的生成条件及防治措施,对地面集输管线中天然气水合物堵塞的生成条件及预测模型进行了研究。     

冰点以下多孔介质中气体水合物的生成动力学研究进展

青藏高原冻土区储存着大量的天然气水合物资源,CO₂置换开采冻土区的天然气水合物可实现天然气水合物的安全开采和温室气体CO₂的地层封存。冰点以下多孔介质中气体水合物的生成动力学,是冻土区天然气水合物置换开采研究领域的难点和热点问题。本文全面综述了冰点以下多孔介质中气体水合物的生成动力学研究进展,讨论了不同体系冰点以下多孔介质中气体水合物的形成机理及其生成特性;详述了冰生成水合物机理及其冰粉/多孔介质体系中气体水合物的生成特性,分析了冰点以下多孔介质中气体水合物生成动力学研究尚待完善和改进的地方。最后本文指出冰点以下多孔介质中水合物的生成过程是由传热、传质等多种因素所控制,揭示不同过程的主导因素及其影响规律是今后研究的重点方向。目前对冰点以下多孔介质中水合物的生成特性及机理的认识尚未成熟,仍需深入研究。     

Metastable states during dissociation of carbon dioxide hydrates below 273 K

In this study, the dissociation of isolated carbon dioxide hydrate particles of sizes in the range 0.25–2.5 mm was investigated. It was found that below the ice melting point, the hydrates dissociated into supercooled water (metastable liquid) and gas. The formation of the liquid phase during CO₂ hydrate dissociation was visually observed, and the pressures of the hydrate dissociation into supercooled water and gas were measured in the temperature range 249–273 K. These pressures agreed well with the calculated data for the supercooled water–hydrate–gas metastable equilibrium (Istomin et al., 2006). In the P–T area on the phase diagram bounded by the ice–hydrate–gas equilibrium curve and the supercooled water–hydrate–gas metastable equilibrium curve, hydrates could exist for a long time because the metastable phase and their stability are not connected to the self-preservation effect. The growth of the metastable CO₂ hydrate film on the surface of supercooled water droplets formed during the hydrate dissociation was observed at pressure above the three-phase supercooled water–hydrate–gas metastable equilibrium pressure but still below the three-phase ice–hydrate–gas equilibrium pressure. It was found that the growth rate of the metastable CO₂ hydrate film was higher by a factor of 25 and 50 than that for methane hydrate and propane hydrate, respectively.     

Phase behavior and kinetics properties of gas hydrates in confinement and its application

Massive amounts of gas hydrates occur naturally in the pores of sediments or fractures in permafrost regions and beneath the oceans. For hydrate formation in confinement, the equilibrium condition can shift to harsher conditions, lowering the water activity and subsequently depressing the hydrate freezing temperature at a given pressure. Conversely, the nucleation and rate of hydrate formation, as well as hydrate conversion can be increased in confinement. Therefore, reliable assessment of the hydrate distribution in nature requires accurate thermodynamic and kinetic models of hydrate formation; however, these models tend to be based upon the properties of bulk hydrates. Hydrate formation and growth promotion in confinement are also potentially interesting for hydrate technological applications, such as gas separation, energy storage, and flow assurance. This paper reviews the thermodynamic and kinetic properties and their interrelations of gas hydrates in confined spaces.     

Structure and thermal expansion of natural gas clathrate hydrates

We report on the structural properties of natural gas hydrate crystals from the Sea of Okhotsk. Using powder X-ray diffraction (PXRD), it was determined that sediments from four locations contained type I gas hydrate, which encage mostly methane (96-98%) and a small amount of carbon dioxide. For all hydrates, the lattice constant was estimated to be at 113 K, which approximately equals that of pure methane hydrate. The result is in good agreement with the structure of artificially synthesized methane + carbon dioxide mixed-gas hydrates. These results suggest that the lattice constant of the natural gas hydrate does not change due to a change of CO₂ gas content. In addition, the thermal expansion of the sampled hydrate was measured for the temperature range of 83-173 K, and the resulting density of the hydrate crystal at 273 K was estimated to be . These results are essential for applying natural gas hydrates as an alternative natural fuel resources.     

水合物储气促进技术研究进展

气体水合物是一种笼形晶体化合物,单位体积的水合物可包含标准状况下160～180（v/v）的天然气,是一种潜在的固态天然气储运方法,受到广泛关注。由于天然气在水中溶解度小,天然气水合物在纯水中通常难以形成,形成的水合物中天然气含量也不高。为提高水合物储存天然气的密度,提高水合物生长速度,研究者探索了多种促进水合物形成的方法,如物理强化以及热力学与动力学促进剂等化学强化方法。本文总结了搅拌、喷雾、鼓泡等机械方法和向水合体系中添加热力学促进剂、动力学促进剂等方法对水合物形成和储气能力的影响,讨论了这些技术措施影响水合物形成与储气能力的机理。指出表面活性剂与其他促进技术的协同是改善水合物生长和储气密度的有效方法,其复合作用机理有待进一步研究。     

An investigation into the laboratory method for the evaluation of the performance of kinetic hydrate inhibitors using superheated gas hydrates

Kinetic hydrate inhibitors (KHIs) are used to prevent gas hydrate formation in gas and oilfield operations. Recently, a new KHI test method was reported in which hydrates are formed and re-melted just above the equilibrium temperature, before the fluids are re-cooled and the performance of the chemical as a KHI is determined. The method, which we have called the superheated hydrate test method, is claimed to be more reliable for KHI ranking in small equipment, giving less scattering in the hold time data due to avoiding the stochastic nature of the first hydrate formation. We have independently investigated this superheated hydrate test method in steel and sapphire autoclave tests using a gas mixture forming Structure II hydrates and a liquid hydrocarbon phase, which was necessary for satisfactory results. Our results indicate that hold times are shorter than using non-superheated hydrate test methods, but they are more reproducible with less scattering. The reduced scattering occurs in isothermal or slow ramping experiments even when the hydrates are melted at more than 10 °C above the equilibrium temperature (T_eq). However, if a rapid cooling method is used, the improved reproducibility is retained when melting hydrate at 2.4 °C above T_eq but lost when warming to 8.4 °C above T_eq. Using the ramping test method, most, but not all the KHIs tested agreed with the same performance ranking obtained using traditional non-superheated hydrate test methods. This may be related to the variation in the dissociation temperature of gas hydrates with different KHIs and different KHI inhibition mechanisms. Results also varied between different size autoclave equipments.     

Decomposition of carbon dioxide hydrate in the samples of natural coal with different degrees of metamorphism

Methane and carbon dioxide hydrates are one of the possible forms in which these gases exist in natural coal (for more detailed discussion see Refs [1,2]). In this work, the decomposition of carbon dioxide hydrate in five samples of natural coal differing from each other in metamorphism degree was investigated experimentally. Carbon dioxide hydrate dispersed in coals was synthesized from water adsorbed in these coals. During a linear temperature rise in an autoclave with the coal + hydrate sample the hydrate decomposition manifests itself as a step of increase in gas pressure, accompanied by a decrease/stabilization of the temperature of coal sample. The dependencies of the amount of hydrate formed on initial coal humidity and on gas pressure during hydrate formation were studied. It was demonstrated that each coal sample is characterized by its own humidity threshold below which hydrate formation in natural coal is impossible. With an increase in gas pressure, the amount of water transformed into hydrate increases. For the studied coal samples, the decomposition of carbon dioxide hydrates proceeds within a definite temperature and pressure range, and this range is close to the curve of phase equilibrium for bulk hydrate.