天然流体包裹体中甲烷水合物生成条件原位变温拉曼光谱研究

准确获取流体包裹体中气体水合物的生成条件一直是传统包裹体分析方法面临的一个难题。文章采用原位拉曼光谱技术分析了天然流体包裹体中甲烷水合物的生成条件。并由常温拉曼光谱分析表明,研究流体包裹体的流体组成为CH4-H2O体系。通过三种方法控制实验温度的变化,在第三种方法实验条件下获得了-170 ℃时甲烷水合物与冰的拉曼光谱,逐渐升温原位观测甲烷水合物的消失温度。原位拉曼光谱检测结果表明,研究包裹体中甲烷水合物的生成温度为7.5 ℃。结合CH4-H2O体系水合物形成条件相平衡计算,得到包裹体中甲烷水合物生成时的压力为5.587 3 MPa。研究结果表明,原位拉曼光谱技术是准确获取流体包裹体种气体水合物生成条件的一种有效方法。     

Formation and dissociation of gas hydrate inclusions during migration in water

The paper studies the process of floating a gas hydrate particle in liquid. The typical depths when gas bubble floating is accompanied by gas hydrate formation (or with zero gain of hydrate) were calculated. The low depths were identified when floating occurs with hydrate dissociation. The model assumes that the gas hydrate formation is limited by heat transfer from interface to the surrounding liquid. The model for gas hydrate dissociation assumes the rate governed by thermal conductivity of hydrate particle and by convective heat transfer to surrounding water. The temperature of the gas hydrate surface equals the phase transition temperature at the given water pressure. Comparative analysis of thermal conductivity and convective heat transfer effects on hydrate dissociation rate was performed for different initial radius of the particle.     

Underground Storage of Natural Gas in Hydrate State: Primary Injection Stage

The paper is devoted to simulation of the initial stage of natural gas hydrate underground storage: gas injection into aquifer just below permafrost rocks. It is based on the mathematical model of multiphase non-isothermal real gas and water flow in porous media. The model takes into account the transformation of gas and water into hydrate at certain temperature, which depends on gas flow pressure. The dynamics of hydrate and water saturation as well as the pressure and temperature fields in a reservoir with given porosity, permeability, and initial values of pressure, temperature and water saturation were studied. An implicit finite-difference scheme is used to approximate the original boundary-value problem. The finite-difference equations are solved using simple iteration and sweeping algorithms. Several examples of calculations corresponding to real cases are given. Calculations have revealed that the final result strongly depends on the combination of porosity and permeability of a reservoir.     

Study on Hydrate Production Behaviors by Depressurization Combined with Brine Injection in the Excess-Water Hydrate Reservoir

Depressurization combined with brine injection is a potential method for field production of natural gas hydrate, which can significantly improve production efficiency and avoid secondary formation of hydrate. In this work, the experiments of hydrate production using depressurization combined with brine injection from a simulated excess-water hydrate reservoir were performed, and the effects of NaCl concentration on hydrate decomposition, temperature change, and heat transfer in the reservoir were investigated. The experimental results indicate that there is little gas production during depressurization in a excess-water hydrate reservoir, and the gas dissociated from hydrate is trapped in pores of sediments. The high-water production reduces the final gas recovery, which is lower than 70% in the experiments. The increasing NaCl concentration only effectively promotes gas production rate in the early stage. The final cumulative gas production and average gas production rate have little difference in different experiments. The NaCl concentration of the produced water is significantly higher than that which is in contact with hydrate in the sediments because the water produced by hydrate decomposition exists on the surface of undissociated hydrate. The high concentration of NaCl in the produced water from the reactor significantly reduces the promoting effect and efficiency of NaCl solution on hydrate decomposition. The injection of NaCl solution decreases the lowest temperature in sediments during hydrate production, and increases the sensible heat and heat transfer from environment for hydrate decomposition. The changes of temperature and resistance effectively reflect the distribution of the injected NaCl solution in the hydrate reservoir.     

In-situ observation for natural gas hydrate in porous medium: Water performance and formation characteristic

Extensive efforts have been made regarding gas hydrate sample reconstruction in the laboratory for a better understanding and development of natural gas resources. Magnetic resonance imaging (MRI) is a useful method for directly observing the reconstruction of methane hydrate, yet relevant studies remain limited. In this study, a 9.4-T 400-MHz MRI instrument was employed to investigate CH₄ hydrate formation in porous media involving various initial water saturation levels and sand diameters. Pressure histories and MRI signal variations were monitored to discuss the process of CH₄ hydrate growth, and the three main formation stages of induction, rapid growth, and slow formation were determined. Furthermore, the liquid water performance in MRI micro-images was analyzed to predict the characteristics of CH₄ hydrate formation. The results indicated that CH₄ hydrate formed in a spatially and temporally random manner and that pore plugging occurred owing to the residual water encased in grown hydrate. Additionally, phase saturations, water conversion percentages, and formation rates were defined to evaluate the effect of sand diameter and initial water saturation on CH₄ hydrate formation. With the reduction in the diameter of quartz glass beads from 400 μm to 100 μm, the average hydrate formation rate increased from 0.0010 min⁻¹ to 0.0034 min⁻¹, respectively. When the initial water saturation decreased to the optimized value (0.22 in this study), the water conversion percentage and hydrate saturation increased.     

显微激光拉曼光谱原位观测甲烷水合物生成与分解的微观过程

采用显微激光拉曼光谱技术对高压透明毛细管中甲烷水合物的生成与分解的微观过程进行了原位观测,初步探讨了甲烷水合物笼型结构的变化规律.结果表明,甲烷水合物在生成过程中,甲烷分子的拉曼峰(2 917 cm-1)逐渐分裂为两个峰(2 905和2 915 cm-1),表明溶解态甲烷分子从单一的化学环境进入了两个有差异的化学环境中...     

不同驱动力下瓦斯水合物生长过程Raman光谱特征

基于煤矿瓦斯(CH₄∶C₂H₆∶N₂=67.5∶22.5∶10)水合物相平衡曲线开展四种驱动力ΔP水合动力学实验,利用可见显微Raman光谱仪获取水合物生长过程光谱图,根据水合物相中C₂H₆ C-C键伸缩振动特征峰Raman位移确定了4组实验中水合物为sⅡ结构。基于van der Waals与Platteeuw模型获取瓦斯水合物生成过程中水合物相气体组分及水合指数变化规律。研究表明： 驱动力的大小影响水合物的稳定性,随着驱动力的增加,CH₄相比C₂H₆逐渐占据更多的孔穴结构,CH₄在水合物相内比例增加,水合物稳定性越强;瓦斯中N₂,CH₄和C₂H₆进入水合物孔穴优先级可以通过分子与水合物孔穴的直径比进行确定,分析认为在sⅡ水合物结构中小孔穴CH₄优先级最高,大孔穴C₂H₆最高;基于瓦斯水合物稳定性,对水合物生长过程客体分子的物质传递规律进行描述,为瓦斯水合物的微观生长提供理论基础。     

固体核磁共振技术在气体水合物研究中的应用

气体水合物是在低温高压条件下由气体和水形成的笼型化合物,主要有I型,II型和H型3种晶体结构,而固体核磁共振（solid state NMR）是测定其水合指数、笼占有率等结构参数的重要手段. 该文综述了固体核磁共振技术的原理及其在水合物研究中的应用,着重介绍固体核磁共振在水合物结构表征、气体组分的鉴定、结构转化、以及在水合物生成/分解动力学过程监测方面的研究进展. 同时,对其实验方法及测试条件也进行了详细的探讨.     

Solution and hydrate formation behind a shock wave in liquid with nitrogen — carbon dioxide bubbles in a presence of surfactant

The processes of solution and hydrate formation behind a shock wave of moderate amplitude were studied experimentally in water with bubbles of nitrogen — carbon dioxide mixture at different initial static pressures in the medium and surfactant concentrations. It is shown that these bubbles do not affect significantly the processes of solution and hydrate formation behind a shock wave during the considered periods. The hypothesis about partial hydration of nitrogen from the gas mixture at intense formation of carbon dioxide hydrate was suggested for the conditions, when the pressure behind the wave is less than the equilibrium pressure of nitrogen hydrate formation at a given temperature. The work was financially supported by the President of RF (NSh-3417.2008.8) and Russian Foundation for Basic Research (Grant No. 06-08-00657).     

Formation,growth and ageing of clathrate hydrate crystals in a porous medium

An experimental study was performed to visually observe the driving force dependence of hydrate growth in a porous medium filled with either liquid water and dissolved CO₂ or liquid water and gaseous CO₂. The given system subcooling, ΔT _sub, i.e. the deficiency of the system temperature from the triple CO₂?hydrate?water equilibrium temperature under a given pressure, ranged from 1.7?K to 7.3?K. The fine dendrites initially formed at ΔT _sub?=?7.3?K changed quickly into particulate crystals. For ΔT _sub?=?1.7?K, faceted hydrate crystals grew and the subsequent morphological change was hardly identified for an eight-day observation period. These results indicate that the physical bonding between hydrate crystals and skeletal materials becomes stronger with decreasing driving force, suggesting that the fluid dynamic and mechanical properties of hydrate-bearing sediments vary depending on the hydrate crystal growth process.     

CH4水合物在SDS和CTAB溶液中的生成特性研究

为探究不同促进剂在甲烷水合物生成过程的微观作用机理,选取动力学促进剂十二烷基硫酸钠(SDS)和热力学促进剂十六烷基三甲基溴化铵(CTAB)作为添加剂,采用分子动力学方法研究其对甲烷水合物生成速率的影响.通过分析势能变化、均方位移、径向分布函数、分子簇生长速率,发现质量分数为0.9%SDS、1.2%SDS、1.2%CTAB、1.6%CTAB的溶液均可促进水合物生成.质量分数为1.2%的SDS溶液水合物生长速率最快,且SDS促进效果优于CTAB.通过分析甲烷分子密度分布云图,发现呈阴性的SDS分子头部基团吸附了大量甲烷分子,水分子受挤压向中间聚集;CTAB含氮的头部基团朝向均相溶液,包含在不稳定的水合物笼中,形成半笼型水合物.相比之下,CTAB溶液中水合物含气率更高.     

Methane hydrate crystal growth in a porous medium filled with methane-saturated liquid water

The nucleation, growth and ageing of methane hydrate crystals were observed visually in a porous medium filled with liquid water presaturated with methane. The pore space dimensions of the porous medium were 1.0?×?10²?µm. The pressure?temperature conditions at which hydrate formation was initiated corresponded to system subcoolings of 3.4?K, 6.7?K, 12.3?K and 14.1?K, respectively, where the system subcooling denotes the difference of the system temperature from the triple methane?hydrate?water equilibrium temperature under a given pressure. Faceted (skeletal) hydrate crystals grew and bridged the pore spaces without intervention of a liquid water layer when the subcoolings were equal or smaller than 6.7?K. The faceted crystals may form a physical bonding with the walls of the porous medium. At the higher subcoolings, the dispersive formation of dendritic crystals and subsequent morphological change into particulate crystals were observed. The bridging of the dendritic crystals is unlikely in the absence of a large amount of additional methane supply due to the dispersive spatial distribution of the dendritic crystals that have dimensions smaller than those of the pore spaces. As a result of the interpretation of the observed variation in the crystal morphology of the methane hydrate formed in liquid water, the dependence of the crystal morphology on the magnitude of the mass transfer of methane molecules in liquid water observed in the porous medium was consistent with that previously observed in a bulk methane–water system.     

静止水滴生成气体水合物的动力学研究

作为喷雾强化方式制备气体水合物的初步研究,本文通过研究静止水滴形成气体水合物过程的传热传质机理,建立气体水合物的生成动力学模型。研究结果表明强化气相与水合物颗粒之间的接触传热对提高水合物的生成速率具有十分重要意义。     

HCFC141b气体水合物快速生成实验研究

气体水合物生成机理是气体水合物研究领域的一个热点,对气体水合物技术的应用有重要意义。先前实验中作者首次发现铁丝同十二烷基苯磺酸钠水溶液的适当组合可以促使HCFC141b气体水合物快速结晶和生长。本文进一步揭示了十二烷基苯磺酸钠和不同金属丝对HCFC141b气体水合物生成过程的影响机理。作者结合国内外已有的研究成果总结得到了促使气体水合物快速结晶成核和生长的关键因素,并从传热传质角度提出了促进气体水合物快速结晶成核和生长的一些建议。     

Theoretical investigation of the possibility of using multicomponent (N2-O2-CH4-Y2O) clathrate hydrates for methane recovery from mine gas

Phase equilibria in a multicomponent ice-gas mixture-hydrate system are investigated for a mixture of nitrogen, oxygen, and methane, depending on the gas phase composition, pressure, and temperature. Equilibrium compositions of the formed hydrates are found, depending on the gas mixture composition. Calculations show that with increasing concentration ofmethane in gas phase the pressure of hydrate formation gradually decreases. It is shown that this pressure at considerable methane concentrations approximately corresponds to partial pressure of methane in the gas phase. Conditions of hydrate formation are calculated in the range of temperatures from 258 to 273 K, at pressures from 1 to 350 atm. The obtained results are in agreement with the known experimental data for hydrates of pure gases-nitrogen, oxygen, and methane.     

Numerical Investigation into the Gas Production from Hydrate Deposit under Various Thermal Stimulation Modes in a Multi-Well System in Qilian Mountain

The primary objective of this study was to investigate the energy recovery performance of the permafrost hydrate deposit in the Qilian Mountain at site DK-2 using depressurization combined with thermal injection by the approach of numerical simulation. A novel multi-well system with five horizontal wells was applied for large-scale hydrate mining. The external heat is provided by means of water injection, wellbore heating, or the combinations of them through the central horizontal well, while the fluids are extracted outside from the other four production wells under constant depressurization conditions. The injected water can carry the heat into the hydrate deposit with a faster rate by thermal convection regime, while it also raises the local pressure obviously, which results in a strong prohibition effect on hydrate decomposition in the region close to the central well. The water production rate is always controllable when using the multi-well system. No gas seepage is observed in the reservoir due to the resistance of the undissociated hydrate. Compared with hot water injection, the electric heating combined with normal temperature water flooding basically shows the same promotion effect on gas recovery. Although the hydrate regeneration is more severe in the case of pure electric heating, the external heat can be more efficiently assimilated by gas hydrate, and the efficiency of gas production is best compared with the cases involving water injection. Thus, pure wellbore heating without water injection would be more suitable for hydrate development in deposits characterized by low-permeability conditions.     

On injection of hydrate-forming gas into a gas-saturated snowy agglomerate while transition through the ice melting point

The paper considers the process of injection of hydrate-forming gas (methane) into a snowy agglomerate (ini-tially saturated with methane). The self-similar problem statement demonstrates that if the warm gas (T_e > 0 °C) is injected under a high pressure (p_e ≥ p_*, where the critical values are found from the initial temperature T₀, pressure p₀, volumetric snow saturation S_i0, and permeability of snow) into the filtration zone with phase transition, this produces four characteristic zones: the nearest zone with all snow transformed into hydrate, therefore, the aggregate filled only with gas and hydrate, the two intermediate zones where gas, snow or water and hydrate are in phase equilibrium state, and the distant zone filled only with gas and snow. The obtained analytical and numerical solutions give an analysis of the influence of key input parameters like initial state of the aggregate, gas injection rate, and its temperature, on the structure and the length of four filtration zones.     

CO2水合物生长特性的分子动力学模拟

采用分子动力学对CO2水合物生长进行模拟并分析其变化规律,探究了CO2水合物晶体生长的微观过程以及不同温度、压力条件对水合物生长特性的影响机理. CO2水合物的生长是从已有晶胞附近向外扩散并逐具有序性的过程,水分子间逐渐形成四面体氢键与CO2共同形成完整的水合物笼. 另外, CO2水合物生长需要合适的过冷度,在压力为30MPa、温度范围265K至275K,水合物笼型晶胞可正常生成,并且温度越低,生成速率越快;在高温290K和300K时,体系分子运动加剧,水合物笼直接散开. 此外,在温度为270K、不同压力条件下,发现相较温度而言,由于CO2溶解度随压力变化的不明显性,导致CO2水合物增长速度伴随压力的变化相对不敏感.     

混合制冷剂气体水合物生成及融解过程实验研究

1引言城市建筑物中，空调作为最大用电设备之一，夏季占建筑物耗电总量的一半以上，为了缓解高峰用电负荷并有效利用低谷电力，解决峰期用电紧张的矛盾，达到总体节能的目的，空调蓄冷移峰节电技术被认为是实现城市供电平衡和建筑节能的重要手段。作为实用的空调蓄冷技术，最为重要的是其蓄冷材料的相变温度与空调工况相适应，即在5～12℃发生相变，且相变潜热大，传热性能好．氟里昂气体水合物作为蓄冷材料，具有适合空调储冷的理想性质，可使水在8～12℃水合结晶，形成暖冰时释放反应热，其反应热与结冰潜热相当[1]。然而，由于一些氟里昂…