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.     

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.     

Clathrate formation and dissociation in vapor/water/ice/hydrate systems in SBA-15, sol-gel and CPG porous media, as probed by NMR relaxation, novel protocol NMR cryoporometry, neutron scattering and ab initio quantum-mechanical molecular dynamics simulation

The Gibbs-Thomson effect modifies the pressure and temperature at which clathrates occur, hence altering the depth at which they occur in the seabed. Nuclear magnetic resonance (NMR) measurements as a function of temperature are being conducted for water/ice/hydrate systems in a range of pore geometries, including templated SBA-15 silicas, controlled pore glasses and sol-gel silicas. Rotator-phase plastic ice is shown to be present in confined geometry, and bulk tetrahydrofuran hydrate is also shown to probably have a rotator phase. A novel NMR cryoporometry protocol, which probes both melting and freezing events while avoiding the usual problem of supercooling for the freezing event, has been developed. This enables a detailed probing of the system for a given pore size and geometry and the exploration of differences between hydrate formation and dissociation processes inside pores. These process differences have an important effect on the environment, as they impact on the ability of a marine hydrate system to re-form once warmed above a critical temperature. Ab initio quantum-mechanical molecular dynamics calculations are also being employed to probe the dynamics of liquids in pores at nanometric dimensions.     

用分子动力学模拟甲烷水合物热激法分解

用分子动力学模拟方法研究甲烷水合物热激法分解，系统地研究注入340 K液态水的结构Ⅰ型甲烷水合物的分解机理.模拟显示水合物表层水分子与高温液态水分子接触获得热能，分子运动激烈，摆脱水分子间的氢键束缚，笼状结构被破坏.甲烷分子获得热能从笼中挣脱，向外体系扩散.热能通过分子碰撞从外层传递给内层水分子，水合物逐层分解.对比注入277K液态水体系模拟结果，得出热激法促进水合物分解. 关键词： 甲烷水合物 分子动力学模拟 热激法     

MRI measurements of CO2 hydrate dissociation rate in a porous medium

After obtaining experimental data of CO₂ hydrate formation and dissociation in a porous medium using magnetic resonance imaging (MRI), the purpose of this study was to analyze the different dissociation rate of CO₂ hydrate using two heating rates. Images were obtained by using a fast spin-echo sequence, and the field of view was set to 40×40×40 mm. The vessel pressure was monitored during hydrate formation and dissociation, which was used to compare with MRI mean intensity. The result indicated that the MRI could visualize hydrate formation and dissociation, and the MRI mean intensity of water was in good agreement with the vessel pressure changes. The hydrate formation and dissociation rates were also quantified using the MRI mean intensity of water. The experimental results showed that the higher heating rate caused the rapid hydrate dissociation.     

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...     

NMR研究甲烷水合物在中孔SBA-15内的生成

利用自行研制的高压釜和原位高压核磁共振研究了甲烷水合物在具有孔径均一的中孔SBA-15中的形成过程. 结果发现在静止的状态下,甲烷在中孔SBA-15内与水也能生成甲烷水合物,但其形成所需要的诱导时间比在纯水的条件下要短,SBA-15可促进甲烷水合物的形成;原位高压¹H和¹³C NMR研究表明即使甲烷过量,在一定压力下,SBA-15孔道内的水也不能完全形成甲烷水合物.     

In situ observations by magnetic resonance imaging for formation and dissociation of tetrahydrofuran hydrate in porous media

Tetrahydrofuran (THF) hydrate has long been used as a substitute for methane hydrate in laboratory studies. This article investigated the formation and dissociation characteristics of THF hydrate in porous media simulated by various-sized quartz glass beads. The formation and dissociation processes of THF hydrate are observed using magnetic resonance imaging (MRI) technology. The hydrate saturation during the formation is obtained based on the MRI data. The experimental result suggests that the third surface has an effect on hydrate formation. THF hydrate crystals lean to form on the glass beads and in their adjacent area as well as from the wall of the sample container firstly. Furthermore, as the pore size diminishes, or as the formation temperature decreases, the nucleation gets easier and the formation processes faster. However, the dissociation rate is mostly dependent on the dissociation temperature rather than on the pore size.     

用分子动力学模拟甲烷水合物热激法结合化学试剂法分解

用分子动力学模拟方法研究甲烷水合物的热激法，化学试剂法，以及热激法结合化学试剂法分解，系统研究温度为277K和340K时添加液态水(WTR)和30wt％乙二醇(EG)溶液对水合物分解的影响.模拟显示WTR与水合物表面水分子形成氢键，破坏水合物原有的氢键平衡，造成笼状结构坍塌，水合物分解.EG分子中的羟基与水合物表面水分子形成氢键，从而破坏原有的稳定结构，造成水合物笼状结构被破坏，达到促进水合物分解，释放甲烷气体的效果.比较温度为277K和340K时添加WTR和30wt％EG溶液对水合物分解效果得出EG(340K)> WTR(340K)>EG(277K)>WTR(277K)，热激法结合化学试剂法能更好促进水合物分解.     

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.     

Effect of Diameter of Granules on Dissociation of Methane Hydrate

The kinetics of dissociation of methane hydrate in air at an external pressure of 1 bar was experimentally studied. It is shown that to describe the mechanism of dissociation of gas clathrate, it is necessary to take into account not only the degree of deviation of temperature and pressure from equilibrium values, but also the diameter of granules. As the diameter decreases, the rate of decomposition of methane hydrate increases significantly. Change in the grain size affects formation of pores and dissociation. The experiment demonstrated a self-preservation mechanism for granule diameters of more than 1 mm. In the case of powder with an average diameter of less than 0.3 mm, there was no self-preservation. The rate of dissociation depends on the combined effect of diffusion, crystallization, and creep.     

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。     

水流动强化天然气水合物降压分解研究

降压法被认为是最经济可行的天然气水合物开采方法,但开采后期驱动力不足、甚至产生水合物的二次生成,因此其应用受到限制。本文将降压法与水流动结合提升水合物分解驱动力,研究不同降压模式和水流动对天然气水合物分解特性的影响。发现当降压结合水流动时,压降为水合物分解提供初始驱动力,且压降越大水合物分解驱动力越大。同时水流动能够加快传热传质过程,为水合物分解提供额外的驱动力。在快速降压结合水流动模式中,较高背压下水流动为水合物分解提供主要的驱动力;在梯度降压结合水流动模式中,降压和水流动共同为水合物提供分解驱动力,对水合物分解的促进作用更加显著。     

Application of low field NMR T2 measurements to clathrate hydrates

Low field (2 MHz) Nuclear Magnetic Resonance (NMR) proton spin–spin relaxation time (T₂) distribution measurements were employed to investigate tetrahydrofuran (THF)—deuterium oxide (D₂O) clathrate hydrate formation and dissociation processes. In particular, T₂ distributions were obtained at the point of hydrate phase transition as a function of the co-existing solid/liquid ratios. Because T₂ of the target molecules reflect the structural arrangements of the molecules surrounding them, T₂ changes of THF in D₂O during hydrate formation and dissociation should yield insights into the hydrate mechanisms on a molecular level. This work demonstrated that such T₂ measurements could easily distinguish THF in the solid hydrate phase from THF in the coexisting liquid phase. To our knowledge, this is the first time that T₂ of guest molecules in hydrate cages has been measured using this low frequency NMR T₂ distribution technique. At this low frequency, results also proved that the technique can accurately capture the percentages of THF molecules residing in the solid and liquid phases and quantify the hydrate conversion progress. Therefore, an extension of this technique can be applied to measure hydrate kinetics. It was found that T₂ of THF in the liquid phase changed as hydrate formation/dissociation progressed, implying that the presence of solid hydrate influenced the coexisting fluid structure. The rotational activation measured from the proton response of THF in the hydrate phase was 31 KJ/mole, which agreed with values reported in the literature.     

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.     

Methane combustion in hydrate systems: Water-methane and water-methane-isopropanol

Kinetics of dissociation of synthetic and natural methane gas hydrates, and also double isopropanol-methane hydrate is investigated. Thermal fields of the sample surfaces are measured by means of thermal imaging in combustion of released methane with clathrate dissociation. The dissociation rates of natural hydrate and double hydrate with isopropanol are many times lower than those of synthetic methane hydrate. Methane combustion is accompanied by formation of a thin water film on the powder surface, which has a strong effect on the heat and mass transfer mechanisms. The experiments demonstrated partial self-preservation for methane hydrate and the absence of self-preservation for double isopropanol-methane hydrate. The experimentally observed dissociation rate of double isopropanol-methane hydrate is considerably lower than that of methane hydrate.     

Methane dissolution inside bulk or porous-medium-confined water at near-hydrate equilibrium conditions

In this study, we perform a series of mass-balance-type calculations, in order to estimate the minimum volume of liquid water required to dissolve completely a single methane gas bubble, located inside different types of domains that are near or under hydrate equilibrium pressure/temperature conditions. We examine the case of methane bubble dissolution in the bulk, along with the cases of methane bubble dissolution within simple/regular networks of pores, where all pores have the same size. In our calculations, we consider experimental values for the equilibrium solubilities of methane in water, along the hydrate-forming line, as well as, values obtained from predictive tools that are based on different thermodynamic models. The effect of aqueous NaCl solutions on the results is also investigated. As a result of the relatively low solubility of methane in water, large volumes of water are required for complete dissolution of a methane bubble.     

Modelling of decomposition of a single gas hydrate particle in water behind the shock wave front

The mathematical model of decomposition of a spherical gas hydrate particle in water behind a 1D wave of the stepped profile (rarefaction wave) is suggested. Contribution of the outer and inner heat flux in a particle to the process of hydrate decomposition is studied. The effect of the gas hydrate particle size, pressure and temperature jumps in liquid on gas hydrate decomposition is investigated.     

Molecular dynamics study on the dissociation of methane hydrate via inorganic salts

Hydrate plugging is a hidden threat to the safe exploitation of oil and gas. Inorganic salts are widely used as thermodynamic inhibitors to effectively prevent the hydrate formation. This study uses a molecular dynamics method to explore the mechanism of the hydrate dissociation via inorganic salts on the micro-scale. We simulated the dissociating process of methane hydrate under different concentration series of NaCl, KCl and CaCl₂ solutions at 273 K, and analysed the changes of ionic structure, transport parameters and kinetic energy in the system of inorganic salt/hydrate. The simulation results successfully revealed the step-by-step dissociation of hydrate, and the differences in dissociation rates among the different inhibitors. The energy needed for hydrate dissociation alters for different inorganic solutions; the energy reaches maximum when KCl is the inhibitor, and lowest when the concentration of CaCl₂ exceeds 30% w/w. We calculated the coordination numbers of all components, including oxygen atoms, cations and anions, and also their diffusion coefficients; analysed the effects of the three inorganic salts on the simulated hydrate structure and its transport; in addition, investigated the mechanism of hydrate dissociation via inorganic salts.     

四氢呋喃水合物形成及饱和度的MRI检测

磁共振成像（MRI）是一种高效无损的检测手段,近年来在工程领域得到了一定的应用. 采用MRI技术对常压下四氢呋喃（THF）水合物在水溶液和玻璃砂2种体系中的生成过程以及饱和度变化进行了检测. 结果表明：MRI是一种对水合物生成过程检测的有效方法;通过阈值分割方法将MRI灰度图像转化为二值图像后可以通过二值图像的积分值对THF水合物的饱和度进行分析.