水合物藏降压开采实验及数值模拟

建立了降压法开采水合物藏数学模型,考虑了气-水-水合物-冰相多相渗流、水合物相变及分解动力学过程、冰-水相变、热传导、对流过程、渗透率变化等对于水合物分解的影响。三维水合物藏模拟表明:在开采前期阶段,可采用降压法,但随着储层能量消耗,产气速度下降很快,需转变开采方式。分析了一些主要参数,如孔隙度、渗透率、饱和度、压力等对水合物开采的影响。     

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.     

The features of gas hydrate dissociation in porous media at warm gas injection

Results of numerical simulation of warm gas injection into a porous medium initially saturated with gas and gas hydrate, accompanied by gas hydrate dissociation, are presented. It is shown that depending on parameters at the outer boundary of the medium (permeable or impermeable to the gas flow) hydrate dissociation can occur both at the frontal boundary and in the extended region.     

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。     

CEMS study of strain induced phase transformation in manganese Hadfield steel

A Conversion Electron Mössbauer Spectroscopy, (CEMS), study of phase transformations in a Hadfield steel induced by high rate strains is reported. Hadfield steel samples were impact deformed and the ensuing changes in the magnetic properties at the deformed zone and its surroundings have been studied by CEMS. The CEMS results are compared with wear tests and optical microscopy and show a formation of martensite by impact deformation only at the surface. Martensite is not produced by compression or tensile stresses but appears after wear tests in proportions that depend on the load and velocity conditions of test. The understanding of martensite phase formation and its evolution during deformation processes is also addressed.     

Monitoring hydrate formation and dissociation in sandstone and bulk with magnetic resonance imaging

Magnetic resonance imaging (MRI) has been shown to be a very effective tool for monitoring the formation and dissociation of hydrates because of the large intensity contrast between the images of the liquid components and the solid hydrate. Tetrahydrofuran/water hydrate was used because the two liquid components are miscible and form hydrate at ambient pressure. These properties made this feasibility study proceed much faster than using methane/water, which requires high pressure to form the hydrate. The formation and dissociation was monitored first in a THF/water-saturated Berea sandstone plug and second in the bulk. In both cases it appeared that nucleation was needed to begin the formation process, i.e., the presence of surfaces in the sandstone and shaking of the bulk solution. Dissociation appeared to be dominated by the rate of thermal energy transfer. The dissociation temperature of hydrate formed in the sandstone plug was not significantly different from the dissociation temperature in bulk.     

热力法开采地层天然气水合物的热动力评价

本文在推导热力作用下水合物地层温度分布基础上,发展了评价热力法开采天然气水合物的热效率(用于水合物分解的热量与输入总的热量之比)和能量效率(即输出能量与输入能量之比)的模型.模型分析表明,水合物地层热物性参数以及水合物饱和度决定了热力法开采的能量效率.在注入蒸汽开采初始条件下,能量效率可以达到7.0.     

Numerical Investigation into the Development Performance of Gas Hydrate by Depressurization Based on Heat Transfer and Entropy Generation Analyses

The purpose of this study is to analyze the dynamic properties of gas hydrate development from a large hydrate simulator through numerical simulation. A mathematical model of heat transfer and entropy production of methane hydrate dissociation by depressurization has been established, and the change behaviors of various heat flows and entropy generations have been evaluated. Simulation results show that most of the heat supplied from outside is assimilated by methane hydrate. The energy loss caused by the fluid production is insignificant in comparison to the heat assimilation of the hydrate reservoir. The entropy generation of gas hydrate can be considered as the entropy flow from the ambient environment to the hydrate particles, and it is favorable from the perspective of efficient hydrate exploitation. On the contrary, the undesirable entropy generations of water, gas and quartz sand are induced by the irreversible heat conduction and thermal convection under notable temperature gradient in the deposit. Although lower production pressure will lead to larger entropy production of the whole system, the irreversible energy loss is always extremely limited when compared with the amount of thermal energy utilized by methane hydrate. The production pressure should be set as low as possible for the purpose of enhancing exploitation efficiency, as the entropy production rate is not sensitive to the energy recovery rate under depressurization.     

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.     

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.     

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     

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.     

Clathrate hydrates modelled with classical density functional theory coupled with a simple lattice gas and van der Waals-Platteeuw theory

Predicting clathrate hydrate phase equilibria is of interest in the area of natural gas exploitation. This proof of concept study presents the application of a simple lattice gas model and classical density functional theory coupled with van der Waals-Platteeuw theory to predict clathrate hydrate phase equilibria for several different hydrate-forming gas species. The dissociation pressure curve is predicted using adsorption isotherms predicted for the gas species in the crystal hydrate lattice. Comparisons are made between predicted phase equilibria (and other properties) and available experimental data.     

Characteristics of the evolution of defect structure during phase transformations in the Pd-H system

The pattern of evolution of the defect structure in the Pd-H system during phase transformations is formulated on the basis of x-ray data. It is shown that once the random dislocations formed during phase transformations in the a phase reach their critical density, they assemble into dislocation walls. This process results in the formation of a cellular dislocation substructure in the α phase. After the formation of the cellular substructure in the α phase the random dislocations created during phase transformations climb into the hydride phase, thereby curtailing the evolution of defect structure in the α phase. The subsequent influx of dislocations into the β phase maintains continued evolution of the defect structure (from cellular to block dislocation substructure). Not until that time is it possible for the evolution of the defect structure in the α phase to terminate, culminating in the formation of a block substructure. The nature of the observed phenomenon is discussed. Fiz. Tverd. Tela (St. Petersburg) 39, 1275–1281 (July 1997)     

Phase field modeling precipitation of β-phase and mechanical properties change in Zr–Nb alloys under neutron irradiation

ABSTRACT

We study microstructure transformation in Zr–Nb system under neutron irradiation and its mechanical properties change under mechanical loads in a form of shear deformation by using phase field methodology. The developed phase field approach takes into account defects dynamics based on reaction rate theory and elastic contribution to study mechanical properties change. A numerical modeling is provided in three stages: sample preparation, irradiation of the prepared sample and mechanical loading of the irradiated sample. A precipitation of β-Niobium particles of the size of several nanometers is discussed. Results of phase field modeling indicate that β-Niobium particles grow slowly during irradiation due to point defects rearrangement. Statistical analysis of dynamics of radiation-induced microstructure transformations is provided. Simulation results of shear deformation of pre-irradiated and post-irradiated alloys are discussed. Maps of local distribution of strain and stress and strain–stress curves are obtained. Results are verified with experimental data.     

Atomic-level simulations of nanoindentation-induced phase transformation in mono-crystalline silicon

Molecular dynamics (MD) simulations of nanoindentation are carried out to investigate the phase transformations in Si with a spherical indenter. Since the phase transformation induced by deformation in micro-scale is closely related to the carrier mobility of the material, it has become a key issue to be investigated for the chips especially with smaller feature size. Up to now, however, it is not possible to carry out the nanoindentation experimentally in such a small feature. Consequently, molecular dynamic simulation on nanoindentation is resorted to and becomes a powerful tool to understand the detailed mechanisms of stress-induced phase transformation in nano-scale. In this study, the inter-atomic interaction of Si atoms is modeled by Tersoff's potential, while the interaction between Si atoms and diamond indenter atoms is modeled by Morse potential. It is found that the diamond cubic structure of Si in the indentation zone transforms into a phase with body-centred tetragonal structure (β-Si) just underneath the indenter during loading stage and then changes to amorphous after unloading. By using the technique of coordinate number the results reveal that indentation on the (0 0 1) surface exhibits significant phase transformation along the <1 1 0> direction. In addition, indentation on the (1 1 0) surface shows more significant internal slipping and spreading of phase transformation than on the (0 0 1) surface. Furthermore, during the indentation process phase transformations of Si are somewhat reversible. Parts of transformed phases that are distributed over the region of elastic deformation can be gradually recovered to original mono-crystal structure after unloading.     

双模晶体相场研究形变诱导的多级微结构演化

本文采用双模晶体相场模型,计算了双模二维相图;模拟了形变诱导六角相向正方相转变过程的多级微结构演化,详细分析了位相差、形变方向对位错、晶界、晶体结构、新相形貌的影响规律.模拟结果表明:形变方向影响正方相晶核的形核位置和生长方向,拉伸时正方相优先在变形带上形核,垂直于形变方向长大,而压缩时正方相直接在位错和晶界的能量较高处形核,平行于形变方向长大;位相差对形变诱发晶界甄没过程有显著影响,体现在能量峰上为,小位相差晶界位错的攀滑移和甄没形成一个能量峰,大位相差晶界位错攀滑移和甄没因分阶段完成而不出现明显的能量峰;形变诱导相变过程中各种因素相互作用复杂,是相变与动态再结晶的复合转变.     

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.     

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.     

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.