含下伏气沉积层内水合物相变与产气特性

含下伏气的水合物沉积层被认为是最具开采潜力的水合物储层类型。本文利用岩心夹持器在恒定围压9 MPa下,研究了连通不同压力下伏气的南海沉积物内天然气水合物生成、分解及产气特征。研究结果表明,水合物饱和度与下伏气初始压力(7.2～8.1 MPa)呈非线性正比关系,而在8.1～8.4 MPa内两者呈负相关。同时,发现在降压开采过程中下伏气为水合物分解提供热量,促进了水合物分解,提高了水合物平均分解速率。此外,下伏气有助于缓解压降速率,从而有效减轻有效应力对水合物沉积层的破坏。下伏气作为开采产气的重要供气源,能提高气体回收率。本文研究结论将为今后降压开采含下伏气的水合物提供一定的理论指导。     

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。     

多孔介质中气体水合物孔隙尺度分布特征

天然气水合物在沉积物中的分布规律对其勘探开发起着至关重要的作用。本文采用X射线计算机断层扫描技术(X-CT),通过原位扫描气体水合物生成与分解各个阶段,研究了水合物在生成与分解过程中在多孔介质中的分布规律。实验结果表明,水合物在多孔介质中的生成位置主要受传热速度及气体扩散的影响,水合物分布呈现随机性;在分解过程中,热刺激法及降压法均导致水合物二次生成,前者可以促进水合物在多孔介质中的均匀分布,后者则使沉积物分布更加均匀。     

激光拉曼光谱在气体水合物研究中的应用

天然气水合物是一种重要的潜在能源。用激光拉曼光谱法表征气体水合物能够为研究水合物形成机理和开采方法提供重要信息。系统介绍了激光拉曼光谱法的基本原理,综述了激光拉曼光谱仪在气体水合物微观表征上的各种实际应用。通过激光拉曼测试可分析水合物气体组成、推测结构类型,再利用经验公式或者相对定量法可计算出其大/小笼的气体占有率和水合数;利用原位拉曼技术可以观测水合物形成和分解的微观过程,解析气体分子进入和离开笼子的进程、进行水合物形成和分解过程中气体浓度变化及水合物形成过程中气体溶解度的测定,辨识水合物系统中的相变过程,进而研究水合物形成和分解动力学;激光拉曼光谱法还可用于研究超高压条件下气体水合物的结构及其变化过程。原位拉曼光谱能够对深海天然气水合物及其环境在原位进行表征;利用拉曼成像技术可以对水合物晶体表面进行系统测定,探求气体组分在晶体表面的分布。随着激光拉曼技术的发展及与其他设备联用水平的提高,激光拉曼光谱仪向便携,高灵敏度发展,能够更广泛深入地进行气体水合物微观研究。     

水合物研制、结构与性能及其在能源环境中的应用

天然气水合物是与能源和环境相关的物质,可以进行甲烷等能源气体的存储和提取,也可以用于对二氧化碳等废气的封存.天然气水合物主要分为三种结构:sI, sII和sH,在本文中对其稳定性、水笼类型和大小以及可俘获气体进行了论述.中子衍射技术是研究水合物的重要手段之一,有着独特的优势.如中子的穿透性可以研究在高压状态下压力腔体内的大块样品;中子对于轻元素的敏感性可以很好地确定水合物当中的碳、氢、氧元素.通过中子衍射和非弹散射可以得到水合物中H/D原子的位置、各向异性振动因子、不同温度压力下的客体分子的水笼占据率、客体分子在水笼中的无序分布、原子核密度分布(通过最大熵方法);通过时间分辨中子,可以检测水合物形成及分解过程的热力学和动力学过程.而利用非弹中子可以得到气体分子平移和旋转振动模式以及分子的量子态转变.通过二氧化碳气体注入对天然气水合物的开采可以实现能源气体甲烷的开采和废气二氧化碳的水合物封存,在减小地质灾害和开采成本上有着独特的优势.     

水合物储层的毛细封闭效应及高压突破机制

含下伏气的天然气水合物储藏是我国海洋水合物矿藏的重要类型,天然气水合物开采过程中,必须考虑下伏气存在产生的影响。目前,仍缺少针对下伏气产生机理的相关研究。本文利用核磁共振可视化实验装置,探究了水合物藏对其下伏气的封闭作用。结果表明,高饱和度水合物藏对外来流体具有阻碍作用,即毛细封闭作用。水合物的存在减小了孔喉半径,使多孔介质内存在较大的毛细管力,最终形成了抑制下伏气运移的水合物封闭层。水合物储层的封闭效应是下伏气稳定存在的基础。此外,降压过程产生的高压差会诱发水合物封闭层的高压突破现象、进而会引起压力骤降,威胁水合物安全开采。水合物开采过程应该考虑避免出现水合物储层高压突破。     

水合物封闭升温及降压分解气液迁移特性

水合物分解过程产生的气液固迁移特性是影响水合物分解速率的关键要素。基于此,搭建了一套可视化的水合物生长及分解特性研究实验系统,通过该系统对封闭升温及降压分解过程中气液迁移特性进行了研究。实验结果表明,水合物在封闭升温分解过程中的气液迁移主要是通过形成气体通道实现的;同时,水合物分解过程中的气液迁移会造成沉积物的体积膨胀,在封闭升温分解过程中,沉积物体积膨胀率随着分解次数的增加而增加,三次分解膨胀率依次为18. 7%,34. 7%和45. 4%。背压为0. 1 MPa的降压分解中,体积膨胀率为64. 7%,温度迅速下降,并伴随着冰的生成或水合物的再次生成阻碍分解,但是降压依然加速了水合物的分解,使得水合物的总分解速率相对于封闭升温分解提高了20. 5%。实验结果对水合物技术应用具有理论和数据支撑作用。     

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.     

水合物防聚剂多相流管线中初步应用技术研究

本文围绕新型水合物化学抑制剂（防聚剂）在海上油气田现场应用过程中将遇到的管道输送工艺设计技术问题开展研究。首次以海上凝析油气田现场采集的油、水和按天然气组分配置的气体为实验介质,加入国内自主研制的水合物防聚剂,在水平透明实验环道上进行了水合物浆液流动压降实验。通过分析实验结果并借助液固两相流有关理论,初步建立了水合物浆...     

水流侵蚀联合热辅助法水合物相变及分布特性

天然气水合物被认为是一种未来潜在替代能源,据估计全球大约90％的水合物分布在海底沉积层中.本文考虑到海洋环境中海水资源巨大,且表层海水的温度高于水合物储层,采用海水-气两相流动结合热辅助法分解水合物,并利用核磁共振成像系统可视地分析了水合物相变特性及空间分布规律.结果表明,水合物相变首先出现在反应釜入口处,随后水合物相...     

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.     

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.     

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.     

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.     

Investigation of Gas-Water-Sand Fluid Resistivity Property as Potential Application for Marine Gas Hydrate Production

The phase fraction measurement of gas-water-sand fluid in downhole is an important premise for safe and stable exploitation of natural gas hydrates, but the existing phase fraction measurement device for oil and natural gas exploitation can’t be directly applied to hydrate exploitation. In this work, the electrical resistivity properties of different gas-water-sand fluid were experimentally investigated using the multiphase flow loop and static solution experiments. The effect of gas phase fraction and gas bubbles distribution, sand fraction and sand particle size on the relative resistivity of the multiphase fluid were systematically studied. The measurement devices and operating parameters were also optimized. A novel combined resistivity method was developed, which demonstrated a good effect for the measurement of phase fractions of gas-water-sand fluid, and will have a good application potential in marine natural gas hydrates exploitation.     

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 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.     

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.     

天然气水合物藏裂缝注热的数值模拟研究

天然气水合物因其能量密度大、储量丰富、无污染等特点而被认为是一种新型的替代能源,如何提升天然气水合物储层渗透率是实现其商业化开采的关键.本研究提出使用人工压裂技术在水合物储层中形成裂缝网络,然后再将高温水注入储层来提升储层渗透率,并对沿裂缝注水过程进行了数值模拟.结果表明:人工压裂后,注入储层的热水能够到达储层深处,形...