天然气水合物储运技术中水合物反应器的研究进展

可观的储气率与自保效应的存在使得天然气水合物能作为一种天然气储运的方式,并且在与其他如液化天然气、压缩天然气储运方式比较时有着自己独到的优势。但由于针对水合物储运的研究起步较晚,利用水合物储运天然气的技术尚未成熟。尤其是在水合物反应器的研究上,生成水合物的速率较低,无法达到工业生产所需要的水平。本文通过调研国内外文献与专利等资料,介绍了国内外天然气水合物储运技术发展状况,简述了水合物生成强化的物理化学手段与机械手段,详述了搅拌式等传统天然气水合物反应器与管式、超重力式等新型天然气水合物反应器的结构与工作原理。根据现有水合物反应器的特点与存在的问题,对水合物反应器的研究方向提出建议：未来应当加快对喷淋式、超重力式与流化床式反应器的放大研究,加快针对不同物理强化手段与机械强化手段的协同作用研究,建立起以天然气储运为目的的水合物反应器评价体系。     

多孔介质中水合物生成与分解二维实验研究

采用电容、压力、温度测试作为监测手段,自行研制了一套天然气水合物二维开采模拟系统,可用于水合物生成与分解过程中温度场、压力场、分布状态、分解前沿推进速度等动态特性的研究。水合物生成与分解实验表明,温度是影响水合物大量生成的主要因素;重复实验会加长生成时间,往往首次实验所耗总时间最短,说明水的记忆效应并不是对于所有实验系统存在的普遍现象;实验表现出来的特殊的压力变化曲线和规律还表明晶核形成对水合物晶体的生成并非绝对重要。理论分析和实验表明,电容法在测试单相水体相变过程中是有效的,水量是影响电容量变化的关键。在水合物生成过程中,随水合物饱和度的增加、水量的不断减少,电容量总体减小趋势明显。电容测试方法在水合物实验方面有一定的可行性,尤其对于研究多孔介质中水合物生成分解过程中各相的流动特性极有意义,但是要实现在水合物研究方面的有效利用还需要大量的切实的实验验证。     

天然气水合物资源勘探开发技术研究进展

天然气水合物储量巨大,是人类理想的潜在的替代能源。对世界天然气水合物资源基本特征和分布情况进行了介绍,对国内外天然气水合物勘探开发技术以及环境效应进行了阐述。     

天然气水合物开采模拟研究进展

介绍了天然气水合物(NGH)的结构及分解的基本特性;总结了电解质及沉积物对NGH形成及分解的影响,概括描述了NGH开采的几种可能方法;提出了NGH开采模拟进一步研究的方向。     

热盐水开采天然气水合物的热力学评价

将多孔介质中天然气水合物在热力作用下的分解过程看作一个移动边界问题,在求解等温边界条件下水合物地层中分解区和未分解区（水合物区）温度场的基础上,推导出热力法开采水合物过程中开采热效率（用于水合物分解的热量与输入热量之比）和能量效率（开采所得甲烷气体的总热值与输入能量之比）的解析表达式.在相同水合物地层条件下,对比注入热盐水（采用NaCl溶液）和热水两种开采方法,得出热盐水中盐的浓度（简称盐度）对开采热效率等的影响.计算结果表明,采用热盐水开采热效率一般在40%～70%.在开采温度300～450 K、盐度0～15%的条件下,热力法开采水合物的能量效率在7.4%～11.3%之间.     

Effect of additives on formation of natural gas hydrate

The formation of natural gas hydrate (NGH) is studied in this work. Kinetics data of hydrate formation with no agitation were collected at various concentrations of the aqueous solutions with different additives such as alkylpolyglucside, sodium dodecyl benzene sulfonate and potassium oxalate monohydrate. Various kinds of additive increased the formation rates of NGH and its storage capacity and reduced the induction time of NGH formation. Moreover, the storage capacity, the induction time and the hydrate formation rate were influenced by the concentration of the aqueous solution.     

The status of exploitation techniques of natural gas hydrate

Natural gas hydrate (NGH) has been widely considered as an alternative form of energy with huge potential, due to its tremendous reserves, cleanness and high energy density. Several countries involving Japan, Canada, India and China have launched national projects on the exploration and exploitation of gas hydrate resources. At the beginning of this century, an early trial production of hydrate resources was carried out in Mallik permafrost region, Canada. Japan has conducted the first field test from marine hydrates in 2013, followed by another trial in 2017. China also made its first trial production from marine hydrate sediments in 2017. Yet the low production efficiency, ice/hydrate regeneration, and sand problems are still commonly encountered; the worldwide progress is far before commercialization. Up to now, many gas production techniques have been proposed, and a few of them have been adopted in the field production tests. Nevertheless, hardly any method appears really promising; each of them shows limitations at certain conditions. Therefore, further efforts should be made on the economic efficiency as well as sustainability and environmental impacts. In this paper, the investigations on NGH exploitation techniques are comprehensively reviewed, involving depressurization, thermal stimulation, chemical inhibitor injection, CO₂–CH₄ exchange, their combinations, and some novel techniques. The behavior of each method and its further potential in the field test are discussed. The advantages and limitations of laboratory studies are also analyzed. The work could give some guidance in the future formulation of exploitation scheme and evaluation of gas production behavior from hydrate reservoirs.     

多孔介质中水合物生成与分解的电阻率性质

A new one-dimensional system for resistivity measurement for natural gas hydrate (NGH) exploitation is designed, which is used to study the formation and decomposition processes of NGH.The experimental results verify the feasibility of the measurement method, especially in monitoring the nucleation and growth of the NGH.Isovolumetric formation experiment of NGH is performed at 2 ℃ and 7.8 MPa.Before the NGH formation, the ini-tial resistivity is measured to be 4-7 Ω·m, which declines to the minimum value of 2-3 Ω·m when NGH begins to nucleate after the pressure is reduced to 3.3 MPa.As the NGH grows, the resistivity increases to a great extent, and finally it keeps at 11-13 Ω·m, indicating the completion of the formation process.The NGH decomposition ex-periment is then performed.When the outlet pressure decreases, NGH begins to decompose, accordingly, the resis-tivity declines gradually, and is at 5-9 Ω·m when the decomposition process ends, which is slightly higher than the resistivity value before the formation of NGH.The occurrence and distribution uniformity of NGH are determined by the distribution and magnitude of the resistivity measured on an one-dimensional sand-packed model.This study tackles the accurate estimation for the distribution of NGH in porous medium, and provides an experimental basis for further study on NGH exploitation in the future.     

不同饱和度的天然气水合物降压分解实验

天然气水合物作为一种新能源已得到世界各国的关注,降压是水合物藏的一种有效开采方式。采用自制的天然气水合物开采模拟实验装置,在多孔介质中生成不同饱和度的天然气水合物,之后进行缓慢降压开采实验。结果表明：降压开采可分为自由气产出、水合物降压分解产气和最后降压产出已分解气三个阶段。在降压分解阶段,当水合物饱和度从16%增加到48%时,平均产气速率先增加后减小,说明水合物饱和度对降压分解产气速率的影响是非线性的。降压分解时,水合物饱和度越大,温度下降幅度越大。实验研究范围内,中等饱和度（32%）的水合物藏降压分解产气速率比较大,降压开采效果较好。     

二氧化碳置换法模拟开采天然气水合物的研究进展

目前实验室模拟开采天然气水合物(NGH)的最主要的方法为外激法,通过注热、降压等方式使水合物分解释放出甲烷(CH₄),外激法最大的问题在于水合物的分解容易造成地层结构变化,导致地质斜坡灾害。利用二氧化碳(CO₂)在水合物相中置换开采CH₄,由于置换过程发生在水合物相中,不改变水合物相结构,因此可以降低地质灾害风险。本文全面介绍了利用CO₂在水合物相从NGH中置换CH₄的研究进展,从置换可行性、动力学模型、模拟研究、实验研究等方面对当前的研究进行了综述,并为进一步发展置换法开采CH₄技术指出了方向。     

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。     

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.     

Evaluation on the natural gas hydrate formation process

Gas hydrates have endowed with great potential in gas storage, and rapid formation of gas hydrates is critical to use this novel technology. This work evaluated the natural gas hydrate formation process, which was compared from six parameters, including conversion of water to hydrate, storage capacity, the rate of hydrate formation, space velocity (SV) of hydrate reaction, energy consumption and hydrate removal. The literature was selected by analyzing and comparing these six parameters mentioned above, meanwhile placing emphasis on the three parameters of storage capacity, the rate of hydrate formation and space velocity of hydrate reaction. Through analysis and comparison, four conclusions could be obtained as follows. Firstly, the overall performance of the stirring process and the spraying process were better than other processes after analyzing the six parameters. Secondly, the additive types, the reactor structure and the reactor size had influence on the natural gas hydrate formation process. Thirdly, the energy consumption via reciprocating impact in the hydrate formation process was higher than that via stirring, spraying and static higee. Finally, it was one key for hydrate removal to realize the hydrate industrial production.     

液化天然气工厂天然气净化工艺的选择

介绍了天然气中水分、硫化氢、二氧化碳、重烃、汞及氮气等杂质对LNG工厂液化的影响,以及天然气的净化工艺.根据某公司液化天然气工厂天然气来源变化,说明天然气的组成对天然气净化工艺选择的影响.     

Experimental investigation of hydrate formation behaviour of a natural gas bubble in a simulated deep sea environment

A vertically flowing, closed circuit, high pressure water tunnel was designed and constructed for holding individual gas bubbles stationary against an opposing flow for detailed observations. Hydrate formation behavior of natural gas bubbles was studied at constant pressure as well as under conditions of controlled decompression designed to simulate buoyant rise of the bubble.A bubble of simulated natural gas suspended in 3°C salt water formed hydrates when the pressure was 4826 kPa or higher. The simulated decompression accompanying buoyant rise had very little effect on hydrate formation behavior of a bubble starting from a pressure of 5516 kPa or above. At lower starting pressures, a slight increase in the reaction rate was detected in the initial stages of a run. The conversion of the simulated natural gas to hydrates was complete in runs starting from a pressure of 4826 kPa or above.     

Energy efficiency analysis of natural gas hydrates production method

The decomposition of natural gas hydrates is a phase change process, which involves the consumption and conversion of various forms of energy, such as electrical energy, chemical energy, and thermal energy. In order to evaluate the economy capacity of natural gas hydrates exploitation, an exergy model was established to calculate the energy efficiency ratio (EER) of hydrate production method. The CO₂ replacement method is taken as a case study to introduce the calculation equation and flow chart of energy efficiency ratio in any production period. The amount of CO₂ injection, gas production and mole fraction of methane in produced gas are three key parameters in the process of CO₂ replacement. The ratio between the amount of gas production and CO₂ injection is defined as production injection ratio to eliminate the influence of deposit size. This work studied the influence of production injection ratio and the mole fraction of methane in produced gas on EER. The results show that the EER of gas hydrates production by CO₂ replacement is between 0.31 and 6.4 under the set conditions, and it increases with the increase of production injection ratio. In addition, increasing the mole fraction of methane in produced gas can reduce the energy consumption for gas separation and increase EER. Therefore, there are two effective ways to increase EER of CO₂ replacement through controlling the amount of gas production and the mole fraction of methane in produced gas. The EER model is established to provide guidance for the optimization of gas hydrate mining process.     

天然气水合物置换开采的能源效率研究

天然气水合物分解是一个相变过程，开采时涉及各种形式能量的消耗和转化，如电能、化学能、热能等。为了科学地评价天然气水合物开采技术的经济性，建立了以有效能（）为核心的能源效率计算方程，并以CO₂置换法开采天然气水合物为例，介绍任意生产周期内能源效率的计算方法和流程框图。在CO₂置换开采天然气水合物的工艺过程中，注气量、产气量和产气中甲烷含量是三个关键参数，将产气量与注气量之比定义为采注比，分析采注比及产气中甲烷含量对能源效率的影响。结果表明：在设定条件下CO₂置换开采天然气水合物的整体能源效率介于0.31～6.4之间；增大采注比，有利于提高能源效率；产气中甲烷的摩尔分率越高，气体分离的能耗越低，能源效率也可显著提高。因此，调控产气量和产气中甲烷摩尔分率是提高CO₂置换法能源效率的主要途径。通过所建立的能效计算方程为天然气水合物开采工艺的优化提供指导。     

Structure‐H gas hydrates in petroleum reservoir fluids

An integrated experimental/modelling investigation was conducted on the potential of newly discovered strueture‐H (sH) hydrates formation in petroleum reservoir fluids. A thermodynamic model was validated against a series of experimental data on a natural gas with various quantities of methylcyclohexane (MCH). Three mixtures were tested where structure‐II (sII), sII/sH and sH were the stable structures. The validated thermodynamic model was employed to predict the stable hydrate structure for a large number of real reservoir fluids, (i.e., black oils, volatile oils and gas condensates). The results showed that sII is the stable hydrate structure for all systems investigated in this work. However, sH might co‐exist with sII in some reservoir fluids where transportation of hydrates as slurry is being considered.     

Numerical study on effects of the cofferdam area in liquefied natural gas storage tank on the leakage and diffusion characteristics of natural gas

The leakage and diffusion characteristics of natural gas were investigated in the condition of the leakage of liquefied natural gas (LNG) in the storage tank. Fluent was adopted to simulate the process in a series of three-dimension unsteady state calculations. The effects of different heights of the cofferdam (1.0 m, 2.0 m and 3.0 m), wind directions, ambient temperature, leakage location, leakage volume on the diffusion process of natural gas were investigated. The diffusion characteristics of the natural gas clouds over cofferdam were found. Under windless condition, when the gas clouds met, the gas clouds rose due to the collision, which made them easier to cross the cofferdam and spread out. The higher the ambient temperature was, the higher the gas concentration around the cofferdam was, and the smaller the gas concentration difference was. When the leakage occurred, the higher cofferdam was more beneficial to delay the outward diffusion of gas clouds. However, when the leakage stopped, the higher cofferdam went against the dissipation of gas clouds. Under windy condition, the time to form stable leakage flow field was faster than that of windless, and the lower cofferdam further reduced this time. Therefore, considering the effect of barrier and dissipation, it was suggested that the rational height of cofferdam should be designed in the range of 1.0 m to 2.0 m. In case of emergency, the leakage of gas should be deduced reasonably by combining the measurement of gas concentration with the rolling of gas clouds. When windless, the leakage area should be entered between the overflows of gas clouds.     

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.