A review: Enhanced recovery of natural gas hydrate reservoirs

Natural gas hydrate (NGH) is a highly efficient and clean energy, with huge reserves and widespread distribution in permafrost and marine areas. Researches all over the world are committed to developing an effective exploring technology for NGH reservoirs. In this paper, four conventional in-situ hydrate production methods, such as depressurization, thermal stimulation, inhibitor injection and CO₂ replacement, are briefly introduced. Due to the limitations of each method, there has been no significantly breakthrough in hydrate exploring technology. Inspired by the development of unconventional oil and gas fields, researchers have put forward some new hydrate production methods. We summarize the enhanced hydrate exploiting methods, such as CO₂/N₂–CH₄ replacement, CO₂/H₂–CH₄ replacement, hydraulic fracturing treatment, and solid exploration; and potential hydrate mining techniques, such as self-generating heat fluid injection, geothermal stimulation, the well pattern optimization of hydrate exploring. The importance of reservoir stimulation technology for hydrate exploitation is emphasized, and it is believed that hydrate reservoir modification technology is a key to open hydrate resources exploitation, and the major challenges in the process of hydrate exploitation are pointed out. The combination of multiple hydrate exploring technologies and their complementary advantages will be the development trend in the future so as to promote the process of hydrate industrialization.     

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。     

Research progress in hydrate-based technologies and processes in China: A review

Natural gas hydrate (NGH) is considered as an alternative energy resource in the future as it is proven to contain about 2 times carbon resources of those contained in the fossil energy on Earth. Gas hydrate technology is a new technology which can be extensively used in methane production from NGH, gas separation and purification, gas transportation, sea-water desalination, pipeline safety and phase change energy storage, etc. Since the 1980s, the gas hydrate technology has become a research hotspot worldwide because of its relatively economic and environmental friendly characteristics. China is a big energy consuming country with coal as a dominant energy. With the development of the society, energy shortage and environmental pollution are becoming great obstacles to the progress of the country. Therefore, in order to ensure the sustainable development of the society, it is of great significance to develop and utilize NGH and vigorously develop the gas hydrate technology. In this paper, the research advances in hydrate-based processes in China are comprehensively reviewed from different aspects, mainly including gas separation and purification, hydrate formation inhibition, sea-water desalination and methane exploitation from NGH by CH₄-CO₂ replacement. We are trying to show the relevant research in China, and at the same time, summarize the characteristics of the research and put forward the corresponding problems in a technical way.     

One‐dimensional productivity assessment for on‐field methane hydrate production using CO2/N2 mixture gas

The direct recovery of methane from gas hydrate‐bearing sediments is demonstrated, where a gaseous mixture of CO₂ + N₂ is used to trigger a replacement reaction in complex phase surroundings. A one‐dimensional high‐pressure reactor (8 m) was designed to test the actual aspects of the replacement reaction occurring in natural gas hydrate (NGH) reservoir conditions. NGH can be converted into CO₂ hydrate by a “replacement mechanism,” which serves double duty as a means of both sustainable energy source extraction and greenhouse gas sequestration. The replacement efficiency controlling totally recovered CH₄ amount is inversely proportional to CO₂ + N₂ injection rate which directly affecting solid ‐ gas contact time. Qualitative/quantitative analysis on compositional profiles at each port reveals that the length more than 5.6 m is required to show noticeable recovery rate for NGH production. These outcomes are expected to establish the optimized key process variables for near future field production tests. © 2014 American Institute of Chemical Engineers AIChE J, 61: 1004–1014, 2015     

石英砂中甲烷水合物的溶解开采实验研究

天然气水合物是天然气与水在低温高压的条件下形成的一种冰状物质,广泛分布于海底和冻土区的沉积物中,资源量巨大,有望成为未来接替能源。在已发现的资源中,有一种类型的天然气水合物位于海底浅表层或裸露于海底,其形成过程和稳定性规律尚不明确。为揭示其稳定性规律,实验研究了石英砂中甲烷水合物的溶解过程。结果表明,水和白油均能有效溶解石英砂中的甲烷水合物,注水溶解的气水体积比约为2,注油溶解的气液体积比约为10,溶解速率主要受液流-水合物的接触情况影响,随水合物饱和度升高而升高。水/油易在石英砂中窜进,形成优势渗流通道,随后气液比逐渐降低。实验结果为深入研究海底浅表层或裸露的天然气水合物的稳定机理提供了基础。     

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。     

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。     

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。     

纯化天然气水合物螺旋分离器流场与性能分析

基于海洋天然气水合物固态流化开采方法的井下原位除砂提纯回填工艺,本文结合试采所得水合物浆体特征,设计用于解决设备磨损、储层坍塌等问题的井下除砂螺旋分离器,利用CFD数值模拟方法研究了入口速度和水合物体饱和度对井下除砂螺旋分离器流场和性能的影响,得到了随着入口速度增加,流场中流体的速度急剧增大,特别是切向速度、分离效率增加。当分离效率为70%以上,分离器内压降急剧增大,表明分离器内部的能量损耗不断增加;随着入口水合物体积分数的增加,螺旋分离器内流场变化微小,水合物分离效率降低,砂分离效率增加;分离效率为80%以上,压降逐渐降低。说明该分离器的最佳操作区为入口速度范围为3～5m/s,水合物入口体积分数15%以下。研究结果表明：本螺旋分离器具有极佳的除砂效果;切向速度是决定分离器分离性能的关键速度,处理量的增大有利于水合物的提纯;海底水合物储层中水合物饱和度变化对螺旋分离器分离效率具有一定的影响,但螺旋分离器对其具有一定的适应能力;揭示了水合物井下螺旋分离器除砂的分离机理,为其设计提供了一定的依据,为海洋水合物储层开采防砂提了一种新的技术及装备。     

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。     

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.     

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.     

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.     

EFFECT OF MAGNETIZATION OF WATER ON INDUCTION TIME AND GROWTH PERIOD OF NATURAL GAS HYDRATE

The effect of diluted solution's magnetization on induction time and growth period of natural gas hydrate (NGH) has been investigated in quiescent reaction system at pressure of 4.5 MPa and temperature of 274 K with SDS as surfactant, by using volume fixed and pressure falling method. Experimental results show that magnetization will have effect on the induction time of NGH. After magnetization with magnetic field intensity of 0.33 T, the induction time of NGH has been reduced to 47 min (average) from 99 min (average) in which there is no magnetization. On the other hand, the induction time has been prolonged after magnetization of the diluted solution with magnetic field intensity of 0.05 T, 0.11 T, 0.22 T, 0.44 T. Especially with magnetic field intensity of 0.11 T, the induction time had even been prolonged to 431 min (average). The effect of magnetization on the growth period of NGH has not been found at the experimental condition.     

Geomechanics involved in gas hydrate recovery

Gas hydrate is regarded as a promising energy owing to the large carbon reserve and high energy density. However, due to the particularity of the formation and the complexity of exploitation process, the commercial exploitation of gas hydrate has not been realized. This paper reviews the physical properties of gas hydrate-bearing sediments and focuses on the geomechanical response during the exploitation. The exploitation of gas hydrate is a strong thermal–hydrological–mechanical–chemical (THMC) coupling process: decomposition of hydrate into water and gas produces multi-physical processes including heat transfer, multi-fluid flow and deformation in the reservoir. These physical processes lead to a potential of geomechanical issues during the production process. Frequent occurrence of sand production is the major limitation of the commercial exploitation of gas hydrate. The potential landslide and subsidence will lead to the cessation of the production and even serious accidents. Preliminary researches have been conducted to investigate the geomechanical properties of gas hydrate-bearing sediments and to assess the wellbore integrity during the exploitation. The physical properties of hydrate have been fully studied, and some models have been established to describe the physical processes during the exploitation of gas hydrate. But the reproduction of actual conditions of hydrate reservoir in the laboratory is still a huge challenge, which will inevitably lead to a bias of experiment. In addition, because of the effect of microscopic mechanisms in porous media, the coupling mechanism of the existing models should be further investigated. Great efforts, however, are still required for a comprehensive understanding of this strong coupling process that is extremely different from the geomechanics involved in the conventional reservoirs.     

Dynamics of hydrate formation and deposition under pseudo multiphase flow

Gas hydrate formation is considered one of the major challenges in the flow assurance of deepwater oil and gas pipelines, as their blockage by hydrate can lead to significant production/economic loss and safety risk. Understanding the hydrate formation and deposition processes can improve the management methods in field development and production. This study used a high‐pressure rocking cell to simulate multiphase flow conditions to visually investigate the hydrate formation and deposition from an oil‐gas‐water system. The changing hydrate morphologies, flow pattern and particle distribution during hydrate formation were studied and a conceptual model was proposed. The relative motion of hydrates to the cell wall and the final morphology of the hydrate chunks are found to be two critical parameters for evaluating hydrate deposition characteristics in the flow system. Five types of hydrate deposition morphologies are observed and these are correlated to the hydrate porosity. © 2017 American Institute of Chemical Engineers AIChE J, 63: 4136–4146, 2017     

天然气水合物勘探与开发研究进展

天然气水合物的勘探技术主要包括似海底反射层、钻孔取芯和测井方法，天然气水合物的开采技术则包括热激发法、降压法和化学剂法。但由于天然气水合物的赋存状态与物化性质，开采时可能会加深全球温室效应、钻井平台及海底滑塌等问题，致使国际上天然气水合物的开采技术研究比较缓慢，目前仍处于探索实验性开采阶段。据有关专家预测，开采技术一旦被突破，日本或美国将在2010年以后，率先实现天然气水合物的商业生产。     

冰点以下多孔介质中气体水合物的生成动力学研究进展

青藏高原冻土区储存着大量的天然气水合物资源,CO₂置换开采冻土区的天然气水合物可实现天然气水合物的安全开采和温室气体CO₂的地层封存。冰点以下多孔介质中气体水合物的生成动力学,是冻土区天然气水合物置换开采研究领域的难点和热点问题。本文全面综述了冰点以下多孔介质中气体水合物的生成动力学研究进展,讨论了不同体系冰点以下多孔介质中气体水合物的形成机理及其生成特性;详述了冰生成水合物机理及其冰粉/多孔介质体系中气体水合物的生成特性,分析了冰点以下多孔介质中气体水合物生成动力学研究尚待完善和改进的地方。最后本文指出冰点以下多孔介质中水合物的生成过程是由传热、传质等多种因素所控制,揭示不同过程的主导因素及其影响规律是今后研究的重点方向。目前对冰点以下多孔介质中水合物的生成特性及机理的认识尚未成熟,仍需深入研究。     

Advances of experimental study on gas production from synthetic hydrate reservoir in China

China has entered the area of new normal economy which requires the harmonious development of energy consumption, environmental protection and economic development. Natural gas hydrate is a potential clean energy with tremendous reserve in China. The successful field test of marine hydrate exploitation in South China Sea created a new record of the longest continuous gas production from natural gas hydrate. However, the corresponding fundamental research is still urgently needed in order to narrow the gap between field test and commercial production. This paper reviewed the latest advances of experimental study on gas production from hydrate reservoir in China. The experimental apparatus for investigating the performance of hydrate dissociation in China has developed from one dimensional to two dimensional and three dimensional. In addition, well configuration developed from one tube to complicated multi-well networks to satisfy the demand of different production models. Besides, diverse testing methods have been established. The reviewed papers preliminary discussed the mechanical properties and the sediment deformation situation during the process of hydrate dissociation. However, most reported articles only consider the physical factor, the coupled mechanism of physical and chemical factor for the mechanical properties of the sediment and the sand production problem should be studied further.     

天然气储运技术及其应用发展前景

现阶段,对于天然气的应用已经非常的普遍,其为能源危及的缓解和促进社会经济有着很重要的作用,其作为一种清洁能源,在促进社会有效发展以及对人们的生活改善和大气保护当中有着很重要的作用。在天然气应用中,输送是很重要的一个环节,输送方式对人们生产、生活用气的安全和利益有着直接影响。