钻井液侵入含天然气水合物地层特性研究
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摘要
天然气水合物(Natural Gas Hydrate,简称Gas Hydrate)是由水分子和天然气气体分子组成的具有笼状结构的似冰雪状结晶化合物,属气体水合物范畴。因其外观像冰且遇火即可燃烧,所以又被称作“可燃冰”、“固体瓦斯”或“气冰”。其中,天然气气体的成分包括烃类(CH4、C2H6、C3H8、C4H10等同系物)和非烃类气体(CO2、N2、H2S等),这些气体赋存于水分子笼形格架内。由于形成天然气水合物的主要气体成分是甲烷,故通常将甲烷分子含量超过99%的天然气水合物称为甲烷水合物(Methane Hydrate)。天然气水合物是一种亚稳态物质,只能在低温、高压条件下稳定存在,自然界中主要存在于海底陆架沉积物和极地永冻层下,并且广泛分布于大陆、岛屿的斜坡地带、活动和被动大陆边缘的隆起处、极地大陆架以及海洋和一些内陆湖的深水环境,甚至外太空也可发现其踪迹。
自从上世纪60年代和80年代分别在永久冻土带和海洋区域发现天然气水合物以来,其在资源、环境和全球变化中的重要意义引起了各国政府、各大油气公司和各类学术研究机构的极大关注,成为当前能源和地球科学研究的一大热点。其研究涉及的领域已从最初的天然气管道的流动保障扩展到资源潜力、钻井安全、地质灾害、碳循环与气候变化等。天然气水合物研究水平已在某种程度上反应了一个国家的综合科技实力和可持续发展潜力。
研究表明,未来针对水合物研究的关键任务是将其由基础研究和发展规划向全面的水合物开采等应用性研究转变。由于已成功实施了若干水合物研究项目,并具有近海岸和阿拉斯加永久冻土带富存水合物的先天优势,美国成为水合物研究领域的引领者之一,其制定出2015年前对阿拉斯加北坡冻土区水合物开采、2025年前实现对海洋地区水合物开采的计划。此外,日本、加拿大、德国、英国、俄罗斯、挪威、韩国、印度、中国等国家都开展了大量的水合物研究工作,其中日本也制定了2018年实现水合物商业开采的计划,西班牙、尼日利亚、智利、哥伦比亚、新西兰和秘鲁等也都对水合物研究表现出了浓厚的兴趣。初步勘探和研究表明,我国水合物储量较为丰富,开展水合物相关研究对满足我国能源需求具有重要战略意义,我国已把水合物开发列入“国家中长期(2006-2020年)科技发展规划”中。与宏观政策相适应,我国有关水合物调查研究、技术体系、实验模拟及其与环境、气候有关的科研活动也有较大幅度增加。
勘探工作是进行水合物储层物性、地质成藏等基础研究,资源评价、开采技术等应用研究的主要资料来源和强有力支撑。应用于水合物地层的勘探方法主要包括地质、地球物理、地球化学和钻探取心等四类。其中钻探取心是最为直接的勘探手段,可以直接获取原位水合物地层的样品进行分析；地球物理测井在取心困难的情况下就成为最为接近水合物地层原位状态的勘探方法。这两种方法在水合物勘探中占有重要地位,而这两种勘探方式都离不开钻井。
通常海洋水合物地层压实固结程度较差,在钻井过程中若采用欠平衡钻井方式,则不利于井壁力学平衡。而且水合物还会因减压而分解,导致地层力学强度急剧降低,更不利于井壁稳定和井内安全。因此,维持孔内压力大于地层孔隙压力、同时不高于破裂压力是水合物钻井较为可取的安全方式。在此条件下,钻井液在水力压差的作用下驱走井壁周围地层孔隙中的原生流体(气、水)而侵入地层。钻井实践证明,钻井液侵入会改变井壁围岩特性,比如岩石强度、孔隙压力等。与钻井液侵入常规油气地层所不同的是,受钻具摩擦生热以及钻井液温度影响,钻井液侵入含水合物地层过程中还可能伴随有水合物的分解,从而加速井壁失稳。此外,在众多的地球物理测井属性中,电阻率和声波速度受水合物的影响最突出。由于海洋区域水合物赋存在固结不好的沉积物中,而声波受压实系数的影响较重,因而电阻率测井又比声波测井和其他测井方法更稳定和可靠。但是,钻井过程中钻井液循环和侵入却对电阻率测井有着显著的影响。比如为抑制水合物在井内形成和保护海洋环境,深水油气和水合物钻井通常采用高盐聚合物水基钻井液体系,当高矿化度钻井液滤液侵入时会严重影响储层特征和电阻率测井准确性。而且盐是热力学抑制剂,其随钻井液侵入会使水合物相平衡曲线向左迁移,导致地层中水合物分解,进一步影响测井识别评价、井周地层稳定和井内安全。因此,研究耦合有水合物分解的水基钻井液侵入含水合物地层的动态特性及其对地层的影响规律对钻井安全预防、测井准确识别和评价、水合物储层保护、水合物资源和环境评估等都具有重要意义和应用价值。
针对上述分析,了解钻井液侵入含水合物地层的特性,并采用实验模拟和数值模拟等手段展开研究具有重要意义,据此,论文的主要研究内容和路线包括以下几个方面：
(1)分析海洋及冻土区典型水合物储层特征,进行人工岩样的制备研究
水合物散布于砂(岩)层孔隙空间是海洋和冻土区最为典型的水合物储层类型之一,同时也最具开采潜力。论文首先对实际的水合物地层岩石物理性质做详细归纳和总结,在此基础上,分析了分散型水合物砂岩储层的主要矿物组成、岩石颗粒尺寸、孔隙分布及连通性、渗流特性等岩石物理特征；使用自主研发的人工岩心制备装置进行人造岩样的制备,并用其模拟真实水合物储层骨架；使用压汞实验仪和渗透率测量仪对所制人工岩样进行孔隙结构分析和渗透性测试,分析人工岩样的物性特征,得到优选的岩心配方和制备工艺；
(2)进行钻井液侵入水合物地层的实验模拟研究
将制备的人造岩心用于模拟实际的水合物沉积层骨架,使用自主研发、委托厂商生产的“天然气水合物渗流开采综合模拟装置”开展钻井液侵入含水合物地层的相关实验研究,旨在了解钻井液侵入过程中地层物性的变化情况,即掌握钻井液侵入过程中水合物分解程度、地层压力、温度、电学性质的变化等基本规律,并与后续的数值模拟研究相互补充和参考；
(3)进行钻井液侵入水合物地层的数值模拟研究
在实验模拟受到时间和实验设备功能限制的情况下,通过数值模拟对钻井液侵入水合物地层的相关特性进行了更深入的研究。论文以中国南海神狐海域水合物地层为背景,利用劳伦斯伯克利国家实验室开发的水合物开采数值模拟软件TOUGH+HYDRATE分析了一定条件下钻井液侵入海洋水合物储层的动态过程及其对地层的影响规律,进行了钻井液侵入水合物地层所受的影响因素分析。
本论文共六个部分,主要章节内容包括：
第一章：本章为论文的绪论部分,首先对天然气水合物做了简单介绍,总结了国内外对天然气水合物的研究历程和现状；对其在全球的分布及储量评估等能源意义,以及自然界中的天然气水合物和人为勘探、开发可能带来的环境问题进行了介绍；并对水合物主要勘探计划和进展情况进行了归纳；介绍了水合物勘探的主要方法,集中分析了水合物地层钻井面临的困难和挑战；引出钻井液侵入水合物地层可能带来的一系列问题,指出了论文研究的目的和意义,并介绍了论文研究的主要内容和技术路线。
第二章：本章主要对实际的水合物地层物性进行总结和分析,目的是弄清楚研究对象的基本特征。从微观、中观和宏观三个尺度对原位储层中水合物的分布模式进行了总结和分类；对水合物地层的电学、声学、热学等基本物性,以及孔隙度、水合物饱和度、渗透性、力学性质等储层特性进行了分析和总结,并对通常获取水合物地层物性的实验模拟、实际岩心分析和测井解释三种途径进行了介绍。
第三章：目前实验室内模拟水合物沉积物样品时都未全面考虑样品骨架的物性是否贴近实际自然界中的水合物沉积物骨架,从而导致实验结果很难反映或准确代表自然界中的实际情况。为此,本章在第二章对含水合物地层物性进行总结和分析的基础上,对用于模拟实际水合物地层人造岩心的制备技术进行了研究。从目前常规的人造岩心种类中选取适合研究目标的人造岩心技术,确定所模拟地层的基本物性参数后设计正交实验。通过对所制得岩心进行渗透率和孔隙度测量,对比实际水合物地层资料,对实验结果和岩心配方、工艺进行评价和分析,得到了一套较为合理的模拟水合物地层人造岩心制作的配方和工艺,可配制不同孔隙度和渗透率的人造岩心用于相关实验研究。这一工作弥补了水合物地层天然岩心紧缺的不足,对本研究的实验部分顺利进行,及今后水合物室内实验研究提供了便利,具有重要意义。
第四章：本章主要是通过实验模拟的手段研究钻井液侵入水合物地层的基本规律和特性。首先对钻井液侵入含水合物地层的过程及原理作了定性分析；然后,介绍了本研究开展过程中自主研制的“水合物地层渗流与开采综合模拟装置”,该装置主要设计初衷就是为研究钻井液侵入含水合物地层特性及其对测井的影响机理,同时也包括了其它功能,比如开采方法研究,综合性较强；利用该设备和第三章优选出的人造岩心进行了水合物形成和分解实验,为钻井液侵入实验的开展奠定了基础；使用盐水模拟实际的海洋钻井液,进行了钻井液侵入水合物地层实验,测试了侵入过程中压力、温度及电阻率变化情况,进一步阐述了钻井液侵入会对原位水合物地层产生扰动。
第五章：在实验模拟的基础上,本章通过数值模拟的方法对钻井液侵入水合物地层特性展开了进一步研究。首先介绍了所使用的水合物开采数值模拟软件TOUGH+HYDRATE的基本情况,对理论模型的建立进行了分析；然后,以南海北部神狐海域天然气水合物钻探工程(GMGS-1)为背景,研究了一定条件下钻井液侵入海洋水合物储层的动态过程及其对地层的影响规律,分析了钻井液密度、温度、盐度以及地层绝对渗透率和地层水合物饱和度对钻井液侵入的影响规律。
第六章：阐述了本文所得出的主要结论和认识,论文的主要创新点,提出了存在的不足和建议。
Natural gas hydrate is a kind of gas hydrate, ice alike crystalline compound composed of water and natural gas molecules with cage structure. Because of its appearance and could ignite with fire, so it is also called "flammable ice","solid gas" or "gas ice". The molecules of natural gas including hydrocarbon (CH4、C2H6、C3H8、C4H10and homologous series) and non-hydrocarbon gases (CO2、N2、H2S etc.), occupied the cavities in water cages. Since methane is the main component of natural gas, the natural gas hydrate with more than99%of methane molecules is commonly referred to as methane hydrate. Gas hydrate is a kind of metastable material, can only be stable under the condition of high pressure and low temperature, mainly exist in bottom sea continental shelf sediments, arctic permafrost, and widely distributed in the slope zone of mainland and islands, uplift of active and passive continental margin, arctic continental shelf and some deep water environment of ocean and inland lake, and even be found in outer space.
Since the natural gas hydrates were found in permafrost and seafloor in1960s and1980s respectively, its significance in resource, environment and global warming has evoked the attention of governments, petroleum giants and academic institutions. The study on gas hydrates including flow assurance, drilling operation safety, geological hazard, carbon cycle and climate change, etc., has become a hotspot in earth science and energy research. The level of natural gas research is a reflection of the comprehensive science and technology and potential of sustainable development of a nation to some extent.
Studies indicated that the future research of gas hydrate have transformed from the basic research and development plan to applied research such as comprehensive gas hydrate exploitation. The United States has successfully implemented hydrate research program, and owns offshore and Alaska permafrost that have abundant hydrate distribution, is one of the leading countries in gas hydrate research, and have planned to exploit gas hydrate in north slope of Alaska permafrost before2015, and in marine sediments before2025. In addition, Japan, Canada, Germany, Britain, Russia, Norway, South Korea, India, China and other countries have also carried out a large amount of hydrate research. Japan has also planned to commercially exploit gas hydrate before2018. Nigeria, Spain, Chile, Colombia, Peru and New Zealand also showed a strong interest in hydrate research.
Preliminary explorations show that the hydrate resource is abundant in China, and the hydrate research has important strategic significance in meeting the energy demand of the country. The gas hydrate research program has been listed in the major project of large scale oil-gas filed and coal bed in the "national medium and long-term (2006-2020) science and technology development plan" in China. In accordance with the macroeconomic policy, the gas hydrate research related scientific activities including investigation, technical system, experimental simulation and environmental and climate issues have increased significantly. Natural gas hydrate has become an important research focus of energy science, and deeply involved in the climate, environment, high technology and global sustainable development.
Gas hydrate exploration is the main source of data and support for basic research, such as physical property of hydrate reservoir, geological accumulation and application research including resource evaluation and production technique of gas hydrate. The prospecting methods applied to the hydrate formation are categorized to geologic, geophysical, geochemical and coring drilling. Among them, the coring drilling is the most direct means of exploration, the samples of in-situ hydrates can be directly obtained from hydrate bearing formation for analysis, whereas the geophysical well logging is the method that most close to the in-situ state of hydrate formation when coring is difficult. Therefore, these two methods play an important role in gas hydrates exploration, and neither could be done without drilling.
Usually marine hydrate formation is in poor degree of consolidation, if it is drilled by underbalanced drilling methods, is not conducive to borehole stability. Hydrate decomposes under reduced pressure, which also significant reducing the strength of formation, leads to severe borehole wall instability. Therefore, it is preferable to maintain borehole pressure greater than the formation pore pressure while less than fracture pressure during the process of hydrate drilling operation. Under the condition of overbalance, the drilling fluid (i.e. the water based drilling fluid) displaces the original pore fluid (gas and water) around the borehole wall and invades the formation by the pressure differential. The practice of drilling operation indicates that the invasion of drilling fluid would alter the rock properties at the borehole wall, including rock strength, pore pressure etc. Different to invasion of common oil and gas reservoir, the invasion of drilling fluid in gas hydrate formation accompanied by hydrate decomposition caused by drilling tools friction and the temperature of drilling fluid. As a result, the instable of borehole wall accelerated. The resistivity and wave speed are mostly influenced by gas hydrate dissociation amongst all the geophysical logging parameters. The marine hydrate bearing sediments are poorly consolidated, so the acoustic speed is highly affected by compact coefficient, therefore the result of resistivity is more stable and reliable. However, the circulation and invasion of drilling fluid have great influence on resistivity logging. For instance, the high concentration salt and polymer water based drilling fluid systems were applied in order to inhibit the reformation in the borehole and protect the marine environment. The invasion of highly mineralization filtrate would severely alter the characteristics of reservoir and accuracy of resistivity logging. The salt, acting as thermodynamic inhibitor, causes the curve of phase equilibrium moving towards left, results in further gas hydrate dissociation, and has greater effects on evaluation of logging, stability of formation around borehole wall and safety within the borehole. Therefore, the study on the dynamic properties and influence on the formation of invasion of gas hydrate bearing formation by water based drilling fluid coupled by gas hydrate dissociation is meaningful and valuable on safety management, accurate identification and evaluation of geophysical logging, protection of gas hydrate reservoir, assessment of gas hydrate resource and environment, and implementation of well observatory system in IODP.
Based on the analysis above, it is important to understand the properties of invasion of gas hydrate formation by drilling fluid, and carry out study by experimental simulation and numerical modeling. The main contents and path of research including:
(1) Analysis of the typical characteristic of marine and permafrost gas hydrate bearing formations, and preparation of artificial gas hydrate sample.
The research on gas hydrate bearing formation of major ocean and permafrost shows that the gas hydrate distributed in sandstone pore is the most typical hydrate reservoir, and is the most promising energy resources. In the paper, the physical properties of actual gas hydrate bearing formation were firstly summed up. Then the main mineral component, rock particle size, pore distribution and connectivity and seepage characteristics of disseminated type of hydrate formation were analyzed. The artificial core preparation device was independently developed for the preparation of rock sample, in order to simulate the real gas hydrate reservoir.
The mercury intrusion instrument and permeability measuring apparatus were applied for the analysis of pore structure and testing of permeability of artificial rock sample. After analyzing the physical property of the artificial stone sample, the optimization of formulation and manufacturing technique of artificial core sample were formed.
(2) The simulation research on invasion of gas hydrate bearing formation by drilling fluid.
The optimized artificial core samples were selected for simulating the skeleton of gas hydrate bearing sediments. With the application of "comprehensive natural gas hydrate seepage exploitation device" which was self-designed, the research were carried out related to the invasion of simulating gas hydrate bearing formation by drilling fluid, aimed at understanding the change of physical property of formation during the process of drilling fluid invasion. That is obtaining the basic rules of gas hydrate decompose, the evolution of pressure and temperature of formation, and the change of electrical properties during the process as a reference to the result of numerical simulation in the subsequent chapters.
(3) Numerical simulation of invasion of gas hydrate bearing formation by drilling fluid.
Since the simulation experiment was limited by the function of equipment and time expense, implementing the issues related to invasion of hydrate formation by drilling fluid with numerical simulation method is a good supplement for experimental research, and the efficiency of research would also enhanced. The numerical simulation took the gas hydrate bearing formation in Shenhu area, northern South China sea as background, utilizing numerical simulation exploitation software TOUGH+HYDRATE developed by Lawrence Berkeley national laboratory to analyze the dynamic process of drilling fluid invasion of marine gas hydrate and its influence on the formation at certain conditions, and evaluated the factors that involved during the process.
The paper consists of six parts. The main contents are as follows:
In the first chapter, firstly the natural gas hydrates were briefly introduced, and the course and state of art of gas hydrate research home and abroad were overviewed. The global distribution, assessment of reserves, as well as gas hydrates in nature, possible environmental problems brought about by human exploration and development were also introduced. The main gas hydrate exploration programs and progresses were summed up. The main methods of gas hydrate exploration were introduced, and the difficulties and problems faced with during drilling operation were analyzed. The problems related to invasion of gas hydrate bearing formations by drilling fluid were introduced and the aim and meaning of the research were also illustrated with the main content and technical route.
In the second chapter, the physical properties of actual gas hydrate bearing formation were summed up and analyzed, for the purpose of understanding the basic characteristics of the object of research. The distribution patterns of in situ gas hydrate reservoir were summarized and classified from the macro, meso and micro dimension. The basic physical properties of gas hydrate bearing formations, such as electrical, acoustic, thermal, and porosity, gas hydrate saturation, permeability and mechanical properties were summarized as well. Finally, the three approaches, experimental simulation, actual core analysis and logging interpretation for obtaining the physical properties of actual gas hydrate were compared.
In the third chapter, the technique of artificial core sample preparation for simulating actual gas hydrate bearing formation was studied. First chose the appropriate technique of artificial core sample from the conventional methods available. Then the basic physical parameters of the simulating formation were determined before the design of the orthogonal experiment scheme. By comparing the permeability and porosity of the core sample prepared with the actual gas hydrate bearing formation, and evaluating and analyzing the result of experiment, formulation of core and technique, a set of artificial core sample formulation and technique suitable for simulating gas hydrate were obtained. Cores with vary porosity and permeability could be prepared for related experimental tests. This work makes up for the shortage of natural hydrate core sample, therefore it's important for the ongoing of the simulating experiment and facilitates the future work in the laboratory.
In the fourth chapter, the basic rules and behaviors of invasion of gas hydrate bearing formation by drilling fluid were studied by experimental simulation. At first, the process and principle of the invasion were analyzed qualitatively. Then the comprehensive simulating device for seepage and exploitation were introduced. The device was designed for the study of the invasion of gas hydrate formation by drilling fluid, with other functions as well. By utilizing the device and optimized artificial core samples, the experiment of gas hydrate forming and dissociation were conducted, which built the basis for the simulating experiment of gas hydrate invasion. The brine was applied to simulating the marine drilling fluid and the experiment of drilling fluid invasion were carried out. The problems were studied by investigating the evolution of pressure, temperature and resistivity during the process of invasion. The results indicated that the invasion of drilling fluid would disturb the in-situ gas hydrate bearing formation,
In the fifth chapter, based on the result of experimental modeling, the problems of drilling fluid were further studied by numerical simulation. Firstly, the numerical simulation exploitation software TOUGH+HYDRATE was introduced and the setup of theoretical model was analyzed. Then the gas hydrate drilling program (GMGS-1) at Shenhu area, northern South China sea were taken as a background, the dynamic process of invasion of marine gas hydrate bearing formation by drilling fluid and its influence on the formation. The factors affecting the invasion of drilling fluid including density, temperature, and salinity of the drilling fluid, absolute permeability and gas hydrate saturation were analyzed as well.
In the last chapter, the main conclusions, understandings and innovations were demonstrated, and the shortcomings and suggestions were also proposed.
自从上世纪60年代和80年代分别在永久冻土带和海洋区域发现天然气水合物以来,其在资源、环境和全球变化中的重要意义引起了各国政府、各大油气公司和各类学术研究机构的极大关注,成为当前能源和地球科学研究的一大热点。其研究涉及的领域已从最初的天然气管道的流动保障扩展到资源潜力、钻井安全、地质灾害、碳循环与气候变化等。天然气水合物研究水平已在某种程度上反应了一个国家的综合科技实力和可持续发展潜力。
研究表明,未来针对水合物研究的关键任务是将其由基础研究和发展规划向全面的水合物开采等应用性研究转变。由于已成功实施了若干水合物研究项目,并具有近海岸和阿拉斯加永久冻土带富存水合物的先天优势,美国成为水合物研究领域的引领者之一,其制定出2015年前对阿拉斯加北坡冻土区水合物开采、2025年前实现对海洋地区水合物开采的计划。此外,日本、加拿大、德国、英国、俄罗斯、挪威、韩国、印度、中国等国家都开展了大量的水合物研究工作,其中日本也制定了2018年实现水合物商业开采的计划,西班牙、尼日利亚、智利、哥伦比亚、新西兰和秘鲁等也都对水合物研究表现出了浓厚的兴趣。初步勘探和研究表明,我国水合物储量较为丰富,开展水合物相关研究对满足我国能源需求具有重要战略意义,我国已把水合物开发列入“国家中长期(2006-2020年)科技发展规划”中。与宏观政策相适应,我国有关水合物调查研究、技术体系、实验模拟及其与环境、气候有关的科研活动也有较大幅度增加。
勘探工作是进行水合物储层物性、地质成藏等基础研究,资源评价、开采技术等应用研究的主要资料来源和强有力支撑。应用于水合物地层的勘探方法主要包括地质、地球物理、地球化学和钻探取心等四类。其中钻探取心是最为直接的勘探手段,可以直接获取原位水合物地层的样品进行分析；地球物理测井在取心困难的情况下就成为最为接近水合物地层原位状态的勘探方法。这两种方法在水合物勘探中占有重要地位,而这两种勘探方式都离不开钻井。
通常海洋水合物地层压实固结程度较差,在钻井过程中若采用欠平衡钻井方式,则不利于井壁力学平衡。而且水合物还会因减压而分解,导致地层力学强度急剧降低,更不利于井壁稳定和井内安全。因此,维持孔内压力大于地层孔隙压力、同时不高于破裂压力是水合物钻井较为可取的安全方式。在此条件下,钻井液在水力压差的作用下驱走井壁周围地层孔隙中的原生流体(气、水)而侵入地层。钻井实践证明,钻井液侵入会改变井壁围岩特性,比如岩石强度、孔隙压力等。与钻井液侵入常规油气地层所不同的是,受钻具摩擦生热以及钻井液温度影响,钻井液侵入含水合物地层过程中还可能伴随有水合物的分解,从而加速井壁失稳。此外,在众多的地球物理测井属性中,电阻率和声波速度受水合物的影响最突出。由于海洋区域水合物赋存在固结不好的沉积物中,而声波受压实系数的影响较重,因而电阻率测井又比声波测井和其他测井方法更稳定和可靠。但是,钻井过程中钻井液循环和侵入却对电阻率测井有着显著的影响。比如为抑制水合物在井内形成和保护海洋环境,深水油气和水合物钻井通常采用高盐聚合物水基钻井液体系,当高矿化度钻井液滤液侵入时会严重影响储层特征和电阻率测井准确性。而且盐是热力学抑制剂,其随钻井液侵入会使水合物相平衡曲线向左迁移,导致地层中水合物分解,进一步影响测井识别评价、井周地层稳定和井内安全。因此,研究耦合有水合物分解的水基钻井液侵入含水合物地层的动态特性及其对地层的影响规律对钻井安全预防、测井准确识别和评价、水合物储层保护、水合物资源和环境评估等都具有重要意义和应用价值。
针对上述分析,了解钻井液侵入含水合物地层的特性,并采用实验模拟和数值模拟等手段展开研究具有重要意义,据此,论文的主要研究内容和路线包括以下几个方面：
(1)分析海洋及冻土区典型水合物储层特征,进行人工岩样的制备研究
水合物散布于砂(岩)层孔隙空间是海洋和冻土区最为典型的水合物储层类型之一,同时也最具开采潜力。论文首先对实际的水合物地层岩石物理性质做详细归纳和总结,在此基础上,分析了分散型水合物砂岩储层的主要矿物组成、岩石颗粒尺寸、孔隙分布及连通性、渗流特性等岩石物理特征；使用自主研发的人工岩心制备装置进行人造岩样的制备,并用其模拟真实水合物储层骨架；使用压汞实验仪和渗透率测量仪对所制人工岩样进行孔隙结构分析和渗透性测试,分析人工岩样的物性特征,得到优选的岩心配方和制备工艺；
(2)进行钻井液侵入水合物地层的实验模拟研究
将制备的人造岩心用于模拟实际的水合物沉积层骨架,使用自主研发、委托厂商生产的“天然气水合物渗流开采综合模拟装置”开展钻井液侵入含水合物地层的相关实验研究,旨在了解钻井液侵入过程中地层物性的变化情况,即掌握钻井液侵入过程中水合物分解程度、地层压力、温度、电学性质的变化等基本规律,并与后续的数值模拟研究相互补充和参考；
(3)进行钻井液侵入水合物地层的数值模拟研究
在实验模拟受到时间和实验设备功能限制的情况下,通过数值模拟对钻井液侵入水合物地层的相关特性进行了更深入的研究。论文以中国南海神狐海域水合物地层为背景,利用劳伦斯伯克利国家实验室开发的水合物开采数值模拟软件TOUGH+HYDRATE分析了一定条件下钻井液侵入海洋水合物储层的动态过程及其对地层的影响规律,进行了钻井液侵入水合物地层所受的影响因素分析。
本论文共六个部分,主要章节内容包括：
第一章：本章为论文的绪论部分,首先对天然气水合物做了简单介绍,总结了国内外对天然气水合物的研究历程和现状；对其在全球的分布及储量评估等能源意义,以及自然界中的天然气水合物和人为勘探、开发可能带来的环境问题进行了介绍；并对水合物主要勘探计划和进展情况进行了归纳；介绍了水合物勘探的主要方法,集中分析了水合物地层钻井面临的困难和挑战；引出钻井液侵入水合物地层可能带来的一系列问题,指出了论文研究的目的和意义,并介绍了论文研究的主要内容和技术路线。
第二章：本章主要对实际的水合物地层物性进行总结和分析,目的是弄清楚研究对象的基本特征。从微观、中观和宏观三个尺度对原位储层中水合物的分布模式进行了总结和分类；对水合物地层的电学、声学、热学等基本物性,以及孔隙度、水合物饱和度、渗透性、力学性质等储层特性进行了分析和总结,并对通常获取水合物地层物性的实验模拟、实际岩心分析和测井解释三种途径进行了介绍。
第三章：目前实验室内模拟水合物沉积物样品时都未全面考虑样品骨架的物性是否贴近实际自然界中的水合物沉积物骨架,从而导致实验结果很难反映或准确代表自然界中的实际情况。为此,本章在第二章对含水合物地层物性进行总结和分析的基础上,对用于模拟实际水合物地层人造岩心的制备技术进行了研究。从目前常规的人造岩心种类中选取适合研究目标的人造岩心技术,确定所模拟地层的基本物性参数后设计正交实验。通过对所制得岩心进行渗透率和孔隙度测量,对比实际水合物地层资料,对实验结果和岩心配方、工艺进行评价和分析,得到了一套较为合理的模拟水合物地层人造岩心制作的配方和工艺,可配制不同孔隙度和渗透率的人造岩心用于相关实验研究。这一工作弥补了水合物地层天然岩心紧缺的不足,对本研究的实验部分顺利进行,及今后水合物室内实验研究提供了便利,具有重要意义。
第四章：本章主要是通过实验模拟的手段研究钻井液侵入水合物地层的基本规律和特性。首先对钻井液侵入含水合物地层的过程及原理作了定性分析；然后,介绍了本研究开展过程中自主研制的“水合物地层渗流与开采综合模拟装置”,该装置主要设计初衷就是为研究钻井液侵入含水合物地层特性及其对测井的影响机理,同时也包括了其它功能,比如开采方法研究,综合性较强；利用该设备和第三章优选出的人造岩心进行了水合物形成和分解实验,为钻井液侵入实验的开展奠定了基础；使用盐水模拟实际的海洋钻井液,进行了钻井液侵入水合物地层实验,测试了侵入过程中压力、温度及电阻率变化情况,进一步阐述了钻井液侵入会对原位水合物地层产生扰动。
第五章：在实验模拟的基础上,本章通过数值模拟的方法对钻井液侵入水合物地层特性展开了进一步研究。首先介绍了所使用的水合物开采数值模拟软件TOUGH+HYDRATE的基本情况,对理论模型的建立进行了分析；然后,以南海北部神狐海域天然气水合物钻探工程(GMGS-1)为背景,研究了一定条件下钻井液侵入海洋水合物储层的动态过程及其对地层的影响规律,分析了钻井液密度、温度、盐度以及地层绝对渗透率和地层水合物饱和度对钻井液侵入的影响规律。
第六章：阐述了本文所得出的主要结论和认识,论文的主要创新点,提出了存在的不足和建议。
Natural gas hydrate is a kind of gas hydrate, ice alike crystalline compound composed of water and natural gas molecules with cage structure. Because of its appearance and could ignite with fire, so it is also called "flammable ice","solid gas" or "gas ice". The molecules of natural gas including hydrocarbon (CH4、C2H6、C3H8、C4H10and homologous series) and non-hydrocarbon gases (CO2、N2、H2S etc.), occupied the cavities in water cages. Since methane is the main component of natural gas, the natural gas hydrate with more than99%of methane molecules is commonly referred to as methane hydrate. Gas hydrate is a kind of metastable material, can only be stable under the condition of high pressure and low temperature, mainly exist in bottom sea continental shelf sediments, arctic permafrost, and widely distributed in the slope zone of mainland and islands, uplift of active and passive continental margin, arctic continental shelf and some deep water environment of ocean and inland lake, and even be found in outer space.
Since the natural gas hydrates were found in permafrost and seafloor in1960s and1980s respectively, its significance in resource, environment and global warming has evoked the attention of governments, petroleum giants and academic institutions. The study on gas hydrates including flow assurance, drilling operation safety, geological hazard, carbon cycle and climate change, etc., has become a hotspot in earth science and energy research. The level of natural gas research is a reflection of the comprehensive science and technology and potential of sustainable development of a nation to some extent.
Studies indicated that the future research of gas hydrate have transformed from the basic research and development plan to applied research such as comprehensive gas hydrate exploitation. The United States has successfully implemented hydrate research program, and owns offshore and Alaska permafrost that have abundant hydrate distribution, is one of the leading countries in gas hydrate research, and have planned to exploit gas hydrate in north slope of Alaska permafrost before2015, and in marine sediments before2025. In addition, Japan, Canada, Germany, Britain, Russia, Norway, South Korea, India, China and other countries have also carried out a large amount of hydrate research. Japan has also planned to commercially exploit gas hydrate before2018. Nigeria, Spain, Chile, Colombia, Peru and New Zealand also showed a strong interest in hydrate research.
Preliminary explorations show that the hydrate resource is abundant in China, and the hydrate research has important strategic significance in meeting the energy demand of the country. The gas hydrate research program has been listed in the major project of large scale oil-gas filed and coal bed in the "national medium and long-term (2006-2020) science and technology development plan" in China. In accordance with the macroeconomic policy, the gas hydrate research related scientific activities including investigation, technical system, experimental simulation and environmental and climate issues have increased significantly. Natural gas hydrate has become an important research focus of energy science, and deeply involved in the climate, environment, high technology and global sustainable development.
Gas hydrate exploration is the main source of data and support for basic research, such as physical property of hydrate reservoir, geological accumulation and application research including resource evaluation and production technique of gas hydrate. The prospecting methods applied to the hydrate formation are categorized to geologic, geophysical, geochemical and coring drilling. Among them, the coring drilling is the most direct means of exploration, the samples of in-situ hydrates can be directly obtained from hydrate bearing formation for analysis, whereas the geophysical well logging is the method that most close to the in-situ state of hydrate formation when coring is difficult. Therefore, these two methods play an important role in gas hydrates exploration, and neither could be done without drilling.
Usually marine hydrate formation is in poor degree of consolidation, if it is drilled by underbalanced drilling methods, is not conducive to borehole stability. Hydrate decomposes under reduced pressure, which also significant reducing the strength of formation, leads to severe borehole wall instability. Therefore, it is preferable to maintain borehole pressure greater than the formation pore pressure while less than fracture pressure during the process of hydrate drilling operation. Under the condition of overbalance, the drilling fluid (i.e. the water based drilling fluid) displaces the original pore fluid (gas and water) around the borehole wall and invades the formation by the pressure differential. The practice of drilling operation indicates that the invasion of drilling fluid would alter the rock properties at the borehole wall, including rock strength, pore pressure etc. Different to invasion of common oil and gas reservoir, the invasion of drilling fluid in gas hydrate formation accompanied by hydrate decomposition caused by drilling tools friction and the temperature of drilling fluid. As a result, the instable of borehole wall accelerated. The resistivity and wave speed are mostly influenced by gas hydrate dissociation amongst all the geophysical logging parameters. The marine hydrate bearing sediments are poorly consolidated, so the acoustic speed is highly affected by compact coefficient, therefore the result of resistivity is more stable and reliable. However, the circulation and invasion of drilling fluid have great influence on resistivity logging. For instance, the high concentration salt and polymer water based drilling fluid systems were applied in order to inhibit the reformation in the borehole and protect the marine environment. The invasion of highly mineralization filtrate would severely alter the characteristics of reservoir and accuracy of resistivity logging. The salt, acting as thermodynamic inhibitor, causes the curve of phase equilibrium moving towards left, results in further gas hydrate dissociation, and has greater effects on evaluation of logging, stability of formation around borehole wall and safety within the borehole. Therefore, the study on the dynamic properties and influence on the formation of invasion of gas hydrate bearing formation by water based drilling fluid coupled by gas hydrate dissociation is meaningful and valuable on safety management, accurate identification and evaluation of geophysical logging, protection of gas hydrate reservoir, assessment of gas hydrate resource and environment, and implementation of well observatory system in IODP.
Based on the analysis above, it is important to understand the properties of invasion of gas hydrate formation by drilling fluid, and carry out study by experimental simulation and numerical modeling. The main contents and path of research including:
(1) Analysis of the typical characteristic of marine and permafrost gas hydrate bearing formations, and preparation of artificial gas hydrate sample.
The research on gas hydrate bearing formation of major ocean and permafrost shows that the gas hydrate distributed in sandstone pore is the most typical hydrate reservoir, and is the most promising energy resources. In the paper, the physical properties of actual gas hydrate bearing formation were firstly summed up. Then the main mineral component, rock particle size, pore distribution and connectivity and seepage characteristics of disseminated type of hydrate formation were analyzed. The artificial core preparation device was independently developed for the preparation of rock sample, in order to simulate the real gas hydrate reservoir.
The mercury intrusion instrument and permeability measuring apparatus were applied for the analysis of pore structure and testing of permeability of artificial rock sample. After analyzing the physical property of the artificial stone sample, the optimization of formulation and manufacturing technique of artificial core sample were formed.
(2) The simulation research on invasion of gas hydrate bearing formation by drilling fluid.
The optimized artificial core samples were selected for simulating the skeleton of gas hydrate bearing sediments. With the application of "comprehensive natural gas hydrate seepage exploitation device" which was self-designed, the research were carried out related to the invasion of simulating gas hydrate bearing formation by drilling fluid, aimed at understanding the change of physical property of formation during the process of drilling fluid invasion. That is obtaining the basic rules of gas hydrate decompose, the evolution of pressure and temperature of formation, and the change of electrical properties during the process as a reference to the result of numerical simulation in the subsequent chapters.
(3) Numerical simulation of invasion of gas hydrate bearing formation by drilling fluid.
Since the simulation experiment was limited by the function of equipment and time expense, implementing the issues related to invasion of hydrate formation by drilling fluid with numerical simulation method is a good supplement for experimental research, and the efficiency of research would also enhanced. The numerical simulation took the gas hydrate bearing formation in Shenhu area, northern South China sea as background, utilizing numerical simulation exploitation software TOUGH+HYDRATE developed by Lawrence Berkeley national laboratory to analyze the dynamic process of drilling fluid invasion of marine gas hydrate and its influence on the formation at certain conditions, and evaluated the factors that involved during the process.
The paper consists of six parts. The main contents are as follows:
In the first chapter, firstly the natural gas hydrates were briefly introduced, and the course and state of art of gas hydrate research home and abroad were overviewed. The global distribution, assessment of reserves, as well as gas hydrates in nature, possible environmental problems brought about by human exploration and development were also introduced. The main gas hydrate exploration programs and progresses were summed up. The main methods of gas hydrate exploration were introduced, and the difficulties and problems faced with during drilling operation were analyzed. The problems related to invasion of gas hydrate bearing formations by drilling fluid were introduced and the aim and meaning of the research were also illustrated with the main content and technical route.
In the second chapter, the physical properties of actual gas hydrate bearing formation were summed up and analyzed, for the purpose of understanding the basic characteristics of the object of research. The distribution patterns of in situ gas hydrate reservoir were summarized and classified from the macro, meso and micro dimension. The basic physical properties of gas hydrate bearing formations, such as electrical, acoustic, thermal, and porosity, gas hydrate saturation, permeability and mechanical properties were summarized as well. Finally, the three approaches, experimental simulation, actual core analysis and logging interpretation for obtaining the physical properties of actual gas hydrate were compared.
In the third chapter, the technique of artificial core sample preparation for simulating actual gas hydrate bearing formation was studied. First chose the appropriate technique of artificial core sample from the conventional methods available. Then the basic physical parameters of the simulating formation were determined before the design of the orthogonal experiment scheme. By comparing the permeability and porosity of the core sample prepared with the actual gas hydrate bearing formation, and evaluating and analyzing the result of experiment, formulation of core and technique, a set of artificial core sample formulation and technique suitable for simulating gas hydrate were obtained. Cores with vary porosity and permeability could be prepared for related experimental tests. This work makes up for the shortage of natural hydrate core sample, therefore it's important for the ongoing of the simulating experiment and facilitates the future work in the laboratory.
In the fourth chapter, the basic rules and behaviors of invasion of gas hydrate bearing formation by drilling fluid were studied by experimental simulation. At first, the process and principle of the invasion were analyzed qualitatively. Then the comprehensive simulating device for seepage and exploitation were introduced. The device was designed for the study of the invasion of gas hydrate formation by drilling fluid, with other functions as well. By utilizing the device and optimized artificial core samples, the experiment of gas hydrate forming and dissociation were conducted, which built the basis for the simulating experiment of gas hydrate invasion. The brine was applied to simulating the marine drilling fluid and the experiment of drilling fluid invasion were carried out. The problems were studied by investigating the evolution of pressure, temperature and resistivity during the process of invasion. The results indicated that the invasion of drilling fluid would disturb the in-situ gas hydrate bearing formation,
In the fifth chapter, based on the result of experimental modeling, the problems of drilling fluid were further studied by numerical simulation. Firstly, the numerical simulation exploitation software TOUGH+HYDRATE was introduced and the setup of theoretical model was analyzed. Then the gas hydrate drilling program (GMGS-1) at Shenhu area, northern South China sea were taken as a background, the dynamic process of invasion of marine gas hydrate bearing formation by drilling fluid and its influence on the formation. The factors affecting the invasion of drilling fluid including density, temperature, and salinity of the drilling fluid, absolute permeability and gas hydrate saturation were analyzed as well.
In the last chapter, the main conclusions, understandings and innovations were demonstrated, and the shortcomings and suggestions were also proposed.
引文
[1]Sloan ED. Clathrate hydrate measurements:microscopic, mesoscopic, and macroscopic[J]. Journal of Chemical Thermodynamics.2003,35(1):41-53.
[2]Sloan ED. Fundamental principles and applications of natural gas hydrates[J]. Nature.2003, 426(6964):353-359.
[3]蒋国盛.天然气水合物的勘探与开发[M]：中国地质大学出版社；2002.
[4]宋召军,刘立.天然气水合物研究现状与展望[J].吉林地质.2003,(004)：64-68.
[5]Lee JY, Ryu BJ, Yun TS et al. Review on the gas hydrate development and production as a new energy resource[J]. KSCE Journal of Civil Engineering.2011,15(4):689-696.
[6]Stoll RD, Bryan GM. Physical properties of sediments containing gas hydrates[J]. Journal of Geophysical Research.1979,84(B4):1629-1634.
[7]Gudmundsson J, Borrehaug A. Frozen hydrate for transport of natural gas. In:2nd International Conference on Natural Gas Hydrate; 1996; Toulouse, France; 1996.
[8]Circone S, Stern LA, Kirby SH. The effect of elevated methane pressure on methane hydrate dissociation[J]. American Mineralogist.2004,89(8-9):1192-1201.
[9]PAULCK UW, DILLON William P. Is the extent of glaciation limited by marine g as hydrates?[J]. Geophysical Research Letters.1991:432-434.
[10]Kvenvolden KA. A review of the geochemistry of methane in natural gas hydrate[J]. Organic Geochemistry.1995,23(11-12):997-1008.
[11]Collett T. Detection and Evaluation of the In-Situ Natural Gas Hydrates in the North Slope Region, Alaska. In; 1983.
[12]Brown TD, Taylor CE, Bernardo MP. Rapid Gas Hydrate Formation Processes:Will They Work?[J]. Energies.2010,3(6):1154-1175.
[13]Happel J, Hnatow MA, Meyer H. The Study of Separation of Nitrogen from Methane by Hydrate Formation Using a Novel Apparatusa[J]. Annals of the New York Academy of Sciences.1994,715(1):412-424.
[14]Mori YH, Mori T. Formation of Gas Hydrate with Cfc Alternative R-134a[J]. Aiche Journal. 1989,35(7):1227-1228.
[15]Aliev AM, Yusifov RY, Kuliev AR et al Method of gas hydrate formation for evaluation of water desalination[J]. Russian Journal of Applied Chemistry.2008,81(4):588-591.
[16]宁伏龙,蒋国盛,张凌等.天然气水合物实验装置及其发展趋势[J].海洋石油.2008,28(002)：68-72.
[17]National Research Council of the National Academies. Realizing the Energy Potential of Methane Hydrate for the United States. Washington:The National Academies Press; 2010.
[18]Gabitto J, Barrufet M. Gas Hydrates Research Programs:An International Review. United States:Prairie View A&M University; 2009.
[19]许红,黄君权,夏斌等.最新国际天然气水合物研究现状与资源潜力评估(上)[J].地质与勘探.2005,25(5)：1-5.
[20]Boswell R, Collett TS. Current perspectives on gas hydrate resources[J]. Energy Environ. Sci. 2010,4(4):1206-1215.
[21]Sloan ED, Koh CA. Clathrate Hydrates of Natural Gases.3rd Ed ed. Boca Raton, FL, USA: CRC Press; 2008.
[22]Wood W, Jung W. Modeling the extent of Earth's marine methane hydrate cryosphere. In: Englezos P, Ripmeester JA, editors. Proceedings of the 6th International Conference on Gas Hydrates(ICGH 2008); 2008; Vancouver, British Columbia, CANADA; 2008. p.6-10.
[23]Trofimuk A, Cherskiy N, Tsarev V. Accumulation of natural gases in zones of hydrate-formation in the hydrosphere[J]. Dolady Akademii Nauk SSSR.1973,212: 931-934.
[24]涂运中.海洋天然气水合物地层钻井的钻井液研究[D].武汉：中国地质大学；2010.
[25]Boswell R. Is Gas Hydrate Energy Within Reach?[J]. Science.2009,325(5943):957.
[26]Fujii T, Saeki T, Kobayashi T et al. Resource assessment of methane hydrate in the eastern Nankai Trough. In:Offshore Technology Conference(OTC 08); Houston,Texas; 2008.
[27]Frye M. Preliminary evaluation of in-place gas hydrate resources:Gulf of Mexico outer continental shelf; 2008.
[28]Collett TS, Agena WF, Lee MW et al. Assessment of gas hydrate resources on the North Slope, Alaska,2008[J]. US Geological Survey Fact Sheet 2008-3073.2008:4p.
[29]Makogon Y, Holditch S, Makogon T. Russian field illustrates gas-hydrate production[J]. Oil & Gas Journal.2005,103(5):43-47.
[30]Walsh T, Stokes P, Panda M et al. Characterization and Quantification of the Methane Hydrate Resource Potential Associated with the Barrow Gas Field. In:Proceedings of the 6th International Conference on Gas Hydrate(ICGH 2008); 2008; Vancouver,British Columbia; 2008.
[31]Heimann M. How stable is the methane cycle?[J]. Science.2010,327(5970):1211.
[32]Shine KP, Derwent R, Wuebbles D et al. Radiative forcing of climate. In:Cambridge University Press, Cambridge, United Kingdom and New York, NY, USA; 1990:41-68.
[33]MacDonald GJ. Role of methane clathrates in past and future climates[J]. Climatic Change. 1990,16(3):247-281.
[34]Watson R, Rodhe H, Oeschger H et al. Greenhouse gases and aerosols[J]. Climate change:the IPCC scientific assessment.1990,1:17.
[35]Kvenvolden KA. Gas Hydrates-Geological Perspective and Global Change[J]. Reviews of Geophysics.1993,31(2):173-187.
[36]Kvenvolden KA. Methane hydrates and global climate[J]. Global Biogeochemical Cycles.1988, 2(3):221-229.
[37]Solomon S. Climate change 2007:the physical science basis:contribution of Working Group I to the Fourth Assessment Report of the Intergovernmental Panel on Climate Change: Cambridge Univ Pr; 2007.
[38]Ning F, Yu Y, Kjelstrup S et al. Mechanical properties of clathrate hydrates:status and perspectives[J]. Energy Environ. Sci.2012,5(5):6779-6795.
[39]Liggins F, Betts RA, McGuire B. Projected future climate changes in the context of geological and geomorphological hazards[J]. Philosophical Transactions of the Royal Society A: Mathematical, Physical and Engineering Sciences.2010,368(1919):2347-2367.
[40]Akerman HJ, Johansson M. Thawing permafrost and thicker active layers in sub-arctic Sweden[J]. Permafrost and Periglacial Processes.2008,19(3):279-292.
[41]Lawrence DM, Slater AG, Tomas RA et al. Accelerated Arctic land warming and permafrost degradation during rapid sea ice loss[J]. Geophysical Research Letters.2008,35(11): L11506.
[42]Maslin M, Owen M, Betts R et al. Gas hydrates:past and future geohazard?[J]. Philosophical Transactions of the Royal Society A:Mathematical, Physical and Engineering Sciences.2010, 368(1919):2369-2393.
[43]Masuda Y, Yamamoto K, Tadaaki S et al. Japan's methane hydrate R&D program progresses to phase 2[J]. Natural Gas & Oil.2018,304:285-4541.
[44]Dallimore S, Collett T. Scientific results from the Mallik 2002 gas hydrate production research well program, Mackenzie Delta, Northwest Territories, Canada:Ottawa (Ont.); 2005.
[45]Hunter RB, Collett TS, Boswell R et al. Mount Elbert Gas Hydrate Stratigraphic Test Well, Alaska North Slope:Overview of scientific and technical program[J]. Marine and Petroleum Geology.2011,28(2):295-310.
[46]Prensky S. A review of gas hydrates and formation evaluation of hydrate-bearing reservoirs. In; 1995; 1995.
[47]Nouze H, Lafoy Y, Geli L. First results of a high resolution seismic study of a bottom simulating reflector in the fairway basin, offshore new Caledonia. In; 2005; 2005.
[48]Tinivella U, Accaino F, Della Vedova B. Gas hydrates and active mud volcanism on the South Shetland continental margin, Antarctic Peninsula[J]. Geo-Marine Letters.2008,28(2): 97-106.
[49]Holbrook W, Hoskins H, Wood W et al. Leg 164 Science Party,1996. Methane hydrate and free gas on the Blake Ridge from vertical seismic profiling[J]. Science.273(5283):1840"C1843.
[50]Collett TS. A review of well-log analysis techniques used to assess gas-hydrate-bearing reservoirs[J]. Geophysical monograph.2001,124:189-210.
[51]McGuire D, Runyon S, Williams T et al. Gas hydrate exploration with 3D VSP technology, North Slope, Alaska[J].2005.
[52]张树林,夏斌.南海北部含油气盆地地层压力预测与监控技术研究[J].石油物探.2004,43(6).
[53]张树林.天然气水合物地震勘探关键技术研究[J].天然气工业.2007,9：365-370.
[54]Dai J, Xu H, Snyder F et al. Detection and estimation of gas hydrates using rock physics and seismic inversion:Examples from the northern deepwater Gulf of Mexico[J]. The Leading Edge.2004,23(1):60.
[55]Chand S, Minshull T, Gei D et al. Elastic velocity models for gas hydrate bearing sediments:a comparison[J]. Geophysical Journal International.2004,159(2):573-590.
[56]Lee M, Hutchinson D, Collett T et al. Seismic velocities for hydrate-bearing sediments using weighted equation[J]. Journal of Geophysical Research.1996,101(B9):20347-20320,20358.
[57]Helgerud M, Dvorkin J, Nur A et al. Elastic-wave velocity in marine sediments with gas hydrates:Effective medium modeling[J]. Geophysical Research Letters.1999,26(13): 2021-2024.
[58]吴志强.地震反射技术在水合物调查评价中的应用前景及设想[J]. Marine Geology.2001, 17(7).
[59]张光学,张明,杨胜雄等.海域天然气水合物地震综合探测技术发展及应用[J].第十届中国科协年会“深水技术产业发展国际研讨会”论文集.2008.
[60]Worthington PF. Petrophysical evaluation of gas-hydrate formations[J]. Petroleum Geoscience. 2010,16(1):53.
[61]Collett T. Well log characterization of sediment porosities in gas-hydrate-bearing reservoirs. In; 1998; 1998.
[62]Collett TS. Well log evaluation of gas hydrate saturations. In; 1998; 1998.
[63]Ebeltoft H, Yousif M, Soergard E. Hydrate Control During Deepwater Drilling:Overview and New Drilling-Fluids Formulations[J]. SPE Drilling and Completion.2001,16(1):19-26.
[64]宁伏龙,吴翔,张凌等.天然气水合物地层钻井时水基钻井液性能实验研究[J].天然气工业.2006.
[65]宁伏龙,蒋国盛,张凌等.影响含天然气水合物地层井壁稳定的关键因素分析[J].石油钻探技术.2008,36(003)：59-61.
[66]张建华,胡启.钻井泥浆滤液侵入储集层的理计算模型[J].石油学报.1994,15(4)：73-78.
[67]Collett TS. A review of well-log analysis techniques used to assess gas-hydrate-bearing reservoirs. In:Geophysical monograph; 2001:189-210.
[68]邓少贵,李智强,范宜仁等.斜井泥浆侵入仿真及其阵列侧向测井响应数值模拟[J].地球物理学报.2010,53(4).
[69]Ebeltoft H, Yousif M, Soergard E. Hydrate control during deepwater drilling:Overview and new drilling-fluids formulations[J]. SPE Drilling & Completion.2001,16(1):19-26.
[70]Ecker C, Dvorkin J, Nur AM. Estimating the amount of gas hydrate and free gas from marine seismic data[J]. Geophysics.2000,65(2):565.
[71]Dvorkin J, Helgerud M, Waite W et al. Introduction to physical properties and elasticity models[J]. Natural Gas Hydrate in Oceanic and Permafrost Environments.2000:245"C260.
[72]Holland M, Schultheiss P, Roberts J et al. Observed gas hydrate morphologies in marine sediments. In; 2008; 2008. p.6-10.
[73]Dvorkin J, Nur A. Seismic amplitudes from gas hydrates[J]. Hart's E & P.2007,80(11):97-98.
[74]Malone R. Gas hydrates topical report[J]. DOE/METC/SP-218, US Department of Energy. 1985:33-50.
[75]Lovell M, Jackson P, Gunn D et al. Petrophysical characterisation of gas hydrate sediments. In; 2002; 2002.
[76]Dai J, Kleinberg R, Xu H et al. Rock Physics Models Of Gas Hydrates And Their Implications In Seismic Detection. In; 2005; 2005.
[77]Dvorkin J, Nur A. Elasticity of high(?)\porosity sandstones:Theory for two North Sea data sets[J]. Geophysics.1996,61:1363.
[78]Fujii K, Yasuda M, Cho B et al. Development of a monitoring system for the JOGMEC/NRCan/Aurora Mallik gas hydrate production test program. In; 2008; 2008.
[79]Riedel M, Bellefleur G, Dallimore SR et al. Amplitude and frequency anomalies in regional 3D seismic data surrounding the Mallik 5L-38 research site, Mackenzie Delta, Northwest Territories, Canada[J]. Geophysics.2006,71(6):B183-B191.
[80]Suzuki K, Ebinuma T, NARITA H. Estimation of the In-Situ Permeabilities of Nankai Trough Hydrate Bearing Sediments From Pressure Temparature Core Samplar (PTCS) Core Measurements. In; 2008; 2008.
[81]Cook AE, Goldberg D, Kleinberg RL. Fracture-controlled gas hydrate systems in the northern Gulf of Mexico[J]. Marine and Petroleum Geology.2008,25(9):932-941.
[82]Collett T, Riedel M, Cochran J et al. Indian national gas hydrate program expedition 01 initial reports:Expedition 01 of the Indian National Gas Hydrate Program from Mumbai, India to Chennai, India:Sites NGHP-01-01 through NGHP-01-21, April 2006-August 2006, Directorate General of Hydrocarbons, Ministry of Petroleum and Natural Gas (India), Noida, India; 2008.
[83]Collett T. Geology of Marine Gas Hydrates and Their Global Distribution. In; 2008; 2008.
[84]Scott M, Randolph P, Pangborn J. Assessment of methane hydrates(permafrost zone of Alaska and deep sediments in oceans)[Final Report, Dec.1978-Jun.1980][J].1980.
[85]Paull CK, Ussler W, Borowski WS et al. Methane-rich plumes on the Carolina continental rise: associations with gas hydrates[J]. Geology.1995,23(1):89.
[86]Yang S, Zhang H, Wu N et al. High concentration hydrate in disseminated forms obtained in Shenhu area, North Slope of South China Sea. In; 2008; 2008. p.6-10.
[87]Spangenberg E. Modeling of the influence of gas hydrate content on the electrical properties of porous sediments[J]. Journal of geophysical research.2001,106(B4):6535-6548.
[88]Moridis G, Collett T, Pooladi-Darvish M et al. Challenges, Uncertainties and Issues Facing Gas Production From Hydrate Deposits in Geologic Systems. In; 2010; 2010.
[89]Judge A. Natural gas hydrates in Canada. In; 1981; 1981. p.320-328.
[90]Jin YK, Lee MW, Collett TS. Relationship of gas hydrate concentration to porosity and reflection amplitude in a research well, Mackenzie Delta, Canada[J]. Marine and Petroleum Geology.2002,19(4):407-415.
[91]Ren SR, Liu Y, Zhang W. Acoustic velocity and electrical resistance of hydrate bearing sediments[J]. Journal of Petroleum Science and Engineering.2010,70(1-2):52-56.
[92]Kleinberg R, Dai J. Estimation Of The Mechanical Properties Of Natural Gas Hydrate Deposits From Petrophysical Measurements. In; 2005; 2005.
[93]Murray D, Kleinberg R, Sinha B et al. Formation evaluation of gas hydrate reservoirs. In; 2005; 2005.
[94]Zimmerman RW, King MS. The effect of the extent of freezing on seismic velocities in unconsolidated permafrost[J]. Geophysics.1986,51:1285.
[95]Foley JE, Burns DR. The sensitivity of seismic responses to gas hydrates. Final report:New England Research, Inc., White River Junction, VT (United States); 1992.
[96]Dvorkin J, Nur A. Rock physics for characterization of gas hydrates[J]. United States Geological Survey, Professional Paper;(United States).1993,1570.
[97]Pearson C, Murphy J, Halleck P et al. Sonic and resistivity measurements on Berea sandstone containing tetrahydrofuran hydrates:a possible analog to natural gas hydrate deposits. In; 1983; 1983. p.973 C978.
[98]Winters WJ, Waite W, Mason D et al. Methane gas hydrate effect on sediment acoustic and strength properties[J]. Journal of Petroleum Science and Engineering.2007,56(1-3): 127-135.
[99]Pearson C. Physical properties of natural gas hydrate deposits:Los Alamos National Lab., NM (USA); 1982.
[100]Pearson C, Halleck P, McGuire P et al. Natural gas hydrate deposits:A review of in situ properties[J]. The Journal of Physical Chemistry.1983,87(21):4180-4185.
[101]Waite W. Thermal conductivity measurements in porous mixtures of methane hydrate and quartz sand[J]. Geophysical Research Letters.2002,29(24):2229.
[102]Henninges J, Huenges E, Burkhardt H. In situ thermal conductivity of gas-hydrate-bearing sediments of the Mallik 5L-38 well[J]. Journal of geophysical research.2005,110(B11): B11206.
[103]Booth J, Winters W, Dillon W et al. Major occurrences and reservoir concepts of marine clathrate hydrates:implications of field evidence[J]. Geological Society, London, Special Publications.1998,137(1):113.
[104]Ginsburg G. Gas hydrate accumulation in deep-water marine sediments[J]. Geological Society, London, Special Publications.1998,137(1):51.
[105]Lee MW, Collett TS. Integrated analysis of well logs and seismic data to estimate gas hydrate concentrations at Keathley Canyon, Gulf of Mexico [J]. Marine and Petroleum Geology.2008, 25(9):924-931.
[106]Moridis GJ, Sloan ED. Gas production potential of disperse low-saturation hydrate accumulations in oceanic sediments[J]. Energy conversion and management.2007,48(6): 1834-1849.
[107]Anderson BI, Collett TS, Lewis RE et al. Using Open Hole and Cased-Hole Resistivity Logs to Monitor Gas Hydrate Dissociation During a Thermal Test in the Mallik 5L-38 Research Well, Mackenzie Delta, Canada[J]. PETROPHYSICS-HOUSTON-.2008,49(3):285.
[108]Boswell R, Shelander D, Lee M et al. Occurrence of gas hydrate in Oligocene Frio sand: Alaminos Canyon Block 818:Northern Gulf of Mexico [J]. Marine and Petroleum Geology. 2009,26(8):1499-1512.
[109]Uchida T, Tsuji T. Petrophysical properties of natural gas hydrates-bearing sands and their sedimentology in the Nankai Trough[J]. Resource Geology.2004,54(1):79-87.
[110]Jin Y, Nagao J, Hayashi J et al. Assessment of the absolute permeability of natural methane hydrate sediments by microfocus X-ray computed tomography. In. p.93"C96.
[111]Minagawa H, Nishikawa Y, Ikeda I et al. Relation between permeability and pore-size distribution of methane-hydrate-bearing sediments. In; 2008; 2008.
[112]Booth JS, Winters WJ, Dillon WP. Circumstantial evidence of gas hydrate and slope failure associations on the United States Atlantic continental margin[J]. Annals of the New York Academy of Sciences.1994,715(1):487-489.
[113]Winters W, Booth J, Nielsen R et al. A Computer(?)\Controlled Gas Hydrate(?)\Sediment Formation and Triaxial Test System[J]. Annals of the New York Academy of Sciences.1994, 715(1):490-491.
[114]Santamarina JC, Ruppel C. The impact of hydrate saturation on the mechanical, electrical, and thermal properties of hydrate-bearing sand, silts, and clay. In; 2008; 2008. p.6"C10.
[115]Pearson C, Murphy J, Hermes R. Acoustic and resistivity measurements on rock samples containing tetrahydrofuran hydrates:laboratory analogues to natural gas hydrate deposits[J]. Journal of Geophysical Research.1986,91(B14):14132-14114,14138.
[116]Archie G. The electrical resistivity log as an aid in determining some reservoir characteristics: Petroleum Technology, v.5[J]. Technical Publication.1942,1422(8).
[117]Yun T, Narsilio G, Santamarina J et al. Instrumented pressure testing chamber for characterizing sediment cores recovered at in situ hydrostatic pressure[J]. Marine Geology. 2006,229(3-4):285-293.
[118]Minagawa H, Ohmura R, Kamata Y et al. Water permeability measurements of gas hydrate-bearing sediments. In; 2005; 2005. p.398"C401.
[119]Winters W, Pecher I, Waite W et al. Physical properties and rock physics models of sediment containing natural and laboratory-formed methane gas hydrate[J]. American Mineralogist. 2004:1221-1227.
[120]Jackson P, Gunn D, Flint R et al. A non-contacting resistivity imaging method for characterizing whole round core while in its liner[J]. Geological Society, London, Special Publications.1997,122(1):1.
[121]王志勇,韩明俊,李强等.人造填砂岩心渗透率影响因素及控制方法[J].科技创新导报.2008,5.
[122]Falser S, Palmer A, Tan T et al. Testing methane hydrate saturated soil using a line dissociation apparatus[J]. Geotechnical Testing Journal, submitted.2012.
[123]孟庆国,业渝光,胡高伟等.沉积物中水合物含气量测定方法[J].海洋地质前沿.2011,08：66-70.
[124]刘瑜,赵佳飞,郭长松等.Ⅰ型和Ⅱ型结构气体水合物的记忆效应[J].物理化学学报.2011,06：1305-1311.
[125]胡高伟,业渝光,张剑等.松散沉积物中天然气水合物生成、分解过程与声学特性的实验研究[J].现代地质.2008,03：465-474.
[126]Winters W, Walker M, Hunter R et al Physical properties of sediment from the Mount Elbert gas hydrate stratigraphic test well, Alaska North Slope[J]. Marine and Petroleum Geology. 2011,28(2):361-380.
[127]Winters WJ, Dugan B, Collett TS. Physical properties of sediments from Keathley Canyon and Atwater Valley, JIP Gulf of Mexico gas hydrate drilling program[J]. Marine and Petroleum Geology.2008,25(9):896-905.
[128]王永军.钻井液井壁侵入深度技术研究[D].2011.
[129]Ning FL, Wu NY, Jiang GS et al. A Method to Use Solar Energy for the Production of Gas from Marine Hydrate-Bearing Sediments:A Case Study on the Shenhu Area[J]. Energies. 2010,3(12):1861-1879.
[130]李淑霞.天然气水合物开采物理模拟与数值模拟研究；2006.
[131]宋海斌,江为为,张文生等.天然气水合物的海洋地球物理研究进展[J].地球物理学进展.2002,17(2)：224-229.
[132]Li G, Moridis GJ, Zhang K et al. Evaluation of Gas Production Potential from Marine Gas Hydrate Deposits in Shenhu Area of South China Sea[J]. Energy Fuels.2010,24(11): 6018-6033.
[133]Zhang K, Moridis GJ, Wu YS et al. A domain decomposition approach for large-scale simulations of flow processes in hydrate-bearing geologic media. In:Proceedings of the 6th International Conference on Gas Hydrates (ICGH 2008); 2008; Vancouver, British Columbia, Canada; 2008.
[134]Moridis GJ, Kowalsky MB, Pruess K. TOUGH+HYDRATE v1.1 User's Manual:A Code for the Simulation of System Behavior in Hydrate-Bearing Geologic Media. In. Berkeley, California:Lawrence Berkeley National Laboratory University of California; 2009.
[135]Wu N, Yang S, Zhang H et al. Preliminary discussion on gas hydrate reservoir system of Shenhu Area, North Slope of South China Sea[J].2008.
[136]Ning Fulong, Zhang Keni, Wu Nengyou et al. Invasion of drilling mud into gas-hydrate-bearing sediments. Part Ⅰ:effect of drilling mud properties. Geophysical Journal International,2013,193(3):1370-1384
[137]Ning Fulong, Wu Nengyou, Yu Yibing et al. Invasion of drilling mud into gas-hydrate-bearing sediments:Part Ⅱ. Effects of geophysical properties of sediments. Geophys. J. Int.,2013,193 (3):1385-1398
[138]宁伏龙,张可霓,吴能友等.钻井液侵入海洋含水合物地层的一维数值模拟研究.地球物理学报,2013,56(1)：204-218
[139]Moridis GJ, Reagan MT. Gas Production From Oceanic Class 2 Hydrate Accumulations. In: Offshore Technology Conference; 2007; Houston, Texas; 2007.
[140]Johnson A, Patil S, Dandekar A. Experimental investigation of gas-water relative permeability for gas-hydrate-bearing sediments from the Mount Elbert Gas Hydrate Stratigraphic Test Well, Alaska North Slope[J]. Marine and Petroleum Geology.2011,28(2):419-426.
[141]Konno Y, Masuda Y, Takenaka T et al. Numerical Study on Permeability Hysteresis During Hydrate Dissociation in Hot Water Injection. In:Proceedings of the 6th International Conference on Gas Hydrates(ICGH 2008); 2008; Vancouver, British Columbia, Canada; 2008.
[142]Waite WF, Kneafsey TJ, Winters WJ et al. Physical property changes in hydrate-bearing sediment due to depressurization and subsequent repressurization[J]. Journal of Geophysical Research-Solid Earth.2008,113(B7):B07102.
[143]Xu WY, Germanovich LN. Excess pore pressure resulting from methane hydrate dissociation in marine sediments:A theoretical approach[J]. Journal of Geophysical Research-Solid Earth. 2006, 111(B1).
[144]Holtzman R, Juanes R. Thermodynamic and hydrodynamic constraints on overpressure caused by hydrate dissociation:Apore-scale model[J]. Geophysical Research Letters.2011,38.
[145]Yousif M, Abass H, Selim M et al. Experimental and theoretical investigation of methane-gas-hydrate dissociation in porous media[J]. SPE Reservoir Engineering.1991,6(1): 69-76.
[146]Masuda Y, Fujinaga Y, Naganawa S et al. Modeling and experimental studies on dissociation of methane gas hydrates in Berea sandstone cores. In:the 3rd International Conference on Gas Hydrates(ICGH 1999); 1999; Salt Lake City, Utah; 1999.
[147]徐同台.钻井工程井壁稳定新技术.北京：石油工业出版社；1999.
[148]Johnson A, Patil S, Dandekar A. Experimental investigation of gas-water relative permeability for gas hydrate bearing sediments from Mount Elbert gas hydrate stratigraphic test well, Alaska North Slope[J]. Marine and Petroleum Geology.2009.
[149]黄兴.水合物对多孔介质渗透性影响的实验研究：大连理工大学；2010.
[150]宋永臣,黄兴,刘瑜等.含甲烷水合物多孔介质渗透性的实验研究[J].热科学与技术.2010,9(001)：51-57.
[2]Sloan ED. Fundamental principles and applications of natural gas hydrates[J]. Nature.2003, 426(6964):353-359.
[3]蒋国盛.天然气水合物的勘探与开发[M]：中国地质大学出版社；2002.
[4]宋召军,刘立.天然气水合物研究现状与展望[J].吉林地质.2003,(004)：64-68.
[5]Lee JY, Ryu BJ, Yun TS et al. Review on the gas hydrate development and production as a new energy resource[J]. KSCE Journal of Civil Engineering.2011,15(4):689-696.
[6]Stoll RD, Bryan GM. Physical properties of sediments containing gas hydrates[J]. Journal of Geophysical Research.1979,84(B4):1629-1634.
[7]Gudmundsson J, Borrehaug A. Frozen hydrate for transport of natural gas. In:2nd International Conference on Natural Gas Hydrate; 1996; Toulouse, France; 1996.
[8]Circone S, Stern LA, Kirby SH. The effect of elevated methane pressure on methane hydrate dissociation[J]. American Mineralogist.2004,89(8-9):1192-1201.
[9]PAULCK UW, DILLON William P. Is the extent of glaciation limited by marine g as hydrates?[J]. Geophysical Research Letters.1991:432-434.
[10]Kvenvolden KA. A review of the geochemistry of methane in natural gas hydrate[J]. Organic Geochemistry.1995,23(11-12):997-1008.
[11]Collett T. Detection and Evaluation of the In-Situ Natural Gas Hydrates in the North Slope Region, Alaska. In; 1983.
[12]Brown TD, Taylor CE, Bernardo MP. Rapid Gas Hydrate Formation Processes:Will They Work?[J]. Energies.2010,3(6):1154-1175.
[13]Happel J, Hnatow MA, Meyer H. The Study of Separation of Nitrogen from Methane by Hydrate Formation Using a Novel Apparatusa[J]. Annals of the New York Academy of Sciences.1994,715(1):412-424.
[14]Mori YH, Mori T. Formation of Gas Hydrate with Cfc Alternative R-134a[J]. Aiche Journal. 1989,35(7):1227-1228.
[15]Aliev AM, Yusifov RY, Kuliev AR et al Method of gas hydrate formation for evaluation of water desalination[J]. Russian Journal of Applied Chemistry.2008,81(4):588-591.
[16]宁伏龙,蒋国盛,张凌等.天然气水合物实验装置及其发展趋势[J].海洋石油.2008,28(002)：68-72.
[17]National Research Council of the National Academies. Realizing the Energy Potential of Methane Hydrate for the United States. Washington:The National Academies Press; 2010.
[18]Gabitto J, Barrufet M. Gas Hydrates Research Programs:An International Review. United States:Prairie View A&M University; 2009.
[19]许红,黄君权,夏斌等.最新国际天然气水合物研究现状与资源潜力评估(上)[J].地质与勘探.2005,25(5)：1-5.
[20]Boswell R, Collett TS. Current perspectives on gas hydrate resources[J]. Energy Environ. Sci. 2010,4(4):1206-1215.
[21]Sloan ED, Koh CA. Clathrate Hydrates of Natural Gases.3rd Ed ed. Boca Raton, FL, USA: CRC Press; 2008.
[22]Wood W, Jung W. Modeling the extent of Earth's marine methane hydrate cryosphere. In: Englezos P, Ripmeester JA, editors. Proceedings of the 6th International Conference on Gas Hydrates(ICGH 2008); 2008; Vancouver, British Columbia, CANADA; 2008. p.6-10.
[23]Trofimuk A, Cherskiy N, Tsarev V. Accumulation of natural gases in zones of hydrate-formation in the hydrosphere[J]. Dolady Akademii Nauk SSSR.1973,212: 931-934.
[24]涂运中.海洋天然气水合物地层钻井的钻井液研究[D].武汉：中国地质大学；2010.
[25]Boswell R. Is Gas Hydrate Energy Within Reach?[J]. Science.2009,325(5943):957.
[26]Fujii T, Saeki T, Kobayashi T et al. Resource assessment of methane hydrate in the eastern Nankai Trough. In:Offshore Technology Conference(OTC 08); Houston,Texas; 2008.
[27]Frye M. Preliminary evaluation of in-place gas hydrate resources:Gulf of Mexico outer continental shelf; 2008.
[28]Collett TS, Agena WF, Lee MW et al. Assessment of gas hydrate resources on the North Slope, Alaska,2008[J]. US Geological Survey Fact Sheet 2008-3073.2008:4p.
[29]Makogon Y, Holditch S, Makogon T. Russian field illustrates gas-hydrate production[J]. Oil & Gas Journal.2005,103(5):43-47.
[30]Walsh T, Stokes P, Panda M et al. Characterization and Quantification of the Methane Hydrate Resource Potential Associated with the Barrow Gas Field. In:Proceedings of the 6th International Conference on Gas Hydrate(ICGH 2008); 2008; Vancouver,British Columbia; 2008.
[31]Heimann M. How stable is the methane cycle?[J]. Science.2010,327(5970):1211.
[32]Shine KP, Derwent R, Wuebbles D et al. Radiative forcing of climate. In:Cambridge University Press, Cambridge, United Kingdom and New York, NY, USA; 1990:41-68.
[33]MacDonald GJ. Role of methane clathrates in past and future climates[J]. Climatic Change. 1990,16(3):247-281.
[34]Watson R, Rodhe H, Oeschger H et al. Greenhouse gases and aerosols[J]. Climate change:the IPCC scientific assessment.1990,1:17.
[35]Kvenvolden KA. Gas Hydrates-Geological Perspective and Global Change[J]. Reviews of Geophysics.1993,31(2):173-187.
[36]Kvenvolden KA. Methane hydrates and global climate[J]. Global Biogeochemical Cycles.1988, 2(3):221-229.
[37]Solomon S. Climate change 2007:the physical science basis:contribution of Working Group I to the Fourth Assessment Report of the Intergovernmental Panel on Climate Change: Cambridge Univ Pr; 2007.
[38]Ning F, Yu Y, Kjelstrup S et al. Mechanical properties of clathrate hydrates:status and perspectives[J]. Energy Environ. Sci.2012,5(5):6779-6795.
[39]Liggins F, Betts RA, McGuire B. Projected future climate changes in the context of geological and geomorphological hazards[J]. Philosophical Transactions of the Royal Society A: Mathematical, Physical and Engineering Sciences.2010,368(1919):2347-2367.
[40]Akerman HJ, Johansson M. Thawing permafrost and thicker active layers in sub-arctic Sweden[J]. Permafrost and Periglacial Processes.2008,19(3):279-292.
[41]Lawrence DM, Slater AG, Tomas RA et al. Accelerated Arctic land warming and permafrost degradation during rapid sea ice loss[J]. Geophysical Research Letters.2008,35(11): L11506.
[42]Maslin M, Owen M, Betts R et al. Gas hydrates:past and future geohazard?[J]. Philosophical Transactions of the Royal Society A:Mathematical, Physical and Engineering Sciences.2010, 368(1919):2369-2393.
[43]Masuda Y, Yamamoto K, Tadaaki S et al. Japan's methane hydrate R&D program progresses to phase 2[J]. Natural Gas & Oil.2018,304:285-4541.
[44]Dallimore S, Collett T. Scientific results from the Mallik 2002 gas hydrate production research well program, Mackenzie Delta, Northwest Territories, Canada:Ottawa (Ont.); 2005.
[45]Hunter RB, Collett TS, Boswell R et al. Mount Elbert Gas Hydrate Stratigraphic Test Well, Alaska North Slope:Overview of scientific and technical program[J]. Marine and Petroleum Geology.2011,28(2):295-310.
[46]Prensky S. A review of gas hydrates and formation evaluation of hydrate-bearing reservoirs. In; 1995; 1995.
[47]Nouze H, Lafoy Y, Geli L. First results of a high resolution seismic study of a bottom simulating reflector in the fairway basin, offshore new Caledonia. In; 2005; 2005.
[48]Tinivella U, Accaino F, Della Vedova B. Gas hydrates and active mud volcanism on the South Shetland continental margin, Antarctic Peninsula[J]. Geo-Marine Letters.2008,28(2): 97-106.
[49]Holbrook W, Hoskins H, Wood W et al. Leg 164 Science Party,1996. Methane hydrate and free gas on the Blake Ridge from vertical seismic profiling[J]. Science.273(5283):1840"C1843.
[50]Collett TS. A review of well-log analysis techniques used to assess gas-hydrate-bearing reservoirs[J]. Geophysical monograph.2001,124:189-210.
[51]McGuire D, Runyon S, Williams T et al. Gas hydrate exploration with 3D VSP technology, North Slope, Alaska[J].2005.
[52]张树林,夏斌.南海北部含油气盆地地层压力预测与监控技术研究[J].石油物探.2004,43(6).
[53]张树林.天然气水合物地震勘探关键技术研究[J].天然气工业.2007,9：365-370.
[54]Dai J, Xu H, Snyder F et al. Detection and estimation of gas hydrates using rock physics and seismic inversion:Examples from the northern deepwater Gulf of Mexico[J]. The Leading Edge.2004,23(1):60.
[55]Chand S, Minshull T, Gei D et al. Elastic velocity models for gas hydrate bearing sediments:a comparison[J]. Geophysical Journal International.2004,159(2):573-590.
[56]Lee M, Hutchinson D, Collett T et al. Seismic velocities for hydrate-bearing sediments using weighted equation[J]. Journal of Geophysical Research.1996,101(B9):20347-20320,20358.
[57]Helgerud M, Dvorkin J, Nur A et al. Elastic-wave velocity in marine sediments with gas hydrates:Effective medium modeling[J]. Geophysical Research Letters.1999,26(13): 2021-2024.
[58]吴志强.地震反射技术在水合物调查评价中的应用前景及设想[J]. Marine Geology.2001, 17(7).
[59]张光学,张明,杨胜雄等.海域天然气水合物地震综合探测技术发展及应用[J].第十届中国科协年会“深水技术产业发展国际研讨会”论文集.2008.
[60]Worthington PF. Petrophysical evaluation of gas-hydrate formations[J]. Petroleum Geoscience. 2010,16(1):53.
[61]Collett T. Well log characterization of sediment porosities in gas-hydrate-bearing reservoirs. In; 1998; 1998.
[62]Collett TS. Well log evaluation of gas hydrate saturations. In; 1998; 1998.
[63]Ebeltoft H, Yousif M, Soergard E. Hydrate Control During Deepwater Drilling:Overview and New Drilling-Fluids Formulations[J]. SPE Drilling and Completion.2001,16(1):19-26.
[64]宁伏龙,吴翔,张凌等.天然气水合物地层钻井时水基钻井液性能实验研究[J].天然气工业.2006.
[65]宁伏龙,蒋国盛,张凌等.影响含天然气水合物地层井壁稳定的关键因素分析[J].石油钻探技术.2008,36(003)：59-61.
[66]张建华,胡启.钻井泥浆滤液侵入储集层的理计算模型[J].石油学报.1994,15(4)：73-78.
[67]Collett TS. A review of well-log analysis techniques used to assess gas-hydrate-bearing reservoirs. In:Geophysical monograph; 2001:189-210.
[68]邓少贵,李智强,范宜仁等.斜井泥浆侵入仿真及其阵列侧向测井响应数值模拟[J].地球物理学报.2010,53(4).
[69]Ebeltoft H, Yousif M, Soergard E. Hydrate control during deepwater drilling:Overview and new drilling-fluids formulations[J]. SPE Drilling & Completion.2001,16(1):19-26.
[70]Ecker C, Dvorkin J, Nur AM. Estimating the amount of gas hydrate and free gas from marine seismic data[J]. Geophysics.2000,65(2):565.
[71]Dvorkin J, Helgerud M, Waite W et al. Introduction to physical properties and elasticity models[J]. Natural Gas Hydrate in Oceanic and Permafrost Environments.2000:245"C260.
[72]Holland M, Schultheiss P, Roberts J et al. Observed gas hydrate morphologies in marine sediments. In; 2008; 2008. p.6-10.
[73]Dvorkin J, Nur A. Seismic amplitudes from gas hydrates[J]. Hart's E & P.2007,80(11):97-98.
[74]Malone R. Gas hydrates topical report[J]. DOE/METC/SP-218, US Department of Energy. 1985:33-50.
[75]Lovell M, Jackson P, Gunn D et al. Petrophysical characterisation of gas hydrate sediments. In; 2002; 2002.
[76]Dai J, Kleinberg R, Xu H et al. Rock Physics Models Of Gas Hydrates And Their Implications In Seismic Detection. In; 2005; 2005.
[77]Dvorkin J, Nur A. Elasticity of high(?)\porosity sandstones:Theory for two North Sea data sets[J]. Geophysics.1996,61:1363.
[78]Fujii K, Yasuda M, Cho B et al. Development of a monitoring system for the JOGMEC/NRCan/Aurora Mallik gas hydrate production test program. In; 2008; 2008.
[79]Riedel M, Bellefleur G, Dallimore SR et al. Amplitude and frequency anomalies in regional 3D seismic data surrounding the Mallik 5L-38 research site, Mackenzie Delta, Northwest Territories, Canada[J]. Geophysics.2006,71(6):B183-B191.
[80]Suzuki K, Ebinuma T, NARITA H. Estimation of the In-Situ Permeabilities of Nankai Trough Hydrate Bearing Sediments From Pressure Temparature Core Samplar (PTCS) Core Measurements. In; 2008; 2008.
[81]Cook AE, Goldberg D, Kleinberg RL. Fracture-controlled gas hydrate systems in the northern Gulf of Mexico[J]. Marine and Petroleum Geology.2008,25(9):932-941.
[82]Collett T, Riedel M, Cochran J et al. Indian national gas hydrate program expedition 01 initial reports:Expedition 01 of the Indian National Gas Hydrate Program from Mumbai, India to Chennai, India:Sites NGHP-01-01 through NGHP-01-21, April 2006-August 2006, Directorate General of Hydrocarbons, Ministry of Petroleum and Natural Gas (India), Noida, India; 2008.
[83]Collett T. Geology of Marine Gas Hydrates and Their Global Distribution. In; 2008; 2008.
[84]Scott M, Randolph P, Pangborn J. Assessment of methane hydrates(permafrost zone of Alaska and deep sediments in oceans)[Final Report, Dec.1978-Jun.1980][J].1980.
[85]Paull CK, Ussler W, Borowski WS et al. Methane-rich plumes on the Carolina continental rise: associations with gas hydrates[J]. Geology.1995,23(1):89.
[86]Yang S, Zhang H, Wu N et al. High concentration hydrate in disseminated forms obtained in Shenhu area, North Slope of South China Sea. In; 2008; 2008. p.6-10.
[87]Spangenberg E. Modeling of the influence of gas hydrate content on the electrical properties of porous sediments[J]. Journal of geophysical research.2001,106(B4):6535-6548.
[88]Moridis G, Collett T, Pooladi-Darvish M et al. Challenges, Uncertainties and Issues Facing Gas Production From Hydrate Deposits in Geologic Systems. In; 2010; 2010.
[89]Judge A. Natural gas hydrates in Canada. In; 1981; 1981. p.320-328.
[90]Jin YK, Lee MW, Collett TS. Relationship of gas hydrate concentration to porosity and reflection amplitude in a research well, Mackenzie Delta, Canada[J]. Marine and Petroleum Geology.2002,19(4):407-415.
[91]Ren SR, Liu Y, Zhang W. Acoustic velocity and electrical resistance of hydrate bearing sediments[J]. Journal of Petroleum Science and Engineering.2010,70(1-2):52-56.
[92]Kleinberg R, Dai J. Estimation Of The Mechanical Properties Of Natural Gas Hydrate Deposits From Petrophysical Measurements. In; 2005; 2005.
[93]Murray D, Kleinberg R, Sinha B et al. Formation evaluation of gas hydrate reservoirs. In; 2005; 2005.
[94]Zimmerman RW, King MS. The effect of the extent of freezing on seismic velocities in unconsolidated permafrost[J]. Geophysics.1986,51:1285.
[95]Foley JE, Burns DR. The sensitivity of seismic responses to gas hydrates. Final report:New England Research, Inc., White River Junction, VT (United States); 1992.
[96]Dvorkin J, Nur A. Rock physics for characterization of gas hydrates[J]. United States Geological Survey, Professional Paper;(United States).1993,1570.
[97]Pearson C, Murphy J, Halleck P et al. Sonic and resistivity measurements on Berea sandstone containing tetrahydrofuran hydrates:a possible analog to natural gas hydrate deposits. In; 1983; 1983. p.973 C978.
[98]Winters WJ, Waite W, Mason D et al. Methane gas hydrate effect on sediment acoustic and strength properties[J]. Journal of Petroleum Science and Engineering.2007,56(1-3): 127-135.
[99]Pearson C. Physical properties of natural gas hydrate deposits:Los Alamos National Lab., NM (USA); 1982.
[100]Pearson C, Halleck P, McGuire P et al. Natural gas hydrate deposits:A review of in situ properties[J]. The Journal of Physical Chemistry.1983,87(21):4180-4185.
[101]Waite W. Thermal conductivity measurements in porous mixtures of methane hydrate and quartz sand[J]. Geophysical Research Letters.2002,29(24):2229.
[102]Henninges J, Huenges E, Burkhardt H. In situ thermal conductivity of gas-hydrate-bearing sediments of the Mallik 5L-38 well[J]. Journal of geophysical research.2005,110(B11): B11206.
[103]Booth J, Winters W, Dillon W et al. Major occurrences and reservoir concepts of marine clathrate hydrates:implications of field evidence[J]. Geological Society, London, Special Publications.1998,137(1):113.
[104]Ginsburg G. Gas hydrate accumulation in deep-water marine sediments[J]. Geological Society, London, Special Publications.1998,137(1):51.
[105]Lee MW, Collett TS. Integrated analysis of well logs and seismic data to estimate gas hydrate concentrations at Keathley Canyon, Gulf of Mexico [J]. Marine and Petroleum Geology.2008, 25(9):924-931.
[106]Moridis GJ, Sloan ED. Gas production potential of disperse low-saturation hydrate accumulations in oceanic sediments[J]. Energy conversion and management.2007,48(6): 1834-1849.
[107]Anderson BI, Collett TS, Lewis RE et al. Using Open Hole and Cased-Hole Resistivity Logs to Monitor Gas Hydrate Dissociation During a Thermal Test in the Mallik 5L-38 Research Well, Mackenzie Delta, Canada[J]. PETROPHYSICS-HOUSTON-.2008,49(3):285.
[108]Boswell R, Shelander D, Lee M et al. Occurrence of gas hydrate in Oligocene Frio sand: Alaminos Canyon Block 818:Northern Gulf of Mexico [J]. Marine and Petroleum Geology. 2009,26(8):1499-1512.
[109]Uchida T, Tsuji T. Petrophysical properties of natural gas hydrates-bearing sands and their sedimentology in the Nankai Trough[J]. Resource Geology.2004,54(1):79-87.
[110]Jin Y, Nagao J, Hayashi J et al. Assessment of the absolute permeability of natural methane hydrate sediments by microfocus X-ray computed tomography. In. p.93"C96.
[111]Minagawa H, Nishikawa Y, Ikeda I et al. Relation between permeability and pore-size distribution of methane-hydrate-bearing sediments. In; 2008; 2008.
[112]Booth JS, Winters WJ, Dillon WP. Circumstantial evidence of gas hydrate and slope failure associations on the United States Atlantic continental margin[J]. Annals of the New York Academy of Sciences.1994,715(1):487-489.
[113]Winters W, Booth J, Nielsen R et al. A Computer(?)\Controlled Gas Hydrate(?)\Sediment Formation and Triaxial Test System[J]. Annals of the New York Academy of Sciences.1994, 715(1):490-491.
[114]Santamarina JC, Ruppel C. The impact of hydrate saturation on the mechanical, electrical, and thermal properties of hydrate-bearing sand, silts, and clay. In; 2008; 2008. p.6"C10.
[115]Pearson C, Murphy J, Hermes R. Acoustic and resistivity measurements on rock samples containing tetrahydrofuran hydrates:laboratory analogues to natural gas hydrate deposits[J]. Journal of Geophysical Research.1986,91(B14):14132-14114,14138.
[116]Archie G. The electrical resistivity log as an aid in determining some reservoir characteristics: Petroleum Technology, v.5[J]. Technical Publication.1942,1422(8).
[117]Yun T, Narsilio G, Santamarina J et al. Instrumented pressure testing chamber for characterizing sediment cores recovered at in situ hydrostatic pressure[J]. Marine Geology. 2006,229(3-4):285-293.
[118]Minagawa H, Ohmura R, Kamata Y et al. Water permeability measurements of gas hydrate-bearing sediments. In; 2005; 2005. p.398"C401.
[119]Winters W, Pecher I, Waite W et al. Physical properties and rock physics models of sediment containing natural and laboratory-formed methane gas hydrate[J]. American Mineralogist. 2004:1221-1227.
[120]Jackson P, Gunn D, Flint R et al. A non-contacting resistivity imaging method for characterizing whole round core while in its liner[J]. Geological Society, London, Special Publications.1997,122(1):1.
[121]王志勇,韩明俊,李强等.人造填砂岩心渗透率影响因素及控制方法[J].科技创新导报.2008,5.
[122]Falser S, Palmer A, Tan T et al. Testing methane hydrate saturated soil using a line dissociation apparatus[J]. Geotechnical Testing Journal, submitted.2012.
[123]孟庆国,业渝光,胡高伟等.沉积物中水合物含气量测定方法[J].海洋地质前沿.2011,08：66-70.
[124]刘瑜,赵佳飞,郭长松等.Ⅰ型和Ⅱ型结构气体水合物的记忆效应[J].物理化学学报.2011,06：1305-1311.
[125]胡高伟,业渝光,张剑等.松散沉积物中天然气水合物生成、分解过程与声学特性的实验研究[J].现代地质.2008,03：465-474.
[126]Winters W, Walker M, Hunter R et al Physical properties of sediment from the Mount Elbert gas hydrate stratigraphic test well, Alaska North Slope[J]. Marine and Petroleum Geology. 2011,28(2):361-380.
[127]Winters WJ, Dugan B, Collett TS. Physical properties of sediments from Keathley Canyon and Atwater Valley, JIP Gulf of Mexico gas hydrate drilling program[J]. Marine and Petroleum Geology.2008,25(9):896-905.
[128]王永军.钻井液井壁侵入深度技术研究[D].2011.
[129]Ning FL, Wu NY, Jiang GS et al. A Method to Use Solar Energy for the Production of Gas from Marine Hydrate-Bearing Sediments:A Case Study on the Shenhu Area[J]. Energies. 2010,3(12):1861-1879.
[130]李淑霞.天然气水合物开采物理模拟与数值模拟研究；2006.
[131]宋海斌,江为为,张文生等.天然气水合物的海洋地球物理研究进展[J].地球物理学进展.2002,17(2)：224-229.
[132]Li G, Moridis GJ, Zhang K et al. Evaluation of Gas Production Potential from Marine Gas Hydrate Deposits in Shenhu Area of South China Sea[J]. Energy Fuels.2010,24(11): 6018-6033.
[133]Zhang K, Moridis GJ, Wu YS et al. A domain decomposition approach for large-scale simulations of flow processes in hydrate-bearing geologic media. In:Proceedings of the 6th International Conference on Gas Hydrates (ICGH 2008); 2008; Vancouver, British Columbia, Canada; 2008.
[134]Moridis GJ, Kowalsky MB, Pruess K. TOUGH+HYDRATE v1.1 User's Manual:A Code for the Simulation of System Behavior in Hydrate-Bearing Geologic Media. In. Berkeley, California:Lawrence Berkeley National Laboratory University of California; 2009.
[135]Wu N, Yang S, Zhang H et al. Preliminary discussion on gas hydrate reservoir system of Shenhu Area, North Slope of South China Sea[J].2008.
[136]Ning Fulong, Zhang Keni, Wu Nengyou et al. Invasion of drilling mud into gas-hydrate-bearing sediments. Part Ⅰ:effect of drilling mud properties. Geophysical Journal International,2013,193(3):1370-1384
[137]Ning Fulong, Wu Nengyou, Yu Yibing et al. Invasion of drilling mud into gas-hydrate-bearing sediments:Part Ⅱ. Effects of geophysical properties of sediments. Geophys. J. Int.,2013,193 (3):1385-1398
[138]宁伏龙,张可霓,吴能友等.钻井液侵入海洋含水合物地层的一维数值模拟研究.地球物理学报,2013,56(1)：204-218
[139]Moridis GJ, Reagan MT. Gas Production From Oceanic Class 2 Hydrate Accumulations. In: Offshore Technology Conference; 2007; Houston, Texas; 2007.
[140]Johnson A, Patil S, Dandekar A. Experimental investigation of gas-water relative permeability for gas-hydrate-bearing sediments from the Mount Elbert Gas Hydrate Stratigraphic Test Well, Alaska North Slope[J]. Marine and Petroleum Geology.2011,28(2):419-426.
[141]Konno Y, Masuda Y, Takenaka T et al. Numerical Study on Permeability Hysteresis During Hydrate Dissociation in Hot Water Injection. In:Proceedings of the 6th International Conference on Gas Hydrates(ICGH 2008); 2008; Vancouver, British Columbia, Canada; 2008.
[142]Waite WF, Kneafsey TJ, Winters WJ et al. Physical property changes in hydrate-bearing sediment due to depressurization and subsequent repressurization[J]. Journal of Geophysical Research-Solid Earth.2008,113(B7):B07102.
[143]Xu WY, Germanovich LN. Excess pore pressure resulting from methane hydrate dissociation in marine sediments:A theoretical approach[J]. Journal of Geophysical Research-Solid Earth. 2006, 111(B1).
[144]Holtzman R, Juanes R. Thermodynamic and hydrodynamic constraints on overpressure caused by hydrate dissociation:Apore-scale model[J]. Geophysical Research Letters.2011,38.
[145]Yousif M, Abass H, Selim M et al. Experimental and theoretical investigation of methane-gas-hydrate dissociation in porous media[J]. SPE Reservoir Engineering.1991,6(1): 69-76.
[146]Masuda Y, Fujinaga Y, Naganawa S et al. Modeling and experimental studies on dissociation of methane gas hydrates in Berea sandstone cores. In:the 3rd International Conference on Gas Hydrates(ICGH 1999); 1999; Salt Lake City, Utah; 1999.
[147]徐同台.钻井工程井壁稳定新技术.北京：石油工业出版社；1999.
[148]Johnson A, Patil S, Dandekar A. Experimental investigation of gas-water relative permeability for gas hydrate bearing sediments from Mount Elbert gas hydrate stratigraphic test well, Alaska North Slope[J]. Marine and Petroleum Geology.2009.
[149]黄兴.水合物对多孔介质渗透性影响的实验研究：大连理工大学；2010.
[150]宋永臣,黄兴,刘瑜等.含甲烷水合物多孔介质渗透性的实验研究[J].热科学与技术.2010,9(001)：51-57.
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