The methane hydrate formation and the resource estimate resulting from free gas migration in seeping seafloor hydrate stability zone

It is a typical multiphase flow process for hydrate formation in seeping seafloor sediments. Free gas can not only be present but also take part in formation of hydrate. The volume fraction of free gas in local pore of hydrate stable zone (HSZ) influences the formation of hydrate in seeping seafloor area, and methane flux determines the abundance and resource of hydrate-bearing reservoirs. In this paper, a multiphase flow model including water (dissolved methane and salt)-free gas hydrate has been established to describe this kind of flow-transfer-reaction process where there exists a large scale of free gas migration and transform in seafloor pore. In the order of three different scenarios, the conversions among permeability, capillary pressure, phase saturations and salinity along with the formation of hydrate have been deducted. Furthermore, the influence of four sorts of free gas saturations and three classes of methane fluxes on hydrate formation and the resource has also been analyzed and compared. Based on the rules drawn from the simulation, and combined information gotten from drills in field, the methane hydrate(MH) formation in Shenhu area of South China Sea has been forecasted. It has been speculated that there may breed a moderate methane flux below this seafloor HSZ. If the flux is about 0.5 kg m⁻² a⁻¹, then it will go on to evolve about 2700 ka until the hydrate saturation in pore will arrive its peak (about 75%). Approximately 1.47 × 10⁹ m³ MH has been reckoned in this marine basin finally, is about 13 times over preliminary estimate.     

含天然气水合物沉积物分解过程的有限元模拟

温度和压力的变化会引起含天然气水合物沉积物的分解,其过程伴随着相态转换、孔隙水压力和气压力耗散、热传导、骨架变形等过程的相互耦合作用。基于多孔介质理论建立了描述含天然气水合物沉积物分解过程的数学模型,考虑了水合物分解产生的水、气流动、水合物相变和分解动力学过程、热传导、骨架变形等过程的耦合作用。基于有限元法,建立了模拟水合物分解过程的数值模型,并编制了计算机分析程序。通过对降压法和升温法开采过程的数值模拟,揭示了在水合物分解过程中沉积物储层的变形、压力、温度等因素的变化规律。结果表明：降压法和升温法都会导致储层变形以及产生超孔隙压力,但两种方法作用效果不同;同时,水合物分解过程包含渗流及热传导作用。     

Chemo‐thermo‐mechanically coupled seismic analysis of methane hydrate‐bearing sediments during a predicted Nankai Trough Earthquake

In the present study, we have developed a numerical method which can simulate the dynamic behaviour of a seabed ground during gas production from methane hydrate‐bearing sediments. The proposed method can describe the chemo‐thermo‐mechanical‐seismic coupled behaviours, such as phase changes from hydrates to water and gas, temperature changes and ground deformation related to the flow of pore fluids during earthquakes. In the first part of the present study, the governing equations for the proposed method and its discretization are presented. Then, numerical analyses are performed for hydrate‐bearing sediments in order to investigate the dynamic behaviour during gas production. The geological conditions and the material parameters are determined using the data of the seabed ground at Daini‐Atsumi knoll, Eastern Nankai Trough, Japan, where the first offshore production test of methane hydrates was conducted. A predicted earthquake at the site is used in the analyses. Regarding the seismic response to the earthquake which occur during gas production process, the wave profiles of horizontal acceleration and horizontal velocity were not extensively affected by the gas production. Hydrate dissociation behaviour is sensitive to changes in the pore pressure during earthquakes. Methane hydrate dissociation temporarily became active in some areas because of the main motion of the earthquake, then methane hydrate dissociation brought about an increase in the average pressure of the fluids during the earthquake. And, it was this increase in average pore pressure that finally caused the methane hydrate dissociation to cease during the earthquake. Copyright © 2016 John Wiley & Sons, Ltd.     

盐类对甲烷水合物稳定性影响研究进展

甲烷水合物稳定性主要控制着甲烷水合物稳定带的厚度,温度、压力、孔隙水盐度和气体组分等因素影响着水合物稳定带的厚度。甲烷水合物的形成与地层水关系密切,而地层水中的各种盐离子(Cl~-、Na~+、Mg~(2+)、SO_4(~2-)、Ca~(2+))以及过渡金属(Fe、Mn、Cu、Co、Ni等)会影响天然气水合物的形成和分解条件。因此,研究盐类对甲烷水合物的稳定性认识有助于更加深入了解天然气水合物的成藏条件。本文分析了氯化物、硫酸盐、碳酸盐三大盐类对甲烷水合物稳定性的影响:同一盐类不同盐度条件下,随着盐度的增加,甲烷水合物相平衡曲线向低温高压偏移。总结了不同盐类和阴阳离子对甲烷水合物的抑制作用大小:在相同浓度、不同盐类条件下,盐类浓度在1.0~1.5 mol/L时盐类对甲烷水合物的抑制作用大小为MgCl_2CaCl_2Na ClKCl,盐类浓度大于1.5 mol/L时CaCl_2的抑制作用较强;阴离子对甲烷水合物的抑制作用大小争议较大,阳离子中Mg~(2+)对甲烷水合物的抑制作用最强。从目前的研究成果来看,已有数据与实际地质条件还存在一定差距,需要在真实实验条件下加强氯化物-硫酸盐-碳酸盐-甲烷-水体系的详细研究。本文提出,将高压可视反应腔与显微激光拉曼技术相结合,有望准确获取天然气水合物稳定形成时的温压条件,明确盐类和阴阳离子的抑制作用大小,以及盐类和离子特性如何影响水合物的形成和稳定,以便为未来的水合物勘探开发提供参考。     

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

为了解松散沉积物中天然气水合物的生成和分解规律以及水合物对沉积物声学特性的影响,在粒径为0.18~0.28mm天然沙中进行了甲烷水合物的生成和分解实验,并利用超声波探测技术和时域反射技术实时测量了反应体系的声学参数与含水量。结果表明:根据水合物的生成和分解速率,可将水合物的生成过程分为初始生长期、快速生长期和稳定期3个阶段,分解过程可分为初始分解期和样品表层水合物快速分解期以及样品内、外层水合物均快速分解期3个阶段;由温度和压力数据的分析,得出水合物先在沉积物表层生长,然后在沉积物内、外层迅速生成;由水合物分解过程3个阶段的平均分解率,得出水合物的分解是一个由慢到快的过程。对声学参数的研究表明:水合物在松散沉积物中先胶结骨架颗粒而生成,使纵波速度和声波衰减在饱和度0~1%之间陡然增大;随后水合物开始在沉积物孔隙中形成悬浮粒子,造成超声波信号在饱和度1%~90%间淬熄,声波速度无法获取。研究结果在揭示沉积物中水合物与颗粒间接触机制的同时,为海上地球物理勘探中地震信号的解释提供了新的思路。     

Geochemical relation between gas hydrates and water venting in the seismic blanking zone on the northern Cascadia continental margin offshore Vancouver Island, Canada

The isotopic composition (δD and δ¹⁸O) and chloride concentration (Cl⁻) of pore waters from the northern Cascadia continental margin offshore Vancouver Island were measured to characterize the relations between the water flow regime and the distribution, formation and dissociation of gas hydrates. The δD values of pore waters in gas hydrate-bearing sediments are slightly higher ( 1‰) than those of seawater as the result of gas hydrate dissociation during core recovery and handling. Within the seismic blanking zone, the δD values were slightly lower (− 1‰) than values measured from sites outside the blanking area (0‰). We attribute these differences to 1) distillation of D-rich water during hydrate formation in the center of the blanking zone and 2) limited migration of pore water between inside and outside of the blanking zone due to different fluid fluxes. In contrast, the δ¹⁸O values and Cl⁻ concentrations do not show significant spatial variation due to decreased isotopic fractionation of oxygen and small fraction of chloride relative to hydrogen isotope during gas hydrate formation. The δD value of pore water, therefore, appears to be a sensitive indicator of gas hydrate occurrence. We estimate that gas hydrate occupied at least 2.0 to 6.3% of sediment pore space using δD distribution in this area.     

水合物储层伺服降压开采模型试验研究

深海水合物赋存于一定的温度和压力环境下,降压开采时降压速率对分解产气速率和储层变形特性影响显著。利用浙江大学自主研发的水合物降压开采试验装置,通过伺服控制降压速率,初步开展了水合物储层模型降压开采试验,研究了储层温度场、孔压场、产气量等的响应特性,探讨了降压速率对产气效率和储层变形特性的影响规律。试验表明：水合物竖井降压开采时,开采井周围储层温度率先下降,分解域由井周逐步向周围发展。适当提高降压速率能够提高储层开采效率,但降压速率过快时易导致水合物重生成,反而不利于水合物高效持续稳定开采,开采时应选择合理的降压速率以达到最优产气效率。开采过程中根据储层孔隙与外界连通程度,储层孔隙状态可分为完全封闭型、局部封闭型和开放型3种类型。储层开采试验完成后,浅层土体出现 3 种不同变形特征的区域：I 区为井周土层,呈漏斗型下陷;II 区土层平坦,无明显扰动痕迹;III 区为边界土层,该处水气产出受阻导致部分气体向上迁移引起土丘状隆起带出现。这些变形特征与气体在储层中的迁移路径和运移模式相关。通过相似性分析,给出了模型与原型分解时间和产气量等的对应关系。     

祁连山冻土区DK-9孔温度监测及天然气水合物稳定带厚度

祁连山冻土区木里盆地三露天井田自2008年首次钻采到天然气水合物实物样品以来,实现了中低纬度高山冻土区天然气水合物勘探的重大突破。天然气水合物钻孔DK-9于2013年发现水合物,通过对该孔长期地温实时监测,获得了稳态的地温数据。结果表明,祁连山多年冻土区聚乎更矿区三露天井田冻土层底界为约163 m,冻土层的厚度达约160 m,冻土层内的地温梯度为138 ℃ /100 m,冻土层以下的地温梯度达485 ℃/100 m。根据天然气水合物形成的温-压条件分析,聚乎更矿区具备较好的天然气水合物形成条件,天然气水合物稳定带底界深度处于510~617 m之间。     

南海北部陆坡西沙海槽XS-01站位沉积物孔隙水的 地球化学特征及其对天然气水合物的指示意义*

天然气水合物是近年来国际上发现的一种新型能源,大量赋存在海底沉积物中。西沙海槽位于南海北部陆坡区,周边有多个大型深水油气田区。对该区地形地貌、地质构造和沉积条件分析以及地球物理BSR分布表明,西沙海槽是我国海洋天然气水合物资源勘查的一个有利远景区。文章主要研究了位于西沙海槽最大BSR区内的XS-01站位沉积物孔隙水的地球化学特征,发现该站位孔隙水阴阳离子浓度和微量元素组成特征变化显示出可能与天然气水合物有关的明显地球化学异常,与国际上己发现有天然气水合物地区的异常相类似。因此,认为该站位是西沙海槽区最有利的天然气水合物赋存区,值得进一步的勘查工作。     

多孔介质中天然气水合物稳定性的实验研究进展

勘探表明天然气水合物多产出于细碎屑沉积物中,其分布和赋存形式受温度、压力、水化学条件等多种物理化学因素的影响。前人的实验研究表明不同孔径尺度中的甲烷水合物稳定性有别于块状、层状水合物,同时孔隙表面的润湿性也是影响因素之一。在综合分析前人研究成果的基础上,系统阐述了孔隙的孔径、孔隙内表面润湿性对所含天然气水合物稳定性的影响规律,总结了可能的内在机理;并指出了当前应当尽快建立包括空间效应、温度、压力和组分等因素的综合天然气水合物相图,查明含天然气水合物沉积物的孔隙结构和表界面特征,建立天然气水合物的稳定性模型,将有助于精确预测天然气水合物的分布和规模,对于水合物开发和甲烷存储技术的研发也有着重要的意义。     

海底水合物矿藏降压开采与甲烷气体扩散过程的数值模拟

在深海条件下采用单井降压法开采的天然气水合物矿藏中,利用TOUGH+HYDRATE软件对其开采过程和甲烷气体扩散过程进行数值模拟。物理模型由上至下依次为上盖层、水合物沉积层和下盖层。将上、下盖层外边界的温度设为恒定,与含水合物沉积层之间有热量和质量交换,数值模型采用二维圆柱坐标网格。模拟结果表明开采过程中井口产气速率是一个升高—降低—波动升高的过程,水合物分解产生的气体有一部分通过上盖层溢出,能在一定程度上增加大气中温室气体的量。开采初期水合物分解速率降低的主要原因是水合物分解产生的甲烷气体在地层中大量累积,开采后期水合物分解速率产生波动的主要原因是发生"气穴现象"。井口附近由于压力变化较快水合物分解最为剧烈,其附近有个低温区存在。上、下盖层附近水合物分解速率也较快。     

Analysis for temperature and pressure fields in process of hydrate dissociation by depressurization

An improved axisymmetric mathematic modeling is proposed for the process of hydrate dissociation by depressurization around vertical well. To reckon in the effect of latent heat of gas hydrate at the decomposition front, the energy balance equation is employed. The semi‐analytic solutions for temperature and pressure fields are obtained by using Boltzmann‐transformation. The location of decomposition front is determined by solving initial value problem for system of ordinary differential equations. The distributions of pressure and temperature along horizontal radiate in the reservoir are calculated. The numeric results indicate that the moving speed of decomposition front is sensitively dependent on the well pressure and the sediment permeability. Copyright © 2010 John Wiley & Sons, Ltd.     

天然气水合物沉积物力学性质的试验研究

利用研制的天然气水合物沉积物合成及力学性质一体化试验设备,以粉细砂土作为土骨架,分别对冰沉积物以及对四氢呋喃(THF)、二氧化碳(CO2)和甲烷3种水合物沉积物进行了室内合成和三轴剪切试验,分析和比较了这4种沉积物样品的应力-应变和强度特性,初步探究了冰和不同气体在水合物沉积物强度中所起的作用。试验结果表明：4种沉积物均表现为塑性破坏;围压越大,水合物沉积物强度越高;在水合物含量相同条件下,不同气体水合物会使水合物沉积物的强度不同。     

中纬度带天然气水合物地球化学勘查技术

祁连山冻土区木里地区天然气水合物矿藏是迄今为止在中纬度带首次发现的水合物矿藏,为了研究中纬度带水合物地球化学勘查技术,选择木里矿区作为方法技术的试验区。试验指标内容有土壤顶空气、酸解烃、碳酸盐和甲烷碳同位素。研究表明:祁连山木里天然气水合物矿藏存在明显的近地表地球化学异常;由甲烷碳同位素和烃类组成判断地表油气化探异常为热解成因,指示该区天然气水合物成藏物质来源于油气和煤成气。进一步研究了中纬度带冻土区天然气水合物成藏模式,指出该区进行天然气水合物勘探的同时应进行石油和煤成气的综合勘探。     

南海北部海区海底沉积物中孔隙水的Cl~-和SO_4~(2-)浓度异常特征及其对天然气水合物的指示意义

报道了中国南海北部海区海底沉积物中孔隙水的Cl-和SO42-质量浓度的变化特征, 圈定了孔隙水中Cl-质量浓度的高值异常区。由于水合物形成过程中的排盐效应, 会使其上覆浅表层沉积物中孔隙水的盐度增高, 因此这些氯离子的高值异常区值得进一步的勘查。对孔隙水中SO42-的质量浓度分析表明, 研究区的一些站位表现出随深度增加SO42-的质量浓度梯度发生明显的变化, 计算的硫酸盐甲烷交接带SMI界面深度均在 10m左右, 与ODP164航次和ODP204航次有天然气水合物的钻孔的SMI界面深度基本吻合, 说明这些站位深部有天然气水合物存在的可能性。     

Geochemical characteristics of sediment pore water from Site XS-01 in the Xisha trough of South China Sea and their significance for gas hydrate occurrence

Gas hydrate is a recently-found new source of energy that mostly exists in marine sediments. In recent years, we have conducted gas hydrate exploration in the South China Sea. The Xisha trough, one of the promising target areas for gas hydrate, is located in the northern margin of the South China Sea, adjacent to several large oil and gas fields. The Xisha trough extends 420 km long with the water depth of 1 500 m in the west part and 3 400 m in the east part and deposits thick sediments with organic matter content of 0.41%–1.02%. Previous studies on topographical features, geological P-T conditions, structural geology, sedimentary geology and geophysical bottom simulating reflectors (BSR) in the Xisha trough suggest that this area is favorable for the formation and accumulation of gas hydrate. In this paper, we present geochemical analyses for the sediment and pore water from a piston core at Site XS-01 in the Xisha trough. Seven pore water samples were analyzed for their anion (Cl⁻, SO₄ ²⁻, Br⁻, I⁻) contents, cation (Na, K, Ca, Mg) contents and trace element (Li, B, Sr, Ba, Rb, Mn) contents. Eight sediment samples were analyzed for stable carbon and oxygen isotopic compositions. A number of geochemical anomalies such as anions (e.g. Cl⁻, SO₄ ²⁻), cations (e.g. Ca, Mg) and trace elements (e.g. Sr, Ba, B) were found in this study. For example, the concentrations of Cl⁻ and SO₄ ²⁻ in pore water show a decreasing trend with depth. The estimated sulfate/methane interface (SMI) is only 18 m, which is quite similar to the SMI value of 23 m in the ODP164 Leg 997 at Blake Ridge. The Ca, Mg and Sr concentrations of pore water also decrease with depth, but concentrations of Ba, and Mg/Ca and Sr/Ca ratios increase with depth. These geochemical anomalies are quite similar to those found in gas hydrate locations in the world such as the Blake Ridge and may be related to the formation and dissociation of gas hydrates. The salt exclusion effect during the gas hydrate formation will cause an increase in major ion concentrations in the pore waters that diffused upward such as Cl. The anaerobic methane oxidation (AMO) may lead to the change of SO₄ ²⁻ and other cations such as Ca, Mg, Sr and Ba in pore water. Low δ ¹³C value of authigenic carbonates is a good indicator for gas hydrate occurrence. However, the bulk sediment samples we analyzed all show normal δ ¹³C values similar to biogenic marine carbonates, and this may also suggest that no gas hydrate-related authigenic carbonates exist or their amount is so small that they are not detectable by using this bulk analytical method. In conclusion, we suggest that the Site XS-01 in the Xisha trough of the northern margin of the South China Sea is a potential target for further gas hydrate exploration. Translated from Quaternary Sciences, 2006, 26(3): 442–448 [译自: 第四纪研究]     

Gas Hydrates in the Qilian Mountain Permafrost, Qinghai, Northwest China

Qilian Mountain permafrost, with area about 10×104 km2, locates in the north of Qinghai-Tibet plateau. It equips with perfect conditions and has great prospecting potential for gas hydrate. The Scientific Drilling Project of Gas Hydrate in Qilian Mountain permafrost, which locates in Juhugeng of Muri Coalfield, Tianjun County, Qinghai Province, has been implemented by China Geological Survey in 2008–2009. Four scientific drilling wells have been completed with a total footage of 2059.13 m. Samples of gas hydrate are collected separately from holes DK-1, DK-2 and DK-3. Gas hydrate is hosted under permafrost zone in the 133–396 m interval. The sample is white crystal and easily burning. Anomaly low temperature has been identified by the infrared camera. The gas hydrate-bearing cores strongly bubble in the water. Gas-bubble and water-drop are emitted from the hydrate-bearing cores and then characteristic of honeycombed structure is left. The typical spectrum curve of gas hydrate is detected using Raman spectrometry. Furthermore, the logging profile also indicates high electrical resistivity and sonic velocity. Gas hydrate in Qilian Mountain is characterized by a thinner permafrost zone, shallower buried depth, more complex gas component and coal-bed methane origin etc.     

A constitutive mechanical model for gas hydrate bearing sediments incorporating inelastic mechanisms

Gas hydrate bearing sediments (HBS) are natural soils formed in permafrost and sub-marine settings where the temperature and pressure conditions are such that gas hydrates are stable. If these conditions shift from the hydrate stability zone, hydrates dissociate and move from the solid to the gas phase. Hydrate dissociation is accompanied by significant changes in sediment structure and strongly affects its mechanical behavior (e.g., sediment stiffenss, strength and dilatancy). The mechanical behavior of HBS is very complex and its modeling poses great challenges. This paper presents a new geomechanical model for hydrate bearing sediments. The model incorporates the concept of partition stress, plus a number of inelastic mechanisms proposed to capture the complex behavior of this type of soil. This constitutive model is especially well suited to simulate the behavior of HBS upon dissociation. The model was applied and validated against experimental data from triaxial and oedometric tests conducted on manufactured and natural specimens involving different hydrate saturation, hydrate morphology, and confinement conditions. Particular attention was paid to model the HBS behavior during hydrate dissociation under loading. The model performance was highly satisfactory in all the cases studied. It managed to properly capture the main features of HBS mechanical behavior and it also assisted to interpret the behavior of this type of sediment under different loading and hydrate conditions.     

Progress in Global Gas Hydrate Development and Production as a New Energy Resource

Natural gas hydrates have been hailed as a new and promising unconventional alternative energy, especially as fossil fuels approach depletion, energy consumption soars, and fossil fuel prices rise, owing to their extensive distribution, abundance, and high fuel efficiency. Gas hydrate reservoirs are similar to a storage cupboard in the global carbon cycle, containing most of the world’s methane and accounting for a third of Earth’s mobile organic carbon. We investigated gas hydrate stability zone burial depths from the viewpoint of conditions associated with stable existence of gas hydrates, such as temperature, pressure, and heat flow, based on related data collected by the global drilling programs. Hydrate-related areas are estimated using various biological, geochemical and geophysical tools. Based on a series of previous investigations, we cover the history and status of gas hydrate exploration in the USA, Japan, South Korea, India, Germany, the polar areas, and China. Then, we review the current techniques for hydrate exploration in a global scale. Additionally, we briefly review existing techniques for recovering methane from gas hydrates, including thermal stimulation, depressurization, chemical injection, and CH4–CO2 exchange, as well as corresponding global field trials in Russia, Japan, United States, Canada and China. In particular, unlike diagenetic gas hydrates in coarse sandy sediments in Japan and gravel sediments in the United States and Canada, most gas hydrates in the northern South China Sea are non-diagenetic and exist in fine-grained sediments with a vein-like morphology. Therefore, especially in terms of the offshore production test in gas hydrate reservoirs in the Shenhu area in the north slope of the South China Sea, Chinese scientists have proposed two unprecedented techniques that have been verified during the field trials: solid fluidization and formation fluid extraction. Herein, we introduce the two production techniques, as well as the so-called “four-in-one” environmental monitoring system employed during the Shenhu production test. Methane is not currently commercially produced from gas hydrates anywhere in the world; therefore, the objective of field trials is to prove whether existing techniques could be applied as feasible and economic production methods for gas hydrates in deep-water sediments and permafrost zones. Before achieving commercial methane recovery from gas hydrates, it should be necessary to measure the geologic properties of gas hydrate reservoirs to optimize and improve existing production techniques. Herein, we propose horizontal wells, multilateral wells, and cluster wells improved by the vertical and individual wells applied during existing field trials. It is noteworthy that relatively pure gas hydrates occur in seafloor mounds, within near-surface sediments, and in gas migration conduits. Their extensive distribution, high saturation, and easy access mean that these types of gas hydrate may attract considerable attention from academia and industry in the future. Herein, we also review the occurrence and development of concentrated shallow hydrate accumulations and briefly introduce exploration and production techniques. In the closing section, we discuss future research needs, key issues, and major challenges related to gas hydrate exploration and production. We believe this review article provides insight on past, present, and future gas hydrate exploration and production to provide guidelines and stimulate new work into the field of gas hydrates.     

松散沉积物中水合物降压分解阵面演化实验及数值模拟

水合物分解阵面是水合物 开采现场监测关注重点之一,其传播速率与水合物开采效率密切相关,但是目前松散沉积物中水合物降压分解阵面演化数据积累明显不足。进行了松散沉积物中水合物降压分解阵面演化实验 ,采用时域反射技术测量了水合物饱和度随时间的变化,分析了水合物分解阵面的传播规律;提出了轴对称水合物降压分解数学模型并进行了适用性验证,通过敏感性分析探讨了影响因素对 水合物分解阵面演化过程的影响关系。基于室内实验和数值模拟认为：(1)水合物降压分解阵面传播距离与其传播时间平方根呈近似线性关系;(2)水合物降压分解阵面传播速率随其传播距离 的增加而迅速减小;(3)水合物降压分解阵面传播速率随着绝对渗透率基准值、气体饱和度初始值和环境温度的增加而增大,随着水合物饱和度初始值、下降指数和出口压力的增加而减小。