OCEANIC METHANE HYDRATE: THE CHARACTER OF THE BLAKE RIDGE HYDRATE STABILITY ZONE, AND THE POTENTIAL FOR METHANE EXTRACTION

Oceanic methane hydrates are mineral deposits formed from a crystalline "ice" of methane and water in sea-floor sediments (buried to less than about 1 km) in water depths greater than about 500 m; economic hydrate deposits are probably restricted to water depths of between 1.5 km and 4 km. Gas hydrates increase a sediment's strength both by "freezing" the sediment and by filling the pore spaces in a manner similar to water-ice in permafrost. Concentrated hydrate deposits may be underlain by significant volumes of methane gas, and these localities are the most favourable sites for methane gas extraction operations. Seismic reflection records indicate that trapped gas may blow-out naturally, causing large-scale seafloor collapse.
In this paper, we consider both the physical properties and the structural integrity of the hydrate stability zone and the associated free gas deposits, with special reference to the Blake Ridge area, SE US offshore, in order to help establish a suitable framework for the safe, efficient, and economic recovery of methane from oceanic gas hydrates. We also consider the potential effects of the extraction of methane from hydrate (such as induced sea-floor faulting, gas venting, and gas-pocket collapse). We assess the ambient pressure effect on the production of methane by hydrate dissociation, and attempt to predict the likelihood of spontaneous gas flow in a production situation.     

多孔介质中甲烷水合物生成的排盐效应及其影响因素

利用不同粒径的多孔介质模拟了海洋天然气水合物的生成过程,测定了孔隙水中主要离子质量浓度的变化.研究结果表明,甲烷水合物的生成过程使周围沉积物孔隙水中离子质量浓度发生异常.水合物生成引起的排盐效应主要取决于耗气量.耗气量越大,生成水合物的量越大,排盐效应也就越强,但孔隙水溶液中不同离子质量浓度的变化并不一致.高频振动大大加快了反应速度;粗颗粒(粒径大于125μm)沉积物对水合物生成速度影响不大,而细颗粒(粒径小于74μm)沉积物则明显阻碍水合物的生成.压力对排盐效应的影响体现在反应时间上.在相同反应条件下,反应时间与过冷温度呈幂函数关系.     

In situ methane hydrate dissociation with carbon dioxide sequestration: Current knowledge and issues

There are large resources of methane gas as hydrates in permafrost and deep-sea sediments around the world. On the other hand, the emissions of carbon dioxide into atmosphere have gone up in the last hundred years. The emitted carbon dioxide can be sequestered as hydrate while helping dissociate the in situ methane hydrates. Such approach can improve the economics of carbon dioxide sequestration and methane hydrate dissociation, and assist in global carbon emissions management and methane hydrate exploitation. This paper summarizes the current knowledge on producing methane gas from hydrates while simultaneously sequestering carbon dioxide gas as hydrates, and discusses the challenges and issues in its implementation.     

THE MANY ORIGINS OF NATURAL GAS

Thermodynamic calculations for the C-O-S-Hsystem indicate that at a fixed oxygen fugacity methane is in a stable phase relative to carbon dioxide at high pressures and low temperatures. At a constant temperature and pressure, methane is favored at low oxygen fugacities. Volcanic gases and near-surface igneous rocks exhibit high values of oxygen fugacity. However, direct measurement of the oxygen fugacity of spinels from peridotites of deep origin indicate that the oxygen fugacity of these rocks is low, corresponding to an iron-wüstite buffer. The relative abundance of the carbon isotopes C¹² and C¹³ varies widely in natural gases. Methane formed by bacterial fermentation is highly enriched in the lighter isotope, while methane from deep deposits is much less so as is the methane flowing from hydrothermal vents on the East Pacific Rise. Except in extreme cases, the carbon isotope ratio cannot be used alone to assess whether methane is biogenic or abiogenic. The carbon isotope ratio in coexisting methane and carbon dioxide can be used to estimate the temperature at which the two gases came into isotopic equilibrium. This ratio indicates a high temperature of equilibration for a number of gas deposits. The carbon and helium isotope ratios together with their geologic settings are strongly suggestive that the large quantities of methane in Lake Kivu and the gases venting along the East Pacific Rise are abiogenic. Methane associated with the Red Sea brines and various geothermal areas may also be in part abiogenic. The high abundance of carbon in the Sun, the atmosphere of the outer planets, carbonaceous chondrites and comets, suggests that carbon may be more abundant in the Earth than it is in near-surface igneous rocks. Such a high abundance could lead to a progressive outgassing of methane at depth, which then is oxidized near the surface or in the atmosphere. Methane hydrates are stable at low temperatures and high pressures. Today, methane hydrates are found in areas of permafrost and in ocean sediments. Methane hydrates in ocean sediments were first formed about 20 mya (million years ago) when the Antarctic ice sheet reached sea level. Terrestrial methane hydrates formed more recently during the glaciations beginning 1.6 mya. Methane hydrates and trapped gas are probably abundant under the Antarctic ice sheet. The formation of methane hydrates may be related to the low values of carbon dioxide in the atmosphere some 20,000 years ago.     

天然气水合物生成的影响因素及敏感性分析

天然气水合物是由某些气体或它们的混合物与水在一定温度、压力条件下生成的一种冰状笼型化合物。进行水合物生成条件的敏感性研究对预防天然气水合物的生成有着重要意义。分析了温度、压力两个主导因素的影响,提出了临界温度的概念;验证了盐类对水合物生成的抑制作用;剖析了天然气各组分对水合物生成的敏感程度。得出:水合物生成温度随着压力的增加而升高,但是存在一个临界温度,当环境温度达到该值时,压力对水合物生成的影响很小;甲烷虽然是生成水合物的主要组分,但当其含量趋近100%时,却不易形成水合物;乙烷不是敏感组分;丙烷对水合物生成的影响较乙烷大;异丁烷这类重烃组分,由于其分子大小和Ⅱ型结构中的大洞穴尺寸相匹配,所以对Ⅱ型结构的稳定能力远大于其它分子,当其含量较小时,就易生成Ⅱ型结构水合物;CO2和HS这类酸性气体,易溶水从而能促进水合物的生成。     

Evaluation of natural gas hydrates as a future methane source

In recent years, attention has been given to obtaining methane gas from natural gas hydrates (NGHs) sediment; but its production, economics, and safety are still far away from being commercially viable for many years, and so more research is needed. NGHs are nonstoichiometric crystalline solid compounds that form from mixtures of water molecules and light weight natural gases such as methane, ethane, propane, and carbon dioxide. They are formed in specific thermodynamic conditions, low temperatures (5–15°C) and high pressures (2–3 MPa), and are found in (a) onshore polar regions beneath permafrost and (b) offshore deep-sea sediments. Methane, NG, is the cleanest fossil fuel and its huge amounts in NGHs have carbon quantities more than double of all fossil fuels. The methods that have been proposed for NG extraction from NGHs include: (a) depressurization, (b) thermal stimulation, and (c) chemical inhibitor injections. The authors review the potential of methane gas from NGHs as an unconventional source of future energy. The formation of NGHs as well as extraction of methane from NGHs coupled with technical and environmental challenges are also addressed.     

水合物储存气体促进技术实验研究

利用多孔介质水合物实验装置研究了含水活性炭体系中水合物储存甲烷的特性。活性炭的大比表面和孔隙水有利于水合物的形成,而其孔隙则不利于水合物的形成。本文以活性炭作为水合物形成的载体,实验研究了甲烷水合物的形成过程。结果表明,含水活性炭体系中水合物结晶成核时间缩短,含水活性炭储存甲烷的能力随着实验压力的升高而增大。在一定的压力和温度条件下,含水率在1左右时,活性炭的储气能力最强。     

南海天然气水合物成矿条件与找矿前景

天然气水合物是一种新近发现的能源矿产,世界各国都非常重视对它的调查研究。南海是西太平洋天然气水合物成矿带的重要组成部分,具备良好的成矿条件和找矿前景,并已发现一系列地球物理和地球化学找矿标志,如模拟海底反射层标志、孔隙水氯离子浓度降低标志、卫星热红外增温异常、甲烷含量异常和热释光异常等,是我国最有希望的找矿远景区。     

多孔介质中天然气水合物生成的主要影响因素

目前有关天然气水合物(以下简称水合物)的研究主要集中在物理化学性质考察和开采(分解)方法探索方面。在进行后者的研究过程中,地层渗流过程的物理模拟至关重要,但目前借助于石油开采研究中广泛应用的填砂管等多孔介质对水合物进行动态过程的研究却鲜有报道。为此,利用河砂填砂管在岩心驱替装置上进行了甲烷水合物生成过程的物理模拟,考察了地层温度、甲烷压力及地层模型性质参数等对水合物生成过程的影响。结果表明:(1)利用冰融水作为地层模型的束缚水可显著提升甲烷水合物的生成速率;(2)多孔介质条件下过程驱动力(即实验压力或温度偏离水合物相平衡对应值的程度)对甲烷水合物的生成起着决定性作用;(3)当甲烷压力高于水合物相平衡压力1.4倍以上,或者实验温度低于相平衡温度3℃以下时,甲烷水合物生成诱导期几乎不随温压条件的变化而变化;(4)渗透率、含水饱和度、润湿性等参数对实验中甲烷水合物的生成率不构成明显影响。     

沉积物中甲烷水合物的CO2置换实验

CO₂置换法是一种具有经济和环境双重效益的天然气水合物开采方法,如何测定CO₂置换沉积物中甲烷水合物的置换速率以及怎样提高置换效率一直备受关注。为此,利用自行研制的实验装置,分别进行了置换温度、甲烷水合物饱和度两个因素影响下的CO₂置换沉积物中甲烷水合物模拟实验,探讨了这两个因素对CO₂置换效率的影响规律,并对得到的影响规律进行了置换反应物理过程和相关理论分析。结果表明：①在实验条件下置换反应过程经历快速反应和缓慢反应两个阶段,快速反应阶段的甲烷产气过程受表层甲烷水合物分解过程所控制,而缓慢反应阶段的甲烷产气过程受气体在孔隙水或者冰内的扩散过程所控制;②甲烷水合物分解方式包括吸收CO₂水合物合成释放的热量而分解与降压引起的分解,前者主要由孔隙水或冰的含量决定,而后者主要与温度和压力条件有关;③置换效率随置换温度的增加和甲烷水合物饱和度初始值的减小而变大,置换出来的甲烷气体量随置换温度和甲烷水合物饱和度初始值的增加而增大。结论认为,CO₂置换法更适用于水合物饱和度较高的海域甲烷水合物地层。