海底天然气水合物相平衡的影响因素

海底沉积物中蕴含着大量的天然气水合物资源.天然气水合物相平衡及其影响因素研究对海底沉积物中水合物的成藏热力学和动力学研究、分布范围和储量估算均具有十分重要的意义.目前关于水合物相平衡影响因素研究大多局限于定性或半定量分析,对不同因素的影响程度及机理关注较少.收集整理了气体组分、孔隙水盐度及离子组分、沉积物粒度和孔隙半径...     

海洋浅表层沉积物和孔隙水的天然气水合物地球化学异常识别标志

天然气水合物是一种赋存在低温,高压条件下海底沉积物中的规模巨大的新型能源,研究表明,地球化学是识别海底天然气水合物赋存的一种有效方法。国际上通过分析由大洋钻探采上来的柱状沉积物和孔隙水的地球化学异常,已建立了一套较为成熟的地球化学识别方法。但是,在没有钻井岩心的情况下,如何通过浅表层（＜20m）沉积物和孔隙水及底层海水的地球化学分析来识别海底可能存在的天然气水合物,是国际国内天然气水合物勘查中面临的一道难题,通过对国际上已有数据和资料的全面总结,尝试提出了一系列在海底浅层条件下识别天然气水合物赋存的地球异常标志,包括底层海水的烃类气体及其同位素组成异常,沉积物有机碳和水的含量异常,沉积物中孔隙水的元素和同位素组成异常,沉积物中气体含量异常及沉积物中自生碳酸盐矿物的化学和同位素组成异常等。这些标志的建立将有助于在我国海域开展天然气水合物的勘查工作。     

天然气水合物的聚集和形成及南海地质条件分析

天然气水合物目前已经成为世界范围的一个研究热点，而我国的天然气水合物研究起步则相对较晚，通过阅读国内外有关文献，总结了天然气水合物在海底的分布特征，聚集和形成机制，产状及其形成机理，甲烷羽的形成过程，天然气水合物在沉积物中的聚集位置通常有两种情况：一是较浅的沉积物（海底以下几米）中，受控于泥底辟，泥火山，断层等；二是较深的沉积物（海底以下几十米，甚至更深）中，受控于流体，当断层延伸至海底时，通常在水合物聚集处的上部发现甲烷羽，天然气以溶解气，游离气或分子扩散的形式运移，在温，压适宜的沉积物中，即水合物稳定带内聚集并形成水合物，水合物的形成过程是：最初形成晶体，呈分散状分布于沉积物中，之后逐渐聚集，生长成结核状，层状，最后形成块状，在细粒的浅层沉积物中，通常以较慢的速度生长，形成分散状的水合物；而在粗粒沉积物中，水合物通常呈填隙状，并且这种产状可能位于较深层位中，我国南海在温度，压力，构造条件，天然气来源等方面都能满足天然气水合物的形成条件，并且在南海也发现了一些水合物存在的标志，如似海底反射层（BSR）以及孔隙水中氯离子浓度的降低。因此，天然气水合物在我国南海海域可能有很好的前景。     

海底天然气水合物地球化学探测技术

海底天然气水合物是未来的新型能源，地球化学探测与分析技术在天然气水合物勘探、研究和开发中发挥巨大作用。简要介绍了天然气水合物地球化学探测方法及相关的分析测试技术，包括海底沉积物、海水、海面低层大气中烃类气体(主要为甲烷)、孔隙水中阴阳离子和同位素地球化学异常等。并对发展天然气水舍物地球化学探测与分析新技术提出建议。     

硫酸盐-甲烷界面与甲烷通量及下伏水合物赋存的关系

硫酸盐-甲烷界面在富甲烷和含天然气水合物的海洋沉积区已经成为一个重要的生物地球化学识别边界.在硫酸盐-甲烷界面之上,沉积物中的硫酸盐因参与分解有机质和甲烷厌氧氧化反应而被消耗,而界面之下沉积物中的甲烷则不断生成,含量逐渐增加.根据该界面附近硫酸盐浓度和甲烷浓度的变化特征,可以判断该区甲烷流体通量的大小,从而指示下伏天然气水合物的可能赋存状况.南海北部陆坡的柱状沉积物孔隙水数据的分析显示,其硫酸盐-甲烷界面埋深比较浅,表明该海域的甲烷通量较高.这种高甲烷通量很可能是由下伏的天然气水合物所引起的,并暗示着该区下伏海底可能有天然气水合物沉积层赋存.     

东北太平洋Cascadia陆缘Orca滑坡触发机理的数值模拟

海底温度和海平面变化可以引起海底天然气水合物分解,导致沉积物孔隙内形成超压,改变沉积物有效应力从而触发海底滑坡。本文建立了与此相关的海底滑坡产生的数值模型,并应用于东北太平洋Cascadia陆缘14～9 kaBP期间发生的Orca滑坡形成过程研究。模拟结果显示在最近18 ka海平面逐渐上升的大背景下,18～14 kaBP期间底水温度升高引起其后的天然气水合物稳定带底界快速上移,并在13.7 kaBP达到1.18 m/ka的高底界上移速率,此时Orca地区稳定带底界粗颗粒层内的高饱和度天然气水合物发生分解,产生114 kPa的流体超压,使地层安全系数显著小于1,触发海底滑坡。因此,海底温度升高引起高饱和度天然气水合物分解可能是东北太平洋Cascadia陆缘Orca海底滑坡的主要触发因素。     

用孔隙水中氯离子浓度异常估算天然气水合物含量

水分子与烃类气体沉积物孔隙中结合形成水合物的过程中,只吸取孔隙中的淡水,而盐类物质不能进入水合物的晶体结构,在水合物形成过程中会引起局部孔隙水离子浓度的浓缩,增加周围沉积物孔隙水的盐度;而当水合物分解时,孔隙水就会被稀释,使得钻孔获得的水合物样品比不含水合物的样品具有更低的盐度.因为C1-是浅层海洋没积物孔隙水中一种丰富且保守的离子,C1-离子浓度变化通常被用来监测天然气水合物的形成和分解.……     

硫酸盐-甲烷界面与甲烷通量及下伏天然气水合物赋存的关系

硫酸盐-甲烷界面在富甲烷和含天然气水合物的海洋沉积区已经成为一个重要的生物地球化学识别边界。在硫酸盐-甲烷界面之上,沉积物中的硫酸盐因参与分解有机质和甲烷厌氧氧化反应而被消耗,而其界面之下沉积物中的甲烷则不断生成,含量逐渐增加。根据该界面附近硫酸盐浓度和甲烷浓度的变化特征,可以判断该区甲烷流体通量的大小,从而指示下伏天然气水合物的可能赋存状况。南海北部陆坡的柱状沉积物孔隙水数据的分析显示,硫酸盐-甲烷界面埋深比较浅,表明该海域的甲烷通量较高。这种高甲烷通量很可能是由下伏的天然气水合物所引起的,并暗示着该区下伏海底可能有天然气水合物沉积层赋存。     

天然气水合物分解对海底斜坡稳定性影响研究进展

天然气水合物作为一种新型能源,已经逐渐引起人们的重视。赋存于海底沉积物中的天然气水合物虽然本身作为亚稳定胶结物对海底有建造作用,但是由于其对特定温度和压力条件的严格依赖,海底温压条件的改变会引起其分解,从而使海底沉积物失稳甚至导致海底滑坡。本研究系统介绍了近年来国内外针对天然气水合物合成、物理性质及对海底稳定性影响进行...     

天然气水合物赋存地层的地震波场模拟及对比

通过分析天然气水合物在海洋中的6种主要赋存状态类型,总结了每种赋存状态之间的相互转化关系及其物性参数计算方法,并应用到地震波场的正演模拟中。对比研究了声波模型、弹性波模型和双相介质模型对各种水合物赋存地层的响应特征,结果表明:1)当地层中存在孔隙充填型水合物且下伏地层不含游离气时,双相介质模拟的含水合物层底界表现负极性特征;当充填结核型水合物时,弹性介质和双相介质模拟的水合物底界反射呈负极性;2)当地层充填颗粒包裹型水合物且下伏地层含游离气时,无论是低频(25 Hz)条件还是提高子波主频(40 Hz),3种介质模拟水合物的地震响应特征都很明显,但水合物层底界反射振幅随偏移距变化的关系存在差异;3)当沉积薄层中充填颗粒间胶结型水合物且下伏地层含游离气时,弹性介质和双相介质模拟水合物薄层底界的反射振幅随偏移距的增大而减小;将水合物类型改为颗粒支撑型并提高子波主频,声波介质和弹性介质模拟水合物层底界的反射振幅随偏移距的增大而减小。     

海洋天然气水合物生成机制的实验研究

天然气水合物在海洋环境中与在纯水溶液中的生成条件有很大的不同。海洋天然气水合物的生成除了受温度和压力的影响外,还要受到孔隙水的化学组成、流体中气体的浓度及沉积物类型的影响。本文综述了国外海洋天然气水合物的实验研究成果及其进展,重点介绍了海洋天然气水合物生成与分解的热力学条件及各种影响因素,并探讨了今后该领域的研究方向和问题。     

Investigation of microbial influences on seafloor gas-hydrate formations

Microbial communities flourish at gas hydrate occurrences in ocean sediments. Studies are reported in this paper on the laboratory production, separation, characterization and hydrate catalysis of biosurfactants from cultures of the Bacillus subtilis bacterium associated with Gulf of Mexico gas-hydrate accumulations. The B. subtilis bacterium from ATCC 21332 species was cultured anaerobically with glucose as carbon-source to produce surfactin, one of the more potent surface active agents known. The surface-active agent was removed from the broth in foam created by bubbling inert gas through the mixture, and biosurfactant was then recovered from the collapsed-foam distilled water solution by acid precipitation and dichloromethane extraction. According to HPLC spectra, five surfactin isomers were identified in the sample of laboratory-generated biosurfactant. Recovered surfactin was then used to perform gas-hydrate formation studies in porous media saturated with the surfactin-water solution. Gas-hydrate induction time and formation rate determinations showed that the anaerobically-produced biosurfactants catalyzed hydrate formation markedly. The tests suggest prolific surfactin production by the B. subtilis bacterium and of other species under prevailing anaerobic conditions around seafloor gas hydrates that promotes hydrate formation and the propensity of the bioproduct to be dispersed in the porous media by natural gas vents.     

Amplitude blanking related to the pore-filling of gas hydrate in sediments

Seismic indicators of gas-hydrate-bearing sediments include elevated interval velocities and amplitude reduction of seismic reflections owing to the presence of gas hydrate in the sediment's pore spaces. However, large amplitude blanking with relatively low interval velocities observed at the Blake Ridge has been enigmatic because realistic seismic models were absent to explain the observation. This study proposes models in which the gas hydrate concentrations vary in proportion to the porosity. Where gas hydrate concentrations are greater in more porous media, a significant amplitude blanking can be achieved with relatively low interval velocity. Depending on the amount of gas hydrate concentration in the pore space, reflection amplitudes from hydrate-bearing sediments can be much less, less or greater than those from corresponding non-hydrate-bearing sediments. This revised version was published online in November 2006 with corrections to the Cover Date.     

Numerical Study on Dissociation of Gas Hydrate and Its Sensitivity to Physical Parameters

The natural gas hydrate resource is tremendous.How to utilize the gas from hydrates safely is researchers' concern.In this paper,a one-dimensional model is developed to simulate the hydrate dissociation by depressurization in hydrate-bearing porous medium.This model can be used to explain the effects of the flow of multiphase fluids,the endothermic process of hydrate dissociation,the variation of permeability,the convection and conduction on the hydrate dissociation.Numerical results show that the hydrate dissociation can be divided into three stages:a rapid dissociation stage mainly governed by hydrate dissociation kinetics after an initially slow dissociation stage governed mainly by flow,and finally a slow dissociation stage.Moreover,a numerical approach of sensitivity analysis of physical parameters is proposed,with which the quantitative effect of all the parameters on hydrate dissociation can be evaluated conveniently.     

基于BP神经网络的天然气水合物相平衡计算及预测

针对天然气水合物相平衡问题,文中提出用基于带动量因子的BP神经网络进行计算和预测。首先用遗传算法优化确定BP神经网络的结构和参数,得到最优化结构的神经网络;其次结合Levenberg-Marquart优化算法,建立天然气水合物相平衡计算及预测的神经网络模型;最后以实验测定的(CH4 CO2 H2S)三元酸性天然气水合物体系的平衡数据为训练和预测样本进行了计算。计算表明,预测结果与实验数据有良好的一致性,而且由于BP神经网络作为所谓的“纯粹”的算法不需要热力学模型,这对于相平衡计算是非常方便的,所以是研究天然气水合物相平衡计算及预测的一种新的有效方法。     

Examination of core samples from the Mount Elbert Gas Hydrate Stratigraphic Test Well, Alaska North Slope: Effects of retrieval and preservation

Collecting and preserving undamaged core samples containing gas hydrates from depth is difficult because of the pressure and temperature changes encountered upon retrieval. Hydrate-bearing core samples were collected at the BPXA-DOE-USGS Mount Elbert Gas Hydrate Stratigraphic Test Well in February 2007. Coring was performed while using a custom oil-based drilling mud, and the cores were retrieved by a wireline. The samples were characterized and subsampled at the surface under ambient winter arctic conditions. Samples thought to be hydrate bearing were preserved either by immersion in liquid nitrogen (LN), or by storage under methane pressure at ambient arctic conditions, and later depressurized and immersed in LN. Eleven core samples from hydrate-bearing zones were scanned using x-ray computed tomography to examine core structure and homogeneity. Features observed include radial fractures, spalling-type fractures, and reduced density near the periphery. These features were induced during sample collection, handling, and preservation. Isotopic analysis of the methane from hydrate in an initially LN-preserved core and a pressure-preserved core indicate that secondary hydrate formation occurred throughout the pressurized core, whereas none occurred in the LN-preserved core, however no hydrate was found near the periphery of the LN-preserved core. To replicate some aspects of the preservation methods, natural and laboratory-made saturated porous media samples were frozen in a variety of ways, with radial fractures observed in some LN-frozen sands, and needle-like ice crystals forming in slowly frozen clay-rich sediments. Suggestions for hydrate-bearing core preservation are presented.     

The enigma of double BSRs: indicators for changes in the hydrate stability field?

 A classical bottom simulating reflector (BSR) and a presently unknown double BSR pattern are detectable in reflection seismic profiles from the Storegga Slide area west of Norway. Pressure and temperature modeling schemes lead to the assumption that the strong BSR marks the base of a hydrate stability zone with a typical methane gas composition of 99%. The upper double BSR may mark the top of gas hydrates and the lower double BSR may represent a relict of former changes of the hydrate stability field from glacial to interglacial times or the base of gas hydrates with a gas composition including heavier hydrocarbons.     

Rock physics modeling for assessing gas hydrate and free gas: a case study in the Cascadia accretionary prism

We investigate the estimation of gas hydrate and free gas concentration using various rock physics models in the Cascadia accretionary prism, which is one of the most intensively studied regions of natural gas hydrate occurrences. Surface seismic reflection data is the most useful and cost-effective in deriving seismic velocity, and hence estimating gas hydrate and free gas across a BSR with depth, if a proper background (without gas hydrate and free gas) velocity is chosen. We have used effective medium theory of Helgerud et al. (EMTH) and, a combination of self-consistent approximation and differential effective medium (SCA-DEM) theory coupled with smoothing approximation for crystalline aggregate. Using the SCA-DEM (non-load-bearing) and EMTH (load-bearing) modeling, we calculate the average saturations of gas hydrate as 17 and 19%, respectively within ~100 m thick sedimentary column using velocity, derived from the surface seismic data. The saturations of gas hydrate are estimated as 15 and 18% using the SCA-DEM, and 20 and 25% using EMTH from the logging-while-drilling and wire-line sonic velocities, respectively. Estimations of gas hydrate from Poisson’s ratio are in average 50% for EMTH and 10% for SCA-DEM theory. We obtain the maximum saturation of free gas as 1–2% by employing the SCA-DEM theory either to seismic or sonic velocities, whereas the free-gas saturation varies between 0.1 and 0.4% for EMTH model. The gas hydrate saturation estimated from the sonic velocity and the free gas saturation derived from both the seismic and sonic velocities using the SCA-DEM modeling match quite well with those determined from the pressure core data in the study region.     

天然气水合物及其实测的地球物理测井特征

沉积盆地内能够形成天然气水合物的先决条件包括：富含分散有机质的沉积物中充有地下水、深水区的水动力处于滞流状态、存在生物成因的气体、压力与温度具有特定的相关关系等。许多科学家提出天然气水合物主要有两种成因机制：（1）先存天然气田因温度或孔隙压力的有利变化而转变为天然气水合物；（2）微生物成因气或热成因气从下部运移至天然气水合物稳定带。     

Occurrence and exploration of gas hydrate in the marginal seas and continental margin of the Asia and Oceania region

Supplies of conventional natural gas and oil are declining fast worldwide, and therefore new, unconventional forms of energy resources are needed to meet the ever-increasing demand. Amongst the many different unconventional natural resources are gas hydrates, a solid, ice-like crystalline compound of methane and water formed under specific low temperature and high pressure conditions. Gas hydrates are believed to exist in large quantities worldwide in oceanic regions of continental margins, as well as associated with permafrost regions in the Arctic. Some studies to estimate the global abundance of gas hydrate suggest that the total volume of natural gas locked up in form of gas hydrates may exceed all known conventional natural gas reserves, although large uncertainties exist in these assessments. Gas hydrates have been intensively studied in the last two decades also due to connections between climate forcing (natural and/or anthropogenic) and the potential large volumes of methane trapped in gas hydrate accumulations. The presence of gas hydrate within unconsolidated sediments of the upper few hundred meters below seafloor may also pose a geo-hazard to conventional oil and gas production. Additionally, climate variability and associated changes in pressure-temperature regimes and thus shifts in the gas hydrate stability zone may cause the occurrence of submarine slope failures.Several large-scale national gas hydrate programs exist especially in countries such as Japan, Korea, Taiwan, China, India, and New Zealand, where large demands of energy cannot be met by domestic supplies from natural resources. The past five years have seen several dedicated deep drilling expeditions and other scientific studies conducted throughout Asia and Oceania to understand gas hydrates off India, China, and Korea. This thematic set of publications is dedicated to summarize the most recent findings and results of geo-scientific studies of gas hydrates in the marginal seas and continental margin of the Asia, and Oceania region.