Particle size effect on the saturation of methane hydrate in sediments – Constrained from experimental results

Except for those occurring at seafloor, most of natural gas hydrate form in sediments and are subject to the influence of sediment. Among these factors, the particle size effect on hydrate saturation level in sediment have been studied with a series of silica sands with various sizes, and the results obtained clearly indicate that particle size does play an important role in affecting the saturation level of hydrate in sediments. The proton relaxation times of water confined in the same series of silica sands, which were determined with NMR measurement, show logarithmic relationship with particle size. By comprehensive consideration of the results of hydrate saturation and water proton relaxation times, the particle size effect observed is tentatively explained by the water availability for hydrate formation in sediments.     

含水合物沉积物相对渗透率研究进展

气-水相对渗透率是天然气水合物现场试采的关键参数。如何测量和评估储层相对渗透率是提高产气效率、实现天然气水合物产业化需要解决的基础问题。从含水合物沉积物相对渗透率的实验测试、数值模拟和模型建立3个方面,总结了含水合物沉积物相对渗透率的研究进展,研究发现,现有含水合物沉积物实验测试大多采用非稳态法,相对渗透率曲线图显示：在同一含水饱和度下,水合物饱和度越大,水的相对渗透率越小,气的相对渗透率变化规律较为复杂;水合物饱和度的变化改变了沉积物的孔隙空间结构,进而影响气-水相对渗透率。数值模拟大多利用孔隙网络模型或持水曲线进行相对渗透率计算,探索水合物生长习性、孔隙赋存特征,并揭示颗粒尺寸、水合物饱和度、润湿性、表面张力等不同因素对气-水相对渗透率的影响差异。梳理多种相对渗透率模型,发现新近提出的考虑毛细作用和孔径分布的含水合物介质相对渗透率模型在模拟含水合物沉积物中的多相流以及解释水合物饱和度的变化方面具有优势。建议下一步克服该模型计算成本较高的缺陷,实现含水合物沉积物多相流物理精确建模。     

Acoustic wave attenuation in the gas hydrate-bearing sediments of Well GC955H,Gulf of Mexico

A better understanding of wave attenuation in hydrate-bearing sediments is necessary for the improved geophysical quantification of marine gas hydrates. Here we compare the attenuation behavior of hydrate-saturated vs water-saturated sediments at site GC955H, in the Gulf of Mexico, which was surveyed during the JIP Leg II expedition. We compute the P-wave attenuation of the gas hydrate bearing sediments using the median frequency shift method on the monopole waveforms. The results show that P-wave attenuation due to low saturation (<?0.4) in hydrate-filled fractures of fine-grained sediment is comparable to that of the water-filled fracture case. On the contrary, P-wave attenuation due to high saturation (>?0.4) in the hydrate-filled pores of coarse-grained sediments can be up to as much as three times more than that of the water-saturated case. The correlation analysis shows that the P-wave attenuation increases with the increasing gas hydrate saturation for the highly saturated gas hydrate-bearing sand interval while the correlation of the P-wave attenuation and hydrate saturation is weak for low saturated gas hydrate-bearing shale interval. The results show that P-wave attenuation is more likely to be used as a geophysical proxy for gas hydrate quantification of highly concentrated coarse-grained sediment rather than for that of fine-grained sediment. To examine the P-wave behavior in sand, we use the improved LCAM model, which accounts for physical factors such as grain boundary roughness and squirt flow to explain the observed differences in P-wave attenuation between hydrate and water-saturated coarse-grained sediment. Our results provide further geophysical evidences for P-wave behavior in the gas hydrate-bearing sediments in the field.     

沉积物孔隙毛细管压力与甲烷水合物饱和度关系研究

To better understand the relationship between the pore capillary pressure and hydrate saturation in sediments, a new method was proposed. First, the phase equilibria of methane hydrate in fine-grained silica sands were measured. As to the equilibrium data, the pore capillary pressure and saturation of methane hydrate were calculated. The results showed that the phase equilibria of methane hydrates in fine-grained silica sands changed due to the depressed activity of pore water caused by the surface group and negatively charged characteristic of silica particles as well as the capillary pressure in small pores together. The capillary pressure increased with the increase of methane hydrate saturation due to the decrease of the available pore space. However, the capillary-saturation relationship could not yet be described quantitatively because of the stochastic habit of hydrate growth.     

低场核磁共振定量测定松散沉积物中含水量的方法

核磁共振通过测定体系中氢质子弛豫的T2谱来确定液态水的含量。采用低场核磁共振技术定量测定松散沉积物体系中的含水量,探讨了沉积物粒径、黏土矿物种类与含量、孔隙水盐度、温度及气体压力等因素对测试结果的影响。由于不同介质体系中孔隙水表面弛豫机制不同,导致低场核磁测定松散沉积物中的含水量偏小。引入校正系数Cm对水量测试值进行了修正,结果表明：沉积物及孔隙水介质本身特性对水量测试结果几乎无影响,相对误差<0.5%,测试精密度<0.20%;温度变化对测试结果影响较大且呈负相关,温度从25 ℃降至1.7 ℃,水量测试值增加了10.71%;压力变化对测试结果的影响与充注气体是否含氢密切相关,不含氢气体的压力变化对测试结果没有影响,而对于含氢气体如甲烷,水量测试结果随压力变化线性增加,甲烷增加到5.05 MPa时,测试结果增加了12.15%。因此,在采用该法测量甲烷水合物生成分解过程中沉积物孔隙水的变化时,必须考虑体系的温度、压力对测试结果的影响,恒温恒压条件下监测的含水量变化能够准确指示甲烷水合物生成分解的微观过程,可望在海洋天然气水合物生成分解微观动力学研究方面得到广泛应用。     

天然气水合物储层反演及饱和度预测

沉积物含天然气水合物后通常会引起速度的增加,与周围地层形成较大的波阻抗差异,利用地震波阻抗反演技术可识别出这种差异,从而预测天然气水合物的分布。测井资料具有较高的纵向分辨率,而地震资料横向分辨率较高,通过井震联合反演可获得天然气水合物准确的空间展布形态。利用井震联合反演技术对南海北部神狐海域天然气水合物储层进行了精细刻画,研究表明,该矿区天然气水合物储层表现为高波阻抗特征,其值域范围为3 450~4 500 m/s·g/cm3,同时根据有效介质模型建立了岩石物理量版,预测了天然气水合物储层的孔隙度和饱和度数据,预测结果与测井解释结果吻合度较高,为天然气水合物的资源评价提供了比较准确的物性数据。     

Hydrate bearing clayey sediments: Formation and gas production concepts

Hydro-thermo-chemo and mechanically coupled processes determine hydrate morphology and control gas production from hydrate-bearing sediments. Force balance, together with mass and energy conservation analyses anchored in published data provide robust asymptotic solutions that reflect governing processes in hydrate systems. Results demonstrate that hydrate segregation in clayey sediments results in a two-material system whereby hydrate lenses are surrounded by hydrate-free water-saturated clay. Hydrate saturation can reach ≈2% by concentrating the excess dissolved gas in the pore water and ≈20% from metabolizable carbon. Higher hydrate saturations are often found in natural sediments and imply methane transport by advection or diffusion processes. Hydrate dissociation is a strongly endothermic event; the available latent heat in a reservoir can sustain significant hydrate dissociation without triggering ice formation during depressurization. The volume of hydrate expands 2-to-4 times upon dissociation or CO₂CH₄ replacement. Volume expansion can be controlled to maintain lenses open and to create new open mode discontinuities that favor gas recovery. Pore size is the most critical sediment parameter for hydrate formation and gas recovery and is controlled by the smallest grains in a sediment. Therefore any characterization must carefully consider the amount of fines and their associated mineralogy.     

Reflectivity template,a quantitative intercept-gradient AVO analysis to study gas hydrate resources – A case study of Iranian deep sea sediments

Presence of gas hydrate and free gas in Iranian part of Makran accretionary prism changes the elastic properties of unconsolidated sediments and produces sharp bottom simulating reflectors (BSRs) which are observed on the 2-D seismic data. Different methods have been applied to estimate the gas hydrate and free gas saturations in marine sediments based on seismic measurements. Most of these methods are based on relating the elastic properties to the hydrate and free gas saturations and remotely estimating their concentration. In this regard, using the effective medium theory (EMT) which was developed for different modes of hydrate distribution is more considered among other rock physics theories. The main concern about saturation estimations based on EMT is that the velocities of the hydrate-bearing sediments primarily depend on how they are distributed within the pore space. Therefore, understanding the modes of hydrate distribution (at least cementing or non-cementing modes) is necessary to decrease the estimation uncertainties.The first intention of paper is to investigate amplitude variation versus offset (AVO) analysis of BSR to determine the hydrate distribution modes. The results from the probable saturation revealed that if the hydrate cements the sediment grains, BSR would show the AVO class IV and if hydrate does not cement the sediment grains, then BSR would show either the AVO class II or class III depending on the free gas saturation just beneath the BSR. The second intention of paper is to introduce some templates called reflectivity templates (RTs) for quantitative study of hydrate resources. These templates are provided based on the EMT to quantify the hydrate and free gas near the BSR. Validation of this approach by synthetic data showed that a reliable quantification could be achieved by intercept-gradient RTs, only if these attributes are determined with a high accuracy and good assumptions are made about the mineralogical composition and porosity of the unconsolidated host sediments. The results of this approach applied to a 2-D marine pre-stack time migrated seismic line showed that less than 10% of the gas hydrate accumulated near to the BSR in anticlinal-ridge type structure of Iranian deep sea sediments. The free gas saturation near to the BSR by assuming a homogeneous distribution was less than 3% and by assuming patchy distribution was about 3–10%.     

Numerical studies of gas hydrate systems: sensitivity to porosity-permeability models

The formation of sub-seafloor gas hydrates in marine environments can be described as a coupled transport and thermodynamic process inside a host sediment matrix undergoing structural evolution. The transport processes are driven by the sedimentary load and induced overpressure gradients, controlled by sediment permeability. In order to accurately model the resulting fluid flow profile, the decrease of sediment permeability during hydrate precipitation has to be taken into account, which affects both the transport of solutes and sediment compaction. In this paper, we investigate how total hydrate abundance is affected by regions of low permeability which deflect the flow field in their vicinity. For this purpose, a two-dimensional numerical hydrate system model was set up which permits to quantify this effect in scenarios where changes in water depth cause lateral variations of the thickness of the hydrate stability field, as well as of hydrate saturation and sediment permeability. The microscopic structure of gas hydrate crystals in the host sediment matrix defines the evolution of the permeability reduction during hydrate formation. Grain-coating precipitates have a stronger tendency to clog flow paths through pore throats than do pore-filling precipitates. Our results clearly show that these pore-scale processes affect the large-scale flow field and hydrate abundance. The sensitivity depends on the model geometry and, for a 5° slope of the seafloor, 4.1% relative difference is predicted for the hydrate saturation according to different porosity-permeability relationships.     

湛江湾海域表层沉积物粒度特征及沉积环境

根据湛江湾海域2020年10月采集的61个表层沉积物样品粒度分析结果,对沉积物粒度参数进行了总结,划分了沉积物类型,结合Pejrup三角图解对湛江湾海域沉积动力环境进行了分区,运用Gao-Collins粒径趋势分析模型,探讨了沉积物运移趋势。结果表明,湛江湾海域表层沉积物类型共有5种,其中砂、粉砂质砂、砂质粉砂分布最广,粒度组成以细砂为主,平均粒径均值为3.93Φ,分选较差,粒度分布曲线以正偏、正态分布为主。沉积动力判别图解揭示湛江湾海域沉积水动力较强,整体表现为湾内比湾外弱、湾外向外海方向逐渐减弱的特征。粒径趋势分析反映出湛江湾内整体向南部潮流深槽方向运移,湾外围绕沉积中心整体呈逆时针方向运移。湛江湾海域表层沉积物的运移和分布主要受泥沙来源及潮流、波浪、沿岸流等沉积动力环境的共同作用,近年来,人类活动的影响愈加明显。     

Geotechnical properties of deep oceanic sediments recovered from the hydrate occurrence regions in the Ulleung Basin, East Sea, offshore Korea

This study presents comprehensive geotechnical data of the natural marine sediments cored from the hydrate occurrence regions during the Ulleung Basin Gas Hydrate Expedition 1 (UBGH1), East Sea, offshore Korea in 2007. Geotechnical soil index properties of the Ulleung Basin sediments, including grain size distribution, porosity, water content, Atterberg limits, specific gravity, and specific surface area, were experimentally determined. These soil index properties were correlated to geotechnical engineering parameters (e.g., shear strength and friction angle) by using well-known empirical relationships. By performing standard consolidation tests on both undisturbed specimens (as recovered from the original core liner after hydrate dissociation) and remolded specimens, stress-dependent mechanical and hydraulic properties (e.g., compressibility and hydraulic conductivity) were measured. The experimental results provide important engineering parameters, and demonstrate the effect of hydrate presence and consequential dissociation to index properties, engineering parameters, and innate sediment structures.     

Experimental formation of massive hydrate deposits from accumulation of CH4 gas bubbles within synthetic and natural sediments

In order for methane to be economically produced from the seafloor, prediction and detection of massive hydrate deposits will be necessary. In many cases, hydrate samples recovered from seafloor sediments appear as veins or nodules, suggesting that there are strong geologic controls on where hydrate is likely to accumulate. Experiments have been conducted examining massive hydrate accumulation from methane gas bubbles within natural and synthetic sediments in a large volume pressure vessel through temperature and pressure data, as well as visual observations. Observations of hydrate growth suggest that accumulation of gas bubbles within void spaces and at sediment interfaces likely results in the formation of massive hydrate deposits. Methane hydrate was first observed as a thin film forming at the gas/water interface of methane bubbles trapped within sediment void spaces. As bubbles accumulated, massive hydrate growth occurred. These experiments suggest that in systems containing free methane gas, bubble pathways and accumulation points likely control the location and habit of massive hydrate deposits.     

不同海域沉积物对尿素吸附的实验模拟研究

本文对采自渤海、黄海和东海3个典型海域的沉积物进行了尿素吸附/解吸的实验室模拟研究,用Freundlich吸附模型和Henry吸附模型分析了不同沉积物对尿素吸附的热力学特性,并研究了温度、沉积物粒径、有机质含量等因素对尿素在沉积物表面吸附的影响。结果表明,沉积物对尿素的吸附/解吸过程总体呈现3个阶段:快速吸附阶段（0~5 h）—慢速吸附阶段（5~12 h）—平衡阶段（12 h之后）。当水体中的尿素浓度较低时,沉积物解吸释放尿素,随着上覆水中尿素浓度逐渐增加,沉积物对上覆水中的尿素产生吸附行为,各海区沉积物对尿素的吸附能力由强至弱依次为渤海、东海、黄海,这可能与沉积物的类型有关。Freundlich方程和Henry方程均可模拟沉积物对尿素的吸附,温度、粒径以及沉积物中有机质含量等因素均对尿素在沉积物上的吸附产生影响,随着温度升高,尿素在沉积物上的吸附量变小,沉积物粒径越小,有机质含量越高,吸附尿素的能力越强,因此,揭示尿素在沉积物表面的环境行为时,必须考虑以上因素的影响。     

Dissolved silica concentrations and reactions in pore waters from continental slope sediments offshore from Cape Hatteras, North Carolina, USA

The pore water concentrations of dissolved silica in sediment cores from the continental slope offshore from Cape Hatteras, North Carolina, varied from 150 to almost 700 μ,M with depth in the top 40 cm of sediment. Sediment cores from 630 to 2010 m depth had very similar profiles of dissolved silica in their pore waters, even though these cores came from regions greatly different in slope, topography, sedimentation rate, and abundance of benthic macrofauna. Cores from 474 to 525 m were more variable, both with respect to pore water dissolved silica profiles, and with respect to sediment texture. Experiments indicate that both the rate of dissolution of silica and the saturation concentration decrease as sediment depth below the sediment-seawater interface increases. These data are consistent with depletion of a reactive silica phase in surface sediment, which may be radiolarian tests, or the alteration of biogenic silica to a less reactive form over time. Experimental results suggest that the pore water dissolved silica concentration in sediments below the top few centimeters may be higher than the sediments could now achieve. The flux of dissolved silica out of these sediments is estimated to be 15 μmoles cm⁻² yr⁻¹.     

南海神狐海域自生黄铁矿分布、形貌特征及其对甲烷渗漏的指示

自生黄铁矿是渗漏甲烷发生甲烷厌氧氧化和硫酸盐还原作用的产物之一,是海底甲烷渗漏活动的有效示踪剂。南海神狐海域是我国天然气水合物研究的重点区域,对神狐海域柱状沉积物中自生黄铁矿含量、分布、形貌等特征进行研究,结果发现自生黄铁矿的含量随深度增加而递增,存在两个异常富集峰段：在第一个黄铁矿富集峰段,黄铁矿以长条状为主,外形较粗,微晶形态以草莓状黄铁矿为主,且粒径均一;在第二个峰段主要以细长的条状黄铁矿为主,由带外壳结构的草莓球颗粒组成,晶粒大小不一,存在二次生长现象。另外还发现胶黄铁矿与自生黄铁矿共生。这些特征反映神狐海域沉积物中存在多期次的甲烷渗漏事件,高通量的甲烷渗漏发生在较浅的层位,可能发生甲烷的有氧氧化而变成缺氧环境,有利于黄铁矿富集在第一个峰段;较低的甲烷渗漏发生在较深的层位,甲烷厌氧氧化和硫酸盐还原作用而形成大量的黄铁矿保存在第二个峰段。因此,神狐海域沉积物中自生黄铁矿的异常富集可以作为地质历史时期甲烷渗漏通量和期次的指示矿物之一。     

南海海底沉积物声学物理参数测定的温度和时间优化研究

海洋沉积物含水率、密度和孔隙度等物理参数是沉积物声学特性研究中的重要指标。由于南海沉积物类型多样、成分复杂, 特别是深海沉积物样品珍贵, 需精确测定沉积物声学及物理参数并无损害地保持沉积物化学性质。文章以黏土、粉砂和砂三种典型海底沉积物为研究对象, 使用环刀法和烘干法, 在不同温度条件下(60℃、80℃、100℃和120℃)测定和分析了这三种沉积物的含水率、密度、孔隙度随烘干时间的变化趋势及特征, 并进行了回归分析和综合研究。结果表明: 1) 对同类型沉积物, 温度越高, 完全失去孔隙水的时间越短, 且失水过程具有阶段性;2) 同一温度下, 三种典型沉积物完全失去孔隙水的时间为t_砂<t_粉砂<t_黏土, 且不同时间段, 失去孔隙水的速率差异较大, 这主要与沉积物的颗粒大小、颗粒间的间隙大小以及烘干后期沉积物中所含的水分均已大部分流失有关;3) 建议声学沉积物样品的烘干温度以80℃左右为宜, 并给出三种沉积物完全烘干的参考时长和临界时间;4) 在温度为80℃时, 将临界时间处的物理参数带入经验方程进行声速预报是可行的。     

Pore fluid geochemistry from the Mount Elbert Gas Hydrate Stratigraphic Test Well, Alaska North Slope

The BPXA-DOE-USGS Mount Elbert Gas Hydrate Stratigraphic Test Well was drilled and cored from 606.5 to 760.1 m on the North Slope of Alaska, to evaluate the occurrence, distribution and formation of gas hydrate in sediments below the base of the ice-bearing permafrost. Both the dissolved chloride and the isotopic composition of the water co-vary in the gas hydrate-bearing zones, consistent with gas hydrate dissociation during core recovery, and they provide independent indicators to constrain the zone of gas hydrate occurrence. Analyses of chloride and water isotope data indicate that an observed increase in salinity towards the top of the cored section reflects the presence of residual fluids from ion exclusion during ice formation at the base of the permafrost layer. These salinity changes are the main factor controlling major and minor ion distributions in the Mount Elbert Well. The resulting background chloride can be simulated with a one-dimensional diffusion model, and the results suggest that the ion exclusion at the top of the cored section reflects deepening of the permafrost layer following the last glaciation (∼100 kyr), consistent with published thermal models. Gas hydrate saturation values estimated from dissolved chloride agree with estimates based on logging data when the gas hydrate occupies more than 20% of the pore space; the correlation is less robust at lower saturation values. The highest gas hydrate concentrations at the Mount Elbert Well are clearly associated with coarse-grained sedimentary sections, as expected from theoretical calculations and field observations in marine and other arctic sediment cores.     

Acoustic response of gas hydrate formation in sediments from South China Sea

Gas hydrate has been recognized as a potential energy resource in South China Sea (SCS). Understanding the acoustic response of gas hydrate formation in the SCS sediments is essential for regional gas hydrate investigation and quantification. The sediments were obtained from gravity core sampling at E 115°12.52363′ N 19°48.40299′. Gas hydrate was formed within a “gas + water-saturated SCS sediments” system. Combination of a new bender element technique and coated time domain reflectometry (TDR) was carried out to study the acoustic response of hydrate occurrence in SCS sediments. The results show the acoustic signal becomes weak when hydrate saturation (S_h) is lower than 14%. The acoustic velocities (Vp, Vs) of the sediments increase with S_h during hydrate formation, and Vs increases relatively faster when S_h is higher than 14%. These results indicate that tiny hydrate particles may firstly float in the pore fluid, which causes a significant acoustic attenuation, but has little influence on shear modulus. As time lapses and S_h approaches 14%, numerous particles coalesce together and contact with sediment particles. As a result, Vs has a sharp increase when hydrate saturation exceeds 14%. Several velocity models were validated with the experimental data, which suggests a combination of the BGTL (Biot–Gassmann Theory modified by Lee) model and the Weighted Equation is suitable to estimate S_h in SCS.     

舟山潮差带海相沉积物的物理和化学特征

为舟山潮差带海相沉积物固结机理的深入研究提供物质基础,采用激光粒度仪分析了海相沉积物的粒度组成,并测试了海相沉积物的化学元素、化合物种类及其相对含量,还使用X-射线衍射技术分析了海相沉物的矿物组成。结果表明:海相沉积物含水率高、初始孔隙比大、呈流塑状,为低液限粉质黏土;活性指数为12.4,属于活动黏性土,矿物的亲水性较好;全盐含量高达9～11.2 g/kg,阳离子交换能力不强,有机质含量(5.82～12.7 g/kg)较高;pH值为7.35～8.36,呈弱碱性,加上孔隙水中K^+,Na^+,Ca²⁺,Mg²⁺的存在,使得高岭石常不稳定,有向伊利石、蒙脱石或绿泥石转化的趋势。