输气管线中天然气水合物形成的地球化学控制因素

对于纯气体形成水合物，甲烷形成的温压条件最高，丁烷最低，乙烷和丙烷介于二之间。在甲烷-乙烷和甲烷-丙烷的二元混合体系中，形成水合物时随甲烷含量增高，形成温度降低、压力增高；对于自然产出天然气的多组分混合体系，随丙烷 丁烷含量增加，水合物形成压力降低，温度增高。增高水合物体系的盐度或加入阻凝剂，水合物的形成压力增高，温度降低。在确定的环境温度条件下，根据天然气成分可以确定天然气形成水合物的最大压力，从而能最大限度地提高输气设备的工作效率；加入阻凝剂或提高体系的盐度也可大大提高输气设备的工作效率。     

冰点下多孔介质中甲烷水合物的生成特性

冰点下水合物在多孔介质的生成是一个复杂的多相转化过程,为了研究冰点下多孔介质中水合物生成过程的水相转化率、气体消耗量与稳定压力等生成特性,在定容条件下,进行不同孔径与粒径的多孔介质中甲烷水合物在冰点下的生成实验。所使用的多孔介质平均孔径为1295 nm、1796 nm和3320 nm。研究结果表明：水合物生成结束时水的转化率随着初始生成压力的增大而增大,随着温度的升高而降低,随着孔径的增大而增大;在相同的孔径下,多孔介质粒径的增大降低了水合物的生成速率但对最终气体消耗量没有影响;在相同的温度下,随着初始生成压力的增大,实验最终压力、气体消耗量与最终水的转化率均随之升高;温度越高,不同的生成初始生成压力下体系的最终稳定压力与水的转化率相差越大;在多孔介质的毛细管作用力与结合水的共同作用下,冰点下水合物生成的水的转化率会大大地降低。在本实验条件下,水相转化为水合物的比例最高为32.39%。     

粒径及孔径分布对天然气水合物形成影响的研究进展

掌握影响天然气水合物(简称水合物)在海底沉积物中形成的因素对其能源和气候环境效应的评估有重要的意义。水合物的含量与沉积物颗粒的粒径紧密相关,水合物多产出于粗砂中。以人工样品为主的实验研究表明,由于孔隙半径产生的毛细管抑制压力,多孔介质的颗粒越细,孔隙越小,一定条件下稳定温度越低(或压力越高)。沉积物颗粒的比表面积与水合物饱和度呈现很高的相关性,比粒径更有优势。利用比表面积可以定量地表示粒径和孔隙大小之间的关系,量化分析孔隙大小对水合物形成的影响。此外,我国南海神狐海域水合物尽管赋存在细粒沉积物中,却具有较高的饱和度,这可能与南海沉积物中富含丰富的有孔虫壳体有关,通过微观层面的观察发现,这些古生物壳体不仅充当了沉积物中的粗砂部分,而且其多孔结构也使沉积孔隙空间增加,从而为水合物富集提供了有利的生长环境和便利的赋存空间。Klauda等的模型假定多孔介质孔径尺寸的概率密度分布函数为正态分布,新的相平衡模型包含了尺寸效应。颜荣涛等把有效孔隙半径和水合物饱和度联系起来,从而将水合物饱和度引入相平衡模型中。分形模型将分形参数与孔隙度建立了关系,但并没有与温压条件等进一步联系起来,对水合物形成和分解的影响还需做进一步的推导和实验。     

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。     

封闭系统中多孔介质甲烷水合物的CT实验研究

阐述了在封闭系统中的查理模型,建立了利用查理定律计算分析甲烷水合物生成和分解的方法。通过实验,对封闭系统中不同含水量多孔介质甲烷水合物生成、发育和分解的实验方法、相平衡条件、生成量关系等进行了探讨。在一定温度差的介质里,水分克服重力向冷端迁移并生成水合物。实验中利用查理数的改变计算水合物的生成量变化,连通性好的含水多孔介质有很好的水—气结合条件,达到平衡条件后迅速生成水合物,在240分钟内完成,含水量线性地影响甲烷水合物的生成量。同时,利用CT扫描方法直接观测含水粗砂在低温—高压环境下的甲烷水合物生成和分解过程,并可以利用CT图像数据计算出多孔介质中水分迁移、区域密度改变和砂体的移动、及分解后介质密度分布变化特征。     

陆域天然气水合物取样关键因素探讨

温度和压力是保持天然气水合物不分解的2个重要参数。依据热物理力学理论和理想气体特性,通过计算机模拟0℃以上甲烷水合物和二氧化碳水合物在不同温度-压力条件下的分解,得到甲烷水合物分解P-T平衡相图,探讨了钻探获取陆域天然气水合物取样温压关系。     

马里亚纳弧前蛇纹岩泥火山无机成因甲烷–氢气水合物形成条件与稳定带发育特征

海洋水合物的成藏不仅需要合适的温度、压力条件,而且需要充足的气源。一般认为大洋区海底沉积物缺乏丰富的有机质,不具备天然气水合物发育的气源条件。然而最近研究表明洋壳广泛的蛇纹岩化作用可以产生大量的无机成因甲烷,并找到了与蛇纹岩化有关的水合物发育证据。蛇纹岩化过程中不仅有甲烷生成,还生成大量的氢气,很可能形成甲烷–氢气水合物。本文根据IODP 366航次钻探资料,应用甲烷–氢气水合物的热力学模型,计算了马里亚纳弧前三个蛇纹岩泥火山钻探实测获得的不同氢气含量条件下的甲烷–氢气水合物稳定带分布特征。结果显示氢气比例越高,计算获得的甲烷–氢气水合物稳定带底界深度越浅。研究的6个马里亚纳弧前蛇纹岩泥火山站位中, IODP 1491、1492、1496、1498四个站位可能具备甲烷–氢气水合物发育温压和气体成分组成条件; IODP 1493、1497站位几乎不具备甲烷–氢气水合物的温压和气体组成条件。     

天然气水合物稳定带的计算方法与参数选择探讨

天然气水合物稳定带的研究对于认识天然气水合物的成矿与分布规律以及资源评价都具有重要的指导意义。在计算稳定带厚度的不同方法之间,特别是在参数的选择上存在很大的差异。通过简单评价天然气水合物稳定带计算的几种方法和参数选择,认为选择压力计算公式时要考虑孔隙水产生的压力、海底以上水柱的压力和大气压;考虑大气压的压力随纬度变化的二阶方程是最符合实际的深度-压力转换方程;通过实验得到的方程只适用于纯水或盐度为33.5‰的海水中纯甲烷的预测;根据热力学理论可以计算不同盐度、不同气体组分的稳定带的温压条件;用相平衡图的方法最简单,但误差很大;通过四阶方程拟合实验数据和热力学数据得到的稳定带厚度更接近实际情况;不同方法预测的稳定带底界与实际含水合物沉积底界很难一致。     

甲烷水合物生成过程中海水常量离子浓度的变化规律

本文自行研制了一套甲烷水合物合成装置,模拟海洋环境甲烷水合物的生成过程,对该过程水合物生成位置、形态、反应时间、环境温压条件进行观测,同时连续测试体系海水中常量离子K+、Na+、Ca2+、Mg2+、C1-、SO42-的浓度及海水盐度,探讨水合物生成过程的温压变化及离子浓度变化之间的关系和离子浓度的变化规律.结果表明,海水中甲烷水合物生成具有很大的随机性,在相同的初始条件下可能有不同的水合物成核、聚集过程;甲烷水合物在生成过程中,耗气量不断增加,孔隙水的盐度和海水中常量阴阳离子的浓度也在不断增加,这种变化具有较高的线性相关性(相关系数为0.9848～0.9950),且不受甲烷水合物生成位置及状态的影响;在水合物生成过程的微环境下耗气量相同时,离子浓度存在细微的差异.这些特征为通过测定海底水合物周围孔隙水中常量离子的浓度初步推算水合物的甲烷耗气量提供了依据.     

钻井液侵入时水合物近井壁地层物性响应特征

目前,国内外学者对钻井液侵入水合物地层的室内实验模拟研究停留在较小尺度上且可靠性难以验证,尚需利用与实际地层物性参数较为贴近的沉积物模型, 开展大尺度的实验模拟,为改善水合物地层钻井过程中钻井液工艺和测井准确识别与评价水合物储层提供依据.根据墨西哥湾水合物地层主要物性参数指标压制了相应的人造岩心,进行了人造岩心钻井液侵入实验.结果表明:水合物在加热分解过程中,温度与压力呈上升趋势,而电阻率先升高后下降,水合物相平衡条件不仅与温压条件有关,还受孔隙水盐度不断变化的影响。钻井液侵入岩心过程中,压力的传递速率快于热量的传递,易使原始岩心孔隙中的水、气在压力升高而温度尚未改变的情况下生成二次水合物.钻井液温度是水合物分解的主要因素,而压差有利于提高孔隙水压力,保持水合物的稳定.高密度钻井液虽有利于形成高压差和抑制水合物在钻井液中形成,但也会导致钻井液低侵并使井周水合物更易分解.因此,在实际水合物地层钻井中,为了减少钻井安全事故,应在安全密度窗口范围内尽可能提高钻井液密度,选用温度较低的钻井液并加入一定量的动力学抑制剂或防漏失剂.电阻率测井应该选用随钻测井方式或者深侧向测井值,从而避免因水合物分解导致的测井失真.      

南海神狐海域天然气水合物声波测井速度与饱和度关系分析

利用南海北部神狐海域A站位的地震和测井资料综合分析神狐海域含天然气水合物沉积层的声波测井速度及水合物饱和度的分布特征和变化规律,并对水合物饱和度的理论计算值和实测值进行对比分析,同时对水合物稳定带的纵波速度特征与饱和度的关系进行了综合研究。结果表明：神狐海域A站位的水合物层厚度约20 m,纵波速度在1 873～2 226m/s之间,水合物饱和度在15.0%～47.3%之间变化,水合物饱和度值相对较高;受海底复杂地质因素的影响,根据岩心孔隙水的氯离子淡化程度实测的水合物饱和度随声波速度的变化并不是单一的正比例关系,而是随声波速度的升高而上下波动,波动幅度在10%～20%之间,总体趋势上随声波速度的升高而升高,并集中分布在理论曲线附近;利用热弹性理论速度模型计算并校正后的水合物饱和度随声波速度的增加而有规律地增加,水合物饱和度的理论计算值与实测数据比较吻合,说明所建立的岩石物理模型正确,模型参数选取合理。根据声波速度计算水合物饱和度这一方法可扩展到整个研究区域,并为研究区的水合物资源量评价提供基础数据。     

海底天然气渗漏形成水合物量的线性动力学模型:以墨西哥湾GC185区块Bush高地为例

世界许多地区如墨西哥湾，存在着大量天然气渗漏并形成水合物的现象，出于科学，生态，气候和安全的需要。人类有必要弄清存在于海底以水合成形式存在的天然气的比例。因此，构建了水合物形成量的线性动力学模型，以分析墨西哥湾GC185块区Bush高地海底渗漏天然气的地质过程和行为。Bush高地渗漏的天然气来源于附近的Jolliet气藏，结果表明，渗漏天然气中约有9％的海底形成了水合物。     

Distribution of gas hydrate reservoir in the first production test region of the Shenhu area,South China Sea

In May and July of 2017, China Geological Survey (CGS), and Guangzhou Marine Geological Survey (GMGS) carried out a production test of gas hydrate in the Shenhu area of the South China Sea and acquired a breakthrough of two months continuous gas production and nearly 3.1 × 10⁵ m³ of production. The gas hydrate reservoir in the Shenhu area of China, is mainly composed of fine-grained clay silt with low permeability, and very difficult for exploitation, which is very different from those discovered in the USA, and Canada (both are conglomerate), Japan (generally coarse sand) and India (fracture-filled gas hydrate). Based on 3D seismic data preserved-amplitude processing and fine imaging, combined with logging-while-drilling (LWD) and core analysis data, this paper discusses the identification and reservoir characterization of gas hydrate orebodies in the Shenhu production test area. We also describe the distribution characteristics of the gas hydrate deposits and provided reliable data support for the optimization of the production well location. Through BSR feature recognition, seismic attribute analysis, model based seismic inversion and gas hydrate reservoir characterization, this paper describes two relatively independent gas hydrate orebodies in the Shenhu area, which are distributed in the north-south strip and tend to be thicker in the middle and thinner at the edge. The effective thickness of one orebody is bigger but the distribution area is relatively small. The model calculation results show that the distribution area of the gas hydrate orebody controlled by W18/W19 is about 11.24 km², with an average thickness of 19 m and a maximum thickness of 39 m, and the distribution area of the gas hydrate orebody controlled by W11/W17 is about 6.42 km², with an average thickness of 26 m and a maximum thickness of 90 m.     

Sensitivity Analysis of Multi-phase Seepage Parameters Affecting the Clayey Silt Hydrate Reservoir Productivity in the Shenhu Area, South China Sea

Natural gas hydrate (NGH) is an important future resource for the 21st century and a strategic resource with potential for commercial development in the third energy transition. It is of great significance to accurately predict the productivity of hydrate-bearing sediments (HBS). The multi-phase seepage parameters of HBS include permeability, porosity, which is closely related to permeability, and hydrate saturation, which has a direct impact on hydrate content. Existing research has shown that these multi-phase seepage parameters have a great impact on HBS productivity. Permeability directly affects the transmission of pressure-drop and discharge of methane gas, porosity and initial hydrate saturation affect the amount of hydrate decomposition and transmission process of pressure-drop, and also indirectly affect temperature variation of the reservoir. Considering the spatial heterogeneity of multi-phase seepage parameters, a depressurization production model with layered heterogeneity is established based on the clayey silt hydrate reservoir at W11 station in the Shenhu Sea area of the South China Sea. Tough + Hydrate software was used to calculate the production model; the process of gas production and seepage parameter evolution under different multi-phase seepage conditions were obtained. A sensitivity analysis of the parameters affecting the reservoir productivity was conducted so that: (a) a HBS model with layered heterogeneity can better describe the transmission process of pressure and thermal compensation mechanism of hydrate reservoir; (b) considering the multi-phase seepage parameter heterogeneity, the influence degrees of the parameters on HBS productivity were permeability, porosity and initial hydrate saturation, in order from large to small, and the influence of permeability was significantly greater than that of other parameters; (c) the production potential of the clayey silt reservoir should not only be determined by hydrate content or seepage capacity, but also by the comprehensive effect of the two; and (d) time scales need to be considered when studying the effects of changes in multi-phase seepage parameters on HBS productivity.     

南海神狐海域水合物一维速度结构研究： 基于中—低饱和度水合物区的约束

高精度OBS探测作为目前研究水合物的常用技术手段,可以获取水合物矿体精细速度结构,在研究天然气水合物饱和度、水合物资源的预测与开发等方面具有重要指导意义。然而正演模拟OBS速度结构是繁琐漫长的过程,构建合理的初始模型是后续精细结构快速成像的重要前提。本研究基于全球18个已探明地震波速度的水合物区,分析了水合物矿体内纵波速度的共性特征和影响因素,拟合了水合物矿体带纵波速度与海水深度、沉积物厚度的经验公式。综合经验公式、OBS数据与多道地震剖面,建立了神狐水合物区横向均匀初始模型,并通过射线追踪与走时拟合模拟了神狐海域的一维纵波速度结构。结果表明,神狐水合物矿体带具有高纵波速度(1.83~1.92 km/s）,游离气层具有低P波速度（1.60~1.70 km/s）,此外,基于全球的水合物速度经验公式对神狐海域速度结构模拟具有重要参考意义,有望为获取神狐海域二维/三维精确速度结构提供可靠的初始模型,进而指导水合物精细勘察与资源评估。     

南海神狐海域水合物三相混合层测井评价方法研究

天然气水合物降压试采过程中,水合物、游离气和水的三相混合层中的游离气首先被采出,从而提高降压效率,促进水合物分解;因此利用岩心刻度测井的方法开展南海神狐海域水合物三相混合层测井评价方法研究,对水合物矿体储量计算以及产业化开采具有重要意义.三相混合层与水合物层相比,其密度和中子孔隙度值均减小,纵波速度明显下降;与气层相比...     

天然气水合物藏品质评价的多级模糊综合评判

天然气水合物作为一种储量巨大的后备能源,近年来已受到广泛关注。建立与天然气水合物藏开发相适应的品质评价模型是其商业开采的前提。针对天然气水合物藏的特点,在文献调研和数值模拟研究的基础上,运用多级模糊综合评判法,对影响天然气水合物藏品质的主要因素进行层次划分和权重统计,建立天然气水合物藏品质评价的多级模糊综合评判模型。最后应用该模型,对4个模拟天然气水合物藏的品质进行了分析,证实了该评价模型的适用性。     

A physicochemical model for the formation of gas hydrates of different structural types in K-2 mud volcano (Kukui Canyon,Lake Baikal)

Earlier, the coexistence of spatially separated layers of gas hydrates of cubic structures I and II (CS-I, CS-II) in the bottom sediment cores from K-2 mud volcano (Kukui Canyon, Lake Baikal) was described. The layers of gas hydrates of different structural types were situated at different depths and overlain by the lacustrine sediments. Hydrate of CS-II contained 13–15 mol.% ethane, whereas CS-I hydrate contained only 3–4 mol.% ethane. We present a physicochemical model explaining the formation of such an unusual natural object. The model suggests that only CS-I hydrate was originally present at the sampling site. Some geologic event (tectonic shifts, landslide, etc.) stopped natural-gas emanation from the mud volcano or increased the heat flow in the hydrate pool. As a result, CS-I hydrate began to dissolve in interstitial water. We assume that the ethane-enriched CS-II hydrate is an intermediate product of the dissociation (dissolution) of CS-I hydrate.     

Application of a Simulation Model for the Formation of Methane Hydrate to the Nankai Trough and the Blake Ridge: Natural Examples of Two End-member Cases

Abstract. Simulation experiments with a one-dimensional static model for formation of methane hydrate are used to demonstrate models of hydrate occurrence and its generation mechanism for two end-member cases. The simulation results compare well with experimental data for two natural examples (the Nankai Trough and the Blake Ridge).
At the MITI Nankai Trough wells, the hydrate occurrence is characterized by strongly hydrated sediments developing just above the BGHS. Such occurrence can be reproduced well by simulation in which the end-member case of upward advective fluid flow from below the BGHS is set. The strongly hydrated sediments is formed by oversaturated solution with free gas which directly enters the BGHS by the upward advective fluid flow. The recycling of dissociated methane of preexisting hydrate also contributes to the increase of hydrate saturation.
At the Site 997 in the Blake Ridge area, the hydrate occurrence is characterized by thick zone with poorly hydrated sediments and no hydrate zone developing above the hydrate zone. Such occurrence can be reproduced well by simulation in which the end-member case of in-situ biogenic production of methane in the sediment of methane hydrate zone is set. The distribution pattern of hydrate saturation is basically controlled by that of TOC. However, the hydrate concentration near the bottom of the hydrate zone is increased by the effect of recycling of dissociated methane of pre-existing hydrate. No hydrate zone expresses the geologic time needed until the local concentration of methane exceeds the solubility by gradual accumulation of in-situ biogenic methane with burial.     

Development and verification of the comprehensive model for physical properties of hydrate sediment

Natural gas hydrate is widely distributed all over the world and may be a potential resource in the near future, whereas hydrate dissociation during the development affects wellbore stability and drilling safety. However, the present modeling of hydrate reservoir parameters ignored the influence of effective stress and only considered the hydrate saturation. In this paper, a series of stress sensitivity experiments for the unconsolidated sandstone were carried out, and the influence of mean effective stress on physical parameters was obtained; a comprehensive model for the physical parameters of hydrate reservoir was developed subsequently. With the help of ABAQUS finite element software, the established comprehensive model was verified by the use of the wellbore stability numerical model of hydrate reservoir. The verification results show that ignoring the effect of mean effective stress on the parameters of hydrate formation aggravates the invasion of drilling fluid into the hydrate formation. Besides, ignoring the stress sensitivity of reservoir physical parameters will underestimate the wellbore instability during hydrate drilling, which will be a threat to the safety of gas hydrate drilling. At the end of the drilling operation, the maximum plastic strain of the model for considering and not considering stress sensitivity was 0.0145 and 0.0138, respectively. Therefore, the established comprehensive model will provide a theoretical support for accurately predicting the engineering geological disasters in hydrate development process.