上扬子地区不同构造位置牛蹄塘组页岩孔隙特征的对比研究

对位于不同构造位置的两条下寒武统牛蹄塘组页岩采石场剖面进行了垂向系统采样研究,并进行了有机地球化学、矿物学及孔隙度测试。酉阳丹泉剖面富有机质层段集中在牛蹄塘组下部,厚度在25 m以上,总有机碳含量(TOC)均大于5.65%,遵义松林剖面仅对下部富有机质页岩进行采样,但基于富有机质层段地球化学垂向变化趋势可进行对比研究。结果表明,页岩微孔体积主要由有机孔提供,且基本不受构造作用影响。松林剖面TOC值越高,伊利石含量越低,介孔体积越小;而构造稳定区页岩介孔体积除部分样品与松林剖面重合外,仍有部分样品介孔体积明显偏高,说明构造位置的差异对页岩介孔具有明显的影响。宏孔体积在TOC大于6.4%时有减小的趋势,但不同构造位置的两剖面样品受构造应力差异影响不明显。构造应力对孔隙的影响主要与岩石的力学性质及伊利石矿物孔的保存能力有关。     

Provenance and tectonic setting of the Lower Cambrian Niutitang formation shales in the Yangtze platform,South China: Implications for depositional setting of shales

Geochemical compositions of the Lower Cambrian Niutitang Formation shales in the southeastern Yangtze Platform margin were investigated for provenance, tectonic setting, and depositional environment. The shale samples are characterized by higher abundances of large ion lithophile elements (Cs, Ba, and Pb), lower abundances of high field strength elements (Cr, Sc, and Co) and transition elements (Th, Zr, Hf, Nb, and Ta) relative to average shale. North American shale composition (NASC) -normalized rare earth element (REE) patterns are observed, with negative Ce anomalies, negative Eu anomalies, and positive Y anomalies. The chemical index of alteration (CIA) varies from 68.67–74.93. Alkali and alkaline element contents and CIA values suggest that the source rocks have undergone moderate weathering. The index of compositional variability (ICV), Zr/Sc and Th/Sc ratios vary from 0.53 to 1.07, 5.31 to 8.18 and 0.52–1.02, respectively. ICV values and relationships between Zr/Sc and Th/Sc ratios indicate negligible sedimentary recycling. The Al₂O₃/TiO₂ (14–26) and TiO₂/Zr (56–77) ratios imply that the source rocks of the investigated shales had intermediate igneous compositions. However, Cr/V ratios and a La/Th–Hf discrimination diagram suggest that the intermediate compositional signal of the source rocks was derived from a mixture of 75% mafic and 25% felsic igneous rocks rather than intermediate igneous rocks. The major source was the Jiangnan continental island arc with bimodal igneous rocks, lying to the south of the study area, together with a contribution from granites and gneisses uplifted and eroded in the Yangtze Block. Discrimination of tectonic setting using major and trace elements indicates that the source rocks originated in a transitional setting from active continental to passive margin, consistent with the failed intracontinental rift model for the evolution of the South China plate. The Niutitang Formation shales were deposited in a rift basin setting under conditions of anoxic bottom water in a redox-stratified water column, with organic-rich shales prospective for shale-gas production being found in deep-water downslope and basin environments rather than the shallow-water shelf.     

阳泉新景矿高煤级煤的孔隙结构分形特征

分形理论是宏观上定量评价储层非均质性的有效手段。以阳泉新景矿高煤级煤样品压汞数据为基础,建立分形几何模型,定量描述了孔隙结构。实验结果表明：样品孔隙以纳米孔为主,孔径、比表面积及孔容也集中分布在纳米孔段。煤样孔径65 nm以上的孔隙具有显著的分形特征,分维值分布范围为2.89~2.99,体积增量呈现阶段式的变化,孔隙结构复杂;孔径65 nm以下孔隙几乎无分形特征,比表面积增量与孔径在对数坐标中呈线性关系;基于分形特征及分子运动规律,将储层孔隙以孔径65 nm为界划分为扩散孔和渗透孔2个大类6个小类。分维值与体积孔隙中值半径、总孔隙体积呈负相关,与孔径65 nm以上的孔隙体积、比表面积呈正相关,与孔隙度无相关性。分形分维值对储层结构具有较全面的表征能力,可以作为综合指标在煤储层孔隙研究中加以应用。     

软土结构性破损的孔径分布试验研究

采用压汞法对天然结构性软土压缩过程孔隙大小分布的演化进行了试验研究，结果表明，当荷载超过结构屈服应力后，尺寸较大的团粒间孔隙首先发生破坏，随着荷载的增大，越来越小的孔隙受到影响，但团粒内孔隙在压缩过程中不发生变化；根据试验结果提出了孔隙结构破损势的概念，并用其表征孔隙分布随荷载变化的规律。     

黔西北下寒武统牛蹄塘组页岩气成藏条件与有利勘探区预测

以野外露头调查、老井复查和岩心样品测试等为基础,通过现场解吸实验和等温吸附模拟的含气性分析,认为黔西北下寒武统牛蹄塘组岩性主要为深水陆棚黑色碳质页岩和浅水陆棚粉砂质页岩,其中富有机质页岩段为牛蹄塘组底部的碳质页岩。页岩沉积厚度大(大于39m)、分布稳定。有机质类型主要为Ⅰ型干酪根,有机碳含量较高(富有机质页岩段平均大于5%),有机质热演化程度处于高—过成熟阶段;页岩储层中微裂缝、微孔隙发育,具较好的孔隙度(平均5.14%)和渗透率(0.011 4×10-3μm2),含气量大(平均1.3 m3/t),具有良好的气资源潜力。预测金沙—息烽以及仁怀两个地区为页岩气勘探有利区。     

页岩孔隙结构研究进展及下扬子古生界页岩孔隙特征

天然气可以吸附或以游离态赋存在富有机质泥页岩及其夹层中,使页岩成为一种重要的非常规储集体。页岩的微米—纳米级孔隙是页岩气富集的重要场所,常规孔隙研究手段难以适用,目前,国际上尚没有关于页岩孔隙类型的统一分类方案。因此,页岩的孔隙结构特征成为页岩气勘探开发中的关键问题。总结近年来页岩孔隙结构的主要研究手段和分类,并初步分析了浙西—皖南下扬子地区古生界页岩的孔隙特征。     

Application of low-pressure gas adsorption to nanopore structure characterisation of organic-rich lower Cambrian shale in the Upper Yangtze Platform,South China

The pores in shales are mainly on a nanometer scale, and the pore-size distribution is vital with regard to the preservation and exploitation of shale gas. This study focuses on the organic-rich lower Cambrian black shale in the Upper Yangtze Platform, South China and investigates their TOC, mineralogical composition and nanopore structure. Low-pressure N₂ and CO₂ adsorption experiments were conducted at 77.35 K and 273.15 K, respectively, and the nanopore structures were characterised by the modified Brunauer–Emmett–Teller, Dubinin–Radushkevich, t-plot, Barrett–Joyner–Halenda and density functional theory (DFT) methods. The results indicate the following. (1) The lower Cambrian shale has a high TOC content (1.77–7.23 wt%) and a high quartz content (27.7–51.6 vol%). The total specific surface area varies from 12.02 to 28.87 m²/g. Both the total specific surface area and quartz content are positively associated with the TOC content. (2) Shale samples with a higher TOC content have a greater number of micropores, resulting in more complicated nanopore structures. Micropore volumes/surface areas and non-micropore surface areas all increase with increasing TOC content, indicating that TOC is the key factor determining the nanopore structure of the lower Cambrian shale. (3) A combination of N₂ and CO₂ adsorption provides the most suitable detection range (～0.3–60 nm) and is both highly reliable and accurate with regard to nanopore structure characterisation.     

湖南省桑植地区下寒武统牛蹄塘组页岩气成藏条件分析

桑植地区发育了牛蹄塘组海相黑色页岩,前人对该区古生界下寒武统页岩气成藏条件研究相对较少。在文献调研的基础上,结合野外实地勘查和试验分析,对桑植下寒武统牛蹄塘组页岩储层地质要素和成藏条件进行研究,以期为该区页岩气下一步勘探开发提供借鉴与参考。结果表明: 沉积环境方面,桑植牛蹄塘组页岩沉积相类型为陆棚相和斜坡相,埋深条件好,厚度大; 有机地化特征方面,有机质丰度在2%以上,干酪根类型主要为Ⅱ1型,少见Ⅰ型,有机质成熟度3.5%,为较好烃源岩; 有机质演化与黏土矿物成岩阶段有较好的对应关系,其成岩矿物转化阶段与有机质生油、生气门限基本一致,源岩处于大量生成干气和裂解气阶段; 储集条件方面,孔隙度为9%,发育了原生孔、次生孔、矿物质孔及天然裂缝、构造裂缝,为页岩气富集提供了空间; 脆性矿物含量高,易造缝造储。整体而言,牛蹄塘组页岩为优质页岩,页岩气的成藏条件为较好—好,其勘探、开发潜力较大。     

Characteristics of Shale Reservoir and Sweet Spot Identification of the Lower Cambrian Niutitang Formation in Northwestern Hunan Province,China

The accumulation and productivity of shale gas are mainly controlled by the characteristics of shale reservoirs;study of these characteristics forms the basis for the shale gas exploitation of the Lower Cambrian Niutitang Formation(Fm),Southern China.In this study,core observation and lithology study were conducted along with X-ray diffraction(XRD)and electronic scanning microscopy(SEM)examinations and liquid nitrogen(N_2)adsorption/desorption and CH_4 isothermal adsorption experiments for several exploration wells in northwestern Hunan Province,China.The results show that one or two intervals with high-quality source rocks(TOC2 wt%)were deposited in the deep-shelf facies.The source rocks,which were mainly composed of carbonaceous shales and siliceous shales,had high quartz contents(40 wt%)and low clay mineral(30 wt%,mainly illites)and carbonate mineral(20 wt%)contents.The SEM observations and liquid nitrogen(N_2)adsorption/desorption experiments showed that the shale is tight,and nanoscale pores and microscale fractures are well developed.BJH volume(V_(BJH))of shale ranged from 2.144×10~(-3) to 20.07×10~(-3) cm~3/g,with an average of11.752×10~(-3) cm~3/g.Pores mainly consisted of opened and interconnected mesopores(2–50 nm in diameter)or macropores(50 nm in diameter).The shale reservoir has strong adsorption capacity for CH_4.The Langmuir volume(V_L)varied from1.63 to 7.39 cm~3/g,with an average of 3.95 cm~3/g.The characteristics of shale reservoir are controlled by several factors:(1)A deep muddy continental shelf is the most favorable environment for the development of shale reservoirs,which is controlled by the development of basic materials.(2)The storage capacity of the shale reservoir is positively related to the TOC contents and plastic minerals and negatively related to cement minerals.(3)High maturity or overmaturity leads to the growth of organic pores and microfractures,thereby improving the reservoir storage capacity.It can be deduced that the high percentage of residual gas in Niutitang Fm results from the strong reservoir storage capacity of adsorbed gas.Two layers of sweet spots with strong storage capacity of free gas,and they are characterized by the relatively high TOCcontents ranging from 4 wt%to 8 wt%.     

阜康矿区煤的孔隙与裂隙特征

煤的孔隙与裂隙是煤层气赋存的空间也是煤层气运移和产出的通道。在新疆阜康矿区三工、建江等7对矿井巷道煤层裂隙观测统计的基础上,采用宏观煤岩分析、显微煤岩分析、压汞实验与煤的孔隙结构分析等方法,研究阜康矿区煤层孔隙与裂隙特性,评价煤层气赋存特征与渗透性。结果表明：阜康矿区煤层孔隙发育以微孔和小孔为主,孔容和比表面积较大,有利于煤层气的吸附和解吸;裂隙发育具有非均质性,矿区西部裂隙最为发育,东部次之,中部不发育;煤岩组分中镜质组的增加会使微小孔增多,有利于煤层气的吸附;中孔孔容对孔隙度具有控制作用;阜康矿区煤层的孔隙率随着镜质体反射率的增大呈增大的趋势。研究结果对新疆阜康矿区煤层气的勘探开发具有一定的理论指导意义。     

水浸干燥后煤的孔隙结构及瓦斯吸附特性变化规律

在富含水煤系或水力措施后的煤层中,受水溶液的浸泡,煤的孔隙结构及吸附特性发生改变,为了深入研究其变化规律,在实验室利用蒸馏水对2种不同变质程度煤样进行了长时间（60 d）浸泡,采用低温N₂吸附实验和CO₂吸附实验测试水浸前后煤样的孔隙结构变化规律,采用高压容量法测试水浸前后煤样的瓦斯吸附特性。结果表明,水浸干燥后煤体孔容和比表面积总体呈降低趋势。其中,低温N₂吸附实验结果表明,煤体中大中孔的比表面积最高可降低48.9%;CO₂吸附实验结果表明,水浸干燥后2种煤样的微孔孔容和比表面积也呈不同程度的降低趋势。将水浸煤样孔隙结构变化分为3个阶段,即矿物质溶出“增孔”阶段、煤基质局部膨胀变形“缩孔”阶段和煤基质整体溶胀变形“扩孔”阶段。此外,水浸干燥后煤对瓦斯的吸附能力下降,主要是由于水浸促使煤体产生膨胀变形,且导致微孔隙相互连通,从而降低了煤体微孔孔容和比表面积,降低瓦斯吸附能力。研究成果对进一步掌握富含水煤系或水力化措施后煤层的瓦斯抽采具有指导意义。     

利用扫描电镜、压汞法、氮气吸附法评价近海黏土孔隙特征

近海地区黏土的微观结构单元--黏土畴中含有大量的粒内孔隙,其孔径小至纳米级,这部分孔隙对黏土的物理指标、水稳性、膨胀性、收缩性等具有重要影响,一般方法很难准确地描述其孔隙特征。试验利用扫描电镜、压汞法、氮气吸附法对湛江黏土的微观孔隙特征及其孔隙发育的控制因素分析,建立微观结构与物理指标、力学行为的相互关系与灵敏性分析。结果表明,湛江黏土具有不良物理性质和良好力学特性指标的异常组合,是一种高灵敏性的强胶结结构性黏性土,其机制主要是：湛江黏土的微观结构为带有胶质联结特性的、定向性无序的开放式絮凝结构,孔隙结构为具有较高的强度和空间稳定性的边－面－角联结的空间网架系统。由于特殊的孔隙网架结构以及“墨水瓶”型孔隙的存在,导致退汞过程出现滞留现象及产生吸附回线。研究表明,联合扫描电镜、压汞法、氮气吸附法能够准确、完整地对近海地区黏土孔隙体系特征进行定性与定量的评价。     

准中4区块致密砂岩孔隙结构特征研究

致密砂岩孔隙结构是影响储层物性、储集性能和渗流特性的主要因素,准确表征岩石的孔隙结构特征是储层评价的重要内容之一。为此通过岩心观察、CT扫描成像及其图像处理等对准噶尔盆地中部4区块董11井致密砂岩储层孔隙结构特征进行了定性及定量综合研究。研究结果表明,采用USM锐化、阈值选取及中值滤波法对微CT扫描灰度图像进行图像处理,可以更好地区分岩石内部骨架和孔隙的边界,提高了图像的分割精度;当数字岩心立方体模型边长在450体素时,孔隙度趋近定值;研究区致密砂岩储层储集空间主要以粒间孔隙和微裂隙为主,伴有少量的解理裂隙,孤立孔隙较多,孔隙形状复杂,分布不均匀;研究区致密砂岩连续截面面孔率分布不均匀,离散性强,在连续截面上面孔率频繁出现极大值与极小值（跳跃性较大）,容易在流体流动的过程中产生压降过大,造成部分孔隙喉道堵塞;研究区致密砂岩储层孔隙大小分布不均匀,孔隙直径在15~35 μm之间,占总孔隙数的60%左右,其面积占18%;直径在50~200 μm的孔隙数量占总孔隙数的20%,其面积占比达60%,为油气赋存提供了有利的储集空间。      

湘西下寒武统牛蹄塘组地球化学特征及其对沉积-构造环境的响应

为深入探讨湘西地区下寒武统牛蹄塘组黑色岩系沉积-构造环境,对三岔剖面黑色岩系进行了详细采样测试,并重点分析了主量、微量及稀土元素地球化学特征。研究结果表明,牛蹄塘组黑色岩系不仅有机碳含量高,而且相比于北美页岩更富集V、Ni、Cr等微量元素。δ~(13)C_(org)及微量元素判别指标V/(V+Ni)、V/Cr、Ni/Co、δU、Ce/La、Ce_(anom)等特征的变化均反映牛蹄塘组沉积期水体属缺氧还原的浅水环境,且Mo/TOC与U_(EF)-Mo_(EF)协同模式表明沉积区当时为一局限海盆环境。稀土元素(REE)中轻稀土相对重稀土富集,且北美页岩标准化分布模式呈近水平略微左倾状,结合元素比值特征和La/YbCe/Yb、La/Yb-ΣREE图解,牛蹄塘组黑色岩系的母岩以长英质岩石为主,但沉积过程也受到海底热液作用影响。同时,根据δCe、δEu的特征与K_2O/Na_2O-SiO_2图解,认为沉积区在早寒武世为被动大陆边缘构造背景。     

黔中隆起及周缘下寒武统牛蹄塘组页岩气勘探前景

文章基于黔中隆起及周缘地区下寒武统牛蹄塘组黑色页岩的野外露头,并与周边钻井资料类比,通过野外地质观测、样品显微薄片等多项实验测试,以地层沉积、岩石学、有机地球化学和泥页岩含气性等为重点,对其下寒武统牛蹄塘组页岩气形成的成藏条件与勘探前景进行了分析。结果表明黔中隆起及其周缘地区下寒武统牛蹄塘组主要发育以盆地相—深水陆棚沉积环境控制的富有机质泥页岩,富有机质泥页岩厚度大(80~160 m),有机质丰度高(平均TOC含量3.63%),有机质类型好(Ⅰ-Ⅱ1型),热演化程度高成熟―过成熟(Ro1.55%),石英等脆性矿物含量丰富(平均46%),泥页岩中发育微米至纳米级微孔隙和微裂缝,且有较好的保存条件,有利于页岩气的形成与富集,具有较好的勘探前景。     

陆相页岩热演化过程中孔隙分形特征

分形维数可定量表征储层孔隙结构的复杂性,为页岩储层评价提供思路。以热模拟获得的不同热演化阶段的鄂尔多斯盆地长7段页岩为研究对象,应用场发射扫描电镜观察了各演化阶段孔隙变化特征,并通过低温液氮吸附实验,研究各个演化阶段页岩孔隙分形特征,运用FHH模型计算页岩孔隙分形维数,探讨了分形维数与有机碳、矿物成分、孔隙结构参数的关系。研究结果表明：低成熟阶段页岩中纳米级有机质孔发育有限,随着成熟度的增加,在有机质内部开始逐渐发育孔隙,同时黏土矿物颗粒间的有机质也开始分解,出现纳米级层间孔,主要发育墨水瓶状孔和少部分的平行板状孔;孔径峰值主要在2~4 nm和40~50 nm,随着成熟度增加,上述2个孔径段的孔隙相对数量增加,分形维数依次增大,分形维数为2.592~2.717,孔隙非均质性增强。分形维数随着有机碳含量的减少而增加,而与石英、黏土矿物含量相关性不明显;随着成熟度增加,微孔和中孔比例增加,平均孔径减小,孔隙表面越复杂,比表面积和分形维数增加;分形维数与总孔隙体积、微孔体积、中孔体积具有很好的正相关性,而与大孔体积相关性较差。     

桂中坳陷环江凹陷上古生界海相页岩储层孔隙结构和分形特征研究

通过有机地化分析、全岩X衍射矿物分析、甲烷等温吸附及低压氮气吸附实验,本文对桂中坳陷环江凹陷上古生界页岩样品的孔隙结构及分形特征进行了研究.结果表明:研究区页岩总有机碳含量(TOC)平均为2.40%,热成熟度(Ro)平均为2.65%,处于过成熟演化阶段.页岩主要的矿物组成为石英和黏土.页岩的比表面积平均为5.86 m2/g,孔容平均为0.014 9 mL/g,平均孔径为11.2 nm.页岩中发育大量的中孔,主要呈两端开口的圆筒形孔或四边开放的平行板状孔.页岩中TOC含量和石英含量越多,微-中孔越发育、比表面积和孔容越大,而平均孔径则变小.通过Frenkel-Halsey-Hill (FHH)模型和氮气吸附实验数据计算得到孔隙表面分形维数D1(平均为2.428 4)和孔隙结构分形维数D2(平均为2.622 2),对应的相对压力(P/P0)分别是0~ 0.45和0.45 ~ 0.99.分形维数D1、D2随着比表面积、孔容的增加而增加,而平均孔径随着前者的增加而减小.分形维数D1、D2、TOC含量、石英含量和甲烷吸附量之间呈现较好的正相关性,但随着黏土矿物含量的增多而减小.分形维数D1与Langmuir压力存在弱负相关性,分形维数D2随Langmuir压力增大有变大的趋势.桂中坳陷西北部页岩分形维数越大,孔隙结构越复杂,其对天然气的吸附和存储能力越强.     

Occurrence and influence of residual gas released by crush methods on pore structure in Longmaxi shale in Yangtze Plate,Southern China

The composition of gas released under vacuum by crushing from the gas shale of Longmaxi Formation in Upper Yangtze Plate, Southern China was systematically investigated in this study. The effect of residual gas release on pore structures was checked using low-pressure nitrogen adsorption techniques. The influence of particle size on the determination of pore structure characteristics was considered. Using the Frenkel-Halsey-Hill method from low-pressure nitrogen adsorption data, the fractal dimensions were identified at relative pressures of 0−0.5 and 0.5−1 as D₁ and D₂, respectively, and the evolution of fractal features related to gas release was also discussed. The results showed that a variety component of residual gas was released from all shale samples, containing hydrocarbon gas of CH₄ (29.58% −92.53%), C₂H₆ (0.97% −2.89%), C₃H₈ (0.01% −0.65%), and also some non-hydrocarbon gas such as CO₂ (3.54% − 67.09%) and N₂ (1.88%−8.07%). The total yield of residual gas was in a range from 6.1 μL/g to 17.0 μL/g related to rock weight. The geochemical and mineralogical analysis suggested that the residual gas yield was positively correlated with quartz (R²=0.5480) content. The residual gas released shale sample has a higher surface area of 17.20−25.03 m²/g and the nitrogen adsorption capacity in a range of 27.32−40.86 ml/g that is relatively higher than the original samples (with 9.22−16.30 m²/g and 10.84−17.55 ml/g). Clearer hysteresis loop was observed for the original shale sample in nitrogen adsorption-desorption isotherms than residual gas released sample. Pore structure analysis showed that the proportions of micro-, meso- and macropores were changed as micropores decreased while meso- and macropores increased. The fractal dimensions D₁ were in range from 2.5466 to 2.6117 and D₂ from 2.6998 to 2.7119 for the residual gas released shale, which is smaller than the original shale. This factor may indicate that the pore in residual gas released shale was more homogeneous than the original shale. The results indicated that both residual gas and their pore space have few contributions to shale gas production and effective reservoir evaluation. The larger fragments samples of granular rather than powdery smaller than 60 mesh fraction of shale seem to be better for performing effective pore structure analysis to the Longmaxi shale.     

渝东南牛蹄塘组与龙马溪组高演化海相页岩全孔径孔隙结构特征对比研究

中国南方主要富有机质海相页岩寒武系牛蹄塘组和志留系龙马溪组是当前页岩气勘探的重要目标地层,但演化程度普遍偏高,孔隙结构复杂。为加深对这种复杂性的认识,通过场发射扫描电镜、高压压汞实验与低温低压吸附实验(CO_2与N_2),对页岩全孔径孔隙结构特征进行对比研究。研究发现,牛蹄塘组孔体积与龙马溪组页岩的孔体积分别介于0.0202~0.0402 m L/g与0.0255~0.0310 m L/g之间,介孔在两套页岩孔体积中所占比例最大。两套页岩比表面积分别介于13.74~41.26 m~2/g与21.42~27.82 m~2/g之间,微孔与介孔几乎提供了两套页岩全部的比表面。孔隙结构的差异主要表现为牛蹄塘组页岩内溶蚀孔和粒间孔较为发育,有机质孔隙发育不均匀;而龙马溪组页岩内粒内孔、粒间孔和有机质孔隙均较为发育;牛蹄塘组在微孔范围内的孔体积与比表面积占有优势,而介孔与宏孔范围内的孔体积与比表面积均小于龙马溪组。根据实验数据结果与文献的调研,两套页岩孔隙结构差异的主要原因主要是成熟度与埋深的不同影响而形成的。