Characterization of shale matrix pore structure via experiment and model

Shale gas reservoirs develop multi-scale pores ranging in size from nanometer to micrometer, the characteristics of gas transport involve the multi-scale pore space which divided into organic and inorganic matrix pores. This paper reveals the shale pore structure with large amounts of organic mesoporous based on the techniques of focused ion beam scanning electron microscopes (FIB-SEM), high-pressure mercury intrusion (MICP), and low-pressure adsorption (LPA), which also shows the size and distribution of these pores. Then the research characterizes effective pore scale via circular tube bundle model with due regard for gas adsorption layer thickness on the walls of organic pores and water film thickness on the walls of inorganic pores, and the investigation of shale pore geometry is significant for designing and developing shale gas reservoirs. This work shows that the widely existing shale mesoporous volume with diameter of 2~50 nm accounts for 81% based on experimental testing, then it reduces to about 76% via effective diameter model calculation.     

渝东南—黔北地区牛蹄塘组页岩微-纳米级孔隙发育特征及主控因素分析

以渝东南-黔北地区牛蹄塘组页岩岩心及野外新鲜露头样品为研究对象,运用低温液氮吸附实验和氩离子抛光扫描电镜观察,划分页岩微纳米级孔隙类型,并对其发育程度和形态结构进行定量表征,结合页岩样品地球化学测试数据,明确页岩微观孔隙发育主控因素,试图建立微纳米级孔隙发育程度与主控因素定性或半定量关系。结果表明：研究区牛蹄塘组页岩微纳米级孔隙分为有机孔、无机孔和微裂缝3大类,包括7个亚类。有机质粒内孔结构特征为球状、细瓶颈状和墨水瓶状,无机孔主要为串珠状、球状和楔状,微裂缝呈四方开口的平行板状、夹板状。有机质粒内孔、矿物粒间孔和微裂缝为主要孔隙类型,且具有较好连通性,可作为页岩气赋存空间和渗流通道。页岩孔隙以中孔为主,其次为宏孔,孔隙直径分布范围主要在1~50 nm。比表面积主要由孔径≤5 nm孔隙所提供,页岩孔隙孔径越小,对比表面积贡献越大,越有利于页岩气吸附聚集,随着孔隙体积的增加,比表面积不断增加。有机碳含量是控制页岩微纳米级孔隙发育和比表面积的最重要内因,特别体现在对微孔和中孔发育的控制上;黏土矿物含量增加能增强页岩吸附能力,但对孔隙体积和比表面积主控作用不明显;脆性矿物含量主要控制宏孔发育,对页岩吸附的贡献可以忽略;热演化程度过低或过高均不利于有机质孔隙的发育,微纳米孔隙体积随着成熟度增加呈现出先增后减的趋势,对于高过成熟页岩,不同干酪根类型的有机质孔隙发育程度和比表面积大小次序为Ⅰ型＞Ⅱ型＞Ⅲ型。     

页岩孔隙研究新进展

随着非常规油气勘探的兴起页岩孔隙研究备受重视,如何研究页岩孔隙已经成为非常规油气首要解决的问题之一,其对页岩油气勘探层位选取、资源潜力评价和油气渗流能力计算具有重要意义。对页岩微—纳米孔隙表征技术、页岩孔隙类别的划分以及页岩孔隙演化规律分别进行了综述并指出存在问题,同时结合最新研究进展对页岩孔隙研究进行展望。提出工业CT—微米CT—纳米CT/FIB系列辐射扫描方法和压汞(MICP)—氮气吸附(N2)—二氧化碳吸附(CO2)流体法是孔隙定量表征的最优方法,通过单井孔隙度测井资料与实验室测定结果建立校正图版指导储层孔隙发育段优选;页岩孔隙分类研究还应该考虑含油气性,利用原子力显微镜等工具加强孔隙含油性研究;孔隙演化规律研究应该采用模拟实验和真实剖面样品对比并结合矿物组成分析等寻找主控因素。     

页岩气储层孔隙系统表征方法研究进展

页岩气是以游离、吸附和溶解状态赋存于暗色泥页岩中的天然气,页岩的孔隙特征是决定页岩储层含气性的关键因 素。页岩孔隙结构复杂,一般以纳米孔隙占优势,用常规储层孔隙的表征方法难以解释美国的高产页岩气系统。因此,页 岩纳米孔隙的表征成为制约页岩气资源评价的关键因素。在综述目前国际上对页岩气储层孔隙表征方法的基础上,对比分 析其各自的适用范围和应用前景。页岩储层孔隙的主要表征方法有3种:(1)以微区分析为主的图像分析技术;(2)以压 汞法和气体等温吸附为主的流体注入技术;(3)以核磁共振、中子小角散射 计算机断层成像技术为代表的非流体注入技术。 图像分析能够直观、方便、快捷地获取孔隙形态等方面的特征;流体注入法在表征微孔隙的孔径分布、比表面积等方面具 有独到优势;非流体注入技术由于其原位、无损分析及粒子高穿透力的特点,使研究多种地质条件下的孔隙特性成为可能。 在目前的技术条件下,应明确各种表征技术的优势与限制,根据实际情况合理建立孔隙研究流程,综合利用多种技术手段 能在不同的尺度下有效表征页岩气储层孔隙。     

应用氩离子抛光-扫描电镜方法研究四川九老洞组页岩微观孔隙特征

微观孔隙结构是页岩储层研究的重点,而扫描电镜方法无法识别机械抛光中由于页岩硬度差异所造成的不规则形貌。本文利用氩离子抛光-扫描电镜方法对四川威远区块九老洞组页岩进行研究,发现了三种孔隙类型:1无机孔以粒间孔和黏土矿物层间孔为主,同时发育晶间孔和生物孔,孔径主体100~500 nm;2有机孔受控于热成熟度或有机黏土复合体,孔径范围数十纳米至数微米;3微裂缝包括成岩收缩裂缝、高压碎裂缝、构造裂缝和人为裂缝,缝宽数微米,缝长数微米至数十微米。研究表明无机孔和微裂缝是九老洞组页岩气的主要储集空间。     

页岩孔隙空间的形成与演化及孔隙对含气性的影响

虽然页岩气的勘探已经在北美以及中国取得了突破,但是对页岩中孔隙空间的形成与发育仍然存在较大的争议,页岩中是否存在有效的孔隙,这些孔隙与气体的赋存有何联系都需要解答。本文对不同地区、不同岩石类型以及不同热成熟度的页岩进行微观分析,对比前人的研究,同时结合四川盆地龙马溪组页岩的实际分析数据,将页岩划分为富有机质页岩和含粉砂质泥页岩。富有机质页岩中有机质纳米孔是主要的孔隙类型,同时也是气体聚集与吸附的主要空间,有机质孔隙度与有机质含量、热成熟度密切相关;含粉砂质泥页岩中以粒间、粒内溶蚀孔为主,由于有机质含量较少,因而受热成熟影响很小。对页岩的孔隙形成机理分析发现,富有机质页岩孔隙度与有机质含量呈正相关,特别是与初始有机碳含量密切相关,因此恢复初始有机碳的含量是评价页岩含气量与含气性的关键。在热演化程度较低时（Ro < 0.6%）,页岩中有机质孔隙不发育,页岩几乎不含气;随着热演化程度升高（Ro = 0.8%）,页岩微孔隙发育,此时页岩以吸附气为主;随着热演化程度增大（Ro > 1.2%）,微孔逐渐向中孔和宏观孔转化,总的比表面积减小,页岩中游离气含量开始增加,吸附气含量减少。     

渝东北下寒武统牛蹄塘组页岩微纳米孔隙结构特征

中国南方下寒武统牛蹄塘组页岩是目前页岩气勘探的主要目的层位之一,然而在渝东北地区其勘探效果不尽如人意,原因在于其孔隙结构特征并未清楚.采用聚焦离子束扫描电子显微镜、纳米C和气体吸附实验等方法对渝东北地区下寒武统牛蹄塘组页岩微纳米孔隙结构进行了定量表征.结果表明,牛蹄塘组页岩的微纳米孔隙类型主要为无机质孔隙,包括粒间孔和粒内孔,而N₂吸附滞后环类型属于4型,对应孔隙类型为单边狭缝型孔隙;牛蹄塘组页岩的平均总孔体积为0.0317mL/g,平均总比表面积为34.7m2/g.牛蹄塘组页岩过高的演化程度导致有机质孔隙不发育,进而导致其微纳米孔隙具有较差的连通性;中孔贡献了绝大部分的孔体积,而微孔则贡献了相对较多的比表面积.      

四川盆地下古生界黑色页岩纳米孔隙形态的影响因素及其地质意义

以场发射扫描电镜与Pores and Cracks Analysis System （PCAS） 图像处理软件为主要研究手段,以形状系数为孔隙形态表征参数,并选取低压N2吸附等为辅助研究手段,对四川盆地及周缘地区的典型钻井A-D 井龙马溪组及筇竹寺组黑色页岩中纳米孔隙的形态特征进行定量研究。研究发现黑色页岩纳米孔隙形态受孔隙类型（赋存位置）、有机质显微组分、地层埋藏深度、热成熟度及孔隙尺寸等因素综合控制。具体体现在：（1） 有机质孔、粒间孔和粒内孔所占比例、孔径分布与孔隙形态具有明显差异,反映这三类孔隙的演化受成岩作用的影响不同。（2） 固体沥青纳米孔隙比其他显微组分中的纳米孔隙更加规则。（3） 与埋藏深度密切相关的压实作用很可能会在垂向上压缩孔隙,一方面令孔径缩小,另一方面让孔隙形态往狭长–裂缝形发展。（4） 有机质孔形态随热成熟度升高总体上会变得更加规则,但这种趋势可能会被孔隙间的合并及压实作用等破坏。（5） 面积更小的孔隙形态往往比面积更大的孔隙更规则。初步研究显示固体沥青纳米孔隙形态代表着高过成熟页岩气储层中主体储集空间所处压力环境,但固体沥青纳米孔隙形态随孔隙压力的演化模式及利用固体沥青纳米孔隙形态表征其所在层系异常高压维持状况及页岩气保存状况的可能性尚需进一步研究。     

四川盆地下古生界黑色页岩纳米孔隙形态的影响因素及其地质意义

以场发射扫描电镜与Pores and Cracks Analysis System （PCAS） 图像处理软件为主要研究手段，以形状系数为孔隙形态表征参数，并选取低压N2吸附等为辅助研究手段，对四川盆地及周缘地区的典型钻井A-D 井龙马溪组及筇竹寺组黑色页岩中纳米孔隙的形态特征进行定量研究。研究发现黑色页岩纳米孔隙形态受孔隙类型（赋存位置）、有机质显微组分、地层埋藏深度、热成熟度及孔隙尺寸等因素综合控制。具体体现在：（1） 有机质孔、粒间孔和粒内孔所占比例、孔径分布与孔隙形态具有明显差异，反映这三类孔隙的演化受成岩作用的影响不同。（2） 固体沥青纳米孔隙比其他显微组分中的纳米孔隙更加规则。（3） 与埋藏深度密切相关的压实作用很可能会在垂向上压缩孔隙，一方面令孔径缩小，另一方面让孔隙形态往狭长–裂缝形发展。（4） 有机质孔形态随热成熟度升高总体上会变得更加规则，但这种趋势可能会被孔隙间的合并及压实作用等破坏。（5） 面积更小的孔隙形态往往比面积更大的孔隙更规则。初步研究显示固体沥青纳米孔隙形态代表着高过成熟页岩气储层中主体储集空间所处压力环境，但固体沥青纳米孔隙形态随孔隙压力的演化模式及利用固体沥青纳米孔隙形态表征其所在层系异常高压维持状况及页岩气保存状况的可能性尚需进一步研究。     

Pore structure and heterogeneity of shale gas reservoirs and its effect on gas storage capacity in the Qiongzhusi Formation

Fine characterization of pore systems and heterogeneity of shale reservoirs are significant contents of shale gas reservoir physical property research.The research on micro-control factors of low productivity in the Qiongzhusi Formation(Fm.)is still controversial.The lower Cambrian Qiongzhusi Fm.in the Qujing,Yunnan was taken as the object to investigate the influence of mineral compositions on the phys-ical properties of the reservoir and the heterogeneity of shale,using the algorithm to improve the char-acterization ability of Atomic Force Microscopy(AFM).The results showed that:(1)The pores are mainly wedge-shaped pores and V-shaped pores.The pore diameter of the main pore segment ranges from 5 to 10 nm.Mesopores are mainly developed in the Qiongzhusi Fm.shale in Well QD1,with the average pore diameter of 6.08 nm.(2)Microscopic pore structure and shale surface properties show strong hetero-geneity,which complicates the micro-migration of shale gas and increases the difficulty of identifying high-quality reservoirs.(3)The increase of clay mineral content intensifies the compaction and then destroys the pores.Conversely,brittle minerals can protect pores.The support and protection of brittle minerals to pores space depend on their content,mechanical properties and diagenesis.(4)Compression damage to pores,large microscopic roughness and surface fluctuations and strong pore structure heterogeneity are the reasons for the poor gas storage capacity of the Qiongzhusi Fm.,which will lead to poor productivity in the Qiongzhusi Fm.     

柴北缘盆地YQ-1井中侏罗统石门沟组泥页岩纳米孔隙特征及影响因素

柴达木北缘(柴北缘)盆地侏罗纪是典型的陆相湖沼盆地,是目前具有页岩气潜力的盆地之一。本文运用氮气吸附、有机碳含量、有机质成熟度、全岩X衍射分析等方法,对柴北缘鱼卡地区YQ - 1井中侏罗统石门沟组泥页岩的纳米孔隙特征及控制因素进行研究。结果表明,石门沟组泥页岩纳米孔隙结构复杂,根据吸附回线及孔径分布特征可划分为两类,第一类以一端不透气性孔和开放性平行板状狭缝孔为主,孔径主要集中在3～5 nm范围内,呈单峰状分布;第二类则以一端不透气性孔和开放性倾斜板狭缝孔为主,孔径主要分布在3～5 nm和8～14 nm范围内,呈双峰状分布。孔径小于50 nm的微孔和介孔是比表面积和孔体积的主要贡献者;黏土矿物含量与微孔、介孔、总孔体积呈正相关;在较低的成熟度制约下,泥页岩有机质孔隙基本不发育,有机质丰度较高的石门沟组上段H9泥页岩TOC含量与微孔、介孔、总孔体积呈负相关性,有机质丰度较差的下段H8泥页岩TOC含量与孔体积相关性则不甚明显;孔隙结构及孔径分布受沉积环境水动力条件影响;黏土矿物是石门沟组泥页岩纳米孔隙的主要提供者,是孔隙发育的主控因素,TOC含量与沉积环境也会对泥页岩孔隙发育产生一定影响。     

沁水盆地阳泉区块上古生界煤系页岩气储层特征

页岩储层特征是进行页岩气储集能力评价的基础内容。为探究高演化阶段煤系页岩气储层性质和优选有利储层,运用岩石热解、X射线衍射、扫描电子显微镜、高压压汞、低温N₂和CO₂气体吸附多种实验方法,对沁水盆地阳泉区块上古生界煤系页岩岩心样品进行储层特征研究。结果表明:沁水盆地阳泉区块上古生界煤系页岩,有机碳含量较高(TOC平均为4.9%),处于过成熟阶段(R_ran平均为2.32%),黏土矿物质量分数较高(平均为50.0%),具有低孔低渗的特征(孔隙率平均为6.61%,渗透率平均为0.006 3×10–3μm2),孔隙类型以粒间孔、粒内孔和微裂缝为主,微米–纳米级孔隙为页岩气的赋存提供了储集空间;孔隙总孔容为0.025 5~0.051 7 mL/g,平均0.038 9 mL/g,总比表面积为12.64~40.98 m2/g,平均28.43 m2/g,微孔(<2 nm)、介孔(2~50 nm)的孔容与比表面积呈良好的正相关性,宏孔(>50 nm)孔容与比表面积则相关性不明显,表明微孔和介孔是阳泉区块煤系页岩气储集的主要载体。总体来说,阳泉区块上古生界煤系页岩具有较好的页岩气储集性能,但页岩储层可压裂性较差,影响页岩气的开发。      

页岩气储层孔隙类型及特征研究:以渝东南下古生界为例

通过薄片分析、扫描电镜及氩离子抛光技术,对渝东南下古生界含气页岩中的孔隙类型及特征进行了分类观察、描述,结合有机碳含量、X衍射、岩石物性、氮气吸附及甲烷等温吸附实验测试,分析了页岩气储层中各类孔隙的储气贡献,探讨这些孔隙对页岩中烃类运移的影响。研究认为,有机质孔隙、颗粒内孔、粒间孔隙及微裂隙是页岩气储层孔隙的4种类型,有机质表面的分散状孔隙多为nm级,石英碎屑可形成粒内或粒间孔隙,黄铁矿颗粒内部小晶体排列分布产生孔隙空间,黏土絮状沉淀形成片粒状结构孔隙,微裂隙普遍发育在页岩基质中,可达mm级。不同类型的孔隙能够为页岩气的赋存提供不同尺度的储集空间,页岩吸附含气量与表征孔隙特征的参数(TOC、BET比表面积、BJH总孔体积)具有显著的正相关关系。微裂隙与粒间孔隙对页岩中烃类的运移最有利。     

Characteristics and Controlling Factors of Shale Oil Reservoir Spaces in the Bohai Bay Basin

The Cenozoic continental strata of the Bohai Bay Basin are rich in shale oil resources, and they contain various types of reservoir spaces that are controlled by complex factors. Using field emission scanning electron microscopy(FESEM), automatic mineral identification and characterization system(AMICS), CO2 and N2 gas adsorption, and focused ion beam scanning electron microscopy(FIB-SEM), the types of shale reservoir spaces in the Bohai Bay Basin are summarized, the spatial distribution and connectivity of the various types of pores are described in detail, the microscopic pore structures are characterized, and the key geological mechanisms affecting the formation and evolution of the reservoir spaces are determined. Three conclusions can be drawn in the present study. First, the shale reservoir spaces in the Bohai Bay Basin can be divided into three broad categories, including mineral matrix pores, organic matter pores, and micro fractures. Those spaces can be subdivided into seven categories and fourteen sub-categories based on the distribution and formation mechanisms of the pores. Second, the complex pore-throat structures of the shale reservoir can be divided into two types based on the shape of the adsorption hysteresis loop. The pore structures mainly include wedge-shaped, flat slit-shaped, and ink bottle-shaped pores. The mesopores and micropores are the main contributors to pore volume and specific surface area, respectively. The macropores provide a portion of the pore volume, but they do not significantly contribute to the specific surface area. Third, the factors controlling the development of microscopic pores in the shale are complex. The sedimentary environment determines the composition and structure of the shale and provides the material basis for pore development. Diagenesis controls the types and characteristics of the pores. In addition, the thermal evolution of the organic matter is closely related to inorganic diagenesis and drives the formation and evolution of the pores.     

聚焦离子束扫描电镜研究微体化石的微观孔隙结构

聚焦离子束扫描电镜(FIB-SEM)是将聚焦离子束切割和扫描电镜结合起来的双束系统,可以在纳米尺度对样品进行切割加工与实时成像。文中用聚焦离子束扫描电镜对兰多维列统(志留系)龙马溪组黑色页岩内的几类微体化石进行了观察研究,并显示牙形刺、几丁石、疑源类均发育有亚微米至纳米级孔隙,这些孔隙可以为页岩气的储集提供有效空间,不同的微体化石孔隙发育的差异可以为页岩中有机质孔隙非均质性成因研究提供重要依据。     

中国油气储层中纳米孔首次发现及其科学价值

油气储层孔隙可分为毫米级孔、微米级孔、纳米级孔3种类型,常规储层孔隙直径一般大于1μm。北美地区页岩气储层纳米级孔径范围为5~160nm,主体为80~100nm。在对中国非常规油气储层研究中,应用场发射扫锚电子显微镜与纳米CT重构技术,首次发现了小于1μm的油气纳米孔。其中,致密砂岩油气储层中纳米级孔隙以颗粒内孔、自生矿物晶间孔及微裂缝为主,喉道呈席状、弯曲片状,孔隙直径范围10~1000nm,主体为300~900nm;页岩气储层纳米级孔隙以有机质内孔、颗粒内孔及自生矿物晶间孔为主,孔隙直径范围5~300nm,主体为80~200nm。纳米级孔是致密储层连通性储集空间的主体。纳米级孔隙系统的发现,改变了微米级孔隙是油气储层唯一微观孔隙的传统认识,为认识常规油气局部富集,非常规油气连续聚集的地质特征、研究连续型油气聚集机理、增加资源潜力具有重要的科学意义。     

利用小角中子散射表征页岩闭孔结构与演化

随着页岩孔隙网络结构表征更加精细与定量化,页岩中闭孔含量、结构与演化引起了广泛关注.为研究页岩的闭孔特征,通过小角中子散射、氮气吸附、高压压汞和氩离子抛光—场发射扫描电镜等实验手段对四川盆地威201(W201)井中下志留统龙马溪组页岩、上奥陶统五峰组页岩和下寒武统筇竹寺组页岩中的闭孔含量及孔隙结构进行了测定,同时分析了...     

The effects of clay minerals and organic matter on nanoscale pores in Lower Paleozoic shale gas reservoirs,Guizhou, China

In organic-rich gas shales, clay minerals and organic matter (OM) have significant influences on the origin, preservation, and production of shale gas. Because of the substantial role of nanoscale pores in the generation, storage, and seepage of shale gas, we examined the effects of clay minerals and OM on nanoscale pore distribution characteristics in Lower Paleozoic shale gas reservoirs. Using the Niutitang and Longmaxi shales as examples, we determined the effects of clay minerals and OM on pores through sedimentation experiments. Field emission–scanning electron microscopy combined with low-pressure N₂ adsorption of the samples before and after sedimentation showed significant differences in pore location and pore size distribution between the Niutitang and Longmaxi shales. Nanoscale pores mostly existed in OM in the Longmaxi shale and in clay minerals or OM–clay composites in the Niutitang shale. The distribution differences were attributed largely to variability in thermal evolution and tectonic development and might account for the difference in gas-bearing capacity between the Niutitang and Longmaxi reservoirs. In the nanoscale range, mesopores accounted for 61–76% of total nanoscale pore volume. Considerably developed nanoscale pores in OM were distributed in a broad size range in the Longmaxi shale, which led to good pore connectivity and gas production. Numerous narrow pores (i.e., pores?<?20 nm) in OM–clay composites were found in the Niutitang shale, and might account for this shale’s poor pore connectivity and low gas production efficiency. Enhancing the connectivity of the mesopores (especially pores?<?20 nm and those developed in OM–clay composites) might be the key to improving development of the Niutitang shale. The findings provide new insight into the formation and evolutionary mechanism of nanoscale pores developed in OM and clay minerals.     

皖南地区古生界页岩孔隙特征及影响因素

为了评估下扬子皖南地区古生界页岩气储层性质,应用扫描电子显微镜、高压压汞法、N₂和CO₂气体吸附法,对皖南地区古生界页岩孔隙特征和孔隙结构进行研究,并探讨页岩孔隙发育的主要影响因素。结果表明,皖南地区古生界页岩孔隙度和渗透率低,页岩样品中常见粒间孔、凝絮孔、溶蚀孔、基质晶间孔和有机质孔,并且发育微米-纳米级孔隙。古生界页岩孔隙中50%以上为微孔和介孔;孔隙结构主要为圆柱孔、狭缝型孔和混合型孔,平均孔径范围为4.17~12.06 nm。页岩孔容和比表面积随着有机碳(TOC)含量的增大而增大;页岩孔隙度随着有机质成熟度(R_o)的增大而减小;页岩孔容随着黏土矿物含量的增加而增大,随着脆性矿物含量的增加而减小。     

Types and Characteristics of the Lower Silurian Shale Gas Reservoirs in and Around the Sichuan Basin

This study analyzed the characteristics and types of the Lower Silurian shale gas reservoirs in and around Sichuan Basin through field observations, slices, Ar-ion-beam milling, scanning electron microscopy, and x-ray diffraction analysis of 25 black shale outcrops and samples. Two main types of shale gas reservoirs were determined, i.e., fractures and pores. Fractures were classified into five categories, i.e., giant, large, medium, small, and micro, according to the features of the shale gas reservoirs, effect of fracture on gas accumulation, and fracture nature. Pore types include organic matter pores, mineral pores (mineral surface, intraparticle, interparticle, and corrosional pore), and nanofractures. The various fracture types, fracture scales, pore types, and pore sizes exert different controls over the gas storage and production capacity. Pores serve as a reservoir for gas storage and, the gas storage capacity can be determined using pores; fractures serve as pathways for gas migration, and gas production capacity can be determined using them.