De-A-steroids in immature marine shales

Three series of de-A-diasterenes have been observed in a variety of immature marine shales. Two of them have been identified by comparison with authentic standards and the structures of the third assigned by extrapolation. The greater complexity in the number of series compared with diasterenes indicates that the ring A degradation occurred to differing extents. The rate of C-20 diagenetic isomerisation in the de-A-diasterenes proceeds at a similar rate to that in diasterenes. Two series of B-ring monoaromatic de-A-steroid hydrocarbons have also been found. Comparison with the B-ring monoaromatic anthrasteroids indicates that the de-A-compounds are 14α(H) and 14β(H) isomers. Diagenetic isomerisation of the 14α(H) isomers to the more stable 14β(H) isomers occurs at a rate similar to that in the B-ring monoaromatic anthrasteroid series.     

Molecular parameters of maturation in the Toarcian shales,Paris Basin,France—I. Changes in the configurations of acyclic isoprenoid alkanes,steranes and triterpanes

The changes in configuration at a number of chiral centres in certain acyclic isoprenoid alkanes, steranes, rearranged steranes and triterpanes of the hopane type in a suite of fourteen Toarcian shales (Paris Basin) have been determined by gas chromatography and combined gas chromatography-mass spectrometry. A sequence of changes in the ratios of various stereoisomers occurs both with increasing maximum depth of burial and in a North-South direction for shallow samples (maximum burial depth < 1000m). These changes cover the full range of maturity shown by the samples. The presence of 5α(H), 14β(H), 17β(H)-steranes in immature samples indicates the presence of a reworked component. The extent of epimerisation at a number of the chiral centres suggests that it relates to the extent of steric hindrance at the centres.     

Acid catalysis of alkyl hydrogen exchange and configurational isomerisation reactions: acyclic isoprenoid acids

Acid-catalysed alkyl hydrogen exchange and configurational isomerisation has been studied in a series of acyclic isoprenoid acids when they were heated at 160°C in the presence of a montmorillonite. Hydrogen exchange occurred between the adsorbed water of the clay surface and the a position of the isoprenoid acids. In cases where this position was chiral, exchange was accompanied by configurational isomerisation. Configurational isomerisation occurred more slowly in experiments conducted without a clay matrix in the presence of water. These results have been rationalized in terms of a reaction mechanism involving protonation of the carbonyl oxygen causing enolization and consequent hydrogen exchange at the a position of the acids. This mechanism was used to account for the relatively fast rate of isomerisation of C-2 chiral centres in sedimentary acyclic isoprenoid acids during maturation.     

Graptolite shales in the continental margins of the Paleozoic Yapetus and Paleothetys (Rheic) Oceans

Graptolite shales are a type of fossil shales that contain a large number of graptolite imprints and remains. These deposits are characterized by high TOC contents (C_org = 2–18%). Based on the data of many studies, graptolite shales are one of the main hydrocarbon sources that formed oil and gas fields in Paleozoic deposits around the world, e.g., the Silurian graptolite shales make up to 9–15% of all hydrocarbons that form the oil and gas fields in the largest petroleum basins.     

沉积环境对页岩气储层的控制作用——以渝东北地区五峰组-龙马溪组为例

以"沉积控相,相控储层"为研究思路,基于野外露头剖面实测与室内实验测试,以及前人的研究成果,探讨渝东北地区上奥陶统五峰组-下志留统龙马溪组沉积环境对页岩气储层的控制作用。研究表明,渝东北地区五峰组-龙马溪组富有机质泥页岩主要发育于滞留浅海陆棚相中,沉积中心页岩厚度可达70~80m,有机碳含量(TOC)最高可达7.56%,平均3.09%。静水缺氧还原沉积环境岩石类型主要以富含有机质的含碳质含粉砂泥(页)岩、含碳质含硅质泥(页)岩、含硅质泥(页)岩、含碳质泥(页)岩、含粉砂泥(页)岩及硅质泥(页)岩为主。页岩矿物成分以石英(平均达62.76%)和黏土矿物(平均达22.61%)为主。缺氧还原环境下沉积的大量黄铁矿形成的黄铁矿晶间孔、黏土矿物层间微孔隙、有机质生烃形成的微孔隙以及脆性矿物控制形成的微裂缝为页岩气提供了良好的储集空间。沉积环境控制的储层发育特征的研究可为页岩展布、有机质丰度、储集空间及其之后有利区评价等研究提供基础。     

Microscopic Pore characteristics and methane sorption capacity of the lower cambrian shales in yangtze platform北大核心CSCD

The lower Cambrian develops a set of organic-rich black shales in Yangtze Platform and is regarded as one of the key layers of shale gas exploration. The microscope pore structure characteristics and methane sorption capacity were investigated using scanning electron microscope, nitrogen adsorption and methane sorption experiments, and then their controlling factors combining with organic matter, mineral compositions were discussed for Niutitang shales in Zunyi area, Mufushan shales in Nanjing area and Huangboling shales in Chizhou area. The results show as below; ( I ) The pores in lower Cambrian shales are mainly dominated by organic pores, interlayer pores in clay minerals and micro-fractures, as well as containing some intergranular pores between brittle mineral grains, honeycomb poies formed by pyrite crystals falling out, and dissolution molds in fossils; ( 2) DKT pore size distributions show the pores is mainly concentrated in the range of less than 4 nm in lower Cambrian shales and kerogens, while a certain amount of pores are above 4 nm are also existed in lower Cambrian shales, which may be contributed by smectite; ( 3)The specific surface area, pore volume and Langmuir methane sorption capacity of the lower Cambrian shales are ranging from 5.58 to 31. 96 inVg, 0.026 to 0.088 mL/g and 1.36 to 5. 3 mL/g, respectively, which are mainly controlled by TOC and smectite contents, but the effect of TOC and smectite on physical properties are quite different for the lower Cambrian shales in different regions; ( 4)The specific surface area of two Niutitang kerogens are 7. 08 and 7. 92 times than that of the shales and methane sorp-Tion capacity of kerogens arc 5.81 and 7.09 times than that of the shales, suggesting that kerogen is a main carrier of methane gas occurrence in.     

1-Pristene as a precursor for 2-pristene in pyrolysates of oil shale from Condor,Australia

Condor oil shale, its demineralised kerogen and kerogen/kaolinite mixtures were flash pyrolysed (400–600°C; 60s) or pyrolysed in a tube furnace (25–600°C; 3°C min⁻¹) and the 1-pristene/2-pristene ratio (1P/2P) in the pyrolysates was determined by gas chromatography-mass spectrometry. 1P was the primary pyrolysis product and 2P was derived from it by mineral-catalysed isomerisation, with the 1P/2P ratio depending upon the residence time of the vapour in the catalyst bed. Previously unreported pristene isomers were detected.     

陆相页岩微观孔隙结构特征及对甲烷吸附性能的影响

页岩的微观孔隙结构对其甲烷吸附性能及页岩油气潜力具有重要影响,前人研究主要集中在海相页岩。该文以四川 盆地川西坳陷上三叠统须家河组五段为例,开展了陆相页岩的探索研究。首先通过低温氮气吸附实验对页岩样品的微观孔 隙结构特征进行了研究,计算了页岩的比表面积、孔径分布、孔体积和平均孔径等孔隙结构参数;然后通过高压甲烷等温 吸附实验,研究了页岩样品的甲烷吸附特征;最后探讨了页岩微观孔隙结构特征对甲烷吸附性能的影响。结果表明,须五 段页岩平均孔径为7.81~9.49 nm,主体孔隙为中孔,也含有一定量的微孔和大孔,孔隙形状以平行板状孔为主,含有少量 墨水瓶形孔。页岩比表面积高出常规储层岩石许多,有利于气体在页岩表面吸附存储,孔径在2~50 nm的中孔提供了主要 的孔体积,构成了页岩中气体赋存的主要空间。在85℃条件下,页岩甲烷吸附的兰氏体积为1.21~4.99 m3/t,不同页岩样品 之间的吸附性能差异明显。页岩的兰氏体积与比表面积之间呈现良好的正相关关系,比表面积与黏土矿物含量呈正相关, 而与总有机碳含量关系不明显。页岩的兰氏体积与微孔和中孔体积之间都具有良好的正相关关系,微孔体积和中孔体积与 总有机碳含量之间存在一定的正相关关系,但是正相关性的程度没有微孔体积和中孔体积与黏土矿物含量之间的关系强 烈。陆相页岩有机质热演化程度相对较低,因此有机孔发育有限：但另一方面同时黏土矿物含量较高,所以其内部发育大 量微孔和中孔,从而构成可观的比表面,影响甲烷吸附能力。     

Aromatic components of coal: relation of distribution pattern to rank

Aromatic distribution patterns have been evaluated for a series of twenty-four German high volatile bituminous B to low volatile bituminous coals of Upper Carboniferous Westphalian C-, B- and A-ages using high performance liquid chromatography and glass capillary gas chromatography. The study concentrates on dicyclic and tricyclic aromatic hydrocarbons most of which have been identified by combined gas chromatography-mass spectrometry. The distribution patterns of the methylhomologs of naphthalene and phenanthrene are strongly controlled by rank. A sudden increase of individual isomer ratios at 0.9% Rm coincides with an abrupt shift of the sporinite fluorescence colour from yellow towards red. A recently developed aromatics-derived maturity parameter, the Methylphenanthrene Index (MPI), correlated well with the vitrinite reflectance data over the whole rank range. Deviations have been attributed to variations of maceral composition or migration phenomena. The influence of artificial thermal alteration (350 and 400dgC) on the aromatic distribution pattern of coal is described.     

Reservoir characteristics and methane adsorption capacity of the Upper Triassic continental shale in Western Sichuan Depression,China

The well-developed continental shale sequences in the Western Sichuan Depression are characterised by extremely low porosity and permeability, complex lithologies and strong lateral facies changes. The overall lack of proper characterisation of the shale properties has restricted gas exploration and development in the region. In this study, shales from the fifth member of the Xujiahe Formation of the Upper Triassic (T₃x⁵) are comprehensively characterised in terms of their organic geochemistry, mineral composition, microscopic pore structure and gas content. In addition, the influence of various geological factors on the adsorbed gas content is investigated. We proposed a new model for predicting the adsorption gas content of continental shale. The T₃x⁵ shale sequence is found to be rich in organic matter but with variable mineral compositions, pore types and reservoir physical properties. The porosity and permeability of shales are better than those of siltstones and fine sandstones interbedded with the shale under an overall densification background. Mesopores (2–50 nm) are common in the shale sequence, followed by micropores and then macropores. The gas-adsorption capacity of organic-rich shales increases with increasing TOC and clay-mineral contents, maturity and pressure, but decreases with increasing quartz content, carbonate minerals and temperature. The gas-adsorption capacity can thus be expressed as a function of organic matter, clay-mineral content, temperature and pressure. The calculated results are in good agreement with the experiment results and indicate that adsorption gas in the studied shales accounts for 78.9% of the total gas content.     

基于地球物理和地球化学数据的页岩油甜点区综合预测:以泌阳凹陷核三段5号页岩层为例

我国页岩油气勘探开发不断取得实质性进展,有望成为未来油气资源的重要接替能源.而提高页岩油储层钻遇率和油气产量的关键是甜点区的预测和评价.以泌阳凹陷核桃园组三段5号富有机质页岩层为研究对象,综合利用多种地球物理方法和地球化学指标,通过岩相、含油性、储集条件和地层压力等关键评价参数分析,探讨了综合信息叠合的页岩油甜点区预测方法.研究表明:（1）脆性矿物含量普遍大于50%,以灰质页岩和粘土质页岩夹粉砂质页岩为主的岩相是页岩油赋存的优势岩相;（2）低自由烃差值和高含油饱和指数均指示高含量游离态页岩油,指示了页岩含油性最好区域;（3）夹层主要发育在深凹区周缘,断裂控制的相互重叠区域或派生断裂控制区微裂缝更为发育;（4）异常高压对页岩油微距离运移和富集的影响较大;（5）基于不同参数门槛值对页岩储层进行综合评价划分,采用综合信息叠合法预测出3类甜点区.本文为多参数综合评价和识别陆相页岩油甜点区提供了有效范例,对指导陆相页岩油勘探具有重要的实践意义.      

南方复杂地区页岩气差异富集机理及其关键技术

针对我国南方海相富有机质页岩时空非均质强、热演化程度高、构造演化历史复杂、页岩气具差异富集和保存条件多样等特点,采用多学科方法对南方五峰组-龙马溪组海相页岩气区进行精细解剖,形成了针对南方复杂地区海相高过成熟页岩气评价参数表征的多项关键技术.研究结果显示富泥硅质页岩和富泥/硅混合质页岩是五峰组-龙马溪组的优质岩相;页岩中孔和宏孔提供了主要的孔体积,微-纳米孔隙结构特征受页岩组分及其孔隙发育程度双重控制;页岩气富集演化具二高、三复杂特点（古温度高,热演化程度高,温压演化复杂,页岩气赋存方式复杂及保存条件复杂）.研究中所提出的页岩岩相表征和优选技术、多尺度储集空间全息表征技术、海相页岩复杂演化改造过程表征技术、初步形成的甜点评价参数体系表征方法可有效地应用于南方五峰组-龙马溪组海相页岩气评价.研究成果可为南方页岩气基础地质调查工程提供技术支撑.      

Differential Characteristics of the Upper Ordovician-Lower Silurian Wufeng-Longmaxi Shale Reservoir and its Implications for Exploration and Development of Shale Gas in/around the Sichuan Basin

The Upper Ordovician Wufeng-Lower Silurian Longmaxi shale is widely distributed in the Sichuan Basin and its periphery, which is the key stratum for marine shale gas exploration and development(ED) in China. Based on sedimentary environment, material basis, storage space, fracability and reservoir evolution data, the reservoir characteristics of the Wufeng-Longmaxi shale and their significance for shale gas ED are systematically compared and analyzed in this paper. The results show that(1) the depocenter of the Wufeng(WF)-Longmaxi(LM) shale gradually migrates from east to west. The high-quality shale reservoirs in the eastern Sichuan Basin are mainly siliceous shales, which are primarily distributed in the graptolite shale interval of WF2-LM5. The high-quality reservoirs in the southern Sichuan Basin are mainly calcareous-siliceous and organic-rich argillaceous shales, which are distributed in the graptolite shale interval of WF2-LM7.(2) Deep shale gas(the burial depth 3500 m) in the Sichuan Basin has high-ultrahigh pressure and superior physical properties. The organic-rich siliceous, calcareous-siliceous and organic-rich argillaceous shales have suitable reservoir properties. The marginal area of the Sichuan Basin has a higher degree of pressure relief, which leads to the argillaceous and silty shales evolving into direct cap rocks with poor reservoir/good sealing capacity.(3) Combining shale gas exploration practices and impacts of lithofacies, depth, pressure coefficient and brittle-ductile transition on the reservoir properties, it is concluded that the favorable depth interval of the Wufeng-Longmaxi shale gas is 2200～4000 m under current technical conditions.(4) Aiming at the differential reservoir properties of the Wufeng-Longmaxi shale in the Sichuan Basin and its periphery, several suggestions for future research directions and ED of shale gas are formulated.     

羌塘盆地中生界海相黑色泥页岩特征及页岩气远景区预测

青藏高原羌塘盆地中生界发育上三叠统肖茶卡组（T3x）、中侏罗统布曲组（J2b）和上侏罗统索瓦组（J3s）3套海相黑色泥页岩,形成于有机质比较丰富且易于保存的营养型还原性沉积环境,以台地相为主,其次为盆地相和三角洲相;厚度在41～474 m范围内,有机碳（TOC）含量平均值为0.25%～8.34%,有机质类型主要为Ⅱ型干酪根,镜质体反射率（Ro）平均值为1.21%～3.0%,处于高-过成熟生气阶段,脆性矿物以石英、长石为主,含量为65%～70%,页岩孔隙度约2%。与美国主要盆地产气页岩各项指标相比较,羌塘盆地中生界海相黑色泥页岩具有厚度大、有机质丰度低、热演化熟度高、脆性矿物种类多、石英含量较低、长石和粘土矿物含量较高及孔隙度低的特征,具备了形成页岩气基本地质条件,是我国海相页岩气勘探的沉积盆地之一,综合评价预测的页岩气远景区以上三叠统肖茶卡组（T3x）分布范围大,其次是布曲组（J2b）和索瓦组（J3s）。     

中上扬子地区下志留统沉积演化与页岩气勘探方向*

通过录井、测井、地震、野外剖面与岩心资料的深入剖析, 探讨中上扬子地区下志留统页岩段的沉积相与总有机碳的关系, 预测页岩气有利勘探区。中上扬子地区下志留统龙马溪组为一套20～268 m厚的黑色页岩夹灰绿色泥质粉砂岩沉积, 在等时框架内自下而上可识别出2个三级层序即SQ1与SQ2, 它们分布稳定、可对比性好。下部层序(SQ1) 的海侵体系域(TST)发育一套有利于页岩气形成的富有机质页岩, 此时期呈现出“北面向次深海敞开、东西南三面受古陆围限、陆棚广布”的沉积格局, 深水陆棚相广泛发育, 面积为255000 km², 平均厚度35 m。受海平面下降的影响, 从下部层序至上部层序水体变浅, 岩相从深水陆棚相黑色页岩向中-浅水陆棚相沙纹层理粉砂质页岩转变。岩相的发育受海平面升降、古陆、海底地形、物源供给等因素的影响, 岩相类型有碳质或硅质或钙质页岩、纹层状页岩、生物扰动粉砂质页岩、沙纹层理的粉砂质页岩、块状砂岩或介壳灰岩薄夹层5类。研究表明, 沉积相对富有机质页岩的形成具有内在的控制作用, 高TOC含量页岩发育于深水陆棚相、中陆棚相和潟湖相中。目前, 已有多口井在龙马溪组页岩获得工业气流, 揭示了该区良好的页岩气勘探前景;综合分析认为涪陵-赤水-仁怀、威远-长宁、鄂西-渝东为中上扬子地区下志留统页岩气勘探的主要方向和有利目标区。     

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。     

Geological and geochemical characteristics of the Middle–Lower Jurassic shales in the Kuqa Depression,Tarim Basin: an evaluation of shale gas resources

Middle–Lower Jurassic terrigenous shales constitute a set of significant hydrocarbon source rocks in the Kuqa Depression of the Tarim Basin. Until recently, however, most investigations regarding this set of hydrocarbon source rocks have mainly focused on conventional oil and gas reservoirs, and little research has been conducted on the formation conditions of shale gases. This research, which is based on core samples from nine wells in the Kuqa Depression, investigated the geological, geochemical, mineralogical and porosity characteristics of the shales, analysed the geological and geochemical conditions for the formation of shale gases, and evaluated the shale gas resource potential. The results show that the distribution of the Middle–Lower Jurassic shales is broad, with thicknesses reaching up to 300–500 km. The total organic carbon (TOC) content is relatively high, ranging from 0.2 to 13.5 wt% with a mean of 2.7 wt%. The remaining hydrocarbon generative potential is between 0.1 and 22.34 mg/g, with a large range of variation and a mean value of 3.98 mg/g. It is dominated by type III kerogen with the presence of minor type II₁ kerogen. The vitrinite reflectance values range from 0.517 to 1.572%, indicating the shales are in a mature or highly mature stage. The shales are mainly composed of quartz (19–76%), clay (18–68%) and plagioclase (1–10%) with mean contents of 50.36 wt%, 41.42 wt%, and 3.37 wt%, respectively. The pore spaces are completely dominated by primary porosity, secondary porosity and microfractures. The porosity is less than 10% and is mainly between 0.5 and 4%, and the permeability is generally less than 0.1 mD. These results classify the shale as a low-porosity and ultra-low-permeability reservoir. The porosity has no obvious correlation with the brittle or clay mineral contents, but it is significantly positively correlated with the TOC content. The maximum adsorbed gas content is between 0.82 and 8.52 m³/t with a mean of 3.37 m³/t. In general, the shale gas adsorption content increases with increasing the TOC content, especially when the TOC content is greater than 1.0%. The volumetric method, used to calculate the geological resources of the Middle–Lower Jurassic shales in the Kuqa Depression, shows that the geological resources of the Middle and Lower Jurassic shales reach 667.681 and 988.115 × 10⁹ m³, respectively with good conditions for the formation of shale gas and good prospects for shale gas exploration.     

Palaeoenvironmental conditions during deposition of the Upper Cretaceous oil shale sequences in the Songliao Basin (NE China): Implications from geochemical analysis

Excellent hydrocarbon source rocks (oil shales), containing Type I organic matter (OM), were deposited in the continental Songliao rift basin during the Late Cretaceous. A major contribution of aquatic organisms (dinoflagellates, green algae, botryococcus) and minor input from macrophytes and land plants to OM accumulation is indicated by n-alkane distribution, steroid composition and δ¹³C values of individual biomarkers. Microbial communities included heterotrophic bacteria, cyanobacteria and chemoautotrophic bacteria, as well as purple and green sulfur bacteria. The presence of methanotrophic bacteria is indicated by ¹³C-depleted methyl hopane. The sediments were deposited in a eutrophic, alkaline palaeolake. Highly reducing (saline) bottom water conditions and a stratified water column existed during OM accumulation of the Qingshankou Formation and Member 1 of the Nenjiang Formation. This is indicated by low pristane/phytane, gammacerane index and MTTC ratios, and the presence of β-carotane and aryl isoprenoids. However, an abrupt change in environmental conditions during deposition of Member 2 of the Nenjiang Formation is indicated by significant changes in salinity and redox-sensitive biomarker ratios. A freshwater environment and suboxic conditions in the deep water prevailed during this period. Higher input of terrigenous OM occurred during deposition of the upper Nenjiang Formation.Good oil-to-source rock correlation was obtained using biomarker fingerprints of oil-stained sandstone from the Quantou Formation and oil shales from the Qingshankou Formation. Based on the extent of isomerisation of C₃₁ hopanes, the oil was most probably derived from oil shales of the Qingshankou Formation in deeper parts of the basin.