Parallel micropetrographic and chemical studies of the solid degradation products from stepwise alkaline permanganate oxidation of a kerogen concentrate

The usefulness of parallel micropetrographic and chemical investigations to illustrate the nature of kerogen is demonstrated from data obtained in the study of the Aleksinac shale (Yugoslavia). To obtain more information about the chemical nature of kerogen, the stepwise oxidation with alkaline permanganate reported earlier has been modified and supplemented with micropetrographic and chemical investigations of partially degraded kerogen concentrates isolated from each degradation step. Five different types of particles were observed in kerogen concentrates. The results both of micropetrographic and of chemical investigations indicate a heterogeneity of the Aleksinac shale kerogen and a different reactivity of the particles observed.     

Improvement of kerogen structural interpretations based on oxidation products isolated from aqueous solutions

A detailed investigation of kerogen oxidation products remaining in aqueous solutions after the usual isolation of degradation products by extraction with ether or precipitation, was carried out for the first time in kerogen structural studies. Three shale samples were investigated: Green River shale (type I kerogen), Toarcian shale, Paris Basin (type II), and Mannville shale, Canada (type III). The yields of acids from aqueous solutions were noticeable: 12.98, 15.32 and 22.32%, respectively, based on initial kerogens. Qualitative and quantitative capillary GC/MS analysis showed that the ratios of different kinds of identified acids depended much on the type of precursor kerogen. Some of the acids identified in aqueous solutions have not been found earlier among the degradation products of the same kerogen samples, or were obtained in different ranges and yields. Consequently, slight modifications were suggested of the image on the nature of various types of kerogens based on examination of ether-soluble acids only. Namely, slightly higher proportions of aromatic and alkane-polycarboxylic acids in the total oxidation products of both type I and type II kerogens indicated larger participation of aromatic and alicyclic and/or heterocyclic structures in these two kerogens. On the other hand, for type III Mannville shale kerogen, a somewhat larger share of aliphatic type structures was demonstrated.     

泥页岩热模拟实验及成岩演化模式

随着泥页岩油气勘探开发的不断推进,对泥页岩的成岩作用研究越来越受到重视。通过对三种不同干酪根类型的泥页岩样品的热模拟实验发现,随着有机质成熟度的增加,干酪根热解生烃产生的有机质孔及不稳定矿物溶蚀孔增加,是泥页岩储集空间增加的主要原因;泥页岩成岩作用类型主要有黏土矿物转化、不稳定矿物溶蚀作用和重结晶作用;结合镜质体反射率,建立了基于热模拟实验的泥页岩综合成岩演化模式。研究表明:不同类型的干酪根在生烃过程中演化特征不同,Ⅰ型干酪根以"解聚型"的途径生烃,以产生有机质边缘孔为主;Ⅲ型干酪根以"平行脱官能团型"的途径生烃,以产生有机质内部孔为主;Ⅱ型干酪根介于两者之间,既可以产生有机质内部孔,也可以产生有机质边缘孔。     

Geochemical technique of organic matter research in deposits enrich in kerogene (the Bazhenov Formation,West Siberia)

The international interest in shale oil has recently provoked special attention to the Russian unconventional oil-source formations, including the Bazhenov Formation of West Siberia, domanik deposits in the Volga–Ural region, and the lower Maikop Group of the Cis-Caucasus. High contents of para-autochthonous soluble organic matter (bitumen) in clayey–carbonate, clayey–siliceous, carbonate–clayey–siliceous rocks with low filtration–capacity properties results in significant uncertainties in the identification of the generation potential of organic matter (OM). Examination of a large database on the OM of the Bazhenov Formation allowed us to propose an optimum complex technique for study of the source rock potential and assessment of the amount of produced hydrocarbons in the kerogen-rich sediments. The investigations include a combination of Rock Eval pyrolysis prior to and after extraction with different solvents, the comparison of bituminological and pyrolytic characteristics, and the determination of the group composition of soluble organic matter, as well as chromatography and chromato-mass spectrometry.     

福建二叠系中统童子岩组页岩气储层特征

为了评价福建省二叠系中统童子岩组页岩气资源开发潜力,开展了野外地质调查及现场解吸测试工作,研究了童子岩组页岩气储层特征及其影响因素。结果表明:福建二叠系中统童子岩组泥页岩干酪根为Ⅲ型;有机碳质量分数普遍在2%以下;R_ran值介于2.52%~5.80%,泥页岩储层处于过成熟演化阶段;泥页岩储层黏土矿物含量较高,脆性矿物含量不高,不利于页岩储层的压裂改造;泥页岩孔隙度较低,渗透率极低,中孔是童子岩组页岩气储存的主要场所;童子岩组含气量总体较低,主要受后期构造运动和岩浆活动影响所致。分析表明:在受影响相对较小的局部块段——加福向斜和抚市向斜,其向斜底部的童子岩组具有页岩气成藏条件。      

松辽盆地古龙页岩油储层干酪根的有机元素组成及其N元素的地球化学意义

对青山口组页岩的317件干酪根样品进行了工业、元素及能谱分析,对样品进行两次校正,引入合理评价干酪根C、H、O、N的指标Ccc、Hcc、Occ、Ncc概念。研究结果显示：古龙凹陷青山口组泥页岩Ⅰ型干酪根具有较高的Hcc、Ncc和很低的Occ,而Ⅲ型干酪根的Occ则较高,Hcc、Ncc较低。Ⅱ干酪根的Hcc和Ncc低于Ⅰ型干酪根,而高于Ⅲ型干酪根;Ⅱ干酪根的Occ高于Ⅰ型和Ⅲ型干酪根。Ncc主要以有机官能团（NH3+）方式存在的于黏土的F F纳缝中,而不是存在于黏土晶胞间的无机N（NH4）。微量元素研究表明,古龙青山口组页岩油储层沉积时经历了十几次干旱咸水环境,因为咸水环境有利于形成黏土的F F凝聚,使发育有NH3+官能团的有机质被吸附在黏土片的F F纳缝之间。随着深度的增加,Ncc的克分子量增加速率是Ccc克分子量增加速率的0. 96~2. 04倍,在青山口组1300~2550 m深度内青一段干酪根的Ncc含量明显比上部的干酪根相对高,主要原因与下部青一段藻类较富集有关,其次与Hcc的快速脱落而使Ncc相对富集有关,间接地揭示了青一段生烃能力较上部强。通过研究Ncc可以间接地知道古环境中的咸度、黏土的孔隙类型及其干酪根的来源。经过论证,Occ和Ncc越大,页岩的封存性也就越好,含油气性也越好。因此,Occ和Ncc值可以作为判别页岩油发育程度的指标。古龙页岩油储层的Ncc和Occ的研究可以提供一些重要的沉积环境、地球化学、黏土结构、干酪根有机质类型和成岩成储及成藏等信息,应该受到重视。     

页岩储层岩石物理模型及地震AVO响应模拟

通过模拟并分析各向异性页岩岩石物理模型,研究页岩中干酪根含量变化对页岩弹性各向异性的影响,其结果为应用AVO方法定量解释页岩储层厚度和干酪根含量提供依据。岩石物理模型预测了页岩速度和各向异性参数随干酪根含量的变化规律。应用传播矩阵方法计算薄层页岩的AVO响应,得到反射系数关于页岩层厚度、入射波频率、干酪根含量和入射角的函数。数值模拟结果表明:在干酪根含量不变且在同一入射角下的反射系数在频率域呈周期变化,该周期与薄层厚度成反比;对同一频率入射波和相同入射角,反射系数幅值随干酪根含量增加而变大。     

Organic matter in Upper Devonian deposits of the Chernyshev Ridge

The study provides the first data on organic matter from Upper Devonian deposits of the Shar’yu River section (Chernyshev Ridge, Northern Urals). Oil shales from the Middle and Middle–Upper Domanik intervals and carbonaceous shales from the Upper Frasnian intervals were analyzed. The biomarker analysis revealed similar characteristics of organic matter from studied samples and Domanik-facies rocks of the Ukhta area. It was also shown that organic matter from the studied Domanik section is characterized by compositional heterogeneity. The biomarker and stable carbon isotope compositions of bitumen extracts, their fractions, and kerogen of the Middle and Middle–Upper Domanik shales are different from those of the Upper Frasnian shale, which may indicate the variation in depositional setting.     

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.     

Chemical characterization of the kerogen from Moroccan Timahdit oil shale by analysis of oxidation products

A 33 step alkaline permanganate degradation of the kerogen from Moroccan Timahdit oil shale (M-Zone) was carried out. A very high total yield of oxidation products was obtained (95.4% based on original kerogen). Detailed GC-MS analyses of ether-soluble acids, acids isolated from aqueous solutions and soluble products of further controlled permanganate dedradation of precipitated, ether-insoluble acids, served as a basis for the quantitative estimation of the participation of various types of products and for comparison with other kerogens. The most interesting finding was the observed uniquely high yield of aromatic oxidation products from an intermediate type I–II kerogen. Taking into account the almost equally dominant aliphatic (50.2%) and aromatic (43.2%) nature of the acidic oxidation products, the existence of an aliphatic cross-linked nucleus mixed with cross-linked aromatic units in the Timahdit shale kerogen is postulated. Uniform distribution of oxidation products throughout the degradation suggested a similar reactivity of the various kerogen constituents towards alkaline permanganate.     

Mesozoic carbonaceous clayey formations of the central russian plate: The problem of their ore potential

Polyfacial organic-reach clayey horizons in Jurassic and Cretaceous sections of the central Russian Plate exhibit a similarity to the domanik beds. These horizons are divided into three major groups of facies. The locally distributed continental facies (group 1) is characterized by the development of uranium and REE mineralization. The lagoon-marine facies (group 2) is similar in lithochemical specialization to the black shale horizon hosting multicomponent ores in southern China. The deep-sea facies (group 3) have been poorly studied, so their metal potential remains unclear. A complex of forecasting and prospecting criteria has been elaborated for revealing the metalliferous facies.     

西澳大利亚珀斯盆地页岩气资源研究

珀斯盆地位于澳大利亚西海岸,是西澳大利亚页岩气资源勘探的重点区域。该盆地属于复杂的凹陷裂谷,海相沉积二叠纪的Carynginia组和早三叠世Kockatea页岩层被认为是潜在的含气地层。通过搜集大量外文文献,全面总结了该盆地含气目标层的地物化特征,Carynginia组的总有机碳含量为1%~15%,干酪根为III型,Ro在0.56~1.91;Kockatea页岩层的总有机碳含量为1%~4%,干酪根为II/III混合型,Ro为0.48~1.93。两组共划分了11各岩相段,其中黑色页岩岩相段和含黄铁矿泥岩段是最重要的生烃含气层。综合考虑地层、地化指标和岩石地球物理性质,圈出了可供参考的页岩气甜点区。     

Distribution of organic matter in a shale clast

The mechanism of petroleum migration is not fully understood. One approach has been to study the distribution of organic matter near contacts between rocks with source character and those with reservoir character. Published studies have been restricted to profiles across the bedding, but the ease of movement of hydrocarbons along and across the bedding may be very different. Gradients for volatile bitumens and kerogen both along and across shale bedding have been established by analyzing a shale clast encased in a sand matrix. In this case, the distribution of volatile bitumens is not controlled by the distribution of kerogen but shows evidence of bitumen movement through the clast. The amount and composition of the volatile bitumens and their distribution suggest that in part they have been introduced into the clast from the surrounding medium, and that the movement of hydrocarbons occurs preferentially along the shale bedding. The composition of the material moving into the clast is not the same as the bulk composition of the external supply but shows a preferential enrichment in normal alkanes, particularly those of shorter chain length.     

Source potential of the upper Jurassic rocks of the Barents Sea petroleum basin

A preliminary assessment of the source potential of the Jurassic section was obtained using organic geochemical data on samples collected from outcrops on Franz Josef Land and Svalbard archipelagoes as well as boreholes in the Barents Sea basin. The presence of organic-rich shale units with good source potential was reported for the first time within the studied section of Early to Middle Jurassic age, along with well-documented Upper Jurassic source rocks. The study provides an assessment of regional variations in the kerogen type, hydrocarbon generation potential, and maturation of organic matter from Jurassic sediments.     

伦坡拉盆地渐新统丁青湖组油页岩特征及其地质意义

伦坡拉盆地丁青湖组油页岩呈北西-南东向断续分布,长约50 km,油页岩有18~22层,薄者0.10 m,厚者8.81 m,一般厚0.70~2.00 m。工业分析数据表明,油页岩属于高灰分、中低含油率、低发热量型。油页岩有机碳质量分数为2.40%~20.23%,平均值7.38%,丰度较高。干酪根镜检显示油页岩有机质类型为腐泥型（Ⅰ型）,镜质体反射率（R_o）值为0.43%~0.71%,平均值为0.52%,说明油页岩有机质处于未成熟-低成熟阶段。油页岩样品检测出丰富的正构烷烃、类异戊二烯烷烃、萜烷化合物和甾烷化合物。饱和烃色谱/质谱特征表明伦坡拉油页岩有机母质来源以水生浮游植物为主。通过生物标志物特征及野外地质观察,揭示了油页岩形成于一定盐度的缺氧还原半深湖-深湖环境。湖盆内各种水生浮游植物、藻类等为油页岩的形成提供了主要的有机母质来源,稳定的构造条件和缺氧的环境有利于有机质的堆积和保存。     

松辽盆地农安地区上白垩统油页岩含油率影响因素

农安油页岩含矿区地处松辽盆地东南隆起区,主要发育于上白垩统青山口组一段、嫩江组一、二段。油页岩有机质的干酪根类型为Ⅰ-Ⅱ₁型,质量较好,处于成岩的未成熟阶段。油页岩含油率与有机碳和氢元素含量间存在明显的线性正相关关系,当有机碳质量分数＞6％或氢质量分数＞1％时构成油页岩。此外,有机质干酪根的显微组分可以反映有机质的类型,与含油率之间也存在一定的相关性。青山口-嫩江组沉积时期,该区温暖湿润的古气候条件、大规模的海侵和缺氧事件影响了油页岩中有机质的丰度和类型,从而影响了油页岩的含油率。     

柴北缘大煤沟组七段(J_2d~7)页岩油资源潜力评价——以大煤沟地区为例

通过对大煤沟地区4口钻井和侏罗系标准剖面的40件大煤沟组七段泥页岩样品进行有机地球化学特征、岩矿特征、储集性能等实验分析。结果表明:样品的总有机碳含量平均值为5.22%;干酪根类型为I-II型,以腐泥质为主;样品有机质成熟度平均值为0.52%,主要为未成熟—低成熟样品;样品的储集空间类型多样、微裂缝发育,有利于页岩油的吸附、存储,矿物组成中大于40%的脆性矿物含量有利于后期的生产压裂。另外,在荧光下,样品断面及层理面具有好的荧光显示,为页岩油的存在提供了直接证据。综合分析认为,大煤沟地区大煤沟组七段具备页岩油形成的地质条件,是中侏罗统页岩油发育的最有利层段。并且在柴北缘范围内,该层段泥页岩单层厚度大,平面上横向分布稳定,结合已有研究成果,初步预测冷湖地区、赛什腾凹陷、鱼卡凹陷、大柴旦—大煤沟地区为柴北缘该层段的页岩油发育有利区。     

开放体系下平凉组页岩干酪根的生烃动力学研究

对鄂尔多斯盆地奥陶系平凉组海相页岩进行了3种升温速率下的 Rock-Eval 热解模拟实验,研究了其干酪根在开放体系下的热解生烃演化特征.通过分析热解烃 S2的产率随温度的变化,结合 Kinetics 生烃动力学专用软件计算,获得了其开放体系下的生油动力学参数,活化能分布范围为(57~81)×4.185 kJ/mol.在此基础上进行的动力学模拟结果与实验数据非常吻合,可较好地将实验数据外推到地质实际过程.此外,发现热解残渣中的 H/C(原子比)值与热解温度、干酪根转化率有较好的相关关系,可建立 H/C 值与转化率或者等效镜质组反射率的可靠模板,表明 Rock-Eval 热解实验与 H/C 值结合,可快速评价下古生界源岩的成熟度、转化率和生烃量等指标,将其应用于资源量计算等方面     

Characterization of Bulgarian oil shale kerogen revealed by oxidative degradation

A 13-step alkaline permanganate degradation of Bulgarian oil shale kerogen concentrate at ambient temperature was carried out. A high yield of oxidation products (90.1%) and a low yield of gaseous products (2.79%) were obtained. IR and ¹H NMR spectroscopic studies have shown that two significantly different types of high molecular products are present in kerogen. Further oxidation of these structures leads to the formation of low molecular aliphatic and aromatic acids, proven by gas chromotography (GC) and gas chromatography-mass spectrometry (GC-MS). The data obtained at these mild conditions allow us to acquire detailed information about the aromatic structures and polymethylene chain lengths in kerogen.The 5-step oxidation of the kerogen at 90 °C provides information about stable aromatic structures. Soluble and insoluble polyfunctional acids in acid medium have close molecular masses and spectral characteristics. The amount of benzene and naphthalene carboxylic acids is 11.3% of the organic matter of the oil shale.     

Changes in the composition of bitumen extracts and chemical structure of kerogen during hydrous pyrolysis

The paper presents data on the composition of biomarkers from bitumen extracts and the chemical structure of kerogen from C_org-rich sedimentary rocks before and after hydrothermal treatment in an autoclave at 300°C. Samples selected for this study are kukersite and Ordovician Dictyonema shale from the Baltics, Domanik oil shale from the Ukhta region, Upper Permian brown coal from the Pre-Ural foredeep, carbonaceous shale from the Oxfordian horizon of the Russian plate, and Upper Jurassic oil shales from the Sysola oil shale bearing region. The rocks contain type I, II, III, and II-S kerogens. The highest yield of extractable bitumen is achieved for Type II-S kerogen, whereas Type III kerogen produces the lowest amount of bitumen. The stages of organic matter thermal maturation achieved during the experiments correspond to a transition from PC_2–3 to MC_1–2. The ¹³C NMR data on kerogen indicate that the aromatic structures of geopolymers underwent significant changes.