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.     

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.     

Multistage alkaline permanganate degradation of a type II kerogen

The products of a 27-step alkaline permanganate degradation of a type II kerogen from a sample of Toarcian shale, Paris Basin, have been studied. The high yield of oxidation products consisted of 1.86% neutrals and bases, 24.48% ether-soluble acids, and 45.95% precipitated, ether-insoluble acids, based on weight of original kerogen. The ether-soluble acids and the soluble products of further permanganate degradation of precipitated acids were found to consist mostly of saturated unbranched C₆–C₂₂ α,ω-dicarboxylic and C₉–C₂₅ monocarboxylic acids. Significant amounts of aromatic monocarboxylic, dicarboxylic and tricarboxylic acids were also found. Alkane tri- and tetracarboxylic acids were obtained in small concentration.     

Structural changes of young kerogen during laboratory heating as revealed by alkaline potassium permanganate oxidation

Kerogen was isolated from a marine sediment from Tanner Basin, offshore California. Samples of the kerogen were heated under an inert atmosphere at various temperatures and times. The heated and unheated kerogens were subjected to alkaline potassium permanganate oxidation followed by GC/ MS analysis of the products. The kerogens yielded primarily aliphatic C₂–C₁₄ α,ω-dicarboxylic acids and benzene mono-to-pentacarboxylic acids. Yields of aliphatic dicarboxylic acids from kerogen decreased with increasing thermal alteration. Yields of benzenecarboxylic acids increased steadily with increasing thermal alteration. The data support the concept that thermal maturation during natural burial of this type of kerogen results in the generation of aliphatic hydrocarbons from an increasingly aromatic residue.     

Evaluation of alkaline permanganate oxidation method for the characterization of young kerogen

Alkaline potassium permanganate oxidation of a young kerogen (lacustrine) and 34 model compounds (saturated and unsaturated fatty acids, hydroxy acid, aliphatic dicarboxylic acids, aliphatic alcohols, normal hydrocarbon, β-carotene, phenolic acids, benzenecarboxylic acids, carbohydrates, amino acids and proteins) were conducted, followed by GC and GC-MS analysis of the degradation products. The stability of the degradation products of kerogen in permanganate solution and the relationship between degradation products and kerogen building blocks were determined.The results showed that aliphatic acids C₁₂–C₁₆ monocarboxylic acids and C₆–C₁₀ α,ω-dicarboxylic acids) were rather susceptible to oxidation compared with benzenecarboxylic acids and the former were degraded into lower molecular weight decarboxylic acids. It was concluded that oxidation at milder conditions (60° C, 1 hr) is appropriate for qualitative and quantitative characterization of the aliphatic structure of young kerogen. It was noteworthy that benzoic acid was produced in a significant amount by oxidation of amino acids (phenylalanine) and proteins, C₁₈-isoprenoidal ketone from phytol, and C₈ and C₉ α,ω-dicarboxylic acids from unsaturated fatty acids, respectively; furthermore, 2,2-dimethyl succinic and 2,2-dimethyl glutaric acids were produced from β-carotene.     

Molecular Structure of Kerogen in the Longmaxi Shale: Insights from Solid State NMR,FT‐IR,XRD and HRTEM

Kerogen plays an important role in shale gas adsorption, desorption and diffusion. Therefore, it is necessary to characterize the molecular structure of kerogen. In this study, four kerogen samples were isolated from the organic-rich shale of the Longmaxi Formation. Raman spectroscopy was used to determine the maturity of these kerogen samples. High-resolution transmission electron microscopy (HRTEM), 13C nuclear magnetic resonance (13C NMR) , X-ray diffraction (XRD) and Fourier transform infrared (FT-IR) spectroscopy were conducted to characterize the molecular structure of the shale samples. The results demonstrate that VReqv of these kerogen samples vary from 2.3% to 2.8%, suggesting that all the kerogen samples are in the dry gas window. The macromolecular carbon skeleton of the Longmaxi Formation kerogen is mainly aromatic (fa’=0.56). In addition, the aromatic structural units are mainly composed of naphthalene (23%), anthracene (23%) and phenanthrene (29%). However, the aliphatic structure of the kerogen macromolecules is relatively low (fal*+falH=0.08), which is presumed to be distributed in the form of methyl and short aliphatic chains at the edge of the aromatic units. The oxygen-containing functional groups in the macromolecules are mainly present in the form of carbonyl groups (fac=0.23) and hydroxyl groups or ether groups (falO=0.13). The crystallite structural parameters of kerogen, including the stacking height (Lc=22.84 ?), average lateral size (La=29.29 ?) and interlayer spacing (d002=3.43 ?), are close to the aromatic structural parameters of anthracite or overmature kerogen. High-resolution transmission electron microscopy reveals that the aromatic structure is well oriented, and more than 65% of the diffractive aromatic layers are concentrated in the main direction. Due to the continuous deep burial, the longer aliphatic chains and oxygen-containing functional groups in the kerogen are substantially depleted. However, the ductility and stacking degree of the aromatic structure increases during thermal evolution. This study provides quantitative information on the molecular structure of kerogen samples based on multiple research methods, which may contribute to an improved understanding of the organic pores in black shale.     

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.     

Structural relationships between a brown coal and its kerogen and humic acid fractions

A South Australian Tertiary brown coal is fractionated into humic acid and kerogen fractions. These related samples are then subjected to a number of different analytical techniques including infrared and¹³C-Nuclear Magnetic Resonance spectroscopies and pertrifluoroacetic acid oxidation. Structural conclusions are drawn from an integrated consideration of the data. Brown coal aliphatic structure is concentrated in the kerogen and the solvent soluble polar acid fractions. The humic acids are the most aromatic and contain a high degree of hydrogen bonding. Only very minor amounts of long polymethylene chain structures are observed in the humic acids, in complete contrast to the kerogen fraction. Different organic detrital origins are proposed for the coal fractions.     

Alkaline permanganate oxidation of kerogens from Cretaceous black shales thermally altered by diabase intrusions and laboratory simulations

Potassium permanganate oxidative degradations were conducted for kerogens isolated from Cretaceous black shales (DSDP Leg 41, Site 368), thermally altered during the Miocene by diabase intrusions and from unaltered samples heated under laboratory conditions (250–500°C).Degradation products of less altered kerogens are dominated by normal C₄–C₁₅ α,ω-dicarboxylic acids, with lesser amounts of n-C₁₆ and n-C₁₈ monocarboxylic acids, and benzene mono-to-tetracarboxylic acids. On the other hand, thermally altered kerogens show benzene di-to-tetracarboxylic acids as dominant degradation products, with lesser or no amounts (variable depending on the degree of thermal alteration) of α,ω-dicarboxylic acids. Essentially no differences between the oxidative degradation products of naturally- and artificially-altered kerogens are observed.As a result of this study, five indices of aromatization (total aromatic acids/kerogen; apparent aromaticity; benzenetetracarboxylic acids/total aromatic acids; benzene-1,2-dicarboxylic acid/benzenedicarboxylic acids; benzene-1,2,3-tricarboxylic acid/benzenetricarboxylic acids) and two indices of aliphatic character (Total aliphatic acids/kerogen; Aliphaticity) are proposed to characterize the degree of thermal alteration of kerogens.Furthermore, a good correlation is observed between apparent aromaticity estimated by the present KMnO₄ oxidation method and that from the ¹³C NMR method (DENNIS et al., 1982).     

高磁场固态碳13核磁共振法研究干酪根的热降解成烃机理

用高磁场(75.46MH_Z)固态碳13核磁共振(NMR)波谱仪研究了抚顺油页岩在热降解模拟试验中干酪根的化学结构变化.为了消除旋转边带的干扰,在应用交叉极化与魔角自旋(CP/MAS)技术的同时,采用了Dixon TOSS技术,从而得到高分辨的波谱图。据此测定了热降解过程中干酪根各种碳结构组成的变化,计算了芳碳率、亚甲基基团平均碳原子数、环缩合指数等一系列干酪根的结构参数,并与干酪根的相对产油潜力相关联.发现干酪根的产油潜力直接与亚甲基基团的含量有关,而芳碳以及与芳碳相连的甲基碳则贡献甚微.文中还对干酪根的热降解成烃机理作了探讨。     

藏北羌塘盆地胜利河油页岩干酪根特征及碳同位素指示意义

胜利河油页岩位于北羌塘盆地南部, 走向长超过34 km, 宽9 km。笔者对该油页岩各岩系干酪根进行了分离、镜鉴、元素分析和碳同位素分析, 结果表明, 该油页岩干酪根为Ⅱ型干酪根, 油页岩中干酪根含量较高, 介于15.79%~20.37%, 具有富氢少氧的特征, 其H/C和O/C比率分别为1.11~1.19和0.08~0.25, 为胜利河地区非常好的烃源岩。油页岩层干酪根13C相对富集, 具有相对较高的δ13CPDB值(-20.79‰~ -21.78‰), 与胜利河地区油页岩母源为较单一的藻类有关。藻类的大量繁殖造成了该类生物死亡埋藏速率远大于氧化速率, 在还原环境下大部分藻类还未被氧化就被埋藏, 从而保留了原始藻类略富13C的特征。胜利河油页岩的空间展布以及规模明显受古泻湖环境的控制。     

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。     

干酪根化学降解产物的碳同位素组成研究

采用一系列温和的化学降解法对松辽盆地南部嫩江组烃源岩的干酪根进行连续的选择性化学降解，并对不同降解产物进行色谱—同位素比值质谱分析。研究表明碱性水解和脱硫产物以一元脂肪酸和正构烷烃为主，其中正构烷烃碳同位素分布曲线呈现一定的“负倾”（即随碳数增加呈现逐渐贫13C）趋势；一元脂肪酸以C16和C18为主，具有明显的偶碳优势，与同碳数的正构烷烃具有相似的碳同位素组成。氧化产物则以一元脂肪酸和α,ω 二元脂肪酸为主，一元脂肪酸低碳数部分呈现“负倾”趋势，高碳数部分则呈现“正倾”的趋势；α,ω 二元脂肪酸与低碳数的一元脂肪酸具有相似的分布，表明它们可能具有相同的母源。对比研究表明JL 30抽提物中正构烷烃可能存在混源的影响，其碳同位素组成是多源混合的结果。     

Differences in the mode of incorporation and biogenicity of the principal aliphatic constituents of a Type I oil shale

Compound-specific stable carbon isotope (δ ) measurements on the aliphatic hydrocarbons released from an immature Tertiary oil shale (Göynük, Turkey) via hydropyrolysis, following solvent extraction and a milder hydrogenation treatment, have further highlighted that significant compositional differences may exist between the principal aliphatic constituents of the solvent extractable (bitumen) phase and the insoluble macromolecular network (kerogen) comprising the bulk of sedimentary organic matter. Whilst inputs from diverse sources; including algae, bacteria and terrestrial higher plants, were implied from analysis of solvent-extractable alkanes, the much larger quantities of kerogen-bound n-alkyl constituents released by hydropyrolysis had a uniform isotopic signature which could be assigned to (freshwater) algae. Remarkably, the aliphatics bound to the kerogen by relatively weak covalent bonds, liberated via catalytic hydrogenation, appeared to comprise mainly allochthonous higher plant-derived n-alkanes. These results provide further compelling evidence that the molecular constituents of bitumen and, indeed, of low-yield kerogen degradation products, are not necessarily reliable indicators of kerogen biogenicity, particularly for immature Type I source rocks. The isotopic uniformity of aliphatic n-hydrocarbons released by the high-conversion hydropyrolysis step for the ultralaminae-rich Göynük oil shale, lends further support to the theory that selective preservation of highly resistant aliphatic biomacromolecules is an important mechanism in kerogen formation, at least for alginite.     

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。     

Structural investigations of sulphur-rich macromolecular oil fractions and a kerogen by sequential chemical degradation

Structural studies of a sulphur-rich kerogen and macromolecular oil fractions from the Monterey Formation were performed by selective sequential chemical degradation. The method provides low-molecular weight compounds as former building blocks of the network which allow detailed analyses on a molecular level. The degradation sequence is based on three subsequently performed reactions—a selective cleavage of sulphur bonds in the first step carried out with Ni(0)cene/LiAlD₄, an ether and ester bond cleavage (BCl₃), and an oxidation of aromatic entities by ruthenium tetroxide as a final step. Each step of this sequence afforded a considerable amount of low-molecular weight material which was separated chromatographically and studied by GC and GC/MS, while the high-molecular weight or insoluble fractions were subjected to the next reaction step.The chemical degradation products—hydrocarbons and carboxylic acids—are discussed in terms of incorporation into the macromolecular structure, distribution of heteroatomic bridges and the genetic relationships between the different macromolecular crude oil fractions and kerogen.Labelling experiments with deuterium provided evidence for a simultaneous linkage by oxygen and sulphur functionalities or by aromatic units and sulphur bonds of cross-linking macromolecular network constituents.The determination of sulphur positions in the macromolecule suggests early diagenetic sulphur incorporation into the biological precursor compounds and subsequent formation of a cross-linked network.     

抚顺盆地油页岩地质特征及其成矿过程

抚顺盆地位于郯庐断裂带北延东支[CD2]抚顺[CD1]密山断裂带上,盆内赋存有厚达200 m的巨厚油页岩层,按含油率高低,可分为上部富矿层和下部贫矿层。富矿层中水平层理发育,含油率多为5%~8%,最高可达12%;贫矿层中层理很少,多数层段含油率小于3%。地球化学分析结果显示,油页岩中有机碳含量较高,最高可达13.1%。油页岩属Ⅰ[CD*2]Ⅱ型干酪根,成熟度较低。整个含油页岩岩系的形成经历了盆地初始裂陷、加速裂陷、稳定发育、较快速裂陷、较慢速裂陷、终止裂陷6个阶段。综合分析表明,油页岩贫矿层形成于盆地周缘夷平程度较高、物源供给较少、盆地基底沉降相对较快、有机质堆积比例较低的浅湖环境;油页岩富矿层形成于盆地周缘夷平程度较高、物源供给较少、盆地基底沉降速率相对缓慢、有机质堆积比例相对较高的浅湖环境。     

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。     

Effect of a dolerite intrusion on triterpane stereochemistry and kerogen in Rundle oil shale,Australia

Stereochemical changes of triterpanes present in extracts from an immature oil shale sequence intruded by a 3-m dolerite sill have been studied by gas chromatography-mass spectrometry (GC-MS). The steric configuration of the hopanes was observed to change from one dominated by the thermally less stable 17β(H), 21β(H) configuration at some distance from the intrusion, to one dominated by the thermally more stable 17α(H), 21β(H) and 17β(H), 21α(H) configurating in the immediate vicinity of the intrusion. In addition, severe alteration of the kerogen appeared to have taken place as a result of the contact metamorphism, and high concentrations of extractable organic matter were observed below the intrusion. Characterization of the kerogens by Curie-point pyrolysis has enabled the effects of the intrusion on the shales to be monitored.