Heteroaromatic moieties in Green River oil shale kerogen

Investigation of the reaction of Green River oil shale kerogen with sodium borohydride in trifluoroacetic acid by infrared spectroscopy has shown the appearance of absorptions representative of lactams. These lactams can be shown to have possible precursors that are heteroaromatic in composition and as such could demonstrate the existence in Green River kerogen of aromatic nitrogen compounds.     

Stereochemical studies of acyclic isoprenoid compounds—V. Oxidation products of Green River Formation oil shale kerogen

Gas chromatographic analysis of the major isoprenoid carboxylic acids and the major ketone (6,10,14-trimethylpentadecan-2-one), derived from successive chromic acid oxidations of the kerogen of Green River Formation oil shale, indicates that their stereochemistry is compatible with the hypothesis that phytol or a derivative with the same carbon skeleton and stereochemistry was incorporated into the kerogen matrix.     

Polar constituents isolated from Green River oil shale

This paper interprets the mass spectrometric, i.r. absorption and NMR data for 22 compounds obtained from a polar fraction of Green River shale. The major constituents analyzed are believed to be of the following compositional types: C_nH_2nO (cyclohexanols and chain isoprenoid ketones), C_nH_2n?10O (tetralones and indanones), C_nH_2n?7N (tetrahydroquinolines), C_nH_2n?11N (quinolines), C_nH_2n?1NO (alkoxypyrrolines), C_nH_2n?5NO₂ (maleimides), C_nH_2n?8 (tetralins), C_nH_2n?12 (naphthalenes) and C_nH_2n?14 (benzylbenzenes). This work expands the present information about nitrogen, oxygen and aromatic constituents indigenous to Green River shale.     

Elemental abundances in Green River oil shale

Spark-source mass spectrometric analysis of pyrolyzed Green River oil shale for trace element distribution showed enhanced concentrations for only lithium and beryllium. In general, trace elemental concentrations were found to be below anticipated crustal amounts. There appears to be no promise of any substantial accumulation of any trace elements within the organic matrix of Green River oil shale.     

Biological markers from Green River kerogen decomposition

Isoprenoid and other carbon skeletons that are formed in living organisms and preserved essentially intact in ancient sediments are often called biological markers. The purpose of this paper is to develop improved methods of using isoprenoid hydrocarbons to relate petroleum or shale oil to its source rock. It is demonstrated that most, but not all, of the isoprenoid hydrocarbon structures are chemically bonded in kerogen (or to minerals) in Green River oil shale. The rate constant for thermally producing isoprenoid, cyclic, and aromatic hydrocarbons is substantially greater than for the bulk of shale oil. This may be related to the substantial quantity of CO₂ which is evolved coincident with the isoprenoid hydrocarbons but prior to substantial oil evolution. Although formation of isoprenoid alkenes is enhanced by rapid heating and high pyrolysis temperatures, the ratio of isoprenoid alkenes plus alkanes to normal alkenes plus alkanes is independent of heating rate. High-temperature laboratory pyrolysis experiments can thus be used to predict the distribution of aliphatic hydrocarbons in low temperature processes such as in situ shale oil production and perhaps petroleum formation. Finally, we demonstrate that significant variation in biological marker ratios occurs as a function of stratigraphy in the Green River formation. This information, combined with methods for measuring process yield from oil composition, enables one to relate time-dependent processing conditions to the corresponding time-dependent oil yield in a vertical modified-in situ retort even if there is a substantial and previously undetermined delay in drainage of shale oil from the retort.     

低成熟油页岩的生排烃作用实验模拟

烃源岩的成熟演化特征对评价一个区域的油气产出背景意义重大。笔者选择准噶尔南部低熟油页岩作为试验样品,分别进行无水变温、等温变水及等水变温条件下的烃源岩热模拟实验,并依据油、气、固体残渣的定性定量检测,分析烃类相态与组成变化。得到以下结果:无水变温及等水变温实验中油产率均在300 ℃时出现最高值,而且在等水变温情况下,200 ℃时的产油率比不加水情况下明显增大;在等温变水情况下,生油量在加10 mL水时最大;干气生成阶段,气态烃主要来自重烃裂解而不是高度演化的干酪根本身,400 ℃热解之后,剩余生烃率大约为5％左右;饱和烃在低温和极端高温时相对比例高,以正构烷烃为绝对优势组分;芳烃比例变化波动较大,以三环、四环芳烃为主,在400 ℃时达到最大值,在500 ℃时跌至最低值;非烃、沥青质相对比例变化与芳烃正好相反。     

An isotopic biogeochemical study of the Green River oil shale

Thirty-five different samples from three different sulfur cycles were examined in this stratigraphically oriented study of the Shell 22x-l well (U.S.G.S. C177 core) in the Piceance Basin, Colorado. Carbon isotopic compositions of constituents of Green River bitumens indicate mixing of three main components: products of primary photoautotrophs and their immediate consumers (delta approximately -30% vs PDB), products of methanotrophic bacteria (delta approximately -85%), and products of unknown bacteria (delta approximately -40%). For individual compounds synthesized by primary producers, delta-values ranged from -28 to -32%. 13C contents of individual primary products (beta-carotane, steranes, acyclic isoprenoids, tricyclic triterpenoids) were not closely correlated, suggesting diverse origins for these materials. 13C contents of numerous hopanoids were inversely related to sulfur abundance, indicating that they derived both from methanotrophs and from other bacteria, with abundances of methanotrophs depressed when sulfur was plentiful in the paleoenvironment. gamma-Cerane coeluted with 3 beta(CH3),17 alpha(H),21 beta(H)-hopane, but delta-values could be determined after deconvolution. gamma-Cerane (delta approximately -25%) probably derives from a eukaryotic heterotroph grazing on primary materials, the latter compound (delta approximately -90%) must derive from methanotrophic organisms. 13C contents of n-alkanes in bitumen differed markedly from those of paraffins generated pyrolytically. Isotopic and quantitative relationships suggest that alkanes released by pyrolysis derived from a resistant biopolymer of eukaryotic origin and that this was a dominant constituent of total organic carbon.     

Relics of biolipids in kerogen of Cambrian Siberian Platform oil shale

Products of thermal cracking of kerogen of Lower-Middle Cambrian oil shale are studied by modern instrumental analytical methods (FTIR, gas chromatography, mass spectrometry, etc.). The analyses demonstrate that the geopolymer kerogen matrix inherited fragments of lipids synthesized by living organisms, including aliphatic fat acids, both free or bounded into glycerol esters, i.e., animal or vegetable fats. It is shown that vegetable pigments (carotenes and xanthophylls) play a crucial role in the formation of monocyclic structures (including molecular alkylbenzene, alkylphenol, and phenylalkane fragments) in kerogen. Since the studied kerogen is rich in esters, it is worth performing alkaline hydrolysis of its macromolecules (ester saponification) before their thermolysis, which inevitably distorts the initial structure of molecular skeletons.     

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.     

The role of kerogen constituents in oil generation in the Gevar'am Formation (Lower Cretaceous), Israel

Kerogen from various samples of the Gevar'am Formation (Early Cretaceous, Israel) were analyzed for their elemental composition, and by I.R. and ESR spectroscopy. The results were compared with other organochemical characteristics of the basin (Amit, 1978, Bull. Am. Assoc. Pet. Geol., V. 62 p. 827–836). The types of organic material and their role in the formation of oil were investigated. It appears that the kerogen is mostly constituted of terrestrially derived organic matter. A small amount of marine-derived organic matter is also inferred. The kerogen of terrestrial origin is a poor oil producer and is expected to generate oil only at a higher stage of maturation than the Gevar'am Formation has attained. Any hydrocarbons that have been generated in this formation were probably generated from that part of the kerogen thought to be marine derived. Thus the Gevar'am Formation is considered as a potential source rock which has generated only a small amount of oil.     

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.     

Long-chain carboxylic acids in pyrolysates of Green River kerogen

Long-chain fatty acids (C₁₀-C₃₂), as well as C₁₄-C21 isoprenoid acids (except for C₁₈), have been identified in anhydrous and hydrous pyrolyses products of Green River kerogen (200–400°C, 2–1000 hr). These kerogen-released fatty acids are characterized by a strong even/odd predominance (CPI: 4.8-10.2) with a maximum at C₁₆ followed by lesser amounts of C₁₈ and C₂₂ acids. This distribution is different from that of unbound and bound geolipids extracted from Green River shale. The unbound fatty acids show a weak even/odd predominance (CPI: 1.64) with a maximum at C₁₄, and bound fatty acids display an even/odd predominance (CPI: 2.8) with maxima at C₁₈ and C₃₀. These results suggest that fatty acids were incorporated into kerogen during sedimentation and early diagenesis and were protected from microbial and chemical changes over geological periods of time. Total quantities of fatty acids produced during heating of the kerogen ranged from 0.71 to 3.2 mg/g kerogen. Highest concentrations were obtained when kerogen was heated with water for 100 hr at 300°C. Generally, their amounts did not decrease under hydrous conditions with increase in temperature or heating time, suggesting that significant decarboxylation did not occur under the pyrolysis conditions used, although hydrocarbons were extensively generated.     

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     

松辽盆地古龙凹陷青山口组生排烃扩张微米孔/缝的发现及其意义

笔者等通过电子背散射、二次成像和能谱分析,结合薄片和反射显微镜观察,发现松辽盆地古龙凹陷青山口组页岩中发育了大量由生排烃扩张形成的微米孔和微米缝。生排烃高压扩张微米孔的特点有：①一般只发育在超高压的页岩油储层中;②一般只发育在黏土质长英页岩中,纯黏土岩少见;③多为近圆形或半圆形,直径多在0. 5 μm到数微米,一般1~2 μm,最大可达8 μm;④孔缘一般为以绿泥石为主的黏土,形成不连续的圈环;圈环上缘的黏土多呈弧形或眉状,绿泥石化明显,在背散射图像中呈亮色;⑤孔内多有自生的纳米级葡萄状或豆渣状黏土,是构成封存油气的物质基础;⑥生排烃高压扩张微米孔可以组合成4种类型：即垂向联结成垂直的排烃烟囱型、垂向联结成倾斜的排烃烟囱型、水平联结成顺层的排烃管型和竖面上联结成更大的片状大孔型。排烃烟囱直或微曲,直立或倾斜;宽1~3 μm,最宽可达200 μm;高十几到30 μm,最大可达1500 μm;顶部多与顺层微米缝（或毫米缝）联结,是排烃烟囱的最终泄压和泄油气的总库;生排烃扩张微米孔孔隙度变化大,面孔率一般在5%~6%,局部面孔率最高可达39. 66%。生排烃高压扩张微米缝的特点有：①一般只发育在超高压的页岩油储层中;②一般只发育在黏土质长英页岩中,纯黏土岩少见;③多以顺页理为主的微米缝为主;④略曲的张性缝,多呈锯齿状,绕过刚性矿物;⑤宽度多在0. 5 μm到数十微米;最宽可达150 μm;⑥多与黄铁矿、白云石、磷灰石等自生矿物伴生;⑦多与生排烃扩张微米孔和排烃烟囱相连。生排烃扩张微米孔缝的形成动力主要有两种：一种是烃类流体的高压扩张力;第二种是烃类流体的化学溶蚀力。笔者等计算了形成这种生排烃微米孔和微米缝的压力,形成生排烃扩张微米孔从1500 m的44. 74 MPa到2500 m深的74. 81 MPa;形成生排烃扩张微米缝的排烃压力稍大,在相同深度比形成生排烃扩张微米孔大3 MPa。生排烃扩张微米孔缝与其他孔缝相连构成了一个储运网络,使储层的储集能力和渗透性大幅增加,是可动用储量的主要贡献者,为古龙页岩油的开发创造了有利条件。生排烃扩张微米孔缝的发现对于古龙页岩油的勘探开发具有重要意义,同时对于页岩油储层的研究具有启发作用。     

Molecular characterization of Type I kerogen from the Green River Formation using advanced NMR techniques in combination with electrospray ionization/ultrahigh resolution mass spectrometry

This study describes a new approach for characterizing high molecular weight compounds in Type I kerogen, involving both nuclear magnetic resonance (NMR) spectroscopy and Fourier transform ion cyclotron mass spectrometry (FTICR-MS). Kerogen isolated from the Mahogany zone of the Green River Formation was examined directly using high resolution magic angle spinning (HRMAS) NMR to obtain liquid-like multidimensional spectra. It was then successively extracted with n-pentane, dichloromethane and pyridine. Pyridine extraction was also performed for comparison with the successive extractions. Using solid-state NMR, we show that the sum of the successive extracts and the single pyridine extract are quantitatively representative of the unextracted kerogen. This suggests that a non-invasive characterization of Green River kerogen can be obtained by examining the soluble extracts, all of which were subjected to ESI-FTICR-MS to identify a wide series of compounds. Series of polar CHO, CHOS and CHON compounds between C₁₂ and C₅₀₊ were found. In all the extracts the two homologous series of acids (C_nH_2nO₂ and C_nH_2n−2O₄) dominated. Collision-induced dissociation was also employed to identify the different functional groups comprising the different series. The CHO series contained carboxylic acid and alkoxyl groups, whereas the CHOS and CHON series contained sulfoxide groups and nitrile-type compounds. The results also show that pyridine extraction can be used either for screening a large series of samples or for the specific study of CHO compounds. However for a detailed and complete study of the different homologous series we recommend using the successive extraction protocol.     

Analysis of some aromatic hydrocarbons in a benzene-soluble bitumen from Green River shale

The hydrocarbon content of an aromatic fraction, isolated from the bitumen of Green River shale, was studied by mass spectrometry, infra-red spectrometry, gas chromatography and a dehydrogenation technique. The hydrocarbon types and their distribution in this aromatic fraction, as determined by mass spectrometry, include the following: C_nH_2n?6(10%), C_nH_{2n?8 (31 %)}, C_nH_2n?10(18%), C_nH_2n?12(12%), C_nH_2n?14(8%) and a series of alkenylbenzenes (20%). The carbon-number range, empirical formulae and quantity of each compound in the major types are reported. Mass spectra of several compounds and homologous mixtures of compounds isolated from the aromatic fraction are also given.     

压力对高硫干酪根轻烃产率的影响

采用金管－高压釜体系对江汉盆地高硫干酪根进行了热解,用氘代正构烷烃作标样,色谱－质谱定量。实验结果表明,压力增加,ｎＣ６和轻烃（ｎＣ６￣ｎＣ１４）的产率明显增加;而对ｎＣ１５和沥青的产率未发现有显著影响。     

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.     

罗子沟盆地下白垩统大砬子组油页岩成矿规律分析

罗子沟盆地油页岩赋存于下白垩统大砬子组二段,埋藏浅,地层倾角缓,含油率为3.51%～14.37%。油页岩具有典型内陆湖泊成因特点,含有大量动植物化石,其成因类型为腐泥型(Ⅰ型)和腐植腐泥型(Ⅱ1型)。大砬子组为一个完整的三级层序,主要油页岩层形成在水进体系域和高水位体系域,含油率高,赋存稳定。从平面上,油页岩富矿中心在CK26、CK30、CK35、CK40孔附近,呈东西向带状分布;在纵向上,共见有29层油页岩,其中有7层为可采油页岩层,2层和3层油页岩呈层状产出,连续、稳定、含油率高,具有巨大的经济开发价值。     

低熟页岩生烃特征的热模拟实验研究

采用高压釜热模拟实验方式对页岩样品的成熟度进行改变,并对成熟度改变过程中页岩的生烃情况及热解参数进行了分析。研究表明:Ro随着温度的增高,分为三个阶段:缓慢变化阶段、中等增加阶段和快速增加阶段。随着R_o的升高,气态烃的产率一直是上升的,而液态烃的产率后期是下降的,裂解烃量(S_2)则由于转化为气态烃等含量迅速降低,但总烃增加量是有变化的。当R_o为0.65%和1.0%时出现二个生烃高峰,这反映了低成熟页岩在生烃演化过程中的三个阶段,即初期热降解阶段、热降解-热裂解阶段和热裂解阶段。而R_o与总烃产率在热模拟过程中则近似呈一条指数曲线关系,根据二个生烃高峰,进而确定了我国陆相盆地页岩气远景区R_o的下限为0.65%,页岩气有利区R_o的下限为1.0%。