A comparison of organosulphur compounds produced by pyrolysis of asphaltenes and those present in related crude oils and tar sands

Asphaltenes and NSO fractions from a variety of oils and tar sands have been characterized by pyrolysis-gas chromatography (Py---GC) using both flame ionization and flame photometric detectors. Organosulphur compounds were not always produced by pyrolysis of the asphaltenes isolated from the biodegraded tar sand extracts although pyrolysis of the NSO fractions produced a series of thiophenes from all of the samples examined. These observations suggest that under certain conditions, asphaltene fractions may be affected by biodegradation, leading to preferential removal of the sulphur containing compounds. In addition, it was observed that Py---GC of asphaltenes permitted oils to be differentiated on the basis of their source rock lithology. Oils derived from carbonate source rocks produced thiophene/benzothiopene ratios <1 whilst the same ratio was >1 for oils derived from shales. Thiophene/dibenzothiophene ratios could be used in a similar manner.     

The determination of biomarker distributions by tandem mass spectrometry

The rapid development of biomarker geochemistry and its application to petroleum exploration problems has been due in no small part to gas chromatography-mass spectrometry (GC-MS). The recent availability of hybrid and triple stage quadrupole mass spectrometers have introduced a number of novel ways for the detection and identification of biomarkers present in extremely complex mixtures of organic compounds from various sources including crude oils and source rock extracts.A triple stage quadrupole mass spectrometer has been used in the MS/MS mode with both a gas chromatograph and direct insertion probe as inlet systems, to develop alternative methods for biomarker analyses. Selected ions formed in the ion source of the mass spectrometer are permitted to enter the collision cell where, following collision with an inert gas, the daughter ions are separated using the third quadrupole. In this manner specific parent/daughter ion relationships are utilized to monitor and resolve classes of biomarkers or individual components from within a complex mixture. Furthermore, deuterated analogues of naturally occurring biomarkers can be utilized for quantitation purposes since the parent/daughter relationship for the standard will differ, depending on the number of deuterium atoms present, even though the relative retention times are identical.The ability of MS/MS to resolve components spectrometrically as well as chromatographically greatly enhances the analytical short-column capabilities of this system. In this paper the utilization of GC-MS/MS and the direct insertion probe MS/MS to determine biomarker distributions in crude oils both qualitatively and quantitatively are discussed. The results from the study show that it is possible to use the probe data to rapidly correlate oils on the basis of their source materials and if necessary select samples for more detailed analysis by GC-MS/MS. A major advantage of the direct insertion probe method is speed of analysis although some component resolution is lost. In an effort to minimize this problem and still maintain the rapid analysis time, the use of short columns in the GC is also described. This approach provides the ability to undertake relatively rapid analyses with limited chromatographic resolution but at relatively high levels of sensitivity.     

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.     

中国新生界咸水湖相烃源岩和原油生物标志物组合特征

我国广泛发育着新生界咸水湖盆,这些湖盆具有独特的沉积环境和生油气条件。咸水湖相烃源岩及其所形成烃类的地球化学特征,既不同于淡水湖相,又不同于海相烃源岩及原油的地球化学特征。介绍了我国咸水湖相中烃源岩及原油的生物标志物组合特性、形成条件及其地球化学意义。     

平庄凹陷烃源岩有机质成熟度评价

平庄凹陷盖层中发育九佛堂组、沙海组和阜新组3套烃源岩,虽然以往围绕煤矿生产展开了大量的煤田地质勘探工作,但石油、天然气勘探工作较少,研究程度较低。为了客观评价平庄凹陷的油气资源,需对烃源岩有机质成熟度进行评判。在对平庄凹陷烃源岩岩石热解、镜质组反射率、生物标志物参数分析的基础上,对平庄凹陷九佛堂组、沙海组烃源岩有机质热演化特征及演化阶段进行了系统研究。结果表明：平庄凹陷烃源岩各参数随埋藏深度的增加变化明显,具有纵向上的连续性和横向上的不均匀性;平庄洼陷烃源岩有机质成熟度处于未成熟—低成熟—成熟阶段,其中,九佛堂组烃源岩是盆地的主要成油岩系;四龙洼陷烃源岩有机质成熟度较低,对盆地成烃贡献不大。     

Source rock potential (TOC + hydrogen index) evaluation by integrating well log and geochemical data

Evaluation of source rock potential using well log data alone, e.g. density or sonic log, is limited to the assessment of total organic carbon (TOC) content. Well logs that directly measure the most important source quality parameter, the hydrogen content of the kerogen, do not exist. Therefore, a method is proposed that combines log-derived TOC data with calibration schemes relating TOC content to Hydrogen Index and maturity for individual source rock sets. The method has been applied to the compositionally heterogeneous Kimmeridge Clay Formation of the North Sea and the homogeneous Lower Toarcian Shale of N.-Germany. The combination of well log and geochemical data greatly improves the accuracy with which the lateral and vertical distribution of source rocks and their potential can be predicted on a basin and prospect level.     

干酪根中类脂肪链含量的测定及石油地质意义

选取了红外光谱中2750～3000cm-1C-H振动峰面积作为反映干酪根中脂肪链含量的特征参数,并以完全饱和脂肪链的微晶石蜡为基准,建立了对干酪根中脂肪链含量进行测定的实验方法,同时讨论了实验条件、无机矿物、干酪根样品加入量等因素的影响。并通过对东营地区不同类型干酪根的低熟烃源岩样品进行的高压热模拟实验,研究了干酪根中脂肪链的百分含量与成熟度、沥青转化率及干酪根原素组成之间的关系。结果表明干酪根中脂肪链含量不仅与干酪根的类型有关,而且随成熟作用增加明显降低,其与热模拟生油量的关系和烃源岩的产烃率曲线相似,在脂肪链含量由15%降至5%时出现一个生油高峰。所以,脂肪链百分含量这一参数有可能成为烃源岩的判别及评价的一个新的重要指标。     

四川盆地海、陆相烃源岩有机质稳定碳同位素组成变化及其地球化学意义

采用质谱和色谱-同位素质谱技术,测定了500余个干酪根及饱和烃、芳烃组份、正构烷烃的δ13C值,以此揭示了四川盆地海、陆相烃源岩有机碳同位素组成随地质时代的变化特点及其在高成熟阶段的演化特征,并结合其他相关分析资料,应用碳同位素剖析了不同类型海、陆相烃源岩的有机质生源及沉积环境。研究结果表明,该盆地从震旦系灯影组到中三叠统雷口坡组的海相地层中,干酪根的碳同位素组成随层位变新呈逐渐变重的趋势,可能的原因之一是浮游植物的进化作用;而上三叠统须家河组至中侏罗统千佛崖组的陆相有机质碳同位素组成则有反向的年代变化,主要与生源构成和沉积环境性质有关。这些海、陆相烃源岩的有机源难以用干酪根δ13C值进行区分,而可用饱和烃与芳烃组份的δ13C及其CV值来区别。海洋和湖泊不同沉积相带烃源岩的干酪根具有明显不同的δ13C值,结合其他相关资料可识别其有机质来源。煤系地层中煤与泥岩在干酪根碳同位素组成上没有可区分性,而两者有不同的正构烷烃碳同位素分布曲线。从成熟晚期到高-过成熟阶段,海、陆相干酪根的碳同位素均变重1~2‰,煤系泥岩的正构烷烃碳同位素分布曲线由负向线型分布向平直型演变。这些碳同位素的变化特征为油气源对比和烃源识别提供了依据。     

鄂尔多斯盆地镇原地区中生界延长组、延安组烃源岩地球化学特征对比分析

依据各种钻井样品的实验测试资料,通过Rock-Eval岩石评价、显微镜下观察、有机元素分析、镜质体反射率、生物标志化合物等分析方法,对鄂尔多斯盆地镇原地区中生界三叠系延长组和侏罗系延安组烃源岩地球化学特征进行了综合评价。综合分析表明,研究区延长组和延安组烃源岩有机质丰度较好;液态烃生成能力较强;干酪根类型以腐殖型为主;有机质正处于油气生成成熟阶段。延长组有机质在湖相还原条件下堆积和保存,延安组有机质在浅湖相及沼泽相的弱还原条件下沉积,所以前者烃源岩的有机质丰度、类型以及成熟度都要好于后者。     

Resistant biomacromolecules in marine microalgae of the classes Eustigmatophyceae and Chlorophyceae: Geochemical implications

Non-hydrolysable macromolecular constituents (i.e. algaenans) were isolated from two out of seven marine microalgae investigated. Nannochloropsis salina and Nannochloropsis sp. from the class of Eustigmatophyceae produce highly aliphatic algaenans. Flash pyrolysis and chemical degradations with HI and RuO₄ allowed for the identification of their chemical structure, which is mainly composed of polyether-linked long-chain (up to C₃₆) n-alkyl units. The building blocks of this polymer were also recognized in lipid fractions. The green microalgae (Chlorophyceae) Chlorella spaerckii, Chlorococcum sp. and Nannochloris sp. were earlier thought to biosynthesize algaenans comprising aliphatic and/or aromatic moieties. However, a new isolation method utilizing trifluoroacetic acid (TFA) prior to the other hydrolyses revealed that the macromolecular material isolated from these three chlorophytes was either hydrolysable with TFA or artefacts from the former method. Similar to algaenans from fresh water green microalgae, the aliphatic eustigmatophyte algaenans are likely to be selectively preserved in depositional environments and might ultimately serve as source rock organic matter of marine crude oils. Furthermore, they may play an important role in the cycling of carbon.     

Hydrous pyrolysis of sediments: Composition and proportions of aromatic hydrocarbons in pyrolysates

Hydrous pyrolysis (closed vessel autoclaving in the presence of excess water) of organic-rich rocks is said to generate oils which closely resemble natural crude oils in their broad characteristics and composition. However there are only a few accounts of the proportions and compositions of hydrocarbons in hydrous pyrolysates and none of these discuss the aromatic hydrocarbon composition in detail. The present paper presents some data on the latter.Hydrous pyrolysis (3 days) of a dolomitic siltstone (Permian, Marl Slate) at 280, 300,320, 340 and 360°C produced significant amounts of oils in which the aromatic hydrocarbons were one and a half to two times as abundant as the saturated hydrocarbons.The overall composition of the aromatic hydrocarbons was similar to most crude oils; the major components isolated by our methods from natural oils and from pyrolysates were C_1–4 alkylnaphthalenes. At the lowest pyrolysis temperature (280°C) the distributions of the more minor components of the pyrolysates (e.g. alkylphenanthrenes, aromatic steroids) were also generally similar to those found in natural crudes. However, a number of components (e.g. methylanthracenes, Diels' hydrocarbon) which are not usually reported in crudes, were also detected and the relative proportions of these increased at the higher temperatures. Hydrous pyrolysis (340°C) of an organic-rich oil shale (Jurassic, Kimmeridge) and an asphaltic-material containing no minerals produced pyrolysates in which many of these unusual compounds were also present. In addition the pyrolysate of the oil-shale contained higher proportions of organic sulphur compounds. It appears that the formation of the unusual compounds is not simply a function of the type of organic matter or mineralogy but rather of the high temperatures or fast heating rates employed.     

塔里木轮南地区原油沥青质的分子结构及其初步应用:热解、甲基化-热解和RICO研究

利用瞬间热解、甲基化-热解和钌离子催化氧化(RICO)降解技术研究了塔里木盆地轮南地区原油沥青质的分子结构,并对其在石油地球化学研究中的指示意义进行了讨论.轮南地区原油沥青质分子中的取代官能团以烷基侧链为主,烷基桥次之,另外还有少量的烷基-环己烷、支链烷烃和苯系物,这些化合物可能大都以C-C键结合到缩合芳环体系上;沥青质分子中的芳环体系大多数可能是萘或菲类型的芳香结构,高度缩合的芳香结构可能较少.轮南地区不同构造带原油沥青质热解产物的一致性指示它们可能来自沉积环境相同的母源.沥青质的分子结构表明,其母源可能主要来自浮游藻类的类脂物.热解产物中较高含量的1,2,3,4-四甲基-苯和2,6-二甲基、2,6,10-三甲基烷烃类化合物的检出表明其母质可能形成于较强的还原环境.沥青质热解产物中姥鲛-1-烯的相对含量较低,RICO产物中一元脂肪酸远高于二元脂肪酸,指示该区原油具有较高的成熟度.部分脂肪酸类化合物通过酯键连接在沥青质分子中,可能反映了原油在储层中经历了生物降解等后生作用.     

Kerogen-mineral reactions at raised temperatures in the presence of water

Kerogen has been artificially matured under “hydrous pyrolysis” conditions in the presence of various minerals in order to investigate the influence of the latter on the organic products. In addition to three clay minerals (montmorillonite, illite, kaolinite), calcium carbonate and limonite were also employed as inorganic substrates. Kerogen (Type II) isolated from the Kimmeridge Blackstone band was heated in the presence of water and a 20-fold excess of mineral phase at two different temperatures (280 and 330°C) for 72 hr. Control experiments were also carried out using kerogen and water only and kerogen under anhydrous conditions. This preliminary study describes the bulk composition of the pyrolysates with detailed analyses of the aliphatic hydrocarbon distributions being provided by gas chromatography and combined gas chromatography-mass spectrometry.In the 280°C experiments, considerably more organic-soluble pyrolysate (15% by weight of original kerogen) was produced when calcium carbonate was the inorganic phase. At 330°C, all samples generated much greater amounts of organic-soluble products with calcium carbonate again producing a large yield (40% wt/wt). Biomarker epimerisation reactions have also proceeded further in the 330°C pyrolysate formed in the presence of calcium carbonate than with other inorganic phases. Implications of these and other observations are discussed.     

凯里-麻江地区油苗与固体沥青的油源分析

对黔南坳陷典型古油藏、残余油气藏的精细解剖对南方海相碳酸盐岩层系油气勘探研究具有重要意义。本文运用碳同位素、饱和烃色谱、饱和烃色质及芳烃色质等技术,对黔东南地区二叠系—寒武系油苗与固体沥青进行了地球化学特征研究和油源分析。研究表明,凯里地区虎庄47井原油、洛棉志留系砂岩油苗和麻江地区奥陶系红花园组固体沥青三者同源,主要来自下寒武统牛蹄塘组的优质烃源岩。而麻江地区早二叠世茅口组油苗与虎庄47井原油明显不同,主要源于下二叠统栖霞组的优质烃源岩。     

四川盆地龙潭组高热演化烃源岩有机质生源及沉积环境探讨

四川盆地龙潭组烃源岩R°值主要变化在2.0％～3.0％范围,干酪根H/C原子比值多数集中在0.3～0.5之间,有机质热演化达到过成熟阶段.它们的各类饱和烃生物标志物组成和分布大都发生了异常变化,限制了其地球化学应用.其芳烃组分和干酪根碳同位素及S、N元素组成还包含着标志有机质生源及沉积环境的信息.川东南地区近海湖沼相含...     

东营凹陷民丰地区天然气生成机理与化学动力学研究

民丰地区天然气存在源岩热解和原油裂解成因的争议。本文采用高压釜封闭体系对该区烃源岩和原油样品分别进行了热模拟实验,从烃类气体生成过程、气态烃与部分单体烃生成动力学特征讨论了二者的生气机理,认为原油裂解比源岩热解生气活化能高30～40 kJ/mol,原油比源岩生气需要更高的热力学条件。模拟实验证实,成熟阶段源岩热解气与原油裂解气相比,以环烷烃和芳烃相对含量低为特征,与民丰地区产出的天然气组成更接近,据此认为该区天然气主要为源岩热解成因。     

The Original Organism Assemblages and Kerogen Carbon Isotopic Compositions of the Early Paleozoic Source Rocks in the Tarim Basin, China

Original organisms are the biological precursors of organic matter in source rocks. Original organisms in source rocks are informative for oil-source rock correlation and hydrocarbon potential evaluation, especially for source rocks which have high-over level of thermal maturity. Systematic identification of original organism assemblages of the Lower Paleozoic potential source rocks and detailed carbon isotopic composition of kerogen analyses were conducted for four outcrop sections in the Tarim basin. Results indicated that the original organism assemblages of the lower part of the Lower Cambrian were composed mainly of benthic algae, whereas those of the Upper Cambrian and the Ordovician were characterized by planktonic algae. Kerogen carbon isotopic data demonstrated that the δ13Ckerogen values of source rocks dominated by benthic algae are lower than ?34‰, whereas the δ13Ckerogen values of source rocks dominated by planktonic algae are higher than ?30‰ in general. We tentatively suggested that the carbon species those are utilized by algae and the carbon isotopic fractionation during photosynthesis are the major controls for the δ13Ckerogen values in the Lower Paleozoic source rocks in the Tarim basin. Correlating the δ13C values of oils exploited in the Tarim basin, the original organism assemblages, and δ13Ckerogen values of source rocks, it implied that the Lower Paleozoic oils exploited in the Tarim basin should be sourced from the source rocks with original organism assemblages dominated by planktonic algae, and the hydrocarbon sourced from the Cambrian benthic algae should be of great exploration potential in future. Original organism assemblages in source rocks can provide important clues for oil-source rocks correlation, especially for the source rocks with high thermal maturity.     

Hydrocarbon source rock variability within the Austin Chalk and Eagle Ford Shale (Upper Cretaceous), East Texas, U.S.A.

The Austin Chalk and Eagle Ford Shale are Upper Cretaceous deposits that extend across Texas from the northeast to southwest. These formations contain organic carbon enriched mudstones and chalks that were deposited during transgressions of the Cretaceous epeiric sea in North America. Recent workers in petroleum geochemistry have demonstrated that these organic enriched rocks possessed attributes common to oil source rocks. The present study of these Austin Chalk and Eagle Ford Shale rocks is from the perspective of organic petrology, and it augments the earlier geochemical work that documented source variability within units of these formations. As with the earlier work, the results of this study show that both formations contain intervals that are, when mature, capable of generating commercial quantities of liquid hydrocarbons. However, this work further revealed that Eagle Ford rocks not only exhibit greater or ganic carbon contents, but also have greater quantities of oil-prone kerogen (fluorescent amorphinite and exinite) when compared with rocks from the Austin Chalk. These source rock differences relate to levels or degrees of organic preservation. Dysaerobic to oxic depositional settings seem to be more characteristic of the Austin Chalk than of the Eagle Ford Shale. Such oxic environments do not consistently favor the preservation of organic matter. Usually, well-preserved kerogen forms under more anoxic conditions, such as those that occurred during deposition of some Eagle Ford units. These anoxic conditions suggest that the geographically more extensive Eagle Ford Shale is a more important source for oil than is the Austin Chalk.     

鄂尔多斯北部直罗组中烃类包裹体地球化学特征及来源分析

对鄂尔多斯盆地东胜地区中侏罗统直罗组砂岩中烃类包裹体进行镜下观察、描述，利用压碎抽提法对烃类包裹体进行色谱—质谱分析，并与白垩系油苗、三叠系油砂及源岩抽提物进行对比，目的是探讨其来源。包裹体油生物标志物成熟度参数，C29ααα甾烷20S/(S+R)、C32αβ藿烷22S/(S+R)比值基本达到平衡值，利用甲基菲指数计算的镜质体反射率参数介于0.64%～0.82％之间，显示包裹体中石油烃已接近成熟—成熟热演化阶段；物质来源及沉积环境参数，ααα20R甾烷百分含量C27>C28相似文献   

中国中西部前陆盆地烃源岩特征与油气资源潜力分析

中国中西部前陆盆地(冲断带)以发育陆相烃源岩为特征。中西部周缘和弧后前陆盆地烃源岩形成于前陆盆地沉积期,包括准噶尔西北缘、准噶尔南缘、塔里木盆地西南缘、吐哈盆地二叠系烃源岩和川西、鄂尔多斯盆地西缘三叠系烃源岩;再生前陆盆地(冲断带)烃源岩主要形成于再生前陆盆地沉积之前的三叠—侏罗系和白垩系、古近系。根据沉积环境可以将烃源岩分为被动大陆边缘海相、残留海—(泻)湖相、湖沼相、内陆坳陷淡水湖相以及内陆坳陷断陷半咸水-咸水湖相烃源岩5种类型,其中湖沼相煤系烃源岩有机质类型为III型,以产气为主,其他烃源岩有机质类型主要为II型,其次为I型,以产油为特征。中国中西部前陆盆地石油潜在资源量为89.17×108t,天然气潜在资源量为101 464×108m3,与国外典型前陆盆地相比,中国前陆盆地具有富气特征。