辽河油田曙光—欢喜岭潜山带烃源岩生排烃模拟实验研究

对辽河油田曙光－欢喜岭潜山带沙三段和沙四段典型的未成熟源岩样品进行了高温高压干体系的生排烃热压模拟实验。研究结果表明：３００－４００℃为该区域烃源岩的主要生排烃阶段;沙四段具有更好的生排油潜力,可能是曙光－欢喜岭潜山带较好的烃源岩;生排烃作用对排出油和残留油中生物标志物的组成具有明显的影响,在油／源对比时应特别注意。     

辽河油田曙光欢喜岭潜山带 烃源岩生排烃模拟实验研究

对辽河油田曙光欢喜岭潜山带沙三段（Ｅｓ３） 和沙四段（Ｅｓ４） 典型的未成熟源岩样品进行了高温高压干体系的生排烃热压模拟实验。研究结果表明：３００ ～４００ ℃（Ｒｏ ＝０ ．３３ ％ ～１ ．３０ ％ ） 为该区域烃源岩的主要生排烃阶段;沙四段具有更好的生排油潜力,可能是曙光－ 欢喜岭潜山带较好的烃源岩;生排烃作用对排出油和残留油中生物标志物的组成具有明显的影响,在油／ 源对比时应特别注意。     

有关煤成油若干问题的探讨

煤可成为气源岩的观点已广为人们所接受,但就煤能否成为有效的油潭岩一直存在激烈争议。本文介绍了煤成油的研究现状,对有关煤成油的各种观点进行了评述,并结合含煤盆地的发育特点和我国南华北石炭、二叠纪合媒地层的实际资料,对含煤地层中两类不同赋有状态的有机质的生烃能力进行了对比,就目前争论最激烈的煤的排径途径和效率进行了详细讨论,最后阐述了煤成油的地化特征。     

煤与泥岩排烃过程中甾、萜烷色层效应差异

利用未混油或混油源岩样品（指在源岩样品中加入一定量石油）进行低温排烃模拟实验，系统研究了煤与泥岩排烃过程中甾、萜烷的色层效应。结果表明，在排烃过程中煤与泥岩甾、萜烷的色层效应存在显著差别。煤排出烃与残留烃之间的甾、萜烷分布产生了明显的变化，许多常用的甾、萜烷参数的变化已难以解释其排出烃与残留烃之间的关系，但泥岩排出烃与残留烃之间的甾、萜烷分布特征仍具有可比性。煤与泥岩表现出的明显不同的甾、萜烷色层效应提示，应用甾、萜烷等生物标志物解决煤成烃问题时必须充分考虑排烃作用的影响，并需进一步探索适用于煤成烃的方法和指标。     

中国侏罗系煤成油若干问题

在阐述了煤成油的概念，总结和评述了煤生油显微组分，生油门限，生油范围和生油高峰等问题后，本文通过吐哈等盆地侏罗系煤生油显微组分组成特征，可溶有机质演化，成熟度和有机质丰度，油源及原油成熟度对比；含煤岩系中煤层和泥岩的厚度及总量和煤及泥岩最高沥青和总烃转化率的对比； 其族组成和煤成原油的族组成特征的对比，提出了中国侏罗系煤成油盆地中泥岩比煤层对煤成油田形成有大的贡献看法。     

煤成油地球化学研究现状与展望

重点评述与煤成油理论及勘探实践有密切关系、并在近几年取得重要进展的煤成烃演化模式、煤的生油能力及排油研究3方面的问题。指出：石油地质化学家已更深刻地认识到了煤成烃模式、阶段因地而异的复杂性;建立判别煤系源岩生油能力的标准是煤成油研究中最为重要的进展之一,其中以依据总生烃潜量（S1+S2）、氯仿沥青“A”和总烃含量与有机碳的相关关系建立的判别方案比较实用和有效;比较系统地评述了（与工业性煤成油气聚集有重要关系的）煤成烃排出问题的4种主要研究方法。进展、存在的问题和分歧。在此基础上,展望了对指导煤成油勘探有重要意义的煤系源岩的分布预测、倾油性的进一步判识及排出问题定量研究的发展趋势。     

初次运移中的同位素分馏效应

在陆相干酪根生排烃过程中,烃类可能会发生同位素分馏效应。干酪根的热降解过程、烃类的二次裂解以及初次运移过程中的扩散都可能发生同位素分馏。下面的初次运移模拟实验通过在源岩中加入氘代的正构十五烷（n-C15D32）来研究初次运移中的同位素分馏。实验结果表明,烃类在富镜质体煤中初次运移会发生比较强的同位素分馏（在不到10 cm距离里发生了约3‰的同位素分馏）,而在丝炭和暗色泥岩的初次运移中的同位素分馏不明显。富镜质体煤有复杂的孔隙结构和较大的比表面积,Ⅲ型干酪根的热降解的区间比较宽,因此生排烃过程比较复杂,比较容易产生同位素分馏。鉴于煤系排烃的这些特点,在油—源对比中,应该考虑生排烃中可能发生的同位素分馏效应。      

煤和煤系泥岩生油能力再评价

煤和分散有机质（煤系泥岩或页岩）对煤成油田的贡献大小一直没有获得统一认识,这导致煤是否具有生排油能力直到现在仍然争论不休。选择了两个典型侏罗系煤和一个煤系泥岩样品,分别进行了限定体系热解生烃模拟,结果表明热解特征较差的泥岩（H／C 0．77,IH 146mg／g）却比中等富氢煤（H／C 0．82,IH 260mg／g）的生油量高出2．7倍,是一般煤（H／C 0．75,IH 199mg／g）生油潜力的6倍。这暗示着在煤成油评价中,不能简单把煤和煤系分散有机质对等进行评价,不然会低估煤系相对分散有机质的贡献而过高估计了煤的作用。热解模拟结果与吐哈盆地台北凹陷煤系岩石中有机质含量对比结果表明,该凹陷煤成油更可能来自于煤系泥岩而不是煤本身。此外,通过分析发现煤中液态烃稳定性较差,一般在低熟阶段就开始裂解生气,因此,被国内外学者普遍采纳的,IH（或S1）随成熟度变化的趋势不能作为判断煤排油门限的有效参考。     

三塘湖盆地马朗凹陷石炭系火山岩系油气成藏主控因素及模式

三塘湖盆地马朗凹陷石炭系主要发育两套烃源岩,分别为哈尔加乌组上段和哈尔加乌组下段,油气藏形成的源控作用十分明显。通过烃源岩和原油地球化学的分析以及油源对比,发现不同类型原油的形成与分布严格受控于对应源岩的分布范围。分析表明,马朗凹陷石炭系火山岩系油气成藏的主控因素是优质烃源岩、强充注油源断裂和有利火山岩相带的合理配置。根据烃源岩与储层的配置关系,石炭系油气藏的形成可以概括为两种模式:一种为风化壳型成藏模式,油气聚集在石炭系火山岩顶部受风化淋漓作用改造的优质储层中,其中的油气来自下部烃源岩,运移通道为与烃源岩相沟通的油源断裂;另一种模式为内幕型成藏模式,储层为流体溶蚀改造的储层,其中聚集的油气来自邻近火山喷发间歇期沉积的炭质泥岩。     

海拉尔盆地煤及煤系泥岩生排烃定量评价

海拉尔盆地具有多煤阶煤分布。煤系源岩生、排烃数据反映:最好的煤层是南上段,其次是大上段;最有利的煤系泥岩是铜钵庙组与南屯组。各凹陷煤系源岩生气量大小顺序为:呼和湖凹陷>贝尔凹陷>乌尔逊凹陷>呼伦湖凹陷。各凹陷煤系源岩生油量多少顺序为:乌尔逊凹陷>呼和湖凹陷>贝尔凹陷>呼伦湖凹陷。煤系源岩排油量大小顺序为:乌尔逊凹陷、贝尔凹陷、呼和湖凹陷、呼伦湖凹陷。可见,乌尔逊凹陷、贝尔凹陷、呼和湖凹陷具有良好的煤成油气勘探前景,是海拉尔盆地寻找煤成气、煤成油资源不可忽视的有利地区。      

Constraining the hydrocarbon expulsion history of the coals in Qinshui Basin, North China, from the analysis of fluid inclusions

From the comprehensive study on the homogenization temperatures and the occurrence of fluid inclusions in the framework minerals of the strata between or above the Carboniferous–Permian coals in the Qinshui basin, Shanxi, three stages are predicted of hydrocarbon expulsion from the coals. Combined with the known history of basin evolution, it is deduced that the expulsion of hydrocarbons happened during the J₁ (210–180 Ma), the early K₁ (150–130 Ma) and K₂E₁ (110–60 Ma). In the early stage, the coals produced and discharged coal-generated oils. The average GOI value of four sandstone samples is relatively high, as they have been exposed to high paleo-oil saturation in the strata between or above the coals. The biomarker compositions of oil-bearing fluid inclusions are similar to those of extracts from the coals, and so it is concluded that those oils were derived from the same family of the coals.     

Evaluation of the liquid hydrocarbon potential of coal by artificial maturation techniques

In certain areas, relatively large accumulations of liquid hydrocarbons have been attributed to coals. Evaluating the source rock potential of coal requires definition of both the generative potential (quantity and composition of generated hydrocarbons), and expulsion efficiency. Hydrous pyrolysis experiments were completed using Tertiary lignites (R_o < 0.35%) from North Dakota and the Far East to evaluate the source rock potential of coal. The North Dakota lignite is vitrinite-rich (93%) and liptinite-poor (3%); the Far East lignite is liptinite-rich (32% of total maceral content). These lignites have Hydrogen Index values of 123 and 483 mg HC/g OC, respectively. Differences in oil-pyrolysate yield, composition, and temperature of maximum pyrolysate yield from hydrous pyrolysis experiments for these two lignites are related to the type and amount of liptinite and vitrinite macerals. A maximum of 48 and 158 mg oil-pyrolysate/g OC is generated and expelled from the North Dakota and Far East lignites, respectively. Although these lignites consist predominantly of gas-prone vitrinitic components, their organic-rich nature can compensate for their poor convertibility to liquid hydrocarbons. The composition of these artificially generated oil-pyrolysates are similar to some non-marine oils, suggesting that this type of organic matter can be a significant contributor to many oils. Although the overall composition of the generated products from the two lignites is similar, the distribution of these products is significantly different. Homologous series of methyl ketones and alkyl benzenes have been identified in both oil-pyrolysates. Their presence and characteristic distribution suggest that microbial degradation occurred during the formation of these lignites. Although many coals generate significate amounts of liquid hydrocarbons that are similar to naturally occurring oils, poor explusion efficiency limits their source rock potential. Significant amounts of liquid products are assimilated by the vitrinitic matrix of most coals prior to expulsion, severely limiting the amount of petroleum available for migration and reservoir accumulation. However, adequate expulsion may occur in certain liptinite-rich coals or coals occurring in unique depositional settings.     

Generation and expulsion of oils from Permian coals of the Sydney Basin,Australia

Organic geochemical and petrological assessment of coals/coaly shales and fine grained sediments, coupled with organic geochemical analyses of oil samples, all from Permo–Triassic sections of the Southern Sydney Basin (Australia), have enabled identification of the source for the widely distributed oil shows and oil seeps in this region. The Permian coals have higher hydrogen indices, higher liptinite contents, and much higher total organic matter extract yields than the fine grained sediments. A variety of source specific parameters obtained from n-alkanes, regular isoprenoids, terpanes, steranes and diasteranes indicate that the oil shows and seeps were generated and expelled predominantly from higher plant derived organic matter deposited in oxic environments. The source and maturity related biomarkers and aromatic hydrocarbon distributions of the oils are similar to those of the coals. The oil-coal relationship also is demonstrated by similarities in the carbon isotopic composition of the total oils, coal extracts, and their individual n-alkanes. Extracts from the Permo–Triassic fine grained sediments, on the other hand, have organic geochemical signatures indicative of mixed terrestrial and prokaryotic organic matter deposited in suboxic environments, which are significantly different from both the oils and coal extracts. The molecular signatures indicating the presence of prokaryotic organic matter in some of the coal extracts and oils may be due to thin sections of possibly calcareous lithologies interbedded within the coal measures. The genetic relationship between the oils and coals provides new evidence for the generation and expulsion of oils from the Permian coals and raises the possibility for commercial oil accumulations in the Permian and Early Triassic sandstones, potentially in the deeper offshore part of the Sydney Basin.     

Coal as a source rock for oil: a review

The geological debate about whether, and to what extent, humic coals have sourced oil is likely to continue for some time, despite some important advances in our knowledge of the processes involved. It is clear that not only liptinites, but also perhydrous vitrinites have the potential to generate hydrocarbon liquids in the course of natural coalification. Some liptinites, especially alginite, cutinite, and suberinite, contain a higher proportion of aliphatic moieties in their structure than other liptinites such as sporinite and resinite and are, therefore, more oil-prone. It is of potential value to be able to predict the several environments of deposition in which coals with high liptinite contents or containing perhydrous vitrinites may have been formed. Review of the distribution of oil-prone coals in time and space reveals that most are Jurassic–Tertiary with key examples from Australia, New Zealand, and Indonesia. Methods based both on experimental simulations and the examination of naturally matured samples have been used to determine the order of generation of hydrocarbons from different macerals. Results are not entirely consistent among the different approaches, and there is much overlap in the ranges of degradation, but it seems probable that in the natural environment vitrinites begin to generate early, followed by labile liptinites such as suberinite, then cutinite, sporinite, and, finally, alginite.Petroleum potential may be determined by experimental simulation of natural coalification or inferred through various micro-techniques, especially fluorescence and infrared (IR) spectroscopy, or bulk techniques such as elemental analysis and ¹³C NMR spectroscopy. The latter three techniques enable a measure of the polymethylene component of the coal, which now appears to be one of the best available approaches for determining petroleum potential. No method of experimental simulation of petroleum generation from coals is without criticism, and comparative results are highly variable. However, hydrous pyrolysis, confined pyrolysis, and forms of open-system hydrous pyrolysis approach acceptable simulations.Whether, and to what degree generated liquid hydrocarbons are expelled, has long been the central problem in ‘oil from coal’ studies. The structure of vitrinite was believed until recently to contain an interconnected microporous network in which generated oil would be contained until an expulsion threshold was attained. Recent studies show the pores are not interconnected. Combined with a dynamic model of pore generation, it now seems that expulsion of hydrocarbons is best explained by activated diffusion of molecules to maceral boundaries and ultimately by cleats and fractures to coal seam boundaries. The main reason for poor expulsion is the adsorption of oil on the organic macromolecule, which may be overcome (1) if coals are thin and interbedded with clastic sediments, or (2) if the coals are very hydrogen-rich and generate large quantities of oil.The existence of oil in vitrinite is attested to by solvent extractions, fluorescence properties, and by microscopic observations of oil and bitumen. Experimental simulation of expulsion of oil from coals has only recently been attempted. The relative timing of release of generated CO₂ and CH₄ could have considerable importance in promoting the expulsion of liquid hydrocarbons but the mechanism is unclear. As it is universally agreed that dispersed organic matter (DOM) in some shales readily generates and expels petroleum, it is curious that few consistent geochemical differences have been found between coal macerals and DOM in interbedded shales.Unambiguous evidence of expulsion from coals is limited, and in particular only a few commercial oil discoveries can be confidently correlated to coals. These include Upper Cretaceous Fruitland Formation coals in the USA, from which oil is produced; New Zealand Tertiary coals; and Middle Jurassic coals from the Danish North Sea. It is likely that coals have at least contributed to significant oil discoveries in the Gippsland Basin, Australia; in the Turpan Basin, China; and in the Kutei and Ardjuna basins in Indonesia, but this remains unproven. Early reports that early Jurassic coals in mid-Norway were a major source of the reservoired oils have been shown to be inaccurate.None of the proposed ‘rules of thumb’ for generation or expulsion of petroleum from coals seem particularly robust. Decisions on whether a particular coal is likely to have been an active source for oil should consider all available geological and geochemical information. The assumptions made in computational models should be well understood as it is likely with new understandings of processes involved that some of these assumptions will be difficult to sustain.     

Stable carbon isotopic fractionation of individual n-alkanes accompanying primary migration: Evidence from hydrocarbon generation–expulsion simulations of selected terrestrial source rocks

The effect of isotopic fractionation during primary migration of hydrocarbons from coals is rarely noticed because it overlaps with the isotopic effects of maturation. In this research, geological chromatography-like effects and possible physical isotopic fractionation effects on n-alkanes during primary migration from four coals and one mudstone were studied through two types of generation–expulsion simulations (generation–expulsion simulations I and II). In order to monitor the kinetic isotopic fractionation effect during primary migration and to differentiate the isotopic effects of primary migration from the isotopic effects of maturation, generation–expulsion simulation was upgraded in two aspects, source rock was separated into at least five layers, and deuterated n-C₁₅D₃₂ was added to the initial layer of the source rock (simulation II). The experimental results suggested that all terrestrial source rocks exhibit significant geological chromatography-like effects in generation–expulsion simulation. Expulsion efficiencies shown by vitrinite-rich coals are much lower than algal cannel, fusinite-rich coal and mudstone. There also exist significant physical isotopic fractionation effects in hydrocarbon primary migration processes from vitrinite-rich coals, but there is no significant isotopic fractionation effect from fusinite-rich brown coal and mudstone. Pore structure and specific surface area of source rock samples were measured by gas adsorption of both N₂ and CO₂. This indicated that vitrinite-rich coals have a higher proportion of microporosity. The differences in pore structure and adsorptive capacity of source rocks may be responsible for differences in expulsion efficiencies and isotopic fractionation effects in generation–expulsion simulations. The isotopic fractionation effect due to primary migration should be considered in making oil-source correlation when vitrinite-rich coals are concerned.     

生排烃过程中正构烷烃单体碳同位素组成的变化特征及其研究意义

通过对生排烃模拟实验产物 (残留油和排出油 )中正构烷烃单体碳同位素组成的测定,揭示出生排烃过程中正构烷烃碳同位素组成的变化特征。研究表明,生烃初期,液态正构烷烃主要来自干酪根的初次裂解,它们的碳同位素组成不论是在排出油中还是在残留油中,随温度的变化都不明显,呈现较相似的分布特征;在生烃高峰期,早期形成的沥青质和非烃等组分的二次裂解以及高碳数正构烷烃可能存在的裂解,使得正构烷烃单体碳同位素组成明显富集13 C,尤其在高碳数部分呈现出较大的差异。另外,实验结果显示排烃作用对液态正烷烃单体碳同位素组成的影响不太显著。     

中国西北侏罗纪煤系显微组分生烃潜力、产物地球化学特征及其意义

从吐哈盆地侏罗纪煤中分离富集了藻类体、孢子体、角质体、镜质体、基质镜质体和丝质体6种主要显微组分,进行了热解及热模拟实验,并对各显微组分热模拟生成的产物热解油进行了碳同位素组成等分析。各显微组分热解生烃潜力及其热解产物热解油的碳同位素组成表明,煤系有机质中藻类体的生油潜力最高,生成的液态烃类的碳同位素组成最轻;孢子体、角质体等陆源富氢组分生烃潜力低于藻类体,生成的液态烃类的碳同位素组成重于藻类体生成的液态烃类,与煤系含油气盆地中原油的碳同位素组成基本一致。这些富氢显微组分应该是煤系有机质中主要的生油显微组分。镜质体和基质镜质体的生油潜力相对较低,其生成的液态烃类的碳同位素组成比一般煤系原油重得多,而且这些组分本身对液态烃具有较强的吸附力,尽管其在煤系有机质中所占的比例很大,仍然难以成为生成液态石油的主要显微组分,只能在高成熟演化阶段成为良好的生气显微组分。丝质体等惰性组分生烃潜力极低,不可能成为生油组分。此外,结合原煤的显微组分组成、生烃潜力和元素分析,提出仅仅以壳质组的含量高低来评价煤的生烃潜力不完全可靠,热解是经济、快速、有效的评价方法。     

PAH refractory index as a source discriminant of hydrocarbon input from crude oil and coal in Prince William Sound,Alaska

Geochemical correlation and differentiation of hydrocarbons from crude oils and coals is difficult. The complex mixture of the hydrocarbon constituents and the dynamic nature of these constituents in the environment as they weather contribute to this difficulty. A new parameter, the polycyclic aromatic hydrocarbon (PAH) refractory index, is defined here to help in this correlation. The PAH refractory index is a ratio of two of the most refractory constituents of most crude oils, namely triaromatic steranes and monomethylchrysenes. These are among the most persistent compounds in oil after deposition in the environment and thus retain reliably the signature of the original petroleum input. This index is utilized in Prince William Sound (PWS) to differentiate three different oils, as well as to provide evidence that coal, not oil, is the dominant source of the PAHs which are prominent constituents of marine sediments from PWS and the Gulf of Alaska.     

Evaluating the timing of oil expulsion: about the inverse behaviour of light hydrocarbons and oil asphaltene kinetics

This paper deals with natural temperature records in the heavy (asphaltenes) and the light fractions (C₇—light hydrocarbons) of petroleum. Two sets of marine oils formed from different source rocks and petroleum systems were studied using asphaltene kinetics and light hydrocarbon analysis. Both fractions have been reported to contain information about the temperature the respective oils have been exposed to in the subsurface. These indicated temperatures generally correspond to the conditions in the source rock when expulsion occurred. Bulk kinetic analysis of reservoir oil asphaltenes as well as light hydrocarbon (LH) analysis (of dimethylpentanes) were used here in order to evaluate the expulsion temperatures. Surprisingly, when considering information coming from both fractions, an inverse trend between LHs expulsion temperatures (Ctemp) and asphaltenes (Tasph.) can be observed—high T_asph (asphaltene temperatures) occur with low LH C_temp (light hydrocarbon expulsion temperatures) and low T_asph can be observed when Ctemp is high. These differences are of fundamental importance for the use of such geochemical data in calibrating numerical basin models. The reason for this inverse behaviour is possibly due to the different expulsion behaviour of light hydrocarbons and the heavy fraction of oils, especially when the source rocks contain only moderate amounts of organic matter. In addition it has to be considered that the temperature predictions obtained using asphaltene kinetic analysis are related to the onset temperature of petroleum expulsion, while light hydrocarbons provide, at best, average expulsion temperatures.     

Hydrocarbon products of coals as revealed by pyrolysis-gas chromatography

The hydrocarbon products generated and released from coals continue to be debated. The Mesozoic and Cenozoic southern hemisphere coals have been described as being capable of generating significant quantities of heavy hydrocarbons (oil-like material) when compared to the Paleozoic coals of the northern hemisphere because of changes in the coal forming community. This hypothesis was examined by comparing the pyrolysis-gas chromatography results of a collection of coals. Preliminary results indicate that the most significant difference in pyrolytic products is in the less than nC₁₅ fraction. The data further indicate that coals generate similar types of hydrocarbons independent of age or geographic position if they contain similar bulk maceral content. Coals rich in vitrinite generate predominately aromatic hydrocarbons with lesser amounts of n-paraffins. Coals rich in algae and other exinites generate largely paraffinic hydrocarbons. Coals rich in resins generate naphthenic and aromatic hydrocarbons. The petroleum generating potential of coals also depends on the coal's expulsion efficiency, which is not addressed by this study.