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1.
Pyrolysis of asphaltenes from crude oils yields significant amounts of crude oil-like material. Studies of asphaltenes and their pyrolysis products from biodegraded and non-biodegraded oils show that biodegradation does not affect the composition of asphaltene. The overall composition of the oil produced from them on pyrolysis is similar to, yet significantly different from, that of the parent oil. From these compositional differences, it is concluded that asphaltene and its pyrolysis products contain geochemical information which is characteristic, and therefore may shed light on the history of the oil prior to asphaltene formation.  相似文献   

2.
Asphaltenes extracted from crude oils are proposed to possess structural features of the related source rock kerogen. For the present study micro-scale sealed vessel pyrolysis (MSSV) and combustion isotope ratio mass spectrometry (GC–C–IRMS) were used to compare gas generation from a whole rock (type II-S kerogen) from southern Italy with that from related sulfur rich asphaltenes isolated from a low maturity heavy crude oil. The purpose of was to determine whether experimental pyrolysis of oil asphaltenes can be used to predict the timing and the chemical and isotopic composition of hydrocarbon gases generated from genetically related kerogen in the source rock during burial maturation. The results show that parameters such as (gas to oil ratio) GOR and oil and gas formation timing are very similar for these two sample types, whereas gas composition, product aromaticity and sulfur content are remarkably different. Slight differences in GOR are mainly due to differences in gas formation characteristics at very high levels of thermal alteration. Secondary gas formation from the whole rock covers a much broader temperature range under geological conditions than that from the asphaltene products. However, it is remarkable that both the onset and the maximum temperature are nearly identical under geological conditions. The observed differences in gas generation characteristics are supported by discrepancies in the carbon isotopic characteristics of the gas range compounds and indicate different precursors and/or mechanisms for gas generated from whole rock and asphaltenes.  相似文献   

3.
Two investigated long-time stored oils, which were produced in the 1960s, show strong compositional changes compared to fresher oil samples from the same well and production zones. Asphaltenes isolated from stored and fresher-produced oil pairs show highly similar results from open-system pyrolysis. However, asphaltenes from long-time stored oils show higher reactivity compared to those from fresher oils. The study shows that differences exist in kinetic models based on asphaltenes from fresh-produced oil and those based on oil that has undergone long-term storage, and that these differences may impact geological predictions using such models. Factors controlling the chemical differences between stored and fresher asphaltenes are unclear and hard to determine, because of a broad range of factors controlling compositional differences between these oil pairs. The difference in chemical kinetics might be related to chemical storage effects, but different well-site sampling techniques between decades, or even incomplete homogenization of the long-time stored oils in barrels before sampling may also have an impact.  相似文献   

4.
The asphaltenes extracted from eight oils and a bituminous sand were coked and studied by transmission electron microscopy and X-ray diffraction to observe the microtextural and structural changes caused by increasing biodegradation. The pyrolysis effluents of asphaltenes were analyzed by chromatography. Biodegradation causes an increase of aromatic hydrocarbons and sulfur during heat-treatment of isolated asphaltenes. During thermal treatment, the more biodegraded the sample, the earlier and the greater the release of aromatics. The microtexture of the asphaltene coke is very sensitive to this early release of aromatics and is used to classify samples as to their degree of biodegradation. In the series, two groups were distinguished.  相似文献   

5.
Biodegraded oils are widely distributed in the Liaohe basin, China. In order to develop effective oil-source correlation tools specifically for the biodegraded oils, carbon isotopic compositions of individual n-alkanes from crude oils and their asphaltene pyrolysates have been determined using the gas chromatography–isotope ratio mass spectrometry technique. No significant fractionation in the stable carbon isotopic ratios of n-alkanes in the pyrolysates of oil asphaltenes was found for anhydrous pyrolysis carried out at temperatures below 340°C. This suggests that the stable carbon isotopic distribution of n-alkanes (particularly in the C16–C29 range) in the asphaltene pyrolysates can be used as a correlation tool for severely biodegraded oils from the Liaohe Basin. Comparison of the n-alkane isotopic compositions of the oils with those of asphaltene pyrolysates shows that this is a viable method for the differentiation of organic facies variation and post-generation alterations.  相似文献   

6.
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.  相似文献   

7.
More than 100 crude oils and 12 oil sands from Alberta, Canada, from stratigraphie units ranging in age from Upper Cretaceous to Middle Devonian, were processed to separate the asphaltenes which were then analysed for C, H, N, O and S and the ESR spectra run to determine g-value, spin number and line width. A factor analysis of these data, together with selected crude oil and reservoir properties, was interpreted in terms of a number of non-thermal processes which can affect the content and composition of asphaltenes during and after thermal maturation. Experiments on the effect of temperature on the signal intensity of free radicals indicate that more than half, and possibly all, the free radicals observed in asphaltenes must arise from charge transfer or closely related equilibria. An important solvent effect is demonstrated in further experiments, in which the more polar the solvent, the more the solvent dispersive forces overcome the associative forces of the asphaltene layers thus leading to lower molecular weights and a change in the charge transfer forces responsible for the ESR signal. The average molecular weight of asphaltenes from heavy, asphaltic, biodegraded crude oils and oil sands is considerably greater than the average molecular weight of asphaltenes from the more paraffinic, mature, non-biodegraded crude oils, and it seems likely that the differences in molecular weight of these asphaltenes are due to the solvent effect of the crude oils, and thus the laboratory observations have been confirmed in the Alberta basin.  相似文献   

8.
Twelve oil samples have been characterised by titration, FT-IR and chromatographic analysis to determine the differences between the organic acid composition of biodegraded and non-biodegraded oils. The biodegraded oils have higher total acid and total base contents, both by titration and extraction. The molecular weight ranges of the extracted acids are lowest in the biodegraded oils, and the equivalent weight calculations indicate a dominance of multi-functional molecules. Gel permeation chromatography gives a molecular weight range with most of the molecules between 300 and 500 g/mol. FT-IR shows that the extracted acids from biodegraded oils are more carboxylic and aliphatic while the non-degraded oils are more phenolic. Molecular analysis of the derivatised extracts give UCM envelopes for biodegraded oils, and no molecular identification. The results indicate that the acidic constituents in biodegraded oils are a product of the biodegradation, as the composition is very different from the non-biodegraded oils.  相似文献   

9.
Nineteen oil samples from Silesian Unit of the eastern Carpathian Overthrust have been characterised geochemically in order to determine the causes of compositional differences among them and elucidating the processes responsible for their differences. Some of analysed crude oils have undergone post-emplacement alteration in the reservoir such as biodegradation and evaporative fractionation. This explains much of the chemical and physical properties variability across individual fields from one tectonic unit. Geochemical correlation based on biomarker distributions showed a close relationship between all oils (included biodegraded oils). However, data based on the whole oil GC analysis of selected oils suggest that the process of evaporative fractionation may change the composition of lower molecular weight hydrocarbons of the oils in this region. This paper outlines the probable mechanisms for oil mixing in the region and describes how this can lead to observable lateral differences in the composition of oils.  相似文献   

10.
For our ancestors, oil seeps were both a fascination and a resource but as the planet's reserves of high quality low density oil becomes increasingly depleted, so there is now a renewed interest in heavier,biodegraded oils such as those encountered in terrestrial seeps. One such seep is Pitch Lake in the Caribbean island of Trinidad, which is the largest natural deposit of asphalt in the world. At the northern end of the Caribbean, oil emerges along a tectonic contact on the island on Cuba. The sources of the oils from these seeps are relatively recent and both are subject to intense weathering due to the tropical conditions. When analysed by gas chromatography(GC) both oils appear as unresolved complex mixtures(UCM) and show a very high degree of biodegradation thus presenting an analytical challenge. In this case study, these two Caribbean seep oils were analysed by comprehensive two dimensional GC with time of flight mass spectrometry(GC×GC-TOFMS) to expose many thousands of the individual compounds that comprise the UCM. The high chromatographic resolution of the GC×GC-TOFMS produced good quality mass spectra allowing many compounds including molecular fossil ‘biomarkers' to be identified. Compound classes included diamondoid hydrocarbons, demethylated hopanes and secohopanes, mono-and tri-aromatic steroids. D-ring aromatised structures of the 8,14-seco-hopanes,including demethylated forms were present in both oils but further demethylation, probably at position C-25 during biodegradation, was only observed in the Pitch Lake oil. Many polycyclic aromatic hydrocarbons(PAHs) were absent although the fungal-derived pentacyclic PAH perylene was present in both oils. The presence of the angiosperm biomarker lupane in the Pitch Lake oil constrained the age to the Late Cretaceous. The higher degree of biodegradation observed in the Cuban oil was likely due to relatively slow anaerobic processes whereas oil within Pitch Lake was probably subject to additional more rapid aerobic metabolism within the lake.  相似文献   

11.
Pyrolysis kinetics are determined for a series of asphaltene samples associated with different types of kerogens. The activation energy distributions obtained for asphaltenes related to type I kerogens cover a wide range, with significant hydrocarbon generation with activation energies above 350 kJ/mol. The ranges of activation energy distributions are relatively narrow for asphaltenes associated with type II and III kerogens, with little hydrocarbons generated with activation energies above 350 kJ/mol. If the type of associated kerogen can be reasonably constrained, the pyrolysis kinetics of the asphaltenes is potentially a very useful tool for assessing the maturity levels of reservoired oils. The results of pyrolysis kinetics indicate that there is still significant potential for asphaltenes to regenerate hydrocarbons.  相似文献   

12.
The isoprenoid, hopanoid and steroid compositions of 15 oils from the most productive oil fields in Cuba were studied to determine source-rock depositional environments and organic matter sources. The oils, which are from the northern geological province of Cuba and can be defined by the position with respect to the overthrust belt, can be grouped into two families: those from the Remedios (1) and those from the Placetas (2) tectonostratigraphic units.Remedios oils contain 17α(H)-diahopane, high relative amounts of 18α(H)-22,29,30-trisnorneohopane and diasteranes, which is indicative of generation from clay-rich source rocks. The crude oils of the Placetas Unit exhibit a sterane/hopane composition consistent with a carbonate origin. Nevertheless, these polycyclic hydrocarbons exhibit significant changes in composition, indicating that several organic matter sources, e.g. a carbonate/evaporitic origin of Varadero and Varadero Sur oils, have contributed to the oils from this Unit. The Remedios oils are more mature [evaluated from the and sterane indices] than the Placetas oils.A wide range of biodegradation levels are encountered in these oils (from 0 to 7–8 using the scale derived by Volkman et al. (1983). The high relative abundance of 25-norhopanes is a distinctive feature of Remedios oils. The presence of these compounds in lightly biodegraded or nondegraded oils corresponds to a mixing of paleobiodegraded oil with more recently sourced nondegraded oil in the reservoir. The most biodegraded oil, Cantel, exhibits and sterane ratios, and hopane ratios that have been altered by microbial attack.  相似文献   

13.
Hydrous pyrolysis (HP) experiments were used to investigate the petroleum composition and quality of petroleum generated from a Brazilian lacustrine source rock containing Type I kerogen with increasing thermal maturity. The tested sample was of Aptian age from the Araripe Basin (NE-Brazil). The temperatures (280–360 °C) and times (12–132 h) employed in the experiments simulated petroleum generation and expulsion (i.e., oil window) prior to secondary gas generation from the cracking of oil. Results show that similar to other oil prone source rocks, kerogen initially decomposes in part to a polar rich bitumen, which decomposes in part to hydrocarbon rich oil. These two overall reactions overlap with one another and have been recognized in oil shale retorting and natural petroleum generation. During bitumen decomposition to oil, some of the bitumen is converted to pyrobitumen, which results in an increase in the apparent kerogen (i.e., insoluble carbon) content with increasing maturation.The petroleum composition and its quality (i.e., API gravity, gas/oil ratio, C15+ fractions, alkane distribution, and sulfur content) are affected by thermal maturation within the oil window. API gravity, C15+ fractions and gas/oil ratios generated by HP are similar to those of natural petroleum considered to be sourced from similar Brazilian lacustrine source rocks with Type I kerogen of Lower Cretaceous age. API gravity of the HP expelled oils shows a complex relationship with increasing thermal maturation that is most influenced by the expulsion of asphaltenes. C15+ fractions (i.e., saturates, aromatics, resins and asphaltenes) show that expelled oils and bitumen are compositionally separate organic phases with no overlap in composition. Gas/oil ratios (GOR) initially decrease from 508–131 m3/m3 during bitumen generation and remain essentially constant (81–84 m3/m3) to the end of oil generation. This constancy in GOR is different from the continuous increase through the oil window observed in anhydrous pyrolysis experiments. Alkane distributions of the HP expelled oils are similar to those of natural crude oils considered to be sourced from similar Brazilian lacustrine source rocks with Type I kerogen of Lower Cretaceous age. Isoprenoid and n-alkane ratios (i.e., pristane/n-C17 and phytane/n-C18) decrease with increasing thermal maturity as observed in natural crude oils. Pristane/phytane ratios remain constant with increasing thermal maturity through the oil window, with ratios being slightly higher in the expelled oils relative to those in the bitumen. Generated hydrocarbon gases are similar to natural gases associated with crude oils considered to be sourced from similar Brazilian lacustrine source rocks with Type I kerogen of Lower Cretaceous, with the exception of elevated ethane contents. The general overall agreement in composition of natural and hydrous pyrolysis petroleum of lacustrine source rocks observed in this study supports the utility of HP to better characterize petroleum systems and the effects of maturation and expulsion on petroleum composition and quality.  相似文献   

14.
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。  相似文献   

15.
生物降解原油地球化学研究新进展   总被引：18，自引：0，他引：18  
生物降解作用是原油的一种重要的蚀变作用,对原油的物性和经济价值有着负面的影响。全球石油大多遭受过生物降解。生物降解作用对常见生物标志物的影响得以较好的描述,综述了近年来高分子量正构烷烃、三环萜烷、25 降藿烷生物降解的新进展。目前对生物降解作用的细节、发生机理尚不十分清楚,讨论了原油喜氧和厌氧降解机制,认为厌氧作用可能起主导作用,降解速率很慢。温度是控制生物降解作用的重要因素,储层温度大于80℃不会发生生物降解作用。生物降解原油多为混源油,介绍了研究生物降解原油的多期成藏方法。沥青质不易生物降解,其热解产物及钌离子催化氧化产物在生物降解原油对比、油源对比中具有重要的作用;最后指出了今后的发展方向。  相似文献   

16.
Analyses of some Australian crude oils show that many contain varying concentrations of A/ B-ring demethylated hopanes. These range from C26 to C34 and have been identified from their retention times and mass spectral data as 17α(H)-25-norhopanes. Comparison of hopane and demethylated hopane concentrations and distributions in source-related, biodegraded oils suggests that demethylated hopanes are biotransformation products of the hopanes. Further, it appears that the process occurs at a late stage of biodegradation, after partial degradation of steranes has occurred. Demethylated hopanes are proposed as biomarkers for this stage of severe biodegradation. The presence of these compounds in apparently undegraded crude oils is thought to be due to the presence of biodegraded crude oil residues which have been dissolved by the undegraded crude oil during accumulation in the reservoir sands. The timing of hopane demethylation, relative to the degradation of other compounds, has been assessed and the progressive changes in crude oil composition with increasing extent of biodegradation have been identified. The use of demethylated hopanes as maturity parameters for severely biodegraded crude oils, and the applicability of established biomarker maturity parameters to such oils, are also discussed.  相似文献   

17.
柯坪隆起区是塔里木盆地海相烃源岩露头发育较好的地区之一,但相关的油气研究报道不多。本文详细研究了塔里木盆地柯坪隆起区油苗的有机地球化学特征并进行了相关的成因分析。阿克苏油苗经历了严重的生物降解作用,饱和烃生物标志物所能提供的成因信息十分有限。原油沥青质组分及储层吸附/包裹烃受后生作用影响较小,综合分析油苗沥青质热解产物与吸附/包裹烃的生物标志物及其碳同位素组成可以获得更多有效的成因信息。研究结果表明,阿克苏油苗与其储层吸附/包裹烃具有不同来源。油苗、沥青质以及沥青质热解产物的碳同位素特征与已经报道的多数海相原油及其沥青质较为接近,与典型的寒武系烃源来源的原油差异显著。而储层吸附/包裹烃与已报道的典型寒武系烃源岩来源油的生物标志物及碳同位素特征比较类似,可能形成于较高的热演化阶段。  相似文献   

18.
Petroleum potential of Baikal deposits   总被引：1，自引：0，他引：1  
We analyzed oils, gases, and bitumens of bottom sediments from natural shows on the southeastern shore of Lake Baikal, in the mouth of the Stvolovaya River near Capes Tolstyi and Gorevoi Utes. Based on a set of geological data, we have established that: (1) the lake oils underwent biodegradation to a variable degree: “Fresh” nondegraded paraffin oil floats up near Cape Gorevoi Utes; in the mouth of the Stvolovaya River and near Cape Tolstyi, aromatic-naphthene oil lacks n-alkanes, monomethyl alkanes, and acyclic isoprenoids; (2) Cenozoic oil originated from the organic matter of fresh-water basins with significant amounts of higher land plant remains, including angiosperm plants (oleanane), which suggests the lake or delta genesis of oil source formations of Cretaceous and younger ages. Judging from the carbon isotope composition (average δ13C = −43.84‰), methane from the bottom sediments near Cape Gorevoi Utes is catagenetic. The initial in-place resources in the Baikal sedimentary basins are estimated by the volumetric-statistical method at 500 mln tons of equivalent hydrocarbons.  相似文献   

19.
In this study,12 crude oil samples were collected and analyzed from the Ordovician reservoir in the Halahatang Depression,Tarim Basin,China.Although the density of oil samples varies considerably,based on saturated hydrocarbon gas chromatographic(GC),saturated and aromatic hydrocarbon gas chromatographic-mass spectrometric(GC/MS) and stable carbon isotopic composition analyses,all the samples are interpreted to represent a single oil population with similar characteristics in a source bed or a source kitchen,organic facies and even in oil charge history.The co-existence of a full suite of n-alkanes and acyclic isoprenoids with UCM and 25-norhopanes in the crude oil samples indicates mixing of biodegraded oil with fresher non-biodegraded oil in the Ordovician reservoir.Moreover,according to the conversion diagram of double filling ratios for subsurface mixed crude oils,biodegraded/non-biodegraded oil ratios were determined as in the range from 58/42 to 4/96.Based on oil density and oil mix ratio,the oils can be divided into two groups:Group 1,with specific density>0.88(g/cm3) and oil mix ratio>1,occurring in the north of the Upper Ordovician Lianglitage and Sangtamu Formation pinchout lines,and Group 2,with specific density<0.88(g/cm3) and oil mix ratio<1,occurring in the south of the pinchout lines.Obviously,Group 2 oils with low densities and being dominated by non-biodegraded oils are better than Group 1 oils with respect to quality.It is suggested that more attention should be paid to the area in the south of the Upper Ordovician Lianglitage and Sangtamu Formation pinchout lines for further exploration.  相似文献   

20.
Twenty crude oils from Paleozoic reservoirs in the Big Horn Basin. Wyoming were fractionated into light hydrocarbons, saturates, monoaromatics. diaromatics, polyaromatics-and-polars. and asphaltenes. Amounts and isotopic composition of each fraction were found to be internally consistent with the degree of maturation of the oil. confirming the established single source origin for these oils. A variation of approximately three per mil in the carbon isotopic composition of the whole oil and individual fraction was explained as being caused by maturation. The isotope-type-curves for these oils, the variations in isotopic composition as a function of compound group-type, were not found to be as simple as commonly believed. Other alteration processes, such as migration and deasphalting, might have influenced the pattern of the isotope distributions among fractions. The conservative nature of mass balance and subsequent isotope flows among various fractions of crude oil showed that the maturation of crude oil consists of consecutive processes leading from larger and more polar components into smaller and less polar components culminating in natural gas. Calculations were made to project the amount of condensates associated with the crude oils, and the amount of natural gas which had been generated from crude oils of a given maturity.  相似文献   

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