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1.
A high abundance of ethyl substituted aromatic hydrocarbons (HCs) relative to their methyl counterparts is an unusual feature of some crude oils. Enhanced stability of ethyl aromatic HCs in the presence of tetralin was observed when individual ethylated compounds were heated with activated carbon in sealed tubes over a range of 170–340 °C. In addition, conversion of the common distribution of alkyl aromatic HCs to an unusual distribution, containing a higher relative abundance of ethyl compounds, was demonstrated by way of closed system heating of the aromatic fraction of a crude oil in the presence of activated carbon. The conditions for this unusual process require the presence of hydrogen donor components, which selectively limit the reaction and depletion of ethylated compounds relative to methylated compounds. The phenomenon has been shown to occur for substituted benzenes, naphthalenes, phenanthrenes and biphenyls. Enhanced abundance of ethyl aromatic HCs relative to their methylated counterparts is therefore proposed as an indicator for secondary reactions of migrated crude oil that has undergone thermal alteration after contact with carbonaceous surfaces in sediments. Application of these principles to selected crude oils and sediment extracts from the Carnarvon and Cooper/Eromanga Basins (Australia) indicates that significant secondary reaction of migrated crude oil has occurred. 相似文献
2.
Abundant aromatic fractions were detected in oils from the Linnan subsag, including aphthalenes, phenanthrenes, triaromatic steroids, biphenyl, fluorenes, dibenzothiophenes, dibenzofuranes, as well as some typical higher plant-sourced compounds, such as pyrene, benzopyrene, fluoranthene, chryaene, benzofluoranthrene, perylene and cadalene. Occurrences of biomarkers indicate that oils from the Linnan subsag are typical terrestrially genetic oils. Developed in the depositional environment is a strong reduction condition typical of brackish-saline lake. Thermal evolution has entered into the mature-high mature stage. 相似文献
3.
采用人工合成标准物质共注实验、与文献报道的保留指数对比并结合异构体的结构及性质的方法,对石油和沉积有机质中 C3-和 C4-烷基取代二苯并噻吩类含硫多环芳烃化合物进行了系统的鉴定。确定了常规色谱质谱（GC-MS）分析中,烷基取代二苯并噻吩异构体在 HP-5MS （5%-苯基甲基聚硅氧烷）色谱柱上的标准保留指数。确认了前人初步鉴定的部分三甲基二苯并噻吩异构体甲基取代基位置,初步比较了 C3-和 C4-烷基取代二苯并噻吩在不同成因石油和沉积有机质中的分布特征,初步探讨了 C3-和 C4-烷基取代二苯并噻吩潜在的地球化学意义。研究结果为今后进一步探索烷基取代二苯并噻吩系列在石油和沉积有机质中的地球化学意义奠定了可靠的基础。 相似文献
4.
Modification of thermal and oxidative properties of biodiesel produced from vegetable oils 总被引：1，自引：1，他引：0
G. El Diwani Ph.D. S. El Rafie Ph.D. 《International Journal of Environmental Science and Technology》2008,5(3):391-400
Trans esterification of three vegetable oils, sunflower oil, linseed oil and mixed oils as; sunflower-soyabean and olein were carried out using methanol, and potasium hydroxide as catalyst. The methyl esters of the corresponding oils were separated from the crude glycerol and characterized by physical-chemical methods to evaluate their thermal properties. This methods are determination of densities, cloud points, pour points, flash points, kinematic viscosities, hydrogen/carbon ratios, sulfur contents, ash contents and triglycerides. The physico-chemical characteristic of biodiesel treated with ozone showed improvement of pour point and flash point indicating higher degree of safety for fuel. Methyl esters mixed with their corresponding ozonated oil were subjected to comparison and evaluation for their thermal properties by the thermo gravimetric analysis differential thermal analysis from which the calculated heat of enthalpy and comparison with the heat of conventional diesel. The results showed that the oxygen content of biodiesel samples treated with ozone increased weight % and resulted in more extensive chemical reaction, promoted combustion characteristics and less carbon residue was produced. Gas chromatography appeared more suitable to address the problem of determining/verifying biodiesel methyl ester and showed that methyl ester content was impurity free. Ultra violet-detection was used for rapid quantization of triglycerols. From the analyses performed biodiesel treated with ozone modified the thermal and oxidative stability shown by the high combustion efficiency indicated by the high heat of enthalpy and reducing the emission of particulate matter. 相似文献
5.
Thiadiamondoids have been analyzed in a suite of Smackover-derived oils from the US Gulf Coast to determine whether their abundance and distribution reflect alteration by thermochemical sulfate reduction (TSR). The sample suite includes oils and condensates having various thermal maturities that are characterized as being unaltered by TSR, altered by TSR, or of uncertain affinities due to inconsistencies between conventional geochemical indicators of TSR. Nearly all samples contain thiadiamondoids, indicating that small amounts of these compounds can be generated from sulfur rich kerogen. TSR results in the generation of H2S, sulfides and thiophenic aromatic hydrocarbons, either by reaction with sulfate or by back reactions with the evolved H2S. Evidence shows that thiadiamondoids originate exclusively from reactions involving TSR. Once generated, their high thermal stability permits thiadiamondoids to accumulate with little further reaction and their abundance reflects not only the occurrence of TSR, but the extent of the alteration. The abundance of thiaadamantanes (1-cage structures) is particularly diagnostic of the onset of TSR. Examination of condensates from reservoirs >180 °C indicates that the thiadiamondoids can be thermally degraded. They are more thermally stable than the dibenzothiophenes, but are less stable than diamondoid hydrocarbons. Their stability appears to increase with increasing cage number, suggesting that the thiatriamantanes are the best proxy for the extent of TSR alteration in very high temperature reservoirs. Polythiadiamondoids (diamondoids with multiple sulfur substitutions) were detected in trace amounts and are also indicators of TSR. 相似文献
6.
R Alexander R.I Kagi S.J Rowland P.N Sheppard T.V Chirila 《Geochimica et cosmochimica acta》1985,49(2):385-395
The distributions of di- and trimethylnaphthalenes in two sedimentary sequences from Western Australia have been examined by capillary gas chromatography and combined gas chromatography-mass spectrometry. A general decrease was observed in the relative proportions of αα-dimethylnaphthalenes and ααβ-trimethylnaphthalenes with increasing thermal maturity. Similar trends were also observed for six crude oils which have very different ratios of ethylcholestane epimers indicating very different thermal histories. These results suggest that changes in the relative abundances of certain methyl substituted naphthalenes may be useful indicators of thermal maturity of sedimentary organic matter, and the use of a number of isomer ratios is illustrated. 相似文献
7.
鄂尔多斯盆地西峰油田原油芳烃地球化学研究 总被引：3，自引：0，他引：3
通过对鄂尔多斯盆地西峰油田原油进行系统地采样和高分辨率的GC-MS分析,研究了原油的芳烃组成特征,进行了油源对比,探讨了原油成因。结果表明:所分析原油属于同一成因类型;烷基萘和含硫芳烃的分布特征与有机质类型和沉积环境密切相关;西峰油田原油形成于弱还原环境,为菌藻类和高等植物母质来源,特别是高等植物为原油的形成做出了重要贡献,成熟度较高。原油地球化学特征和上三叠统延长组长7油层组烃源岩相似,反映了原油主要来源于长7油层组。这些研究结果为盆地石油的进一步勘探提供了一定科学依据。 相似文献
8.
为揭示不同成因类型原油的三维全扫描荧光特征及其主控因素,对50个不同成因类型的原油的三维荧光特征进行了分析。原油样品代表了未熟—低熟至高成熟度范畴原油、淡水与咸水湖相、沼泽相成因原油、高蜡低硫与低蜡高硫油、常规油与重质油等类型。结果表明,分析原油三维荧光谱图及其定量参数有所差异。原油的荧光强度随芳烃含量增加而增加,沼泽相高蜡油荧光强度总体高于湖相原油;荧光强度随成熟度增加而降低、荧光主峰波长随成熟度增加而变短,反映芳烃总量与相对高分子量芳烃丰度具有降低趋势。稠油的荧光谱图不同于常规油,具有波长分布范围宽、主峰不明显等特征。成熟度、母源岩有机质类型与生源、次生改造等多种因素对原油的三维荧光特征有控制作用。 相似文献
9.
海相碳酸盐岩二苯并噻吩类化合物成熟度参数研究进展与展望 总被引：8，自引：1，他引：7
热成熟度是评价各地质时期沉积盆地烃源岩和油气演化的必要参数。近二十余年国内外研究结果表明,二苯并噻吩系列化合物成熟度参数有望成为高 -过成熟阶段海相碳酸盐岩及其油气有效分子成熟度指标。建立高 -过成熟阶段碳酸盐岩烃源岩二苯并噻吩系列化合物成熟度参数与岩石Ro(通过沥青反射率或海相镜质体反射率换算 )之间的关系式是目前国内外石油地球化学界尚未解决的问题。该关系式的建立对我国下古生界和中上元古界碳酸盐岩来源之油、气成熟度Ro值的确定及油、气 /源岩对比研究将提供比较可靠的新方法。对指导我国海相地层油气勘探具有广阔的应用前景。 相似文献
10.
Light hydrocarbons (LHs) are one of the main petroleum fractions in crude oils, and carry much information regarding the genetic origin and alteration of crude oils. But secondary alterations—especially biodegradation—have a significant effect on the composition of LHs in crude oils. Because most of the LHs affected in oils underwent only slight biodegradation (rank 1 on the biodegradation scale), the variation of LHs can be used to describe more the refined features of biodegradation. Here, 23 crude oils from the Dawanqi Oilfield in the Tarim Basin, NW China, eleven of which have been biodegraded to different extents, were analyzed in order to investigate the effect of slight to minor biodegradation on C6–C7 LHs. The study results showed that biodegradation resulted in the prior depletion of straight-chained alkanes, followed by branched alkanes. In slight and minor biodegraded oils, such biodegradation scale could not sufficiently affect C6–C7 cycloalkanes. For branched C6–C7 alkanes, generally, monomethylalkanes are biodegraded earlier than dimethylalkanes and trimethylalkanes, which indicates that branched alkanes are more resistant to biodegradation, with the increase of substituted methyl groups on parent rings. The degree of alkylation is one of the primary controlling factors on the biodegradation of C6–C7 LHs. There is a particular case: although 2,2,3-trimethylbutane has a relative higher alkylation degree, 2,2-dimethylpentane is more resistant to biodegradation than 2,2,3-trimethylbutane. 2,2-Dimethylpentane is the most resistant to biodegradation in branched C6–C7 alkanes. Furthermore, the 2-methylpentane/3-methylpentane and 2-methylhexane/3-methylhexane ratios decreased steadily with increasing biodegradation, which implies that isomers of bilateral methyl groups are more prone to bacterial attack relative to mid-chain isomers. The position of the alkyls on the carbon skeleton is also one of the critical factors controlling the rate of biodegradation. With increasing biodegradation, Mango’s LH parameters K1 values decrease and K2 values increase, the values of n-heptane and isoheptane decrease, and the indices of methylcyclohexane and cyclohexane increase. LH parameters should be applied cautiously for the biodegraded oils. Because biodegraded samples belong to slight or minor biodegraded oils, the values of n-heptane and isoheptane from Dawanqi Oilfield can better reflect and determine the “Biodegraded” zone. When the heptane value is 0–21 and the isoheptane value is 0–2.6, the crude oil in Dawanqi Oilfield is defined as the “Biodegraded” zone. 相似文献
11.
借助于定量GC—MS分析技术,系统分析了一组取自辽河油田生物降解程度不同的原油芳烃馏分中三芴系列的组成特征。结果表明在生物降解过程中三芴系列化合物很容易遭受生物降解。母体三芴化合物在原油轻微降解阶段抗降解能力相似,其相对组成保持基本稳定,仍可指示沉积环境的性质;但进入中等及以上程度降解作用后,抗生物降解能力出现差异,相对组成发生变异,失去其环境意义。在甲基三芴系列中,甲基硫芴的抗降解能力强于甲基芴和甲基氧芴,降解速率不一致,组成特征不断变化,使甲基三芴系列相对组成不能指示沉积环境的性质。“三芴系列”被细菌消耗的速率不同,整个生物降解过程中其相对组成都在发生变化,因此对生物降解原油而言,无论其降解程度如何,“三芴系列”相对组成特征均不能有效的指示沉积环境的性质。 相似文献
12.
塔北隆起雅克拉油气田原油成因特征 总被引：1，自引：0，他引：1
针对雅克拉油气田多个含油气层位的原油,进行了一系列的地球化学测试分析,对雅克拉油气田原油的地球化学特征、成因特征进行了解剖。研究结果表明,雅克拉油气田深浅不同层位原油轻烃组成与轻烃单体烃碳同位素、类异戊二烯烷烃组成以及原油与馏分碳同位素组成具有明显的海相原油特征;深浅层原油三环萜烷、C28甾烷、三芳甾烷和甲基三芳甾烷以及原油与馏分碳同位素组成皆具有典型上奥陶统来源油的特征,与寒武-下奥陶统来源油特征差异明显,暗示雅克拉油气田原油来源于上奥陶统烃源层。 相似文献
13.
Diamondoids are hydrocarbons with a carbon skeleton that is superimposable on the diamond lattice. Adamantane is the cage-shaped primary unit of diamondoids and occurs widely in sediments and petroleum. The first report of adamantane isolated from petroleum extends back seven decades, but the precursors and reaction mechanisms for the formation of adamantane and related diamondoids in sediments has remained unclear. We report the formation of alkyl adamantanes by heating β-ionone with activated carbon in closed system pyrolysis experiments in the range 170-320 °C. In addition, hydrogen exchange, demethylation, methyl transfer and isomerisation reactions were observed when the model compounds adamantane and 1,3-dimethyladamantane were heated at moderate temperature with activated carbon. A reaction pathway for the formation and reactions of alkyl adamantanes is proposed on the basis of ring isomerisation of adamantane to protoadamantane on the activated carbon surface. The carbonaceous surface reactions described help account for the occurrence and distribution of alkyl adamantanes in petroleum basins, as evidenced by the strong linear relationships between compound pairs related by isomerisation and demethylation for a set of crude oils from the Carnarvon Basin, Western Australia. 相似文献
14.
The reactions of a terminal alkene (1-octadecene) and a polymethyl phenol (2,3,6-trimethylphenol) on activated carbon have been investigated in closed system pyrolysis experiments in the temperature range 170-340 °C. The reaction products of 1-octadecene included methane, isomeric octadecenes, methyl substituted alkanes, alkyl aromatics and an homologous series of n-alkanes with carbon numbers indicative of progressive single carbon depletion of the reactant. The reaction products of 2,3,6-trimethylphenol also contained methane, as well as C1-C4 methyl phenols produced by demethylation and methyl transfer reactions. A carbon surface reaction involving the formation of a reactive single carbon intermediate (i.e. methylene/carbene) is proposed. This reaction accounts for the products observed from the pyrolysis experiments and also is consistent with liquid hydrocarbon distributions found in petroleum basins. Methane was the dominant (ca. 85% of C1-C4) gaseous hydrocarbon product of 2,3,6-trimethylphenol but accounted for only ca. 17% of the C1-C4 hydrocarbons from 1-octadecene. These findings suggest that single carbon surface reactions may play an important role in the geochemical formation of crude oil and natural gas and that the composition of the source material and therefore the type of organic compounds undergoing such reactions, influences the hydrocarbon gas composition in sedimentary basins. 相似文献
15.
辽东凹陷南洼斜坡带旅大29油田在沙河街组二段获得了高产轻质原油和天然气，展现了良好的勘探潜力。为了进一
步明确其原油母质来源、沉积环境和烃源岩层位，对原油、油砂样品和围区烃源岩样品进行了系统的地球化学分析和油源
对比。研究结果表明，原油为低硫（0.0733%）、高蜡（20.77%） 的轻质成熟原油。原油样品饱和烃色谱完整，主峰碳为
C19，显示未遭受明显生物降解作用。油砂样品埋藏较浅，部分遭受生物降解等的影响，饱和烃色谱基线呈现明显的
“UCM”鼓包现象。原油和油砂样品具有低C19 三环萜烷/C23 三环萜烷（0.10~0.18）、低C24 四环萜烷/C26 三环萜烷（0.49~
0.53）、低C27重排甾烷/C27甾烷（0.30~0.43）、中等伽马蜡烷指数（0.14~0.17） 和中等-高4-甲基甾烷参数（0.30~0.36），且
具有相对较重的全油碳同位素值（-27.1‰）。原油母质形成于淡水—微咸水的湖泊沉积环境，母源有机质以藻类等低等水
生生物为主，陆源有机质输入较少。旅大29油田原油主要来源于辽中凹陷和辽东凹陷沙三段烃源岩，同时有少量辽中凹陷
沙四段烃源岩的贡献。研究区高蜡轻质原油的形成主要受控于烃源岩母质来源，藻类等低等水生生物是高蜡轻质原油形成
的重要母质。 相似文献
16.
辽东凹陷南洼斜坡带旅大29油田在沙河街组二段获得了高产轻质原油和天然气,展现了良好的勘探潜力。为了进一
步明确其原油母质来源、沉积环境和烃源岩层位,对原油、油砂样品和围区烃源岩样品进行了系统的地球化学分析和油源
对比。研究结果表明,原油为低硫（0.0733%）、高蜡（20.77%） 的轻质成熟原油。原油样品饱和烃色谱完整,主峰碳为
C19,显示未遭受明显生物降解作用。油砂样品埋藏较浅,部分遭受生物降解等的影响,饱和烃色谱基线呈现明显的
“UCM”鼓包现象。原油和油砂样品具有低C19 三环萜烷/C23 三环萜烷（0.10~0.18）、低C24 四环萜烷/C26 三环萜烷（0.49~
0.53）、低C27重排甾烷/C27甾烷（0.30~0.43）、中等伽马蜡烷指数（0.14~0.17） 和中等-高4-甲基甾烷参数（0.30~0.36）,且
具有相对较重的全油碳同位素值（-27.1‰）。原油母质形成于淡水-微咸水的湖泊沉积环境,母源有机质以藻类等低等水
生生物为主,陆源有机质输入较少。旅大29油田原油主要来源于辽中凹陷和辽东凹陷沙三段烃源岩,同时有少量辽中凹陷
沙四段烃源岩的贡献。研究区高蜡轻质原油的形成主要受控于烃源岩母质来源,藻类等低等水生生物是高蜡轻质原油形成
的重要母质。 相似文献
17.
本文用GC-MS技术分析了美国南佛罗里达盆地Sunnliand原油和油源岩抽提物中的芳烃,以便探讨碳酸盐岩环境中芳烃的分布特征,并用来重建古环境.Sunnliand原油和油源岩中含较半富的萘、菲、二苯并噻吩和三芳甾烷等化合物,甲基二苯并噻吩异构体呈V型分布.芴、氧芴和硫芴三系列化合物的相对含量以及其他地球化学特征如:Pr/Ph<1、正烷烃在C22-C30范围内呈偶碳优势、无或很少有二环倍半萜、含丰富的含硫芳烃等,指示Sunnliand原油和油源岩形成于海相强还原高盐环境.Sunnliand原油和油源岩中检出的一些化合物如:D环芳构化8,14-断藿烷、长链烷基苯、长链烷基苯并噻吩以及很高的延伸藿烷(C31-C35)和C24、C26四环萜烷表明Sunniland有机质有细菌输入.成熟度参数指示Sunniland原油和油源岩属未成熟至低成熟. 相似文献
18.
M. Dorbon J.M. Schmitter P. Garrigues I. Ignatiadis M. Ewald P. Arpino G. Guiochon 《Organic Geochemistry》1984,7(2):111-120
Carbazole, its alkyl derivatives and higher benzologs have been selectively isolated from six different crude oils. In all samples, benzocarbazoles are major constituents of a series which may extend up to dibenzocarbazole derivatives. The distribution includes unsubstituted parent compounds and shows a maximum content of methyl and dimethyl substituted species. Sixteen individual constituents have been identified by means of comparison with reference compounds using gas chromatography, mass spectrometry and high resolution spectrofluorimetry. So far, no generally acceptable explanation has been given for the origin of these compounds, which presumably are the most stable ones in their respective series of aromaticity. Thus, carbazole derivatives may result from a complex sequence of reactions during kerogen formation, not allowing the recognition of precursing molecules. The geochemical significance of this series of nitrogen compounds needs to be clarified, requiring further studies. 相似文献
19.
1IntroductionTheTarimBasin ,NWChina,istheonlybasininChinawherenotonlymarine ,butalsoter restrialindustrialoilandgaspoolsaredeveloped .TheterrestrialoilandgaspoolshavebeenfoundintheKuchedepressioninthenorthernpartofthebasinanditsfrontupliftarea (Fig .1) .ThesourcerocksoftheterrestrialoilandgaspoolsareTriassicandJurassiclacustrinemudstonesandswampcoals.ThebiomarkersfromthesaturatedfractionsofTriassicandJurassicterrestrialsourcerocksandFig .1 .LocationofTriassicandJurassicterrestrialsource… 相似文献
20.
银额盆地查干凹陷原油地化特征及油源对比 总被引：11，自引：1，他引：11
银额盆地东部查干凹陷首次发现轻质低硫成熟原油，其饱和径含量在90％以上，成熟度相当于镜煤反射率Ro1．0％左右，是生油高峰阶段的产物；原油全碳同位素δ^13C值－31．1‰。原油生物标志物中类异戊二烯含量较高，植烷与姥皖烷均势；三环萜烷含量高于五环萜烷；含有较高的TS C29、Ts、C30重排藿烷、伽马蜡烷；藿烷中以C50藿烷为主，C32以上升藿烷含量极低；孕甾烷含量高；甾烷中以C29甾烷为主，C27甾烷含量也较高，异胆甾烷含量高于胆甾烷；重排甾烷含量低；甾烷的含量与萜烷含量相当，是典型的湖相原油。已发现的天然气中甲烷含量达80％，为湿气。原油和源岩生物标志物组成特征分析对比表明下白垩统巴音戈壁组源岩是主要油源岩。生物标志物特征示原油具有一定的运移效应。 相似文献