塔里木塔中隆起古生界原油咔唑类化合物的分布及意义

石油在运移过程中,极性含氮化合物与围岩(如孔隙、裂缝、断层等)表面相互作用。随着运移距离增加,其在原油中的含量不断降低,并发生石油极性含氮化合物的分馏作用。以前的研究表明,石油中咔唑类含氮化合物的分布受母质类型、沉积环境、成熟度的影响很小,而主要受石油运移的影响。本文主要运用咔唑类化合物的分布来研究石油的运移并迫踪烃源岩。文中对来自塔里木盆地塔中地区6口井的7个原油样品的咔唑类化合物的类型、含量及其分布特征作了详细的探讨。得到     

油气运移方向探讨——以南堡凹陷1号构造带为例

提要：利用原油中含氮化合物的组成和绝对浓度的变化并结合烃类生物标志化合物指标的研究,探讨了南堡凹陷1号构造带油气的运移特征。结果表明,原油中含氮化合物的分布和组成特征较好地指示了该区的油气运移效应。随着运移作用的加强,含氮化合物绝对浓度下降,“屏蔽”型与“暴露”型化合物的比值增加,油气沿着1号断层外侧的砂体,向构造的高部位运移。这与烃类生物标志化合物的成熟度参数变化所揭示的油气运移方向相一致,也与该区油气分布和勘探实践吻合较好。但两个参数间又存在区别,用生物标志化合物的组成和分布来指示油气运移分馏作用时,由于分馏作用较弱,各井间的数值变化较小。而含氮化合物的分馏作用较强,各参数随着运移距离的增加发生显著变化,且受成熟度的影响较小,更有利于油气运移方向的判别。     

福山凹陷西部地区原油地化特征与油源对比

福山凹陷是北部湾盆地的重要含油气单元,是一个“小而肥”的富生烃凹陷.充分利用烃源岩和原油的有机地球化学等分析测试数据,针对凹陷内研究较少的西部地区的原油进行地化特征分析,进而研究该区油气藏的油源.研究结果显示凹陷西部原油主要为轻质油,族组分以高饱和烃和芳烃含量、低非烃+沥青质含量为特点.凹陷西部的原油生油母质为陆源高等植物和低等水生生物的混合来源,为陆相湖盆混合型母质特征,不同区块不同层段原油的生油母质具有一定的差别.研究区生油母质沉积环境为偏淡水氧化沉积环境的湖沼相,结合原油成熟度,可将研究区原油划分为3类:(1) 美台-红光流三上段原油,具有“中等成熟度,低奥利烷含量”特征;(2) 永安流一上段原油,具有“高成熟度,高奥利烷含量”特征;(3) 朝阳流一上段原油,具有“低成熟度,中等奥利烷含量”特征.进一步油源对比结果显示,美台-红光地区流三段原油来自流三段和流二下段烃源岩,而永安地区的流一段烃源岩为永安地区的原油提供油源.      

刍云深水凹陷高成熟原油芳烃地球化学特征研究

对白云凹陷采集的27个原油样品的芳烃组成进行了系统的研究。其分布特征和相对含量表明,原油母质具明显的陆源高等植物输入特征,沉积环境以氧化环境为主,根据萘系列、菲系列、二苯并噻吩系列化合物的相对含量分布差异,优选有效的烷基萘、烷基菲、烷基二苯并噻吩成熟度指标,综合分析了白云凹陷原油成熟度特征。原油总体属于成熟一高成熟原油,结合生物标志化合物组成可划分为A、B两类,A类原油的成熟度高于B类原油。还选用有效的成熟度参数探讨了白云凹陷油气运移规律,如三甲基萘比值,该参数指示油气运移方向沿白云主洼中心向周围运移,且邻近番禺低隆起,运移方向由西向东,即沿着成熟度由高到低方向运移。     

渤海湾盆地东濮凹陷西斜坡地区原油中脱羟基维生素E的控制因素研究

为探究盐湖相原油中脱羟基维生素E类化合物(MTTC)的组成分布特征及其控制因素,本文以渤海湾盆地东濮凹陷西斜坡地区古近系沙河街组原油为例,对MTTC的组成分布特征及其绝对浓度与原油成熟度、母质沉积环境等因素之间的关系进行了分析.结果 表明,研究区原油中MTTC绝对浓度与其母质沉积环境密切相关.不同沉积环境样品中的MTTC指纹特征近似,而绝对浓度差异极大,故建议对原油母质沉积环境刻画时最好有MTTC绝对定量数据,而不能仅仅依赖于MTTC指纹特征.此外,MTTC不仅存在于未熟、低熟样品中,在成熟样品中也有检出.当成熟度未达到高、过熟阶段,对于成熟度相似的样品,古盐度是其生成、保存的主控因素.高盐环境更有利于MTTC的生成和保存.     

溱潼凹陷斜坡带原油物性和地化特征及成因

原油的物性和地化特征是油气成藏过程的综合反映,能预测油气运移距离、母源性质、保存条件等成藏要素。将溱潼凹陷的原油划分为超重油、重质油、中质油三类。平面上,相同层系的原油从深凹带向外斜坡带物性逐渐变差、成熟度降低,含硫量增加。纵向上,从深层向浅层原油物性逐渐变差。原油成熟度与形成环境具有良好相关性,低熟原油形成于咸化泥灰岩。外斜坡普遍发育低成熟油,深凹带阜二段烃源岩在三垛初期生成低熟油,三垛末期生成成熟油,低熟油先充注,后期成熟原油驱替低熟油不断运聚到外斜坡成藏。溱潼凹陷斜坡带油源比较充足,原油经过较长距离运移,阜三段剥蚀带也是有利的勘探区。原油物性受油源、油气运移、氧化作用、生物降解等因素影响,油源差异和油气运移对原油物性的环带状分布起主要作用,而保存条件对于局部原油物性变化起重要作用。     

吐哈盆地原油和烃源岩单烃碳同位素组成特征及油源对比探讨

本文测定了吐哈盆地原油和部分烃源岩的单烃碳同位素组成，利用单烃碳同位素组成及其分布模式和样品生物标志物的分布和组合特征研究沉积环境和母质输入特征，进行原油成因类型划分和油源对比探索。吐哈盆地原油可划分为三类:一类是典型沼泽相-湖沼相煤成油，如台北凹陷各油田侏罗系原油；二类是湖相原油，如托参１井三叠系原油；三类是浅湖相原油，如胜金口油田中侏罗统原油。油源对比认为目前吐哈盆地侏罗系产出的原油由中下侏罗统煤系地层有机质生成，而托克逊凹陷三叠系原油由上二叠统湖相泥岩生成。     

鄂尔多斯盆地上三叠统延长组原油地球化学特征及油源分析

分析了鄂尔多斯盆地延长组原油的生物标志化合物组成特征,并对其进行油源对比,探讨了其成因。研究表明,鄂尔多斯盆地上三叠统延长组原油属于同一成因类型;原油有机母质为菌藻类和高等植物的混源型,原油形成于弱还原和淡水或微咸水环境,为成熟原油。油源对比表明,鄂尔多斯盆地上三叠统延长组原油主要来自长7油层组烃源岩。     

原油不同极性含氮化合物的氮同位素组成特征

氮是原油的重要组成元素,主要赋存在非烃和沥青质中,依据其极性差异分为碱性与非碱性2种类型。相较于其他组成元素,原油氮同位素的研究非常有限,不同极性含氮组分的氮同位素特征研究更是缺乏。本次研究应用杜马斯燃烧法原理,利用EA-IRMS连用技术测定了江汉油田6个原油样品不同极性含氮化合物的δ~(15)N和δ~(13)C。结果表明,不同极性含氮化合物的氮同位素组成具有明显的差异,碱性氮的δ~(15)N为9.7‰~11.8‰,明显轻于非碱性氮(11.4‰~14.5‰),原因可能是2种含氮组分的形成机制不同,碱性氮形成于成岩作用早期,δ~(15)值主要受原始母质的影响,而非碱性氮在热演化过程中的富集,氮同位素值更重,利用氮同位素有益于进一步明确原油中含氮化合物的演化机制及其地球化学意义。     

准噶尔盆地西北缘车排子凸起上、下层系原油的地球化学特征差异及其意义

根据原油物性、化学组成、生物标志化合物以及稳定碳同位素等特征,将准噶尔盆地车排子地区各层系的原油划分为2组:一组是储集在侏罗系及以下层系的原油(下层系原油),另一组是储集在白垩系及以上层系的原油(上层系原油)。同一组原油的物理和化学特征相似,而不同组的原油则相差较大。下层系原油为同一来源,来自二叠系烃源岩;上层系原油亦为同一来源,主要来自侏罗系。利用含氮化合物分布特征对该区进行油源划分和对比的结果与用密度、粘度、原油族组成和生物标志化合物等参数所得到的结果完全吻合,可见含氮化合物也可以用于原油类型划分和油源对比方面的研究。最后建立了车排子凸起的油气成藏模式:车排子凸起紧邻凹陷,油源条件充足;构造位置有利,是油气运移的优势指向区;该区发育的众多断层和不整合面,为油气的运移提供了良好的通道。油气沿断裂垂向运移时遇到不整合面则发生侧向运移,从而在空间上构成"Z"字形或呈阶梯状的运移路线,最终形成油藏类型多、含油层系多的成藏面貌。     

低熟油、烃源岩中含氮化合物分布规律及其地球化学意义

对八面河地区原油、油砂以及不同成熟度和岩性有异的烃源岩中吡咯类化俣物的分布特征及其潜在的地球化学意义进行了探讨。结果表明，随着成熟度的增加，八面河地区烃源岩中吡咯类化合物中屏蔽化程度高的异构体比屏蔽化程度低的异构体富集，咔唑及苯并咔唑系列中低相对分子质量的同系物比高相对分子质量的同系物富集，苯并[a]咔唑比苯并[c]咔唑富集。八面河地区原油中吡咯类化合物有较为明显的运移分馏效应，观察到高、低相对分子质量的同系物间的运移分馏效应比不同类型异构体间的分馏效应更为显著，而前者受成熟度的影响可能相对小于后者；发现吡咯类化合物的油气运移分馏效应不仅体现于不同氮官能团屏蔽、半屏蔽和暴露三类异构体间，同样体现于同一类型的同分导师构体之间，指示此类化合物有较强的活性。吡咯类化俣物与烃类化合物一样具有多方面潜在的地球化学意义。     

准噶尔盆地北三台地区湖相原油咔唑类化合物的地球化学特征

准噶尔盆地北三台地区北 82井、北 83井和沙 10 8井湖相原油咔唑类化合物的分布特征表明,油气运移作用是影响该区原油中咔唑类化合物分布的重要因素。沿油气运移方面,咔唑类化合物具有明显的分馏效应。总的趋势是原油中咔唑类化合物、高分子量的烷基咔唑化合物和苯并咔唑化合物的含量逐渐减少,低分子量咔唑和甲基咔唑,以及具屏蔽效应的二甲基咔唑和苯并 [a]咔唑异构体的相对含量则逐渐增加。利用咔唑类化合物的分馏效应,可有效地指示油气运移方向。     

Characteristics of Oil Sources from the Chepaizi Swell,Junggar Basin,China

<正>So far there has been no common opinion on oil source of the Chepaizi swell in the Junggar Basin.Therefore,it is difficult to determine the pathway system and trend of hydrocarbon migration, and this resulted in difficulties in study of oil-gas accumulation patterns.In this paper,study of nitrogen compounds distribution in oils from Chepaizi was carried out in order to classify source rocks of oils stored in different reservoirs in the study area.Then,migration characteristics of oils from the same source were investigated by using nitrogen compounds parameters.The results of nitrogen compounds in a group of oil/oil sand samples from the same source indicate that the oils trapped in the Chepaizi swell experienced an obvious vertical migration.With increasing migration distance,amounts and indices of carbazoles have a regular changing pattern(in a fine linear relationship).By using nitrogen compounds techniques,the analyzed oil/oil sand samples of Chepaizi can be classified into two groups.One is the samples stored in reservoir beds of the Cretaceous and Tertiary,and these oils came from mainly Jurassic source rock with a small amount of Cretaceous rock;the other is those stored in the Jurassic,Permian and Carboniferous beds,and they originated from the Permian source.In addition,a sample of oil from an upper Jurassic reservoir(Well Ka 6), which was generated from Jurassic coal source rock,has a totally different nitrogen compound distribution from those of the above-mentioned two groups of samples,which were generated from mudstone sources.Because of influence from fractionation of oil migration,amounts and ratios of nitrogen compounds with different structures and polarities change regularly with increasing migrating distance,and as a result the samples with the same source follow a good linear relationship in content and ratio,while the oil samples of different sources have obviously different nitrogen compound distribution owing to different organic matter types of their source rocks.These conclusions of oil source study are identical with those obtained by other geochemical bio-markers. Therefore,nitrogen compounds are of great significance in oil type classification and oil/source correlation.     

酒西盆地石油非均质性的控制因素

运用先进的分析测试手段对来自酒西盆地六个油田的 2 0多个油样进行了全油碳同位素、饱和烃气相色谱与质量色谱及正构烷烃分子碳同位素等较为全面的分析与研究。确定源岩相、水洗、生物降解作用与成熟度不是酒西盆地石油非均质性的控制因素。最后选取 1 5个油样进行中性吡咯氮化合物分析,用中性吡咯氮中的咔唑类化合物作为运移参数,较为详细地研究原油的运移分馏作用。此类化合物作为运移参数的基本原理是石油运移过程中,不同结构的咔唑类化合物与水及岩石中矿物发生吸咐作用的强烈程度不同,导致不同的运移分馏作用。根据咔唑类化合物的变化得出控制酒西盆地石油组成非均质性的主要因素是油气运移分馏作用,证实酒西盆地石油运移方向主要是从西至东,青西凹陷是其油源区。     

Study on secondary migration of hydrocarbons in Tazhong area of Tarim Basin in terms of carbazole compounds

Fractionated carbazoles have been detected for the first time in crude oils from the Tazhong area of the Tarim Basin, and these nitrogen compounds were successfully utilized in the study of petroleum migration. Alkylcarbazoles are quite abundant in all the samples analyzed; small amounts of benzocarbazoles were detected only in some of the sample, and dibenzocarbazoles were not found in the oils. Based on the distributions of G1, G2 and G3 types of C₂-alkylcarbazoles, the ratio of C₃-/C₂-carbazoles and the relative concentrations of alkylcarbazole and alkylbenzocarbazole, oils in the Carboniferous C_III reservoir in the Tazhong uplift are thought to have laterally migrated to the high level of Tazhong structure No. 4 from both northwest and southeast. The study here also shows that oils in the area may have undergone long-distance migration. This project is financially supported by the China National Petroleum Corporation and the State Educational Commission.     

高邮凹陷韦庄地区原油吡咯类含氮化合物运移分馏效应

高邮凹陷韦庄地区具有正常和轻微生物降解2类原油, 对油气运移方向一直存在争议.根据2类原油中含氮化合物浓度、屏蔽型含氮化合物的相对含量与反映原油生物降解的地化参数C₂₁-/C₂₂+、Pr/nC₁₇等nC₁₇物降解作用对该区原油中含氮化合物的相对含量及其分布影响不明显, 运移作用仍然是造成含氮化合物分馏的主要因素.自东向西、东北向西南方向, 韦X11井、韦6 - 2井、韦5 - 19井、韦8井原油中屏蔽型咔唑的相对含量依次增大, 分别为11.6 2 %, 10.6 6 %, 12.70 %, 13.88%;暴露型咔唑的相对含量则表现出相反的变化趋势, 分别为30.6 0 %, 2 8.5 6 %, 2 6.4 3%, 2 4.6 2 %.由此明确了本区油气自东、东北方向向西、西南方向注入, 深凹带和车逻鞍槽提供了主要油源.      

塔里木盆地哈得逊及相邻地区原油含氮化合物分布特征及油藏充注方向探讨

塔里木盆地哈得逊及相邻地区存在一些化学组成相似的中一高密度原油。对原油中含氮化合物浓度和相对组成特征进行了较系统的研究，结果表明，原油中含氮化合物分布特征和原油的运移分馏效应存在较好的成因联系。随着运移作用的加强，“屏蔽”型与“暴露”型或“半屏蔽”型化合物的比值增加，含氮化合物浓度下降，且不同化合物之间的比值均表现出较强的协同变化关系。含氮化合物运移参数的分布特征表明，哈得4油田原油总体上具有由北向南的运移和充注过程。这与区域上原油的运移方向是一致的。     

Reservoir geochemistry of the Tazhong Oilfield in the Tarim Basin, China, Part II. Migration, accumulation and mixing of crude oils

Measurements of the absolute and relative concentrations of nitrogen-containing compounds in crude oils from different reservoir strata (Ordovician, Silurian and Carboniferous) in the Tazhong region of the Tarim Basin, Xinjiang, China, showed that even though there are quite a number of factors affecting the distributional and compositional characteristics of neutral nitrogen-containing compounds in crude oils, the distributional and compositional characteristics of crude oils whose source conditions are approximate to one another are influenced mainly by the migration and fractionation effects in the process of formation of oil reservoirs. In addition, crude oils in the Tazhong region show obvious migration-fractionation effects in the vertical direction. Carboniferous crude oils are characterized by high migration parameters and low compound concentrations, just in contrast to Ordovician crude oils. This indicates that crude oils from shallow-level oil reservoirs were derived from those of deep-level oil reservoirs via faults, unconformable contact or carrier beds. Crude oils from the Tazhong region show some migration-fractionation effects in the lateral direction, but mixing of crude oils derived from different hydrocarbon source rocks in the process of formation of oil reservoirs made it more complicated the migration and accumulation of crude oils, as well as the formation of oil reservoirs.     

Release of organic nitrogen compounds from Kerogen via catalytic hydropyrolysis

High hydrogen pressure pyrolysis (hydropyrolysis) was performed on samples of solvent extracted Kimmeridge Clay Formation source rock with a maturity equivalent to ca. 0.35% vitrinite reflectance. We describe the types and distributions of organic nitrogen compounds in the pyrolysis products (hydropyrolysates) using GC-MS. Compounds identified included alkyl-substituted indoles, carbazoles, benzocarbazoles, quinolines and benzoquinolines. The distributions of the isomers of methylcarbazoles, C₂-alkylcarbazoles and benzocarbazoles in the hydropyrolysates were compared to a typical North Sea oil. The hydropyrolysates compared to the North Sea oil, showed increased contributions from alkylcarbazole isomers where the nitrogen group is "exposed" (no alkyl substituents adjacent to the nitrogen functionality) and appreciable levels of benzo[b]carbazole relative to benzo[a]- and benzo[c]carbazoles. Hydropyrolysis is found to be an ideal technique for liberating appreciable quantities of heterocyclic organic nitrogen compounds from geomacromolecules. The products released from the immature Kimmeridge Clay are thought to represent a potential source of nitrogen compounds in the bound phase (kerogen) able to contribute to the free bitumen phase during catagenesis.     

Genesis of Oils in Eastern Kamchatka: Evidence from Hydrocarbon Biomarkers

Gas chromatography and gas chromatography–mass spectrometry data on oils from wells and seeps in the Eastern Kamchatka Basin indicate that, according to their composition and the distributions of biomarker molecules, these oils can be classified into three groups, which differ in the composition of the parent organic matter, litho–facies sedimentation conditions, and catagenetic transformations. Oils from the wells were determined to be produced by organic matter of the sapropel type of marine facies in the main oil window (MC₂). Condensate from the natural seep was generated at higher catagenesis grades (MC_2–3) by organic matter of the sapropel–humus type of littoral facies. Uzon oil shows are demonstrated to be formed in a continental environment by organic matter of the humus–sapropel type and were not genetically related to oil from the Paleogene–Neogene source rocks of the Bogachevka Formation.