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。     

塔里木盆地群4井原油吡咯类含氮化合物地球化学研究

在塔里木盆地群４井原油中成功地分离并检测出丰富的吡咯类含氮化合物-链基咔唑类，而链基苯并咔唑和链基二苯并咔唑则未被发现。链基咔唑中以二甲基咔唑、C₃-咔唑和C₄-咔唑为主。在甲基咔唑和二甲基咔唑中又鉴别出多个异构体。甲基咔唑中G2 G3含量相当，而二甲基咔唑中G3占优势。在我国，原油含氮化合物研究刚刚起步。实践证明，该类化合物是研究油气运移的可靠的、专属性强的标志化合物。通过本项研究，我们认为群４井原油已经历了长距离的运移。     

胡庆油田湖相原油咔唑类化合物的地球化学特征

胡庆油田湖相原油成熟度低，多为低成熟原油，生物降解作用轻微，原油中含有丰富的咔唑类化合物。分析表明，原油成熟度对咔唑类化合物含量及相对组分影响明显，源岩沉积环境对其也有一定的影响，而生物降解作用对咔唑类化合物含量及相对组分影响很小。原油中咔唑类化合物含量、链基咔唑/苯并咔唑及苯并咔唑比值受原油成熟度与沉积环境影响明显，已不适合用来指示油气运移距离，而二甲基咔唑同分异构体比值所受影响小，仍可作为油气运移的有效参数。     

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     

运用原油吡咯类含氮化合物研究塔里木盆地塔中地区石油的二次运移

在塔里木盆地塔中地区的原油中分离和检测到咔唑类含氮化合物,并成功地将其应用于油气运移研究,烷基咔唑类化合物大量存在于所分析的样品中,苯并咔唑只在部分样品检测到且含量小,而二苯并卟唑则未发现,根据Ｃ２烷基咔唑的Ｇ１,Ｇ２和Ｇ３结构类型的分布,Ｃ３－咔唑／Ｃ２－咔唑比值以及烷基咔唑与苯并烷基咔唑的相对含量可知,塔中地区石炭系Ｃ３油组的石油分别从北西和南东两个方向向塔中４号构造的高点侧向运移,研究还表明     

辽河西部凹陷油气运移特征及其影响因素

辽河西部凹陷油气十分富集,油气藏类型复杂,油气相态多样发育,不同构造带油气运移特征存在差异。本文主要根据原油中咔唑类含氮化合物浓度和相关参数,以及储层流体包裹体的发育特征,结合油气相态及物性分布特征,探讨了辽河西部凹陷油气运移特征以及影响因素。研究表明,中央隆起带原油中咔唑类化合物浓度高、异构化参数变化小,油气包裹体主要呈线状分布,在切穿矿物加大边的裂隙中,油气运移通道以走滑形成的东西向雁列式或帚状断裂为主,运移动力主要为流体异常压力;斜坡带原油中咔唑类化合物浓度及其相关异构化参数变化明显,油气包裹体多分布在石英与长石颗粒次生加大边中,呈群体面状分布,显示较强荧光特征,油气主要由洼陷带至斜坡带以扇三角洲前缘分支河道指状砂体或辫状河道砂体为运移通道,以水动力与浮力推动,远源或近源运移成藏;陡坡带原油中咔唑类化合物总浓度以及异构化参数存在变化,以台安大洼断裂带或指状砂体为运移通道、以异常流体压力为动力近源运移成藏;古潜山原油咔唑类化合物总浓度低,参数变化明显,主要以不整合面或基底断裂为运移通道,以异常流体压力为动力近源运移成藏。油气运移聚集时间主要在东营期,自北往南油气成藏时间逐渐变晚,与沙三段、沙四段生烃期较为匹配。     

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.      

准噶尔盆地中部Ⅰ区块现今油气运移方向研究

根据石油成熟度梯度、原油中吡咯类含氮化合物丰度和异构体参数变化特征以及原油中高分子量正构烷烃的分布特征,结合车—莫古隆起的构造演化,探讨了准噶尔盆地中部Ⅰ区块油藏可能的油气运移方向。结果表明,研究区原油间运移分馏效应十分复杂,近期原油主要运移方向是由南向北,即油气是从南部的征1井区向沙1井、庄1井区运移。     

金湖凹陷西斜坡油气运移分子地球化学研究

应用非烃技术、多馏分绝对定量技术,在分析苏北金湖凹陷原油、烃源岩地球化学特征、油源对比的基础上,重点对吡咯类含氮化合物在岩-油、油-油运移中的分馏效应进行了研究,并对骨架相似的另两类杂原子化合物-氧芴 (二苯并呋喃 )、硫芴 (二苯并噻吩 )的运移分馏效应作了初步探讨。结果表明,金湖凹陷西斜坡原油中吡咯类化合物具有较好的运移分馏效应,油气主体运移方向为东北至西南,相邻的三河次凹为其主要的油源区;杂原子化合物-氧芴、硫芴系列运移分馏效应不及吡咯类;绝对定量技术可弥补常规生物标志物在油气二次运移过程中异构体间分馏效应难以观察的不足,可作为继非烃技术后的另一评价油气运移过程的重要工具。     

鄂尔多斯盆地马岭油田延9油层组油气运移研究

我们首次对马岭油田延9油层组原油充注点和运移方向、期次、通道及动力进行了系统地研究。结果表明,马岭油田延9油层组原油中咔唑类化合物的运移分馏效应明显,不同地区原油样品中咔唑类化合物异构体分布特征反映了延9原油具有3个充注点,运移方向为向南东方向和向北西方向运移;纵向上是由下向上,即从延10以下层位向上运移的方向。油藏储层包裹体均一化温度分布呈现出两个主峰温度,说明油气经历了两次运移期和充注期。研究资料显示马岭油田延9油层组原油运移通道在纵向上主要是河道深切谷和延9与延10油层组河道砂体的相互纵向叠置直接接触部位,或者是延10油层组泥岩很薄处形成的油气运移窗口;横向上为联通的多分支河道。油气运移的纵向动力主要为毛细管力和剩余压力。该研究成果对鄂尔多斯盆地侏罗系油气的进一步勘探和开发具有一定的指导意义。     

塔北地区三叠系油藏原油中性含氮化合物和烷基苯酚的运移分馏作用

塔北地区三叠系油藏原油中性含氮化合物和烷基苯酚自南向北存在着运移分馏作用,表现为中性含氮化合物的绝对浓度由高变低,屏蔽型化合物相对富集而部分屏蔽型化合物和裸露型化合物相对贫瘠,1,8 DMCA/1,7 DM CA,1,8 DMCA/2,7 DMCA,1,8 DMCA/部分屏蔽化合物,1,8 DMCA/裸露化合物的比值由小变大,而 [a]/[c]的比值则由大变小,烷基苯酚化合物 2 MPH/3 MPH和 2,6 DMPH/2,3 DMPH的比值亦由小变大。此外同一构造带中原油自西向东,从下而上中性含氮化合物同样存在着运移分馏效应。研究还表明塔北地区三叠系原油横向上自南向北,从吉拉克地区向桑塔木断垒和轮南断垒带方向运移,而侧向上原油从下而上,自西至东进行了运移和调整     

煤和泥岩不同温度条件下非烃中咔唑类化合物的演化特征

在密闭体系中,200～450℃的条件下进行了煤和泥岩加水的模拟实验,分析了实验产物非烃中咔唑类化合物的演化特征,并讨论了不同温度条件下非烃中咔唑类化合物的演化的机理.实验结果表明,非烃中咔唑类化合物是沉积有机质成岩过程的产物,其含量和组成受有机质成熟度影响较大.该研究结果不仅加深了对非烃中咔唑类化合物演化机理的认识,而...     

Applicability of Carbazole Migration Indices in Continental Rift Basins: A Case Study of Western Lujiapu Depression in Kailu Basin, NE China

<正>Kailu Basin in which the Western Lujiapu Depression is located is a typical continental rift basin.Biomarker parameters of the oils indicate that depositional facies and environments vary between the Bao 1 and Bao 14 fault blocks with a higher saline environment in the Bao 1 fault block, but such difference has no significant impact on carbazole abundance and distribution.Maturity and migration distance are the main controls on carbazole abundance and distribution in the Western Lujiapu Depression.The commonly used migration indices,such as ratios of nitrogen shield isomers to nitrogen exposed isomers(1-/4-methylcarbazole ratio,1,8-/2,4-dimethylcarbazole(DMC) ratio and half-shield/exposed-DMC ratio),absolute concentrations of alkylated carbazoles and BC ratio(=benzo [a]carbazole/(benzo[a]carbazole+benzo[c]carbazole)) increase at the low mature range and decrease at a higher mature range with increasing maturity.At relatively low maturity stage(Rc0.77%), maturation has reversal effects with migration on the ratios of nitrogen shield isomers to nitrogen exposed isomers,which may cover migration influence and makes these parameters fail to indicate migration effects.Valid migration indicators at this maturity stage are concentrations of alkylated carbazoles and BC ratios,which can provide ideal tools for migration direction assessment even within short migration distance.Maturity effects should be taken into account when carbazole compounds are applied to indicate migration direction,and at different maturity stages,these commonly used parameters have different validity in tracing migration direction.Coupled with our previous study in the Eastern Lujiapu Depression,a conceptual model of the variation of nitrogen migration indices can be established for terrestrial rifted basins,that is,strong fractionation lateral migration model through sandy beds,weak fractionation vertical migration model along faults,and maturity impacts on migration assessment.     

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.     

Carbazoles and benzocarbazoles confirm migration of leaked petroleum through caprocks and overlaying formations of Valhall Well 2/8-8 in the North Sea

A wildcat may not result in a petroleum prospect; however, it may indicate potential need for frontier exploration, since petroleum could leak into economic accumulations. Carbazoles and benzocarbazoles are nitrogen compounds in petroleum and can be employed to explicitly explain migration direction and distance of leaking petroleum. The hypothesis of this study is that the mechanism of the reaction involving the attraction of carbazoles to clay minerals on the matrix of the walls along their migration pathways determines the isomer that is preferentially attached to the mineral matrix. The objectives of this study are (a) to produce a profile for carbazoles and benzocarbazoles ratios in the cap rock overlying the reservoir, (b) to compare carbazole and benzocarbazole ratios to 20S/(20S + 20R) αααC₂₉ Sterane maturity ratios (c) to infer migration direction from the carbazoles and benzocarbazoles ratio. Samples used were side wall cores and drill cuttings of water-based mud drilling. The EOM (extractable organic matter) from various formations overlying the reservoir was obtained using Soxtherm Automatic Equipment. The TPH (total petroleum hydrocarbon) was obtained from the EOM by using a precleaned isolute C₁₈ 500 mg / 3 mL column, eluted with hexane, while the polars were eluted with dichloromethane. Fractionation into saturates and aromatics was done using a silver nitrate–silica gel column. The profiles of 1,8/1,3 and 1,8/2,4 dimethyl carbazoles and the benzocarbazoles ratios show a vertical gradient of decreasing ratio with increasing vertical distance from the reservoir. This corroborates the %VRo equivalent of 20S/(20S + 20R) αααC₂₉ Sterane and the carbazole ratios infer vertical migration of leaked petroleum.     

Correlation and migration studies of North Central Sumatra oils

The Central Sumatra Basin (CSB) is a prolific petroleum-producing basin and its petroleum systems have been extensively studied. The widely occurring Tertiary lacustrine shale, Brown Shale, has long been recognized as the main source rock for tens of billions of barrels of oil in place. The oils produced from different fields display significant variation in source characteristics that have been attributed to variation in source facies. Despite this generalized recognition of the oil source, the links between major oil accumulations and many possible source kitchens throughout the basin have not been established as detailed oil-source correlation, and oil migration routes are not well defined. For continued exploration in the region, detailed genetic grouping and migration routes of the oils were evaluated through geochemical characterization of numerous oils from various fields in the northern part of Central Sumatra. Biomarker and carbon isotopic data indicate that the oils are quite similar geochemically but form several genetic groups on the basis of subtle but persistent differences in source facies. The groupings appear geographically meaningful and show association of the different oil groups with various troughs. Carbazole distributions show consistency in suggesting differences in relative migration distance among the oils within each genetic group. By combining the oil grouping and carbazole distributions with geological data, models of migration directions and pathways for oils in North Central Sumatra have been constructed.     

Distribution of carbazole derivatives in petroleum

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.