An invariance in the carbazoles of petroleum

A remarkable invariance in the ratio of 1,3-dimethylcarbazole （DMC） to 1,6-DMC was discovered in crude oils from the Pearl River Mouth Basin, South China Sea. The remarkably invariant ratio is kept at a constant of about unity regardless of their concentrations, sources or maturities for the sampies. In combination with the molecular structures of 1,3- and 1,6-DMCs, the invariance might indicate that the nitrogen compounds share a common precursor with a skeleton of 1-methylcarbazole and are formed through methylation at C3 and C6 with an essentially identical rate.     

Carbazole distributions in rocks from non-marine depositional environments

Pyrrolic nitrogen compounds have been studied from extracts of the rocks collected from the Tertiary saline lacustrine strata in the Qaidam basin and the Middle-Lower Jurassic coal-bearing strata in the Turpan basin, NW China. Biomarker signatures revealed the presence of three sample groups, related to saline lacustrine conditions in the Qaidam Basin, and freshwater lake and swamp depositional settings in the Turpan Basin. Significant differences in carbazole distributions were observed among the sample groups from different depositional environments. Generally, a strong predominance of 1,4- + 1,5-dimethylcarbazoles over 1,3- + 1,6-dimethylcarbazoles was found for the Qaidam rocks from the saline lacustrine settings, with a ratio of 1,3- + 1,6-/1,4- + 1,5-dimethylcarbazole ranging from 0.35 to 0.66, while enhanced amounts of 1,3- + 1,6-dimethylcarbazoles relative to 1,4- + 1,5-dimethylcarbazoles were detected for the Turpan samples from the swamp environments, with the 1,3- + 1,6-/1,4- + 1,5-dimethylcarbazole ratio >0.8. Samples from the freshwater lake environments in the Turpan Basin showed intermediate values for the 1,3- + 1,6-/1,4- + 1,5-dimethylcarbazole ratio. In addition, a predominance of 2,4-dimethylcarbazole over 2,6-dimethylcarbazole was observed for the Qaidam samples, whereas most Turpan samples showed elevated amounts of 2,6-dimethylcarbazole relative to 2,4-dimethylcarbazole. Moreover, 3-methylcarbazole occurred as the least abundant C₁-carbazole isomer for most Qaidam rocks, while the Turpan samples from swamp settings often showed an enhanced abundance of 3-methylcarbazole. The 1,3- + 1,6-/1,4- + 1,5-dimethylcarbazole ratio was observed to have a positive correlation with 3-/4-methylcarbazole, 2,6-/2,4-dimethylcarbazole and Pr/Ph, respectively. These observations may indicate that C₁- and C₂-carbazoles with a methyl group at C-3 (C-6) prevailed for swamp settings, whereas isomers with a methyl at C-4 (C-5) were dominant for the freshwater or saline lacustrine environments. Although variations in benzocarbazoles were detected in the bitumens, an obvious correlation was not observed for the different depositional environments.     

Migration Fractionation of Neutral Nitrogen Compounds of Crude Oils from Tabei Oilfield in the Tarim Basin, China

The absolute amounts and relative distributions of neutral nitrogen compounds in the Tabei oilfield (e. G. Blocks Ln1-Ln1 1) showed remarkable migration fractionation in the vertical direction. From Ordovician reservoirs (O) to oil legs TⅢ and T Ⅰ of Triassic reservoirs in blocks LN1-LN11, the concentrations of [a] [c] decreased from 1. 59μg/g, 0.49μg/g to 0.17 μg/g (oil). The ratios of various alkylcarbazole isomers, such as 1,8-dimethylcarbazole/nitrogenpartially shielded isomers and 1,8-dimethylcarbazole/nitrogen-exposed isomers, were adopted as the indicators of petroleum migration. The ratios increased from 0.13, 0.20 to 0.67 and from going from the south to the north of the Tabei oilfield, the absolute concentrations of neutral nitrogen compounds decreased drastically, and the nitrogen-shielded isomers were enriched relative to nitrogen-exposed isomers and nitrogen-partially shielded isomers. Crude oils in the Tabei oilfield migrated laterally from the Jilake structure to the Sangtamu fault uplift and Lunnan fault uplift, and crude oils in the same fault uplift migrated and remigrated vertically from Ordovician reservoirs, to oil legs TⅢ to TⅠ of Triassic reservoirs.     

Effects of Biodegradation on the Distribution of Alkylcarbazoles in Crude Oils

We have investigated the distributions of alkylcarbazoles in a series of crude oils with different biodegradation extents, in combination with biomarker parameters, stable carbon isotopic ratios and viscosities. The analyses showed that slight biodegradation has little effect on alkylcarbazoles. The concentrations of C₀-, C₁-, and C₂-carbazoles seem to display a slight decrease with biodegradation through the moderately biodegraded stage, and an abrupt decrease to the heavily biodegraded stage. The relative concentrations of C₀-, C₁-, and C₂-carbazoles do not show any apparent change in the non-heavily biodegraded stages, but through non-heavily biodegraded to heavily biodegraded stages, the percentages of C₀- and C₁-carbazoles decrease, and those of C₂-carbazoles increase significantly, which may indicate that C₂-carbazoles are more resistant to biodegradation than lower homologous species. As to C₂-carbazole isomers, the relative concentrations of the pyrrolic N-H-shielded, pyrrolic N−H partially shielded and pyrrolic N-H-exposed isomers do not show any obvious variation in the non-heavily biodegraded oil, but there is an abrupt change through the mid-biodegraded stage to the heavily biodegraded stage. This project was financially supported by the Youth Knowledge-Innovation Foundation of CNPC (No. 00Z1304).     

New maturation parameters based on naphthalene and phenanthrene isomerization and dealkylation processes aimed at improved classification of crude oils (Southeastern Pannonian Basin,Serbia)

Aiming at improved classification of crude oils, naphthalene and phenanthrene isomerization and dealkylation processes were considered in detail as a possible basis to select new maturation parameters. Crude oils originating from the Banat depression (Southeastern Pannonian Basin, Serbia) were used as objects of our study. Four new maturation parameters are proposed in this paper. Two of them are based on dimethylnaphthalene (DMN) and trimethylnaphthalene (TMN) isomerization reactions: DN_x = (1,3-DMN + 1,6-DMN)/(1,4-DMN + 1,5-DMN) and TNy = (1,3,6-TMN + 1,3,7-TMN)/(1,3,5-TMN + 1,4,6-TMN). The other two are based on demethylation of dimethyl-and trimethylphenanthrenes (DMP and TMP) into corresponding methylphenanthrenes (MP): MDR = ΣMP/ΣDMP and MTR = ΣMP/ΣTMP. The new parameters’ advantageous applicability was demonstrated by factor analysis, comparing them with maturation parameters known from literature. The text was submitted by the authors in English.     

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。     

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.     

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.     

Fractionation of azaarenes during oil migration

A comparative study of alkylbenzoquinolines in crude oils and rock extracts (bitumens) from Japan and Sumatra shows that the ratios of nitrogen-masked isomers (NMIs) to nitrogen-exposed isomers (NEIs), and the ratio of higher homologs to lower homologs is higher in crude oils than in corresponding bitumens. Also, a regular increase in the ratios of NMIs to NEIs with increasing migration distance is observed for a series of crude oils from the Sarukawa Oil Field, northeastern Japan. These results are attributed to the preferential migration of NMIs caused by their weak adsorption on clay minerals and/or their low solubility in interstitial water, and the selective removal of lower honologs caused by their irreversible adsorption onto clays during oil migration, which are regarded as geochromatographic phenomena. It is suggested that those ratios can be used to estimate the degree of fractionation of oils during primary and secondary migration.     

Stable carbon isotopic compositions of individual aromatic hydrocarbons as source and age indicators in oils from western Australian basins

The present study aims to establish the factors controlling the stable carbon isotopic compositions (δ¹³C) of individual aromatic hydrocarbons analysed by compound specific isotope analysis (CSIA) in crude oils from western Australian petroleum basins of varying age and facies type. This paper reports δ¹³C values of individual aromatic hydrocarbons, like alkylbenzenes, alkylnaphthalenes, alkylphenanthrenes and methylated biphenyls. The main aims are to confirm the origin (source) and age of these oils based on CSIA of selected aromatic compounds and to understand why the Sofer plot is ineffective in establishing the source of western Australian petroleum systems. The bulk δ¹³C of saturated and aromatic hydrocarbon fractions of crude oils have been previously used to differentiate sources, however, many Australian crude oils are not classified correctly using this method. The oils were classified as marine by the δ¹³C values of individual aromatic compounds and as terrigenous based on the bulk δ¹³C data (Sofer plot).The oils where the δ¹³C values of 1,6-DMN and 1,2,5-TMN isomers are most negative are indicative of a marine source, whereas oils with a less negative values for the 1,6-DMN and 1,2,5-TMN isomers are derived from marine source rocks that contain a significant terrigenous component. Similarly, oils with the least negative δ¹³C values for the 1-MP and 1,9-DMP isomers reflect varying inputs of terrigenous organic matter to the their marine source rocks. Plots of P/DBT and Pr/Ph concentration ratios versus δ¹³C values of DMP, 1,6-DMN, 1,2,5-TMN, 1-MP and 1,9-MP are constructed to establish the relative amount of terrigenous organic matter contributing to the source rock of a series of marine oils. The ratios of P/DBT and Pr/Ph plotted against the δ¹³C values of the aromatic isomers (such as 1,6-DMN, 1,2,5-TMN, 1-MP and 1,9-MP) provide a novel and convenient way to discriminate crude oils derived from different source rocks that contain varying amounts of marine and terrigenous organic matter.     

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。     

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     

银额盆地查干凹陷原油地化特征及油源对比

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。     

塔中83井区表生岩溶缝洞体系中油气的差异运聚作用

叠合盆地海相碳酸盐岩介质油气运聚机理是油气勘探必须解决的关键科学问题之一,选择代表性储层介质进行系统油气运聚作用分析有利于为解决这一关键科学问题提供范例。塔中83井区鹰山组储层是典型的表生岩溶缝洞体系储层,油气主要分布在岩溶体系的水平潜流带中,油水关系复杂,油水界面倾斜。本区原油和天然气性质参数在NE向断层与NW向断层的交汇部位异常高,而随着远离断层交汇部位逐渐降低,并顺构造脊有规律的降低,说明断层交汇部位是本区油气的注入点,而油气运移的主输导通道沿本区的鼻状构造展布。这一认识为系统分析表生岩溶缝洞体系油气运聚机理奠定了地质基础。基于碳酸盐岩表生岩溶的相关研究成果,建立了表生岩溶缝洞体系的基本模型。在分析油气在表生岩溶缝洞体系运聚过程的基础上,认为复杂缝洞体系中油气的差异运聚原理是产生这种现象的关键。油气运移过程受储层含水程度控制,油气总是首先将临近充注点的孔隙或缝洞充满后,才能继续向远处运移,并沿油气运移路径顺次充满远处的孔洞缝体系。所形成的油气水分布规律受储层含水程度,储层中能导致油气侧向运移的侧向联通通道、局部缝洞单元与侧向联通通道的关系及其油气溢出点和晚期气侵强度的联合控制。岩溶缝洞体系中油气运聚过程及其所形成的油气分布规律对叠合盆地下构造层碳酸盐岩油气勘探具有重要的启发,油气勘探不仅要通过地球物理方法识别优质储层发育的部位,还应该尽量描述优质储层的孔洞缝结构,结合油气运移方向和主输导通道的空间展布规律指导油气勘探。     

Evidence of Oil Sources and Migration in Triassic-Jurassic Reservoirs in the South Tianhuan Depression of the Ordos Basin,China Based on Analysis of Biomarkers and Nitrogen-Bearing Compounds

Abstract: The Ordos Basin is an important intracontinental sedimentary basin in western China for its abundant Mesozoic crude oil resources. The southern part of the Tianhuan Depression is located in the southwestern marginal area of this Basin, in which the Jurassic and Triassic Chang-3 are the main oil-bearing strata. Currently, no consensus has been reached regarding oil source and oil migration in the area, and an assessment of oil accumulation patterns is thus challenging. In this paper, the oil source, migration direction, charging site and migration pathways are investigated through analysis of pyrrolic nitrogen compounds and hydrocarbon biomarkers. Oil source correlations show that the oils trapped in the Jurassic and Chang-3 reservoirs were derived from the Triassic Chang-7 source rocks. The Jurassic and Chang-3 crude oils both underwent distinct vertical migration from deep to shallow strata, indicating that the oils generated by Chang-7 source rocks may have migrated upward to the shallower Chang-3 and Jurassic strata under abnormally high pressures, to accumulate along the sand bodies of the ancient rivers and the unconformity surface. The charging direction of the Jurassic and Chang-3 crude oils is primarily derived from Mubo, Chenhao, and Shangliyuan, which are located northeast of the southern Tianhuan Depression, with oils moving toward the west, southwest, and south. The results show that an integration of biomarker and nitrogen-bearing compound analyses can provide useful information about oil source, migration, and accumulation.     

鄂尔多斯盆地古峰庄—王洼子地区长9油层组流体过剩压力与油气运移研究

近几年,在鄂尔多斯盆地上三叠统长9油层组中不断有新的油气发现,因而对长9油层组石油运移的认识对进一步的勘探开发愈发重要。本文通过对古峰庄－王洼子地区延长组长7—长9油层组流体过剩压力的计算,并结合地球化学特征分析,对该地区长9油藏形成时的油气运移的动力特征进行了研究。结果表明,古峰庄—王洼子地区延长组长9油层组石油和长7油层组烃源岩具有相似的地球化学特征,长9原油可能主要来自于其上部长7油层组源岩。长7油层组源岩层具有远远大于长9油层的过剩压力分布,二者之间具有14 MPa以上过剩压力差值,成为长7油气向长9油层组储层运移的主要动力。     

马朗凹陷断裂-烃源岩空间配置关系与石油垂向运移特征

马朗凹陷的原油类型可以划分为3大类,Ⅰ类原油来自二叠系芦草沟组,Ⅱ类原油来自石炭系哈尔加乌组,Ⅲ类原油为Ⅰ与Ⅱ类原油的混源油。通过断裂活动强度、垂向输导断裂与烃源岩的匹配关系的研究,结合原油含氮化合物的分析资料,分析了马朗凹陷油气的垂向运移特征。研究表明,断层的断裂活动强度控制着油气的垂向运移能力,垂向输导断裂与烃源岩相匹配时,烃源岩生成的油气才能向上运移至上覆地层聚集成藏。二叠系芦草沟组烃源岩厚度中心附近的垂向输导断裂断穿侏罗系,所以,芦草沟组烃源岩生成的Ⅰ类原油可以运移至侏罗系聚集成藏,而石炭系哈尔加乌组烃源岩附近的断裂大都未断至二叠系和侏罗系,所以哈尔加乌组烃源岩生成的Ⅱ类原油未能运移到侏罗系聚集成藏,而主要在石炭系成藏。与断裂输导分析相配合,含氮化合物可以很好示踪油气的垂向运移方向,沿断裂从深层到浅层,原油含氮化合物总浓度逐渐降低,1,8DMC/1,3 DMC或1,8DMC/2,4 DMC值增大。     

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。     

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。