Application of backflush and micro-flow techniques to the analysis of C5-C13 hydrocarbons in crude oils and its geochemical significance

An Agilent 6890N GC equipped with both FID and Agilent 5975 MSD analyzer has been employed to analyze C5-C13 hydrocarbon fractions of crude oils. A technical combination of program temperature volatilizer injection, backflush and micro-flow controller afforded a fine separation of C5-C13 compounds on a PONA column with the heavy part of crude oils being cut off before entering the analytical column. Both GC-FID chromatogram and GC-MS mass chromatograrns (MID and full scan) could be obtained at the same time. The retension time differences of nC6-nC13 alkanes between GC and TIC were in the range of 0.02-0. 58 minutes. Totally 286 peaks have been assigned group compositions. Results on 8 typical oil samples from CNPC Key Laboratory Crude Oil Library showed that the characteristics of C6-C13 hydrocarbon group composition could be used in oil-oil correlation studies.     

利用芳烃参数探讨塔里木盆地库车坳陷原油中高丰度重排藿烷类的成因

通过色谱-质谱技术,系统剖析了塔里木盆地库车坳陷具有不同丰度重排藿烷的原油饱和烃与芳烃分子组成特征,并应用芳烃参数对原油中高-异常高丰度重排藿烷的成因进行了探讨。研究发现,具有高-异常高丰度重排藿烷的原油其二环+三环芳烃占总芳烃相对百分含量很高,平均值大于98%;而低丰度重排藿烷类的原油中其相对百分含量较低,说明陆源高等植物可能为重排藿烷的重要生物来源。原油中重排藿烷类化合物相对丰度与氧芴(OF)含量具有正相关性,揭示两者形成过程可能具有相似的沉积环境。研究区原油甲基菲比值MPR值主要介于1.00~1.18之间,对应的Ro值分布范围为0.88%~0.92%,暗示这些原油中重排藿烷类化合物相对丰度的高低与成熟度关系不大。有鉴于此,塔里木盆地库车坳陷原油中重排藿烷类化合物的相对丰度主要受控于烃源岩沉积环境和生物来源。在弱氧化-弱还原环境中,水体盐度较低,陆源高等植物的贡献越大越有利于重排藿烷类化合物的形成。     

不同沉积环境下原油氮同位素的地球化学特征

氮是原油中的重要组成元素,但是由于原油含氮量较低,碳氮比高,造成氮同位素样品制备困难。为揭示不同沉积环境原油的氮同位素分布特征及其主要影响因素,依据杜马斯燃烧法原理,利用EA-IRMS连用技术测定几个典型沉积盆地原油的氮、碳同位素组成。结果表明:不同沉积环境原油氮同位素组成具有明显的差异,海相沉积环境原油氮同位素明显轻于陆相沉积环境的原油;陆相沉积环境中原油氮同位素组成特征受沉积环境的盐度及氧化还原程度的影响,源于弱氧化-弱还原环境的原油氮同位素组成明显偏重,这是该沉积环境有利于反硝化作用的进行所致;原油的氮同位素组成可以有效用于原油的油源分析和对比,原油的氮同位素组成可能是油气地球化学中一项重要指标。     

中国南方泥盆纪、石炭纪深水沉积环境沉积特征、构造活动及含油气性

中国南方在泥盆、石炭纪时,裂陷运动在被动陆缘和陆内产生许多裂陷槽,形成相对于浅水碳酸盐台地的台间斜坡—海槽深水沉积环境。台间海槽可分为继承性深水台间海槽和泥盆纪时发育起来的台间海槽;台缘斜坡分为跌积边缘型和沉积边缘型。文章描述了上述各深水环境相特征。从区域构造背景和海槽分布方向性、分组性、火山活动、断裂差异升降方面论述了斜坡—海槽的构造活动性。斜坡—海槽的深水沉积环境和岩相,提供了油气生成、储集、运移、圈闭、聚集和保存的有利条件。     

七种成品油中多环芳烃指纹特征与鉴别

采用气相色谱质谱,对市售的93#汽油(C1)、97#汽油(C2)、0#柴油(C3)、-10#柴油(C4)、齿轮油(C5)、润滑油(C6)、燃料油(C7)进行了提取离子色谱分析,通过多环芳烃原始指纹、相对浓度比值分布特征、诊断比值等指标对7种成品油进行了对比分析.结果表明:原始指纹图谱和各类多环芳烃在总多环芳烃中的分布特征均可表明同类成品油具有较高的相似性;通过多环芳烃特征诊断比值比对,现有诊断比值完全可用于鉴别各类成品油.     

苏北盆地泰州组原油有机地球化学特征及成因

苏北盆地泰州组现今仍是一个新的勘探领域,根据苏北盆地海安凹陷泰州组原油的饱和烃和芳烃的馏分组成、分子地球化学参数等油源分析,显示泰州组原油来自泰二段烃源岩,系统阐述了泰州组原油的地球化学特征,并对其沉积环境、成油母质类型、热演化程度及油源进行了讨论。两者具有相似的地球化学特征,甾烷相对丰富,萜烷以藿烷为主,甾烷以规则甾烷占绝对优势。泰州组原油的生油母质主要来源于菌藻类的低等生物,而高等植物则较少;有机质沉积环境整体为咸化、还原环境,但又有所差异,以富安断层为界,断层西北侧盐度高,还原性强,而断层东南侧盐度低,还原性弱;原油成熟度低,处于低熟-未熟阶段。     

四川广元上寺、旺苍罐子坝上二迭—下、中三迭统牙形刺研究

本文对该区上二迭—下、中三迭统碳酸盐岩地层的沉积相和牙形刺进行了研究,重点研究了牙形刺的属种和组合,在野外及室内岩石薄片鉴定的基础上,对各组、段的碳酸盐岩相进行了初步划分,从而阐述了牙形动物受沉积环境和岩性控制的关系。本文还讨论了该区牙形刺颜色变化对油气勘探的意义。     

北部湾盆地涠西南凹陷原油成因类型及分布特征

在大量采集涠西南凹陷烃源岩和原油饱和烃色谱、色谱-质谱、碳同位素等资料基础上，对涠西南凹陷烃源岩特征进行分析，根据地球化学特征差异划分为A、B、C等3类烃源岩。系统分析原油有机地球化学特征差异性，对不同层系原油物性进行统计梳理，依据甾、萜烷、饱和烃组成等进行原油成因类型划分，将涠西南凹陷原油分为A、B1、B2、C1和C2等3大类5亚类。通过油源精细对比和原油空间分布特征分析，A类原油来源于A类源岩，主要分布在1号、2号和3号断裂附近及东南部的斜坡部位；B1和B2类原油来源于B类源岩，其中B1类原油主要分布在2号断裂附近，B2类原油主要在3号断裂附近；C1和C2类原油来源于C类源岩，C1类原油分布在与B1类原油相近的区域，C2类原油主要集中分布在2号断裂与3号断裂接近交互的部位。     

High molecular weight (C35+)n-alkanes of Neogene heavily biodegraded oil in the Qianmiqiao region, North China

With wax content of 1.62%, heavy oil has been produced from the sandstone reservoirs of Neogene Guantao Formation (Ng1Ⅲ). In the GC and GC-MS RIC profiles of its aliphatic fraction, n-alkanes are totally lost, which shows the result of heavy biodegradedation. However, the remaining trace C13-C36 n-alkanes can be still seen from its m/z 85 mass chromatogram. In addition, a complete series of C35-C73 high molecular weight (HMW) n-alkanes was detected by high-temperature gas chromatography (HTGC). The HMW n-alkane series shows a normal distribution pattern, a major peak at nC43, obvious odd-carbon-number predominance, CPI37-55 and OEP45-49 values up to 1.17 and 1.16-1.20 respectively. The present study not only has conformed the strong resistibility of HMW n-alkanes to biodegradation in crude oils as concluded by previous researchers, but also has provided some significant information on source input and maturity for the heavily biodegraded oil in the Qianmiqiao region.     

Geochemical identification of coal-sourced oils and interbedded shale-sourced oils as revealed by compound specific carbon isotopic analysis

To date, questions remain as to how to differentiate between coaland interbedded shale-sourced oils in coal measures. Based on the hypothesis that δ¹³C value of sedimentary organic matter is controlled by the depositional environment and productivities of biota grown in such depositional setting, this note examines compound specific carbon isotopic profiles from coal and interbedded shale extracts using the gas chromatography-isotope ratio mass spectrometry technique (GC/IRMS). The results show that compound specific carbon isotope values from coal extracts are enriched in¹³C relative to that of interbedded shale extracts, and provide useful information in characterizing coal- and interbedded shale-sourced oils in coal measures. An example for its successful application from the Turpan Basin, Northwestern China is presented.     

Isotopic composition characteristics and identification of immature and lowmature oils

Isotopic composition characteristics and the significance of immature and low-mature oils are first systematically discussed. The carbon isotopes of the whole oil can be divided into two groups, one has δ¹³C main peak values ranging from -30‰ to -29 and the other from -27‰ to-25‰, they are related to lacustrine and salt-lake facies or swamp facies, respectively. The carbon isotopic fractionation among different group components is relatively small, usually less than 2‰ and the biggest difference in fractionation often occurs between saturated and aromatic fractions. Their δD values vary between -180‰ and -130‰ The main peak of their δD values concentrates between -170‰ and -150‰, suggesting a domination of lacustrine fades. However, the secondary peak ranges from -160‰ to -150‰, showing a frequent salinization of paleo-water bodies. The average δ¹³C values of the methane vary between -50‰ and -52‰, about 10‰ lighter than those of mature oils. There is a relatively good correlationship between immature and low-mature oils and their source rocks in carbon isotopic compositions of group fractions and monohydrocarbons; moreover, compared with the source rocks of mature oils, that of immature oils is often relatively depleted in¹³C, which is one of the characteristics of immature oils, differing from those of mature oils.     

Constraints on the diversity of crude oil types in the Lunnan Oilfield, Tarim Basin, NW China

Hydrocarbons, include heavy oils, normal oils, waxy oils and light oils, condensate oils and gases were all found in Lunnan Oilfield, the occurrences of hydrocarbons with complicated physical properties indicates a complicated distribution of reservoirs. By the drilling data, the distribution pattern had been found that, in plan view, the density of crude oils in the western part is heavier than that of oils in the eastern part in Lunnan region, namely the crude oils were mainly found in the western part while the natural gases were mainly found in the eastern, which shows that an obvious differentiation in the east and west part was presented in the Lunnan region. Furthermore, in vertical view, the light hydrocarbons were mainly found in the Carboniferous reservoir while the heavier hydrocarbons were mainly found in the Ordovician and Triassic reservoirs. By analysis of the semi-logarithm distribution of n-alkanes, biomarker ratios and stable carbon isotopic compositions of crude oils, we have found that two oil families and discontinuous distribution were presented in hydrocarbons in Lunnan Oilfield. This kind of discontinuous distribution of geochemical parameters was not from continuous fractionation in migration process. The biodegraded heavy oil reservoirs in western part belong to the lower matured oil family, while the light or condensate oils reservoirs belong to higher matured oil family. Thus, a mixed filling of hydrocarbons was occurred in the middle part in Lunnan Oilfield and resulted in the occurrence of waxy oil. The mixed filling model may help to explain the distribution pattern of hydrocarbon reservoirs in Lunnan Oilfield, especially can lead to a relatively consistent explanation for all kinds of geochemical data, such as physical properties, pyrrolic nitrogen compounds, biomarker parameters and stable carbon isotopic compositions.     

安塞地区长10段原油地球化学特征及油源探讨

通过对安塞油田G52井长10段原油样品的地球化学分析,系统地研究了原油的分子标志化合物的分布特征,并且进行了油源对比.研究结果表明,长10段原油饱和烃中以低碳数正构烷烃分布为主,呈单峰态分布,主峰碳为nC21,无明显奇偶优势,规则甾烷中ααα20RC27,C28,C29呈"L"型分布,ββ构型甾烷丰度较高.萜烷系列中三环萜烷的丰度中等,五环三萜类中Ts,C29Ts以及18a(H)-重排藿烷的丰度明显偏高,伽马蜡烷指数较低,而常规的升藿烷系列化合物丰度不高,明显受成熟度的影响.由此表明长10段原油主要来源于淡水或微咸水的弱氧化-还原环境,是以低等水生生物或藻类输入为主的湖相烃源岩,而且已经达到高成熟阶段.G52井长10段与长6—长9段原油和研究区烃源岩生标分布以及相关参数对比表明,长10段原油与长9段烃源岩生物标志化合物特征具有相似性,初步认为长10段原油主要来自长9段烃源岩.     

鄂尔多斯盆地富县地区延长组原油生物标志物特征及油源对比

 系统采集鄂尔多斯盆地南部中生界的烃源岩、富县地区延长组原油及油砂样品,对它们的饱和烃馏分进行GC-MS 分析,通过对生物标志物组成特征的研究探讨富县地区延长组原油的来源。结果表明:根据Pr/Ph,8β(H)-补身烷和C30重排藿烷相对含量,鄂尔多斯盆地南部中生界烃源岩可划分为A₁、A₂、A₃、A₄、B 类,富县地区延长组原油可划分为Ⅰ、Ⅱ、Ⅲ类,目前发现的原油主要是第Ⅰ类;第Ⅰ类原油来自A₁类烃源岩(深湖相沉积相带的长7 油页岩),第Ⅱ类原油来自A₂类烃源岩(深湖-半深湖沉积相带的长7 暗色泥岩),第Ⅲ类原油来自A₃类烃源岩(半深湖沉积相带的长7 暗色泥岩)。     

高邮凹陷原油轻烃地球化学特征及群组划分

 高邮凹陷是苏北盆地油气潜力最大的凹陷,对该凹陷马家嘴、黄珏、富民、永安等9大油田原油样品的C₆~C₇轻烃特征、Mango轻烃参数及轻烃对比、蚀变星图和成熟度参数展开系统对比研究。C₆~C₇轻烃中富含正己烷,苯相对含量低,正庚烷、甲基环己烷和二甲基环戊烷的相对含量相差不大,显示高邮凹陷原油母质类型为腐泥-腐殖型。Mango轻烃参数K₁平均值为0.97,表明高邮凹陷原油具有相似的沉积环境;上含油气系统的K₂较大,平均值为0.31,表明陆源输入较大;中含油气系统的K₂较小,平均值为0.22,表明水源输入较大,下含油气系统介于两者之间,K₂平均值为0.27。由轻烃星图对比、庚烷值和异庚烷指数显示,上含油气系统的成熟度高,保存条件好;中含油气系统原油成熟度低,受次生演化作用明显;下含油气系统原油处于成熟阶段。     

油指纹鉴别中特征比值的t检验比较法

介绍了基于油品特征比值进行油指纹鉴别的t检验比较法,包括方法原理、特征比值的筛选及鉴别原则,并分别以某原油及其风化样品的油指纹鉴别和2种不同原油的油指纹鉴别为例,说明了t检验法在两个油品鉴别中应用的有效性,该方法将传统油指纹鉴别中繁杂的谱图比较或抽象的数值比较转化直观简洁图形判别,减小了目视谱图比较的主观随意性和人为差别,并提出了量化指标,使得鉴别结果更加可靠,利于油指纹鉴别方法的标准化和推广.同时综合文献也给出应用t检验法进行油指纹鉴别的局限性.     

塔北轮南地区油气成因与成藏探讨

通过对塔里木轮南地区不同层位、不同部位原油烃类化学组成的剖析 ,认为该区原油至少可分为两种不同的成因类型 ,可能存在多成藏期次 .三叠系、侏罗系原油化学组成与分布均一 ,其与轮南中西部断垒、桑塔木断垒西部奥陶系原油性质极为接近 ,以低分子量正构烷烃占优势 ,重排补身烷与重排甾烷、三环萜烷及Ts不甚发育 ,C2 3 三环萜烷为主峰 ,相对低值C2 7/C2 9甾烷等为特征 (第I类 ) ,奥陶系原油还具有中性氮化合物含量高的特征 ;以两断垒带东部石炭系、奥陶系为代表的原油以高值饱芳比、正构烷烃主峰碳后移、高含量C15 重排倍半萜与重排甾烷、低含量中性氮化合物、C2 0 三环萜烷为主峰、相对高值C2 7/C2 9甾烷、甾烷 /藿烷、Ts/ (Ts+Tm)、三环萜 /五环萜值等为特征 (第Ⅱ类 ) .轮南地区原油类型不同由主系油源不同所致 .烃类与非烃类运移指标反映奥陶系、石炭系原油具有自西而东的运移趋势 ;三叠系原油具有不太明显的由北而南的运移趋势 .烃类指标反映三叠系、侏罗系与同类型奥陶系原油间的运移分馏效应不太明显 ,其可能来自相同的烃源岩但成烃与成藏期不同     

起泡剂发泡特性及其影响因素研究

通过对泡沫复合体系发泡特性的静态实验研究,评价了泡沫复合体系发泡特性及泡沫稳定性.通过细玻璃管测定法和综合发泡能力的经验公式,讨论了表面活性剂类型和结构、聚合物分子量、碱浓度、地层水矿化度、温度及原油性质对体系发泡性能的影响.通过研究,得到了泡沫复合驱中表面活性剂、碱和聚合物都存在一个合理的浓度临界值,且随着矿化度、温度和原油轻质含量的增加,体系的综合发泡能力降低的结论.同时得到了不同表面活性剂类型中,硫酸盐型表面活性剂发泡效果最好,磺酸盐直链型次之;而同一类型表面活性剂中,随着表面活性剂碳链长度的增加,发泡效果变好,但碳链增加到一定长度后,综合发泡能力下降的认识.     

聚类分析在油源对比研究中的应用

利用烃源岩、原油(包括油砂)的生物标记化合物的聚类分析研究原油(包括油砂)碳同位素,结果表明,三塘湖盆地的原油可以分成3类,第一类原油包括马朗凹陷的绝大部分和侏罗系的一部分,与中二叠统烃源岩有关;第二类原油主要分布于条湖凹陷,部分位于马朗凹陷,与下二叠统和石炭系烃源岩有关;第三类原油主要为油砂,相关性较差,可能受到了较强生物降解作用的影响.塘参1井侏罗系原油可能来源于下二叠统或石炭系.     

东营凹陷细粒沉积岩岩相组合特征

综合应用岩芯、薄片、全岩X射线衍射等资料,根据岩石组分、沉积构造、TOC和碳酸盐晶体结构等指标划分东营凹陷沙四上-沙三下亚段细粒沉积岩岩相,该段主要发育富有机质纹层状隐晶泥质灰岩、富有机质纹层状微晶泥质灰岩、富有机质纹层状灰质泥岩、富有机质层状泥质灰岩、富有机质层状灰质泥岩、富有机质块状灰质泥岩、含有机质层状灰质泥岩和含有机质层状膏质泥岩相等8种岩相。结合地球化学元素资料恢复的古气候、古盐度、古水深及古水体的氧化还原性和古物源等指标恢复细粒沉积岩的沉积环境,进而明确不同沉积环境细粒沉积岩岩相组合特征及成因。在此基础上,建立了东营凹陷沙四上-沙三下亚段细粒沉积岩的沉积模式。该成果对陆相页岩油勘探有重要指导作用。