青海柴达木盆地南八仙油气田油源与成藏机理

柴达木盆地南八仙油气田不同油气藏间原油性质特征变化明显,油层在纵向井段上分布范围逾3000余m。通过地球化学实验并结合构造等地质条件分析,认为该区各种深、浅层油气藏中的原油具有煤成烃的基本地球化学特征,并且为同一来源,油源为临近地区较深部位中侏罗统煤系地层;该区深、浅层原油物性间的差异也反映在地球化学指标上,其成因或成藏机理是：深部早期油藏在断裂等地质作用下发生了明显的蒸发分馏作用,其分馏出的产物在浅部再次聚集成藏。     

轮南低凸起气洗作用响应及定量评价

自喜山期, 过量干气自东向西对轮南低凸起原始油藏的大规模侵入、冲刷, 诱发本区持续性气洗分馏作用的发生.在各组分气液溶解平衡的格架下, 气洗作用将导致残余油中正构烷烃的大量损失以及次生凝析气藏的形成.地球化学研究表明, 残余油与凝析油中轻烃组分(C₆-C₈) 的变化趋势具有典型的气洗分馏特征.同时, 基于气洗作用模型, 通过对各层系原油正构烷烃相对蒸发量(Q) 的计算, 定量描述了轮南地区气洗作用的强度.计算结果显示, 奥陶系的油气藏曾遭受强烈的气洗作用, 原油中正构烷烃的相对蒸发量由东向西表现出依次递减的特征.其中, 轮古东地区Q值高达97%;位于轮南低凸起中部的轮古2井以及轮古18井地区, 正构烷烃相对蒸发量较小(Q=20%~76%); 而在更加靠近西部的轮古17及轮古100井, 其原油中正构烷烃分布正常(Q=0), 并未发生气洗分馏作用.另一方面, 石炭系以及三叠系的油气藏均表现出未遭受气洗作用的特征, 证实了喜山期大量干气的优势运移通道被限制于海西早期运动所形成的奥陶系岩溶缝洞体系中的事实.因此, 奥陶系, 尤其是位于临近气源区的轮古东地区, 是轮南地区气藏的有利靶区.      

Phase—Controlled and Gas—Washing Fractionations During the Formation of Petroleum Reservoirs

By PVT fractionation experiments to model phase-controlled and gaw-washing fractionations during the formation of petroleum reservoirs,the authors measured the physical and chemical properties of products formed in different fractionation staes and made a correlative analysis of the influence of depressurization and gas washing on oil/gas molecular composition and the rule of fractionation.The analytical results showed that gas washing is an important factor affecting the physical properties of crude oils.and also can be regarded as a good genetic interpretation of marine wax-high oils in the Tarim region,Xinjiang,China.Phase-controlled and gaw-washing fractionations can lead to the formation of condensates and their differences in chemical composition from crude oils are a direct reflection of evaporating fractionation.Phasecontrolled and gaw-washing fractionations have a great influence on the composition of molecular compounds and relevant parameters.So phase-controlled and gas-washing fractionations during the formation of petroleum reservoirs are not only favorable to identifying different processes of formation of petroleum reservoirs,but also to the scientific application of routine geochemical parameters.     

PVT分馏实验中链状烷烃分子的行为

通过PVT分馏实验模拟油藏形成过程中的温压和气洗分馏作用,测量不同实验不同分馏阶段产物的烷烃分子组成,其结果表明:①大量的非热成因凝析油应主要与气洗作用有关;②降压和气洗分馏作用的相似性主要表现为原生油中Pr/Ph、(Pr+Ph)/(nC₁₉+nC₂₀)和nC₁₀/(nC16+nC₂₅)等比值的降低;③降压和气洗分馏作用差异性表现为凝析油链烷烃参数上相反的变化规律;④温压和气洗作用可以引起某些成因或类型参数(如Pr/Ph)的明显变化。这一认识将有助于油气成藏过程的确定和常规地化指标的科学应用。     

Re-Examination of the Oil and Gas Origins in the Kekeya Gas Condensate Field, Northwest China–A Case Study of Hydrocarbon-Source Correlation Using Sophisticated Geochemical Methods

This work discussed the origins, alteration and accumulation processes of the oil and gas in the Kekeya gas condensate field based on molecular compositions, stable carbon isotopes, light hydrocarbons, diamondoid hydrocarbons and biomarker fingerprints. A comparison study is also made between the geochemical characteristics of the Kekeya hydrocarbons and typical marine and terrigenous hydrocarbons of the Tarim Basin. Natural gas from the Kekeya gas condensate field is derived from Middle–Lower Jurassic coal measures while the condensates are derived from Carboniferous–Permian marine source rocks with a higher maturity. In the study area, both natural gas and condensates have experienced severe water washing. A large amount of methane was dissolved into the water, resulting in a decrease in the dryness coefficient. Water washing also makes the carbon isotopic compositions of the natural gas more negative and partially reverse. Considering that the gas maturities are higher than once expected, gas generation intensity in the study area should be much stronger and the gas related to the Jurassic coal measures could promise a greater prospecting potential. As a result of evaporative fractionation, the Kekeya condensates are enriched in saturates and lack aromatics. Evaporative fractionation disguises the original terrigenous characteristics of the light hydrocarbons associated with the natural gas, making it appear marinesourced. Thus, alteration processes should be fully taken into consideration when gas–source correlations are carried out based on light hydrocarbons. With the condensates discovered in the study area all being "migration phase", the pre-salt Cretaceous and Jurassic reservoirs may promise great exploration potential for the "residual phase" hydrocarbons. This research not only is of significance for oil and gas exploration in the southwest Tarim Basin, but also sheds light on the oil/gas-source correlations in general.     

Fractionated aromatic petroleums and the generation of gas-condensates

Based on experimental and observational evidence, a mode of origin involving evaporative fractionation is proposed for a class of petroleums enriched in light aromatic and naphthenic hydrocarbons (benzene, toluene, meta-xylene, para-xylene, methylcyclopentane, cyclohexane, and methylcyclohexane). Progressive gas loss from gas-saturated oil is suggested as the causal mechanism, with simultaneous loss of light ends in gaseous solution, and accompanying fractionation. These processes were simulated experimentally.Residual oils exhibit the following changes in their remaining light hydrocarbons, <C₉: (1) increase in aromaticity (in aromatic hydrocarbons relative to normal alkanes of molecular weight); (2) increase in “normality” (in unbranched alkanes and naphthenes relative to branched isomers), and (3) decrease in paraffinicity (in paraffins relative to naphthenes). Retrogressive changes in maturity indicators take place leading to spurious evidence of immaturity in residual oils and the derived evaporative condensates.The phenomena occur in many basins, and are a key to understanding major aspects of petroleum variability. On the basis of aromaticity and paraffinicity relationships, evaporative gas-condensates are distinguishable from those generated by thermal cracking. Unfractionated thermal gas-condensates are rare. Evaporative condensates are the daughter products of oils which have suffered evaporative fractionation.     

高蜡凝析油或轻质油的分布特征与成因机理

介绍了中国部分含油气盆地中的高蜡凝析油或轻质油的地球化学特征及其在地域上和层位上的分布规律,并以大港千米桥古潜山高蜡凝析油气藏、吐哈盆地西部凹陷部分高蜡凝析油田或轻质油田、塔里木盆地柯克亚凝析油气田、盐城凹陷的高蜡凝析油藏为例,总结了几种高蜡凝析油或轻质油的成因模式,即煤系腐殖型烃源岩热演化生烃、运移分馏作用、混合作用或"气洗作用"等.     

渤海湾盆地渤中19-6气田凝析油特征及油气关系

2018年中国东部最大整装凝析气田——渤中19-6气田的发现,一举打开了渤海湾盆地深层天然气勘探的新领域,展现了油型盆地天然气勘探的巨大潜力。渤中凹陷发育多套不同成熟度的烃源岩,位于渤中凹陷西南部的渤中19-6气田凝析油与天然气并存,近年来于该地区的天然气成因及形成条件多有研究,但是对于凝析油的形成则少有研究。本文以渤中19-6气田为例,探讨多套烃源岩发育的复杂油气区凝析油的成因及与天然气的关系。渤中19-6气田6个凝析油样品化学组成及其变化特征精细分析对比表明:该区凝析油以低碳数正构烷烃为主,含有较丰富的环己烷、甲基环己烷等环烷烃和苯、甲苯等低碳数芳烃,金刚烷类化合物较发育,高碳数生物标志化合物含量较低,综合判断凝析油属于混合偏腐殖型高熟原油。结合该区凝析油与天然气对比结果认为,该区凝析油和天然气属于同一套烃源岩在同一阶段所生成的烃类化合物,两者相伴而生,均属于烃源岩原生产物。     

Carbon isotope geochemistry of Paleozoic oils from Big Horn Basin

Twenty crude oils from Paleozoic reservoirs in the Big Horn Basin. Wyoming were fractionated into light hydrocarbons, saturates, monoaromatics. diaromatics, polyaromatics-and-polars. and asphaltenes. Amounts and isotopic composition of each fraction were found to be internally consistent with the degree of maturation of the oil. confirming the established single source origin for these oils. A variation of approximately three per mil in the carbon isotopic composition of the whole oil and individual fraction was explained as being caused by maturation. The isotope-type-curves for these oils, the variations in isotopic composition as a function of compound group-type, were not found to be as simple as commonly believed. Other alteration processes, such as migration and deasphalting, might have influenced the pattern of the isotope distributions among fractions. The conservative nature of mass balance and subsequent isotope flows among various fractions of crude oil showed that the maturation of crude oil consists of consecutive processes leading from larger and more polar components into smaller and less polar components culminating in natural gas. Calculations were made to project the amount of condensates associated with the crude oils, and the amount of natural gas which had been generated from crude oils of a given maturity.     

柴达木盆地西部第三系咸水湖相原油地球化学特征

在系统分析柴达木盆地西部各油田40余个原油样品碳同位素和饱和烃、芳烃组成的基础上,全面剖析了该地区第三系湖相原油的地球化学特征.研究结果表明,这些原油具有特殊的碳同位素组成和异常的生物标志物分布.其全油碳同位素偏重(-26‰～-24‰);正构烷烃系列单体烃碳同位素分布曲线呈水平状,表现出类同于海相有机质的碳同位素组成特征.它们的生物标志物中正烷烃系列兼具奇碳和偶碳优势双重碳数分布模式;呈强植烷优势,Pr/Ph值大多<0.6;伽玛蜡烷普遍异常丰富,C35藿烷含量高,表征高盐、厌氧的咸水湖相沉积环境性质.芳烃组份以萘、菲系列为主,而二苯并噻吩等含硫有机化合物相对含量较低,反映该地区咸水湖相原油源岩沉积相的特殊性.柴西各油田原油地球化学参数在区域上呈规律性变化趋势,与其源岩沉积相的时空变迁相一致.     

Biodegradation and migrational fractionation of oils from the Eastern Carpathians, Poland

Nineteen oil samples from Silesian Unit of the eastern Carpathian Overthrust have been characterised geochemically in order to determine the causes of compositional differences among them and elucidating the processes responsible for their differences. Some of analysed crude oils have undergone post-emplacement alteration in the reservoir such as biodegradation and evaporative fractionation. This explains much of the chemical and physical properties variability across individual fields from one tectonic unit. Geochemical correlation based on biomarker distributions showed a close relationship between all oils (included biodegraded oils). However, data based on the whole oil GC analysis of selected oils suggest that the process of evaporative fractionation may change the composition of lower molecular weight hydrocarbons of the oils in this region. This paper outlines the probable mechanisms for oil mixing in the region and describes how this can lead to observable lateral differences in the composition of oils.     

川东北飞仙关组鲕滩气藏天然气运聚效率

设计进行了封闭体系下原油裂解成气的模拟实验, 建立并标定了原油裂解成气及其碳同位素分馏的化学动力学模型, 以罗家寨气田罗家7井为例分别进行了地质应用.生烃动力学研究发现, 飞仙关组古油藏具备“高效气源灶”的特点, 原油在中晚侏罗世172~151Ma约20Ma时期内裂解殆尽, 且原油裂解气的生成与其运聚成藏作用具有良好的时空匹配关系, 由此可促成飞仙关组气藏天然气的高效运聚.碳同位素分馏动力学研究证实甲烷成藏参与率达87%.利用生烃动力学与碳同位素分馏动力学结合的方法对天然气的运聚效率进行探讨是一个新的有效途径.      

Environmental geochemistry of calcium isotopes： Applications of a new stable isotope approach

1IntroductionIn nature, calcium has six naturally occurring sta-ble isotopes with atomic mass units (amu) and the a-bundances of40Ca (96.941%),42Ca (0.647%),43Ca (0.135%),44Ca (2.086%),46Ca (0.004%)and48Ca (0.187%) are presented in this paper.These analyt…     

东海油气表层地球化学勘查指标的讨论

海洋表层沉积物中气相、液相、固相物质成分和物理化学参数能反映深部油气藏的分布,可作为油气化探指标。文中讨论了东海表层沉积物间隙水液态烃、成岩作用环境指标Fe³⁺/Fe²⁺ 、热释碳酸盐(△C)、沉积岩细粒级样品分离。选择了东海油气表层化探主要指标和参考指标。△C的矿物成分主要是铁锰的碳酸盐系列,东海沉积物△C矿物成分以菱铁矿为主。△C成因上的多解性决定了△C作为油气化探指标的局限性。     

New data on composition and properties of Lower Cambrian crude oils in Lena region,Irkutsk oil and gas basin

Two groups of oils are considered: condensates and light oils from the terrigenous Lower Cambrian section, and oils occurring in the halogen-carbonate section. Preliminary conclusions on different cycles of oil formation in the terrigenous and carbonate complexes are drawn from the study of chemical composition, optical activity, and distribution of microelernents in the oils. The Parfenovo horizon of Markovo field is considered as a differentiated oil and gas deposit. -- Author.     

The Impact of Aqueous Medium on Gas Yields and Kinetic Behaviors of Hydrogen Isotope Fractionation during Organic Matter Thermal Degradation

In order to recognize the impact of aqueous medium on gas yields and the kinetic behaviors of hydrogen isotope fractionation during organic matter thermal degradation, the gold tube apparatus was used to conduct thermal simulation experiments by mixing the nC18 with the water of different properties and proportions. The yields of natural gas components, the relation among hydrogen isotope composition of each component and the experimental temperatures vs. heating rates have been obtained, and the results indicate that under the higher temperature conditions, the hydrous experiment has obvious impact on gas yields, such as when more water is added, higher amounts of hydrocarbon gas and H2 are yielded, and the existence of water obviously prolongs the temperature interval with the existence of heavy hydrocarbon gas. It also shows that the hydrogen isotope of hydrocarbon gas generated by the hydrous experiment is obviously lighter than that generated by the anhydrous experiment, and with the increasing amount of added water, the δD value of hydrocarbon gas gradually decreases. Compared with gas yields, the variation of δD value is more sensitive to aqueous medium in the thermal simulation experiment. However, compared with the amount of the added water, the aqueous medium property has smaller impact on the gas yields, which still shows the inherit effect on hydrogen isotope composition of aqueous medium. Through the model simulation and the isotope fractionation behavior analysis, it is validated that the hydrogen isotope fractionation process can be well described by the chemical kinetic model. The difference of reaction fraction of normal methane and D-containing methane is large, corresponding to the same activation energy. The content of normal methane is obviously higher in the part with lower activation energy, while the content of D-containing methane is higher in the part with higher activation energy. Therefore, it will result in larger hydrogen isotope fractionation amplitude, and the δD values will be more sensitive to the variation of maturity. Meanwhile, the average activation energy of methane generation from nC18 in the hydrous experiment is higher than that in the anhydrous experiment, and the greater amount of added water, the larger the average activation energy of methane generation reaction. This has laid foundation for its exploratory application in the study of gas reservoir forming history and the gas-source correlation, which indicates the research and application prospects in this orientation.     

热液体系水-岩作用过程中的氧氢同位素行为

论述水-岩作用过程氧氢同位素地球化学行为特征。列举西华山钨矿、台上金矿、白乃庙金矿和额仁陶勒盖银矿的水-岩体系氧（氢）同位素组成特征。论证了开放体系单阶段和二阶段水-岩反应中氧同位素行为接近于封闭体系氧同位素交换演变轨迹，具有成因指示意义，但不具定量意义。探讨了大气降水热液矿床矿体产出位置与氧同位素组成之间关系。本文还指出开放体系中氢同位素动力分馏行为控因复杂，主要由于1H相对富集于各种含氢气体中逃逸出热液体系，使热液体系氢同位素地球化学行为偏离理论演化轨迹，因此氢同位素组成的成因指示意义远不如氧同位素。     

油成甲烷碳同位素分馏的化学动力学及其初步应用

利用金管实验装置,在高压、恒速升温的条件下对塔里木盆地2个油样进行了热解成气实验,结合GC和碳同位素分析,得到了甲烷生成率、甲烷碳同位素与实验温度和升温速率的关系。由此建立并标定了油成甲烷及其碳同位素分馏的化学动力学模型。结果表明：2个油样生成甲烷气时的平均活化能差别不大,但活化能的分布有所差异;¹²C生成的活化能在低值区稍高,而在高值区稍低,从而使生成¹²C的平均活化能稍低于¹³C。正是¹²C、¹³C甲烷生成的活化能分布上的这一微小的差异,导致了甲烷生成时碳同位素的明显分馏。所得模型在塔里木盆地的初步应用显示,英南2气藏天然气主要为晚近期的阶段聚集气,而满东1气藏天然气可能为累积聚集。     

Variations in Stable Carbon Isotopic Composition of n-Alkanes from Ordovician- and Triassic-Derived Oils in Lunnan Oilfield, Tarim Basin, NW China: Global Paleoenvironmental Constraints

1IntroductionInthelastdecade,theGC C IRMStechniquehasbeenwidelyappliedinthestudyoffossilfu els (Bjoryetal.,1 990 ,1 991 ,1 992 ,1 994a ,1 994b ;Schoelletal.,1 994) ,biomarkers (Schoelletal.,1 992 )andpaleoenvironment(Pancostetal.,1 999) ,aswellasofpaleoceanography (Kenni cuttetal.,1 990 ) ,biogeochemistry (e .g .Hayesetal.,1 990 )andenvironmentalsciences (O’Malleyetal.,1 994) .Stablecarbonisotopicanalysesweremadeofacoupleofcompound specifictypesincludingn alkanes,isoprenoids,lighthydr…     

含油气盆地油气同位素地球化学研究概述

以气体地球化学国家重点实验室工作为主，简要概述了对我国含油气的同位素地球化学研究。1．烃气的同位素地球化学：讨论了天然气成因新模式与气藏烃气同位素组成的关系，低演化阶段天然气同位素分馏的二阶段模式，云南中小盆地天然气低演化系列同位素特征及用储层解析气作油气源对比。2．稀有气体同位素地球化学：阐述了^3He/^4He值与中国构造分区，幔源氮的复合成藏和幔源甲烷问题以及气源对比等。3．液态烃同位素地球化学：简述了轻烃碳氢同位素特征及氢同位素作为判别古沉积介质盐度的指标，概述了未熟一低熟油同位素特征及在自然剖面上油和源油抽提物碳同位素分馏特征及其机理。