柴东欧南凹陷石炭系烃源岩有机质富集的影响因素

柴达木盆地东部地区欧南凹陷是石炭系油气运聚成藏的有利构造单元,具有一定勘探潜力,但对有机质富集机理认识不清导致对优质烃源岩分布的预测缺乏有效指导,制约了油气勘探进程.基于地球化学分析、XRD、SEM等分析测试,对石炭系烃源岩矿物组分、 有机质丰度、 干酪根类型、 热演化程度、 形成环境、TOC与主要矿物关系等进行了综合...     

海相烃源岩二次生烃潜力定量评价新方法

烃源岩二次生烃的演化过程是残余干酪根热解演化与残留油热裂解转化两个既相互联系又完全不同的物理化学反应过程的叠加。本文利用自制高压釜热压生烃模拟实验装置,采取分阶段连续递进模拟实验方式,以海相烃源岩样品为例分别评价了残余干酪根的生烃潜力与残留可溶有机质转化油气潜力,建立了一套不同起始与终止成熟度海相烃源岩二次生烃潜力的定量评价方法,并首次明确提出了干酪根生油指数KIo、干酪根生气指数KIg、干酪根生烃指数KIh等评价烃源岩生烃潜力的参数,弥补了ROCK EVAL热解评价方法无法分别评价烃源岩在不同生烃演化阶段所生成的“油”或“烃气”潜力的不足。     

渤海莱州湾凹陷不同类型烃源岩活化能影响因素分析

选取不同干酪根类型的低熟烃源岩作为剖析对象,从干酪根类型、干酪根中有机硫含量、可溶有机质和黏土矿物对烃源岩活化能的影响进行研究,结果表明:Ⅱ₁和Ⅰ干酪根活化能分布范围窄,Ⅱ₂和Ⅲ干酪根活化能分布范围宽,干酪根平均活化能Ⅲ>Ⅱ₂>Ⅰ>Ⅱ₁;有机硫含量高的干酪根平均活化能低,有机硫对烃源岩生烃起催化作用;可溶有机质的存在影响烃源岩平均活化能的大小和分布特征,可溶有机质分布在活化能低值区间,对烃源岩生烃起催化作用;烃源岩黏土矿物中伊/蒙混层含量高,平均活化能高;伊利石含量高,平均活化能低,伊利石对烃源岩生烃起催化作用。      

松辽盆地北部宾参1井白垩系烃源岩的认识和评价及其意义

宾参1井是松辽盆地北部宾县断陷中的第一口参数井,钻遇白垩系地层,自下至上依次为沙河子组、营城组、登娄库组、泉头组和青山口组。在对宾参1井白垩系暗色泥岩进行一系列有机地球化学样品分析测试的基础上,从有机碳(TOC)、氯仿沥青"A"、有效碳(PC)、生烃潜量Pg(S1+S2)、热解峰温Tmax值、镜质体反射率(Ro)、烃源岩气相色谱特征、干酪根碳同位素特征、干酪根元素特征和源岩甾萜烷特征等方面着手,从有机质丰度、有机质类型和有机质成熟度三个角度认识该井白垩系烃源岩,并进行烃源岩的初步评价,认为:(1)青一段干酪根主要为Ⅱ1和Ⅱ2型,其中、下部已进入生油门限,属于非—差烃源岩,个别深度段为较好烃源岩,其上部及青二、三段处于未成熟阶段;(2)泉头组和登娄库组干酪根主要为Ⅲ型,已进入成熟生油阶段,前者属于非—差烃源岩,后者属于差烃源岩;(3)营城组和沙河子组干酪根主要为Ⅲ型,有些层段为Ⅱ2型,处于高成熟—过成熟阶段,以生气为主。对该井白垩系烃源岩的认识和初步评价为勘探程度极低的宾县凹陷含油气前景的评价预测和石油地质研究奠定了基础,具有现实意义和重要的理论意义。     

中国海相不同类型原油与沥青生气潜力研究

本文通过固体沥青、沥青砂岩及加入不同介质原油与稠油的加水密闭热压模拟实验,对比研究了海相原油与沥青的气体产率特征、生气潜力及其影响因素.结果表明原油与沥青的生气潜力除与岩性、演化程度有关外,还与其所含可溶有机质性质和组成等密切相关,H/C原子比越大,最大烃气产率越高,生烃气潜力越大.储集岩或运移途径岩石中的原油与沥青,当其再次达到成熟-高成熟阶段时,可以作为新的轻质油气或者天然气源岩.     

海相碳酸盐岩中矿物结合有机质的组成及成烃演化

对高成熟程度的碳酸盐岩有机质进行了地球化学研究,发现在可溶有机质与干酪根之间存在着成熟度上的差异,这种差异是矿物对沥青组份的保护作用所致.矿物结合有机质无论在组成还是在分布上都与游离态有机质有较大不同,随着成熟度的增加,由于结合态有机质的释放,这种不同逐渐消失,研究表明,矿物结合有机质的释放约在过成熟阶段早期,其量可达几百个ppm.因而在碳酸盐岩地层中,除了干酷根成油气外,在高成熟区亦可能存在着由矿物结合有机质形成的“高温”石油.     

封闭体系有机质与有机碳氢氮恢复动力学研究

在封闭体系的条件下,对典型的Ⅰ、Ⅱ、Ⅲ型干酪根在热演化过程中的损失进行生烃动力学研究,获得了Ⅰ、Ⅱ、Ⅲ型干酪根的总量、有机碳、氢以及氮质量损失动力学参数。用Kinetics软件计算了封闭体系干酪根有机碳丰度、氢碳原子比和氮碳原子比的恢复系数。认为在对高成熟—过成熟干酪根进行生烃评价时,Ⅰ、Ⅲ型干酪根残余有机碳丰度需要进行恢复,而Ⅱ型干酪根残余有机碳丰度不需要恢复。三种类型干酪根的氢碳原子比均需要进行恢复。     

滇东罗平地区中三叠统中发现液态油苗

通过1∶5万区调填图,在云南罗平地区中三叠统关岭组二段薄层泥晶灰岩中首次发现液态油苗。该稠油显示主要分布在层间晶洞中,表现为干沥青及稠油共存状态。有机地球化学研究表明,氯仿沥青“A”的含量为67×10-6,有机质类型以腐泥型Ⅰ型为主。镜质体干酪根反射率R0为2.84%,Tmax=568℃,表明有机质处于高成熟阶段。液态油苗的显示对于进一步评价南盘江盆地的油气勘探前景具有重要的价值和意义。     

Biological marker distribution in coexisting kerogen, bitumen and asphaltenes in Monterey Formation diatomite, California

Organic-rich (18.2%) Monterey Formation diatomite from California was studied. The organic matter consist of 94% bitumen and 6% kerogen. Biological markers from the bitumen and from pyrolysates of the coexisting asphaltenes and kerogen were analyzed in order to elucidate the relationship between the various fractions of the organic matter. While 17 alpha(H), 18 alpha(H), 21 alpha(H)-28,30-bisnorhopane was present in the bitumen and in the pryolysate of the asphaltenes, it was not detected in the pyrolysates of the kerogen. A C40-isoprenoid with "head to head" linkage, however, was present in pyrolysates of both kerogen and asphaltenes, but not in the bitumen from the diatomite. The maturation level of the bitumen, based on the extent of isomerization of steranes and hopanes, was that of a mature oil, whereas the pyrolysate from the kerogen showed a considerably lower maturation level. These relationships indicate that the bitumen may not be indigenous to the diatomite and that it is a mature oil that migrated into the rock. We consider the possibility, however, that some of the 28,30-bisnorhopane-rich Monterey Formation oils have not been generated through thermal degradation of kerogen, but have been expelled from the source rock at an early stage of diagenesis.     

Biological Marker of Middle Jurassic Oil Shale Sequence From Shuanghui Area,Northern Tibetan Plateau

BIOLOGICAL MARKER OF MIDDLE JURASSIC OIL SHALE SEQUENCE FROM SHUANGHUI AREA,NORTHERN TIBETAN PLATEAU     

Origins of natural gases from marine strata in Northeastern Sichuan Basin (China) from carbon molecular moieties and isotopic data

To determine the origin, maturity, formation mechanism and secondary process of marine natural gases in Northeastern Sichuan area, molecular moieties and carbon isotopic data of the Carboniferous and Triassic gases have been analyzed. Typical samples of marine gas precursors including low-maturity kerogen, dispersed liquid hydrocarbons (DLHs) in source rocks, residual kerogen and oil have been examined in a closed system, and several published geochemical diagrams of gas origins have been calibrated by using laboratory data. Results show that both Carboniferous and Triassic gases in the study area have a thermogenic origin. Migration leads to stronger compositional and weak isotopic fractionation, and is path dependent. Carboniferous gases and low-H₂S gases are mainly formed by secondary cracking of oil, whereas high-H₂S gases are clearly related to the TSR (Thermal Sulfate Reduction) process. Gases in NE Sichuan show a mixture of heavy (¹³C-enriched) methane in comparison to the lower maturated ethane of Triassic gas samples, suggesting a similar source and maturity for ethane and propane of Carboniferous gases, and a mixture of heavy ethane to the propane for Triassic gases. Based on the data plotted in the diagram of Chung et al. (1988), the residual kerogen from Silurian marine shale and palaeo oil reservoirs are the main source for Carboniferous gases, and that the residual kerogen from Silurian and Permian marine rocks and Permian paleao oil reservoirs constitute the principal source of Triassic gases.     

准噶尔盆地四棵树凹陷烃源岩地球化学特征及其对车排子凸起油气聚集的贡献

准噶尔盆地西南缘四棵树凹陷主要分布侏罗系、白垩系和古近系3套潜在烃源岩,其中侏罗系八道湾组烃源岩有机质丰度较高,有机质类型以Ⅲ型为主,部分为Ⅱ2型,生烃潜力较高;三工河组烃源岩有机质丰度、类型明显偏差,生烃潜力较低;西山窑组泥岩有机质丰度较高,但由于受西山窑组沉积末期构造抬升导致地层剥蚀的影响,烃源岩厚度较小,总体上生烃条件较差;白垩系烃源岩在四棵树凹陷最大厚度可达300 m,处于低熟阶段,生烃潜力较小;古近系烃源岩有机质丰度较高、类型好,但成熟度偏低,生烃条件较差。侏罗系八道湾组烃源岩处于主要生油阶段;白垩系烃源岩已达到生烃门限,处于低熟—中等成熟阶段;古近系烃源岩成熟度偏低,目前仍处于未熟到低熟阶段。油源对比表明,四棵树凹陷北部斜坡及车排子凸起带原油主要来源于四棵树凹陷及沙湾凹陷侏罗系烃源灶,后期受到白垩系低熟油源灶的侵染,古近系烃源岩的油源贡献有限。     

松辽盆地农安地区上白垩统油页岩含油率影响因素

农安油页岩含矿区地处松辽盆地东南隆起区,主要发育于上白垩统青山口组一段、嫩江组一、二段。油页岩有机质的干酪根类型为Ⅰ-Ⅱ₁型,质量较好,处于成岩的未成熟阶段。油页岩含油率与有机碳和氢元素含量间存在明显的线性正相关关系,当有机碳质量分数＞6％或氢质量分数＞1％时构成油页岩。此外,有机质干酪根的显微组分可以反映有机质的类型,与含油率之间也存在一定的相关性。青山口-嫩江组沉积时期,该区温暖湿润的古气候条件、大规模的海侵和缺氧事件影响了油页岩中有机质的丰度和类型,从而影响了油页岩的含油率。     

海相高演化烃源岩总有机碳恢复系数研究

在5000余块海相烃源岩样品筛选结果的基础上, 根据90余块不同类型未成熟-成熟烃源岩的加水热压模拟实验结果, 并与自然演化剖面相结合, 对烃源岩有机质的变化规律及其恢复系数进行研究.海相优质烃源岩在未成熟-低成熟阶段(R_o < 0.8%) TOC (totalorganiccarbon) 变化不明显, 在成熟阶段中晚期TOC_残余随成熟度增加逐渐降低, 到高成熟-过成熟阶段变化又不明显.高成熟-过成熟优质烃源岩TOC_原始一般Ⅰ型最高降低40%, 恢复系数1.68;Ⅱ₁型最高降低32%, 恢复系数1.48;Ⅱ₂型最高降低24%, 恢复系数1.32.低有机质烃源岩(一般指0.3% < TOC < 1%) 随TOC变低, 降低幅度和恢复系数均逐渐变小, 当0.3% < TOC < 0.5%时, TOC_原始恢复系数约1.2, 当TOC < 0.3%时, TOC_原始恢复系数接近1, 可以不进行恢复.固体沥青和高有机质页岩(TOC > 30%) TOC_原始高成熟-过成熟阶段也不需要进行恢复.海相烃源岩(0.3% < TOC < 30%) 自然剖面生烃潜量的减少和模拟生排烃量的增加与TOC_残余的减少相吻合.      

北黄海盆地LV井侏罗系烃源岩特征及油源对比

对北黄海盆地LV井中、上侏罗统烃源岩及上侏罗统原油（油砂抽提物）进行常规有机地球化学分析和碳同位素测试,分析研究烃源岩和原油的地球化学特征并探讨原油的来源问题。测试结果显示,侏罗系烃源岩达成熟-高熟阶段,有机质类型以Ⅲ型为主。中侏罗统烃源岩有机碳含量较高,但生烃潜能、氯仿沥青“A”及总烃含量低值,属于差的烃源岩。干酪根碳同位素总体偏重（-24.4‰～-23.5‰）,与原油碳同位素特征（-29‰左右）差异显著,排除与原油的母岩关系。上侏罗统烃源岩有机碳含量较中侏罗统低,但生烃潜能、氯仿沥青“A”及总烃含量高值。上侏罗统烃源岩抽提氯仿沥青“A”碳同位素（-26‰～-21.5‰）特征、单体烃碳同位素分布模式及甾萜烷生物标志物特征都与原油相似,综合分析认为原油应该来源于上侏罗统中干酪根类型较好、母质为混源的成熟烃源岩。     

Oil-generation kinetics for organic facies with Type-II and -IIS kerogen in the Menilite Shales of the Polish Carpathians

The Menilite Shales (Oligocene) of the Polish Carpathians are the source of low-sulfur oils in the thrust belt and some high-sulfur oils in the Carpathian Foredeep. These oil occurrences indicate that the high-sulfur oils in the Foredeep were generated and expelled before major thrusting and the low-sulfur oils in the thrust belt were generated and expelled during or after major thrusting. Two distinct organic facies have been observed in the Menilite Shales. One organic facies has a high clastic sediment input and contains Type-II kerogen. The other organic facies has a lower clastic sediment input and contains Type-IIS kerogen. Representative samples of both organic facies were used to determine kinetic parameters for immiscible oil generation by isothermal hydrous pyrolysis and S₂ generation by non-isothermal open-system pyrolysis. The derived kinetic parameters showed that timing of S₂ generation was not as different between the Type-IIS and -II kerogen based on open-system pyrolysis as compared with immiscible oil generation based on hydrous pyrolysis. Applying these kinetic parameters to a burial history in the Skole unit showed that some expelled oil would have been generated from the organic facies with Type-IIS kerogen before major thrusting with the hydrous-pyrolysis kinetic parameters but not with the open-system pyrolysis kinetic parameters. The inability of open-system pyrolysis to determine earlier petroleum generation from Type-IIS kerogen is attributed to the large polar-rich bitumen component in S₂ generation, rapid loss of sulfur free-radical initiators in the open system, and diminished radical selectivity and rate constant differences at higher temperatures. Hydrous-pyrolysis kinetic parameters are determined in the presence of water at lower temperatures in a closed system, which allows differentiation of bitumen and oil generation, interaction of free-radical initiators, greater radical selectivity, and more distinguishable rate constants as would occur during natural maturation. Kinetic parameters derived from hydrous pyrolysis show good correlations with one another (compensation effect) and kerogen organic-sulfur contents. These correlations allow for indirect determination of hydrous-pyrolysis kinetic parameters on the basis of the organic-sulfur mole fraction of an immature Type-II or -IIS kerogen.     

泥灰岩的生、排烃模拟实验研究

本文采用加水热模拟实验方法对东濮凹陷卫城地区下第三系低熟泥灰岩进行了生、排烃模拟实验研究，重点分析了液态产物（热解油、沥青Ａ、沥青Ｃ）的特征及演化规律。热解油中轻质烃（Ｃ₆－Ｃ₁₄）占有重要的地位，其相对含量随演化程度的增高变化特征是从大到小然后再增大，轻质烃的准确定量为评价泥灰岩的生油量提供了重要参数；热解油、沥青Ａ、沥表Ｃ三者的产率及组成变化的对比研究反映了泥灰岩（碳酸盐岩）中不同赋存状态有机质对成烃的贡献以及排烃机制。     

Vanadyl porphyrins in exploration: maturity indicators for source rocks and oils

The Porphyrin Maturity Parameter (PMP), which is derived from the vanadyl porphyrin distribution, is an excellent parameter for: (1) identifying the zone of hydrocarbon generation from marine source rock extracts; and (2) determining from oils the thermal maturity of their source rocks at expulsion.The PMP is measured using a methodology which is inexpensive, reliable and faster than earlier methods, allowing it to be used as a routine exploration tool. The PMP may be a more reliable maturity indicator for marine organic matter than some conventional methods such as vitrinite reflectance. Unlike most conventional maturity parameters guided by processes other than kerogen conversion, the reactions causing PMP evolution directly monitor the generation of bitumen and the concurrent thermal degradation of kerogen.Measurements on hydrous pyrolyzates from the Monterey Formation (offshore California), source rock bitumens from the Devonian-Mississippian Bakken Shale (Williston Basin), and Miocene Monterey equivalent source strata (San Joaquin Basin, California) illustrate the method. In all cases reviewed so far, PMP begins increasing at the onset of hydrocarbon generation and increases systematically and predictably as kerogen decomposition proceeds.In oils generated from high-S marine kerogens, PMP reflects the maturity of the source rock at the time of oil expulsion, provided that the oil does not undergo subsequent reservoior maturation or mixing with in-situ bitumen.     

Biomarker analysis of the upper Jurassic Naokelekan and Barsarin formations in the Miran Well-2, Miran oil field,Kurdistan region,Iraq

The Miran oilfield is one of the new oil fields in Kurdistan region, northern Iraq, located in the Sulaimani Governorate. Twelve Cuttings samples from the Upper Jurassic Naokelekan and Barsarin formations in well Miran-2 were selected for detailed organic geochemical investigations. All the samples were subjected to bitumen extraction in order to study any biomarkers present using gas chromatography-mass spectrometry. The dominance of low-molecular-weight n-alkanes and other calculated parameters indicate a marine source for the organic matter derived from planktonic algal and bacterial precursors deposited under anoxic conditions. The isoprenoids/n-alkanes ratios indicate type II and mixed II/III kerogen for both formations. The type II/III kerogen is characteristic of transitional environment under anoxic to dysoxic conditions as also indicated by the homohopane index for studied samples. More argillaceous carbonate rocks were deposited when reducing conditions were prevalent. Medium to high gammacerane index values in the rock extracts probably indicate a stratified water column during deposition of both formations. The studied samples from both formations have entered peak oil window maturity as reflected from the biomarker ratios from both aliphatic and aromatic fractions of the extracts.     

Organic geochemistry of the kerogen and bitumen from the Ohio Shale by pyrolysis-gas chromatography

An exposure of the Ohio Shale at Bristol Ridge, Ohio in the Bellefontaine Outlier was sampled into 53 channel units. Proximate and elemental (CHN) analyses were performed on these samples to determine the concentration of organic matter. The organic content averaged 6.82% with the highest both in the lower half (11.08%) and extreme upper part (10.43%) of the section.Fragmentation of the kerogen of each of the whole rock samples was accomplished by pyrolyzing for 10 s at 750°C in the injection port of a gas chromatograph with a FID detector. The concentration and distribution of the diagnostic hydrocarbons fragmented at this temperature were used to infer the molecular construction of the high molecular weight kerogens. The suite of identified hydrocarbons for each of the samples throughout the section was similar, but a very large fluctuation in the amount of pyrolysis products was observed. This fluctuation is strongly related to organic richness as defined by the proximate and elemental analyses. The identification of diagnostic normal alkanes and aromatics and SCI indicates that the kerogen assemblage is composed of both marine and terrestial components — most likely a mixed Type II kerogen. The contribution of individual aromatic and normal alkanes is variable, which suggests that there were minor fluctuations in the proportions of terrestrial and marine organic matter during decomposition.Bitumen pyrolized from the whole rock and bitumen removed by Soxhlet extraction using a 4:1 benzene/methanol solvent mixture were analyzed. Comparison of these two techniques yield similar pristane/phytane ratios and Carbon Preference Index (CPI) values. On decomposition the whole rock bitumen exhibited a mean pristane/phytane ratio of 1.5 and a mean CPI value of 1.4, whereas the Soxhlet-extracted bitumen exhibited a mean pristane/phytane ratio of 1.6 and a mean value of 1.3. The low pristane/phytane ratios from this outlier indicates a possible marine environment, with reducing conditions existing immediately below the sediment-water interface. The CPI values also indicate the sedimentary sequence is thermally immature. Reflectance of the vitrinite (%R_o 0.05) and fluorescence (Q 0.93) of the algal bodies indicate a maturation at the beginning of the oil window or at boundary between thermal immaturity and maturity.