The occurrence of fatty acids in immature source rocks and their distribution characteristics

The fatty acids in extractable bitumen and kerogen of immature source rocks of the Liaohe Basin and Jiyang sag were investigated in this study. The result showed that the bitumen fatty acids were mainly associated with non-hydrocarbon fraction and that the kerogen fatty acids with some tightly bound fatty acids were mainly bounded in a net structure of kerogen by ester bonds. For the investigated source rocks, the fatty acids in bitumen, bound fatty acids and tightly bound acids in kerogen ranged in 0.01%—0.073.9%, 0.005%— 0.045 5% and 0.005%— 0.010% respectively. Among the fatty acids analyzed in this study, mono-carboxylic acids, a , w -di-carboxylic acids and hydroxy acids accounted for 70%—100%, 0%—30% and <10% respectively. It was also found that the mono-carboxylic acids with longer chains mainly existed in bitumen, and that the a , w -di-carboxylic acids and hydroxy acids mainly existed in kerogen. From above, it was assumed that the mono-car- boxylic acids in bitumen might have played an important role in the hydrocarbon generation from fatty acids in immature source rocks.     

Organic compositions of lacustrine source rocks in Jiyang super-depression and its implication to petroleum geology

IMMATURE OIL WAS FIRST DISCOVERED IN WELL YI18 IN CHINA [1]. FROM THEN ON, MORE AND MORE IMMATURE OILS WERE DISCOVERED IN JIYANG SUPER-DEPRESSION, FOR EXAM- PLE, SOUTHERN SLOPE OF DONGYING DEPRESSION, GUNAN SAG IN ZHANHUA DEPRESSION, TAOERHE, DAWANGZHUANG…     

干酪根热解聚沥青中的脂烃生物标记物

将干酪根在超临界态溶剂存在下进行热解聚,抽出物中的脂烃生物标记物的分析表明,抚顺与茂名油页岩干酪根中有相当多的陆源高等植物参与生成。甾烧萜烷的成熟度参数表明,热解聚沥青的成熟度很低。对于干酪根通过热解聚形成未熟或低熟原油的可能性作了初步探讨。     

Origin of immature sulfur-rich oil in Jianghan oil field

Chemical structure of immature sulfur-rich kerogen and composition of immature sulfur-rich crude oil in Jianghun oil field have been studied. In molecular level, crude oil differs from thermolysed and chemolysed products of kerogen but does resemble the bitumen in immature sulfur-rich source rock. Therefore, immature sulfur-rich oil may be derived from the expelling of bitumen rather than from thermal cracking of kerogen.     

松辽盆地朝长地区原油的地球化学特征

松辽盆地朝长地区原油的成熟度普遍较低,大多数原油仍保留正烷烃奇偶优势,这主要与半咸水咸水环境中藻类母质生源输入有关。长２０井的原油既具有正烷烃奇偶优势,又具有较低甾萜烷异构体比值,属于典型的低熟原油。从长２０井低熟原油中检测到了一定量的２８,３０二降藿烷,这说明源岩形成于极度厌氧的环境。此外,在原油中还发现了藿１７（２１）烯系列,这进一步揭示了原油的低熟性。其它原油虽具有正构烷烃的奇偶优势,但甾萜烷参数均比较高,可能为低熟油与成熟油的混合作用所致。     

生油岩原始有机碳恢复方法的探讨

本文在前人工作的基础上,根据物质平衡原理和热模拟实验揭示了干酪根演化过程,探讨了沉积有机质在热降解中的转化与“消耗”,确定了各种类型成油母质在不同成熟阶段中碳的演化规律,找出了生油岩实测有机碳与干酪根中碳的对应关系,提出了各种生油岩有机碳恢复系数。文中给出了泥质岩和碳酸盐岩的应用实例。     

Identification of the Kukersite-type source rocks in the Ordovician Stratigraphy from the Tarim Basin, NW China

Due to the importance of the Gloeocapsomorpha Prisca （G. prisca）-enriched source rocks, which belong to Kukersite-type source rocks in the Lower Paleozoic Ordovician strata, it has received great attentions during the petroleum exploration as to whether there are the Kukersite-type source rocks developed in the major hydrocarbon source strata of the Upper and Middle Ordovician in the Tarim Basin. Using pyrolysis-gas chromatography-mass spectrography to analyse kerogens from source rocks in the lime- mud mound with moderate maturity, study reveals that there are the Kukersite-type source rocks in the Ordovician strata of the Tarim Basin. The pyrolysis products showed a low content of 〉n-C19 normal alkanes with a significant odd-even predominance between n-C13 and n-Cl7, long-chain alky substituted alkylbenzene and alkylthiophene isomers and distinctive distribution of 5-N- alkyl-1, 3-Benzenediol and its homologous. Based on the geographic environment characteristics of G. Prisca, the molecular dis- tributions of crude oil from the Lower Paleozoic petroleum systems in the Tarim Basin and characteristics of kerogen pyrolysis products from the Middle and Upper Ordovician source rocks, the results suggested that it is less possible to develop the G. Pris- ca-enriched Kukersite-type source rocks in the major hydrocarbon source rocks in the Middle and Upper Ordovician strata in the Tarim Basin. However, the benthic macroalga and planktonic algae-enriched source rocks are the main contributors.     

铀对Ⅰ型低熟烃源岩生烃演化的影响

在Ⅰ型低熟烃源岩中加入砂岩型铀矿石的条件下进行生烃模拟实验,对比无铀-加铀样品生烃模拟实验产物的相关参数,探讨油气生成过程中无机铀所起的作用。结果表明:铀的存在促使长链烃类在400℃后裂解成低相对分子质量短链烃,烃类相对分子质量降低,向干气演化,CO2和H2大量生成,且铀的存在使得这一变化的温度点提前50℃;铀可以促进总油生成高峰的提前到来;350℃为铀使烯烃产量变化的转折温度点,烯烃开始向烷烃转变;铀的存在能提高模拟实验中生成的烯烃的异构化程度,并在整体上使生成的烯烃分子在晶格中排得更加紧密;加铀的烃源岩样品的生烃模拟实验产物在族组成、饱和烃气相色谱、生物标志化合物等方面表现出更加成熟的特征,铀可以使有机质的成熟度提高,有利于低熟烃源岩早期生成低熟油气,使铀的存在成为未熟-低熟油气形成的可能无机促进因素之一,这种提前生成的少量油气可以使所在储层变为亲油性,为后期大规模生成的油气运移成藏提供有利的条件,使得即使是致密的储层,也能形成大规模的工业油气藏。     

The comparison of biomarkers released by hydropyrolysis and Soxhlet extraction from source rocks of different maturities

The Permian Dalong Formation(P2d) source rocks from the mature Guangyuan outcrop section and the overmature Wangcang outcrop section in Sichuan Basin were selected.The Soxhlet extraction and kerogen catalytic HyPy were conducted on the P2d source rocks.The biomarkers obtained by both methods were compared to discuss their difference and the influence extent of thermal maturation on covalently bound biomarkers.The results show that covalently bound biomarkers can hardly be correlated to the corresponding free biomarkers due to severe thermal alterations and/or interference of migrated hydrocarbons in both outcrop sections and thermal maturation have much lower influence on covalently bound biomarkers in kerogens than on free biomarkers in Soxhlet extracts.The application of HyPy in study of biomarker geochemistry can reduce the thermal maturation effect on biomarkers(Ro≤2.4%) to a greater extent and the interference of migrated hydrocarbons between interbedded layers.The covalently bound biomarkers released by HyPy are useful in the study of biomarker geochemistry and oil-source correlation on high-overmature source rocks.     

Molecular organic geochemical evidence for paleoenvironmental changes at 11.87–12.28 m in GS-1 sedimentary core, Gucheng Lake, East China

Organic lipids with different occurrence modes in a sedimentary core in a subtropical freshwater lake, Gucheng Lake, were sequentially extracted, separated and analyzed. The down-core variations of OEP index of alkanes, C_18:2/C_18:0 ratios of fatty acids, ratios of bound, fatty acids to free fatty acids, thermo-maturity indices of hopanoid hydrocarbons and rerative concentrations of sedimentary minerals revealed an evident increasing in allochthonous input from rock detritus below 12.28 m in the sedimentary profile. The distribution pattern of tightlybound β-hydroxy fatty acids indicated a difference in bacterial communities above and below the boundary, as well as the gammacerane index may assign a significant change in lake water salinity. The evidence, in general, suggested that a significant paleoenvironmental change had taken place in ca. 9.6 kaBP on the regional basis.     

大港探区下古生界奥陶系烃源岩地化特征

通过油源对比发现位于大港探区孔西潜山构造的孔古3井油源来自奥陶系烃源岩,进一步的地球化学分析表明;奥陶系碳酸盐岩平均有机碳含量为0.14%,平均氯仿沥青“A”含量为0.11%,平均总烃含量57.6 ppm,已达到生油岩有机质丰度下限值,部分样品已达到好较好生油岩的有机质丰度指标;干酪根类型主要为Ⅱ1型、Ⅰ1型和Ⅱ2型;大部分样品有机质已处于高成熟~成熟演化阶段。大港探区下古生界奥陶系地层分布广泛,这为大港探区寻找古生界原生油气藏奠定了基础,预示着大港探区古生界原生油气藏具有广阔勘探前景。     

川东沥青来源分析和结构分析

宣南圈闭中探明了石炭系、Ch-F等大规模气藏,前景可观,但对于焦质烃的气源研究还存在争议。文章对宣南圈闭焦质烃进行碳同位素、饱合烃组分及生物标志物进行分析,研究其成因和气源类型,从而最终确定其主力烃源岩。Ch－F储层焦质烃集中分布在27.54‰～29.4‰,最大相差为1.8‰,而石炭层焦质烃碳同位素集中于-26.6‰～-29.7‰之间;正构烷烃的碳数分布模式相似,都呈单峰型分布,CH-F焦质烃正构烷烃主峰碳数在C20附近,而石炭系黄龙组焦质烃主峰碳数在C18附近,石炭系演化程度稍高。综合认为,石炭系与Ch-F焦质烃具有同源性,天然气主要为原油高温裂解生成,认为固体焦质烃及天然气主要来源于志留系龙马溪组泥岩,并有少量的龙潭组干酪根裂解生气的混入。     

Determining the temperature of petroleum formation from the kinetic properties of petroleum asphaltenes

Knowledge of the timing and location of petroleum formation is important in assessing the extent of available reserves in hydrocarbon-forming basins. This can be predicted from the thermal history of a basin and the kinetic parameters that characterize the thermal breakdown of kerogen in source rocks. At present, the kinetic parameters of kerogen breakdown are experimentally determined using immature rock samples from basin margins, but questions remain about the accuracy of this approach, especially when significant variability is observed within individual source units. Here we show that the kinetics of hydrocarbon generation from petroleum asphaltenes can be used to determine the temperature conditions of the actual source rock at the time of expulsion of the sampled petroleum. This relationship reflects the structural similarity of asphaltenes to the parent kerogen. We expect that our approach may be used as a comparatively simple alternative method for assessing the petroleum generation characteristics of a given basin, which will allow for better estimates of the available oil resources and the risks associated with their exploration.     

歧口凹陷沙一段低熟烃源岩评价

利用烃源岩有机质丰度、生排烃特征、发育古环境、有机岩石学及原油特征等手段,探讨歧口凹陷沙一段低熟烃源岩生烃、排烃特征。研究结果表明,歧口凹陷沙一段低熟烃源岩有机质丰度高、类型好,具有集中排烃、高效排烃的特点。沙一下段烃源岩发育的环境主要为干旱气候下的咸水环境。藻类及显微组分中的矿物沥青基质是低熟烃源岩形成低熟油气的物质基础。歧口凹陷存在大量未熟-低熟的原油。     

半封闭半开放体系下不同演化程度干酪根的太赫兹光谱特性

本文应用太赫兹时域光谱技术研究了灰色泥岩在半封闭半开放体系下经历不同生烃模拟温度、压力所得干酪根的光学性质,获得了不同干酪根样品在太赫兹波段的吸收谱和折射率,结合样品的镜质体反射率,建立了干酪根在不同演化阶段的生烃模式,分析了干酪根样品在地质升温速率下的自然演化过程及主生烃期,为研究烃源岩的演化及油气生成提供了参考．     

Characterization and origin types of immature and low-mature amorphous kerogen in terrestrial source rocks

The microfluorescent technique was applied to investigate the fluorescence alteration patterns of amorphous kerogen of the terrestrial source rocks of China. Two fluorescence parameters, I ₅₄₆ ²⁰ andR were suggested, which can be taken to divide the amorphous kerogen into five types: algae amorphinite, biodegraded amorphinite A, B, C, and humic amorphous. On the basis of this, the Rock-Eval analysis results of source rocks were used to investigate the hydrocarbon generating potential of these amorphinite.     

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.     

鄂尔多斯盆地宜川地区上古生界烃源岩评价

依据氢指数（HI）、降解率（PC/TOC）等两个方面的地球化学指标,按照煤系地层烃源岩有机质类型划分标准,对研究区的山西-太原组烃源层的有机质类型作剖析,进行上古生界烃源岩系统评价。研究认为,本溪组烃源岩主要是泥岩,有机质丰度平均2.51%,泥岩干酪根母质类型主体属腐殖型干酪根,即Ⅲ型干酪根;太原组暗色泥岩有机质丰度平均2.26%,煤层比较发育,有机质丰度平均81.66%;山西组的泥岩比较发育,泥岩有机质丰度平均2.26%,煤层有机质丰度平均72.66%。本区上古生界干酪根显微组分都以镜质组为主,显示干酪根母质为腐殖型,即Ⅲ型干酪根,热成熟度演化较高,Ro都大于2.5%,Tmax为490℃以上,表明泥岩已达到过成熟阶段,本区暗色泥岩及煤层属中等—好气源岩,此次烃源岩的认识对该区下一步的勘探提供重要的依据。     

Distribution and characterization of C31 sterane from cretaceous sediments and oils, Songliao Basin, China

Relatively high abundance of C₃₁ steranes has been identified from cretaceous source rocks and crude oils in the Songliao Basin, China. C₃₁ steranes which occur as ten isomers were tentatively identified as 4, 22, 23, 24-tetrametyhlcholestane based on their retention time and mass spectrum. They bear a lower thermal stability and occur as important components in the immature oils of Chaochang region because they have three-methyl groups in their side chain. The relatively high abundance of C₃₁ steranes in the samples can indicate the source input of some special algae in the brackish and saline environment. Therefore they can be used as very useful bimarkers for organic facies analysis and oil correlation. Their biological source perhaps related to the dinoflagellate such asG. foliaceum andP. foliaceum. The gorgostanol are considered as possible precursors for the putative C₃₁4-methyl sterane which formed in the stage of diagenesis.     

沁水盆地石炭-二叠煤系地层烃源岩特征及生烃有利区评价

对山西沁水盆地石炭－二叠煤系地层烃源岩的有机地化资料进行分析总结。结果表明,山西组和太原组煤岩样品显微组分以镜质组为主,其次为惰质组,稳定组分（壳质组＋腐泥组）的质量分数一般低于11.2％;干酪根 H／C 原子比主要集中在0.20～0.85,O／C 原子比主要集中在0.02～0.10,属高演化Ⅲ型有机质;煤岩碳同位素普遍偏重,为－23‰～－25.6‰;沥青“A”中,饱和烃的质量分数大多数＜25％,芳烃为11％～58％,饱／芳比值一般为＜0.4。煤系泥岩显微组分以镜质组为主,其次是惰质组,壳质组较低;H／C 原子比主要在0.25～0.75,O／C 原子比主要在0.03～0.20,属高演化Ⅲ型有机质,小部分属于Ⅱ2型有机质;碳同位素偏重,为－23.5‰～－25.9‰,饱和烃质量分数＜25％,大部分＜20％。太原组灰岩以Ⅱ2型干酪根为主,碳同位素轻于山西组及太原组煤岩及泥岩,主要在－26.0‰～－30.0‰。制定了适合沁水盆地煤系地层中煤岩和泥岩的生烃潜力评价标准,对烃源岩有利生烃区进行评价。综合认为,沁水盆地山西组煤岩总体上是中等－好烃源岩,以盆地两翼为好,中部和南部为中等－差烃源岩;太原组煤岩总体上为中等－好烃源岩,两翼大部分为好烃源岩,沁县－祁县－榆次－榆社一带以及南部地区为差－中等烃源岩;沁水盆地山西组泥岩总体上为中等偏差的烃源岩,只有西部部分地区为好烃源岩,盆地中部地区烃源岩生烃潜力比两翼差;太原组泥岩总体上为中等偏差的烃源岩,西部局部地区为好烃源岩,盆地边缘比盆地中央的生烃潜力稍大一些。