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1.
Surface sediments from the Outer Continental Shelf of Alaska were analyzed for hydrocarbons as part of an environmental survey sponsored by NOAA/BLM. Sediments were collected from the proposed oil lease areas of Beaufort Sea, southeastern Bering Sea, Norton Sound, Navarin Basin, Gulf of Alaska, Kodiak Shelf and lower Cook Inlet. Data on normal and branched alkanes and di- and triterpenoids from capillary gas chromatography (GC) and gas chromatography-mass spectrometry (GC/ MS) indicate that the area displays little evidence of petroleum hydrocarbons (i.e., seeps) except at a few isolated stations. Beaufort Sea sediments have the highest hydrocarbon budget, whereas Kodiak Shelf sediments have the lowest. The molecular markers of the hydrocarbons are of a mixed marine autochthonous and terrestrial allochthonous origin. Norton Sound and Cook Inlet sediments contain the highest levels of terrigenous lipids and Kodiak Shelf the lowest. The abundance of alkenes implies that relatively low oxidizing conditions exist in some of the depositional areas studied, suggesting that extraneous petroleum hydrocarbons introduced into these sediments would be expected to have a relatively long residence time. The distribution of polynuclear aromatic hydrocarbons (PAH) is complex and shows a pyrolytic origin. The data on perylene strongly favor the hypothesis that it is “performed” from terrigenous precursors and transported into the marine environment with no apparent in situ generation. Polynuclear aromatic hydrocarbons of diagenetic origin are probably dominant in Gulf of Alaska and Kodiak Shelf sediments.Two stations, north of Kalgin Island, in lower Cook Inlet and one in southeastern Bering Sea show typical weathered petroleum distribution of n-alkanes and triterpenoids. Probable pathways of transport and fate of petroleum hydrocarbons in case of an oil spill are also briefly discussed.  相似文献   

2.
A selection of Precambrian kerogens has been characterized by Curie-point pyrolysis combined with gas chromatography and gas chromatography-mass spectrometry. The resulting pyrograms can be classified into two groups. The first group of pyrograms is derived from kerogens whose pyrolysis products are dominated by alkanes, alkenes and alkadienes, whereas the second group contains pyrograms from kerogens that produce complex mixtures of branched hydrocarbons dominated by components at every third carbon number (C9, C12, C15, C18, C21, and up to C33). It is suggested that these branched hydrocarbons may remotely represent remains of isoprenoid hydrocarbons, or other branched hydrocarbons, of the original organisms.  相似文献   

3.
An alkane distribution in which isoprenoid alkanes are present in excess of n-paraffins and pristane, phytane, and norpristane (in this order) are the major components, has been found in two different beds of the Irati oil shale, Brazilian Permian formation of São Mateus do Sul, Paranã.  相似文献   

4.
Mathematical models have been developed which simulate both random and nonrandom thermal cracking of branched and straight-chain hydrocarbons. Application of these models to n-paraffins suggests that thermal cracking alone cannot be the dominant mechanism in formation of the n-paraffin distributions present in crude oils. Application to isoprenoid hydrocarbons indicates that nonrandom cracking could be important in producing the isoprenoid distributions found in oils.Results of the mathematical modeling show that methane formation should, as predicted from energy considerations, be kinetically disfavored. It therefore is likely that substantial quantities of methane are produced from saturated hydrocarbons only under thermal conditions more severe than those under which oil is produced.The mathematical models employed are adaptable for other geochemical applications, such as isotope fractionation.  相似文献   

5.
《Organic Geochemistry》1986,9(4):183-192
Laboratory simulations of petroleum formation were examined by stable carbon isotope studies of five cryogenic distillation fractions of the gases produced by thermal treatment of organic substrates. Simple heat treatment (pyrolysis) of substrates was contrasted with heat treatment in the presence of nickel and vanadium sulfides, ammonia, and water (catalysis). The effect of substrate/catalyst ratio on the isotopic composition of gases was also examined. All reactions were carried out at 440°C, and ambient pressure. Plots of stable carbon isotope ratio versus distillation temperature, for substrates representing marine and terrestrial organic matter, were compared to literature values for natural petroleum accumulations, and to the pyrolysis of Green River oil shale.  相似文献   

6.
高压-工频电加热原位裂解油页岩是吉林大学与俄罗斯托木斯克理工大学合作研究的具有占地面积小、污染小、工艺简单等优点的油页岩开采技术。先对油页岩使用高压电击穿,再使用电加热的二步法,可以达到快速裂解油页岩的效果。为了确定裂解油页岩的工艺参数,以及更好地掌握高压-工频电加热裂解油页岩技术,本文对油页岩在有、无氧气条件下的裂解过程进行了热分析试验。试验表明,在有氧与无氧加热条件下,都可完成油页岩的裂解,且裂解过程是相同的,都属于二段式裂解过程。氧在油页岩加热裂解时具有驱动作用,可以降低油页岩的裂解温度、节省能量、提高裂解速度。  相似文献   

7.
《Applied Geochemistry》1988,3(5):441-453
Green River shale (Type I kerogen), Yaamba shale (Type II kerogen) and Sarufutsu coal (Type III kerogen) were heated to various temperatures using Rock-Eval. The amount of hydrocarbons generated and weight loss by pyrolysis were measured to obtain a better understanding of petroleum generation. After the pyrolysis experiments, elemental analysis (C, H), vitrinite reflectance (%Ro) measurement, maceral observation, infrared spectroscopy (IR) and13C-NMR spectroscopy were carried out on the coal samples. Changes in H/C atomic ratio, IR and NMR spectra indicate that experiments by Rock-Eval resemble those of the natural evolution of kerogen. However, the petrographic changes of the coal show more similarity to coal liquefaction and coking than to natural coalification. Changes in the amount of generated hydrocarbons with increasing maturation show that Type II kerogen produces more hydrocarbons than does Type I when Ro does not exceed 1.1%. Petroleum generation curves for the three samples were concordant with trends in natural systems, and a conceptual model of petroleum generation curve classified into three types is proposed, namely (1) curve of total amount enerated, (2) curve of generation rate, and (3) curve of fluid composition. Changes of IR and NMR spectra after pyrolysis imply that generated hydrocarbons are derived from aliphatic C structures of kerogen macromolecules. Moreover, the difference in genetic potential between Type I and Type III reflects different amounts of aliphatic structures. Type I is assumed to have a simple assemblage (mainly polymethylene carbons), and Type III is assumed to have a more complex variety of structures that are responsible for the difference in generation rates between the two kerogen Types. A quantitative analysis of C species of various bond structure by13C-NMR confirms that petroleum generation is the process of bond cleavage of kerogen macromolecules; lower-energy bonds decrease at an earlier stage of reaction, while aromatic carbons with higher bond energies survive to form graphitic structure at postmature stages. Emphasis is placed on the idea that the most important and direct factor in petroleum generation is a change in the molecular structure of kerogen with increasing maturation. NMR and other methods providing information about molecular structures of kerogen will become strong tools for evaluating source rocks and sedimentary basins in the future.  相似文献   

8.
黄骅坳陷齐家务地区的油源对比   总被引:2,自引:3,他引:2  
黄骅坳陷齐家务地区储油层主要为下第三系沙河街组沙一下段白云质灰岩。该区原油具有高密度、高粘度、高含硫量、中低凝固点、高初馏点和高胶质和沥青质含量等物理性质。在地球化学特征上,高碳数正构烷烃具有明显的奇偶优势,类异戊二稀烷烃具有植烷优势,甾烷组成具有明显的C27ααα甾烷优势,沙一段泥页岩的三环萜烷不发育、伽马蜡烷比较发育。这些地球化学特征表明该区原油为未熟-低熟油。分析原油和沙一段泥页岩的伽马蜡烷/C30藿烷与C29降藿烷/C30藿烷的关系以及伽马蜡烷/C30藿烷与Pr/Ph之间的关系,并结合地球化学特征,认为齐家务地区的烃源岩主要是沙一下段的泥页岩。  相似文献   

9.
Aliphatic and aromatic hydrocarbons in sediments of the middle and lower Mississippi Fan and two intraslope basins in the Gulf of Mexico are derived from terrestrial organic matter and thermogenic, mature hydrocarbons. The terrestrial hydrocarbon component consists primarily of terrigenous, plant biowaxes (n-alkanes with 21 to 33 carbons). The occurrence of thermogenic hydrocarbons in immature near-surface sediments, their molecular distributions and concentration variations with depth suggest that the majority of these mature hydrocarbons have migrated from a source much deeper in the sediment column. A portion of the thermogenic hydrocarbons may be derived from recycled material and includes phenanthrene, methyl phenanthrenes, chrysene and benzopyrenes. The migrated, thermogenic hydrocarbons include normal and isoprenoid alkanes with less than 21 carbons, naphthalene, methyl naphthalenes, ethyl naphthalenes and other aromatics of similar volatility (i.e., biphenyl, acenaphthene and fluorene). Triterpane, sterane and aromatized sterane distributions suggest that the thermogenic hydrocarbons at both sites have a common source and are overprinted with immature sediment hydrocarbons. The biomarker distributions and carbon isotopic compositions of the thermogenic hydrocarbons are atypical for petroleum produced in the Gulf of Mexico. Molecular distributions of the hydrocarbons are constant, regardless of the present depth of occurrence, suggesting that they have migrated in a separate phase. The upward migration of hydrocarbons from deeper sources is a wide-spread phenomenon in the Gulf of Mexico with several documented cases of massive seepage (visible oil) as well as the more diffuse permeation of Pleistocene sediments of the Mississippi Fan and two intraslopes reported here.  相似文献   

10.
In an attempt to evaulate the hypothesis that petroleum formation can be simulated using high temperatures, Green River Shale from Colorado, U.S.A., was subjected to closed-system pyrolysis for 16 hr at temperatures ranging from 300 to 500°C. Variations in the pyrolysis products (gases, volatile liquids, and organics extracts) over this temperature range duplicate the variations observed in many in situ studies of petroleum maturation.The sequence of products formed over this temperature range was used to define five different zones of maturation reactions: (1) a heterobond cracking zone; (2) a labile carbon bond cracking zone; (3) a free radical synthesis zone; (4) a wet gas formation zone; and (5) a dry gas formation zone. This high temperature simulation of maturation can be used to test other factors in petroleum formation such as mineral catalysis.  相似文献   

11.
通过密封金管-高压釜体系对珠江口盆地番禺低隆起-白云凹陷北坡恩平组炭质泥岩的干酪根(PY),在24.1 MPa压力、20℃/hr(373.5~526℃)和2℃/h(343~489.2℃)两个升温速率条件下进行热模拟生烃实验,分析气态烃(C1 5)和液态烃(C6 14和C14+)的产率,以及沥青质和残余有机质碳同位素组成。同时与Green River页岩(GR)和Woodford泥岩(WF)的干酪根,分别代表典型的I型和II型干酪根进行对比研究。结果显示PY热演化产物中总油气量明显低于GR和WF干酪根,且气态烃(C1 5)最高产率是液态烃的1.5倍,揭示恩平组炭质泥岩主要以形成气态烃为主。在热演化过程中,有机质成熟度和母质类型是控制油气比的主要因素,气态烃和轻烃的产率比值主要受热演化成熟度的影响。干酪根残余有机质碳同位素和沥青质碳同位素在热演化过程中受有机质成熟度的影响较小,δ13C残余和δ13C沥青质可以间接反映原始母质的特征,为高演化烃源岩油气生成提供依据。  相似文献   

12.
Hydrous and anhydrous closed-system pyrolysis experiments were conducted on a sample of Mahogany oil shale (Eocene Green River Formation) containing Type-I kerogen to determine whether the role of water had the same effect on petroleum generation as reported for Type-II kerogen in the Woodford Shale. The experiments were conducted at 330 and 350 °C for 72 h to determine the effects of water during kerogen decomposition to polar-rich bitumen and subsequent bitumen decomposition to hydrocarbon-rich oil. The results showed that the role of water was more significant in bitumen decomposition to oil at 350 °C than in kerogen decomposition to bitumen at 330 °C. At 350 °C, the hydrous experiment generated 29% more total hydrocarbon product and 33% more C15+ hydrocarbons than the anhydrous experiment. This is attributed to water dissolved in the bitumen serving as a source of hydrogen to enhance thermal cracking and facilitate the expulsion of immiscible oil. In the absence of water, cross linking is enhanced in the confines of the rock, resulting in formation of pyrobitumen and molecular hydrogen. These differences are also reflected in the color and texture of the recovered rock. Despite confining liquid-water pressure being 7-9 times greater in the hydrous experiments than the confining vapor pressure in the anhydrous experiments, recovered rock from the former had a lighter color and expansion fractures parallel to the bedding fabric of the rock. The absence of these open tensile fractures in the recovered rock from the anhydrous experiments indicates that water promotes net-volume increase reactions like thermal cracking over net-volume decrease reactions like cross linking, which results in pyrobitumen. The results indicate the role of water in hydrocarbon and petroleum formation from Type-I kerogen is significant, as reported for Type-II kerogen.  相似文献   

13.
Long-chain fatty acids (C10-C32), as well as C14-C21 isoprenoid acids (except for C18), have been identified in anhydrous and hydrous pyrolyses products of Green River kerogen (200–400°C, 2–1000 hr). These kerogen-released fatty acids are characterized by a strong even/odd predominance (CPI: 4.8-10.2) with a maximum at C16 followed by lesser amounts of C18 and C22 acids. This distribution is different from that of unbound and bound geolipids extracted from Green River shale. The unbound fatty acids show a weak even/odd predominance (CPI: 1.64) with a maximum at C14, and bound fatty acids display an even/odd predominance (CPI: 2.8) with maxima at C18 and C30. These results suggest that fatty acids were incorporated into kerogen during sedimentation and early diagenesis and were protected from microbial and chemical changes over geological periods of time. Total quantities of fatty acids produced during heating of the kerogen ranged from 0.71 to 3.2 mg/g kerogen. Highest concentrations were obtained when kerogen was heated with water for 100 hr at 300°C. Generally, their amounts did not decrease under hydrous conditions with increase in temperature or heating time, suggesting that significant decarboxylation did not occur under the pyrolysis conditions used, although hydrocarbons were extensively generated.  相似文献   

14.
The reactions of a terminal alkene (1-octadecene) and a polymethyl phenol (2,3,6-trimethylphenol) on activated carbon have been investigated in closed system pyrolysis experiments in the temperature range 170-340 °C. The reaction products of 1-octadecene included methane, isomeric octadecenes, methyl substituted alkanes, alkyl aromatics and an homologous series of n-alkanes with carbon numbers indicative of progressive single carbon depletion of the reactant. The reaction products of 2,3,6-trimethylphenol also contained methane, as well as C1-C4 methyl phenols produced by demethylation and methyl transfer reactions. A carbon surface reaction involving the formation of a reactive single carbon intermediate (i.e. methylene/carbene) is proposed. This reaction accounts for the products observed from the pyrolysis experiments and also is consistent with liquid hydrocarbon distributions found in petroleum basins. Methane was the dominant (ca. 85% of C1-C4) gaseous hydrocarbon product of 2,3,6-trimethylphenol but accounted for only ca. 17% of the C1-C4 hydrocarbons from 1-octadecene. These findings suggest that single carbon surface reactions may play an important role in the geochemical formation of crude oil and natural gas and that the composition of the source material and therefore the type of organic compounds undergoing such reactions, influences the hydrocarbon gas composition in sedimentary basins.  相似文献   

15.
Organic geochemical evaluation of thirty-two Aptian to Campanian shale samples from seven wells drilled on the shelf of the Orange Basin (southwestern Atlantic margin) was carried out in order to determine their origin, depositional environment, thermal maturity and hydrocarbon potential. The shale samples, selected to represent highstand, lowstand and transgressive systems tracts, were analysed by Rock–Eval pyrolysis for total organic C characteristics and by gas chromatography (GC) and gas chromatography–mass spectrometry (GC–MS) for n-alkanes, aliphatic isoprenoid hydrocarbons and biomarkers (steranes, hopanes and tricylic terpanes). For most of the shale samples Rock–Eval data, hydrogen (HI) and oxygen index (OI) point to mainly Type III terrigenous organic matter. Only a few samples of Turonian age reveal a higher proportion of marine organic matter being classified as Type II/III or Type II. Biomarker parameters suggest that the samples are deposited under suboxic to oxic environmental conditions. Rock–Eval data and biomarker maturity parameters assign for most of the samples a maturity level at the beginning of the oil window with some more mature samples of Aptian, Albian and Cenomanian age. The hydrocarbon generation potential is low for most of the shelf shales as indicated by the S2/S3 ratio and HI values. Exceptions are some samples of Turonian and Aptian age.  相似文献   

16.
胜利河油页岩位于青藏高原腹地的羌塘盆地,具单层厚度薄、区域延伸长的特点,为羌塘盆地新发现的又一处海相油页岩.采用GC-MS(IRMS)分析方法对该油页岩进行了研究,结果表明,胜利河油页岩(11层以及13层)含有丰富的正烷烃、类异戊二烯烃、萜类化合物和甾类化合物.正构烷烃呈前高后低的单峰型分布,nC15、nC16为主峰碳,轻烃组分占有绝对优势,OEP值0.96~0.97,接近平衡值1.00,Pr/Ph为0.57~0.75,显示弱的植烷优势;萜烷丰度顺序为五环三萜烷》三环萜烷》四环萜烷;规则甾烷呈不对称的"V"字型分布,表现为C27》C29》C28的分布特征.这些特征与剖面中其他岩性的生物标志物特征存在一定的差异,9层泥晶灰岩C21-/C21 值为0.86,轻烃优势并不明显;14层泥灰岩C21-/C21 值为0.41,具有明显的重碳优势;9层泥晶灰岩以及12层泥灰岩规则甾烷呈C29》C27》C28的特征也与油页岩层存在显著的差异.这些差异不仅反映了油页岩层与其他岩性间生物母源输入的差异,也反映了他们之间沉积环境的不同.胜利河地区油页岩的形成是综合因素控制的结果,古地理变化、海平面升降、生物群差异以及气候的变化均对该区油页岩的形成有一定的影响.  相似文献   

17.
分步瞬时热解法可以有效的用于研究干酪根(或其他相关样品)结构组分随温度变化而演变的详细特征。利用分步瞬时热解法从300℃到600℃共分七个温度点,依次对绿河页岩干酪根样品进行热模拟分析。结果表明:在300℃时,绿河页岩干酪根样品基本没有热解产物,在350℃时可检测到少量吸附烃但含量极少;400℃、450℃和500℃是热解产物十分丰富的三个温度点,主要产物是成对出现的正构烷烃和直链烯烃,同时含有一定量的异构烷烃和姥鲛-1-烯;随着热解温度升高,异构烷烃和长链烃类的相对含量逐渐减少;姥鲛-1-烯在400℃和450℃一直占据主要地位;550℃出现了长碳链烷烃(C27~C32),很有可能是绿河页岩干酪根样品中类似于绿藻等的组分经高温裂解产生的;600℃之后热解产物基本消失,说明在低温阶段干酪根裂解作用就基本完全。另外,绿河页岩干酪根样品在不同温度点的瞬时热解均给出了相应的产物组分构成,对比研究发现,其产物种类及相对含量具有逐渐变化的特征,由此将更有利于研究干酪根的热演化及其成烃机制。  相似文献   

18.
根据Leco(莱科)、岩石热解、GC(气相色谱)和GC-MS(气相色谱/质谱)等分析,开展了柴达木盆地北缘团鱼山地区中侏罗统石门沟组油页岩有机地球化学特征研究,探讨了油页岩的生烃潜力、有机母质来源、沉积环境及成矿差异。结果表明:石门沟组页岩段共发育3层油页岩(自下而上分别为油1、油2和油3),油页岩w(TOC)较高,平均值为8.16%,有机质类型为Ⅰ型和Ⅱ1型,整体生烃潜力较好,且油1、油2的生烃潜力高于油3;样品中检测出丰富的正构烷烃、类异戊二烯烷烃、甾类化合物、萜类化合物和芳香烃化合物,其中,正构烷烃呈单峰式分布,主峰碳数为nC23或nC27,Pr/Ph值为0.20~1.08,油1、油2的C27/C29值、芳基类异戊二烯烃、藿烷和藿烯质量分数明显比油3高,揭示油1、油2形成于强还原条件,有机母质来源以低等水生生物为主,油3形成于弱还原-还原条件,有机母质来源具有陆源高等植物与低等水生生物双重生源特征。结合油页岩特征的差异及古湖泊条件,说明较深的湖水并不是形成优质油页岩的必要条件,藻类、细菌等提供优质有机质的生物输入以及底层水的强还原条件更有利于优质油页岩的形成。  相似文献   

19.
在野外地质考察、岩心观察和大量测试数据分析的基础上,对我国东北地区桦甸盆地始新统桦甸组和美国犹他盆地始新统绿河组油页岩中类异戊二烯烷烃、甾类和萜类等生物标志化合物特征进行了详细的对比研究,并探讨其对两地油页岩在有机质来源及古沉积环境上的差异指示意义。结果表明:在GC谱图上,桦甸油页岩Pr/Ph为1.47~2.03,具姥鲛烷优势;而绿河油页岩Pr/Ph为0.34~0.44,具植烷优势。GC-MS分析表明:桦甸油页岩规则甾烷C27-C28-C29呈反"L"型分布,∑(C27+C28)/∑C29为0.63~2.52;绿河油页岩规则甾烷C27-C28-C29呈钝角不对称"V"型分布,∑(C27+C28)/∑C29为0.96~1.20。桦甸油页岩萜类化合物中萜烯>ββ构型霍烷>αβ构型霍烷,以C29萜烯占优势;绿河油页岩中五环三萜烷>三环萜烷>四环萜烷,并检出丰富的γ-蜡烷和β-胡萝卜烷。两地油页岩生物标志化合物特征参数的对比分析揭示:桦甸油页岩为水生生物和高等植物双重生源,但细菌及藻类等水生生物的贡献较大,主要形成于弱还原淡水沉积环境;绿河油页岩有机质来源主要为细菌和藻类等水生生物,主要形成于强还原咸水沉积环境。  相似文献   

20.
无机生油假说及其在中国的应用前景   总被引:5,自引:1,他引:4       下载免费PDF全文
袁学诚  李善芳 《中国地质》2012,39(4):843-854
无机生油假说认为,原油和天然气和近地表的生物物质没有根本联系,它们是生成于地幔内的非生物来源的碳氢化合物。因而油气不是一个不可再生资源,而是一个可再生资源。无机生油假说得到地质学、物理学和化学等三个基本学科的支持。在地质观察上,发现全球许多大油田的油气储藏与原始生物物质之间数量上有巨大落差,难于解释它们是由生物生成的。此外,有许多地区在结晶基底或变质基底内,或直接位于其上的沉积岩中发现石油。从生物生油假说来说,也是无法理解的。在化学上,早在二战期间,德国已由人工合成石油(费托合成),并生产了占德国战争中用油的9%的石油。无可争辩地说明,无机可以生成石油。根据化学(物理学)热力学理论分析确认,甲烷是唯一一种在标准温压条件(温度为298.15 K;压力为101325 Pa)下稳定的碳氢化合物,从甲烷形成正常烷属烃只有在压力>3×106kPa、温度>700°C时(相当于地下深度约100 km)才有可能。在地壳内的温压条件下由生物变质形成石油的假说,与化学热力学的基本原则相抵触。从氧化的有机分子,如碳水化合物(C6H12O6)形成较高的碳氢化合物在任何条件下都是不可能的。根据我国长期对深部构造的研究,笔者认为在中国东部及西太平洋蘑菇云岩石圈地幔发育的地区是寻找巨型无机油气田的有利地区,建议在发育蘑菇云岩石圈地幔地区开展无机油气田的勘探,并在无机油气田远景地区布置超深参数钻,以评价含油气远景。另外建议加强物探工作,尤其是研究地震勘探处理基底内三维含油气构造的技术。  相似文献   

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