Kinetic study of hydrocarbon generation of oil asphaltene from Lunnan area, Tabei uplift

The molecular compositions and molecular carbon isotopic compositions of gas hydrocarbons produced in the hydrocarbon generation of oil asphaltene from Lunnnan area were investigated by pyrolysis of asphaltene sealed in gold tube in a limited system. The experimental results indicated that oil asphaltene from Lunnan area had relatively high generation potential of methane. However, the molecular compositions and molecular carbon isotopic compositions of gas hydrocarbons in the hydrocarbon generation of oil asphaltene exhibited different characteristics from that of gas hydrocarbons by primary cracking of kerogen and secondary cracking of oil. Based on kinetic simulation with paleo-geothermal data of oil reservoir, the methane produced by cracking of oil asphatene was characterized by relatively light carbon isotopic compositions. This result could not explain relatively heavy carbon isotopic compositions of natural gas from Lunnan area. Pyrolysis of kerogen from source rocks under very high temperature probably made remarkable contributions to natural gas from Lunnan area.     

Constraints on the origins of hydrocarbon gas from compositions of gases at their site of origin

It is widely accepted that natural gas is formed from thermal decomposition of both oil in reservoirs and, to a lesser extent, the organic matter in shales from which the oil was derived. But laboratory pyrolysis experiments on shales do not reproduce the methane-rich composition typical of most gas reservoirs, leading to suggestions that other mechanisms, such as transition-metal catalysis, may be important. The discrepancy might, however, instead arise because gas (and oil) deposits have migrated from their source rocks, so that the reservoir composition might not be representative of the composition in the source rocks where the hydrocarbons were generated. To address this question, we have analysed gas samples coproduced with oils directly from a source rock (the Bakken shales, North Dakota, USA) where the local geology has prevented significant hydrocarbon migration. The methane contents of these Bakken-shale gases are much lower than that of conventional gas reservoirs, but are consistent with that from pyrolysis experiments on these shales. Thus, because these Bakken gases form with (rather than from) oils, we argue that compositional differences between gases from source rocks and conventional gas deposits result from fractionation processes occurring after hydrocarbon expulsion from the source rock.     

论冀中地区O、C—P凝析气藏的形成条件

据凝析油轻烃组成、甲烷及其同系物碳同位素组成、天然气与源岩吸附气指纹时比、双环倍半萜组合特征及地质结构的综合分析,查明O、C—P大多数提析气藏的油气主要来源于石炭—二叠系煤系腐植型有机质,混入了部分下第三系的油气。对石炭—二叠系成烃特点的分析表明,R。=0.6%～1.3%,以成气为主,生油为辅,原始油气比一般大于1OOCm3/t。成熟期的石炭—二叠系有机质的成烃特点和具备油气富集的良好地质条件是O、C—P凝析气藏形成的基本条件。     

Groundbreaking gas source rock correlation research based on the application of a new experimental approach for adsorbed gas

Many years of experimentation have led to the development and improvement of equipment and methods used to make gas source rock correlations.By crushing samples using a ball mill and directly collecting adsorbed gases in the absence of aqueous media under high vacuum conditions,most possible interference factors,such as atmospheric pollution,crushing-induced pyrolysis,and gas collection by aqueous media are eliminated.This greatly enhances the volume percentage of hydrocarbon gas in the acquired adsorbed gases,with maxima up to more than 80%.The actual measurement of carbon isotopic series can be carried out to such an extent as to be δ13C1-δ13C5.A preliminary study using newly established equipment and methods has indicated the following.(1) The carbon isotopic composition of ethane in adsorbed gases on hydrocarbon source rocks can be used to distinguish the types of source rocks.This is consistent with results obtained by using organic geochemical parameters for source rocks,and illustrates that it is highly feasible to use the carbon isotopic composition of ethane in natural gases as a parameter for distinguishing the types of source rocks.(2) The thermal evolution degree(Ro) of hydrocarbon-source rocks calculated in terms of the carbon isotopic composition of methane in adsorbed gases on hydrocarbon source rocks agrees well with the vitrinite reflectance actually measured in the source rocks.This confirms the reliability of the relationship between the carbon isotopic composition of methane in natural gases and the thermal evolution degree determined using statistics.(3) Finally,a direct gas source correlation method for natural gases has been established,and the expression of log Ro vs.δ13C1 established in terms of actually measured δ13C1 values of methane in absorbed gases.Ro values of hydrocarbon source rocks have been established as well,thus creating favorable conditions for precise oil-and-gas source correlations in exploration areas.     

Changes in carbon dioxide during an oceanic anoxic event linked to intrusion into Gondwana coals

The marine sedimentary record exhibits evidence for episodes of enhanced organic carbon burial known as 'oceanic anoxic events' (OAEs). They are characterized by carbon-isotope excursions in marine and terrestrial reservoirs and mass extinction of marine faunas. Causal mechanisms for the enhancement of organic carbon burial during OAEs are still debated, but it is thought that such events should draw down significant quantities of atmospheric carbon dioxide. In the case of the Toarcian OAE (approximately 183 million years ago), a short-lived negative carbon-isotope excursion in oceanic and terrestrial reservoirs has been interpreted to indicate raised atmospheric carbon dioxide caused by oxidation of methane catastrophically released from either marine gas hydrates or magma-intruded organic-rich rocks. Here we test these two leading hypotheses for a negative carbon isotopic excursion marking the initiation of the Toarcian OAE using a high-resolution atmospheric carbon dioxide record obtained from fossil leaf stomatal frequency. We find that coincident with the negative carbon-isotope excursion carbon dioxide is first drawn down by 350 +/- 100 p.p.m.v. and then abruptly elevated by 1,200 +/- 400 p.p.m.v, and infer a global cooling and greenhouse warming of 2.5 +/- 0.1 degrees C and 6.5 +/- 1 degrees C, respectively. The pattern and magnitude of carbon dioxide change are difficult to reconcile with catastrophic input of isotopically light methane from hydrates as the cause of the negative isotopic signal. Our carbon dioxide record better supports a magma-intrusion hypothesis, and suggests that injection of isotopically light carbon from the release of thermogenic methane occurred owing to the intrusion of Gondwana coals by Toarcian-aged Karoo-Ferrar dolerites.     

Main controlling factors for hydrocarbon reservoir formation and petroleum distribution in Cratonic Area of Tarim Basin

The Cratonic Area of the Tarim Basin is lo-cated in the central part of the basin, developing primarilywith Cambrian marine source rocks and secondly Middle toUpper Ordovician marine and Carboniferous-Permiantransitional facies source rocks. The source rocks werematured in the changeable period and space, formingmultiple hydrocarbon generating centers during the periods.The Cratonic Area experienced multiple tectonic orogenies,forming several palaeouplifts. The matching conditionbetween effective hydrocarbon generating centers and thepalaeouplifts in various periods is the main control factor forthe formation and distribution of hydrocarbon reservoirs.The palaeouplifts have experienced multiple hydrocar-bon-filling phases, several periods of modifications and evenbreakdown. The palaeouplifts and the adjacent slopesaround the effective hydrocarbon generating center composethe most favorable places for hydrocarbon accumulation.The hydrocarbon phase is related with the evolution of thehydrocarbon generating center. In the Tarim Basin'sCratonic Area, reservoirs were mostly formed during lateHercynian. The originally formed hydrocarbon reservoirswhich are adjacent to source kitchens and in the goodpreservation condition are the most favorable prospectingtargets. Hydrocarbon is richly accumulated under theregional caprock, surrounding the faulted trends, and overand below the unconformity surfaces. Reservoirs in theCarboniferous sandstone, Ordovician karstic weatheredcrust and carbonate rock inside the buried hill compose themain intervals for hydrocarbon accumulation. Carboni-ferous and Silurian sandstone pinchout reservoirs andcarbonate lithologic reservoirs with rich fractures and poresare the main targets for further prospecting.     

Discussion of gas enrichment mechanism and natural gas origin in marine sedimentary basin, China

There are abundant natural gas resources in Chinese marine sedimentary basin. The exploration hot shots of natural gas are the Palaeozoic marine strata here in recent years, and several large scale gas fields have been discovered. Chinese Palaeozoic high-post matured and coal measure hydrocarbon source rocks are mainly prone to gas generation in the present. This research considered that gas source rocks and TSR are the key cause of gas enrichment of marine strata. High-quality argillaceous and coal measure hydrocarbon rocks are distributed widely in the Palaeozoic marine strata, which have been in highly matured phase in the present. The argillaceous source rock generally contains various sulfates that could accelerate crude oil cracking to gas for TSR occurrence, and coal measure source rock mainly generates gas, so Chinese marine basin gives priority to accumulating gas. Marine strata have not founded oil reservoirs in the Sichuan Basin and Ordos Basin, and they consist mainly of dry gas. Marine natural gases are the mixed gases of oil cracking gas and coal-formed gas in a general way, oil cracking gases contain usually some H2S and CO2. Hydrocarbon carbon isotopes are very complicated, and methane and ethane isotopic values bear apparent reversal caused by thermal evolution and mixing among different genetic types of natural gas. Coal-formed gases are the main component of Chinese marine natural gas. The Upper Permian of the Sichuan Basin and the Carboniferous-Permian of the Ordos Basin coal measure hydrocarbon source rock present large hydrocarbon generation po- tential, which are the prospecting highlight of marine natural gas hereafter. Oil cracking gas exploration will be paid much attention to in the Tarim Basin because of the lack of coal measure hydrocarbon source rock.     

Discussion of gas enrichment mechanism and natural gas origin in marine sedimentary basin,China

There are abundant natural gas resources in Chinese marine sedimentary basin. The exploration hot shots of natural gas are the Palaeozoic marine strata here in recent years, and several large scale gas fields have been discovered. Chinese Palaeozoic high-post matured and coal measure hydrocarbon source rocks are mainly prone to gas generation in the present. This research considered that gas source rocks and TSR are the key cause of gas enrichment of marine strata. High-quality argillaceous and coal measure hydrocarbon rocks are distributed widely in the Palaeozoic marine strata, which have been in highly matured phase in the present. The argillaceous source rock generally contains various sulfates that could accelerate crude oil cracking to gas for TSR occurrence, and coal measure source rock mainly generates gas, so Chinese marine basin gives priority to accumulating gas. Marine strata have not founded oil reservoirs in the Sichuan Basin and Ordos Basin, and they consist mainly of dry gas. Marine natural gases are the mixed gases of oil cracking gas and coal-formed gas in a general way, oil cracking gases contain usually some H2S and CO2. Hydrocarbon carbon isotopes are very complicated, and methane and ethane isotopic values bear apparent reversal caused by thermal evolution and mixing among different genetic types of natural gas. Coal-formed gases are the main component of Chinese marine natural gas. The Upper Permian of the Sichuan Basin and the Carboniferous-Permian of the Ordos Basin coal measure hydrocarbon source rock present large hydrocarbon generation potential, which are the prospecting highlight of marine natural gas hereafter. Oil cracking gas exploration will be paid much attention to in the Tarim Basin because of the lack of coal measure hydrocarbon source rock.     

Origin and migration of natural gases in central area of Western Sichuan Depression

The chemical and isotopic compositions of nine natural gas samples from Xiaoquan, Xinchang and Hexinchang fields in the central part of Western Sichuan Depression were measured. All of the samples consist mainly of CH, and the contents of hydrocarbons are > 99 % in volume with the gas wetness > 0.5 % . The methane 8" C, and ethane S^C; values of these gases are > - 37%c and > - 27%e respectively. The results indicate that hydrocarbons were formed via thermogenesis. The hydrocarbons in Xiaoquan field were generated from source rocks at early mature and mature stages, while the hydrocarbons in Xinchang and Hexinchang fields came from source rocks at mature and late mature stages respectively. In addition, the isotope ratios and the chemical compositions of the gases from Xinchang field varied with depth, indicating that the hydrocarbons were derived from the deeply buried and the mature source rocks of Upper Triassic age and had experienced a long distance migration.     

A hydrothermal origin for isotopically anomalous cap dolostone cements from south China

The release of methane into the atmosphere through destabilization of clathrates is a positive feedback mechanism capable of amplifying global warming trends that may have operated several times in the geological past. Such methane release is a hypothesized cause or amplifier for one of the most drastic global warming events in Earth history, the end of the Marinoan 'snowball Earth' ice age, ～635?Myr ago. A key piece of evidence supporting this hypothesis is the occurrence of exceptionally depleted carbon isotope signatures (δ(13)C(PDB) down to -48‰; ref. 8) in post-glacial cap dolostones (that is, dolostone overlying glacial deposits) from south China; these signatures have been interpreted as products of methane oxidation at the time of deposition. Here we show, on the basis of carbonate clumped isotope thermometry, (87)Sr/(86)Sr isotope ratios, trace element content and clay mineral evidence, that carbonates bearing the (13)C-depleted signatures crystallized more than 1.6?Myr after deposition of the cap dolostone. Our results indicate that highly (13)C-depleted carbonate cements grew from hydrothermal fluids and suggest that their carbon isotope signatures are a consequence of thermogenic methane oxidation at depth. This finding not only negates carbon isotope evidence for methane release during Marinoan deglaciation in south China, but also eliminates the only known occurrence of a Precambrian sedimentary carbonate with highly (13)C-depleted signatures related to methane oxidation in a seep environment. We propose that the capacity to form highly (13)C-depleted seep carbonates, through biogenic anaeorobic oxidation of methane using sulphate, was limited in the Precambrian period by low sulphate concentrations in sea water. As a consequence, although clathrate destabilization may or may not have had a role in the exit from the 'snowball' state, it would not have left extreme carbon isotope signals in cap dolostones.     

准噶尔盆地东道海子凹陷油气成因及成藏期次分析

采集东道海子凹陷的烃源岩样品和油气样品,对样品进行有机碳、热解、饱和烃色谱及碳同位素等地球化学分析。在此基础上对东道海子凹陷烃源岩进行评价,研究认为石炭系烃源岩为一套高—过成熟的有机质类型差的中等烃源岩,二叠系烃源岩为一套成熟—高成熟的有机质类型好—较好烃源岩,侏罗系烃源岩为一套成熟的有机质类型差的中等烃源岩。该区油气成因复杂,通过油气的地球化学特征分析及油气源对比分析,结果表明既有来源于二叠系烃源岩的原油和天然气,也有来源于侏罗系的原油,还有来源于石炭系的天然气。油气成因的复杂导致油气成藏期次的多样,油气的成熟度及油气包裹体研究表明,既有一期成藏的油气,也有多期成藏的油气。     

Crude-oil biodegradation via methanogenesis in subsurface petroleum reservoirs

Biodegradation of crude oil in subsurface petroleum reservoirs has adversely affected the majority of the world's oil, making recovery and refining of that oil more costly. The prevalent occurrence of biodegradation in shallow subsurface petroleum reservoirs has been attributed to aerobic bacterial hydrocarbon degradation stimulated by surface recharge of oxygen-bearing meteoric waters. This hypothesis is empirically supported by the likelihood of encountering biodegraded oils at higher levels of degradation in reservoirs near the surface. More recent findings, however, suggest that anaerobic degradation processes dominate subsurface sedimentary environments, despite slow reaction kinetics and uncertainty as to the actual degradation pathways occurring in oil reservoirs. Here we use laboratory experiments in microcosms monitoring the hydrocarbon composition of degraded oils and generated gases, together with the carbon isotopic compositions of gas and oil samples taken at wellheads and a Rayleigh isotope fractionation box model, to elucidate the probable mechanisms of hydrocarbon degradation in reservoirs. We find that crude-oil hydrocarbon degradation under methanogenic conditions in the laboratory mimics the characteristic sequential removal of compound classes seen in reservoir-degraded petroleum. The initial preferential removal of n-alkanes generates close to stoichiometric amounts of methane, principally by hydrogenotrophic methanogenesis. Our data imply a common methanogenic biodegradation mechanism in subsurface degraded oil reservoirs, resulting in consistent patterns of hydrocarbon alteration, and the common association of dry gas with severely degraded oils observed worldwide. Energy recovery from oilfields in the form of methane, based on accelerating natural methanogenic biodegradation, may offer a route to economic production of difficult-to-recover energy from oilfields.     

裂谷盆地火山活动与油气藏的形成

我国东部裂谷盆地主要生储油层系中常发育有基性浅成侵入岩、火山岩和火山碎屑岩。在火成岩发育区常见油气富集 ,并伴有非烃气藏。喷发在生油岩沉积环境中的玄武岩及其火山碎屑岩可以改变有机质富集状况 ;侵入生油层的辉绿岩等可以使局部具有特殊的油气生成能力 ;火山活动放出的二氧化碳等非烃气体可以直接形成气藏。研究发现 ,火成岩发育区的生油岩具有早熟和油气生成量特别大等特点 ;火成岩发育区一般是盆地内构造应力低值区 ,也是圈闭和油气藏集中发育区。此外 ,火成岩及相关油气藏具有储集空间发育、油气充注率高、油气保存条件好等优点。以东营凹陷等火成岩发育区为实例 ,分析并阐明了有关问题     

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。     

Multi-origin alkanes related to CO2-rich, mantle-derived fluid in Dongying Sag, Bohai Bay Basin

With the newly obtained carbon isotope data for the natural gas, a pilot study of multiple-sourced alkanes related to the mantled-derived fluid is presented. The carbon isotope values of alkanes in the Dongying Sag possess thefea tures indicating a general organic origin. However, there are two sub-populations in the isotopic data set, which reflect two specific types of origins. In gene ral, the sub-population with high δ13CCH4 values is related to the CO2-rich, mantle-derived fluid, and it is distributed in the belts where mantle-derived fluid flow and basic volcanic activities have occurred. Geological and geochemical studies demonstrate that this variation of methane carbon isotope values in the Dongying Sag is unrelated with the basin bury and thermal histories, types of source rocks, and reactions between basin fluid and rocks. Mixing of mantle-derived fluid and organic sourced hydrocarbons is probably the cause for the variation .     

东濮凹陷西南部晚古生代-早新生代烃源研究

东濮凹陷西南部有石炭系-二叠系和沙三段两套主力烃源岩,其生烃能力及对油气成藏的贡献影响着该区勘探层系和目标的评价,尤其是沙三段能否生气、气藏是否混源等存在不同的观点。应用碳同位素、稀有气体同位素、天然气组分、色谱-质谱等多种地球化学方法,进行了油、气源对比及烃源岩地球化学特征研究。研究认为,沙三段烃源岩有机质以Ⅱ₂型~Ⅲ型干酪根为主,丰度较高,为差-中等烃源岩;石炭系-二叠系烃源岩有机质以Ⅲ型干酪根为主、丰度高,为好-优质烃源岩。工区原油来自沙三段;沙三段烃源岩具有先生原油,再进入高成熟阶段生成具有重碳同位素特征的煤型气的特点,石炭系-二叠系烃源岩主要生成煤成气,两种气混合成为工区重要的天然气来源;两套烃源岩共同供烃的区带是该区最有利的勘探方向。     

神狐深水海域天然气水合物成藏的气源条件

为深入分析南海北部神狐深水海域天然气水合物形成的气源控制因素,以神狐海域天然气水合物调查区为重
点研究对象,在基础调查资料和相关钻探成果的综合研究基础上,全面探讨了神狐海域天然气水合物成藏的气源供给
条件。研究结果表明：（1）神狐海域浅层400～1 200 m 以内具备良好的适合微生物成因甲烷气体生成条件,生物气生
气潜力巨大;（2）深部古近系文昌组湖相和恩平组煤系两套成熟烃源岩,亦以生气为主,能够提供一定数量的热解气
补充之;（3）深部成熟热解气通过纵向断层或底辟通道垂向运移至浅层海底,在浅部与微生物气一起侧向运移至天然
气水合物稳定域内形成混合型天然气水合物藏。     

鄂尔多斯盆地西北部奥陶系“三元”主控成藏规律

通过对鄂尔多斯盆地西北部奥陶系烃源岩、储集层及天然气展布规律的研究,探讨其天然气成藏规律。奥陶系烃源岩主要分布在上统乌拉力克组和拉什仲组,以海相泥岩为主;储层主要发育在中统克里摩里组和桌子山组,依据岩石类型、孔隙结构,可分为岩溶孔洞型储层和白云岩晶间溶孔型储层;天然气藏的形成受烃源岩、储层和圈闭的"三元"主控,具有有效烃源岩控制天然气区域分布、优质储层控制天然气聚集带展布、有效圈闭控制气藏分布特征。鄂尔多斯盆地西北部的西侧气藏主要为油型气,东侧主要为煤型气,均为上生下储的成藏模式。     

渤深6潜山天然气成因及成藏条件

孤西断裂带深层天然气来源多,成因复杂,混源现象普遍.针对这一问题,运用天然气组分、稳定碳同位素、轻烃组成、稀有气体同位素和伴生原油生物标志物等多种指标,与邻区天然气进行对比,认为该区带中渤深6潜山下古生界天然气主要为高成熟油型气,混有部分伴生气;天然气与原油同源,主要源自渤南洼陷Es4上烃源岩,也存在Es3下烃源岩的贡献.成藏条件分析表明:气源条件充足,储盖组合良好,沟通油气源的断层和不整合面发育,生烃期晚,天然气保存有利,是该区油气富集的关键.     

确定有效烃源岩有机质丰度下限的一种新方法——以鄂尔多斯盆地陇东地区上三叠统延长组湖相泥质烃源岩为例

以鄂尔多斯盆地陇东地区三叠系上三叠统延长组长4+5、长6、长7和长9段暗色泥岩为例,利用有机碳与氯仿沥青"A"转化率、热解有机质相对生烃量(IHC=S1/w(TOC),%)的关系,建立了适合研究区的湖相有效泥质烃源岩的有机质丰度下限值.热解S1和氯仿沥青"A"含量代表烃源岩中的已生烃量,在不排烃情况下,随有机碳含量增加而增大,当其减小时则表明有烃类的排出.代表有机质相对生烃量的热解参数IHC和沥青转化率(w(A)/w(TOC),%)随有机碳含量增加而开始降低的转折部位对应的有机碳含量即为有效烃源岩的下限值,研究区的有机碳质量分数为1.1%,相应的热解S1+S2下限值为2.2 mg/g,氯仿沥青"A"质量分数下限值为0.03%,总烃质量分数下限值为150×10-6.该下限值主要适合于研究区湖相有效烃源岩的识别,不同含油气盆地不同层段的有效烃源岩有机质丰度下限值应根据相应的分析数据加以确定.