裂谷盆地生油层中火山岩及其矿物与有机质的相互作用——油气生成的催化和加氢作用研究进展及展望

我国裂谷盆地生油层中常有火山岩发育。在研究它们共生模式的基础上,利用地球化学和模拟实验等手段探索埋藏成岩期火山矿物与有机质的相互作用。初步成果表明,一些火山矿物对有机质生烃具有催化和加氢作用,可以使生油岩在较低温度和压力条件下生成较多的油气。但是不同火山矿物对油气生成的催化加氢效果及其动力学特征、这种成因类型的油气识别方法、成藏模式等,还需深入研究。因此,本研究对于丰富油气成因理论、提供新的找油领域具有重要意义。     

中国中新生代咸化湖盆烃源岩沉积的问题及相关进展

我国东部断陷湖盆和西部坳陷湖盆第三系均有蒸发岩与烃源岩共生现象。前者水体深、咸化范围小，在氯化盐和碳酸盐沉积环境中形成了优质烃源岩，后者水体浅、咸化范围大，在氯化盐和硫酸盐沉积环境中发育了优质烃源岩，作者认为两种湖盆出现的水体分层是有机质堆积和保存的重要条件。济阳坳陷和柴达木盆地为两类咸化湖盆的典型代表，对它们的研究可以深化蒸发岩-烃源岩共生区油气地质的认识、促进勘探发展。     

裂谷盆地的火山热液活动和油气生成

我国东部裂谷盆地主力烃源岩中均不同程度地发育有玄武岩和辉长岩等基性火成岩,并且伴有规模不等的热液活动。火山热液活动会给烃源岩带来热量,促使有机质快速生烃和异常成熟。玄武岩活动期间的热液作用为烃源岩提供了大量矿物质和养料,使周围泥质岩富含碳酸盐和有机质,可以形成优质烃源岩;热液活动向烃源岩提供了大量过渡金属元素,作者的实验证明了过渡金属对有机质生烃具有强烈的催化作用,使烃源岩在较低温度下生成较多数量的油气;火成岩周围的烃源岩可以提前进入生烃门限。     

Interactions between basalts and oil source rocks in rift basins： CO2 generation

Basalts interbedded with oil source rocks are discovered frequently in rift basins of eastern China, where CO2 is found in reservoirs around or within basalts, for example in the Binnan reservoir of the Dongying Depression. In the reservoirs, CO2 with heavy carbon isotopic composition (δ13C>-10‰ PDB) is in most cases accounts for 40% of the total gas reserve, and is believed to have resulted from degassing of basaltic magma from the mantle. In their investigations of the Binnan reservoir, the authors suggested that the CO2 would result from interactions between the source rocks and basalts. As the source rocks around basalts are rich in carbonate minerals, volcanic minerals, transition metals and organic matter, during their burial history some of the transition metals were catalyzed on the thermal degradation of organic matter into hydrocarbons and on the decomposition of carbonate minerals into CO2, which was reproduced in thermal simulations of the source rocks with the transition metals (Ni and Co). This kind of CO2 accounts for 55%-85% of the total gas reserve generated in the process of thermal simulation, and its δ13C values range from -11‰- -7.2‰ PDB, which are very similar to those of CO2 found in the Binnan reservoir. The co-generation of CO2 and hydrocarbon gases makes it possible their accumulation together in one trap. In other words, if the CO2 resulted directly from degassing of basaltic magma or was derived from the mantle, it could not be accumulated with hydrocarbon gases because it came into the basin much earlier than hydrocarbon generation and much earlier than trap formation. Therefore, the source rocks around basalts generated hydrocarbons and CO2 simultaneously through catalysis of Co and Ni transition metals, which is useful for the explanation of co-accumulation of hydrocarbon gases and CO2 in rift basins in eastern China.     

中国断陷盆地主要生油岩中的火山活动及其意义

通过对断陷盆地主力生油岩中普遍存在的基碱性火山岩的分析,认为水下火山喷溢环境是优质生油岩赖以形成的主导因素。岩浆、火山的高温无机气液具有加温、加氢、催化作用,是生油岩有机质在浅埋藏的低成熟阶段形成油气的主要动力。这种沉积有机质在火山作用下形成的油气称为有机一无机混合成因的油气。重视油源岩系的火山活动研究,发展多源成烃学说,可以开拓油气勘探新领域。     

粘土矿物对有机质生烃的催化作用

烃源岩的有机质主要以有机粘土复合体的形式存在。有机质生烃是一种有机粘土化学反应。反应过程中,有机质与粘土之间存在质子和电子迁移,粘土通过对水分子的吸附和离解为有机质加氢裂解提供H+,而有机质生成的有机酸激活了粘土的催化活性,也为蒙皂石伊利石化反应创造了条件。烃源岩不同粘土矿物的选择性催化特征是影响油气组成的最重要因素。粘土的催化活性大小和发育时间是决定烃源岩生烃潜力大小的因素。由于烃源岩在蒙皂石伊利石化阶段具有最大的催化活性,而且与有机质生烃反应同步,因此富含伊$蒙混合层的烃源岩是世界含油气盆地的最有利烃源岩。不同地质时期的烃类地质储量与烃源岩膨胀性粘土的丰度有密切关系。     

湖相烃源岩中的火山—热液深源物质与油气生成耦合关系研究进展*

陆内湖相烃源岩系是中国含油气盆地广泛发育的一类组分复杂且富含有机质的细粒沉积岩。随着非常规油气资源需求量日益增加,该岩系被作为致密油或页岩油层系受到广泛关注。然而,其极细的粒度增加了精细岩石学、矿物学研究难度,使它长期被简单视为陆源沉积岩。研究发现,该岩系中发育丰富的火山喷发及热液喷流产生的深源物质,并与油气的生成和富集表现出了极强的耦合关系。因此,探索深源物质如何参与烃源岩形成并影响油气生成亟待深入研究。作者详细总结并探讨了国内外近年来关于湖相烃源岩成因以及火山—热液活动带来的深源物质与油气形成关系的现阶段新发现与认识。并结合笔者研究团队基于新疆三塘湖盆地二叠系芦草沟组烃源岩的新发现,采用精细的岩石学、矿物学方法,结合无机和有机地球化学等方法,初步开展了该耦合关系的机理研究。认为火山—热液深源物质参与了烃源岩的沉积与成岩作用,并与正常湖相沉积物共同影响着油气的形成。建议重新认识湖相烃源岩的物质组成,从而拓展陆相生油理论,同时为同类型非常规油气资源勘探开发提供理论指导。     

东营凹陷牛38井沙河街组烃源岩生排烃评价

东营凹陷牛38井沙河街组三段烃源岩从沙三下亚段向沙三中-上亚段为一从高水位深湖相向低水位前三角洲相发展的沉积旋回,该沉积环境控制从下向上发育不同类型的有机质。相应地,该段烃源岩品质从下向上变差,其中沙三中亚段上部及沙三中亚段中部烃源岩产烃能力小,沙三下亚段烃源岩整体品质好,局部存在优质烃源岩。其优劣性体现了在该段烃源岩中,Ⅰ型干酪根具有高的生产力,而Ⅲ型、Ⅱ₂型干酪根生烃潜力很低,基本为无效有机质。计算结果显示不同数据点的烃源岩单位质量原始生烃潜量可相差3个数量级,体现了烃源岩存在强烈的非均质性。有机碳的非均质性分布为其提供了物质基础,而湖盆的旋回式沉积及湖平面的波动性变化是其内在原因。同时,本文也提供一种计算生排烃量的新方法,结果表明该方法较为有效可行。     

Thermal simulation of basic volcanic fluid influence on different source rocks

Based on thermal simulation experiment, interactions between volcanic fluids and source rocks were studied. Gas generations in the dry system and fluid system under different temperatures were analyzed. The results showed that the various types of source rocks are similar in composition, containing gaseous C1-C5 hydrocarbons, H2 and CO2 whose gas yields increase with increasing temperature. The gas yield of source rocks of type I is the high- est, followed by type II, and that of source rocks of type III is the lowest, indicating that the yield of hydrocarbon gases is related to their hydrocarbon generating potential. Although the generating potential of type III is the lowest, it can still be regarded as a useful gas source when it is buried deeply enough. The basic volcanic fluid restrains the generation of gaseous hydrocarbons in different types of source rocks, but promotes the generation of inorganic gases.     

地质条件下湖相烃源岩生排烃效率与模式

烃源岩排烃研究是油气地球化学研究中最薄弱的环节,而排烃效率又是准确评价常规油气与非常规页岩油气资源的关键参数。目前对于烃源岩排烃效率的认识差异很大,尚未建立完整的各种类型有机质湖相烃源岩在地质条件下生排烃效率与模式。本文以中国渤海湾、松辽等4个大型湖相含油气盆地以及酒泉青西凹陷、泌阳凹陷等9个中小型湖相富油盆地/断陷为对象,通过15000余个湖相烃源岩样品在自然热演化过程中热解生烃潜力指数的变化研究,揭示了湖相烃源岩在地质条件下的生排烃特征,构建了湖相烃源岩在地质条件下的生排烃效率与模型。无论是大型湖相沉积盆地还是中小型断陷盆地,甚至是盐湖相沉积盆地,烃源岩生排烃特征基本一致。随着成熟度的增高,湖相烃源岩排烃效率逐渐增高,在低成熟阶段排烃效率较低,在成熟与高成熟阶段具有高或很高的排烃效率。Ⅰ型、Ⅱ型有机质类型烃源岩排烃模式相似,相对排烃效率在低成熟阶段小于45%,成熟生油高峰时达85%~90%,至生油窗下限时达90%以上;累积排烃效率在低成熟阶段小于10%,生油高峰时达50%~60%,生油窗下限时达75%~85%,主要的排烃阶段在镜质组反射率0.7%~1.2%之间,生油窗阶段生成并排出了绝大部分烃类。湖相Ⅲ型有机质烃源岩排烃效率明显低于Ⅰ、Ⅱ型有机质烃源岩,生油窗阶段累积排烃效率仅为50%左右,主要生排烃阶段在镜质组反射率0.8%~2.0%之间。控制湖相烃源岩排烃量和排烃效率的主要因素是有机质丰度、类型和成熟度,而盆地类型、断裂发育程度、烃源岩沉积环境、相邻输导层孔渗条件等因素均不影响烃源岩排烃与排烃效率。     

玛湖凹陷风城组烃源岩特征与生烃模式

基于最新油气勘探成果及烃源岩有机地化分析数据和热模拟实验结果,评价了准噶尔盆地玛湖凹陷下二叠统风城组烃源岩的生烃能力,并进一步建立其生烃模式。研究区风城组发育一套沉积环境、岩性复杂多变的碱性湖泊相烃源岩,沉积水体盐度、碱度及成岩环境等变化快,致使源岩岩性复杂多变。其残余有机质丰度不高,类型为Ⅰ—Ⅱ型,大部分处于成熟阶段,热演化进程较慢。该组三个地层段均发育中—好烃源岩,少部分为很好烃源岩。风城组碱性湖泊相源岩生烃能力、模式与正常湖相源岩基本一致,为单峰式生油高峰,但其特点为生油持续时间长、总产油率远高于产气率、转化率高,主体处于生油阶段。油气勘探实践也证实玛湖凹陷是以含油为主的油气系统,在浅层或深层均以形成油藏为主。     

东营凹陷盐湖相天然气生成的热模拟试验

东营凹陷民丰地区沙四段是典型的盐湖相沉积,也是本区重要的烃源灶和天然气产层。为了研究不同盐类物质与烃源岩在高成熟阶段的相互作用,采用高压釜封闭体系模拟了东营凹陷盐湖相烃源岩的天然气生成过程。结果表明：碳酸盐、硫酸盐、氯化盐对烃源岩热解生成天然气有强催化作用,同烃源岩热解相比,550℃时气态烃产率分别增加了35%、77%和46%。在4组热模拟气的气态烃组成及热模拟气与民丰地区天然气的轻烃组分比较中发现,上述蒸发盐类不仅改变了气态烃产物中各单组分化合物的生成路径,影响了气态烃产物的组成,而且在盐类物质参与作用下,烃源岩热解的气态烃组成与民丰地区天然气更接近。     

生烃动力学、同位素动力学方法在烃源岩研究中的应用

生烃动力学、同位素动力学常用于烃源岩评价、油气源对比研究中。生烃动力学参数结合盆地热史,可恢复烃源岩在任一时代的生烃史,对构造复杂盆地的二次生烃研究具有独特的优势。利用生烃动力学方法可以实现有机质总量的恢复,在此基础上对高—过成熟样品原始有机质丰度是否有必要恢复进行了讨论;而基于生烃动力学的油气源对比综合考虑热史、成藏期次、成藏过程等各种地质参数对烃源岩生烃的影响,是一种动态的研究方法。     

Variscan and post-Variscan lead–zinc mineralization, Rhenish Massif, Germany: evidence for sulfide precipitation via thermochemical sulfate reduction

A mechanical decrepitation device coupled with a gas chromatograph has been used to characterize the molecular composition of gaseous and liquid hydrocarbons contained in minerals. Application of this technique allows the identification of low-molecular-weight n-alkanes and some aromatic hydrocarbons in sulfides and gangue minerals from epigenetic Variscan and post-Variscan lead–zinc deposits in the Rhenish Massif, Germany. Based on the analysis of 200 samples, Variscan and post-Variscan mineralization can be distinguished by the composition of associated hydrocarbons. Variscan sulfides and gangue minerals contain high abundancies of methane. In contrast, n-alkanes in the C₂–C₉ range and aromatic hydrocarbons (benzene, toluene) are dominant in post-Variscan mineralization. The absence of high-molecular-weight hydrocarbons in ore minerals suggests highly mature gas associated with hydrothermal activity, during which hydrothermal fluids caused an increase in thermal maturation of organic matter and the generation of low-molecular-weight hydrocarbons in the adjacent organic-rich rocks. The hydrocarbon compositions contained in fluid inclusions of Variscan and post-Variscan minerals are probably governed by the maturation level of the potential source rocks. In Variscan time tectonic brines (T > 175 °C) generated predominantly methane, whereas basement brines (T < 175 °C) expelled higher-molecular-weight hydrocarbons (wet gases, condensates, aromatic hydrocarbons) from adjacent rocks during the Mesozoic event. The specific role of hydrocarbons in sulfide precipitation via thermochemical sulfate reduction is indicated by geochemical characteristics of organic matter associated with the Plombières Pb–Zn deposit, in eastern Belgium. Intense alteration phenomena were observed in near-ore kerogens, compared with unaltered kerogens far from the ore body, as well as by a very high maturity (5.40% R_o), a systematic depletion in ¹²C towards the vein-type mineralization, high atomic S/C ratios (0.49), and by low atomic H/C ratios (0.29). The data suggest that hydrothermal solutions caused a drastic increase in the thermal maturation of organic matter within the adjacent wall rock. Increased thermal maturation resulted in increased δ¹³C-values of organic carbon due to the preferential release of ¹²C. The change in the organic matter to a H-depleted and S-enriched bulk composition in association with sulfide ores strongly suggests that thermochemical sulfate reduction was responsible for organic degradation. Thus, thermochemical sulfate reduction probably triggered base metal sulfide precipitation in Variscan and post-Variscan ore deposits of the Rhenish Massif. Finally, based on data from this study and previous investigations, new genetic models are presented for both Variscan and post-Variscan mineralization in the Rhenish Massif. Received: 15 September 1999 / Accepted: 2 December 1999     

生烃动力学、同位素动力学方法在烃源岩研究中的应用

生烃动力学、同位素动力学常用于烃源岩评价、油气源对比研究中.生烃动力学参数结合盆地热史,可恢复烃源岩在任一时代的生烃史,对构造复杂盆地的二次生烃研究具有独特的优势.利用生烃动力学方法可以实现有机质总量的恢复,在此基础上对高-过成熟样品原始有机质丰度是否有必要恢复进行了讨论;而基于生烃动力学的油气源对比综合考虑热史、成藏期次、成藏过程等各种地质参数对烃源岩生烃的影响,是一种动态的研究方法.     

不同类型烃源岩排烃模式对比及差异性探究

烃源岩的排烃是准确预测含油气盆地油气资源必须涉及的一个非常重要的环节,为了得到不同有机质类型烃源岩的排烃效率、排烃机理,选取不同有机质类型烃源岩进行了黄金管模拟实验,总结了不同类型烃源岩在各演化阶段产物的变化特征与排烃效率。结果表明,烃源岩类型对总生成油与残留油中轻重烃的比例影响较大,但是对排出油中轻重烃的比例影响较低,排出油中均表现为在未熟—成熟阶段以重烃为主,在高熟—过熟阶段以轻烃为主。烃源岩的类型对生排油量的影响明显,烃源岩的类型越好,生排油量越高。Ⅰ型烃源岩的生排油量最高,Ⅲ型烃源岩最低。烃源岩类型越好,排油效率越高。Ⅲ型烃源岩排油效率低,与其生成气态烃较多、显微组分中镜质组含量较高有关。      

三塘湖盆地上二叠统芦草沟组烃源岩地球化学特征

三塘湖盆地上二叠统芦草沟组分布面积广、厚度大、有机碳含量高,具好的生烃潜力,是盆地内主力烃源岩。烃源岩样品可溶有机质中含有丰富的脂肪酸、脂肪酸酯等含羰基化合物,随着埋深增加,饱和烃和芳烃含量递增,非烃含量和有机碳则呈递减趋势,表明含羰基化合物对源岩生烃有较大的贡献。饱和烃的各项指标显示,烃源岩的沉积环境为咸化湖相还原环境,母质输入以水生生物为主,陆源物质输入较少。诸多证据表明,在沉积初期和成岩早期细菌输入较多,细菌输入有机质构成了原始有机质的一部分,细菌改造原始有机质并产生前述含羰基化合物,在热作用和微生物作用下均可成烃。     

祁连山木里地区侏罗系窑街组烃源岩生烃潜力评价

祁连山木里坳陷侏罗系窑街组煤系泥岩和煤有机质丰度、有机质类型和有机质成熟度分析结果表明, 窑街组煤系泥岩为好的烃源岩, 有机质类型为Ⅱ₁型, 处于成熟阶段, 以生油为主, 生气为辅; 煤为差等烃源岩, 有机质类型为Ⅲ型, 处于成熟阶段, 富氢基质镜质体含量高, 具有一定的生烃潜力。综合其它层位烃源岩分析结果, 认为窑街组煤系泥岩和晚三叠世尕勒得寺组湖相泥岩为祁连山木里地区天然气水合物的主要气源岩。      

济阳坳陷前古近纪烃源岩生烃潜力分析

济阳坳陷前古近系发育多套低勘探程度层系,下古生界寒武系—奥陶系、上古生界石炭系—二叠系和中生界都具有一定的生烃能力并可以提供油气资源。不同地质时期构造和沉积背景的差异形成了具有不同地球化学特征的烃源岩。本文综合地质资料、烃源岩热解和TOC分析资料、镜质体反射率资料、全岩显微组分分析资料、饱和烃和芳香烃色质资料等,系统分析了济阳坳陷前古近系烃源岩分布特征、地化特征和资源潜力。下古生界海相碳酸盐岩系烃源岩分布局限,有机质丰度较低,但类型较好,具有一定的供烃能力。上古生界煤系烃源岩分布范围广,有机质丰度较高,有机质类型相对较差,以生气为主,复杂的构造演化特征导致了这套源岩以二次生气为主。中生界发育了煤系源岩和湖相泥岩两套烃源岩,有机质类型中等,局部发育中等—好烃源岩,成熟度空间差异较大。总体来看,济阳坳陷三套前古近系烃源岩中,上古生界煤系源岩品质最佳,中生界次之,下古生界相对较差。     

The contribution of bacteria to organic matter in coal-measure source rocks

On the basis of GC–MS analysis, a suite of nine coal-measure source rocks (Ro 0.51%–0.63%) from the southern margin of Junggar basin was found to contain many biomarkers for bacterially-generated hydrocarbons: hopane, sesquiterpene, C₂₃+ monomethyl alkanes (even carbon predominance), and C₂₄+ alkyl cyclohexane. Rock–eval and microscope analysis indicate that vitrinite (especially desmocollinite and homocollinite) plays a significant role in the generation of hydrocarbons in coal-measure source rocks. Vitrinite performs this role by absorbing ultramicroscopic organic matter, generally in the form of resins or bacterial plastids. C₂₃+ monomethyl alkanes (even carbon predominance) and C₂₄+ alkyl cyclohexane series compounds are derived from bacterial metabolites of higher plants. The ultramicro organic matter adsorbed by vitrinite source rocks in the study area is probably ultramicro bacterial plastids. Because the organic matter of higher plants with low hydrogen content has been transformed into organic matter rich in hydrogen by bacteria, the hydrocarbon generation capacity of source rocks is greatly improved. In other words, in coal-measure source rocks, bacteria play an important role in hydrocarbon generation.