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。     

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。     

低成熟油页岩的生排烃作用实验模拟

烃源岩的成熟演化特征对评价一个区域的油气产出背景意义重大。笔者选择准噶尔南部低熟油页岩作为试验样品,分别进行无水变温、等温变水及等水变温条件下的烃源岩热模拟实验,并依据油、气、固体残渣的定性定量检测,分析烃类相态与组成变化。得到以下结果:无水变温及等水变温实验中油产率均在300 ℃时出现最高值,而且在等水变温情况下,200 ℃时的产油率比不加水情况下明显增大;在等温变水情况下,生油量在加10 mL水时最大;干气生成阶段,气态烃主要来自重烃裂解而不是高度演化的干酪根本身,400 ℃热解之后,剩余生烃率大约为5％左右;饱和烃在低温和极端高温时相对比例高,以正构烷烃为绝对优势组分;芳烃比例变化波动较大,以三环、四环芳烃为主,在400 ℃时达到最大值,在500 ℃时跌至最低值;非烃、沥青质相对比例变化与芳烃正好相反。     

Role of water in hydrocarbon generation from Type-I kerogen in Mahogany oil shale of the Green River Formation

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.     

中国典型海相富有机质页岩的生气机理

目前页岩生烃的评价体系主要停留在静态条件下,忽略了成烃的动态过程,不能正确评价页岩原始的生烃潜力.采用生烃动力学模拟实验方法,分别对一个相对低成熟的典型海相富有机质页岩及其干酪根样品开展封闭体系和半开放体系下的人工熟化,并对熟化后的两个系列样品进行黄金管生气动力学模拟实验.对裂解产物中气态烃化合物、轻烃类化合物以及碳同位素开展了定量分析,结果表明,甲烷生成过程被划分为4个阶段,即生油（小于1.0% EayR_o）、凝析油生成（1.0%~1.% EayR_o）、湿气生成（1.%~2.2% EayR_o）和干气生成阶段（大于2.2% EayR_o）;页岩中甲烷的最大产率主要来自干酪根的初次裂解（占22.7%）、可排沥青（占7.6%）和残余沥青（占19.6%）的二次裂解;经过早期排烃作用的页岩样品仍有大量的可溶沥青,在高-过成熟阶段其可以与干酪根、不可溶沥青相互作用,成为晚期主要的页岩生气母质.      

试论轻烃形成过程中过渡金属的催化作用

轻烃和天然气是由富含干酪根矿物基质上过渡金属的催化作用形成，而不是干酪根和重质烃的热催化作用所致。催化作用是通过不同碳数闭作用，碳－碳及碳－金属键的断裂作用来实现的，它在轻烃形成的几个重要转化反应中起重作用，本文围绕着过渡金属的催化机理和轻烃的催化成因等基本问题展开经，目的在于不断探讨油气成因的新理论。     

Carbon isotopes of organic matter from the upper Jurassic oil shales from the Volgian-Pechora shale province and its accumulation mechanisms

The isotopic composition of carbon from the organic matter of late Jurassic oil shales from the Volgian-Pechora shale province is studied. The existence of a dependence between C_org content in the rock and the isotopic composition of kerogen carbon is ascertained. The content of the heavy carbon isotope increases with increasing C_org. This dependence is accounted for by the progressive accumulation of isotopically heavy hydrocarbons of the initial organic matter due to sulfurization. The data on the isotopic composition of individual n-alkanes of bitumen in the rocks and the data on the absence of isotopic fractionation between thermobitumen and the residual kerogen from oil shales from the Volgian-Pechora shale province obtained by treating shale in an autoclave in the presence of water are presented first in this paper.     

Thermal depolymerization of kerogen and formation of immature oil

Two Chinese immature oil shales from the continental deposits of kerogen type I and II have been thermally treated combined with the technique of supercritical fluid extraction at 630–650 K and 15–25 MPa in a semi-continuous laboratory scale apparatus. Toluence is selected as the solvent. Up to 70–80% of the kerogen matrix can be converted to a thermal bitumen and extracted simultaneously. The chemical structural parameters from the NMR, IR, XRD, ESR and EA analyses of the kerogen and the thermal bitumen show striking resemblance in nature. It implies that the thermal bitumen is primarily a depolymerized product of the kerogen. Based on the GC/MS spectra of the aliphatic eluate of the thermal bitumen, the predominance of the odd/even ratio of the alkanes and the epimeric ratios, such as 20S(20S + 20R) of C-29 steranes and 22S/(22S + 22R) of C-32 terpanes, show that the maturity of the thermal bitumen from these oil shales is comparable to that of commercial immature oils from East China. The thermal bitumen is thought to be an intermediate product of the thermal degradation of kerogen.Since the thermal bitumen is mainly composed of asphaltenes and resins, it has a structure of gel. The gel-state bitumen may turn to sol-state readily due to its low aromaticity and polarity, or due to selective adsorption of asphaltenes by clay minerals. Then the migration potential of the bitumen is enhanced.Consequently, under favorable geological conditions, the thermal depolymerization of kerogen seems to be a probable mechanism to explain the formation of immature oils.     

Determining the Main Gas-generation Phase of Marine Organic Matters in Different Occurrence States using the Kinetic Method

This paper probes the determination of the main gas-generation phase of marine organic mattes using the kinetic method. The main gas-generation phase of marine organic matters was determined by coupling the gas generation yields and rates in geological history computed by the acquired kinetic parameters of typical marine organic matters （reservoir oil, residual bitumen, lowmaturity kerogen and residual kerogen） in both China and abroad and maturity by the EasyRo（%） method. Here, the main gas-generation phase was determined as Ro%=1.4%-2.4% for type Ⅰ kerogen, Ro%=1.5-3.0% for low-maturity type Ⅱ kerogen, Ro%=1.4-2.8% for residual kerogen, Ro%=1.5-3.2% for residual bitumen and Ro%=1.6-3.2% for reservoir oil cracking. The influences on the main gas-generation phase from the openness of the simulated system and the ＂dead line＂ of natural gas generation are also discussed. The results indicate that the openness of simulation system has a definite influence on computing the main gas-generation phase. The main gas-generation phase of type Ⅱ kerogen is Ro%=1.4-3.1% in an open system, which is earlier than that in a closed system. According to our results, the ＂dead line＂ of natural gas generation is determined as Ro=3.5 % for type Ⅰ kerogen, Ro=4.4-4.5% for type Ⅱ kerogen and Ro=4.6% for marine oil. Preliminary applications are presented taking the southwestern Tarim Basin as an example.     

四川盆地深层海相碳酸盐岩气藏成藏模式

四川盆地深层碳酸盐岩气藏主要指中三叠统雷口坡组及更老层位海相碳酸盐岩为储层形成的气藏,一般(曾)埋深在4500m之下,按类型可分为原生气藏(生气中心、储气中心和保气中心位于同一层位内)和次生气藏(生气中心、储气中心与保气中心位于不同层位)2类。原生气藏储层内含有大量沥青, 天然气主要为原油裂解气。次生气藏储层内不含沥青, 但天然气仍然主要为原油裂解气。原生气藏的成藏模式有三中心叠合模式、储气中心解体模式、三中心短距离移位模式和缺乏保气中心模式。次生气藏的成藏模式主要以天然气跨层运移为主要特征, 其气源来自于先存的天然气藏。三中心叠合模式的原油裂解气成藏效率最高,储气中心解体模式的原油裂解气成藏效率中等,三中心短距离移位模式和次生气藏形成模式的原油裂解气成藏效率较低,保气中心缺乏模式的原油裂解气成藏效率为零。因此,在勘探策略上应重视三中心叠合和储气中心解体模式形成的原生气藏的勘探,同时应关注由震旦系灯影组古气藏(储气中心)破坏而形成的下古生界次生气藏。     

Hydrocarbon-generating potential of the Eocene Thebes Formation,Gulf of Suez: 1D basin modeling as a supplementary tool for source rock evaluation

The present work provides high-resolution modeling of the thermal maturation of the Eocene Thebes Formation using a multi-1D approach. The model focuses not solely on the thermal maturity but also on timing of hydrocarbon generation (primary generation and secondary cracking), adsorption by organic matter, and expulsion. The time-lapse conceptual model was developed using well log data, geochemical analyses, and composite logs. The stratigraphic sequence of the Belayim Marine oil field was subdivided into a time series based on the tectonic framework of the Gulf of Suez. An elevated basal heat flow has been assigned throughout the rifting phases and basin evolution. The simulation developed for seven wells reveals variations in burial, thermal history, and accordingly the thermal maturity. The predicted thermal maturity ranges from immature to mature with a different tendency to generate hydrocarbons (both primary generation of oil and/or gas secondary cracking) dependent on kerogen type, basin development, and burial history. Hydrocarbon generation (oil) starts after the Messinian Time Event during the deposition of the Post-Zeit Formation. Hydrocarbon generation was related to burial rather than basin evolution for the 113-M-27, BM-23, BM-65, and BM-70 wells. Conversely, generation correlated principally to basin development particularly Messinian Time Event for the 113-M-34 well. Expulsion occurred subsequent to generation of thermogenic gas (secondary cracking of generated oil). It is not possible to investigate the relationship between the production index and thermal maturity as a consequence of expulsion that reduced the S1 values. The different levels of thermal maturity (potential, active, and effective source rock) allow for the differentiation of regions of potential hydrocarbon accumulation that were charged from the Thebes Formation.     

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。     

九十年代煤系烃源岩研究新进展

综述了９０年代煤系烃源岩研究取得新成果：未成熟－低成熟油气研究和勘探实践的成功突破了传统的干酪根热降解生烃理论,形态有机质分类体系更加完善,只有无定形体的分类仍有待进一步探讨,大量研究表明烃源岩的所有组分都有一定的生烃能力,但不同组分因其化学组成和结构不同而生烃能力相差悬殊,除了镜质体之外的其它有机组分的反射率（加沥青和动物碎屑体）和包裹体均一温度等多种方法均可用来确烃源岩成熟度,以有机岩石学研究为基础,应用组分组合概念划分的有机质类型,弥补了有机地球化学方法的局限性。     

Evaluation of the petroleum composition and quality with increasing thermal maturity as simulated by hydrous pyrolysis: A case study using a Brazilian source rock with Type I kerogen

Hydrous pyrolysis (HP) experiments were used to investigate the petroleum composition and quality of petroleum generated from a Brazilian lacustrine source rock containing Type I kerogen with increasing thermal maturity. The tested sample was of Aptian age from the Araripe Basin (NE-Brazil). The temperatures (280–360 °C) and times (12–132 h) employed in the experiments simulated petroleum generation and expulsion (i.e., oil window) prior to secondary gas generation from the cracking of oil. Results show that similar to other oil prone source rocks, kerogen initially decomposes in part to a polar rich bitumen, which decomposes in part to hydrocarbon rich oil. These two overall reactions overlap with one another and have been recognized in oil shale retorting and natural petroleum generation. During bitumen decomposition to oil, some of the bitumen is converted to pyrobitumen, which results in an increase in the apparent kerogen (i.e., insoluble carbon) content with increasing maturation.The petroleum composition and its quality (i.e., API gravity, gas/oil ratio, C₁₅₊ fractions, alkane distribution, and sulfur content) are affected by thermal maturation within the oil window. API gravity, C₁₅₊ fractions and gas/oil ratios generated by HP are similar to those of natural petroleum considered to be sourced from similar Brazilian lacustrine source rocks with Type I kerogen of Lower Cretaceous age. API gravity of the HP expelled oils shows a complex relationship with increasing thermal maturation that is most influenced by the expulsion of asphaltenes. C₁₅₊ fractions (i.e., saturates, aromatics, resins and asphaltenes) show that expelled oils and bitumen are compositionally separate organic phases with no overlap in composition. Gas/oil ratios (GOR) initially decrease from 508–131 m³/m³ during bitumen generation and remain essentially constant (81–84 m³/m³) to the end of oil generation. This constancy in GOR is different from the continuous increase through the oil window observed in anhydrous pyrolysis experiments. Alkane distributions of the HP expelled oils are similar to those of natural crude oils considered to be sourced from similar Brazilian lacustrine source rocks with Type I kerogen of Lower Cretaceous age. Isoprenoid and n-alkane ratios (i.e., pristane/n-C₁₇ and phytane/n-C₁₈) decrease with increasing thermal maturity as observed in natural crude oils. Pristane/phytane ratios remain constant with increasing thermal maturity through the oil window, with ratios being slightly higher in the expelled oils relative to those in the bitumen. Generated hydrocarbon gases are similar to natural gases associated with crude oils considered to be sourced from similar Brazilian lacustrine source rocks with Type I kerogen of Lower Cretaceous, with the exception of elevated ethane contents. The general overall agreement in composition of natural and hydrous pyrolysis petroleum of lacustrine source rocks observed in this study supports the utility of HP to better characterize petroleum systems and the effects of maturation and expulsion on petroleum composition and quality.     

Structures of micas synthesized at high pressures and temperatures

Thermal karst, exposed in mine shafts, has been significantly developed in the commercial stratum of oil shales. Geochemical investigations in this karst have for the first time established the secondary changes in the kerogen of the oil shales, namely, an anomalous content of bituminoid A + C, the presence of processes of aromatization, the significant amount of hydrocarbon compounds and humic acids, and changes in the elemental composition of the residual organic matter (in particular, an increase in the C/H ratio). The secondary changes suggest that a favorable geochemical and thermobaric environment existed in the thermal karst for intense bitumen formation. The results obtained are of interest in the study of the kerogen of oil shales as a possible parental source for oil and gas. —Authors.     

生排烃过程中正构烷烃单体碳同位素组成的变化特征及其研究意义

通过对生排烃模拟实验产物 (残留油和排出油 )中正构烷烃单体碳同位素组成的测定,揭示出生排烃过程中正构烷烃碳同位素组成的变化特征。研究表明,生烃初期,液态正构烷烃主要来自干酪根的初次裂解,它们的碳同位素组成不论是在排出油中还是在残留油中,随温度的变化都不明显,呈现较相似的分布特征;在生烃高峰期,早期形成的沥青质和非烃等组分的二次裂解以及高碳数正构烷烃可能存在的裂解,使得正构烷烃单体碳同位素组成明显富集13 C,尤其在高碳数部分呈现出较大的差异。另外,实验结果显示排烃作用对液态正烷烃单体碳同位素组成的影响不太显著。     

烃源岩生气增压定量评价模型及影响因素

Ⅲ型干酪根烃源岩生气增压定量评价是一个复杂过程, 因为Ⅲ型干酪根以生气为主的同时伴生少量的油生成, 而且在达到一定的温度条件下原油还将逐渐裂解成天然气.在考虑烃源岩生烃过程中天然气的渗漏和排出、氢指数对生烃量的影响、原油裂解成气、生烃作用产生的超压对孔隙水, 油和干酪根的压缩作用、天然气在孔隙水和石油中的溶解作用等因素的基础上建立了Ⅲ型干酪根烃源岩生烃增压定量评价模型, 并对模型参数进行敏感性分析.Ⅲ型干酪根烃源岩生气增压受到烃源岩孔隙度、成熟度、有机质丰度、天然气残留系数等多种参数的影响.有机碳含量、氢指数和天然气残留系数3个参数中以氢指数对Ⅲ型干酪根烃源岩生烃增压产生的影响最大, 天然气残留系数影响最小.天然气残留系数只要大于0.2就可以产生超压, 表明保存条件不是Ⅲ型干酪根烃源岩形成生烃增压最主要的控制因素.      

富有机质的黑色页岩和油页岩的有机岩石学特征与生、排烃意义

用近代有机岩石学与有机地球化学分析相结合的方法，对比研究了我国四川盆地等下古生界富有机质沉积的海相黑色页岩,和渤海湾盆地下第三系湖相油页岩的显微有机组成特征与热演化生烃、排烃作用的关系。观测分析结果表明:黑色页岩热演化程度很高，目前热解烃含量很低，但残余有机碳含量达1％～3％，黑色页岩中保存了早期生油阶段由无定型有机质生油作用转化而形成的微粒体有机质，和未排出的石油演变而来的残余沥青，表明其为原始生烃性能很好的烃源岩。根据黑色页岩中微粒体和残余沥青的含量，可用来了解已生—排烃量和再沉降埋深过程中古油藏储层沥青、微粒体和残余沥青再生气对古生界碳酸盐气藏的贡献。富有机质沉积的下第三系湖相油页岩热演化程度不高，游离烃（S1为0.2～1.4 mg/g）和热解烃（S2为8～44 mg/g），有机碳含量达2.4％～8％，是生油性能很好的烃源岩，油页岩中不仅存在强荧光的藻和无定型有机质，而且油页岩的纹层中广泛存在富有机质的荧光沥青，反映了有利于排烃运移的信息，表明是本区生油贡献最大的烃源岩。富有机质黑色页岩和油页岩的沉积结构构造特征、有机质的赋存形式、热演化中变化过程的对比观察结果表明:其生烃、排烃作用既有很多相似性，又有一定差别。     

压力对高硫干酪根轻烃产率的影响

采用金管－高压釜体系对江汉盆地高硫干酪根进行了热解,用氘代正构烷烃作标样,色谱－质谱定量。实验结果表明,压力增加,ｎＣ６和轻烃（ｎＣ６￣ｎＣ１４）的产率明显增加;而对ｎＣ１５和沥青的产率未发现有显著影响。     

Discovery of Early Tertiary Hydrothermal Activity and Its Significance in Oil／Gas Geology,Dougpu Depression,Henan Province,China

Data from the super-deep wells(PS10,PS14 and YS1)led to the discovery of widespread met-al-bearing hydrothermal fluids (or hot brines) related to basic magmas in the Lower Tertiary clastic sequence in the Dongpu Depression .In terms of SEM and EDAX analyses, pore-casting thin section examination of sandstone ,the composition and forming temperature of fluid inclusions ,the trace ele-ment composition of mustone and kerogen and organic geochemical analyses, it is demonstrated that the hydrothermal fluids existing in the area studied are ejecting fluids, which have a close bearing on diagenesis and sedimentation, rather than intrusive veins along the tectonic fractures.The main indicators of hydrothermal activity are:(1)abnormal alteration of kerogen;(2) high-temperature altered mineral assemblage;(30abnormal distribution of hydrocarbons;(4) specific assemblages and abnormal contents of heavy metals in mudstone and kerogen;(5) specific composi-tion of complex compounds and assemblages of fluid inclusions in sandstone;(6) periodic basaltic magma activity.Results of geological observations and laboratory simulating experiments demonstrated that the hydrothermal fluids have a close bearing on hydrocarbon generation in the Dongpu Depression. Two aspects of the effect of hydrothermal fluids are noticed:hydrothermal hydrocarbon production and strong metal catalysis in oil and gas generation.