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。     

The role of sulfur in the pyrolysis of kerogen

Sulfur plays an important role in the generation and evolution of hydrocarbon from organic matter. Here, a pyrolysis experiment in closed system was performed on Maoming oil shales kerogen (Type Ⅰ), Maoming oil shales kerogen added with sulfur ether and Maoming oil shales kerogen added with sulphur. The results suggest that the existence of sulfur can result in: (i) higher yield of hydrocarbons generated from the kerogen; (ii) decrease of the temperature for the maximum generation of heavy hydrocarbons (the C15+ fraction) by 20℃; (iii) decrease of the temperature for the maximum generation of the aromatics fraction by 40℃, and (iv) acceleration of the aromatization process. The pyrolysates from kerogen added with sulfur are similar to the heating products of the sulfur-rich kerogen as reported in the literatures. It seems that the sulfur catalysis is also an important factor that can make the sulfur-rich kerogen generate low-mature oil at the earlier diagenesis stage, except for the weakness of the C-S and S-S bonds.     

“石油无机成因说”的理论与实践

对石油的无机成因理论进行了评述,其中包括地幔脱气论、中地壳与费-托合成说、板块构造与费-托合成说.沥青、原油、干酪根的Pb-Sr-Nd同位素,原油及沥青中高含量的微量元素以及原油中的有机化合物均揭示了原油无机生成的科学依据,这是中国科学家对石油地质学的重大贡献.石油的无机成因理论是可以指导油气勘探的,并以辽宁义县-北票地区、苏南地区、鄂尔多斯盆地伊盟隆起、四川松潘-甘孜褶皱带、柴达木盆地为例讨论了寻找大油气田的可能性.     

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.     

Simulation experiments for evolution of fatty acids in immature source rocks

The anhydrous, hydrous and bitumen-extrac- ted simulations were carried out for the immature source rocks from the Liaohe sag. It has been shown from the result that with increasing temperature in simulation experiments, the fatty acids content decreased at first and then increased. The decrease of fatty acids in immature rocks is presumably related to alkanes generation in immature oils, whilst the increase may be related to the fact that some additional fatty acids are generated from kerogen and the tightly bound fatty acids in kerogen are released as bound fatty acids in kerogen and unbound fatty acids in bitumen. The fact that the bitumen generated from kerogen contains fatty acids has demonstrated that some bound and tightly bound fatty acids in kerogen can be transferred into bitumen. The preferential fatty acids in the immature source rocks are found to be mono-carboxylic acids with longer chains, whilst krogen contains relatively more di-carboxylic acids. It has been found that the fatty acids in immature source rocks can be changed from that with more longer chains to that with more shorter chains when evolution extent has been increased. Based on simulation results and the fact that the majority of fatty acids in immature oils are those with longer chains, it is inferred that the contribution of fatty acids to forming alkanes in immature oils mainly takes place at the evolution stage with R₀ <0.6%. The simulation experiments have also demonstrated that H₂O could promote the generation of fatty acids with more di-carboxylic acids and delay alkanes formation from fatty acids.     

准东三台—北三台地区储层沥青和稠油特征与成因分析

根据原油、储层抽提物和烃源岩地球化学特征,对三台—北三台地区储层沥青和稠油成因进行分析,并研究沥青和稠油对勘探的影响.结果表明:该区稠油和储层沥青分布广泛,稠油主要分布在侏罗系和三叠系地层中,沥青主要分布在侏罗系头屯河组及其以上地层中;稠油和储层沥青均表现出严重生物降解的特征,且来源单一,主要来自二叠系平地泉组烃源岩;三台—北三台地区储层沥青和重质稠油主要是低—未成熟阶段的原油遭严重生物降解的结果,中质稠油主要是成熟阶段原油遭中等生物降解或散失所致;研究区源岩生烃高峰期产物并没有遭受严重破坏,具有较好勘探前景,下步勘探应以中细砂岩分布带和构造下倾部位储层为主要目标.     

Simulation experiment of immature oil genetic mechanism in lake facies of semi-salt water

The Immature calcareous shale in the south slope of Dongying sag, Jiyang depression, plays a significant role in immature oil genesis, and is sampled to make simulation experiment. The geochemical characters of the products of soluble organic matter and kerogen are researched respectively. The yields of the two components and their relations are made out. The contribution ratio between soluble organic matter and kerogen undergoing earty degradation in lake facies of semi-salt water is figured out for the first time, so the research into the genetic mechanism of immature oil is developed.     

东濮凹陷西部斜坡带混合原油地球化学特征

东濮凹陷西部斜坡带原油地球化学特征同凹陷内其他地区原油明显不同,而研究程度相对较低.系统分析了原油饱和烃、芳烃组成及生物标志物,研究结果表明:原油生油母质类型较好,以低等水生生物为主,陆源高等植物占次要地位;原油中伽玛蜡烷含量高,类异戊二烯烃呈植烷优势,表明源岩沉积环境为强还原的半咸化-咸化湖相;原油成熟度参数具有不一致性,表明原油并非是低熟油,应为混合原油,其主要来源于沙三段成熟烃源岩.     

河北省下花园地区下马岭组碳酸盐生油岩热模拟实验

对下马岭组灰岩进行了热模拟实验,对碳酸盐岩腐泥型有机质的热演化规律进行了研究,划分了其演化阶段,给出了成熟度指标和各阶段油气产率.研究表明,矿物对有机质热演化的影响,在成熟阶段主要表现为催化作用;在高过成熟阶段则主要表现为对干酪根裂解、脱氧和缩合有阻碍作用.沥青“C”的某些成熟度指标可较好地反映有机质成熟度;在缺乏镜质体时焦沥青反射率可作为有效的成熟度指标.此外还对比了岩样和干酪根的模拟结果,以及沥青“A”和“C”的差异.     

准噶尔盆地滴南地区原油地球化学特征及油源

对准噶尔盆地东道海子凹陷滴南地区的滴南1、滴南7、滴南8等井原油与烃源岩地球化学特征分析,探论该区油源关系。通过对原油的族组成、碳同位素、饱和烃色谱、甾萜烷化合物及轻烃参数、烃源岩的生物标志化合物的研究,结果表明：东道海子凹陷二叠系平地泉组烃源岩处于低成熟－成熟阶段,三环萜烷含量高,Ts＜Tm,γ蜡烷含量低,甾烷中 C27、C28、C29呈反“L”形分布。滴南地区二叠系原油和储层抽提物地球化学参数及甾萜烷特征与平地泉组烃源岩相似,具有亲缘关系。侏罗系原油具有侏罗系烃源岩来源的特征。     

Oil cracking： An important way for highly efficient generation of gas from marine source rock kitchen

The potentials of gas generation by kerogen in the late period and by crude oil cracking are closely related to the origin of natural gas in the high- to over mature marine area and their exploration perspectives. The carbon structure of kerogens, with different types and at different evolution stages, have been experimentally studied using the high magnetic field solid ^13C nuclear magnetic resonance technique in order to determine the oil and gas potential of kerogens. Results show that the contents of gas potential carbon（GPC） of types Ⅰ, Ⅱ, Ⅲ kerogens at the high- to over mature stage are very low, indicating their weak gas-generating capacity and limited gas production; however, the content of oil potential carbon（OPC） of the low mature type Ⅰ kerogen is much higher, implying that a large amount of crude oil generated during the oil-generating period will be the material for later gas generation by oil cracking. The kinetic experiment of gas generation by crude oil cracking shows that, when the temperature is about 160℃（R0=1.6%）, the crude oil will start to produce large amounts of gas; the temperature range for major gas generation of crude oil is higher than that of the kerogens, and the gas production is 2 to 4 times higher than that of kerogens. The natural gas derived from oil cracking （called oil-cracked gas） is much abundant in methyl hexamethylene, which is quite different from the natural gas produced by thermal degradation of kerogens （named kerogen degradation gas） at high- to over mature stage.     

东濮凹陷地区东营组低熟原油地球化学特征及油源分析

对东濮凹陷文留地区东营组原油的族组分、饱和烃色谱特征和生物标志化合物等资料的分析,结果表明东营组含油砂岩抽提物饱和烃一般在50%左右、非烃+芳烃为50%、沥青质一般小于5%;饱和烃同位素变化范围为-27.3‰~-28.1‰,族组分之间的碳同位素分馏效应小;饱和烃色谱特征差别较大。这主要是与原油不同深度时生物降解作用的程度有关。甾萜烷系列中C27和C29重排甾烷含量低,重排甾烷/规则甾烷的比值在0.1左右,C2920S/(20S+20R)为0.2~0.4,三环萜烷、四环萜烷含量低,Ts大于Tm,奥利烷与γ蜡烷含量高,反映了高盐度沉积环境下形成的未熟-低熟油特征。油源对比结果显示文留地区西部沙河街组第三段源岩与东营组油藏具有较好的亲源关系。     

环湾论——鄂尔多斯盆地延长组深层石油成藏规律

探讨鄂尔多斯盆地三叠系延长组湖湾区暗色泥岩生烃潜力及环湖湾区石油成藏规律。通过分析湖湾区暗色泥岩生烃指标(TOC、S1+S2、HI、氯仿沥青"A"含量、烃含量、干酪根类型及有机质成熟度)、原油成熟度,综合湖湾区分流河道砂岩发育特征及与泥岩接触关系分析,结果表明:1湖湾区暗色泥岩为好-中等烃源岩,可以成为生烃灶;2延伸入湖湾区的分流河道砂岩、湖湾砂坝砂岩为石油运移通道,石油由湖湾沿分流河道向外运移;3湖湾西侧发育砂岩上倾尖灭圈闭,湖湾内砂坝为透镜体状岩性圈闭;4由湖湾近源运移到岩性圈闭中形成侧生侧储或自生自储岩性油藏。该结果使鄂尔多斯盆地延长组的生烃区面积及石油勘探区域得到扩大。     

盐水介质中煤的早期热解生烃特征和动力学

利用高压釜反应装置，在水介质下对繁峙褐煤进行了低演化阶段的热压模拟实验，考察了碳酸钠盐水介质对热解产物生成过程的影响，探讨了产物的生成特征及动力学。盐水介质的存在，对褐煤热解生烃过程具有一定的催化作用，提高了气态产物和热解沥青的收率，而对热解沥青的进一步热解生油过程几乎没有影响。动力学计算结果表明，在１００℃的地质温度下，碳酸钠介质的存在，可使气态产物和热解沥青的生成速率提高５０％～１００％．碳酸钠碱性水介质的催化作用，可借助于溶剂效应和电子诱导效应理论进行初步的解释。     

气相色谱-质谱联用判识稠油井主产层

针对稠油的黏度高,族组成中非烃和沥青含量高,饱和烃和芳香烃含量低,全烃色谱图很难反映各油层与井口原油的差异性,应用气相色谱指纹判识稠油井的主要产油层位困难等问题,利用辽河油田某多层混采稠油井各产油层的储层岩石（储层沥青）和混采原油作样品,进行饱和烃和芳香烃色谱-质谱实验,通过星形图分析、聚类分析、因子分析等技术的分析和研究,有效地判识了该多层混采稠油井的主要产油层位,并提出了有针对性的生产调整建议,从实施情况来看,效果明显。该方法具有适用性强、投资少、周期短、准确、快速等特点,有推广应用的前景。     

油页岩注蒸汽原位开采数值模拟

注高温蒸汽是一种有效的油页岩原位加热开采方法。参考美国绿河地区某油页岩原位电加热开采项目,采用CMG油藏数值模拟软件建立油页岩原位加热开采的数值模型,将其中的电加热井改为注高温蒸汽井,求解油页岩的温度场、干酪根浓度和产油量,对比电加热和蒸汽加热的优缺点,并讨论注入蒸汽速率和加热范围这两个主要因素对油页岩原位开采的影响。结果表明:与电加热相比,注蒸汽加热时油页岩层温度更高,干酪根分解更快,页岩油产量峰值到达时间更早;随注入速率增大、加热范围减小,干酪根热解反应加快,页岩油产出结束较早。     

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.     

龙门山南段前陆冲断带内的古油气藏

通过对龙门山南段地表沥青发育特征及分布规律的研究,对比不同层位中流体充注特征,结合该地区构造演化史,证实了龙门山南段冲断带内曾经存在过古油(气)藏,重塑了古油(气)藏形成和破坏的过程。研究表明,沥青主要分布于观雾山组和灯影组次生溶孔、溶洞和裂缝中;以灯影组中沥青最为发育,侧向延伸稳定,垂向充填较厚,说明研究区曾存在过古油(气)藏。晚三叠世以前,来源于松潘-甘孜海盆的油藏流体,由西向东运移充注于现今前陆冲断带内的震旦系灯影组、泥盆系和二叠系储集空间中形成古油藏;晚三叠世盆山转换时期,古油藏随着前陆盆地的快速沉降而被深埋,油裂解成气而形成古气藏;随着冲断带向前陆盆地扩展,赋存于前陆盆地内的古气藏被破坏。     

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．     

油气分段捕获揭示震旦——寒武系天然气成藏过程

烃源岩生烃具有时间和空间上的序列性,构造活动和圈闭的形成也具有阶段性,加之富集型古油藏和分散型滞留原油产生的裂解气也会大量运移聚集,因此,油气成藏可能经历多个阶段。基于以上油气分段捕获原理"将今论古"地分析四川盆地南部威远、资阳、高石梯-磨溪3个典型构造的震旦系-寒武系天然气成藏过程与成藏规律,从而预测其他未知区块的成藏潜力。研究认为,高磨地区作为继承性古隆起,震旦系-寒武系圈闭几乎捕获了烃源岩从早期生油到晚期干酪根生气所有阶段的油气;威远、资阳震旦系-寒武系圈闭则仅捕获了部分阶段的油气,对于未知区块-泸州古隆起区来讲,其震旦系-寒武系能捕获生气高峰及其以后阶段所有的天然气,包括分散型滞留原油裂解气和晚期干酪根裂解气,如果落实好储层和圈闭,天然气勘探潜力很大。