珠江口盆地珠三坳陷不同沉积环境下烃源岩和原油中长链三环萜烷、二环倍半萜烷分布特征及地球化学意义

应用长链三环萜烷、二环倍半萜烷系列标志化合物,对珠江口盆地珠三坳陷文昌A、B凹陷3类重要烃源岩及相关原油的沉积环境和油源进行了研究。结果显示,3类烃源岩及相关原油中萜烷分布特征差异明显,这种差异性主要受控于烃源岩的沉积环境及有机质输入类型,表现在：①文昌B凹陷文昌组中深湖相烃源岩及相关原油中,长链三环萜烷以C₂₁为主峰碳,C₂₀—C₂₁—C₂₃呈山峰型分布,二环倍半萜烷高含8β(H)?升补身烷,含很低的重排补身烷和补身烷,揭示其有机质输入以低等水生生物为主,形成于偏还原的沉积环境;②文昌B凹陷文昌组浅湖相烃源岩及相关原油中,代表沉积环境和有机质输入类型的指标分布形态和相对含量具有双重特征,其母源兼有湖相低等水生生物及陆源高等植物输入贡献,形成于弱氧化—氧化的沉积环境;③文昌A凹陷恩平组浅湖相烃源岩及相关原油中,长链三环萜烷以C₂₀为主峰碳,峰形呈快速下降型,二环倍半萜烷高含重排补身烷,而含较低的8β(H)?升补身烷和补身烷,揭示其有机质输入以陆源高等植物为主,形成于偏氧化—氧化的沉积环境。     

准噶尔盆地三台地区原油地球化学特征(为庆祝克拉玛依油田勘探开发50周年而作)

根据准噶尔盆地东部三台地区（含北三台南段和吉木萨尔凹陷及其南缘）原油的轻烃对比星图,原油饱和烃m（Pr）/m（Ph）值、β-胡萝卜烷含量特征,三类规则甾烷的组成、妊甾烷的含量特征及其成熟度指标,三、四环萜烷和γ-蜡烷的组成特征,以及应用原油二环倍半萜的重排补身烷与8β（H）-补身烷的比值及4,4,8,8,9-五甲基＋氢化萘（PMDHN）与4,4,8,9,9-PMDHN的比值和C30藿烷及菲、甲基菲化合物等的组成可将本区原油从成因上分为3类,第1类源于中二叠统平地泉组-芦草沟组烃源岩,为本区的主体原油;第2类则源于侏罗系烃源岩;第3类源于石炭系巴塔玛依内山组烃源岩.源于二叠系的原油其油源区从东到西分别为吉木萨尔凹陷、天山山前凹陷和阜康凹陷,侏罗系原油则主要源于阜康凹陷的侏罗系烃源岩,而源于石炭系的原油其油源区在工区内部.     

双环倍半萜的分布特征及其意义

对中国南海原油样品的分析发现，双环倍半萜异常丰富。双环倍半萜分布特征显示，A区原油重排补身烷含量相对较高，C区原油补身烷含量相对较高，这一特征与塔里木盆地海相和湖相原油特征相一致，暗示南海A、C区原油可能属不同成因类型；这一特征与其原油分子组成的非均质性在油区内的变化颇具一致性。此外，绝对定量分析发现，多数原油样品双环倍半萜的含量基本上恒定于1000－2000μg/g之内；但藿烷含量的变化幅度十分明显，变化范围为179－4130μg/g，这可能预示双环倍半萜可能存在与藿烷不同的生物先质。     

准噶尔盆地三台地区原油地球化学特征

根据准噶尔盆地东部三台地区(含北三台南段和吉木萨尔凹陷及其南缘)原油的轻烃对比星图,原油饱和烃m(Pr)/m(Ph)值、β-胡萝卜烷含量特征,三类规则甾烷的组成、妊甾烷的含量特征及其成熟度指标,三、四环萜烷和γ-蜡烷的组成特征,以及应用原油二环倍半萜的重排补身烷与8β(H)-补身烷的比值及4,4,8,8,9-五甲基+氢化萘(PMDHN)与4,4,8,9,9-PMDHN的比值和C_(30)藿烷及菲、甲基菲化合物等的组成可将本区原油从成因上分为3类,第1类源于中二叠统平地泉组-芦草沟组烃源岩,为本区的主体原油;第2类则源于侏罗系烃源岩;第3类源于石炭系巴塔玛依内山组烃源岩。源于二叠系的原油其油源区从东到西分别为吉木萨尔凹陷、天山山前凹陷和阜康凹陷,侏罗系原油则主要源于阜康凹陷的侏罗系烃源岩,而源于石炭系的原油其油源区在工区内部。     

江陵凹陷西南原油分子组成非均质性及其意义

对江陵凹陷西南区原油样品的地球化学分析表明,原油具有高丰度的伽马蜡烷及较低的Pr/Ph值,预示其来源于较强还原性的盐湖相沉积。原油分子组成非均质性预示两类不同成因类型原油的存在：Ⅰ类原油主要特征为相对较高C24-四环萜烷/C26三环萜烷比值和较低三环萜烷/藿烷、补身烷/藿烷、菲/藿烷、Ts/Tm比值;Ⅱ类原油其主要特征为相对较低C24-四环萜烷/C26-三环萜烷比值和较高三环萜烷/藿烷、补身烷/藿烷、菲/藿烷、Ts/Tm比值。两类原油区域性分布特征预示研究区区至少存在两套油气富聚体系。     

典型海相油和煤成油饱和烃生物标志化合物特征研究

通过对塔里木盆地塔中隆起典型海相原油和吐哈盆地典型煤成油的饱和烃生物标志化合物系统剖析,对比分析了海相油与煤成油在饱和烃生标组合上的差异。海相油中Pr/Ph小于1,补身烷含量远高于升补身烷含量,三环萜烷含量丰富、富含C23、C24三萜化合物且C24四环萜烷含量较低,Ts/Tm较高、且伽马蜡烷含量明显高于煤成油,C27规则甾烷含量较高,而重排化合物含量较低。煤成油中Pr/Ph大于2.5,升补身烷含量高于补身烷含量,三环萜烷含量很低、富含C19、C20三萜化合物且C24四环萜烷含量较高,Ts/Tm很低、基本不含伽马蜡烷,C29规则甾烷含量相对较高;富含重排化合物。2类原油饱和烃生物标志化合物分布模式与组成特征揭示了其有机质的来源、类型、成熟度与沉积环境的差异。     

哈得4油田及其相邻地区原油萜类化合物分布特征及地球化学意义

在哈得逊及其相邻地区存在一系列化学组成较为相似的海相成熟原油。具有时代意义的生物标志物的油源对比结果表明,这些原油具有同源特点。通过定性和定量研究,发现这些原油中的萜类化合物的浓度和相对组成的差异在较大程度上与原油的成熟度有关。通过对这些原油中萜类化合物分布特征的研究,可为塔里木盆地成熟海相原油的油源研究提供一些重要的借鉴。认为在用C15-8β(H)-补身烷与C16-8β(H)-升补身烷的比值、三环萜烷与藿烷的比值等参数进行油源研究时,哈得4油田及其相邻地区原油中萜类化合物的这种分布现象应予以充分注意。     

塔北地区不同海相源岩原油的识别

原油物性和饱和烃、芳烃分析资料表明，塔里木盆地塔北隆起一带的海相原油可分为碳酸盐岩原油和泥质岩原油。前者合硫量大于0．3％，相对较高，后者则低于0．3％。碳酸盐岩原油中重排蔬烷化合物较少，Ts／Tm和C15重排二环化合物／C15补身烷的值均小于1．0，C29和C35藿烷含量较高，含硫化合物中苯并喷吩含量相对高于二苯并噻吩。泥质岩原油的这些生物标志物组成和分布特征与碳酸盐岩原油的完全不同，反映出两类原油的源岩在沉积环境和岩性方面的差异。在轮南地区，这两类原油分布呈明显的分区性。     

鄂尔多斯盆地南部镇泾地区中生界原油地球化学特征及油源分析

系统采集了鄂尔多斯盆地南部镇泾地区中生界的烃源岩、原油及油砂样品,对它们抽提物中的饱和烃馏分进行GC-MS分析,研究饱和烃生物标志化合物组成特征,探讨研究区中生界原油的来源.研究表明:根据姥植比、C30重排藿烷和8β(H)-补身烷相对含量,镇泾地区中生界烃源岩可划分为A1、A2、A3、B4类,原油可划分为Ⅰ、Ⅱ2类.Ⅰ类原油来自深湖相沉积相带的长7油页岩(A1类),Ⅱ类原油来自深湖—半深湖沉积相带的长7暗色泥岩(A2类).长7油页岩是鄂尔多斯盆地南部中生界的主力烃源岩,各油层组的原油主要来自该烃源岩.     

塔北地区没海相源岩原油的识别

原油物性和饱和烃、芳烃分析资料表明，塔里木盆地塔北降起一带的海相原油可分为碳酸盐岩原油和泥质岩原油。前者含硫量大于０．３％，相对较高，后者则低于０．３％。碳酸盐岩原油中重排萜烷化合物较少，Ｔｓ／Ｔｍ和Ｃ１５重排二环化合物／Ｃ１５补身烷的值均小于１．０，Ｃ２９和Ｃ３５藿烷含量较高，含硫化合物中苯关噻吩含量相对高于二苯并噻吩，泥质岩原油的这些生物标志物组成和分布特征与碳酸盐岩原油的完全不同，反映出两类     

Bicyclic sesquiterpenoids as maturity indicator in oils of Qingdong Sag,Bohai Bay Basin,China

Immature oils were proved to be existed in Es₄^u reservoirs based on GC-MS and carbon isotope analysis of oil sand and source rocks in Qingdong sag. By comprehensive discussion with compositional data from different sags in China, bicyclic sesquiterpenoids are related to thermal maturity and can be used in oil maturity identification. A new indicator, 4,4,8,9,9-pentamethyl decahydronaphthalene /8β(H)-homodrimane, is proposed for distinguishing immature and mature oils in the study area. It signifies mature when this ratio value is higher than 0.34, and immature when the value is lower than 0.34. The varying structures of the two compounds determines their stability.     

柴达木盆地北缘块断带原油的地化特征及油源问题

柴达木盆地北缘断层纵横交错,控制着本区的构造格局和中新生界地层的岩性和厚度,故称北缘块断带。其范围西起昆特依凹陷,东至旺尕秀地区,北界阿尔金山—祁连山山前断裂带,南邻葫芦山、埃姆尼克山一线,面积约三万平方公里(图1)。      

塔里木盆地西南部皮山北新1井白垩系油气成因

皮山北新1井位于塔里木盆地麦盖提斜坡皮山北1号背斜构造高部位,该井在白垩系获得油气,但油气源存在较大争议。原油轻烃特征表明,该井原油具有Ⅰ型母质类型来源的特征;原油饱和烃特征表明,生烃母质以泥质岩为主,但与塔河、玉北奥陶系原油有一定差异。原油二维色谱分析表明,该井原油与玉北、塔河、巴楚泥盆系原油均位于海相泥页岩的范畴;原油碳同位素特征表明,该井原油母质类型差于玉北奥陶系及巴楚巴什托石炭系原油。该井原油成熟度高于玉北奥陶系原油。通过该井白垩系油气与其周缘塔西南4套主力烃源岩生标特征的对比,认为皮山北新1井白垩系原油主要来源于塔西南海相石炭系烃源岩;天然气生源母质类型与塔西南柯克亚气田类似,有侏罗系腐殖型有机质来源天然气的贡献。皮山北新1井白垩系新层系油气成因研究将有助于拓展塔西南中新生界碎屑岩油气勘探领域。      

Preliminary Insights on the Crude Oil Maturation Effects on Asphaltene Stability and Processing

Abstract

Geochemical characterization of crude oils is one important classification and exploration tool within the oil business. One maturation parameter is the ratio of cyclic/open demetallized porphyrins (ratio DPEP types/Ethio types). Chromatographic properties of porphyrinic compounds are briefly reviewed. One high-performance liquid chromatography (HPLC) method was selected for measurement of the DPEP/Ethio parameter. This tool is suited for whole crude oils, vacuum residua, and nonvolatile fractions such as asphaltenes.

Exploratory data from heavy, medium, and light crude oils; their vacuum residua; and asphaltenes suggest a correlation between maturity [DPEP/(DPEP + Ethio) parameter] and aspects such as solid deposition and processability during upgrading operations.

Results with the studied set of samples will be discussed by considering “Earth” (time under reservoir conditions) as a reactor that steadily converts hydrocarbon mixtures, disproportioning them into two major types: I. light ends, II. molecules with a set of undesirable properties such as extended condensation, loss of alkyl appendages, higher density, higher intermolecular aggregation tendency, and high coking indexes. Examples with Venezuelan crude oils will illustrate these aspects.     

APPLICATION OF BIOMARKERS AND STABLE CARBON ISOTOPES TO ASSESS THE DEPOSITIONAL ENVIRONMENT OF SOURCE ROCKS AND THE MATURATION OF CRUDE OILS,EAST ZEIT FIELD,SOUTHERN GULF OF SUEZ,EGYPT

Four crude oil samples were collected from the producing wells EZ A-11, EZ A-1, EZ A-14 and EZ A-7 of East Zeit Field, offshore southern Gulf of Suez, Egypt. These crude oil samples represent the producing Kareem, Rudeis, Nukhul and Nubia reservoirs respectively. The crude oils were subjected to a variety of organic geochemical analyses including Gas Chromatography (GC), Gas Chromatography-Mass Spectrometry (GC-MS). In addition to stable carbon isotopes were done for the saturate and aromatic fractions and trace elements analysis. The organic geochemical results suggest the presence of two different types of oils that were originated from two different source environments. The Lower Miocene Kareem, Rudeis and Nukhul oils have a V/Ni ratios of 2, Ts/Tm ratio less than 1, Oleanane index of more than 20% and a gammacerane index of around 10%. Such results suggest that the Miocene crude oils were generated from an angiosperm-rich, Tertiary source rocks with high terrestrial input. The Nubian crude oil has a V/Ni ratio equal 3.2, Ts/Tm ratio less than 1, Oleanane index less than 20% and high gammacerane index of more than 30% suggesting a marine saline-source depositional environment of Late Cretceous or younger rich in type-II kerogen with minor terrestrial influence. The maturation parameters of the Miocene and Nubian crude oils obtained from aromatic and fraction imply marginally mature to mature oils. The Nubian crude oil however, was generated at a relatively higher maturation level than that of the Miocene oils. Also, the maturation level of the Miocene oils is in accordance with their relative stratigraphic position with the Nukhul reservoired oil being the most mature.     

APPLICATION OF BIOMARKERS AND STABLE CARBON ISOTOPES TO ASSESS THE DEPOSITIONAL ENVIRONMENT OF SOURCE ROCKS AND THE MATURATION OF CRUDE OILS, EAST ZEIT FIELD, SOUTHERN GULF OF SUEZ, EGYPT

Four crude oil samples were collected from the producing wells EZ A-11, EZ A-1, EZ A-14 and EZ A-7 of East Zeit Field, offshore southern Gulf of Suez, Egypt. These crude oil samples represent the producing Kareem, Rudeis, Nukhul and Nubia reservoirs respectively. The crude oils were subjected to a variety of organic geochemical analyses including Gas Chromatography (GC), Gas Chromatography-Mass Spectrometry (GC-MS). In addition to stable carbon isotopes were done for the saturate and aromatic fractions and trace elements analysis. The organic geochemical results suggest the presence of two different types of oils that were originated from two different source environments. The Lower Miocene Kareem, Rudeis and Nukhul oils have a V/Ni ratios of 2, Ts/Tm ratio less than 1, Oleanane index of more than 20% and a gammacerane index of around 10%. Such results suggest that the Miocene crude oils were generated from an angiosperm-rich, Tertiary source rocks with high terrestrial input. The Nubian crude oil has a V/Ni ratio equal 3.2, Ts/Tm ratio less than 1, Oleanane index less than 20% and high gammacerane index of more than 30% suggesting a marine saline-source depositional environment of Late Cretceous or younger rich in type-II kerogen with minor terrestrial influence. The maturation parameters of the Miocene and Nubian crude oils obtained from aromatic and fraction imply marginally mature to mature oils. The Nubian crude oil however, was generated at a relatively higher maturation level than that of the Miocene oils. Also, the maturation level of the Miocene oils is in accordance with their relative stratigraphic position with the Nukhul reservoired oil being the most mature.     

CB油田C3断块原油饱和烃地球化学特征

运用GC-MS分析技术系统剖析C3断块原油饱和烃的地球化学特征,认为C3断块阜一段原油与泰一段、赤山组原油为不同成因类型的原油。尽管原油正构烷烃都以nC25为主峰碳,且都呈现明显的后峰型分布,但主要烃组分比值明显不同。分析结果显示,浅部的阜一段原油成熟度高于深部的泰一段、赤山组原油,同样显示了原油成因类型的差异。     

适用于炼化一体化企业原油分类方法的探讨

传统的原油化学特性分类方法是根据原油关键馏分性质将原油划分为石蜡基、中间基和环烷基原油。实际工作中发现这种分类方法对炼油装置下游配套乙烯、重整（芳烃）装置的炼化一体化企业实用性不强,不便于企业按原油类别优化采购、存储和加工。研究发现,按原油直馏重石脑油馏分性质将原油划分为裂解料型、重整料型和过渡型原油三类更便于炼化一体化企业的实际应用。     

Catalytic Neutralization Method for Naphthenic Acid Removal in Crude Oil by Alumina Supported Ca and Ba Catalysts

The presence of naphthenic acids in crude oils has caused a major corrosion problem to the production equipment, storage and transport facilities in the petroleum industry. To overcome this problem, catalytic neutralization method will be investigated on real petroleum crude oil sample with various parameters study such as the type of basic chemical used, dosing amount, type of catalyst, catalyst calcination temperature, and catalyst ratio of basic metal and dopant. Potential catalyst was characterized by XRD, NA, and TGA-DTA for its physical properties. Cu/Ca(10:90)/Al₂O₃ catalyst with calcination temperature of 1000°C was an effective catalyst for all three types of crude oil. In the presence of catalyst, all three types of crude oil samples showed enhancement in the removal of naphthenic acid.     

石油中不同环数芳烃化合物的精细分离和制备

石油族组分的分离和制备过程是后续分子组成、同位素分析的基础。由于同分异构体多，传统技术制备的芳烃化合物组分仍然无法满足单体化合物的同位素分析要求。采用两种不同的分离方案对原油中的多环芳烃进行精细的分离和制备，其中“一步法”是直接将脱沥青质的原油样品经过一次氧化铝/硅胶层析柱，用不同体积比的石油醚/二氯甲烷混合溶剂进行洗脱；“两步法”先将原油采用常规的族组分分离方法得到芳烃馏分，再将芳烃馏分经氧化铝层析柱，用不同比例的石油醚/二氯甲烷混合溶剂进行洗脱，可得到不同环数芳烃的组分。对洗脱出来的不同组分进行色谱—质谱分析（GC-MS），与“一步法”相比，“两步法”可以更好地实现单环、双环与三环芳烃化合物的分离制备，其中，石油醚/二氯甲烷（99/1，V/V）的混合溶剂可以制备单环芳烃化合物；石油醚/二氯甲烷（9/1，V/V）混合溶剂可制备得到以双环芳烃化合物占绝对优势的组分；石油醚/二氯甲烷（8/2，V/V）混合溶剂则可制备得到三环芳烃化合物组分。