石油中饱合烃类的喇曼特征

本文试通过一些饱合烃类标样的喇曼分析,总结出石油中饱和烷烃组分的最大喇曼特征是在2700~2970 cm-1区域有一系列强烈的喇曼效应,有三种情况:1)直链烷烃类是以—CH3链基对称喇曼效应(约2872 cm-1)最强;2)带异构骨架链烷烃类是以—CH链基喇曼效应(约2911 cm-1)最强;3)环烷烃类是以—CH2链基对称喇曼效应(约2857 cm-1)最强。另外异构骨架在748 cm-1处有一强的喇曼效应,烷烃环基在804 cm-1处有一个强的喇曼效应。并发现不同的烃或烃混合物,若结构基团相同,喇曼谱图也相同;在混合烃组分(或烃类包裹体)的喇曼谱图中2905~2921 cm-1间喇曼峰应是—CH基团,而不能单作甲烷存在的证据。     

鄂尔多斯盆地定边地区山西组流体包裹体的拉曼光谱特征

拉曼光谱技术是对流体包裹体进行无损分析的重要手段。本文应用激光拉曼技术对鄂尔多斯盆地定边地区山西组石英矿物颗粒中流体包裹体组分特征进行分析研究,发现该区包裹体主要呈现2种拉曼光谱图:分别是代表芳烃存在的荧光型拉曼光谱图和代表饱和烃存在的饱和烃型拉曼光谱图。从所测得的2种谱图来看,该地层包裹体捕获于煤系烃源岩的生烃演化阶段,进一步分析发现在石英颗粒的Ⅰ期、Ⅱ期次生加大边中的包裹体的拉曼谱图主要显现2250 cm~(-1)±和2945 cm~(-1)±拉曼谱峰,而裂缝中的包裹体除了具有与其相同的峰值之外,在600~1500 cm~(-1)之间亦显示出多个拉曼谱峰,说明存在于这2种构造中的包裹体处于不同的煤系烃源岩演化之中,因此所测包裹体组分不完全相同。该研究测得的拉曼光谱图揭示了研究区山西组地层中流体包裹体的主要组分,并且反映了包裹体被捕获时的成烃流体组分变化特征,对最终确定当时地层的流体环境及其与煤系烃源岩生烃演化之间的关系有着重要意义。     

盘星藻烷烃生物标志物特征及其热演化试验的初步研究

本文以盘星藻作为典型样品，研究淡水水生单细胞藻类的烷烃生物标志特征及其热解生烃特征。实验结果表明，盘星藻生烃主要分成四大类：正烷烃、稀烃、无环类异戊二烯和二环萜类。ｎＣ１７在正烷烃组分中占５１．６％。检出一组Ｃ２０的二环萜类同分异构体，其含量相当于正浣烃含量的９７．１％。盘星藻热解生烃也以低碳数烃类为主，与高等植物来源的烃类相区别；甾烷Ｃ２９／（Ｃ２７＋Ｃ２８＋Ｃ２９）值为０．５左右，与海洋浮游生     

包裹体类型和成分特征在油气运移研究和油气储层评价中的应用——以赤水气田为例

包裹体类型和成分的不同,反映了油气的不同演化程度和不同运移期次。赤水地区二叠系、三叠系储层中有各种盐水包裹体和烃类包裹体。论述了不同世代胶结物中包裹体的类型特征和成分特征,及它们的划分标志。依据单个包裹体激光拉曼光谱测定数据,得出常规的包裹体中“甲烷基本浓度”,以及本次提出的甲烷/总有机组分含量比值和烷烃/总有机组分含量比值,并由此分析油气运移特征和进行储层评价。分析认为,在同一块岩样中,若存在两种以上明显的不同演化程度、不同有机组分的多种类型包裹体,则说明本区具有两次以上的油气运移。有利的油气储集层段应有较多的油气初次运移和二次运移的烃包裹体,尤其应有反映油气最终演化的有机组分标志。     

沥青包裹体的拉曼光谱特征

对石油中的沥青质组分进行了拉曼光谱分析,发现有两种不同的拉曼光谱特征的沥青质:一是具碳质拉曼特征峰的沥青质,二是无碳质拉曼特征峰的沥青质,将前者称为碳质沥青质.对储集砂岩中的深色沥青质包裹体拉曼分析并据其拉曼光谱图特征将这类包裹体分为三种类型:含碳质沥青包裹体、碳质沥青包裹体和沥青包裹体.如果烃包裹体形成后经历了地质构造应力而破裂和地热作用而发生轻组分移出,就形成了沥青包裹体;若再经地质高温变质作用而发生了碳化,就形成碳质沥青包裹体;若只经历地质高温变质作用而发生碳化,组分热解但未移出,可能会形成含碳质沥青包裹体.     

塔中4油田石炭系储层不同赋存态烃类分子和碳同位素对比研究

塔中421井和塔中402井石炭系油层2个原油样和8个油砂样连续抽提组分甾烷、萜烷分布特征和正构烷烃单体碳同位素组成具有明显的差异,具有不同的来源。塔中421井上石炭统3个油砂样自由态组分、束缚态组分和油气包裹体具有伽马蜡烷和C28甾烷相对含量高、正构烷烃单体碳同位素组成重的特征,划分为Ⅰ类原油,对比认为主要来源于寒武系-下奥陶统烃源岩。塔中421井和塔中402井上石炭统的2个油样具有伽马蜡烷和C28甾烷相对含量低、并且正构烷烃单体碳同位素组成轻的特征,划分为Ⅱ类原油,其来源尚不明确。塔中402井石炭系上、中和下统的5个油砂样各类组分具有介于Ⅰ、Ⅱ类原油之间的特征,为Ⅰ和Ⅱ类原油的混合物。5个油砂样从自由态组分、束缚态组分至油气包裹体Ⅰ类原油含量依次增高,Ⅱ类原油含量依次降低。2口井8个油砂样从自由态组分、束缚态组分至油气包裹体C23三环萜烷／（C23三环萜烷＋C30藿烷）和C21／（C21＋∑C29）甾烷比值都依次降低,反映了油气充注过程中,原油成熟度不断升高。塔中4井区储层油砂不同吸附态烃类分子与碳同位素的研究结果反映塔中4油田具有多种油气来源,经历长期油气充注过程,寒武系-下奥陶统烃源岩在地史上对该区具有成烃贡献。     

南黄海盆地含烃热液流体活动：流体包裹体证据

南黄海盆地勿南沙隆起古生界地层的地热和地球化学异常一直受到众多地质学家和地球化学家的关注。本文联用显微测温和激光拉曼光谱技术对南黄海盆地勿南沙隆起的常州(CZ)-2-1井二叠系栖霞组灰岩石英脉中的流体包裹体进行了详细研究。根据岩石学特征、室温下包裹体相态特征和成分差别,这些包裹体可以分成三大类六小类。流体包裹体拉曼光谱分析结果表明包裹体中含有甲烷和有机物,证明了该区曾经有含烃类流体活动。显微测温分析表明流体包裹体的均一温度在214℃～305℃之间,远高于该区正常沉积的盆地古地温,暗示包裹体捕获了热液流体。根据岩石学观察和测温分析结果,样品中主要存在三期流体包裹体,其均一温度和流体的甲烷浓度分别为:214℃,0.1347mol/L;265℃,0.1722mol/L;305℃,0.3370mol/L。包裹体甲烷浓度随均一温度升高呈增大的趋势。本次研究证实南黄海盆地勿南沙隆起区曾存在含烃热液流体活动,这些实验结果可以为合理解释热异常和地球化学异常提供证据。     

贵州大厂锑矿有机质与有机成矿作用

用有机地球化学方法对矿区与右江盆地有机质的分析研究表明，容矿的大厂层有机碳与锑含量相对较高；有机包裹体主要是气态烃包裹体与沥青包裹体，在气态烃包裹体中含0％～30％的液态烃，发暗黄色荧光；有机气相成分中四种烷烃甲烷、乙烷、丙烷、丁烷均有显示；从主成矿期萤石中的沥青及右江盆地再沉积火山碎屑岩中的干酪根的生物标志物测定结果来看，二者在正烷烃、类异戊二烯烷烃、萜烷与甾烷标志物特征上较为接近，表明右江盆地沉积物中的有机质与锑矿中的有机质有亲缘关系。模拟实验证明原油对锑有较强的萃取迁移能力；而有机质在锑成矿过程中主要起三方面的作用：淋滤、萃取迁移及还原沉淀。     

有机包裹体显微傅里叶红外光谱和荧光光谱测定及其意义

应用显微光度术、显微傅里叶红外光谱（Ｍｉｃｒｏ－ＦＴ．ＩＲ）结合均一温度测量,对胜利油气区下第三系沙河街组沙三段中有机包裹体进行了研究。区分出两类有机包裹体,即原生有机包裹体和次生有机包裹体。有机包裹体荧光特征和显微傅里叶红餐光谱定量研究表明：（１）原生有机包裹体中含有硫醇化合物,其烃类有机质烷基碳链较长,碳原子数约为１５－１７;次生有机包裹体中除含有硫醇外,还含有一定量的Ｈ２Ｓ,其烃类肯机质烷基     

临清坳陷德南洼陷含油气性的流体包裹体分析

应用流体包裹体观察和激光拉曼探针等微观技术对临清坳陷东北部的德南洼陷流体包裹体特征及成分、压力等物理化学条件的研究表明,研究区共有6种类型的包裹体:单相盐水包裹体、富液相包裹体、富气相包裹体、含液态CO2三相包裹体、富液态烃有机包裹体、富气态烃有机包裹体,其中富液态烃有机包裹体的均一温度为100～140°C的较多.包裹体的液相成分主要为H2O和Cl-,气相成分主要为CO2、CH4以及微量的C2H6等,包裹体成分研究结果表明在古近系和新近系中主要为未成熟-低成熟的液态烃流体活动;在古生界及部分上部层段中主要为成熟、高成熟的气态烃流体活动.根据盐水溶液包裹体的均一温度和冷冻温度计算得出研究区的流体压力为10～95 MPa,其中,在烃类流体大量排出运移时期经历过压力由突破到释放的过程;初步评价了区内的油气有利远景区.     

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。     

A preliminary evaluation model for reservoir hydrocarbon generating potential established based on dissolved hydrocarbons in oilfield water

OILFIELDWATER,WHICHEXISTSCONCOMITANTLYWITH OILORGASINSUBSURFACERESERVOIRS,ISAKINDOFIMPOR TANTCOMPONENTOFRESERVOIRFLUIDANDALSOISADRIVING FORCEANDCARRIERFORHYDROCARBONMIGRATION,ACCUMULA TIONANDHYDROCARBONRESERVOIRFORMATION.OILFIELDWA TER,HYDROCARBONANDRESER…     

不同采出程度下石油组分变化特征

利用GHM烃分析仪对水驱模拟实验过程中不同阶段的采出原油进行分析,研究其原油组成的变化规律,探索原油组成与采出程度之间的内在关系。实验表明 :原油的采出程度与采出流体PV数之间具有良好的对应关系;随着采出程度逐渐提高,原油中正构烷烃的碳数范围及主峰碳数逐渐后移,原油的轻 /重比值呈现降低趋势。实验还证明,某些在空间上呈圆柱型、具有规则支链的分子比相近碳数的直链分子更容易被驱出。该项研究对于从微观角度深入探索驱油机理、提高原油采收率具有实际意义。     

油层不同开采时期原油组分变化特征

运用有机地球化学分离、分析技术对取自塔里木盆地的东河、塔中和轮南油田不同时期开采出的原油样品进行剖析,研究其宏观组成和微观分子在时空上的变化规律。分析结果表明,原油饱 /芳比值随开采时间的推移呈下降的趋势;饱和烃与非烃 +沥青质的含量变化有很好的相关性。随着开采时间的增长,原油中正构烷烃的主峰碳数后移,原油的轻 /重组分比降低。原油碱性氮、有机酸等非烃类化合物随开采时间的推移也呈降低的趋势。这些变化与原油在驱替过程中的自然色层吸附作用机理和原油中各种组分的相互作用关系有关。该项研究对于深入探索驱油机理、预测原油润湿性和提高采收率具有重要的实际意义。     

鄂尔多斯盆地奥陶系烃源岩支链烷烃特征及其地质意义

通过对鄂尔多斯盆地奥陶系马家沟组6口井烃源岩岩芯样品饱和烃的GC /MS分析,系统论述了烃源岩中支链烷烃的鉴定方法和依据,检测到碳数分布范围为C₁₅~C₂₁的中等链长的支链烷烃,主要包括2-甲基（异构）、3-甲基（反异构）、高位取代单甲基支链烷烃、双甲基支链烷烃和无环类异戊二烯烷烃;其中异构烷烃和反异构烷烃碳数分布范围较广且短、中、长链都有分布。结合研究区的沉积特征及其他有机地球化学指标,认为鄂尔多斯盆地奥陶系马家沟组中等链长的单甲基支链烷烃来源于一些特殊细菌和藻类,其中蓝细菌为最可能直接输入母质;其次一些异养细菌对原始沉积物的改造也是中等链长支链烷烃富集的重要原因之一;长链的2-甲基异构和3-甲基反异构烷烃可能与热催化重排有很大的关系。     

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。     

高温高压条件下铁岭灰岩晶包有机质的饱和烃演化特征

对铁岭灰岩抽提除去沥青“Ａ”后的残渣进行高温高压模拟实验,模拟实验研究表明,晶包有机质的释放与温度与温度和压力有关,高压有利于晶包有机质释放。晶包有机质和干酪根主要释放出低碳数烷烃,Ｐｒ／ｎＣ１７、Ｐｈ－ｎＣ１８在热演化过程中变化不大,Ｐｒ／Ｐｈ则波动较大。     

Pyrite-hydrocarbon Interaction under Hydrothermal Conditions: an Alternative Origin of H2S and Organic Sulfur Compounds in Sedimentary Environments

Sulfate rocks and organic sulfur from sedimentary organic matter are conventionally assumed as the original sulfur sources for hydrogen sulfide(H_2S) in oil and gas reservoirs. However,a few recent experiments preliminarily indicate that the association of pyrite and hydrocarbons may also have implications for H_2S generation,in which water effects and natural controls on the evolution of pyrite sulfur into OSCs and H_2S have not been evaluated. In this study,laboratory experiments were conducted from 200 to 450° C to investigate chemical interactions between pyrite and hydrocarbons under hydrothermal conditions. Based on the experimental results,preliminary mechanism and geochemical implications were tentatively discussed. Results of the experiments showed that decomposition of pyrite produced H_2S and thiophenes at as low as 330°C in the presence of water and n-pentane. High concentrations of H_2S were generated above 450°C under closed pyrolysis conditions no matter whether there is water in the designed experiments. However,much more organic sulfur compounds(OSCs) were formed in the hydrous pyrolysis than in anhydrous pyrolysis. Generally,most of sulfur liberated from pyrite at elevated temperatures was converted to H_2S. Water was beneficial to breakdown of pyrite and to decomposition of alkanes into olefins but not essential to formation of large amounts of H_2S,given the main hydrogen source derived from hydrocarbons. In addition,cracking of pyrite in the presence of 1-octene under hydrous conditions was found to proceed at 200°C,producing thiols and alkyl sulfides. Unsaturated hydrocarbons would be more reactive intermediates involved in the breakdown of pyrite than alkanes. The geochemistry of OSCs is actually controlled by various geochemical factors such as thermal maturity and the carbon chain length of the alkanes. This study indicates that the scale of H_2S gas generated in deep buried carbonate reservoirs via interactions between pyrite and natural gas should be much smaller than that of thermochemical sulfate reduction(TSR) due to the scarcity of pyrite in carbonate reservoirs and the limited amount of long-chained hydrocarbons in natural gas. Nevertheless,in some cases,OSCs and/or low contents of H_2S found in deep buried reservoirs may be associated with the deposited pyrite-bearing rock and organic matters(hydrocarbons),which still needs further investigation.     

Characterization of Precambrian kerogens by analytical pyrolysis

A selection of Precambrian kerogens has been characterized by Curie-point pyrolysis combined with gas chromatography and gas chromatography-mass spectrometry. The resulting pyrograms can be classified into two groups. The first group of pyrograms is derived from kerogens whose pyrolysis products are dominated by alkanes, alkenes and alkadienes, whereas the second group contains pyrograms from kerogens that produce complex mixtures of branched hydrocarbons dominated by components at every third carbon number (C₉, C₁₂, C₁₅, C₁₈, C₂₁, and up to C₃₃). It is suggested that these branched hydrocarbons may remotely represent remains of isoprenoid hydrocarbons, or other branched hydrocarbons, of the original organisms.     

Abiotic formation of hydrocarbons under hydrothermal conditions: Constraints from chemical and isotope data

To understand reaction pathways and isotope systematics during mineral-catalyzed abiotic synthesis of hydrocarbons under hydrothermal conditions, experiments involving magnetite and CO₂ and H₂-bearing aqueous fluids were conducted at 400 °C and 500 bars. A robust technique for sample storage and transfer from experimental apparatus to stable isotope mass spectrometer provides a methodology for integration of both carbon and hydrogen isotope characterization of reactants and products generated during abiogenic synthesis experiments. Experiments were performed with and without pretreatment of magnetite to remove background carbon associated with the mineral catalyst. Prior to experiments, the abundance and carbon isotope composition of all carbon-bearing components were determined. Time-series samples of the fluid from all experiments indicated significant concentrations of dissolved CO and C₁-C₃ hydrocarbons and relatively large changes in dissolved CO₂ and H₂ concentrations, consistent with formation of additional hydrocarbon components beyond C₃. The existence of relatively high dissolved alkanes in the experiment involving non-pretreated magnetite in particular, suggests a complex catalytic process, likely involving reinforcing effects of mineral-derived carbon with newly synthesized hydrocarbons at the magnetite surface. Similar reactions may be important mechanisms for carbon reduction in chemically complex natural hydrothermal systems. In spite of evidence supporting abiotic hydrocarbon formation in all experiments, an “isotopic reversal” trend was not observed for ¹³C values of dissolved alkanes with increasing carbon number. This may relate to the specific mechanism of carbon reduction and hydrocarbon chain growth under hydrothermal conditions at elevated temperatures and pressures. Over time, significant ¹³C depletion in CH₄ suggests either depolymerization reactions occurring in addition to synthesis, or reactions between the C₁-C₃ hydrocarbons and carbon species absorbed on mineral surfaces and in solution.