辽河油田生物降解原油沥青质热解产物中单体化合物碳同位素组成

生物降解原同在我国分布广泛并且在重油资源中占有一定的比例。本文通过采用单体化合物碳同位素分析技术对取自辽河油田西部凹陷的重油以及它们沥青质组分的热解产物进行单体碳同位素测定,来研究原油沥青质热解产物中正构烷烃单体碳同位素的组成及其一物降解油的指示意义。研究结果表明,沥青质热解产物中正构烷烃组分的单体碳同位素组成可用于生物降解较严重的重油样品进行油／油相比,并且与原油中的正构烷烃单体碳同位素组成的对     

非烃和沥青质热模拟生烃研究

为弄清楚非烃＋沥青质热演化过程中的生烃情况，对未熟非烃＋沥青质进行了低温模拟生烃实验，实验结果表明非烃＋沥青质在低温条件下（＜250℃）生成烃类气体量很少，主要以生成液态烃为主，液态烃转化率最高可达388mg/g，所生成的液态烃表现出明显的奇碳优势，为未熟－低熟油。原始母质类型不同的非烃＋沥青质模拟产物特征有所不同。非烃＋沥青质对未熟－低熟油的生成有重要意义。     

不同密度镜质组的热解色谱特征及生烃潜力的研究

摘要：用热解色谱（Ｒｏｃｋ－Ｅｖａｌ）对２个褐煤样、３个气煤样的２８个分离组分进行了研究,揭示了不同密度镜质组组分之间生烃潜力具有较大的差异性;镜质组不仅可以作为重要的生气母质,而且还可以作为重要的生油母质。     

初论原油单体烃系列碳同位素分布特征与生油环境之间的关系

生油盆地主要分为陆相和海相环境，陆相盆地主要有淡水－微咸水、淡水和半咸水－咸水三种湖相沉积环境，其中不同沉积相中有机质类型和丰度不同，这反映在它们所形成原油的单体烷烃碳同位素分布上有区别。高等植物出现前后的海相沉积油源岩中有机质类型有着较为明显的差别，泥盆纪以前的成油母质以细菌、蓝绿藻等原核生物为主，而石炭纪以后以真核生物（包括浮游植物、浮游动物等）为主，这样它们所形成原油的单体烃类碳同位素分布各     

有限圈闭复杂沥青质稠油层钻井难点与对策

中东YD油田为海相碳酸盐岩地层,Kazh地层分布着活跃的非均质沥青质稠油,高压并含有酸性气体,为非目的层,需要钻穿并封隔该层后对下部产层进行开发。由于沥青质稠油层分布不均,孔隙压力不确定,对钻井工程造成了极大的挑战。在一期施工中,3口井由于沥青质稠油的侵入被迫工程弃井,未能实现工程目的。针对此世界性难点问题,开展了沥青质稠油侵入机理实验研究、固化剂研制、控压钻井技术应用等一系列配套工艺技术研究,提出了复杂沥青质稠油层安全钻井技术对策,现场应用取得较好的效果。     

塔里木轮南地区原油沥青质的分子结构及其初步应用:热解、甲基化-热解和RICO研究

利用瞬间热解、甲基化-热解和钌离子催化氧化(RICO)降解技术研究了塔里木盆地轮南地区原油沥青质的分子结构,并对其在石油地球化学研究中的指示意义进行了讨论.轮南地区原油沥青质分子中的取代官能团以烷基侧链为主,烷基桥次之,另外还有少量的烷基-环己烷、支链烷烃和苯系物,这些化合物可能大都以C-C键结合到缩合芳环体系上;沥青质分子中的芳环体系大多数可能是萘或菲类型的芳香结构,高度缩合的芳香结构可能较少.轮南地区不同构造带原油沥青质热解产物的一致性指示它们可能来自沉积环境相同的母源.沥青质的分子结构表明,其母源可能主要来自浮游藻类的类脂物.热解产物中较高含量的1,2,3,4-四甲基-苯和2,6-二甲基、2,6,10-三甲基烷烃类化合物的检出表明其母质可能形成于较强的还原环境.沥青质热解产物中姥鲛-1-烯的相对含量较低,RICO产物中一元脂肪酸远高于二元脂肪酸,指示该区原油具有较高的成熟度.部分脂肪酸类化合物通过酯键连接在沥青质分子中,可能反映了原油在储层中经历了生物降解等后生作用.     

干酪根化学降解产物的碳同位素组成研究

采用一系列温和的化学降解法对松辽盆地南部嫩江组烃源岩的干酪根进行连续的选择性化学降解，并对不同降解产物进行色谱—同位素比值质谱分析。研究表明碱性水解和脱硫产物以一元脂肪酸和正构烷烃为主，其中正构烷烃碳同位素分布曲线呈现一定的“负倾”（即随碳数增加呈现逐渐贫13C）趋势；一元脂肪酸以C16和C18为主，具有明显的偶碳优势，与同碳数的正构烷烃具有相似的碳同位素组成。氧化产物则以一元脂肪酸和α,ω 二元脂肪酸为主，一元脂肪酸低碳数部分呈现“负倾”趋势，高碳数部分则呈现“正倾”的趋势；α,ω 二元脂肪酸与低碳数的一元脂肪酸具有相似的分布，表明它们可能具有相同的母源。对比研究表明JL 30抽提物中正构烷烃可能存在混源的影响，其碳同位素组成是多源混合的结果。     

饱和烃经5分子筛络合前后单体烃碳同位素分析对比研究

通过对自配标准样品(正构烷烃)进行5分子筛吸附试验,测定了用5分子筛吸附法分离前后正构烷烃、异构烷烃和环烷烃碳同位素值,探讨试验前后碳同位素值的变化。尽管实验过程中样品经过85℃长时间加热回流及吸附样品的5分子筛用氢氟酸酸化处理,但实验结果经仪器检测,证明该方法对正构烷烃碳同位素值影响因素不大。本文还介绍了原油和煤可溶有机质中饱和烃络合前后的单体烃碳同位素分析方法。并在前人工作的基础上,改进采用微型索氏抽提加热回流实验装置,既提高了样品的回收率,也减少了样品中轻组分的损失。     

准噶尔盆地滴南凸起含油储集岩分子与碳同位素地球化学研究

从滴南凸起10个含油储集岩样品分步提取了自由态油气组分、束缚态油气组分和油气包裹体组分,各组分进一步做色谱、色谱-质谱和正构烷烃单体碳同位素分析。根据生物标志物组成,可将10个含油储集岩样分为两类：第一类包括D2-1和D18-12个侏罗系油砂样,第二类包括其他8个采自侏罗系、二叠系和石炭系含油储集岩样。两类样品生物标志物组成差异主要有：（1）第一类样品各类油气组分三环萜烷含量明显低于第二类样品;（2）第一类样品 C20、C21和 C23三环萜烷含量比较接近,其分布模式为 C20＆lt;C21＆gt;C23,第二类样品这3个化合物含量差异较大,且分布模式为C20＆gt;C21＆gt;C23;（3）第一类样品伽马蜡烷和β-胡萝卜烷相对含量高于第二类样品;（4）第一类样品C27甾烷含量较低而C28甾烷含量较高,第二类样品则相反。可以推断第一类样品自由态组分、束缚态组分和油气包裹体均来源于二叠系烃源岩而第二类样品各类油气组分则来源于石炭系烃源岩。第一类样品油气包裹体成熟度明显高于自由态组分和束缚态组分,表明早期充注原油的成熟度高于晚期充注的原油,总体上各类油气组分成熟度位于生油高峰阶段（Ro 0.8%~1.1%）。第二类样品从自由态组分、束缚态组分至油气包裹体成熟度依次降低,表明早期充注原油的成熟度低于晚期充注的原油,总体上各类油气组分成熟度位于高-过成熟阶段（Ro〉1.25%）。第一类样品各类油气组分正构烷烃单体碳同位素组成相对较轻,第二类样品各类油气组分正构烷烃单体碳同位素组成有一定的差异,组成较轻者与第一类样品各类油气组分接近。     

Geochemistry and genesis of heavy oil in the Erlian Basin

1Introduction StudyonheavyoilintheErlianBasin,NorthChi na,hasbeenreportedbysomescholars(DouLironget al.,1995;TangJietingetal.,1992),butthegene sisandformingmechanismofheavyoilneedtobefur therstudied.Thepapersyntheticallydiscussedthege ochemistry,genesisandinspissationseriesofheavyoil intheErlianBasinbaseduponalargenumberofsta tisticsdataonthephysicalpropertiesofdifferenttypes ofheavyoil,theGCanalysesofsaturatedandaromatic hydrocarbons,andtheGC MSanalysesofsteranesand terpanes. T…     

Hydrous pyrolysis of sediments: Composition and proportions of aromatic hydrocarbons in pyrolysates

Hydrous pyrolysis (closed vessel autoclaving in the presence of excess water) of organic-rich rocks is said to generate oils which closely resemble natural crude oils in their broad characteristics and composition. However there are only a few accounts of the proportions and compositions of hydrocarbons in hydrous pyrolysates and none of these discuss the aromatic hydrocarbon composition in detail. The present paper presents some data on the latter.Hydrous pyrolysis (3 days) of a dolomitic siltstone (Permian, Marl Slate) at 280, 300,320, 340 and 360°C produced significant amounts of oils in which the aromatic hydrocarbons were one and a half to two times as abundant as the saturated hydrocarbons.The overall composition of the aromatic hydrocarbons was similar to most crude oils; the major components isolated by our methods from natural oils and from pyrolysates were C_1–4 alkylnaphthalenes. At the lowest pyrolysis temperature (280°C) the distributions of the more minor components of the pyrolysates (e.g. alkylphenanthrenes, aromatic steroids) were also generally similar to those found in natural crudes. However, a number of components (e.g. methylanthracenes, Diels' hydrocarbon) which are not usually reported in crudes, were also detected and the relative proportions of these increased at the higher temperatures. Hydrous pyrolysis (340°C) of an organic-rich oil shale (Jurassic, Kimmeridge) and an asphaltic-material containing no minerals produced pyrolysates in which many of these unusual compounds were also present. In addition the pyrolysate of the oil-shale contained higher proportions of organic sulphur compounds. It appears that the formation of the unusual compounds is not simply a function of the type of organic matter or mineralogy but rather of the high temperatures or fast heating rates employed.     

Carbon isotopic composition of individual n-alkanes in asphaltene pyrolysates of biodegraded crude oils from the Liaohe Basin, China

Biodegraded oils are widely distributed in the Liaohe basin, China. In order to develop effective oil-source correlation tools specifically for the biodegraded oils, carbon isotopic compositions of individual n-alkanes from crude oils and their asphaltene pyrolysates have been determined using the gas chromatography–isotope ratio mass spectrometry technique. No significant fractionation in the stable carbon isotopic ratios of n-alkanes in the pyrolysates of oil asphaltenes was found for anhydrous pyrolysis carried out at temperatures below 340°C. This suggests that the stable carbon isotopic distribution of n-alkanes (particularly in the C₁₆–C₂₉ range) in the asphaltene pyrolysates can be used as a correlation tool for severely biodegraded oils from the Liaohe Basin. Comparison of the n-alkane isotopic compositions of the oils with those of asphaltene pyrolysates shows that this is a viable method for the differentiation of organic facies variation and post-generation alterations.     

Ruthenium-ion-catalyzed oxidation of asphaltenes and oil-source correlation of heavy oils from the Lunnan and Tahe oilfields in the Tarim Basin, NW China

The identification of marine source rocks in the Tarim Basin is debated vigorously. The intention of this paper is to investigate the asphahenes in heavy oils from the Lunnan and Tabe oilfields and Well TD2 with ruthenium-ions-catalyzed oxidation technique (RICO), in order to explore its role in oil-oil and oil-source correlations, The RICO products included n-alkanoic acids, α,ω-di-n-alkanoic acids, branched alkanoic acids, tricyclic terpanoic acids, hopanoic acids, gammacerane carboxylic acid , regular sterane carboxylic acids and 4-methylsterane carboxylic acids. The n-alkyl chains and biomarkers bounded on the asphaltenes were of unsusceptibility to biodegradation. The distribution and absolute concentrations of n-alkanoic acids in the RICO products of heavy oils from the Lunnan and Tabe oilfields are different from those of Well TD2. The biomarkers bounded on the asphahenes, especially steranes, have a distribution trend similar to that of the counterparts in saturates. The sterane carboxylic acids and 4-methylsterane carboxylic acids in the RICO products of heavy oils from the Lunnan and Tahe oilfields, dominated by C30 sterane and C31 4-methylsterane carboxylic acids, respectively, are significantly different from those of the heavy oils of Well TD2, whose dominating sterane and 4-methylsterane carboxylic acids are C28 sterane and C29 4-methylsterane acids, respectively. The RICO products of the asphaltenes further indicate that the Middle-Upper Ordovician may be the main source rocks for heavy oils from the Lunnan and Tabe oilfields.     

东营南坡生物降解稠油中微量元素特征及其地质意义

正石油中除了主要成分烃类外,还存在一些非烃组分,包括含氮、硫、氧化合物和微量元素(Algeo and Li Chao,2020)。随着现代检测技术的进步,原油中目前可以鉴定出约80多种微量元素,包括镧系和锕系稀土元素。这些不同的元素在原油中含量差异巨大,反映了原油在烃源岩层和输导层中地球化学行为的差异,因而可以通过原油中微量元素的差异研究其母源特征、运移特征以及次生变化特征。本文以广泛发育于东营南坡东段的生物降解稠油为研究对象,分析不同密度和粘度原油中微量元素的含量及相关参数的特征,揭示生物降解作用对原油微量元素构成的影响,并论述其地质意义。     

准噶尔盆地西北缘超覆带侏罗系油砂地球化学特征及Re-Os同位素定年

盆地边缘浅部的油气充注史研究是探讨油气流体和砂岩型铀矿关系面临的关键难题。对准噶尔盆地西北缘超覆带侏罗系油砂提取物进行饱和烃GC-MS分析、碳同位素测试及Re-Os同位素定年。结果表明,样品普遍遭受了至少5级的生物降解,部分甾烷化合物参数已不能客观反映油源特征。而萜烷抗降解能力强,其分布谱图比较相似,C20、C21、C23三环萜烷的相对丰度呈“上升型”;C23/H比值为0.75~1.34;G/H比值为0.27~0.65;以上指示了石油的母质以湖相低等水生生物输入为主,形成于半咸水、偏还原的沉积环境。样品的氯仿沥青“A”及族组分的碳同位素组成较轻且几乎一致,均低于-28‰,进一步表明该区侏罗系中的石油具有相同来源,初始来源于玛湖坳陷二叠系风城组,而与佳木河组和乌尔禾组的关系不大。油砂Re-Os同位素测年首次获得了等时线年龄为(155±51) Ma,表明西北缘侏罗系在晚侏罗世-早白垩世发生了一期大规模的油气充注,进而掩盖和保护了中、下侏罗统于中、晚侏罗世阶段形成的古层间氧化带型铀矿体,并增加了找矿难度。     

辽河油田稠油中贵金属分布和赋存状态研究

以辽河油田稠油为研究对象,通过原子吸收光谱、实沸点蒸馏等手段,研究了辽河油田稠油中Au、Ag、Pt和Pb等贵金属在不同馏分中的分布特征.结果表明,经过实沸点蒸馏后,贵金属不同沸程温度的原油馏分中含量和分布存在很大差异,Au、Ag、Pt、Pd主要集中在渣油馏分中,在沸点》508℃的渣油馏分中Au、Ag、Pt、Pd的比例分别是93.4%、76.9%、73.4%和68.0%;采用选择性萃取的方法对金在稠油中的存在形态的初步研究发现,金在稠油中主要以有机配合物和少量无机配合物形式存在.     

小太平山油砂油地球化学及生物降解特征

采用小太平山同一层位不同深度且连续的油砂样品,对油砂油的地球化学及生物降解特征进行分析。小太平山油砂油在生物降解作用下产生了丰富的25-降霍烷,常规藿烷和甾烷也发生了一系列变化。由于分子结构和稳定性不同,抗降解能力不同,C_(21)/C_(23)三环萜烷、伽马蜡烷/C_(30)藿烷、Ts/Tm、C_(30)重排藿烷/C_(30)藿烷值、αααC_(27)R/αααC_(29)R、C_(28)αααR/C_(29)αααR、C_(29)ααα20R/αββ20S、C_(29)ααα20R/αββ20R、C_(27)重排甾烷/(规则甾烷+重排甾烷)、常规藿烷异构体降解为25-降霍烷的比例,均反映出油砂油的生物降解程度随深度的增加而增大。小太平山油砂油随含水饱和度的增加降解程度增大,证实地层水有利于细菌类微生物的迁移、营养物质的传递,促进原油的生物降解及25-降霍烷的产生。