实验室条件下微生物降解原油的地球化学特征研究

通过对胜利油田四个正常原油样品微生物作用前后的族组分及饱和烃色谱质谱分析,发现实验室条件下微生物对原油有明显的降解作用。微生物作用以后的原油族组分其饱和烃相对含量降低,饱/芳比也明显降低,而芳烃、非烃和沥青质的相对含量都不同程度的升高。通过饱和烃色谱-质谱分析,发现微生物作用以后原油正构烷烃被严重降解,姥/植(Pr/Ph)比值和∑C_21-/∑C₂₂₊比值都明显降低。微生物作用原油后能产生表面活性剂,造成了培养基表面张力的降低。     

原油中常见化合物的全二维气相色谱-飞行时间质谱分析

全二维气相色谱-飞行时间质谱分析是近年来发展起来的一项全新的复杂混合物分离分析技术,该技术在分离石油烃类化合物方面显示出比传统一维色谱-四极杆质谱分析更强的优越性。通过不同类型原油的全二维气相色谱-飞行时间质谱分析,建立生物解降原油饱和烃组分和轻质原油烃类组分(饱和烃与芳烃)的分析方法,得到了甾烷、萜烷和芳烃化合物的二维平面点阵图和三维立体图。结果表明,该方法在原油的萜类化合物和轻质原油的饱和烃与芳烃同时分离方面取得了良好的结果,许多在普通一维色谱分析中不能分离或分离效果不佳的共馏化合物得到了很好的分离。     

景谷盆地低熟油的特征及对云南第三纪盆地勘探的启示

笔者从景谷原油的基本物理性质,族组成和饱和烃特征,原油和原油单烃同位素分析,论述了景谷原油的低熟性。根据原油的甾,萜烷的地球化学特征,了原油的成熟度和其生油母质类型,并对原油芳烃主要含量的三芳甾烃,菲,萘系列化合物特征进行了探讨。通过对景谷原油的低熟性,分析了云南第三纪盆地陇川－腾冲区,保山－耿马区、大理区和东区的成烃类型和发找油气的方向。     

芳烃化合物组成及其在油气地球化学中的应用

芳烃化合物是烃源岩和原油中非常重要的有机族组分,与饱和烃一样含有丰富的地球化学信息。应用GC-MS能检测到的芳烃化合物可分为常规多环芳烃、含NSO杂环芳烃、芳香甾萜烷及脱羟基维生素E。它们的一些参数可作为母质来源、热成熟度、沉积环境和油气运移判识的有效指标,是饱和烃地球化学研究的重要补充和佐证,对油气勘探与开发有重要的实际意义,但生物降解、混源油等因素会影响这些参数的正确性。应用全二维气相色谱-飞行时间质谱仪(GC×GC-TOF)对生物降解油芳烃中的鼓包化合物UCM(unresolve dcomple xmixtures)进行探索性研究取得了一定的效果,这也将是今后芳烃研究的重要方向。     

济阳拗陷特殊生物降解油的初步研究

济阳拗陷草古100平19井奥陶系储层原油,饱和烃馏分均已损失殆尽,仅残余藿烷系列化合物;同时,芳烃馏分化合物也已损失殆尽,仅残余三芳甾烷系列化合物。上述芳烃化合物俱已损失殆尽的蚀变特征,在相关文献中的报道较为少见。原油中不受水洗作用影响的正构烷烃和不受生物降解作用影响的有机硫化合物(苯并噻吩和二苯并噻吩)均已损失殆尽,显然暗示了原油蚀变是遭受水洗作用和生物降解作用共同作用的结果。原油芳烃馏分的“UCM”鼓包幅度明显大于饱和烃馏分的“UCM”鼓包,暗示了芳烃化合物的降解速率平行甚至超过饱和烃的降解速率。原油中低分子量芳烃化合物的快速降解,暗示了油藏可能是在氧化条件下而非在还原条件下发生蚀变的。     

珠江口盆地番禺低隆起轻质原油地球化学特征及其对比研究

珠江口盆地番禺低隆起轻质原油的密度小于0.83 g/cm3,饱和烃质量分数高(71%～93%),不含沥青质等.从原油族组成、轻烃特征、碳同位素、生物标记化合物等方面综合分析了原油的地球化学特征.轻质原油的姥鲛烷/植烷峰面积比值高(6.1～7.4),碳同位素较重(-27.09‰～-26.48‰)、重排甾烷相对含量较高、重排甾烷/规则甾烷峰面积比值为0.65～0.95,C304-甲基甾烷相对含量较低,双环倍半萜烷相对含量较高,双环倍半萜烷/五环三萜烷峰面积比值为3.33～18.09.研究表明轻质原油的成熟度较高(镜质体反射率Ro＞1.0%),原油母岩的沉积环境为弱氧化条件,母质以陆源高等植物输入为主,细菌和藻类也有少量贡献;运用轻烃参数,金刚烷化合物、生物标记化合物的相对含量和碳同位素值及系列指标进行的油油和油源对比研究表明,轻质原油具有相同母源和成因,油源可能主要为珠江口盆地白云凹陷渐新统恩平组煤系烃源岩.     

渤海湾盆地渤中凹陷原油地球化学特征研究

渤海湾盆地油气资源十分丰富、类型多样。通过对渤中凹陷19个原油样品地球化学特征的系统研究,揭示了该区不同类型、不同性质原油在物理性质、化学组成、生物标志物分布与组成、正构烷烃单体烃碳同位素等方面的差异。研究表明,渤中凹陷存在凝析油、正常油和生物降解原油。凝析油具有低密度、低粘度、低含蜡、饱和烃含量高,非烃、沥青质和芳烃含量低的特征,生物降解原油则反之。凝析油和生物降解原油中的重排补身烷丰度都大于8β（H）-补身烷的丰度,C24四环萜烷丰度低。渤中凹陷原油正构烷烃单体烃碳同位素组成分为两类：一类具有较轻的碳同位素组成,其同位素值介于-2．75％～-2．95％之间;另一类的碳同位素组成则较重,一般介于-2．40％--2．75％之间。     

海拉尔盆地贝尔凹陷原油芳烃化合物组成和分布特征

通过色谱-质谱分析,对海拉尔盆地贝尔凹陷35个原油样品进行聚类分析,将之分成4类.Ⅰ类原油是贝尔凹陷原油主体,占分析样品的77%,特点足菲系列含量高,平均值为64.7%,三芳甾类化合物和三芴类化合物含量次之,分别为11.42%和11.81%.Ⅱ类原油为高三芳甾类原油,三芳甾类化合物占芳烃化合物的53.9%,是该类原油的主要成份,非系列化合物含量较低,为32.5%,萘系列含量和三芴化合物含量最低,分别为0.6%和3.54%.Ⅲ类原油为高菲系列和高萤蒽含量原油,菲系列为64%,萤蒽含量高达11%,是其它原油的16倍以上.Ⅳ类原油具有高萘、高三芴化合物和低菲系列化合物的特点,分别占原油芳烃馏分的30%、32%和26%,三芳甾类化合物含量低,占3.6%.这充分说明海拉尔箍地烃源岩沉积期间有不同的沉积环境,原油有不同的牛烃母质.Ⅱ类原油以藻类为主要生烃母质,Ⅲ类原油以高等植物为主,Ⅰ类原油介于Ⅱ类和Ⅲ类原油之间,为混合型生烃母质.Ⅳ原油沉积环境和前三类原油明显不同,为咸水强还原湖相沉积环境.     

低熟湖相泥质烃源岩中不同赋存状态可溶有机质的地球化学特征

烃源岩的矿物组成可能会对可溶有机质的赋存状态产生显著的影响,进而影响烃源岩的生排烃行为以及页岩油资源的勘探开发。本文对东营凹陷沙河街组两个低熟湖相泥质烃源岩进行了分级抽提实验,获取了烃源岩中不同赋存状态的可溶有机质,依次为:呈游离态的和以物理吸附在干酪根或矿物表面的可溶有机质(氯仿沥青"A")、与碳酸盐矿物紧密结合或被其包裹的可溶有机质(氯仿沥青"C")、与硅酸盐矿物或干酪根紧密结合的可溶有机质(氯仿沥青"E")。通过气相色谱-质谱联用仪(GC-MS)和傅里叶变换-离子回旋共振质谱(FT-ICR MS)等分析手段,研究了各种赋存状态可溶有机质族组成、饱和烃以及极性化合物的组成及分布特征。结果显示:两种烃源岩的氯仿沥青"A"都约占总可溶有机质的90%左右,且氯仿沥青"A"和氯仿沥青"E"含量可能与总有机碳含量有关。不同赋存状态可溶有机质在族组成上存在明显的差异:自氯仿沥青"A"至"C"再至"E",饱和烃和芳烃含量依次下降,而胶质和沥青质的含量依次上升,这可能与不同矿物基质对可溶有机质的选择性吸附或富集作用差异有关。FT-ICR MS分析结果显示:中性含氮化合物主要富集在氯仿沥青"A"中,而氯仿沥青"C"和"E"中的极性化合物主要为各种强极性的含氧化合物。本工作对揭示低熟湖相泥质烃源岩中可溶有机质的富集机理具有重要意义。     

塔北隆起深层海相油藏中原油及族组分碳同位素组成的纵向分布特征及其地质意义

利用MAT252同位素质谱仪分析了塔里木盆地塔北隆起深层海相油藏中原油及族组分的碳同位素组成。研究表明该区深层海相油藏中原油的全油碳同位素组成主要受生源控制,受热力作用影响较小;而在继承生源的碳同位素组成的基础上,热力作用将对原油族组分的碳同位素组成及其逆转和分馏产生重要影响。总的趋势是随着油藏埋藏深度的增大和热力作用的加强,饱和烃组分的碳同位素组成逐渐变重,而沥青质组分的碳同位素组成不断变轻,族组分碳同位素逆转程度和分馏程度有所加强,并出现饱和烃﹥芳烃﹥非烃﹥沥青质的整体逆转现象。塔北隆起深层海相原油族组分的碳同位素组成的纵向变化特征,可以反映出热力作用对原油稳定性的影响。     

北黄海盆地LV井侏罗系油砂抽提物地球化学特征

对北黄海盆地侏罗系两块含油砂岩的抽提物进行了常规的有机地球化学分析和碳同位素测试,结果表明它们具有不同的地球化学特征:埋藏较深的油砂抽提物属正常原油,饱和烃以正构烷烃为主,色谱图显示单峰型正态分布;而埋藏较浅的油砂抽提物,在饱和烃色谱图中有明显的UCM鼓包,同时含有完整的低碳数的正构烷烃、姥鲛烷和植烷,全油及族组成碳同位素分布范围广,为-24.7‰~-32.3‰,其中,全油及沥青质碳同位素偏重,饱和烃和芳烃碳同位素轻,反映出遭受了强烈的生物降解作用。与成熟度相关的生物标志物参数显示,原油已进入成熟—高成熟阶段。生物标志物和碳同位素组成表明,母质是在水体较浅的湖相环境下沉积的,受陆源高等植物和低等水生藻类的双源控制。综合判断,研究区存在两期油气充注。     

Fluorescence micro-spectrometry of synthetic and natural hydrocarbon fluid inclusions: crude oil chemistry,density and application to petroleum migration

The fluorescence spectra of crude oils, synthesized as hydrocarbon fluid inclusions (hcfi) in NaCI crystals, have been recorded and correlated with crude oil chemical analysis. The crude oils represent a wide range in total hydrocarbons, saturate and aromatic fractions, and resin-asphaltene concentration. The fluorescence properties (Lambda max and Q) of the hydrocarbon fluid inclusions display a systematic red shift to longer wavelengths from 440 nm to 595 nm with increasing aromatic content and increasing concentration of NSO-bearing compounds. A positive correlation also exists between Lmax-Q and the thermal maturity parameters nC17/pristane and nC₁₈/phytane. First order linear regression equations provide a method for constraining the chemical composition of natural hydrocarbon fluid inclusions. Lmax and Q correlate positively with oil density (°API), providing for an indirect method of estimating the API of a natural hydrocarbon fluid inclusion assemblage. Fluorescence spectra of non-biodegraded crude oils from the Upper Devonian Birdbear Formation, Saskatchewan, Canada, have been correlated with regionally widespread hcfi within carbonate carrier beds and reservoir rocks of the same formation. The two most dominant types of hcfi spectra match well with the fluorescence spectra from crude oils within the Birdbear Formation. A third, less common population of very-blue fluorescing hcfi (Lmax=415440 nm, Q ≤ 0.10) also occur within fractures, intercrystalfne cements or in fossil overgrowths. The Lmax-Q-API-chemical correlations establised for the synthetic hcfi suggests that the °API of these inclusions is probably > 45° and the saturate/aromatic ratio ranges from 3.2 to 5.1. Spectra from hcfi within quartz overgrowths and cements, fractures and carbonate cements from sandstone reservoirs in the Jeanne d'Arc Basin offshore Newfoundland, compared with fluorescence spectra of crude oils suggests that some of the reservoirs may have been filled by a relatively low maturity oil and then a higher maturity oil. This is reflected in the intermediate spectra of the crude oils relative to the spectra of two separate hcfi events. Other reservoirs appear to have been charged with a relatively high gravity oil which was later biodegraded. This is marked by a blue region spectra for the hcfi compared with a red-shifted spectra for the crude oil (°API = 19). The API of the original unaltered oil which charged the reservoir is estimated to be between 32 and 38° using the Lmax-Q-API relationship established for the synthetic hcfi.     

柴达木盆地西部第三系咸水湖相原油地球化学特征

在系统分析柴达木盆地西部各油田40余个原油样品碳同位素和饱和烃、芳烃组成的基础上,全面剖析了该地区第三系湖相原油的地球化学特征.研究结果表明,这些原油具有特殊的碳同位素组成和异常的生物标志物分布.其全油碳同位素偏重(-26‰～-24‰);正构烷烃系列单体烃碳同位素分布曲线呈水平状,表现出类同于海相有机质的碳同位素组成特征.它们的生物标志物中正烷烃系列兼具奇碳和偶碳优势双重碳数分布模式;呈强植烷优势,Pr/Ph值大多<0.6;伽玛蜡烷普遍异常丰富,C35藿烷含量高,表征高盐、厌氧的咸水湖相沉积环境性质.芳烃组份以萘、菲系列为主,而二苯并噻吩等含硫有机化合物相对含量较低,反映该地区咸水湖相原油源岩沉积相的特殊性.柴西各油田原油地球化学参数在区域上呈规律性变化趋势,与其源岩沉积相的时空变迁相一致.     

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。     

珠江口盆地白云凹陷珠江组、珠海组烃源岩倾油倾气性判识

LW3-1-1井是珠江口盆地白云凹陷白云深水区钻探的一口深水井,在4个目的层钻遇工业气流。该井在中新统珠江组和渐新统珠海组钻遇大套泥岩。烃源岩地球化学分析表明中新统珠江组有机质丰度低,有机质类型为Ⅲ型,Ro0.5%,IH200mg/g,氯仿沥青"A"GC-MS分析结果在TIC上显示的几乎全是芳烃系列化合物,正构烷烃不可见,表征中新统珠江组烃源岩倾气。渐新统珠海组有机质丰度中等,有机质类型为Ⅲ—ⅡB型,Ro介于0.44%～0.54%间,IH主要为200～300mg/g,氯仿沥青"A"GC-MS分析结果在TIC上芳烃化合物和正构烷烃并存,表征珠海组是以倾气为主,但也有部分层段是倾油气的。珠海组在分子组成上较珠江组明显富含正构烷烃,表明珠海组的倾油气性比珠江组强。     

Effect of water washing on hydrocarbon compositions of petroleum sandstone reservoir rocks in Tarim Basin, NW China

Gross compositions and distribution of saturated and aromatic hydrocarbons in Carboniferous sandstone reservoire rocks in oil and water zones for Tzhong-10 well of the Zhongyang Uplift in the Tarim Basin were studied in dteail by means of Rock-Eval Pyrolysis,thin-chromatograph-flame ionization detection(TLC-FID),gas chromatography,gas chromatography-mass spectrometry.The results suggest that the gross composition of reservoir hydrocarbons between the oil zone and the water zone show significant differences,Water wahing has a dramatic effect on saturated hydrocarbon blomarkers,especially drimane series compounds,Drimane series compounds in the water zone have been depleted completely.However,the contents of tricyclic iterpanes and pentacyclic triterpanes tend to decrease slightly,but the water-zone reservoir hydrocarbons contian a large amount of gammacerane.This suggests that gammacerane be more resistant to water washing than diterpanes and homohopanes.The contents of pregnane,homopregrane,diasteranes relastively decrease as a result of water washing.Water washing has a noticeable effect on polycyclic aromatic hydrocarbon compounds,especially aromatic sulfur compounds,and the contents of dibenzothiophene series compounds and benzonaplyiothipophene decrease significantly as a result of water washing.However,the conterts of bicyclic and tricyclic aromatic hydrocarbons decrase slightly and those of tetracyclic and pentacyclic aromatic hydrocarbons,especially benzofluoranthene and benzopyrenes,increase markedly owing to adecrease in light aromatie hydrocarbons as a result of water washing.     

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…     

Particulate oil spill recovery. I,Oil sorption properties of plastic foams

Reusable, reticulated, polyurethane foams are broadcast at sea, absorb oil in the presence of water, are recovered, oil removed and foam particles rebroadcast. Combining dimensional and mathematical analysis with experimental data, a mathematical model of foam sorption efficacy and rate is developed showing the system to be practical. Oil viscosity, wave height, recovery ship speed, and system geometry influence foam selection.     

Organic matter and deposition conditions of the Kashpir oil shales

The composition of organic matter was investigated in the oil shales and country rocks of the Kashpir deposit. The analysis of the aromatic fraction of bitumen showed the presence of isorenieratene derivatives, which indicates the accumulation of the sequence under anoxic conditions in the bottom waters of a paleobasin. Special attention was given to the composition of organosulfur compounds from the bitumen of rocks and products of kerogen pyrolysis. The concentrations of hydrocarbon structures occurring in the bitumen in a free state and in sulfur-bearing derivatives are comparable. The composition of the pyrolysis products of kerogen depends on the concentration of organic carbon in the rock: carbon-rich rock varieties contain kerogen whose pyrolysis yields relatively high concentrations of organosulfur compounds and low total contents of n-alkanes/n-alkenes-1.     

海拉尔盆地贝尔凹陷轻质油层录井综合识别与评价

海拉尔盆地贝尔凹陷的油层主要为轻质原油(轻油)层。含轻油砂岩岩心颜色浅,具较浓油气味,普照浅黄色,二次观察含油颜色不明显,油气味变淡或消失,二次荧光普照无荧光颜色。轻油密度范围为0.79～0.82 g/cm³,粘度为1.60～5.40 mPa·s。轻油全烃最大值一般大于0.50%,比值大于3.0。热解分析总烃含量值大于2.00 mg/g,原油轻重指数为2～6。轻油气相色谱分析反映碳数分布范围为nC₈-nC₂₅、主峰碳数为nC₁₈-nC₂₀,进行二次气相色谱分析,色谱呈直线形态。利用单位重量储层的含油量与有效孔隙度交汇图版可识别出油层、油水同层、水层;将原油轻重组分指数与原油的密度、粘度进行回归分析,建立原油类型判别标准及图版,实现轻油层及稠油层的判别。根据静态产能指数和动态产能指数识别高产、工业、低产和偏干4类油层,预测符合率大于90%。