塔里木盆地原油噻吩类化合物的组成特征及地球化学意义

对塔里木盆地典型原油噻吩类化合物含量和组成特征研究,发现不同类型原油苯并萘噻吩和二苯并噻吩系列化合物占芳烃化合物的百分含量相差明显,海相油含量最高,湖相油次之,而煤成油最低。本文提出了４－甲基二苯并噻吩／二苯并噻吩、（２＋３）－甲基二苯并噻吩／二苯并噻吩比值是区分海相油和湖相油新的有机地球化学参数。二苯并噻吩系列化合物最大烷化度表明海相油呈现出高烷化度,而陆相油则表现为低烷化度,即从海相泥灰岩原油、海相碳酸盐岩原油到湖相油和煤成油依次减少。这是因为富硫与贫硫干酪根在生烃过程中的环化作用或支链化作用程度差异所造成的。     

江汉盆地西南缘原油中含硫化合物的分布特征及其地球化学意义

对江汉盆地西南缘12个原油样品中含硫化合物分布特征的研究表明,原油中二苯并噻吩系列化合物和苯并萘并噻吩系列化合物分别占芳烃总量的4.61%～9.79%和0.27%～1.32%,与烃源岩中含硫化合物的含量一致,反映原油中含硫化合物的含量与沉积环境有关.原油含硫化合物的内组成表明,咸水环境有利于二甲基二苯并噻吩和三甲基二苯并噻吩系列化合物的相对富集.4-甲基二苯并噻吩/1-甲基二苯并噻吩峰面积比值(MDR)在低成熟阶段(Ro＜0.7%)的变化范围较小,当成熟度进一步增加时,因热稳定性较差的1-甲基二苯并噻吩向其他化合物转化的速度加快,相对丰度降低,而4-甲基二苯并噻吩的相对丰度增加,致使MDR值随成熟度的增加而很快增大.同时,DR值受到沉积条件的影响,可能指示沉积环境的咸水化程度.2 3-甲基二苯并噻吩/二苯并噻吩峰面积比值与4-甲基二苯并噻吩/二苯并噻吩峰面积比值之间表现为正相关,说明2 3-甲基二苯并噻吩与4-甲基二苯并噻吩的形成机理相似,同样受沉积环境和成熟度的影响.     

西秦岭拉尔玛金矿热水硅质岩中的分子古生物学研究

拉尔玛金矿热水成因硅质岩中的分子古生物学研究表明;其正烷烃以碳数分布于Ｃ１６～Ｃ３６,主峰碳为Ｃ２９为特征,除此,还鉴定出规则类异戊二烯和胡萝卜烷系列化合物,烷基环己烷系列,长链三环萜烷,五环三萜烷,甾类分子化石和烷基噻吩系列化合物,烷基四氢噻吩系列化合物,二苯并噻吩,甲基二苯并噻吩等含硫芳烃以及菲及其同系物等非含硫芳烃分子化石,氯仿沥青“Ａ”族组成Ｑ型聚类分析表明拉尔玛金矿硅质岩与现代蓝绿藻和绿     

苯并噻吩系列化合物的成因模拟及其地球化学意义

在硫和β胡萝卜素反应产物中有丰富的苯并噻吩系列化合物,在硫与饱和链状化合物反应产物中既有噻吩系列化合物也有苯并噻吩系列化合物。所以推断苯并噻吩系列是硫作用于噻吩系列或含侧链的苯而形成的。噻吩系列和苯并噻吩系列的相对含量可以指示成熟度:在沉积条件相同的前提下,前者多后者少指示成熟度低,反之则指示成熟度高。     

噻吩系列化合物的形成机理模拟

通过模拟实验发现硫能和各种链状化合物反应形成噻吩系列化合物。其反应机理可能是：硫先作用于链状化合物将其改造成共轭烯中间体,其他硫再从这个部位进入碳骨架从而形成该类化合物。硫还可进一步和噻吩系列反应形成更复杂的含硫芳烃,而温度升高会促进这种反应,所以噻吩系列的含量可以作为成熟度指标,在沉积条件相同的前提下,噻吩系列含量高指示成熟度低,反之则指示成熟度高。     

典型有机硫化合物热演化的加水热解实验研究

14种典型含硫化合物在 200～ 330 ℃温度区间、在有低硫褐煤和硫抑制剂存在条件下的加水热模拟实验结果表明,大多数结构类型的含硫化合物是结构不稳定的化合物,它们的热稳定性差异很大,不同结构类型的含硫化合物所对应的热解温度不同, 它们在不同温度段产物的分布也不尽相同,这表明单个硫化合物的地球化学行为差异很大,而单个有机硫化合物在有机质热成熟过程中的转换特征基本上可以依据其生成硫化氢、二次含硫化合物以及大分子含硫化合物的量来描述.另一方面,硫化氢作为主要热解产物表明硫化合物分解生成硫化氢是有机硫化合物成熟转化的主要机理性过程.在所调查的化合物中,苯并噻吩、二苯并噻吩、二苯硫和噻蒽等在最高热解温度下也不发生任何化学反应,表明这些化合物代表了稳定型结构的硫化合物,这与这些化合物广泛存在于成熟原油和沉积有机质中的状况是一致的.上述结果还显示含硫化合物的种类和结构类型是受有机质的成熟度或演化阶段控制的.     

塔里木盆地深层碳酸盐岩中不同赋存形式芳烃化合物组成

通过对塔参1井深层（＞5 700 m）碳酸盐岩游离有机质（氯仿沥青“A”）和包裹有机质（氯仿沥青“C”）中芳烃化合物组成和成熟度参数对比研究发现,芳烃化合物组成中菲和二苯并噻吩系列化合物较为丰富,菲和〖JX-*9〗〖XCQQ.TIF;%80%80〗〖JX*9〗等系列化合物丰度随埋深增加而增大,而二苯并噻吩、苯并萘并噻吩和芴等系列化合物丰度表现出相反的规律,这反映出不同芳烃系列化合物在高过成熟阶段热稳定性的差异。同一样品两种赋存形式芳烃化合物组成和成熟度参数明显不同,芳烃化合物成熟度参数和烷基化程度都反映出包裹有机质成熟度低于游离有机质,说明包裹有机质的热演化作用受到了抑制。在高过成熟阶段仍有部分芳烃参数仍可以用来表征深层有机质热演化程度,这些参数包括:菲系列烷基化指标（C1 P /C4 P、C1 P /C3 P、 C2 P /C4 P 、C2 P /C3 P）、以及二苯并噻吩系列化合物中MDR、C1/C3 DBT、2,4/1,4 DMDBT和4,6/1,4 DMDBT参数;虽然DBT/P比值被认为指示沉积环境的有效参数,但塔参1井深层样品研究表明,该参数与热演化程度关系密切,为高过成熟度阶段较好的成熟度参数。      

膏盐盆地高硫原油中的长链烷基噻吩类化合物

本文报道了江汉膏盐盆地第三系高硫原油中新的含硫化合物——七个系列的烷基噻吩类和五个系列的烷基四氢化噻吩类。两类化合物的碳数范围以及分布特征与原油烷烃的分布十分相似；即高C20异构烷基噻吩与四氢化噻吩以及偶碳优势分布。含硫化合物可能是膏盐环境高硫原油的特征性生物标志化合物，是早期阶段硫或硫化氢与烷烃的反应产物。     

美国南佛罗里达盆地Sunniland原油和油源岩中芳烃的地球化学

本文用GC-MS技术分析了美国南佛罗里达盆地Sunnliand原油和油源岩抽提物中的芳烃,以便探讨碳酸盐岩环境中芳烃的分布特征,并用来重建古环境.Sunnliand原油和油源岩中含较半富的萘、菲、二苯并噻吩和三芳甾烷等化合物,甲基二苯并噻吩异构体呈V型分布.芴、氧芴和硫芴三系列化合物的相对含量以及其他地球化学特征如:Pr/Ph<1、正烷烃在C₂₂-C₃₀范围内呈偶碳优势、无或很少有二环倍半萜、含丰富的含硫芳烃等,指示Sunnliand原油和油源岩形成于海相强还原高盐环境.Sunnliand原油和油源岩中检出的一些化合物如:D环芳构化8,14-断藿烷、长链烷基苯、长链烷基苯并噻吩以及很高的延伸藿烷(C₃₁-C₃₅)和C₂₄、C₂₆四环萜烷表明Sunniland有机质有细菌输入.成熟度参数指示Sunniland原油和油源岩属未成熟至低成熟.     

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。     

Dibenzofuran Series in Terrestrial Source Rocks and Crude Oils and Applications to Oil-Source Rock Correlations in the Kuche Depression of Tarim Basin, NW China

1IntroductionTheTarimBasin ,NWChina,istheonlybasininChinawherenotonlymarine ,butalsoter restrialindustrialoilandgaspoolsaredeveloped .TheterrestrialoilandgaspoolshavebeenfoundintheKuchedepressioninthenorthernpartofthebasinanditsfrontupliftarea (Fig .1) .ThesourcerocksoftheterrestrialoilandgaspoolsareTriassicandJurassiclacustrinemudstonesandswampcoals.ThebiomarkersfromthesaturatedfractionsofTriassicandJurassicterrestrialsourcerocksandFig .1 .LocationofTriassicandJurassicterrestrialsource…     

不同煤级煤的微孔介孔演化特征及其成因

为了探讨煤的微孔介孔演化特征及其成因,在华北二叠纪煤盆地,采取7个不同煤化程度的煤样,分别采用低压CO₂吸附法和液氮吸附法对各煤样的纳米孔隙进行表征;基于密度泛函理论、DA（Dubinin—Astakhov）、DR（Dubinin—Radushkevich）、BET、BJH等方程计算孔隙表面参数;分析煤的微孔（孔径<2 nm）和介孔（孔径2~50 nm）的孔径分布、孔容和比表面积随煤级变化的规律;并探讨微孔形成的主控因素及介孔的形成机制。研究结果表明:微孔孔容和比表面积与煤的镜质体反射率高度正相关,微孔在吸附中占绝对支配性主导地位;微孔孔径分布曲线呈双峰分布,不同煤级煤样的曲线形态相似,极微孔随煤级增加最快;介孔比表面积和孔容随煤级增加逐渐下降,介孔孔径分布呈单峰分布,随着煤级的增加,煤的BET比表面积先减少后增加,呈U形分布;微孔的形成应主要受控于煤的类微晶参数和芳香层片间的堆垛结构,而介孔的形成应主要受控于煤侧链的变化和煤的基本结构单元间隙。      

Dibenzofuran Series in Terrestrial Source Rocks and Crude Oils and Applications to Oil-Source Rock Correlations in the Kuche Depression of Tarim Basin, NW China

Ten series of aromatic hydrocarbon compounds (biphenyl, naphthalene, phenanthrene, anthracene, retene, chrysene, benzoanthracene, dibenzofuran, fluorene, dibenzothiophene) isolated from seven Triassic and Jurassic lacustrine mudstone samples and three swamp coal samples, as well as five crude oil samples collected in the Kuche depression of the Tarim Basin,NW China, have been analysed by GC-MS techniques. It is found that the relative abundances of dibenzofuran series are higher in the three swamp coal samples than those in the lacustrine mudstone samples. Based on the similar relative abundances of dibenzofuran series, especially dibenzofuran compound, in the TICs of aromatic hydrocarbons, crude oils from wells SA3 (K), YTK5(E,K) and QL1 (E) are thought to have been derived predominantly from the coals of the Lower Jurassic Yangxia Formation or Middle Jurassic Kezilenuer Formation, whereas those from wells YM7 (O) and YHI (E) were derived mainly from Triassic and Jurassic lacustrine mudstones in the Kuche depression. This is the first report about how to distinguish coal-generated oils from lacustrine mudstone-generated oils in the Kuche depression in terms of the dibenzofuran series.The present paper has enlightening and directive significance for further oil-source rock correlations and oil and/or gas exploration in the Kuche depression of the Tarim Basin.     

海相高过成熟页岩芳烃特征及页岩气意义

为了合理评价我国南方下古生界页岩有机质热演化程度,研究其与页岩含气性关系;采用气相色谱-质谱联用仪对中扬子地区6口调查井、3个露头剖面的20件页岩样品的芳烃馏分进行了分析,并对代表不同区域的6件样品进行显微激光拉曼测试.分析结果显示拉曼D、G峰参数可以很好地计算过成熟至球粒石墨阶段高演化样品的有机质成熟度;拉曼D峰的子峰包含有芳烃含量的重要信息,随着有机质热演化程度的增加,与芳烃含量有关的D₄子峰强度不断降低.芳烃中菲系列化合物和二苯并噻吩系列化合物在_RmcR_o=2.73%~4.67%范围内的演化具有明显规律性;虽然甲基菲成熟度公式在该阶段已经不适用,但表征3-MP+2-MP相对含量的参数F1仍是很好的有机质成熟度指标;在有机质过成熟演化阶段,F1先随成熟度增加逐渐增加至0.74附近（R_o=3%附近）,之后随成熟度增加逐渐减小.二苯并噻吩化合物参数2,4-/1,4-DMDBT和4,6-/1,4-DMDBT在过成熟阶段随成熟度增加而增大,两值分别增至2和4.5时对应页岩等效镜质体反射率为4%.页岩芳烃系列化合物在过成熟阶段随有机质热演化程度增加而发生的异构化作用和脱甲基作用与有机质的比表面积变化有较好的耦合作用,与页岩气调查井的气显情况也有较好的相关性;页岩芳烃特征对过成熟阶段页岩气的生成具有重要的指示意义,可以作为我国南方下古生界有机质过成熟地区页岩气勘探的有效指标.      

利用芳烃化合物预测生物降解原油的粘度

利用薄层色谱-氢火焰离子检测和溶剂选择抽提-定量GC/MS分析技术,对辽河油田冷43/37断块区21个原油样品进行了粘度与饱和烃、芳烃化合物相关性研究.结果发现原油粘度随饱和烃族组成含量降低而升高,与芳烃族组成无关,但与萘、菲、二苯并噻吩系列芳烃化合物的绝对浓度及其在总芳烃中的百分含量关系密切.就不同粘度范围的原油,其芳烃化合物参数与粘度的相关性亦不尽相同.文中还初步建立了适应不同粘度范围的一系列粘度预测模型。     

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.     

超临界CO2对烟煤和无烟煤化学结构的影响

超临界CO₂对煤化学结构的改造对煤层CO₂封存能力极为关键。论文开展了模拟埋深1500m （62.5℃、15 MPa）条件下4组不同变质程度煤的ScCO₂-H₂O体系与煤岩地球化学反应实验。通过傅里叶变换红外光谱和X射线粉末衍射实验获得了反应前后煤化学结构演化特征,探讨了煤化学结构演化的机理。结果表明:ScCO₂作用后,煤中脂肪烃链长度普遍增加,仅肥煤的芳香烃丰度增大,肥煤、瘦煤和贫煤含氧基团丰度的增大主要由氢键基团含量的增加贡献,无烟煤含氧基团丰度则主要受低分子化合物溶出的影响。ScCO₂引起的溶胀作用造成肥煤和瘦煤芳香层面之间交联键断裂,芳香微晶内部结构疏松,而芳香层面内C_Ar-C_Ar交联的形成提高了肥煤和瘦煤芳香性和芳香环缩合度;贫煤和无烟煤中非稠合多苯结构脱落使芳香微晶内部更紧凑,脂肪烃链长度的增加则降低了贫煤和无烟煤芳香性和芳香环缩合度。      

Organic geochemistry and petrography of Tertiary coals and carbonaceous shales from Argentina

A series of eight Tertiary coal and carbonaceous shale samples with vitrinite reflectance values between 0.50 and 0.58% were extracted, fractionated and the saturated and aromatic hydrocarbons analysed for characteristic components by GC and GC-MS. Additionally, a microscopical study was undertaken in order to obtain a more precise picture of the samples under investigation.The saturated hydrocarbon fractions displayed the typical n-alkane distribution for coals of this rank, with CPI values between 2.0 and 3.1. Among the branched/cyclic compounds, pristane and α, β-homohopane were recognised as relevant components pointing to an oxic depositional environment. Detection of benzohopanes (C₃₂–C₃₅) in the aromatic hydrocarbon fractions suggests that bacteriohopanetetrol was a significant constituent of the coal biomass. Taking into consideration the Pr/Ph ratios, ash contents and microscopical characteristics of the samples, aspects of the possible degradation of hopanetetrol to homohopane are discussed. Resin-derived diterpenoids with the phyllocladane and kaurane skeleton were tentatively identified and, although minor compounds, they are interpreted to be a sign of the contribution of Podocarpaceae and Araucareaceae to the coal swamp.Aromatic compounds were dominated by alkylnaphthalene derivatives, presumably formed by C-ring cleavage and aromatisation of higher plant-derived pentacyclic triterpenois, which were main components in the high-boiling range of the fractions investigated. Angiosperms (especially Fagaceae) are postulated as source for these polycyclic compounds and, hence, for some of the polyalkylated aromatic bicyclics detected.     

Characterization of coal maceral concentrates by curie-point pyrolysis mass spectrometry

A set of 30 maceral concentrates consisting of 5 exinites (sporinites), 14 vitrinites and 11 inertinites (fusinites and semifusinites) was analyzed by Curie-point pyrolysis mass spectrometry in combination with computerized multivariate statistical analysis techniques. Seventeen samples, representing sink/flotation concentrates of 7 different coals, were obtained through the British National Coal Board, whereas the remaining samples represent cesium-chloride density-gradient centrifugation fractions of two different U.S. coals prepared at the University of Utah.It is found that vitrinites, (semi)fusinites and, to some extent, sporinites show qualitatively similar rank-related changes, such as a decrease in dihydroxybenzene signals and an increase in napthalene signals with increasing rank. In fact, the overall pyrolysis MS patterns of inertinities show a close similarity to those of vitrinites of corresponding carbon content (as obtained from higher rank coals).Notwithstanding these similarities, however, the presence of basic differences in maceral structure is indicated by relatively minor but characteristic peak series in the liptinite (sporinite) as well as inertinite samples. Whereas inertinite spectra show relatively pronounced peak series at the high mass end of the spectrum which can be tentatively identified as representative of polynuclear aromatic compounds, sporinites are characterized by series of branched aliphatic and/or alicyclic polyenic hydrocarbons, possibly representing isoprenoids and related biomarker compounds.     

Developments in high-resolution solid-state13C NMR spectroscopy of coals

The recent development of “second generation” NMR experiments on coals is discussed in this paper. Such experiments have three aims: (1) To determine the extent to which quantitative aromaticity measurements can be made on coals by cross polarization-magic angle spinning (CP/MAS); (2) To obtain more detailed information on coal structure and reactivity than that given by the simple aromaticity measurements possible at the time; (3) To follow reaction pathways when coal is chemically modified. In this plenary lecture the relevant literature is reviewed, and new experimental work in all three areas outlined above is reported. Experimental evidence is presented which shows that aromaticity measurements on a bituminous coal by cross polarization (CP) or single pulse techniques give identical results. Relaxation data for naphthalene polymers suggest that these structures in coal are seen in CP experiments. Dipolar dephasing experiments suggest that the average size of the coal vitrinite molecule does not increase with increase in coal rank due to aromatic substitution reactions. Various relaxation experiments demonstrate how different carbon types can be distinguished in both¹³C-labelled and unlabelled coals.