昆明盆地晚新生代沉积物中不同类型干酪根热解产物特征及地化意义

本文用与相色谱法鉴定了昆明盆地晚新生代沉积物中干酪根热解产物,干酪根的热解色谱表明,热解产物的主要成分为正烷烃、正烯烃、类异戌二烯烷烃、类异戌二烯烯烃和烷基苯等。Ⅰ型干酪根的热解产物主要是正烷烃、正烯烃,而在Ⅲ型干酪根热解产物中,烷基苯、姥鲛烯-1和姥鲛烯-2很丰富,通过研究不同类型干酪根的热解产物组成特征表明,热解-色谱法为研究沉积有机质的成熟度、有机质类型和沉积环境,提供了重要信息。     

Pr／Ph值与煤化程度的关系及成煤环境意义

Ｐｒ／Ｐｈ值与煤化程度的关系及成煤环境意义窦廷焕，高菊芬（煤炭科学研究总院西安分院７１００５４）关键词姥鲛烷，植烷，煤化作用，煤相中国图书资料分类法分类号Ｐ５９３作者简介窦廷焕男５７岁高级工程师煤田地质１引言类异成二烯烷烃的主要组分姥鲛烷（２，６，１...     

Corynespora foveolatum菌孢原生烃类与热解产物烷烃生物标志物特征

以一种类似地层中蠕虫状无孔多胞孢的现代真菌孢子Ｃｏｒｙｎｅｓｐｏｒａ ｊｏｖｅｏｌａｔｕｍ菌孢（竹棒孢）为样品,研究了地层中同类菌孢的原生烷烃生物标志物及其热解生烃特征。实验结果表明,Ｃｏｒｙｎｅｓｐｏｒａ ｆｏｖｅｏｌａｔｕｍ菌孢原生烃类烷烃组分主要由正构烷烃组成,并以ｎＣ２９为主峰碳,ｎＣ２９占正烷烃总量的４２．８％。除含量不高的植烷和姥鲛烷外,几乎不含异烷烃和烯烃,烷基苯和烷基环已烷的含量也     

青海湖沉积物中的无环类异戊二烯化合物

本文用GC-MS分析了青海湖沉积物中无环类异戊二烯化合物的特征。青海湖沉积物中姥鲛烷/植烷比值(Pr/Ph)都小于1,表明沉积物沉积时的环境是还原(缺氧)条件。沉积物中的C_(18)类异戊二烯酮相对正烷基-2-酮随深度增加有减少趋势,这可能是C_(18)类异戊二烯酮向其烷烃对应物转化的结果。作者还首次报道了青海湖沉积物中的植烯醛和姥鲛烯醛,它们是植醇降解过程中重要的中间产物。它们的检出对植醇成岩过程中各步骤解释具有一定意义。     

煤岩显微组份和全煤热解色谱分析

随着石油勘探的深入和发展，煤和含煤沉积的生油问题，已经越来越引起人们的重视。为此，笔者选择了准噶尔盆地侏罗系富氢组份含量高的煤样和富镜质组的煤岩样品，采用快速热解法，对其显微组份和全煤的热解生烃潜势进行了研究。结果表明:（１）Ｒ_０值为０.３７～０.３９％的未成熟煤岩样品中，壳质组和镜质组在３５０～４５０℃温度区间有最大热解峰面积Ｓ_２。（２）富氢组份含量高的样品中，热解产物以正构烷烃＋正构烯烃为主，其次为芳烃化合物。（３）镜质组或富镜质组的煤岩样品中，Ａ１６００/Ｍｇ值较高时，热解产物在Ｃ_６-Ｃ_１５范围内，某些芳烃化合物成为主峰。（４）惰性组生烃能力最差，在较高温度下，形成含量很低的正构烷烃和烯烃，或在气态烃范畴产生少量烃类，或基本不产生热解产物。（５）随着加热时间的延长或原煤样品演化程度的升高，烯烃含量减少或消失，可能是干酪根转化过程中的残余氢为烯烃的氢化作用提供了氢源，使烯烃转化为烷烃的缘故。     

判别碳酸盐岩是烃源岩还是储集岩的指标

<正> 在实际勘探中,碳酸盐岩既可作为烃源岩,也可作为储集岩存在。确定碳酸盐岩中含有的烃类是原生的,还是从它处运移而来的,这在勘探实践中有着指导意义。为此目的,许怀先等用岩石热解分析方法做了大量研究工作。结果表明岩石中原油的热蒸发烃高峰温度和干酪根热解烃高峰温度具有显著差异:干酪根热解产烃高峰温度 T_(max)为400～600℃;原油热蒸发烃最高峰温度 T_(max)为300～400℃。由此可以区分原油的热蒸发烃和干酪根的热解烃,并进一步判定当最高热解峰温 T_(max)>400℃时,该岩石为烃源岩,而当T_(max)<400℃时,则为储集岩。对干酪根热解的进一步研究表明,不同成熟度的干酪根在不同的热降解温度范围内的产烃量是不同的。低成熟度的干酪根在450～600℃范围内所产生的烃占热解烃的5%     

矿物对原油裂解影响的实验研究

在限定体系下（密封金管）,对原油、原油＋蒙脱石和原油＋方解石进行了裂解产气模拟实验。结果表明,原油＋蒙脱石裂解的甲烷和总气态烃（C1-C5）产率在大多数实验温度点与纯原油裂解基本相同,只有在高温度点才相对偏高,反映了蒙脱石对原油裂解的催化效应。原油＋方解石裂解的甲烷和总气态烃的产率则在大多数实验温度点比纯原油裂解相对偏低,并且在高温度点明显偏低,表明方解石对原油裂解具有抑制作用。纯原油和原油＋方解石裂解气态烃产物中异构烷烃和烯烃的相对含量基本相同,而原油＋蒙脱石裂解气态烃产物中异构烷烃和烯烃的含量则明显偏高。依据2℃／h和20℃／h两个升温速率甲烷和总气态烃产率,应用美国Lawrence Liverinore国家实验室开发的Kinetics软件模拟了纯原油、原油＋蒙脱石和原油＋方解石裂解生成甲烷和总气态烃的动力学参数,推算了在地质条件下原油裂解主要阶段的温度范围。     

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.     

角质体热角产烃的实验研究

本文在严格的煤岩显微组分分离富集的基础上，采用岩石热解、热解气相色谱以及开放体系下热模拟等方法，系统地对贵州水城上二叠统龙潭组（P3l)煤中角质体的生烃潜力、热角烃组成特征、生烃模式进行了研究，结果显示：角质体具有很高的生烃潜力，其S1 S2为308.33mg/g，远高于丝质体（S1 S2为26mg/g)和基质镜质体（S1 S2为192mg/g)，而与树皮体（S1 S2为297mg/g)相当，另外，角质体为一种好的生油组分，其热解烃中油占了67%（197.47mg/g)；角质体热角产物主要为碳数较低的正构烷烃、烯烃化合物，此外苯、烷基苯（甲苯、二甲苯）、萘系化合物所占比例较高，而姥鲛烷和植烷含量则较少，本区角质体的主要生烃区间介于420-450℃之间（对应的R0为1.1%-1.5%)，生烃高峰在425-435℃范围内，最大产烃率对应的温度为430℃，角质体这种生烃潜力高，并且在高成熟度下大量生烃的特点对在成熟度普遍较高的华南地区寻找油气田具有重要的现实意义。     

页岩热成熟过程中残余干酪根演化特征

用低熟的页岩样品进行半开放体系压机热模拟实验,研究页岩热演化过程中残余干酪根的赋存演化特征。实验结果表明页岩中残余干酪根可分为微米级粒间有机质、微米级粒内有机质和纳米级粒间有机质。不同赋存形式有机质的热演化特征不同,微米级残余干酪根在Ro,Easy值为0.82%时已发生热裂解,到Ro,Easy值为1.45%时,微米级粒间残余干酪根被消耗殆尽,微米级粒内残余干酪根仍有一定生烃潜力;而纳米级粒间残余干酪根在Ro,Easy值为1.45%时才开始热裂解,在Ro,Easy值为2.66%时,仍有部分干酪根残留在孔隙中。伴随有机质热裂解过程,页岩中矿物组成特征也发生变化,矿物溶蚀和再沉淀作用使得页岩矿物组成整体上沿着长英质矿物含量增加、碳酸盐矿物减少、黏土矿物含量基本不变的趋势演化。干酪根热裂解生烃使得其体积缩小,在干酪根和矿物之间形成收缩有机孔,随着热演化程度的升高,收缩有机孔的孔径逐渐变大,最后转变为矿物粒间孔/粒内孔。长石和碳酸盐矿物易发生溶蚀,成熟阶段,矿物溶蚀孔开始形成,在之后的演化阶段,溶蚀孔的发育程度逐渐变强。有机质孔的发育具有非均质性,温度(成熟度)是影响其发育的重要因素。     

Modeling of catagenetic transformation of organic matter from a Riphean mudstone in hydrous pyrolysis experiments: Biomarker data

The catagenesis of organic matter (OM) was modeled by the hydrous pyrolysis of a Riphean mudstone. Microscopic observations of the processes operating during kerogen heating to 600°C were conducted in a diamond anvil cell. The results of pyrolysis in an aqueous environment were used to calculate the activation energies of kerogen cracking and derive chemical kinetic models for OM catagenesis. Isothermal experiments were carried out for 3 days at temperatures of 300, 310, …, 360, and 370°C. The maximum bitumen yield was obtained at 330°C followed by thermal cracking at higher temperatures. The aromatic and saturated hydrocarbons from rock bitumen, hydrous pyrolyzates, and kerogen flash pyrolyzates were analyzed by chromatography-mass spectrometry. We also discuss the problem of extrapolation of high-temperature pyrolysis results to geologic observations under the conditions of regional catagenesis.     

Origin of low-molecular-weight alkylthiophenes in pyrolysates of sulphur-rich kerogens as revealed by micro-scale sealed vessel pyrolysis

Micro-scale sealed vessel (MSSV) pyrolysis experiments have been conducted at temperatures of 150, 200, 250, 300, 330 and 350°C for various times on a thermally immature Type II-S kerogen from the Maastrichtian Jurf ed Darawish Oil Shale (Jordan) in order to study the origin of low-molecular-weight (LMW) alkylthiophenes. These experiments indicated that the LMW alkylthiophenes usually encountered in the flash pyrolysates of sulphur-rich kerogens are also produced at much lower pyrolysis temperatures (i.e. as low as 150°C) as the major (apart from hydrogen sulfide) sulphur-containing pyrolysis products. MSSV pyrolysis of a long-chain alkylthiophene and an alkylbenzene indicated that at 300°C for 72 h no β-cleavage leading to generation of LMW alkylated thiophenes and benzene occurs. In combination with the substantial production of LMW alkylthiophenes with a linear carbon skeleton at these conditions, this indicated that these thiophenes are predominantly formed by thermal degradation of multiple (poly)sulfide-bound linear C₅–C₇ skeletons, which probably mainly originate from sulphurisation of carbohydrates during early diagenesis. LMW alkylthiophenes with linear carbon skeletons seem to be unstable at MSSV pyrolysis temperatures of ≥330°C either due to thermal degradation or to methyl transfer reactions. LMW alkylthiophenes with a branched carbon skeleton most likely derive from both multiple (poly)sulfide-bound branched C₅–C₇ skeletons and alkylthiophene units present in the kerogen.     

现代松粉的热变质实验研究

本文通过现代松粉较大样品量的热模拟定量研究，认为松粉具有很大的生烃潜力，其特性接近于１类干酪根。以甲烷为主的伴生烃类气体最高产率达２４７ｍ３/ｔ。液态烃包括轻烃和抽提物，产率最高分别达６６．８ｋｇ/ｔ和９４．８ｋｇ/ｔ。受热变质的松粉，低温阶段主要是收缩变小，逐步出现裂隙和本体与气囊分离，３５０℃以上完全破碎。随温度升高松粉及碎片的颜色不断加深，主要调１５０℃以下为黄，２００℃～３００℃为棕，２５０℃～４５０℃为棕黑，５００℃以上为黑。色度指数和镜质组反射率值也随温度升高而增大。     

珠江口盆地番禺低隆起-白云凹陷北坡干酪根热演化模拟与生烃

通过密封金管-高压釜体系对珠江口盆地番禺低隆起-白云凹陷北坡恩平组炭质泥岩的干酪根(PY),在24.1 MPa压力、20℃/hr(373.5~526℃)和2℃/h(343~489.2℃)两个升温速率条件下进行热模拟生烃实验,分析气态烃(C1 5)和液态烃(C6 14和C14+)的产率,以及沥青质和残余有机质碳同位素组成。同时与Green River页岩(GR)和Woodford泥岩(WF)的干酪根,分别代表典型的I型和II型干酪根进行对比研究。结果显示PY热演化产物中总油气量明显低于GR和WF干酪根,且气态烃(C1 5)最高产率是液态烃的1.5倍,揭示恩平组炭质泥岩主要以形成气态烃为主。在热演化过程中,有机质成熟度和母质类型是控制油气比的主要因素,气态烃和轻烃的产率比值主要受热演化成熟度的影响。干酪根残余有机质碳同位素和沥青质碳同位素在热演化过程中受有机质成熟度的影响较小,δ13C残余和δ13C沥青质可以间接反映原始母质的特征,为高演化烃源岩油气生成提供依据。     

Alternaria tenuis菌孢热模拟生烃试验研究Ⅰ

本文以类似于地层中常见的无孔多胞孢的现代菌类-Ａｌｔｅｒｎａｒｉａｔｅｎｕｉｓ菌孢进行热模拟生烃试验，分为常温、１００℃、２００℃、２５０℃、３００℃、４００℃、５００℃七个温度级试样，进行气体、族组分、元素、热解色谱、红外光谱、差热等分析，所获结果表明菌类也是良好的生油（气）原始母质，相当于Ⅰ型或Ⅰ-Ⅱ型干酪根，３００℃-４００℃是菌类热模拟产烃高峰期，菌孢的热模拟试验清晰地显示了其有机质热演化和油气形成历程。     

1-Pristene as a precursor for 2-pristene in pyrolysates of oil shale from Condor,Australia

Condor oil shale, its demineralised kerogen and kerogen/kaolinite mixtures were flash pyrolysed (400–600°C; 60s) or pyrolysed in a tube furnace (25–600°C; 3°C min⁻¹) and the 1-pristene/2-pristene ratio (1P/2P) in the pyrolysates was determined by gas chromatography-mass spectrometry. 1P was the primary pyrolysis product and 2P was derived from it by mineral-catalysed isomerisation, with the 1P/2P ratio depending upon the residence time of the vapour in the catalyst bed. Previously unreported pristene isomers were detected.     

Biomarker distributions in asphaltenes and kerogens analysed by flash pyrolysis-gas chromatography-mass spectrometry

Biomarker distributions in a suite of asphaltenes and kerogens have been analysed by flash pyrolysis directly coupled to a GCMS system. Attention has been focussed on biomarkers of the sterane and triterpane types. The sample suite under investigation consists of sediments with different kerogen types and some crude oils. Biomarker distributions in the pyrolysates have been compared with the “free” biomarkers in the corresponding saturated hydrocarbon fractions.The analyses show significant differences between the distributions of the free biomarkers and those in the pyrolysates. The latter have lower amounts of steranes while diasteranes are absent or present at low concentrations only. In the triterpane traces a shift of maximum intensity from C₃₀ (free compounds) to C₂₇/C₂₉ is observed. Furthermore, the pyrolysates contain a set of triterpenes (not present among the free compounds), and there is a selective loss of “non-regular” triterpanes that are present in the saturated hydrocarbon fractions. The observed differences between pyrolysates and free hydrocarbons can be explained partly by the processes occurring during pyrolysis such as bond rupture and subsequent stabilisation of primary pyrolysis products. To a certain extent these differences also show that maturation processes occurring in sediments have effects on free biomarker molecules different from those on molecules that are enclosed in a macromolecular matrix (kerogen or asphaltenes).Differences between biomarker distributions of asphaltene and kerogen pyrolysates are relatively small. A comparison with the pyrolysates from extracted whole sediments suggests that these differences are mainly caused by interactions between the organic material and the mineral matrix during pyrolysis.Oil asphaltenes behave differently from sediment asphaltenes as their pyrolysates are more similar to the corresponding saturated hydrocarbon fractions, i.e. the differences described above are observed to a much smaller extent. This different behaviour appears to be the result of coprecipitation of a part of the maltene fraction with the oil asphaltenes.     

The polymer-like organic material in the Orgueil meteorite

The insoluble organic material in the Orgueil (Cl) chondrite was analyzed by combined high vacuum pyrolysis-gas chromatography-mass spectrometry. Stepwise pyrolyses at 150, 300, 450 and 600°C of Orgueil meteorite powder which had been exhaustively extracted with solvents yielded a series of alkenes and alkanes to C₈, an extensive series of alkylbenzene isomers, thiophene, alkylthiophenes, and benzothiophene, together with the nitrogen- and oxygen-containing breakdown products, acetonitrile, acrylonitrile, benzonitrile, acetone and phenol. The Orgueil polymer fragmentation products are very similar both qualitatively and quantitatively to pyrolysis products of solvent-extracted Pueblito de Allende (C3) chondrite described in the literature.Changes in the relative abundances of polymer degradation products between 150 and 600°C imply the preferential loss of aliphatic and certain heteroatomic portions of the polymer at lower temperatures to leave highly condensed aromatic and heteroaromatic portions of the polymer which begin to fragment only at 450–600°C. The Orgueil polymer-like matter thus appears to be a complex mixture of polymerized materials having different thermal stabilities. Similarities between vacuum pyrolyzates of the Orgueil polymer and terrestrial kerogen suggest the possibility that meteorite organic matter may have been subjected on the meteorite parent bodies to diagenetic processes similar to those by which terrestrial kerogen is formed.     

Effect of hydrocarbon volatility and adsorption on source-rock pyrolysis

Petroleum source-rock evaluations by pyrolysis are based on the concept that free hydrocarbons in rock samples are volatilized below 300°C while hydrocarbons cracked from kerogen come off at higher temperatures. The pyrolysis of pure hydrocarbons with different mineral matrices shows that free hydrocarbons containing 16 or more carbon atoms may not be evolved eblow 300°C, but at varying higher temperatures. The extent to which this occurs depends on the hydrocarbon volatility, the mineral matrix and the pyrolysis instrument design. Source-rock parameters which use the P₁ (S₁) peak may be not be reproducible between instruments if the rock contains appreciable amounts of high molecular weight hydrocarbons.     

Release of sulfur- and oxygen-bound components from a sulfur-rich kerogen during simulated maturation by hydrous pyrolysis

An immature sulfur-rich marl from the Gessosso-solfifera Formation of the Vena del Gesso Basin (Messinian, Italy) has been subjected to hydrous pyrolysis (160 to 330°C) to simulate maturation under natural conditions. The kerogen of the unheated and heated samples was isolated and the hydrocarbons released by selective chemical degradation (Li/EtNH₂ and HI/LiAlH₄) were analysed to allow a study of the fate of sulfur- and oxygen-bound species with increasing temperature. The residues from the chemical treatments were also subjected to pyrolysis–GC to follow structural changes in the kerogens. In general, with increasing hydrous pyrolysis temperature, the amounts of sulfide- and ether-bound components in the kerogen decreased significantly. At the temperature at which the generation of expelled oil began (260°C), almost all of the bound components initially present in the unheated sample were released from the kerogen. Comparison with an earlier study of the extractable organic matter using a similar approach and the same samples provides molecular evidence that, with increasing maturation, solvent-soluble macromolecular material was initially released from the kerogen, notably as a result of thermal cleavage of weak carbon–heteroatom bonds (sulfide, ester, ether) even at temperatures as low as 220°C. This solvent-soluble macromolecular material then underwent thermal cleavage to generate hydrocarbons at higher temperatures. This early generation of bitumen may explain the presence of unusually high amounts of extractable organic matter of macromolecular nature in very immature S-rich sediments.