高煤级煤—隐晶质石墨的Raman光谱表征及结构演化

拉曼光谱能够反映碳材料结构的有序程度和结构缺陷,可用来表征高煤级煤—隐晶质石墨演化过程中结构变化。通过对受岩浆热变质影响的不同变形变质程度样品的拉曼参数与面网间距（d₀₀₂）之间关系的研究表明：G峰位置与d₀₀₂呈现阶梯变化,能较好地区分出石墨与高煤级煤,S₂峰位、D₁、G半峰宽与d₀₀₂呈较好的线性关系;D₁与G峰峰位差和半峰宽比随d₀₀₂减小而减小,S₂与S₄峰的峰位差随d₀₀₂减小先增大后减小,而其强度比及面积比逐渐增大;d₀₀₂与拉曼参数关系显示两次明显的结构演化跃变,即无烟煤至变质无烟煤阶段,R_max>6.5%、P（D₁-G）<235 cm^-1、P（S₂-S₄）>525 cm^-1以及半峰宽比显著下降、L_a/L_c迅速降低,为芳构化、芳环缩合作用增强向芳环叠片拼叠转变;半石墨至石墨演化阶段,P（D₁-G）、I_D1/I_G与A_D1/A_G显著降低,L_a、L_c迅速增加。以d₀₀₂为标度能较好地反映煤结构在不同演化阶段的Raman光谱特征。     

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。     

新疆库车俄霍布拉克煤矿下1煤中藻类体的研究

运用光学显微镜等煤岩学研究方法对新疆库车俄霍布拉克煤矿S₁、S₃、S₄和S₅ 4个钻孔揭露的下₁煤层的显微组分进行了详细研究。结果显示,在4个下₁煤层样品(S₁-1、S₃-1、S₄-1、S₅-1)中都含有藻类体;在S₁-1样品的煤砖光片中,一些煤粒显示藻类体密集分布,成层堆积,形成藻煤夹层,水平纹理明显,根据这些藻煤颗粒的粒径推断藻煤夹层的厚度大于2cm, S₁-1样品中的藻类体个体较小,在蓝光激发下发黄绿色荧光,显示蜂窝状结构;在S₃-1、S₄-1和S₅-1共3个样品的煤砖光片中,藻类体个体较大,常散布在基质镜质体中或与其他组分共生,在蓝光激发下发黄绿色、黄色荧光,显示蜂窝状结构。下₁煤层中出现分散的和聚集的结构藻类体,指示该煤层形成于潮...     

湘西北地区下寒武统牛蹄塘组页岩有机地球化学与矿物组成特征

文章以湘西北地区下寒武统牛蹄塘组页岩为研究对象,分析其有机地球化学及无机矿物特征,重点对其烃源岩生物标志化合物特征进行分析。结果表明:该套页岩残余有机碳（TOC）含量高、氯仿沥青"A"含量低、生烃潜量"S₁+S₂"较小,镜质组反射率R_o在2.3%~3.19%之间,达到了过成熟阶段,以生成干气为主。分子生物标志化合物结果显示正构烷烃呈双峰型,碳数大于C₂₂的中-高碳数烃占优势;Pr/Ph平均值为0.31,植烷优势明显,指示强还原的海相沉积环境;萜烷丰度顺序为五环三萜烷>三环萜烷>四环萜烷,γ-环蜡烷与C₃₀霍烷的比值普遍大于0.3,指示其沉积母质以浮游生物及海洋性自养菌为主,含有部分藻类;Ts/（Ts+Tm）在0.35~0.38之间,与镜质组反射率对成熟度的检测结果相互印证;规则甾烷C₂₇ > C₂₉ > C₂₈,指示其母质来源以浅海生物来源为主,所有样品中均检测出孕甾烷、升孕甾烷、重排甾烷及4-甲基甾烷,表明其经历过微生物降解作用。全岩矿物组分分析显示该套页岩具备较好的开发物性条件和较强的吸附性能。综合以上分析结果,提出研究区牛蹄塘组页岩具备较好的页岩气成烃成藏的物质条件,并为该区深入开展页岩气勘探目标区优选奠定了很好的工作基础。      

华北地区煤的显微组分结焦性热台试验

为探讨煤的显微组分的结焦性，对不同变质程度煤的镜质组、壳质组和惰性组分别进行了显微镜热台加热试验．在加热过程中，活性组分经历了３个明显不同的变化阶段，即变形阶段、胶质体形成阶段以及固化阶段．随煤变质程度的增加，镜质组的初变温度和胶质体形成时的温度逐渐增大，而固结温度变化规律不明显；壳质组在低变质阶段因受热而挥发掉，但随煤级增高其变形程度减弱；半镜质组在受热过程中也有变形和少量胶质体形成，而惰性组只发生微弱变化．在低变质阶段，活性显微组分形成的焦炭显微结构以各向同性为主；随变质程度的增高，焦炭显微结构中各向异性成分比例增大     

生物降解作用对原油中烷基菲分布的影响

辽河盆地冷东油田原油来源单一,成熟度相近,生物降解是导致原油中烷基菲含量和组成发生变化的主要原因。通过对不同降解程度油砂样品中烷基菲含量和分布的详细地球化学分析,发现中等程度生物降解（3到5级）使烷基菲含量大大降低,而异构体相对含量的变化主要发生在中等程度生物降解之后（4级以上）,原油遭受4级以下生物降解影响时,烷基菲参数仍能有效指示成熟度。烷基菲生物降解的难易程度明显受烷基化程度的控制,C₃-菲比低烷基取代化合物的抗生物降解能力强,但甲基菲比菲更容易降解,推测这与甲基菲的脱甲基作用有关。生物降解对烷基菲各异构体的消耗有强烈的选择性,在9位或 10位上取代的烷基菲比其他位置取代的烷基菲抗生物降解能力强,根据烷基菲系列中化合物相对含量随生物降解程度的变化,确定了甲基菲、C₂-菲和C₃-菲各异构体的生物降解顺序,研究成果为芳烃成熟度参数的合理选用和生物降解定量评价提供了依据。     

鄂尔多斯盆地东缘石西区块上古生界烃源岩地球化学特征及形成环境

石西区块位于鄂尔多斯盆地东缘中部,目前发现区块内致密砂岩气资源丰富,查清其烃源岩发育情况及控制因素对油气勘探具有重要的理论和实践意义。笔者等采集石西区块内的本溪组、太原组和山西组的烃源岩样品,利用Leco CS-200、Rock-Eval 6、ICP-OES、ICP-MS等手段对其有机地球化学特征和元素地球化学特征进行表征。结果显示,炭质泥岩中总有机碳(TOC)、生烃潜力(游离烃+热解烃,即S₁+S₂)、氢指数(HI,热解烃×100/总有机碳)的平均值分别为4.50%、0.52‰、829.16‰,煤中总有机碳(TOC)、生烃潜力(S₁+S₂)、氢指数(HI)的平均值分别为61.53%、4.41‰、723.02‰。V/(V+Ni)、Ni/Co、V/Cr、δU、Sr/Ba、Sr/Cu等值显示优质烃源岩沉积时期为气候温暖湿润,盐度较高的弱氧化—还原环境,从本溪组到山西组沉积过程中,沉积水体的还原性有逐渐减弱的趋势。古生产力指标(Ni_EF、Cu_EF)表明山西组古生...     

晋城无烟煤储存游离态CO2理论容量及其影响因素

深部煤层游离态CO₂理论存储容量随深度增加而变化。基于山西沁水盆地南部煤样测试基本数据,对游离态CO₂煤层存储容量进行计算,并分析其随深度变化规律。基于建立的煤层游离态CO₂存储容量计算模型显示,煤储层游离态CO₂存储容量受孔隙度、含气饱和度、地层温度、地层压力等共同作用的影响。CO₂注入后改变煤储层物性会导致理论存储量有不同程度增加,但存储量增值与实验煤样颗粒大小有关;应力作用下煤储层孔隙度随埋深呈负指数降低规律会显著降低CO₂存储容量,含气饱和度增大会显著增大存储量。     

沉积环境对煤层含气量的控制:以沁水盆地寿阳地区太原组15#煤为例

煤层性质的差异是影响煤层气富集及高产的重要因素。沉积环境控制了煤层厚度及展布、煤岩煤质特征、有效盖层厚度和岩性组合等,对煤层气富集具有重要控制作用。本研究根据钻井岩心、录井、测井及前人研究成果,对沁水盆地北部寿阳地区太原组进行了沉积环境及层序地层综合分析,并对15^#煤顶、底板系统的沉积环境及岩相古地理进行精细刻画,总结沉积环境对煤层含气量的控制作用,并进一步划分有利煤储集层沉积相带。寿阳地区太原组下部主要发育浅海陆棚—障壁岛—潟湖沉积体系,上部主要发育三角洲平原沉积体系。太原组沉积时期为1个三级层序尺度的海侵—海退过程,并进一步可划分为6个四级层序(S₁—S₆)。四级层序S₁发育潮坪—潟湖—障壁岛沉积体系,各沉积相与15^#煤含气量关系由好到差依次为潟湖、潮坪、障壁岛;S₂发育障壁岛—潟湖—潮坪—浅海陆棚沉积体系,各沉积相与15^#煤含气量关系由好到差依次为潟湖(灰岩厚)、泥质陆棚、碳酸盐岩陆棚、潟湖、潮坪、障壁岛。根据S₁     

煤岩组分化学结构随热演化变化与生烃性研究

应用显微傅立叶红外光谱分析,研究了胜利油田附近的石炭系太原组煤烃源岩中主要生烃有机组分化学结构特征。结果表明,荧光镜质体富含芳烃结构和含氧有机结构,而树脂体和角质体富含脂肪烃结构,荧光镜质体和树脂体烷基烃碳链短或支化程度高。随热演化程度增高,荧光镜质体和树脂体红外光谱参数(CH₂+CH₃) C=C和CH₂ CH₃比值逐渐减小,而孢子体和角质体的这两个参数先增后减,反映出荧光镜质体与树脂体具早期生烃特点,而孢子体与角质体生烃演化具弱—强—弱特性,具生烃高峰期。     

Coal as a source rock for oil: a review

The geological debate about whether, and to what extent, humic coals have sourced oil is likely to continue for some time, despite some important advances in our knowledge of the processes involved. It is clear that not only liptinites, but also perhydrous vitrinites have the potential to generate hydrocarbon liquids in the course of natural coalification. Some liptinites, especially alginite, cutinite, and suberinite, contain a higher proportion of aliphatic moieties in their structure than other liptinites such as sporinite and resinite and are, therefore, more oil-prone. It is of potential value to be able to predict the several environments of deposition in which coals with high liptinite contents or containing perhydrous vitrinites may have been formed. Review of the distribution of oil-prone coals in time and space reveals that most are Jurassic–Tertiary with key examples from Australia, New Zealand, and Indonesia. Methods based both on experimental simulations and the examination of naturally matured samples have been used to determine the order of generation of hydrocarbons from different macerals. Results are not entirely consistent among the different approaches, and there is much overlap in the ranges of degradation, but it seems probable that in the natural environment vitrinites begin to generate early, followed by labile liptinites such as suberinite, then cutinite, sporinite, and, finally, alginite.Petroleum potential may be determined by experimental simulation of natural coalification or inferred through various micro-techniques, especially fluorescence and infrared (IR) spectroscopy, or bulk techniques such as elemental analysis and ¹³C NMR spectroscopy. The latter three techniques enable a measure of the polymethylene component of the coal, which now appears to be one of the best available approaches for determining petroleum potential. No method of experimental simulation of petroleum generation from coals is without criticism, and comparative results are highly variable. However, hydrous pyrolysis, confined pyrolysis, and forms of open-system hydrous pyrolysis approach acceptable simulations.Whether, and to what degree generated liquid hydrocarbons are expelled, has long been the central problem in ‘oil from coal’ studies. The structure of vitrinite was believed until recently to contain an interconnected microporous network in which generated oil would be contained until an expulsion threshold was attained. Recent studies show the pores are not interconnected. Combined with a dynamic model of pore generation, it now seems that expulsion of hydrocarbons is best explained by activated diffusion of molecules to maceral boundaries and ultimately by cleats and fractures to coal seam boundaries. The main reason for poor expulsion is the adsorption of oil on the organic macromolecule, which may be overcome (1) if coals are thin and interbedded with clastic sediments, or (2) if the coals are very hydrogen-rich and generate large quantities of oil.The existence of oil in vitrinite is attested to by solvent extractions, fluorescence properties, and by microscopic observations of oil and bitumen. Experimental simulation of expulsion of oil from coals has only recently been attempted. The relative timing of release of generated CO₂ and CH₄ could have considerable importance in promoting the expulsion of liquid hydrocarbons but the mechanism is unclear. As it is universally agreed that dispersed organic matter (DOM) in some shales readily generates and expels petroleum, it is curious that few consistent geochemical differences have been found between coal macerals and DOM in interbedded shales.Unambiguous evidence of expulsion from coals is limited, and in particular only a few commercial oil discoveries can be confidently correlated to coals. These include Upper Cretaceous Fruitland Formation coals in the USA, from which oil is produced; New Zealand Tertiary coals; and Middle Jurassic coals from the Danish North Sea. It is likely that coals have at least contributed to significant oil discoveries in the Gippsland Basin, Australia; in the Turpan Basin, China; and in the Kutei and Ardjuna basins in Indonesia, but this remains unproven. Early reports that early Jurassic coals in mid-Norway were a major source of the reservoired oils have been shown to be inaccurate.None of the proposed ‘rules of thumb’ for generation or expulsion of petroleum from coals seem particularly robust. Decisions on whether a particular coal is likely to have been an active source for oil should consider all available geological and geochemical information. The assumptions made in computational models should be well understood as it is likely with new understandings of processes involved that some of these assumptions will be difficult to sustain.     

The rank evaluation of South Brazilian Gondwana coals on the basis of different chemical and physical parameters

Rank evaluation of South Brazilian Gondwana coals according to the American (American Society for Testing and Materials, ASTM) and German (Deutsche Industrie Normen, DIN) standard specifications or on the basis of Alpern's Universal Classification has too often led to conflicting results.When any attempt is made to determine the rank of Brazilian coals by using methods established for the Northern Hemisphere coals, two sorts of difficulties arise: namely, (1) the reflectence measurements do not indicate the real degree of coalification of the organic matter because of the liptinitic impregnations of the vitrinites, and (2) random reflectance values (R_ran, moisture, volatile-matter and carbon contents as well as the calorific value do not correlate when plotted on the ASTM and DIN classification schemes.In addition, when rank determinations are carried out by using fluorescence measurements and geochemical analyses the results are at variance in relation to those determined by the conventional chemical and physical parameters.It is suggested that the rank evaluation of South Brazilian coals is far more meaningful if carried out by reflectance measurements on vitrinites along with fluorescence measurements on sporinites, alginites and coal extracts.     

Some chemical structural features of coals of differing maceral distributions and stratigraphy

Six North American bituminous coals (four Carboniferous and two Cretaceous) and eight maceral concentrates from Carboniferous British seams have been heated with tetralin and hydrogen to 400°C. The hexane-soluble parts of the products were separated by column chromatography and the fractions were then analyzed by gas chromatography/mass spectrometry. In all cases the aromatic hydrocarbon fraction was a very complex mixture containing a number of alkylated biphenyls, diphenylmethanes and -ethanes, and polycyclic compounds. However single ioncchromatography (m/z = 142) showed that, in addition to these, the products from five of the six American coals contained homologous series of long chain n-alkylnapththalenes with alkyl groups extending to C₁₆. In other fractions from the American coals, homologous series of n-alkylfurans and alkylphenols were found to be major components, as also were many alkylcyclohexenones related to isophorone. Extensive homologous series of n-alkyl aromatics were not detected in products from any of six vitrinites from British seams, though series of n- and iso-alkylphenols were found in the products from two sporinite concentrates. A number of polycyclic ketones apparently related to sterols were found in the products from the British vitrinites but not from any American coals. Reasons for what appear to be systematic structural differences between the American and British coals are discussed. Differences in stratigraphy are noted and it seems not impossible that differences in source vegetation are significant.     

Petro-chemical investigation of some perhydrous Indian coals

An attempt has been made to study the petro-chemical characteristics of some high sulphur sub-bituminous coal samples from Makum coalfield, Assam, India. The proximate and ultimate analyes were carried out and forms of sulphur were determined and their relationships with the Maceral constituents (vitrinite, liptinite, and inertinite) were investigated. The macerals (vitrinite+liptinite+inertinite) have significant relationships (R²>0.500) with volatile matter and carbon, whereas weak correlations were seen with rest of the physico-chemical characteristics of the coals. The study reveals that these coals are rich in vitrinites and sulphur and are aromatic in nature. These coals have good hydrocarbon potential.     

西北侏罗纪低成熟煤中镜质组热解产物特征及地质意义

镜质组是腐殖煤中最主要的显微组分,其结构极为复杂。采用单一的实验手段,很难对镜质组结构进行深入研究。采用低温热解、高温热解及TMAH在线甲基化热解3种瞬时热解方法,对镜质组结构中吸附烃、与大分子相连的支链基团中非极性及极性组分分别进行研究。实验结果表明,吸附烃特征决定于镜质组类型及成熟度两种因素。均质镜质体吸附烃以芳烃为主,而基质镜质体吸附烃以正构脂肪烃为主。热解产物中,芳烃所占比例随基质镜质体成熟度的增加而变大;基质镜质体高温热解主要产物为正构脂肪烃,其次为芳烃和酚类,而均质镜质体高温热解主要产物为酚类,其次为芳烃,脂肪烃所占比例较小。TMAH甲基化研究表明,镜质组结构中含有丰富的脂肪酸,而脂肪酸有可能是煤成油的主要母质来源之一。镜质组不同条件下的热解产物特征说明,不同镜质组具有明显的结构差异,并对其生烃特征具有重要影响。     

Tracing the origins of polymethylene moieties in coal

Many coals have been shown to contain long polymethylene segments (up to C₃₀ and longer) which crack to ethylene, propylene, butadiene and other low molecular weight hydrocarbons when the coals are pyrolyzed. The polymethylene content varies in different coals and can be 10% or more in low rank coals. Cannel coals may contain up to 20% polymethylene. Polymethylene moieties are either very low or absent in low-volatile bituminous coals and anthracite.A method of analysis for polymethylene in coals, based on liquefaction in a donor solvent followed by ¹H NMR spectroscopy has been described. With this analysis, it has been shown that polymethylene moieties are present in higher concentrations in exinite macerals than in vitrinites or inertinites. Analysis of peats also show the presence of polymethylene components at levels similar to that found in coal. Analysis of various parts of present-day plants also shows the presence of polymethylene materials in concentrations varying significantly from one kind of plant to another. Within a given plant type, some parts of the plant appear to be richer in polymethylene than others. Spores and pollen are frequently especially rich in polymethylene, accounting for the corresponding high concentration in exinite macerals in coal.Samples of Texas Eocene lignites representing a depositional time interval of 15–20 million years and three distinctly different climatic and vegetational conditions were analyzed for polymethylene contents. The differences in polymethylene levels are consistent with differences in flora and support the idea that the original plants are the sources of polymethylene components in coal.     

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.     

The application of FAMM (Fluorescence Alteration of Multiple Macerals) analyses for evaluating rank of Paraná Basin coals, Brazil

Combining vitrinite reflectance (VR) and fluorescence alteration of multiple macerals (FAMM) analyses provide insights into the chemical nature of vitrinites (i.e., perhydrous vs. orthohydrous vs. subhydrous compositions) in Permian Gondwana coals of the Paraná Basin, Brazil. The FAMM-derived equivalent VR (EqVR) values and relationships with VR can be determined according to calibration curves based largely on Permian Gondwana coals of eastern Australia.The analytical results indicate that vitrinites in the Paraná Basin coals studied generally range from orthohydrous to perhydrous, with interpreted VR suppression ranging up to 0.2% absolute for the most perhydrous case. The EqVR values of the Santa Catarina coals, which range from about 0.85% to 0.95% differ from VR values by about 0.10–0.15% absolute, potentially having significant implications on coal utilization.The causes of vitrinite reflectance suppression in the Paraná Basin coals are as yet poorly understood, but are likely to be related to a combination of factors.     

华北煤变质作用对煤含气量和渗透率的影响

通过华北和美国煤层气地质条件的对比, 基于华北煤变质特点, 指出了区域岩浆热变质有利于提高煤层含气量和渗透率, 并对其作用机理进行了初步探讨.在中国, 经受燕山期岩浆侵入影响之前的煤级较低, 因此在快速增温的高温作用下, 煤层气再次发生即“叠加生烃”或“叠加成气”的潜力大, 孔、裂隙系统发育更趋完善, 区域岩浆热变质的生气时间晚而利于煤层气保存.叠加有区域岩浆热变质形成的煤级分带, 包括高煤级煤和中煤级煤在内都将明显提高煤的含气量和渗透率, 因此, 华北地区应重视在区域岩浆热变质煤中寻找煤层气勘探目标.