Comparison between natural and artificial maturation series of humic coals from the Mahakam delta,Indonesia

Type III (humic) organic matter from the Mahakam delta (Indonesia) was chosen to compare artificial and natural coal series. Powdered and concentrated immature organic matter was heated in sealed gold tubes for 24 hr at temperatures ranging from 250 to 550°C and under pressures ranging from 0.5 to 4 kb, with and without water. Both elemental and Rock-Eval analyses were used to characterize the products. A comparison between our results, published data and the natural model shows that, quantitatively, natural maturation is simulated better when pyrolysis is performed under confined conditions (no free volume, no diluting inert gas). Thus, pyrolysis in a medium swept by an inert gas, vacuum pyrolysis and some pyrolysis in sealed glass tubes must be considered to be poor simulation tools. The presence of water does not seem to have an essential effect. Allowing the hydrocarbons formed to reach a certain value of partial pressure seems to be important. Results are unchanged when external pressure varies from 0.5 to 4 kb.     

Characterisation of brown coal humic acids and modified humic acids using pyrolysis gcms and other techniques

It has been proposed that Victorian brown coal can be considered as a two-component structure — a lignocellulosic “host”, containing various amounts of weakly bound or entrapped “guest” material together with very small amounts of inorganic and/or mineral matter. The latter predominantly consists of wax esters and/or terpenoid material. In this paper we describe attempts to gain structural information regarding the more complex, “host” component of the coal. Our initial model compound has been humic acid that can be readily obtained from the coal by alkaline extraction. It has been found that “pure” humic acid, free from material associated with the “guest” components of the coal, can be obtained by a highly selective, low-yielding alkaline extraction. This humic acid has been studied by nmr spectroscopy and pyrolysis gas chromatography-mass spectroscopy (py-gc/ms). The products arising from py-gc/ms have been compared with those obtained from similar pyrolysis of whole coals. Alkylation of humic acids using alkyl halides in the presence of base has been successfully carried out and reactivity of the resulting materials compared with those of the parent coal and humic acid.     

A study of the kinetic parameters of individual macerals from Upper Permian coals in South China via open-system pyrolysis

A unique Upper Permian coal, Leping coal, is widely distributed in South China. The coal samples studied in the paper were collected from two mines in the Shuicheng coalfield of Guizhou Province, southwest China. The geochemical works including coal petrography, maceral content, Rock–Eval pyrolysis, and kinetic modelling of hydrocarbon-generating have been carried out on whole coal and individual macerals. The higher contents of volatile matter, elemental hydrogen, and tar yield, and the high hydrocarbon generation potential of the Leping coals are attributed to their high content of “barkinite”, a special liptinite maceral.The hydrocarbon generation potential of “barkinite” (S₂=287 mg/g, hydrogen index (HI)=491 mg/g TOC) is greater than that of vitrinite (S₂=180 mg/g, HI=249 mg/g TOC), and much higher than that of fusinite (S₂=24 mg/g, HI=35 mg/g TOC). At the same experimental conditions, “barkinite” has a higher threshold and a narrower “oil window” than those of vitrinite and fusinite, and consequently, can generate more hydrocarbons in higher coalification temperature and shorter geological duration. Data from the activation energy distributions indicate that “barkinite” has a more homogenous chemical structure than that of vitrinite and fusinite. The above-mentioned characteristics are extremely important for exploring hydrocarbon derived from the Leping coals in South China.     

Interactions between organic matter and minerals in two bituminous coals of different rank

The association between specific mineral and organic constituents in two Asturian bituminous coals of different rank was studied. For this, raw coals were fractionated by density and the variation of a number of parameters was followed in parallel. Results of coal chemical analyses, including analyses for 22 elements, were used to establish the elemental association with coal organic matter. Petrographic analyses determined the distribution of macerals among densimetric fractions, vitrinite reflectance being at a minimum in the intermediate density fractions. Mineral species were identified by X-ray diffraction, FT-IR spectroscopy and Mössbauer spectroscopy. Comparison of trends for different parameters determined using this set of techniques allowed classification of the various minerals according to their association with organic matter. Carbonates seem to be specifically associated with the organic matter of the low-volatile bituminous coal whereas sulfides concentrate in the organic matter of the high-volatile bituminous coal. Vitrinite is the maceral exhibiting the most probable association with inorganic matter. The possibility of a merely physical association of fine-grained detrital minerals with organic matter cannot be excluded; nevertheless, one must bear in mind that even this type of interaction is important due to its effect on various coal preparation and utilization processes.     

The degree of oxidation of iron in synthetic iron-magnesian biotites

Summary Chemical analytical and pyrolytical methods have been used to study the Fe⁺²/Fe⁺³ ratios and dehydroxylation reactions in synthetic biotites. It has been found for the biotites with Fe/(Fe + Mg) of 20 to 70 mole % that the oxidation degree decreases from 26 to 16% with increasing iron. Based on the measured amounts of water and hydrogen released during pyrolysis it is inferred that the deprotonization is a dominant reaction at low temperatures (T 600°C), accompanied by dehydration as the temperature increases. Depending on the composition, a complete dehydroxylation takes place at T 900 °C, and the measured amount of water corresponds to the iron oxidation degree in the starting samples. The results of this study have important implications with respect to determination of the formation conditions of biotite-bearing rocks, and also for improvement of the techniques for determination of different valence of iron and water.

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Le degré d'oxidation du fer en biotites synthétiques contenants le fer et le magnésium

Résumé Des méthodes chimiques et pyrolitiques ont été utilisées pour l'étude des rapports Fe⁺²/Fe⁺³ et de la réaction de la déhydroxilation en biotites synthétiques. On a trouvé pour les biotites avec Fe/(Fe + Mg) de 20-70 mole % que le degré d'oxidation décroît à partir de 26 jusqu'à 16% pendent que le contenu du fer s'accroît. Sur la base de la quantité d'eau et hydrogène liberée pendant la pyrolyse, on infère que la déprotonisation est une réaction dominante à températures basses (T = 600°C), mais quand la température s'accroît, la déprotonisation est accopagnée de la déhydratation. Dépendant de la composition il y a une déhydroxilation complète à T = 900°C, et la quantité de l'eau mesurée correspond au degré d'oxidation du fer dans les specimens initials. Les résultats de cette étude infuencent la détermination des conditions de formation des roches contenantes biotite et aussi l'amélioration des techniques de la détermination du fer de valences différentes et de l'eau.

     

煤中干酪根的成熟度与菲的吸附行为间的关系

将云南先锋褐煤采用热模拟的实验方法制得一组成熟度不同的煤,并将煤中的干酪根用于对菲的吸附研究.结果表明:随着干酪根成熟度的增加,有机质结构变得紧密、刚硬,还原性和芳香性增强.不同成熟度干酪根的内部结构和性质与菲的吸附行为间存在一定的关系.随着干酪根内部结构的刚性和芳香性的增强,吸附等温线的非线性逐渐增强.对于成熟度相对较低的干酪根,随着成熟度的增加,吸附容量逐渐增大,而对于成熟度相对较高的干酪根,随着成熟度的增加,吸附容量却减小.     

Oil-generating coals of the San Juan Basin, New Mexico and Colorado, U.S.A.

Coal beds of the Upper Cretaceous Fruitland Formation in the San Juan Basin of northwestern New Mexico and southwestern Colorado have significant liquid hydrocarbon generation potential as indicated by typical Rock-Eval Hydrogen Indexes in the range of 200–400 mg hydrocarbon/g organic carbon (type II and III organic matter). Small, non-commercial quantities of oil have been produced from the coal beds at several locations. The oils are characterized by high pristane/phytane (ca 4) and pristane/n-C₁₇ ratios (ca 1.2), abundant C₂₁₊ alkanes in the C₁₀₊ fraction with a slight predominance of odd carbon-numbered n-alkanes, abundant branched-chain alkanes in the C₁₅₊ region, and a predominance of methylcyclohexane in the C₄----C₁₀ fraction. The oils are indigenous to the Fruitland Formation coals and probably migrated at thermal maturities corresponding to vitrinite reflectance values in the range 0.7–0.8%. Although the oils found to date are not present in commercial amounts, these findings illustrate the potential of some coals to generate and expel oil under conditions of moderate thermal heating.     

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.     

构造煤化学结构演化与瓦斯特性耦合机理

煤是对应力和应变非常敏感的一种特殊岩石,在不同的应力-应变环境和构造应力作用下,煤的物理结构、化学结构及其光性特征等都将发生显著变化,从而形成具有不同结构特征的、不同类型的构造煤。构造煤在变形的过程中,镜质组反射率将发生规律性变化,并被较为广泛地应用于煤田构造的定量研究,高温高压变形实验也证实了这一现象。为了深入探讨煤镜质组光性组构变化的微观机理,将X-射线衍射、顺磁共振和核磁共振等技术应用于不同类型构造煤以及高温高压实验变形煤的化学结构研究。研究表明,构造煤化学结构演化与镜质组反射率的演化具有密切的内在联系,镜质组反射率的光性异常是构造煤化学结构演化在物理光学性质上的具体体现。不同类型的构造煤由于物理和化学结构上的不同,导致瓦斯含量和透气性等瓦斯特性上的重大差异,糜棱煤特殊的物理和化学结构决定了其高含气量和低透气性的特征,是矿井瓦斯突出的危险地带,因此,可以通过构造煤分布规律的研究,进行矿井瓦斯富集与突出危险性的评价与预测,为矿井瓦斯灾害的研究提供新的思路和方法。     

低熟煤中的孢粉与常量元素和微量元素的相关性初探

运用电离耦合等离子体原子发射光谱(ICP-AES)和X射线荧光光谱分析(XRF),对新疆八道湾煤矿中侏罗统西山窑组煤中的孢粉角质层进行了分析,测定了煤中的常量和微量元素。并对煤中孢粉和共伴生元素进行了回归分析,探讨了微量和常量元素的煤岩学及孢粉学属性,在微量元素与孢粉的煤相学应用方面作了初步尝试。结果表明,成煤的蕨类植物孢子和裸子植物花粉与某些常量元素和微量元素有着很高的相关性;蕨类植物孢子和裸子植物花粉的相对含量在煤中具有互补性,决定了它们与微量元素的关系也具有一定的互补性。     

煤中剪切指向标志的类型讨论

通过与岩石中的剪切指向标志对比,初步研究了煤中的剪切指向标志。发现了如羽状脉体等特殊的指向标志。煤中剪切指向标志研究,是岩层构造运动学分析的主要内容,可判别局部剪应力方向,进而为确定应力场提供依据。     

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.     

原油族组分在煤中留存能力的研究

研究了煤及其干酪根对不同组分油气的留烃能力.将原油分成5个组分,引入溶胀理论,对低、中、高成熟度的煤及其干酪根在不同溶解度参数的溶剂中进行了溶胀实验,获得不同成熟度的煤及其干酪根的溶胀特征,进而得到不同成熟度的煤及其干酪根对5个组分的留烃能力.R°在0.4%～1.25%范围内的煤及其干酪根,其溶胀比随着煤的成熟度增加而降低;而R°大于1.25%的干酪根,其溶胀度则随着Ⅲ型干酪根的成熟度的增加而升高.在"油窗"范围内,随着成熟度的变化,煤和Ⅲ型干酪根的溶胀比降低,表明其留烃能力在下降.对于具有中等溶解度参数的组分,其留烃能力下降约20%.     

The structural evolution of organic matter during maturation of coals and its impact on petroleum potential and feedstock for the deep biosphere

The structural evolution of coals during coalification from peat to the end of the high volatile bituminous coal rank (VR_r = 0.22–0.81%) has been studied using a natural maturity series from New Zealand. Samples were studied using a range of standard coal analyses, Rock–Eval analysis, infrared spectroscopy (IR), X-ray photoelectron spectroscopy (XPS), and pyrolysis gas chromatography (Py-GC). The structural evolution of coal during diagenesis and moderate catagenesis is dominated by defunctionalisation reactions leading to the release of significant amounts of oxygen and thereby to an enrichment of aromatic as well as aliphatic structures within the residual organic matter. Based on the evolution of pyrolysis yields and elemental compositions with maturity it can be demonstrated that oxygen loss is the major cause for increasing Hydrogen Index values or hydrocarbon generating potentials of coals at such maturity levels. For the first time, the loss of oxygen in form of CO₂ has been quantified. During maturation from peat to high volatile bituminous coal ranks ∼10–105 mg CO₂/g TOC has been released. This is equivalent to 2.50E−4 to 1.25E−3 mg CO₂ generated from every litre of sediment per year falling into the range of deep biosphere utilisation rates. Immature coals, here New Zealand coals, therefore manifest the potential to feed deep terrestrial microbial life, in contrast to more mature coals (VR_r > ∼0.81%) for which defunctionalisation processes become less important.     

淮北煤田二叠纪煤中伴生元素的亲和性研究

以淮北煤田二叠纪10、7、3煤层样品为研究对象，采用仪器中子活化法（INNA）测试了煤中42个伴生元素的含量，将其与华北石炭-二叠纪和中国煤中的伴生元素含量、范围进行了对比，并对伴生元素中主量元素含量和灰分的关系、微量元素的共生组合特点以及稀土元素含量与灰分的关系、稀土元素分布模式进行了初步分析。结果表明，对环境有影响的Ba、Co、Cr、Cu、Mo、Th、V、W、Zn、Ti元素在研究区煤中相对富集，Al、Ti、K、Na等元素与灰分有较好的相关性，Ca、Mg、Fe和灰分的相关性较差，稀土元素与灰分正相关且具有相似的分配模式，普遍存在Eu亏损现象，说明煤中伴生元素的主要来源是陆源物质。     

内蒙古胜利煤田0-1孔煤中微量元素地球化学特征

运用电感耦合等离子体质谱和煤质分析等技术方法,对内蒙古胜利煤田0-1号钻孔揭露的早白垩世1、2和4号煤层(共20个煤分层,1个夹矸)进行了研究。结果显示,1、2号煤层的挥发分产率大于44%,透光率小于50%,煤类为褐煤;4号煤层挥发分产率42%,透光率53%,煤类为次烟煤(长焰煤);1、2号煤层灰分和硫含量较高,4号煤层灰分和硫含量较低。与世界煤微量元素含量平均值相比,1、2和4号煤层中Sb富集,V、Zr、Nb、Hf、W等元素轻微富集,其它微量元素的含量接近或低于世界煤含量的平均值。1、2和4号煤层中稀土元素和钇(REY)含量较低,根据上地壳标准值(La/Lu)N比值,所有煤分层均显示重稀土富集类型特征,而煤中泥岩夹矸则显示轻稀土富集类型特征。     

中国煤中有机硫的分布及其成因

对来自全国26个省、市、自治区的290个煤样中有机硫的质量分数测试及研究,发现煤中有机硫质量分数基本分布在0%¹.0%范围内。在低硫煤中硫分以有机硫为主,在高硫煤中以无机硫为主。中、高硫煤中,广西、湖南等地区很大一部分煤中硫分以有机硫为主。在所采集的样品中,高有机硫煤(有机硫>1%)均分布在华南、华北两大聚煤区,属于石炭、二叠纪煤。高有机硫煤中有机硫质量分数的变化与变质程度无明显关系。煤炭形成过程中海水作用的影响,是导致煤中有机硫含量偏高的最主要原因。     

低阶煤显微组分对一氧化碳的吸附性能

研究低阶煤中不同显微组分对CO气体的吸附性能,对低阶煤自燃发火的预测与防治具有指导意义。对低阶煤中的惰质组与镜质组分别进行了30℃、40℃、50℃、55℃、60℃和65℃的等温吸附实验以及煤质分析、煤岩分析和傅立叶红外光谱(FTIR)分析。结果表明:当温度一定(T≤50℃)时,煤对CO的吸附量与压力之间的关系可用Langmuir方程来描述;当温度较高(T>50℃)时,煤对CO的吸附量与压力之间呈线性增加关系,且可采用Henry方程来描述,但此时温度对煤吸附CO的影响较复杂,有待进一步研究;此外,因低阶煤中的丝质体、含氧官能团和负电性官能团含量普遍较高,尤其羟基—OH含量较高,从而对煤中惰质组吸附CO产生较大的影响,而对镜质组吸附CO的影响较小。     

重庆长河碥矿煤的微量元素地球化学特征

运用煤岩学和地球化学的理论和方法,对重庆长河碥矿晚三叠世须家河组煤中微量元素进行了研究。结果表明,长河碥矿各煤层中明显富集Pb,其平均值为29.58μg/g。长河碥矿煤中潜在的有害微量元素Be (5.9μg/g)、Cr (28.6μg/g)、Cu (34.06μg/g)、As (10.03μg/g)和Th (12.49μg/g)均较富集;稀土元素含量为59.79²87μg/g,均值为136.92μg/g,略高于中国煤中稀土元素总量均值(119.7μg/g),高于美国煤中的稀土元素总量均值(53.59μg/g)。8煤中稀土元素含量异常可能是地下水淋滤作用的结果。长河碥矿煤中有害微量元素主要受控于陆源物质的供给。     

Structure and origin of terpenoid hydrocarbons in some German coals

Hydrocarbon extracts of coal samples from major coal fields in West Germany have been investigated by gas chromatography-mass spectrometry (GC/MS). The samples are of Carboniferous and Tertiary age and derive from limnic and paralic environments, the Saar District, the Ruhr Area and the Lower Rhine Basin.Differences in facies, maturity and age reflected in the distribution patterns of the extracted alkylcyclohexanes. An unexpected occurrence of cyclic diterpenoid hydrocarbons in some samples of Carboniferous age has been found. The tetracyclic compounds mainly show phyllocladane type structures and can serve as source indicators.Hydrocarbons obtained from chemical degradation of the macromolecular material of the samples also revealed phyllocladane-type compounds which are normally associated to resins of modern and extinct familes of conifers. Origin and structural variations of this class of hydrocarbons are discussed in terms of maturity and palaeobotanical implications.