Facies recognition of some Tertiary coals applied to prediction of oil source rock occurrence

Coals are oil source rocks in many of the Tertiary basins of Southeast Asia. The precursors of these hydrogen rich and oxygen poor coals are coastal plain peats which have mainly developed in an everwet and tropical climate. In these environments water flow and reworking can concentrate liptinitic kerogen in preference to vitrinitic kerogen. The distribution, petrography and chemistry of the coaly Miocene source rocks present in the Kutai Basin are described. The recognition of environmental controls on the accumulation of potentially oil-prone coals and coaly shales in deltaic environments is an aid to predictive source bed recognition in petroleum exploration. Comments on the environment of deposition of coaly sediments in the basins of the Norwegian Sea are discussed with reference to their possible oil and/or gas sourcing potential. The Triassic - Jurassic coals of the Haltenbanken area may become more oil-prone towards the delta margins, and facies mapping could aid oil exploration in this area.     

Coalification in Carboniferous sediments from the Lötschberg base tunnel

Vitrinite reflectance (Rr), proximate analysis and carbon isotope composition (δ¹³C) have been used to characterise coal samples from two zones of Late Carboniferous sediments (Gastern and Ferden) in the Aar massif where they are penetrated by the Lötschberg base tunnel (constructed between 1999 and 2005). Samples are characterised by variable ash yields (21.7–93.9%; dry basis); those with ash yields of less than ~50% and with volatile matter content (V;dry ash-free basis) within the limits 2 < V% ≤ 8 are anthracite. Values of Rr range from 3.89% to 5.17% and indicate coalification to the rank of anthracite and meta-anthracite in both Gastern and Ferden Carboniferous zones. Samples of anthracite and shale from the Gastern Carboniferous exhibit a relatively small range in δ¹³C values (–24.52‰ to –23.38‰; mean: –23.86‰) and are lighter than anthracite samples from the Ferden Carboniferous (mean: –22.20‰). The degree of coalification in the Gastern and Ferden Carboniferous zones primarily depends on the maximum rock temperature (T) attained as a result of burial heating. Vitrinite reflectance based estimates of T range from ~290° –360 °C. For a proposed palaeogeothemal gradient of 25 ° C/km at the time of maximum coalification the required overburden is attributable to relatively thin autochtonous Mesozoic/Cenozoic sedimentary cover of the Aar massif and Gastern granite and deep tectonic burial beneath advancing Helvetic, Ultrahelvetic and Prealpine (Penninic) nappes in Early Oligocene to Miocene.     

The petroleum generation potential and effective oil window of humic coals related to coal composition and age

A worldwide data set of more than 500 humic coals from the major coal-forming geological periods has been used to analyse the evolution in the remaining (Hydrogen Index, HI) and total (Quality Index, QI) generation potentials with increasing thermal maturity and the ‘effective oil window’ (‘oil expulsion window’). All samples describe HI and QI bands that are broad at low maturities and that gradually narrow with increasing maturity. The oil generation potential is completely exhausted at a vitrinite reflectance of 2.0–2.2%R_o or T_max of 500–510 °C. The initial large variation in the generation potential is related to the original depositional conditions, particularly the degree of marine influence and the formation of hydrogen-enriched vitrinite, as suggested by increased sulphur and hydrogen contents. During initial thermal maturation the HI increases to a maximum value, HI_max. Similarly, QI increases to a maximum value, QI_max. This increase in HI and QI is related to the formation of an additional generation potential in the coal structure. The decline in QI with further maturation is indicating onset of initial oil expulsion, which precedes efficient expulsion. Liquid petroleum generation from humic coals is thus a complex, three-phase process: (i) onset of petroleum generation, (ii) petroleum build-up in the coal, and (iii) initial oil expulsion followed by efficient oil expulsion (corresponding to the effective oil window). Efficient oil expulsion is indicated by a decline in the Bitumen Index (BI) when plotted against vitrinite reflectance or T_max. This means that in humic coals the vitrinite reflectance or T_max values at which onset of petroleum generation occurs cannot be used to establish the start of the effective oil window. The start of the effective oil window occurs within the vitrinite reflectance range 0.85–1.05%R_o or T_max range 440–455 °C and the oil window extends to 1.5–2.0%R_o or 470–510 °C. For general use, an effective oil window is proposed to occur from 0.85 to 1.7%R_o or from 440 to 490 °C. Specific ranges for HI_max and the effective oil window can be defined for Cenozoic, Jurassic, Permian, and Carboniferous coals. Cenozoic coals reach the highest HI_max values (220–370 mg HC/g TOC), and for the most oil-prone Cenozoic coals the effective oil window may possibly range from 0.65 to 2.0%R_o or 430 to 510 °C. In contrast, the most oil-prone Jurassic, Permian and Carboniferous coals reach the expulsion threshold at a vitrinite reflectance of 0.85–0.9%R_o or T_max of 440–445 °C.     

自燃煤有机地球化学特征研究

通过有机地球化学研究，发现神府、焦坪、灵武三种自燃煤的ＣＨ２Ｃｌ２抽提率、族组分组成、有机地球化学参数有较大的差别。色谱曲线表现为两种类型，即单峰型和双峰型。生物标志物组合也有较大的差别。由于这种有机地球化学特征的不同，导致了自燃煤的自燃属性的不同。因而，有机地球化学方法可以用于自燃煤的研究。     

Chemistry of alkali extraction of brown coals—I. Kinetics, characterisation and implications to coalification

Three Australian brown coals have been separated into humin and humic acid fractions and studied by high resolution solid state ¹³C NMR spectroscopy and Fourier transform IR spectroscopy. The aromatic rings of the humic acids are highly substituted showing that extensive cross linking must have occurred during formation from wood lignin and tannin. However, the humins contain more aliphatic carbon and hydrogen than the corresponding humic acids. This shows that little cross linking has occurred with other components of the brown coal such as resins, waxes cutin and algal detritus, and cross linking has not rendered the aromatics alkali insoluble. The kinetics of extraction are complex and not simple first order. This is reflected in the chemical composition of the humic acid which is extraction temperature dependent. We also observed that there is a conversion of aromatic carbon to aliphatic carbon and gas during extraction, probably by alkaline oxidation, resulting in ring opening. A range of suitable model compounds have been studied to confirm this finding. Such a mechanism may account for the modification of lignin in oxidising environments such as those occurring in the initial stages of coalification (lignite or brown coal formation) and in soils.     

高煤级煤粗粒体反射率的演化轨迹

通过系统测试，查明了镜质体油浸最大反射率在２．０％～１０．０％之间的样品中粒粒体反射率的演化轨迹，发现其最大反射率的演化具有“转折”特征。粗粒体化学结构的“非石墨化碳”性质、物理结构的“富微孔性”及构造应力的作用是控制反射率演化的主要因素。     

腐植煤中的超细纹层

利用超薄切片透射电镜分析技术，在华北东部太原组和山西组、吐─哈盆地侏罗系腐植煤中检出了超细纹层。超细纹层在腐植煤中呈分散状、间隔状和密集状，前二者主要存在于无结构镜质体中，后者则存在于沥青质体或层状藻类体条带中。超细纹层来源于微藻类细胞的抗分解外壁，是藻类在超微层次的重要表现形式。腐植煤形成过程中藻类的贡献较藻类体数量所反映的要高。     

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.     

Multifacetted study of a cretaceous coal with algal affinities—II. Composition of liquefaction products

Two hydrogen-rich lithobodies of highly alipathic character from a coal occurring in southwest Utah, have been studied. Bituminite (>50%), vitrinite (25–30%) and liptodetrinite (7–12%) are the principal macerals. The hexane-soluble products of hydrogenating the lithotypes at 400° with tetralin and hydrogen have been analyzed by GC-MS. Products identified include homologous series of alkylated naphthalenes, phenols, furans, cyclohexenones and hydroxy-pyridines. In the case of furans, the alkyl groups extend beyond C₃₀. Materials released by Soxhlet extraction with pyridine consist chiefly of homologous series of fatty acids and their methyl esters and of methyl alkyl ketones, which were not found in the hydrogenation products. The long alkyl chains in these substances can account for about 75% of the alkanes found in the hydrogenation products but not in the extracts. Most of the compounds mentioned in the foregoing are thought to be physically held or trapped in the coal, rather than chemically combined in its macromolecular network. Except for the fatty acids, the origins of these substances are difficult to identify.     

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.