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1.
Leping coal is known for its high content of “barkinite”, which is a unique liptinite maceral apparently found only in the Late Permian coals of South China. “Barkinite” has previously identified as suberinite, but on the basis of further investigations, most coal petrologists conclude that “barkinite” is not suberinite, but a distinct maceral. The term “barkinite” was introduced by (State Bureau of Technical Supervision of the People's Republic of China, 1991, GB 12937-91 (in Chinese)), but it has not been recognized by ICCP and has not been accepted internationally.In this paper, elemental analyses (EA), pyrolysis-gas chromatography, Rock-Eval pyrolysis and optical techniques were used to study the optical features and the hydrocarbon-generating model of “barkinite”. The results show that “barkinite” with imbricate structure usually occurs in single or multiple layers or in a circular form, and no definite border exists between the cell walls and fillings, but there exist clear aperture among the cells.“Barkinite” is characterized by fluorescing in relatively high rank coals. At low maturity of 0.60–0.80%Ro, “barkinite” shows strong bright orange–yellow fluorescence, and the fluorescent colors of different cells are inhomogeneous in one sample. As vitrinite reflectance increases up to 0.90%Ro, “barkinite” also displays strong yellow or yellow–brown fluorescence; and most of “barkinite” lose fluorescence at the maturity of 1.20–1.30%Ro. However, most of suberinite types lose fluorescence at a vitrinite reflectance of 0.50% Ro, or at the stage of high volatile C bituminous coal. In particular, the cell walls of “barkinite” usually show red color, whereas the cell fillings show yellow color under transmitted light. This character is contrary to suberinite.“Barkinite” is also characterized by late generation of large amounts of liquid oil, which is different from the early generation of large amounts of liquid hydrocarbon. In addition, “barkinite” with high hydrocarbon generation potential, high elemental hydrogen, and low carbon content. The pyrolysis products of “barkinite” are dominated by aliphatic compounds, followed by low molecular-weight aromatic compounds (benzene, toluene, xylene and naphthalene), and a few isoprenoids. The pyrolysis hydrocarbons of “barkinite” are mostly composed of light oil (C6–C14) and wet gas (C2–C5), and that heavy oil (C15+) and methane (C1) are the minor hydrocarbon.In addition, suberinite is defined only as suberinized cell walls—it does not include the cell fillings, and the cell lumens were empty or filled by corpocollinites, which do not show any fluorescence. Whereas, “barkinite” not only includes the cell walls, but also includes the cell fillings, and the cell fillings show bright yellow fluorescence.Since the optical features and the hydrocarbon-generating model of “barkinite” are quite different from suberinite. We suggest that “barkinite” is a new type of maceral.  相似文献   

2.
栓皮栎的热模拟特征及木栓质的成烃演化   总被引：3，自引：0，他引：3  
由于大多数沉积有机质或煤层中的木栓质体在很低演化阶段荧光就消失了，使得地球化学家和煤岩学家往往低估了木栓质体对成烃的贡献。利用显微镜荧光检测和显微傅里叶红外光谱技术对现代植物栓皮栎的树皮进行人工热模拟研究，结果表明现代木栓组织和木检质成分是一种高度偏油的有机质，在低热力条件下释放出大量的以异构烃和环烷烃为主的液态烃类，大约在镜质体反射率为０．５％之前，生成Ｃ６＋烃类总量的２／３以上。现代木栓热模拟生烃现象要滞后于地质体中的木栓质体，它不能完全复制木栓质体的自然熟化过程  相似文献   

3.
The organic maceral suberinite is widely believed to be a contributor to immature or low mature oils with Ro < 0.5% in some coal and terrigenous sequences. However, its evolution of hydrocarbon generation, especially in the relatively high maturation stage of Ro > 0.5%, has not been sufficiently characterized. This issue was addressed herein using periderm cork tissues of the modern angiosperm Quercus suber (suberin), which is a possible bio-precursor of suberinite, in artificial bacterial degradation and hydrous pyrolysis experiments. Integrated studies were conducted, including analyses on the compositions of hydrocarbon yields and the content variations that were generated during the experiments, gas chromatography (GC) analyses of generated oils and spectral fluorescence observations, and Rock-Eval and Fourier Transform Infrared (FTIR) microspectroscopic studies on solid residues. Analytical results indicate that suberin and suberinite have long and complex hydrocarbon generation histories. In general, the hydrocarbon that is generated during bacterial degradation is predominantly gas and present in relatively limited amounts, while the oils mainly are generated during hydrous pyrolysis. Furthermore, the oil generation has two peaks that correspond to Ro of approximately 0.35–0.50% and 0.80–1.10%. In composition, the early generated oil mainly consists of long chain waxy and oxygen containing compounds, while the late generated oil is relatively enriched in aromatic compounds. These features can be ascribed to the chemical nature (e.g., composition and structure) of suberin. It is a type of insoluble and high molecular weight polyester compound that contains large quantities of long chain structure dicarboxylic acids and alcohols. Consequently, the deoxygenization of these compounds can take place under relatively low thermodynamic conditions, generating liquid oil that is dominated by a long chain structure and oxygen-containing waxy compounds. In contrast, the degradation of the phenolic compounds results in the second oil generation peak. Therefore, suberinite has a two stage and relatively long oil generation history and is a good bio-precursor for coal-derived oil generation.  相似文献   

4.
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.  相似文献   

5.
Mathematical models of hydrocarbon formation can be used to simulate the natural evolution of different types of organic matter and to make an overall calculation of the amounts of oil and/or gas produced during this evolution. However, such models do not provide any information on the composition of the hydrocarbons formed or on how they evolve during catagenesis.From the kinetic standpoint, the composition of the hydrocarbons formed can be considered to result from the effect of “primary cracking” reactions having a direct effect on kerogen during its evolution as well as from the effect of “secondary cracking” acting on the hydrocarbons formed.This report gives experimental results concerning the “primary cracking” of Types II and III kerogens and their modelling. For this, the hydrocarbons produced have been grouped into four classes (C1, C2–C5, C6–C15 and C15+). Experimental data corresponding to these different classes were obtained by the pyrolysis of kerogens with temperature programming of 4°C/min with continuous analysis, during heating, of the amount of hydrocarbons corresponding to each of these classes.The kinetic parameters of the model were optimized on the basis of the results obtained. This model represents the first step in the creation of a more sophisticated mathematical model to be capable of simulating the formation of different hydrocarbon classes during the thermal history of sediments. The second step being the adjustment of the kinetic parameters of “secondary cracking”.  相似文献   

6.
The bulk properties and bitumen molecular compositions of a rank-series of 38 humic coals from the New Zealand Coal Band (Cretaceous–Cenozoic) have been analysed to investigate early maturation processes affecting coaly organic matter through diagenesis to moderate catagenesis (Rank(Sr) 0.0–11.8, Ro 0.23–0.81%). The samples comprise a relatively restricted range of vitrinite rich coal types formed largely from higher land plant material under relatively oxic conditions, but with a significant contribution from microbial biomass. With increasing rank, total organic carbon contents show a general increase, whereas moisture and asphaltene contents decrease. Bitumen yields also decrease through the stages of diagenesis and early catagenesis (Rank(Sr) < 9, Ro < 0.55%), indicating partial loss of initial bitumen during early maturation. Thermal generation of hydrocarbons begins slowly at Rank(Sr)  5–6 (Ro  0.40%) as indicated by the constant occurrence and gradual increase of isoprenoids (e.g., pristane and phytane) and hopanoids in their more mature αβ configuration. This early phase of catagenesis, not previously recognised in New Zealand coals, is followed at Rank(Sr)  9 (Ro  0.55%) by the main catagenesis phase characterised by a more rapid increase in the generation of hydrocarbons, including total n-alkanes, isoprenoids and αβ-hopanes. Changes in the maturity of New Zealand coals can be traced by the Carbon Preference Index and several hopane maturity parameters, including 22S/(22S + 22R), αβ/(αβ + βα) and ββ/(αβ + βα + ββ).  相似文献   

7.
This paper discusses the occurrence of 28,30-dinor-17α,18α,21β-hopane (bisnorhopane) in stratigraphically, fairly well preserved Viking Group sections from wells in local depressions in the North Viking Graben Area. The results show the presence of high relative amounts of bisnorhopane in the “Syn-rift sections”, whilst the “Post-rift sections” contain little or no bisnorhopane. Since most exploration wells are drilled on structural highs, primarily penetrating the “Post-rift Draupne”, this may explain why many analyzed source rock sections in this area contain little bisnorhopane.As a correlation of Draupne sections using the vertical, relative bisnorhopane distributions, it is suggested to be a potential stratigraphic marker for the area, indicating the presence of “Syn-rift Draupne” sediments.The relative bisnorhopane amounts follow a logarithmic reduction with depth and thermal maturity. The bisnorhopane signal is nearly extinguished at 3700 m depth at a maturity of Ro = 0.9–1.0%.  相似文献   

8.
Thermal maturity was determined for about 120 core, cuttings, and outcrop samples to investigate the potential for coalbed gas resources in Pennsylvanian strata of north-central Texas. Shallow (< 600 m; 2000 ft) coal and carbonaceous shale cuttings samples from the Middle-Upper Pennsylvanian Strawn, Canyon, and Cisco Groups in Archer and Young Counties on the Eastern Shelf of the Midland basin (northwest and downdip from the outcrop) yielded mean random vitrinite reflectance (Ro) values between about 0.4 and 0.8%. This range of Ro values indicates rank from subbituminous C to high volatile A bituminous in the shallow subsurface, which may be sufficient for early thermogenic gas generation. Near-surface (< 100 m; 300 ft) core and outcrop samples of coal from areas of historical underground coal mining in the region yielded similar Ro values of 0.5 to 0.8%. Carbonaceous shale core samples of Lower Pennsylvanian strata (lower Atoka Group) from two deeper wells (samples from ~ 1650 m; 5400 ft) in Jack and western Wise Counties in the western part of the Fort Worth basin yielded higher Ro values of about 1.0%. Pyrolysis and petrographic data for the lower Atoka samples indicate mixed Type II/Type III organic matter, suggesting generated hydrocarbons may be both gas- and oil-prone. In all other samples, organic material is dominated by Type III organic matter (vitrinite), indicating that generated hydrocarbons should be gas-prone. Individual coal beds are thin at outcrop (< 1 m; 3.3 ft), laterally discontinuous, and moderately high in ash yield and sulfur content. A possible analog for coalbed gas potential in the Pennsylvanian section of north-central Texas occurs on the northeast Oklahoma shelf and in the Cherokee basin of southeastern Kansas, where contemporaneous gas-producing coal beds are similar in thickness, quality, and rank.  相似文献   

9.
A mechanical decrepitation device coupled with a gas chromatograph has been used to characterize the molecular composition of gaseous and liquid hydrocarbons contained in minerals. Application of this technique allows the identification of low-molecular-weight n-alkanes and some aromatic hydrocarbons in sulfides and gangue minerals from epigenetic Variscan and post-Variscan lead–zinc deposits in the Rhenish Massif, Germany. Based on the analysis of 200 samples, Variscan and post-Variscan mineralization can be distinguished by the composition of associated hydrocarbons. Variscan sulfides and gangue minerals contain high abundancies of methane. In contrast, n-alkanes in the C2–C9 range and aromatic hydrocarbons (benzene, toluene) are dominant in post-Variscan mineralization. The absence of high-molecular-weight hydrocarbons in ore minerals suggests highly mature gas associated with hydrothermal activity, during which hydrothermal fluids caused an increase in thermal maturation of organic matter and the generation of low-molecular-weight hydrocarbons in the adjacent organic-rich rocks. The hydrocarbon compositions contained in fluid inclusions of Variscan and post-Variscan minerals are probably governed by the maturation level of the potential source rocks. In Variscan time tectonic brines (T > 175 °C) generated predominantly methane, whereas basement brines (T < 175 °C) expelled higher-molecular-weight hydrocarbons (wet gases, condensates, aromatic hydrocarbons) from adjacent rocks during the Mesozoic event. The specific role of hydrocarbons in sulfide precipitation via thermochemical sulfate reduction is indicated by geochemical characteristics of organic matter associated with the Plombières Pb–Zn deposit, in eastern Belgium. Intense alteration phenomena were observed in near-ore kerogens, compared with unaltered kerogens far from the ore body, as well as by a very high maturity (5.40% Ro), a systematic depletion in 12C towards the vein-type mineralization, high atomic S/C ratios (0.49), and by low atomic H/C ratios (0.29). The data suggest that hydrothermal solutions caused a drastic increase in the thermal maturation of organic matter within the adjacent wall rock. Increased thermal maturation resulted in increased δ13C-values of organic carbon due to the preferential release of 12C. The change in the organic matter to a H-depleted and S-enriched bulk composition in association with sulfide ores strongly suggests that thermochemical sulfate reduction was responsible for organic degradation. Thus, thermochemical sulfate reduction probably triggered base metal sulfide precipitation in Variscan and post-Variscan ore deposits of the Rhenish Massif. Finally, based on data from this study and previous investigations, new genetic models are presented for both Variscan and post-Variscan mineralization in the Rhenish Massif. Received: 15 September 1999 / Accepted: 2 December 1999  相似文献   

10.
Based on the tested data of pressure and vitrinite reflectance of some wells in sedimentary basins, abnormal high pressure is regarded as not the only factor to retard the increase of vitrinite reflectance (R o). Apart from the types of the organic matter, the physical environment (temperature and pressure) and chemical environment (fluid composition and inorganic elements) will result in the abnormal vitrinite reflectance values in the sedimentary basins. This paper tested trace elements and vitrinite reflectance data from the the abnormal high pressure and normal pressure strata profiles, respectively, and found that the acidic and lower salinity starta are favorable for the increase of R o. By discussing the corresponding relationship between the contents of some trace elements in the mudstone and the vitrinite reflectance values, the typical trace elements were found to suppress and/or catalyze the vitrinite reflectance of organic matter, while the elements of Ca, Mn, Sr, B, Ba and P may result in the retardation of R o. However, elements of Fe, Co, Zn, Ni and Rb may catalyze the organic matter maturation. This study is conductive to the organic maturation correction, oil and gas assessment and thermal history reconstruction by the paleothermometry. Translated from Acta Geologica Sinica, 2006, 80(11): 1760–1769 [译自: 地质学报]  相似文献   

11.
The kerogen of a sample of Estonian Kukersite (Ordovician) was examined by spectroscopic (solid state 13C NMR, FTIR) and pyrolytic (“off-line”, flash) methods. This revealed an important contribution of long, linear alkyl chains in Kukersite kerogen. The hydrocarbons formed upon pyrolysis are dominated by n-alkanes and n-alk-1-enes and probably reflect a major contribution of selectivity preserved, highly aliphatic, resistant biomacromolecules from the outer cell walls of Gloeocapsomorpha prisca. This is consistent with the abundant presence of this fossilized organism in Kukersite kerogen. In addition high amounts of phenolic compounds were identified in the pyrolysates. Series of non-methylated, mono-, di- and trimethylated 3-n-alkylphenols, 5-n-alkyl-1,3-benzenediols and n-alkylhydroxybenzofurans were identified. All series of phenolic compounds contain long (up to C19), linear alkyl side-chains. Kukersite kerogen is, therefore, an aliphatic type II/I kerogen, despite the abundance of free phenolic moieties. This study shows that phenol-derived moieties are not necessarily associated with higher plant-derived organic matter.The flash pyrolysate of Kukersite kerogen was also compared with that of the kerogen of the Guttenberg Oil Rock (Ordovician) which is also composed of accumulations of fossilized G. prisca. Similarities in the distributions of hydrocarbons and sulphur compounds were noted, especially for the C1–C6 alkylbenzene and alkylthiophene distributions. However, no phenolic compounds were detected in the flash pyrolysate of the Guttenberg kerogen. Possible explanations for the observed similarities and differences are discussed.  相似文献   

12.
Aromatic hydrocarbons from benzene extracts of New Albany Shale were characterized. A biomarker that has a molecular weight of 546 and a structural configuration consistent with that of an alkyl-aromatic hydrocarbon (C40H66) was tentatively identified. It was found that the relative concentrations of the biomarker are indicative of differing levels of thermal maturity of the shale organic matter. A 40-carbon bicyclic carotenoid (C40H48) is proposed as the geochemical precursor of this biomarker. Thermal maturity of the shale organic matter can also be differentiated by observing differences in “fingerprints” as obtained by field-ionization mass spectrometry on the aromatic hydrocarbon fraction. Using this technique, we found that the more mature shale samples from southeastern Illinois contain more low molecular weight extractable aromatic hydrocarbons and the less mature shale samples from northwestern Illinois contain more high molecular weight extractable aromatic hydrocarbons. It was demonstrated that field-ionization and tandem mass spectrometric techniques through fingerprint and individual compound identification, are useful for shale aromatic hydrocarbon fraction characterization and for thermal maturation interpretation.  相似文献   

13.
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%Ro or Tmax 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, HImax. Similarly, QI increases to a maximum value, QImax. 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 Tmax. This means that in humic coals the vitrinite reflectance or Tmax 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%Ro or Tmax range 440–455 °C and the oil window extends to 1.5–2.0%Ro or 470–510 °C. For general use, an effective oil window is proposed to occur from 0.85 to 1.7%Ro or from 440 to 490 °C. Specific ranges for HImax and the effective oil window can be defined for Cenozoic, Jurassic, Permian, and Carboniferous coals. Cenozoic coals reach the highest HImax 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%Ro 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%Ro or Tmax of 440–445 °C.  相似文献   

14.
Marine, organic-rich rock units commonly contain little for vitrinite reflectance (VR0) measurement, the most commoly used method of assessing thermal maturity. This is true of the Lower Jurassic “Nordegg Member”, a type I/II, sulphur-rich source rock from the Western Canada Sedimentary Basin. This study examines the advantages and pitfalls associated with the use of Rock-Eval Tmax and solid bitumen reflectance (BR0) to determined maturity in the “Nordegg”. Vitrinite reflectance data from Cretaceous coals and known coalification gradients in the study area are used to extrapolate VR0 values for the “Nordegg”.Tmax increases non-linearly with respect to both BR0 and extrapolated VR0 values. A sharp increase in the reflectaance of both solid bitumen and vitrinite occurs between Tmax 440–450°C, and is coincident with a pronounced decrease in Hydrogen Index values and the loss of solid bitumen and telalginite fluorescence over the same narrow Tmax interval. This Tmax range is interpreted as the main zone of hydrocarbon generation in the “Nordegg”, and corresponds to extrapolated VR0 values of 0.55–0.85%. The moderate to high sulphur contents in the kerogen played a significant role in determining the boundaries of the “Nordegg” oil window.A linear relationship between BR0 and extrapolated VR0, as proposed elsewhere, is not true for the “Nordegg”. BR0 increases with respect to extrapolated VR0 according to Jacob's (1985) formula (VR0=0.618×(BR0)+0.40) up to VR0≈0.72% (BR0≈0.52%). Beyond this point, BR0 increases sharply relative to extrapolated VR0, according to the relatioship VR0 = 0.277 × (BR0) + 0.57 (R2 = 0.91). The break in the BR0−VR0 curve at 0.72%VR0 is thought to signifiy the peak of hydrocarbon generation and represents a previously unrecognized coalification jump in the solid bitumen analogous to the first coalification jump of liptinites.  相似文献   

15.
Organic-rich samples derived from a Middle Cambrian Formation in the Georgina Basin, and from the Middle Proterozoic of the McArthur Basin in northern and central Australia, yielded alginite ranging from immature oil shale material to overmature residue. A maturation scale has been developed based on the thermal evolution of alginite as determined from reflectance and fluorescence. The coalification path of alginite is marked by jumps in contrast to the linear path of wood-derived vitrinite. Six zones have been recognised, ranging from undermature (zone I), through the mature (zones II/III), followed by a stable stage of no change (zone IV) to the overmature (zones V and VI). The onset of oil generation in alginite as evident from the present study is at 0.3% Ro Alg. and is expressed in a change of fluorescence from yellow to brown, and a coalification jump from 0.3 to 0.6% Ro of Alg. In many boreholes zone III can be distinguished between 0.6 and 0.8% Ro of Alg. where subsequent oil generation occurs. Zones II and III represent the oil window.A zone of little or no change designated zone IV, at of alginite follows zones II/III. A marked coalification jump characterises zone V, where a pronounced change in reflectance occurs to >1.0% Ro Alg., signifying peak gas generation. The border of oil preservation lies at the transition of zone V and VI, at 1.6% Ro Alg. In zone VI gas generation only occurs.Comparison of reflectance results with experimental and geochemical pyrolysis data supports high activation energies for hydrocarbon generation from alginite, and therefore a later onset of oil generation than other liptinite macerals (i.e. cutinite, exinite, resinite) as well as a narrow oil window.Transmission electron microscopy (TEM) confirms that alginite does not go through a distinct intermediate stage but that the percentage of unreacted organic matter decreases as maturation proceeds. A clear distinction can be made in TEM between immature alginite, alginite after oil generation, and alginite residue following gas generation. Alginite beyond 1.6% Ro acquires very high densities and the appearance of inertinite in TEM.Bitumens/pyrobitumens make a pronounced contribution to the organic matter throughout the basins and have been shown to effect pyrolysis results by suppressing Tmax. The bitumens/pyrobitumens have been divided into four groups, based on their reflectance and morphology, which in turn appears to be an expression of their genetic history. Their significance is in aiding the understanding of the basins' thermal history, and the timing of oil and gas generation.  相似文献   

16.
《Applied Geochemistry》1988,3(5):441-453
Green River shale (Type I kerogen), Yaamba shale (Type II kerogen) and Sarufutsu coal (Type III kerogen) were heated to various temperatures using Rock-Eval. The amount of hydrocarbons generated and weight loss by pyrolysis were measured to obtain a better understanding of petroleum generation. After the pyrolysis experiments, elemental analysis (C, H), vitrinite reflectance (%Ro) measurement, maceral observation, infrared spectroscopy (IR) and13C-NMR spectroscopy were carried out on the coal samples. Changes in H/C atomic ratio, IR and NMR spectra indicate that experiments by Rock-Eval resemble those of the natural evolution of kerogen. However, the petrographic changes of the coal show more similarity to coal liquefaction and coking than to natural coalification. Changes in the amount of generated hydrocarbons with increasing maturation show that Type II kerogen produces more hydrocarbons than does Type I when Ro does not exceed 1.1%. Petroleum generation curves for the three samples were concordant with trends in natural systems, and a conceptual model of petroleum generation curve classified into three types is proposed, namely (1) curve of total amount enerated, (2) curve of generation rate, and (3) curve of fluid composition. Changes of IR and NMR spectra after pyrolysis imply that generated hydrocarbons are derived from aliphatic C structures of kerogen macromolecules. Moreover, the difference in genetic potential between Type I and Type III reflects different amounts of aliphatic structures. Type I is assumed to have a simple assemblage (mainly polymethylene carbons), and Type III is assumed to have a more complex variety of structures that are responsible for the difference in generation rates between the two kerogen Types. A quantitative analysis of C species of various bond structure by13C-NMR confirms that petroleum generation is the process of bond cleavage of kerogen macromolecules; lower-energy bonds decrease at an earlier stage of reaction, while aromatic carbons with higher bond energies survive to form graphitic structure at postmature stages. Emphasis is placed on the idea that the most important and direct factor in petroleum generation is a change in the molecular structure of kerogen with increasing maturation. NMR and other methods providing information about molecular structures of kerogen will become strong tools for evaluating source rocks and sedimentary basins in the future.  相似文献   

17.
The presence of shale oil in the Cretaceous Hengtongshan Formation in the Tonghua Basin, drilled by the well TD-01, has been discussed in this geological investigation for the first time. To evaluate the high-quality source rocks of Cretaceous continental shale oil, the distribution characteristics and the evolution of the ancient environment, samples of shale were systematically analyzed in terms of sedimentary facies, organic geochemistry, and organic carbon isotopic composition. The results demonstrate that a TOC value of 1.5% represents the lower-limit TOC value of the high-quality source rocks. Source rocks have an aggregate thickness of 211 m and contain abundant organic matter, with TOC values of 2.69% on average and a maximum value over 5.44%. The original hydrocarbon-generative potential value(S_1+S_2) is between 0.18 mg/g and 6.13 mg/g, and the Ro is between 0.97% and 1.40%. The thermal maturation of the source rocks is relatively mature to highly mature. The δ13C value range is between -34.75‰ and -26.53‰. The ratio of saturated hydrocarbons to aromatic hydrocarbons is 1.55 to 5.24, with an average of 2.85, which is greater than 1.6. The organic types are mainly type Ⅱ_1, followed by type Ⅰ. The organic carbon source was C_3 plants and hydrophytes. The paleoclimate of the Hengtongshan Formation can be characterized as hot and dry to humid, and these conditions were conducive to the development of high-quality source rocks. A favorable paleoenvironment and abundant organic carbon sources provide a solid hydrocarbon generation base for the formation and accumulation of oil and gas in the shale of the Tonghua Basin.  相似文献   

18.
The purpose of the study is to better understand the relationship between organic matter optical properties and the presence of potentially large oil and gas accumulations in Arctic Canada. The type and thermal maturity of the dispersed organic matter of the Mesozoic formations in the southern Sverdrup Basin, Melville Island, have been studied using organic petrology and Rock-Eval pyrolysis.All types of organic matter are present in the strata of Mesozoic age. Hydrogen-rich liptinite is dominated by alginite (Botryococcus and Tasmanites), dinoflagellate cysts and amorphous fluorescing matrix. Sporinite, cutinite, resinite and liptodetrinite made up the lesser hydrogen-rich exinite. Vitrinite reflectance in Cretaceous sediments ranges from 0.36 to 0.65% Ro; in Jurassic sediments it ranges from 0.40 to 1.0% Ro and in the Triassic from 0.45 to 1.30% Ro, showing an overall increase with depth of burial.Cretaceous sediments of the Deer Bay Formation are thermally immature and contain organic matter of terrestrial origin. The Upper Jurassic shales of the Ringnes Formation contain predominantly organic matter of liptinitic and exinitic origin with a considerable vitrinitic input. At optimum maturation levels, potential source beds of this formation would have a good hydrocarbon-generating potential. The hydrocarbon potential, however, would be limited to the generation of gases due to the leanness of the source rocks. Parts of the Lower Jurassic Jameson Bay Formation are organic-rich and contain a mixed exinitic/vitrinitic organic matter, Botryococcus colonial algae but visible organic matter is dominated by high plant remains (mainly spores). The Schei Point Group shales and siltstones contain organic matter of almost purely marine origin, whereas the predominantly higher plant-derived organic matter found in the Deer Bay, Jameson Bay and partly in the Ringnes formations have higher TOC. Among the Schei Point Group samples, the Cape Richards and Eden Bay members of the Hoyle Bay Formation are richer in TOC (>2.0%) than the Murray Harbour Formation (Cape Caledonia Member). This may reflect differences in the level of maturity or in the depositional environment (more anoxic conditions for the former).Regional variations in the level of thermal maturity of Mesozoic sediments in Sverdrup Basin appear to be a function of burial depth. The Mesozoic formations thicken towards the basin centre (NNE direction), reflecting the general pattern of increasing thermal maturity north of Sabine Peninsula. However, the regional thermal-maturation pattern of the Mesozoic is not solely a reflection of the present-day geothermal gradient, which indicates that anomalous zones of high geothermal gradient may have existed in the past, at least since when the Mesozoic sediments attained maximum burial depth. The contour pattern of the regional variation of maturity at the base of numerous Triassic formations is similar to that of the structural contours of the Sverdrup Basin, indicating that present-day maturation levels are largely controlled by basin subsidence.  相似文献   

19.
Organic petrology (incident light microscopy) of Middle Devonian inter-reef laminates and Devonian-Mississippian epicontinental black shales, Williston Basin, Canada, indicates that algal bloom episodes and consequential bacterial activity played a significant role in the accumulation of amorphous, bituminite III-rich organic microfacies. Corpohuminite-like algal akinete cells produced by filamentous algae during algal bloom periods are persistent maceral inclusions within the potential hydrocarbon source rock intervals. These cells (%Ro mean range 0.24-0.90) are regarded as positive indicators of stressful palaeoenvironmental conditions. Unicellular Tasmanites and Leiosphaeridia marine alginite and variably degraded alginite remnants (“ghosts”) within the amorphous kerogen may be products of cell lysis, photo-oxidation and microbial alteration; these processes are characteristic of algal bloom periods. Minute (ca. 1 μm) spheroidal and coccoidal bacteria-like macerals are dispersed throughout the bituminite III network, attesting to the importance of microbial activity within the water column and sediment during and after organic matter accumulation. Dispersed granules, laminations and replacement textures of micrinite-like macerals within bituminite III are interpreted as remnants of microbial alteration rather than a residual product of thermal maturation and hydrocarbon generation.  相似文献   

20.
Four shallow boreholes were drilled in the Hils syncline, northern Germany, in order to determine quantitatively the amount of hydrocarbons generated and expelled during maturation of a typical kerogen-type-II-bearing source rock. The holes penetrated the carbonceous Lias shales (Posidonia shale, Lower Toarcian) and part of the adjacent Dogger α and Lias δ mudstones. The maturity of the organic matter in the cores recovered ranges from immature (0.48% R̄0) to overmature 1.45% R̄0) due to location of the Hils syncline in the vicinity of the Vlotho Massif, which is deep-seated intrusive body. Facies variations of the Lias within the short geographical distances in the study area are negligible.Organic matter mass balance calculations were based on detailed organic geochemical analyses of residual material in the Lias shales (kerogen, bitumen etc.) and on the evidence of a uniform initial composition of these sediments in the study area. Dead carbon determinations supported this latter criterion but were not used as a parameter in the calculations.About 50% of the initial kerogen was transformed into oil, gas and inorganic compounds during the vitrinite reflectance increase from 0.48 to 0.88% R̄o and only marginally more during the maturity increase from 0.88 to 1.45% R̄o. Only a small portion of the generated material remained in the source rock even at a relatively early stage of generation (0.68% R̄o). Expulsion efficiency of oil plus gas reached a value of 86% at the end of the main generation stage (0.88% R̄o).  相似文献   

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