湖南雪峰山地区干酪根的拉曼光谱研究

干酪根是沉积有机质的主体,是石油地质工作研究的重要对象,目前利用激光拉曼光谱进行干酪根的研究较少。雪峰山地区干酪根的拉曼光谱测试结果表明:干酪根的一级拉曼光谱峰位差与镜质体反射率之间有着系统的规律性变化,在Ro<2.4%时,峰位差随Ro的增大迅速增大,其相关系数为0.82;Ro在2.4%~2.9%之间时,二者关系不明显,离散度较大;Ro>2.9%时,峰位差随Ro的增大逐渐减小,相关系数为0.88。镜质体反射率是衡量有机质成熟度和热演化程度的重要指标,干酪根的拉曼光谱特征与镜质体反射率之间的关系表明激光拉曼光谱法可以成为有机质成熟度和热演化程度研究的新方法。     

ESR assessment of kerogen maturation and its relation with petroleum genesis

Petroleum hydrocarbons are formed by breakdown of kerogen preserved in source rocks throughout the process of catagenesis. This process is accompanied by free radical generation in kerogen. The availability of measuring free radicals in kerogen using ESR to deduce a maturation estimation of potential source rocks has been hindered due to the presence of the solvent-extractable organic molecules (SEOM) trapped within the kerogen matrix. Spin concentration (Ns) of the kerogen treated with pyridine (K_Py) represents the paramagnetic centers of the kerogen matrix itself and provides a potential parameter to evaluate kerogen maturation.     

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.     

Electron-probe microanalysis of light elements in coal and other kerogen

Recent advances in electron microprobe technology including development of layered synthetic microstructures, more stable electronics and better matrix-correction programs facilitated routine microanalysis of the light elements in coal. Utilizing an appropriately equipped electron micro-probe with suitable standards, it is now possible to analyze directly the light elements (C, O and N, if abundant) in coal macerals and other kerogen. The analytical results are both accurate compared to ASTM methods and highly precise, and provide an opportunity to access the variation in coal chemistry at the micrometre scale. Our experiments show that analyses using a 10 kV accelerating voltage and 10 nA beam current yield the most reliable data and result in minimum sample damage and contamination. High sample counts were obtained for C, O and N using a bi-elemental nickel-carbon pseudo-crystal (2d = 9.5 nm) as an analyzing crystal.Vitrinite isolated from anthracite rank coal proves the best carbon standard and is more desirable than graphite which has higher porosity, whereas lower rank vitrinite is too heterogeneous to use routinely as a standard. Other standards utilized were magnesite for oxygen and BN for nitrogen. No significant carbon, oxygen or nitrogen X-ray peak shifts or peak-shape changes occur between standards and the kerogen analyzed. Counting rates for carbon and oxygen were found to be constant over a range of beam sizes and currents for counting times up to 160 s. Probe-determined carbon and oxygen contents agree closely with those reported from ASTM analyses. Nitrogen analyses compare poorly to ASTM values which probably is in response to overlap between the nitrogen K α peak with the carbon K-adsorption edge and the overall low nitrogen content of most of our samples.Our results show that the electron microprobe technique provides accurate compositional data for both minor and major elements in coal without the necessity and inherent problems associated with mechanically isolating macerals. Studies to date have demonstrated the level of compositional variability within and between macerals in suites of Canadian coals.     

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.     

Using reflectance crossplots and rotational polarization for determining first-cycle vitrinite for maturation studies

Vitrinite reflectance on dispersed sedimentary organic matter is traditionally determined from histograms of vitrinite and inertinite reflectance measured on either whole rock samples or kerogen concentrates, or from particles usually in whole rock preparations chosen by morphology and relative reflectance to be first-cycle vitrinite. This paper discusses an alternative method: discrimination of first-cycle vitrinite using apparent maximum and minimum reflectance data plotted on reflectance crossplots. The use of crossplots increases the confidence that the macerals identified as first-cycle vitrinite are optically similar. The maximum–minimum data, in this study, were collected on a quantitative reflectance microscope outfitted with rotational polarization, a technique that eliminates the usual difficulty in collecting such data on very small macerals by stage rotation.     

The transmittance color index of amorphous organic matter: a thermal maturity indicator for petroleum source rocks

Since the mid-1980s, Texaco has used the transmittance color index (TCI) of amorphous kerogen as an indicator of kerogen thermal maturation. The technique simply involves the direct measurement of a white-light spectrum as it is transmitted through a particle of amorphous organic matter (AOM). In brief, TCI values are obtained by the analysis of white light originating from a 100-W 6-V tungsten lamp attached to a photometric microscope. The assignment of particular TCI values is based on the increasing curvature of spectra with increasing maturity. TCI curves shift from an average wavelength around 580 nm for samples of immature, amorphous kerogen (i.e., material with a mean, random vitrinite reflectance of about 0.20%) to about 660 nm for samples containing very dark brown to some black particulate material (i.e., kerogen with a mean, random vitrinite reflectance of about 2.15%). The range of TCI values covers all zones of petroleum generation and preservation. In our opinion, TCI can provide as accurate a basis for maturation interpretations as is available from vitrinite reflectance (or from the mean random reflectance of some zooclasts, such as graptolites and chitinozoans), or the widely used visual estimate the thermal alteration index (TAI) or the similarly determined conodont color index (CAI). TCI is probably most useful, however, in those situations where the rocks to be examined have not yet reached the semianthricite coalification stage (≈2.0% vitrinite reflectance).     

鄂尔多斯盆地热演化程度异常分布区及形成时期探讨

鄂尔多斯盆地在中生代晚期存在一期构造热事件,本文在对大量的镜质体反射率、火成岩年龄、磷灰石裂变径迹等资料分析的基础上,对构造热事件发生的时间、存在的地区及形成机理进行了深入的研究。鄂尔多斯盆地中生代晚期地热异常区主要分布在盆地南部的吴旗—庆阳—富县一带,构造热事件主要发生在中生代晚期早白垩世约140～100Ma,构造热事件持续时间约在10～40Ma之间。鄂尔多斯盆地中生代晚期构造热事件发生的根本原因在于中生代晚期岩石圈深部的热活动增强,盆地南部岩石圈深部热活动性更强,早白垩世鄂尔多斯盆地处于一种弱拉张的构造环境,地幔发生底侵作用,岩石圈减薄,发生岩浆侵入和喷发。异常地温场形成可能与秦岭造山带燕山晚期强烈的构造活动导致鄂尔多斯盆地岩石圈深部活动有密切的关系。     

Evaluation of the petroleum composition and quality with increasing thermal maturity as simulated by hydrous pyrolysis: A case study using a Brazilian source rock with Type I kerogen

Hydrous pyrolysis (HP) experiments were used to investigate the petroleum composition and quality of petroleum generated from a Brazilian lacustrine source rock containing Type I kerogen with increasing thermal maturity. The tested sample was of Aptian age from the Araripe Basin (NE-Brazil). The temperatures (280–360 °C) and times (12–132 h) employed in the experiments simulated petroleum generation and expulsion (i.e., oil window) prior to secondary gas generation from the cracking of oil. Results show that similar to other oil prone source rocks, kerogen initially decomposes in part to a polar rich bitumen, which decomposes in part to hydrocarbon rich oil. These two overall reactions overlap with one another and have been recognized in oil shale retorting and natural petroleum generation. During bitumen decomposition to oil, some of the bitumen is converted to pyrobitumen, which results in an increase in the apparent kerogen (i.e., insoluble carbon) content with increasing maturation.The petroleum composition and its quality (i.e., API gravity, gas/oil ratio, C₁₅₊ fractions, alkane distribution, and sulfur content) are affected by thermal maturation within the oil window. API gravity, C₁₅₊ fractions and gas/oil ratios generated by HP are similar to those of natural petroleum considered to be sourced from similar Brazilian lacustrine source rocks with Type I kerogen of Lower Cretaceous age. API gravity of the HP expelled oils shows a complex relationship with increasing thermal maturation that is most influenced by the expulsion of asphaltenes. C₁₅₊ fractions (i.e., saturates, aromatics, resins and asphaltenes) show that expelled oils and bitumen are compositionally separate organic phases with no overlap in composition. Gas/oil ratios (GOR) initially decrease from 508–131 m³/m³ during bitumen generation and remain essentially constant (81–84 m³/m³) to the end of oil generation. This constancy in GOR is different from the continuous increase through the oil window observed in anhydrous pyrolysis experiments. Alkane distributions of the HP expelled oils are similar to those of natural crude oils considered to be sourced from similar Brazilian lacustrine source rocks with Type I kerogen of Lower Cretaceous age. Isoprenoid and n-alkane ratios (i.e., pristane/n-C₁₇ and phytane/n-C₁₈) decrease with increasing thermal maturity as observed in natural crude oils. Pristane/phytane ratios remain constant with increasing thermal maturity through the oil window, with ratios being slightly higher in the expelled oils relative to those in the bitumen. Generated hydrocarbon gases are similar to natural gases associated with crude oils considered to be sourced from similar Brazilian lacustrine source rocks with Type I kerogen of Lower Cretaceous, with the exception of elevated ethane contents. The general overall agreement in composition of natural and hydrous pyrolysis petroleum of lacustrine source rocks observed in this study supports the utility of HP to better characterize petroleum systems and the effects of maturation and expulsion on petroleum composition and quality.     

Structural modifications of vitrinite and alginite concentrates during pyrolitic maturation at different heating rates. A combined infrared, C NMR and microscopical study

Immature vitrinite samples from a Miocene lignite seam of western Germany (H/C = 1.14, O/C = 0.41) and alginite concentrates from a Tasmanite deposit of Australia (H/C = 1.60, O/C = 0.10) were pyrolyzed in a stream of argon at heating rates of 0.1 and 2.0°C/min up to temperatures varying from 200 to 670°C. The solid maceral residues were subjected to elemental and microscopical analysis and studied by IR and ¹³C CP/MAS NMR spectroscopy with respect to structural modifications.The maximum pyrolytic weight loss amounts to 60% of the initial organic matter in the case of vitrinite and to 85% for alginite, the onset of degradation reactions being shifted to higher temperatures with increasing rate of heating. Both infrared and NMR spectra of the vitrinite samples indicate a rapid decomposition of the cellulose component upon heating whereas lignin related structures such as aromatic ether linkages remain remarkably stable. The main hydrocarbon release from vitrinite occurs at very early evolution stages (T_max = 296°C, R_m = 0.20% at 0.1°C/min; T_max = 337°C, R_m = 0.23 at 2.0°C/min). Hydrocarbon generation from alginite requires higher temperatures (T_max = 388 and 438°C) and is completed within a distinctly narrower temperature range.The pronounced increase of vitrinite reflectance between 350 and 670°C seems to be associated with a rather time-consuming reorganization of the residual organic material. The concomitant growth of polyaromatic units is illustrated by the increasing intensity ratio of the aromatic ring stretching vibration bands at 1600 and 1500 cm⁻¹. These reactions are moreover marked by increasing loss of phenolic oxygen and by increasing conversion of aliphatic carbon into fixed aromatic carbon.     

The effect of oil expulsion or retention on further thermal degradation of kerogen at the high maturity stage: A pyrolysis study of type II kerogen from Pingliang shale,China

High maturity oil and gas are usually generated after primary oil expulsion from source rocks, especially from oil prone type I/II kerogen. However, the detailed impacts of oil expulsion, or retention in source rock on further thermal degradation of kerogen at the high maturity stage remain unknown. In the present study, we collected an Ordovician Pingliang shale sample containing type II kerogen. The kerogens, which had previously generated and expelled oil and those which had not, were prepared and pyrolyzed in a closed system, to observe oil expulsion or oil retention effects on later oil and gas generation from kerogen. The results show that oil expulsion and retention strongly impacts on further oil and gas generation in terms of both the amount and composition in the high maturity stage. Gas production will be reduced by 50% when the expulsion coefficient reaches 58%, and gas from oil-expelled kerogen (less oil retained) is much drier than that from fresh kerogen. The oil expulsion also causes n-alkanes and gas compounds to have heavier carbon isotopic compositions at high maturity stages. The enrichment of ¹³C in n-alkanes and gas hydrocarbons are 1‰ and 4–6‰ respectively, compared to fresh kerogen. Oil expulsion may act as open system opposite to the oil retention that influences the data pattern in crossplots of δ¹³C₂–δ¹³C₃ versus C₂/C₃, δ¹³C₂–δ¹³C₃ versus δ¹³C₁ and δ¹³C₁–δ¹³C₂ versus ln(C₁/C₂), which are widely used for identification of gas from kerogen cracking or oil cracking. These results suggest that the reserve estimation and gas/source correlation in deep burial basins should consider the proportion of oil retention to oil expulsion the source rocks have experienced.     

孔隙率、级配参数对粉土双轴压缩性状影响的颗粒流分析

针对颗粒流法中颗粒几何参数等对土体宏观力学性质的影响进行了数值模拟,并将数值模拟结果与室内模型试验验证进行了对比。对二维、三维下土体级配及孔隙率进行了理论分析,并提出二维数值试样颗粒数目及孔隙率转换公式。采用PFC2D软件进行了6组参数验证及24组交叉对比（含4组级配、3组孔隙率及2类接触模型）双轴压缩试验。结果表明：孔隙率对土体力学性质的影响大于级配;随着孔隙率增加,土体强度峰值逐渐降低,对应轴向应变增大,体应变则由剪胀性逐渐向剪缩性过渡。当孔隙率较低时,采用线性及Hertz-Mindlin (H-M)接触模型得到的模拟结果均较接近;而当孔隙率升高时,建议采用H-M接触模型,以更好地反映土体到达强度峰值后产生的后续剪胀效应。