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1.
The rate constants of the cyclisation reaction of 2,3-dimethylbiphenyl to give 1-methylfluorene under non-catalytic conditions have been obtained at five temperatures between 460 and 500°C. The activation energy, activation entropy and frequency factor for the reaction have been determined from the experimental data. These kinetic parameters were then used to calculate the temperature ranges where the reaction occurs under natural conditions in sedimentary sequences which have experienced different heating rates. The coincidence of the measured and calculated values has been taken as evidence that the cyclisation reaction occurs in sediments under non-catalytic conditions. 相似文献
2.
《Geochimica et cosmochimica acta》1987,51(12):3105-3111
Petroleum samples and organic extracts from two sedimentary sequences have been analysed using capillary gas chromatography and GC-MS techniques for isomeric methylbiphenyls, ethylbiphenyls and dimethylbiphenyls. The relative abundances of isomers with substituents in the ortho positions decrease with increasing depth (maturity) in both sedimentary sequences. Accordingly, these compounds appear to offer potential as indicators of thermal maturity of sediments. 相似文献
3.
对鄂尔多斯盆地奥陶系平凉组海相页岩进行了3种升温速率下的 Rock-Eval 热解模拟实验,研究了其干酪根在开放体系下的热解生烃演化特征.通过分析热解烃 S2的产率随温度的变化,结合 Kinetics 生烃动力学专用软件计算,获得了其开放体系下的生油动力学参数,活化能分布范围为(57~81)×4.185 kJ/mol.在此基础上进行的动力学模拟结果与实验数据非常吻合,可较好地将实验数据外推到地质实际过程.此外,发现热解残渣中的 H/C(原子比)值与热解温度、干酪根转化率有较好的相关关系,可建立 H/C 值与转化率或者等效镜质组反射率的可靠模板,表明 Rock-Eval 热解实验与 H/C 值结合,可快速评价下古生界源岩的成熟度、转化率和生烃量等指标,将其应用于资源量计算等方面 相似文献
4.
C1 and C2-alkylbiphenyls have been analysed in crude oils and sediment extracts by capillary gas chromatography after preliminary isolation procedures involving TLC and HPLC. The abundance of 2-methylbiphenyl relative to 3-methylbiphenyl has been measured in samples from two sedimentary sequences. 2-Methylbiphenyl decreases in relative abundance with increasing thermal maturity of the sediments in both sedimentary sequences. These isomeric methylbiphenyls are potentially useful as thermal maturity indicators for crude oils. 相似文献
5.
Samples from two argillaceous formations (Opalinus Clay and Posidonia Shale) of near-identical maturity from northern Switzerland were subjected to a geochemical characterisation of organic matter and to confined-system pyrolysis experiments. Throughout the study area, the characteristics of organic matter are similar, indicating a spatially homogeneous sedimentary facies. Posidonia Shale contains marine organic matter deposited in a reducing environment, while a predominantly terrigenous source and a more oxidising environment of deposition was identified for Opalinus Clay. In the western and central parts of the study area, organic maturity is close to the onset of oil generation. In the easternmost part, a higher maturity has been reached due to a deeper burial below thick Tertiary Molasse deposits.Isothermal pyrolysis experiments were conducted at temperatures between 250 and 390 °C over 24 h. Bitumen yields increase along similar pathways for both Opalinus Clay and Posidonia Shale, but the maximum values are displaced by 10–20 °C. Data pertaining to maturity were determined from GC–MS analyses of saturated hydrocarbons, and specific attention was given to C29-sterane and C32-hopane isomerisation ratios. The evolution of these parameters with rising temperature is slightly different in the two formations, which is attributed to the contrasting organic facies. The pyrolysis data, together with literature data from natural basins, were used to calculate kinetic parameters for C29-sterane and C32-hopane, assuming a single-step isomerisation scheme according to the Arrhenius law. The resulting values based on pyrolysis data alone are very similar to those based on the combination of pyrolysis and natural data. Activation energies are similar in both formations, while the frequency factors are up to one order of magnitude higher for Posidonia Shale when compared to Opalinus Clay. For the Benken site, maximum temperature during Cretaceous burial was calculated on the basis of the kinetic data, using the TTI approach. The resulting temperatures of 75–80 °C are 5–10 °C below those derived in the literature from apatite fission-track analysis, vitrinite reflectance and basin modelling. 相似文献
6.
The generation of bulk petroleum, liquid and gaseous hydrocarbons from the Duvernay Formation was simulated by heating immature kerogens in a closed system (MSSV pyrolysis) at four different heating rates (0.013, 0.1, 0.7 and 5.0 K/min). Using the established parallel reaction kinetic model, temperature and compositional predictions were tested to be suitable for geological conditions by comparing the laboratory results with natural changes in source bitumens and reservoir oil maturity sequences from the Duvernay Formation. In the case of bulk liquid and gaseous hydrocarbons, the above kinetic calculations can be considered valid because their maximum yields are independent of laboratory heating rates. In contrast, the contents of paraffins, aromatics and sulfur compounds show a pronounced heating rate dependence. Extrapolated to geological heating rates, the compositional predictions are consistent with the bulk composition of natural products in the Duvernay-petroleum system showing an increase of paraffinicity and hydrogen content. In contrast to that, the “hump” decreases with decreasing heating rate, a trend which is confirmed by the low amounts of unresolved compounds in natural high maturity products. Because of these heating-rate dependent compositional changes, geological predictions of natural molecular composition by the commonly used kinetic models are not suitable. 相似文献
7.
R Alexander R.I Kagi S.J Rowland P.N Sheppard T.V Chirila 《Geochimica et cosmochimica acta》1985,49(2):385-395
The distributions of di- and trimethylnaphthalenes in two sedimentary sequences from Western Australia have been examined by capillary gas chromatography and combined gas chromatography-mass spectrometry. A general decrease was observed in the relative proportions of αα-dimethylnaphthalenes and ααβ-trimethylnaphthalenes with increasing thermal maturity. Similar trends were also observed for six crude oils which have very different ratios of ethylcholestane epimers indicating very different thermal histories. These results suggest that changes in the relative abundances of certain methyl substituted naphthalenes may be useful indicators of thermal maturity of sedimentary organic matter, and the use of a number of isomer ratios is illustrated. 相似文献
8.
Kinetic parameters were determined for the first time, via open-system pyrolyses, on algaenans (highly resistant biomacromolecules that are selectively preserved during kerogen formation) isolated from extant microalgae. Parallel studies were also carried out on 10 kerogens exhibiting, with one exception, a low level of maturity. These kerogens included samples chiefly derived from the selective preservation of the above algaenans and samples mainly, or almost exclusively, derived from the “natural vulcanization” pathway. Important differences in activation energy (Ea) distributions were observed between the four algaenans investigated and correlated with their chemical structures. The kerogens predominantly derived from algaenan-selective preservation (Pula alginite, NE 70 and BJ 248 Torbanites, Rundle Oil Shale) also exhibited pronounced differences in Ea distributions. These distributions provided: (i) information on the diversity of the source materials; and (ii) reflected the occurrence of important differences in chemical structures and thermal behaviour between three of the tested kerogens, even though they are all classified as low maturity type I. The Kimmeridge Clay samples and the Lorca Oil Shale showed broad Ea distributions shifted to low energies when compared with the above algaenans and kerogens. Such shifts reflect an important (or even almost exclusive for some of these kerogens) contribution of materials originating from sulphur incorporation into various lipids during early diagenesis. Finally, the kinetic data derived for the nine low maturity fossil samples were extrapolated to a very low, geological heating rate of 3°C Ma−1 and the generation rate curves and cumulative yield curves thus obtained were compared. 相似文献
9.
Polarized macromolecular compounds in typical lacustrine and marine shale oils collected from the Ordos Basin and Tarim Basin of China were analyzed by FT-ICR-MS. Maturity was taken into consideration by diagenesis physical simulation experiments on shale oils, which had been collected at various temperature and pressure stages. The results showed that similar components existed in non-hydrocarbon and asphaltenes and the main peak compound classes of Nl and 02 were potential parameters for identifying typical marine oil and lacustrine oil in China. Nitrogen compounds/（nitrogen compounds and oxygen compounds）, such as Nl/（O2＋Nt）, NL/（Oa＋Nt）, Ni/（NiO1＋N1O2） are the maturity indicators, which are related with C-N and C-O bond energy. Differences in molecular components and weights between marine and lacustrine oils are the effective index to identify source maturity and sedimentary environment. 相似文献
10.
<正>Kailu Basin in which the Western Lujiapu Depression is located is a typical continental rift basin.Biomarker parameters of the oils indicate that depositional facies and environments vary between the Bao 1 and Bao 14 fault blocks with a higher saline environment in the Bao 1 fault block, but such difference has no significant impact on carbazole abundance and distribution.Maturity and migration distance are the main controls on carbazole abundance and distribution in the Western Lujiapu Depression.The commonly used migration indices,such as ratios of nitrogen shield isomers to nitrogen exposed isomers(1-/4-methylcarbazole ratio,1,8-/2,4-dimethylcarbazole(DMC) ratio and half-shield/exposed-DMC ratio),absolute concentrations of alkylated carbazoles and BC ratio(=benzo [a]carbazole/(benzo[a]carbazole+benzo[c]carbazole)) increase at the low mature range and decrease at a higher mature range with increasing maturity.At relatively low maturity stage(Rc0.77%), maturation has reversal effects with migration on the ratios of nitrogen shield isomers to nitrogen exposed isomers,which may cover migration influence and makes these parameters fail to indicate migration effects.Valid migration indicators at this maturity stage are concentrations of alkylated carbazoles and BC ratios,which can provide ideal tools for migration direction assessment even within short migration distance.Maturity effects should be taken into account when carbazole compounds are applied to indicate migration direction,and at different maturity stages,these commonly used parameters have different validity in tracing migration direction.Coupled with our previous study in the Eastern Lujiapu Depression,a conceptual model of the variation of nitrogen migration indices can be established for terrestrial rifted basins,that is,strong fractionation lateral migration model through sandy beds,weak fractionation vertical migration model along faults,and maturity impacts on migration assessment. 相似文献
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12.
Lea Di Paolo Valerio Olivetti Sveva Corrado Luca Aldega Maria Laura Balestrieri Rosanna Maniscalco 《地学学报》2014,26(5):363-371
An extensive dataset of vitrinite reflectance, FTIR parameters on organic matter, illite content in mixed layers illite‐smectite, apatite fission tracks and U‐Th/He dating has been used to reconstruct the stepwise propagation of the Eastern Sicily fold‐and‐thrust belt during Late Palaeogene and Neogene times. The results indicate that the fold‐and‐thrust belt is divisible into two levels of thermal maturity. These levels consist of a less evolved level of thermal maturity that records limited sedimentary burial and minor heating, and a more evolved level of thermal maturity that indicates tectonic burial and exhumation at different times. Deformation and exhumation of shallowly buried units are linked to wedge forward propagation by low‐angle thrusts, whereas the evolution of deeply buried units is associated with tectonic imbrications by duplex formation and steep thrusts. The two tectonic styles alternate during evolution of the fold‐and‐thrust belt under low erosion rates. 相似文献
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14.
Demineralisation of a sedimentary rock with HF liberates a fraction of extractable organic matter (OM) that is not accessible with standard extraction techniques, which is known as Bitumen II. This fraction displays lower maturity parameters than the free extractable OM (Bitumen I). Studies of successive conventional extraction have found that the later steps show a decrease in maturity similar to that observed for Bitumen II. We aimed to investigate whether or not Bitumen II is simply the result of residual Bitumen I left over from the initial extraction.A series of successive Soxhlet extraction steps was performed on a highly mineralised sample from the Paleoproterozoic Here’s Your Chance (HYC) Pb–Zn–Ag deposit in the Northern Territory of Australia. The study showed that the extraction efficiency for polycyclic aromatic hydrocarbons (PAHs) decreased with increasing molecular weight. Maturity parameters based on methyl phenanthrenes generally decreased with successive extraction steps. This is because the thermodynamically more stable β isomers were preferentially extracted over the α isomers, so later extraction steps contained a greater proportion of α isomers. Bitumen II was prepared from a previously-studied sample from the same sample pit. It showed a decrease in maturity parameters relative to Bitumen I, but the distribution of PAHs did not match those of the later Bitumen I extraction steps. We conclude that Bitumen II did not result from incomplete extraction of Bitumen I. As Bitumen II is preserved within the kerogen–mineral matrix, it has potential for tracing the migration and maturation history of ancient or thermally altered systems. 相似文献
15.
海相碳酸盐岩烃源岩热解动力学研究:全岩和干酪根的对比 总被引：12，自引：3，他引：9
我国海相碳酸盐岩地层分布广泛,厚度巨大,经历的地质历史较长,特点是有机质丰度低,多处于高过成熟阶段.碳酸盐岩烃源岩评价对我国的油气资源评价与勘探至关重要.用生烃动力学方法来研究碳酸盐岩生油气过程是一个值得探索的研究方向.本文通过生烃动力学热模拟实验,求取了碳酸盐岩全岩和其干酪根不同烃类组分(甲烷、 C2～ C5气态烃)的生成动力学参数并进行对比.结果表明,在生烃动力学热解实验中,全岩和其干酪根具有相似的动力学参数,采用烃源岩应该比干酪根更符合实际,但是干酪根样品可以测得更为详细的实验数据,因此可以根据样品的情况,选择合理且易行的实验条件.在此基础上,以本文得到的参数作为参照指标,用动力学方法外推到地质实际中,可准确地提出适合我国的碳酸盐岩生烃定量模型,能为碳酸盐岩的资源评估等方面给出定量数值,从而为有效烃源岩的定量评价提供一种新的方法和途径. 相似文献
16.
Insolation weathering and hygric dilatation: two competitive factors in stone degradation 总被引：2，自引：0，他引：2
In the natural environment, temperature and moisture are very important parameters in stone degradation. Therefore, on 28 samples from different lithologies (magmatic, metamorphic and sedimentary rocks) thermal and hygric expansion measurements were performed in order to constrain their behaviour related to environmental changes. It was shown that marbles, even those that are dolomitic, are sensitive to temperature impacts. For rocks with clay minerals the effect of temperature may be responsible for shrinking. Finally the amount of residual strain, i.e. the formation of microcracks due to temperature action controls the rate of stone degradation. For most sedimentary rocks no residual strain after heating was observed. In contrast to most magmatic and metamorphic low-porosity rocks, sedimentary rocks contain swelling minerals (like smectite and even phyllosilicates), which are very sensitive to hygric attacks. The cycles of wetting and drying, i.e. the natural environmental effects, may significantly control the deterioration velocity caused by hygric expansion. 相似文献
17.
The source rock sample of the Shahejie Formation（upper Es4） in Jiyang Sag was pyrolyzed under open system with the Rock-Eval-Ⅱapparatus,and then kinetic model parameters were calibrated for investigating the effect of uncertainty of pre-exponential factors on kinetic parameters and geological applications,where the parallel first-order reaction rate model with an average pre-exponential factor and discrete distribution activity energies was used.The results indicate that when the pre-exponential factor changes from low to high,an extreme value for residual errors occurs.And with the increasing pre-exponential factor,the distribution shape of activation energies are nearly the same,but the values of activation energies move higher integrally,and the average activation energy increases about 12 kJ/mol for every 10-fold of the pre-exponential factors.Extrapolating the geological heating rate of 3.3℃/Ma,the results show that with the increases in pre-exponential factor, the geological temperature corresponding to TR0.5（transforming ratio of hydrocarbon generation is 50%） increases gradually,and the additional temperature gradually decreases.Combined with geochemical data of source rock,the kinetic parameters with different pre-exponential factors are used to calculate the transformation ratio of hydrocarbon generation,and the result indicates that kinetic parameters corresponding to the better optimized pre-exponential factor are more suitable.It is suggested that the risk assessment of hydrocarbon generation kinetic parameters should be enhanced when using the kinetic method to appraise the oil-gas resources.Meantime,the application result of different kinetic parameters should be verified with geological and geochemical data of source rock in the target area;therefore,the most suitable kinetic parameters for target can be obtained. 相似文献
18.
通过对塔里木盆地煤及其显微组分以1K/min升温速率在开放体系下进行热模拟实验(Tmax=1200℃),确定了CH4与N2生成动力学参数。根据化学反应动力学原理,当煤岩生成CH4和N2为25个一级平行反应且具有相同频率因子(Ao=1.0×1013s-1)时,生成CH4与N2每个反应对应的活化能可以通过实验数据与理论计算拟合,获得Gaussian型活化能分布特征为:CH4在活化能为42～90kcal/mol内,煤、镜质组、壳质组、丝质组和半丝质组生成CH4的主频活化能分别为60、52、50、70和66kcal/mol;N2在活化能为60～108kcal/mol内,其主频活化能分别为74、108、100、108和102kcal/mol。根据这些实验动力学参数,推测了煤岩在地质升温速率为5.3K/Ma时CH4的转化率:CH4在地质温度为20℃时开始形成;当地质温度为160℃时,煤岩中CH4已生成总量的80%。镜质组和壳质组CH4转化率要高于煤岩。 相似文献
19.
在对赵凹油田安棚深层系核（核桃园组）三下段砂体的研究中，从岩性特征，结构和成分成熟,沉只构造及古生物特征等方面总经了该区沉积的相标志，结合研究区的沉积背景，笔者认为该区沉积环境为扇三角洲相，并进一步划分了亚相和同相，提出了研究区扇三角洲相的沉积模式，并对扇三角洲砂体的类型进行了研究。该区发育扇三角洲前缘亚相和前扇三角洲两种亚相，近岸水道和远岸水道微相比较发育；距离物源较近，沉积物搬运距离短，沉积物粒度较粗，结构成熟度和成分成熟度较低，水动力较强，在砾岩和粗砂岩中发育有块状层理，平行层理和交错层理，砂体类型对储集层物性有明显的控制作用。 相似文献
20.
A least-squares inverse method is applied to the estimation of optimum kinetic parameters with statistical error bounds from concentration data obtained in isothermal hydrous pyrolysis experiments. The inverse method requires the specification of a data-parameter relationship (e.g., classical kinetic theory), the prior covariance matrices of data and parameter errors, as well as the prior central estimates of data and parameters. The reaction scheme considered is the common case of kerogen breakdown by Gaussian-weighted independent parallel first-order reactions and bitumen cracking by a single first-order reaction. The nonlinearity of the problem is reduced by a logarithmic transformation, which suggests a parameterization in terms of logarithmic concentrations, activation energies, and logarithmic Arrhenius factors. The linearized variance analysis is valid for the case studied, and the posterior covariance matrix reveals which parameters are constrained by the data. We find that the statistical errors in the average activation energy and the associated Arrhenius factor are strongly correlated. Hence, the parameters which determine the temperature dependence of the reaction rate have not been resolved independently. Furthermore, the kinetic results are very sensitive to the presence of a distribution of activation energies in kerogen breakdown. This distribution is not constrained by the data. As a consequence, neglecting the consideration of distributions of activation energies results in activation parameter values which are much too low. This is the major reason for the commonly encountered discrepancy between kinetic parameter values obtained from hydrous pyrolysis and micropyrolysis experiments, respectively. 相似文献