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辽河西部凹陷古近系烃源岩生烃动力学特征 总被引：4，自引：0，他引：4
针对辽河西部凹陷不同岩性、不同干酪根类型18块样品进行了较详细的开放体系生烃动力学研究, 模拟结果反映出相同岩性不同有机质类型烃源岩动力学特征存在较大的差异, 有机质类型越好, 平均活化能越小, 主频活化能对应的反应分数越大, 活化能分布范围越窄, 表明有机质类型对烃源岩生烃动力起着决定性作用.应用平行一级反应模型, 结合埋藏史、热史对辽河西部凹陷古近系烃源岩生烃史进行了定量研究, 层位上, 西部凹陷沙三、沙四段是主力烃源岩, 分别占总生烃量的63.9%和18.5%, 其次为沙一二段和东营组, 4套烃源岩累计生烃量为328.09×108t;东营期是主要的生烃时期. 相似文献
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烃源岩生烃动力学广泛应用于含油气盆地烃源岩评价与勘探中。为模拟低成熟烃源岩的实际沉积环境,实验选取了抽提有机质后的东营凹陷下第三系沙河街组三、四段烃源岩为矿物催化剂,以十八烷酸甲酯为模型化合物,在高压下做矿物低温催化脂肪酸酯脱羧生烃动力学实验。求取了化学反应的动力学参数,并分析了烃源岩层段的pH值与Eh值。结果表明,矿物对脂肪酸酯的脱羧生烃具有明显的催化作用,用连串反应模型处理脂肪酸酯的水解反应基本上为一级反应,而生烃反应则基本上为零级反应。认为对于同一类型的烃源岩,其所处的氧化还原环境对有机质的生烃有较大的影响;而对于不同的烃源岩,矿物的组成则起着非常重要的作用。 相似文献
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台北凹陷煤中有机质的成烃动力学模型及其初步应用 总被引：12，自引：0，他引：12
在恒速升温热解实验和ＰＹ－ＧＣ分析结合的基础上，利用数学优化求解技术，建立并标定了台北凹陷煤有机质成油成气的化学动力学模型。结合我们近期报导的木栓质体成烃的动力学模型，定量计算了干酪根成油、木栓质体成油的理论剖面，并进一步定量探讨了吐哈盆地台北凹陷烃源岩评价中的生烃门限、木栓质的早期生烃及有机质原始生烃潜力和原始丰度的恢复等问题。 相似文献
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烃源岩的非均质性、动力学模型中频率因子的不确定性、热模拟实验条件(开放/封闭程度、加水与否、升温速率)以及热模拟实验的再现性都将影响有机质成烃动力学模型参数, 进而影响油气资源潜力评价结果的可信度.对此, 从多个盆地不同类型有机质样品(18块)的开放体系(Rock-Eval)热模拟实验入手, 选取SFF模型和MFF模型来描述不同类型有机质样品成烃动力学特征, 对比地质外推结果的差异性.其中采用SFF模型低估了具有较低和较高活化能有机质的生烃潜力(反应分数), 而采用MFF模型可以避免这一问题, 同时频率因子随活化能的升高而升高, 能有效解决频率因子不确定性的问题.同时采用算术平均法和依据S2加权平均法对不同类型样品的动力学参数求取平均动力学参数, 并以3.3 ℃/Ma的升温速率进行外推, 对比分析了不同类型有机质外推结果的差异性.最后, 通过对两种模型依据S2加权平均法获得的动力学参数在松辽盆地黑鱼泡凹陷实际应用表明, 应用MFF模型计算得出的生烃门限深度为1 700 m, 与前人研究结论一致.表明采用MFF模型和S2加权平均法获得的动力学参数进行资源评价具有较高可信度. 相似文献
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辽东湾海域勘探面积超过1.5×104 km2,200余口探井集中在构造高部位,洼陷部位烃源岩样品很少,这给油气资源评价带来很大困难。为了查明不同洼陷、不同层位、不同性质烃源岩的油气生成情况,进行了生烃动力学研究,得到了定量评价油气生成的效果。首先根据地球化学分析,选出不同类型的未成熟烃源岩样品,进行生烃热模拟实验,对实验数据进行了一级平行生烃反应的活化能计算,得到不同母质类型烃源岩活化能分布模型;再根据不同洼陷、不同层位烃源岩热演化历史和生烃动力学特征,计算了它们的油气生成率,再现了各个洼陷和层位烃源岩的油气生成过程。这为辽东湾烃源岩评价和油气资源预测提供了依据。 相似文献
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采用生烃动力学方法对鄂尔多斯已熟烃源岩进行模拟实验,与以往结果有所不同,实验证明在源岩二次生烃过程中,慢速升温并不利于液态烃的生成,而快速升温才更有利于生成液态烃。这可能是因为在慢速升温条件下,有机质可以有足够长时间缩聚成超大基团,而快速升温则易造成中等分子链的断裂,从而导致快速升温时抽提物产率高于慢速升温。因此,升温速率的差异对有机质的演化影响不只是影响反应速率,更重要的是会改变反应路径,从而对于像鄂尔多斯这样存在二次生烃的盆地,应适当重视那些高地温梯度区块石油资源的寻找。 相似文献
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镜质体成烃反应动力学模型的标定及其在热史恢复中的应用 总被引：2，自引：0，他引：2
镜质体反射率（Ｒｏ）与其生烃率有关，因此，由Ｒｏ应可求取其生烃率；同时，在求取了镜质体成烃反应动力学参数之后，若已知其受热史，则可计算出镜质体的生烃率；反过来，若已知镜质体的生烃率，应可反推其受热史。基于这一基本原理，本文在建立和标定镜质体成烃反应动力学模型的基础上推导了可将其应用于存在着抬升、剥蚀和古地温非线性变化等复杂地质条件下热史恢复的原理模型，结合海拉尔盆地海参７井的实测Ｒｏ值，有效地恢复了其古热史。 相似文献
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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
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为了揭示不同实验条件下有机质生烃动力学特征及其地质应用的差异性,对松辽盆地煤样进行了开放体系(Rock-Eval)和密闭体系(金管)的恒速升温热模拟实验。根据实验产物产率与温度关系标定了开放系下的有机质成油、成气及密闭体系下有机质成气动力学模型;将标定的2种体系下的动力学参数以实验室升温速率和地质升温速率条件下进行外推,表明密闭体系下的成气转化率相对开放体系下的变化要慢,原因在于开放体系下煤样热解生气为初次裂解,而密闭体系下煤样生气是初次裂解和二次裂解共同贡献的结果。进一步将2种体系下获得的生气动力学参数结合松辽盆地徐家围子地区埋藏史、热史资料进行应用表明:应用开放体系获得的动力学参数外推计算的生气门限对应时间(115 Ma)要比实际生气门限对应时间(110 Ma)偏早;应用密闭体系获得的动力学参数外推计算的生气门限对应时间(92 Ma)要比实际生气门限对应时间偏晚。 相似文献
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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
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WANG Min LU Shuangfang XUE Haitao WANG Weiming LIU Min DONG Qi WANG Guihua 《《地质学报》英文版》2011,85(3):702-711
In order to contrast the hydrocarbon generation kinetic characteristics from different types of organic matter (OM), 18 samples from different basins were pyrolyzed using Rock-Eval-II apparatus under the open system. From the experimental results, the curve of hydrocarbon generation rate vs. temperature can be easily obtained, which usually can be used to optimize kinetic parameters (A, E, F) of the hydrocarbon generation model. In this paper, the parallel first-order reaction with a single frequency factor model is selected to describe the hydrocarbon generation kinetic characteristics. The hydrocarbon generation kinetic parameters reveal that the types of compound structures and chemical bonds of the lacustrine facies type I OM are relatively homogeneous, with one dominating activation energy. The types of chemical bonds of the lacustrine facies type II2 OM and the terrestrial facies type III OM are relative complex, with a broad activation energy distribution, and the reaction fraction of the preponderant activation energy drops with the decrease of hydrogen index. The impact of the activation energy distribution spaces on the geological extrapolation of kinetic parameters is also investigated. The results show that it has little effect on the hydrocarbon transformation ratio (TR) and therefore, the parallel first-order reaction model with proper number of activation energies can be better used to describe the hydrocarbon generation process. The geological extrapolation results of 18 samples of kinetic parameters show that the distribution range of the hydrocarbon generation rate of the type I OM is relatively narrow and the hydrocarbon generation curve is smooth. In comparison, the distribution range of the hydrocarbon generation for type II1 and type II2-III OM are quite wide, and the hydrocarbon generation curves have fluctuation phenomena. The distribution range of the hydrocarbon generation rate and the fluctuation phenomena are related to the kinetic parameters of OM; the narrower the activation energy distribution, the narrower the hydrocarbon generation rate distribution, and the smoother the hydrocarbon generation curve, and vice versa. 相似文献
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I. Lerche 《Mathematical Geology》1991,23(1):137-155
Several different proposed models of thermocatalytic cracking of kerogen to hydrocarbons are exhibited. The specific models are then combined into a single generic, encompassing framework. For laboratory pyrolysis measurements of kerogen degradation and of thermal generation of hydrocarbons, inverse methods are used to show how to determine the relevant distributions of kinetic parameters consistent with the measured data. 相似文献
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Elodie Salmon Françoise Behar François Lorant Patrick G. Hatcher Pierre Metzger Paul-Marie Marquaire 《Organic Geochemistry》2009,40(3):400-415
The thermal reactivity of organic matter in source rocks is usually kinetically represented by a set of parallel and independent first order reactions. The approach assumes that only defunctionalisation reactions take place upon thermal decomposition, regardless of the chemical nature of kerogen. We have developed a new method for evaluating maturation pathways for an important kerogen-forming geopolymer, algaenan from the alga Botryococcus braunii (B. braunii), involving molecular dynamic reactive modelling based on quantum mechanics to reproduce maturation. To achieve this, a structural model is first constructed on the basis of models from the literature and analytical characterization of our samples using modern 1D and 2D nuclear magnetic resonance spectroscopy (NMR), Fourier transform infrared spectroscopy (FTIR) and elemental analysis (EA). Then, thermal decomposition of the algaenan is performed at low conversion in order to describe the initial transformations analytically. In an additional step, the observed chemical changes are quantitatively and qualitatively compared to simulated maturation from the molecular models. From this simulated maturation detailed reaction schemes are extracted for primary cracking mechanisms. 相似文献
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We use a kinetic model of a metamorphic system to study the effect of competing rates of reaction, fluid injection, and heating on the evolution of the reaction pathway in temperature/composition space at constant pressure. We show that for rocks in contact with mixed volatile (e.g., CO2-H2O) fluids the reaction path may be quite different from what is expected from equilibrium-based petrologic models. Equilibrium-based models, used to understand the development of rock systems undergoing mineral reactions during a metamorphic event, rely on the Gibbs phase rule and only consider stable phases. For constant pressure, the temperature-composition paths follow univariant curves and significant reactions may occur at invariant points. By contrast, the more general kinetic treatment is not constrained by equilibrium, although with the proper competing rates equilibrium is a possible endmember of the kinetic approach. The deviation from equilibrium depends on the competing rates of reaction, heating, and fluid injection. A key element required by the kinetic approach is the inclusion of metastable reactions in the formulation, whereas such reactions are irrelevant for equilibrium-based models. Metastable reactions are often involved in a complex interplay with common prograde stable metamorphic reactions. We present model results for the well-studied CaO-MgO-SiO2-CO2-H2O (CMS) system to show how the system evolves under kinetic control. Our simulations and discussion focus on the behavior of the CMS system under a number of closed and open system conditions. Special attention is paid to closed system behavior in the vicinity of the (first) isobaric invariant point (with Dol, Qtz, Tlc, Cal, and Tr). Also, for open systems with massive fluid infiltration we consider heating rates varying from contact to regional metamorphic conditions. For some geologically reasonable rates of reactions, heating, and fluid injection, our results demonstrate that equilibrium conditions may be significantly overstepped in metamorphic systems. We used overall mineral reactions in this model with rates based on experimental results. Future models could rely on more fundamental dissolution and precipitation reactions. Such an extension would require additional kinetic rate data, as well as mineral solubilities in mixed volatile fluids.Editorial responsibility: J. Hoefs 相似文献
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In this paper, we have attempted a diagnostic study of the turbulence characteristics of the ABL by means of two one-dimensional models. The first model uses a first order non-local closure, based on the Transilient Turbulence Theory, for parameterizing turbulent fluxes. while the second model uses second order local closure for parameterizing these. The models have been applied to conduct case studies using the Kytoon data taken at Kharagpur, during 17th–21st June, 1990, as part of the MONTBLEX programme. Our findings bring out various interesting features regarding the non-local and local turbulent statistics such as kinematic fluxes, turbulence kinetic energy, vertical velocity variance, the contribution of the eddies of various sizes to the fluxes at different level and the mixing lengths. The one-dimensional anisotropy of the turbulent eddies has been revealed by the findings from the transilient model. The vertical variation of the turbulence kinetic energy, as computed directly by the second order model, is found to be strongly correlated with the vertical velocity variance. In particular, for stably stratified boundary layers, identification of two distinct zones of the turbulence kinetic energy and corresponding vertical velocity maxima is possible, which has been interpreted as positive evidence of patchy turbulence in the boundary layer. 相似文献