共查询到20条相似文献，搜索用时 15 毫秒
1.
This study compares kinetic parameters determined by open-system pyrolysis and hydrous pyrolysis using aliquots of source rocks containing different kerogen types. Kinetic parameters derived from these two pyrolysis methods not only differ in the conditions employed and products generated, but also in the derivation of the kinetic parameters (i.e., isothermal linear regression and non-isothermal nonlinear regression). Results of this comparative study show that there is no correlation between kinetic parameters derived from hydrous pyrolysis and open-system pyrolysis. Hydrous-pyrolysis kinetic parameters determine narrow oil windows that occur over a wide range of temperatures and depths depending in part on the organic-sulfur content of the original kerogen. Conversely, open-system kinetic parameters determine broad oil windows that show no significant differences with kerogen types or their organic-sulfur contents. Comparisons of the kinetic parameters in a hypothetical thermal-burial history (2.5 °C/my) show open-system kinetic parameters significantly underestimate the extent and timing of oil generation for Type-IIS kerogen and significantly overestimate the extent and timing of petroleum formation for Type-I kerogen compared to hydrous pyrolysis kinetic parameters. These hypothetical differences determined by the kinetic parameters are supported by natural thermal-burial histories for the Naokelekan source rock (Type-IIS kerogen) in the Zagros basin of Iraq and for the Green River Formation (Type-I kerogen) in the Uinta basin of Utah. Differences in extent and timing of oil generation determined by open-system pyrolysis and hydrous pyrolysis can be attributed to the former not adequately simulating natural oil generation conditions, products, and mechanisms. 相似文献
2.
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
3.
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
4.
V. N. Melenevskii 《Geochemistry International》2012,50(5):425-436
The catagenesis of organic matter (OM) was modeled by the hydrous pyrolysis of a Riphean mudstone. Microscopic observations
of the processes operating during kerogen heating to 600°C were conducted in a diamond anvil cell. The results of pyrolysis
in an aqueous environment were used to calculate the activation energies of kerogen cracking and derive chemical kinetic models
for OM catagenesis. Isothermal experiments were carried out for 3 days at temperatures of 300, 310, …, 360, and 370°C. The
maximum bitumen yield was obtained at 330°C followed by thermal cracking at higher temperatures. The aromatic and saturated
hydrocarbons from rock bitumen, hydrous pyrolyzates, and kerogen flash pyrolyzates were analyzed by chromatography-mass spectrometry.
We also discuss the problem of extrapolation of high-temperature pyrolysis results to geologic observations under the conditions
of regional catagenesis. 相似文献
5.
The Menilite Shales (Oligocene) of the Polish Carpathians are the source of low-sulfur oils in the thrust belt and some high-sulfur oils in the Carpathian Foredeep. These oil occurrences indicate that the high-sulfur oils in the Foredeep were generated and expelled before major thrusting and the low-sulfur oils in the thrust belt were generated and expelled during or after major thrusting. Two distinct organic facies have been observed in the Menilite Shales. One organic facies has a high clastic sediment input and contains Type-II kerogen. The other organic facies has a lower clastic sediment input and contains Type-IIS kerogen. Representative samples of both organic facies were used to determine kinetic parameters for immiscible oil generation by isothermal hydrous pyrolysis and S2 generation by non-isothermal open-system pyrolysis. The derived kinetic parameters showed that timing of S2 generation was not as different between the Type-IIS and -II kerogen based on open-system pyrolysis as compared with immiscible oil generation based on hydrous pyrolysis. Applying these kinetic parameters to a burial history in the Skole unit showed that some expelled oil would have been generated from the organic facies with Type-IIS kerogen before major thrusting with the hydrous-pyrolysis kinetic parameters but not with the open-system pyrolysis kinetic parameters. The inability of open-system pyrolysis to determine earlier petroleum generation from Type-IIS kerogen is attributed to the large polar-rich bitumen component in S2 generation, rapid loss of sulfur free-radical initiators in the open system, and diminished radical selectivity and rate constant differences at higher temperatures. Hydrous-pyrolysis kinetic parameters are determined in the presence of water at lower temperatures in a closed system, which allows differentiation of bitumen and oil generation, interaction of free-radical initiators, greater radical selectivity, and more distinguishable rate constants as would occur during natural maturation. Kinetic parameters derived from hydrous pyrolysis show good correlations with one another (compensation effect) and kerogen organic-sulfur contents. These correlations allow for indirect determination of hydrous-pyrolysis kinetic parameters on the basis of the organic-sulfur mole fraction of an immature Type-II or -IIS kerogen. 相似文献
6.
7.
Using the results of the first paper in this series, which dealt with an inverse procedure for hydrocarbon generation, this paper focuses on case histories and numerical implementation of the model. Experimental data on residual kerogen analysis have been used with the inverse procedure to examine the applicability of the model to hydrocarbon generation directly from the degradation of kerogen, and to derive the kinetic parameters for the construction of a prediction equation. Energy-dependent channeling probability distributions are used to exhibit the stability of the model in describing the processes of kerogen degradation. The numerical methods for the solution of the inverse procedure and a sensitivity analysis are also discussed. 相似文献
8.
Pyrolysis kinetics are determined for a series of asphaltene samples associated with different types of kerogens. The activation energy distributions obtained for asphaltenes related to type I kerogens cover a wide range, with significant hydrocarbon generation with activation energies above 350 kJ/mol. The ranges of activation energy distributions are relatively narrow for asphaltenes associated with type II and III kerogens, with little hydrocarbons generated with activation energies above 350 kJ/mol. If the type of associated kerogen can be reasonably constrained, the pyrolysis kinetics of the asphaltenes is potentially a very useful tool for assessing the maturity levels of reservoired oils. The results of pyrolysis kinetics indicate that there is still significant potential for asphaltenes to regenerate hydrocarbons. 相似文献
9.
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
10.
This paper deals with the dissolution of magnesia in aqueous carbon dioxide, in the absence and presence of ultrasound. The particle size, reaction temperature and solid / liquid ratio were chosen parameters. The reaction was homogeneous first-order reaction model according to kinetic data and the activation energy was found to be 17.5 kJ/mol in both cases. The effect of ultrasound is on the pre-exponential factor A in the Arrhenius equation. An empirical relation was also given, which relates the rate constant to ultrasound power. 相似文献
11.
采用黄金管—高压釜封闭体系,对吐哈盆地艾试1井的泥岩和煤岩进行了低温热解实验。根据实验结果,分别求取了干气（C1）、湿气（C2～C5）生成过程的初始动力学参数,然后将单一活化能的动力学参数进一步优化为具有高斯分布的活化能,优化后的动力学参数能较好拟合实验数据。利用优化后的动力学模型模拟了吐哈盆地丘东凹陷八道湾组天然气早期生成过程,并将模拟结果与实际地质资料进行了对比。结果表明,经过优化后的低温恒温热解动力学,能有效评价早期生气过程;在丘东次陷发现的天然气,与八道湾组源岩关系密切。 相似文献
12.
海相烃源岩二次生烃潜力定量评价新方法 总被引：1，自引：0，他引：1
烃源岩二次生烃的演化过程是残余干酪根热解演化与残留油热裂解转化两个既相互联系又完全不同的物理化学反应过程的叠加。本文利用自制高压釜热压生烃模拟实验装置,采取分阶段连续递进模拟实验方式,以海相烃源岩样品为例分别评价了残余干酪根的生烃潜力与残留可溶有机质转化油气潜力,建立了一套不同起始与终止成熟度海相烃源岩二次生烃潜力的定量评价方法,并首次明确提出了干酪根生油指数KIo、干酪根生气指数KIg、干酪根生烃指数KIh等评价烃源岩生烃潜力的参数,弥补了ROCK EVAL热解评价方法无法分别评价烃源岩在不同生烃演化阶段所生成的“油”或“烃气”潜力的不足。 相似文献
13.
An investigation is given of sensitivity analysis, synthetic tests, and application to geological conditions of an inverse kinetic model for residual kerogen analysis. Using kinetic parameters derived from different experimental data a sensitivity analysis study allows a discussion of the discrepancies in predictions of kerogen degradation rates and cumulative amounts of kerogen degraded with temperature, time, and depth of sediments. The synthetic tests and the application examine the applicability to different geological conditions and the uncertainty in predictions of hydrocarbon generation. The study shows that when average values of the kinetic parameters derived from different experimental conditions and samples are used under geological conditions, the modeled kerogen degradation rates and cumulative amount of kerogen degraded are uncertain by about 25°C in temperature, 12.5 My in time and 600 m in depth. 相似文献
14.
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
15.
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
16.
利用干酪根热解动力学模拟实验研究塔里木盆地下古生界古地温 总被引：9，自引：0，他引：9
通过热解动力学模拟实验，对塔里木盆地塔参1井奥陶系干酪根的热演化过程进行了模拟，以此基础上利用KINETICS软件求取干酪根镜质体反射率（R0）的生成动力学参数，并结合塔参1井的沉积埋藏史，计算塔参1井寒武－奥陶系的古地温，这对于研究塔里木盆地下古生界高过成熟烃源岩的古地温是一种新方法。 相似文献
17.
利用爱沙尼亚奥陶系含藻干酪根未成熟生油岩样品的加水热模拟实验结果,计算了下古生界藻干酪根在各不同演化阶段的平均表观活化能和频率因子。发现其演化的整个过程不完全符合化学反应的一级反应,而是分段符合,动力学参数随演化程度的升高而先降低后增加。其计算结果对于我国下古生界及中上元古界生油层盆地模拟和资源评价具有重要的参考价值。 相似文献
18.
通过有压力的黄金管封闭体系生烃模拟实验和GC-IRMS测定,结合GOR-Isotope Kinetics专用软件,求取了塔里木盆地库车坳陷三叠系-侏罗系烃源岩生成甲烷的碳同位素动力学参数。结合地质背景,探讨了克拉2气田天然气的成因。克拉2气田天然气主要来源于早中侏罗世煤系烃源岩,属阶段捕获气,为-5Ma以来的天然气聚集,对应成熟度范围Ro为1．3％-2．5％。在此基础上,建立了克拉2气田天然气运聚成藏动力学模式,从而为天然气定量评价和动态研究提供了新思路。 相似文献
19.
In laboratory simulation of oil generation, products from closed systems pyrolysis of immature source rocks in the presence of water gives the closest match to petroleum compositions observed in nature. Fresh biomass can also be converted to fluids by pyrolysis, but in the absence of the sedimentary diagenetic transformations, the initially much higher oxygen content gives high yields of oxygen containing products. In this work, the reactions that occur during hydrous pyrolysis of a Kimmeridge source rock, a brown coal and two polymeric waste materials from alginate production are compared in terms of quantities of the main products and kinetic models of the reaction systems. The biomass pyrolysis and the simulated maturation are described in similar reaction networks. Conversion of biomass to fluids occurred with reaction networks and activation energy distributions comparable to the brown coal, while for the Kimmeridge source rock reactions a simpler reaction network could be used. The biomass samples gave a high degree of conversion to fluid products, and higher yields of bitumen than the coal. 相似文献
20.
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