基质镜质体成烃动力学特征研究

干酪根、煤以及显微组分生烃过程中的动力学参数(如活化能分布特征等)是其内部分子结构的宏观反映,据此可以判断有机质内部成键特征,评价生油门限、生油高峰,计算不同温度范围油气生成量等。笔者利用岩石热解仪(Rock-Eval型)对贵州水城含树皮体煤中的主要组成——基质镜质体的成烃动力学特征进行了研究,并与树皮体、丝质体进行比较,结果表明,基质镜质体的平均活化能为200kJ/mol,大于树皮体的平均活化能(177kJ/mol),而小于丝质体的平均活化能(324kJ/mol),由此推断,在相同的热演化条件下,基质镜质体、树皮体、丝质体三者的生烃顺序为树皮体→基质镜质体→丝质体。从基质镜质体生烃活化能分布特征图上可以看出,基质镜质体有4次主要生烃期,其对应的活化能分布范围及产烃率分别为191.25—192.5kJ/mol、12.19%,195—196.25kJ/mol、7.25%,197.5—198.75kJ/mol、39.82%,216.25kJ/mol、18.64%,据此可以认为:基质镜质体主要由4种不同类型键组成。在活化能191.25—198.75kJ/mol范围内,基质镜质体的累计生烃率达60%左右,这说明基质镜质体产烃较集中(在较短的地质剖面或温度范围内形成大量烃类物质),其含量高(煤岩三大组分之一),因此对煤成烃资源有较大的贡献。     

开放体系下平凉组页岩干酪根的生烃动力学研究

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     

柳树河油页岩的热解特征及动力学

利用岩石-热解评价仪研究了200～600 ℃不同升温速率（10、15、20、25、30 ℃/min）下柳树河盆地油页岩热解生烃特征,利用Friedman法和Sestak反应机制,求出了油页岩的反应活化能和反应函数,建立了热解动力学模型,可用于计算热解生烃率和达到某一转化率所需要的时间。研究发现,油页岩的反应活化能并不是一个定值,随着反应温度的增加逐渐增大。这是因为油页岩热解是一个极其复杂的多步反应过程,在不同的温度区间内具有不同的反应机理。     

贵州水城地区晚二叠世含树皮体煤成烃特性研究

采用岩石热解、热解气相色谱以及有机岩石学等方法。对贵州水城含树皮体煤及其主要组分－－树皮体的生烃潜力、烃类组成特征和成烃演化规律进行了详细的研究。结果表明：本区含树皮体煤友及树皮体的生烃潜力、氢指数和扔机碳含量都较高,含树皮 煤主要生烃温度区间和生烃高峰期分别为４００￣５００℃和４２０￣４５０℃;热模拟产物以轻质烃（凝析油或轻质油）占绝对优势,湿气次之;气态烃与液态烃演化模式截然不同,液态烃产率在     

煤岩显微组分的活化能研究

热解反应中活化能（E）与生烃率的关系是煤（干酪根）结构组成的反映，这就如同指纹一样，在成熟度相同的条件下，不同的显微组分其动力特征不同。煤及显微组分化学结构的确定目前地球化学研究领域中的一个难点。利用岩石热解（Rock-Eval）、热解气相色谱（PY－GC）以及开放体系下热模拟方法，对树皮体、镜质体和丝质体不同生烃率所对应的活化能进行测定和计算，在此基础上对上述组分的化学结构进行探讨。结果显示，三种组分的生烃率－活化能关系图以及由此所反映的化学结构明显不同：树皮体热解生烃主要集中在低活化能区，其化学结构相对较为单一，主要由脂族结构组成，芳香结构及杂原子官能团相对较少；镜质体的生烃活化能稍高，其结构比树皮体要复杂些，以烷基苯和甲氧基苯为主；丝质体生烃主要集中在高活化能区，化学结构更为复杂些，除以烷基及甲氧基苯为主外，还含有一定数量的杂原子官能团以及短链脂肪烃。另外，上述三种组分的平均活化能明显不同，其中树皮体的最低，丝质体的最高，镜质体的介于两者中间。因此，生油门限也存在很大差别，在相同的热演经条件下，三者的生烃顺序依次为树皮体→镜质体→丝质体。     

碳酸盐岩干酪根催化降解生烃过程及动力学研究

以甘肃平凉地区奥陶系碳酸盐岩干酪根为对象,利用热模拟实验方法和化工催化原理,从热解生烃组成特征、生烃量及生烃动力学等方面考察了不同介质对干酪根热解生烃过程的影响。结果表明,碳酸盐岩对干酪根生烃过程具有反催化作用,随着温度的增加,反催化作用越明显。膏岩CaSO₄则表现出正催化作用,各种盐类对干酪根生烃过程影响较小。干酪根热解动力学研究表明,生烃动力学参数活化能E与视频率因子A之间不是独立变化的,它们之间存在一定的关系,即:E与lnA呈线形关系,这对于认识碳酸盐岩干酪根的化学结构及热解生烃机理具有一定的参考价值。     

生油岩热解生烃潜力及生烃动力学研究

利用岩石评价仪(R0cK EVAL I)对某凹陷30块生油岩进行了热解生烃和生烃动力学研究。在热解实验中，用类型指数、生烃潜量、最大热解峰温Tmax、等指标对上侏罗统3个层位的生油岩进行了母质类型、成熟度和生烃能力评价，结果表明，母质类型好、有机质丰富的未成熟生油岩的热解生烃量要比相同的已成熟生油岩高得多，说明选择未成熟生油岩热解对评价其生油能力的重要性。在对另2个未成熟生油岩的热解模拟实验中，得到了生烃率与温度之间的关系，并由此计算了生油岩的表观活化能、频率因子等动力学参数。     

爱沙尼亚干酪根催化降解生烃过程及动力学研究

以爱沙尼亚油页岩干酪根为对象,利用热模拟实验方法和化工催化原理,考察了不同介质对干酪根热解生烃过程的影响,从热解生烃量、生烃组成特征及生烃动力学等方面进行了探讨。结果表明:膏岩对干酪根的生烃具有明显催化作用,碳酸盐岩对干酪根的生烃具有一定反催化作用,各种盐类对干酪根的生烃量影响较小。干酪根热解动力学研究表明,生烃动力学参数表观活化能E与视频率因子A两者之间不是独立变化的,而是具有一定的关系,即:E与lnA之间服从直线关系(R=0.99),这些认识对于深入探讨爱沙尼亚油页岩干酪根的化学结构、建立热解动力学模型具有一定的参考价值。     

不同升温速率下树皮体的热重特征变化

中国特有煤种——树皮煤,因具有高氢、高挥发分及高焦油产率等特点而备受关注,而其中富含的特殊显微组分——树皮体,其热性质一直未得到深入研究,直接影响树皮煤的合理利用。采用热重分析仪对不同升温速率下树皮体、镜质体及原煤(树皮煤)的热解失重特征进行了对比研究,并结合工业分析和元素分析结果,讨论了树皮体的化学性质。研究表明:随着升温速率的增加,树皮体、镜质体和树皮煤的TG和DTG曲线均不同程度的向右侧高温区移动,最大失重速率相应减小,升温速率对树皮体的DTG曲线变化影响较大。尽管使用的升温速率不同,而树皮体的DTG曲线峰形均具有窄而尖的特点,说明树皮体的受热变化比较剧烈。同时,树皮体的总失重量均大于镜质体和树皮煤。     

煤中有机质二次生烃迟滞性及其反应动力学机制

采用自然成熟度系列与其预热残渣系列样品相结合方式, 通过热解模拟方法, 对煤中有机质二次生烃迟滞性显现特征和化学反应动力学机制进行了探讨.结果表明: 二次生烃起始成熟度增高, 二次生烃峰位成熟度呈规律性后移, 二次生烃作用“死线”位于R_o=4.0 %左右; 二次生烃峰位成熟度与起始成熟度之差随起始成熟度的增高呈抛物线式演化, 二次生烃的绝对迟滞性和相对迟滞性均呈阶段性演化, 由此可对二次生烃迟滞深度进行预测; 二次生烃半峰宽随起始成熟度呈阶段性演化, 暗示二次生烃起始成熟度位于生油高峰附近的烃源岩, 其生烃量可能相对较大.同时, 原始样品平均活化能的演化经历了4个阶段, 它们与热解生烃量及二次生烃迟滞性的阶段性演化特征高度吻合, 揭示出二次生烃作用严格受控于反应动力学的地球化学机制.      

Hydrocarbon Generation Kinetic Characteristics from Different Types of Organic Matter

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.     

Maturity Control on the Patterns of Hydrocarbon Regeneration from Coal

Rock-Eval pyrolysis and Py-GC experiments on naturally and artificially matured coal samples were carried out. The results suggest that both depolymerization and defuctionalization exist during the maturation and evolution of coal. The patterns of hydrocarbon regeneration are diverse at different stages of the maturation and evolution. When the vitrinite reflectance (R0) is 0.7%-0.9%, bitumen is the richest in coal while activation energy is the minimum, and the temperature of peak yield is lower than that of primary hydrocarbon generation. However, if reflectance is greater than 0.9%, defunctionalization predominates and the temperature of peak regeneration is shown in lagging compared with the primary hydrocarbon generation. When reflectance is out of the "oil window", the peak temperature of hydrocarbon regeneration and that of the primary hydrocarbon generation seems to be continuous.     

吐哈盆地丘东次凹低熟气的生成与动力学研究

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（C1）、湿气（C2～C5）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。     

油成甲烷碳同位素分馏的化学动力学及其初步应用

利用金管实验装置,在高压、恒速升温的条件下对塔里木盆地2个油样进行了热解成气实验,结合GC和碳同位素分析,得到了甲烷生成率、甲烷碳同位素与实验温度和升温速率的关系。由此建立并标定了油成甲烷及其碳同位素分馏的化学动力学模型。结果表明：2个油样生成甲烷气时的平均活化能差别不大,但活化能的分布有所差异;¹²C生成的活化能在低值区稍高,而在高值区稍低,从而使生成¹²C的平均活化能稍低于¹³C。正是¹²C、¹³C甲烷生成的活化能分布上的这一微小的差异,导致了甲烷生成时碳同位素的明显分馏。所得模型在塔里木盆地的初步应用显示,英南2气藏天然气主要为晚近期的阶段聚集气,而满东1气藏天然气可能为累积聚集。     

Effect of Uncertainty of the Pre-Exponential Factor on Kinetic Parameters of Hydrocarbon Generation from Organic Matter and its Geological Applications

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 TR_0.5（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.     

The Impact of Aqueous Medium on Gas Yields and Kinetic Behaviors of Hydrogen Isotope Fractionation during Organic Matter Thermal Degradation

In order to recognize the impact of aqueous medium on gas yields and the kinetic behaviors of hydrogen isotope fractionation during organic matter thermal degradation, the gold tube apparatus was used to conduct thermal simulation experiments by mixing the nC18 with the water of different properties and proportions. The yields of natural gas components, the relation among hydrogen isotope composition of each component and the experimental temperatures vs. heating rates have been obtained, and the results indicate that under the higher temperature conditions, the hydrous experiment has obvious impact on gas yields, such as when more water is added, higher amounts of hydrocarbon gas and H2 are yielded, and the existence of water obviously prolongs the temperature interval with the existence of heavy hydrocarbon gas. It also shows that the hydrogen isotope of hydrocarbon gas generated by the hydrous experiment is obviously lighter than that generated by the anhydrous experiment, and with the increasing amount of added water, the δD value of hydrocarbon gas gradually decreases. Compared with gas yields, the variation of δD value is more sensitive to aqueous medium in the thermal simulation experiment. However, compared with the amount of the added water, the aqueous medium property has smaller impact on the gas yields, which still shows the inherit effect on hydrogen isotope composition of aqueous medium. Through the model simulation and the isotope fractionation behavior analysis, it is validated that the hydrogen isotope fractionation process can be well described by the chemical kinetic model. The difference of reaction fraction of normal methane and D-containing methane is large, corresponding to the same activation energy. The content of normal methane is obviously higher in the part with lower activation energy, while the content of D-containing methane is higher in the part with higher activation energy. Therefore, it will result in larger hydrogen isotope fractionation amplitude, and the δD values will be more sensitive to the variation of maturity. Meanwhile, the average activation energy of methane generation from nC18 in the hydrous experiment is higher than that in the anhydrous experiment, and the greater amount of added water, the larger the average activation energy of methane generation reaction. This has laid foundation for its exploratory application in the study of gas reservoir forming history and the gas-source correlation, which indicates the research and application prospects in this orientation.     

沥青质催化降解特征及动力学研究

采用热解气相色谱仪 (Py-GC),对东营凹陷烃源岩可溶有机质中的沥青质进行了热解模拟实验。考察了蒙脱石和K₂CO₃ 介质对沥青质催化降解过程的影响,求得了沥青质的催化降解动力学参数。结果表明,在K₂CO₃ 介质存在下,沥青质热解生成气态烃、轻烃和重烃的收率均有明显的提高,模拟温度下总检测烃收率提高了约 2 0 %;在蒙脱石介质存在下,除重烃收率下降外,气态烃和轻烃收率均有所提高,模拟温度下总检测烃收率提高了约 10 %。与之相对应,除蒙脱石存在下重烃的生成活化能有所增加外,介质的存在均不同程度地降低了其它各热解产物的生成活化能。最后,对沥青质的催化降解机理进行了初步的探讨.     

低成熟石油烃源岩的动力学研究

本文介绍了对东营凹陷下第三系沙河街组沙四段上部具有不同自然熟化程度的低成熟石油烃源岩进行动力学研究的结果。结果表明，浅埋藏、低成熟、低有机丰度且与碳酸盐岩相关的源岩具相对较高的烃产率和平均活化能；平均活化能可能会掩盖低熟成烃特征。依据研究结果，指出当前进入门限埋深以下且具有低活化能生烃母质存在的牛１１样品可能在浅埋藏、低成熟时曾为该区（八面河低熟油田）低成熟石油的形成提供了油源。另外，笔者通过对样品可溶有机质抽提前后活化能分布对比研究，指出了低活化能分布范围内的生烃母质主要为可溶有机质。并且进而提出本区低成熟石油的成油下限埋深划分至２８００ｍ为宜，其对应的下限反应活化能不超过１７７ＫＪ/ｍｏｌ。