烃源岩非均质性对有机质生烃动力学参数影响及评价

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.      

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.     

东营凹陷牛38井沙河街组烃源岩生排烃评价

东营凹陷牛38井沙河街组三段烃源岩从沙三下亚段向沙三中-上亚段为一从高水位深湖相向低水位前三角洲相发展的沉积旋回,该沉积环境控制从下向上发育不同类型的有机质。相应地,该段烃源岩品质从下向上变差,其中沙三中亚段上部及沙三中亚段中部烃源岩产烃能力小,沙三下亚段烃源岩整体品质好,局部存在优质烃源岩。其优劣性体现了在该段烃源岩中,Ⅰ型干酪根具有高的生产力,而Ⅲ型、Ⅱ₂型干酪根生烃潜力很低,基本为无效有机质。计算结果显示不同数据点的烃源岩单位质量原始生烃潜量可相差3个数量级,体现了烃源岩存在强烈的非均质性。有机碳的非均质性分布为其提供了物质基础,而湖盆的旋回式沉积及湖平面的波动性变化是其内在原因。同时,本文也提供一种计算生排烃量的新方法,结果表明该方法较为有效可行。     

未熟-低熟油生成机理的化学动力学研究及其初步应用

对树脂体、木栓质体、可溶有机质、富硫有机质、经细菌强烈改造过的有机质等各类与未熟─低熟油产出密切相关的样品及部分参照样品所进行的系统的化学动力学定量研究显示,虽然未熟─低熟油的产出和富集可能与多种不同的地质条件或因素有关,但它们的共同之处在于这些有机质较常规有机质具有明显偏低的成烃活化能。化学动力学模型的初步应用显示,这些有机质的确能在浅于常规生烃门限的地质条件下开始大量成烃,从而定量阐明了业已报道的各种地质条件下未熟─低熟油产出和富集的机理.     

鸡西盆地早白垩世烃源岩沉积有机相划分和评价

鸡西盆地早白垩世烃源岩的岩石类型是湖相泥岩、碳质泥岩和煤。根据其有机岩石学、沉积学和有机地球化学的特征,将该区沉积有机相划分为3种类型：高位沼泽有机相、滨浅湖-沼泽有机相和半深湖-深湖有机相。其中滨浅湖-沼泽有机相分布面积广泛,是最重要的生烃相带,有机质以Ⅲ型为主,生烃性能变化大,既可生油又可生气;半深湖-深湖有机相有机质为Ⅱ型,部分Ⅲ型,生烃性能良好并以生油为主,但分布面积局限;高位沼泽有机相由于处于盆地边缘,对生烃贡献不大。     

有机质成烃动力学模型研究综述

目前有机质成烃动力学模型主要有总包反应模型、串联反应模型、无数平行一级反应模型及平行一级反应模型几种。不同学者之间得到的动力学参数存在较大差异。有机质成烃动力学模型的进一步研究 ,有助于其在油气勘探中的应用     

江西乐平树皮煤热解生烃动力学研究

为了探讨树皮煤的生烃特征,对江西乐平树皮煤进行了3种升温速率下的Rock-Eval热解模拟实验,通过分析热解烃的产率随温度的变化,应用Optkin动力学软件对树皮煤进行热力学参数计算。结果表明:树皮煤的生烃潜力高,活化能分布范围窄,到达相应的温度后能够在短时间内大量生烃。通过与前人研究对比,认为树皮体的活化能分布受热解动力学模型、热解实验温度、升温速率、样品的纯度、成熟度等多种因素影响。     

准噶尔盆地石炭系不同类型烃源岩生烃模拟研究

选取不同沉积环境发育的多种类型的烃源岩,通过烃源岩生烃热模拟实验,对比分析不同类型烃源岩的生烃产物、产率特征及生烃演化规律。结果表明,准噶尔盆地石炭系不同沉积环境发育的烃源岩产烃能力差异较大,最大烃产率从高到低依次为:弧间盆地泥岩、弧后盆地泻湖相泥岩、残留洋盆滨浅海相泥岩、沉凝灰岩。烃源岩的产烃率大小受控于其母质与埋藏热演化条件,有机质类型越好,产烃率相对越高;而受火山作用影响越剧烈,产烃率越低。下石炭统广泛发育的弧间、弧后盆地暗色泥质岩类烃源岩具备高产烃率,为有利烃源岩发育区,乌伦古坳陷和滴水泉地区为准噶尔盆地石炭系油气勘探的有利方向。     

加水热模拟中深湖与煤系泥岩地化特征比较

通过深湖泥岩和煤系泥岩的加水热模拟研究认为,在热模拟实验过程中,深湖泥岩和煤系泥岩显示不同特征,并且其演化有差别。深湖泥岩利于液态原油的生成,并且转化率高于煤系泥岩。深湖泥岩残余可溶有机质饱和烃含量高于煤系泥岩,非烃含量则低于煤系泥岩。深湖泥岩胶质 /沥青质和饱芳比均随温度升高而降低,而煤系泥岩的胶质 /沥青质随温度升高有增加趋势,其饱芳比的变化则不大或有降低趋势。深湖泥岩的T_max难以指示演化阶段,其干酪根碳同位素值明显轻于煤系泥岩,它们的值均随温度的升高而变重。     

Studying of liquid thermolysis products of various types of immature kerogen in sedimentary lacustrine rocks from the valjevo-Mionica basin,Serbia, and the effect of Pt<Superscript>4+</Superscript> and Ru<Superscript>3+</Superscript> ions on their yield and the hydrocarbon composition

Liquid thermolysis products of various types of immature kerogen from sedimentary lacustrine rocks from the Valjevo-Mionica basin in Serbia were studied to evaluate the generation potential of kerogen contained in the organic matter (OM) of the rocks, determine the composition of the biomarkers and alkylaromatics in the liquid thermolysis products, and elucidate the effect of Pt⁴⁺ and Ru³⁺ ions (which were added in the form of inorganic salts) on the yield and hydrocarbon composition of the liquid thermolysis products. For this purpose, representative bitumen-free samples A and B of the sedimentary rocks were subjected to thermolysis under various conditions. Rock A contains high amount of immature organic matter, which is dominated by kerogen type I/II and was generated under strongly reduced sedimentation conditions at a high salinity. Sample B is poorer in immature OM than sample A, and the OM of the former contains kerogen type II/III and was generated predominantly in a reduced environment. The content of the liquid products and the concentrations of hydrocarbons obtained in the course of thermolysis of bitumen-free sample A and the typical oil distribution of the biomarkers and alkylaromatics in the thermolysis products confirm a high generation potential of OM in this rock. In all of our experiments on the thermolysis of bitumen-free sample B, the yield of liquid products and hydrocarbons is low. According to the kerogen type, the thermolysis of this rock generates much gases. The Pt⁴⁺ and Ru³⁺ ions (added in the form of simple inorganic salts) increased the yield of liquid (kerogen type I/II) and gaseous (kerogen type II/III) products. During the thermolysis of various type of immature kerogen in the lacustrine sedimentary rocks at a temperature of 400°C, the OM attained maturation corresponding to the early catagenesis level. Saturated biomarkers and alkylaomatics in the thermolysis products of both samples display typical oil distributions. The type of the source OM most strongly affects the composition of n-alkanes and alkylnaphthalenes. The metal ions used in this research served as catalysts for the methylation process during the thermolysis of immature kerogen, regardless of its type. The effect of the Pt⁴⁺ and Ru³⁺ ions on other transformations of the hydrocarbons, for example, the destruction of high-molecular n-alkanes to low-molecular ones and on isomerization reactions in molecules of polycyclic biomarkers and alkylaromatics to thermodynamically more stable isomers in the thermolysis products is controlled, first of all, by the type of the source OM.     

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。     

试论泌阳断陷陆相层序水进体系域的油气地质意义

泌阳断陷湖盆陆相层序水进体系域以退积型扇三角洲为其沉积主体，靠近构造枢纽的陡坡带边缘，冲积扇相域越来越窄，而向盆内则由滨浅湖逐渐过渡为半深湖。断陷湖盆水体属水进型湖泊。水进体系域中油气潜在储集体包括冲积扇的辫状河道砂体及扇三角洲的分流河道、水下分流河道、河口砂坝和前缘席状砂体。但由于它们形成的古环境及物理化学条件的不同，其砂砾岩中所含粘土矿物类型及数量亦有显著差异，对其储集性能将产生不同程度的影响。     

烃源岩催化酯生烃动力学研究——以东营凹陷沙河街组三、四段烃源岩为例

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。     

断陷湖盆陡坡带油气成藏类型及其分布规律探讨

断陷湖盆陡坡带油气生、储、盖层的发育与陆相层序中的体系域具有一定的成因联系,不同的陆相层序样式可构成不同的生、储、盖层组合,综合考虑陆相层序储集体类型及其特征,将断陷湖盆陡坡带油气成藏类型归纳为三大类,八亚类,十种。它们分别是：岩性上倾尖灭,岩性下倾尖灭,岩性透镜体,岩性相变,地层不整合,地层削截,地层超覆,地层退覆,构造－岩性复合,构造－地层复合等油气成藏类型,这些油气成藏类型在断陷湖盆陡坡带陆相层序各个体系域中的分布具不均衡性,以水进体系域为最,其次为水退休系域和高水位体系域,低水位体系域较少,从陆相层序各体系域中成藏类型的空间展布规律来看,水进体系域是陆相断陷湖盆陡坡带油气勘探的重要目的层段。     

苏里格地区山西组烃源岩地化特征及生烃能力评价

鄂尔多斯盆地苏里格地区上古生界地层为海陆交互及河流-湖泊三角洲相的石炭-二叠系含煤岩系。下二叠统山西组发育煤和暗色泥岩二类烃源岩。根据苏里格及周边地区大量钻井岩芯样品的残余有机碳含量,干酪根同位素,有机质显微组份组成,干酪根镜质体反射率（Ro）等地球化学数据,综合分析了下二叠统山西组烃源岩的有机质丰度,类型和热演化程度。采用有机碳产烃率法,分别计算了煤层和暗色泥岩的生烃强度。在此基础上,结合苏里格地区山西组成藏特征,综合评价认为山西组生烃能力居于中等偏低的级别。     

An application of least-squares inverse analysis in kinetic interpretations of hydrous pyrolysis experiments

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.     

柴西地区上干柴沟组上段咸水湖相烃源岩生烃条件研究

柴西地区上干柴沟组上段(N12)烃源岩的沉积水体环境为咸水湖相。其烃源岩的有机质总体丰度不高;有机质类型主要有腐殖腐泥型和腐殖型,具体分布受烃源岩所处位置及沉积环境控制;有机质成熟度多为未成熟-低成熟;有机质的烃转化率较高,反映其大部分有机质已经进入生烃门限,少量已经进入生烃高峰期。其烃源岩具有咸化湖泊相未熟-低熟有机质生烃的特点,而其生烃机理很可能是藻类生物类脂物和细菌的早期成烃。柴西地区上干柴沟组上段(N12)烃源岩作为该区未熟-低熟石油主要源岩之一,具有非常大的勘探潜力。     

松辽盆地他拉哈西地区下白垩统青山口组下部沉积微相分析

笔者通过观察岩心,结合测井、录井资料,采用沉积学最新分析方法,查明了主要研究层青山口组(K1qn)下部发育的沉积微相类型及其特征,建立了相标志,同时查明了不同体系域沉积相、亚相、微相的空间展布.研究层段发育的沉积类型有湖泊相和湖底扇相,湖泊相主要为半深湖-深湖亚相,湖底扇相区分为内扇和外扇两个亚相.通过单井相划分和3条不同方向的联井剖面查明沉积微相在纵向上的变化,利用沉积微相平面分布图分析了研究区各沉积微相的平面分布特征.纵向上研究层段底部湖底扇较发育,向上湖底扇的面积逐渐减小.平面上,以深湖-半深湖沉积为主,在研究区的西侧、西南和西北地区发育湖底扇.湖底扇具有多期性、多物源的特点.该区的主体砂岩为碎屑流、浊流成因的湖底扇砂,其典型特征是厚层暗色的深湖-半深湖亚相的烃源岩夹由重力流成因的湖底扇,上下均呈突变接触关系,具有很好的隐蔽油藏成藏的条件.     

东南亚地区烃源岩特征与主控因素

通过对东南亚主要含油气盆地沉积、构造特征的研究,揭示其烃源岩具有多期发育的特点.其中,始新统、渐新统和中新统是东南亚主要的3套烃源岩;前新生代生油岩分布局限,但具有一定的生烃潜力.以新生代河流-三角洲近岸沉积环境、含陆源干酪根的煤系和碳质页(泥)岩为主,其次为湖相和海相沉积环境泥岩和页岩.有机碳含量均已达到中等-好的源岩标准,以Ⅱ-Ⅲ型干酪根为主,大部分烃源岩都处于成熟到过成熟阶段.新生代烃源岩主要受盆地演化阶段和沉积环境两大地质因素控制,与区域海侵作用的方向和规模密切相关.烃源岩有机质类型的不同和热演化程度的差异,是形成东南亚地区多类型油气藏的重要因素之一.      

渤海莱州湾凹陷不同类型烃源岩活化能影响因素分析

选取不同干酪根类型的低熟烃源岩作为剖析对象,从干酪根类型、干酪根中有机硫含量、可溶有机质和黏土矿物对烃源岩活化能的影响进行研究,结果表明:Ⅱ₁和Ⅰ干酪根活化能分布范围窄,Ⅱ₂和Ⅲ干酪根活化能分布范围宽,干酪根平均活化能Ⅲ>Ⅱ₂>Ⅰ>Ⅱ₁;有机硫含量高的干酪根平均活化能低,有机硫对烃源岩生烃起催化作用;可溶有机质的存在影响烃源岩平均活化能的大小和分布特征,可溶有机质分布在活化能低值区间,对烃源岩生烃起催化作用;烃源岩黏土矿物中伊/蒙混层含量高,平均活化能高;伊利石含量高,平均活化能低,伊利石对烃源岩生烃起催化作用。