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1.
To investigate the effect of Mn ore on the chemical components and isotopic compositions of gas products during kerogen pyrolysis in the absence or presence of water, a series of pyrolysis experiments on Type-I kerogen with manganese carbonate and/or water were conducted in closed gold capsules at 325–600?°C for 72?h with 300?bar. The heavy hydrocarbon gas yields increased significantly over 450?°C due to the participation of manganese. As for isotopic compositions, the manganese catalysis caused a decrease in the 13CCH4 and an increase in the 13CC2H6 over 475?°C; the δD values of methane generated during anhydrous pyrolysis with manganese carbonate are much lower than those produced by the pyrolysis of kerogen alone. Furthermore, the δD values are the most negative during hydrous pyrolysis with manganese ore. In addition to the thermal decomposition of manganese carbonate to form carbon dioxide, water provides sources of hydrogen and oxygen to form H2 and CO2. Manganese carbonate inhibits the association of sulfur-free radicals to hydrogen to form H2S. The i-C4/n-C4 ratio for gas products was evidently higher due to the existence of manganese and water, they can enhance the carbocation mechanism.  相似文献   

2.
对华北下花园地区下马岭组及鄂尔多斯盆地延长组2组低成熟泥岩全岩及分离的干酪根样品开展有水热解实验,探讨了烃源岩源内无机矿物对有机质生烃及同位素分馏的影响。实验结果表明,两组全岩有水体系液态烃及气态烃产率不同程度低于干酪根有水体系,CO2及H2产率则明显偏高。同时,全岩有水热解体系气体产物异构烃含量相对较低,表明烃源岩中无机矿物的加入抑制了水-有机质的反应并一定程度上改变了反应途径。稳定同位素的分析结果表明,相同热演化程度下,2组全岩及相应干酪根热解生成的甲烷碳同位素变化不大,但前者生成的二氧化碳碳同位素显著升高,且气态烃氢同位素更低。表明全岩有水热解体系下,烃源岩中的无机矿物参与到有机质热解过程中,改变了CO2产率及同位素组成,并存在H2间接加氢作用。   相似文献   

3.
为了探讨含铁矿物对水—有机质生气的影响,基于黄金管热模拟装置,选用了高熟干酪根样品开展了3组有水体系(干酪根+水、干酪根+黄铁矿+水、干酪根+磁铁矿+水)的恒温热解实验。气体产物的定量分析结果表明,黄铁矿和磁铁矿的加入均导致干酪根在有水体系下气态烃产率一定程度的降低。比如,水—黄铁矿体系和水—磁铁矿体系在Easy%RO=3.08%时CH4产率相比单独有水体系分别降低8.5 mL/gTOC和13.3 mL/gTOC。水—黄铁矿体系CO2产率及碳稳定同位素值明显高于单独有水体系和水—磁铁矿体系,含铁矿物(尤其是磁铁矿)加入的热解体系的H2S产率明显低于单独有水体系。气体组成分析结果表明,含铁矿物的加入明显提高了烃类气体的干燥系数,同时导致异构烷烃相对含量的降低。水—磁铁矿体系气体产物氢同位素值相对低于单独有水体系,表明磁铁矿的加入促进了早期H2的生成而与有机质之间发生了加氢作用。这些结果表明,含铁矿物的加入可能抑制了碳正离子的反应,水—有机质的加氢生气可能主要是自由基反应。  相似文献   

4.
油气生成过程实验研究的思考与展望   总被引:9,自引:2,他引:7       下载免费PDF全文
油气生成过程的研究是以热解实验为基础、动力学研究为工具、紧密结合盆地地质条件的系统研究方法。在总结现有研究成果的基础上,作者认为:1)加水热解适于模拟石油生成,限定体系热解可以很好地模拟石油与天然气生成/裂解实验体系,可进行含水热解实验;2)半封闭的幕式排烃热解设备尚待开发;3)压力对有机质成熟和生烃/原油裂解均有一定影响,但压力下二者的演化进程可能并不同步;4)以单一升温速率为基础的动力学研究将不被国内外同行认可;5)有压力的生烃、同位素演化动力学模型值得进一步研究;6)由于水的存在,除了水溶性催化剂外,大多数地质催化剂对生烃的影响可能并不显著,但对油气在储层中的裂解可能有作用;7)天然气的成分、同位素变化与聚集史密切相关,应给予足够的重视;8)无机质以及加水热解动力学研究、非烃气体生成与同位素演化的动力学具有潜在的科学研究价值。   相似文献   

5.
Thermal simulation experiment of hydrocarbon generation and expulsion is an important method for the study of source rock evolution. The role played by water in organic material evolution was clarified by summarizing the effect of water on different pyrolysis systems. According to the results, the hydrous experiment has a better hydrocarbon generation rate than the anhydrous experiment in the closed system. In the semi-open system, high-pressure water vapor has good effect to gas generation, while near-critical water (NCW) improves the oil and total hydrocarbon productive rate. So, it is inferred that NCW improves the conversion of kerogen to hydrocarbon reactions, and increases the dissolving capacity of hydrocarbons.  相似文献   

6.
解剖烃源岩自然演化规律,结合生烃实验模拟,对有机质生烃耗水机制进行深入研究,并对生烃耗水量进行计算,研究生烃耗水与油气运移及成藏的关系.模拟实验采用加水液压与不加水柱压2种条件,对比两种情况下有机质演化过程中的地球化学特征,重点研究生烃潜力及碳转化率的变化.研究结果表明,有机质在生烃演化过程中与水相互作用,对干酪根的影响表现为活化部分无效碳,对已降解的产物表现为进一步加氢,导致总生烃潜力增加.在耗水机制研究基础上提出了生烃耗水量的计算方法,对东营凹陷主力烃源岩的计算结果表明,Es4上烃源岩耗水区间大,耗水量也较大.Es3下、Es3中烃源岩生烃耗水区间、耗水量依次变小.生烃耗水对油气运移和成藏有重要影响,可以提高生烃母质碳降解率以增大流体体积,并且增加烃源岩孔隙流体的压力和含油饱和度.生烃耗水和成岩耗水区间相匹配,强化了油气运移的动力,有利于形成自生自储和下生上储油气藏.图6表2参24  相似文献   

7.
在天然气成因类型研究中,如何有效识别干酪根与原油裂解气一直是一个难题。选取不同类型干酪根、不同性质原油开展半封闭—半开放体系的热压生排烃模拟实验及其产物的地球化学分析研究,并对典型的干酪根、原油裂解气(田)进行了地球化学统计和比对。研究表明,干酪根热解气与原油裂解气中烷烃组分及其碳同位素组成显示相似的演化特征,Ln(C2/C3)值均呈早期近似水平和晚期近似垂向变化特征,在高过成熟阶段Ln(C2/C3)值与δ13C213C3差值具有快速增大的趋势,二者趋同性变化特征指示了生气母质的高温裂解过程,但这些指标不是干酪根与原油裂解气的判识标志,提出天然气中烷烃分子及同位素组成的有机组合是判断有机质(干酪根、原油)高温裂解气的可靠指标,却并不能直接识别干酪根热解气或原油裂解气;非烃组分的演化特征具有明显的差异性,干酪根热解气以高含氮气(N2)为主,原油裂解气往往高含硫化氢(H2 S), N2、H2 S含量作为一项重要指标可以与烷烃气同位素组成相结合有效区别干酪根与原油裂解气,分析结果与四川盆地、塔里木盆地不同油气田的地质实际相吻合。天然气中烃类和非烃组成的综合分析为有效判断干酪根与原油裂解气提供了新的途径。  相似文献   

8.
利用常规高压釜热压模拟仪和仿真地层热压生排烃模拟仪对南方海相不同类型烃源进行生烃模拟实验,研究发现不同类型原油烃气产率最高,分散可溶有机质烃气产率次之,产率最低的为不同类型千酪根。不同类型烃源烃气产率与烃源的有机碳含量、可溶有机质含量高低、有机质类型有密切关系,与烃源原始成熟度具有较好负相关性。烃源碳同位素组成决定产物甲烷碳同位素组成的演化规律,碳同位素组成较轻的烃源其产物甲烷碳同位素组成总体上要轻于碳同位素组成较重烃源的甲烷碳同位素组成。不同类型烃源产物甲烷碳同位素组成随热模拟温度增高具有先变轻再变重的演化特征,但不会重于其烃源的碳同位素组成。乙烷等碳同位素组成也随着热模拟温度增高逐渐变重,演化至生烃高峰时,碳同位素组成接近于其烃源碳同位素组成,可以示踪烃源。当演化至高过成熟阶段,乙烷等δ^13C值大于其烃源碳同位素值,故不能仅用重烃碳同位素组成判断天然气母质类型。不同类型干酪根与可溶有机质CO2组分和同位素组成演化规律具有明显区别,可溶有机质生成的CO2和甲烷之间同位素分馏程度要比不同类型干酪根的大。在不同类型烃源生烃过程中,干酪根和液态烃碳同位素组成主要受母质类型控制,继承效应强,同位素分馏程度较小,具有很好的示踪意义,可以用于油源对比和烃源示踪研究。  相似文献   

9.
烃源岩的生烃过程是在地层孔隙空间内有机质受温度、上覆岩层静岩压力和高地层流体压力(PVT-L共控)等多种作用下的一种复杂的物理化学反应过程。然而目前常用的生烃模拟实验(高压釜加水生烃模拟)大多是在一个低流体压力、无静岩压力、相对较大的生烃空间下进行的,与实际地质情况差异较大。选用南襄盆地泌阳凹陷核三段未熟泥岩分别开展了PVT-L共控和常规高压釜方式加水模拟实验,不同演化阶段干酪根的傅里叶变换红外光谱对比分析表明:(1)伴随着脂族结构裂解、含氧基团脱落及芳香结构缩合,干酪根演化明显呈现出缓慢生油、快速生油和结束生油3个阶段;(2)脂肪度参数IAL、饱芳比参数IL/R和含氧度参数IO表明,同等温度条件下常规高压釜加水模拟脂肪链和含氧基团的热裂解反应更为剧烈,PVT-L共控模拟则相对平缓,380℃时仍伴随有较强的生烃能力;(3)PVT-L共控模拟条件下饱和烃的芳构化程度更低,可能与其限定空间内较高的流体压力有关;(4)含氧度在成熟中期间歇的轻微增大,暗示水对干酪根生烃过程也许有重要的作用。2种不同模拟方式下干酪根红外光谱特征上的差别,暗示其在生烃反应机理上存在较大差异,在热模拟实验研究中要根据研究目的合理选择模拟方式,设置实验条件。   相似文献   

10.
Abstract

Asphaltenes precipitated by the use of pentane, heptane and decane solvents from Saudi Arabian Light (AL) and Saudi Arabian Heavy (AH) crude oils 370°C + residua have been investigated by thermal gravimetric analysis and pyrolysis - gas chromatographic analysis at 350°C and 520°C. Gas chromatographic analysis of the gases evolved during pyrolysis has shown that CO, CO2 and CH4 constitute the major portion of the gases evolved at 350°C from pentane and heptane asphaltenes of AH residue and from pentane asphaltenes of AL residue. Whereas gases evolved from decane asphaltenes are dominated by CO2 and C2-C4 hydrocarbon gases. At 520°C, hydrogen and methane represent 56-80 vol %of the gases evolved from all the four asphaltenes. The amounts of C1-C4 hydrocarbon gases increased with an increase in the carbon number of the precipitating solvent at 350°C and decreased at 520°C. The presence of up to C36 normal alkane hydrocarbon has been indicated in the maltenes produced from these asphaltenes. The loss of nitrogen from AH asphaltenes during pyrolysis remained low (1-6 wt %), whereas the losses of oxygen and sulphur ranged from 58 to 74 wt % and 10 to 29 wt %, respectively.  相似文献   

11.
选择川西北矿山梁地区低成熟沥青,采用封闭金管-高压釜体系,以20℃/h和2℃/h的升温速率进行生烃热模拟实验,分析了气体产物组分、产率和烃类气体碳同位素组成及变化特征。结果表明,沥青具有较强的产气潜力,是一种重要的生气有机母质;甲烷、乙烷和丙烷气体的碳同位素值分别为-50.85‰~-37.53‰、-37.93‰~-13.75‰和-37.10‰~-6.45‰。低演化阶段出现δ13C213C3,之后,不同碳数烃类气体碳同位素组成关系为δ13C113C213C3。沥青热模拟甲烷最终碳同位素值为-37.53‰,轻于川中威远地区震旦系-寒武系常规天然气(-32.3‰~-34.7‰)和页岩气(-35.1‰~-37.3‰)的甲烷碳同位素值。川中威远地区常规天然气可能为具较重甲烷碳同位素的干酪根裂解气与具较轻甲烷碳同位素的原油裂解气的混合气。而页岩气中则可能富含更多的原油裂解气,干酪根裂解气相对较少。将生烃动力学结果应用到川中高科1井可见,早-中侏罗世,寒武系烃源岩进入主生油期,生成原油排出,部分进入到震旦系继续生气,侏罗纪进入主生气期及其在早白垩世后期进入生气末期,气态烃转化率达94%,比残留在寒武系中的沥青多约20%。  相似文献   

12.
有机体及其沉积演化产物的氢同位素地球化学研究进展   总被引:4,自引:3,他引:1  
从有机体、现代沉积物、干酪根、煤、石油和天然气的氢同位素组成特征来看,不同赋存状态有机质的氢同位素组成具有不同的特征。有机体的氢同位素组成首先受控于共生水介质的氢同位素组成,而共生水介质的氢同位素组成具有继承效应,族组分的氢同位素继承效应更为明显。相同水环境形成的有机体中类脂化合物的δD值小于蛋白质和碳水化合物的该值,同一环境的现代沉积物中脂肪酸的氢同位素小于腐殖酸的氢同位素组成。干酪根的氢同位素组成和源岩沉积环境有着密切的关系,可以指示沉积时水的盐度,而与干酪根的类型关系不大。在热演化过程中干酪根的稳定的同位素组成基本不发生变化。煤岩主要形成于淡水环境,有整体贫D的趋势。同一煤岩组分中藻质体的氢同位素组成较轻,丝质组的最重,镜质组的介于二者之间。石油的氢同位素组成取决于生油母质的氢同位素组成,因此也可以反映源岩的沉积环境。母质干酪根类型和成熟度对石油的氢同位素组成影响不大。同一石油样品中不同族组分的氢同位素具有饱和碳氢化合物<芳香族碳氢化合物<含氮、硫、氧化合物的特征。天然气的氢同位素也是母质氢同位素的反映,另外它还受成熟度的影响。因此,天然气氢同位素组成可以反映源岩的沉积环境,同时在某种程度上也可以指示。  相似文献   

13.
Pyrolysis experiments were performed on Green River and Monterey Formation kerogens (Types I and II, respectively) with and without calcite, illite, or montmorillonite at 300 degrees C for 2 to 1,000 hours under dry and hydrous conditions. Pyrolysis products were identified and quantified, and a material balance of product and reactants resulted. Significant differences were found in the products generated by pyrolysis of kerogens with and without minerals. Both illite and montmorillonite adsorb a considerable portion (up to 80%) of the generated bitumen. The adsorbed bitumen is almost exclusively composed of polar compounds and asphaltenes that crack to yield low molecular weight compounds and insoluble pyrobitumen during prolonged heating. Montmorillonite shows the most pronounced adsorptive and catalytic effects. With calcite however, the pyrolysis products are similar to those from kerogen heated alone, and bitumen adsorption is negligible. Applying these results to maturation of organic matter in natural environments, we suggest that a given type of organic matter associated with different minerals in source rocks will yield different products. Furthermore, the different adsorption capacities of minerals exert a significant influence on the migration of polar and high molecular weight compounds generated from the breakdown of kerogen. Therefore, the overall accumulated products from carbonate source rocks are mainly heavy oils with some gas, whereas light oils and gases are the main products from source rocks that contain expandable clays with catalytic and adsorptive properties.  相似文献   

14.
鄂尔多斯盆地砂岩型铀矿流体包裹体特征   总被引:4,自引:0,他引:4  
对鄂尔多斯盆地北部东胜地区的砂岩型铀矿赋矿多口钻井的岩心样品的流体包裹体的均一温度、盐水包裹体的盐度以及主成分和氢氧同位素组成系统的测定结果表明,该砂岩型铀矿赋矿砂岩至少经历过2期热流体活动,成矿流体温度有2个峰值,即高温段140~180℃和低温段100~120℃。成矿流体盐度NaCl主要分布约为4%~10%,但不同钻孔的样品有多个不同的峰值。流体中以水为主要成分,其次为CO2和CH4等,其他气体含量很少。流体包裹体的氢-氧同位素分析表明,成矿流体的δ18O值为9.8‰~12.3‰,δD值分布为-5‰~-48.6‰。氢-氧同位素图解投点全部落在建造水的范围内,部分为变质水,据此推测,成矿流体可能是原生的岩浆水和大气降水形成的混合变质水和建造水。  相似文献   

15.
A series of anhydrous closed-system pyrolysis experiments were performed on pure pristane and octacosane and a sample from the Maoming oil shale to measure the effect of thermal maturation on pristane and phytane carbon isotopic fractionation compared with individual n-alkanes. The result showed that pyrolysis of pure pristane and octacosane caused 1.8‰ and 5.1‰ increase in δ13C values, respectively. Experiments on the oil shale sample showed 2.0‰ and 2.2‰ variations in pristane and phytane δ13C values, respectively, but an average 5.5‰ enrichment in 13C for the individual n-alkanes. This indicates that the effect of thermal maturation on pristane and phytane δ13C values is weaker compared with n-alkanes. The results further suggest that the stable carbon isotopic distribution of pristane and phytane can be used as a correlation tool.  相似文献   

16.
The aspects, such as composition, temperature, viscosity, and fluidity, of basic volcanic fluids are greatly different from acidic volcanic fluids. In order to further complement the conceptual model of the influence of volcanic fluids on source rocks in petroliferous basins, this research uses the thermal simulation experiment to analyze the characteristics and reasons of the ratio of alkanes to acid, dry coefficient, and carbon isotope in the dry and fluid systems. The results show that, the ratio of alkanes to acid of all samples in the two systems will increase with the rise of temperature and presents features of the dry system higher than the fluid system, which indicates that the basic volcanic fluids restrain the generation of gaseous hydrocarbons. The dry coefficient of the fluid system at the range of 300–400°C is greater than that of the dry system, while smaller at the range of 400–450°C, which indicates that the basic volcanic fluids promote the generation of CH4 in low temperature. In the two systems, δ13CO2 of all samples have no obvious change as the rising of temperature, but in the fluid system the proportion of carbon isotopic will increase with the rising of temperature, which shows that carbonate exists in the volcanic fluids. The carbon isotopes of gaseous hydrocarbon in three samples are presented as δ13C1 < δ13C2 < δ13C3, and it accords to general pyrolysis regularity without reversal phenomenon, which indicates alkane gases produced by pyrolysis of three samples are of organic origin.  相似文献   

17.
Organic geochemical and petrological investigations were carried out on Cenomanian/Turonian black shales from three sample sites in the Tarfaya Basin (SW Morocco) to characterize the sedimentary organic matter. These black shales have a variable bulk and molecular geochemical composition reflecting changes in the quantity and quality of the organic matter. High TOC contents (up to 18wt%) and hydrogen indices between 400 and 800 (mgHC/gTOC) indicate hydrogen‐rich organic matter (Type I‐II kerogen) which qualifies these laminated black shale sequences as excellent oil‐prone source rocks. Low Tmax values obtained from Rock‐Eval pyrolysis (404–425 MC) confirm an immature to early mature level of thermal maturation. Organic petrological studies indicate that the kerogen is almost entirely composed of bituminite particles. These unstructured organic aggregates were most probably formed by intensive restructuring of labile biopolymers (lipids and/or carbohydrates), with the incorporation of sulphur into the kerogen during early diagenesis. Total lipid analyses performed after desulphurization of the total extract shows that the biomarkers mostly comprise short‐chain n‐alkanes (C16–C22) and long‐chain (C25–C35) n‐alkanes with no obvious odd‐over‐even predominance, together with steranes, hopanoids and acyclic isoprenoids. The presence of isorenieratane derivatives originating from green sulphur bacteria indicates that dissolved sulphide had reached the photic zone at shallow water depths (~100m) during times of deposition. These conditions probably favoured intensive sulphurization of the organic matter. Flash pyrolysis GC‐MS analysis of the kerogen indicates the aliphatic nature of the bulk organic carbon. The vast majority of pyrolysis products are sulphur‐containing components such as alkylthiophenes, alkenylthiophenes and alkybenzothiophenes. Abundant sulphurization of the Tarfaya Basin kerogen resulted from excess sulphide and metabolizable organic matter combined with a limited availability of iron during early diagenesis. The observed variability in the intensity of OM sulphurization may be attributed to sea level‐driven fluctuations in the palaeoenvironment during sedimentation.  相似文献   

18.
通过对塔里木盆地煤及其显微组分进行以1 K/min升温速率的开放体系热模拟实验(最高实验温度为1 200℃),获得了煤岩与各显微组分气态产物产率与累计产量变化。对比分析了煤及其显微组分生成气态产物CH4、N2和CO变化特征,其中 N2生成温度高于CH4和CO; H2生成时间与CH4相一致(说明了氢为烃类气体形成的关键因素)。煤及其显微组分生烃潜力具有壳质组>镜质组>煤>半丝质组≥ 丝质组的特征,说明煤岩生烃潜力主要由其显微组分控制;虽然壳质组在煤岩中含量很低,但生烃潜力高于其他显微组分。煤岩生成的N2具有双峰型特征,说明了前后峰N2具有不同来源,前者来源于无机矿物(如含铵粘土)的分解,后者来源于有机质热降解;显微组分生成N2主要为高温阶段,说明了显微组分在分离过程中可能造成部分无机矿物的损失。  相似文献   

19.
Abstract

Whole-rock analyses by x-ray powder diffraction and Rock-Eval pyrolysis studies were carried out on the Cenomanian/Turonian Dereköy formation shales from four sample sites in the Lower Antalya Nappe in the western Taurus region (SW Turkey) to determine rock-forming mineral assemblages, their abundance in bulk composition, and clay matrix effect on hydrocarbon yield during Rock-Eval pyrolysis. These studies indicate that the rock-forming minerals are mostly quartz (3–68%), clay minerals (32–81%) including smectite and illite, and rare to common calcite (0–39%), feldspar (0–5%) and mica (0–11%). High total organic carbon (TOC) contents (up to 42 wt%) and corrected hydrogen indices between 538 and 642 (mg HC/g TOC) correspond to marine organic matter (Type II kerogen) and excellent oil-prone hydrocarbon source rocks. Strong positive correlation (R 2 = 0.84 to 0.96) between hydrocarbon yield (S 2) and TOC content implies that the positive values of x and y-intercepts are relatively high, with values ranging between 1–13.117 mg pyrolysable hydrocarbon in 1 g of rock. These results mean that the clay matrix is the main agent of adsorbtion, and high amounts of hydrocarbon retention must be present.  相似文献   

20.
流体包裹体中气体碳同位素测定新方法及其应用   总被引:5,自引:1,他引:4  
采用热爆裂法和真空球磨法提取流体包裹体中CO2和CH4等多种气体,以灵敏度较高的Delta S仪器测定其碳同位素值。由于热爆裂法产生CO影响CH4碳同位素测定,而真空球磨法不会改变气体的性质,因此,真空球磨法提取的气体反映真实古流体的性质,测定的碳同位素值比较可靠。采用该种方法对鄂尔多斯盆地中部气田奥陶系储层方解石脉中包裹体的烃类气体进行了碳同位素测定,结果表明,烃类气体δ13C1分布在-2.673%~-4.360%,δ13C2分布在-2.253%~-2.580%,δ13C3分布-2.141%~-2.626%,其组成具有上古生界天然气的特征,并与下古生界天然气差别较大;推测鄂尔多斯盆地中部气田下古生界天然气成藏期有两期,早期可能主要以上古生界煤型气来源为主。  相似文献   

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