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1.
热成因甲烷碳同位素分布的形成机制 总被引：3，自引：1，他引：3
很多学者从不同的角度用不同的方法模拟了从有机母质 (包括煤和干酪根等气源 )形成天然气 (甲烷 )时的碳同位素分馏效应 ,建立了碳同位素分馏效应的很多模型 ,同时也讨论了催化作用和成烃后作用对天然气碳同位素的影响。但这些理论模型和模拟实验结果都还不能完全地拟合自然界中热成因甲烷碳同位素的分布 ,也未能从本质上完全阐明其碳同位素的分馏机制。其原因是各种模型的前提假设都未能完全满足复杂的自然界条件。今后工作的重点应放在用化学动力学的方法建立更完善的模型上 ,同时也应当重点考虑催化作用和成烃后作用对天然气同位素的影响。 相似文献
2.
Yunyan Ni Geoffrey S. Ellis Barry Katz Yongchun Tang 《Geochimica et cosmochimica acta》2011,75(10):2696-2707
Based on quantum chemistry calculations for normal octane homolytic cracking, a kinetic hydrogen isotope fractionation model for methane, ethane, and propane formation is proposed. The activation energy differences between D-substitute and non-substituted methane, ethane, and propane are 318.6, 281.7, and 280.2 cal/mol, respectively. In order to determine the effect of the entropy contribution for hydrogen isotopic substitution, a transition state for ethane bond rupture was determined based on density function theory (DFT) calculations. The kinetic isotope effect (KIE) associated with bond rupture in D and H substituted ethane results in a frequency factor ratio of 1.07. Based on the proposed mathematical model of hydrogen isotope fractionation, one can potentially quantify natural gas thermal maturity from measured hydrogen isotope values. Calculated gas maturity values determined by the proposed mathematical model using δD values in ethane from several basins in the world are in close agreement with similar predictions based on the δ13C composition of ethane. However, gas maturity values calculated from field data of methane and propane using both hydrogen and carbon kinetic isotopic models do not agree as closely. It is possible that δD values in methane may be affected by microbial mixing and that propane values might be more susceptible to hydrogen exchange with water or to analytical errors. Although the model used in this study is quite preliminary, the results demonstrate that kinetic isotope fractionation effects in hydrogen may be useful in quantitative models of natural gas generation, and that δD values in ethane might be more suitable for modeling than comparable values in methane and propane. 相似文献
3.
川东北飞仙关组鲕滩气藏天然气运聚效率 总被引：3，自引：1，他引：2
设计进行了封闭体系下原油裂解成气的模拟实验, 建立并标定了原油裂解成气及其碳同位素分馏的化学动力学模型, 以罗家寨气田罗家7井为例分别进行了地质应用.生烃动力学研究发现, 飞仙关组古油藏具备“高效气源灶”的特点, 原油在中晚侏罗世172~151Ma约20Ma时期内裂解殆尽, 且原油裂解气的生成与其运聚成藏作用具有良好的时空匹配关系, 由此可促成飞仙关组气藏天然气的高效运聚.碳同位素分馏动力学研究证实甲烷成藏参与率达87%.利用生烃动力学与碳同位素分馏动力学结合的方法对天然气的运聚效率进行探讨是一个新的有效途径. 相似文献
4.
干酪根中不同结构和官能团具有不同的碳同位素组成,这种差异可以用有机质碳同位素热力学同位素因子（β因子）进行预测。煤岩模拟实验产物中,δ13CCO2相对烃类气体而言明显偏重,这与干酪根中羧基的β13C较大有关。含水实验产物的δ13CCO2轻于无水实验产物的δ13CCO2是由于含水实验中所增加CO2的碳同位素组成相对较轻造成的,含水实验增加的CO2产率是由β13C相对较小的部分亚甲基碳通过断裂、氢转移、以及与水反应转变而来。模拟实验低温阶段（≤300℃）,甲氧基中的甲基断裂可能的甲烷形成的主要方式。而甲氧基的β13C大于甲基,所以低温阶段出现了甲烷碳同位素组成先较重后变轻的现象。 相似文献
5.
王万春 《矿物岩石地球化学通报》2007,26(3):269-275
微生物降解使有机化合物的稳定碳、氢同位素发生不同程度分馏的研究在有机污染物来源和微生物环境修复等领域取得了长足进展,并对原油和天然气微生物降解研究有借鉴意义。微生物作用下的同位素分馏为动力同位素分馏,导致重同位素在残余物中富集。影响微生物降解有机物同位素分馏的主要因素有微生物的降解代谢途径、辅酶作用、降解类型与程度、同位素质量差异和有机物碳数等。不同的微生物代谢途径代表不同的生物化学反应,造成了同位素分馏的显著差异;辅酶对反应的催化作用使微生物作用造成的同位素分馏更加复杂。低碳数正构烷烃遭受微生物降解程度越高,碳、氢同位素的分馏也越大,同位素变重与降解程度之间有明显的相关性。但对于复杂化合物,由于降解的多级反应,同位素分馏与降解程度间的相关性并不明显。在同样降解程度下,氢同位素分馏大于碳同位素分馏,低碳数正构烷烃的同位素分馏大于高碳数正构烷烃的同位素分馏。 相似文献
6.
天然气运移的气体同位素地球化学示踪 总被引：16，自引：0，他引：16
本文通过鄂尔多斯等含油气盆地内岩石酸解烃、罐顶气和同源多产层天然气碳同位素组成的变化，从实例剖析出发，探讨了天然气运移时气体同位素组成的变化及其对天然气运移的示踪。天然气在通过沉积地层中孔隙系统和微裂隙运移时，天然气中的甲烷碳同位素会发生一定的分馏，而乙烷以上重烃碳同位素几乎不发生分馏；在天然气层所在深度，罐顶气甲烷碳同位素组成与天然气一致，在天然气层附近，罐顶气甲烷碳同位素则明显偏离了热演化趋势线；烃源岩酸解烃与其同源的天然气重烃碳同位素组成具有较好的一致性和可比性。由此，可利用气体组分碳同位素的上述变化特征，追索天然气的运移作用。 相似文献
7.
A Study of the Migration and Accumulation Efficiency and the Genesis of Hydrocarbon Natural Gas in the Xujiaweizi Fault Depression 总被引：1，自引：1，他引：0
In order to investigate the migration and accumulation efficiency of hydrocarbon natural gas in the Xujiaweizi fault depression, and to provide new evidence for the classification of its genesis, a source rock pyrolysis experiment in a closed system was designed and carried out. Based on this, kinetic models for describing gas generation from organic matter and carbon isotope fractionation during this process were established, calibrated and then extrapolated to geologic conditions by combining the thermal history data of the Xushen-1 Well. The results indicate that the coal measures in the Xujiaweizi fault depression are typical ＂high-efficiency gas sources＂, the natural gas generated from them has a high migration and accumulation efficiency, and consequently a large-scale natural gas accumulation occurred in the area. The highly/over matured coal measures in the Xujiaweizi fault depression generate coaliferous gas with a high δ^13C1 value （〉 -20‰） at the late stage, making the carbon isotope composition of organic alkane gases abnormally heavy. In addition, the mixing and dissipation through the caprock of natural gas can result in the negative carbon isotope sequence （δ^13C1 〉δ^13C2 〉δ^13C3 〉δ^13C4） of organic alkane gases, and the dissipation can also lead to the abnormally heavy carbon isotope composition of organic alkane gases. As for the discovery of inorganic nonhydrocarbon gas reservoirs, it can only serve as an accessorial evidence rather than a direct evidence that the hydrocarbon gas is inorganic. As a result, it needs stronger evidence to classify the hydrocarbon natural gas in the Xujiaweizi fault depression as inorganic gas. 相似文献
8.
生物─热催化过渡带油气关系 总被引：3，自引：1，他引：3
本文在辽河盆地原油和天然气之间碳氢同位素关系研究的基础上，系统地研究了中国生物─热催化过渡带油气的地球化学特征，特别是它们之间同位素组成关系，划分出油气的不同组合类型，从而证明生物─热催化过渡带油气的自生自储特征，认为过渡带是油气形成聚集的重要垂向演化层段。同时为完善烃类形成的多源复合和多阶连续提供了佐证。 相似文献
9.
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. 相似文献
10.
长岭断陷深层天然气成藏期研究 总被引：1，自引：0，他引：1
利用榆深1井营城组未熟样品的热模拟实验、碳同位素分馏实验以及长深1等井的流体包裹体测试结果,在热史恢复的基础上,根据化学动力学和碳同位素分馏动力学理论,从烃源岩生烃史、甲烷碳同位素分馏效应以及包裹体均一温度等方面,对长岭断陷天然气成藏期加以判断。长岭断陷甲烷碳同位素均值为-33.11‰,碳同位素分馏效应显示天然气为116 Ma以来累积聚集成藏;生烃史表明营城组源岩在100～67.7 Ma大量生气,沙河子组在125～74 Ma达到生气高峰;同时包裹体证据表明查干花次洼的烃类气主要在110～78 Ma聚集成藏,伏龙泉次洼主要在110～1 Ma成藏。成藏期的判断结果说明:长岭断陷沙河子组早期生成的天然气未聚集成藏,仅116 Ma以后生成的天然气才具有成藏贡献,损失约14%左右;而营城组烃源岩生烃较晚,有利于成藏,包裹体证据也印证这一观点。 相似文献
11.
含油气盆地油气同位素地球化学研究概述 总被引：18，自引：7，他引：18
以气体地球化学国家重点实验室工作为主，简要概述了对我国含油气的同位素地球化学研究。1．烃气的同位素地球化学：讨论了天然气成因新模式与气藏烃气同位素组成的关系，低演化阶段天然气同位素分馏的二阶段模式，云南中小盆地天然气低演化系列同位素特征及用储层解析气作油气源对比。2．稀有气体同位素地球化学：阐述了^3He/^4He值与中国构造分区，幔源氮的复合成藏和幔源甲烷问题以及气源对比等。3．液态烃同位素地球化学：简述了轻烃碳氢同位素特征及氢同位素作为判别古沉积介质盐度的指标，概述了未熟一低熟油同位素特征及在自然剖面上油和源油抽提物碳同位素分馏特征及其机理。 相似文献
12.
烃类的有机(生物)与无机(非生物)来源--油气成因理论思考之二 总被引：6，自引：1，他引：5
自然界烃类的大规模形成是有机-无机物质相互作用的结果。在烃类物质两大组成元素中,碳的来源多以有机质为主,特别是液态烃,而氢却有多种来源。有机氢来自有机质,无机氢主要来自同沉积水,还有深部挥发分中的氢,同沉积水中的氢则以多种途径进入烃类。本从油田水的垂向演化及其与非油田水的对比、烃类物质的氢同位素组成及其与源岩沉积环境的关系、成烃加水与否的模拟实验,以及世界大型油气田分布与构造带的关系等方面,论述了烃类形成的有机与无机的相互作用,特别是烃类中氢的无机来源的本质,并对氢的来源及其加氢作用机制进行了分析,对油气形成理论的完善和在油气勘探中的应用有一定参考价值。 相似文献
13.
以气体地球化学国家重点实验室工作为主,简要概述了对我国含油气的同位素地球化学研究。1. 烃气的同位素地球化学:讨论了天然气成因新模式与气藏烃气同位素组成的关系,低演化阶段天然气同位素分馏的二阶段模式,云南中小盆地天然气低演化系列同位素特征及用储层解析气作油气源对比。2. 稀有气体同位素地球化学:阐述了3He/4He值与中国构造分区, 幔源氦的复合成藏和幔源甲烷问题以及气源对比等。3. 液态烃同位素地球化学:简述了轻烃碳氢同位素特征及氢同位素作为判别古沉积介质盐度的指标,概述了未熟-低熟油同位素特征及在自然剖面上油和源岩抽提物碳同位素分馏特征及其机理。 相似文献
14.
新疆十红滩层间氧化带型砂岩铀矿同位素地球化学研究 总被引：13，自引：1，他引：13
文章在对吐哈盆地十红滩层间氧化带型砂岩铀矿床地下水和粘土矿物的氢、氧同位素，钙质砂岩的碳、氧同位素，黄铁矿和长石的铅、硫同位素组成进行分析测试的基础上，系统总结了矿床的地球化学特征；认为形成层间氧化带和铀矿化的层间水主要来自大气降水，研究区水与有机烃类气体同位素交换、强烈的蒸发作用和水岩反应是控制地下水和矿物中同位素分馏的主要机制，层间氧化带和铀富集成矿是地下水在低温、常压下对围岩长期作用的结果，钙质砂岩的碳和黄铁矿的硫均主要为生物有机成因，盆地深部的煤成油、气也参与了成矿作用。 相似文献
15.
Kinetic Parameters of Methane Generated from Source Rocks in the Kuqa Depression of Tarim Basin and Their Application 总被引：2，自引：0，他引：2
LI Xianqing XIAO Xianming MI Jingkui TANG Yongchun XIAO Zhongyao LIU Dehan SHEN Jiagui YANG Yunfeng WANG Yan DONG Peng 《《地质学报》英文版》2008,82(1):154-163
In a thermal simulation experiment of gold tubes of closed-system, calculating with the KINETICS and GOR-ISOTOPE KINETICS software, kinetic parameters of gas generation and methane carbon isotopic fractionation from Triassic-Jurassic hydrocarbon source rocks in the Kuqa depression of Tarim Basin are obtained. The activation energies of methane generated from Jurassic coal, Jurassic mudstone and Triassic mudstone in the Kuqa Depression are 197-268 kJ/mol, 180-260 kJ/mol and 214-289 kJ/mol, respectively, and their frequency factors are 5.265×10^13 s^-1, 9.761×10^11 s^-1 and 2.270×10^14 s^-1. This reflects their differences of hydrocarbon generation behaviors. The kinetic parameters of methane carbon isotopic fractionation are also different in Jurassic coal, Jurassic mudstone and Triassic mudstone, whose average activation energies are 228 kJ/mol, 205 kJ/mol and 231 kJ/mol, respectively. Combined with the geological background, the origin of natural gas in the Yinan-2 gas pool is discussed, and an accumulation model of natural gas is thus established. The Yinan- 2 gas is primarily derived from Jurassic coal-bearing source rocks in the Yangxia Sag. Main gas accumulation time is 5-0 Ma and the corresponding Ro is in the range from 1.25 %-1.95 %. The loss rate of natural gas is 25 %-30 %. 相似文献
16.
煤层气的成因是石油地质学研究的热点.煤层气聚集存在着"累积聚气"和"阶段聚气"两种形式, 对于"阶段聚气" 的煤层气成因判识的地球化学研究还很薄弱.通过森林沼泽泥炭在不同温度下制备的样品进行热模拟实验, 首次获得了不同演化阶段甲烷、乙烷和二氧化碳的碳、氢同位素组成和演化规律.发现随着原始样品演化程度越高, 生成的甲烷和乙烷的碳、氢同位素组成具有变重的趋势; 同时, 甲烷和乙烷碳同位素组成明显地受原始样品演化程度的影响, 而氢同位素组成主要与成熟度密切相关.确定了成煤有机质在不同演化阶段生成的气体碳、氢同位素组成.首次获得了成煤有机质不同演化阶段热解气体碳、氢同位素组成与Ro之间的关系式.建立了甲烷与乙烷的碳、氢同位素之间的关系式, 形成了甲烷碳、氢同位素组成相关图.根据这些为研究不同成熟度区间生成的煤层气成因提供了科学数据, 为"阶段聚气"的煤层气地球化学特征认识及其成因判识提供了科学依据.并且, 将这些研究结果应用到我国沁水盆地南部煤层气研究, 认为该地区煤层气是在中侏罗世以后聚集而成, 具有"阶段聚气"的特征, 证明了热模拟研究成果对自然界煤层气成因的判识具有重要的科学意义. 相似文献
17.
天然气水合物是一种新型的洁净能源。甲烷天然气水合物是储量最丰富的一种类型,常出现在深海中或极地大陆上,其生成的过程中会发生同位素的分馏效应。通过实验室模拟水合物生成的过程,利用天然海水与甲烷或二氧化碳气体反应,以及更接近实际生成环境的甲烷-海水-沉积物动态聚散实验,对甲烷水合物和二氧化碳水合物生成前后δ13C值进行测定,研究水合物生成过程中δ13C的变化情况。实验证明,水合物反应中碳同位素分馏是存在的,其变化程度明显小于氧同位素和氢同位素。甲烷水合物碳同位素的分馏系数αC的值为1000 3~1000 9。二氧化碳水合物生成反应后气相的碳、氧同位素变轻,重同位素趋向于进入水合物中,二氧化碳水合物碳同位素的分馏系数αC的值为1000 7~1001 2。海水中溶解的CO2气体在甲烷水合物形成过程中会被水合物捕获,从而使得δ13CDIC值变小,重的碳同位素趋于进入水合物中,而较轻的碳同位素留在海水中。但由于海水中含有的溶解CO2气体有限,经过多轮水合物动态聚散后δ13CDIC值的变化幅度会越来越小。 相似文献
18.
19.
流体包裹体在油气地质地球化学中的应用 总被引：13，自引：3，他引：10
流体包裹体研究是油气形成和成藏定量化研究的重要手段。本文总结了油气藏中流体包裹体的地质地球化学意义及其在石油、天然气研究中的应用,探讨了烃源岩和储层流体包裹体在确定源岩演化、沉积环境、有机母质类型、成熟度、油气运移充填期次等方面的应用,指出目前流体包裹体油气地球化学研究应关注的几个前沿方向：①在流体包裹体分析实验技术中,单个包裹体分析技术在油气地质定量化研究中具有重要的作用;②通过有机包裹体自然剖面与模拟实验对比研究烃类流体运移分馏,为建立油气成藏过程地球化学示踪指标提供基础参数;③通过储层中不同期次有机包裹体的化学组成、同位素组成、生物标志化合物与圈闭中已经聚集成藏的油气地球化学特征的对比研究,确定圈闭中油气的成因、来源和充填过程;④有机包裹体成烃作用研究为碳酸盐岩生烃和深层油气成因理论提供依据;这些方向的研究成果为深化油气理论、提高勘探水平具有重要意义。 相似文献
20.
MENG Qingqiang SUN Yuhu TONG Jianyu FU Qi ZHU Jun ZHU Dongy JIN Zhijun 《《地质学报》英文版》2015,89(5):1616-1624
Hydrogen gas accelerates hydrocarbon generation, but little is known about its distribution and origin in petroliferous basins, which has hindered the further exploration.Taken the Jiyang Depression in eastern China as an example, this study collected natural gas from different tectonic units, and analyzed various geochemical characters including gas contents, and carbon and hydrogen isotopic composition.The result shows that:(1) hydrogen gas is widespread distributed, but its content is very low, which typically ranges from 0.01% to 0.1% in this region;(2) the ratios of H2/3He, indicative of the origins of hydrogen gas, suggest that mantle-derived hydrogen is dominant.Even in tectonically stable areas absent with deep fluid activities, there is also mantle-derived;(3) the isotopic composition of hydrogen falls in the range of –798‰ to –628‰(relative to VSMOW standard).In areas with deep-derived fluids, the hydrogen gas has a similar isotopic composition with the previously documented deep-sourced gas, with lighter isotopic composition.In contrast, hydrogen gas has a heavier isotopic composition in relatively stable areas.The isotopic signatures suggest that there is a mixture of mantle- and crust-derived hydrogen gas in the relatively stable area, which is consistent with the H2/3He ratios.Therefore, it is clear that the hydrogen gas has a much wider distribution than found in the deep-derived fluid area, resulting in a much broader area with hydrogenating effect for resource rock.This understanding will provide new insights for hydrocarbon generation research and resource assessment in petroliferous basins. 相似文献