Thermogravimetry-differential thermal analysis coupled with chromatography as a thermal simulation experimental method and its application to gaseous hydrocarbons from different source rocks

In this paper a thermogravimetry-differential thermal analysis method coupled with chromatography （TG-DTA-GC） has been adopted to simulate the generation of gaseous hydrocarbons from different hydrocarbon source rocks such as coals, mudstones, and carbonate rocks with different maturities. The temperature programming for thermal simulation experiment is 20℃/min from ambient temperature to 700℃. As viewed from the quantities and composition of generated gaseous hydrocarbons at different temperatures, it is shown that low-mature coal has experienced the strongest exothermic reaction and the highest loss of weight in which the first exothermic peak is relatively low. Low-mature coal samples have stronger capability of generating gaseous hydrocarbons than high-mature samples. The amounts and composition of gaseous hydrocarbons generated are closely related not only to the abundance of organic carbon in source rocks, but also to the type of kerogen in the source rocks, and their thermal maturity. In the present highly mature and over-mature rock samples organic carbon, probably, has already been exhausted, so the production of gaseous hydrocarbons in large amounts is impossible. The contents of heavy components in gaseous hydrocarbons from the source rocks containing type- Ⅰ and - Ⅱ kerogens are generally high ; those of light components such as methane and ethane in gaseous hydrocarbons from the source rocks with Ⅲ-type kerogens are high as well. In the course of thermal simulation of carbonate rock samples, large amounts of gaseous hydrocarbons were produced in a high temperature range.     

海相原油沥青质作为特殊气源的生气特征及其地质应用

应用高压封闭体系,对塔里木盆地海相原油中的沥青质组分进行了热裂解模拟实验,从气态烃产率及碳同位素演化、焦沥青的生成等方面,探讨了沥青质作为特殊气源的生气机理。运用Kinetics动力学软件,计算得到沥青质裂解的动力学参数（活化能和指前因子）,在此基础上,将模拟实验结果外推至地质条件下,探讨其动力学模型的实际应用。结果表明,沥青质裂解气在Easy%Ro值0.8左右开始生成,在Easy%Ro值2.65左右其转化率达到1。Easy%Ro为0.9时沥青质裂解进入主生气期（转化率0.1）,Easy%Ro为2.3时主生气期结束（转化率0.9）。研究成果可为中国海相层系裂解气的判识、资源评价及勘探决策等提供实验和理论依据。     

山东夏甸金矿烃类组分特征与幔源流体成矿作用探讨

烃类是成矿流体中的重要气相组分之一,与其他气态组分相比烃类则具有组分多元化和性质稳定的特点,同时烃类各组分间的相关特征和配分规律是成矿流体演化过程(氧化-还原条件、温度、压力等环境因素)的重要参数,因此烃类组分宏观和微观特征可以作为成矿物质来源、成矿流体演化以及流体间混合叠加规律的研究工具和手段.宏观上烃类组分在夏甸金矿不同类型地质体中的含量值差异明显:滦家河型花岗岩和硅质岩烃类含量很高,而胶东群变质岩、脉岩、金矿体及矿化蚀变带烃类含量明显偏低;通过烃类组分相关性、配分及比值特征等微观规律研究,可以推测夏句金矿的成矿作用与滦家河型花岗岩不存在直接关系,而与胶东群变质岩和深源的中.基性脉岩具有密切联系,表现出不同类型流体之间的叠加、改造特征,反映了夏甸金矿床乃至整个胶东矿集区具有地幔流体参与并和壳源流体发生不同程度混合,促进成矿物质运移并在合适的条件和构造空间沉淀富集的成矿特点.     

鄂尔多斯盆地北部上古生界油气运聚特征及其铀成矿意义

鄂尔多斯盆地北部上古生界储层流体包裹体类型、均一温度、捕获压力及其变化的研究表明,上古生界液态烃和天然气具有长期运聚两期充注的特点,捕获压力在平面上为南高北低、北东部最低,成藏后大量天然气散失和油气向北东方向迁移,及砂岩型铀矿的地球化学特性等暗示油气可能为东胜大型铀矿的形成提供了必要条件。     

Heating rate dependency of petroleum-forming reactions: implications for compositional kinetic predictions

The generation of bulk petroleum, liquid and gaseous hydrocarbons from the Duvernay Formation was simulated by heating immature kerogens in a closed system (MSSV pyrolysis) at four different heating rates (0.013, 0.1, 0.7 and 5.0 K/min). Using the established parallel reaction kinetic model, temperature and compositional predictions were tested to be suitable for geological conditions by comparing the laboratory results with natural changes in source bitumens and reservoir oil maturity sequences from the Duvernay Formation. In the case of bulk liquid and gaseous hydrocarbons, the above kinetic calculations can be considered valid because their maximum yields are independent of laboratory heating rates. In contrast, the contents of paraffins, aromatics and sulfur compounds show a pronounced heating rate dependence. Extrapolated to geological heating rates, the compositional predictions are consistent with the bulk composition of natural products in the Duvernay-petroleum system showing an increase of paraffinicity and hydrogen content. In contrast to that, the “hump” decreases with decreasing heating rate, a trend which is confirmed by the low amounts of unresolved compounds in natural high maturity products. Because of these heating-rate dependent compositional changes, geological predictions of natural molecular composition by the commonly used kinetic models are not suitable.     

腐殖煤气态产物演化特征的模拟实验研究

本文较详细地探讨了成熟阶段腐殖煤在加水热模拟过程中气态产物的演化特征。成熟阶段的煤仍具有相当的生烃潜力,其主要生烃阶段仍以生油为主,生气相对较少。生油高峰之后由于液态产物的大量热裂解才开始进入气态烃的大量生成阶段。由于地质条件下煤中的可溶有机质十分丰富,在高演化阶段由可溶有机质进一步裂解是煤成气的重要来源。非烃主要形成于早期阶段。成熟煤生成的气态烃中甲烷为之主要成分,非烃中H₂为主,其次为CO₂,甲烷的碳同位素值明显低于乙烷,而乙烷和丙烷的碳同位素值差别较小,并且随演化程度的增加各气态组分的碳同位素值差别愈来愈小。     

Genetic suppositions of oil and gas formation and conditions of hydrocarbon deposits in Mesozoic-Cenozoic sediments in the Caspian Sea shelf

Source rocks are present in all the stratigraphic units of the Mesozoic-Cenozoic deposits of the Turkmen shelf in the Caspian Sea. The highest source rock potential is characteristic of I terrigenous and carbonate-terrigenous rocks of Middle Jurassic age, and the Aptian, Paleogene, Neogene and Apsheron stages of the Quaternary system. To reveal the formation conditions of hydrocarbon deposits within Southwestern Turkmenistan, the principle of chemical thermodynamics is primarily used via the calculation of the free energy of gaseous hydrocarbons. This showed that hydrocarbon deposits within the topmost depositional complex (the red-colored strata of the Middle Miocene at the Akchagyl and Apsheron stages) are syngenetic; their formation was due to lateral migration from even-aged deposits from depression zones neighboring the uplifts.     

Thermal simulation of basic volcanic fluid influence on different source rocks

Based on thermal simulation experiment, interactions between volcanic fluids and source rocks were studied. Gas generations in the dry system and fluid system under different temperatures were analyzed. The results showed that the various types of source rocks are similar in composition, containing gaseous C1-C5 hydrocarbons, H2 and CO2 whose gas yields increase with increasing temperature. The gas yield of source rocks of type I is the high- est, followed by type II, and that of source rocks of type III is the lowest, indicating that the yield of hydrocarbon gases is related to their hydrocarbon generating potential. Although the generating potential of type III is the lowest, it can still be regarded as a useful gas source when it is buried deeply enough. The basic volcanic fluid restrains the generation of gaseous hydrocarbons in different types of source rocks, but promotes the generation of inorganic gases.     

Geochemical characterization of adsorbed light gaseous alkanes in near surface soils of the eastern Ganga basin for hydrocarbon prospecting

This study aims to assess the hydrocarbon potential of Ganga basin utilizing the near surface geochemical prospecting techniques. It is based on the concept that the light gaseous hydrocarbons from the oil and gas reservoirs reach the surface through micro seepage, gets adsorbed to soil matrix and leave their signatures in soils and sediments, which can be quantified. The study showed an increased occurrence of methane (C₁), ethane (C₂) and propane (C₃) in the soil samples. The concentrations of light gaseous hydrocarbons determined by Gas Chromatograph ranged (in ppb) as follows, C₁: 0–519, C₂: 0–7 and C₃: 0–2. The carbon isotopic (VPDB) values of methane varied between ?52.2 to ?27.1‰, indicating thermogenic origin of the desorbed hydrocarbons. High concentrations of hydrocarbon were found to be characteristic of the Muzaffarpur region and the Gandak depression in the basin, signifying the migration of light hydrocarbon gases from subsurface to the surface and the area’s potential for hydrocarbon resources.     

烃类组分在金属矿床的成矿理论和矿产勘查研究中的应用

很多的研究证据表明烃类组分在自然界赋存空间和范围非常广泛:如地表和近地表的各类岩石和土壤,现代海底烟囱、海槽现代活动热水区和火山喷发气体,深源的基性-超基性岩和玄武岩包裹体,甚至在碳质球粒陨石中都有烃类组分的存在.因此对烃类组分的研究不应局限于石油、天然气和煤炭等能源矿床,而应该推广到各类金属矿床及其流体的研究中来.与其他气态组分如CO2、H2S、N2、H2等相比,烃类具有组分多元化和性质稳定的特点,同时烃类各组分间的相关特征和配分规律是其地质流体演化过程(氧化-还原条件、温度、压力等环境因素)中的重要参数.为直观表现烃类组分综合特征和流体混合、叠加演化过程中烃类组分细微变化,本文提出建立烃类组分标准化背景的研究思路,探索性地将具有幔源流体特征的峨眉山玄武岩作为烃类组分的标准化背景,其意义类似于选择球粒陨石作为标准化稀土元素背景的建立.通过在云南个旧和广西大厂锡多金属矿、陕西马鞍桥金矿等多个典型金属矿床上实际应用,表明该研究方法能将各类地质体烃类组分差异性和演化的规律性得到直观体现,将单纯的烃类组分宏观异常特征归纳、发展为对烃类组分的叠加改造、配分模式以及相关特征的微观规律研究,将过去烃类组分仅作为有机质参与金属成矿的表征现象,发展成为能应用于成矿物质来源、成矿流体演化及成矿作用和规律研究的工具和手段.     

Ancient continental margins and comparative analysis of their oil-and-gas bearing

Analysis of peculiarities in the distribution of hydrocarbon accumulations within the basins of Phanerozoic continental margins, which had completed their evolution, and complicated peripheral regions of ancient Laurasian and Gondwanian platforms nowadays, has enabled us to reveal certain regularities related to two stages in the evolution of sedimentary basins. The first stage of evolution of sedimentary basins (period of existence of the continental margin proper) is related to large accumulations of fluid and gaseous hydrocarbons in the margins of continents belonging to the Laurasian megablock; for the margins of continents belonging to Gondwana, this period was reflected in the formation of large gas accumulation only (in the Permian). At the second stage of sedimentary basin evolution, large oil and gas accumulations were formed in areas associated with fore deeps, which were laid in the boundary of the Gondwanian platforms and fold belts. In comparison, in fore deeps that emerged in the marginal parts of Laurasian platforms, less significant accumulations of fluid and gaseous hydrocarbons were found (Table 1). The results of comparative analysis in oil-and-gas bearing basins located in the margins of the Laurasian and Gondwanian megablocks would help in purposeful exploratory works for oil and gas.     

Proteins as a possible source material of low molecular weight petroleum hydrocarbons

Low temperature cracking experiments of a representative protein, at temperatures not far above the observed temperature range of 130–160°C of mature California oil source rocks, indicate the formation of all gaseous and of some gasoline range hydrocarbons of petroleum. Based on protein derivatives only it is estimated that a maximum of at least 3–8% by weight of the total organic matter of oil source sediments may be converted into such hydrocarbons. This is in addition to hydrocarbons originating from lipids.     

Place and time of formation of oil and gas in the orogenic region of southeastern Central Asia

We recognize three principal geotectonic stages in the development of this area: pre-Mesozoic geosynclinal, Mesozoic-Paleogene platformal, and Neogene-Quaternary epiplatformal. Whereas the depths of generation of liquid and gaseous hydrocarbons in the platformal stage did not exceed 5000 m, these depths differed significantly during the phase of postplatformal activation and were more than 6000 - 8000 m. As a result of short-lived orogenic movements, zones of generation of liquid hydrocarbons could be distributed to depths 6500 m and more. This indicates that there is more evidence In favor of discovering deep-seated oil in sediments of young fold regions than on the platforms.

The possibility of the existence of an upper zone of gas formation is supported and the history of geologic development and conditions of petroleum formation in the fold regions indicates the need for a differentiated assessment of the prospects of oil and gas. —Author.     

含铀物质对有机质生烃的实验研究

采用密闭容器水热模拟实验方法,考察含铀物质对有机质热解生烃过程的影响。对热模拟实验产物分析发现,在暗色泥岩和煤岩样品中加入含铀物质后,气态烃和液态烃的生烃量都有比较明显的增加。其中煤岩的气态烃产量平均增加值为34%,而泥岩样品平均增加值也达到了30%以上。液态烃产率分析表明,含铀矿物也促进了泥岩和煤岩的液态烃产率。从泥岩氯仿沥青‘A’族组成分析表明,加入催化剂后泥岩的饱和烃和芳烃在高温阶段具有规律性的明显增大的趋势,反映出非烃和沥青质,甚至不溶有机质向相对稳定的饱和烃转化以及芳烃随演化程度增加的高聚合作用。综合以上分析,认为放射性铀对油气生成具有氧化催化作用。     

Abiogenic and Biochemogenic Alteration of Basaltic Glass under Low-Temperature Conditions

The material for investigations was obtained in Iceland in the area of active volcanism and tectonics in the recent rift zone under cold-temperate and humid climate and glacial conditions. The presence of abundant remnants of microbiota differently mineralized by palagonite was established in weathering zone on the surface of basaltic glass fragments situated at the top of hyaloclastites devoid of terrestrial vegetation. This gives conclusive evidence for the biochemogenic nature of palagonization in basaltic glass under these conditions. Among a number of possible reasons of the origination of palagonite, the most interesting is the relation of microbiological processes to the influx of gaseous hydrocarbons from the depth. This mechanism needs further investigations.     

天然气运移的气体组分的地球化学示踪

本文通过我国不同含油气盆地典型地区岩石酸解气、罐顶气和天然气中化学组分分析,结合天然气的形成和盆地的地质演化,研究了天然气运移时组分的变化。结果表明,天然气通过地层孔隙系统运移时,组分会发生明显分馏,表现在甲烷相对重烃、异构丁烷相对正构丁烷的优先迁移。酸解气、罐顶气和成藏天然气中C₁/C₂+、iC₄/nC₄及总烃/非烃等比值,是天然气运移示踪的有效指标。     

烃源岩有限空间温压共控生排烃模拟实验研究

烃源岩的生烃反应是在其限定的孔隙空间中承受高静岩压力和流体压力下进行的,然而受实验装置和条件的限制,目前大多数的生排烃模拟实验都是在一个低压、相对较大的生烃空间下进行的,与实际地质情况差异较大。通过对同一样品分别进行有限空间和常规高压釜方式加水模拟实验对比研究发现:（1）有限空间热压模拟实验的气态产物更接近地质实际。气体组分中烃气占有更大的比重;重烃气的保存下限大于常规模拟,延迟了重烃气向甲烷的转化;烯烃含量比常规加水模拟条件下更少,基本检测不到。（2）有限空间的限制使水介质参与成烃反应的作用增强,其限定空间内较高的流体压力延迟了油向烃气的转化过程,有利于液态油的生成和保存。（3）有限空间下高压液态水介质条件有利于烃类的排出。     

Phase states of hydrous–hydrocarbon fluids at elevated and high temperatures and pressures: Study of the forms and maximal depths of oil occurrence in the Earth’s interior

Based on synthetic fluid inclusions in quartz grown at 240–490°C and 7–150 MPa in aqueous–oil solutions, the behavior, composition, and phase states of liquid, gaseous, and solid hydrocarbons (HC) were studied. Investigations were performed using common and fluorescent microscopy, microthermometry, local common and high-temperature IR Fourier spectroscopy, Raman spectroscopy, chromatography, and X-ray and microprobe analysis. The data obtained allowed us to understand the influence of thermobaric conditions and volume proportions of the oil, aqueous, and gaseous phases on the composition, phase state, and behavior of hydrous–hydrocarbon fluids and estimate the forms and probable maximal depths of the origin of oil in the Earth’s interior.     

泥炭的热模拟研究──过渡带气形成机理探讨

本文对现代泥炭进行了低温长时间模拟实验研究,并探讨了过渡带气的形成机理。甘南泥炭气、液态烃产率高。液态烃由热解油和残余气仿沥青“Ａ”两部分组成,热解油中以Ｃ_５─Ｃ_１４较轻馏分为主,残余氯仿沥青“Ａ”则以非烃、沥青质为主。随热演化程度增高,烃类增加,非烃和沥青质急剧减少。模拟气体组成以非烃气体（ＣＯ_２等）为主,随温度升高,气态烃产率升高,烃类气体中以甲烷为主。２００℃～４００℃温度下产生的甲烷碳同位素δ１３Ｃ为－５３.８２～－３３.６６‰。研究表明低热演化阶段伴随腐殖物质的降解和干酪根的分子重排作用能产生甲烷同位素较轻的生物－热催化过渡带气。     

正构二十四烷裂解成气碳同位素动力学模拟及其地质意义

以甲烷的量子化模型及正构二十四烷(n C24)金管限定体系裂解成气实验为基础,从理论上进一步论述了量子化模型应用于重烃气体（乙烷和丙烷）碳同位素动力学模拟的适应性,计算了甲烷、乙烷及丙烷生烃动力学与碳同位素动力学参数, 重点探讨了δ13C2与δ13C3变化的主控因素。研究结果表明, n C24裂解生成的气态烃碳同位素与早期报道的n C18、n C25及原油裂解生成的气态烃碳同位素具有可比性,可应用于地质条件下解释原油裂解气的某些地球化学特征。n C24生烃地质模型表明,其在150～160℃是稳定的,主要裂解温度介于180～200℃之间,与目前所报道的原油裂解地质模型吻合。随热解程度的增加,δ13C2与δ13C3体现了比δ13C1更明显的变化。气藏充注历史控制的同位素累积效应对天然气碳同位素有很大的影响,与累积聚集气相比,阶段聚集气的δ13C变重,并在更大程度上影响了演化曲线的分异。在此基础上,应用n C24裂解成气碳同位素分馏地质模型探讨了塔里木盆地某些油气藏天然气碳同位素值变化的原因。