评价干酪根生油气量的一种新方法

用压力差示扫描量热仪(PDSC)研究了我国茂名、抚顺、黄县油页岩干酪根(Ⅰ,Ⅱ型)及黄县褐煤(Ⅲ型)在热降解时的化学结构变化。试验中发现,在氧气压力为1.5MPa时,各种干酪根的PDSC图谱都出现两个放热峰。由放热峰的积分面积可计算出各干酪根的表观芳碳率。由此提出了计算干酪根生油、气量的新方法,可根据干酪根在热降解时的“残留脂碳率”与“干酪根质量系数”的演化图计算出生油岩的生油量和生气量,也可以根据干酪根热降解时的脂构碳、芳构碳的分布计算干酪根生油、气量的简化模式,由脂构碳的热解动力学参数计算出生油岩的油气生成量。     

干酪根热解平行反应模型中表观活化能与视频率因子的关联

本文考察了三种类型干酪根以及抚顺和茂名油页岩热解反应的动力学特性,对由平行反应模型所求得的表观活化能及视频率因子进行了数学关联。关联式表明,视频率因子的对数值与表观活化能成一直线关系。由此关系可以推出,所有平行反应在某一特定温度下具有一个相同的反应速率常数。根据直线的斜率,还可以比较不同类型干酪根热降解反应的难易程度。     

Origin of immature sulfur-rich oil in Jianghan oil field

Chemical structure of immature sulfur-rich kerogen and composition of immature sulfur-rich crude oil in Jianghun oil field have been studied. In molecular level, crude oil differs from thermolysed and chemolysed products of kerogen but does resemble the bitumen in immature sulfur-rich source rock. Therefore, immature sulfur-rich oil may be derived from the expelling of bitumen rather than from thermal cracking of kerogen.     

Kinetic study of hydrocarbon generation of oil asphaltene from Lunnan area, Tabei uplift

The molecular compositions and molecular carbon isotopic compositions of gas hydrocarbons produced in the hydrocarbon generation of oil asphaltene from Lunnnan area were investigated by pyrolysis of asphaltene sealed in gold tube in a limited system. The experimental results indicated that oil asphaltene from Lunnan area had relatively high generation potential of methane. However, the molecular compositions and molecular carbon isotopic compositions of gas hydrocarbons in the hydrocarbon generation of oil asphaltene exhibited different characteristics from that of gas hydrocarbons by primary cracking of kerogen and secondary cracking of oil. Based on kinetic simulation with paleo-geothermal data of oil reservoir, the methane produced by cracking of oil asphatene was characterized by relatively light carbon isotopic compositions. This result could not explain relatively heavy carbon isotopic compositions of natural gas from Lunnan area. Pyrolysis of kerogen from source rocks under very high temperature probably made remarkable contributions to natural gas from Lunnan area.     

铀对Ⅰ型低熟烃源岩生烃演化的影响

在Ⅰ型低熟烃源岩中加入砂岩型铀矿石的条件下进行生烃模拟实验,对比无铀-加铀样品生烃模拟实验产物的相关参数,探讨油气生成过程中无机铀所起的作用。结果表明:铀的存在促使长链烃类在400℃后裂解成低相对分子质量短链烃,烃类相对分子质量降低,向干气演化,CO2和H2大量生成,且铀的存在使得这一变化的温度点提前50℃;铀可以促进总油生成高峰的提前到来;350℃为铀使烯烃产量变化的转折温度点,烯烃开始向烷烃转变;铀的存在能提高模拟实验中生成的烯烃的异构化程度,并在整体上使生成的烯烃分子在晶格中排得更加紧密;加铀的烃源岩样品的生烃模拟实验产物在族组成、饱和烃气相色谱、生物标志化合物等方面表现出更加成熟的特征,铀可以使有机质的成熟度提高,有利于低熟烃源岩早期生成低熟油气,使铀的存在成为未熟-低熟油气形成的可能无机促进因素之一,这种提前生成的少量油气可以使所在储层变为亲油性,为后期大规模生成的油气运移成藏提供有利的条件,使得即使是致密的储层,也能形成大规模的工业油气藏。     

干酪根热解聚沥青中的脂烃生物标记物

将干酪根在超临界态溶剂存在下进行热解聚,抽出物中的脂烃生物标记物的分析表明,抚顺与茂名油页岩干酪根中有相当多的陆源高等植物参与生成。甾烧萜烷的成熟度参数表明,热解聚沥青的成熟度很低。对于干酪根通过热解聚形成未熟或低熟原油的可能性作了初步探讨。     

Oil cracking： An important way for highly efficient generation of gas from marine source rock kitchen

The potentials of gas generation by kerogen in the late period and by crude oil cracking are closely related to the origin of natural gas in the high- to over mature marine area and their exploration perspectives. The carbon structure of kerogens, with different types and at different evolution stages, have been experimentally studied using the high magnetic field solid ^13C nuclear magnetic resonance technique in order to determine the oil and gas potential of kerogens. Results show that the contents of gas potential carbon（GPC） of types Ⅰ, Ⅱ, Ⅲ kerogens at the high- to over mature stage are very low, indicating their weak gas-generating capacity and limited gas production; however, the content of oil potential carbon（OPC） of the low mature type Ⅰ kerogen is much higher, implying that a large amount of crude oil generated during the oil-generating period will be the material for later gas generation by oil cracking. The kinetic experiment of gas generation by crude oil cracking shows that, when the temperature is about 160℃（R0=1.6%）, the crude oil will start to produce large amounts of gas; the temperature range for major gas generation of crude oil is higher than that of the kerogens, and the gas production is 2 to 4 times higher than that of kerogens. The natural gas derived from oil cracking （called oil-cracked gas） is much abundant in methyl hexamethylene, which is quite different from the natural gas produced by thermal degradation of kerogens （named kerogen degradation gas） at high- to over mature stage.     

Reassessing the first appearance of eukaryotes and cyanobacteria

The evolution of oxygenic photosynthesis had a profound impact on the Earth's surface chemistry, leading to a sharp rise in atmospheric oxygen between 2.45 and 2.32 billion years (Gyr) ago and the onset of extreme ice ages. The oldest widely accepted evidence for oxygenic photosynthesis has come from hydrocarbons extracted from approximately 2.7-Gyr-old shales in the Pilbara Craton, Australia, which contain traces of biomarkers (molecular fossils) indicative of eukaryotes and suggestive of oxygen-producing cyanobacteria. The soluble hydrocarbons were interpreted to be indigenous and syngenetic despite metamorphic alteration and extreme enrichment (10-20 per thousand) of (13)C relative to bulk sedimentary organic matter. Here we present micrometre-scale, in situ (13)C/(12)C measurements of pyrobitumen (thermally altered petroleum) and kerogen from these metamorphosed shales, including samples that originally yielded biomarkers. Our results show that both kerogen and pyrobitumen are strongly depleted in (13)C, indicating that indigenous petroleum is 10-20 per thousand lighter than the extracted hydrocarbons. These results are inconsistent with an indigenous origin for the biomarkers. Whatever their origin, the biomarkers must have entered the rock after peak metamorphism approximately 2.2 Gyr ago and thus do not provide evidence for the existence of eukaryotes and cyanobacteria in the Archaean eon. The oldest fossil evidence for eukaryotes and cyanobacteria therefore reverts to 1.78-1.68 Gyr ago and approximately 2.15 Gyr ago, respectively. Our results eliminate the evidence for oxygenic photosynthesis approximately 2.7 Gyr ago and exclude previous biomarker evidence for a long delay (approximately 300 million years) between the appearance of oxygen-producing cyanobacteria and the rise in atmospheric oxygen 2.45-2.32 Gyr ago.     

半封闭半开放体系下不同演化程度干酪根的太赫兹光谱特性

本文应用太赫兹时域光谱技术研究了灰色泥岩在半封闭半开放体系下经历不同生烃模拟温度、压力所得干酪根的光学性质,获得了不同干酪根样品在太赫兹波段的吸收谱和折射率,结合样品的镜质体反射率,建立了干酪根在不同演化阶段的生烃模式,分析了干酪根样品在地质升温速率下的自然演化过程及主生烃期,为研究烃源岩的演化及油气生成提供了参考．     

红外光谱法研究油页岩及干酪根的生油能力

采用Lorentzian分峰拟合,A-C因子和含100%脂肪链的微晶石蜡为标准物质的方法对油页岩及去矿物油页岩干酪根红外吸收光谱进行了研究,分析了干酪根中各种烃的成分和含量.结果表明:油页岩及去矿物油页岩中有机质均为Ⅱ型干酪根;去矿物能使支链从干酪根主链上脱落,但去矿物程度不宜过大.随着去矿物程度加深,干酪根脂肪链含量、红外谱图中CH2与CH3吸收峰面积的比值和脂氢/芳氢面积比值先增大,后减小;油页岩经酸碱处理后,干酪根中脂肪链的含量可达到54.06%,CH2与CH3吸收峰面积的比值为7.11,脂氢和芳氢的面积比值为2.73.无机矿物质的去除使干酪根的生油潜力得到提高.     

等离子体氧低温灰化仪的试制及应用

根据低温等离子体氧氧化的基本原理及文献资料,自行设计研制了一套能用于固体燃料低温灰化的等离子体氧低温灰化仪。实验结果表明,仪器的性能良好。在氧流速为 50mL/min,真空度小于 0.26kPa,高频发生器输出50W时,该仪器可对煤或油页岩试样进行正常的低温灰化。灰化时间与灰化后的残留有机碳达到国外同类仪器工作的水平。对仪器的氧化反应器与真空系统的接口作了新的设计,使气体中残余的等离子体氧充分复合为分子态,保证了仪器的长期安全操作。该仪器可用于测定煤和油页岩矿物质的含量;还可用于直接测定油页岩中有机质的氢碳比。     

Thermal simulation of the formation and evolution of coalbed gas

Thermal simulation experiment of gas generation from the peat and the coals were performed using the high temperature and pressure apparatus, at temperature ranging from 336.8-600℃, a pressure of 50MPa and two heating rates of 20℃/h and 2℃/h, and the evolution and formation of coalbed gas components were studied. Results show that for the coals, the gaseous products are mainly composed of hydrocarbon gases. However, for the peat the content of hydrocarbon gases in gaseous products is lower than that of non-hydrocarbon components. In the generated hydrocarbon gases methane is predominant and heavy hydrocarbon gases (C2-5) are present in small amount. Meanwhile, carbon dioxide (CO2) predominates the generated non-hydrocarbon gases, and hydrogen (H2) and sul-furated hydrogen (H2S) are existent in trace amount. It is also observed that temperature is the main factor controlling the evolution of coalbed gas generation. With increasing vitrinite reflectance, methane rapidly increases, CO2 sightly increases, and C2-5 hydrocarbons first increase and then decrease. The peat and Shanxi formation coal have a higher generative potential of coalbed gases than coals and Taiyuan formation coal, respectively, reflecting the effect of the property of organic matter on the characteristics of coalbed gas component generation. In this study, it is found that low heating rate is favorable for the generation of methane, H2 and CO2, and the decomposition of C2-5 hydrocarbons. This shows that heating time plays an important controlling role in the generation and evolution of coalbed gases. The results obtained from the simulation experiment in the study of coalbed gases in natural system are also discussed.     

乙烯-醋酸乙烯共聚物降凝剂对尼罗原油的特殊改性作用规律

利用流变测量手段对尼罗原油添加EVA降凝剂前后流变参数的变化规律进行了研究，结果表明尼罗原油中加入EVA降凝剂后，凝点不变，但低温下的屈服值减小（凝点处降低幅度为70%），反常点由38℃升至45℃，原油的非牛顿流体温度范围向高温方向扩展，此外掺加不同比例轻油的尼罗原油加剂后依然存在反常点升高的现象。最后根据实验数据计算得出相同条件下原油析出蜡晶浓度远小于其实际内相浓度，证明了原油中蜡晶溶剂化层的存在，进一步完善了降凝剂对含有较多极性胶质的高凝易黏原油的改性机理。     

New concept on coal structure and new consideration for the generation mechanism of oil from coal

The traditional two_phase structural model of coal based on the chemical covalence bonding has to be revised since recent discoveries of powerful mixed solvent such as CS-2/C-5H-9N, giving extra high yields in coal extraction at room temperature. It is believed that the physically associated interactions play important roles in the structure of coal. A composite model of coal is suggested. The organic matter of coal is mainly composed of some parts: the rigid 3_D macromolecules linked with chemical bonds; the polar molecules of high and moderate molecular weights, corresponding to asphaltenes and resins; the hydrocarbons with lower molecular weights. The polar molecules are associated by physical interactions (such as hydrogen bonding, charge transfer interactions, π_π interactions of aromatic sheets, etc.) each other and with macromolecules to form the network structure, in which some smaller nonpolar molecules are trapped. Based on the new concept of the composite coal model, some considerations for the generation mechanism of oil from coal have approached. Since the energy level of physical association is much lower than the chemical covalent bonding, the upper threshold of oil window for the generation of oil from coal seems not to be limited strictly after the theory of oil generation at the latter stage of the kerogen maturation. It looks reasonable to pay more attention to the geological conditions including the salt, water, minerals and environments of the sedimentation. The evolution process of physically associated interactions in the composite structure of coal and the generation of oil is thought to be intimately influenced by these factors.     

Determining the temperature of petroleum formation from the kinetic properties of petroleum asphaltenes

Knowledge of the timing and location of petroleum formation is important in assessing the extent of available reserves in hydrocarbon-forming basins. This can be predicted from the thermal history of a basin and the kinetic parameters that characterize the thermal breakdown of kerogen in source rocks. At present, the kinetic parameters of kerogen breakdown are experimentally determined using immature rock samples from basin margins, but questions remain about the accuracy of this approach, especially when significant variability is observed within individual source units. Here we show that the kinetics of hydrocarbon generation from petroleum asphaltenes can be used to determine the temperature conditions of the actual source rock at the time of expulsion of the sampled petroleum. This relationship reflects the structural similarity of asphaltenes to the parent kerogen. We expect that our approach may be used as a comparatively simple alternative method for assessing the petroleum generation characteristics of a given basin, which will allow for better estimates of the available oil resources and the risks associated with their exploration.     

Constraints on the origins of hydrocarbon gas from compositions of gases at their site of origin

It is widely accepted that natural gas is formed from thermal decomposition of both oil in reservoirs and, to a lesser extent, the organic matter in shales from which the oil was derived. But laboratory pyrolysis experiments on shales do not reproduce the methane-rich composition typical of most gas reservoirs, leading to suggestions that other mechanisms, such as transition-metal catalysis, may be important. The discrepancy might, however, instead arise because gas (and oil) deposits have migrated from their source rocks, so that the reservoir composition might not be representative of the composition in the source rocks where the hydrocarbons were generated. To address this question, we have analysed gas samples coproduced with oils directly from a source rock (the Bakken shales, North Dakota, USA) where the local geology has prevented significant hydrocarbon migration. The methane contents of these Bakken-shale gases are much lower than that of conventional gas reservoirs, but are consistent with that from pyrolysis experiments on these shales. Thus, because these Bakken gases form with (rather than from) oils, we argue that compositional differences between gases from source rocks and conventional gas deposits result from fractionation processes occurring after hydrocarbon expulsion from the source rock.     

盆地数值模拟方法研究与发展

以近年来国内外盆地数值模拟方法研究的新成果为基础,综述了其发展概况、研究动态和应用效果,并引出了一些新的概念和思路.对模拟模型的研究表明,时一温积分比时一温指数更能准确地反映有机质的热成熟度,生烃模型既要考虑不同干酪根类型的化学动力学反应机理,又要包括各演化阶段生烃量的计算.由于烃类以与水呈独立的相态发生初次运移的可能性更大,因此可以计算出油和气曲排出量.二维模拟模型在挪威Haltenbanken地区的应用表明,除浮力和断层封闭作用外,超压和水力压裂因素在烃类的二次运移和聚集过程中起着重要的控制作用.     

M盆地烃源岩有机显微组分特征与生烃潜力初探

Ｍ盆地烃源岩主要分布于下白垩统ＡｂｕＧａｂｒａ组,为一套半深湖－深湖的沉积建造,主要生油岩为深灰色、灰黑色泥页岩．其中的原油具有高蜡、低硫和低气油比的特征．通过对烃源岩地球化学特征和烃源岩有机显微组分特征研究证实,该套烃源岩主要生油组分为陆源有机质经细菌降解形成的腐殖无定形,其次为壳质组;生油能力较弱的镜质组和惰质组含量较低．对主要烃源岩模拟生烃特征进行了研究,结果表明：这种有机质油气转换系数较大,并具有“两期生油”的特征,第一个生油高峰对应的模拟温度为３４５℃,第二个生油高峰为４２５℃,产生的油气具有生油量大、生气量小的特点．     

用钌离子催化氧化法研究干酪根及其显微组分的化学结构

用钌离子选择性催化氧化法研究了茂名油页岩干酪根、山西蒲县藻煤藻类体、长广树皮煤的树皮体以及山西繁峙褐煤镜质组的化学结构。研究结果表明 ,茂名油页岩干酪根和蒲县藻煤藻类体的化学结构均以醚 /酯键形式交联的中等链长的脂链结构为主 ,繁峙褐煤镜质组中的芳香结构仍保留着木质素基本结构单元的单环结构 ,同时含有丰富的脂族化合物。这些脂族化合物可能来自这一富氢显微组分中的超微类脂体。长广树皮煤中树皮体以少于 4个环的稠环化学结构为主 ,由小于C12 的脂链交联成大分子     

油页岩固定床干馏过程三维数值模拟

主要研究了固定床内油页岩干馏过程的三维数值模拟。通过对固定床内气固相间传热传质过程的分析,建立了完整的气固两相传热传质模型,并采用多孔介质模型与流动模型相结合,将干馏过程中水分析出和干馏油气的析出过程通过用户自定义接口添加到模拟过程中。针对实际工况进行了模拟研究并与实验结果进行比对,吻合程度较好。此外,分别从进气速度和进气温度等方面进行对比分析,研究结果表明当进气速度提高0.5倍时,干馏进程加快1 600 s。当进气速度降低0.5倍时,干馏进程延缓4 200 s,换热效率明显降低。进气温度提高100℃,干馏进程加快600 s,油页岩中干酪根热解过程前期水分最大蒸发速率提高约11.4%。当进气温度降低100℃时,干馏进程延缓1 300 s,干酪根热解过程前期水分最大蒸发速率降低约24.7%。在气体热载体和传质过程的共同作用下,靠近进气位置的底部颗粒与周围环境气体中水蒸气及干馏油气之间的浓度梯度小于上部颗粒,这也是固定床内上部颗粒干馏进程较慢的一个重要原因。