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。     

湖相生物碎屑灰岩热模拟气特征

通过对山东平邑盆地下第三系湖相生物碎屑灰岩加水热模拟气的研究,探讨了热解气的产率、组成及结构参数的变化特征。湖相生物碎屑灰岩热解气总体上以非烃气为主要组分,非烃中又以ＣＯ２含量最高,其高含量与碳酸盐岩分解有关;其次为Ｎ２和Ｈ２,ＣＯ含量甚微。烃气中以烷烃为主,烯烃含量很低。在正异构烃组成中异构烃含量相对高。干燥系数和酸烷比随模拟温度升高而规律变化,可以用来衡量有机质的成熟度。     

煤的加水热模拟气特征对比

为探讨煤成气的生成特征和演化规律，对两种不同有机质类型煤进行了加水热模拟生气实验研究。认为，有机质类型对于煤的热模拟气生成特征和烃气产率有决定作用。非烃气中的氢气、一氧化碳与二氧化碳含量之间呈负相关，这与水参与反应有关。甲烷的形成与水的作用关系密切。不同的热模拟气在成熟—高成熟演化阶段差异明显，有机质类型越差，热模拟气中甲烷相对越多，干燥系数相对越大，异丁烷／正丁烷越高；反之，甲烷相对越少，干燥系数越小，异丁烷／正丁烷低，区别越明显。演化程度增加时，热模拟气之间的差别减小。总烃气和甲烷的产率随温度升高而增加，而重烃有产率高峰存在，正好对应于生油窗的底界。     

煤系烃源岩生气热模拟实验研究

为了客观评价煤系烃源岩的生气特征和生气量,采用限定体系黄金管热模拟实验技术,对采自鄂尔多斯盆地的不同地质时代煤系烃源岩(煤岩和煤系泥岩)样品进行了生气热模拟实验研究,详细讨论了煤系烃源岩热解生气特征与气体碳同位素变化。结果表明,煤系烃源岩具有较好的生气性能,煤岩与煤系泥岩热解生成气态烃产率相差不大,两者具有相似的生气演化特征,即随热模拟温度升高,煤岩和煤系泥岩热解生成甲烷的产率逐渐增加,甲烷最大产率分别达211.69 m3/t和184.47 m3/t,而C2-5产率是先增加后降低,在热模拟温度430℃~470℃达到最大值,分别为19.14 m3/t和6.87 m3/t;煤岩和煤系泥岩热解气组分碳同位素值总体上随热模拟温度升高而变重,且相同热模拟温度时具有δ13C1δ13C2δ13C3的特征,其中煤系泥岩热解气甲烷、乙烷碳同位素值较煤岩分别偏轻0.3‰~2.1‰和1.4‰~3.7‰。在此基础上,建立了煤系烃源岩(煤岩和煤系泥岩)的生气模式。     

TSR对碳酸盐岩中沥青生烃影响的模拟实验

利用地层孔隙热压生排烃模拟仪实验装置,对采自四川盆地西北部广元矿山梁地区下寒武统具高有机质含量、高氢指数和低成熟度特征的固体沥青,开展了模拟地层条件下的"沥青+白云岩+去离子水"(系列A)和"沥青+白云岩+硫酸镁+去离子水"(系列B)生排烃实验。结果表明,这两个系列的气体产率具有较大差异,其中,加入硫酸镁的系列(系列B)发生了热化学硫酸盐还原反应(TSR),使气态烃和非烃气体的产率增大,同时也加速了重烃气体的裂解,导致重烃气体大量裂解的温度降低。     

湖相烃源岩混合型母质成烃演化特征热模拟研究

为探讨湖相有机质成烃演化特征,选择混合型母质烃源岩进行加水模拟实验,以探讨混合型母质的成烃特征。研究表明,湖相混合型母质具较强的生油和生气能力,液态油产率随温度先增后降,生油窗明显。天然气形成于整个演化过程中,但主要形成于生油高峰后。气态产物主要有非烃气如氢气、氮气、一氧化碳、二氧化碳等,以及烃气(如从甲烷到C6+重烃)和一些烯烃。气体中二氧化碳含量最高,其次为氢气、甲烷和其他气体。二氧化碳在整个生油阶段都有较高含量,但随温度升高而降低,实际地质条件下大量二氧化碳主要都通过水合作用等而消耗殆尽,利于储集层次生孔隙的形成,氮气在生油早期含量高,氢气和烃类气体含量随温度升高而增加,实际气藏中由于氢气化学活性强而基本消耗掉了。正、异构烷烃之比随温度升高而增加,利用该参数时应注意热演化的影响。     

氧化作用对气态烃组成和碳同位素组成的影响

通过加水模拟实验,揭示了气态烃在被矿物氧化过程中分子组成和碳同位素组成的变化.实验结果表明,随着反应时间的延长,气态烃、非烃 (H2、 CO2、 H2S)组成及碳同位素组成发生了明显且很有规律的变化.气态烃碳数越高,氧化速率越快,碳同位素变化 (增重 )越大.当氧化剂为赤铁矿或赤铁矿 硫酸镁时, CH4含量没有明显降低,δ 13C值增重 1‰～ 2‰; C2H6含量最后 (288h)降低了约 20%,δ 13C值增重约 3‰; C3H8含量最后降低了约 50%,δ 13C值增重约 5‰; Ic4h10含量在 72 h时即降低了约 80%,氧化速率远高于 Nc4h10.非烃 CO2的含量增加了 1.26～ 1.71倍.当氧化剂为硫酸镁时, CH4含量明显增高,最多时增加了 34.7%,δ 13C值增重约 8‰; C2H6含量在 72 h时降低了约 14%,在 144 h时降低了约 85%,δ 13C值增重约 24‰; C3H8含量在 72 h时降低了约 65%,在 144 h时降低了 98%以上; Ic4h10和 Nc4h10在 72 h时即降低了 90%以上.非烃 CO2含量最多增加了 1.86倍, H2S最多增加了 9.62倍.这些实验结果对认识天然气藏在矿物氧化过程中分子组成和碳同位素组成的变化具有重要意义.     

泥炭的热模拟实验及其在煤层气研究中的应用

采用高温高压多冷阱热解实验装置,在温度和压力分别为336.8~600℃和 50MPa,升温速率为 20℃/h和 2℃/h条件下,对泥炭进行了热解生气的模拟实验,获得了烃类甲烷和C₂-C₅气体以及非烃二氧化碳、氢气和硫化氢气体的产率和体积分数数据,研究了热模拟产物气体的组分特征和热演化过程。结果表明,泥炭高温热解产物气体主要由非烃二氧化碳气体组成,其次为烃类甲烷和C₂-C₅气体。随着实验温度的增高,非烃气体体积分数呈下降趋势,烃类气体体积分数呈上升趋势。不同升温速率实验条件下,泥炭样品热解生气表现出不同的特征,主要体现了时间因素控制着泥炭的生烃过程和生烃量,这符合化学反应动力学时间与温度之间互补的原理。并且与煤岩热解生气特征进行了对比,表明泥炭比煤岩具有更高的产烃气能力。根据热模拟实验研究结果,探讨了煤层气形成方面的地球化学意义。      

原油在储层介质中的加水裂解生气模拟实验

采用高温高压热模拟实验方法,开展了原油在砂岩和火成岩储层介质中的加水裂解生气模拟实验研究.结果表明,原油开始大量裂解的温度是400℃,随模拟温度增加,甲烷相对含量增大,乙烷以上重烃气尤其是丙烷相对含量减小.其中砂岩的油水混合物裂解生气主要发生在450～500℃之间,生气窗范围小,对应的烃气产率高,火成岩的油水混合物裂解生气主要发生在450～600℃之间,生气窗范围大,对应的烃气产率小.模拟烃气的组分碳同位素分馏显著,随模拟温度增加呈变重趋势.在裂解生气过程中,水解加氢和催化作用对烃气的组成、产率和碳同位素分布有重要影响。     

原油在储层介质中的加水裂解生气模拟实验

采用高温高压热模拟实验方法,开展了原油在砂岩和火成岩储层介质中的加水裂解生气模拟实验研究.结果表明,原油开始大量裂解的温度是400℃,随模拟温度增加,甲烷相对含量增大,乙烷以上重烃气尤其是丙烷相对含量减小.其中砂岩的油水混合物裂解生气主要发生在450～500℃之间,生气窗范围小,对应的烃气产率高,火成岩的油水混合物裂解生气主要发生在450～600℃之间,生气窗范围大,对应的烃气产率小.模拟烃气的组分碳同位素分馏显著,随模拟温度增加呈变重趋势.在裂解生气过程中,水解加氢和催化作用对烃气的组成、产率和碳同位素分布有重要影响.     

Quantitative estimation of overpressure caused by oil generation in petroliferous basins

Oil generation can be the dominant overpressure mechanism in low permeability source rocks because of the volume increase upon conversion of organic matter to less dense oil during the petroleum generation process. To quantitatively express the relationship between oil generation and overpressure in source rocks, an equation for the pressure change due to oil generation was derived to quantitatively estimate the overpressure generated in the source rock by considering of the episodic fluid expulsion and parameters, such as the residual oil coefficient, source rock porosity, transformation ratio, TOC (total organic carbon), hydrogen index, the compressibility of Type I kerogen, oil and pore water. The equation was then calibrated with the results from physical simulation experiments in a closed pyrolysis system. Sensitivity analyses on the residual oil coefficient, TOC and hydrogen index were performed to investigate the dominant parameters controlling overpressure due to oil generation. A good correlation was achieved between measured overpressure from the physical simulation experiments and the calculated data using the derived equations for the pressure change due to oil generation, suggesting that the equation can be used to quantitatively estimate overpressure caused by oil generation in source rocks. Many parameters can affect overpressure caused by oil generation, including residual oil coefficient, source rock porosity, TOC, hydrogen index, and transformation ratio. Sensitivity analyses indicate that the most effective parameter on the pressure change due to oil generation in the source rocks is the residual oil coefficient, implying that the internal pressure seal for the source rock is the most important parameter for overpressure development caused by oil generation. Overpressure cannot be generated from oil generation if the residual oil coefficient is less than 0.75. Source rock TOC and hydrogen index have moderate effects on the pressure change caused by oil generation. Overpressure can be generated when the TOC content is as low as 0.5% provided the source rocks have a good internal pressure seal.     

Relation between source rock properties and wireline log parameters: An example from Lower Jurassic Posidonia Shale, NW-Germany

The relationships between source rock quality and wireline log parameters were established for the Lower Jurassic Posidonia Shale, the most prolific petroleum source rock of Central Europe. Wireline logs used are the gamma ray spectrometry, density, sonic and various resistivity logs. The organic geochemical parameters considered include the organic carbon content, hydrogen index, and the hydrocarbon potential expressed by pyrolysis yield. The case history presented is based on a continuous core through the entire Posidonia Shale interval from a location where this source rock is immature. Care was taken to detect and to avoid samples and log values influenced by bore hole roughness and fractures. Fair correlations were observed only between uranium content from gamma ray spectrometry log and organic carbon content. No correlation was recognized between uranium content and kerogen type as defined by hydrogen indices. For various reasons density, sonic, and resistivity logs did not provide useful data in this study.Three rock units with irregular, high and low uranium contents could be differentiated. Possible causes for this tripartition are different environments during deposition and postdepositional redistribution of uranium during early diagenesis and in association with fractures.     

Similarities and differences in hydrous pyrolysis of biomass and source rocks

In laboratory simulation of oil generation, products from closed systems pyrolysis of immature source rocks in the presence of water gives the closest match to petroleum compositions observed in nature. Fresh biomass can also be converted to fluids by pyrolysis, but in the absence of the sedimentary diagenetic transformations, the initially much higher oxygen content gives high yields of oxygen containing products. In this work, the reactions that occur during hydrous pyrolysis of a Kimmeridge source rock, a brown coal and two polymeric waste materials from alginate production are compared in terms of quantities of the main products and kinetic models of the reaction systems. The biomass pyrolysis and the simulated maturation are described in similar reaction networks. Conversion of biomass to fluids occurred with reaction networks and activation energy distributions comparable to the brown coal, while for the Kimmeridge source rock reactions a simpler reaction network could be used. The biomass samples gave a high degree of conversion to fluid products, and higher yields of bitumen than the coal.     

内蒙古海拉尔盆地侏罗系烃源岩地球化学特征

在海拉尔盆地外围及周边地区选取了31块侏罗系野外烃源岩分析样品,进行了总有机碳、岩石中可溶有机质的抽提和岩石热解分析;针对该区侏罗系烃源岩,共对17口井岩心进行了取样地化分析,利用气相色谱-质谱对烃源岩氯仿抽提物及重要生物标志化合物开展了定性与定量检测,目的是对源岩地球化学特征进行系统评价,为下一步油气基础地质调查奠定基础.结果表明,海拉尔盆地外围及周边地区的侏罗系部分的烃源岩有机质丰度较高,应具备较好的生烃物质基础.海拉尔盆地侏罗系烃源岩总体属于淡水-半咸水环境,有机质类型多样,成熟度普遍较高.甾类化合物中以规则甾烷为主,沉积物中具有较高丰度的以五环三萜烷为主的三环萜烷化合物,显示了其应以藻类生源为主,高等植物为主的陆相沉积中的相对含量则较低.伽马蜡烷的含量普遍很低.OEP呈偶碳数优势,并且缺失高分子正构烷烃,说明烃源岩成熟度演化早期受到了微生物降解作用.     

煤系热解参数及其与有机碳的相关性

通过对煤系热解参数之间及其与有机碳含量的研究,分析了煤系热解参数与有机碳的关系,认为煤系热解参数及有机碳含量变化范围均较宽,不同热解参数之间具有一定的相关性。Ｓ１、Ｓ２和Ｓ１＋Ｓ２与有机碳具正相关关系,基本可以用于评价有机质丰度。热解类型指数Ｓ２／Ｓ３、氢指数、氧指数和Ｓ３明显地受有机碳的影响,尤其Ｓ２／Ｓ３受到的影响更为明显,这样就影响有机质类型的评价。给出了各参数间的相关关系式,这对于煤系烃源     

造山的高原——青藏高原巨型造山拼贴体和造山类型

有机质丰度是传统评价烃源岩方法的重要指标,笔者认为有机粘土复合体是烃源岩有机质的主要赋存形式。有机质生烃反应是一种有机粘土化学反应,有机质脱羧基反应是有机粘土的氧化-还原反应,有机质的热解反应是一个加氢裂解过程,含有剩余C0是烃源岩的基本特征,它说明在烃源岩生烃反应中C0始终是有剩余的,不会因为C0的不足而影响烃源岩的生烃能力。笔者认为制约烃源岩生烃能力大小的不是烃源岩C0的丰度,而是氢的来源和丰度,烃源岩粘土通过吸附水分子为生烃反应提供H+能力(Br nsted酸性)的大小和时间是决定生烃潜力大小的关键。烃源岩粘土的不同催化特性是影响油气组成的重要因素,蒙皂石对甾烷的异构化有明显促进作用。     

海相成熟干酪根生气潜力评价方法研究

高成熟阶段干酪根热解氢指数（HI）非常低,在热成熟度指标镜质组反射率Ro为2.0%以上的Ⅰ或Ⅱ型有机质,一般都在20 mg/gTOC以下,甚至接近0 mg/gTOC,因此,一般认为这种干酪根生烃能力极低。本文通过对不同成熟阶段的干酪根采用元素分析和热解模拟实验相结合的方法,发现HI指数很低的高过成熟阶段干酪根仍然具有一定的生气能力,生气潜力是HI指数的数倍,如HI指数为12 mg/gTOC的样品,H/C原子比为046,生气能力仍然为65 mg/gTOC,占总生烃能力的15%左右,说明成熟—过成熟有机质HI指数不适合衡量生气潜力。同时发现,干酪根生气能力与H/C原子比具有极好相关性,相关系数达到096,通过回归公式所获得有效生气干酪根H/C原子比下限为026。     

Changes in gas composition during simulated maturation of sulfur rich type II-S source rock and related petroleum asphaltenes

Asphaltenes extracted from crude oils are proposed to possess structural features of the related source rock kerogen. For the present study micro-scale sealed vessel pyrolysis (MSSV) and combustion isotope ratio mass spectrometry (GC–C–IRMS) were used to compare gas generation from a whole rock (type II-S kerogen) from southern Italy with that from related sulfur rich asphaltenes isolated from a low maturity heavy crude oil. The purpose of was to determine whether experimental pyrolysis of oil asphaltenes can be used to predict the timing and the chemical and isotopic composition of hydrocarbon gases generated from genetically related kerogen in the source rock during burial maturation. The results show that parameters such as (gas to oil ratio) GOR and oil and gas formation timing are very similar for these two sample types, whereas gas composition, product aromaticity and sulfur content are remarkably different. Slight differences in GOR are mainly due to differences in gas formation characteristics at very high levels of thermal alteration. Secondary gas formation from the whole rock covers a much broader temperature range under geological conditions than that from the asphaltene products. However, it is remarkable that both the onset and the maximum temperature are nearly identical under geological conditions. The observed differences in gas generation characteristics are supported by discrepancies in the carbon isotopic characteristics of the gas range compounds and indicate different precursors and/or mechanisms for gas generated from whole rock and asphaltenes.     

内蒙古林西地区上二叠统林西组烃源岩有机岩石学特征

内蒙古东部林西地区是二连盆地外围石炭-二叠系油气勘探的重要潜力区之一．为了研究上二叠统林西组烃源岩有机岩石学特征,对野外露头剖面的林西组烃源岩开展了总有机碳、有机显微组分、镜质体反射率及岩石热解等测试分析.结果表明：林西组烃源岩总有机碳分布在0.63%～1.30%,平均为0.87%,所有样品含量均大于0.6%;有机显微组分分布在0.27%～3.66%,平均值为2.08%,其中95.24%的样品达到1.0%以上,表明有机质丰度达到了“较好”至“好”级别;镜质体反射率分布在1.26%～2.58%,平均值为1.88%,其中90.47%的样品含量大于1.3%,镜质体反射率较高,表明有机质成熟度达到“高成熟”至“过成熟”阶段;岩石热解氢指数分布在8×10-3～89×10^-3,平均为27.52×10^-3,表明有机质类型归属于Ⅲ型.综合评价表明林西地区上二叠统林西组烃源岩属于“较好—好”烃源岩,生烃潜力较大,具有较好的油气资源前景.     

中国海相不同类型原油与沥青生气潜力研究

本文通过固体沥青、沥青砂岩及加入不同介质原油与稠油的加水密闭热压模拟实验,对比研究了海相原油与沥青的气体产率特征、生气潜力及其影响因素.结果表明原油与沥青的生气潜力除与岩性、演化程度有关外,还与其所含可溶有机质性质和组成等密切相关,H/C原子比越大,最大烃气产率越高,生烃气潜力越大.储集岩或运移途径岩石中的原油与沥青,当其再次达到成熟-高成熟阶段时,可以作为新的轻质油气或者天然气源岩.