凝析油形成新模式——原油蒸发分馏机制研究

经典的石油生产理论认为凝析油是源岩高成熟阶段、或是陆相有机质于低成熟阶段的直接产物。本文在资料、数据分析的基础上结合我国塔北海相油田的实际地质地化资料提出原油蒸发分馏机制是凝析油形成的一种重要途径，并确认了塔北油田的诸多原油曾曹受了程度不一的蒸发分馏作用具有成熟度正常的凝析油形成。     

东海盆地西湖凹陷油岩地球化学特征及原油成因来源

东海盆地西湖凹陷具有大量的原油资源,但对于原油成因讨论较少.采集西湖凹陷多个油样和岩样,利用气相色谱和傅里叶红外光谱等手段,全面分析了该区烃源岩和原油的地球化学特征,综合讨论了原油来源以及凝析油和高蜡轻质油的成因.研究结果表明,平湖组煤系源岩均处于热演化的成熟阶段,其中碳质泥岩和煤岩以陆源生物为主要生源,其干酪根类型为Ⅲ型,暗色泥岩则具有陆源生物和水生生物双重生源贡献,其干酪根类型Ⅱ-Ⅲ型,同时碳质泥岩和煤的生油潜力远高于泥岩.原油主要为凝析油和轻质油,凝析油具有低密度、低蜡等“六低一高”的特点,轻质油具有高蜡特质,而且轻烃组分有明显差异.生标参数显示大部分原油为腐殖型,少部分原油表现出具有腐殖和腐泥母质的特点,同时该区原油均处于中等成熟阶段.油油对比和油岩对比表明大部分油来自平湖组碳质泥岩和煤岩,具有典型Ⅲ型腐殖油的特征;少部分油来自暗色泥岩,具有Ⅱ-Ⅲ型油的特征(总体上仍偏腐殖型).凝析油和轻质油的物性及轻烃组分的差异与源岩母质无关.凝析油是干酪根在成熟演化阶段生成的原油遭受蒸发分馏作用的结果,高蜡轻质油除了是“蒸发分馏作用”的残余油外,还有部分是“混合作用”的结果.      

塔中台盆区原油正构烷烃摩尔浓度分布特征及意义

塔里木盆地塔中地区原油性质的多样性和复杂性十分罕见;分析表明,成熟作用和源岩相很可能是原油多样性的次要因素,主要影响因素可能与多期成藏或成藏后储层内的次生蚀变作用有关。本文对照正构烷烃摩尔浓度分布图版,辨别了塔中地区不同构造单元原油正构烷烃摩尔浓度的分布类型,分析了原油遭受次生蚀变作用的程度,以及蒸发分馏作用、气洗作用发生的原因及其对原油物性的影响。结果表明,由于运移通道以及与油气源的距离等因素,从塔中Ⅰ号断裂坡折带至中央断垒带,蒸发分馏作用和气洗作用发生的频率逐渐降低,但基态原油分布频率有增高的趋势。并且Ⅰ号断裂坡折带部分凝析油、高蜡油的形成主要与上述蒸发分馏、气洗、晶析等储层内的次生蚀变作用有关。     

塔里木盆地气－液溶解平衡机制下的原油轻烃行为及其地质意义

塔北地区普遍存在气顶型凝析气藏和带油环的凝析气藏。与传统烃类热演化理论相矛盾的是：１）天然气的成熟度远高于油环原油或凝析油；２）高－过成熟天然气与同藏的原油间存在明显的物性不匹配。结合地质背景，认为这种矛盾是由后期形成的干气进入已形成的油藏并溶解原油轻烃这一过程所致，凝析气中的轻烃是气－液溶解平衡的产物。地质历史时期凝析气与油环分离或产生凝析油气藏或混入其它油藏的蒸发分馏作用过程导致了轻烃的油藏再分配，形成了塔北地区纵向上原油轻烃的“反序”分布趋势及某些参数的异常分布。认为烃类的气－液相溶解平衡作用是原始原油轻烃分布特征后期演变的主要控制机制之一。其实质是不同性质轻烃气液两相差异性分配基础上的物理化学分异过程。     

塔里木盆地气－液溶解平衡机制下的原油轻烃行为及其地质意义

塔北地区普遍存在气顶型凝析气藏和带油环的凝析气藏。与传统烃类热演化理论相矛盾的是:１）天然气的成熟度远高于油环原油或凝析油；２）高－过成熟天然气与同藏的原油间存在明显的物性不匹配。结合地质背景，认为这种矛盾是由后期形成的干气进入已形成的油藏并溶解原油轻烃这一过程所致，凝析气中的轻烃是气－液溶解平衡的产物。地质历史时期凝析气与油环分离或产生凝析油气藏或混入其它油藏的蒸发分馏作用过程导致了轻烃的油藏再分配，形成了塔北地区纵向上原油轻烃的“反序”分布趋势及某些参数的异常分布。认为烃类的气－液相溶解平衡作用是原始原油轻烃分布特征后期演变的主要控制机制之一。其实质是不同性质轻烃气液两相差异性分配基础上的物理化学分异过程。     

松辽盆地北部深层凝析油及油型气的成因研究

松辽盆地北部深层发现的凝析油及油型气扩大了油田的勘探潜力.应用单体烃碳同位素、生物标志化合物等分析技术,结合地质背景对凝析油、天然气和固体沥青进行的地球化学研究表明:深层凝析油包括煤成凝析油和泥质烃源岩形成的凝析油,前者芳烃含量高、单体烃碳同位素重,后者饱和烃含量高、单体烃碳同位素轻,生物标志化合物对比,二者均来自于沙河子组烃源岩;油型气甲烷碳同位素轻,一般小于-45‰,且甲烷与乙烷之间碳同位素分馏明显,属原油裂解成气特征,油型气与煤型气混合可能是深层天然气碳同位素系列倒转的重要原因之一;火山岩储层中的固体沥青有机地球化学分析,有机碳含量0.08%～0.16%,氢指数49～297 mg/g,Ro大约为1.87%,表征固体沥青现今的成烃潜力较小,原油向天然气转化主要发生在高成熟阶段的晚期,对应的地质年代大约是嫩江组-明水组沉积末(80～65 Ma).原油向天然气转化的事实启示,深层天然气勘探要兼顾古油藏的研究.     

松辽盆地北部深层凝析油及油型气的成因研究

松辽盆地北部深层发现的凝析油及油型气扩大了油田的勘探潜力。应用单体烃碳同位素、生物标志化合物等分析技术，结合地质背景对凝析油、天然气和固体沥青进行的地球化学研究表明：深层凝析油包括煤成凝析油和泥质烃源岩形成的凝析油，前芳烃含量高、单体烃碳同位素重，后饱和烃含量高、单体烃碳同位素轻，生物标志化合物对比，二均来自于沙河子组烃源岩；油型气甲烷碳同位素轻，一般小于-45‰，且甲烷与乙烷之间碳同位素分馏明显，属原油裂解成气特征，油型气与煤型气混合可能是深层天然气碳同位素系列倒转的重要原因之一；火山岩储层中的固体沥青有机地球化学分析，有机碳含量0．08％～0．16％，氢指数49～297mg／g，R0大约为1．87％，表征固体沥青现今的成烃潜力较小，原油向天然气转化主要发生在高成熟阶段的晚期，对应的地质年代大约是嫩江组一明水组沉积末(80～65Ma)。原油向天然气转化的事实启示，深层天然气勘探要兼顾古油藏的研究。     

凝析油的多种成因概述

本文概述了国内外对凝析油成因类型及地质产状的研究。凝析油是特定物化条件下液态烃逆蒸发的产物,不仅可以形成于有机质演化的高成熟阶段,也可以形成于中-低成熟阶段。凝析油按其成因可以分为三类。高成熟腐泥型凝析油最为重要。它是高温下高分子量烃类热裂解的产物,多产于盆地深处,与高成熟的生油岩(R_0＞1.3%)有关。低(未)成熟树脂型凝析油是以树脂体为主的有机质在低成熟阶段降解产物。本文介绍了有关树脂体热解色谱分析成果。其热解温度低,产物中富含倍半萜和三环双萜。该类凝析油与含过渡型有机质的低中等成熟度的生油岩有关(R_0;0.4—1.0%)。煤型凝析油是煤系地层中类脂组分在气-肥煤阶段热解的产物。具短侧链的镜质组也可以形成低分子量烃类。该类凝析油富含芳香烃。煤系地层中显微组分的分异影响了凝析油、轻质油和高蜡油的分布。     

松辽盆地齐家-古龙凹陷凝析油气藏成因

为了阐明齐家-古龙凹陷所发现的凝析油气藏的成因, 结合研究区凝析油气藏所处的地质背景、油油对比认识, 设计进行了原油的热蒸发模拟实验.结果表明, 区内凝析油与下伏的黑油同源, 这暗示了其次生成因; 实验室热蒸发模拟实验支持上部的凝析油为下部黑油的热蒸发作用所产生.这种热蒸发作用可能是通过断层或微裂缝实现的.热蒸发成因将使区内形成大规模的凝析气藏的可能性减小, 勘探的有利目标应该在有利于蒸发作用发生的通道、但目前埋深仍然较大、温压较高的地区.      

白云凹陷原油金刚烷化合物研究

针对白云凹陷油气共存的分布格局,轻质油藏、挥发性油藏及凝析油气藏中原油或凝析油因常规的甾萜类异构化参数等均已接近或达到其平衡值,难以有效判断其成熟度,导致无法准确界定该区挥发性油藏及凝析油为原生热成因抑或油藏受晚期天然气改造而成的次生成因的问题。本次研究采用气相色谱-质谱-质谱(GC-MS-MS)方法对白云凹陷原油及凝析油中金刚烷类化合物进行分析及绝对浓度测定,通过金刚烷参数指标对已发现原油及凝析油成熟度进行了界定,并探讨凝析油成因。研究表明,白云凹陷不同构造原油及凝析油成熟度差异大,白云主洼北部番禺低隆起和白云东洼凝析油金刚烷浓度在5000～10000μg/g之间,为高成熟阶段与天然气伴生的原生性凝析油,根据金刚烷指标参数推算的等效镜质组反射率(Rc)为1.3%～1.6%;白云东洼原油、白云主洼东部凝析油与挥发性油藏、油藏轻质油以及白云西洼挥发油、轻质油金刚烷浓度多在4000μg/g以下,为生油高峰后期产物,根据金刚烷指标参数推算的Rc为1.1%～1.3%,且白云主洼东部、白云西洼凝析油及挥发油可能为成熟阶段的原油遭受天然气改造而成的次生凝析油或挥发油。     

我国凝析油的成因类型及其地球化学特征和意义

近十几年的勘探实际表明，在我国一些含油气盆地中，许多天然气藏均伴生一定量的凝析油（或轻质油）。按母质类型可将凝析油分为海相腐泥型有机质生成的凝析油、煤系地层腐殖质有机质生成的凝析油、陆相混合型有机质生成的凝析油。本文较详细地从成因机理上讨论了这三种不同成因凝析油的形成特点。海相腐泥型有机质一般在有机质热演化达到高成熟－过成熟阶段，由干酪根或早期形成的高分子液态烃热裂解才形成凝析油。煤系地层中腐殖型有机质从低成熟到过成熟各个阶段所生成的一定量的液态烃一般主要以凝析油的状态与天然气相伴生。陆相混合型有机质从低成熟到过成熟阶段也都可能形成凝析油。利用凝析油单体烃的组份特征，石蜡指数和庚烷值对我国主要含油气盆地凝析油的成熟度进行了计算，所得结果，大都与地质实际相吻合。研究表明我国凝析油成熟度的分布范围从低成熟到过成熟均有。三种不同成因的凝析油其地球化学特征具有一定差异，煤系地层腐殖型有机质形成的凝析油从组份来讲相对富含芳烃，其芳烃含量一般为１６.２～２３.５%，饱和烃/芳烃值为３.２～５.２，同时其姥鲛烷/植烷值相对较高，通常均大于３；而海相腐泥型有机质生成的凝析油则相对富含饱和烃，其饱/芳比值为１１.８～１８.２，同时姥蛟烷/植烷值较低，一般小于1。陆相混合型有机质生成的凝析油则介于二者之间。三类不同成因的凝析油它们的芳烃组份(蔡系、联苯系和药系)和低分子生物标记物(菇类化合物)以及烷烃和芳烃组份的碳同位素组成都具有明显的差异。利用凝析油的这些地球化学特征可以有效地判识凝析油的成熟度和成因类型，从而确定与之相伴生的天然气的成因或来源。     

Relationship between rank and distribution of methylaromatic hydrocarbons for condensates of different origins

Aromatic hydrocarbon fractions from thirty gas condensates have been analysed by capillary GC and high resolution Shpol'skii spectroscopy for the determination of the relative distribution in methylphenanthrene (MP), dimethylphenanthrene (DMP) and methylpyrene (MPy) series. The measured maturity indices, MPI, DMPI and MPyI which appeared previously suitable for rocks, coals and crude oils have been tested for the recognition of rank levels of condensates. MPI and DMPI exhibit a remarkedly similar evolution which allows the differentiation of the samples analysed in these works. Such studies extend the applicability of alkylaromatic hydrocarbon ratios to the characterization of maturity level of condensates which range from immature-marginally mature to overmature samples, partially biodegraded or not.     

Assessment of generation temperatures of crude oils

Biological marker maturity parameters were used to estimate the minimum HC generation temperatures of crude oils from Eastern Hungary. More than 50 oils and oil shows were analysed. Molecular- and homologous-ratios of biological marker compounds (triterpanes, steranes, mono- and triaromatic steroid hydrocarbons) were used as maturation parameters. The oils have at least five maturity stages, i.e. they have been generated under different thermal conditions. The highest reservoir temperature in each group was chosen as the best estimate of the groups' temperature just below the generation temperature, i.e. reservoirs of the group might be expected to be at shallower depths (lower temperatures) than those of the generation zone due to vertical migration into pools. For each maturation level, a threshold temperature range for genesis was inferred from reservoir temperatures; they are from 130–135°C for the least mature oils to 210–215°C for the most mature oils. In the least mature oils cracking was not observed, hence carbon–carbon cracking reactions had not taken place during their genesis. The most mature oils are intensively cracked oils; they are almost condensates. Two major genetic groups (families) of oils were found in the area. Both are present in each maturation level. The effects of migration were checked, and no influence on maturation was found. A number of the oils are in overpressured reservoirs within, or just above, the zone of the present-day active oil generation, hence the present-day temperatures of the pools must have been maximum temperatures. Contrary to the traditionally accepted temperature range for petroleum generation–maturation reactions (50–150°C), there is strong evidence from this study that the onset of oil generation requires temperatures higher than 130°C and is still proceeding above 215°C.     

渤海湾盆地渤中19-6气田凝析油特征及油气关系

2018年中国东部最大整装凝析气田——渤中19-6气田的发现,一举打开了渤海湾盆地深层天然气勘探的新领域,展现了油型盆地天然气勘探的巨大潜力.渤中凹陷发育多套不同成熟度的烃源岩,位于渤中凹陷西南部的渤中19-6气田凝析油与天然气并存,近年来于该地区的天然气成因及形成条件多有研究,但是对于凝析油的形成则少有研究.本文以渤...     

Carbon isotope geochemistry of Paleozoic oils from Big Horn Basin

Twenty crude oils from Paleozoic reservoirs in the Big Horn Basin. Wyoming were fractionated into light hydrocarbons, saturates, monoaromatics. diaromatics, polyaromatics-and-polars. and asphaltenes. Amounts and isotopic composition of each fraction were found to be internally consistent with the degree of maturation of the oil. confirming the established single source origin for these oils. A variation of approximately three per mil in the carbon isotopic composition of the whole oil and individual fraction was explained as being caused by maturation. The isotope-type-curves for these oils, the variations in isotopic composition as a function of compound group-type, were not found to be as simple as commonly believed. Other alteration processes, such as migration and deasphalting, might have influenced the pattern of the isotope distributions among fractions. The conservative nature of mass balance and subsequent isotope flows among various fractions of crude oil showed that the maturation of crude oil consists of consecutive processes leading from larger and more polar components into smaller and less polar components culminating in natural gas. Calculations were made to project the amount of condensates associated with the crude oils, and the amount of natural gas which had been generated from crude oils of a given maturity.     

Crystallization sequences of Ca-Al-rich inclusions from Allende: An experimental study

The equilibrium crystallization sequence at 1 atmosphere in air of a melt corresponding in composition to the average composition of Type B Ca-Al-rich inclusions from the Allende meteorite is: spinel (1550°C) → melilite (1400°C; Åk22) → anorthite (1260°C) → Ti-Al-rich clinopyroxene (1230°C; “Ti-fassaite”). The melilite becomes increasingly åkermanitic with decreasing temperature. The pyroxene is similar in composition to fassaites from Type B inclusions. Preliminary results suggest that the crystallization sequence is similar at oxygen fugacities near the iron-wüstite buffer.The results of these experiments have been integrated with available phase equilibrium data in the system CaO-MgO-Al₂O₃-SiO₂TiO₂ and a phase diagram for predicting the crystallization sequences of liquids with compositions of coarse-grained Ca-Al-rich inclusions has been developed.Available bulk compositions of coarse-grained inclusions form a well-defined trend in terms of major elements, extending from Type A and Bl inclusions near the spinel-melilite join to more pyroxene-rich Type B2 inclusions. The trend deviates from the expected sequence of solid condensates from a nebular gas at P = 10^?3 atm if pure diopside is assumed to be the clinopyroxene that condenses. The Type A-B1 end of the trend is similar in composition to calculated equilibrium condensates at 1202–1227°C and the trend as a whole parallels the sequence of condensates expected from diopside condensation at ~ 1170°C. The trend is consistent to first order with the condensation of solid Ti-rich fassaite in place of pure diopside at higher temperatures than those at which pure diopside is predicted to condense. Partially molten condensates may be likely in this case or if the nebular pressure is higher than 10^?3 atm.     

高蜡凝析油或轻质油的分布特征与成因机理

介绍了中国部分含油气盆地中的高蜡凝析油或轻质油的地球化学特征及其在地域上和层位上的分布规律,并以大港千米桥古潜山高蜡凝析油气藏、吐哈盆地西部凹陷部分高蜡凝析油田或轻质油田、塔里木盆地柯克亚凝析油气田、盐城凹陷的高蜡凝析油藏为例,总结了几种高蜡凝析油或轻质油的成因模式,即煤系腐殖型烃源岩热演化生烃、运移分馏作用、混合作用或"气洗作用"等.     

Condensate glasses from the Zhamanshin crater. II. Zhamanshinites

Condensate glasses of two types were found during the SEM and TEM investigation of zhamanshinite samples within volumetrically dominant melt glass: silica-rich glasses similar to irghizite-type condensates and moderately silicic sodium-rich glasses deposited in voids in zhamanshinites. The latter are characterized by globular morphology, high contents of volatile components, and presence of inclusions a few hundred nanometers in size. The differences of the zhamanshinite-type condensate glasses from irghizitetype condensates are related to their slower cooling and closeness of the pore space system. The results of the investigation of melt glasses of various color groups from the same samples are presented for comparison. The glasses of each group appeared to be homogeneous at the SEM level, but inhomogeneous at the TEM scale.     

High-temperature condensates in chondrites and the environment in which they formed

Chemical compositions of melilitee and titaniferous pyroxenes in calcium- and aluminum-rich inclusions in carbonaceous chondrites are consistent with their origin as hightemperature condensates from a gas of solar composition. Thermodynamic calculations indicate that the highest temperature minerals equilibrated with the gas at temperatures in excess of 1400°K. The lack of evidence for direct condensation of gas to liquid enables us to set an upper limit to the pressure when the inclusions formed which may be as low as 2.2 × 10^?3atm. Glasses, which are commonly found in chondrules, are interpreted as quench products of liquids formed by secondary reheating of primary solid condensates. The high-temperature inclusions constitute evidence that accretion of grains to cm-sized objects occurred at a very early stage in the evolution of the solar nebula.