High-molecular heteroatomic components of crude oils of the Timan–Pechora petroliferous basin

Based on the experimentally measured parameters of elemental composition, average molecular masses, and PRM spectrometry data, we calculated the average structural parameters of resin and asphaltene molecules in Paleozoic crude oil of some oilfields in the Timan–Pechora petroliferous basin. The values of the structural parameters of cyclic and aliphatic fragments in the molecules of resin–asphaltene components of the crudes studied here are within the ranges established earlier for high-molecular compounds of crudes from other petroliferous basins. The average structural-group characteristics of resins in crudes from carbonate reservoirs vary over narrow ranges of values independently of the age and depth of occurrence of the reservoir. The resinous fractions of crudes from terrigenous horizons show symbatic enrichment with paraffin fragments and depletion with naphthene fragments of molecules with depth. This points to the presence of a paragenesis of petroleum hydrocarbons and heteroatomic compounds in the Earth’s interior.     

The influence of biodegradation on resins and asphaltenes in the Liaohe Basin

Asphaltenes are traditionally considered to be recalcitrant to microbial alteration. Resins and asphaltenes of seven biodegraded oils extracted from reservoir cores of two columns (Es3 and Es1) of the Lengdong oilfield in the Liaohe Basin, NE China, were studied to test this hypothesis. Elemental (C, H, N, O, S) and isotopic compositions (δ¹³C and δ¹⁵N) were measured, FT-IR was used to study the oxygenated functionalities of both resins and asphaltenes, and Py–GC–MS was used to elucidate how alkyl side chains of asphaltenes were altered during biodegradation. We conclude that the products of biodegradation, such as carboxylic acids, phenol and alcohols, may not only contribute to the resin fraction of crude oils, but also are linked with functionalities of resins and asphaltenes. The amount of asphaltenes increases because some resin molecules are enlarged and their polarity increased such that they can be precipitated by hexane as newly generated asphaltenes. Thus, the hydrocarbons that are progressively consumed during biodegradation can pull the δ¹³C of asphaltene fraction closer to the δ¹³C of the altered resins and hydrocarbons that were consumed.     

The use of carbon and sulfur isotopes as correlation parameters for the source identification of beach tar in the southern California borderland

Carbon and sulfur isotope ratios and total sulfur content are used to correlate beach tars depositing near Los Angeles with their probable sources. Analysis is confined strictly to the asphaltene fraction of petroleum owing to the insensitivity of this fraction to weathering processes.The δ¹³C, δ³⁴S and % S of the asphaltene fraction of natural offshore seep oils range from ?22.51 to ?23.20%., +7.75 to + 15.01%. and 4.45 to 8.27%, respectively. Values for local offshore production wells overlapped those for the natural seepage, ranging from ?22.10 to ?22.85%., ?2.96 to 13.90%., and 0.81 to 8.00%. Analytical values for these parameters show that tanker crudes imported into the area are not similar to the California oils. Analysis of the same parameters in beach tars collected during 1976–1977 indicates a close match with the potential source oils, thus it is concluded that these parameters are useful for identifying petroleum sources, even after 2–4 weeks of weathering. Results indicate that 55% of the tars in Santa Monica Bay are derived from natural oil seepage 150km to the northwest at Coal Oil Point, 26% are derived from natural oil seepage in Santa Monica Bay, and 19% are derived from unknown sources.Models of tar transport are inferred which are consistent with the seasonal deposition pattern. Tar from Coal Oil Point natural oil seeps is transported southward in the southern California gyre during the spring, summer and fall seasons, but probably undergoes northward transport during the winter season due to the surfacing of the Davidson Current. Tar from the Santa Monica Bay natural oil seeps moves onshore, but deposition rate seems to depend on seepage flow rate.     

Evaluating the timing of oil expulsion: about the inverse behaviour of light hydrocarbons and oil asphaltene kinetics

This paper deals with natural temperature records in the heavy (asphaltenes) and the light fractions (C₇—light hydrocarbons) of petroleum. Two sets of marine oils formed from different source rocks and petroleum systems were studied using asphaltene kinetics and light hydrocarbon analysis. Both fractions have been reported to contain information about the temperature the respective oils have been exposed to in the subsurface. These indicated temperatures generally correspond to the conditions in the source rock when expulsion occurred. Bulk kinetic analysis of reservoir oil asphaltenes as well as light hydrocarbon (LH) analysis (of dimethylpentanes) were used here in order to evaluate the expulsion temperatures. Surprisingly, when considering information coming from both fractions, an inverse trend between LHs expulsion temperatures (Ctemp) and asphaltenes (Tasph.) can be observed—high T_asph (asphaltene temperatures) occur with low LH C_temp (light hydrocarbon expulsion temperatures) and low T_asph can be observed when Ctemp is high. These differences are of fundamental importance for the use of such geochemical data in calibrating numerical basin models. The reason for this inverse behaviour is possibly due to the different expulsion behaviour of light hydrocarbons and the heavy fraction of oils, especially when the source rocks contain only moderate amounts of organic matter. In addition it has to be considered that the temperature predictions obtained using asphaltene kinetic analysis are related to the onset temperature of petroleum expulsion, while light hydrocarbons provide, at best, average expulsion temperatures.     

The physicochemical characteristics and hydrocarbon composition of crude oils of the Timan–Pechora petroliferous basin

The total hydrocarbon composition and average structural-group characteristics of typical Paleozoic crude oils of the Timan–Pechora petroliferous basin are described. The hydrocarbon (HC) types of crudes are compared, which were conventionally determined from the composition of their gasoline fractions, by mass-spectrometric analysis of the HC composition of crudes, and by structural-group analysis of crudes, based on radiospectrometric data. The analyses have shown the presence of 30 structural types of HCs with up to 43 carbon atoms. The whole series of members up to C43 are specific only for HCs with no more than three rings in the molecule. It has been established that the carbonate strata in the basin under investigation, independently of the depth of their occurrence and the age of the host deposits, generate and accumulate heavy high-resin high-sulfur oils rich in alicyclic structures and assigned by HC composition to the naphthene–methane or even naphthene type. Terrigenous reservoirs here abound in crudes of methane–naphthene type. The contents of sulfur and resinous substances and the fraction of carbon atoms in alicyclic HC structures decrease as the depth of occurrence of the host deposits grows, thus reflecting the known gradual process of “methanization” of petroleum composition.     

江汉盐湖盆地中高成熟原油的地球化学特征及油源探讨

江汉盐湖盆地中钟76井潜江组潜四段3300m以下发现的高成熟轻质原油,其基本特征是：饱和烃含量特高,非烃和沥青质含量很低;富含植烷、伽马蜡烷、C35升藿烷、孕甾烷和C27胆甾烷等指示高盐度、强还原环境的生物标志物。尤其明显的是C27-C29甾烷异构化程度高,αββ20R和20S峰十分突出,C29甾烷的两个参数值均大于等于0．5,指示了原油的成熟度已处于高成熟阶段。根据油源条件分析,认为该地区潜江组潜一段至潜四上段烃源岩埋深浅于3000m,P值小于1％,处于未成熟-成熟阶段,不具有形成高成熟原油的可能性,只有潜四下段烃源岩已进入生烃高峰高成熟早期阶段,能够提供轻质原油的油源。生物标志物多项地球化学资料及参数综合对比表明,本区两种成因类型的高成熟原油,其油源确系来自潜四下段两种不同沉积环境形成的泥质灰岩和灰质泥岩,明显具有近源运移聚集、自生、自储的特征,这展示了该地区潜四下段及其下覆的古潜山深层油气勘探有着良好的前景。     

Geological and geochemical studies of heavy oil reservoirs in China

Thickened heavy oils in China are genetically characteristic of continental fades. As to their physico-chemical properties, these oils are very high in viscosity and low in sulphur and trace element contents. In the group constituents, the concentrations of non-hydrocarbons and asphaltene are very high but those of saturated hydrocarbons and aromatics are very low. The gas chromatograms of alkanes show that these heavy oils have high abundances of iso - alkanes and cyclic hydrocarbons. In all the steroids and terpenoids, bicyclic sesquiterpenoids, tricyclic diterpenoids, re - arranged steranes and gammacerane are strongly biodegradation - resistent. The formation of heavy oil reservoirs is controlled mainly by late basin ascendance, biodegradation, flushing by meteoric water and oxidation in the oil - bearing formations. According to their formation mechanisms, heavy oil reservoirs can be classified as four categories: weathering and denudation, marginal oxidation, secondary migration and thickening of bottom water. Spatially, heavy thick oil reservoirs are distributed regularly: they usually show some paragenetic relationships with normal oil reservoirs. Heavy oil reservoirs often occur in structural highs or in overlying younger strata. Their burial depth is about 2000m. Horizontally, most of them are distributed on the margins of basins or depressions. Weng Weijin, Guo Jiaofeng and Li Huaqi also took part in this work.     

垦西特稠油化学降粘机理的研究

详细研究了胜利油田垦西特稠油中的胶质、沥青质用降粘剂处理前后的红外特征吸收峰和透射电镜照片的变化。由红外光谱数据和透射电镜分析可知,降粘剂分子借助强的形成氢键的能力和渗透、分散作用进入胶质和沥青质片状分子之间,破坏了胶质、沥青质分子平面重叠的聚集体,使聚集结构变得疏松,表明聚集有序性降低是稠油降粘的主要机理。     

Re-Os elemental and isotopic systematics in crude oils

Analysis of 12 worldwide oil samples show that Re and Os abundances are positively correlated with the asphaltene content of oil. Light oils with <1% asphaltene content have basically no measurable Re or Os. Within oil, Re and Os are present dominantly in the asphaltene fraction (>83%), with <14% Re and Os found in the maltene fraction, this distribution is similar to other trace metals such as V and Mo. Rhenium and Os could be present in oil as metalloporphyrin complexes, but given their abundance in the asphaltene component they are also likely bound by heteroatomic ligands. The ¹⁸⁷Re/¹⁸⁸Os and ¹⁸⁷Os/¹⁸⁸Os values in asphaltene calculated at the estimated time of oil generation (Os_i) are similar to those of the whole oil, as expected from the elemental results. This suggests that the asphaltene fraction can be used to approximate the Re-Os isotopic compositions of the whole oil. Os isotopic compositions in oils show a considerable range, from ¹⁸⁷Os/¹⁸⁸Os of 1.9-6.0, and they correlate positively with the age of the proposed source rock. Re/Os ratios also show a large range and overlap the Re/Os ratios found in typical oil source rocks such as organic rich shale.     

Carbon isotopic composition of individual n-alkanes in asphaltene pyrolysates of biodegraded crude oils from the Liaohe Basin, China

Biodegraded oils are widely distributed in the Liaohe basin, China. In order to develop effective oil-source correlation tools specifically for the biodegraded oils, carbon isotopic compositions of individual n-alkanes from crude oils and their asphaltene pyrolysates have been determined using the gas chromatography–isotope ratio mass spectrometry technique. No significant fractionation in the stable carbon isotopic ratios of n-alkanes in the pyrolysates of oil asphaltenes was found for anhydrous pyrolysis carried out at temperatures below 340°C. This suggests that the stable carbon isotopic distribution of n-alkanes (particularly in the C₁₆–C₂₉ range) in the asphaltene pyrolysates can be used as a correlation tool for severely biodegraded oils from the Liaohe Basin. Comparison of the n-alkane isotopic compositions of the oils with those of asphaltene pyrolysates shows that this is a viable method for the differentiation of organic facies variation and post-generation alterations.     

海底冷泉渗漏流体的总S和总Ca浓度变化及影响因素

通过对卡斯卡迪亚水合物脊和墨西哥湾布什山冷泉渗漏流体的原位测定总S和总Ca浓度分析,发现渗漏流体的总S和总Ca浓度约为海水浓度的50%~70%,讨论了冷泉流体活动特征以及流体的总S和总Ca浓度的控制因素。在这两个冷泉渗漏区海底渗漏流体的总S和总Ca浓度随时间变化的趋势比较一致,均是发生在流体渗漏流量速率高频变化周期。流体的总S和总Ca浓度的降低,可能主要受冷泉区海底广泛存在的甲烷缺氧氧化作用控制,同时也可能受到水合物分解、粘土矿物的去水反应和油气藏破坏产生的纯水的稀释作用的影响。     

Geochemical significance of chemical composition and ESR properties of asphaltenes in crude oils from Alberta,Canada

More than 100 crude oils and 12 oil sands from Alberta, Canada, from stratigraphie units ranging in age from Upper Cretaceous to Middle Devonian, were processed to separate the asphaltenes which were then analysed for C, H, N, O and S and the ESR spectra run to determine g-value, spin number and line width. A factor analysis of these data, together with selected crude oil and reservoir properties, was interpreted in terms of a number of non-thermal processes which can affect the content and composition of asphaltenes during and after thermal maturation. Experiments on the effect of temperature on the signal intensity of free radicals indicate that more than half, and possibly all, the free radicals observed in asphaltenes must arise from charge transfer or closely related equilibria. An important solvent effect is demonstrated in further experiments, in which the more polar the solvent, the more the solvent dispersive forces overcome the associative forces of the asphaltene layers thus leading to lower molecular weights and a change in the charge transfer forces responsible for the ESR signal. The average molecular weight of asphaltenes from heavy, asphaltic, biodegraded crude oils and oil sands is considerably greater than the average molecular weight of asphaltenes from the more paraffinic, mature, non-biodegraded crude oils, and it seems likely that the differences in molecular weight of these asphaltenes are due to the solvent effect of the crude oils, and thus the laboratory observations have been confirmed in the Alberta basin.     

Pyrolysis of asphaltenes: a source of geochemical information

Pyrolysis of asphaltenes from crude oils yields significant amounts of crude oil-like material. Studies of asphaltenes and their pyrolysis products from biodegraded and non-biodegraded oils show that biodegradation does not affect the composition of asphaltene. The overall composition of the oil produced from them on pyrolysis is similar to, yet significantly different from, that of the parent oil. From these compositional differences, it is concluded that asphaltene and its pyrolysis products contain geochemical information which is characteristic, and therefore may shed light on the history of the oil prior to asphaltene formation.     

Geochemical study of a series of biodegraded oils: Microtexture and structure of their coked asphaltenes

The asphaltenes extracted from eight oils and a bituminous sand were coked and studied by transmission electron microscopy and X-ray diffraction to observe the microtextural and structural changes caused by increasing biodegradation. The pyrolysis effluents of asphaltenes were analyzed by chromatography. Biodegradation causes an increase of aromatic hydrocarbons and sulfur during heat-treatment of isolated asphaltenes. During thermal treatment, the more biodegraded the sample, the earlier and the greater the release of aromatics. The microtexture of the asphaltene coke is very sensitive to this early release of aromatics and is used to classify samples as to their degree of biodegradation. In the series, two groups were distinguished.     

硫酸盐热化学还原作用的启动机制研究

硫酸盐热化学还原作用(TSR)是导致高含硫化氢天然气生成和聚集、碳酸岩盐储层酸化和溶蚀的重要因素,是地质盆地内烃-水-岩三者之间的复杂反应。本文利用黄金管热模拟实验,对TSR反应的可能启动机制及控制因素进行了研究。通过不同盐溶液与原油的热解实验,证实了硫酸盐的存在是启动TSR反应的必要因素,MgSO4比CaSO4和Na2SO4更容易启动TSR反应,体系中盐度的增加会加速H2S的生成。实验结果表明,不同水介质条件下,TSR反应的程度与溶液的离子强度呈正相关,弱酸性环境并不足以启动TSR反应;原油中不稳定含硫化合物的含量越高越有利于TSR反应的发生,饱和链烷烃比原油中其它组分更容易引发TSR反应,且大分子烷烃比小分子烷烃更容易被硫酸盐氧化。     

Geological and Geochemical Studies of Heavy Oil Reservoirs in China

Thickened heavy oils in China are genetically characteristic of continenta .As to their physico-chemical properties,these oils are very high in viscosity and low in sulphur and trace element con-tents.In the group constituents,the concentrations of non-hydrocarbons and asphaltene are very high but those of saturated hydrocarbons and aromatics are very low.The gas chromatograms of alkanes show that these heavy oils have high abundances of iso-alkanes and cyclic hydrocarbons.In all the steroids and terpenoids ,bicyclic sesquiterpenoids,tricyclic diterpenoids,re-arranged steranes and gammacerane are strongly bildegradation-resistent.The formation of heavy oil reservoirs is controlled mainly by late basin ascendance,biodegradation,flushing by meteoric water and oxidation in the oil-bearing formations.Ac-cording to their formation mechanisms,heavy oil reservoirs can be classified as four categories:weathering and denudation,marginal oxidation,secondary migration and thickening of bottom water .Spacially,heavy thick oil reservoirs are distributed regularly:they usually show some paragenetic relationships with normal oil reservoirs.Heavy oil reservoirs often occur in structural highs or in overlying younger strata.Their burial depth is about 200m.Horizontally,most of them are distributed on the margins of basins or depressions.     

成岩作用对储层孔隙的影响--以辽河盆地荣37块气田下第三系为例

通过对岩芯、铸体薄片、阴极发光薄片观察及X－衍射分析,认为辽河盆地下第三系砂岩储层成岩作用中的压实作用和胶结作用减小和破坏储层孔隙,溶蚀作用则增加储层孔隙,且后者仅在一定深度范围内作用,并从沉积相、砂岩的成因及岩屑成份等方面探讨了成岩作用对储层孔隙度的影响。     

吐哈盆地西部地区高蜡凝析油和轻质油的地球化学特征及成因分析

吐哈盆地西部地区中、新生界储层中广泛分布着轻质油和凝析油。这些原油具有低密度、低粘度、中等—高含蜡量的特点 ,含蜡量为 5 .5 %～ 2 2 .1% ,高分子量正构烷烃 (n C35～ n C87)含量较高 ,属中—高蜡轻质油或凝析油 ,其地球化学特征及成因机理既不同于常规的高蜡原油 ,又不同于一般意义上的凝析油。吐哈盆地中、新生界高蜡凝析油或轻质油主要来源于侏罗系湖相泥岩和煤系地层中泥岩或煤 ,其形成主要取决于烃源岩的有机显微组分和有机质演化程度。研究区侏罗系湖相泥岩和煤系地层泥岩或煤岩中有机显微组分均以镜质组和壳质组为主 ,壳质组中角质体和木栓质体含量较高 ,具备了既可形成凝析油 ,又可形成高蜡油的条件。由于镜质组与部分壳质组演化形成烃类化合物的活化能相当 ,因此又具备高蜡油与凝析油共生的地球化学条件     

Organic geochemical characteristics of crude oils from the Masila Basin, eastern Yemen

The Masila Basin is an important hydrocarbon province in Yemen, but the origin of hydrocarbons and their generation history are not fully understood. In this regard, 10 crude oils from different petroleum reservoir sections in the Masila Basin were characterized by a variety of biomarker and non-biomarker parameters using GC, GC-MS and stable carbon isotope techniques. Oils from the Masila Basin display pristane/phytane (Pr/Ph) ratios ranging from 1.7 to 2.0, low sulfur content, high C₃₅ homohopane index, relatively high C₂₇ sterane concentrations and relatively high tricyclic terpanes suggesting a marine clay source rock that was deposited in mildly anoxic to suboxic conditions with dominantly algal organic matter. C₂₉ 20S/(20S + 20R) steranes and ββ/(ββ + αα) sterane ratios indicate that the Masila oils have reached peak oil window maturity. Another related feature of these oils is the absence of 18α (H)-oleanane, which suggests a source age older than Cretaceous. The carbon isotope compositions are similar to those of the potential source rocks, which range from −25.4‰ to −28.3‰, indicating a marine environment. The new data presented in this paper suggest that the Masila oils constitute one oil family and that the oil originated from the Upper Jurassic Madbi source rock in the basin.