注水开发过程中原油的水洗作用初探

注水开发过程中的水洗作用是一个以往被忽略,但又十分重要的问题.通过对3口井、时间间隔为20年的6个原油样品系统的地球化学测试与对比研究,探讨了注水开发过程中水洗作用对原油的改造作用以及各种地球化学参数的变化特征和规律.结果表明,在注水开发过程中,水洗作用对芳烃的影响远大于饱和烃,主要表现在芳烃组分的含量明显降低,一些芳烃类化合物的含量和芳烃参数也发生了显著的变化.认为这些变化是注水开发过程中原油遭受水洗作用的特征性标志,并对油源对比和油气运移等研究具有参考意义.     

Geochemical Characteristics of Crude Oils from Zao-V Oil Measures in Shenjiapu Oilfield

The geochemical characteristics of crude oils from Zao-V oil measures in the Shen-jiapu oilfield are systematically described in terms of the fractional composition of crude oils, GC characteristics of saturated hydrocarbon fraction of crude oils and the characteristics of their bio-markers. The deposifional environment, type and evolution of the biological source are also discussed. All pieces of evidence such as low saturated hydrocarbon fraction, high resin and asphalt, high isoprenoid alkane, weak odd-carbon number predominance ( CPI ranging from 1.23 to 1,29, OEP ranging from 1.14 to 1.16) and low sterane and terpane maturity parameters show these crude oils are immature oils. Low Pr/Ph ratios (0.66 -0.88) and high gammacer-ante/C31 hopane ratios ( 0.59 - 0.86 ) indicate the source rocks were formed in a slightly saline to brackish reducing lake depositional environment. Gas chromatographic characteristics of the saturated hydrocarbon fraction and the predominance of C30 hopane in terpane series and C29 sterane in sterane series indicate the biological source of the crude oils is composed mainly of bacterial and algal organic matter, and some algae are perhaps the main contributor of organic matter to the source rocks.     

Waxes and asphaltenes in crude oils

High molecular weight (HMW) hydrocarbons (>C₄₀) and asphaltenes are important constituents of petroleum and can cause problems related to crystallization and deposition of paraffin waxes during production and transportation as well as in the formation of tar mats. However, traditional methods to isolate asphaltene fractions, by adding 40 volumes in excess of low boiling point solvents such as pentane, hexane or heptane, can produce asphaltene fractions which are contaminated with a significant amount of microcrystalline waxes (>C₄₀). The presence of these microcrystalline waxes in the asphaltene fractions has the potential to provide misleading and ambiguous results in modeling and treatment programs. The sub-surface phase behaviour of an asphaltene fraction will be quite different from that of a wax-contaminated asphaltene fraction. Similarly accurate modelling of wax drop-out requires information on pure wax fractions and not asphaltene-dominated fractions. Hence the goal of this paper is to describe a novel method for the preparation of wax-free asphaltene fractions. In addition, this method provides a quantitative subdivision of the wax fraction into pentane soluble and insoluble waxes which, when correlated with physical properties of crude oil such as viscosity, pour point, cloud point, etc., may help explain causes of wax deposition during production, transportation and storage of petroleum.     

Biodegradation and water washing effect on gasoline range hydrocarbons and quality of crude oils from HJN and MKM fields of upper Assam basin,India

The crude oils from Oligocene and Miocene formation of upper Assam basin have moderate API gravity and significant wax content. Crude oils from HJN and MKM fields of upper Assam basin are being produced from Oligocene and Miocene sands. These oils are somewhat biodegraded in nature as evidenced from their API gravity, density, bulk composition, GC fingerprints and relative concentrations of compounds in the gasoline range. It is observed from whole oil gas chromatographic data that the lighter hydrocarbons are more effected as a result of biodegradation and water washing than the heavier components. In the gasoline range compounds highest degradation of n-alkanes are observed followed by iso- and cyclo- alkanes. The extent of the effect of biodegradation of the gasoline range compounds in crude oil samples cannot be illustrated by the concentrations of the compounds. The concentrations only describe qualitative differences in molecular composition. This difficulty can be overcome by using parameters called degradative loss (%). This parameter shows exactly how much loss or gain has taken place in the gasoline range compounds. Within the gasoline range compounds, n-alkanes, Benzene baring HJN 15 and MKM 14 and Toluene experienced degradative loss indicating effects of both biodegradation and water washing in these oils. Cyclo-alkanes are least effected by biodegradation followed by iso-alkanes in all the oils. The extent of biodegradation and water washing is different for each oils from HJN and MKM fields as indicated by the degradative loss (%) of the compounds in the gasoline range.     

CHARACTERISTICS OF AROMATIC HYDROCARBONS IN CRUDE OILS

Crude oils from different basins in China ,Australia and New Zealand were analyzed to character-ize aromatic hydrocarbons produced in different environments by means of GC/MS .The distributions of some common compounds such as naphthalene, phenanthrene, chrysene,pyrene, fluoranthene, fluorine,dibenzothiophene and dibenzofuran were found to be related to sedimentary environments.Especially the relative contents of fluorenes ,dibenzofurans and dibenzothiophenes can be used to di-vide the oils into three types(1) saline or marine carbonate environment;(2) fresh-brackish water lake;(3) swamp and coal-bearing sequence.A romatic biomarkers (e.g.retene, nor-abietene,derivatives of lupeol and β-amyrin)represent higher plant inpults with respect to the precursors of crude oils. High contents of sulphur-containing compounds like benzothiophene and dibenzothiophene series indicate a reducing sulphur-abundant diagenetic condition .The benzohopane series (C32-C35) was identified both in hypersaline and coal-bearing basins, and it is postulated to be the result of strong bacteria activity.In all the sam-ples, a complete series of alkyl benzenes was analyzed .The similarity of its carbon-number distrbu-tion with that of n-alkanes probably suggests their genetic relationship. The distribution of the methylphenanthrene series reflects the evolution degree of crude oils,MPI holding a positive correlation with C29-sterane 20S/(20S 20R).     

Bicyclic sesquiterpenoids and diterpenoids in Australian crude oils

Bicyclanes previously reported only in heavily biodegraded Texas Gulf Coast crudes have been found to be ubiquitous in Australian crude oils of non-marine origin from four different basins. The compounds are present in oils, thought to be derived from the same or similar sources, that have undergone varying degrees of biodegradation. They are also found to be present in oils of different geological age. In addition a series of tricyclic diterpenoid hydrocarbons was common to four oils from the Gippsland Basin. Four of these compounds had the molecular formula C₂₀H₃₄ and mass spectral fragmentation patterns suggested they were mono-unsaturated diterpenoids. The presence of unsaturated diterpenoids in crude oils appears to be a unique observation. It is proposed that the diterpenoids may be the source of the bicyclanes also observed in these oils.     

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.     

Comparison of Michigan Basin crude oils

Michigan Basin oils from the Ordovician Trenton, Silurian Niagaran, and Devonian Dundee formations have been geochemically compared by GC, GC-MS, and carbon isotope mass spectrometry. One oil from each formation was selected for detailed analysis which included measurement of individual n-alkane δ¹³C values. The Ordovician and Devonian oils are strikingly similar to one another, yet clearly different from the Silurian oil. This pattern is unexpected because Ordovician and Devonian reservoirs are physically separated by the Silurian strata. From time-temperature considerations, the Devonian oil probably was formed in older strata and has migrated to its present location. Our analyses suggest a common source for the Devonian and Ordovician oils.     

Geochemical characteristics of Ordovician crude oils in the northwest of the Tahe oil field,Tarim basin

Forty-six crude oil samples were selected from the Ordovician in the northwestern part of the Tahe oilfield for detailed molecular geochemical and isotopic analysis, including group compositions, carbonhydrogen isotopes and gas chroma-tograms of saturated hydrocarbons, as well as the characteristics of terpane, sterane and other biomarkers, indicating that crude oils are of the same origin from different districts in the Tahe oilfield and were derived from the same source kitchen (or oil source formation), i.e., mainly stemming from marine hydrocarbons. Detailed studies of oil physical properties of 25-honpane revealed that such oils have heavy or thick oil qualities due to biodegradation. Comprehensive assessment in terms of five maturity parameters shows that the oils from the Ordovician with Ro values varying from 0.80% to 1.59% are widely distributed in the northwest of the Tahe oilfield.     

Fixed-ammonium in clays associated with crude oils

The association of ammonium (NH₄⁺) silicates with organic-rich sedimentary environments has stimulated interest in the chemical cycle of N, and its possible application as an indicator of in situ organic maturation reactions or crude oil migration. Fixed-NH₄ in clay minerals was determined from three hydrocarbon occurrences of similar depositional environment but different ages, depth and thermal maturity, to determine whether anomalously high NH₄-substitution occurs near mature hydrocarbons. Results show higher fixed-NH₄ concentrations in marginally mature mudstones than in immature sediments. The highest fixed-NH₄ concentrations were found in clays from sandstone reservoirs containing migrated crude oil.Fixed-NH₄ in clays from Holocene oil seep sediments in the Gulf of Mexico continental slope, offshore Louisiana, averages 0.08 wt % and increases with depth in shallow cores (420 cm), reflecting an early diagenetic trend that is apparently not influenced by migrating crude oil. Programmed pyrolysis shows that the sediments are thermally immature (av.T_max = 419°C). High Hydrogen Index values (av.= 359mg/g) are the result of biodegraded crude oil, and a high Oxygen Index (av.= 182mg/g) reflects the presence of authigenic carbonate.Fixed-NH₄ averages 0.16 wt % in Wilcox Group (Eocene) mudstones enclosing two sandstone reservoirs at Fordoche Field, onshore Louisiana. In comparison to these mudstones, anomalously high NH₄-fixation appears to occur in reservoir clay minerals. Pyrolysis shows that the sediments are marginally mature for crude oil generation (av.T_max = 432°C). Average Hydrogen Index (187 mg/g) and Oxygen Index values (75 mg/g) are consistent with oil-prone Type II and Type III kerogen. Increased pyrolysis Production Index values and solvent extraction shows the presence of migrated crude oil. This suggests that a reaction which releases NH₃ during crude oil generation or migration is recorded byNH₄⁺ substitution in clays.Fixed-NH₄ and total organic carbon (TOC) at Fordoche Field show no statistically significant correlation, suggesting that NH₄⁺ substitution in clay minerals is not simply related to the amount of organic matter in the section, but is also influenced by the presence of crude oil. Once NH₄⁺ has been fixed in clays, it is a more stable hydrocarbon proximity indicator than pore fluid tracers, because it is less influenced by later chemical or geological changes.     

Distribution of diaromatic nitrogen bases in crude oils

Azanaphthalene derivatives were identified in 9 petroleum samples. In all investigated crude oils; the number of alkyl substituents was found to extend up to C₉ with a maximum most often for C₆; unsubstituted parent compounds are absent. Two distinct types of azanaphthalenes occur: solely methylated derivatives which are abundant in most crude oils of Cretaceous or Miocene ages, and compounds bearing alkyl chains of up to 4 carbon atoms, with a majority of 8-isopropyl quinoline derivatives, which dominate in a California crude oil of Pliocene age.     

Comparison of crude oils and their alteration products

A simple method is proposed for using gas Chromatographic data on the high molecular weight saturated fractions of crude oils to make comparisons of source materials, migration mechanisms and, in particular, alteration processes within reservoirs. The preferential loss of normal alkanes by bacterial attack on a light crude is one of several processes readily followed using this scheme.     

Measurement of partition coefficients of phenol and cresols in gas-charged crude oil/water systems

An instrument has been constructed for monitoring the partition coefficients of phenol and cresols between crude oil and water under sub-surface conditions. The device has the capacity for introducing methane gas into crude oil, thereby allowing measurements under live oil (solution gas-containing) conditions. The partition coefficients of phenol and cresols have been measured in crude oil: water substrates under “live” oil and “dead” oil (without solution gas) conditions over a temperature range 25–150 °C. Over the range investigated it is seen that the introduction of gas (crude oil saturated at 100 bar with methane) into the system resulted in an approximate doubling of partition coefficients compared to the equivalent dead oil: brine systems. The partition coefficient data obtained using the device may be employed in a number of petroleum exploration and production activities such as the determination of residual oil saturation of a water-flooded petroleum reservoir. Partition coefficient measurements may help in predicting toxic organic solute loadings in oilfield discharge waters.     

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.     

Petroporphyrins in Gaosheng crude oil

China's Gaosheng crude oil is characterized as being high in nickel and low in vanadium. Nickel porphyrins were extracted with dimetrylformamide, concentrated by absorption chromatography and demetallized with methylsulfonic acid. The concentrate of demetallized porphyrins was then separated by centrifugal thin-layer chromatography, in which DPEP, ETIO, Di-DPEP, Rhdo-ETIO, Rhdo-DPEP and Rhodo-Di-DPEP types of porphyrin were identified by mass spectrometry and UV-VIS spectroscopy. The possible geochemical pathways from DPEP to Di-DPEP and from Di-DPEP to Rhodo-DPEP series are discussed.     

乌兰花凹陷原油特征及成因

乌兰花凹陷是二连盆地南部新发现的富油凹陷,对乌兰花凹陷原油物理性质和地球化学性质进行了系统的分析以揭示其特征及来源。原油物理性质显示,乌兰花凹陷原油比重（API gravity）介于20.2°~40.0°之间,主体为正常原油。原油生物标志化合物参数表明,不同构造带之间原油特征存在差异,可以划分为两类原油。一类以土牧尔构造带原油为主,具有低姥值比（Pr/Ph）和C₂₁/C₂₃三环萜烷,相对较高的伽马蜡烷/C₃₁藿烷和规则甾烷/C₃₀藿烷的特征,原油主要为烃源岩在成熟阶段早期的产物,主要以藻类来源为主。另一类原油包括赛乌苏和红井构造带原油,具有高姥值比（Pr/Ph）和C₂₁/C₂₃三环萜烷,相对较低的伽马蜡烷/C₃₁藿烷和规则甾烷/C₃₀藿烷,主要为陆源有机质和藻类有机质混合来源,原油具有更高的成熟度。原油碳同位素和正构烷烃单体烃碳同位素表明这两类原油应是一套烃源岩在不同成熟阶段的产物,原油主要来源于南洼槽阿尔善组烃源岩。阿尔善组烃源岩的非均质性和成熟度导致了两类原油的差异。      

New data on composition and properties of Lower Cambrian crude oils in Lena region,Irkutsk oil and gas basin

Two groups of oils are considered: condensates and light oils from the terrigenous Lower Cambrian section, and oils occurring in the halogen-carbonate section. Preliminary conclusions on different cycles of oil formation in the terrigenous and carbonate complexes are drawn from the study of chemical composition, optical activity, and distribution of microelernents in the oils. The Parfenovo horizon of Markovo field is considered as a differentiated oil and gas deposit. -- Author.     

Terpenoid biomarker distributions in low maturity crude oils

Twenty-seven heavy crude oils of diverse origin were geochemically assessed with respect to both bulk and mlecular composition for the purpose of identifying and quanttfying valid biomarker parameters for low maturity oils. The low thermal maturity level of many of these oils is evident from the bulk and alipathic chromatographic data, and oil sourced from both marine and terrigenous organic matter are represented. Selective metastable ion monitoring (SMIM) was employed to measure separately the distribution of C₂₇, C₂₈, and C₂₉ sterane isomers. The useful maturity indicators include the C₂₉ 5α(H) 20S/20R ratio, the relative quantity of the biological sterane configuration in each of the total normal C₂₇, C₂₈, and C₂₉ steranes, and the rearranged to normal sterane ratio. In addition, C₂₇ rearranged steran es appear to form at a faster rate than C₂₈ or C₂₉ rearranged steranes. However, the isomerization of the C₂₇ biological component appears to occur at a slower rate than the C₂₉ counterpart suggesting that the former may be used as a maturity parameter at higher levels of thermal maturation. In the triterpane distributions, the C₂₇ trisnorhopane isomers and the moretane to hopane ratios appear to be both source and maturity related and cannot be used as successful maturity parameters in oils unless they share a common source. The C₃₁₊ hopane 22S/22R equilibrium ratio appears to increase with increasing molecular weight (C₃₁–C₃₄).