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.     

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.     

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.     

包气带中原油的迁移和降解研究

在石油的开采和集输过程中,常常有大量的原油抛洒和泄漏,这对土壤和植物地造成严重污染,本文通过大量野外和室内的原油渗透试验,含油地层的淋滤试验和石油的生物降解试验,来研究石油污染物在包气带中迁移,转化和降解规律,从而地下水石油污染的潜在性作出科学的评价。     

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).     

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.     

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。      

Interaction of crude oils and water in Sakhalin oil fields

Distribution of the specific gravity of oil and the yield of fractions up to 300° is considered as a function of hypsometric position of the samples with respect to the pool outline. Relationship is determined between the difference in specific gravity of edge- and crest oils and the carbon dioxide ion content in edgewaters; it is explained by oxidation of oil by the waters. It is demonstrated by means of graphs for Ekhabi and Tungor oil fields that oxidation is more important than the force of gravity, in the distribution of the properties of oil throughout the deposit. The flushing effect of waters on the light petroleum fractions proves to be less significant that the oxidation effect. Calculation shows that the loss of oil by oxidation is small at depths below 600 m; losses by water flushing are even smaller, but rise rapidly at shallower depths. -- Author.     

Demethylated hopanes in crude oils and their applications in petroleum geochemistry

Analyses of some Australian crude oils show that many contain varying concentrations of A/ B-ring demethylated hopanes. These range from C₂₆ to C₃₄ and have been identified from their retention times and mass spectral data as 17α(H)-25-norhopanes. Comparison of hopane and demethylated hopane concentrations and distributions in source-related, biodegraded oils suggests that demethylated hopanes are biotransformation products of the hopanes. Further, it appears that the process occurs at a late stage of biodegradation, after partial degradation of steranes has occurred. Demethylated hopanes are proposed as biomarkers for this stage of severe biodegradation. The presence of these compounds in apparently undegraded crude oils is thought to be due to the presence of biodegraded crude oil residues which have been dissolved by the undegraded crude oil during accumulation in the reservoir sands. The timing of hopane demethylation, relative to the degradation of other compounds, has been assessed and the progressive changes in crude oil composition with increasing extent of biodegradation have been identified. The use of demethylated hopanes as maturity parameters for severely biodegraded crude oils, and the applicability of established biomarker maturity parameters to such oils, are also discussed.     

Wastewater dephosphorization using crude clays

The present work aims to establish the possibility of using local clays to treat wastewater. Thus, three clay samples extracted from two localities in the south of Côte d’Ivoire have been studied in their crude state. The qualitative physicochemical study that consisted in measurement of pH variation and argillaceous particles zeta potential showed that the Nieki-Agneby clay and the Beige Anyama clay presented disposal to uptake phosphate ions in solution at pH 5. For each clay, it is shown that the tension accompanying the sorption of a phosphate ion could be estimated to ?5 mV. Differences in their composition and in the number of hydrating molecules of water were also accessible. The quantitative study performed with the Nieki-Agneby clay thereafter consisted following the sorption kinetic. The adsorption was found to reach the maximum after 5 h. of exchange, and almost 400 μg phosphate ions in per gram of clay were fixed. Future studies will focus on the modification of these materials in order to increase their sorption capacity.     

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.     

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).     

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.     

The effect of biodegradation on steranes and terpanes in crude oils

Steranes and terpanes biodegrade at a slower rate than isoprenoids and survive moderate biodegradation. Heavy biodegradation results in destruction of regular steranes, survival of diasteranes (20R better than 20S) and tricyclic terpanes and transformation of hopanes to Ring A/B demethylated hopanes. These survivors can be used as source fingerprints in biodegraded crudes. The structure of predominant steranes in undegraded to moderately degraded fossil fuels was proven to be 14β, 17β(H) (20R + S) by molecular spectroscopy. These compounds plus the 20S epimers of regular 5α-steranes (20R) were identified as major constituents and their 5β-counterparts as minor components in a cholestane isomerizate (300°C, Pt on C), allowing assessment of relative thermodynamic stabilities. An observed increase of optical activity in heavily degraded crudes from three different basins is interpreted to be the result of bacterial transformation of terpanes and steranes to new optically active species plus enrichment of the latter by n + isoparaffin depletion rather than total bacterial synthesis. Diagnostic ion profiling by GC-MS-C is a convenient tool for surveying the relative abundance of individual diasteranes and regular steranes plus distinguishing epimeric and ring skeletal isomeric series in complex fossil fuel mixtures. A new practical method of determining the absolute quantities of individual steranes by spiking with 5β-cholane and integration of mass chromatograms is described.     

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.     

原油含硫化合物分离及分析方法新进展

原油中含硫化合物组成与结构信息广泛应用于油气勘探、石油运输和炼化以及环境保护.目前,挥发性和半挥发性含硫化合物的研究相对成熟,但是对大分子含硫化合物的结构认识相对薄弱.本次研究系统调研了国内外含硫化合物的分离和分析方法,总结了各方法的原理、实验流程、优缺点、应用和意义.含硫化合物分离方法主要包括化学转化方法和柱层析分离方法,可以有效分离噻吩类、硫醚类、亚砜类、硫醇类以及含硫多环芳烃类化合物.高分辨质谱和全二维气相色谱对高分子含硫化合物表征提供了技术支持.总体而言,对高分子含硫化合物的分子结构、来源、成岩演化过程及其生物标志物等信息的研究相对欠缺,建议加强对低成熟高硫原油的研究,探索高分子含硫化合物的赋存形式和地球化学意义,为石油勘探开发进一步提供指导信息.     

Impact of anaerobic biodegradation on alkylphenanthrenes in crude oil

The biodegradation of crude oil by microorganisms from well Luo-801, China, was examined in cultures grown under conditions that promoted either methanogenesis or sulfate reduction, at 35 °C and 55 °C. Headspace gas and oil compositions were characterized at 180 d and 540 d. Alkylphenanthrenes are relatively recalcitrant to bacterial attack and the biodegradation of these compounds appeared to be insignificant after 180 d under both conditions, but is evident after 540 d. The depletion of alkylphenanthrenes was monitored through evaluation of the ratio of alkylphenanthrenes to the most bioresistant, analyzed component (C₂₈ 20R triaromatic steroid hydrocarbon) and isomer susceptibility also was evaluated by relative abundance comparison within the compound class. The influence of growth temperature varied. Only slight differences in alkylphenanthrene concentrations were observed after 180 d whereas the greater degrees of biodegradation were observed at 35 °C in the methanogenic culture and at 55 °C in the sulfate reducing culture. Overall, higher biodegradation rates occur under sulfate reducing condition, which is consistent with the conclusion that methanogens are generally less able to compete for substrates than sulfate reducers. The biodegradation susceptibility of alkylphenanthrenes decreases with increasing degree of alkylation, i.e., phenanthrene (P) and methylphenanthrenes (MPs) were more easily biodegradable than C₂-alkylphenanthrenes (C₂-Ps) and C₃-alkylphenanthrenes (C₃-Ps). Biodegradation selectivity for specific homologues is not striking for the limited time duration of the experiments. However, 3-MP seems slightly more vulnerable than other methylphenanthrene isomers and 1,7-DMP has slightly higher ability to resist biodegradation than the other C₂-P isomers. The commonly used thermal maturity parameters derived from methylphenanthrene isomer ratios are altered insignificantly by biodegradation and remain valid for geochemical assessment. This information should be useful for assessing the limits of in situ crude oil biodegradation.     

Detection of organic biomarkers in crude oils using ToF-SIMS

In this study, we show that time of flight-secondary ion mass spectrometry (ToF-SIMS) can be used to detect organic biomarkers, such as hopanes and steranes, in non-fractionated crude oils, without extraction and chemical preparation. Hopanes and steranes may provide valuable information on the history of life on early Earth, particularly if they are present in fluid inclusions in ancient rocks. Due to the presence of different generations of inclusions in even very small rock samples, it would be advantageous to find a method capable of detecting biomarkers in single oil rich fluid inclusions. The capability of ToF-SIMS for detailed chemical analysis of very small sample amounts makes it a potential technique for such analysis, and in this work this possibility is explored. The presence of hopanes and steranes in four different crude oils of different ages and stages of biodegradation was investigated using ToF-SIMS and GC–MS. By combining analyses of biomarker standards, crude oils and chromatographic oil fractions, specific peaks for the different biomarkers were identified in the ToF-SIMS spectra. The presence of these peaks in the spectra from the crude oil samples could be attributed to the biomarkers based on exact mass determination and by comparison with the spectra from the biomarker containing and biomarker lacking fractions, respectively. In addition, the results show that a significant biomarker signal may be obtained from a 10 μm² oil sample, demonstrating the potential of ToF-SIMS for analysis of single oil bearing fluid inclusions, which in turn may contribute to a better understanding of the early history of life on Earth.