TWO-DIMENSIONAL SOLUBILITY PARAMETER MAPPING OF HEAVY OILS

The solubility and insolubility of heavy oils and their fractions in dilute mixtures with various solvents were used to characterize heavy oil interactions. A two-dimensional solubility parameter, developed for the selection of solvents for organic polymers, was found to group all the solvents for each heavy oil fraction in polygon areas when the complexing solubility parameter component was plotted against the field force solubility parameter component. All fractions of Cold Lake vacuum residua, except for the saturate fraction, form concentric solubility areas. Therefore, in going in the direction of decreasing aromaticity from coke to asphaltenes to resins to aromatics, all solvents for the previous fraction in the series are also solvents for all subsequent fractions in the series. As a result, asphaltenes can be precipitated, but not extracted, from heavy oils. This is attributed to the interaction among polynuclear aromatics being the dominate interaction in petroleum that causes insolubility in hydrocarbon liquids. However, the paraffinic chains on the same petroleum molecules limit their solubility in highly complexing liquids. In contrast, even vacuum gas oils from the Exxon Donor Solvent coal liquefaction process are insoluble in aromatic liquids but soluble in moderately complexing liquids because of hydrogen bonding, resulting from oxygen functionality. Hydrotreating of these coal derived vacuum. gas oils reduces their oxygen functionality and increases their solubility areas so that they become compatible with petroleum liquids.     

TWO-DIMENSIONAL SOLUBILITY PARAMETER MAPPING OF HEAVY OILS

ABSTRACT

The solubility and insolubility of heavy oils and their fractions in dilute mixtures with various solvents were used to characterize heavy oil interactions. A two-dimensional solubility parameter, developed for the selection of solvents for organic polymers, was found to group all the solvents for each heavy oil fraction in polygon areas when the complexing solubility parameter component was plotted against the field force solubility parameter component. All fractions of Cold Lake vacuum residua, except for the saturate fraction, form concentric solubility areas. Therefore, in going in the direction of decreasing aromaticity from coke to asphaltenes to resins to aromatics, all solvents for the previous fraction in the series are also solvents for all subsequent fractions in the series. As a result, asphaltenes can be precipitated, but not extracted, from heavy oils. This is attributed to the interaction among polynuclear aromatics being the dominate interaction in petroleum that causes insolubility in hydrocarbon liquids. However, the paraffinic chains on the same petroleum molecules limit their solubility in highly complexing liquids. In contrast, even vacuum gas oils from the Exxon Donor Solvent coal liquefaction process are insoluble in aromatic liquids but soluble in moderately complexing liquids because of hydrogen bonding, resulting from oxygen functionality. Hydrotreating of these coal derived vacuum. gas oils reduces their oxygen functionality and increases their solubility areas so that they become compatible with petroleum liquids.     

中质润滑油各组分的氧化属性及其对264抗氧剂的感受性

考察了大庆20^#透平油基础油及华北减二线精制油组成与其氧化安定性的关系。油中多环芳烃能显著提高饱和烃的氧化安定性,其次是双环芳烃;单环芳烃及饱和烃的氧化安定性较差。两种油中的胶质有一定抗氧活性,发现其中含有屏蔽酚型天然抗氧剂。同时还考察了油中最适芳烃量、硫化物及氮化物对其氧化安定性的影响。研究了两种油中各组分对264-二叔丁基对甲酚抗氧剂的感受性,两种油来源不同,其感受性有所差异。华北油比大庆油感受性好,两种油中胶质、碱性氮化物及单环芳烃的存在均使其感受性变差,硫化物则提高其感受性。     

渣油热反应体系中第二液相形成与液相掺兑物的关系

向渣油体系中掺兑具有不同芳香度和芳香性分布的液相掺兑物，能够不同程度地改变渣油热反应体系中第二液相的相分离特性，从而改变渣油热反应体系的生焦特性。液相掺兑物的芳香度越高，芳香性分布范围越宽，其抑制第二液相形成和推迟相分离点出现时间的作用越显著。     

Aromatic Steroids in Mideastern Crude Oils: Identification and Geochemical Application

The aromatic fractions of three crude oil samples from Iraq, Iran, and Saudi Arabia were isolated by using the method of silver ion-silica solid-phase extraction. Two series of aromatic steroids were recognized in these fractions using computerized gas chromatography-mass spectrometry corresponding to mono- and triaromatic steroids applying the mass chromatography at m/z 253 and m/z 231. The mass chromatogram traces show considerable differences that allow the use of the aromatic steroid distribution patterns as fingerprint for these oils. The oils contain significant amounts of mono- and triaromatic steroids having the C-24 ethylsteroid skeleton abundant in terrestrial sources. The abundance ratios of the short- to long-chain components of the mono- and triaromatic steroid hydrocarbons, together with the steroid aromatization parameter, indicate that the Iraqi and Saudi oils are at advanced maturity levels relative to the Iranian oil.     

Specifics of the group and homological compositions of aromatic hydrocarbons in some Azerbaijani crude oils

The distribution character and the composition of hydrocarbons in Azerbaijani oils of different types were studied. Concentrates of aromatic hydrocarbons were isolated from the 50° fractions of crude oils and oil residues boiling above 450°C. The structural-group composition of the isolated aromatic hydrocarbons was studied by spectral methods (mass spectrometry and ¹H NMR spectroscopy).     

THE MIDDLE CAMBRIAN SUCCESSION IN THE CENTRAL BALTIC BASIN: GEOCHEMISTRY OF OILS AND SANDSTONE RESERVOIR CHARACTERISTICS

Some 36 oilfields, all producing from Middle Cambrian (Deimena Group) sandstones, are located in the central Baltic Basin in an area covering onshore Lithuania and Kaliningrad (Russia) and the adjacent offshore. This paper presents new data on the composition of crude oils from fields in this area and reviews the reservoir properties of the Deimena Group sandstones. Twenty‐one crude oil samples from fields in Lithuania and Kaliningrad were analysed by standard techniques including GC and GC‐MS. The oils had densities of 790.5 to 870.0 kg/m³, and had low asphaltene (<2.2%) and sulphur (<0.44%) contents. The gasoline fraction (b.p. >200°C) ranged from 12–34%. The saturated hydrocarbon content was 35.3 to 77.8%, and the ratio of saturate to aromatic hydrocarbons was 2.1–5.2, indicating long‐distance migration or high thermal maturities. GC analyses of saturate fractions indicated a composition dominated by n‐alkanes with a maximum at C₁₃–C₁₅ and reduced abundance in the C₂₀–C₃₅ range. The analysed crude oil samples are characterized by relatively low concentrations of steranes and triterpanes. Biomarker data indicated an algal origin for the precursor organic matter and a clastic‐dominated source rock. Sterane isomerization ratios imply that the oils are in general relatively mature. Exceptions are samples from the Juzno Olempijskoye and Deiminskoye fields, Kaliningrad, which were early mature. Oil from well Gondinga‐l (Lithuania) was lightly fractionally evaporated and has a relatively higher density, higher viscosity, higher asphaltene content and lower content of saturated fractions. Stable carbon isotope ratios of crude oils and saturated and aromatic fractions were analysed. Whole oils showed little carbon isotope variation, but there were significant differences in δ¹³C ratios for saturated and aromatic fractions. The geochemical data show differences in oil sourcing and indicate the possible existence of different kitchen areas in the Kaliningrad region. Vertical and lateral variations in Deimena Group reservoir properties are controlled by variations in quartz cementation. In fields in western Lithuania, sandstone porosity ranges from 0.7 to 20% and permeability from 20 mD to 300 mD; in fields onshore Kaliningrad, porosity is up to 34% and gas permeability up to 4.8 D. Wide variations in porosity and permeability occur at a field scale.     

紫外光谱技术在油藏地球化学研究中的应用

鉴于用色谱指纹法研究生物降解稠油油藏的连通性和监测二层合采井产能贡献方面有一定局限性(此类油藏缺少正构烷烃，色谱定量定性分析困难)，讨论了紫外光谱技术在油藏(特别是生物降解稠油藏)地球化学研究中的应用。研究表明：具有共轭键芳烃组份是原油总吸光度的主要贡献者，且具有加和性，因运聚过程有别，油层内原油芳烃浓度必有一定的差异；不同原油紫外吸收特征不同，通过吸光系数可以判断其相似性及差异性；根据单层油、混合油、配比油的紫外吸收特征(特征指纹)，可用紫外光谱技术计算合采井单层产能贡献和判断油藏流体连通性。     

伊朗原油生产润滑油基础油的工业试验

进行了伊朗原油减二、减三线、减四线及脱沥青油采用糠醛精制、酮苯脱蜡和白土精制传统加工工艺生产润滑油基础油的工业放大试验。结果表明,伊朗减二线及脱沥青油基础的粘度指数大于９０,与ＨＶ１１５０及ＨＶ１１５０ＢＳ基础油的具体指标有一定差距,其它质量指标分别达到ＨＶ１１５０和ＨＶ１１５０ＢＳ基础油的技术要求;伊朗减三线、减四线基础油的粘度指数小于９０,其它质量指标分别达到ＨＶ１４００和ＨＶ１６５０基础油的     

高环烷烃铝材轧制基础油氧化安定性能的研究

选用了一种低硫、低芳烃铝材轧制基础油,在GCMS-QP2010型气相色谱质谱联用仪上分析了它的化学组成,并采用紫外分光光度法测定其芳烃含量,在SH0206变压器油氧化安定仪上测定油品的氧化安定性,运用红外光谱分析法测定了油品氧化前后官能团的变化。试验结果表明：该基础油为高环烷烃基础油,其氧化安定性较差,在氧化过程中产生了酸、酯;在基础油中添加酚类抗氧剂和金属减活剂能明显提高油品的氧化安定性,且两种抗氧剂有着良好的协同作用。     

大庆、辽河油浆窄馏分的环状结构、组成的比较

选择大庆和辽河油浆为研究对象，采用超临界流体萃取分馏技术将其切割成窄馏分，运用常规分析方法结合质谱和核磁共振氢谱分析，得到大庆，辽河油浆窄馏分的饱和分中链烷烃和环烷烃的组成及芳香分中的环系组成，并得到了油浆窄馏分及其芳香分的平均结构，结果表明，大庆及辽河油浆窄馏分中芳香分中的各类环状结构随收率呈规律性变化，均以四环芳烃含量最多，辽河油浆窄馏分的芳香性高于对应的大庆油浆馏分。     

STRUCTURAL CHARACTERIZATION OF PETROLEUM BASED FEEDSTOCKS FOR CARBON BLACK PRODUCTION

Some selected petroleum based feedstocks have been characterized by ¹H and ¹³C NMR spectroscopy for their possible use as carbon black feedstock (CBFS). Feedstocks studied are pyrolysis tars, clarified oils, aromatic extracts and vacuum residue. Analysis of average structural NMR parameters show that pyrolysis tars because of their being highly aromatic in character (high BMCI) are the most suitable feedstock for carbon black. Aromatic extracts rank the next. Clarified oils of Indian refinery origin needs further processing due to middle distillate mode refining severity.     

Kinetics of thermal degradation of macromolecular petroleum compounds in the presence of fatty acid triglycerides

The kinetics of thermal degradation of high-molecular-mass fractions of crude oil mixed with rapeseed oil has been studied by dynamic thermogravimetry. The structural parameters of the average molecule of vacuum residues of crude oils processed at Naftan and the Mozyr refinery and hydrocarbon oils, resins, and asphaltenes isolated from the residues have been first determined by NMR and IR spectroscopy. It has been shown that the addition of rapeseed oil can increase the rate of thermal degradation of heavy petroleum residues, with the character of the effect of the vegetable oil on the kinetics of the process being determined by structural features of macromolecular petroleum compounds, namely, the relative amount of aromatic units and the length of alkyl chains.     

Compositional Changes in Hydrotreated Naphthenic Oil under Ultraviolet Radiation

Compositional changes of hydrotreated naphthenic oil during ultraviolet (UV) radiation were studied in detail. First, liquid-solid chromatography was used to separate the initial oil and the UV-irradiated oil into three different fractions: saturates, aromatics, and polars. Then, each fraction's compositional changes were evaluated using a series of instrument technologies including gas chromatography-mass spectroscopy (GC-MS), infrared spectroscopy (IR), atmospheric pressure chemical ionization mass spectroscopy (APCI/MS), and X-ray photo electron spectroscopy (XPS), respectively. The results show that after UV radiation, the UV-irradiated sample exhibited a decrease in saturates concomitant with an increase in the aromatic and polar fractions. For saturates and aromatics, the UV-irradiated sample exhibited a decrease in alkanes, diaromatics, and polyaromatics concomitant with an increase in other aromatics. The UV light had no significant effect on the cycloalkanes. For polars, a relatively large amount of oxygen-containing compounds, such as hydroxyl, carbonyl, and carboxyl groups, was formed in the presence of UV light. XPS data show that a type of S 2pa compound in the initial oil disappears and could be converted to SO₄^2-. No obvious changes of molecular weight distribution were observed. A part of polar compounds in the UV-irradiated oil might come from aromatic photooxidation in the initial oil.     

橡胶填充油玻璃化温度的研究

通过差示扫描量热仪(DSC)测定了橡胶填充油及其不同馏分的玻璃化温度.研究证实,橡胶填充油的组成与它的玻璃化温度存在一定的相关性:未分馏橡胶填充油的玻璃化温度,介于其饱和烃与芳香烃馏分各自的玻璃化温度之间;同时从分子结构角度用自由体积理论阐释了上述关系,目前有关橡胶填充油的玻璃化温度尚未见报道.     

塔里木盆地古城墟隆起顺南1井古油藏热裂解过程的分子碳同位素地球化学记录

塔里木盆地古城墟隆起顺南1井高成熟度轻质原油被认为是典型的热裂解残余油。研究揭示顺南1井原油中高丰度的苯系物和丰富的稠环芳烃,是其在地质历史上经历强烈热裂解的次生产物之一;苯系物应为热裂解、环化、芳构化过程的中间产物,而稠环芳烃可能指示了缩聚过程。烃类分子裂解—缩聚过程诱发的碳同位素分馏,不仅使顺南1井原油正构烷烃分子碳同位素较下古生界含油气系统中正常原油的重8‰~10‰,而且烷基萘系物分子碳同位素也比下古生界含油气系统中的正常原油重6‰~8‰。研究结果进一步实证了与裂解成因相关的芳烃分子及其稳定碳同位素组成是判识深层—超深层油藏是否经历热蚀变的有效手段,其对于准确评估深层—超深层油气相态与资源格局具有重要意义。     

GEOCHEMICAL CHARACTERIZATION OF CENTRAL NIGER DELTA OILS

Oil samples from six oilfields in the Central Niger Delta were analyzed for normal alkanes, aliphatic isoprenoid hydrocarbons, aromatic hydrocarbons and biomarkers using gas chromatography (GC) and gas chromatography-mass spectrometry (GC-MS). The study was carried out with the aim of assessing the origin and thermal maturity of the oils and the depositional environment of the organic matter from which they were derived, and to evaluate similarities (or differences) among the oils from the Central Niger Delta in comparison to those from other parts of the Delta. The ratios of n-alkanes and aliphatic isoprenoids showed that Pr/nC₁₇ ranged from 0.56 to 0.86 while Ph/nC₁₈ ranged from 0.22 to 0.31 indicating that the oils were derived from organic matter of both terrestrial and marine origin. Pristane/phytane ratios ranged from 2.67 to 3.50, suggesting that the organic matter was deposited in generally oxidizing environments. The oleanane index, which ranged from 0.07 to 1.39, and other biomarker data also indicate contributions from both marine and terrestrial organic matter. Both saturated and aromatic hydrocarbon biomarker data indicate that the oils are thermally mature. The study showed that the Central Niger Delta oils have organic geochemical characteristics similar to those of oils from other parts of the Delta. However, there is a striking difference in the distribution of aromatic hydrocarbons, and this may in future be used as a tool with which oils from different parts of the Delta can be differentiated.     

辽河西部凹陷重油聚集条件与原油稠变特征

辽河西部凹陷重油的形成、分布和规模,主要取决于后期的构造运动特征,其聚集条件与常规油有一定的差别;随重油比重、粘度增大,自身封堵能力增强,可形成不同类型的油藏。我们用气相色谱、色质、碳同位素等,对辽河西斜坡系统取样样品进行分析,发现稠变作用不仅对甾萜化合物产生影响,而且对多环芳烃也有一定的影响,其影响的顺序大致是:萘系列、菲系列、(艹屈)系列、三芳甾烷系列。同时,稠变作用也会造成原油及各族组分较大幅度的稳定碳同位素分馏。     

GEOCHEMICAL CHARACTERIZATION AND RELATIONSHIP OF OILS AND SOLID BITUMENS FROM SE TURKEY

Solid bitumens from the Seridhalivein, occurring in the Upper Cretaceous—Palaeocene Germav Formation, and five oils from different oilfields in SE Turkey, were investigated by a variety of organic geochemical methods. Based on biomarker distributions (pristane/phytane, carbon number preference (CPI), Norhopane/hopane, extended hopane distribution, pregnanes/regular steranes), a marine carbonate depositional environment is inferred for the source of these oils. The oils are "early mature', as indicated by their ethylcholestane 20S/20S + 20R ratios, and the 17α(H), 21β(H)-bishomohopane 22S/22S + 22R ratios. Differences in relative abundance of some compounds typical of higher salinities in the depositional environment (docosane, pregnane) suggest different sources of facies variations within a common source. No aromatic sulfur compounds were detected in the oils.
The solid bitumens were characterized by a high abundance of dibenzothiophenes, naphthalenes, phenanthrenes and their alkyl-substituted homologues in the aromatic fractions, and an abundance of n-alkanes in the saturate fraction. The high maturity of the solid bitumen (epi-impsonite, R %equiv. ∽ 1.2) makes an interpretation on the origin of these substances difficult. An origin due to biodegradation of sulfur-rich oil is excluded, since the alkane and aromatic fractions do not show signs of a severe microbial degradation. The absence of sulfur compounds in the oil extracts and the pyrolysis products of the asphaltene fraction show genetic differences between the oils and solid bitumens of SE Turkey. Pyrolysis of the asphaltenes from the bitumen extracts and of the unextracted bitumens produced sulfur compounds similar to those found in the aromatic fraction.     

Compositional Changes in Hydrotreated Naphthenic Oil under Ultraviolet Radiation

Abstract

Compositional changes of hydrotreated naphthenic oil during ultraviolet (UV) radiation were studied in detail. First, liquid–solid chromatography was used to separate the initial oil and the UV-irradiated oil into three different fractions: saturates, aromatics, and polars. Then, each fraction's compositional changes were evaluated using a series of instrument technologies including gas chromatography-mass spectroscopy (GC-MS), infrared spectroscopy (IR), atmospheric pressure chemical ionization mass spectroscopy (APCI/MS), and X-ray photo electron spectroscopy (XPS), respectively. The results show that after UV radiation, the UV-irradiated sample exhibited a decrease in saturates concomitant with an increase in the aromatic and polar fractions. For saturates and aromatics, the UV-irradiated sample exhibited a decrease in alkanes, diaromatics, and polyaromatics concomitant with an increase in other aromatics. The UV light had no significant effect on the cycloalkanes. For polars, a relatively large amount of oxygen-containing compounds, such as hydroxyl, carbonyl, and carboxyl groups, was formed in the presence of UV light. XPS data show that a type of S 2pa compound in the initial oil disappears and could be converted to SO₄ ^2?. No obvious changes of molecular weight distribution were observed. A part of polar compounds in the UV-irradiated oil might come from aromatic photooxidation in the initial oil.