Evaluation of saturated and aromatic hydrocarbons oil-oil maturity correlation parameters (SE Pannonian Basin, Serbia)

Twenty three crude oils from the Serbian part of the Pannonian Basin (14 from the Vojvodina Province and 9 from the Drmno Depression) were investigated, aimed at an evaluation of oil-oil maturity correlation parameters based on the distribution and abundance of saturated biomarkers and alkylarene constituents. Factor and cluster analyses were used for this purpose. Factor analyses using varimax rotation were first run separately, i.e., of maturity parameters based on the abundance of (a) n-alkanes and isoprenoids, (b) steranes and triterpanes, (c) alkylnaphthalenes, and (d) alkylphenanthrenes. These analyses yielded 9 important "maturity factors". Eight of them, showing higher than 30 % of variance, were further involved in another factor analysis, as well as in cluster analysis using the Ward method. In this way, all maturity parameters based on saturated biomarkers and alkylarenes were evaluated and ranged, considering the fact that the observed factors represented their linear combinations. The results showed that in the correlation of crude oils from the Serbian part of the Pannonian Basin, the most important were maturity parameters based on isomerization reactions involving one methyl group in thermodynamically less stable alpha-methylnaphthalenes, ethylnaphthalenes, dimethylnaphthalenes and methylphenanthrenes, and their change into more stable isomers with the methyl group in the beta-position in the aromatic ring. Processes constituting high loadings factor 2 and factor 3 parameters were also defined. Hierarchy between the "factors" and parameters were controlled, and approved, by cluster analysis using the Ward method. Finally, the investigated crude oils were correlated by factor and cluster analyses, using all the important "maturity factors". Differences in maturity were observed between the Vojvodina and Drmno Depression crude oils, as well as between oils originating from South Banat, North Banat and the Velebit oil field (Vojvodina locality)

Phenanthrene and Methylphenanthrene Isomers in Maturity Assessment of Biodegraded Crude Oils (Sakhalin, Russia)

This paper is aimed at defining two new advantageous maturation parameters based on distribution and abundance of phenanthrene (P) and methylphenanthrene (MP) isomers in the tricyclic fraction of aromatic hydrocarbons: MPI 3+1/PAI 1 and [2(2-MP+3-MP)+P]/1-MP. The applicability of newly proposed parameters was checked by correlation analysis. Depth of the reservoir rock, diasterane maturation parameter, as well as several typical aromatic fraction maturation parameters were used for this purpose. The examined oils (fourteen samples from nine oil fields of Sakhalin Island, Russia), were of Miocene age and from reservoir rocks of relatively wide range of depths (73-2841 m). All samples represented biodegraded, or mixtures of biodegraded and nonbiodegraded oils [1]

Термический и каталитический крекинг смесей асфальтены / мальтены

The composition of the products of thermal and catalytic cracking of mixtures of deasphaltened crude oil (DAO) or maltenes with 0, 8, 12, 16 % of asphaltenes was studied. Cracking was carried out in a batch reactor at a temperature of 450 °C for 2 hours. Microsized NiCrWC powder as an additive for catalytic cracking was used. Data on the composition of products of cracking were obtained. It was found out that in the course of thermal and catalytic cracking of DAO mixtures with different content of asphaltenes the yield in gaseous and solid by-products increased with increase in their content. At the same time, the yield of distillate fractions ibp‑360 °C also increased, while the content of secondary resins and asphaltenes decreased. The structure of the initial asphaltenes undergone significant changes in the course of thermal and catalytic cracking. Hence, they decreased in size, became more aromatic and had a much lower number of alkyl substituents. It was noted that the addition of NiCrWC in the cracking of DAO mixtures with different asphaltene content did not significantly affect the destruction of asphaltenes and did not contribute to an increase in the yield of the ibp – 360 °C fractionВ работе изучен состав продуктов термического и каталитического крекинга смесей деасфальтенизированной нефти (DAO) с 0, 8, 12, 16 % асфальтенов. Крекинг проводился в реакторах (автоклавах) при температуре 450 °C в течение 2 часов. При каталитическом крекинге в качестве добавки использовался NiCrWC в виде порошка микронного размера. Получены данные по составу продуктов крекинга. Установлено, что в процессе термического и каталитического крекинга смесей DAO с различным содержанием асфальтенов по мере увеличения их содержания увеличивается выход побочных – газообразных и твердых продуктов; при этом также увеличивается выход дистиллятных фракций НК‑360 °C, снижается содержание вторичных смол и асфальтенов. Структура исходных асфальтенов претерпевает значительные изменения в процессе термо- и каткрекинга – они уменьшаются в размерах, становятся более ароматичными с гораздо меньшим количеством алкильных заместителей. Отмечено, что добавка NiCrWC при крекинге смесей DAO с различным содержанием асфальтенов не оказывает значимого влияния на деструкцию асфальтенов и не способствует увеличению выхода фракции НК‑360 о

Hierarchy of maturation parameters in oil-source rock correlations. case study: Drmno depression, southeastern Pannonian Basin, Serbia and Montenegro

Hierarchy of triterpane, sterane, naphthalene and phenanthrene maturation parameters in oil-source rock correlations (Drinno depression, southeastern part of the Pannonian Basin, Serbia and Montenegro) was evaluated. Different triterpane and sterane parameters were found to be very similar in all investigated samples. Phenanthrene and naphthalene maturation parameters demonstrated much less uniformity, and thus higher applicability. In order to establish a detailed hierarchy of these maturation parameters, the factor analysis was used. Parameters based on isomerization reactions (alpha - gt beta) of methylnaphthatenes and methylphenanthrenes, having high loadings, defined the statistically most significant factor 1. Parameters based on dealkylation processes of dimethyl- and trimethylphenanthrenes into methylphenanthrenes, having extremely high loadings values, determined factor 2. In the last significant, factor 3, high loadings were observed with triterpane and sterane parameters. The factor analysis involving just the phenanthrene and naphthalene isomerization parameters, classified methylphenanthrene isomerization parameters into factor 1. Among the naphthalene isomerization maturation parameters a certain hierarchy was also observed, which depended on whether the parameters represented isomer ratios which differed on the position of one or two alkyl groups. General conclusion based on factor analysis is in agreement with theoretical presumptions concerning the transformations of phenanthrene and naphthalene isomers. (c) 2006 Elsevier B.V. All rights reserved

Thermal Transformations of Asphaltenes at a Temperature of 120 °C

Проведен термолиз асфальтенов трех тяжелых нефтей при температуре 120 °C в токе N2 с выводом образующихся продуктов из реакционной зоны. На основании данных о составе и структуре продуктов термолиза установлено, что при 120 °C нефтяные афальтены подвержены термической деструкции за счет разрыва ковалентных связей с образованием газа, масел и смол, суммарное содержание которых может превышать 13 % мас. Показано, что основными направлениями термических превращений асфальтенов в процессе термолиза являются увеличение фактора ароматичности со снижением доли нафтенового и алифатического углерода. Реакционная способность и глубина термических превращений асфальтеновых молекул зависят от количества в них реакционных центров, представляющих собой слабую алифатическую гетероатомную связь С–Het и/или Het–Het, дестабилизированную электроноакцепторными функциональными группами и нафтеноароматическими структурными блоками с высоким содержанием гетероатомов. Именно комплексное воздействие дестабилизирующих факторов снижает энергию разрыва связи С–Het и/или Het–Het и делает возможной ее распад при 120 °CThermolysis of asphaltenes from three heavy oils was carried out at a temperature of 120 °C in a current of N2 with the withdrawal of the resulting products from the reaction zone. Composition and structure analysis of thermolysis products showed, that at 120 °C petroleum afaltenes are subject to thermal destruction due to breaking of covalent bonds with the formation of gas, oils and resins, exceed 13 % by weight. It is established that the main directions of asphaltene thermal transformations during thermolysis are an increase aromaticity and decrease content of naphthenic and aliphatic carbon. The reactivity and thermal transformations intensity of asphaltene molecules depend on the number of reaction centers in them. Reaction centers represent a weak aliphatic heteroatomic C–Het and/or Het–Het bond, destabilized by electron acceptor functional groups and naphthenicaromatic structural blocks with a high content of heteroatoms. It is complex effect of destabilizing factors reduces the energy of breaking the C–Het and/or Het–Het bond and makes it possible for it to decompose at 120 °

The Effect of Carbonates and Silicates on the Cracking of a Mixture of Fuel Oil and Mechanically Activated Oil Shale

Исследован совместный крекинг смеси механоактивированного горючего сланца (МО ГС) и мазута, смеси деминерализованного МО ГС и мазута. Данные по составу жидких продуктов показали, что после удаления минеральных компонентов горючий сланец легче подвергается разрушению за счет высвобождения керогена. Показано, что в полученных жидких продуктах крекинга смеси мазут — деминерализованный МО ГС доля масел увеличивается до 74,6 % мас. В составе газообразных продуктов крекинга заметно снижается количество водорода, метана и этана. По данным фракционного состава жидких продуктов установлено, что при крекинге смесей мазута и МО ГС после удаления карбонатов и силикатов увеличивается доля бензиновых и дизельных фракцийThe study cracking of a mixture of mechanically activated oil shale (MO OSh) and fuel oil, a mixture of demineralized MO GS and fuel oil has been investigated. The data on the composition of liquid products showed that after the removal of mineral components, oil shale is more easily destroyed due to the release of kerogen. It is shown that in the obtained liquid products of the cracking of the mixture of fuel oil – demineralized MO OSh, the proportion of oils increases to 74.6 % wt. In the composition of gaseous products of cracking, the amount of hydrogen, methane and ethane is noticeably reduced. According to the data on the fractional composition of liquid products, it was found that during the cracking of mixtures of fuel oil and MO HS, after the removal of carbonates and silicates, the proportion of gasoline and diesel fractions in

Transformation of Resinous Components of the Ashalcha Field Oil during Catalytic Aquathermolysis in the Presence of a Cobalt-Containing Catalyst Precursor

The aim of this work was to study the fractional composition of super-viscous oil resins from the Ashalcha field, as well as the catalytic aquathermolysis product in the presence of a cobalt-containing catalyst precursor and a hydrogen donor. The study was conducted at various durations of thermal steam exposure. In this regard, the work enabled the identification of the distribution of resin fractions. These fractions, obtained by liquid adsorption chromatography, were extracted with individual solvents and their binary mixtures in various ratios. The results of MALDI spectroscopy revealed a decrease in the molecular mass of all resin fractions after catalytic treatment, mainly with a hydrogen donor. However, the elemental analysis data indicated a decrease in the H/C ratio for resin fractions as a result of removing alkyl substituents in resins and asphaltenes. Moreover, the data of 1H NMR spectroscopy of resin fractions indicated an increase in the aliphatic hydrogen index during catalytic aquathermolysis at the high molecular parts of the resins R3 and R4. Finally, a structural group analysis was carried out in this study, and hypothetical structures of the initial oil resin molecules and aquathermolysis products were constructed as well