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

Origin, organic geochemistry, and estimation of the generation potential of Neogene lacustrine sediments from the Valjevo-Mionica Basin, Serbia

This paper reports an investigation of 60 samples of lacustrine sedimentary rocks of Neogene age lying at depths of 0-400 m in the Valjevo-Mionica Basin, Serbia. The goal of the study was to determine the origin and type of primary organic matter (OM), the degree of thermal alteration, the generation potential of OM from the rocks of this basin, and conditions in the sedimentation environment during the formation of the rocks. The potential of OM of the rocks was estimated on the basis of the thermolysis of a representative sample after its preliminary debituminization. Using data on C(org) and bitumen contents and S1, S2, and HI Rock-Eval pyrolysis parameters, the samples were divided into three groups. The first and second groups include rocks recovered from depths up to 200 m, and the third group comprises samples from depths of 200-400 m. The investigation of the inorganic constituents of the rocks and biomarker composition showed that the samples of each of these groups were formed under significantly different climatic conditions, which influenced both the composition of primary organic matter and the conditions of the sedimentation environment, which eventually affected the abundance and quality of OM in the rocks. The yield of the liquid fraction and concentration of hydrocarbons obtained during the thermolysis of the debituminized sample of the first group (showing the highest C(org) content), the character of n-alkane and sterane distribution in the saturated fraction of thermolysis products, and the thermal maturity indices calculated from the composition of steranes supported the high generation potential of OM from these rocks

Studying of liquid thermolysis products of various types of immature kerogen in sedimentary lacustrine rocks from the valjevo-Mionica basin, Serbia, and the effect of Pt4+ and Ru3+ ions on their yield and the hydrocarbon composition

Liquid thermolysis products of various types of immature kerogen from sedimentary lacustrine rocks from the Valjevo-Mionica basin in Serbia were studied to evaluate the generation potential of kerogen contained in the organic matter (OM) of the rocks, determine the composition of the biomarkers and alkylaromatics in the liquid thermolysis products, and elucidate the effect of Pt4+ and Ru3+ ions (which were added in the form of inorganic salts) on the yield and hydrocarbon composition of the liquid thermolysis products. For this purpose, representative bitumen-free samples A and B of the sedimentary rocks were subjected to thermolysis under various conditions. Rock A contains high amount of immature organic matter, which is dominated by kerogen type I/II and was generated under strongly reduced sedimentation conditions at a high salinity. Sample B is poorer in immature OM than sample A, and the OM of the former contains kerogen type II/III and was generated predominantly in a reduced environment. The content of the liquid products and the concentrations of hydrocarbons obtained in the course of thermolysis of bitumen-free sample A and the typical oil distribution of the biomarkers and alkylaromatics in the thermolysis products confirm a high generation potential of OM in this rock. In all of our experiments on the thermolysis of bitumen-free sample B, the yield of liquid products and hydrocarbons is low. According to the kerogen type, the thermolysis of this rock generates much gases. The Pt4+ and Ru3+ ions (added in the form of simple inorganic salts) increased the yield of liquid (kerogen type I/II) and gaseous (kerogen type II/III) products. During the thermolysis of various type of immature kerogen in the lacustrine sedimentary rocks at a temperature of 400A degrees C, the OM attained maturation corresponding to the early catagenesis level. Saturated biomarkers and alkylaomatics in the thermolysis products of both samples display typical oil distributions. The type of the source OM most strongly affects the composition of n-alkanes and alkylnaphthalenes. The metal ions used in this research served as catalysts for the methylation process during the thermolysis of immature kerogen, regardless of its type. The effect of the Pt4+ and Ru3+ ions on other transformations of the hydrocarbons, for example, the destruction of high-molecular n-alkanes to low-molecular ones and on isomerization reactions in molecules of polycyclic biomarkers and alkylaromatics to thermodynamically more stable isomers in the thermolysis products is controlled, first of all, by the type of the source OM

Validation of data on polycyclic biomarkers, naphthalenes, phenanthrenes, and alkyldibenzothiophenes obtained by gas chromatographic-mass spectrometric analysis of hydrocarbon concentrates

The possibility of using the data on the hydrocarbon composition obtained by analysis of hydrocarbon concentrates for geochemical studies has been shown on the example of Pannonian Basin (Serbia) crude oils of different genetic types and different degrees of thermal maturity and biodegradation. A high convergence of the values of geochemical parameters calculated on the basis of the composition of steranes and terpanes, alkylnaphthalenes, phenanthrenes, and dibenzothiophenenes in hydrocarbon concentrates and chromatographic fractions isolated from them has been found by correlation analysis

New maturation parameters based on naphthalene and phenanthrene isomerization and dealkylation processes aimed at improved classification of crude oils (Southeastern Pannonian Basin, Serbia)

Aiming at improved classification of crude oils, naphthalene and phenanthrene isomerization and dealkylation processes were considered in detail as a possible basis to select new maturation parameters. Crude oils originating from the Banat depression (Southeastern Pannonian Basin, Serbia) were used as objects of our study. Four new maturation parameters are proposed in this paper. Two of them are based on dimethylnaphthalene (DMN) and trimethylnaphthalene (TMN) isomerization reactions: DNx = (1,3-DMN + 1,6-DMN)/(1,4-DMN + 1,5-DMN) and TNy = (1,3,6-TMN + 1,3,7-TMN)/(1,3,5-TMN + 1,4,6-TMN). The other two are based on demethylation of dimethyl-and trimethylphenanthrenes (DMP and TMP) into corresponding methylphenanthrenes (MP): MDR = Sigma MP/Sigma DMP and MTR = Sigma MP/Sigma TMP. The new parameters' advantageous applicability was demonstrated by factor analysis, comparing them with maturation parameters known from literature

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