Vol 59, No 2 (2019)

The importance of oil as the most important mineral necessary for the progress of the world economy sharply raises the question of the exhaustion or inexhaustibility of its resources. The answer to this question is closely related to ideas about the origin of oil and hydrocarbons in general. In this article, the question of the origin of hydrocarbons is considered in the light of the proposed hypothesis of the origin and evolution of the Earth as an open system genetically related to the origin of the Universe. According to this hypothesis, the processes of gravitational collapse and the opposite process expansion, including that by an explosion, coexist in unlimited space, prevailing in one or another of its areas. The original substance (core) of the Earth is a fragment of the “dark matter” of an exploding neutron star. The planet Earth has an age corresponding to that of the Big Bang (about 15 billion years). The evolution of the Earth has two stages: pregeological and geological. The beginning of the geological stage of the Earth evolution is determined by the age of the most ancient artifacts in Earth’s crust. The core of the Earth emits excess neutrons, some of which decay immediately after separation from the nucleus to form a proton–electron pair or a hydrogen atom. A mixture of neutrons, protons, electrons, and nascent chemical elements is the “broth” in which chemical elements and their isotopes, as well as the simplest gases and complex compounds, are formed as a result of chaotic collisions. Neutron–proton–hydrogen (NPH) transformation, first formulated by I.M. Belozerov is the main process determining the development of the Earth. The formation of chemical elements and their isotopes occurs initially though the combination of two hydrogen nuclei into an α-particle, which is the helium nucleus and an integral part of the nuclei of chemical elements, primarily having a multiple of four. Due to the special features of their structure, hydrogen, oxygen, and carbon are of particular importance for the formation of complex compounds. In the process of synthesis of the simplest gases and complex elements, water, methane, carbon dioxide, hydrogen sulfide, and nitrous oxide are formed. The Belozerov–Sharov– Minin hypothesis proposed and this paper are not intended to intensify the discussion between advocates of the organic and inorganic hypotheses of oil origin. The paper calls for enhancing research, both theoretical and practical, aimed at increasing the source base of oil and other hydrocarbons by discovering new fields at various depths, both on land and in water areas. Oil is inexhaustible as long as neutron fluxes are emitted by the Earth core. The physical basis of the hypothesis under consideration is set out in the monograph by I.M. Belozerov “Nature through the Physicist Eyes” and in joint publications of the authors of the hypothesis, including data reported by other researchers. The geological rationale and the geological implications of the hypothesis are based on the results of research of the authors of this paper using information published by other researchers. References to the studies discussed in the above publications are not duplicated. On the basis of the hypothesis in question, particular recommendations on the formulation of forecasting and prospecting works can be given.

Using the techniques of proton nuclear magnetic resonance (¹H NMR) relaxometry and near-infrared spectroscopy, a multiextremun nature of dependencies of physicochemical properties, fractality, and quantization of changes in ¹H NMR parameters that determine phase transitions between types of petroleum disperse systems in the order: Hydrocarbons ⇔ Crude oil ⇔ Atmospheric residue ⇔ Vacuum residue ⇔ Asphalt ⇔ Carbenes ⇔ Coke, has been experimentally established. A model of structural–dynamic transitions, associated with a change in the intermolecular pair potential characterized by a number of minima is proposed.

Catalysts based on a palladium sol supported on acid-activated montmorillonite in the Na form (Pd-sol/NaHMM) have been tested in the n-hexane isomerization reaction. An increase in the Pd content from 0.1 to 0.35% leads to an increase in the catalyst activity. The C₆₊ isomer selectivity remains stable and fairly high: it is 94.6–98.0% in the presence of the catalysts with a Pd content of 0.1 or 0.35%, respectively. The maximum conversion of n-hexane over the 0.35%Pd catalyst is 52.6% at a temperature of 400°C; the addition of mordenite leads to a slight decrease in conversion to 50.9%. The maximum conversion at 400°C in the presence of the 0.1%Pd catalyst and the mordenite-modified catalyst is 45.0 and 50.4%, respectively. The maximum yield of isomeric hexanes over the zeolite-free 0.35%Pd and 0.1%Pd catalysts is 44.9 and 39.3%, respectively. In the presence of the mordenite-containing 0.35%Pd/NaHMM+HM catalyst and the low-percentage 0.1%Pd/NaHMM+HM catalyst, the C₆ isomer yield is 44.3 and 43.0%, respectively. The amount of hydrocracking products does not exceed 0.7%. The particle size of the Pd sols is 3.5–5 nm, as determined on a JEM 2100 high-resolution transmission electron microscope. The elemental composition of the Pd-sol/NaHMM catalysts containing different amounts of palladium and the catalysts modified with mordenite has been determined by energy dispersive X-ray fluorescence spectroscopy.

Statistical processing of experimental data to reveal the optimal conditions for nitration of higher linear α-olefins with nitrogen oxide in polar and nonpolar solvent media has been carried out. The influence of various factors (temperature, time, reactant feed rate) on the yield and composition of nitro products has been shown.

The anthracene coking process has been investigated in the temperature range of 400–600°C. It has been shown that intermolecular interaction of two anthracene molecules resulting in the elimination of hydrogen and the formation of a C–C bond between the middle rings begins at a temperature of 450°C. Increasing the coking temperature to 500–600°C leads to the formation of poorly crystallized graphite. In the case of pure anthracene, the formation of micron-sized spherical carbon particles occurs. The addition of carbon nanotubes to anthracene leads to the formation of the carbon “coat” covering their surface. The thickness of the carbon “coat” depends on the temperature of coking. An amorphous carbon layer observed on the surface of carbon nanotubes has a thickness of 1–2 nm in the case of coking temperature of 450°C or 10–15 nm in the case of coking at 600°C.

The emerging fuel crisis necessitates a shift in focus towards alternative renewable forms, so that sustainable development can be achieved. Bio-oil is a promising alternative renewable source of energy which is a third generation bio-fuel. Algae are a popular candidate for bio-fuel production due to their high lipid contents, ease of cultivation and rapid growth rate. In this study, Hydrothermal liquefaction of Scenedesmus obliques biomass cultivated in photo-bio-reactor (PBR) from wastewater was studied. The influence of process parameters on the bio-oil yield and bio-oil upgrading was analysed. Different S. obliques biomass to water ratios (0.025, 0.05, 0.075 and 0.1 g/ml) were liquefied at diverse temperatures ranging from 200 to 340°C under 5 MPa N₂ gas atmosphere. The influence of catalyst on bio-oil upgradation was studied at varying catalyst loading of the range 1–5 wt %. Bio-oil was analysed using Gas Chromatography Mass Spectroscopy (GC-MS) and Fourier Transform Infrared Spectroscopy (FTIR). Results showed a maximum bio-oil yield of 24.57 wt % at 300°C, 15 g/200 ml biomass load and 2.5 wt % NaOH at 60 min holding time. Also, it was found that the gas generated from liquefaction process contained 22 vol % Hydrogen gas, 18 vol % Carbon dioxide gas, 27 vol % Carbon monoxide gas, 22 vol % of methane gas and a small amount of other gaseous components (H₂S). HTL bio-oil was upgraded and it resulted in 30.15 wt % yield with higher degree of C₇−C₂₁ range hydrocarbons in it.

The transformation of alumina-supported palladium salts during isothermal treatment in a reducing atmosphere has been studied to determine the optimum reduction temperature for the Pd/Al₂O₃ catalyst. It has been found that the interaction of palladium acetylacetonate with alumina surface sites is stronger than the interaction of the acetate complex. Owing to this factor, the diameter of the resulting active-ingredient particles is smaller in the case of the former precursor in the entire temperature range of reductive treatments. The optimum reduction temperature for the supported palladium salts is 500°С; this temperature provides the formation of palladium particles characterized by the maximum conversion of methylacetylene and propadiene at a high selectivity for conversion to propylene. The systems activated at temperatures of up to 400°C exhibit low activity in the hydrogenation of methylacetylene and propadiene; this behavior is attributed to an incomplete reduction of palladium from Pd salts to form oxidized and coordinatively unsaturated species of the active ingredient.

A series of propargylamine derivatives possessing bactericidal activity against sulfate-reducing bacteria has been synthesized on the basis of bicyclo[2.2.1]hept-5-ene-2-yl-methylamine. It has been shown that in the case of interaction of aminated norbornene with propargyl bromide, corresponding adducts of the norbornene series which contain a terminal acetylene bond and an amino group in the side chain are formed depending on the molar ratio. Synthesized N-propargylbicyclo[2.2.1]hept-5-ene-2-yl-methylamine is a very reactive compound and can participate in various reactions, in particular, by the amino group or the double bond, to form new derivatives. It has been found that all the synthesized substances at their concentration of 500 mg/L fully inhibit the growth of sulfate-reducing bacteria.

In this study Support Vector Machine (SVM) and Lump Kinetic Model was used to predict the hydrocracking products yield by using data which obtained from Tehran Refinery in Iran. The minimum calculated squared correlation coefficient and key parameters of SVM were used to evaluate the SVM performance. Output variables of SVM model were optimized for hydrocracking products. Kinetic parameter and mean squared error values for the 4-Lumped Kinetic models have been developed. Mean Squared Errors (MSE) of training set for Diesel, Naphtha and LPG were obtained 0.179, 0.116, and 0.174 and for testing set are 0.164, 0.148, and 0.132, respectively. It can be concluded that SVM can be used as a reliable and accurate estimation method with comparison between SVM data and Tehran refining unit. Such validated models may be regarded as valuable tools for process optimization, control, design, catalyst selection and provide a better insight into the process.