Heavy Oil Residues Research Articles

Investigation of the process and products of plasma treatment of asphaltenes

The results of experiments on plasma processing of the samples of high-molecular fraction of the asphaltenes emitted from the asphaltite representing natural bitumen are reported. The asphaltite, according to its structure and properties, can serve as an analog of heavy oil residues of oil refining. The asphaltenes are treated with the plasma of an arc discharge in a laboratory reactor in ambient air. The structure and properties of the resulting carbon materials are determined by the methods of X-ray diffractometry, thermogravimetric analysis, differential scanning calorimetry, IR-spectroscopy, X-ray fluorescent analysis and laser diffraction. It is found out that during plasma processing of asphaltenes a mixture of gases consisting mainly of H 2 and CH 4 with CO 2 , CO, NO, SO 2 , H 2 S impurities is formed, and an polydisperse carbon material is formed with the structure of graphite, containing the elements present in the initial asphaltite forms: vanadium, nickel, iron, calcium, aluminum, sulfur, silicon and chlorine. The optimum modes of the arc reactor performing the plasma processing of asphaltenes (30 s and current 100 A), allowing to achieve the maximum yield of hydrogen and graphite-like material, are defined.

Dependence of TBP (true boiling point) curve for oil on the method for determining the fractional composition

The subject of this study is the study of methods for determining the fractional composition of oil. 
 The purpose of this work is to assess the influence of the method of determining the fractional composition on the oil TIC on the example of the Salymskoye field. 
 This article describes the comparative results of determining the fractional composition of the oil of the Salym field, obtained by three different methods: atmospheric vacuum distillation, the Engler method, simulated distillation in a gas chromatographic column. 
 The results obtained show which currently depends on the goals and objectives is a more effective method for the study of heavy oils, oil residues and petroleum products.

Co-Processing of Heavy Oil Residues and Sunflower Husk into Synthetic Hydrocarbons

Co-Processing of Heavy Oil Residues and Sunflower Husk into Synthetic Hydrocarbons

Petroleum coking additive is a raw material for production of metallurgical coke. Part 1. Formation of sintering properties of petroleum coking additive (review)

A significant proportion of the entire mass of waste from the oil refining industry is accounted for heavy sour oil residues, and one of the most common solutions in the world is the recycling of these wastes to obtain petroleum cokes. However, the high sulfur content often does not allow to find a qualified application and a market for the obtained sulfide carbon materials. In this work, a review of the scientific and technical literature on the industrial use of petroleum coking additive (PCA) - petroleum coke with a volatile matter yield of 15 to 25%, as a partial replacement for scarce coking coals in the charge in the metallurgical coke production. As a result of the review and analysis of scientific and technical literature, indicators were established that affect the formation of sintering properties of PCA and the boundary conditions for its use as part of a coal charge. It is shown that the use of petroleum coke with a volatile matter yield of less than 15% (wt.) worsens the quality of the obtained metallurgical coke, reducing its strength characteristics CSR and increasing its reactivity CRI, and the introduction into the coal charge from 5 to 50% (wt.) PCA with a content of volatile substances of 15–25% (wt.) provides an improvement in the quality of the resulting metallurgical coke. It is noted that, along with an important indicator, as the yield of volatile substances, which affects the formation of sintering properties of PCA, its group chemical composition, determined by solubility in various solvents (α-, β- and γ-fractions), plays an equally decisive role.The work was carried out within the framework of the State Assignment of the Ministry of Education and Science of the Russian Federation on NIR 0792-2020-0010 "Development of scientific foundations for innovative technologies for processing heavy hydrocarbon raw materials into environmentally friendly motor fuels and new carbon materials with controlled macro- and microstructural organization of the mesophase."

Physico-Chemical Study of Coked Catalyst Particles Obtained from Hydrocracking Process of Heavy Oil Residues with Natural Alumosilicates

Physico-Chemical Study of Coked Catalyst Particles Obtained from Hydrocracking Process of Heavy Oil Residues with Natural Alumosilicates

Characterization of liquid products obtained from catalytic binary co-cracking of residual fuel oil with various waste plastics

Recycling polymeric waste and heavy oil residues are important for energy recovery and raw material processing. Catalytic pyrolysis is a unique technology used to generate alternative energy, and it can stands out to be one of the environmentally friendly and alternative routes for the generation of renewable energy. Limited study has been reported in the literature on the co-cracking of residual fuels with waste plastics to establish its properties and potential. In this study, we have characterized the products in liquid form resulting from the co-cracking of residual fuel oil (RFO) with plastic waste in an isothermal condition. The characterization was carried out using nuclear magnetic resonance (1H NMR & 13C NMR), Fourier transforms infrared spectroscopy (FTIR), gel permeation chromatography (GPC), bomb calorimetry, and ultimate analyzer, in addition to the characterization of the flashpoint, pour point, and density. As a result of co-cracking, the liquid exhibits a significant decline in the overall molecular weight and an increase in the content of saturated aliphatic carbon and a decrease in the protonated aromatic carbons with aliphatic compounds as the primary constituent were observed from the spectra, having a pour point of 291.15–192.15 K and high calorific values between 42–45 MJ/kg. The characteristics of the liquid reveal a synergistic effect of co-cracking and demonstrate the potential of the co-cracking process of waste plastics with residual fuel to be an alternate source of energy and added-value chemical product recovery routes.

Oxidation of Vacuum Residue with the Addition of Crumb Rubber

The actual problem of the oil refining industry is to improve the process of oxidation of heavy oil residues and the properties of oil bitumen. One way to solve the problem is to add modifiers. The addition of modifiers leads to an intensification of the oxidation process and an increase in the characteristics of the bituminous binders. The work aims to study the effect of adding rubber crumb on the process of vacuum residue oxidation and the properties of the obtained rubber-bitumen binders (RBB). The influence of the size of crumb rubber and its content, the mixing stage and oxidation modes on the properties of rubber-bitumen binders are determined. Vacuum residue from the Omsk oil refinery was used as a raw material, which was modified with crumb rubber with a dispersion of 0.6‒1.0 mm and less than 0.6 mm. The novelty of the research is the addition of crumb rubber to the vacuum residue and the oxidation process to obtain bitumen. The product of vacuum residue oxidation for 2 h at 260 °С with preliminary mixing of 2 wt.% crumb rubber with particle sizes less than 0.6 mm at 180 °С and additional mixing of 8 wt.% crumb rubber after oxidation corresponds to the brand of rubber-bitumen binder RBB 60/90. The rubber-bitumen binder is characterized by high elasticity and low Fraas point. Рrepared аsphalt concrete mixture based on RBB corresponded to type B according to physical and mechanical parameters. The complex shear modulus of the samples decreases with the temperature increase. Short-term aging resulted in increased shear modulus for all samples.

Получение 2-этилгексаноата никеля — прекурсора катализаторов крекинга тяжелого углеводородного сырья

This article describes a method for producing a precursor of a nanoscale catalyst for catalytic cracking of straight-run fuel oil, vacuum gas oil, heavy oils and heavy oil residues - nickel 2-ethylhexanoate. The method for obtaining nickel 2-ethylhexanoate salts consists in the interaction of an aliphatic carboxylic acid with an aqueous solution of ammonia, taken in an equimolecular ratio, in an aqueous phase at a temperature of 20-65°C for 20-60 min to obtain a water-soluble ammonium salt of a carboxylic acid in the first stage, introducing an aqueous solution of metal chloride to a solution of an ammonium salt of a carboxylic acidin the second stage, extracting the resulting metal salt of an aliphatic carboxylic acid with an organic solvent, characterized in that 2-ethylhexanoic acid is used as an aliphatic carboxylic acid, and as a metal chloride - nickel chloride, an organic solvent.The yields of nickel 2-ethylhexanoate, depending on the reaction conditions are 89-98%.

Новые подходы к моделированию превращений в нефтяных дисперсных системах в условиях пузырьковой кавитации

An approximate mathematical model is proposed for the transformation of liquid hydrocarbons under the influenceof physicochemical phenomena occurring at the phase boundaries and during phase transitions under conditions of bubble cavitation excited by a source of ultrasonic vibrations. Practical applications of such effects can be alternative processes of industrial oil refining, technologies for increasing the yield of light distillates, intensification of the processing of heavy oil fractions and residues, petrochemical processes of oil refining.

Повышение эффективности теплообменной сети установки замедленного коксования

Thermal integration of technological processes of oil refining is the most effective tool in the design and reconstruction of existing industrial facilities. The rational use of the heat of internal flows is especially important for energy-intensive processes of processing heavy oil residues, such as delayed coking. In this article, a model of the existing heat exchange network of the coke production process was constructed, for which a pinch analysis was carried out and the energy saving potential was determined. The analysis also revealed violations of the basic pinch rules made during the design of the existing circuit and proposed an option to increase its energy efficiency based on the re-linking of existing equipment without involving an additional heat exchange surface.

Математическое моделирование реактора процесса термолиза тяжелых нефтяных остатков

Based on mathematical processing of experimental data, this paper provides a mathematical description of the industrial reactor of the process of thermalize of heavy oil residues. This paper provides a mathematical description (model) of the industrial reactor of the process of thermalize of heavy oil residues. The proposed mathematical description allows you to calculate different typesof reactors. The example of the thrombolysis process of a particular oil buzzer shows the choice of the optimal version of the hardware design of the process of thrombolysis of heavy oil residues during the design. The mathematical model can be used in the process at an industrial reactor to obtain a specified quality of oil-baking additives. The economic calculation showed the possibilityof increasing the company's margin profit.

Hydrodynamic activation of heavy oil residues

Objectives. Recently, there has been a tendency to increase the volume of high-viscosity heavy oils in the total volume of oil produced. The processing of these oils requires new technological approaches. This task is closely related to the need to increase the depth of oil refining. Among the approaches proposed to solve these problems, mechanochemical activation, which is based on the cavitation effect produced by ultrasonic or hydrodynamic methods, has been suggested. This study evaluated the effects of cavitation in increasing the depth of oil refining.Methods. Straight-run and “secondary” oil products were used as raw materials: vacuum gas oil, catalytic cracking gas oil, and fuel oil. Activation was carried out in a high-pressure disintegrator. The principle of operation was to compress the oil product and then pass it through a diffuser. When the oil was passed through the diffuser, there was a sharp pressure release to atmospheric pressure, which caused cavitation in the hydrodynamic flow. The pressure gradient on the diffuser and the number of processing cycles ranged from 20 to 50 MPa and 1 to 10, respectively. The density, refractive index, and the fractional composition of petroleum products were determined using standard and generally accepted methods.Results. This paper reports the influence of mechanochemical activation of petroleum products on their physical and chemical characteristics. An increase in the pressure gradient and the number of processing cycles leads to a decrease in the boiling point of the petroleum products and their density and an increase in the yield of fractions that boil off below 400 °C. The yield of the fractions with boiling points of 400–480 °C and the remainder were reduced. The density and refractive index of fractions with boiling points up to 480 °C decreased, and the density of the residue increased. The effects of cavitation (an increase in the yield of fractions with boiling points up to 400 °C and a decrease in the density of the petroleum products) increased with increasing pressure gradient and the number of processing cycles.Conclusions. The changes in the density, boiling point, and the yield of fractions increased with increasing the pressure from 20 to 50 MPa and the number of hydrodynamic cavitation cycles from 1 to 5. Increasing the number of processing cycles to more than five had little additional effect. The effects of cavitation increased with increasing initial density of the oil product. The average molecular weight of these fractions was estimated from the densities and boiling points of individual fractions of the petroleum products. The calculation confirmed the assumption regarding the course of cracking reactions of petroleum products under the influence of cavitation and indicates the course of the compaction processes.

Influence of Asphaltenes on the Low-Sulphur Residual Marine Fuels’ Stability

The effects of asphaltenes from two heavy oil residues on the sedimentation stability of residual marine fuels were assessed and compared. As base components of residual marine fuels, the vacuum residue (VacRes) and visbreaking residue (VisRes) were taken. The heptane-insoluble fractions (HI-fractions), including asphaltenes, isolated from vacuum residue and visbreaking residue, were analyzed to determine the elemental composition (XRF) and cluster parameters (XRD). The results of the analysis of the parameters of the asphaltene cluster (HI-fraction) for vacuum residue and visbreaking residue showed that dγ – 6.1 and 5.9 Å, Lc – 26.72 and 20.78 Å, and La – 7.68 and 7.20 Å. The sedimentation stability of residual marine fuel was determined according to the ISO 10307-1-2009 (TSA) method and described using ternary phase diagrams. The ratio of stable compositions to the total number of possible compositions (with a step of 10 wt%) was 65/66 or 98.5% for residual marine fuel comprising a mixture VacRes/ULSD/LCGO (vacuum residue/ultra-low sulphur diesel/light catalytic gas oil). Meanwhile, the ratio of stable compositions to the total number of possible compositions was 38/66 or 57.6% for residual marine fuel comprising a mixture VisRes/ULSD/LCGO (visbreaking residue/ultra-low sulphur diesel/light catalytic gas oil).

Production of High Purity Biosurfactants Using Heavy Oil Residues as Carbon Source

Typically, oil pollution cleanup procedures following first response actions include dispersion. Crude oil is biodegradable, and its bioavailability can be increased when dispersed into very fine droplets by means of chemical surfactants. Although their use is widely spread in many applications, the latter may prove toxic, depending on the extent of use. The use of biological means, such as bioremediation and biosurfactants, has emerged over the past years as a very promising ‘green’ alternative technology. Biosurfactants (BSs) are amphiphilic molecules produced by microorganisms during biodegradation, thus increasing the bioavailability of the organic pollutants. It is their biodegradability and low toxicity that render BSs as a very promising alternative to the synthetic ones. Alcanivorax borkumensis SK2 strain ability to produce BSs, without any impurities from the substrate, was investigated. The biosurfactant production was scaled up by means of a sequencing batch reactor (SBR) and a heavy oil residue substrate as the carbon source. The product is free from substrate impurities, and its efficiency is tested on oil bioremediation in the marine environment. The product’s dispersion efficiency was determined by the baffled flask test. The production method proposed can have a significant impact to the market, given the ever-increasing demand for ecologically friendly, reliable, commercially viable and economically competitive environmental cleanup techniques.

Development of new compositions for dust control in the mining and mineral transportation industry

Dust control in summer and winter periods is a topical problem associated with conducting open pit mining operations; however, at negative temperatures the additional requirements are imposed on dust suppressants. Preventive compositions are proposed, in which light and heavy gas oils, obtained from catalytic cracking and delayed coking, are used as base components. Involvement of heavy fractions allows to increase the flash point, thereby reducing the flammability of dust suppressant, improve its adhesion properties by increasing the content of polyaromatic hydrocarbons and reduce the cost of the final product. In order to improve low-temperature and adsorption properties of developed dust suppressants, heavy oil residues (cracking residue and tar) are included in their composition in various concentrations: 2-10 wt.%. Alternative compositions of dust suppressants, obtained by water emulsification of vinylated alkyd oligomer, are developed; the ability of this dispersion to form strong films on dusty surfaces is examined. The efficiency of using aqueous solution of vinylated alkyd oligomer as a summer dust suppressant is demonstrated. The results of this study include the development of new preventive compositions with improved low-temperature properties and confirmation of the theoretical part of the study by the results of performance tests on a laboratory facility.Alternative compositions of dust suppressors have been developed, which were obtained by emulsifying a vinyl alkyd oligomer (VAO) in water; the ability of this dispersion to form strong films on dusty surfaces has been studied. The efficiency of using an aqueous solution of vinyl alkyd oligomer in the summer period as a dust suppressant is shown. The results of this study are the development of new prophylactic formulations with improved low-temperature properties and confirmation of the theoretical part of the study by the results of tests of operational characteristics in a laboratory facility.

Effects of the Composition and Molecular Structure of Asphaltenes on the Properties of Heavy Petroleum Feedstock Represented by Heavy Oil from the Ashalchinskoye Field and Two Vacuum Residue Samples

A combination of analytical methods (including CHNS-O elemental analysis, X-ray diffraction, 1H and 13C NMR spectroscopy, MALDI-TOF and ICP mass spectrometry) was used to determine the elemental composition and average molecular and structural parameters of asphaltenes isolated from a heavy oil sample from the Ashalchinskoye field and vacuum residue samples from two different Russian oil refineries. The study identified differences in the nano-aggregate size of asphaltenes in heavy oil and vacuum residues, and evaluated the effects of the composition and molecular structure of asphaltenes on the composition and properties of the heavy petroleum feedstock samples.

Obtaining Pure Vanadyl Porphyrins from Heavy Oil Residues to Form Bases of Catalysts for Different Processes

Obtaining Pure Vanadyl Porphyrins from Heavy Oil Residues to Form Bases of Catalysts for Different Processes

ЖОЛ ТӨСЕУГЕ АРНАЛҒАН БИТУМДАРДЫҢ НЕГІЗГІ ФИЗИКА-ХИМИЯЛЫҚҚАСИЕТТЕРІ

The most urgent in the oil refining industry, along with the deepening of oil refining, are the problems of improving the quality of oil products, which include heavy oil residues, such as bitumen. Despite the widespread use of petroleum bitumen in road construction, the demand for bitumen is not fully satisfied, because the quality of many bituminous materials does not fully meet the modern requirements of the construction industry.Conformance of bitumen obtained by synthetic method for using it in road construction was reviewed in this article. Some main physical and chemical properties of bitumen were described. Received results meet with specification and we can make the conclusion that synthesized bitumen can be used for road surface.

Investigation of the parameters of the process of obtaining low-sulfur coke from heavy oil residues in the presence of a recycling agent

The current state of the oil refining industry is characterized by obtaining high-quality products that meet environmental requirements. An important issue is the deep processing of oil, as well as the use of oil waste as raw materials. In this regard, there is an interest in putting oil raw materials into operation through destructive processes: catalytic cracking, thermal cracking, visbreaking, coking, and processing of most of the oil waste. The article shows the possibility of producing coke with a low sulfur content from heavy oil waste from a domestic oil field. The physical and chemical properties of the extracted distillates are determined by chromatographic analysis and determined that the group-hydrocarbon composition corresponds to the composition of fractions obtained from primary atmospheric distillation. The process of obtaining of low-sulfur coke used as a conductor and oxidizer of electric current and raw materials in the production of structural material in the presence of a recycling agent from heavy oil waste from the Kumkol field was studied.

Carbon Materials from Coal Tar and Heavy Oil Residues

Carbon Materials from Coal Tar and Heavy Oil Residues