Light Distillate Research Articles

IMPROVEMENT OF CATALYTIC CRACKING FOR DEEPEN OF OIL REFINING

At the moment, there is a situation in the world in which the volume of proven reserves of light oils is decreasing, and the volume of reserves of heavy oils are increasing. The processing of heavy hydrocarbons is becoming more complicated and does not provide the necessary depth of extraction of light distillates. Large capital expenditures are required to ensure the specified oil refining depth parameter.The deepening of oil refining is developing through the development and implementation of flexible technological schemes and advanced high-intensity environmentally friendly thermocatalytic and hydrogenation processes for deep processing of vacuum gas oils and oil residues, which include catalytic cracking.Catalytic cracking allows not only to increase the depth of oil refining, but also to ensure the production of a high-octane component of commercial gasoline. In addition, the products are gases rich in propane-propylene and butane-butylene fractions which are used as raw materials for petrochemical synthesis and production of motor fuel components.Currently, the problem of improving the catalytic cracking process is quite acute, because at existing installations, catalytic systems are being replaced with domestic analogues, the raw materials of the process are becoming heavier due to the use of deep vacuum distillation of oil and the need for high-quality commercial products and petrochemical raw materials is increasing.Therefore, the paper proposes to use a modeling method to predict the process indicators. The mathematical model will allow us to develop technical solutions to optimize the operation of the catalytic cracking unit in order to increase the depth of processing of hydrocarbon raw materialsBased on monitoring the operation of an industrial catalytic cracking plant, experimental dependences of the effect of process parameters on the yield of target products were obtained, systems of differential equations of material balance were developed, experimental and calculated data on the model were compared.Regression analysis was used to determine the existence of dependence, and the correlation method was used to describe the nature of the relationships. The main parameters of the catalytic cracking process are described, such as temperature, pressure drop, catalyst level and steam consumption. The dependences of the output parameters on each other (gasoline, butane-butylene and propane-propylene fractions) were revealed. The model is obtained in the form of a generalized formula based on a combination of complex methods in the analysis. The adequacy of the obtained equation has been confirmed using existing software. A new software solution has been proposed for the selection of optimal process parameters based on the previously compiled model.

Upgrading vacuum residue in a supercritical CO2 environment with polypropylene and steam: Insights into products distribution and characterization of liquid products

The pyrolysis of vacuum residue (VR) using polypropylene (PP) under supercritical carbon dioxide (scCO2) conditions represents a novel approach to converting this abundant and difficult-to-process feedstock into lighter liquid products. In this paper, a set of experiments was performed to analyze the impact of scCO2, PP and steam on the yields of pyrolysis products (i.e., liquid, gas and coke) and characteristics of the liquid fractions. The findings indicated notable improvements when scCO2 was used instead of subcritical CO2 in the pyrolysis of VR with PP. These included decreased viscosity and improved API gravity, alongside increased maltene yield and reduced coke yield. Furthermore, the inclusion of PP markedly elevated the quality of the obtained liquid, whereas steam + scCO2 primarily affected the product distribution by raising the yield of coke and gas fractions. VR pyrolysis under scCO2 conditions at 380 °C, 8 MPa, PP/VR ratio of 0.23 for 60 min in a batch system, without the use of catalyst, resulted in the highest liquid yield of 83.7 ± 1.9 wt%, and minimum coke yield of 9.8 ± 1.3 wt%. Under these conditions, the upgraded liquid consisted of 75.2 wt% light and middle distillates with boiling points below 350 °C. Additionally, the proportion of oxygenates in the pyrolysis oil reduced by 60.5 %, improving its heating value. Moreover, adding PP to the upgrading process resulted in a higher proportion of isoparaffins, cycloparaffins, and aromatics, coupled with a decrease in olefins, aligning the liquid specifications more closely with fuel standards.

КОМПЛЕКСНЫЙ ПОДХОД К ПЕРЕРАБОТКЕ УЛОВЛЕННЫХ НЕФТЕПРОДУКТОВ

The scheme for the formation of captured (return) petroleum products from an oil refinery has been studied. A new scheme for processing captured petroleum products has been proposed, which makes it possible to reduce the amount of trapped petroleum products through qualified processing of light and middle distillate fractions. The rational use of the heavy fraction is proposed

Desulfurization of Light Distillate by Catalytic Oxidation Integrated with Emulsification

Desulfurization of Light Distillate by Catalytic Oxidation Integrated with Emulsification

Modelling and Simulation Studies on the Characteristic Behaviour of Macroalgae Derived Bio-Oil

Abstract With the expanding need for renewable and sustainable energy resources, the demand for biomass derived bio-oil particularly microalgae or macroalgae based bio-oil is growing. In this regard, understanding the characteristics of bio-oil as a function of several influencing operational parameters is essential. In this study modelling and simulation technique based on Aspen HYSYS was applied to investigate the characteristics of macroalgae Ulva prolifera derived bio-oil from Hydrothermal Liquefaction (HTL) process as a function of the influencing parameters like temperature, kinematic viscosity, and weight percent of the bio-oil assay, cut yield behaviour, and standard liquid density. Modelling and simulation help to optimise the process parameters and design the process layout for large-scale production. According to the simulation results the cut yield of off gases, light naphtha, heavy naphtha, light distillate, heavy distillate, gas oil and residues are shown at specific final boiling point (FBP) temperatures of 70 °C, 70 °C - 110 °C, 110 °C - 221.1 °C, 221.1 °C - 304.4 °C, 304.4 °C - 371.1 °C, 371.1 °C - 537.8 °C and 537.7 °C respectively. Whereas, above a temperature of 300 °C, the weight percentage of aromatic components increased steadily. The increase in percentage composition of the aromatic components is due to the reduction of the paraffinic components. The density of the liquid bio-oil was steadily increasing until a temperature of 200 °C.

Molecular Characterization of Hydrocarbons in Petroleum by Ultrahigh-Resolution Mass Spectrometry

The progress in ultrahigh-resolution mass spectrometry (UHRMS) and related technologies has significantly promoted the development of petroleomics. The study of petroleomics has greatly broadened our knowledge of the composition of petroleum at the molecular level, especially heavy fractions that cannot be analyzed by gas chromatography (GC)-based methods. To date, heteroatom-containing (O, N, S, and metal atoms) compounds in petroleum have been studied extensively by UHRMS. Nevertheless, the main components of petroleum, hydrocarbon compounds, have remained out of reach of petroleomics characterization for a long time because they are too difficult to be softly and efficiently ionized for UHRMS analysis. It is undoubtedly the case that petroleum hydrocarbons should not be the missing part of petroleomics characterization since they play important roles not only as feeding pools for various high value-added petroleum products but also as critical biomarkers for geochemistry studies. Here, the most recent breakthroughs in petroleomics characterization of hydrocarbon compounds using UHRMS rather than conventional methods have been reviewed. Innovations of soft ionization methods can transform non-polar hydrocarbon molecules into molecular ions or quasi-molecular ions that are reachable for UHRMS without fragmentation. The development of data processing methods has assisted the decoding of the complicated UHRMS data to visualize the molecular composition and structure of hydrocarbon compounds. These advances make it possible to see the whole picture of petroleum compositions, from light distillation fractions to heavy distillation fractions, and from small volatile molecules to large non-volatile ones. The applications of UHRMS-based methods for petroleomics characterization of hydrocarbon compounds in crude oils and various petroleum samples including fuel oil, slurry, and even asphaltene have made a great contribution to petrochemistry and geochemistry studies, especially in the fields of molecular refining and biomarker discovery.

Refinement of limonene epoxides from the light distillate of tire pyrolysis oil via catalytic epoxidation

The light fractions of tire pyrolysis oil (TPO) are rich in valuable chemicals, such as limonene, but the utilization of TPO-derived limonene or limonene derivatives was limited by the difficulties to separate limonene from the rest compounds, especially p-cymene which has a similar molecular structure and physical properties (molecular size, melting point and boiling point) as limonene. In order to utilize limonene and separate p-cymene, this study took advantage of the difference in oxidizability between limonene and p-cymene, and proposed a method of epoxidizing TPO before the separation. After epoxidation, limonene was successfully converted into limonene epoxides, while aromatic compounds in TPO such as p-cymene were inert and non-oxidizable. Limonene epoxides have a higher boiling point than p-cymene, so the limonene epoxides can be easily refined by distillation. In order to accelerate the oxidation of limonene, a peroxophosphotungstate catalyst was used as a sustainable solvent-free process. The fraction of TPO between 160 and 190 °C which has 298 g/L limonene was tested in this study. The epoxidation of the TPO160-190 could reach complete conversion to limonene 1,2-oxides and diepoxide limonene. The resulting oil could be divided into p-cymene enriched fraction and limonene epoxides enriched fraction by simple distillation, and the limonene epoxides enriched fraction contained more than 80% of limonene epoxides. The catalytic mechanism was proposed with the assistance of FT-IR, GC–MS, and 31P NMR analysis. This work presents a novel strategy of epoxidizing limonene for limonene epoxide and p-cymene separation, which could bring a breakthrough for limonene epoxide and p-cymene production from waste-derived oils.

Impacts of support properties on the vacuum residue slurry-phase hydrocracking performance of Mo catalysts

To deeply understand the effects of support properties on the performance of Mo-based slurry-phase hydrocracking catalysts, four Mo-based catalysts supported on amorphous silica alumina (ASA), γ-Al2O3, ultra-stable Y (USY) zeolite and SiO2 were prepared by the incipient wetness impregnation method, respectively, and their catalytic performances were compared in the vacuum residue (VR) hydrocracking process. It is found that the Mo/ASA catalyst exhibits the highest VR conversion among the different catalysts, indicating that both the appropriate amount of acid sites, especially B acid sites and larger mesoporous volume of ASA can enhance the VR hydrocracking into light distillates. Furthermore, Mo catalysts supported on the different supports show quite different product distributions in VR hydrocracking. The Mo/ASA catalyst provides higher yields of naphtha and middle distillates and lower yields of gas and coke compared with other catalysts, it is attributed to the highest MoS2 slab dispersion, the highest sulfuration degree of Mo species, and the most Mo atoms located at the edge sites for the Mo/ASA catalyst, as observed by HRTEM and XPS analyses. These features of Mo/ASA are beneficial for the hydrogenation of intermediate products and polycyclic aromatic hydrocarbons to restrict the gas and coke formation.

Influence of FeP and Al(H2PO4)3 Nanocatalysts on the Thermolysis of Heavy Oil in N2 Medium

The high viscosity of heavy oil is the main challenge hindering its production. Catalytic thermolysis can be an effective solution for the upgrading of heavy oil in reservoir conditions that leads to the viscosity reduction of native oil and increases the yield of light fractions. In this study, the thermolysis of heavy oil produced from Ashalchinskoye field was carried out in the presence of FeP and Al(H2PO4) nanocatalysts at a temperature of 250 °C in N2 gas environment. It was shown that Al(H2PO4)3 and FeP catalysts at a concentration of 0.5% significantly promoted the efficiency of the heavy oil thermolysis and are key controlling factors contributing to the acceleration of chemical reactions. The Al(H2PO4)3 + NiCO3 nanoparticles were active in accelerating the main chemical reactions during upgrading of heavy oil: desulfurization, removal of the side alkyl chains from polyaromatic hydrocarbons, the isomerization of the molecular chain, hydrogenation and ring opening, which led to the viscosity reduction in heavy oil by 42%wt. Moreover, the selectivity of the Al(H2PO4)3 + NiCO3 catalyst relative to the light distillates increased up to 33.56%wt., which is more than two times in contrast to the light distillates of initial crude oil. The content of resins and asphaltenes in the presence of the given catalytic complex was reduced from 34.4%wt. to 14.7%wt. However, FeP + NiCO3 nanoparticles contributed to the stabilization of gasoline fractions obtained after upgraded oil distillation. Based on the results, it is possible to conclude that the thermolysis of heavy oil in the presence of FeP and Al(H2PO4)3 is a promising method for upgrading heavy oil and reducing its viscosity.

Production of Distilled Bitumen from High-Viscosity Crude Oils of Ukrainian Fields

The characteristics of initial crudes of Yablunivske field (Poltava, Ukraine) and the properties of blended crudes have been examined to select the ways of their further processing. The crude oils were found to be heavy high-sulfuric oils without light distillates. The possibility of obtaining paving bitumen from blended crudes under study has been considered. Distilled bitumen obtained through distillation of this blend was found to meet the requirements for commercial paving bitumen 100/150. To improve the durability and resistance to aging of resulting bitumen, a polymeric modifier was added. The modifier amount of 3 wt.% was found to be appropriate to improve the operational characteristics of obtained bitumen to those of BMW 60/90 grade.

In Situ Upgrading of Heavy Crude Oil: Comparative Study of the Performance of Cu-, Fe-, Ni-, or Zr-Containing Water-Based Catalysts

The world continues experiencing a steady decrease in the availability of conventional light or even medium crude oils, and hence, refineries inevitably face the challenge of processing increasing amounts of (extra) heavy crude oils while preserving their economic targets. This requires changes/improvements in existing refining technologies for converting heavy crude oil, which may be conveniently preceded by an improvement in its flowing properties in the underground reservoir itself. In this context, this research focuses on the use of liquid catalysts containing Cu, Fe, Ni, or Zr for upgrading in situ a heavy crude oil stream (12.6 °API) in a bench-scale batch-stirred reactor operated at 380 °C and 10.8 MPa for 1 h, in the presence of high-purity hydrogen. Upon reaction, the heavy crude oil properties improve while catalysts undergo in situ transformations identifying from the analysis of residual solid recovered from the bottom of the reactor, the formation of some metallic sulfides and oxides (by X-ray diffraction (XRD)), which exhibit Bronsted and/or Lewis-type acidity (via Fourier transform infrared (FT-IR) spectroscopy). While converting ca. 43% of the heavy crude oil residue fraction (>524 °C), the Zr-containing catalyst, which exhibits relatively strong Bronsted and Lewis acid sites thus increasing the cracking rate, decreases the kinematic viscosity (1444–24 cSt, at 37.5 °C) as well as the amount of asphaltenes (28–13 wt %) and sulfur (5.14–2.8 wt %), and increases the content of light and middle distillates (18.9–34.1 wt %) along with the API gravity (12.6–21°). The results indicate that the use of liquid catalyst appears as a promising option on the way to development of an “inside-reservoir technology” for heavy crude oil processing.

Взаимосвязь содержания асфальтенов в нефтях Северного Каспия и качества получаемых нефтепродуктов в процессе первичной переработки

The article highlights the problem of improving the quality of the products obtained during the primary processing of oil from the fields of the Northern Caspian. Objects, methods and characteristics of oil raw materials are presented.The influence of a constant magnetic field in a dynamic mode on the yield of light fractions during the processing of oil from the Yury Korchagin and Vladimir Filanovsky fields has been studied. The results of a study of the influenceof a magnetic field on oil on the qualitative characteristics of the obtained products of atmospheric distillation and the yield of light distillates are presented. The relationship between the content of asphaltenes in the original oiland the results of atmospheric distillation of pre-activated oil feedstock is shown.

Улучшение физико-химических свойств прямогонной дизельной фракции посредством магнитного поля

the article discusses issues related to unconventional methods of activation of hydrocarbon raw materials, which include: the use of electromagnetic and ultrasonic fields, magnetic pulse and other. The purpose of the presented work is to study the influence of the magnetic field on the oil of the North Caspian field during its primary processing and to analyze the physico-chemical properties of the obtained light distillates. As a result of fractional distillation, a diesel fraction with improved performance characteristics was obtained. It was found that when exposed to magnetic induction of 0.3 Tl and a linear flow velocity of 0.2 m/s, the cetane number increases by 6 units, density and kinematic viscosity decrease by an average of 15%.

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.

Zbor sastava kolektora i temperaturnih uslova za separaciju dijamanata procesom flotiranja

Quantitative and qualitative regularities of a collector low and high molecular weight fractions distribution between solid and liquid phases in foam separation process were determined with the use of extraction-spectrophotometrical technique. The feasibility of producing a collector with optimal ratio of fractions of light distillates, hydrocarbon oils, resin, and asphaltenes by mixing M-40 fuel oil with diesel fuel oil in specified ratios was substantiated. It was shown that applying compound collectors with M-40 fuel oil weight percentage of 60-70 enabled increasing diamond recovery by 2.7-3.5%. Similar increase was also achieved when using F-5 bunker fuel oil diluted by 10-18% with diesel oil fraction. The optimal temperature of 24 °C for initial ore feed conditioning with flotation agents and foam separation providing maximum diamond recovery into concentrate and high selectivity was determined. The proposed collectors and temperature conditions enabled increasing diamond recovery.

Rhazes’ Contributions to Alchemy and Pharmacy

Context: Persia has been the cradle of science across human history. Many of today’s concepts in science, such as the finite speed of light and alcohol distillation, were first proposed by Persian scientists. Mohammad ibn Zakariya Razi (Rhazes) is undoubtedly one of the greatest Persian scientists over human history. Evidence Acquisition: In this paper, in addition to a brief review of the history of pharmacy and chemistry sciences in Persia, Rhazes’ valuable books in the fields of pharmacy and chemistry, along with a brief description of them, were introduced. Data were extracted from different historical and bibliography books and also the citation databases of PubMed, Scopus, and Google Scholar. Results: Rhazes’ books and treatises in the fields of pharmacy and chemistry have been classified into three categories: (1) the books and treatises containing some sections on pharmacy like Al-Hawi fi al-Tibb (Liber Continens) and Al-Mansouri fi al-Tibb, (2) those written merely on pharmacy, like Qarabadin (pharmacopeia), and (3) the books focusing on alchemy (kimia), like Sirr al-Asrar (Secret of secrets) and Al Asrar (Liber Secretorum). Three volumes of Al Hawi fi al-Tibb were applied as a reference in pharmacology in Western universities for many years. Sirr al-Asrar is his most important book on alchemy, describing raw materials used in alchemy, experimental apparatus necessary for alchemical investigations, and detailed procedures for the chemical manipulation of arsenic and sulfur. Conclusions: These valuable manuscripts demonstrate the ancient heritage of Persians and the great roles and contributions of Persian scientists in the history of science.

About the effectiveness of hydrocarbon diluents for pipeline transportation of high viscosity heavy and waxy oil

Deposits of tight high viscosity heavy and waxy oil are becoming increasingly important in the world economy. They are also of particular importance in Russia, where the fields of easy accessible oil are practically depleted, and the newly discovered ones are located mainly in the northern latitudes of the country, which complicates their delivery to places of consumption, and use of so-called "special methods" (heating, chemical reagents) leadsytanb to an increase Cost. Despite the abundance of such methods, one can distinguish one of the most accessible and understandable from the point of view of the physico-chemical effect - dilution with hydrocarbon diluents, as can be effectively used by adding ready-made motor fuels and light distillates of oil, as well as - cheaper stable gas condensate, also co-produced in oil fields.In the present work, the experience of blending high viscosity heavy and congealing waxy oil with various types of hydrocarbon diluents has been considered with the aim of improving the operational properties of hydrocarbon crude, the transport and processing of which are associated with high costs due to the peculiarities of the composition and properties of the oil. The results of laboratory experiments on dilution of heavy and congealing oils with diesel fuel and stable gas condensate are given, on the basis of which recommendations on the effective usage these special methods. Keywords: oil; rheology; effective viscosity; pour point; hydrocarbon diluent; stable gas condensate.

Characteristics of fractionated drop-in liquid fuel of plastic wastes from a commercial pyrolysis plant

Pyrolysis is a waste conversion technology to solve an increasing plastic waste issue worldwide. Waste plastic pyrolysis fuel from a commercial-scale pyrolysis plant (10 ton/day) was comprehensively investigated using distillation methods by separating the crude pyrolysis fuel to isolate the diesel-like pyrolysis fuel fraction (C9–C25 for fraction 2 + fraction 3, middle distillate). Other fractions were C5–C10 for the light distillate (fraction 1), and >C25 for the heavy distillate (fraction 4). The relationship between the fuel boiling point and liquid vapor temperature were found for designing a scaled-up oil separation process. The diesel grade pyrolysis fuel fraction comprised approximately 70–80% of the crude pyrolysis fuel, wherein it had values of 43–45 MJ/kg, 1–6 cSt, and 12–42 mgKOH/goil. Meanwhile, the elemental ratios of the crude pyrolysis oil improved to 0.1 for O/C and 1.9 for H/C after separation, close to petroleum fuels (0.0 O/C and 1.95 H/C). The highest relative chemical composition was the olefins (46% in fraction 1 and 41% in fraction 2), whereas the paraffin was approximately 15–20% in the light fraction. Finally, the potential CO2 reduction for the plastic waste-to-energy process was evaluated, revealing that a total of 0.26 tCO2/tonwaste of emissions could be avoided during the waste plastic pyrolysis process.

Catalytic evaluation of metal azolate framework-6 in pristine and metal doped modes in upgrading heavy residual fuel oil

Despite the attracted widespread attention to the metal organic frameworks (MOFs) as advanced materials, they have not been inspected as catalytic additive in upgrading heavy oil. Herein, MAF-6, a nominated member of MOF vast family with high hydrophobicity and large structural cavities of 18.4A° was examined in catalytic upgrading of heavy residual fuel oil in pristine and molybdenum-doped modes. Integration of the MOF matrice with molybdenum was implemented to impart additional catalytic properties leading to the further improvement in catalytic upgrading performance. Both synthesized pristine and in-situ Mo-doped MAF-6s were characterized by XRD, FESEM, N2 adsorption-desorption, elemental mapping, ICP, and Raman analyses. The outcomes confirmed the high purity, crystallinity and porosity of both catalysts and the successful positioning of phosphomolybdic acid entities throughout the Mo-doped MAF-6 skeleton. Introduction of a small dosage (0.7 wt %) of either catalyst to the heavy oil was able to reduce the gas evolution and coke formation albeit with similar product distribution in comparison with thermal upgrading. However, conducting the viscosity and asphaltene content measurements, CHNS, TGA and 1HNMR analyses on catalytically upgraded oils emerged qualitative differences. TGA results revealed that pristine and Mo-doped MAF-6s were able to produce 62 and 58.3 wt % light and middle distillates, respectively, compared to the thermal upgrading with 54.8 wt % yield. However, Mo-doped-MAF-6 acted more efficiently achieving deeper asphaltene conversion up to 54.6 % and more intense viscosity drop to 98 cSt versus thermal upgrading with 49 % asphaltene conversion and viscosity reduction to 157 cSt. Catalytic upgrading with MAF-6 also yielded a liquid with 128 cSt viscosity without any further asphalten reduction.

ВЛИЯНИЕ УЛЬТРАЗВУКА НА ТЕРМОХИМИЧЕСКУЮ ПЕРЕРАБОТКУ МАЗУТА С ДОБАВКАМИ СЛАНЦА ПРИ РАЗНЫХ ДАВЛЕНИЯХ

This article presents the results of the influence of ultrasonic exposure (UE) on the process of thermochemical destruction of fuel oil in the presence of shale of Kenderlyk field at different pressure intervals (3.5-5.5 MPa). A number of experiments were performed before and after ultrasonic exposure to select the working pressure for thermochemical processing of shale and fuel oil. Analysis of the results of pressure influence on the yield of thermochemical processing products shows that with increasing process pressure there is an increase of yield of gas, gasoline fraction (up to 180°C) and diesel fractions (180-360 °C) reaching maximum values in the range of 5.0 MPa. The yield of fractions that boil off at temperatures more than 360 °C are decreased with increasing pressure in the range of 3.5-5.5 MPa, and then begins to grow sharply with increasing pressure. After ultrasonic exposure at a temperature of 80 °C, a frequency of 22 kHz and 25 minutes of soaking the total yield of light distillates increases to 65.0 mass%. This is 10 units higher than without the use of UE.