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While studying the structural and group composition of aromatic hydrocarbons in liquid fractions of the products of catalytic oxycracking of vacuum gas oil, as well as their molecular weight distribution, it was revealed that monocyclic aromatic hydrocarbons predominate in their composition. Their concentration is lower than in the traditional catalytic cracking sample and decreases in 1% OCC > CC > 2% OCC. Among the identified polyaromatic hydrocarbons, naphthalene and its homologs dominate at 1% oxycracking, and phenanthrene and its homologs dominate at 2% oxycracking; at a 1% degree of oxidation, the amount of naphthalene exceeds the indicators of traditional catalytic cracking by almost 2 times, while at a 2% degree of oxidation, this figure decreases by 4 times, which is the smallest among the studied samples. The cresol content also increased significantly. The concentration of fluorene, phenanthrene, and anthracene decreases, but only slightly. In oxycracking products at a 2% degree of oxidation, the content of all PAH groups is the lowest among the samples under consideration. The trend towards a drop in benzo-containing PAHs, noted for traditional catalytic cracking products, is also true for this sample. [ABSTRACT FROM AUTHOR]

This paper introduces a new methodology for a routine metal analysis of plastic waste (PW) and PW blended with petroleum feedstock such as vacuum gas oil and VGO (PW/VGO). For such purposes, recycled polyethylene and polypropylene plastic were selected to mimic the potential feeds to be integrated at the Fluid Catalytic Cracking unit (FCC) to produce valuable products. Elements such as P, Ca, Al, Mg, Na, Zn, B, Fe, Ti, and Si were included in the method development. Different sample preparation methods were evaluated, such as microwave-assisted acid digestion (MWAD) and dry/wet ashing, followed by a fusion of the ash with lithium borate flux. Some PW homogenization pretreatments, such as cryogenic grinding and hot press molding, were also covered. The finding of this work suggests that MWAD with HNO3 and H2O2 is adequate for both types of samples and is the quickest sample preparation; however, the sample needed to be homogenized, and recoveries for Si and Ti may be biased for PW due to the limited solubilities of these elements in the nitric acid media. Carbon removal is required before fusion sample preparation and analysis due to the amount of carbon in PW samples. The sample needed to be homogenized for wet ash fusion but not for the pre-ash (dry) method. A benefit to the damp ash pretreatment is that the ash for the sample was created in the same crucible used for fusion digestion, avoiding material loss during sample management. Fusion from wet ash or carbon removal allowed for better acid solubility for Si and Ti in PW. The results of the PW samples evaluated matched well with those of both sample preparation methodologies. For most elements, precision was <10% regardless of the sample preparation; however, Fe and P had some variation using wet ash fusion, possibly due to contamination in an open digestion system or variation due to being close to the method limit of quantification (LOQ). The methodology reported here is robust enough to be implemented as routine analysis in any laboratory facility. [ABSTRACT FROM AUTHOR]

The article presents a mathematical model of the vacuum gas oil hydrocracking process, which takes into account chemical transformations of the grouped components, including n-paraffins C22-C40, iparaffins C22-C40, n-paraffins C5-C21, i-paraffins C5-C21, naphthenes, aromatics, resins, hydrocarbon gas, and the reactions of coke formation and its accumulation on the catalyst surface during the operation cycle. The model also includes the equation for calculation of temperature profile during the process and the equation for calculation of the catalyst activity depending on the content of coke accumulated. The results on the influence of the hydrogen-containing gas consumption and the feedstock flow rate on the coke content on the catalyst, the activity of the catalyst and the temperature profile in the catalyst layers, obtained by calculations using a model, are presented. It is shown that hydrogen-containing gas consumption has optimal values depending on the feedstock flow rate, which ensure the maintenance of the maximum possible catalyst activity and the required depth of feedstock conversion. The optimal consumption of hydrogen-containing gas is determined at different feedstock flow rates. The increase in the feedstock flow rate by 20 m³/h from 220 m³/h to 240 m³/h requires increasing in the hydrogen-containing gas consumption by 500 kg/h from 9500 kg/h to 10000 kg/h. Maintaining hydrogen-gas consumption higher than optimal is impractical because it leads to decrease in the temperature of the process lower than favorable for the target reactions thus decreasing the depth of feedstock conversion with simultaneous increasingly more lower influence on the coke formation and increased operational costs. [ABSTRACT FROM AUTHOR]

The current trends in research and development of FCC catalyst is focused on the formulation of active matrices that serve as pre-crackers, with the objective of reducing the diffusional resistance of the longer chain hydrocarbon molecule in the feed. In this study, an aluminosilicate active matrix was synthesised from metakaolin using hydrothermal method. The experimental variables that were varied were hydrothermal temperature, in the range of 80 to 110 ℃, and hydrothermal time, in the range of 12 to 72 hours, to investigate the best conditions for synthesising the active matrix. Subsequently, the active matrix was subjected to a series of analyses, including X-ray fluorescence, X-ray diffraction, N2 physisorption, NH3-temperature programmed desorption, Fourier transform infrared spectroscopy, scanning electron microscopy and thermogravimetry, with the objective of determining its composition, crystal characteristics, surface characteristics, acidity, functional groups, material structure, and thermal characteristics. Additionally, the active matrix was tested for its intrinsic cracking activity using the micro activity test (MAT). The results indicate that the best temperature for hydrothermal synthesis of the active matrix is 80 °C. The active matrix synthesised with a heating time of 24 hours demonstrated the highest light cycle oil yield, reaching 38.9 wt%. Meanwhile, the active matrix synthesised at 48 hours exhibited the most favourable characteristics, with a specific surface area of 144.23 m²/g and a pore volume of 0.9933 cm³/g, as well as the highest cracking conversion of 70.0 wt%. [ABSTRACT FROM AUTHOR]

The results of study of catalytic vacuum gas oil oxycracking process in presence of metal zeolite catalysts are presented. Screening of oxides of 10 modifying transition metals (Cu, Ti, V, Cr, Fe, Co, Ni, Cd, Mo, and W) made it possible to disclose the basic differences in the behavior of the catalytic systems. Based on the data obtained, an activity series were constructed (based on the total yield of light fractions): Mo > Ti > Cr > Ni > Fe >W > V > Cd > Co > Cu. Best results for the target fractions were obtained in the presence of molybdenum, titanium, and vanadium zeolite systems (for 195/200-300°C fractions) and for tungsten-containing system (for hydrocarbon gas). Comparison of vacuum gas oil conversion data obtained under catalytic oxycracking conditions with bond strength of the surface oxygen of the metal oxides made it possible to establish their correspondence and to recommend this criterion for choosing catalysts for the process. [ABSTRACT FROM AUTHOR]

The catalytic vacuum gas oil oxycracking process in the presence of zeolite-containing OMNIKAT-210P catalyst was studied. It was observed that temperature and degree of oxidation have the same effect on the degree of feedstock conversion and the yield of reaction products, whereas temperature and contact time are antithetical. Introduction of oxygen was found to facilitate diesel fraction and hydrocarbon gas formation. Determination of physicochemical characteristics of narrow fractions made it possible to assess the quality of the potential commercial straight-run products of vacuum gas oil oxycracking, depending on the technological conditions of the process. [ABSTRACT FROM AUTHOR]

Relevance. The need to accumulate data on nitrogen-containing compounds of heavy fractions, the share of which in secondary oil refining is steadily increasing every year. With the weight of raw materials the amount of sulfur-, nitrogen- and oxygen-containing components in it increases. The high content of heteroatomic compounds has a negative impact on catalytic processing, the quality and performance characteristics of the products obtained, and the environment. One of the widespread processes for upgrading crude oil, in particular, vacuum gas oil, is hydrotreating. However, during the catalytic hydrodesulfurization of heavy distillates the reactions of hydrogenolysis of organic sulfur compounds are inhibited in the presence of nitrogen-containing compounds. At the same time, the degree of hydrodenitrogenation of heavy oil fractions is relatively low. It is known that petroleum nitrogen-containing compounds are divided into nitrogenous bases titrated with acid solutions and nonbasic nitrogen compounds. Nitrogenous bases are represented mainly by alkylbenzo- and alkylnaphthenobenzo derivatives of pyridine. Nonbasic compounds may include benzologs of pyrrole and amides. Determining the composition of nitrogen-containing compounds in vacuum gas oil and studying their transformations during hydrotreatment is an important and actual problem. Aim. Comparative study of high- and low-molecular nitrogenous bases and nonbasic nitrogen-containing compounds of vacuum gas oil of Kazakhstan oil before and after hydrotreating. Objects. Samples taken before and after the catalytic hydrotreatment of vacuum gas oil from Kazakhstan oil. Methods. Hydrotreatment, elemental analysis, potentiometric titration, benzene cryoscopy, IR and 1H NMR spectroscopy, structural group analysis. Results. The paper introduces a comparative characteristic of the composition and structure of high and low molecular weight nitrogenous bases from the original and hydrotreated vacuum gas oil. Under the conditions of hydrotreatment, the total removal of nitrogen was 6.56 wt %, and the content of Nbas. decreased by 36%. At the same time, nitrogenous bases in the hydrotreated product are characterized by low molecular weights. Using IR spectroscopy, similar structural fragments were identified in the nitrogen compounds of the original and hydrotreated vacuum gas oil: pyridine rings (1573–1574 cm–1), carboxylic (3209–3225 and 1701–1709 cm–1) and sulfoxide (1032–1033 cm–1) groups. Among the nitrogen-containing compounds of the original vacuum gas oil, amides (1647–1648 cm–1) were identified, which are absent in the composition of nitrogen-containing compounds of the hydrotreated vacuum gas oil. Hydrocarbon skeletons of molecules include aromatic (1599–1602 cm–1) and aliphatic fragments (2860–2960 and 1454–1460, 1377, 723–727 cm–1). In accordance with the results of the structural group analysis, the averaged molecules of high and low molecular weight nitrogenous bases of the original and hydrotreated vacuum gas oil are represented by naphthenoaromatic structures with different alkyl framing. The differences observed between the values of individual structural parameters of the nitrogenous bases average molecules of the original and hydrotreated vacuum gas oil may indicate the compounds transformations under study during hydrotreatment.

Ultrasonic treatment is a suitable method for refinery processes that Acoustic cavitation is a technique that allows high levels of energy to be released into the liquid, which leads to changes in fluid properties such as a decrease in viscosity. Additionally, it's an effective way to improve the economic feasibility of physicochemical processing to enhance the quality of the product. In this work, vacuum gas oil with viscosity of 8.4 c.st, provided by Iraqi refineries, was treated by ultrasound radiation and studied the effect of several parameters on viscosity such as sonication time (5,10,15,20,30) min, power amplitude(10,20,30,40,50)watt, and frequency (20,30,40,50) kHr. It was found from the results that the viscosity decreased from (8.4) c.st to (5.82) c.st, which represents a percentage reduction of up to 30.7% compared to the value before treatment. This result was obtained after 30 min., also the 50% of ultrasound power is the appropriate to reduce the viscosity, where The experiment showed that 20 kHz of ultrasound frequency has a decreasing effect on the viscosity as the percentage reaches 30%. [ABSTRACT FROM AUTHOR]

Kinetic studies of hydrodesulfurization (HDS) and hydrodenitrogenation (HDN) reactions were performed. The hydrogenating activity of the synthesized Ni6PMonW(12–n)/Al2O3 catalysts was compared with that of the commercial reference catalyst in the process of hydrotreating of heavy mixed oil feedstock. It was shown that the HDS reaction is described by a pseudosecond order equation, and HDN, by a pseudofirst order equation. The obtained hydrogenates meet the requirements to the quality of feedstock for catalytic cracking plants in terms of coking capacity and sulfur and nitrogen contents. [ABSTRACT FROM AUTHOR]

The article is devoted to the use of residual products of combined thermo- and hydrocracking of heavy resid and vacuum gas oil into high-demand marketable petroleum products (into bitumen products) in conformity with Russian and international quality standards. [ABSTRACT FROM AUTHOR]

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It was shown that oxidation followed by heat treatment is an effective method for desulfurization of vacuum gas oil. Patterns of changes in the quantitative content of the thiophene series compounds in liquid cracking products of vacuum gas oil and liquid cracking products of pre-oxidized vacuum gas oil are described. A mixture of hydrogen peroxide and formic acid (molar ratio 3:4) was used as the oxidation system. The hypothetical mechanism for the formation of thiophene, benzo- and dibenzothiophene and their homologues from high-molecular weight components of the initial vacuum gas oil and its oxidation products is proposed. Presumably, main path of formation considerate compounds is thermal decomposition of high-molecular weight sulfur-containing components. On the basis of IR spectroscopy and structure-group analysis data, the averaged structures of such components were constructed. The influence of pre-oxidation and its conditions on the value of the rate constants for the formation of thiophene, benzo- and dibenzothiophene and their homologues during thermal cracking of initial and oxidized vacuum gas oils is studied. • Oxidation followed by heat treatment is an effective way to desulfurize vacuum gas oil. • Hypothetical formation mechanism of sulfur aromatic compounds during cracking is proposed. • Pre-oxidation feedstock affects on the formation rate of sulfur compounds during cracking. [ABSTRACT FROM AUTHOR]

A unit for separating heavy vacuum gas oil of a stabilized composition from a wide fraction of vacuum gas oil with a capacity of 65,000 tons per year is designed and implemented at an industrial enterprise. Technical solutions, as well as the results of operating the unit, are described. Experimental studies into technological modes are carried out using a laboratory model of the distillation column. A previously developed mathematical model of multicomponent distillation is used to calculate an industrial column with a new regular packing, where the mixture is represented as pseudo-binary in terms of fractions. In addition, software packages for plate-by-plate calculations of the column are applied. The main and auxiliary equipment for the developed vacuum distillation unit is selected. [ABSTRACT FROM AUTHOR]

Background: The Waste2Road project exploits new sustainable pathways to generate biogenic fuels from waste materials, deploying existing industrial scale processes. One such pathway is through pyrolysis of wood wastes. Methods: The hereby generated pyrolysis liquids were hydrogenated prior to co-feeding in a fluid catalytic cracking (FCC) pilot plant. So-called stabilized pyrolysis oil (SPO) underwent one mild hydrogenation step (max. 200 °C) whereas the stabilized and deoxygenated pyrolysis oil (SDPO) was produced in two steps, a mild one (maximum 250 °C) prior to a more severe process step (350 °C). These liquids were co-fed with vacuum gas oil (VGO) in an FCC pilot plant under varying riser temperatures (530 and 550 °C). The results of the produced hydrocarbon gases and gasoline were benchmarked to feeding pure VGO. Results: It was proven that co-feeding up to 10 wt% SPO and SDPO is feasible. However, further experiments are recommended for SPO due to operational instabilities originating from pipe clogging. SPO led to an increase in the hydrocarbon gas production from 45.0 to 46.3 wt% at 550 °C and no significant changes at 530 °C. SDPO led to a rise in gasoline yield at both riser temperatures. The highest amount of gasoline was produced when SDPO was co-fed at a 530 °C riser temperature, with values around 44.8 wt%. Co-feeding hydrogenated pyrolysis oils did not lead to a rise in sulfur content in the gasoline fractions. The highest values were around 18 ppm sulfur content. Instead, higher amounts of nitrogen were observed in the gasoline. Conclusions: SPO and SDPO proved to be valuable co-refining options which led to no significant decreases in product quality. Further experiments are encouraged to determine the maximum possible co-feeding rates. As a first step, 20-30 wt% for SPO are recommended, whereas for SDPO 100 wt% could be achievable.

[Display omitted] • Influence of HDT depth on material balance of FCC process was studied. • Hydrotreating does not influence valuable olefins yield. • Prehydrotreating decreases sulfur in liquid products. • Removal of N compounds increases activity of FCC catalyst. • Increase of HDT depth results in the increase of hydrogen transfer coefficient. The present work studies the influence of nitrogen compounds in hydrotreated fluid catalytic cracking (FCC) feedstock on the material balance of FCC process focused on petrochemistry. Vacuum gas oil was hydrotreated at the temperatures of 340–370 °C in typical FCC pretreatment conditions. The obtained hydrotreated products contained 370−750 ppm of nitrogen and 150−820 ppm of sulfur. Hydrotreated feedstock was exposed to the FCC process over a zeolite catalyst at the laboratory unit with a fixed bed catalyst at 527 °C and catalyst/oil ratio - 2−6. The FCC feedstock before and after hydrotreatment and FCC products were characterized by different methods to study the effect of nitrogen compounds on the FCC process. [ABSTRACT FROM AUTHOR]

Full-cycle hydrocracking process was used to treat the mixed inferior hydrogenation feedstocks of vacuum gas oil CVGO) mixed with coker gas oil(CGO) and FCC diesel. The effects of different conversion depths on product distribution and product quality were investigated. The results showed that the full-cycle hydrocracking process could achieve the production target of producing diesel oil and aviation kerosene flexibly. Under the scheme of maximum production of diesel oil, the yield of diesel oil was 80 %, and the cetane number could be maintained above 58; under the scheme of maximum production of aviation kerosene, the yield of qualified aviation kerosene could reach 46%, and the cetane number of by-product diesel could be up to 79. [ABSTRACT FROM AUTHOR]

The methane-hydrogen fraction is a gaseous hydrocarbon by-product during oil processing for obtaining petroleum products. Until recently, the methane-hydrogen fraction was used as furnace oil in internal technological processes at a refinery. Some of the low-calorie methane-hydrogen fraction was burned in flares. Driven by the prospect of the methane-hydrogen fraction use as a fuel alternative to natural gas for burning in thermal power plants boilers, it became necessary to study the methane-hydrogen fraction combustion processes in large volumes. The conversion of ON-1000/1 and ON-1000/2 furnaces from the combustion of the methane- hydrogen fraction with combustion heat of 25.45 MJ/m3 to the combustion of the composition with combustion heat of 18.8 MJ/m3 leads to a decrease in temperature in the flame core for 100 °C as an average. The intensity of flame radiation on the radiant tubes decreases. Therefore, the operation of furnaces during combustion of methane-hydrogen fraction with a low heat of combustion at the gas oil hydro-treating unit is carried out only with a fresh catalyst, which allows lower flame temperatures in the burner.The experiments to determine the concentration of nitrogen oxides NOx and the burning rate w of the methane-hydrogen fraction in the ON-1000/1 furnace and natural gas in the TGM-84A boiler, depending upon the heat of combustion Qnr were carried out. The obtained results showed that the increase in the hydrogen content Н2 from 10.05 % to 18.36% (by mass) results in an increase in the burning rate w by 45%. The burning rate of natural gas with methane CH4 content of 98.89% in the TGM-84A boiler is 0.84 m/s, i.e. it is 2.5 times lower than the burning rate of the methane- hydrogen fraction with H2 content of 10.05%. The distributions of heat flux from the flame qf over the burner height h in the TGM-84A boiler were obtained in case of natural gas burning and calculation of burning of the methane-hydrogen fraction with a hydrogen content of 10.05% and methane of 28.27%. The comparison of the obtained data shows that burning of methane- hydrogen fraction causes an increase in the incident heat flux qf at the outlet of the burner.

Thermal and catalytic pyrolysis of vacuum gas oil in a flow-type reactor were investigated. The main patterns in the yield of the targeted products of the process – ethylene, propylene and butylenes – are identified. The effect of the catalyst on change in the conditions of catalytic pyrolysis compared with thermal pyrolysis is described. A mathematical model of the process is proposed. [ABSTRACT FROM AUTHOR]

In this study, a novel, simple, high yield, and scalable method is proposed to synthesize highly porous MoS2/graphene oxide (M−GO) nanocomposites by reacting the GO and co-exfoliation of bulky MoS2 in the presence of polyvinyl pyrrolidone (PVP) under different condition of ultrasonication. Also, the effect of ultrasonic output power on the particle size distribution of metal cluster on the surface of nanocatalysts is studied. It is found that the use of the ultrasonication method can reduce the particle size and increase the specific surface area of M−GO nanocomposite catalysts which leads to HDS activity is increased. These nanocomposite catalysts are characterized by XRD, Raman spectroscopy, SEM, STEM, HR-TEM, AFM, XPS, ICP, BET surface, TPR and TPD techniques. The effects of physicochemical properties of the M−GO nanocomposites on the hydrodesulfurization (HDS) reactions of vacuum gas oil (VGO) has been also studied. Catalytic activities of MoS2-GO nanocomposite are investigated by different operating conditions. M9-GO nanocatalyst with high surface area (324 m2/g) and large pore size (110.3 Å), have the best catalytic performance (99.95%) compared with Co-Mo/γAl2O3 (97.91%). Density functional theory (DFT) calculations were also used to elucidate the HDS mechanism over the M−GO catalyst. It is found that the GO substrate can stabilize MoS2 layers through weak van der Waals interactions between carbon atoms of the GO and S atoms of MoS2. At both Mo- and S-edges, the direct desulfurization (DDS) is found as the main reaction pathway for the hydrodesulfurization of DBT molecules.

The organosulfur compounds of mixed raw materials—vacuum gas oil in a mixture with heavy coking gas oil reactions group kinetic were investigated during hydrotreating at a hydrogen pressure of 5 MPa at various temperatures (360, 390, 420 °C) and LHSV of 0.5, 1.0, 2.0 and 4.0 h−1 in the presence of Ni6–MonW12-n/γ-Al2O3 sulfide catalysts, prepared on the base of phosphoromolybdenum and phosphorotungstenheteropolyacids. The total sulfur content was determined in feed and hydrogenates. A kinetic model describes the process of hydrodesulfurization of vacuum gas oil in hydrotreating on Ni6–MonW12-n/γ-Al2O3 catalysts based on phosphomolybdenum and phosphotungsten heteropolyacides (HPAs) has been selected. The adequacy of the kinetic model of the 2nd order was verified by means of the coefficient of determination and based on the values of the Fisher criterion. The optimal modes of the vacuum distillate hydrotreating process may be selected on the base of obtained data on the kinetics of hydrodesulfurization (HDS) reactions. The kinetic characteristics of the HDS and hydrodearomatization (HDA) reactions of the mixed feed compounds on Ni6–MonW12-n/γ-Al2O3 catalysts based on phosphor–molybdenum and phosphotungsten HPA were determined with the usage of chosen model. The Ni6PMo12/γ-Al2O3 catalyst was most active one in the HDS reaction. The activity of catalyst samples in hydrogenation reactions was investigated. It was shown that the most active sample is Ni6PMo4W8/γ-Al2O3. [ABSTRACT FROM AUTHOR]

A developed HLaY-containing catalyst in an aluminum-pillared montmorillonite matrix in the Na- and CaNa-forms was tested for cracking of vacuum gas oil into the target products gasoline and light gas oil. The gasoline yield increased from 58.5 to 62.5% over the steam-treated catalyst Al(2.5)CaNaHMM + HLaY. The catalyst Al(2.5)CaNaMM + HLaY on unactivated montmorillonite was tested for light gas oil production. The maximum yield of light gas oil of 65.9-65.1% was obtained after steam treatment of this catalyst at a 2:1 catalyst to feedstock ratio. The influence of steam treatment on the phase composition, porous structure, elemental composition, and acidic properties of the studied catalysts was analyzed by XRD, BET, NH3 thermal desorption, and x-ray fluorescence. [ABSTRACT FROM AUTHOR]

A number of cracking catalyst samples containing Me–Mg–Al mixed oxides have been prepared. Cobalt, zinc, copper, and cerium were used as additional metals in the mixed oxide composition. When studying the cracking of a vacuum gas oil–sunflower oil mixture, catalysts containing Co–Mg–Al or Zn–Mg–Al mixed oxides were found to increase both the conversion rate of the mixed feedstock by 5.0 wt % compared to a sample containing the mixed oxide free of additional metal, and the gasoline yield by 1.6–3.0 wt %. It was discovered that the modification of mixed oxides with cobalt or zinc cations has no significant effect on the distribution of inorganic products, thereby indicating sustained catalytic activity during the decarboxylation reaction. The catalytic tests also demonstrated that catalyst samples containing mixed Mg–Al oxides with copper cations exhibited enhanced decarbonylation effect, as well as low conversion rates of the mixed feedstock and low gasoline yield, which is probably associated with the poisoning impact of copper oxide on Y zeolite. [ABSTRACT FROM AUTHOR]

A hierarchical Beta zeolite has been successfully mass‐prepared hydrothermally and dynamically in a pilot‐scale autoclave by an economical and simple process with low‐cost raw materials. The characterization results indicated that the pilot‐scale hierarchical Beta zeolite has the same textural, structural, and acidic properties like the bench‐scale sample. Moreover, the catalyst composed of the pilot‐scale hierarchical H‐Beta zeolite showed higher activity and selectivity to the middle distillate than that containing microporous Beta zeolite in catalytic hydrocracking of vacuum gas oil (VGO) evaluated by an industrial pilot installation in running of 3000 h, due to the increased accessibility and the reduction of diffusion constraint of large molecules to acid sites in the Beta zeolite framework. [ABSTRACT FROM AUTHOR]

The kinetics of the formation of oxygen-free hydrocarbon compounds obtained during the process of oxidation of vacuum gas oil at 450–550 °C for 2700 s of conducting of the process was studied. It was established that the highest rate of hydrocarbon formation was noted for the C1–C4 fraction starting from the moment the process started and up to 900 s (1.76 × 10−8 – 4.58 × 10−8). For other fractions, reaction rate maximums were noted: for C5–C9—300 s from the start of the process; for C10–C12—in the interval between 300 and 900 s, i.e. at 600 s process duration; for the raw fractions C22–C30, C31–C35 and C36–C40, grew after 1800s. The data on the influence of the process temperature on the rate of hydrocarbon formation allowed us to establish that the oxycracking process is limited by the formation of C10–C16 hydrocarbon fractions. The increase in contact time to a greater extent affects the rate of formation of hydrocarbons C1–C4 and C17–C21. The features of the rate of hydrocarbon production as a function of the amount of oxygen were found out: the rate of formation of hydrocarbons C1–C4 and C17–C21 increases with increasing oxygen content (in the case of C17–C21 it passes through a minimum); C5–C9 and C13–C16—monotonously decreases; C10–C12 passes through a maximum at an oxidation state of 1%, which undoubtedly indicates the role of oxygen in the destructive processes of the formation of hydrocarbons that do not contain oxygen under oxycracking conditions. [ABSTRACT FROM AUTHOR]

• Flow reactor (kg/day) data of NiMo/SiO 2 -Al 2 O 3 hydrocracking of vacuum gas oil and wax. • Competitive adsorption directionally explains lower oil conversion in presence of wax. • Competitive adsorption directionally explains higher S and N conversion with wax. • Bulk solubility effects explain magnitude of change in conversion caused by wax. The hydrocracking of vacuum gas oil (VGO) and a mixture of 90 wt% VGO and 10 wt% wax was investigated. The study provided insight into processing of naturally waxy petroleum, as well as refinery co-processing of Fischer–Tropsch products with petroleum. The investigation was performed using flow reactor system at kilogram per day scale. Hydrocracking was investigated over a sulfided NiMo/SiO 2 -Al 2 O 3 catalyst in the temperature range 330–410 °C at 9.5 MPa and LHSV of 1.3 h−1 with H 2 -to-feed ratio of 620 normal m3/m3. Atmospheric residue conversion of the VGO was 8–12% higher than conversion of VGO + wax at 330–380 °C, and 24% higher at 410 °C. Hydrodesulfurization conversion of the feed (3 wt% S) was less for VGO than for VGO + wax. Hydrodenitrogenation conversion of the feed (0.2 wt% N) was less for VGO than for VGO + wax. Directionally the observations could be explained in terms of competitive adsorption. However, the extent of the difference in atmospheric residue conversion was more than could be explained by competitive adsorption and VGO dilution by wax. It was postulated that changes in the bulk solubility characteristics of the liquid contributed to alter the relative concentration of species at the catalyst surface based on the change in the solubility parameter of the bulk liquid relative to the individual species. In this way it was possible to also account for the extent of the conversion difference observed during hydrocracking of VGO and VGO + wax at similar conditions. [ABSTRACT FROM AUTHOR]

The kinetics of the formation of oxygen-containing compounds during oxycracking of vacuum gas oil was experimentally studied. The kinetic parameters of the process of formation of oxygen-containing compounds in five target fractions under oxycracking conditions are established: reaction rates, rate constants, reaction orders, activation energies. The average reaction rate of the formation of oxygen-containing compounds in oxycracking products in the first 600 s is limited by the rate of oxidation of the C10–C12 fraction, further from 600 up to 900 s by the oxidation of the C5–C9 fraction (during this period, the direction/mechanism of the formation of OCC in this fraction changes), and after 900 s—the fractions C1–C4. The presence of the induction period indicates that the formation of oxygen-containing compounds in the C1–C4 fraction occurs according to the unbranched chain mechanism, and C5–C9 and C22–C30—through the chain with degenerate branching. The combination of experimental and calculated data indicates a joint homogeneous heterogeneous oxycracking mechanism of vacuum gas oil, which excludes the single-valued contribution of only the volume or only the surface of the catalyst. It is shown that under oxycracking conditions the process proceeds both in the kinetic and in the internal transition region, depending on the temperature. [ABSTRACT FROM AUTHOR]

In this research, based on actual data gathered from an industrial scale vacuum gas oil (VGO) hydrocracker and artificial neural network (ANN) method, a model is proposed to simulate yields of products including light gases, liquefied petroleum gas (LPG), light naphtha, heavy naphtha, kerosene, diesel and unconverted oil (off-test). The input layer of the ANN model consists of the catalyst, feed and recycle flow rates, and bed temperatures, while the output neurons are yields of those products. The results showed that the AAD% (average absolute deviation) of the developed ANN model for training, testing, and validating data are 0.445%, 1.131% and 0.755%, respectively. Then, by considering all operational constraints, the results confirmed that the decision variables (i.e., recycle rate and bed temperatures) generated by the optimization approach can enhance the gross profit of the hydrocracking process to more than $0.81 million annually, which is significant for the economy of the target refinery.

Four nonlinear regression techniques were explored to model gas oil viscosity on the base of Walther’s empirical equation. With the initial database of 41 primary and secondary vacuum gas oils, four models were developed with a comparable accuracy of viscosity calculation. The Akaike information criterion and Bayesian information criterion selected the least square relative errors (LSRE) model as the best one. The sensitivity analysis with respect to the given data also revealed that the LSRE model is the most stable one with the lowest values of standard deviations of derivatives. Verification of the gas oil viscosity prediction ability was carried out with another set of 43 gas oils showing remarkably better accuracy with the LSRE model. The LSRE was also found to predict better viscosity for the 43 test gas oils relative to the Aboul Seoud and Moharam model and the Kotzakoulakis and George.

This work presents characterization data and viscosity of 34 secondary vacuum gas oils (H-Oil gas oils, visbreaker gas oils, and fluid catalytic cracking slurry oils) with aromatic content reaching up to 100 wt.%. Inter-criteria analysis was employed to define the secondary VGO characteristic parameters which have an effect on viscosity. Seven published empirical models to predict viscosity of the secondary vacuum gas oils were examined for their prediction ability. The empirical model of Aboul-Seud and Moharam was found to have the lowest error of prediction. A modification of Aboul-Seoud and Moharam model by separating the power terms accounting for the effects of specific gravity and average boiling point improves the accuracy of viscosity prediction. It was discovered that the relation of slope of viscosity decrease with temperature enhancement for the secondary vacuum gas oil is not a constant. This slope increases with the average boiling point and the specific gravity augmentation, a fact that has not been discussed before.

Inter-criteria analysis was employed in VGO samples having a saturate content between 0.8 and 93.1 wt.% to define the statistically significant relations between physicochemical properties, empirical structural models and vacuum gas oil compositional information. The use of a logistic function and employment of a non-linear least squares method along with the aromatic ring index allowed for our newly developed correlation to accurately predict the saturate content of VGOs. The empirical models developed in this study can be used not only for obtaining the valuable structural information necessary to predict the behavior of VGOs in the conversion processes but can also be utilized to detect incorrectly performed SARA analyses. This work confirms the possibility of predicting the contents of VGO compounds from physicochemical properties and empirical models.

In this work, the regularities of vacuum gas oil hydrocracking process were revealed; namely, key components of reacting mixture and key reactions were identified, thermodynamic regularities of the key reactions were established, and influence of technological parameters, such as temperature and pressure, on the conversion of the key components was estimated. [ABSTRACT FROM AUTHOR]

This paper presents the results of testing a catalyst system developed for the demetallization and desulfurization of vacuum gas oil and heavy coker gas oil mixture at a pressure of 6 MPa, a temperature of 360-370°C, and a feed volumetric rate of 1 h-1 for obtaining a product having a sulfur content of 0.05 wt.%. The composition of RMB 30 marine fuel is developed with the application of a distillate fraction obtained from secondary processes and a depressant-dispersant additive in order to bring the pour point to the requirements of GOST32510-2013. [ABSTRACT FROM AUTHOR]

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We report recent progresses of combining comprehensive two-dimensional gas chromatography (2DGC or GC × GC) separation, field ionization (FI), and time-of-flight mass spectrometry (TOF MS) for the detailed analysis of vacuum gas oil distillation (VGO) cuts. 2DGC separates petroleum molecules by the combination of boiling point and polarity. FI generates molecule ions-only mass spectra. TOF MS allows accurate mass analysis of hydrocarbon molecules. A new data analysis strategy is implemented for compositional analysis. First, all masses were separated into nominal mass classes. Since petroleum homologues have unique Kendrick mass defects (KMD), KMD plots were generated for easy recognition of homologues series within each nominal mass class. Finally, KMD windows were imposed for complete resolution of petroleum molecules. Using this approach, a total of 16 hydrocarbon types, 14 sulfur types, and their carbon number distributions were determined in the three VGO distillation cuts. Two series of geological biomarkers were also revealed by the analysis. [ABSTRACT FROM AUTHOR]

Three blends of Zhenhai vacuum gas oil blended with straight-run diesel, FCC LCO and coker diesel(mass ratio of 1: 1) are used as feedstocks. The hydrofining catalyst/hydrocracking catalyst system with high denitrification activity is used. The volume ratio of hydrogen to oil is 800: 1 and 1 200: 1 at the reaction pressure of 15. 7 MPa, the temperature of the cracking section is 370 °C, the volume space velocity of the refined and modified section is 1. 0 h-1 and 1. 5 h-1 respectively, and the mass fraction of nitrogen in the refined oil is controlled to be less than 10 n-g/g- The effects of blending different kinds of diesel on the distribution and properties of hydrocracking products are investigated under reaction conditions. The results show that the distribution of hydrocracking products and the quality of hydrocracking products change obviously after blend- ing different kinds of diesel due to the change of the properties of feedstocks. The blending of straight-run diesel can increase the yield of heavy naphtha with high aromatic potential, and the blending of FCC diesel or coker diesel can greatly increase the yield of intermediate distillate, but the product properties such as smoke point of jet fuel and cetane number of diesel can also be significantly worse. [ABSTRACT FROM AUTHOR]

Demetallization of a mixture of vacuum gas oil with heavy coker gas oil on CoMo/γ-Al2O3 catalysts with different pore structures was studied, and the influence of the catalyst pore structure on the process results was demonstrated. For the demetallization catalysts to be effective, their pore size should be restricted not only from below but also from above. When using samples with broad pores, effects of the hydrodesulfurization and hydrodemetallization inhibition can arise owing to adsorption of supramolecular structures of heavy residues, in particular, of asphaltenes. [ABSTRACT FROM AUTHOR]

Activities of HCeY vacuum gas-oil cracking catalysts based on the H-form of Fe-modified kaolinites from Kazakhstan deposits with and without zeolites are reported. The physicochemical properties of the catalysts were determined. The main cracking product of vacuum gas oil on Fe-modified H-kaolinites without zeolites was light gas oil, the yields of which was 65.3-67.3%. Adding zeolite increased the gasoline yield up to 22% with rather high feedstock conversion (up to 90.3%). [ABSTRACT FROM AUTHOR]

• A superstructure model is proposed to design and optimize the co-processing of bio-oil and VGO. • The optimal biomass feedstock and the bio-oil production process can be obtained. • Two scenarios with different bio-oil co-processing ratio and FCC processing capability are adopted to illustrate the model. • The impurity flows during the co-processing process are analyzed and discussed. • The effects of bio-oil co-processing ratio and FCC processing capability are investigated. The prices of the bio-diesel and bio-gasoline are normally significantly high when compared to the petroleum-derived fuels. The co-processing of bio-oil and vacuum gas oil in a fluid catalytic cracker (FCC) has been proposed to utilize existing refinery infrastructures while lowering bio-fuel prices. Nonetheless, the integration of the bio-oil production and the existing refinery remains unknown. In this work, a superstructure model is proposed to design and optimize the co-processing process by selecting the optimal biomass feedstock and the bio-oil production process (fast pyrolysis or catalytic pyrolysis). Furthermore, the impacts of the FCC processing capability and bio-oil co-processing ratio on the economics as well as the selection of bio-oil production process are also investigated. As revealed by the results of two scenarios, pulpwood is the optimal biomass feedstock and the fast pyrolysis ought to be selected for producing bio-oil when its co-processing ratio and the FCC processing capability are both relatively high. [ABSTRACT FROM AUTHOR]

The possibility of using of the catalytic system based on formic acid and a transition metal salt in the presence of hydrogen peroxide for desulfurization of nonhydrotreated vacuum gas oil has been explored. Conditions for effective oxidation of organic sulfur compounds and maximal extraction of oxidized compounds from the feedstock have been selected. It has been shown that the catalysts based on tungsten salts are the most effective those for oxidative desulfurization of heavy feedstock. Under optimum conditions, the degree of desulfurization of vacuum gas oil was 89%. [ABSTRACT FROM AUTHOR]

Abstract In order to assess the utility of fluid catalytic cracking (FCC) for upgrading bio-oils derived from the hydrothermal liquefaction (HTL) of microalgae, 10 wt% HTL algae bio-oil was blended with heavy vacuum gas oil (HVGO) and co-processed in a Short Contact Time Microactivity unit. Compared to pure HVGO, addition of 10 wt% HTL algae bio-oil caused a modest decrease in conversion at all catalyst-to-oil ratios, with marginally increased catalyst coking being observed for the blended feed. The resulting liquid products contained a higher percentage of decant oil (DCO) and a lower percentage of gasoline than those obtained when HVGO alone was employed as feed, the amount of light cycle oil (LCO) being similar in both cases. Nearly complete heteroatom removal from the blended feed was observed, the extent of denitrogenation achieved being particularly noteworthy given that nitrogen-bearing compounds are much more abundant in algae-derived bio-oils than in HVGO. Overall, results indicated that while 10% bio-oil in HVGO would be economically unfavorable when compared to upgrading HVGO alone, it is nonetheless amenable to co-processing and may offer advantages over pyrolysis oils as an FCC feed. Finally, additional means to optimize the commercial application of this process are proposed based on techno-economic considerations. Graphical abstract Unlabelled Image Highlights • Bio-oil was obtained from wet algae by means of continuous hydrothermal liquefaction. • 10 wt% HTL bio-oil in heavy vacuum gas oil was upgraded via fluid catalytic cracking. • Near complete removal of heteroatoms (i.e., sulfur, oxygen and nitrogen) was effected. • Denitrogenation extent was striking given the abundance of nitrogen in algal bio-oil. • The technical feasibility of co-processing HTL algal bio-oil via FCC was demonstrated. [ABSTRACT FROM AUTHOR]

Graphical abstract Highlights • Aluminosilicates based additives decrease sulfur content by 39% than FCC catalyst. • Additives on Al-MCM-41, Al-SBA-15 are more active in sulfur removal than Al-SBA-16. • Modification by metals (Al, La) leads to increasing of acidity and sulfur removal. Abstract Mesoporous silica oxides MCM-41, SBA-15 and SBA-16 were synthesized and modified to form aluminosilicates with Al/Si atomic ratio of 1/400. In order to improve thermal and mechanical stability the alumina phase was intercalated. The resulted Al-MCM-41/Al 2 O 3 , Al-SBA-15/Al 2 O 3 , Al-SBA-16/Al 2 O 3 supports were impregnated with 5% lanthanum and tested as sulfur reduction additives to equilibrium microspherical zeolite–containing cracking catalyst (e-cat). The well-ordered pore arrangement and incorporation of alumina atoms into mesoporous framework were confirmed by X-ray diffraction (XRD), transmission electron microscopy (TEM) and 27Al solid-state magic angle spinning nuclear magnetic resonance (MAS NMR) spectroscopy. To compare the sulfur reduction activity with respect to the nature of the support, the textural properties and acidity were studied by low-temperature nitrogen adsorption/desorption (N 2 adsorption/desorption) and temperature programmed desorption of ammonia (NH 3 -TPD) techniques. Catalytic cracking of vacuum gas oil (VGO) over e-cat mixed with mesoporous supported La additives (10 wt%) synthesized was carried out on a micro activity testing (MAT) laboratory unit at 500 °C and catalyst/feedstock weight ratio of 3.4 to compare the morphology of mesoporous structure and sulfur reduction activity. In order to assess the support effect on catalytic performance a comparative study of La/Al 2 O 3 and mesoporous La supported additives was carried out. Hydrothermal stability of additives was also studied by means of steaming procedure at the temperature of 700 °C (100% steam) for 2 h. [ABSTRACT FROM AUTHOR]