Gasoline Fraction Research Articles

Effect of Hydrogen-Donor of Heavy Crude Oil Catalytic Aquathermolysis in the Presence of a Nickel-Based Catalyst

The transformations of oil components from the Zyuzeevskoye field during catalytic aquathermolysis in the presence of a nickel-containing catalyst precursor and hydrogen donors were studied. It was found that the yield of gasoline and diesel fractions increased by more than 36% in the case of catalytic aquathermolysis in the presence of tetralin. The maximum conversion of asphaltenes was achieved with a simultaneous slowing down of coke formation by four times. The calculation of the structural-group parameters of initial asphaltenes and the products of thermal cracking and catalytic aquathermolysis was made, and the hypothetical construction of their molecular structures was proposed. It was established that the phase composition, ratio, and morphology of nickel catalysts after catalytic aquathermolysis (CA) and catalytic aquathermolysis with tetralin (CA+T) depend on the amount of “free” hydrogen and are represented by Ni0.96S and Ni9S8.

Catalytic advances in vacuum gas oil hydrocracking

Hydrocracking still maintains the pivotal role in the industry owing to the production of highly demanded transportation fuels. Having comprised pretreatment of VGO, comparative research onrecent catalysts, this review paper provides athorough picture about all consecutive steps in the hydrocracking process of vacuum gasoil. Discussing recovery of VGO from vacuum residue with minimum sulfur content, the focus was put on the catalyst characterizations and their influence on the conversion of VGO, the yield of middle distillate, gasoline as well asnaphtha. Both zeolite and amorphous catalysts have undergone a comparative analysis interms of their hydrocracking properties as well as catalytic activities during provided conditions. The article also examines the process of hydrocracking of vacuum gas-oil from Baku oils with the participation of modified aluminosilicate catalyst containing Ni, Mo to obtain high-quality raw materials for environmentally friendly diesel fuel and catalytic cracking process. The hydrocracking process of vacuum gas-oil conducted at 3-8 MPa pressure, 400-450 °C temperature range, in a flow-type Hungarian unit with a reactor capacity of 200 ml. During the investigations of temperature on hydrocracking process it was revealed that, when temperature rises from 400 to 460 °С the yield of diesel fraction increases from 35 to 50% wt. The yield of gasoline fraction constitutes 0-6% wt. and the produce of residue fraction decreases from 65% to 45%. With increasing of temperature from 400 °C to 450 °C the amount of sulphur decreases from 0.01% to 0.005% in composition of diesel fraction. Keywords: vacuum gasoil; hydrocracking; diesel fraction; alumosilicate; catalyst; hydrodesulfurization.

Characterization Studies for Derived Biodiesel from the Fluid Catalytic Cracking (FCC) of Waste Cooking Oil through a Fixed Fluidized Bed (FFB)

Biodiesel production through transesterification or catalytic hydrogenation using vegetable oil is a sustainable method, but it has the downsides of by-product generation and a higher cost. Therefore, in this study, waste cooking oil was selected as a raw material, and fluidized catalytic cracking was carried out on the catalyst (LDO-75) through a fixed-fluidized-bed (FFB) reactor. The effects of the reaction temperature, catalyst–oil ratio and weight hourly space velocity (WHSV) on the yield of pyrolysis gas, gasoline, diesel and heavy oil fractions were studied. The composition of the pyrolysis gas was determined by gas chromatography (GC), the composition of the gasoline fraction was analyzed by gas chromatography-mass spectrometry (GC-MS), and the characteristics of the diesel and heavy oil fractions were determined by nuclear magnetic resonance (NMR). The results show that light olefins are the main products of pyrolysis gases, and the liquid products are mainly composed of aromatic compounds. In addition, the catalytic cracking process of waste cooking oil fluid is proposed, indicating that the process of the catalytic cracking of waste cooking oil fluid includes deoxygenation, oligoaromatization and hydrodeoxygenation. The results of this study will provide a basis for the high value-added utilization of waste cooking oil.

Hybrid Gasoline Production from Black Liquor through Coprocessing

A new route is presented as a stepwise upgrading process from black liquor issued from the kraft process to hybrid gasoline: (i) hydrothermal liquefaction (HTL) to produce biocrude, (ii) removal of alkaline metal salts, (iii) hydrodeoxygenation (HDO) for oxygen removal and decrease of molar weight, and finally (iv) coprocessing with vacuum gas oil (VGO) by catalytic cracking to produce gasoline as a second-generation transportation biofuel. A high degree of deoxygenation was found to be quite beneficial to the further cracking of the refined crude oil into gasoline fractions. Thus, for this coprocessing step, it was found that, by limiting the percentage of added pretreated biocrude to about 10 wt %, high naphtha yields (45% compared to 48% for pure VGO cracking) were maintained, and without a significant change in the coke yield. This result is promising since naphtha, the gasoline-rich fraction, is the main target product in FCC. More research is needed in the detailed characterization of the coprocessing products and in checking the quality and compatibility of the hybrid fuel with gasoline standards. Further optimization in the HTL and HDO steps can likely be achieved, possibly allowing coprocessing of larger quantities of HDO biocrude than 10 wt %.

Integrated Processes of the Reforming and Isomerization of Gasoline Fractions for the Production of Environmentally Friendly Motor Gasolines

Integrated Processes of the Reforming and Isomerization of Gasoline Fractions for the Production of Environmentally Friendly Motor Gasolines

Two-stage thermal and catalytic cracking of polypropylene using natural clinoptilolite in a catalytic step to petrochemicals and fuels

Raw natural clinoptilolite from the Slovak deposit in Nižný Hrabovec and clinoptilolite treated with solution of hydrochloric acid (0.1 M) were used to promote cracking of polypropylene (PP), as a representative of the second most common plastic in municipal waste, into valuable gaseous and liquid hydrocarbons. The influence of catalyst was studied using two-stage cracking apparatus. The process consisted of batch semiflow thermal cracking reactor connected to flow catalytic reactor operating at 450 °C. The cracking activity of fresh, unregenerated and regenerated clinoptilolite was studied. The cracking activity into gaseous hydrocarbons was the highest with fresh catalyst (28.1 % for raw and 53.4 % for acid-modified catalyst). It represented an increase of 11.3 % and 36.6 %, respectively, in comparison with thermal cracking. The content of valuable methylpropene in gas was markable (up to 27.1 wt %). It was confirmed that catalytic cracking of PP with unregenerated and regenerated catalyst was also effective although the cracking activity of those catalysts slightly decreased. All catalysts produced narrower range of C5-C14 hydrocarbons in the liquid fraction (mainly gasoline fraction) compared to thermal cracking (C5-C20 hydrocarbons).

Deep aerobic desulfurization of fuels over iron–сontaining zeolite based catalysts

Herein, we present a new approach to the design of the catalysts for aerobic oxidation of sulfur-containing compounds. Iron-containing zeolite-based (ZSM-5, ZSM-12) catalysts were synthesized and successfully tested in oxidation of model mixtures as well as real petroleum fractions. The catalysts were characterized by means of X-ray diffraction (XRD), X-ray fluorescence spectroscopy (XRF), scanning electron microscopy (SEM), ultraviolet–visible spectroscopy (UV/Vis), temperature programmed desorption of ammonia (NH3-TPD), and low-temperature nitrogen adsorption-desorption. Among these catalysts Fe-ZSM-12 demonstrated the best activity: exhaustive oxidation of dibenzothiophene (DBT) in the presence of this catalyst was achieved in 2 h at 150°C. Influence of the reaction conditions (temperature, amount of catalyst, and time) on the conversion of the model substrate was studied. It was shown that in the presence of Fe-ZSM-12 catalyst activation of molecular oxygen proceeds via formation of superoxide radical. Fe-ZSM-12 exhibited an excellent stability and retained its activity after 10 cycles of oxidation. Under optimal reaction conditions sulfur content in straight-run gasoline fraction was reduced from 807 to 43 ppm, in diesel fraction – from 1898 to 150 ppm. Two-dimensional GC-MS analysis of diesel fraction before and after desulfurization indicates high selectivity of the process. Possibility of sulfur dioxide formation during the aerobic oxidative desulfurization process was studied for the first time. The use of zeolite-based catalysts containing transition metals for aerobic oxidation of sulfur-containing compounds is a promising approach for clean fuel production.

Sulfur containing mixed wastes in anaerobic processing by new immobilized synthetic consortia

Methanogenic biotransformation of unusual substrates (sulfur (S)-containing wastes: non-purified vacuum gas oil, straight-run gasoline fraction (Naphtha), gas condensate, and straight-run diesel fraction) coming from oil industry after their oxidative desulfurization was investigated. Nitrogen-containing wastes (hydrolysates of chicken manure and Chlorella vulgaris biomass) were added as co-substrates to mixture with oil industry wastes. The 100 % conversion of S-organic compounds to inorganic sulfide accumulated in the reaction liquid medium was achieved with simultaneous production of biogas containing high methane percent (greater than 70 %). Polishing of effluents from methane tank was carried out by denitrifying oxidation of ammonium (DEAMOX). The high process efficiency was due to use of original immobilized artificial consortia at the stage of methanogenesis and DEAMOX. This study reveals the real potential in the processing of very complex mixtures of large-scale wastes, usually inhibiting methanogenesis, by developing biocatalysts based on synthetic biology approaches.

Wood Derived Fast Pyrolysis Bio-liquids as Co-feed in a Fluid Catalytic Cracking Pilot Plant: Effect of Hydrotreatment on Process Performance and Gasoline Quality.

Co-feeding biogenic feeds in fluid catalytic cracking (FCC) units benefits from exploiting existing refinery assets to produce biogenic fuels. It is the most cost-effective way to comply with step-by-step increasing the target of renewable energy in road and rail transport of the European Union. Fast pyrolysis bio-liquids derived from wood offer a unique opportunity to reach those targets without having to address the typical food vs fuel debate. In the present work bio-liquids derived from pinewood in different stages of treatment were tested for their processability in a pilot scale fluid catalytic cracking plant at 550 °C. Specific focus is on the quality of the derived gasoline fractions. All samples were co-fed with vacuum gas oil, a typical FCC feed. Relevant parameters to qualify the produced gasoline as blending component were analyzed. As main results, none of the parameters examined significantly affect the quality of the—now partially biogenic—gasolines, demonstrating the potentiality of the co-FCC process as a possible near future pathway to ensure high biofuel contents in commercially available fuels.

Catalytic upgrading of heavy oil from the Ashalchinskoye oilfield

The work deals with study the effect of the NiCrWC catalyst on the composition of the products of catalytic cracking of heavy oil at a temperature of 450 °C for 100 minutes is established. The relevance of research aimed at studying the catalytic activity in the processing of heavy oil. It has been installed that the addition of NiCr-WC promotes the retardation of coke and asphaltenes formation and an increase in the destruction of high-molecular components of heavy oil. The use of a catalyst makes it possible to increase the yield of gasoline and diesel fractions by 35.8 wt % compared to the initial oil. Due to the formation of gaseous products, the removal of 2 wt % of sulfur from oil is observed. The data of X-ray phase analysis and scanning electron microscopy show that metal oxides are sulfidized on the surface of nichrome particles to form sulfides of these metals. It was found that NixSy and CrxSy formed on the catalyst surface contribute to an increase in the degradation of oil resins and asphaltenes.

Investigation of the hydroisomerization of diesel fractions with different concentration of nitrogen-containing compounds on bifunctional catalysts based on ZSM-23 and non-noble metals

Bifunctional catalysts based on NiMo(W) sulfides and a ZSM-23-Al2O3 composite support have been synthesized. Their properties were studied in the transformations of diesel fractions with different nitrogen content (< 1, 10 and 20 ppm). It was demonstrated that the synthesized catalysts could be used to obtain hydrogenizates with the limiting filterability temperature  –38 °C, which comply with the requirements of GOST R 55475-2013 to the content of gasoline fraction and aromatic compounds, and the derived cetane number. Properties of the developed catalysts based on NiMo and NiW sulfides and characteristics of the corresponding hydrogenizates were compared with each other. In addition, properties of the developed samples were compared with the properties of a foreign commercial platinum catalyst for isodeparaffinization. The synthesized catalysts were found to be less selective than the reference sample, but more stable to N-containing compounds in the feedstock.

Energy loss and comprehensive performance analysis of a novel high-efficiency hybrid cycle hydrogen-gasoline rotary engine under off-design conditions

The rotary engine is a potential power device for unmanned aerial vehicle. In this paper, a novel X-type hydrogen-gasoline rotary engine using high efficiency hybrid cycles (HEHCs) is proposed to realize the high efficiency and low carbon dioxide emission. Firstly, the zero-dimensional single-zone models are established for the X-type rotary engine using theoretical (ideal cycle and ideal working fluid of air), ideal (ideal cycle and real working fluid) and real (real cycle and real working fluid) HEHCs. The type I and II losses are introduced to indicate the energy losses from theoretical HEHC to ideal HEHC and from ideal HEHC to real HEHC, respectively. Furthermore, the effects of hydrogen doping fraction of gasoline-hydrogen hybrid fuel, ignition angle and rotational speed on type I and II losses are studied. Finally, the variation trends of cycle efficiency, indicated power, indicated fuel cost and indicated carbon dioxide emission (ICDE) are revealed under different operation conditions. The results show that the increasing hydrogen doping fraction rises the type I and II losses, while the increasing ignition angle or rotational speed declines the above losses. The maximum cycle efficiencies of real HEHC with pure gasoline and hydrogen doping fraction of 0.3 are 42.6% and 41.5% at the optimal ignition angles of 330° and 345°, respectively. The cycle efficiency of real HEHC is increased by 1.3% at the rotational speed of 9000 rpm with the increase of hydrogen doping fraction of 0.3. The indicated fuel cost and ICDE for the hydrogen doping fraction of 0.3 is 19.2% higher and 28.2% lower than that for pure gasoline under optimal ignition angles, respectively. The increasing hydrogen doping fraction reduces the effect of rotational speed on the cycle efficiency, indicated fuel cost and ICDE.

Activity features of catalysts for thermocatalytic hydrogenation processing of polymer waste

The aim of this study was to obtain new catalysts for the processing of carbon-containing polymer waste based on polyethylene and polypropylene, represented mostly by lids from beverages bottled in plastic containers, which accumulate in huge quantities in landfills, by the method of thermocatalytic hydrogenation into liquid fuels and other products. The process was carried out in the presence of fuel oil as a binder, a source of hydrogen and additional hydrocarbons. Thus, two tasks can be solved simultaneously: recycling the polymer waste and obtaining the alternative raw materials from the polymer waste in order to save resources and improve the environmental situation in general. New catalysts based on activated zeolite modified with Mo(VI) and W(VI) salts of various concentrations for the thermocatalytic hydrogenation processing of waste plastics into motor fuels were synthesized. The composition, structure, morphology and adsorption properties of the catalysts were determined by different physicochemical methods. The suitability of the obtained catalysts for use in the thermocatalytic hydrogenation processing of plastic waste into fuels was determined. The catalysts were tested during the processing of a mixture of polyethylene-polypropylene: a paste-forming agent (fuel oil) at T=450 °C and a pressure of 0.6 MPa. The individual and group composition of gasoline, diesel and gas oil fractions was determined by chromatography coupled with mass spectrometry. The maximum yield of the gasoline fraction (16.9 wt.%) and diesel fraction (39.31 wt.%) was obtained on a 2%W(VI)/diatomite catalyst.

Pyrolysis of solid polymer waste and properties of obtained products

Pyrolysis of solid polymer waste (car tires) was investigated in the temperature range of 350–6500C for 15–105 minutes. It was established that the maximum yield of a liquid product (58%) was observed in the temperature range of 520–5400С. The obtained pyrocondensate was compared with oil and it was stated that pyrolysis condensate was quite heavy, but had low kinematic viscosity and average molecular weight. It was determined that the most part of sulfur (1.27–2.1%) remained in the solid residue during the rubber pyrolysis. Unsaturated hydrocarbons (12.9%) in pyrolysis oil were found due to the presence of double bonds in rubber and the formation of double bonds during the polymer destruction. It was found that increasing the pyrolysis temperature from 400 to 6000C led to a decrease in polycyclic naphthenes and an increase in the proportion of aromatic ring in the molecule due to the cleavage of alkyl substituents. The fractional composition of pyrolysis products obtained in the temperature range of 520–5400C was determined. The yield of the gasoline fraction, the diesel fraction and the residue was 26–28 wt.%, 18–23 wt.% and 45–47 wt.%, respectively. Comparison of the properties of fractions obtained from pyrocondensate with traditional petroleum products showed that the content of sulfur compounds for gasoline and diesel fractions was overestimated due to the presence of sulfur vulcanizing agent in rubber. The content of aromatic compounds, density and viscosity were slightly increased in those fractions. The properties of the fraction 3500C (end of boiling) were almost the same as those of fuel oil.

Use of by-Product Gasoline Fractions Produced by Combining Fuel and Petrochemical Production

Use of by-Product Gasoline Fractions Produced by Combining Fuel and Petrochemical Production

Hydrocracking of Crude Palm Oil over Bimetallic Oxide NiO-CdO/biochar Catalyst

The bimetallic oxide NiO-CdO/biochar catalyst was prepared by coprecipitation and calcination methods. Characterizations of catalyst were carried out using Fourier Transform Infra Red (FTIR), Surface Area Analyzer (SAA), X-ray Diffraction (XRD), and Scanning Electron Microscope-Energy Dispersive X-ray (SEM-EDX) mapping methods. The catalyst showed a good average crystalized size of 12.30 nm related to the nanoparticles and high dispersion of Ni and Cd metals on the biochar surface. Analysis of liquid fuel products was observed using Gas Chromatography - Mass Spectrometry (GC-MS) which was separated to the main product of gasoline fraction (C6–C10), and the second product of kerosene fraction (C11–C16), and diesel fraction (C17–C23). The presence of the catalyst in the hydrocracking resulted in more liquid product of 56.55 wt% than the thermal cracking with a liquid product of 20.55 wt%. The best performance activity of catalyst was found at a temperature of 150 °C with high selectivity to hydrocarbon fuel with 12 types of gasoline fractions (39.24 wt%) compared to gasoline fractions obtained at higher hydrocracking temperatures of 250 °C and 350 °C. The results of this study showed that the bimetallic oxide catalyst supported with biochar from palm kernel shell plays an important role in the hydrocracking process to increase the selectivity of the gasoline fraction. Copyright © 2022 by Authors, Published by BCREC Group. This is an open access article under the CC BY-SA License (https://creativecommons.org/licenses/by-sa/4.0).

Selection of Solvents for the Removal of Asphaltene–Resin–Paraffin Deposits

In this study, we aimed to select the optimal solvents for the removal of asphaltene–resin–paraffin deposits. The effectiveness of various solvents was determined based on the asphaltene–resin–paraffin deposits (ARPDs) of the Zhanaozen (Ozen) crude oil field. These deposits affect the geological, physical, and technological conditions of the oil field, thus influencing its development. According to the results, we found that the most effective composite solvent is a composition comprising a 50% gasoline fraction and a 50% kerosene fraction. This composition showed mass loss of deposits of 97.7% and a dissolving power of 93.5 g/cm3 after 5 h. We confirmed the effectiveness of this composition by the paraffinic type of the deposits, which is explained by the high content of paraffin in the oil from the Zhanaozen field. Aromatic solvents showed a relatively low dissolving power compared with aliphatic solvents, which also confirms the low content of resins and asphaltenes in the ARPD.

IMPROVING THE ENVIRONMENTALITY OF MOTOR GASOLINE

The article considers measures aimed at improving the environmental situation of large cities by reducing the harmful effects of exhaust gases generated during the operation of road transport. It is substantiated that a direct increase in the environmental friendliness of motor gasoline is the most promising approach to reducing the toxicity of exhaust gases. This increase can be achieved by reducing dissolved hydrocarbon gases (C4H10 and iso-C4H10) and metals (Pb, Fe, Mn) in gasoline; facilitation of the fractional composition of gasoline (including the end-boiling temperature); reduction in gasoline content of sulfur, aromatic hydrocarbons and olefins. Reducing these undesirable, from an environmental point of view, components will improve the quality of gasoline to the Euro-5 requirements adopted in Ukraine, as well as significantly extend the service life of special catalysts installed on motor vehicles to clean exhaust gases.
 The effect on the gasoline fraction (PK – 180 °C) and commercial gasoline A-95, oxygenates (methyl tert-butyl ether and ethyl alcohol) and 1,3-diphenyltriazene was studied. It is established that the use of 1% of the mass. 1,3-diphenyltriazene, in the composition of straight-run gasoline allows to increase its resistance to detonation by 12 points, reduce the toxicity of exhaust gases by 24% in terms of CO and 17% in terms of CH. It was determined that the addition of 1,3-diphenyltriazene to commercial gasoline A-95 in the amount of 1% by weight, in contrast to oxygenates, does not lead to a deterioration in the evaporation of gasolines and their physical stability.
 The use of 1,3-diphenyltriazene in commercial gasoline, due to its positive properties, in the future will optimize the use of other additives, including oxygenates, which are widely used today in the technology of commercial gasoline.

Co-processing catalytic fast pyrolysis oil in an FCC reactor

Studies of co-processing catalytic fast pyrolysis (CFP) oil with vacuum gas oil (VGO) are conducted in a Davison Circulating Riser (DCR). The CFP oil (CFPO) for this study was produced by upgrading fast-pyrolysis vapors from pine in an ex-situ fixed-bed reactor. CFPOs were co-processed at up to a volume fraction of 0.05 with VGO at 521 °C and 257 kPa. The yields of oil, aqueous phase, tail gas, and coke were measured. The amount of coke was determined from the carbon containing components in the regenerator flue gas. A compositional analysis was conducted with gas chromatography and elemental analyzers. The organic liquids were distilled into gasoline, jet-fuel, diesel, and resid fractions. A biocarbon analysis was conducted on the organic phase and its individual boiling-point fractions. The results show a small decrease in liquid yield and a generally increased gas yield when co-processing CFPO with VGO. The experiments showed that 75%–100% of biocarbon is incorporated into liquid fuels relative to fossil carbon, depending on catalyst and CFPO. The measurements indicate that cracked CFPO components are predominantly included in the jet-fuel and diesel fractions. A techno-economic analysis (TEA) estimated the minimum fuel selling price (MSFP) for fuel-range products derived from FCC co-processing of CFPO at 24 to 29 $/GJ ($2.90 to $3.50 per gasoline-gallon equivalent; GGE) at a yield of 4.87–7.14 GJ/t(biomass) or 40–58 GGE/t.

Oxidative desulfurization of the straight-run gasoline fraction from the gas condensate of the Karachaganak field

An annual increase in the consumption of the automobile fuels makes us look for new ways of their obtaining. It is also important that the environmental and operational requirements for the quality of the motor fuels, obtained during oil production (associated petroleum gas, gas condensate) are systematically made more rigorous. One of the ways to solve the problems described above is to use the process of oxidative desulfurization to improve the quality of the petroleum products. In this case, oxidative desulfurization of the straight-run gasoline fraction, obtained from the gas condensate of the Karachaganak field, has been carried out. The oxidation process has been carried out with hydrogen peroxide in the presence of salts of the transition metals, molybdenum and vanadium. The optimal technological parameters (Patm, T=600C, 2 h, H2O2:S=4:1 (mol), Me:S=1:100 (mol)) of the oxidation process for the straight-run gasoline fractions have been selected. Under the optimal conditions of the oxidation process, the total sulfur content has been reduced by 89.9%. It has been shown that the molybdenum compounds exhibit greater activity in the oxidation of sulfur-containing compounds at a temperature of 600C, as compared to the vanadium compounds. A schematic diagram of the purification of the gasoline fractions from the sulfur-containing compounds by oxidative desulfurization, followed by its extraction desulfurization with the most effective N,N-dimethylformamide has been presented.