Heavy Gas Oil Research Articles

Role of Catalyst in Optimizing Fluid Catalytic Cracking Performance During Cracking of H-Oil-Derived Gas Oils

Three H-Oil gas oils, heavy atmospheric gas oil (HAGO), light vacuum gas oil (LVGO), heavy vacuum gas oil (HVGO), and two their blends with hydrotreated straight run vacuum gas oils (HTSRVGOs) were cracked on two high unit cell size (UCS) lower porosity commercial catalysts and two low UCS higher porosity commercial catalysts. The cracking experiments were performed in an advanced cracking evaluation fluid catalytic cracking (FCC) laboratory unit at 527 °C, 30 s catalyst time on stream, and catalyst-to-oil (CTO) variation between 3.5 and 7.5 wt/wt The two high UCS lower porosity catalysts were more active and more coke selective. However, the difference between conversion of the more active high UCS lower porosity and low UCS higher porosity catalysts at 7.5 wt/wt CTO decreased in the order 10% (HAGO) > 9% (LVGO) > 6% (HVGO) > 4% (80% HTSRVGO/20% H-Oil VGO). Therefore, the catalyst performance is feedstock-dependent. The four studied catalysts along with a blend of one of them with 2% ZSM-5 were examined in a commercially revamped UOP FCC VSS unit. The lower UCS higher porosity catalysts exhibited operation at a higher CTO ratio achieving a similar conversion level with more active higher UCS lower porosity catalysts. However, the higher UCS lower porosity catalysts made 0.67% Δ coke that was higher than the maximum acceptable limit of 0.64% for this particular commercial FCC unit (FCCU), which required excluding the HVGO from the FCC feed blend. The catalyst system containing ZSM-5 increased the LPG yield but did not have an impact on gasoline octane. It was found that the predominant factor that controls refinery profitability related to the FCCU performance is the FCC slurry oil (bottoms) yield.

Hydrodesulfurization reactions group kinetics of “vacuum gas oil–deasphalted vacuum residues–heavy coker gasoil” feedstock in the presence of a Ni6–PMonW12-n/γ-Al2O3 catalysts

Hydrodesulfurization reactions group kinetics of “vacuum gas oil–deasphalted vacuum residues–heavy coker gasoil” feedstock in the presence of a Ni6–PMonW12-n/γ-Al2O3 catalysts

Design of an environmentally friendly fuel based on a synthetic composite nano-catalyst through parameter estimation and process modeling

Abstract In this paper, oxidative desulfurization (ODS) process is studied for the purpose of removing the sulfur components from light gas oil (LGO) via experimentation and process modeling. A recently developed (by the authors) copper and nickel oxide based composite nano-catalyst is used in the process. The ODS experiments are conducted in a batch reactor and air is used as an oxidizer under moderate operation conditions. Determination of the kinetic parameters with high accuracy is necessary of the related chemical reactions to develop a helpful model for the ODS operation giving a perfect design of the reactor and process with high confidence. High conversion of 92% LGO was obtained under a reaction temperature of 413 K and reaction time of 90 min for synthesized Cu Ni /HY nano-catalyst. Here model based optimization technique incorporating experimental data is used to estimate such parameters. Two approaches (linear and non-linear) are utilized to estimate the best kinematic parameters with an absolute error of less than 5% between the predicted and the experimental results. An environmentally friendly fuel is regarded the main goal of this study, therefore the optimization process is then employed utilizing the validated model of the prepared composite nano-catalyst to get the optimal operating conditions achieving maximum conversion of such process. The results show that the process is effective in removing more than 99% of the sulfur from the LGO resulting in a cleaner fuel.

Design of new activated carbon based adsorbents for improved desulfurization of heavy gas oil: experiments and kinetic modeling

Abstract In this work, adsorption desulfurization is considered for making cleaner fuel. New efficient adsorbents have been designed by using two active metal oxides mainly potassium permanganate (KMnO4) and potassium phosphate (KPO4·3H2O) on Activated Carbon (AC). Ultrasonic assisted impregnation method (IWI) is used in designing the adsorbents offering high pore volume, pore size, surface chemistry, and high surface area. Use of ultrasonic method increases the dispersion of the active material (groups) on AC leading to increased number of collisions between O-atom on AC-support resulting in high sulfur removal from fuel. KMnO4 on AC shows higher adsorption capacity towards sulfur than KPO4·3H2O at the same operating conditions. New results with respect to sulfur removal has obtained compared with those obtained by previous studies. Finally, the adsorption kinetic parameters of such process are developed. Thomas and Yoon–Nelson models and the experimental data are used for this purpose using linear and non-linear regression analysis. Yoon–Nelson kinetic model fits well with the experiments data better than Thomas kinetic model in the entire adsorption column system.

Improving the extraction of sulfur-containing compounds from fuel using surfactant material in a digital baffle reactor

Abstract Extraction desulfurization process (EDP) for dibenzothiophene (DBT) from model light gas oil (LGO) improved using solvent mixture with new surfactant material (sodium thiosulfate) in digital baffle batch reactor (DBBR). Surfactant material was help increase extraction surface through increase dispersion of solvent in LGO. Reactor design was the best designer where negligible region of died zone in the reactor, rotation of fuel beside of wall, because adding the baffle on the wall. The blade design was distributes hexagonal holes that help liquid cross with solvent and this increases mixing and mass transfer DBT from model LGO to solvent. Operational conditions effects on extractive desulfurization process (EDP) it’s found such as solvent mixture (methanol, ethanol and toluene) to LGO model ratio, speed of impeller, extraction temperature, extraction time and effect surfactant were explored. Optimal experimental results represented that the extraction conditions were; (methanol = 10 ml, ethanol = 10 ml, toluene = 10 ml and volume of cocktail solvent equal to 30 ml MET))/model of LGO ratio speed of impeller 450 rpm, extraction time 21 min and extraction temperature 85 °C. Maximum DBT removal from model LGO was obtained at 89.8%, at this operating condition. Higher polarity of DBT was obtained when solvent used 30 ml MET. For removal dibenzothiophene (DBT) from model light gas oil, the results indicate that the extraction desulfurization process is suitable method to improve fuel quality.

Influence of Steam Treatment on the Properties of HLaY-Containing Cracking Catalysts in an Aluminum-Pillared Montmorillonite Matrix

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.

Разработка технологических схем по увеличению отбора вакуумного газойля

The analysis of the operation of the vacuum columns of the ELOU AVT units showed that in a number of cases the half-gas contains up to 30% of vacuum gas oil with a boiling point of up to 560 ° C. A comparative analysis of three options for deepening the selection of heavy vacuum gas oil during the distillation of fuel oil has been carried out. A traditional scheme with a pressure reduction at the top of the vacuum column, the rectification of a half-sludge without heating it after the main vacuum column in an additional its subsequent rectification in the second column, with the selection of heavy vacuum gas oil. The analysis of the operation of the vacuum column of the vacuum rectification unit ELOU AVT-6 was carried out. The process was simulated in the environment of the software product Aspen HYSYS, the possibility of increasing the selection of heavy vacuum gas oil in the process of deep vacuum rectification of tar was theoretically proved. The advantages and disadvantages of two-column vacuum distillation of fuel oil are considered. Structural design of the rectification column and raw material input device is proposed.

Synthesis of sulfur-doped porous carbon from heavy coker gas oil and its application in CO2 capture

Elemental sulfur is used to cross-link heavy coker gas oil (HKGO) with only 0.44 wt% olefinic hydrogen content in the absence of solvent; subsequent pyrolysis yields sulfur-doped porous carbon with Brunauer–Emmett–Tell (BET) surface area (s.a.) around 1714–1785 m2 g−1.

Catalytic Upgrading of Heavy Oil using FCC Equilibrated Catalyst

Heavy crude oil is an important unconventional hydrocarbon resources that can be upgraded to useful petroleum products. However, heavy oil has some challenges due to its high viscosity, low mobility coupled with its low API gravity, these features make processing and transportation of heavy oil quite challenging. Consequently, there is need to upgrade heavy oil using suitable technique and appropriate catalyst. In this study, an equilibrated FCC catalyst (E-CAT) was sourced from a refinery, characterized using XRD, XRF and FT-IR techniques and tested in upgrading heavy crude oil. In a preliminary work, heavy gas oil (HGO) and vacuum gas oil (VGO) were used as model oils. They were cracked in a high pressure-high temperature batch reactor at varying temperatures of 350, 400 and 450oC, initial pressure of 1MPa and catalyst-to-oil ratio of 0.01 for the catalytic reaction. Parameters studied include viscosity reduction and change in structural composition of the model oils before and after upgrading using FT-IR technique. Results of VGO upgrade showed viscosity reduction of 3.5, 10 and 32% after thermal upgrade at 350,400, 450oC and 10, 15 and 42% after catalyst addition at the temperatures respectively. The HGO upgrading result showed viscosity reduction of 4, 7 and 24% after thermal upgrade at 350, 400 and 450 oC respectively and 6, 13 and 33% viscosity reduction after catalyst addition correspondingly. FT-IR results suggest the formation of saturated hydrocarbons an indication of the formation of valuable products after upgrading reactions with a better results recorded after catalyst addition. Results from the experimental investigation showed that the E-Cat has the potential to be used in heavy crude oil upgrading

ИССЛЕДОВАНИЕ ЭКСТРАКЦИИ КАНЦЕРОГЕННЫХ ПОЛИЦИКЛОАРЕНОВ В АППАРАТЕ С НАСАДКОЙ

Experimental study of the extraction of polycycloarenes from a mixture of heavy vacuum gas oil and deasphalted oil extract in a packed bed column was carried out. Extraction process was performed using a mixed extractant N-methylpyrrolidone/ethylene glycol. The description of the experimental apparatus, the experimental techniques and the results of the experiment are presented.

Nitrogen compounds removal from oil-derived middle distillates by MIL-101(Cr) and its impact on ULSD production by hydrotreating

Oil-derived middle distillates (straight-run gas oil and mixture with light cycle oil and coker gas oil) for Ultra-Low Sulfur Diesel (ULSD) production by HyDroTreating (HDT) were pretreated by selective Nitrogen Organic Compounds (NOC) adsorption. Highly crystalline Metal-Organic Framework (MOF) MIL-101(Cr) prepared with propylene oxide (proton scavenger) as textural improver was used to that end. MOF was characterized by N2 physisorption, X-ray diffraction, thermal analysis, infrared, Raman and UV-vis spectroscopies, and electron microscopy (SEM and HR-TEM). NOC removal was carried out at room temperature and atmospheric pressure, the adsorbent being easily regenerable under mild conditions. Extruded MOF efficiently removed NOC from real feedstocks to concentrations ~ 80 ppm which allowed ULSD production at much milder conditions to those used during pristine feedstocks HDT. Operating temperature could be significantly diminished (from 350 to 330 °C, at 56 kg cm−2 (5.77 MPa), LHSV = 1.5 h−1, H2/oil = 2500 ft3 bbl−1 (445 m3 m−3)) which could notably prolong cycle life of NiMo/Al2O3 formulation used.

Изучение изменения фракционного состава при гидроочистке под высоким давлением легкого газойля коксования

Slavneft-YANOS PJSC plans to commission delayed coking unit in 2025, and the key task is to increase the depth of oil refining and increase the share of high-margin petroleum products. As a result of evaluating the change of 95% of the diesel fuel boiling point during hydrotreatment at high hydrogen pressure, it was concluded that it is possible to expand the fractional composition of light coker gasoil at expense of heavy coker gasoil.

Composite catalysts for the catalytic processing of fuel oil

The paper describes the catalytic cracking of heavy petroleum feedstock on catalysts based natural Taizhuzgen zeolite and Narynkol clay (Kazakhstan). Catalytic cracking was studied on fuel oil of the M-100 brand taken from the LLP Pavlodar Oil Chemistry Refinery (Kazakhstan). Air was added into the reaction medium. It was found that under optimal conditions, the conversion of the heavy residue of M-100 fuel oil reaches 46.2%, when cracking the initial fuel oil, the yield of the middle distillate fraction is 85.7 wt. % due to the content of 41.1 wt. % residual light gas oil in the resulting products. The optimal composite catalyst allows carry out the cracking of heavy oil residues without preliminary purification and with a high degree ofconversion to diesel fraction.

Исследование зависимости температуры размягчения от содержания мезофазы в нефтяных пеках, полученных из тяжелой пиролизной смолы и декантойля

Samples of petroleum pitches were obtained from heavy pyrolysis resin and decantoil (heavy gas-oil of catalytic cracking) by thermal polycondensation at atmospheric pressure, temperatures of 380–400 and 410–440°С (for resin and decantoil, respectively) and isothermal holding time of 30–480 min. Analysis of the dependence of the softening point on the mesophase content for the obtained samples showed that at the same mesophase content, decantoil pitches exhibit a lower softening point compared to pyrolysis resin pitches, for which, even at 30 % mesophase, the softening point approaches 300°C. This suggests that it is impossible to obtain pitch from pyrolysis resin with high mesophase content without preliminary preparation (for example, by hydrogenation). On the other hand, it has been shown that for pitches from decantoil, it is possible to isolate the mesophase up to 65% or more with a softening point not higher than 250°C.

Conversion of heavy gasoil into ultra-low sulfur and aromatic diesel over NiWRu/TiO2–γAl2O3catalysts: Role of titanium and ruthenium on improving catalytic activity

This contribution deals with about selective conversion of heavy gas oils into middle distillates fuels that meet ultra-low sulfur and aromatic compound quality standards by using a novel NiWRu/TiO2–γAl2O3catalyst under typical hydrotreatment conditions. A diesel fuel fraction having sulfur, nitrogen and aromatics compound content of about 50 ppm, 10 ppm and 15 v%, respectively, was obtained when the reactor was operated atT = 370 °C,P = 12.4 MPa, LHSV = 0.5 h−1and H2/hydrocarbon ratio = 800 Nm3/m3. Titanium and ruthenium additives used in the preparation of the NiWRu/TiO2–γAl2O3catalyst, remarkably improved the catalytic activities for the hydrogenolysis, hydrogenation and hydrocracking reactions compared to the reference NiW/γAl2O3catalyst. The coprecipitation of titanium and aluminum hydroxides produced a catalyst support having greater surface area, pore volume and surface acidity. An improvement in mechanical properties of the support extrudates was also observed. Characterization analysis by XPS, AUGER and XRD techniques of the TiO2–γAl2O3support suggested the formation of an aluminum-titanate mixed phase (AlxTiyOz) having a non-well-defined stoichiometry. The NiW/TiO2–γAl2O3and NiWRu/TiO2–γAl2O3exhibited a greater surface dispersion of the supported nickel and tungsten species compared to the NiW/γAl2O3catalyst. The promoter effect of ruthenium on the NiW bimetallic system caused a strong increase in both hydrogenolysis and hydrogenation reactions. Hydrodenitrogenation and hydrocracking reactions were also favored by the increase in the hydrogenation capacity and in the surface acidity of the catalyst. The highest conversion levels for all investigated reactions were obtained when the NiWRu/TiO2–γAl2O3catalyst was prepared by co-impregnation of Ni and Ru in a second step. This catalyst showed sulfur tolerance properties when the reaction was conducted in the presence of different H2S partial pressures. The catalytic behavior of the NiWRu/TiO2–γAl2O3catalyst was explained by the existence of a promoting effect between separated Ni and Ru sulfides species and the NiWS phase (dual mechanism).

Performance enhancement of adsorption desulfurization process via different new nano-catalysts using digital baffle batch reactor and mathematical modeling

Several new homemade nano-catalysts are prepared here to reduce sulfur compound found in light gas oil (LGO) utilizing the adsorption desulfurization technique. The effect of different support materials (Fe2O3, Cr2O3 and CdO) having the same particle size (20 nm) on the adsorptive desulfurization performance for loading 5% nickel sulfate (5 wt%NiO) as an active component for each catalyst, is studied. Oxidative desulfurization process (ODS) in a novel digital baffle batch reactor (DBBR) is used to evaluate the performance of the catalysts prepared. Moderate operating conditions are employed for the ODS process. The efficient new nano-catalysts with for the removal of sulfur are found to be 93.4%, 85.6% and 62.1% for NiO/Fe2O3, NiO/Cr2O3 and NiO/CdO, respectively at 175 °C, 75 min and 2 ml of H2O2. The best kinetic model and the half-live period for the nano-catalysts related to the relevant reactions have also been investigated here.

Tracking Elemental Composition through Hydrotreatment of an Upgraded Pyrolysis Oil Blended with a Light Gas Oil

The physical properties of crude bio-oils preclude their direct use as fuel. Specifically, their high oxygen content results in undesirable acidity and poor thermal stability. Therefore, the remova...

Distillation of vacuum gas oil in a column with new packings

A description of the technological scheme of the unit for separating the fraction of vacuum gas oil (FVG) is given, where the process of separation of heavy gas oil from FVG takes place in the column. The main focus of the work is on the design of a distillation column using the new structured roll packing. The fractional composition of the feedstock, by-product, light gas oil, and the target product, which is heavy gas oil, is presented. Requirements for the design of a structured packing in terms of pressure drop and separation efficiency are formulated. A structured roll packing with corrugations and rough surface having specific surface area of 300 m2/m3 is chosen. The diagram and photograph of the packing are presented. Comparative values of specific pressure drop for several structured packings are given. It is shown that the selected packing provides the lowest hydraulic resistance. For mathematical modeling and calculation of the multicomponent distillation process, a system of mass transfer equations with interfacial bulk sources of transfer components is used. In this case, for the conditional component, a fraction at the specified boiling points is used. As a result of solving the system of equations with boundary conditions, the profiles of the fractions along the height of the packed bed are found and the structural characteristics of the structured packing are selected that meet the requirements for the top and bottom of the column. Calculations of a vacuum distillation column with this packing are carried out and it is found that the bed height of 6 meters is sufficient to meet the requirements for the fractional composition of the upper and lower products, while meeting the pressure drop requirements. The developed scientific and technical solutions have been implemented at a refinery in Malaysia and correspond to the technical specifications for the design of the unit.

Influence of oligomethylenaryl sulphonates based on the light gas oil of catalytic cracking on the process of biocorrosion

This article presents the results of studies in the field of synthesis of water-soluble salts of oligomethylene aryl sulfonates synthesized using aromatic hydrocarbons contained in the gas oil fraction of the catalytic cracking process of oil as raw materials. Based on the synthesized various salts of oligoaromatic sulfonic acids (sodium, potassium, ammonium salts), solutions of various concentrations (35; 75; 150; 200 mg/l) were prepared and their effect on the vital activity of sulfate-reducing bacteria at a temperature of 30…32 °С for 7…14 days was studied. It was found that complex salts synthesized on the basis of oligomeric sulfonic acids of aromatic hydrocarbons of the gas oil fraction (N-1, N-2, N-3) at a concentration of 150 mg/l exhibit more than 90%, and at a concentration of 200 mg/l, 100% bactericidal effect and completely inhibits the growth of bacteria. It was revealed that the synthesized salts of sulfonic acids exhibit a relatively higher antimicrobial activity against SRB than the industrial bactericidal inhibitors AMDOR-IK-7 and AMDOR-IK-10 taken as a reference. Based on the studies, it was found that the synthesized salts of oligosulfonic acids completely inhibit the growth of sulfate-reducing bacteria at much lower concentrations compared to the industrially used bactericidal inhibitors taken as a reference. In particular, at a concentration of 150 mg/l, the bactericidal effect is more than 90% against 75…80% for the standard.

Hydrocracking of a Heavy Vacuum Gas Oil with Fischer–Tropsch Wax

Catalytic hydrocracking represents an optimal process for both heavy petroleum fractions and Fischer–Tropsch (FT) wax upgrading because it offers high flexibility regarding the feedstock, reaction conditions and products’ quality. The hydrocracking of a heavy vacuum gas oil with FT wax was carried out in a continuous-flow catalytic unit with a fixed-bed reactor and a co-current flow of the feedstock and hydrogen at the reaction temperatures of 390, 400 and 410 °C and a pressure of 8 MPa. The increasing reaction temperature and content of the FT wax in the feedstock caused an increasing yield in the gaseous products and a decreasing yield in the liquid products. The utilisation of the higher reaction temperatures and feedstocks containing the FT wax showed a positive influence on the conversion of the fraction boiling above 400 °C to lighter fractions. Although the naphtha and middle distillate fractions obtained via atmospheric and vacuum distillations of the liquid products of hydrocracking did not comply with the particular quality standards of automotive gasolines and diesel fuels, the obtained products still present valuable materials which could be utilised within an oil refinery and in the petrochemical industry.