Hydrocracking Of Vacuum Gas Oil Research Articles

Impact of lanthanum ion exchange and steaming dealumination on middle distillate production using nanosized Y zeolite catalysts in hydrocracking reactions.

In the field of hydrocracking reactions, achieving optimal middle distillate yields remains a persistent challenge with commercially available zeolite Y catalysts. This limitation is attributed to challenges related to diffusion constraints within the catalyst. In response, we present a promising solution not only to these problems but also to the challenges encountered in nanosized Y zeolites when attempting to generate acidic sites within their structure and when analyzing their performance in vacuum gas oil hydrocracking. NiMo catalysts based on nanosized Y zeolites with different crystal sizes exchanged with lanthanum, effectively address diffusion issues and significantly enhance catalyst performance compared to dealuminated nanosized and commercial Y zeolite under the same reaction conditions. The catalysts were characterized by TGA, ICP-OES, XPS, N2 physisorption, FT-IR for pyridine acidity, TEM-mapping, and the 3-methyl thiophene reaction to test the hydrogenating capacity. Surface analysis and microscopy showed greater porosity in the catalysts with smaller zeolites and different arrangements of their components. The catalysts based on steamed protonated nanosized Y zeolites with a larger size and lanthanide nanosized Y zeolite with a smaller size yielded more middle distillates. Research provides a comprehensive analysis, providing a correlation between the catalytic performance and the size of the nanosized Y zeolite.

Hierarchical submicrosized Y zeolites prepared by sequential desilication–dealumination post-synthesis modification and their catalytic performance in vacuum gas oil hydrocracking

The desilication-dealumination process allowed the production of structurally more stable submicrometric Y zeolites with hierarchical porosity and high crystallinity.

Post‐Synthetic Ensembling Design of Hierarchically Ordered FAU‐type Zeolite Frameworks for Vacuum Gas Oil Hydrocracking

AbstractZeolites hold importance as catalysts and membranes across numerous industrial processes that produce most of the world's fuels and chemicals. In zeolite catalysis, the rate of molecular diffusion inside the micropore channels defines the catalyst's longevity and selectivity, thereby influencing the catalytic efficiency. Decreasing the diffusion pathlengths of zeolites to the nanoscopic level by fabricating well‐organized hierarchically porous architecture can efficiently overcome their intrinsic mass‐transfer limitations without losing hydrothermal stability. We report a rational post‐synthetic design for synthesizing hierarchically ordered FAU‐type zeolites exhibiting 2D‐hexagonal (P6mm) and 3D‐cubic (Ia d) mesopore channels. The synthesis involves methodical incision of the parent zeolite into unit‐cell level zeolitic fragments by in situ generated base and bulky surfactants. The micellar ensembles formed by these surfactant‐zeolite interactions are subsequently reorganized into various ordered mesophases by tuning the micellar curvature with ion‐specific interactions (Hofmeister effect). Unlike conventional crystallization, which offers poor control over mesophase formation due to kinetic constraints, crystalline mesostructures can be developed under dilute, mild alkaline conditions by controlled reassembly. The prepared zeolites with nanometric diffusion pathlengths have demonstrated excellent yields of naphtha and middle‐distillates in vacuum gas oil hydrocracking with decreased coke deposition.

Post-Synthetic Ensembling Design of Hierarchically Ordered FAU-type Zeolite Frameworks for Vacuum Gas Oil Hydrocracking.

Zeolites hold importance as catalysts and membranes across numerous industrial processes that produce most of the world's fuels and chemicals. In zeolite catalysis, the rate of molecular diffusion inside the micropore channels defines the catalyst's longevity and selectivity, thereby influencing the catalytic efficiency. Decreasing the diffusion pathlengths of zeolites to the nanoscopic level by fabricating well-organized hierarchically porous architecture can efficiently overcome their intrinsic mass-transfer limitations without losing hydrothermal stability. We report a rational post-synthetic design for synthesizing hierarchically ordered FAU-type zeolites exhibiting 2D-hexagonal (P6mm) and 3D-cubic (Ia d) mesopore channels. The synthesis involves methodical incision of the parent zeolite into unit-cell level zeolitic fragments by in situ generated base and bulky surfactants. The micellar ensembles formed by these surfactant-zeolite interactions are subsequently reorganized into various ordered mesophases by tuning the micellar curvature with ion-specific interactions (Hofmeister effect). Unlike conventional crystallization, which offers poor control over mesophase formation due to kinetic constraints, crystalline mesostructures can be developed under dilute, mild alkaline conditions by controlled reassembly. The prepared zeolites with nanometric diffusion pathlengths have demonstrated excellent yields of naphtha and middle-distillates in vacuum gas oil hydrocracking with decreased coke deposition.

Coprocessing Partially Hydrodeoxygenated Hydrothermal Liquefaction Biocrude from Forest Residue in the Vacuum Gas Oil Hydrocracking Process

Coprocessing Partially Hydrodeoxygenated Hydrothermal Liquefaction Biocrude from Forest Residue in the Vacuum Gas Oil Hydrocracking Process

Combining USY and ZSM-23 in Pt/zeolite hydrocracking catalyst to produce diesel and lube base oil with improved cold flow properties

The effect of the combined use of three-dimensional large-pore USY zeolite and one-dimensional medium-pore ZSM-23 zeolite to enhance the cold flow properties of hydrocracking products was studied. Based on the results of monozeolite catalysts testing in hexadecane hydroconversion, the compositions of bizeolite catalysts for vacuum gas oil hydrocracking were selected. The catalyst compositions were selected, considering that both zeolite components operate in a similar temperature range and contribute to hexadecane conversion. It has been shown that due to an appropriately selected combination of USY and ZSM-23 zeolites in the catalyst, both zeolites perform together, complementing each other, which ensures good conversion of both n-alkanes and isoalkanes during vacuum gas oil hydrocracking. As a result, it is possible to significantly improve the cold flow properties of the obtained hydrocracking products while maintaining the activity and selectivity for the target products of Pt/USY-ZSM-23 catalyst at the level of conventional Pt/USY catalyst. The cold filter plugging point of the diesel fraction decreases from −10 to less than −44 °C and the pour point from −17 to less than −50 °C. The pour point of lube base oil decreases from 23 to less than −27 °C. The improvement of the cold flow properties is accompanied by only a slight worsening of the other important product characteristics, such as diesel fraction cetane index and lube base oil viscosity index.

Опыт производства битумной продукции из остаточных продуктов комбинированной установки гидрокрекинга гудрона АО «ТАИФ-НК»

The article is devoted to the use of residual products of combined thermal and hydrocracking of vacuum residue and vacuum gasoil into demanded marketable petroleum products - into bitumen products in accordance with Russianand international quality standards.

Comparison of parallel and in-series reaction schemes for kinetic modeling of VGO hydrocracking

An analysis of the reaction pathways developed during the hydrocracking of vacuum gas oil (VGO) was carried out using kinetic models based on parallel and in-series reaction schemes. A methodology that considers diverse crucial factors was applied for the estimation of kinetic parameters based on experimental data reported for VGO hydrocracking using a Ni-Mo-F3.6/ASA-Al2O3 catalyst in a temperature range of 380–410 °C and 10 mPa. The results of a kinetic model that considers parallel reaction pathways presented a better fit than kinetic parameters reported in the literature. While, models based on in-series reaction schemes indicated that some reaction pathways present considerable values of the kinetic coefficients. Every set of kinetic parameters was analyzed by sensitivity analysis, parity plot, and residual analysis to ensure that these values are the most suitable for the experimental data and reaction scheme used. Each kinetic model presented an adequate fit with the experimental data, obtaining values of AAE less than 5 %.

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.

Analysis of kinetic models for hydrocracking of heavy oils for In-situ and Ex-situ applications

In-situ processing has been suggested as an alternative for upgrading heavy oils and bitumen directly in the reservoir. However, there is not much information on the kinetic of the reactions occurring during this process. In this work, all the kinetic models reported so far for the in-situ and ex-situ upgrading of heavy crude oil or residue using nanocatalyst and hydrogen are discussed. Most of the kinetic models are based on the lumping approach and assume a first-order of reaction. The approaches used to calculate the kinetic parameters do not ensure reaching the global minimum of the objective function to determine their optimal values. The lowest energy demanding reactions for the hydrocracking of residue, vacuum gasoil, and distillates are in series as reported by almost all kinetic models. The calculated activation energies agree that gas fraction is only formed by residue conversion, and reactions are mainly carried out in series rather than in parallel under the studied conditions.

Hydrocracking of Heavy Vacuum Gas Oil with Petroleum Wax

Petroleum heavy vacuum gas oil (HVGO) containing 10 wt.% of petroleum wax was hydrocracked at 390–430 °C and under the pressure of 18 MPa over a Ni W/amorphous silica-alumina catalyst in a continuous-flow fixed-bed reactor. The hydrocracking of a reference feed (neat HVGO) was carried out under the same reaction conditions. The physico-chemical properties of primary products obtained via laboratory atmospheric-vacuum distillation (heavy naphtha, middle distillates and distillation residue) were evaluated. Most products prepared from the mixed feedstock had a similar or lower density and sulfur content than the products obtained from the hydrocracking of the neat HVGO. The heavy naphtha fractions obtained from mixed feedstock contained slightly more n-alkanes and iso-alkanes and less naphthenes and aromatics. Similarly, middle distillates obtained from the mixed feedstock contained slightly more n-alkanes and less aromatics and had cetane index higher by up to 2 units.

Исследование процесса гидрокрекинга вакуумного газойля в присутствии цеолитсодержащего катализатора, модифицированного переходными металлами

The article presents the results of hydrocracking of vacuum gas oil. The effect of volume rate on the course of the process has been studied. The study of the effect of the volumetric velocity on the hydrocracking of the vacuum gas oil at a pressure of 5 MPa and at a temperature of 440°C shows that the favorable volumetric velocity is between 0.8–1.0 h–1. As the volume ratio increases from 1.5 to 2 h–1, the amount of sulfur and unsaturated hydrocarbons increases in the diesel fraction, while the yield of the diesel fraction decreases. The density of the diesel fraction and the boiling point of 50% increase.

Effect of rare earths on acidity of high-silica ultrastable REY zeolites and catalytic performance of NiMo/REY+Al2O3 catalysts in vacuum gas oil hydrocracking

A series of low-sodium ultrastable Y zeolites (SiO 2 /Al 2 O 3 ≈ 25) partially exchanged with different amounts of rare earth ions (RE 2 O 3 = 0.55–3.32 wt%) was prepared and characterized by XRD, IR spectroscopy, elemental analysis, N 2 adsorption, as well as 29 Si and 27 Al NMR. The effect of RE content on the number and relative strength of acid sites of REY zeolites was studied by IR spectroscopy of absorbed CO and pyridine. The increase in the RE content in the zeolites leads to a decrease in the concentration of strong Brønsted acid sites (BAS) in faujasite cages (bridged Si–O(H)–Al groups), especially the concentration of stronger BAS associated with Si–O(H)–Al groups polarized by extra-framework aluminum species. At the same time, the concentration of less acidic OH groups connected with extra-framework ions increases possibly due to the formation of additional RE–O(H)–Al groups. The total number of BAS in all the samples remains close. An increase in the RE 2 O 3 content from 0.55 to 3.32 wt% decreases almost by half the ratio of strong BAS in faujasite cages to less acidic extra-framework BAS. The catalytic performance of NiMo/(30 wt% REY + 70 wt% Al 2 O 3 ) catalysts was evaluated in hydrocracking of vacuum gas oil. The enhanced hydrocracking activity and selectivity to middle distillates are mainly achieved due to the optimal acidity of the zeolites. • Synthesis of USY zeolites (Si/Al≈12.5) exchanged with different amount of RE ions. • Strong BAS/less acidic extraframework BAS ratio decreases with RE content increase. • Stronger BAS (Si–O(H)–Al groups polarized by EFAL species) are exchanged first. • Additional BAS are associated with the formation of RE–O(H)–Al groups in supercages. • NiMo/REY + Al 2 O 3 with optimal acidity exhibits improved hydrocracking performance.

Mapping technique for oil refining processes and products

The technique is proposed for visualizing the product compositions and the refractodenses (trajectories) of oil refinery processes, based on measuring the refractive index and density of the liquid product flows of operating procedures, computing the specific refraction and refraction intercept, and constructing a Kurtz-Lorentz identification map, the center of which is the “polymethylene center”. Trajectories-refractodenses of the processes of atmospheric-vacuum distillation of oil, catalytic reforming, hydrocracking of vacuum and heavy gas oil, products of secondary oil refining (motor gasoline, diesel fuel, catalytic cracking gasoline, light catalytic cracking gas oil) and their fractional distillation have been constructed. An express method is also proposed for evaluating the group hydrocarbon compositions of straight-run oil fractions, upon which we propose a three-digit composition marking of straight-run fractions. It is shown that the logarithms of isomeric alkanes contents in straight-run oil fractions are linearly correlated with their molar enthalpies of vaporization.

Study the pressure effect on hydrocracking process of vacuum gasoil

The paper presents the results of study on the pressure effect on hydrocracking process of vacuum gasoil from the mixture of Baku oils with the presence of aluminosilicate catalyst modified Ni, Mo. Hydrocracking of vacuum gasoil in the presence of aluminosilicate catalyst, modified Ni, Mo has been carried out in 3−8 MPa pressure in the temperature interval of 400−450 оС with the speed of 0.7−2.0 h-1 on Hungarian unit with reactor capacity in 200 ml. The pressure effect on the hdyrocracking process has been studied in the diapason of 3-8 MPa. It was defined that while the pressure is increasing from 3 to 5 MPa, the yield of diesel fraction also increases from 35 to 44 % mass. The pressure increase from 5 to 8 MPa increases the yield of diesel fraction for 48 %, i.e. the growth of only for 4 % is observed. It was considered practical to conduct hydrocracking process in 5MPa, as the pressure increase from 5 to 8 MPa leads to the significant increase of capital expenses.

Role of zeolite content in Ni-Mo/β-USY zeolite catalyst on hydrocracking of n-hexadecane and vacuum gas oil in a batch reactor and a fixed-bed reactor

In this paper, different materials that involved amorphous silica–alumina and hydrothermally synthesized beta zeolite and treated Y zeolite (USY) were introduced as parts of the hydrocracking catalyst supports. The prepared supports were used for preparation of Ni-Mo/silica alumina–zeolite catalysts by wetness impregnation method. The prepared catalysts were characterized by BET, temperature programmed desorption (TPD), temperature programmed reduction (TPR), and field emission – scanning electron microscopy (FE–SEM) methods. Effect of zeolite type and content on hydrocracking of n-hexadecane and vacuum gas oil in a batch and a fixed-bed reactor was investigated. Also, the content of coke formed after reaction was measured by thermal gravimetric methods (TGA). Hydrocracking was done at 400 °C and 55 bar. The hydrocracking of vacuum gas oil results showed that in the Ni-Mo/10B-30USY catalyst containing higher USY zeolite with high total acidity, selectivity to middle distillate was higher than the other (90%). Moreover, the Ni-Mo/10B-30USY catalyst in hydrocracking of n-hexadecane had a higher yield (82%) and was more selective to heavier products (C9–C12). The findings indicated that in the Ni-Mo/10B-30USY catalyst, coke content was more than the other due to high acidity.

Impact of Feedstock Properties on the Deactivation of a Vacuum Gas Oil Hydrocracking Catalyst

The aim of this study was to understand the impact of vacuum gas oil (VGO) properties on the deactivation rate of a hydrocracking catalyst (nickel–molybdenum sulfide dispersed on a carrier containing USY zeolite). For this purpose, two hydrotreated feeds of different densities, organic nitrogen (∼120–150 ppmw) and aromatic content, were hydrocracked under operating conditions that favor catalyst deactivation, that is, high temperature (T = 418 °C) and high space velocity (LHSV = 3 h–1). The catalyst performance was followed by measuring the VGO conversion (370 °C+ petroleum cut) and determining the apparent kinetic constants for the main hydrocracking reactions (cracking, hydrodenitrogenation, hydrodesulfurization, and aromatics hydrogenation). The experiments were stopped after different times on stream (either 6 or 30 days) in order to assess the evolution of the catalyst as a function of time. The spent catalysts, obtained from three different reactor locations, were characterized by elemental and textural analyses and by thermogravimetry to investigate the quantity and nature of the coke formed. Catalytic tests with different model compounds (toluene and n-heptane) were carried out to determine the residual activity of the hydrogenating and acid catalyst functions. It was found that, at the evaluated conditions, both the nature and the content of organic nitrogen and aromatics compounds of the feedstock have a determinant role in the deactivation rate. Organic nitrogen determines the ratio between available metal and acid sites. The aromatics generate coke precursors on the available acid sites. Both factors play a coupled role that promotes coke deposition on the catalyst surface, which leads to an increase in the deactivation rate on top of the end boiling point of the feed.

Different approaches to convert waste polyolefins into automotive fuels via hydrocracking with a NiW/HY catalyst

Different approaches to upgrade waste plastic and vacuum gasoil (VGO) blends via hydrocracking have been investigated. The approaches have consisted on using different charges: (i) neat VGO; (ii) neat plastic pyrolysis oil (PPO); (iii) a PPO/VGO blend; (iv) a high-density polyethylene (HDPE)/VGO blend; and (v) a ternary PPO/HDPE/VGO blend. The runs have been conducted in a batch reactor at: 400–440 °C; 80 bar; catalyst to oil mass ratio, 0.1 gcat gcharge−1; and reaction time, 2 h. Obtained products have been grouped in different lumps, which are defined according to their boiling point range: gas, naphtha, light cycle oil (LCO), heavy cycle oil (HCO), wax (unconverted plastic) and coke. The concentration of the families of compounds (n-paraffins, isoparaffins, olefins, naphthenes and aromatics with 1, 2 and 3+ rings) has been also determined. Results expose that composition of products is improved with respect to that obtained in the hydrocracking of VGO with both binary and ternary blends. The naphtha and LCO obtained in the hydrocracking of PPO/VGO and PPO/HDPE/VGO blends have a lower concentration of aromatics than the lumps of the VGO, making them more attractive to be added to the pools of fuels in refinery.

ОЦЕНКА ВОЗМОЖНОСТИ ПОЛУЧЕНИЯ РАСТВОРИТЕЛЯ С НИЗКИМ СОДЕРЖАНИЕМ АРОМАТИЧЕСКИХ УГЛЕВОДОРОДОВ В АО «АНХК»

. In connection with the emerging demand for gasoline solvent with a low content of
 aromatic hydrocarbons we carrier out the analysis of intermediate products obtained in JSC " ANHK " 
 suitable for the producing of the solvent. The most suitable for the separation of the fraction are gaso line fractions producing from the hydrogenation product of the hydrocracking of light vacuum gas oil 
 and the hydrogenation product of high conversion hydrogenation of the heavy middle distillate frac tions. We performed work on the recovery of a narrow fraction of gasoline solvent and its tests for 
 compliance with the requirements.

Исследование закономерностей и разработка модели процесса гидрокрекинга вакуумного газойля

In this work, the regularities of the vacuum gasoil hydrocracking process were studied, which include: determination of the key components of the reacting mixture and key reactions, studying the thermodynamic regularities, identification of the regularities of the influence of technological parameters on the transformation of the key reacting components. The model of the process was developed.