The effect of Si/Al ratio of zeolite Y on the performance of NiW catalysts for second stage hydrocracking was studied. The zeolites were characterized by IR spectroscopy of adsorbed pyridine, low-temperature N2 adsorption, and temperature-programmed desorption of ammonia. The observed decrease of Bronsted and Lewis acid sites concentration relates to the increase of Si/Al ratio in zeolites. According to HRTEM and XPS, sulfide component of catalysts differs in morphology, NiWS phase content and tungsten sulfidation degree. The catalysts were tested in hydrocracking of model (squalane) and real feedstock (unconverted oil (UCO) from two-stage industrial hydrocracker) at different temperatures. The increase of Si/Al ratio in zeolites was found to result in the decrease of catalytic activity and the increase of selectivity to middle distillates. However, similar selectivity of 52 and 53% at the 50% of UCO conversion was observed for catalysts containing zeolites with Si/Al ratio 24 and 37 respectively. This can be attributed mainly to the differences in the textural properties of the zeolites. The catalyst based on amorphous silica-alumina (without zeolites) was found to have a higher selectivity to middle distillates and lower activity as compared to zeolite-based catalysts.

NiW catalysts for second stage hydrocracking were prepared by impregnation of granulated supports with ultrastable zeolite Y content of 5-30 wt%; amorphous silica-alumina content of 45-20 wt%; and gamma-Al2O3 content of 50 wt%. The catalysts were studied by low-temperature N-2 adsorption, HRTEM, XPS and IR spectroscopy of adsorbed pyridine. Sulfide NiWS particles have been revealed to be similar in all the catalysts according to HRTEM and XPS. It has been shown that concentration of Bronsted acid sites increases with increasing of zeolite content in the catalysts. Hydrocracking tests were carried out at a pressure of 16.0 MPa, a LHSV of 1.4 h(-1) and H-2 to oil ratio of 750 (v/v). Two samples of unconverted oil with nitrogen content of 11 and 65 ppm obtained from the products of VGO hydrocracking under different severities were used as the feedstocks. The higher zeolite content the higher activity of the catalyst was achieved. However, the increase of zeolite content leaded to the decrease of selectivity to diesel. It has been found that increasing of nitrogen content in the feedstock was followed by a sharp decline in catalyst activity while the change in selectivity to diesel was insignificant. Optimal zeolite content in the support for studied conditions and feedstock with nitrogen content of 65 ppm was 20 wt%.

The effect of crystallization parameters on the properties of nanocrystalline zeolites Y has been studied to optimize the synthesis conditions. Zeolites Y are prepared by the three-stage hydrothermal crystallization with a gradual rise in synthesis temperature from room temperature to 60°C using the Na 2 O/SiO 2 ratio in the reaction mixture and the number and duration of individual synthesis stages as variable synthesis parameters. It has been shown that an increase in the Na 2 O/SiO 2 molar ratio in the reaction mixture above 9.6 leads to a change in the crystallization selectivity and causes formation of zeolite X with a crystal size of 200 nm as a crystalline product. An increase in the duration of the synthesis stage at 60°C is accompanied by increase in the crystal size and entails formation of an analcime impurity phase. A decrease in the duration of reaction mixture aging stages at 25 and 38°C leads to an increase in the zeolite Y nanocrystal sizes and a decrease in the crystalline product yield. It has been found that a pure zeolite Y phase with a nanocrystal size of 320–350 nm and a SiO 2 /Al 2 O 3 ratio of 3.6–4.2 is formed during the three-stage synthesis from a (7.2–9.6)Na 2 O · Al 2 O 3 · 14.4 SiO 2 · 290 H 2 O reaction mixture with a yield of 0.60–0.88 g/g of reaction mixture.

Results from improving gasoline production efficiency by using a computer system, taking into account intermolecular interactions of blend components in calculating octane numbers of various grades of blended products and the composition change of the feedstock in reforming, isomerization, alkylation, and catalytic cracking processes, are analyzed. The computer system can be used to determine quickly and precisely the optimal component ratio that ensures production of commercial gasolines conforming to all current regulatory requirements.

It is proposed that the sulfide NiMo system supported on alumina-SAPO-31 composite (NiMo/Al2O3-SAP catalyst) be used to obtain high-quality diesel fuel from a mixture of straight run diesel (SRGO) and light cycle oil (LCO) produced by fluid catalytic cracking (FCC). It is shown that the use of this catalyst ensures the synthesis of diesel fuel of higher quality upon hydroprocessing a feedstock with 30 wt % LCO, compared to the traditional sulfide NiMo/Al2O3 or CoMo/Al2O3 catalysts. It is found that the content of aliphatic hydrocarbons is raised in the products of hydrotreatment, compared to the initial feedstock. This confirms the ability of NiMo/Al2O3-SAP catalyst to facilitate the reaction of ring opening. Using the proposed catalyst should improve the quality of diesel fuels obtained via the hydroprocessing of LCO-containing feedstock.

The hydrogenation/hydrodeoxygenation of methyl-substituted carbonyl compounds to preserve the isomeric structure of a product is one way of controlling its amount of oxygen and improving the chemical stability of motor fuel components. The integration of hydrogenation and dehydration catalysts in one reaction space is an bright example of processes that proceed on these catalysts and positively affect each other. In comparison with the hydrogenation Ni-catalyst, the transformation of 2,4-dimethyl-3-pentanone into 2,4-dimethylpentane over the same catalyst loaded jointly with a zeolite is accompanied by a several-fold increase in hydrogenation rate and operational stability. In the process, the complete hydrodeoxygenation of the parent ketone is observed. Such composite loading can be used to replace bifunctional catalysts.

The results from industrial tests of technology developed earlier for the reactivation of CoMo/Al 2 O 3 catalyst for the deep hydrotreating of diesel fuel, including the oxidative regeneration of the catalyst with subsequent treatment using organic complexing agents, are presented. Samples of the catalyst, fresh and at different stages of its reactivation, are investigated using a set of analytical and physicochemical methods. The chemical composition, textural characteristics, mechanical strength, structure of the active sulfide component (TEM, XPS) are determined. Catalytic tests are performed that include lifetime tests (360 h) in the hydrotreatment of a straight-run diesel fraction. The restoration of the physicochemical and catalytic properties is observed for a sample subjected to oxidative regeneration with subsequent treatment using organic complexing agents. An industrial batch of deep hydrotreatment catalyst reactivated by this technology is loaded into an L-24-6 industrial plant facility and ensures stable purification of straight-run diesel fuel containing up to 10% of light catalytic cracking gas oil to a residual sulfur content of less than 10 ppm. Comparison of the obtained results and data on the industrial operation of fresh catalysts shows that the technology developed by the Institute of Catalysis and PAO Gazprom Neft ensures almost complete restoration of the properties of the deactivated catalysts.

New Russian catalysts for deep hydrotreatment and hydrocracking of vacuum gasoil (VGO) were developed at the Boreskov Institute of catalysis in cooperation with the Institute for Hydrocarbon Processing and Topchiev Institute of Petrochemical Synthesis. The work was supported by the JSC Gazpromneft-Omsk Refinery under the Complex Project «Creation of the technology for the production of import-substituting catalysts for deep hydroconversion of vacuum gasoil» in the framework of the Federal Targeted Program “Research and Development in Priority Areas of the Scientific and Technological Complex of Russia for 2014–2020”. The high efficiency of the catalysts was experimentally proved. Preliminary works on implementation of the developed technologies for the production of the VGO hydrotreatment and hydrocracking catalysts including production of the catalyst components (amorphous aluminosilicates, zeolites) are in progress now.

Industrial testing of the developed technology for reactivation of the CoMo/Al 2 O 3 catalysts for deep hydrotreatment of diesel fuel was the oxidative regeneration of the catalyst followed by the treatment with organic complexing agents. A series of analytic and physicochemical techniques were used for studying samples of the catalyst, both fresh and at different stages of the reactivation. The chemical composition, textural parameters, mechanical strength and the structure of the active sulfide component were determined (TEM, XPS). Catalytic and life (360 h) tests were conducted using hydrotreatment of the straight-run diesel fraction. The physicochemical and catalytic properties of the sample were demonstrated to restore after the said treatments. The reactivated industrial catalyst for the deep hydrotreatment was loaded to an industrial reactor L-24-6 and demonstrated the stable operation in purifying the straight-run diesel fuel (containing up to 10 % of light catcracking gasoil) to provide no more than 10 ppm of the residual sulfur. The results obtained were compared to the performance of fresh industrial catalysts to show that the developed technology ensures practically complete restoration of properties of the deactivation catalysts.

A NiMo sulfide system with an alumina support containing aluminosilica phosphate SAPO-31 (catalyst NiMo/Al 2 O 3 -SAP) was suggested for synthesis of high-quality diesel fuel from a mixture of straight-run diesel fraction and light catcracking gasoil (LCCG). Against the traditional NiMo/Al 2 O 3 or CoMo/Al 2 O 3 sulfide catalysts, this catalyst was demonstrated to provide production of higher quality diesel fuel through hydroupgrading of the feedstock containing 30 wt.% LCCG. The fact that the proportion of aliphatic hydrocarbons is higher in the products than in the feedstock indicates the activity of the NiMo/Al 2 O 3 -SAP catalyst to ring opening. Application of the suggested catalyst will allow the quality of diesel fuels to be improved during hydroupgrading of the LCCG-containing feedstock.

A NiMo sulfide system with an alumina support containing aluminosilica phosphate SAPO-31 (catalyst NiMo/Al 2 O 3 -SAP) was suggested for synthesis of high-quality diesel fuel from a mixture of straight-run diesel fraction and light catcracking gasoil (LCCG). Against the traditional NiMo/Al 2 O 3 or CoMo/Al 2 O 3 sulfide catalysts, this catalyst was demonstrated to provide production of higher quality diesel fuel through hydroupgrading of the feedstock containing 30 wt.% LCCG. The fact that the proportion of aliphatic hydrocarbons is higher in the products than in the feedstock indicates the activity of the NiMo/Al 2 O 3 -SAP catalyst to ring opening. Application of the suggested catalyst will allow the quality of diesel fuels to be improved during hydroupgrading of the LCCG-containing feedstock.

FIELD: fuel. SUBSTANCE: invention describes a method of controlling content of oxygen in high-octane component of motor fuel based on carbonyl compounds of general formula, where R 1 is H, or alkoxide -O-C n H 2n+1 , or a hydrocarbon radical of general formula -C n H 2n+1 ; R 2 is a hydrocarbon radical of general formula -C n H 2n+1 ; n is a number from 1 to 5 or mixture thereof, and controlling chemical stability of this component consists in that, carbonyl compounds of said general formula or mixture thereof in gaseous phase in excess hydrogen are passed over a layer of composite material, consisting of a mechanical mixture of a hydrogenation catalyst and a dehydration catalyst, at temperature of 100–400 °C and pressure of 1–100 atm. EFFECT: technical result consists in increasing activity, selectivity and stability of operation of catalysts for hydrogenation of branched ketones to corresponding branched alkanes, and/or alcohols and/or their mixtures. 8 cl, 1 tbl, 28 ex