RU2763723C1 - Method for preparation of diesel fuel hydrotreating catalyst - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: invention relates to methods for the preparation of catalysts intended for the processing of diesel fuel with a high content of secondary fractions. A method for preparing a diesel fuel hydrotreating catalyst is described, characterized by the fact that the catalyst is prepared by impregnating a carrier containing 0.001-0.05б wt. %, of Na and additionally containing on its surface isolated La atoms with an average size of 0.1 nm, consisting of a chemical bond La-O-Al, with a surface density of 2-50 atoms per 10 nm² of the surface and a ratio of Al atoms to the number of La atoms equal to 50-10000, and the carrier consists of low-temperature forms of aluminum oxide, γ- and χ-Al₂O₃ in the following ratios, wt. %: (50-95):(50-5), an aqueous solution simultaneously containing a mixture of complex compounds [Со(Н₂О)₂(С₆Н₅О₇)]₂[Mo₄O₁₁(С₆Н₅О₇)₂] and Co₂[H₂P₂Mo₅O₂₃]; at the same time, the concentrations of the solution components provide the composition, wt. %: [Со(Н₂О)₂(С₆Н₅О₇)]₂[Mo₄O₁₁(С₆Н₅О₇)₂] 6.0-12.0, Co₂[H₂P₂Mo₅O₂₃] 21.0-30.0, carrier being the rest; followed by sulfidation. The resulting catalyst has a specific surface area of 120-200 m²/g, a pore volume of 0.30-0.50 cm³/g, an average pore diameter of 8-13 nm. After sulfidation according to known methods, the catalyst contains, wt. %: Mo 10.7-13.5; Co 3.5-4.2; S 9.0-11.5; P 1.4-1.9; carrier being the rest.

EFFECT: production of a catalyst having high activity and stability in the target reactions occurring during the hydrotreating of diesel fuel with a high content of secondary fractions.

5 cl, 1 tbl, 9 ex

Description

The invention relates to methods for the preparation of hydrotreating catalysts intended for the processing of diesel fuel with a high content of secondary fractions.

Hydrotreating of diesel fractions is one of the key processes in the processing of petroleum fractions. Currently, fractions of secondary processes, such as coking gas oils, are added to straight-run diesel fractions in order to increase the depth of oil refining. This leads to a heavier hydrocarbon composition of the diesel fraction supplied for processing, as well as to an increase in the content of sulfur and nitrogen-containing compounds. The addition of secondary fractions requires the catalyst to operate at a higher temperature. In this regard, the development of hydrotreating catalysts with a higher activity in the processing of diesel fuel with a high content of secondary fractions is an extremely urgent task.

Various methods are known for the preparation of supported catalysts for the hydrotreatment of hydrocarbon feedstocks, however, a common disadvantage for them is their low activity in the conversion of sulfur-containing compounds.

Most often, catalysts containing oxides of cobalt and molybdenum deposited on alumina are used to carry out the hydrodesulfurization of petroleum feedstocks. So known hydrodesulfurization catalyst [RU 2002124681, C10G45/08, B01J23/887, 05/10/2004], containing cobalt oxide, molybdenum oxide and aluminum oxide, characterized in that it has a ratio of components, wt.%: cobalt oxide 3, 0-9.0, molybdenum oxide 10.0-24.0 wt.%, aluminum oxide the rest, specific surface area 160-250 m ² /g, mechanical crushing strength 0.6-0.8 kg/mm ² . At the same time, the hydrotreating process is carried out at a temperature of 310-340°C, a pressure of 3.0-5.0 MPa, with a hydrogen/feedstock ratio of 300-500 nm ³ /m ³ and a feed space velocity of 1.0-4.0 h ^{- 1} . The main disadvantage of such a hydrotreating catalyst is the high sulfur content in the resulting products.

In recent years, for the preparation of hydrotreating catalysts, the method of depositing active metals on an already formed support has been used. Aluminum oxide with a certain size and shape of granules and certain textural characteristics is most often used as a carrier. The carrier is often modified with various additives. In this case, modifying additives are introduced into the carrier or before the stage of its formation, by coprecipitation of modifiers and aluminum from joint solutions [Journal of Catalysis 115 (1989) 441-451, Journal of Materials Research 33 (2018) 3570-3579, Catalysis Today 133-135 (2008) 267-276], or by mixing aluminum hydroxide with a modifying compound at the stage of preparing a molding paste [RU 2319543, B01J23/88, 21.09.2006], or introducing an additive by impregnation into the molded carrier, followed by drying and calcination [ Catalysis Today 107-108 (2005) 551-558; Energy & Fuels 25 (2011) 3100-3107].

The introduction of active metals, most often Co, Ni, Mo and W, into the composition of the catalyst is carried out by impregnating the shaped carrier with aqueous solutions of their salts. In this case, they can be used as separate deposition of active metals by impregnation in several stages [RU 2242501, C10G45/08, 20.12.2004; RU 2246987, B01J37/02, 27.02.2005], and their application from joint solutions stabilized by various agents [RU 2073567, B01J37/02, 05.10.1995; RU 2216404, B01J37/02, 20.11.2003; RU 2306978, B01J23/88, 09/27/2007; RU 95117374, B01J37/02, 11/20/1996].

In order to increase the hydrodesulfurizing activity of catalysts, a carrier with improved textural characteristics is used in their preparation, while the specific surface of the catalyst reaches 300 m ² /g, and the average pore diameter lies in the range of 8–11 nm, which provides good access of sulfur-containing molecules to the active sites of the catalyst . Thus, a catalyst is known [RU 2192923, C10G45/08, B01J27/188, B01J35/10, 11/20/2002] based on aluminum oxide, which contains, in terms of the weight content of the oxide: 2-10 wt.% cobalt oxide CoO, 10- 30 wt.% molybdenum oxide MoO ₃ and 4-10 wt.% phosphorus oxide P ₂ O ₅ , with a BET surface area in the range of 100-300 m ² /g and an average pore diameter in the range of 8-11 nm.

A known preparation method allows to obtain a diesel fraction hydrodesulfurization catalyst [RU 2313392, B01J37/02, 12/27/2007], having a pore volume of 0.3-0.7 ml/g, a specific surface of 200-350 m ² /g and an average pore diameter 9-13 nm, containing the following components, wt.%: cobalt compounds with a concentration of 2.5-7.5 in terms of CoO, molybdenum compounds with a concentration of 12-25 in terms of MoO ₃ , citric acid with a concentration of 15-35, boron compounds 0.5-3.0 in terms of B ₂ O ₃ , aluminum oxide Al ₂ O ₃ - the rest, while cobalt, molybdenum, citric acid and boron can be part of complex compounds of various stoichiometry.

A known method of preparing a hydrotreating catalyst [RU 2472585, B01J23/882, 20.01.2013], containing, wt%: Mo - 8.0-15.0; Co or Ni - 2.0-5.0; S - 5.0-15.0; B - 0.5-2.0; C - 0.5-7.0; Al ₂ O ₃ - the rest, while the carrier contains, wt.%: B - 0.7-3.0, Al ₂ O ₃ - the rest, and has a specific surface of 170-300 m ² /g, pore volume 0.5 -0.95 cm ³ /g, the average pore diameter is 7-22 nm and is a particle with a cross section in the form of a trefoil with a circumscribed circle diameter of 1.0-1.6 mm and a length of up to 20 mm, having a mechanical strength of 2.0- 2.5 kg/mm.

A common disadvantage for the above methods of preparation is the low activity of the resulting catalysts in the conversion of sulfur-containing compounds.

The closest to the proposed technical solution is described in [EN 2732243, B01J37/02; B01J37/08; C10G45 / 04, 09/14/2020] a method for preparing a catalyst, which consists in impregnating a carrier containing, in terms of non-metal oxides, SiO ₂ - 0.1-20 wt.% and B ₂ O ₃ - 0-10 wt.%, sodium - not more than 0.03 wt.%, γ- and χ-Al ₂ O ₃ - the rest, and the ratio of low-temperature forms of aluminum oxide χ-Al ₂ O ₃ and γ-Al ₂ O ₃ in the carrier is (0-40):( 100-60) wt.%, an aqueous solution simultaneously containing a mixture of complex compounds [Co(H ₂ O) ₂ (C ₆ H ₅ O ₇ )] ₂ [Mo ₄ O ₁₁ (C ₆ H ₅ O ₇ ) ₂ ], Co ₂ [H ₂ P ₂ Mo ₅ O ₂₃ ] and (NH ₄ ) ₄ [Mo ₄ (C ₆ H ₅ O ₇ ) ₂ O ₁₁ ], followed by drying, while the concentration of the components of the solution provide a catalyst that includes in its composition, wt.%: [Co (H ₂ O) ₂ (C ₆ H ₅ O ₇ )] ₂ [Mo ₄ O ₁₁ (C ₆ H ₅ O ₇ ) ₂ ] - 11.42-18.9, Co ₂ [H ₂ P ₂ Mo ₅ O ₂₃ ] - 12.1-22.6 and (NH ₄ ) ₄ [Mo ₄ (C ₆ H ₅ O ₇ ) ₂ O ₁₁ ] - 3.25-4.73, carrier - the rest; followed by sulfiding and obtaining a catalyst composition, wt.%: 11-14 Mo, 2-4 Co, 0.8-1.5 P, 9.0-11.4 S; carrier - the rest; while the media contains, wt.%: SiO ₂ - 0.01-20.0 and B ₂ O ₃ - 0-10; Al ₂ O ₃ - the rest.

The main disadvantage of the known catalyst is that it has a non-optimal chemical composition for the conversion of diesel fractions with a high content of secondary hydrocarbon fractions containing unsaturated compounds. This results in faster deactivation of the catalyst.

The invention solves the problem of developing an efficient method for preparing a catalyst for the hydrotreatment of diesel fuel with a high content of secondary hydrocarbon fractions.

EFFECT: method leads to the production of a catalyst having high activity and stability in target reactions occurring during the hydrotreatment of diesel fuel with a high content of secondary fractions.

The problem is solved by a method for preparing a catalyst for the hydrotreatment of diesel fuel with a high content of secondary fractions, in which the catalyst is prepared by impregnating a support containing 0.001-0.05 wt.% Na, as well as isolated La atoms on the surface with an average size of 0.1 nm, consisting in a chemical La-O-Al bonds, with a surface density of 2-50 atoms per 10 nm ^{2 of the} surface and a ratio of Al atoms to the number of La atoms equal to 50-10000 , consisting of low-temperature forms of aluminum oxide γ- and χ-Al ₂ O ₃ in the ratios (50-95):(50-5) wt.%, aqueous solution, simultaneously containing a mixture of complex compounds [Co(H ₂ O) ₂ (C ₆ H ₅ O ₇ )] ₂ [Mo ₄ O ₁₁ (C ₆ H ₅ O ₇ ) ₂ ] and Co ₂ [H ₂ P ₂ Mo ₅ O ₂₃ ], followed by drying, while the concentration of the components of the solution provide a catalyst that includes, wt.%: [Co(H ₂ O) ₂ (C ₆ H ₅ O ₇ )] ₂ [Mo ₄ O ₁₁ (C ₆ H ₅ O ₇ ) ₂ ] - 6.0-12.0, Co ₂ [H ₂ P ₂ Mo ₅ O ₂₃ ] - 21, 0-30.0, carrier - the rest; followed by sulfidation according to known methods. Carrier is impregnated by moisture capacity with an aqueous solution simultaneously containing a mixture of complex compounds [Co(H ₂ O) ₂ (C ₆ H ₅ O ₇ )] ₂ [Mo ₄ O ₁₁ (C ₆ H ₅ O ₇ ) ₂ ] and Co ₂ [ H ₂ P ₂ Mo ₅ O ₂₃ ], while the impregnation is carried out at a temperature of 25-80°C for 15-60 min with occasional stirring. After impregnation, the catalyst is dried in air at a temperature of 100-200°C for 2-4 hours after sulfiding according to known methods, the catalyst contains, wt.%: Mo - 10.7-13.5; Co - 3.5-4.2; S - 9.0-11.5; P - 1.4-1.9; carrier - the rest, while the carrier contains 0.001-0.05 wt.% Na, has isolated La atoms on the surface with an average size of 0.1 nm, consisting in the La-O-Al chemical bond, with a surface density of 2-50 atoms per 10 nm ² surface and the ratio of Al atoms to the number of La atoms equal to 50-10000 , and the carrier consists of low-temperature forms of aluminum oxide γ- and χ-Al ₂ O ₃ in the ratios (50-95):(50-5) wt. %. The resulting catalyst has a specific surface of 120-200 m ² /g, a pore volume of 0.30-0.50 cm ³ /g, an average pore diameter of 8-13 nm, and is a particle with a cross section in the form of a circle, trefoil or quatrefoil with a diameter circumscribed circle 1.0-1.6 mm and up to 20 mm long.

Exit the content of the catalyst components for the claimed boundaries leads to a decrease in the activity of the catalyst.

The output of the ratio of the number of Al atoms to the number of La atoms on the surface of the support beyond the stated limits, on the one hand, leads to uneven dispersion of lanthanum atoms over the surface of the support, on the other hand, it prevents the formation of the La-O-Al bond, and leads to a decrease in the obtained on its basis hydrotreating catalyst.

The presence of isolated lanthanum atoms on the surface of the carrier is confirmed by ring dark field imaging in a scanning transmission electron microscope (HAADF-STEM). The surface density of La atoms in this invention is 5-50 atoms per 10 nm ² .

The ratio of the number of Al atoms to the number of La atoms, which is in the carrier in the range from 50 to 10,000, is confirmed by spectra obtained by energy dispersive X-ray spectroscopy (EDX method).

The essence of this method lies in the fact that with the help of a beam of electrons of a certain energy, the atoms of the studied sample are excited, which at the same time emit x-ray radiation characteristic of each chemical element, the so-called characteristic x-ray radiation. In this case, the conclusion about the quantitative and qualitative composition of the sample is made on the basis of a study of the energy spectrum of such radiation.

The presence of a mixed phase composition of aluminum oxide, consisting of χ-Al ₂ O ₃ and γ-Al ₂ O ₃ in different proportions, is confirmed by X-ray phase analysis (XRF). Quantitative analysis of the phase composition of the carrier for the hydrotreating catalyst is carried out according to pre-built calibration curves. When analyzing the γ- and χ-Al ₂ O _{3 system, the} reference lines correspond to 42.6° (γ) and 45.9° (χ).

The technical result is achieved as follows:

1. The chemical composition of the catalyst obtained by the claimed method causes high activity in the target reactions occurring during the hydrotreatment of diesel fuel with a high content of secondary fractions. The presence in the composition of the catalyst carrier of isolated La atoms with an average size of 0.1 nm, consisting in the La-O-Al chemical bond, with a surface density of 2-50 atoms per 10 nm ^{2 of the} surface and a ratio of Al atoms to the number of La atoms equal to 50-10000 , and low-temperature forms of aluminum oxide - γ- and χ-Al ₂ O ₃ - in the following ratios, wt.%: (50-95): (50-5) provides catalyst resistance to sintering and coking processes under reaction conditions, minimizing undesirable chemical interaction between active metals (Co and Mo) and the carrier, and selective production of the most active sulfide component in hydrotreatment - CoMoS type II phase, which provides high catalyst activity in the conversion of sulfur- and nitrogen-containing components of the feedstock.

2. Introduction of a mixture of complex compounds [Co(H ₂ O) ₂ (C ₆ H ₅ O ₇ )] ₂ [Mo ₄ O ₁₁ (C ₆ H ₅ O ₇ ) ₂ ] and Co ₂ [H ₂ P ₂ Mo ₅ O ₂₃ ] prevents their crystallization at the stage of drying and provides further formation in the catalyst, during its operation in hydrotreatment, fine particles of the most active component - CoMoS type II phase.

3. Introduction into the catalyst composition of isolated La atoms with an average size of 0.1 nm, consisting in the La-O-Al chemical bond, with a surface density of 2-50 atoms per 10 nm ^{2 of the} surface and a ratio of Al atoms to the number of La atoms equal to 50- 10000, and low-temperature forms of aluminum oxide γ- and χ-Al ₂ O ₃ in the ratios (50-95):(50-5) wt.% contributes to the achievement of textural characteristics of the catalyst, providing access to all molecules of the raw material to be converted to the active component.

4. The claimed preparation conditions - impregnation by moisture capacity at a temperature of 25-70 ° C for 25-60 minutes with occasional stirring, drying in air at a temperature of 100-200 ° C for 2-4 hours in conjunction with the concentrations of the components of the impregnating solutions used and the characteristics of the carrier used - provide a catalyst having the optimal chemical composition, wt.%: [Co(H ₂ O) ₂ (C ₆ H ₅ O ₇ )] ₂ [Mo ₄ O ₁₁ (C ₆ H ₅ O ₇ ) ₂ ] - 6.0-12.0, Co ₂ [H ₂ P ₂ Mo ₅ O ₂₃ ] - 21.0-30.0; while the carrier contains 0.001-0.05 wt.% Na, has isolated La atoms on the surface with an average size of 0.1 nm, consisting in the La-O-Al chemical bond, with a surface density of 2-50 atoms per 10 nm ^{2 of the} surface and the ratio of Al atoms to the number of La atoms equal to 50-10000, and the carrier consists of low-temperature forms of aluminum oxide γ- and χ-Al ₂ O ₃ in the following ratios, wt.%: (50-95):(50-5).

Description of the proposed technical solution.

A support is prepared containing isolated La atoms with an average size of 0.1 nm, consisting in a La-O-Al chemical bond, with a surface density of 2-50 atoms per 10 nm ^{2 of the} surface and a ratio of Al atoms to the number of La atoms equal to 50-10000 , and the carrier contains 0.001-0.05 wt.% Na and consists of low-temperature forms of aluminum oxide γ- and χ-Al ₂ O ₃ in the ratio, wt.%: (50-95):(50-5).

Take a sample of the product of rapid heat treatment of hydrargillite (PBTOG), having a specific surface area of at least 200 m ² /g and meeting the following requirements, wt.%:

- proportion of hydrargillite (gibbsite), no more than 3;

- proportion of boehmite, not more than 10;

- proportion of disordered χ-like Al ₂ O ₃ (X-ray amorphous or amorphous phase, or ρ-Al ₂ O ₃ ), not less than 87;

- the proportion of weight loss during calcination at 800°C, within 6-10;

- proportion of sodium oxide (Na ₂ O), not more than 0.3.

For example, a CTA product (TU 2175-040-03533913-2007), obtained in a centrifugal drum-type reactor CEFLAR [RU 2264589, F26B7 / 00, 20.11.2005], or thermally activated aluminum hydroxide TGA (TU 24.42.12-146) can be used. -60201897-2018), obtained in tubular reactors in a stream of hot gases [RU 2219128, C01F 7/44, 12/20/2003]. It is allowed to use a similar product manufactured according to other specifications, but it must meet the above requirements.

A portion of the starting material is crushed in a mill (ball, planetary, jet or any other) to agglomerates of particles with an average volume diameter of 5-25 μm. In some cases, PBTOG is used in the initial state, i.e. without grinding, then the fractional composition of the particle agglomerates is preserved.

A portion of PBTOG is hydrated with stirring for 2-4 hours in weakly concentrated solutions of nitric acid heated to 50±5°C (acid module not more than 0.1). After that, the resulting suspension is filtered under vacuum and washed with either distilled water or technically prepared sodium-free water. As a result, a wet cake is obtained - a cake containing not more than 0.05 wt.%, but not less than 0.001 wt.% sodium, in terms of dry matter.

The hydrothermal treatment of the cake is carried out in an autoclave in aqueous solutions of nitric acid with the addition at the initial stage of a given amount of a lanthanum-containing source, mainly lanthanum nitrate, at a suspension temperature of 140-180°C for 6-16 hours. After completion of the hydrothermal treatment, the suspension is cooled to a given temperature, but not higher than 90°C, the autoclave is unloaded, the contents of the vessel are repulped with distilled or technically prepared water until a pseudoboehmite-containing suspension suitable for spray drying is obtained.

Next, drying is carried out in a spray dryer at an air temperature at the inlet to the dryer not higher than 350°C and continuous mixing of the repulped suspension. Moreover, drying is carried out both with the help of pneumatic spray nozzles, and with the help of liquid (mechanical) nozzles.

The finished powder of aluminum hydroxide is unloaded from the receiving tank (glass) of the cyclone dust collector of the spray dryer.

Next, a plastic mass is prepared by mixing and peptizing the resulting powder in a mixer with Z-shaped blades in the presence of an aqueous solution of ammonia.

The finished plastic mass is reloaded from the mixer into the extruder and forced through the die opening, which ensures the production of extrudates of the finished carrier with a cross section in the form of a circle, trefoil or quatrefoil with a circumscribed circle diameter of 1.0-1.6 mm and a length of up to 20 mm.

Then heat treatment of the extrudates is carried out, which includes a preliminary stage of drying. The extrudates are kept in an oven at a temperature of (120±10)°C for 2 hours. Heat treatment is carried out in a muffle furnace with the supply of dried air into the furnace chamber. The extrudates in a porcelain cup are placed in an oven and calcined at a temperature of (550±10)°C for 4 hours.

As a result, a support for a hydrotreating catalyst is obtained, which contains on its surface isolated lanthanum atoms with a size of about 0.1 nm, consisting in the La-O-Al chemical bond, with a surface density of 5-50 atoms per 10 nm ^{2 of the} surface and the ratio of the number of Al atoms to the number of La atoms equal to 50-10000, and the ratio of low-temperature forms of aluminum oxide χ-Al ₂ O ₃ and γ-Al ₂ O ₃ in the carrier in wt.% is (50-95):(50-5); characterized by a specific surface area of 200-300 m ² /g, a pore volume of 0.5-0.85 cm ³ /g, an average pore diameter of 7-13 nm and is a granule with a cross section in the form of a circle, trefoil or quatrefoil with a diameter circumscribed circle 1.0-1.6 mm and up to 20 mm long. The carrier also contains impurity sodium in the amount of 0.001-0.05 wt.%, and sodium is part of the low-temperature forms of aluminum oxide γ- and χ-Al ₂ O ₃ .

A supported catalyst is prepared using this carrier. First, an impregnation solution is prepared containing a mixture of complexes [Co(H ₂ O) ₂ (C ₆ H ₅ O ₇ )] ₂ [Mo ₄ O ₁₁ (C ₆ H ₅ O ₇ ) ₂ ] and Co ₂ [H ₂ P ₂ Mo ₅ O ₂₃ ]. To do this, weigh the given amount of molybdenum oxide MoO ₃ , cobalt hydroxide Co(OH) ₂ , citric acid monohydrate and phosphoric acid. A graduated cylinder measures a given amount of distilled water. A measured amount of water is poured into the flask and the anchor of a magnetic stirrer is placed. The flask is placed on the heating surface of a heated magnetic stirrer. Set the speed of rotation of the stirrer 300 rpm and the temperature of the solution 70°C. A measured amount of citric acid is loaded into the flask and mixed under visual control. Then weighed portions of cobalt hydroxide, molybdenum oxide and phosphoric acid are added to the citric acid solution in the flask with constant stirring. The solution is stirred until a homogeneous transparent reddish-pink solution containing a mixture of complexes [Co(H ₂ O) ₂ (C ₆ H ₅ O ₇ )] ₂ [Mo ₄ O ₁₁ (C ₆ H ₅ O ₇ ) ₂ ] and Co ₂ [H ₂ P ₂ Mo ₅ O ₂₃ ] and does not contain turbidity, bubbles and foam. The solution contains cobalt and molybdenum in the form of a mixture of complexes [Co(H ₂ O) ₂ (C ₆ H ₅ O ₇ )] ₂ [Mo ₄ O ₁₁ (C ₆ H ₅ O ₇ ) ₂ ] and Co ₂ [H ₂ P ₂ Mo ₅ O ₂₃ ].

The prepared solution is poured into a calibrated measuring cylinder, after which the volume of the solution is adjusted to a predetermined amount by adding distilled water.

The modified carrier is impregnated with the resulting solution, and the carrier is impregnated according to moisture capacity. Impregnation is carried out at a temperature of 25-70°C for 15-60 min with occasional stirring. After impregnation, the catalyst is dried in air at a temperature of 100-200°C.

As a result, a catalyst is obtained containing, wt.% [Co(H ₂ O) ₂ (C ₆ H ₅ O ₇ )] ₂ [Mo ₄ O ₁₁ (C ₆ H ₅ O ₇ ) ₂ ] - 6.0-12 .0, Co ₂ [H ₂ P ₂ Mo ₅ O ₂₃ ] - 21.0-30.0; carrier - the rest; the carrier additionally contains on its surface isolated La atoms with an average size of 0.1 nm, consisting in the La-O-Al chemical bond, with a surface density of 2-50 atoms per 10 nm ^{2 of the} surface and a ratio of Al atoms to the number of La atoms, equal to 50-10000, and the carrier consists of low-temperature forms of aluminum oxide γ- and χ-Al ₂ O ₃ in the ratios (50-95):(50-5) wt.%. The catalyst has a specific surface area of 120-200 m ² /g, a pore volume of 0.30-0.55 cm ³ /g, an average pore diameter of 8-13 nm, and is particles with a cross section in the form of a circle, trefoil or quatrefoil with a circumscribed circle diameter of 1.0-1.6 mm and up to 20 mm long. After sulfiding according to known methods, the catalyst contains, wt.%: Mo - 10.7-13.5; Co - 3.5-4.2; S - 9.0-11.5; P - 1.4-1.9 , carrier - the rest; while the carrier contains on its surface isolated La atoms with an average size of 0.1 nm, consisting in the La-O-Al chemical bond, with a surface density of 2-50 atoms per 10 nm ^{2 of the} surface and a ratio of Al atoms to the number of La atoms equal to 50-10000, and the carrier consists of low-temperature forms of aluminum oxide γ- and χ-Al ₂ O ₃ in the ratio, wt.%: (50-95):(50-5).

The essence of the invention is illustrated by the following examples.

Example 1 according to the well-known solution [RU 2732243, B01J37/02; B01J37/08; C10G45/04, 09/14/2020].

The carrier is prepared as follows. Take 150 g of powdered PBTOG product, grind in a ball mill to agglomerates of particles with an average volume diameter of 5-25 μm. Next, the crushed powder is hydrated with continuous stirring in a weakly concentrated (0.3 wt.%) solution of nitric acid at a temperature of 50 ° C for 2 hours. Then the suspension is filtered under vacuum using a Buchner funnel and a Bünsen flask through Blue Ribbon type filter paper. and washed with distilled water to a residual sodium content in terms of dry solids - 0.03 wt.%. As a result, a wet cake is obtained. The cake is loaded into an autoclave, into which a 1.5% solution of nitric acid is added until the pH of the suspension reaches 1.0-2.0. To the suspension is added with stirring 0.25 ml of liquid polymethylsiloxane brand PMS-50 (GOST 13032-77). The autoclave vessel is heated to 160°C and incubated for 10 hours Next, the autoclave vessel is cooled to room temperature. The suspension is unloaded and dried in a spray dryer at a coolant temperature at the separator inlet not higher than 350°C to obtain a dry powdered pseudoboehmite. A weighed portion of 150 g of pseudoboehmite powder is placed in the trough of a mixer with Z-shaped blades, peptized with a 2.5% aqueous solution of ammonia, and then extruded at a pressure of 50-60.0 MPa through a spinneret, which ensures the production of particles with a cross section in the form of a circle with a diameter circumscribed circle 1 mm. The shaped granules are dried at 120°C and calcined at 550°C. The result is a carrier containing, wt.%: silicon compound in terms of non-metal oxide SiO ₂ - 0.1, sodium - 0.03, γ-Al ₂ O ₃ - the rest. Next, prepare a solution of a mixture of complexes [Co(H ₂ O) ₂ (C ₆ H ₅ O ₇ )] ₂ [Mo ₄ O ₁₁ (C ₆ H ₅ O ₇ ) ₂ ], Co ₂ [H ₂ P ₂ Mo ₅ O ₂₃ ] and (NH ₄ ) ₄ [Mo ₄ (C ₆ H ₅ O ₇ ) ₂ O ₁₁ ], for which 15.1 g of citric acid, 23.8 g of molybdenum oxide MoO ₃ , 6.7 are successively dissolved in 40 ml of distilled water with stirring g of cobalt (II) hydroxide Co (OH) ₂ and 2.5 ml. orthophosphoric acid (85%). After complete dissolution of all components by adding distilled water, the volume of the solution was adjusted to 80 ml. The resulting solution contains 16.55 g [Co(H ₂ O) ₂ (C ₆ H ₅ O ₇ )] ₂ [Mo ₄ O ₁₁ (C ₆ H ₅ O ₇ ) ₂ ], 15.06 g Co ₂ [H ₂ P ₂ Mo ₅ O ₂₃ ] and 4.17 g (NH ₄ ) ₄ [Mo ₄ (C ₆ H ₅ O ₇ ) ₂ O ₁₁ ]. 100 g of the resulting carrier is impregnated with 80 ml of a solution of a mixture of complexes [Co(H ₂ O) ₂ (C ₆ H ₅ O ₇ )] ₂ [Mo ₄ O ₁₁ (C ₆ H ₅ O ₇ ) ₂ ], Co ₂ [H ₂ P ₂ Mo ₅ O ₂₃ ] and (NH ₄ ) ₄ [Mo ₄ (C ₆ H ₅ O ₇ ) ₂ O ₁₁ ] at 60°C for 30 min. Then the catalyst is dried in air for 4 hours at 100°C.

The calcined catalyst contains, wt %: 18.0 MoO ₃ , 4.1 CoO, P ₂ O ₅ - 2.3, carrier - the rest; while the media contains SiO ₂ - 0.1 wt.%, γ-Al ₂ O ₃ . Next, the catalyst is sulfided according to one of the known methods. In this case, the catalyst is sulfided with a straight-run diesel fraction containing an additional 1.5 wt.% of a sulfiding agent - dimethyl disulfide (DMDS) - at a space velocity of the sulfiding mixture of 2 h ^-1 and a ratio of H ₂ /feedstock = 300 at a temperature of not more than 340 ° C . Then the catalyst is tested in the hydrotreatment of mixed diesel fuel prepared by mixing fractions, vol.%: 83 - straight-run diesel fraction; 13 - catalytic cracking light gas oil, 4 - delayed coking light gas oil. The raw material contains 0.45 wt.% sulfur, 250 ppm nitrogen, has a density of 0.879 g/cm ³ , boiling range - 186-380°C, T ₉₅ - 405°C. Hydrotreating conditions: feed space velocity 2.3 h ^-1 ratio H ₂ /feedstock = 500 nm ³ H ₂ /m ³ feedstock, pressure 4.0 MPa, starting temperature 350°C. Further, the temperature is raised in jumps of 10°C per day to 370°C. If the residual sulfur content in the resulting diesel fuel does not reach 10 ppm at 370°C, the temperature is raised in steps of 1°C to a value at which the residual sulfur content in the hydrotreated product becomes equal to 10 ppm. After sulfiding, the catalyst contains, wt.%: 12.0 Mo, 3.2 Co, 1.0 P and 9.7 S, the carrier is the rest; while the media contains SiO ₂ - 0.1 wt.%, γ-Al ₂ O ₃ - the rest. The catalyst has a specific surface of 145 m ² /g, a pore volume of 0.35 cm ³ /g, an average pore diameter of 9.0 nm, and is a particle with a cross section in the form of a circle with a circumscribed circle diameter of 1.0 mm and a length of up to 20 mm.

Examples 2-9 illustrate the proposed technical solution.

Example 2

The carrier for the hydrotreating catalyst is prepared as follows. Take 150 g of a powder product of rapid heat treatment of hydrargillite (PBTOG), grind in a ball mill to agglomerates of particles with an average volumetric diameter of 5-25 μm. Next, the crushed powder is hydrated with continuous stirring in a weakly concentrated (0.3 wt.%) solution of nitric acid at a temperature of 50±5°C for 2 hours.

The suspension is then filtered under vacuum using a Buchner funnel and a Bunsen flask through Blue Ribbon filter paper and washed with distilled water until a residual sodium content of 0.04 wt.%. As a result, a wet cake is obtained.

The cake is loaded into an autoclave, into which a 1.5% solution of nitric acid is added until the pH of the suspension reaches 1.0-2.0. A solution of lanthanum nitrate (TU 2013-036-469133-78-2019) in the amount of 25 g is added to the suspension with stirring. The autoclave vessel is heated to 180°C and kept for 16 h. Then the autoclave vessel is cooled to room temperature.

The suspension of aluminum hydroxide is unloaded and dried in a spray dryer using a pneumatic nozzle at a coolant temperature at the separator inlet of 220-350°C.

A portion of 150 g of the obtained aluminum hydroxide powder is placed in the trough of a mixer with Z-shaped blades, peptized with a 2.5% aqueous solution of ammonia, and then extruded at a pressure of 50.0-60.0 MPa through a spinneret, which provides a particle with a cross section of in the form of a trefoil with a circumscribed circle diameter of 1.0 mm.

The shaped granules are dried at 120°C and calcined at 550°C for 4 hours.

As a result, a support is obtained containing isolated La atoms with an average size of 0.1 nm, consisting in a La-O-Al chemical bond, with a surface density of 45-50 atoms per 10 nm ² surface and a ratio of Al atoms to La atoms equal to 50; sodium - 0.05 wt.%; χ- and γ-Al ₂ O ₃ - the rest, and the ratio of low-temperature forms of aluminum oxide χ- and γ-Al ₂ O ₃ in the carrier in wt.% is 50:50.

Next, prepare a solution of a mixture of complexes [Co (H ₂ O) ₂ (C ₆ H ₅ O ₇ )] ₂ [Mo ₄ O ₁₁ (C ₆ H ₅ O ₇ ) ₂ ] and Co ₂ [H ₂ P ₂ Mo ₅ O ₂₃ ], for which 4.6 g of citric acid C ₆ H ₈ O ₇ , 9.8 g of cobalt (II) hydroxide Co (OH) ₂ , 30.5 g of molybdenum oxide MoO ₃ and 5.4 ml of orthophosphoric acid are successively dissolved in 40 ml of distilled water with stirring (85%). After complete dissolution of all components, the volume of the solution is adjusted to 80 ml by adding distilled water. The resulting solution contains 6.3 g [Co(H ₂ O) ₂ (C ₆ H ₅ O ₇ )] ₂ [Mo ₄ O ₁₁ (C ₆ H ₅ O ₇ ) ₂ ] and 30.1 g Co ₂ [H ₂ P ₂ Mo ₅ O ₂₃ ].

100 g of the resulting carrier is impregnated with 80 ml of a solution of a mixture of complexes [Co(H ₂ O) ₂ (C ₆ H ₅ O ₇ )] ₂ [Mo ₄ O ₁₁ (C ₆ H ₅ O ₇ ) ₂ ] and Co ₂ [H ₂ P ₂ Mo ₅ O ₂₃ ] at 60°C for 30 min. Then the catalyst is dried in air for 4 hours at 100°C.

Next, the catalyst is sulfided according to known methods analogously to example 1. After sulfiding, the catalyst contains, wt.%: Mo - 13.5; Co - 4.2; P - 1.9; S - 11.3; carrier - the rest; wherein the carrier contains isolated La atoms with an average size of 0.1 nm, consisting in the chemical bond La-O-Al, with a surface density of 45-50 atoms per 10 nm ² surface and the ratio of Al atoms to La atoms equal to 50; sodium - 0.05 wt.%; χ- and γ-Al ₂ O ₃ - the rest, and the ratio of low-temperature forms of aluminum oxide χ- and γ-Al ₂ O ₃ in the carrier in wt.% is 50:50. The catalyst has a specific surface of 120 m ² /g, a pore volume of 0.3 cm ³ /g, an average pore diameter of 8.0 nm, and is a particle with a cross section in the form of a trefoil with a circumscribed circle diameter of 1.0 mm and a length of up to 20 mm .

Next, hydrotreatment of mixed diesel fuel is carried out analogously to example 1.

Example 3

The carrier is prepared according to example 2, only the hydration of the PBTOG powder is carried out for 4 hours, and the filtration is carried out with technically prepared water to a residual Na content of 0.001 wt.%. After that, a solution of lanthanum nitrate in the amount of 12.5 g is added to the suspension in the autoclave vessel, and the vessel is heated to 140°C and held for 6 hours. with a cross section in the form of a trefoil with a diameter of 1.6 mm.

As a result, a support is obtained containing isolated La atoms with an average size of 0.1 nm, consisting in a La-O-Al chemical bond, with a surface density of 25-30 atoms per 10 nm ² surface and a ratio of Al atoms to La atoms equal to 100; sodium - 0.001 wt.%; χ- and γ-Al ₂ O ₃ - the rest, and the ratio of low-temperature forms of aluminum oxide χ- and γ-Al ₂ O ₃ in the carrier in wt.% is 31:69.

Next, prepare a solution of a mixture of complexes [Co (H ₂ O) ₂ (C ₆ H ₅ O ₇ )] ₂ [Mo ₄ O ₁₁ (C ₆ H ₅ O ₇ ) ₂ ] and Co ₂ [H ₂ P ₂ Mo ₅ O ₂₃ ], for which 6.1 g of citric acid C ₆ H ₈ O ₇ , 9.1 g of cobalt (II) hydroxide Co (OH) ₂ , 27.4 g of molybdenum oxide MoO ₃ and 4.7 ml of phosphoric acid (85 %). After complete dissolution of all components, the volume of the solution is adjusted to 80 ml by adding distilled water. The resulting solution contains 8.6 g [Co(H ₂ O) ₂ (C ₆ H ₅ O ₇ )] ₂ [Mo ₄ O ₁₁ (C ₆ H ₅ O ₇ ) ₂ ] and 27.1 g Co ₂ [H ₂ P ₂ Mo ₅ O ₂₃ ].

100 g of the resulting carrier is impregnated with 80 ml of a solution of a mixture of complexes [Co(H ₂ O) ₂ (C ₆ H ₅ O ₇ )] ₂ [Mo ₄ O ₁₁ (C ₆ H ₅ O ₇ ) ₂ ] and Co ₂ [H ₂ P ₂ Mo ₅ O ₂₃ ] at 50°C for 30 min. Then the catalyst is dried in air for 4 hours at 120°C.

Next, the catalyst is sulfided according to known methods analogously to example 1. After sulfiding, the catalyst contains, wt.%: Mo - 12.6; Co - 4.0; P - 1.7; S - 10.5; carrier - the rest; wherein the carrier contains isolated La atoms with an average size of 0.1 nm, consisting in the chemical bond La-O-Al, with a surface density of 25-30 atoms per 10 nm ² surface and the ratio of Al atoms to La atoms equal to 100; sodium - 0.001 wt.%; χ- and γ-Al ₂ O ₃ - the rest, and the ratio of low-temperature forms of aluminum oxide χ- and γ-Al ₂ O ₃ in the carrier in wt.% is 31:69. The catalyst has a specific surface of 135 m ² /g, a pore volume of 0.38 cm ³ /g, an average pore diameter of 8.7 nm, and is a particle with a cross section in the form of a trefoil with a circumscribed circle diameter of 1.6 mm and a length of up to 20 mm .

Next, hydrotreatment of mixed diesel fuel is carried out analogously to example 1.

Example 4

The carrier is prepared according to example 2, only a solution of lanthanum nitrate in the amount of 6.3 g is added to the suspension in the autoclave vessel, while the autoclave vessel is kept at a temperature of 140 ° C for 16 hours.

As a result, a support is obtained containing isolated La atoms with an average size of 0.1 nm, consisting in a La-O-Al chemical bond, with a surface density of 12-15 atoms per 10 nm ² surface and a ratio of Al atoms to La atoms equal to 200; sodium - 0.05 wt.%; χ- and γ-Al ₂ O ₃ - the rest, and the ratio of low-temperature forms of aluminum oxide χ- and γ-Al ₂ O ₃ in the carrier in wt.% is 25:75.

Next, prepare a solution of a mixture of complexes [Co (H ₂ O) ₂ (C ₆ H ₅ O ₇ )] ₂ [Mo ₄ O ₁₁ (C ₆ H ₅ O ₇ ) ₂ ] and Co ₂ [H ₂ P ₂ Mo ₅ O ₂₃ ], for which 6.6 g of citric acid C ₆ H ₈ O ₇ , 8.1 g of cobalt (II) hydroxide Co (OH) ₂ , 24.5 g of molybdenum oxide MoO ₃ and 4.1 ml of phosphoric acid (85 %). After complete dissolution of all components, the volume of the solution is adjusted to 80 ml by adding distilled water. The resulting solution contains 9.6 g [Co(H ₂ O) ₂ (C ₆ H ₅ O ₇ )] ₂ [Mo ₄ O ₁₁ (C ₆ H ₅ O ₇ ) ₂ ] and 24.1 g Co ₂ [H ₂ P ₂ Mo ₅ O ₂₃ ].

100 g of the resulting carrier is impregnated with 80 ml of a solution of a mixture of complexes [Co(H ₂ O) ₂ (C ₆ H ₅ O ₇ )] ₂ [Mo ₄ O ₁₁ (C ₆ H ₅ O ₇ ) ₂ ] and Co ₂ [H ₂ P ₂ Mo ₅ O ₂₃ ] at 40°C for 60 min. Then the catalyst is dried in air for 4 hours at 140°C.

Next, the catalyst is sulfided according to known methods analogously to example 1. After sulfiding, the catalyst contains, wt.%: Mo - 11.6; Co - 3.7; P - 1.6; S - 9.8; carrier - the rest; wherein the carrier contains isolated La atoms with an average size of 0.1 nm, consisting in the chemical bond La-O-Al, with a surface density of 12-15 atoms per 10 nm ² surface and the ratio of Al atoms to La atoms equal to 200; sodium - 0.05 wt.%; χ- and γ-Al ₂ O ₃ - the rest, and the ratio of low-temperature forms of aluminum oxide χ- and γ-Al ₂ O ₃ in the carrier in wt.% is 25:75. The catalyst has a specific surface area of 143 m ² /g, a pore volume of 0.40 cm ³ /g, an average pore diameter of 10.1 nm, and is a trefoil-shaped particle with a circumscribed circle diameter of 1.0 mm and a length of up to 20 mm.

Next, hydrotreatment of mixed diesel fuel is carried out analogously to example 1.

Example 5

The carrier is prepared according to example 4, only a solution of lanthanum nitrate in the amount of 3.1 g is added to the suspension in the autoclave vessel. In this case, the finished suspension of aluminum hydroxide after hydrothermal treatment is cooled to 90°C.

As a result, a support is obtained containing isolated La atoms with an average size of 0.1 nm, consisting in a La-O-Al chemical bond, with a surface density of 8-10 atoms per 10 nm ² surface and a ratio of Al atoms to La atoms equal to 400; sodium - 0.05 wt.%; χ- and γ-Al ₂ O ₃ - the rest, and the ratio of low-temperature forms of aluminum oxide χ- and γ-Al ₂ O ₃ in the carrier in wt.% is 19:81.

Next, prepare a solution of a mixture of complexes [Co (H ₂ O) ₂ (C ₆ H ₅ O ₇ )] ₂ [Mo ₄ O ₁₁ (C ₆ H ₅ O ₇ ) ₂ ] and Co ₂ [H ₂ P ₂ Mo ₅ O ₂₃ ], for which 7.9 g of citric acid C ₆ H ₈ O ₇ , 7.5 g of cobalt (II) hydroxide Co (OH) ₂ , 21.8 g of molybdenum oxide MoO ₃ and 3.5 ml of phosphoric acid (85 %). After complete dissolution of all components, the volume of the solution is adjusted to 80 ml by adding distilled water. The resulting solution contains 11.9 g [Co(H ₂ O) ₂ (C ₆ H ₅ O ₇ )] ₂ [Mo ₄ O ₁₁ (C ₆ H ₅ O ₇ ) ₂ ] and 21.1 g Co ₂ [H ₂ P ₂ Mo ₅ O ₂₃ ].

100 g of the resulting carrier is impregnated with 80 ml of a solution of a mixture of complexes [Co(H ₂ O) ₂ (C ₆ H ₅ O ₇ )] ₂ [Mo ₄ O ₁₁ (C ₆ H ₅ O ₇ ) ₂ ] and Co ₂ [H ₂ P ₂ Mo ₅ O ₂₃ ] at 30°C for 15 min. Then the catalyst is dried in air for 4 hours at 160°C.

Next, the catalyst is sulfided according to known methods analogously to example 1. After sulfiding, the catalyst contains, wt.%: Mo - 10.7; Co - 3.5; P - 1.4; S - 9.0; carrier - the rest; wherein the carrier contains isolated La atoms with an average size of 0.1 nm, consisting in the chemical bond La-O-Al, with a surface density of 8-10 atoms per 10 nm ² surface and the ratio of Al atoms to La atoms equal to 400; sodium - 0.03 wt.%; χ- and γ-Al ₂ O ₃ - the rest, and the ratio of low-temperature forms of aluminum oxide χ- and γ-Al ₂ O ₃ in the carrier in wt.% is 19:81. The catalyst has a specific surface area of 157 m ² /g, a pore volume of 0.41 cm ³ /g, an average pore diameter of 12.5 nm, and is a trefoil-shaped particle with a circumscribed circle diameter of 1.0 mm and a length of up to 20 mm.

Next, hydrotreatment of mixed diesel fuel is carried out analogously to example 1.

Example 6

The carrier is prepared according to example 4, only lanthanum nitrate 6-water is added to the suspension in the vessel of the autoclave in the form of a crystalline hydrate in the amount of 0.45 g in terms of anhydrous lanthanum nitrate.

As a result, a support is obtained containing isolated La atoms with an average size of 0.1 nm, consisting in a La-O-Al chemical bond, with a surface density of 6-7 atoms per 10 nm ² surface and a ratio of Al atoms to La atoms equal to 1000; sodium - 0.05 wt.%; χ- and γ-Al ₂ O ₃ - the rest, and the ratio of low-temperature forms of aluminum oxide χ- and γ-Al ₂ O ₃ in the carrier in wt.% is 13:87. The difference from example 3 also lies in the fact that after adding an aqueous solution of ammonia to the pseudoboehmite powder and obtaining a plastic mass, the plastic mass is extruded at a pressure of 50.0-60.0 MPa through a spinneret, which ensures the production of particles with a cross section in the form of a quatrefoil with a diameter of the described circumference 1.2 mm and length up to 20 mm.

Next, prepare a solution of a mixture of complexes [Co (H ₂ O) ₂ (C ₆ H ₅ O ₇ )] ₂ [Mo ₄ O ₁₁ (C ₆ H ₅ O ₇ ) ₂ ] and Co ₂ [H ₂ P ₂ Mo ₅ O ₂₃ ], for which 6.6 g of citric acid C ₆ H ₈ O ₇ , 8.1 g of cobalt (II) hydroxide Co (OH) ₂ , 24.5 g of molybdenum oxide MoO ₃ and 4.1 ml of phosphoric acid (85 %). After complete dissolution of all components, the volume of the solution is adjusted to 80 ml by adding distilled water. The resulting solution contains 9.6 g [Co(H ₂ O) ₂ (C ₆ H ₅ O ₇ )] ₂ [Mo ₄ O ₁₁ (C ₆ H ₅ O ₇ ) ₂ ] and 24.1 g Co ₂ [H ₂ P ₂ Mo ₅ O ₂₃ ].

100 g of the resulting carrier is impregnated with 80 ml of a solution of a mixture of complexes [Co(H ₂ O) ₂ (C ₆ H ₅ O ₇ )] ₂ [Mo ₄ O ₁₁ (C ₆ H ₅ O ₇ ) ₂ ] and Co ₂ [H ₂ P ₂ Mo ₅ O ₂₃ ] at 25°C for 30 min. Then the catalyst is dried in air for 2 hours at 180°C.

Next, the catalyst is sulfided according to known methods analogously to example 1. After sulfiding, the catalyst contains, wt.%: Mo - 11.6; Co - 3.7; P - 1.6; S - 9.8; carrier - the rest; wherein the carrier contains isolated La atoms with an average size of 0.1 nm, consisting in the chemical bond La-O-Al, with a surface density of 6-7 atoms per 10 nm ² surface and the ratio of Al atoms to La atoms equal to 1000; sodium - 0.05 wt.%; χ- and γ-Al ₂ O ₃ - the rest, and the ratio of low-temperature forms of aluminum oxide χ- and γ-Al ₂ O ₃ in the carrier in wt.% is 13:87. The catalyst has a specific surface area of 139 m ² /g, a pore volume of 0.36 cm ³ /g, an average pore diameter of 9.9 nm, and is a quatrefoil-shaped particle with a circle diameter of 1.2 mm and a length of up to 20 mm.

Next, hydrotreatment of mixed diesel fuel is carried out analogously to example 1.

Example 7

The carrier is prepared according to example 6, only lanthanum nitrate 6-aqueous is added to the suspension in the vessel of the autoclave in the form of a crystalline hydrate in the amount of 0.05 g in terms of anhydrous lanthanum nitrate, extruded at a pressure of 50.0-60.0 MPa through a spinneret, providing particles with a cross section in the form of a circle with a diameter of 1.2 mm.

As a result, a support is obtained containing isolated La atoms with an average size of 0.1 nm, consisting in a La-O-Al chemical bond, with a surface density of 5 atoms per 10 nm ² surface and a ratio of Al atoms to La atoms equal to 10,000; sodium - 0.05 wt.%; χ- and γ-Al ₂ O ₃ - the rest, and the ratio of low-temperature forms of aluminum oxide χ- and γ-Al ₂ O ₃ in the carrier in wt.% is 5:95. The difference from example 6 also lies in the fact that after adding an aqueous solution of ammonia to the pseudoboehmite powder and obtaining a plastic mass, the plastic mass is extruded at a pressure of 50.0-60.0 MPa through a spinneret, which ensures the production of particles with a cross section in the form of a circle with a diameter of the described circumference 1.2 mm and length up to 20 mm.

Next, prepare a solution of a mixture of complexes [Co (H ₂ O) ₂ (C ₆ H ₅ O ₇ )] ₂ [Mo ₄ O ₁₁ (C ₆ H ₅ O ₇ ) ₂ ] and Co ₂ [H ₂ P ₂ Mo ₅ O ₂₃ ], for which 4.6 g of citric acid C ₆ H ₈ O ₇ , 9.8 g of cobalt (II) hydroxide Co (OH) ₂ , 30.5 g of molybdenum oxide MoO ₃ and 5.4 ml of orthophosphoric acid are successively dissolved in 40 ml of distilled water with stirring (85%). After complete dissolution of all components, the volume of the solution is adjusted to 80 ml by adding distilled water. The resulting solution contains 6.3 g [Co(H ₂ O) ₂ (C ₆ H ₅ O ₇ )] ₂ [Mo ₄ O ₁₁ (C ₆ H ₅ O ₇ ) ₂ ] and 30.1 g Co ₂ [H ₂ P ₂ Mo ₅ O ₂₃ ].

100 g of the resulting carrier is impregnated with 80 ml of a solution of a mixture of complexes [Co(H ₂ O) ₂ (C ₆ H ₅ O ₇ )] ₂ [Mo ₄ O ₁₁ (C ₆ H ₅ O ₇ ) ₂ ] and Co ₂ [H ₂ P ₂ Mo ₅ O ₂₃ ] at 60°C for 30 min. Then the catalyst is dried in air for 3 hours at 200°C.

Next, the catalyst is sulfided according to known methods analogously to example 1. After sulfiding, the catalyst contains, wt.%: Mo - 13.5; Co - 4.2; P - 1.9; S - 11.3; carrier - the rest; carrier - the rest; wherein the carrier contains isolated La atoms with an average size of 0.1 nm, consisting in the chemical bond La-O-Al, with a surface density of 2-5 atoms per 10 nm ² surface and the ratio of Al atoms to La atoms equal to 10,000; sodium - 0.05 wt.%; χ- and γ-Al ₂ O ₃ - the rest, and the ratio of low-temperature forms of aluminum oxide χ- and γ-Al ₂ O ₃ in the carrier in wt.% is 5:95. The catalyst has a specific surface area of 195 m ² /g, a pore volume of 0.30 cm ³ /g, an average pore diameter of 13.0 nm, and is a particle with a circular cross section with a circumference diameter of 1.2 mm and a length of up to 20 mm.

Next, hydrotreatment of mixed diesel fuel is carried out analogously to example 1.

Example 8

The carrier is prepared according to example 3, only for the production of aluminum hydroxide a liquid nozzle is used at a liquid pressure of 0.6 MPa at the stage of spray drying.

As a result, a support is obtained containing isolated La atoms with an average size of 0.1 nm, consisting in a La-O-Al chemical bond, with a surface density of 25-30 atoms per 10 nm ² surface and a ratio of Al atoms to La atoms equal to 100; sodium - 0.001 wt.%; χ- and γ-Al ₂ O ₃ - the rest, and the ratio of low-temperature forms of aluminum oxide χ- and γ-Al ₂ O ₃ in the carrier in wt.% is 31:69.

Next, prepare a solution of a mixture of complexes [Co (H ₂ O) ₂ (C ₆ H ₅ O ₇ )] ₂ [Mo ₄ O ₁₁ (C ₆ H ₅ O ₇ ) ₂ ] and Co ₂ [H ₂ P ₂ Mo ₅ O ₂₃ ], for which 6.1 g of citric acid C ₆ H ₈ O ₇ , 9.1 g of cobalt (II) hydroxide Co (OH) ₂ , 27.4 g of molybdenum oxide MoO ₃ and 4.7 ml of phosphoric acid (85 %). After complete dissolution of all components, the volume of the solution is adjusted to 80 ml by adding distilled water. The resulting solution contains 8.6 g [Co(H ₂ O) ₂ (C ₆ H ₅ O ₇ )] ₂ [Mo ₄ O ₁₁ (C ₆ H ₅ O ₇ ) ₂ ] and 27.1 g Co ₂ [H ₂ P ₂ Mo ₅ O ₂₃ ].

100 g of the resulting carrier is impregnated with 80 ml of a solution of a mixture of complexes [Co(H ₂ O) ₂ (C ₆ H ₅ O ₇ )] ₂ [Mo ₄ O ₁₁ (C ₆ H ₅ O ₇ ) ₂ ] and Co ₂ [H ₂ P ₂ Mo ₅ O ₂₃ ] at 60°C for 30 min. Then the catalyst is dried in air for 4 hours at 120°C.

Next, the catalyst is sulfided according to known methods analogously to example 1. After sulfiding, the catalyst contains, wt.%: Mo - 12.6; Co - 4.0; P - 1.7; S - 10.5; carrier - the rest; wherein the carrier contains isolated La atoms with an average size of 0.1 nm, consisting in the chemical bond La-O-Al, with a surface density of 25-30 atoms per 10 nm ² surface and the ratio of Al atoms to La atoms equal to 100; sodium - 0.001 wt.%; χ- and γ-Al ₂ O ₃ - the rest, and the ratio of low-temperature forms of aluminum oxide χ- and γ-Al ₂ O ₃ in the carrier in wt.% is 31:69. The catalyst has a specific surface of 200 m ² /g, a pore volume of 0.47 cm ³ /g, an average pore diameter of 9.4 nm, and is a particle with a cross section in the form of a trefoil with a circumscribed circle diameter of 1.6 mm and a length of up to 20 mm .

Next, hydrotreatment of mixed diesel fuel is carried out analogously to example 1.

Example 9

The carrier is prepared according to example 2, only for the production of aluminum hydroxide a liquid nozzle is used at a liquid pressure of 2 MPa at the stage of spray drying.

As a result, a support is obtained containing isolated La atoms with an average size of 0.1 nm, consisting in a La-O-Al chemical bond, with a surface density of 45-50 atoms per 10 nm ² surface and a ratio of Al atoms to La atoms equal to 50; sodium - 0.05 wt.%; χ- and γ-Al ₂ O ₃ - the rest, and the ratio of low-temperature forms of aluminum oxide χ- and γ-Al ₂ O ₃ in the carrier in wt.% is 50:50.

Next, prepare a solution of a mixture of complexes [Co (H ₂ O) ₂ (C ₆ H ₅ O ₇ )] ₂ [Mo ₄ O ₁₁ (C ₆ H ₅ O ₇ ) ₂ ] and Co ₂ [H ₂ P ₂ Mo ₅ O ₂₃ ], for which 4.6 g of citric acid C ₆ H ₈ O ₇ , 9.8 g of cobalt (II) hydroxide Co (OH) ₂ , 30.5 g of molybdenum oxide MoO ₃ and 5.4 ml of orthophosphoric acid are successively dissolved in 40 ml of distilled water with stirring (85%). After complete dissolution of all components, the volume of the solution is adjusted to 80 ml by adding distilled water. The resulting solution contains 6.3 g [Co(H ₂ O) ₂ (C ₆ H ₅ O ₇ )] ₂ [Mo ₄ O ₁₁ (C ₆ H ₅ O ₇ ) ₂ ] and 30.1 g Co ₂ [H ₂ P ₂ Mo ₅ O ₂₃ ].

100 g of the resulting carrier is impregnated with 80 ml of a solution of a mixture of complexes [Co(H ₂ O) ₂ (C ₆ H ₅ O ₇ )] ₂ [Mo ₄ O ₁₁ (C ₆ H ₅ O ₇ ) ₂ ] and Co ₂ [H ₂ P ₂ Mo ₅ O ₂₃ ] at 60°C for 30 min. Then the catalyst is dried in air for 4 hours at 120°C.

Next, the catalyst is sulfided according to known methods analogously to example 1. After sulfiding, the catalyst contains, wt.%: Mo - 13.5; Co - 4.2; P - 1.9; S - 11.3; carrier - the rest; wherein the carrier contains isolated La atoms with an average size of 0.1 nm, consisting in the chemical bond La-O-Al, with a surface density of 45-50 atoms per 10 nm ² surface and the ratio of Al atoms to La atoms equal to 50; sodium - 0.05 wt.%; χ- and γ-Al ₂ O ₃ - the rest, and the ratio of low-temperature forms of aluminum oxide χ- and γ-Al ₂ O ₃ in the carrier in wt.% is 50:50. The catalyst has a specific surface of 185 m ² /g, a pore volume of 0.46 cm ³ /g, an average pore diameter of 10.0 nm, and is a particle with a cross section in the form of a trefoil with a circumscribed circle diameter of 1.0 mm and a length of up to 20 mm .

Next, hydrotreatment of mixed diesel fuel is carried out analogously to example 1.

The results of testing the catalysts of examples 2-9 in hydrotreating are shown in the table.

Thus, as can be seen from the above examples, the catalyst obtained by the proposed method due to its chemical composition has a high desulfurizing activity, significantly exceeding the activity of the prototype catalyst in the hydrotreatment of diesel fuel with a high content of secondary fractions of catalytic cracking feedstock.

Table. Results of Testing Catalysts in the Hydrotreatment of Blended Diesel Fuel

Sample Catalyst 1 (prototype) 2 3 4 5 6 7 eight 9 Surface density of La atoms per 10 nm ² 0 45-50 25-30 12-15 8-10 6-7 2-5 25-30 45-50 Mass ratio of phases χ- and γ-Al ₂ O ₃ 0 50:50 31:69 25:75 19:81 13:87 5:95 31:69 50:50 Na content, wt.% 0.03 0.05 0.001 0.05 0.05 0.05 0.05 0.001 0.05 The temperature to reach the residual sulfur content is less than 10 ppm 380 376 371 374 376 377 379 369 372

Claims (5)

1. A method for preparing a catalyst for hydrotreating diesel fuel, characterized in that the catalyst is prepared by impregnating a support containing 0.001-0.05 wt.% Na and having on its surface isolated La atoms with an average size of 0.1 nm, consisting in the chemical bond La- O-Al, with a surface density of 2-50 atoms per 10 nm ^{2 of the} surface and a ratio of Al atoms to the number of La atoms equal to 50-10000, consisting of low-temperature forms of aluminum oxide γ- and χ-Al ₂ O ₃ in the ratios (50- 95): (50-5) wt.%, an aqueous solution simultaneously containing a mixture of complex compounds [Co (H ₂ O) ₂ (C ₆ H ₅ O ₇ )] ₂ [Mo ₄ O ₁₁ (C ₆ H ₅ O ₇ ) ₂ ] and Co ₂ [H ₂ P ₂ Mo ₅ O ₂₃ ], followed by drying, while the concentration of the components of the solution provide a composition, wt.%: [Co(H ₂ O) ₂ (C ₆ H ₅ O ₇ ) ] ₂ [Mo ₄ O ₁₁ (C ₆ H ₅ O ₇ ) ₂ ] - 6.0-12.0, Co ₂ [H ₂ P ₂ Mo ₅ O ₂₃ ] - 21.0-30.0, carrier - rest , and followed by sulfiding; while the resulting catalyst has a specific surface of 120-200 m ² /g, pore volume of 0.30-0.50 cm ³ /g, the average pore diameter of 8-13 nm. 2. The method according to claim 1, characterized in that the carrier is impregnated in terms of moisture capacity with an aqueous solution simultaneously containing a mixture of complex compounds [Co(H ₂ O) ₂ (C ₆ H ₅ O ₇ )] ₂ [Mo ₄ O ₁₁ (C ₆ H ₅ O ₇ ) ₂ ] and Co ₂ [H ₂ P ₂ Mo ₅ O ₂₃ ], while the impregnation is carried out at a temperature of 25-80°C for 15-60 min with occasional stirring. 3. The method according to p. 1, characterized in that after impregnation, the catalyst is dried in air at a temperature of 100-200°C for 2-4 hours. 4. The method according to p. 1, characterized in that after sulfiding the catalyst contains, wt.%: Mo - 10.7-13.5; Co - 3.5-4.2; S - 9.0-11.5; P - 1.4-1.9; carrier - the rest; while the carrier contains 0.001-0.05 wt.% Na and has on its surface isolated La atoms with an average size of 0.1 nm, consisting in the La-O-Al chemical bond, with a surface density of 2-50 atoms per 10 nm ² surface and the ratio of Al atoms to the number of La atoms, equal to 50-10000, and the carrier consists of low-temperature forms of aluminum oxide γ- and χ-Al ₂ O ₃ in the ratios (50-95):(50-5) wt.%. 5. The method according to p. 1, characterized in that the resulting catalyst is a particle with a cross section in the form of a circle, trefoil or quatrefoil with a circumscribed circle diameter of 1.0-1.6 mm and a length of up to 20 mm.