RU2763725C1 - Method for producing low-sulfur diesel fuel - Google Patents

Abstract

FIELD: oil processing.

SUBSTANCE: invention relates to methods for producing low-sulfur diesel fuels. The invention relates to a method consisting in the transformation of straight-run and containing up to 30% secondary diesel fractions at a temperature of 340-380°C, a pressure of 3.5-8.0 MPa, a mass consumption of raw materials of 1.0-2.5 h^-1, a volume ratio of hydrogen/raw materials of 300-800 m³/m³ in the presence of a heterogeneous catalyst. The catalyst is obtained by sulfidation of 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. After sulfidation, 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. In this case, the carrier contains 0.001-0.05 wt. %, of Na and additionally contains 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 surface and a ratio of Al atoms to 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). The 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.

EFFECT: production of diesel fuel containing less than 10 ppm of sulfur during hydrotreating of straight-run diesel fractions and those containing up to 30% of secondary diesel fractions.

4 cl, 1 tbl, 14 ex

Description

The invention relates to catalytic methods for producing low-sulphur diesel fuels from straight-run and mixed diesel fuels with a high content of secondary fractions.

Obtaining diesel fuels with low sulfur content is one of the most important tasks of modern oil refining. 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. Accordingly, the conditions of the hydrotreating process are unnecessarily harsh due to the low activity of the catalysts. For hydrotreatment of mixed diesel fractions on known catalysts with low activity, it is necessary to increase the starting temperature of the hydrotreatment process, which leads to rapid deactivation of the catalysts. In this regard, an extremely urgent task is the creation of new processes for the production of low-sulfur diesel fuels based on the use of highly active domestic catalysts, which further allow the production of motor fuels that meet the Euro-5 standard for sulfur content, at the lowest possible starting temperature of the hydrotreatment process.

Existing factory hydrotreatment units operate in a fairly narrow range of temperatures, flow rates, and pressures. Thus, for most Russian installations for deep hydrotreating of diesel fuels, the pressure usually does not exceed 4.0 MPa, the feedstock consumption is 1.0-2.5 h ^-1 , the hydrogen/feedstock volume ratio is 300-500 nm ³ /m ³ . The starting temperature of the hydrotreatment process should be as low as possible, since the rate of deactivation and the catalyst life between regenerations depend on it. Thus, the main tool that allows you to change the amount of sulfur in the products obtained, without significant changes in the conditions of the hydrotreatment process and the reconstruction of plants, is the selection of the characteristics of the catalysts used, of which the most important is catalytic activity. There are various methods of hydrotreating diesel fuel, but the main disadvantage for them is the high residual sulfur content in the products obtained, due to the low activity of the catalysts used.

Thus, a method for producing low-sulfur diesel fuel is known [RU 2100408, C10G 65/04, 12/27/1997], according to which the hydrotreatment process is carried out in 2 stages with intermediate heating of the gas-feed mixture using at the 1st stage an aluminum-nickel-molybdenum catalyst with a predominant pore radius 9-12 nm and at the 2nd stage - aluminum-nickel-molybdenum or aluminum-cobalt-molybdenum catalyst with a predominant pore radius of 4-8 nm at a mass ratio of catalysts of the 1st and 2nd stages 1: (2-6). The process is carried out at a temperature of 250-350°C in the 1st stage and 320-380°C in the 2nd stage. The main disadvantage of this method is the high sulfur content in the resulting diesel fuel, as a rule, it lies in the range of 100-500 ppm.

A known method of hydrotreating diesel fractions [Smirnov V.K., Kapustin V.M., Gantsev V.A., Chemistry and technology of fuels and oils, No. 3, 2002, p. 3], consisting in the passage of raw materials at 330-335 ° C, a pressure of 2.5-2.7 MPa, with a ratio of hydrogen-containing gas / raw materials of 250-300 m ³ /m ³ and a volumetric feed rate of raw materials of 2.5-3 h ^{- 1} through a reactor filled with a mixture of RK-012 + TNK-2000(AKM) + TNK-2003(ANM) catalysts. In this process, a residual sulfur content in the resulting diesel fraction is reached at the level of 800-1200 ppm.

Most often, the processes of hydrodesulfurization of petroleum feedstock are carried out in the presence of catalysts containing oxides of cobalt and molybdenum deposited on aluminum oxide. Thus, there is a known method of catalytic hydrotreating of crude oil [EN 2192923, B01J 27/188, C10G 45/08, 20.10.2002]. The process is carried out at 200-480°C at a pressure of 0.5-20 MPa at a feedstock consumption of 0.05-20 h ^-1 and a hydrogen consumption of 100-3000 l/l of raw materials, while using a catalyst based on aluminum oxide, which contains in terms of oxide content, wt.%: 2-10 cobalt oxide CoO, 10-30 molybdenum oxide MoO ₃ and 4-10 phosphorus oxide P ₂ O ₅ , with a surface area according to the BET method in the range of 100-300 m ² /g and average pore diameter in the range of 8-11 nm.

A known method of hydrodesulfurization of crude oil [RU 2002124681, C10G 45/08, B01J 23/887, 10.05.2004], where the hydrotreatment process is carried out at a temperature of 310-340°C, a pressure of 3.0-5.0 MPa, at a ratio of hydrogen/ raw material 300-500 nm ³ /m ³ and a volumetric feed rate of 1.0-4.0 h ^-1 while using a catalyst containing cobalt oxide, molybdenum oxide and aluminum oxide, characterized in that it has a ratio components, wt.%: cobalt oxide 3.0-9.0, molybdenum oxide 10.0-24.0, aluminum oxide the rest, the catalyst has a specific surface of 160-250 m ² /g, mechanical crushing strength 0.6- 0.8 kg / mm ^2.

A known process for the hydrotreating of hydrocarbons [RU 2402380, B01J 21/02, C10G 45/08, 27.10.2010], which consists in the conversion of petroleum distillates with a high sulfur content at a temperature of 320-400°C, a pressure of 0.5-10 MPa, weight consumption of raw materials 0.5-5 h ^-1 volume ratio of hydrogen/feedstock 100-1000 m ³ /m ³ in the presence of a heterogeneous catalyst containing a bimetallic complex compound [M(H ₂ O) _x (L) _y ] ₂ [Mo ₄ O ₁₁ (C ₆ H ₅ O ₇ ) ₂ ], where L is a partially deprotonated form of citric acid C ₆ H ₆ O ₇ . x=0 or 2; y=0 or 1; M - Co ²⁺ and/or Ni ²⁺ in the amount of 30-45 wt.%, which corresponds to the content in the catalyst calcined at 550°C, wt.%: MoO ₃ - 14.0-23.0; CoO and/or NiO - 3.6-6.0; B ₂ O ₃ - 0.6-2.6, Al ₂ O ₃ - the rest, and 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 of 9- 13 nm.

A common disadvantage for all of the above hydrotreating processes and catalysts for these processes is that with their use either it is not possible to achieve a residual sulfur content in diesel fuels at the level of 10 ppm at all, or the specified residual sulfur content is achieved at high temperatures of the hydrotreating process, excluding them. use at factory settings.

The closest to the proposed technical solution is described in [RU 2732944, C10 G 45/08, 09/24/2020] the method of hydrotreating mixed and straight-run diesel fractions with a high sulfur content at elevated pressure and heating in a hydrogen-containing gas stream in the presence of a heterogeneous catalyst 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 ] - 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, the carrier is the rest, while the carrier contains , wt.%: in terms of oxides of non-metals SiO ₂ - 0.1-20 and B ₂ O ₃ - 0-10; sodium - no more than 0.03; 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 in wt.% is (0-40):(100-60). The catalyst has a specific surface of 140-180 m ² /g, a pore volume of 0.35-0.70 cm ³ /g, an average pore diameter of 9-13.5 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. Before hydrotreatment, the catalyst is sulphided to obtain 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 carrier contains, wt.%: SiO ₂ - 0.1-20 and B ₂ O ₃ - 0-10; Al ₂ O ₃ - the rest.

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

EFFECT: obtaining diesel fuel containing less than 10 ppm of sulfur during straight-run hydrotreatment and containing up to 30% secondary diesel fractions.

The problem is solved in a way obtaining low-sulfur diesel fuel at elevated pressure and heating in a stream of hydrogen-containing gas in the presence of a heterogeneous catalyst, characterized in that the catalyst used contains, wt.%: [Co(H₂O)₂(WITH₆H₅O₇)]₂[Mo₄O_eleven(WITH₆H₅O₇)₂] - 6.0-12.0, Co₂[H₂P₂Mo₅O₂₃] - 21.0-30.0, the carrier - the rest; 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 additionally contains isolated La atoms on its 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 nm² surface and the ratio of Al atoms to La atoms, equal to 50 - 10000, and the carrier consists of low-temperature forms of aluminum oxide γ- and χ-Al₂O₃ in ratios (50-95):(50-5) wt.%. In this case, the catalyst has a specific surface of 120-200 m²/g, pore volume 0.30-0.50 cm³/g, the average pore diameter is 8-13 nm and 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. The process is carried out at a temperature of 340-380°C, a pressure of 3.5-8.0 MPa, a mass flow rate of raw materials of 1.0-2.5 h^-one, hydrogen/feedstock volume ratio 300-800 m³/m³. Straight-run or diesel fractions containing up to 30% of secondary fractions with a boiling point up to 410°C are used as feedstock.

An essential feature of the proposed method for producing low-sulfur diesel fuel compared with the prototype is that they use a catalyst that contains, 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; 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 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 surface and the ratio of Al atoms to 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.%. Such a chemical composition of the catalyst contributes to the further selective formation of the most active CoMoS type II phase in the target hydrotreatment reactions, which ensures the production of low-sulphur diesel fuel at a low temperature of the hydrotreatment process. The catalyst used 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 circumscribed circle diameter of 1.0-1.6 mm and up to 20 mm long. Such catalyst particle sizes and textural characteristics provide access for all feedstock molecules to be converted to the active component.

The technical result is achieved as follows:

1. The claimed chemical composition of the catalyst determines the maximum 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 ratios (50-95): (50-5) wt.% ensures the stability of the catalyst to the processes of sintering and coking under the reaction conditions, minimizing undesirable chemical interaction between the active metals (Co and Mo) and a carrier, and the selective production of the most active sulfide component in hydrotreatment - CoMoS type II phase, which provides a high activity of the catalyst in the conversion of sulfur- and nitrogen-containing components of the feedstock.

2. The presence in the catalyst 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 ] in the claimed concentrations ensures further formation in the catalyst, during its operation in hydrotreatment, of the most active component - CoMoS type II phase in the form of particles of optimal morphology for catalysis, localized in the molecules of the raw material accessible to all to be converted.

3. The presence in the composition of the catalyst 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 alumina 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.

Hydrotreating of straight-run or containing up to 30% secondary diesel fractions with a boiling point up to 410°C is carried out at a temperature of 340-380°C, a pressure of 3.5-8.0 MPa, a mass flow rate of raw materials of 1.0-2.5 h ^-1 , volume ratio of hydrogen/feedstock 300-800 m ³ /m ³ in the presence of a catalyst 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, the carrier is the rest; 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 additionally contains isolated La atoms on its 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 surfaces and the ratio of Al atoms to 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). The 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 circumscribed circle diameter of 1.0-1.6 mm and up to 20 mm long.

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

Example 1 according to the well-known solution [RU 2732944, C10 G 45/08, 09/24/2020].

The carrier is prepared as follows. Take 150 g of powdered PBTOG product, crushed 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 filter paper of the Blue Ribbon type. 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 grade 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 powdery 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 formed granules are dried at a temperature of 120°C and calcined at a temperature of 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, 2.3 R ₂ O ₅ , carrier γ-Al ₂ O ₃ - the rest; while the media contains SiO ₂ - 0.1 wt.%. 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 the sulfiding agent dimethyl disulfide (DMDS) at a space velocity of the sulfiding mixture of 2 h ^-1 and a ratio of H ₂ /feed = 300 at a temperature of not more than 340°C.

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 area 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 circular cross section with a circumscribed circle diameter of 1.0 mm and a length of up to 20 mm.

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.

The results of testing the catalyst according to example 1 in hydrotreating are shown in the table.

Examples 2-13 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. Next, 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 molded 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.

Example 10

The carrier and catalyst are prepared according to example 8. The sulfidation of the catalyst and the process of hydrotreating mixed diesel fuel using it is carried out according to example 1, with the difference that the following process conditions are maintained: pressure 3.5 MPa, feed space velocity 1.0 h ^-1 , ratio H ₂ /raw material is 500 nm ³ H ₂ /m ³ raw material.

Example 11

The carrier and catalyst are prepared according to example 8. The sulfiding of the catalyst and the process of hydrotreating mixed diesel fuel using it is carried out according to example 1, with the difference that the following process conditions are maintained: pressure 5.0 MPa, feed space velocity 2.0 h ^-1 , the ratio of H ₂ /raw material 800 nm ³ H ₂ /m ³ raw material.

Example 12

The carrier and catalyst are prepared according to example 8. The sulfiding of the catalyst and the process of hydrotreating mixed diesel fuel using it is carried out according to example 1, with the difference that the following process conditions are maintained: pressure - 8.0 MPa, feed space velocity - 2.5 h ^{- 1} , the ratio of H ₂ /feedstock - 800 nm ³ H ₂ /m ³ feedstock.

Example 13

The carrier and catalyst are prepared according to example 8. The sulfiding of the catalyst and the process of hydrotreating mixed diesel fuel using it is carried out according to example 1, with the difference that the following process conditions are maintained: pressure - 8.0 MPa, feed space velocity - 2.5 h ^{- 1} , the ratio of H ₂ /feedstock - 800 nm ³ H ₂ /m ³ raw materials and as raw materials take blended diesel fuel prepared by mixing fractions, vol.%: 70 - straight-run diesel fraction; 20 - catalytic cracking light gas oil, 10 - delayed coking light gas oil. The raw material contains 0.51 wt.% sulfur, 320 ppm nitrogen, has a density of 0.901 g/cm ³ , boiling range - 186-400°C, T ₉₅ - 410°C.

Example 14

The carrier and catalyst are prepared according to example 8. The sulfiding of the catalyst and the process of hydrotreating mixed diesel fuel using it is carried out according to example 1, with the difference that the following process conditions are maintained: pressure - 5.0 MPa, feed space velocity - 1.5 h ^{- 1} , the ratio of H ₂ /feedstock - 450 nm ³ H ₂ /m ³ feedstock and straight-run diesel fraction is taken as raw material. The raw material contains 0.3 wt.% sulfur, 80 ppm nitrogen, has a density of 0.860 g/cm ³ , boiling range - 100-370°C, T ₉₅ - 385°C.

The results of testing the catalysts of examples 2-14 in hydrotreating are shown in the table.

Thus, as can be seen from the above examples, the proposed method for producing low-sulfur diesel fuel using a catalyst with a designated chemical composition provides hydrotreatment of diesel fuel with a high content of secondary fractions to less than 10 ppm sulfur under less severe conditions compared to the prototype.

Table. Results of hydrotreatment of blended diesel fuel

Sample Catalyst 1 (prototype) 2 3 4 5 6 7 eight 9 10 eleven 12 thirteen 14 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 25-30 25-30 25-30 25-30 25-30 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 31:69 31:69 31:69 31:69 31:69 Na content, wt.% 0.03 0.05 0.001 0.03 0.03 0.03 0.03 0.001 0.05 0.001 0.001 0.001 0.001 0.001 The temperature to achieve a residual sulfur content of less than 10 ppm 380 376 371 374 376 377 379 369 372 365 359 348 367 340

Claims (4)

1. A method for producing low-sulfur diesel fuel, which consists in the hydrotreatment of straight-run and secondary diesel fractions at elevated pressure and heating in a hydrogen-containing gas stream in the presence of a heterogeneous catalyst, characterized in that the catalyst used is obtained by sulfiding the 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 - the rest; 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 support contains 0.001-0.05 wt.% Na and 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 the ratio of atoms Al to 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 120-200 m ² /g, pore volume 0.30-0.50 cm ³ /g, average pore diameter 8-13 nm. 2. The method according to p. 1, characterized in that straight-run or diesel fractions containing up to 30% of secondary fractions with a boiling point up to 410 ° C are used as feedstock. 3. The method according to p. 1, characterized in that the process is carried out at a temperature of 340-380°C, a pressure of 3.5-8.0 MPa, a mass flow rate of raw materials of 1.0-2.5 h ^-1 , a hydrogen/feedstock volume ratio of 300-800 m ³ /m ³ . 4. The method according to claim 1, characterized in that the catalyst 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 a length of up to 20 mm.