RU2689735C1 - Hydrofining catalyst for diesel fuel - Google Patents

Abstract

FIELD: chemistry.SUBSTANCE: disclosed is a hydrotreating catalyst for diesel fuel, which includes compounds of cobalt, molybdenum, phosphorus and a carrier. Catalyst contains, wt %: [Co(HO)(CHO)][MoO(CHO)] – 7.7–32.0; CO[HPMoO] – 11.1–29.0; carrier – balance; carrier contains, wt. %: aluminum borate AlBOwith norbergite structure – 5.0–25.0; γ-AlO– balance.EFFECT: obtaining a catalyst having maximum activity in target reactions occurring during hydrofining of mixed diesel fuel containing distillates of secondary oil refining processes.3 cl, 5 ex, 1 tbl

Description

The invention relates to Hydrotreating catalysts for the production of petroleum products with low sulfur content.

Currently, diesel fuel is produced in Russia containing no more than 10 ppm of sulfur in accordance with GOST R 52368-2005. (EN 590-2004). Diesel fuel EURO. Technical conditions. In recent years, the proportion of secondary fractions containing hard-to-convert sulfur compounds and nitrogen compounds, which inhibit the conversion of sulfur-containing compounds, is constantly increasing in the raw materials of hydrotreating units. For hydrotreatment of mixed diesel fractions on known catalysts with low activity, it is necessary to increase the starting temperature of the hydrotreating process, which leads to a rapid deactivation of the catalysts. In this regard, an extremely urgent task is the creation of new highly active catalysts, allowing to obtain motor fuels with low residual sulfur content from raw materials with a high content of secondary fractions at the lowest possible starting temperature of the hydrotreating process.

Various supported catalysts for hydrotreating hydrocarbon feedstocks are known; however, a common drawback for them is the low activity in the conversion of sulfur-containing compounds.

Most often for carrying out the hydrodesulfurization of crude oil using catalysts containing oxides of cobalt and molybdenum supported on alumina. So known catalyst hydrodesulfurization [RF Application No. 2002124681, C10G 45/08, B01J 23/887, 16.09.2002], containing in its composition 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, alumina else, specific surface 160-250 m ² / g, mechanical crushing strength 0.6-0.8 kg / mm ² 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 space feed rate of 1.0-4.0 hours ^{- 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 use the method of deposition of active metals on an already formed carrier. As the carrier most often used aluminum oxide with a certain size and shape of the granules and certain textural characteristics. The carrier is often modified with various additives, including boron compounds. In this case, modifying additives are introduced into the carrier either prior to the stage of its formation, by co-precipitating modifiers and aluminum from joint solutions [Journal of Catalysis 115 (1989) 441-451], or by mixing aluminum hydroxide with a modifying compound at the stage of preparing a paste for molding [US No. 6147432], or enter the additive by the method of impregnation into a molded carrier, followed by drying and calcining [Catalysis Today 107-108 (2005) 551-558].

The introduction of active metals, most often Co, Ni, Mo and W into the catalyst, is carried out by impregnation of the molded carrier with aqueous solutions of their salts. This can be used as a separate application of active metals by impregnation in several stages [of the Russian Federation No. 2222501, 2246987], and their application from joint solutions stabilized by various agents [of the Russian Federation No. 2073567, 2216404, 2306978].

In order to increase the hydrodesulfurization activity of the catalysts in their preparation, a carrier with improved textural characteristics is used, 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 ensures good access of sulfur-containing molecules to the active sites of the catalyst . Thus, a catalyst is known [RF No. 2192923, C10G 45/08, B01J 27/188, B01J 35/10, 20.11.2002] based on aluminum oxide, which contains, in terms of the weight content of 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 surface area according to the BET method in the range of 100-300 m ² / g and an average pore diameter in the range of 8-11 nm.

A known catalyst for hydrotreating petroleum fractions [RF No. 22286846, B01J 23/78, B01J 23/83, C10G 45/08, 10.11.2006], which contains oxides of cobalt, molybdenum, sodium, lanthanum, boron and phosphorus and has the following composition, wt. . %: CoO 2.5-4.0; MoO ₃ 8.0-12.0; Na ₂ O 0.01-0.08; La ₂ O ₃ 1.5-4.0; P ₂ O ₅ 2.0-5.0; B ₂ O ₃ 0.5-3.0; Al ₂ O ₃ - the rest.

A known catalyst for hydrodesulfurization of the diesel fraction [RF No. 2313392, B01J 37/02, B01J 21/02, C10G 45/08, 13.10.2006], having a pore volume of 0.3-0.7 ml / g, specific surface area 200-350 m ² / g and an average pore diameter of 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 of 0.5-3.0 in terms of on 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 different stoichiometry.

Known hydrotreating catalyst [US Pat. Of the Russian Federation No. 2472585, B01J 23/882, 01.20.2013], containing, by weight. %: 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 media contains, by weight. %: B - 0.7-3.0; Al ₂ O ₃ is the rest and has a specific surface of 170-300 m ² / g, a pore volume of 0.5-0.95 cm ³ / g and an average pore diameter of 7-22 nm, and is a particle with a cross-section in the form of a trefoil with diameter of circumscribed circle is 1.0-1.6 mm and length up to 20 mm, having mechanical strength 2.0-2.5 kg / mm.

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

Closest to the proposed technical solution is described in [Pat. Of the Russian Federation No. 2636398, B01J 23/882, 09.11.2016] a catalyst containing, by weight. %: [Co (H ₂ O) ₂ (C ₆ H ₅ O ₇ )] ₂ [Mo ₄ O ₁₁ (C ₆ H ₅ O ₇ ) ₂ ] 33.0-43.0%; carrier - the rest; while the media contains, by weight. %: aluminum borate Al ₃ BO ₆ with the structure of norbergite - 5.0-25.0; sodium - not more than 0.03; γ-Al ₂ O ₃ - the rest. The catalyst has a specific surface of 130-180 m ² / g, a pore volume of 0.35-0.65 cm ³ / g, an average pore diameter of 7-12 nm, and is a particle with a cross section in the form of a circle, a trefoil or a four leaf clover with the diameter described circumference 1.0-1.6 mm and a length of up to 20 mm. After sulphidation by known methods, the catalyst contains, by weight. %: Mo - 10.0-14.0; Co - 3.0-4.3; S - 6.7-9.4; the carrier is the rest.

The main disadvantage of the known catalyst is that it has a non-optimal chemical composition, which causes its low activity in hydrotreating diesel fuel.

The present invention solves the problem of creating an improved Hydrotreating catalyst, characterized by an optimal chemical composition.

EFFECT: obtaining a catalyst having maximum activity in targeted reactions occurring during hydrotreating of mixed diesel fuel containing distillates of secondary refining processes.

The problem is solved by a catalyst for Hydrotreating of hydrocarbons, which contains, by weight. %: [Co (H ₂ O) ₂ (C ₆ H ₅ O ₇ )] ₂ [Mo ₄ O ₁₁ (C ₆ H ₅ O ₇ ) ₂ ] - 7.7-32.0; Co ₂ [H ₂ P ₂ Mo ₅ O ₂₃ ] - 11.1 - 29.0; carrier - the rest; while the media contains, by weight. %: aluminum borate Al ₃ BO ₆ with the structure of norbergite - 5.0-25.0; γ-Al ₂ O ₃ - the rest.

The catalyst has a specific surface area of 120-190 m ² / g, a pore volume of 0.35-0.65 cm ³ / g, an average pore diameter of 7-12 nm, and is a particle with a cross section in the form of a circle, a trefoil or a quatrefoil with the diameter described circumference 1.0-1.6 mm and a length of up to 20 mm. After sulphidation by known methods, the catalyst contains, by weight. %: Mo - 10.0-16.0; Co - 2.7-4.5; P- 0.8-1.8; S - 6.7-10.8; the carrier is the rest.

A distinctive feature of the proposed catalyst in comparison with the prototype is its chemical composition, namely, that the inventive catalyst contains, by weight. %: [Co (H ₂ O) ₂ (C ₆ H ₅ O ₇ )] ₂ [Mo ₄ O ₁₁ (C ₆ H ₅ O ₇ ) ₂ ] - 7.7-32.0; Co ₂ [H ₂ P ₂ Mo ₅ O ₂₃ ] - 11.1 - 29.0; carrier - the rest; while the media contains, by weight. %: aluminum borate Al ₂ BO ₆ with the structure of norbergite - 5.0-25.0; γ-Al ₂ O ₃ - the rest. The output content of the catalyst components for the claimed boundaries leads to a decrease in the activity of the catalyst.

The second distinguishing feature of the proposed catalyst in comparison with the prototype is that it has a specific surface of 120-190 m ² / g, a pore volume of 0.35-0.65 cm ³ / g, an average pore diameter of 7-12 nm, and represents particles with a cross-section in the form of a trefoil or a four-leaf with a circumferential diameter of 1.0-1.6 mm and a length of up to 20 mm.

The technical result consists of the following components:

1. The presence of two bimetallic 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 drying stage and ensures the further formation of highly dispersed particles of the most active component, CoMoS phase type II, during hydrotreatment of the catalyst.

2. The claimed chemical composition of the catalyst determines the maximum activity in the target reactions occurring during the hydrotreatment of hydrocarbons. The presence of phosphorus and boron compounds in the composition of the catalyst in the form of cobalt diphosphate pentamolybdate Co ₂ [H ₂ P ₂ Mo ₅ O ₂₃ ] and aluminum borate Al ₂ BO ₆ with the structure of norbergite with the claimed concentration provides a level of acidity that contributes to the maximum conversion of nitrogen compounds that inhibit the conversion of sulfur-containing compounds.

Description of the proposed technical solution.

Prepare media containing aluminum borate Al ₂ BO ₆ with the structure of norbergite and γ-Al ₂ O ₃ .

Take a sample of the product of thermal activation of hydrargillite (PTH), prepared according to the technology of centrifugal thermal activation (IC SB RAS, TU 2175-040-03533913-2007), or any other technology that provides PTH with the following characteristics: mass fraction of X-ray amorphous phase,%, not less than 80; the proportion of mass loss during calcination at (900 ± 20) ° С,% - 10-12; specific surface, m ² / g, not less than 120; total pore volume (capacity), cm ³ / g, not less than 0.1; mass fraction of gibbsite (hydrargillite),%, not more than 5; mass fraction of sodium oxide,%, not more than 0.5. A portion is ground in a planetary mill to particles with an average size of 20 microns.

A portion of the crushed powder is hydrated with stirring for two hours in low-concentrated solutions of nitric acid heated to 50 ° C (acid module 0.03). After that, the resulting suspension is filtered under vacuum and repeatedly washed with distilled water. The result is a wet sediment. Hydrothermal treatment of the washed precipitate is carried out in an autoclave in aqueous solutions of nitric acid with the addition of a specified amount of boric acid at a solution temperature above 100 ° C. After completion of the hydrothermal treatment, the solution is cooled to room temperature, the autoclave is discharged, and the contents of the vessel are repulped with distilled water until a suspension is suitable for spray drying. Next, carry out the drying in a spray dryer at an air temperature at the entrance to the dryer 280 ° C and continuous stirring of the suspension. The finished boron-containing aluminum hydroxide powder is discharged from the glass of the spray dryer cyclone dust collector.

Next, prepare the molding material by mixing and peptizing the obtained powder in a laboratory mixer with Z-shaped blades in the presence of an aqueous solution of ammonia. The ammonia solution was prepared so that the amount of ammonia water 25% was 1.5 ml per 40 g of powder after spray drying.

The finished plastic mass is transferred from the mixer to the molding cylinder of the laboratory extruder and pushed through the die hole to provide extrudates of the finished carrier with a circular cross-section, trefoil or tetrafoil from the top of the trefoil to the middle of the base from 1.0 to 1.6 mm.

This is followed by heat treatment of the extrudates, including drying and calcining. Drying of the extrudates is carried out in a drying oven at a temperature of (110 ± 10) ° C for 2 hours. Heat treatment is carried out in a muffle furnace with a supply of compressed air into the furnace. The extrudates in a porcelain dish were placed in an oven and calcined at a temperature of (550 ± 10) ° C for 4 hours.

Ready media contains, by weight. %: aluminum borate Al ₃ BO ₆ with the structure of norbergite - 5.0-25.0; γ-Al ₂ O ₃ - the rest, and has a specific surface of 200-280 m ² / g, a pore volume of 0.6-0.8 cm ³ / g, an average pore diameter of 7-12 nm, and represents particles with a cross section of a circle, a trefoil or a four-leaf with a circumference of 1.0-1.6 mm and a length of up to 20 mm.

The aluminum borate Al ₃ BO ₆ with the structure of norbergite, which is part of the carrier, is particles with sizes from 10 to 200 nm, characterized by interplanar distances of 3.2 and 2.8 A, with an angle of 53.8 ° between them.

Using this carrier, a supported catalyst is prepared. First, an impregnating solution is prepared that contains two bimetallic complex compounds in the specified ratios - cobalt molybdenum citrate [Co (H ₂ O) ₂ (C ₆ H ₅ O ₇ )] ₂ [Mo ₄ O ₁₁ (C ₆ H ₅ O ₇ ) ₂ ] and the cobalt salt diphosphate pentamolybdate Co ₂ [H ₂ P ₂ Mo ₅ O ₂₃ ]. For this purpose, given amounts of ammonium paramolybdate (NH ₄ ) ₆ Mo ₇ O ₂₄ ⋅4H ₂ O, cobalt (II) basic carbonate COCO ₃ ⋅mCo (OH) ₂ ⋅nH ₂ O, orthophosphoric acid, citric monohydrate are weighed. Measured cylinder measure the specified amount of distilled water. A measured amount of water is poured into the flask and an anchor of the magnetic stirrer is placed. The flask is placed on the heating surface of a heated magnetic stirrer. Set the rotation speed of the stirrer 300 rpm and the temperature of the solution 60 ° C. A predetermined amount of orthophosphoric acid is poured, a measured amount of citric acid is loaded into the flask and stirred under visual inspection. Then, a portion of ammonium paramolybdate is added to the flask to a solution of citric acid with constant stirring and maintaining the solution temperature (60 ± 5) ° C. The solution is stirred until a homogeneous transparent solution is obtained containing a mixture of complex compounds — molybdenum citrate (VI) (NH ₄ ) ₄ [Mo ₄ (C ₆ H ₅ O ₇ ) ₂ O ₁₁ ] and diphosphate pentamolybdate H ₆ P ₂ Mo ₅ O ₂₃ . A weighed amount of cobalt (II) basic carbonate is added to the previously obtained aqueous solution of molybdenum citrate (VI) and diphosphate pentamolybdate. In this case, the liquid foams, and its temperature rises to 70 ° C. Stirring is continued at (65-70) ° C to obtain a homogeneous transparent solution of dark cherry color, not containing dregs, bubbles and foam. The solution contains cobalt and molybdenum in the form of a bimetallic complex compound [Co (H ₂ O) ₂ (C ₆ H ₅ O ₇ )] ₂ [Mo ₄ O ₁₁ (C ₆ H ₅ O ₇ ) ₂ ], as well as cobalt, molybdenum and phosphorus in the form of cobalt diphosphate pentamolybdate 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 the specified amount by adding distilled water.

The resulting solution is impregnated with boron-containing carrier, while using the impregnation of the carrier on the capacity. Impregnation is carried out at a temperature of 15-70 ° C for 25-60 minutes with occasional stirring. After impregnation, the catalyst is dried in air at a temperature of 100-200 ° C.

As a result, get the catalyst containing, by weight. % [Co (H ₂ O) ₂ (C ₆ H ₅ O ₇ )] ₂ [Mo ₄ O ₁₁ (C ₆ H ₅ O ₇ ) ₂ ] - 7.7-32.0; Co ₂ [H ₂ P ₂ Mo ₅ O ₂₃ ] - 11.1 - 29.0; carrier - the rest; while the media contains, by weight. %: aluminum borate Al ₃ BO ₆ with the structure of norbergite - 5.0-25.0; γ-Al ₂ O ₃ - the rest. The catalyst has a specific surface area of 120-190 m ² / g, a pore volume of 0.35-0.65 cm ³ / g, an average pore diameter of 7-12 nm, and is a particle with a cross section in the form of a circle, a trefoil or a quatrefoil with the diameter described circumference 1.0-1.6 mm and a length of up to 20 mm. After sulphidation by known methods, the catalyst contains, by weight. %: Mo - 10.0-16.0; Co - 2.7-4.5; P- 0.8-1.8; S - 6.7-10.8; carrier - the rest; while the media contains, by weight. %: aluminum borate Al ₂ BO ₆ with the structure of norbergite - 5.0-25.0; γ-Al ₂ O ₃ - the rest.

The invention is illustrated by the following examples.

Example 1. According to the well-known decision [Pat. Of the Russian Federation No. 2636398].

First, prepare the carrier, for which 150 g of the product of thermal activation of hydrargillite is ground in a planetary mill to a particle size in the range of 20-50 microns. Next, the powder is hydrated with stirring and heated in a solution of nitric acid with a concentration of 0.5%. Then the suspension on a funnel with a paper filter is washed with distilled water until the residual sodium content in the powder is not more than 0.03%. The washed and pressed pellet is transferred to an autoclave, to which is added a solution of 2.3 g of boric acid in 1 liter of a 1.5% solution of nitric acid, having a pH of 1.4. The autoclave is heated to 150 ° C and held for 12 hours. Next, the autoclave is cooled to room temperature and the resulting suspension is dried on a spray dryer at an air inlet temperature of 155 ° C and the suspension is continuously stirred, and the dried powder is collected in the receiving tank of the dryer. A weighed 150 g of powder is placed in a mixer trough with Z-shaped blades, peptized with 2.5% aqueous ammonia solution, and then extruded at a pressure of 60.0 MPa, through a spinneret, which provides particles with a trefoil section with a diameter of circumscribed 1.6 mm. Molded granules are dried at a temperature of 120 ° C and calcined at a temperature of 550 ° C. The result is a carrier containing, by weight. %: aluminum borate Al ₃ BO ₆ with the structure of norbergite - 5.0; γ-Al ₂ O ₃ - the rest.

Next, prepare a solution of the bimetallic complex compound [Co (H ₂ O) ₂ (C ₆ H ₅ O ₇ )] ₂ [Mo ₄ O ₁₁ (C ₆ H ₅ O ₇ ) ₂ ], for which successively in 100 ml of distilled water with stirring 73.3 g of citric acid C ₆ H ₈ O _{7 are} dissolved; 89.87 g of ammonium paramolybdate (NH ₄ ) ₆ Mo ₇ O ₂₄ x4H ₂ O and 30.1 g of cobalt (II) carbonate basic aqueous CoCO ₃ ⋅mCo (OH) ₂ ⋅nH ₂ O. After complete dissolution of all components, the addition distilled water volume of the solution is adjusted to 200 ml. 100 g of the obtained carrier is impregnated according to the capacity of 67 ml of a solution of the bimetallic complex compound [Co (H ₂ O) ₂ (C ₆ H ₅ O ₇ )] ₂ [Mo ₄ O ₁₁ (C ₆ H ₅ O ₇ ) ₂ ] at 20 ° С within 60 minutes. Then the catalyst is dried in air at 100 ° C.

The catalyst contains, by weight. %: [Co (H ₂ O) ₂ (C ₆ H ₅ O ₇ )] ₂ [Mo ₄ O ₁₁ (C ₆ H ₅ O ₇ ) ₂ ] - 38.4 carrier — the rest; while the media contains, by weight. %: aluminum borate Al ₃ BO ₆ with the structure of norbergite - 5.0; γ-Al ₂ O ₃ - the rest.

The catalyst has a specific surface area of 150 m ² / g, a pore volume of 0.55 cm ³ / g, an average pore diameter of 13 nm, and consists of particles with a trefoil-shaped cross-section with a diameter of 1.6 mm and a length of 20 mm. The catalyst part of the aluminum borate Al ₃ BO ₆ with the structure of norbergite is particles with sizes from 10 to 200 nm, characterized by interplanar distances of 3.2 and 2.8 A, with an angle of 53.8 ° between them.

Next, the catalyst is sulfided by one of the known methods. In this case, the catalyst is sulfided with a straight-run diesel fraction containing an additional 1.5 wt. % sulfiding agent - dimethyl disulfide (DMDS), when the flow rate of the sulfiding mixture is 2 h ^-1 and the ratio of hydrogen / raw materials = 300 at a temperature not exceeding 340 ° C. The result is a catalyst that contains, wt. %: Mo - 12.5; Co — 3.85; S - 8.3; carrier - the rest; while the media contains, by weight. %: aluminum borate Al ₃ BO ₆ with the structure of norbergite - 5.0; γ-Al ₂ O ₃ - the rest.

Next, the catalyst is tested in the Hydrotreating mixed diesel fuel prepared by mixing, about. % - 87 - straight-run diesel fraction; 11 - light catalytic cracking gas oil, 2 - light delayed coking gas oil. The raw material contains 0.374% sulfur, 200 ppm nitrogen, has a density of 0.866 g / cm ³ , boiling range 186-360 ° С, T ₉₅ - 350 ° С. Hydrotreating conditions: the volumetric feed rate is 2.5 h ^-1 , the ratio of H ₂ / raw materials = 500 nm ³ H ₂ / m ³ raw materials, pressure of 3.8 MPa, the starting temperature of 350 ° C. Then the temperature jumped up to 10 ° С per day up to 370 ° С. In case of failure to reach the residual sulfur content in the resulting diesel fuel of 10 ppm at 370 ° C, the temperature jumped at 1 ° C to a value at which the residual sulfur content in the hydrotreating product became 10 ppm.

The results of catalyst testing in hydrotreating are given in the table.

Examples 2-5 illustrate the proposed technical solution.

Example 2

The media is prepared as in example 1. The result is a media containing, by weight. %: aluminum borate Al ₃ BO ₆ with the structure of norbergite - 5.0; γ-Al ₂ O ₃ - the rest.

Next, prepare a solution containing cobalt molybdenum citrate salt [Co (H ₂ O) ₂ (C ₆ H ₅ O ₇ )] ₂ [Mo ₄ O ₁₁ (C ₆ H ₅ O ₇ ) ₂ ] and the cobalt diphosphate pentamolybdate Co ₂ [ H ₂ P ₂ Mo ₅ O ₂₃ ]. To this end, 2.23 ml of an 85% orthophosphoric acid solution, 9.6 g of citric acid C ₆ H ₈ O _{7 are} dissolved in 30 ml of distilled water with stirring; 23.17 g of ammonium paramolybdate (NH ₄ ) ₆ Mo ₇ O ₂₄ x4H ₂ O and 6.8 g of cobalt (II) carbonate basic aqueous CoCO ₃ ⋅mCo (OH) ₂ ⋅nH ₂ O. After complete dissolution of all components, the addition distilled water volume of the solution was adjusted to 67 ml. The resulting solution contains 18.83 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 16.75 g Co ₂ [H ₂ P ₂ Mo ₅ O ₂₃ ]. 100 g of the carrier is impregnated on capacity of 67 ml of a solution of bimetallic 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 ] at 20 ° C for 60 minutes. Then the catalyst is dried in air at 100 ° C for 4 hours

The catalyst contains, by weight. %: [Co (H ₂ O) ₂ (C ₆ H ₅ O ₇ )] ₂ [Mo ₄ O ₁₁ (C ₆ H ₅ O ₇ ) ₂ ] - 13.9; Co ₂ [H ₂ P ₂ Mo ₅ O ₂₃ ] - 12.4; carrier - the rest; while the media contains, by weight. %: aluminum borate Al ₃ BO ₆ with the structure of norbergite - 5.0; γ-Al ₂ O ₃ - the rest. The catalyst has a specific surface area of 180 m ² / g, a pore volume of 0.65 cm ³ / g, an average pore diameter of 12 nm, and is a trefoil-shaped particle with a circumferential diameter of 1.6 mm and a length of up to 20 mm.

After sulphidation, as in Example 1, a catalyst was obtained which contains wt. %: Mo - 10.0; Co — 2.7; P-0.8; S — 6.7; carrier - the rest; while the media contains, by weight. %: aluminum borate Al ₃ BO ₆ with the structure of norbergite - 5.0; γ-Al ₂ O ₃ - the rest.

The results of catalyst testing in hydrotreating are given in the table.

Example 3

Prepare the carrier according to the method similar to example 2, with the difference that the washed and pressed pellet is transferred to an autoclave, to which is added a solution of 5.98 g of boric acid in 1 liter of 1.5% aqueous solution of nitric acid. Granulation is carried out through a spinneret, which provides particles with a trefoil-shaped cross-section with a circumference of 1.3 mm. The remaining operations and loading components in the preparation of the carrier are similar to examples 1 and 2.

The result is a carrier containing wt. %: aluminum borate Al ₃ BO ₆ with the structure of norbergite - 12.0; γ-Al ₂ O ₃ - the rest.

Next, prepare a solution containing cobalt molybdenum citrate salt [Co (H ₂ O) ₂ (C ₆ H ₅ O ₇ )] ₂ [Mo ₄ O ₁₁ (C ₆ H ₅ O ₇ ) ₂ ] and the cobalt diphosphate pentamolybdate Co ₂ [ H ₂ P ₂ Mo ₅ O ₂₃ ]. To this end, 2.92 ml of an 85% orthophosphoric acid solution, 11.3 g of citric acid C ₆ H ₈ O _{7 are} successively dissolved in 30 ml of distilled water with stirring; 29.35 g of ammonium paramolybdate (NH ₄ ) ₆ Mo ₇ O ₂₄ x4H ₂ O and 8.54 g of cobalt (II) carbonate basic aqueous CoCO ₃ ⋅mCo (OH) ₂ ⋅nH ₂ O. After complete dissolution of all components, the addition distilled water volume of the solution was adjusted to 67 ml.

100 g of the carrier is impregnated on capacity of 67 ml of a solution of bimetallic 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 ] at 50 ° C for 25 min. Then the catalyst is dried in air at 150 ° C for 2 hours

The catalyst contains, by weight. %: [Co (H ₂ O) ₂ (C ₆ H ₅ O ₇ )] ₂ [Mo ₄ O ₁₁ (C ₆ H ₅ O ₇ ) ₂ ] - 15.4; Co ₂ [H ₂ P ₂ Mo ₅ O ₂₃ ] - 15.3; carrier - the rest; while the media contains, by weight. %: aluminum borate Al ₂ BO ₆ with the structure of norbergite - 12.0; γ-Al ₂ O ₃ - the rest. The catalyst has a specific surface area of 150 m ² / g, a pore volume of 0.55 cm ³ / g, an average pore diameter of 11 nm, and consists of particles with a trefoil-shaped cross-section with a diameter of 1.3 mm and a circumscribed circumference of up to 20 mm.

After sulphidation, as in Example 1, a catalyst was obtained which contains wt. %: Mo - 12.0; Co — 3.2; P-1.0; S - 8.1; carrier - the rest; while the media contains, by weight. %: aluminum borate Al ₃ BO ₆ with the structure of norbergite - 12.0; γ-Al ₂ O ₃ - the rest.

The results of catalyst testing in hydrotreating are given in the table.

Example 4

Prepare the carrier according to the method similar to example 2, with the difference that the washed and pressed pellet is transferred to an autoclave, to which is added a solution of 14.63 g of boric acid in 1 l of a 1.5% solution of nitric acid. Granulation is carried out through a die, providing particles with a cross section in the form of a circle with a diameter of 1.0 mm. The remaining operations and loading components in the preparation of the carrier are similar to examples 1 and 2.

The result is a carrier containing wt. %: aluminum borate Al ₃ BO ₆ with the structure of norbergite - 25.0; γ-Al ₂ O ₃ - the rest.

Next, prepare a solution containing cobalt molybdenum citrate salt [Co (H ₂ O) ₂ (C ₆ H ₅ O ₇ )] ₂ [Mo ₄ O ₁₁ (C ₆ H ₅ O ₇ ) ₂ ] and the cobalt diphosphate pentamolybdate Co ₂ [ H ₂ P ₂ Mo ₅ O ₂₃ ]. To do this, in 30 ml of distilled water with stirring and heating to 70 ° C, 6.05 ml of an 85% solution of orthophosphoric acid, 6.22 g of citric acid C ₆ H ₈ O _{7 are} successively dissolved; 44.9 g of ammonium paramolybdate (NH ₄ ) ₆ Mo ₇ O ₂₄ x4H ₂ O and 10.46 g of cobalt (II) carbonate basic aqueous CoCO ₃ ⋅mCo (OH) ₂ ⋅nH ₂ O. After complete dissolution of all components, the addition distilled water volume of the solution is adjusted to 65 ml.

100 g of carrier are impregnated with a capacity of 65 ml of a solution of bimetallic 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 ] at 70 ° C for 45 min. Then the catalyst is dried in air at 200 ° C for 2 hours.

The catalyst contains, by weight. %: [Co (H ₂ O) ₂ (C ₆ H ₅ O ₇ )] ₂ [Mo ₄ O ₁₁ (C ₆ H ₅ O ₇ ) ₂ ] - 7.7; Co ₂ [H ₂ P ₂ Mo ₅ O ₂₃ ] - 29.0; carrier - the rest; while the media contains, by weight. %: aluminum borate Al ₃ BO ₆ with the structure of norbergite - 25.0; γ-Al ₂ O ₃ - the rest. The catalyst has a specific surface of 140 m ² / g, a pore volume of 0.45 cm ³ / g, an average pore diameter of 9 nm, and is a particle with a cross section in the form of a circle with a diameter of 1.0 mm and a length of up to 20 mm.

After sulphidation, as in Example 1, a catalyst was obtained which contains wt. %: Mo - 16.0; Co — 4.1; P-1,8; S - 10.7; carrier - the rest; while the media contains, by weight. %: aluminum borate Al ₃ BO ₆ with the structure of norbergite - 25.0; γ-Al ₂ O ₃ - the rest.

The results of catalyst testing in hydrotreating are given in the table.

Example 5

Prepare the media according to the method similar to example 3, with the difference that the granulation is carried out through the die plate, providing particles with a cross section in the form of a quatrefoil with a circumferential diameter of 1.6 mm. The remaining operations and loading components in the preparation of media similar to example 3.

Next, prepare a solution containing cobalt molybdenum citrate salt [Co (H ₂ O) ₂ (C ₆ H ₅ O ₇ )] ₂ [Mo ₄ O ₁₁ (C ₆ H ₅ O ₇ ) ₂ ] and the cobalt diphosphate pentamolybdate Co ₂ [ H ₂ P ₂ Mo ₅ O ₂₃ ]. To this end, 2.59 ml of an 85% orthophosphoric acid solution, 28.8 g of citric acid C ₆ H ₈ O _{7 are} successively dissolved in 30 ml of distilled water with stirring and heating to 70 ° C; 43.3 g of ammonium paramolybdate (NH ₄ ) ₆ Mo ₇ O ₂₄ x4H ₂ O and 13.33 g of cobalt (II) carbonate basic aqueous CoCO ₃ ⋅mCo (OH) ₂ ⋅nH ₂ O. After complete dissolution of all components, the addition distilled water volume of the solution was adjusted to 67 ml.

100 g of the carrier is impregnated on capacity of 67 ml of a solution of bimetallic 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 ] at 70 ° C for 30 min. Then the catalyst is dried in air at 120 ° C for 4 hours

The catalyst contains, by weight. %: [Co (H ₂ O) ₂ (C ₆ H ₅ O ₇ )] ₂ [Mo ₄ O ₁₁ (C ₆ H ₅ O ₇ ) ₂ ] - 32.0; Co ₂ [H ₂ P ₂ Mo ₅ O ₂₃ ] - 11.1; carrier - the rest; while the media contains, by weight. %: aluminum borate Al ₃ BO ₆ with the structure of norbergite - 12.0; γ-Al ₂ O ₃ - the rest. The catalyst has a specific surface of 120 m ² / g, a pore volume of 0.35 cm ³ / g, an average pore diameter of 7 nm, and consists of particles with a four-leaf shape with a diameter of 1.6 mm and a circumscribed circle up to 20 mm.

After sulphidation, as in Example 1, a catalyst was obtained which contains wt. %: Mo - 16.0; Co — 4.5; P-0.8; S - 10.8; carrier - the rest; while the media contains, by weight. %: aluminum borate Al ₃ BO ₆ with the structure of norbergite - 25.0; γ-Al ₂ O ₃ - the rest.

The results of catalyst testing in hydrotreating are given in the table.

Thus, as can be seen from the above examples, the proposed catalyst, due to its chemical composition, has a high desulfurizing and diazotizing activity, significantly exceeding the activity of the prototype catalyst in hydrotreating diesel fuel.

Claims (3)

1. The catalyst for Hydrotreating diesel fuel, comprising in its composition compounds of cobalt, molybdenum, phosphorus and the carrier, characterized in that it contains, by weight. %: [Co (H ₂ O) ₂ (C ₆ H ₅ O ₇ )] ₂ [Mo ₄ O ₁₁ (C ₆ H ₅ O ₇ ) ₂ ] - 7.7-32.0; CO ₂ [H ₂ P ₂ Mo ₅ O ₂₃ ] - 11.1-29.0; carrier - the rest; while the media contains, by weight. %: aluminum borate Al ₃ BO ₆ with the structure of norbergite - 5.0-25.0; γ-Al ₂ O ₃ - the rest. 2. The catalyst according to claim 1, characterized in that it has a specific surface of 120-190 m ² / g, a pore volume of 0.35-0.65 cm ³ / g, an average pore diameter of 7-12 nm and represents particles with section in the form of a circle, a trefoil or a four-leaf with a circumferential diameter of 1.0-1.6 mm and a length of up to 20 mm. 3. The catalyst according to claim 1, characterized in that after sulfidization it contains, by weight. %: Mo - 10.0-16.0; Co - 2.7-4.5; P - 0.8-1.8; S - 6.7-10.8; carrier - the rest; while the media contains, by weight. %: aluminum borate Al ₃ BO ₆ with the structure of norbergite - 5.0-25.0; γ-Al ₂ O ₃ - the rest.