RU2626398C1 - Catalyst for hydrotreating hydrocarbon raw materials - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: catalyst is described containing, wt %: [Co(H₂O)₂(C₆H₅O₇)]₂[Mo₄O₁₁(C₆H₅O₇)₂] 33.0-43.0%; carrier - the rest; the carrier comprising, wt %: aluminium borate Al₃BO₆ with the structure of norbergite - 5.0-25.0; sodium - not more than 0.03; γ-Al₂O₃ - the rest. The aluminium borate Al₃BO₆ with the structure of norbergite is a particle with dimensions of 10 to 200 nm, characterized by interplanar distances of 3.2 and 2.8 A, with an angle between them of 53.8°. The catalyst has a specific surface area of 130-180 m²/g, a pore volume of 0.35-0.65 cm³/g, the average pore diameter is 7-12 nm and is particles with a section in the form of a circle, trefoil or quatrefoil with a diameter of the circumscribed circle of 1.0-1.6 mm and the length of up to 20 mm. After sulphiding by the known techniques, the catalyst contains, wt %: Mo - 10.0-14.0; Co - 3.0-4.3; S = 6.7-9.4; carrier - the rest.

EFFECT: producing a catalyst having maximum activity in target reactions occurring when hydrocarbon material is hydrotreated.

4 cl, 1 tbl, 7 ex

Description

The invention relates to hydrotreating catalysts for the production of low sulfur oil products.

At present, Russian refineries have switched to the production of motor fuels that, in terms of residual sulfur content, meet the new Russian and European standards [GOST R 52368-2005. (EN 590-2004). Diesel fuel EURO. Technical conditions; GOST R 51866-2002. (EN 228-1999). Unleaded gasoline.]. Since the existing brands of Russian catalysts do not allow drastically reducing the sulfur content in the products obtained without tightening the conditions for the hydrotreatment process, it is extremely urgent to create new catalysts that allow obtaining motor fuels with a low residual sulfur content under the conditions of the processes carried out at Russian oil refineries without them radical reconstruction.

Various supported catalysts for hydrotreating hydrocarbons are known, but a common disadvantage for them is the high residual sulfur content in the resulting products.

Most often, catalysts containing cobalt and molybdenum oxides supported on alumina are used to carry out hydrodesulfurization of petroleum feedstocks. So known catalyst hydrodesulfurization [RF Application No. 2002124681, C10G 45/08, B01J 23/887, 09/16/2002], 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 wt. %, the rest is aluminum oxide, the specific surface is 160-250 m ² / g, the mechanical crushing strength is 0.6-0.8 kg / mm ² . In this case, the hydrotreating process is carried out at a temperature of 310-340 ° C, a pressure of 3.0-5.0 MPa, with a hydrogen / feed ratio of 300-500 nm ³ / m ³ and a bulk feed rate of 1.0-4.0 h ^{- 1} . The main disadvantage of such a hydrotreating catalyst is the high sulfur content in the resulting products.

Reducing the residual sulfur content in the resulting petroleum products is achieved by using catalysts with increased activity. Previously, hydrotreating catalysts were most often prepared by wet mixing of aluminum hydroxide with compounds of active metals, followed by molding, drying and calcination. Such catalysts are described in RF patents No. 1774555, 2073566, 2103065, 2137541, 2147256, 2189860, 2271861. A common disadvantage for these catalysts is the low activity in hydrotreating.

In recent years, the method of depositing active metals on an already formed support has been used to prepare hydrotreating catalysts. As a carrier, alumina with a certain size and shape of granules and certain texture characteristics is most often used. The carrier is often modified with various additives, including boron compounds. At the same time, modifying additives are introduced into the carrier either before the stage of its formation, by coprecipitation of 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 preparation of paste for molding [ US No. 6147432], or introduce the additive by impregnation into a molded carrier, followed by drying and calcination [Catalysis Today 107-108 (2005) 551-558].

The introduction of active metals, most often Co, Ni, Mo, and W, into the composition of the catalyst is carried out by impregnating the formed support with aqueous solutions of their salts. Moreover, they can be used as separate deposition of active metals by impregnation in several stages [RF No. 2242501, 2246987], and their application from joint solutions stabilized by various agents [RF No. 2073567, 2216404, 2306978].

In order to increase the hydrodesulfurization activity of the catalysts, a carrier with improved texture 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 centers of the catalyst . So, the known catalyst [RF No. 2192923, C10G 45/08, B01J 27/188, B01J 35/10, 11/20/2002] 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 About 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 catalyst for hydrotreating oil fractions [RF No. 2286846, 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 a diesel fraction [RF No. 2313392, B01J 37/02, B01J 21/02, C10G 45/08, 10/13/2006], having a pore volume of 0.3-0.7 ml / g, a specific surface area of 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 various stoichiometry.

A common disadvantage for the above catalysts is that with their use it is not possible to achieve a low residual sulfur content in the resulting products.

Closest to the proposed technical solution is described in [Pat. RF №2472585, B01J 23/882, 01/20/2013] a catalyst 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 carrier contains, by weight. %: B - 0.7-3.0; Al ₂ O ₃ - the rest and has a specific surface area 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 the diameter of the circumference described is 1.0-1.6 mm and a length of up to 20 mm, having a mechanical strength of 2.0-2.5 kg / mm.

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

The present invention solves the problem of creating an improved hydrotreating catalyst, characterized by:

1. The optimal chemical composition of the catalyst, the carrier of which contains as a component that determines the catalytic properties of aluminum borate Al ₃ BO ₆ with the structure of norbergite with a concentration of 5.0-25.0 wt. % This component provides a level of acidity that helps minimize undesirable chemical interaction between active metals (Co and Mo) and the support, and selectively produces the most active sulfide component in hydrotreatment — Co (Ni) MoS type II phase.

2. Optimum texture characteristics due to the presence in the catalyst of aluminum borate particles Al ₃ BO ₆ with a norbergite structure, which are particles with sizes from 10 to 200 nm, contributing to the preparation of a support and catalyst, the pore volume and size of which provide access to all raw materials to be converted to the active component.

EFFECT: obtaining a catalyst having maximum activity in the target reactions occurring during hydrotreatment of hydrocarbon feedstocks.

The problem is solved by a catalyst for hydrotreatment 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 ] 33.0-43.0%; the carrier is the rest; wherein the carrier contains, by weight. %: aluminum borate Al ₃ BO ₆ with norbergite structure - 5.0-25.0; sodium - not more than 0.03; γ-Al ₂ O ₃ - the rest. In this case, the aluminum borate catalyst Al ₃ BO ₆ with the structure of norbergite, which is part of the catalyst, is a particle with sizes from 10 to 200 nm, characterized by interplanar distances of 3.2 and 2.8 A, with an angle between them of 53.8 °.

The catalyst has a specific surface area 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, trefoil or four-leaf with the diameter described circumference 1.0-1.6 mm and a length of up to 20 mm.

After sulfidation by known methods, it contains, by weight. %: Mo - 10.0-14.0; Co - 3.0-4.3; S 6.7-9.4; the carrier is the rest; wherein the carrier contains, by weight. %: aluminum borate Al ₃ BO ₆ with norbergite structure - 5.0-25.0; sodium - not more than 0.03; γ-Al ₂ O ₃ - 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 ) ₂ (C ₆ H ₅ O ₇ )] ₂ [Mo ₄ O ₁₁ (C ₆ H ₅ O ₇ ) ₂ ] 33.0-43.0%; the carrier is the rest; wherein the carrier contains, by weight. %: aluminum borate Al ₃ BO ₆ with norbergite structure - 5.0-25.0; sodium - not more than 0.03; γ-Al ₂ O ₃ - the rest. The output of the content of the catalyst components over 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 area 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 represents particles with a cross section in the form of a circle, trefoil or four-leaf with a diameter of the circumscribed circle of 1.0-1.6 mm and a length of up to 20 mm.

The third distinctive feature of the proposed catalyst in comparison with the prototype is that the aluminum borate Al ₃ BO ₆ with the norbergite structure included in the composition is particles with sizes from 10 to 200 nm, characterized by interplanar distances of 3.2 and 2.8 A, with an angle between them of 53.8 °.

The technical result consists of the following components:

1. The inventive chemical composition of the catalyst determines the maximum activity in the target reactions occurring during hydrotreatment of hydrocarbons. The presence in the composition of the aluminum borate catalyst Al ₃ BO ₆ with a norbergite structure with the claimed concentration provides an acidity level that minimizes the undesirable chemical interaction between the active metals (Co and Mo) and the support, and selectively produces the most active sulfide component in the hydrotreatment - CoMoS type II phase .

2. The presence in the composition of the catalyst of aluminum borate Al ₃ BO ₆ with a norbergite structure consisting of particles with sizes from 10 to 200 nm, characterized by interplanar distances of 3.2 and 2.8 A, with an angle between them of 53.8 °, helps to achieve texture characteristics of the catalyst that provide access to all the conversion of raw materials molecules to the active component.

3. The presence in the composition of the catalyst of the 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 ] provides further formation in the catalyst, when it operation in hydrotreating, the most active component is CoMoS type II phase in the form of particles optimal for catalysis morphology, localized in raw materials accessible to all molecules to be converted.

Description of the proposed technical solution.

A support is prepared containing aluminum borate Al ₃ BO ₆ with the structure of norbergite and γ-Al ₂ O ₃ .

Take a portion of the product of thermal activation of hydrargillite (PTAG) prepared by centrifugal thermal activation technology (IC SB RAS, TU 2175-040-03533913-2007), or any other technology providing PTAG with the following characteristics: mass fraction of the X-ray amorphous phase,%, not less than 80; fraction of weight loss during calcination at (900 ± 20) ° C,% - 10-12; specific surface, m ² / g, not less than 120; total pore volume (moisture 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 crushed in a planetary mill to particles with an average size of 20 microns.

A weighed portion of the ground powder is hydrated with stirring for two hours in weakly concentrated nitric acid solutions heated to 50 ° C (acid module 0.03). Then the resulting suspension is filtered under vacuum and washed repeatedly with distilled water. The result is a wet cake. Hydrothermal treatment of the washed precipitate is carried out in an autoclave in aqueous nitric acid solutions with the addition of a predetermined 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 unloaded, the contents of the vessel are repulped with distilled water to obtain a suspension suitable for spray drying. Next, drying is carried out on a spray dryer at an air temperature of 280 ° C at the inlet of the dryer and the suspension is continuously stirred. The finished powder of boron-containing aluminum hydroxide is discharged from a glass of a cyclone dust collector of a spray dryer.

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

The finished plastic mass is loaded from the mixer into the molding cylinder of the laboratory extruder and pressed through the hole of the die, providing extrudates of the finished carrier with a cross-section in the shape of a circle, trefoil or four-leaf with a size from the top of the trefoil to the middle of the base from 1.0 to 1.6 mm.

Then heat treatment of the extrudates is carried out, including drying and calcining. Extrudates are dried in an oven at a temperature of (110 ± 10) ° C for 2 hours. Heat treatment is carried out in a muffle furnace with compressed air supplied to the furnace. The extra dates in a porcelain cup were placed in an oven and calcined at a temperature of (550 ± 10) ° C for 4 hours.

The finished carrier contains, by weight. %: aluminum borate Al ₃ BO ₆ with norbergite structure - 5.0-25.0; sodium - not more than 0.03; γ-Al ₂ O ₃ - the rest, and has a specific surface area 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 is a particle with a cross section of in the form of a circle, a trefoil or a four-leaf with a diameter of the circumscribed circle of 1.0-1.6 mm and a length of up to 20 mm.

The aluminum borate Al ₃ BO ₆ included in the support with the norbergite structure is a particle with sizes from 10 to 200 nm, characterized by interplanar distances of 3.2 and 2.8 A, with an angle between them of 53.8 °.

Using this support, a supported catalyst is prepared. First, an impregnation solution is prepared containing 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 ]. To do this, the specified amounts of ammonium paramolybdate (NH ₄ ) ₆ Mo ₇ O ₂₄ ⋅ 4H ₂ O, cobalt (II) of the main carbonate CoCO ₃ ⋅mCo (OH) ₂ ⋅nH ₂ O, and citric acid monohydrate are weighed out. A measured cylinder measures the specified amount of distilled water. A measured amount of water is poured into the flask and the anchor of the 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 60 ° C. The metered amount of citric acid is charged into the flask and mixed under visual inspection. Then, a weighed portion of ammonium paramolybdate is added to the solution of citric acid with constant stirring and maintaining the temperature of the solution (60 ± 5) ° C. The solution is stirred until a uniform transparent solution is obtained containing the complex compound molybdenum (VI) citrate (NH ₄ ) ₄ [Mo ₄ (C ₆ H ₅ O ₇ ) ₂ O ₁₁ ]. A portion of cobalt (II) basic carbonate is added to the previously prepared aqueous solution of molybdenum (VI) citrate. In this case, the liquid foams, and its temperature rises to 70 ° C. Stirring is continued at (65-70) ° C until a homogeneous clear dark cherry solution is obtained that does not contain turbidity, 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 ].

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

The resulting solution is impregnated with a boron-containing support, and either the impregnation of the support by moisture capacity or from excess solution is used. The impregnation is carried out at a temperature of 15-90 ° C for 5-60 minutes with periodic stirring, in the case of impregnation from the excess solution after impregnation, the excess solution is drained from the catalyst and used to prepare the following batches of catalyst. After impregnation, the catalyst is dried in air at a temperature of 100-200 ° C.

As a result, a catalyst is obtained containing [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%; the carrier is the rest; wherein the carrier contains, by weight. %: aluminum borate Al ₃ BO ₆ with norbergite structure - 5.0-25.0; sodium - not more than 0.03; γ-Al ₂ O ₃ - the rest. In this case, the aluminum borate catalyst Al ₃ BO ₆ with the structure of norbergite, which is part of the catalyst, is a particle with sizes from 10 to 200 nm, characterized by interplanar distances of 3.2 and 2.8 A, with an angle between them of 53.8 °.

After sulfidation by known methods, the catalyst contains wt. %: Mo - 10.0-14.0; Co - 3.0-4.3; S 6.7-9.4; the carrier is the rest; wherein the carrier contains, by weight. %: aluminum borate Al ₃ BO ₆ with norbergite structure - 5.0-25.0; sodium - not more than 0.03; γ-Al ₂ O ₃ - the rest.

The invention is illustrated by the following examples.

Example 1

According to the known decision [Pat. RF №2472585]

, со средним размером агломератов 30-40 мкм, содержащего примеси в количестве, мас. %, не более: Na₂O - 0,002; Fe₂O₃ - 0,01; SiO₂ - 0,015 при непрерывном перемешивании в смесителе с Z-образными лопастями добавляют 3 мл концентрированной азотной кислоты, 80 мл водного раствора, содержащего 7 г оксида бора В₂О₃ и 5 г кислородсодержащих соединений, в качестве которых используют смесь 2,5 г триэтиленгликоля и 2,5 г пентаэритрита. Весовые отношения компонентов смеси - гидроксид алюминия : вода : азотная кислота : оксид бора : кислородсодержащие соединения =1:0,8:0,03:0,07: 0,05.To 100 g of AlOOH aluminum hydroxide powder having a boehmite structure with a crystal size of 45-60

, with an average agglomerate size of 30-40 microns, containing impurities in an amount, wt. %, no more: Na ₂ O - 0.002; Fe ₂ O ₃ - 0.01; SiO ₂ - 0.015 with continuous stirring in a mixer with Z-shaped blades add 3 ml of concentrated nitric acid, 80 ml of an aqueous solution containing 7 g of boron oxide B ₂ About ₃ and 5 g of oxygen-containing compounds, which use a mixture of 2.5 g triethylene glycol and 2.5 g of pentaerythritol. The weight ratio of the components of the mixture is aluminum hydroxide: water: nitric acid: boron oxide: oxygen-containing compounds = 1: 0.8: 0.03: 0.07: 0.05.

The resulting paste is stirred at 95 ° C for 10 min, then formed through a die with a cross section in the form of a trefoil with a diameter of the circumscribed circle of 1.6 mm at a pressure of 0.5 MPa. The obtained granules are dried in an oven at 150 ° C for 2 hours, then calcined at 600 ° C for 4 hours.

The result is a carrier containing In - 3.0 wt. %, Al ₂ O ₃ - the rest; having a specific surface area of 300 m ² / g, a pore volume of 0.5 cm ³ / g, an average pore diameter of 7 nm, representing particles with a cross section in the form of a trefoil with a diameter of the circumscribed circle of 1.0 mm, a length of up to 20 mm, having mechanical strength 2.0 kg / mm.

Next, a bimetallic compound corresponding to the formula [Co (H ₂ O) ₂ (C ₆ H ₅ O ₇ )] ₂ [Mo ₄ O ₁₁ (C ₆ H ₅ O ₇ ) ₂ ] is synthesized in solution, for which 70 ml of distilled water with stirring, 53.5 g of citric acid C ₆ H ₈ O ₇ , 71.0 g of ammonium paramolybdate (NH ₄ ) ₆ Mo ₇ O ₂₄ × 4H ₂ O, 17.3 g of cobalt hydroxide Co (OH) ₂ , 7 are successively dissolved , 5 g of ethylene glycol dimethyl ether. Next, by adding distilled water, the solution volume is adjusted to 150 ml.

20 g of the obtained carrier are impregnated with a moisture capacity of 10 ml of a solution containing 7.6 g of a bimetallic compound of the composition [Co (H ₂ O) ₂ (C ₆ H ₅ O ₇ )] ₂ [Mo ₄ O ₁₁ (C ₆ H ₅ O ₇ ) ₂ ] and 0.5 g of ethylene glycol dimethyl ether. The catalyst was dried in air at 250 ° C for 2 hours and sulfidized according to one of the known methods. In this case, the catalyst is sulfidated by straight-run diesel fraction containing an additional 1.5 wt. % sulfidizing agent - dimethyldisulfide (DMDS), with a volumetric feed rate of sulfidizing mixture of 2 h ^-1 and a hydrogen / feed ratio = 300 according to the following program:

- drying the catalyst in a hydrotreatment reactor in a stream of hydrogen at 140 ° C for 2 hours;

- wetting the catalyst straight run diesel fraction for 2 hours;

- supply of a sulfidizing mixture and an increase in temperature to 240 ° C with a rate of temperature rise of 25 ° C / h;

- sulfidation at a temperature of 240 ° C for 8 hours (low temperature stage);

- an increase in the temperature of the reactor to 340 ° C with a rate of temperature rise of 25 ° C / h;

sulfidation at a temperature of 340 ° C for 8 hours

The resulting catalyst contains, by weight. %: Mo - 8.0; Co - 2.0; S is 5.0; B - 2.0; C is 0.5; Al ₂ O ₃ - the rest.

The catalyst is tested in hydrotreating diesel fuel containing 0.32% sulfur, 200 ppm nitrogen, having a density of 0.847 g / cm ³ , a boiling range of 210-360 ° C, T ₉₅ - 352 ° C. Hydrotreating conditions: a volumetric feed rate of 2.5 h ^-1 , a ratio of H ₂ / feed = 500 nm ³ H ₂ / m ^{3 of} feed, a pressure of 3.8 MPa, a temperature of 350 ° C.

The catalyst is also tested in hydrotreating a vacuum gas oil.

Hydrotreating of vacuum gas oil (3.0% sulfur, 1200 ppm nitrogen, KK 560 ° C) is carried out at 370 ° C, a pressure of 9.0 MPa, a mass flow rate of vacuum gas oil of 1 h ^-1 , a volume ratio of hydrogen / feedstock of 500.

The test results of the catalyst in hydrotreatment are shown in the table.

Examples 2-7 illustrate the proposed technical solution.

Example 2

First, a carrier is prepared, for which 150 g of the product of thermal activation of hydrargillite is crushed in a planetary mill to particles ranging in size from 20-50 microns. Next, the powder is hydrated with stirring and heating 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 to a residual sodium content in the powder of not more than 0.03%. The washed and pressed cake is transferred to an autoclave, to which 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 is added. The autoclave is heated to 150 ° C and held for 12 hours. Next, the autoclave is cooled to room temperature and the suspension obtained is dried on a spray dryer at an air temperature at the inlet of the dryer 155 ° C and the suspension is continuously stirred, the dried powder is collected in the receiving tank of the dryer. A sample of 150 g of powder is placed in a trough of a mixer with Z-shaped blades, peptized with a 2.5% aqueous solution of ammonia, and then extruded at a pressure of 60.0 MPa through a die, providing particles with a cross section in the form of a trefoil with a diameter of the circumference described 1.6 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, by weight. %: aluminum borate Al ₃ BO ₆ with the structure of norbergite - 5.0; sodium - 0.03; γ-Al ₂ O ₃ - the rest.

Next, 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 ] is prepared, for which in 100 ml of distilled water with stirring successively 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 × 4H ₂ O and 30.1 g of cobalt (II) carbonic basic aqueous CoCO ₃ ⋅mCo (OH) ₂ ⋅nH ₂ O. After complete dissolution of all components, By adding distilled water, the solution volume is adjusted to 200 ml. 100 g of the obtained support are impregnated with a moisture 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 ° C for 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%; the carrier is the rest; wherein the carrier contains, by weight. %: aluminum borate Al ₃ BO ₆ with the structure of norbergite - 5.0; sodium - 0.03; 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 represents particles with a cross section in the form of a trefoil with a diameter of the circumscribed circle of 1.6 mm and a length of up to 20 mm. The aluminum borate catalyst Al ₃ BO ₆ with the structure of norbergite, which is a part of the catalyst, consists of particles with sizes from 10 to 200 nm, characterized by interplanar distances of 3.2 and 2.8 A, with an angle between them of 53.8 °.

Next, the catalyst is sulfidized analogously to example 1. The result is a catalyst that contains, by weight. %: Mo - 12.5; Co - 3.85; S is 8.3; the carrier is the rest; wherein the carrier contains, by weight. %: aluminum borate Al ₃ BO ₆ with the structure of norbergite - 5.0; sodium - 0.03; γ-Al ₂ O ₃ - the rest.

Next, carry out hydrotreating of hydrocarbon feeds analogously to example 1.

The test results of the catalyst in hydrotreatment are shown in the table.

Example 3

The carrier is prepared according to a method similar to Example 2, with the difference that the washed and pressed cake is transferred to an autoclave, to which a solution of 5.98 g of boric acid in 1 liter of a 1.5% solution of nitric acid is added. The remaining operations and loading of components in the preparation of the media are similar to example 2.

The result is a carrier containing wt. %: aluminum borate Al ₃ BO ₆ with the structure of norbergite - 12.0; sodium - 0.028; γ-Al ₂ O ₃ - the rest.

100 g of the obtained carrier are impregnated with a moisture 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 ] from Example 2. 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%; the carrier is the rest; wherein the carrier contains, by weight. %: aluminum borate Al ₃ BO ₆ with the structure of norbergite - 12.0; sodium - 0.028; γ-Al ₂ O ₃ - the rest.

Next, the catalyst is sulfidized analogously to example 1. The result is a catalyst that contains wt. %: Mo - 12.5; Co - 3.85; S is 8.3; the carrier is the rest; wherein the carrier contains, by weight. %: aluminum borate Al ₃ BO ₆ with the structure of norbergite - 12.0; sodium - 0.028; γ-Al ₂ O ₃ - the rest.

Next, carry out hydrotreating of hydrocarbon feeds analogously to example 1.

The test results of the catalyst in hydrotreatment are shown in the table.

Example 4

The carrier is prepared according to a method similar to Example 2, with the difference that the washed and pressed cake is transferred to an autoclave, to which a solution of 14.63 g of boric acid in 1 liter of a 1.5% solution of nitric acid is added. The remaining operations and loading of components in the preparation of the media are similar to example 2.

The result is a carrier containing, by weight. %: aluminum borate Al ₃ BO ₆ with the structure of norbergite - 25.0; sodium - 0.023; γ-Al ₂ O ₃ - the rest.

100 g of the obtained carrier are impregnated with a moisture capacity of 66 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 ] from Example 2. Then the catalyst is dried in air at 200 ° 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%; the carrier is the rest; wherein the carrier contains, by weight. %: aluminum borate Al ₃ BO ₆ with the structure of norbergite - 25.0; sodium - 0.023; γ-Al ₂ O ₃ - the rest.

Next, the catalyst is sulfidized analogously to example 1. The result is a catalyst that contains wt. %: Mo - 12.5; Co - 3.85; S is 8.3; the carrier is the rest; wherein the carrier contains, by weight. %: aluminum borate Al ₃ BO ₆ with the structure of norbergite - 25.0; sodium - 0.023; γ-Al ₂ O ₃ - the rest.

Next, carry out hydrotreating of hydrocarbon feeds analogously to example 1.

The test results of the catalyst in hydrotreatment are shown in the table.

Example 5

Prepare the medium according to example 3.

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 ] is prepared, for which it is successively dissolved in 100 ml of distilled water with stirring 63.27 g of citric acid C ₆ H ₈ O ₇ ; 77.58 g of ammonium paramolybdate (NH ₄ ) ₆ Mo ₇ O ₂₄ × 4H ₂ O and 26.0 g of cobalt (II) carbonic basic aqueous CoCO ₃ ⋅mCo (OH) ₂ ⋅nH ₂ O. After complete dissolution of all components, By adding distilled water, the solution volume is adjusted to 200 ml. At room temperature, 100 g of the obtained support are impregnated with a moisture 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 ]. Then the catalyst is dried in air at 120 ° 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 ] - 32.7%; the carrier is the rest; wherein the carrier contains, by weight. %: aluminum borate Al ₃ BO ₆ with the structure of norbergite - 12.0; sodium - 0.028; 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 15 nm, and represents particles with a cross section in the form of a trefoil with a diameter of the circumscribed circle of 1.6 mm and a length of up to 20 mm. The aluminum borate catalyst Al ₃ BO ₆ with the structure of norbergite, which is a part of the catalyst, consists of particles with sizes from 10 to 200 nm, characterized by interplanar distances of 3.2 and 2.8 A, with an angle between them of 53.8 °.

Next, the catalyst is sulfidized analogously to example 1. The result is a catalyst that contains, by weight. %: Mo - 10.0; Co - 3.0; S 6.7; the carrier is the rest; wherein the carrier contains, by weight. %: aluminum borate Al ₃ BO ₆ with the structure of norbergite - 12.0; sodium - 0.028; γ-Al ₂ O ₃ - the rest.

Next, carry out hydrotreating of hydrocarbon feeds analogously to example 1.

The test results of the catalyst in hydrotreatment are shown in the table.

Example 6

The carrier is prepared in the same manner as in Example 3, with the difference that the molding paste is extruded at a pressure of 60.0 MPa through a die, providing particles with a cross-section in the form of a circle with a diameter of 1.0 mm.

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 ] is prepared, for which 100 ml of distilled water is heated to 80 ° C and with stirring, 85.3 g of citric acid C ₆ H ₈ O _{7 are} successively dissolved; 104.53 g of ammonium paramolybdate (NH ₄ ) ₆ Mo ₇ O ₂₄ × 4H ₂ O and 35.05 g of cobalt (II) carbonic basic aqueous CoCO ₃ ⋅mCo (OH) ₂ ⋅nH ₂ O. After complete dissolution of all components, By adding distilled water, the solution volume is adjusted to 200 ml.

Next, impregnation of the carrier from the excess solution is used. 100 g of the obtained carrier are loaded into a flask placed in a water bath heated to 80 ° C, 200 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 ], also heated to 80 ° C. The impregnation is continued for 20 minutes with periodic stirring, after which the excess solution is separated from the wet catalyst. Then the catalyst is dried in air at 200 ° 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 ] - 42.95%; the carrier is the rest; wherein the carrier contains, by weight. %: aluminum borate Al ₃ BO ₆ with the structure of norbergite - 12.0; sodium - 0.028; γ-Al ₂ O ₃ - the rest.

The catalyst has a specific surface area of 130 m ² / g, a pore volume of 0.35 cm ³ / g, an average pore diameter of 10 nm, and represents particles 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. The aluminum borate catalyst Al ₃ BO ₆ with the structure of norbergite, which is a part of the catalyst, consists of particles with sizes from 10 to 200 nm, characterized by interplanar distances of 3.2 and 2.8 A, with an angle between them of 53.8 °.

Next, the catalyst is sulfidized analogously to example 1. The result is a catalyst that contains, by weight. %: Mo - 14.0; Co - 4.3; S 9.4; the carrier is the rest; wherein the carrier contains, by weight. %: aluminum borate Al ₃ BO ₆ with a norbergite structure of -12.0; sodium - 0.028; γ-Al ₂ O ₃ - the rest.

Next, carry out hydrotreating of hydrocarbon feeds analogously to example 1.

The test results of the catalyst in hydrotreatment are shown in the table.

Example 7

The carrier is prepared in the same way as in example 3, with the difference that the molding paste is extruded at a pressure of 60.0 MPa through a die, providing particles with a cross section in the form of a four-leaf with a diameter of 1.6 mm.

Next, impregnation of the carrier from excess solution is used. 100 g of the obtained carrier are loaded into a flask placed in a water bath heated to 30 ° C, 133 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 ] from Example 5, also heated to 30 ° C. The impregnation is continued for 60 minutes with periodic stirring, after which the excess solution is separated from the wet catalyst. Then the catalyst is dried in air at 120 ° C.

The resulting 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 ] - 35.9%; the carrier is the rest; wherein the carrier contains, by weight. %: aluminum borate Al ₃ BO ₆ with the structure of norbergite - 12.0; sodium - 0.028; γ-Al ₂ O ₃ - the rest.

The catalyst has a specific surface area of 175 m ² / g, a pore volume of 0.6 cm ³ / g, an average pore diameter of 14 nm, and represents particles with a four-leaf cross-section with a diameter of the circumscribed circle of 1.6 mm and a length of up to 20 mm. The aluminum borate catalyst Al ₃ BO ₆ with the structure of norbergite, which is a part of the catalyst, consists of particles with sizes from 10 to 200 nm, characterized by interplanar distances of 3.2 and 2.8 A, with an angle between them of 53.8 °.

Next, the catalyst is sulfidized analogously to example 1. The result is a catalyst that contains wt. %: Mo - 11.7; Co - 3.6; S 7.9; the carrier is the rest; wherein the carrier contains, by weight. %: aluminum borate Al ₃ BO ₆ with the structure of norbergite - 12.0; sodium - 0.028; γ-Al ₂ O ₃ - the rest.

Next, carry out hydrotreating of hydrocarbon feeds analogously to example 1.

The test results of the catalyst in hydrotreatment are shown in the table.

Thus, as can be seen from the above examples, the proposed catalyst due to its chemical composition and texture due to the presence in the composition in the given concentrations of aluminum borate Al ₃ BO ₆ with a norbergite structure, which is a particle with sizes from 10 to 200 nm, characterized by interplanar spacings 3.2 and 2.8 A, with an angle between them of 53.8 °, has a high activity that significantly exceeds the activity of the prototype catalyst in hydrotreating hydrocarbon feedstocks.

Claims (4)

1. The catalyst for hydrotreatment of hydrocarbons, including cobalt, molybdenum and a 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 ] 33.0-43.0%; the carrier is the rest; wherein the carrier contains, by weight. %: aluminum borate Al ₃ BO ₆ with norbergite structure - 5.0-25.0; sodium - not more than 0.03; γ-Al ₂ O ₃ - the rest. 2. The catalyst according to claim 1, characterized in that the aluminum borate Al ₃ BO ₆ catalyst with the structure of norbergite is a particle with a size of 10 to 200 nm, characterized by interplanar distances of 3.2 and 2.8 A, with an angle between them of 53.8 ° . 3. The catalyst according to claim 1, characterized in that it has a specific surface area 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 section in the form of a circle, trefoil or four-leaf with a diameter of the circumscribed circle of 1.0-1.6 mm and a length of up to 20 mm. 4. The catalyst for hydrotreating hydrocarbons according to claim 1, characterized in that after sulfidation it contains, by weight. %: Mo - 10.0-14.0; Co - 3.0-4.3; S 6.7-9.4; the carrier is the rest; wherein the carrier contains, by weight. %: aluminum borate Al ₃ BO ₆ with norbergite structure - 5.0-25.0; sodium - not more than 0.03; γ-Al ₂ O ₃ - the rest.