RU2687734C1 - Method of catalytically cracking gasoline hydrotreating catalyst preparation - Google Patents

Abstract

FIELD: technological processes.SUBSTANCE: invention relates to methods of producing catalysts for hydrotreatment of catalytic cracking gasoline and can be used in oil refining industry. Described is a method of preparing a catalyst, comprising impregnating a support which contains, wt. %: aluminum borate AlBOwith norbergite structure – 5.0–25.0; sodium – not more than 0.03; amorphous aluminosilicate 30–50; γ-AlO– balance; aqueous solution containing bimetallic complex compound [Co(HO)(CHO)][MoO(CHO)], with subsequent drying, wherein concentrations of components of solution are such that enable to obtain catalyst, which contains, wt. %: [Co(HO)(CHO)][MoO(CHO)] 17.4–27.4; carrier – balance; wherein the carrier contains, wt. %: aluminum borate AlBOwith norbergite structure – 5.0–25.0; sodium – not more than 0.03; amorphous aluminosilicate 30–50; γ-AlO– balance.EFFECT: technical result is achieving higher hydrodesulphurisation activity of catalyst in hydrotreatment of catalytic cracking gasolines, as well as high selectivity of the catalyst, which is expressed in reducing the degree of hydrogenation of olefin hydrocarbons and reducing the value of falling octane number of catalytic cracking gasoline during hydrotreatment.7 cl, 1 tbl, 4 ex

Description

The invention relates to methods for the preparation of hydrotreating catalysts, namely, catalysts for the selective hydrotreatment of catalytic cracking gasoline (BPC) and can be used in the refining industry.

Currently BPC is one of the main components of commercial gasoline. The proportion of BKK in the petrol fund of the refinery is 30-40%, while up to 95% of the amount of sulfur is supplied to compounded gasolines [Sylvette Brunet, Damien Mey, Guy Perot, Christophe Bouchy, Fabrice Diehl. On the hydrodesulfurization of FCC gasoline: a review. Applied Catalysis A: General. - 2005. - 278. P. 143-172]. To obtain gasoline that meets modern requirements, it is necessary to reduce the sulfur content in the BPC, which is achieved using hydrotreating processes.

BPC is characterized by a high content of olefinic hydrocarbons and has a relatively high octane number. Hydrogenation of olefinic hydrocarbons contained in BPC when hydrotreating leads to a decrease in the octane number. Thus, it is desirable to hydrotreat BPC to the required sulfur content with the minimum degree of hydrogenation of olefinic hydrocarbons. In this regard, an urgent task is the creation of new methods for the preparation of catalysts that allow hydrotreating BPC to the required sulfur content with a minimum degree of olefinic hydrocarbons hydrogenation and a minimum decrease in the octane number.

There are various methods for the preparation of catalysts for the selective hydrotreatment of BKK.

Thus, there is a known method of preparing a catalyst for hydrotreating a heavy fraction of BPC containing 8-19 wt. % MoO ₃ and 2-6 wt. % CoO and / or NiO, the rest is Al ₂ O ₃ , consisting in two stages of impregnation of previously calcined alumina carrier, first with a solution of ammonium molybdate, and then with a solution of cobalt nitrate and / or nickel nitrate with intermediate heat treatment at a temperature of 100-200 ° C and final calcination at 400-650 ° C. The technical result consists in obtaining a product - a component of commercial gasoline - with a sulfur content of less than 0.05 wt. % with loss of octane number less than 0.5 points [Pat. Of the Russian Federation No. 2225501, C10G 45/08, 09/05/2003]. The disadvantage of this method of preparation of the catalyst is the high sulfur content in the hydrotreating product.

To increase the selectivity of catalysts for hydrotreating BPC in their preparation can be used carriers containing jointly aluminum oxide and modifying components. In the application US No. 2005023192, C10G 45/04, 03.02.2005, describes a method for preparing a hydrotreating catalyst BPC using a carrier based on alumina modified with oxide, at least one metal selected from the series: iron, chromium, cobalt, nickel , copper, zinc, yttrium, scandium, metals of the lanthanide group.

Magnesium oxide can also be used as the main component of the carrier. In Pat. USA No. 4140626, C10G 23/02, 20.02.1979, describes the process of hydrotreating BPC using a catalyst containing a metal of Group VIB of the Periodic Table and a metal of Group VIII of the Periodic Table, deposited on a carrier containing at least 70 wt. % magnesium oxide.

A common disadvantage of these methods for the preparation of catalysts is the low octane number and high residual sulfur content in the CCLs produced on the described catalysts.

The closest in technical essence and the achieved effect to the proposed technical solution is the method of preparation of the catalyst described in US Pat. Of the Russian Federation No. 2575638, B01J 29/076, B01J 23/882, C10G 45/08, 01.12.2015. A method is described for preparing a catalyst for selective hydrotreatment of catalytic cracking gasoline, including cobalt and molybdenum in the form of oxides; silicon in the form of amorphous aluminosilicate, aluminum in the form of γ-Al ₂ O ₃ and amorphous aluminosilicate, while the components are contained in the following concentrations, wt. %: MoO ₃ - 3.0-12.0; CoO - 0.8-4.6; amorphous aluminosilicate containing silicon and aluminum in a weight ratio of Si / Al from 0.1 to 1.0, - 3.9-86.6%, Al ₂ O ₃ - the rest. The catalyst has a specific surface of 150-350 m ² / g, a pore volume of 0.3-0.9 cm ³ / g, an average pore diameter of 5-15 nm, is a trefoil-shaped particle with a diameter of 1.3-1.7 mm and a length of up to 20 mm, having a bulk mechanical strength, determined by the method of Shell 1471, not less than 1.0 MPa. The method consists in the impregnation of pre-prepared media containing, by weight. %: amorphous aluminosilicate - 5-90%, Al ₂ O ₃ - the rest, specific surface 150-350 m ² / g, pore volume 0.5-1.1 cm ³ / g, average pore diameter 5-15 nm, representing particles with a trefoil cross section with a diameter of 1.3-1.7 mm and a length of up to 20 mm, having a strength of at least 1.0 kg / mm, an aqueous solution containing ammonium paramolybdate and cobalt (II) nitrate, followed by drying and calcined. The carrier is obtained by molding a paste obtained by mixing an AlOOH powder with a boehmite structure, amorphous silica-alumina powder with a Si / Al mass ratio of 0.1 to 1.0, water and nitric or acetic acid through a trefoil in the form of a trefoil with pressure up to 10 MPa, s subsequent drying and calcining at a temperature of from 500 to 600 ° C.

The disadvantage of this method of preparation is the low activity of the resulting catalyst in the desulfurization and a significant decrease in the octane number of gasoline under hydrotreatment under conditions under which the residual sulfur content is not more than 10 ppm.

The present invention solves the problem of creating an improved method of preparing a catalyst for hydrotreating BPC, characterized by an optimal chemical composition and optimal textural characteristics of the resulting catalyst.

The technical result is an increased hydrodesulfurization activity of the catalyst in the hydrotreatment of catalytic cracking gasolines, as well as an increased selectivity of the catalyst, resulting in a decrease in the degree of hydrogenation of olefinic hydrocarbons and a decrease in the value of the decrease in the octane number of catalytic cracking gasoline.

The problem is solved by the method of preparation of the catalyst Hydrotreating BPC, comprising in its composition cobalt, molybdenum and a carrier 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 ] 17.4-27.4%; 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; amorphous aluminosilicate 30-50; γ-Al ₂ O ₃ - the rest. The amorphous aluminosilicate contained in the catalyst contains silicon and aluminum in a mass ratio of from 0.2 to 0.3. The catalyst has a specific surface area of 220-280 m ² / g, a pore volume of 0.7-0.9 cm ³ / g, an average pore diameter of 9-12 nm, which is a particle with a cross-section in the shape of a trefoil or a circle with a diameter of 1.3- 3.0 mm and a length of up to 20 mm, having a bulk mechanical strength, determined by the method of Shell 1471, not less than 1.0 MPa.

At the stage of preparation of the granulated carrier, the molding composition is prepared by the method of mixing and peptizing the obtained powders of boron-containing aluminum hydroxide: amorphous aluminosilicate with a Si / Al mass ratio of 0.2-0.3: water: citric acid with mass ratios of components equal to 1: 0.6, respectively. -1.0: 0.9: 0.045. the molding mass in the mixer with Z-shaped blades is mixed for 30-45 minutes, extruded through a spinneret with holes, the shape and size of which provide granules with a cross-section in the shape of a trefoil and a circle with a circumference of 1.3-3.0 mm , dried at a temperature of 100-150 ° C and calcined at a temperature of 550-650 ° C.

Impregnation of the carrier by capacity with an aqueous solution 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 ] is used, and impregnation is carried out at a temperature of 20-80 ° C for 20-60 minutes with occasional stirring, after impregnation, the catalyst is dried in air at a temperature of 100-150 ° C for 2-4 hours.

A distinctive feature of the proposed method of preparation of the catalyst Hydrotreating BPC in comparison with the prototype is the composition of the resulting catalyst, wt. %: [Co (H ₂ O) ₂ (C ₆ H ₅ O ₇ )] ₂ [Mo ₄ O ₁₁ (C ₆ H ₅ O ₇ ) ₂ ] 17.4-27.4%; 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; amorphous aluminosilicate 30-50; γ -Al ₂ O ₃ - the rest.

The output of the content of the components beyond the claimed limits leads to a decrease in the activity and / or selectivity of the catalyst.

The second significant feature of the proposed method of preparation of the catalyst is that the resulting catalyst contains amorphous aluminosilicate with a mass ratio of Si / Al from 0.2 to 0.3. The use of amorphous aluminosilicate with a Si / Al ratio beyond the specified range also leads to a decrease in the activity and / or selectivity of the catalyst.

The third distinguishing feature of the proposed method of preparation of the catalyst is that at the stage of preparing a granular carrier, the molding material is prepared by mixing and peptizing the obtained boron-containing aluminum hydroxide: amorphous silica-alumina: water: citric acid powders with mass ratios of components equal to 1: 0.6-1 , 0: 0.9: 0.045, the molding material in the mixer with Z-shaped blades is mixed for 30-45 minutes, extruded through a die with holes, the shape and size of which effectiveness to obtain granules having a cross section in the form of a trefoil and a circle with a diameter of 1.3-3.0 mm circle described, dried at a temperature of 100-150 ° C and calcined at a temperature of 550-650 ° C.

The fourth distinguishing feature of the proposed method of preparation of the catalyst is that impregnation of the carrier on the basis of capacity with an aqueous solution 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 ], while the impregnation is carried out at a temperature of 20-80 ° C for 20-60 minutes with occasional stirring, after impregnation, the catalyst is dried in air at a temperature of 100-150 ° C for 2-4 hours

The technical result of the proposed method of preparation of the catalyst Hydrotreating BPC consists of the following components:

1. The optimal chemical composition and optimal textural characteristics of the catalyst prepared by the claimed method, provide the product of hydrotreatment BKK with low sulfur content with a minimum degree of hydrogenation of olefinic hydrocarbons and a minimum decrease in the octane number.

2. Used amorphous aluminosilicate and aluminum borate Al ₃ BO ₆ with the structure of norbergite in the composition of the carrier can increase the selectivity of the catalyst in the hydrorefining of the BPC and reduce the octane drop in gasoline during hydrotreating. The acid centers of aluminosilicate and aluminum borate contribute to the double bond isomerization and skeletal isomerization of olefinic hydrocarbons, which, on the one hand, leads to the transformation of terminal olefins into more resistant to hydrogenation, internal olefins, and, on the other hand, contributes to the formation of more branched hydrocarbons with high octane.

Description of the proposed technical solution.

First, an alumina carrier is prepared, with optimal textural and acidic characteristics, due to the presence of aluminum borate Al ₃ BO ₆ with the structure of norbergite and amorphous aluminosilicate.

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 20-40 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 is not more than 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 120 ° 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 the spray dryer at an air temperature at the entrance to the dryer is not more than 280 ° C and the continuous stirring of the suspension. The finished boron-containing aluminum hydroxide powder is discharged from the glass of the spray dryer cyclone dust collector.

Further, using one of the known methods, an amorphous aluminosilicate powder is obtained with a Si / Al weight ratio from 0.2 to 0.3 and a sodium content of not more than 0.03%, which, for example, can be prepared by mixing solutions of aluminum sulfate and sodium silicate (liquid glass) in a water-ammonia solution with the separation of the formed precipitate on the filter, washing it with excess water and air drying.

Next, prepare the molding material by mixing and peptization obtained powders of boron-containing aluminum hydroxide and amorphous aluminosilicate in a laboratory mixer with Z-shaped blades in the presence of an aqueous solution of citric acid. The citric acid solution is prepared in such a way that the amount of citric acid monohydrate C ₆ H ₈ O ₇ × H ₂ O is not more than 5 g per 100 ml of water.

The components are taken in the following mass ratios: aluminum hydroxide powders: amorphous silica-alumina: water: citric acid = 1: 0.6-1.0: 0.9: 0.045.

Stirring is continued for 30-45 minutes. The result is a homogeneous plastic paste. The resulting paste is extruded through a die with holes, the shape and size of which provide the production of granules with a trefoil-shaped cross section and a circle with a circumference of 1.3-3.0 mm. The resulting carrier is dried at a temperature of 100-150 ° C and calcined at a temperature of 550-600 ° C. Next, the carrier is crushed along the length to the particles of the desired size.

The result is a homogeneous white carrier, representing particles with a cross-section in the form of a trefoil or a circle with a diameter of 1.3-3.0 mm and a length of up to 20 mm, having a strength of at least 1.0 kg / mm. 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; amorphous aluminosilicate 30-50; γ-Al ₂ O ₃ - the rest, and has a specific surface area of 250-300 m ² / g, a pore volume of 0.8-1.0 cm ³ / g, an average pore diameter of 10-13 nm.

Using this carrier, a supported catalyst is prepared. First, an impregnating 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 ]. For this purpose, given amounts of ammonium paramolybdate (NH ₄ ) ₆ Mo ₇ O ₂₄ ⋅4H ₂ O, cobalt (II) basic carbonate СОСО ₃ ⋅mCo (ОН) ₂ ⋅nH ₂ O, citric acid 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 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 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 obtained aqueous solution of molybdenum citrate (VI). 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 ].

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 a carrier containing boron-containing alumina and amorphous aluminosilicate, using impregnation of the carrier according to moisture capacity. Impregnation is carried out at a temperature of 20-80 ° C for 20-60 minutes with occasional stirring.

After impregnation, the catalyst is dried in air at a temperature of not more than 100-150 ° C for 2-4 hours.

The result is 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 ] 17.4-27.4%; 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; amorphous aluminosilicate 30-50; γ-Al ₂ O ₃ - the rest. The amorphous aluminosilicate contained in the catalyst contains silicon and aluminum in a mass ratio of from 0.2 to 0.3. The catalyst has a specific surface area of 220-280 m ² / g, a pore volume of 0.7-0.9 cm ³ / g, an average pore diameter of 9-12 nm, which is a particle with a cross-section in the shape of a trefoil or a circle with a diameter of 1.3- 3.0 mm and a length of up to 20 mm, having a bulk mechanical strength, determined by the method of Shell 1471, not less than 1.0 MPa.

The invention is illustrated by the following examples:

Example 1. (According to known technical solution)

со средним размером агломератов 40-50 мкм, содержащего примеси в количестве, мас. %, не более: Na₂O - 0,005; Fe₂O₃ - 0,01; SiO₂ - 0,015, и 70 г аморфного алюмосиликата с соотношением Si/Al равным 0,9. Далее в смеситель добавляют раствор, полученный смешением 100 мл дистиллированной воды и 8,0 мл концентрированной азотной кислоты, имеющей плотность 1,4 г/см³. Готовую массу продавливают через отверстие фильеры, обеспечивающее получение экструдатов готового носителя с сечением в форме трилистника с размером от вершины трилистника до середины основания от 1,3 до 1,7 мм. Затем проводят термообработку, включающую в себя сушку и прокалку. Сушку экструдатов проводят в сушильном шкафу при температуре 110°С. Затем экструдаты прокаливают в муфельной печи при температуре 550°С в течение 4 ч.In the laboratory mixer place 30 g of AlOOH aluminum hydroxide powder having a boehmite structure with a crystal size.

with an average size of agglomerates of 40-50 microns, containing impurities in an amount by weight, %, no more than: Na ₂ O - 0.005; Fe ₂ O ₃ - 0.01; SiO ₂ - 0,015, and 70 g of amorphous aluminosilicate with a ratio of Si / Al equal to 0.9. Next, the solution added by mixing 100 ml of distilled water and 8.0 ml of concentrated nitric acid having a density of 1.4 g / cm ^{3 is} added to the mixer. The finished mass is pushed through the die hole, providing the extrudates of the finished carrier with a trefoil-shaped cross-section with a size from the top of the trefoil to the middle of the base from 1.3 to 1.7 mm. Then, heat treatment is carried out, including drying and calcining. Drying of the extrudates is carried out in a drying oven at 110 ° C. Then the extrudates are calcined in a muffle furnace at a temperature of 550 ° C for 4 hours.

A portion of the prepared carrier weighing 50 g is placed in a round about bottom flask. Then, 30 ml of an aqueous solution containing 3.43 g of ammonium paramolybdate and 2.37 g of cobalt (II) nitrate are poured into the flask with the carrier. Impregnation is carried out for 1 h at a temperature of a water bath of 70 ° C and constant rotation of the flask with a preparing catalyst. At the end of the impregnation, uniformly colored granules were obtained which did not contain a bright spot in the center at the break. After impregnation, the catalyst granules are dried at 120 ° C for 4 hours, then calcined at a temperature of 550 ° C for 3 hours in a stream of air. The resulting catalyst has the following composition (wt.%): Mo - 3.7%; Co - 0.85%; amorphous aluminosilicate - 66.5%; Al ₂ O ₃ - the rest.

The catalyst is tested in the hydrotreating of catalytic cracking gasoline, which is carried out in a flow reactor under the following conditions: the feed flow rate is 2 h ^-1 , the H ₂ / feed ratio is 350 nl / nl, and the pressure is 1.7 MPa. The starting temperature of the Hydrotreating is 230 ° C, after which the temperature was raised by steps of 2-3 ° C until the residual sulfur content in the Hydrotreating products was reached 10 ppm. This temperature, which is an indicator of the activity of the catalyst, was recorded in the table.

The raw material used is a wide fraction of BPC with boiling range of n. - 220 ° С, sulfur content 224 ppm, nitrogen 50 ppm, maleic number 0.7, octane number by the research method 90.9 and by the motor method 79.9. Prior to catalytic testing, the catalyst may be sulphided by known methods. The test results are shown in the table.

Examples 2-4 illustrate the proposed technical solution.

Example 2

First, a boron-containing aluminum hydroxide powder is prepared, 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% aqueous 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.

Then prepare the media. Mixing is carried out in a laboratory mixer with Z-shaped blades. A measured 100 g of boron-containing aluminum hydroxide powder having a loss on ignition at 550 ° C of 25% is loaded into the mixer tank. Measured 100 g of powder of amorphous aluminosilicate with a ratio of Si / Al = 0.3, having a loss on ignition at 550 ° C of 24.5%, is loaded into the capacity of the mixer. The powders are mixed for 15 minutes.

To measure in a glass beaker 180 ml of distilled water add 9 g of citric acid, the solution is stirred until complete dissolution of citric acid. The prepared solution is poured into a mixture of boron-containing aluminum hydroxide and amorphous silica-alumina, and stirred until a plastic molding material is obtained. Mixing time averages 30 minutes.

The finished mass is transferred from the mixer to the molding cylinder of the laboratory extruder and pushed through the die opening to provide pellets with a trefoil section of 1.3 mm in diameter.

The resulting carrier is dried at a temperature of 120 ° C and calcined at a temperature of 550 ° C. Next, the carrier is crushed along the length to the particles of the desired size.

Next, a bimetallic compound is synthesized in solution, 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 ], for which in 60 ml of distilled water 9.8 g of citric acid C ₆ H ₈ O _{7 are} successively dissolved with stirring; 9.0 g of ammonium paramolybdate (NH ₄ ) ₆ Mo ₇ O ₂₄ × 4H ₂ O, 3.0 g of cobalt (II) basic COCO ₃ ⋅mCo (OH) ₂ ⋅nH ₂ O carbonate. Further, by adding distilled water the solution volume adjusted to 90 ml.

90 g of the obtained carrier are impregnated with water capacity for 20 minutes at 20 ° C. 90 ml of a solution containing 19.2 g of the bimetallic compound with 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 ]. The catalyst is dried in air at 100 ° C for 4 h.

The result is 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 ] 17.4%; carrier - the rest; while the media contains, by weight. %: aluminum borate Al ₃ BO ₆ with the structure of norbergite - 5.0; sodium - 0.02; amorphous aluminosilicate 50; γ-Al ₂ O ₃ - the rest. The amorphous aluminosilicate contained in the catalyst contains silicon and aluminum in a mass ratio of 0.3. The catalyst has a specific surface of 280 m ² / g, a pore volume of 0.9 cm ³ / g, an average pore diameter of 9 nm, and is a trefoil-shaped cross-section with a diameter of 1.3 mm and a length of up to 20 mm, having a bulk mechanical strength , determined by the method of Shell 1471 - 1.0 MPa.

Testing in the hydrotreatment of catalytic cracking gasoline was carried out analogously to example 1. The test results are shown in the table.

Example 3

The boron-containing aluminum hydroxide powder is prepared analogously to example 2, with the difference that a solution of 5.98 g of boric acid in 1 l of a 1.5% nitric acid solution having a pH of 1.4 is added to the washed and wrung aluminum hydroxide pellet.

The operations for preparing the carrier are identical to Example 2, with the difference that 80 g of amorphous aluminosilicate powder are added to a measured Z-bladed laboratory mixer to measured 100 g of boron-containing aluminum hydroxide hydroxide powder having loss on ignition at 550 ° C with 25% Si / Al = 0.2, having a loss on ignition at 550 ° C of 25.5%, is loaded into the container of the mixer. To the powders add a solution of 9 g of citric acid in 180 ml of water. The paste is stirred for 45 minutes, pushed through a die hole, providing granules with a trefoil section with a diameter of 3 mm, the granules are dried at 100 ° C and calcined at 650 ° C.

Next, a bimetallic compound is synthesized in solution, 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 ], for which in 60 ml of distilled water 11.48 g of citric acid C ₆ H ₈ O _{7 are} successively dissolved with stirring; 11.96 g of ammonium paramolybdate (NH ₄ ) ₆ Mo ₇ O ₂₄ × 4H ₂ O, 4.0 g of cobalt (II) basic COCO ₃ ⋅mCo (OH) ₂ ⋅nH ₂ O carbonate. Next, by adding distilled water the volume of the solution adjusted to 90 ml.

100 g of the obtained carrier are impregnated with a capacity of 90 ml of a solution containing 25.5 g of a bimetallic compound with the composition [Co (H ₂ O) ₂ (C ₆ H ₅ O ₇ )] ₂ [Mo ₄ O ₁₁ for 40 minutes at 50 ° C. (C ₆ H ₅ O ₇ ) ₂ ]. The catalyst is dried in air at 120 ° C for 3 hours.

The result is 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 ] 22.5%; carrier - the rest; while the media contains, by weight. %: aluminum borate Al ₃ BO ₆ with the structure of norbergite - 12.0; sodium - not more than 0.02; amorphous aluminosilicate 40; γ-Al ₂ O ₃ - the rest. The amorphous aluminosilicate contained in the catalyst contains silicon and aluminum in a mass ratio of 0.2. The catalyst has a specific surface area of 245 m ² / g, a pore volume of 0.8 cm ³ / g, an average pore diameter of 10 nm, and is a trefoil-shaped cross-section with a diameter of 3.0 mm and a length of up to 20 mm, having a bulk mechanical strength determined by the method of Shell 1471 - 1.3 MPa.

Testing in the hydrotreatment of catalytic cracking gasoline was carried out analogously to example 1. The test results are shown in the table.

Example 4

The boron-containing aluminum hydroxide powder is prepared as in Example 2, with the difference that a solution of 14.63 g of boric acid in 1 l of a 1.5% nitric acid solution having a pH of 1.4 is added to the washed and wrung aluminum hydroxide cake in an autoclave.

The operations for preparing the carrier are identical to example 2, with the difference that 60 g of amorphous aluminosilicate powder are added to a measured Z-bladed laboratory mixer to measured 100 g of boron-containing aluminum hydroxide hydroxide powder having loss on ignition at 550 ° C of 25%. Si / Al = 0.25, having a loss on ignition at 550 ° C 25%, is loaded into the mixer tank. To the powders add a solution of 9 g of citric acid in 180 ml of water. The paste is stirred for 45 minutes, pushed through the die opening, providing granules with a cross section in the form of a circle with a diameter of 3 mm, the granules are dried at 150 ° C and calcined at 600 ° C.

Next, a bimetallic compound is synthesized in solution, 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 ], for which 50 ml of distilled water 14.36 g of citric acid C ₆ H ₈ O _{7 are} successively dissolved with stirring; 14.96 g of ammonium paramolybdate (NH ₄ ) ₆ Mo ₇ O ₂₄ × 4H ₂ O, 5.0 g of cobalt (II) basic carbonate COCO ₃ ⋅mCo (OH) ₂ ⋅nH ₂ O. Next, by adding distilled water, the solution volume adjusted to 80 ml.

100 g of the obtained carrier are impregnated at a capacity of 80 ml of a solution containing 31.9 g of a bimetallic compound with the composition [Co (H ₂ O) ₂ (C ₆ H ₅ O ₇ )] ₂ [Mo ₄ O ₁₁ for 1 hour at 80 ° C. (C ₆ H ₅ O ₇ ) ₂ ]. The catalyst is dried in air at 150 ° C for 2 hours.

The result is 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 ] 27.4%; carrier - the rest; while the media contains, by weight. %: aluminum borate Al ₃ BO ₆ with the structure of norbergite 25,0; sodium - 0.03; amorphous aluminosilicate 30; γ-Al ₂ O ₃ - the rest. The amorphous aluminosilicate contained in the catalyst contains silicon and aluminum in a mass ratio of 0.25. The catalyst has a specific surface area of 220 m ² / g, a pore volume of 0.7 cm ³ / g, an average pore diameter of 12 nm, and consists of particles with a cross section in the shape of a circle with a diameter of 3.0 mm and a length of up to 20 mm, having a bulk mechanical strength , determined by the method of Shell 1471 - 1.6 MPa.

Testing in the hydrotreatment of catalytic cracking gasoline was carried out analogously to example 1. The test results are shown in the table.

As can be seen from the above examples, the proposed catalytic cracking gasoline hydrotreatment catalysts have a higher activity and selectivity in comparison with the prototype catalyst.

Claims (7)

1. The method of preparation of the catalyst for Hydrotreating a hydrocarbon feedstock containing molybdenum, cobalt compounds and a carrier, characterized in that the catalyst is prepared by impregnating a carrier that contains, by weight, wt. %: aluminum borate Al ₃ BO ₆ with the structure of norbergite - 5.0-25.0; sodium - not more than 0.03; amorphous aluminosilicate 30-50; γ-Al ₂ O ₃ - the rest; an aqueous solution 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 ], followed by drying, the concentration of the components of the solution provide 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 ] 17.4-27.4. 2. The method according to claim 1, characterized in that the resulting catalyst has a specific surface area of 220-280 m ² / g, a pore volume of 0.7-0.9 cm ³ / g, an average pore diameter of 9-12 nm, is a particle with a cross-section in the shape of a trefoil or a circle with a diameter of 1.3-3.0 mm and a length of up to 20 mm, having a volumetric mechanical strength, determined by the method of Shell 1471, not less than 1.0 MPa. 3. The method according to p. 1, characterized in that the amorphous aluminosilicate contained in the catalyst contains silicon and aluminum in a mass ratio of from 0.2 to 0.3. 4. A method according to claim 1, characterized in that at the stage of preparing a granulated carrier, molding material is prepared by mixing and peptizing the obtained boron-containing aluminum hydroxide: amorphous silica-alumina: water: citric acid powders with mass ratios of components equal to 1: 0.6- 1.0: 0.9: 0.045. 5. The method according to p. 1, characterized in that at the stage of preparation of the granulated carrier, the molding material in the mixer with Z-shaped blades is mixed for 30-45 minutes, extruded through a spinneret with holes, the shape and size of which provide the production of granules with cross section in the form of a trefoil and a circle with a circumference of 1.3-3.0 mm, dried at a temperature of 100-150 ° C and calcined at a temperature of 550-650 ° C. 6. The method according to p. 1, characterized in that use the impregnation of the carrier on the capacity of an aqueous solution 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 ], while the impregnation is carried out at a temperature of 20-80 ° C for 20-60 minutes with occasional stirring. 7. The method according to p. 1, characterized in that after impregnation, the catalyst is dried in air at a temperature of 100-150 ° C for 2-4 hours