RU2626402C1 - Method for preparing hydrotreatment catalyst of hydrocracking raw materials - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: invention relates to methods for preparing hydrotreatment catalysts of petroleum fractions with a boiling point above 360°C for producing raw materials with a low content of sulfur and nitrogen, which is further processed in the hydrocracking process. The method for preparing a catalyst, comprising the carrier impregnation, which comprises, wt %: aluminium borate Al₃BO₆ with the structure of norbergite - 5.0-25.0; sodium - not more than 0.03; -γAl₂O₃ - the rest, with an aqueous solution of a bimetallic complex compound [Ni (H₂O)₂]₂[Mo₄O₁₁(C₆H₅O₇)₂] followed by drying. The catalyst contains, wt %: [Ni (H₂O)₂]₂[Mo₄O₁₁(C₆H₅O₇)₂] 29.0-36.0%; carrier - the rest. The carrier impregnation is used by the moisture capacity or from a solution excess. Impregnation is carried out at the temperature of 20-80°C for 20-60 minutes with occasional stirring. After impregnation, the catalyst is dried in air at the temperature of 100-200°C. The catalyst has specific surface area of 130-180 m²/g, the pore volume of 0.35-0.65 cm³/g, the average pore diameter is 10-15 nm and particles with section in the form of 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.

EFFECT: producing a catalyst having the maximum activity in the desulfurization and denitrogenation reactions occurring during the hydrotreatment of petroleum fractions with a boiling point above 360 degrees.

5 cl, 7 ex, 1 tbl

Description

The invention relates to methods for the preparation of oil refining catalysts, in particular to methods for the preparation of catalysts for preliminary hydrotreating oil fractions with a boiling point above 360 ° C, designed to produce low sulfur content, which is further processed in the process of hydrocracking.

At present, the hydrocracking process is the most dynamically developing catalytic oil refining process, since it allows increasing the depth of oil refining and improving the quality of the products obtained by converting heavy oil fractions into low-sulfur middle distillates, from which high-quality aviation kerosene and diesel fuels are obtained. Since the characteristics of specific variants of hydrocracking processes and the quality of the products obtained are largely determined by the properties of the catalysts used, the development of methods for preparing improved hydrocracking catalysts, including catalysts for preparing raw materials for hydrocracking, is an extremely important and urgent task.

Modern hydrocracking processes, as a rule, include several successive stages, in the first of which preliminary hydrotreating of fractions with a boiling point above 360 ° C is carried out to obtain raw materials with a low content of sulfur, nitrogen and polycyclic aromatic compounds. The need for the maximum possible reduction in the content of these components in the feed is due to the fact that they are catalytic poisons for catalysts of subsequent stages. Further, such hydrotreated feed is fed to hydrocracking carried out on zeolite-containing catalysts. The most typical examples of multi-stage processes are described in patents [Pat. RF №2470989, 11/27/2011; Pat. RF №2565669, 10.10.2015; Pat. RF №2595041, 08/20/2016]. In these process variants, the first stage uses known catalysts containing metals of groups VIb and VIII of the periodic system supported on an alumina or aluminosilicate carrier. The main disadvantage of these catalysts is low desulfurization and deazotizing activity.

In this regard, catalysts and methods for preparing catalysts intended for hydrotreating or hydrotreating hydrocarbon feedstocks combining high desulfurization and deazotizing activity are being actively developed in the world.

So known is a method of preparing a catalyst [RF Application No. 2012154275, B01J 31/02, 07/10/14], including: (a) processing the composition of the catalyst precursor, comprising at least one metal of group 6 of the Periodic table of the elements, at least one metal of groups 8-10 of the Periodic Table of the Elements, the first organic compound containing at least one amino group and at least 10 carbon atoms, or the second organic compound containing at least one carboxylic acid group and at least least 10 carbon atoms kind, with the formation of an organic compound-treated catalyst precursor composition, and (b) heating said organic-treated catalyst precursor composition at a temperature of from about 195 ° C to about 250 ° C for a period of time sufficient for the first or second organic compounds reacted with the formation of additional unsaturated carbon atoms in situ, not present in the first or second organic compounds, but not so long that more than 50 mass. % of the first or second organic compounds evaporated, thus forming a catalyst precursor composition containing in situ unsaturated carbon atoms.

A known method of producing a catalyst for hydroprocessing [RF Application No. 2010012058, B01J 27/185, 07/27/2011], comprising the following stages: a) at least one stage of impregnation of a dry and / or calcined catalyst precursor containing at least one element group VIII and / or at least one element of group VIB and an amorphous carrier, using an impregnating solution consisting of at least one phosphorus-containing compound dissolved in at least one polar solvent with a dielectric constant above 20; b) at least one stage of maturation of the specified impregnated catalyst precursor obtained in stage a); moreover, the specified stage of ripening is carried out at atmospheric pressure, at a temperature in the range from ambient temperature to 60 ° C during the ripening period from 12 to 340 hours; c) a drying step without a subsequent calcining step of said catalyst precursor obtained in step b).

There is also a method of producing a catalyst [RF Application No. 2014130016, B01J 37/02, 02/10/2016]. This method, based on a catalyst precursor containing a carrier based on alumina and / or silica-alumina and / or zeolite and containing at least one element of group VIB and, possibly, at least one element of group VIII wherein said method comprises impregnating said precursor with a solution of (C ₁ -C ₄ ) dialkyl succinate, characterized in that it comprises the following steps:

1) impregnation (stage 1) of the specified dried, calcined or regenerated precursor with at least one solution containing at least one carboxylic acid other than acetic acid, then keeping and drying at a temperature of less than 200 ° C, possibly followed by heat treatment at temperature less than 350 ° C; 2) subsequent impregnation (stage 2) with a solution containing at least one (C1-C4) dialkyl succinate, then exposure and drying at a temperature of less than 200 ° C without a subsequent calcination step; and the fact that the catalyst precursor and / or the solution of stage 1 and / or the solution of stage 2 contains phosphorus.

A known method of preparing a catalyst for hydrotreating oil fractions [RF No. 2286846, B01J 23/78, B01J 23/83, C10G 45/08, 11/10/2006], including the stage of preliminary modification of the carrier. This preparation method consists in preparing the carrier according to the following procedure — aluminum hydroxide is mixed with a solution of boric acid and a nitric acid solution of lanthanum carbonate, followed by drying and calcination, and then impregnating the resulting carrier with a solution of cobalt nitrate and ammonium paramolybdate at a pH of 2.0-3.5 and a temperature of 40-80 ° C in the presence of phosphoric acid. The resulting catalyst 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 common disadvantage for the above methods for the preparation of catalysts is that with their use it is not possible to prepare catalysts that achieve low residual sulfur and nitrogen in the resulting hydrotreatment products.

The closest in its technical essence and the achieved effect to the claimed method of preparation of the catalyst is the method described in [US Pat. RF No. 2472585, B01J 23/882, 01/20/2013], which consists in applying to the boron-containing support a bimetallic complex compound [M (H ₂ O) _x (L) _y ] ₂ [Mo ₄ O ₁₁ (C ₆ H ₅ O ₇ ) ₂ ], where: M = Co ²⁺ or Ni ²⁺ ; L is a partially deprotonated form of citric acid C ₆ H ₆ O ₇ ; x is 0 or 2; y = 0 or 1, and at least one oxygen-containing organic compound from an aqueous solution by impregnation by moisture capacity or by impregnation from excess solution, followed by drying and sulfidation. The concentrations of the bimetallic complex compound [M (H ₂ O) _x (L) _y ] ₂ [Mo ₄ O ₁₁ (C ₆ H ₅ O ₇ ) ₂ ] and the oxygen-containing organic compound in solution, as well as the conditions for drying and sulfidation, are to provide in the finished catalyst the following content of components wt. %: Mo - 8.0-15.0; Co or Ni - 2.0-5.0; S - 5.0-15.0; B - 0.5-2.0; C - 0.5-7.0; Al ₂ O ₃ - the rest. The catalyst is impregnated at a temperature of 15-90 ° C for 5-60 minutes, after impregnation, the catalyst is dried in air at a temperature of 100-250 ° C and sulfidized by treatment in hydrogen sulfide, or in a mixture of hydrogen sulfide and hydrogen at temperatures up to 450 ° C.

The main disadvantage of the prototype, as well as other known methods for the preparation of hydrotreating catalysts, is the high content of sulfur and nitrogen in hydrotreated products.

The present invention solves the problem of creating an improved method of preparation of the 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, which helps minimize undesirable chemical interaction between active metals (Ni and Mo) and the support, and selectively produces the most active sulfide component in hydrotreatment - type II NiMoS phase.

2. Optimum textural characteristics of the support and catalyst, the volume and pore size of which provide access to all active molecules to be converted to the active component. The achievement of these characteristics is ensured, on the one hand, by the presence in the catalyst of aluminum borate particles Al ₃ BO ₆ with a norbergite structure, which is particles with sizes from 10 to 200 nm, and, on the other hand, by peptization of the molding paste at an increased concentration of ammonia.

3. The presence in its composition of a Nickel compound, which has increased desulfurizing, hydrogenating and deazotizing activity under the process conditions used for hydrotreating oil fractions with a boiling point above 360 ° C.

4. The optimal conditions for the deposition of the bimetallic complex compound (Ni (H ₂ O) ₂ ] ₂ [Mo ₄ O ₁₁ (C ₆ H ₅ O ₇ ) ₂ ] and subsequent drying, ensuring the preservation of the composition of aluminum borate Al ₃ BO ₆ with the structure norbergite, which 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 °.

5. The optimal ratios of the components, providing a catalyst having the following chemical composition, wt. %: [Ni (H ₂ O) ₂ ] ₂ [Mo ₄ O ₁₁ (C ₆ H ₅ O ₇ ) ₂ ] 29.0-36.0%; 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 problem is solved by the method of preparation of a hydrotreating catalyst for hydrocracking raw materials, which includes molybdenum, nickel, boron and aluminum compounds, which consists in the fact that the catalyst is prepared by impregnating a carrier that 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; an aqueous solution of the bimetallic complex compound [Ni (H ₂ O) ₂ ] ₂ [Mo ₄ O ₁₁ (C ₆ H ₅ O ₇ ) ₂ ], followed by drying.

The problem is also solved by the fact that when impregnating using such a ratio of components that the resulting catalyst contains, by weight. %: [Ni (H ₂ O) ₂ ] ₂ [Mo ₄ O ₁₁ (C ₆ H ₅ O ₇ ) ₂ ] 29.0-36.0%; 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 problem is also solved by using impregnation of the carrier in terms of moisture capacity, or from excess solution, while the impregnation is carried out at a temperature of 20-80 ° C for 20-60 minutes with periodic stirring, and after impregnation, the catalyst is dried in air at a temperature of 100-200 ° C.

The main distinguishing feature of the proposed method for the preparation of the catalyst in comparison with the prototype is that for the preparation of the supported catalyst, a carrier is used containing wt. %: 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, while the aluminum borate Al ₃ BO ₆ included in the support with the structure of norbergite 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 second distinguishing feature of the proposed method for the preparation of the catalyst in comparison with the prototype is that the resulting catalyst has a specific surface area of 130-180 m ² / g, pore volume of 0.35-0.65 cm ³ / g, average pore diameter of 10-15 nm, and is a particle 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 output of the average pore diameter beyond the claimed framework leads to a decrease in the activity of the catalyst.

Also a hallmark of the proposed method for the preparation of the catalyst in comparison with the prototype, is that for the preparation of the catalyst using aqueous solutions of the bimetallic complex compounds [Ni (H ₂ O) ₂ ] ₂ [Mo ₄ O ₁₁ (C ₆ H ₅ O ₇ ) ₂ ] and a carrier containing aluminum borate Al ₃ BO ₆ with a norbergite structure in a ratio of components providing a catalyst containing, by weight. %: [Ni (H ₂ O) ₂ ] ₂ [Mo ₄ O ₁₁ (C ₆ H ₅ O ₇ ) ₂ ] 29.0-36.0%; the carrier is the rest.

Another distinctive feature of the proposed method for the preparation of the catalyst in comparison with the prototype, is that for the preparation of the catalyst, the carrier is impregnated with respect to moisture capacity or from excess solution, while the impregnation is carried out at a temperature of 20-80 ° C for 20-60 minutes with periodic stirring, and after impregnation, the catalyst is dried in air at a temperature of 100-200 ° C. Such preparation conditions ensure that the composition of the aluminum borate catalyst Al ₃ BO ₆ with the structure of norbergite, representing 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 ° and lead to a catalyst having specific surface area 130-180 m ² / g, pore volume 0.35-0.65 cm ³ / g, average pore diameter 10-15 nm, and representing particles with a cross section in the form of a circle, trefoil or four-leaf with a diameter of the circumscribed circle 1 , 0-1.6 mm and a length of up to 20 mm and containing th wt. %: [Ni (H ₂ O) ₂ ] ₂ [Mo ₄ O ₁₁ (C ₆ H ₅ O ₇ ) ₂ ] 29.0-36.0%; 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 technical effect of the proposed method for the preparation of the catalyst consists of the following components:

1. The inventive method of preparation provides for the preparation of a catalyst, the chemical composition of which determines its maximum activity in the target reactions occurring during hydrotreating of hydrocarbon feedstocks. 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 helps minimize undesirable chemical interaction between active metals (Ni and Mo) and the support, and selectively produces the most active sulfide component in hydrotreatment - type II NiMoS phase II .

2. The use of a carrier containing aluminum borate Al ₃ BO ₆ with norbergite structure for the preparation of the catalyst 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 °, which helps to achieve texture characteristics of the catalyst, in particular, the average pore diameter in the range of 10-15 nm, providing access to all active molecules to be converted to the active component.

3. The use of bimetallic complex compounds [Ni (H ₂ O) ₂ ] ₂ [Mo ₄ O ₁₁ (C ₆ H ₅ O ₇ ) ₂ ] for the preparation of the catalyst ensures the further formation in the catalyst, during its operation in hydrotreating, of the most active component Particle-type NiMoS phase II is optimal for catalysis morphology, localized in raw materials accessible to all molecules to be converted.

4. The use of impregnation and drying of the catalyst under the claimed conditions ensures the preservation of the composition of the catalyst initially present in the composition of the aluminum borate Al ₃ BO ₆ with the structure of norbergite representing particles with sizes from 10 to 200 nm, characterized by interplanar distances of 3.2 and 2.8 A, s the angle between them is 53.8 °, the presence of which in the catalyst in the claimed concentrations promotes a combination of acid and texture characteristics that ensure maximum catalyst activity in the target reactions hydrotreating s.

Description of the proposed technical solution.

First, 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 that provides PTAG with the following characteristics: mass fraction of the X-ray amorphous phase,%, not less than 80; the proportion 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 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 solutions of nitric acid 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 at the inlet of the dryer of at least 150 ° C and continuous stirring of the suspension. 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 peptization of the obtained powder in a laboratory mixer with Z-shaped blades in the presence of a 2.5% aqueous solution of ammonia. 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) ° С for 2 hours. Heat treatment is carried out in a muffle furnace with compressed air supplied to the furnace. The extrudates in a porcelain cup were placed in an oven and calcined at a temperature of (550 ± 10) ° С 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 ² / g, an average pore diameter of 10-15 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 [Ni (H ₂ O) ₂ ] 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, nickel (II) carbonic basic aqueous NiCO ₃ ⋅mNi (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. The rotation speed of the stirrer is set at 300 rpm and the solution temperature is 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 solution temperature (60 ± 5) ° С. 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 nickel (II) carbon dioxide basic water is added to the previously obtained aqueous solution of molybdenum (VI) citrate. In this case, the liquid foams, and its temperature rises to 70 ° C. Stirring is continued at (75-80) ° C until a uniform, clear solution of bright green color is obtained, free of turbidity, bubbles and foam. The solution contains nickel and molybdenum in the form of a bimetallic complex compound [Ni (H ₂ O) ₂ ] 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 20-80 ° C for 20-60 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 [Ni (H ₂ O) ₂ ] ₂ [Mo ₄ O ₁₁ (C ₆ H ₅ O ₇ ) ₂ ] 29.0-36.0%; 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 10-15 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, the catalyst contains wt. %: Mo - 10.0-14.0; Ni 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 40-50 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 2 мл концентрированной азотной кислоты, 70 мл водного раствора, содержащего 5 г борной кислоты Н₃ВО₃ и 3 г этиленгликоля. Весовые отношения компонентов смеси - гидроксид алюминия : вода : азотная кислота : борная кислота : этиленгликоль = 1:0,7:0,02:0,05:0,03.To 100 g of AlOOH aluminum hydroxide powder having a boehmite structure with a crystal size

, with an average agglomerate size of 40-50 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 2 ml of concentrated nitric acid, 70 ml of an aqueous solution containing 5 g of boric acid H ₃ BO ₃ and 3 g of ethylene glycol. The weight ratio of the components of the mixture is aluminum hydroxide: water: nitric acid: boric acid: ethylene glycol = 1: 0.7: 0.02: 0.05: 0.03.

The resulting paste is stirred at room temperature for 40 minutes, then formed through a die with a cross section in the form of a trefoil with a diameter of the circumscribed circle of 1.5 mm at a pressure of 6.0 MPa. The obtained granules are dried in an oven at 110 ° C for 2 hours, then calcined at 550 ° C for 4 hours.

The result is a carrier containing In - 1.0 wt. %, Al ₂ O ₃ - the rest; having a specific surface area of 250 m ² / g, a pore volume of 0.95 cm ³ / g, an average pore diameter of 13 nm, which is a particle with a cross section in the form of a trefoil with a diameter of the circumscribed circle 1.4 mm, length up to 20 mm.

A bimetallic compound of the composition, [Ni (H ₂ O) ₂ ] ₂ [Mo ₄ O ₁₁ (C ₆ H ₅ O ₇ ) ₂ ] is synthesized, for which 40.5 g of C ₆ citric acid are successively dissolved in 70 ml of distilled water with stirring H ₈ O ₇ ; 71.0 g of ammonium paramolybdate (NH ₄ ) ₆ Mo ₇ O ₂₄ × 4H ₂ O and 17.3 g of nickel hydroxide Ni (OH) ₂ . 15 ml of ethylene glycol was added to the resulting solution, and the volume of the solution was adjusted to 160 ml by adding water.

20 g of the carrier are impregnated with a moisture capacity of 16 ml of an aqueous solution of [Ni (H ₂ O) ₂ ] ₂ [Mo ₄ O ₁₁ (C ₆ H ₅ O ₇ ) ₂ ] and ethylene glycol. The catalyst is dried in air at 100 ° 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 at 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 - 13.0; Ni - 3.4; S 9.6; B - 0.5; C - 6.7; Al ₂ O ₃ - the rest.

Next, hydrotreating the hydrocracking feed is carried out, using vacuum gas oil having a boiling range of 360-570 ° C, containing 3.5% sulfur and 0.2% nitrogen. Hydrotreating is carried out at a pressure of 10.0 MPa, a feed rate of 0.7 h ^-1 , a volume ratio of hydrogen / feed is 1200 nm ³ / m ³ , and a temperature of 380 ° C. 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 inlet temperature of 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 wt. %: 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 [Ni (H ₂ O) ₂ ] ₂ [Mo ₄ O ₁₁ (C ₆ H ₅ O ₇ ) ₂ ] is prepared, for which 48.91 g of citric acid C are successively dissolved in 100 ml of distilled water with stirring ₆ H ₈ O ₇ ; 89.87 g of ammonium paramolybdate (NH ₄ ) ₆ Mo ₇ O ₂₄ × 4H ₂ O and 31.4 g of basic nickel carbonate NiCO ₃ ⋅mNi (OH) ₂ ⋅nH ₂ O. After complete dissolution of all components by adding distilled water, volume the solution was adjusted to 200 ml. 100 g of the obtained carrier are impregnated with a moisture capacity of 67 ml of a solution of the bimetallic complex compound [Ni (H ₂ O) ₂ ] 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 resulting catalyst contains wt. %: [Ni (H ₂ O) ₂ ] ₂ [Mo ₄ O ₁₁ (C ₆ H ₅ O ₇ ) ₂ ] - 32.4%; 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 wt. %: Mo - 12.5; Ni - 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, hydrotreating the hydrocracking feed is carried out analogously to Example 1. The results of testing the catalyst in hydrotreating 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 support are impregnated with a moisture capacity of 67 ml of a solution of the bimetallic complex compound [Ni (H ₂ O) ₂ ] ₂ [Mo ₄ O ₁₁ (C ₆ H ₅ O ₇ ) ₂ ] from Example 2. Then, the catalyst is dried in air at 100 ° FROM.

The resulting catalyst contains wt. %: [Ni (H ₂ O) ₂ ] ₂ [Mo ₄ O ₁₁ (C ₆ H ₅ O ₇ ) ₂ ] - 32.4%; 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; Ni - 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, hydrotreating the hydrocracking feed is carried out analogously to Example 1. The results of testing the catalyst in hydrotreating 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 wt. %: 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 support are impregnated with a moisture capacity of 66 ml of a solution of the bimetallic complex compound [Ni (H ₂ O) ₂ ] ₂ [Mo ₄ O ₁₁ (C ₆ H ₅ O ₇ ) ₂ ] from Example 2. Then, the catalyst is dried in air at 200 ° FROM.

The resulting catalyst contains wt. %: [Ni (H ₂ O) ₂ ] ₂ [Mo ₄ O ₁₁ (C ₆ H ₅ O ₇ ) ₂ ] - 32.4%; 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; Ni - 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, hydrotreating the hydrocracking feed is carried out analogously to Example 1. The results of testing the catalyst in hydrotreating are shown in the table.

Example 5

Prepare the media as in example 3.

A solution of the bimetallic complex compound [Ni (H ₂ O) ₂ ] ₂ [Mo ₄ O ₁₁ (C ₆ H ₅ O ₇ ) ₂ ] is prepared, for which 42.23 g of C ₆ citric acid are successively dissolved in 100 ml of distilled water with stirring H ₈ O ₇ ; 77.58 g of ammonium paramolybdate (NH ₄ ) ₆ Mo ₇ O ₂₄ × 4H ₂ O and 27.1 g of basic nickel carbonate NiCO ₃ ⋅mNi (OH) ₂ ⋅nH ₂ O. After complete dissolution of all components, adding volume of distilled water the solution was adjusted to 200 ml.

100 g of the obtained support at room temperature are impregnated with a moisture capacity of 67 ml of a solution of the bimetallic complex compound [Ni (H ₂ O) ₂ ] ₂ [Mo ₄ O ₁₁ (C ₆ H ₅ O ₇ ) ₂ ]. Then the catalyst is dried in air at 120 ° C.

The resulting catalyst contains wt. %: [Ni (H ₂ O) ₂ ] ₂ [Mo ₄ O ₁₁ (C ₆ H ₅ O ₇ ) ₂ ] - 29.3%; 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.

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 wt. %: Mo - 10.0; Ni - 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, hydrotreating the hydrocracking feed is carried out analogously to Example 1. The results of testing the catalyst in hydrotreating 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 [Ni (H ₂ O) ₂ ] ₂ [Mo ₄ O ₁₁ (C ₆ H ₅ O ₇ ) ₂ ] is prepared, for which 56 are successively dissolved in 100 ml of distilled water while heating to 80 ° C and stirring. 9 g of citric acid C ₆ H ₈ O ₇ ; 104.53 g of ammonium paramolybdate (NH ₄ ) ₆ Mo ₇ O ₂₄ × 4H ₂ O and 36.5 g of basic nickel carbonate NiCO ₃ ⋅mNi (OH) ₂ ⋅nH ₂ O. After complete dissolution of all components by adding distilled water, volume the solution was adjusted to 200 ml.

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 80 ° C, 200 ml of a solution of the bimetallic complex compound [Ni (H ₂ O) ₂ ] ₂ [Mo ₄ O ₁₁ (C ₆ H ₅ O ₇ ) is poured into the flask ) 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 resulting catalyst contains wt. %: [Ni (H ₂ O) ₂ ] ₂ [Mo ₄ O ₁₁ (C ₆ H ₅ O ₇ ) ₂ ] - 35.8%; 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 wt. %: Mo - 14.0; Ni - 4.3; S 9.4; 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, hydrotreating the hydrocracking feed is carried out analogously to Example 1. The results of testing the catalyst in hydrotreating 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, which provides 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 [Ni (H ₂ O) ₂ ] ₂ [Mo ₄ O ₁₁ (C ₆ H ₅ O ₇ ) is poured into the flask ) 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 wt. %: [Ni (H ₂ O) ₂ ] ₂ [Mo ₄ O ₁₁ (C ₆ H ₅ O ₇ ) ₂ ] - 30.6%; 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; Ni - 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, hydrotreating the hydrocracking feed is carried out analogously to Example 1. The results of testing the catalyst in hydrotreating are shown in the table.

Thus, as can be seen from the above examples, the proposed method of preparation provides a catalyst that allows you to get raw materials for hydrocracking with a much lower sulfur and nitrogen content than using a catalyst prepared by the prototype method.

Claims (5)

1. A method of preparing a catalyst for hydrotreating a hydrocracking feedstock by applying a bimetallic complex compound to a boron-containing support comprising molybdenum and nickel compounds, characterized in that the catalyst is prepared by impregnating the support, which contains, wt. %: 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; an aqueous solution of the bimetallic complex compound [Ni (H ₂ O) ₂ ] ₂ [Mo ₄ O ₁₁ (C ₆ H ₅ O ₇ ) ₂ ], followed by drying. 2. The cooking method according to p. 1, characterized in that the resulting catalyst contains, by weight. %: [Ni (H ₂ O) ₂ ] ₂ [Mo ₄ O ₁₁ (C ₆ H ₅ O ₇ ) ₂ ] 29.0-36.0%; 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. 3. The preparation method according to p. 1, characterized in that the resulting 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 10-15 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. 4. The method of preparation according to claim 1, characterized in that the carrier is impregnated by moisture capacity or from excess solution, while the impregnation is carried out at a temperature of 20-80 ° C for 20-60 minutes with periodic stirring. 5. The cooking method according to claim 1, characterized in that after impregnation, the catalyst is dried in air at a temperature of 100-200 ° C.