RU2386476C2 - Catalyst for deep hydrofining oil fractions and method of preparing said catalyst - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: invention relates to chemistry and more specifically to preparation of catalysts for deep hydrofining oil fractions and can be used in oil refining and petrochemical industry. The catalyst for deep hydrofining oil fractions contains aluminium oxide, cobalt oxide and phosphomolybdic heteropolycomplex or vanadiummolybdic heteropolycomplex or phosphovanadiummolybdic heteropolycomplex with the following content of components in wt %: phosphomolybdic heteropolycomplex [P·(MoO₃)₁₂] 14.3-27.5; cobalt oxide CoO 3.2-8.5; aluminium oxide 64.0-82.5; or phosphovanadiummolybdic heteropolycomplex [P·(V₂O₅)_0.5(MoO₃)₁₁] 14.8-28.4; cobalt oxide CoO 3.2-8.5; aluminium oxide 63.1-82.0; or vanadiummolybdic heteropolycomplex [V·(MoO₃)₁₂] 14.4-27.8; cobalt oxide CoO 3.2-8.5; aluminium oxide 63.7-82.4. The method of preparing the catalyst involves impregnation of an aluminium oxide support with a solution of group VIII and VI metal compounds, where the combined impregnating solution contains a molybdenum heteropolycompound selected from (NH₄)₃[PMo₁₂O₄₀]·10H₂O, (NH₄)₃[PVMo₁₁O₄₀]·8H₂O or (NH₄)₃[VMo₁₂O₄₀]·₁₀H₂O cobalt nitrate Co(NO₃)₂·6H₂O with molar ratio Mo/Co equal to 1.7-2.3, stabilised 25-35 ml 30% H₂O₂ per 100 ml of the impregnating solution, with pH of the medium equal to 1.5-5.0 and single impregnation with aluminium oxide is carried out with subsequent drying and calcination at temperature not above 400°C.

EFFECT: obtaining a catalyst with given properties of an oxide precursor of a sulphide phase, and design of a method of preparing the said catalyst where the main active component (molybdenum) and a modifier (P and/or V) are brought into contact at molecular level in well defined ratios.

3 cl, 7 ex, 2 tbl

Description

The invention relates to the field of chemistry, and in particular to the field of production of catalysts intended for deep hydrotreating of oil fractions, and can be used in the oil refining and petrochemical industries.

Known catalysts for hydrotreating petroleum fractions contain molybdenum and / or tungsten and cobalt and / or nickel in oxide form deposited on the surface of a porous heat-resistant metal oxide. Catalytic compositions comprising various modifying additives are also known. So, according to [RU 2197323, B01J 23/88, B01J 21/12, publ. 01/27/2003] modifying compounds of elements: Si, B, F, P, etc. are introduced partially or in full into the carrier, alumina. According to [A.S. 1657227 USSR, 01J 37/02. No. 4,658,231 / 04; declared 12/19/88; publ. 06/23/91. Bull. No. 23 - 3 pp.] Modifying additive of vanadium, as well as molybdenum, is introduced into peptized aluminum hydroxide, molding, drying, calcining and impregnation of the calcined support with a solution of nickel salt are performed. Both of these technical solutions make it possible to produce inexpensive modified catalysts that are not active enough in the deep hydrotreating of oil fractions.

A known method for the preparation of hydrotreating catalysts is the extrusion of a mass of aluminum hydroxide mixed with Co and / or Ni and Mo and / or W salts. In this case, the active components are added to aluminum hydroxide peptized with any monobasic acid (RU 2189860, B01J 37/04, 23/882, 09/27/02; 2137541, B01J 23/88, C10G 45/08, 09/20/99). The precursors of the active component are the hardly soluble salts of molybdenum and tungsten, mainly ammonium molybdenum acid (NH ₄ ) ₆ Mo ₇ O ₂₄ · 4H ₂ O, and cobalt and nickel salts, mainly nitrates (RU 2137541, B01J 23/88, 20.09 .99). The main disadvantage of the catalysts obtained by this method is their low activity, which does not allow for deep hydrotreating of oil fractions. This is due to the fact that part of the active components introduced into the mass of aluminum hydroxide is not located on the active surface of the catalyst, but is enclosed in a volume of Al ₂ O ₃ .

Another known method for the preparation of hydrotreating catalysts is a method for impregnating alumina with solutions of active component compounds, drying and calcining. The application of the active components is carried out both by sequential impregnation from separate solutions, and by single-stage impregnation from a joint solution. To stabilize the joint solution of the compounds Co (Ni) and Mo (W), mineral acids, mainly phosphoric acid, are added to the impregnation solutions. The main disadvantage of co-impregnating solutions of Co (Ni) and Mo (W) compounds stabilized with inorganic phosphorus-containing acids is their low stability in the presence of an excess of phosphoric acid and NH ⁴⁺ ion due to precipitation of Co or Ni phosphates and ammonium phosphormolibdates. To create stable joint impregnating solutions, a concentrated ammonia solution is also used, which forms complex compounds with Co (Ni), which prevents the formation of molybdate deposits of these metals. In the case of ammonia impregnation in an insufficiently concentrated ammonia solution, precipitation of Co or Ni molybdates is possible.

According to [RU 2313389, B01J 23/882, B01J 27/885, publ. 12/27/2007] the impregnating solution is stabilized with phosphoric and citric acid. The disadvantage in this case is the presence of phosphoric acid in the solution, which can lead to a decrease in its stability. Molybdenum-containing anions, depending on the pH of the solution, can have a different degree of polymerization of molybdenum, forming isopolyanions. The use of organic acids as a complexing agent leads to the fact that the degree of polymerization of molybdenum in solution is uncertain and depends on many factors. As a result, it is impossible to create an oxide precursor of the active phase of sulfide molybdenum-containing catalysts with a certain, predetermined degree of polymerization of molybdenum.

An analogue is a catalyst for hydrotreating oil fractions and a method for its preparation [US Pat. 2147255 RF, IPC ⁷ B01J 23/88, C10G 45/08. No. 98105317/04; declared 03/17/98; publ. 01/27/2000. BI No. 10 - 6 p.]. The described catalyst contains 10-14% molybdenum oxide, 3-5% nickel oxide or cobalt oxide, 1.02-4.08% silicon-tungsten complex, the rest is aluminum oxide. The main disadvantage of this catalyst is the low content of the heteropolycomplex of tungsten (active component) and silicon (modifier), which is formed when the catalyst is calcined after the carrier is impregnated with tungsten acid. A method for producing this catalyst is also described. The main disadvantage of this method is that the main active component - molybdenum - in the amount of 10-14% is introduced into the peptized mass of aluminum hydroxide, after which extrusion molding, drying and calcination are carried out. As a result, a substantial part of molybdenum is not on the active surface of the catalyst, but in the volume of aluminum oxide inert in catalysis. The promoter, nickel or cobalt, is applied on the formed support surface from a combined solution of silicotungsten acid and nickel nitrate and is aimed at reducing the formation of aluminum-nickel spinel, but calcination of the finished catalyst at 500 ° C leads to the migration of part of Co or Ni into the volume of aluminum oxide and the formation of spinel , which excludes this part of the promoter from catalysis.

The technical solution allows for deep hydrotreating of oil fractions of both straight-run and secondary origin. A catalyst is proposed which contains phosphoformolybdenum, or vanadium-molybdenum, or phosphorus-vanadium-molybdenum heteropolycomplex of molybdenum on the active surface, and a method for its preparation, in which at the stage of impregnation of the oxide form of the catalyst, contact is made at the molecular level between the main active component (molybdenum), the modifier (P and / or V ) and a promoter (cobalt) in strictly specified ratios. A limitation of the calcination temperature of the finished catalyst (not higher than 400 ° C) is introduced in order to prevent complete thermal decomposition of the heteropoly complex and to preserve its structure on the catalyst surface. After sulfidation of the oxide precursor, the CoMoS / Al ₂ O ₃ catalyst has a regular layered structure, a higher dispersion of the active phase, which is cobalt promoted and modified with P and / or V additives. The modified sulfide phase has a higher Lewis acidity, sulfide sulfur mobility and higher density anionic vacancies. It is anionic vacancies that are responsible not only for the hydrogenolysis of the CS bond, but also for the hydrogenation of aromatic rings in thiophene derivatives. Oil fractions of secondary origin contain stable sulfur compounds, such as dibenzo, naphthbenz and dinaphthiophenes, especially alkyl substituted ones. It is known that the transformations of such compounds proceed by several mechanisms, one of which includes the stage of hydrogenation of aromatic fragments of hybrid molecules.

A distinctive feature of the present invention is the totality of the proposed solutions, including: a catalyst for the deep hydrotreating of oil fractions containing alumina, cobalt oxide and a phosphoromolybdenum heteropolycomplex, or a vanadium-molybdenum heteropolycomplex, or a phosphorovanadium-molybdenum heteropolycomplex, with the following contents:

phosphorus-molybdenum heteropoly complex [P · (MoO ₃ ) ₁₂ ] 14.3-27.5 cobalt oxide CoO 3.2-8.5 aluminium oxide 64.0-82.5

or

phosphonovanadium molybdenum heteropoly complex [P · (V ₂ O ₅ ) _0.5 (MoO ₃ ) ₁₁ ] 14.8-28.4 cobalt oxide CoO 3.2-8.5 aluminium oxide 63.1-82.0

or

vanadium molybdenum heteropoly complex [V · (MoO ₃ ) ₁₂ ] 14.4-27.8 cobalt oxide CoO 3.2-8.5 aluminium oxide 63.7-82.4

Use of molybdenum as starting compounds for the synthesis of catalysts for heteropoly compounds (NH ₄ ) ₃ [PMo ₁₂ O ₄₀ ] · 10H ₂ O, (NH ₄ ) ₃ [PVMo ₁₁ O ₄₀ ] · 8H ₂ O, (NH ₄ ) ₃ [VMo ₁₂ O ₄₀ ] · 10H ₂ O, the molecules of which simultaneously comprise the main active component (Mo) and the modifier; use for impregnation of the carrier of the joint impregnating solution of the indicated heteropoly compounds of molybdenum and cobalt nitrate stabilized with 25-35 ml of 30% H ₂ O ₂ per 100 ml of impregnating solution; the molar ratio Mo / Co = 1.70-2.30 in the impregnating solution and in the catalyst necessary to create a promoted sulfide phase; the pH of the impregnating solution is 1.5-5.0, at which the existence of the above heteropoly compounds is possible; evacuation of the weighed portion of the carrier before its contact with the impregnating solution, which allows uniform impregnation of the entire active surface, including the surface of the "dead end"pores; the use of elevated temperatures of the impregnating solution with a high concentration of the molybdenum compound in it, which allows it to maintain its chemical and physical stability; final calcination of the catalyst at temperatures no higher than 400 ° C, which leads to complete cleavage of ammonia, which is part of the ammonium ion, but does not destroy the structure of the above heteropolycomplexes (confirmed by experiments combining DTA and PC spectroscopy). These solutions together make it possible to synthesize a catalyst that allows for deep hydrotreating of oil fractions at process parameters that correspond to the capabilities of domestic hydrotreatment plants.

The technical result of the present invention is a catalyst with the desired properties of the oxide precursor of the sulfide phase and a method for its preparation, in which contact is made at the molecular level between the main active component (molybdenum) and the modifier (P and / or V) in strictly defined proportions. The synthesis method allows you to enter into the composition of the alumina-cobalt-molybdenum catalyst heteropolycomplex of molybdenum with phosphorus, or vanadium, or phosphorus and vanadium.

The technical result is achieved by the fact that the catalyst for the deep hydrotreating of oil fractions contains alumina, cobalt oxide and a phosphorus-molybdenum heteropolycomplex, or a vanadium-molybdenum heteropolycomplex, or a phosphorus-vanadium molybdenum heteropolycomplex with the following content of components, wt.%:

phosphorus-molybdenum heteropoly complex [P · (MoO ₃ ) ₁₂ ] 14.3-27.5 cobalt oxide CoO 3.2-8.5 aluminium oxide 64.0-82.5

or

phosphonovanadium molybdenum heteropoly complex [P · (V ₂ O ₅ ) _0.5 (MoO ₃ ) ₁₁ ] 14.8-28.4 cobalt oxide CoO 3.2-8.5 aluminium oxide 63.1-82.0

or

vanadium molybdenum heteropoly complex [V · (MoO ₃ ) ₁₂ ] 14.4-27.8 cobalt oxide CoO 3.2-8.5 aluminium oxide 63.7-82.4

as well as a method of preparing a catalyst, comprising impregnating an alumina carrier with a solution of metal compounds of groups VIII and VI. A joint impregnation solution is prepared containing a molybdenum heteropoly compound selected from (NH ₄ ) ₃ [PMo ₁₂ O ₄₀ ] · 10H ₂ O, (NH ₄ ) ₃ [PVMo ₁₁ O ₄₀ ] · 8H ₂ O or (NH ₄ ) ₃ [VMo ₁₂ O ₄₀ ] · 10H ₂ O and cobalt nitrate Co (NO ₃ ) ₂ · 6H ₂ O with a Mo / Co molar ratio of 1.7-2.3, stabilized with 25-35 ml of 30% H ₂ O ₂ per 100 ml of impregnating solution, at a pH of 1.5–5.0, and a single impregnation of alumina is carried out with an impregnating solution at temperatures of 20-90 ° C, followed by drying and calcination at temperatures not exceeding 400 ° C.

The starting compounds for preparing a joint impregnating solution, the conditions for impregnating the support with a joint impregnating solution, and calcining the prepared catalysts are given in Table 1. The support was a γ-Al ₂ O ₃ extrudate in the form of a trefoil with a diameter of 1.2-1.3 mm and a length of 4-6 mm.

The catalysts were tested in the form of particles of 0.25-0.5 mm in size, prepared by grinding and dispersing the initial granules of the calcined catalyst. The catalysts were sulfidized at atmospheric pressure and a temperature of 400 ° C in a mixture of 20% vol. H ₂ S and H ₂ for 2 hours. Such sulfidation conditions, according to N. Tops⌀e, make it possible to obtain the CoMoS type II active phase on the catalyst surface. Testing of the activity of the catalysts was carried out in a laboratory flow unit under hydrogen pressure. Download sulfidized catalyst 20 cm ³ . The reactor is specially designed so that the test results of the catalysts coincide with the industrial data, which is confirmed by comparing the results of the experimental run in industry and testing on the same industrial catalyst using one raw material. Raw materials for testing was a mixture of 90% vol. straight run diesel fraction and 10% vol. light gas oil catalytic cracking and had the following characteristics: ρ ₄ ²⁰ = 0.8583; n _D ²⁰ = 1.4806; a sulfur content of 1.19 wt% (11,900,000,000 ^-1).; boiling point 185 ° C; boiling point 96% vol. 365 ° C. Test conditions: partial pressure of hydrogen 4.0 MPa, the frequency of hydrogen circulation of 600 nl / l of raw materials, the volumetric feed rate of 1.4 h ^-1 , the temperature in the reactor 320, 340, 360 and 380 ° C. Hydrogenates were separated from hydrogen in a separator at a pressure almost equal to the pressure in the reactor and a temperature of 20 ° C, then subjected to treatment with 10% NaOH solution for 15 min, washed with distilled water to neutral wash water, dried for 1 day over calcined CaCl ₂ . Sulfur content was determined using an X-ray fluorescence analyzer. The average value was taken from three parallel measurements. The characteristics and test results of the catalysts are presented in table.2.

Example 1

To prepare a joint impregnating solution of the salts of the active components, 16.8 g of (NH ₄ ) ₃ [PMo ₁₂ O ₄₀ ] · 10H ₂ O are dissolved in 49.5 ml of hot distilled water and 16.5 ml of a 30% solution of H ₂ O are added. ₂ . To the resulting solution was added 12.5 g of cobalt nitrate Co (NO ₃ ) ₂ · 6H ₂ O and stirred. The solution is acidified with monobasic mineral acid to a pH of 1.5. A solution with a temperature of 20 ° C is impregnated with 82.5 g of alumina carrier in terms of moisture capacity. The resulting catalyst is dried at a temperature of 80, 100, 120 ° C for 2 hours at each temperature; then the temperature is increased at a rate of 1 ° C / min to a temperature of 400 ° C, at which the catalyst is kept for 2 hours in a stream of air.

The composition of the finished catalyst, wt.%: 14.3 [P · (MoO ₃ ) ₁₂ ]; 3.2 CoO; 82.5 Al ₂ O ₃ .

Example 2

To prepare a joint impregnating solution of salts of the active components, 32.4 g of (NH ₄ ) ₃ [PMo ₁₂ O ₄₀ ] · 10 H ₂ O are dissolved in 33.3 ml of hot distilled water and 17.9 ml of a 30% solution of H ₂ O are added ₂ . To the resulting solution was added 33.1 g of cobalt nitrate Co (NO ₃ ) ₂ · 6H ₂ O and stirred. The solution is acidified with monobasic mineral acid to pH 3.0. A solution with a temperature of 90 ° C is impregnated with 64.0 g of alumina carrier in terms of moisture capacity. The resulting catalyst is dried and calcined according to example 1.

The composition of the finished catalyst, wt.%: 27.5 [P · (MoO ₃ ) ₁₂ ]; 8.5 CoO; 64.0 Al ₂ O ₃ .

Example 3

To prepare a joint impregnating solution of salts of the active components, 17.6 g of (NH ₄ ) ₃ [PVMo ₁₁ O ₄₀ ] · 8H ₂ O were dissolved in 49.2 ml of hot distilled water and 16.4 ml of a 30% solution of H ₂ O were added. ₂ . To the resulting solution was added 12.5 g of cobalt nitrate Co (NO ₃ ) ₂ · 6H ₂ O and mixed. The solution was acidified with monobasic mineral acid to a pH of 2.5. A solution with a temperature of 20 ° C was impregnated with 82.0 g of alumina support in terms of moisture capacity. The resulting catalyst was dried and calcined according to example 1.

The composition of the finished catalyst, wt.%: 14.8 [P · (V ₂ O ₅ ) _0.5 (MoO ₃ ) ₁₁ ]; 3.2 CoO; 82.0 Al ₂ O ₃ .

Example 4

To prepare a joint impregnating solution of salts of the active components, 34.0 g of (NH ₄ ) ₃ [PVMo ₁₁ O ₄₀ ] · 8H ₂ O are dissolved in 32.8 ml of hot distilled water and 17.7 ml of a 30% solution of H ₂ O are added ₂ . To the resulting solution was added 33.1 g of cobalt nitrate Co (NO ₃ ) ₂ · 6H ₂ O and stirred. The solution is acidified with monobasic mineral acid to a pH of 2.5. A solution with a temperature of 90 ° C is impregnated with 63.1 g of alumina carrier in terms of moisture capacity. The resulting catalyst is dried and calcined according to example 3.

The composition of the finished catalyst, wt.%: 28.4 [P · (V ₂ O ₅ ) _0.5 (MoO ₃ ) ₁₁ ]; 8.5 CoO; 63.1 Al ₂ O ₃ .

Example 5

To prepare a joint impregnating solution of salts of the active components, 17.0 g of (NH ₄ ) ₃ [VMo ₁₂ O ₄₀ ] · ₁₀ H ₂ O are dissolved in 49.4 ml of hot distilled water and 16.5 ml of a 30% solution of H ₂ O are added ₂ . To the resulting solution was added 12.5 g of cobalt nitrate Co (NO ₃ ) ₂ · 6H ₂ O and stirred. The solution is acidified with monobasic mineral acid to a pH of 1.5. A solution with a temperature of 20 ° C is impregnated with 82.4 g of alumina carrier in terms of moisture capacity. The resulting catalyst is dried and calcined according to example 1.

The composition of the finished catalyst, wt.%: 14.4 [V · (MoO ₃ ) ₁₂ ]; 3.2 CoO; 82.4 Al ₂ O ₃ .

Example 6

To prepare a joint impregnating solution of salts of the active components, 32.7 g of (NH ₄ ) ₃ [VMo ₁₂ O ₄₀ ] · 10H ₂ O are dissolved in 33.1 ml of hot distilled water and 17.8 ml of a 30% solution of H ₂ O are added ₂ . To the resulting solution was added 33.1 g of cobalt nitrate Co (NO ₃ ) ₂ · 6H ₂ O and stirred. The solution is acidified with monobasic mineral acid to a pH of 1.5. A solution with a temperature of 90 ° C is impregnated with 63.7 g of alumina carrier in terms of moisture capacity. The resulting catalyst is dried and calcined according to example 1.

The composition of the finished catalyst, wt.%: 27.8 [V · (MoO ₃ ) ₁₂ ]; 8.5 CoO; 63.7 Al ₂ O ₃ .

Example 7 (prototype example 5)

The composition of the finished catalyst, wt.%: 12.0 MoO ₃ ; 4.5 CoO; [SiO ₂ · 12WO ₃ ] 2.55; 80.95 Al ₂ O ₃ .

Table 1 Compounds of molybdenum used for the preparation of catalysts, conditions for impregnation of the carrier and calcination of the finished catalyst N Molybdenum heteropoly compound The molar ratio of Mo: Co in the composition of the impregnating solution The amount of 30% H ₂ O ₂ , ml, per 100 ml of impregnation solution pH of the impregnation solution Media impregnation temperature, ° С one (NH ₄ ) ₃ [PMo ₁₂ O ₄₀ ] · 10H ₂ O 2,3 25 1,5 twenty 2 (NH ₄ ) ₃ [PMo ₁₂ O ₄₀ ] · 10H ₂ O 1.7 35 3.0 90 3 (NH ₄ ) ₃ [PVMo ₁₁ O ₄₀ ] · 8H ₂ O 2,3 25 2.5 twenty four (NH ₄ ) ₃ [PVMo ₁₁ O ₄₀ ] · 8H ₂ O 1.7 35 2.5 90 5 (NH ₄ ) ₃ [VMo ₁₂ O ₄₀ ] · 10H ₂ O 2,3 25 1,5 twenty 6 (NH ₄ ) ₃ [VMO ₁₂ O ₄₀ ] · 10H ₂ O 1.7 35 1,5 90 7 According to the prototype

table 2 The composition of the catalysts and the residual sulfur content in hydrogenates N Heteropoly complex of molybdenum The content in the catalyst, wt.% The molar ratio of Mo: Co in the composition of the catalyst The residual sulfur content in the hydrogenate at the test temperature, mln ^-1 Soo heteropoly complex of molybdenum 320 ° C 340 ° C 360 ° C 380 ° C one [P · (MoO ₃ ) ₁₂ ] 3.2 14.3 2,3 174 120 70 35 2 [P · (MoO ₃ ) ₁₂ ] 8.5 27.5 1.7 165 115 63 26 3 [P · (V ₂ O ₅ ) _0.5 (MoO ₃ ) ₁₁ ] 3.2 14.8 2,3 162 106 51 25 four [P · (V ₂ O ₅ ) _0.5 (MoO ₃ ) ₁₁ ] 8.5 28,4 1.7 123 84 40 17 5 [V · (MoO ₃ ) ₁₂ ] 3.2 14,4 2,3 169 one hundred 64 thirty 6 [V · (MoO ₃ ) ₁₂ ] 8.5 27.8 1.7 173 91 47 22 7 * [SiO ₂ · 12WO ₃ ] 2.55% CoO 4.5% MoO ₃ 12.0% 512 380 273 262

Claims (3)

1. The catalyst for the deep hydrotreating of oil fractions containing aluminum oxide, cobalt oxide and a phosphorus-molybdenum heteropoly complex or a vanadium-molybdenum heteropoly complex or a phosphorus vanadium-molybdenum heteropoly complex with the following components, wt.%:
phosphorus-molybdenum heteropoly complex [P · (MoO ₃ ) ₁₂ ] 14.3-27.5 cobalt oxide CoO 3.2-8.5 aluminium oxide 64.0-82.5
or
phosphonovanadium molybdenum heteropoly complex [P · (V ₂ O ₅ ) _0.5 (MoO ₃ ) ₁₁ ] 14.8-28.4 cobalt oxide CoO 3.2-8.5 aluminium oxide 63.1-82.0
or
vanadium molybdenum heteropoly complex [V · (MoO ₃ ) ₁₂ ] 14.4-27.8 cobalt oxide CoO 3.2-8.5 aluminium oxide 63.7-82.4 2. A method of preparing a catalyst, comprising impregnating an alumina carrier with a solution of Group VIII and VI metal compounds, characterized in that a joint impregnating solution is prepared containing a molybdenum heteropoly compound selected from (NH ₄ ) ₃ [PMO ₁₂ O ₄₀ ] · 10H ₂ O, ( NH ₄ ) ₃ [PVMO ₁₁ O ₄₀ ] · 8H ₂ O or (NH ₄ ) ₃ [VMo ₁₂ O ₄₀ ] · 10H ₂ O and cobalt nitrate Co (NO ₃ ) ₂ · 6H ₂ O at a molar ratio of Mo / Co, equal to 1.7-2.3, 25-35 ml of stabilized 30% H ₂ O ₂ per 100 ml of impregnating solution at pH 1.5-5.0 and made single impregnation with alumina followed by drying and n okalivaniem at temperatures not exceeding 400 ° C. 3. The method according to claim 2, characterized in that the impregnation of the carrier granules is carried out after creating a vacuum in a vessel containing a weighed portion of the carrier and keeping the weighed portion of the carrier in vacuum for 30 minutes (evacuation of the carrier).