RU2569682C2 - Composition and method for preparation of carrier and catalyst of deep hydrofining of hydrocarbon stock - Google Patents

Abstract

FIELD: process engineering.

SUBSTANCE: invention relates to catalyst of deep hydrofining of hydrocarbon stock consisting of one or several bimetallic complex compounds of metals of VIII and VIB groups applied on modified carrier of definite composition. Catalyst features specific surface of 180-350 m²/g, pore volume of 0.3-0.6 cm³/g, pore mean diameter of 8.5-13.0 nm. Besides, invention relates to catalyst carrier. The latter consists of the composition of aluminium gamma-oxide and oxides of non-metals: phosphorus and/or boron, and oxides of transition metals: nickel and/or cobalt, or one of oxides of precious metals: platinum, rhodium, ruthenium at the following ratio of components, wt %: non-metal oxides - 0.5-1.3, transition metal oxides - 0.5-5.0 or oxides of precious metal - 0.3-0.8, aluminium oxide - 99.0-93.5. It features specific surface of 200-370 m²/g, pore volume of 0.5-1.0 cm³/g, pore mean diameter of 8.5-13.5. Invention relates also to production of this carrier. This is executed by impregnation of aluminium gamma-oxide with compounds of boron and/or phosphorus, transition metals (nickel and/or cobalt) or one of precious metals platinum, rhodium, ruthenium with drying at 80-120°C (5 h) and calcination at 300°C (2 h). Then, this process comprises one-pass impregnation of carrier with water solution with pH 1.5-3.0 containing at least one of heteropolyanions of the series [CO₂Mo₁₀O₃₈H₄]^6-, [Co(OH)₆Mo₆O₁₈]^4-, [Ni(OH)₆Mo₆O₁₈]^4-, [Ni₂Mo₁₀O₃₈H₄]^6-, [P₂Mo₅O₂₃]^6-, [SiMo₁₂O₄₀]^4-, [PMo₁₂O₄₀]^3-M. Here, cobalt is represented by one of series including cobalt hydroxide, cobalt carbonate CoCO₃ and basic cobalt carbonate. Here, nickel is represented by one of series including nickel hydroxide, nickel carbonate NiCO₃ and basic nickel carbonate. Impregnation solution stabiliser represents carboxylic acid containing at least one carboxyl group and 1-20 carbon atoms.

EFFECT: higher catalytic capacity of catalyst and catalyst efficiency.

15 cl, 2 tbl, 12 ex

Description

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

Recently, the need for the production of motor fuels with ultra-low sulfur content (less than 10 ppm) is growing. In the coming years, the largest tonnage refining process remains hydrotreating, and its role will increase due to the tightening of sulfur standards in gasoline and diesel fuel, as well as with an increase in the depth of oil refining and the involvement of unconventional hydrocarbon resources in oil refining.

The vast majority of hydrotreating catalysts are supported Co (Ni) Mo (W) / Al ₂ O ₃ systems, sometimes including other elements of the periodic system in their composition to improve or modify their catalytic properties. The synergy of the catalytic effect of Co (Ni) and Mo (W) sulfides is ensured by the formation of the Co (Ni) MoS phase during the sulfidation of the catalyst, in which highly dispersed MoS ₂ crystallites are decorated with promoter atoms (Co or Ni). At least two types of active components of sulfide catalysts are distinguished: Co (Ni) MoS phases of types I and II. The type II CoMoS phase significantly exceeds the type I phase in activity and is characterized by a weak interaction of the active components with the carrier and, therefore, a greater degree of sulfidation. In most cases, type II phases are in the form of multilayer packages of MoS ₂ , although this is not their mandatory property.

The disadvantage of traditional domestic catalysts CoMo / Al ₂ O ₃ and NiMo (W) / Al ₂ O ₃ is the low catalytic activity, which does not allow for the production of motor fuels with ultra-low sulfur content, due to the presence of type I active phase on the surface, as well as low activity in catalysis individual sulfides of transition metals and inactive spinels of the Ni (Co) Al ₂ O _{4 type} formed during the migration of promoter atoms at high-temperature calcination stages.

In recent years, to create catalysts for the deep hydrotreatment of hydrocarbon feedstocks, methods have been used to form the active component on the surface of a carrier that is optimal in texture and properties due to the following approaches:

1. The use of carriers with optimal textural characteristics, allowing maximum dispersion of the active component and uniformly apply it to the pores accessible to reagent molecules. For these purposes, carriers are synthesized with a developed specific surface (not lower than 200 m ² / g), pore volume (0.5-0.9 cm ³ / g) and a narrow pore size distribution, while the proportion of pores is 75-350 Å in size. should be at least 70-75% of the total pore volume (US 3840472, B01J 27/19, C10G 45/08, 8.10.74; 2003/0173256; 4818743, B01J 23/85, 04.04.89; 4879265, B01J 23 / 24, 07.11.89, RF No. 2192923, C10G 45/08, B01J 27/188, B01J 35/10, 11/20/2002; RF No. 2377067, B01J 21/04, C10G 45/04, B01J 23/58, B01J 23 / 75, B01J 23/755, B01J 27/18, 12/27/2009, etc.). This pore size distribution provides not only high availability of sulfur-containing compounds to the surface of the active component, but also reduces the possibility of pore coking.

2. The use of alumina carriers modified with additives of boron and / or phosphorus and / or rare earth metal (US 3755150, C10G 45/08, 08/28/1973; US 4392985, B01J 27/188, C10G 45/08; US 4500424, B01J 027 / 185, 02.19.1985; US 4818743, B01J 027/185, 04.04.1989, RF No. 2192923, C10G 45/08, B01J 27/188, B01J 35/10, 11/20/2002; RF No. 2197323, B01J 23/88, B01J 21/12, B01J 23/882, B01J 23/883, B01J 23/885, B01J 23/887, C10G 45/08, 01/27/2003; Russian Federation No. 2306978, B01J 23/88, B01J 23/83, B01J 37 / 02, September 27, 2007, etc.) that perform the functions of decreasing the concentration of the main centers on the surface of the carrier, decreasing the interaction of the oxide precursor, as well as increasing the mechanical strength and thermal stability s. The disadvantage of this method is manifested in the high content of additives, which lead to a decrease in catalytic stability due to accelerated deposition of coke.

3. Modification of alumina carriers with additives of titanium oxides (RF 2155637, B01J 23/88, 09/10/2000, etc.), zirconium and silicon (US 6267874, 07/31/2001; RF No. 2197323, B01J 23/88, B01J 21/12, B01J 23/882, B01J 23/883, B01J 23/885, B01J 23/887, C10G 45/08, 01/27/2003, etc.), additives of amorphous aluminosilicates and zeolites (US 5686374, B01J 29/10, 11.11.97 , Russian Federation No. 2311959, B01J 37/02, B01J 23/88, B01J 29/40, B01J 29/18, B01J 32/00, C10G 45/06, etc.) to increase the acid properties of the carrier. The main disadvantage of this method is the expensive synthesis technology of modified alumina carriers, for example, the use of silicon and aluminum alkoxides and elevated temperatures (40-90 ° C) as precursors for the co-precipitation and aging of gels in the case of inorganic silicon and aluminum compounds (US 6267874, 07/31/2001).

A common disadvantage for the above carriers is the increased acidity, which leads to accelerated coke deposits and catalyst deactivation. The technical solution of the present invention is the presence in the composition of the carrier of a transition or noble metal, which under the conditions of the hydrotreatment process is able to activate molecular hydrogen. Due to its high reactivity, activated hydrogen is actively involved in the target reactions and the hydrogenation of coke precursors, thereby increasing catalytic stability. Thus, the use of a new carrier, which is gamma-alumina, modified with an acid and metal additive, provides high catalyst performance.

Highly active hydrocarbon hydrotreating catalysts are prepared using the following approaches:

1. The use of "soft" modes of heat treatment of the catalyst at temperatures no higher than 200 ° C (US 2003/0173256, 09/18/2003; US 7618916 B2, 11/17/2009; RF No. 2402380, B01J 23/882, B01J 23/883, B01J 21 / 02, B01J 21/04, B01J 37/02, C10G 45/08, B01J 38/62, 10/27/2010, etc.) and sulfidation (US 4879265, 11.11.1989, US 2003/0173256, 09/18/2003, etc. .). The disadvantage of this method is that the oxide precursor may not completely sulfide, and the dispersion of the active phase of the catalyst is low.

2. An increase in the amount of introduced metal (for example, up to 20-29 wt.% MoO ₃ ), optimization of the Co (Ni) / Mo (W) ratio and catalyst sulfidation conditions to increase the amount of type II phase (US 4879265, B01J 027/19, 07/07/1989; US 2003/0173256; US 2006/00545536, 03.16.2006, etc.). The main disadvantage of this synthesis method is the difficulty in preparing concentrated impregnating solutions, the stage of application of active components, as well as the reduction of their dispersion.

3. The introduction into the active component of additives with a hydrogenating ability, for example Ni, W, or platinum group metals (Pt, Pd, Rh) to increase the hydrogenating ability of the catalyst (US 6267874, B01J 21/12, 07/31/2001). The main disadvantage of this method is the expensive technology for the synthesis of modified alumina carriers, due to the joint use of modified silicon-containing additives, carriers, so that the concentration of the Brainsted centers was at least 50 μmol / g, and platinum group metals.

4. The use of bimetallic compounds as precursors, including heteropoly compounds (RF №2103065 B01J 37/02, B01J 23/882, B01J 23/883, B01J 27/188, 01/27/1998; US 2004/0132614 A1, 07/08/2004; US 007687430 B2, 03/30/2010; RF No. 2385764 B01J 23/882, B01J 37/02, 04/10/2010; RF No. 2386476 B01J 23/88, B01J 23/882, B01J 27/199, B01J 37/02, 20.04. 2010; RF No. 2387475 B01J 21/04, B01J 27/19, B01J 27/24, C10G 45/08, 04/27/2010; RF No. 2414963 B01J 21/04, B01J 21/08, B01J 23/30, B01J 23 / 14, B01J 37/02, B01J 23/755, B01J 23/28, B01J 23/20, B01J 27/14, C10G 45/08, 03/27/2011, etc.). The main disadvantage of this method is the difficulty of controlling the composition of heteropoly compounds on the surface of the carrier caused by the oxide-oxide interaction of the precursor-carrier, especially in the thermal stages of preparation.

5. The use of organic additives that reduce the formation of crystallized phases such as CO ₃ O ₄ and CoAl ₂ O ₄ and oxide-oxide interaction of the precursor with the carrier (US 4879265, 11/11/1989; US 2003/0173256, 09/18/2003; US 6540908 B1, 01.04 .2003; US 6923904 B1, 08/02/2005; US 7235173 B2, 06/26/2007; US 7605107 B2, 10/20/2009; US 7618916 B2, 11/17/2009; RF №2402380, B01J 23/882, B01J 23/883, B01J 21/02, B01J 21/04, B01J 37/02, C10G 45/08, B01J 38/62, 10.27.2010, etc.). The disadvantage of these catalysts is the interaction of organic additives with the Mo (W) precursor, which reduces the rate of its sulfidation, as well as the use of solutions containing counter ions (ammonium cations, nitrate anions, etc.) that can reduce the dispersion of the oxide precursor, as well as interfere with the interaction of Mo (W) and Co (Ni) particles.

A common drawback for the above catalysts and methods for their preparation is that with their use it is not possible to achieve ultra-low residual sulfur content, low content of nitrogen-containing compounds and aromatic hydrocarbons in the resulting products, as well as rapid catalyst deactivation caused by coke deposits, particle agglomeration (sintering) active phase and the formation of individual sulfides during the operation of the catalysts, especially at elevated temperatures.

Closest to the proposed solution is a method of preparing a catalyst for deep hydrotreatment of hydrocarbon feedstock, in which at the stage of impregnation a complex oxygen-containing compound of molybdenum and cobalt and / or nickel is added. As a carrier, the catalyst contains alumina or alumina with the addition of silica or zeolite. A method of producing a catalyst includes dissolving molybdenum oxide and cobalt carbonate in a mixture of complexing organic acids (citric, lactic, malonic, acetic, formic) [RU 2314154, B01J 23/882, B01J 23/883, 01/10/2008].

The disadvantage of this method of preparation of the catalyst is that molybdenum-containing anions, depending on the pH of the solution, can have different degrees 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. The catalytic properties of the prototype catalyst do not allow to obtain products with ultra low sulfur content, low aromatic hydrocarbons.

The technical result of the present invention is the creation of a new composition and method of preparation of the carrier and catalyst for the deep hydrotreatment of hydrocarbons. The technical result is achieved by introducing a bimetallic complex compound of metals of the VIII and VIB groups of the Periodic system onto a modified carrier, which consists of a composition of gamma-alumina, non-metal oxides: phosphorus and / or boron, transition metal oxides: nickel and / or cobalt, or one of the noble metal oxides: platinum, rhodium, ruthenium, with the following content, wt.%: non-metal oxides 0.5-1.5, transition metal oxides 0.5-5.0 or noble metal oxides 0.3-0, 8, alumina 99.2-91.5%; the catalyst has a specific surface area of 180-350 m ² / g, a pore volume of 0.3-0.6 cm ³ / g, an average pore diameter of 8.5-13.0 nm.

The bimetallic complex compound contains at least one of the following heteropolyanions [CO ₂ Mo ₁₀ O ₃₈ H ₄ ] ^6- , [Co (OH) ₆ Mo ₆ O ₁₈ ] ^4- , [Ni (OH) ₆ Mo ₆ O ₁₈ ] ^4- , [Ni ₂ Mo ₁₀ O ₃₈ H ₄ ] ^6- , [P ₂ Mo ₅ O ₂₃ ] ^6- , [SiMo ₁₂ O ₄₀ ] ^4- , [PMo ₁₂ O ₄₀ ] ^3- , while the content is calcined at 550 ° C, the MoO ₃ catalyst is 14.0-23.0% wt., CoO and / or NiO - 4.0-6.5% wt. The catalyst is in the form of cylinders or trefoils.

The alumina support for deep hydrotreating hydrocarbon catalysts consists of a composition of gamma-alumina, non-metal oxides: phosphorus and / or boron, and also contains transition metal oxide: nickel and / or cobalt, or one of the noble metal oxides: platinum, rhodium, ruthenium, with the following content, wt.%: non-metal oxides 0.5-1.5, transition metal oxides 0.5-5.0 or noble metal oxides 0.3-0.8, aluminum oxide 99.2-91, 5%; has a specific surface area of 200-370 m ² / g, pore volume 0.5-1.0 cm ³ / g, average pore diameter 8.5-13.5 nm.

A method of obtaining a carrier for a catalyst for the deep hydrotreatment of hydrocarbon feeds is that gamma alumina is impregnated with compounds of boron and / or phosphorus, a transition metal (nickel and / or cobalt) or a noble metal (one of a number of platinum, rhodium, ruthenium), subsequent drying at 80-120 ° C (5 h) and calcination at 300 ° C (2 h). At least one of the following compounds is used as boron compounds: orthoboric acid H ₃ BO ₃ , pyroboric acid H ₂ B ₄ O ₇ , ammonium metaborate NH ₄ BO ₂ , ammonium borate (NH ₄ ) ₃ BO ₃ , ammonium tetraborate (NH ₄ ) ₂ B ₄ O ₇ , as phosphorus compounds - phosphoric acid H ₃ PO ₄ , metaphosphoric acid HPO ₃ , pyrophosphoric acid H ₄ P ₂ O ₇ , ammonium hydrogen phosphate (NH ₄ ) ₂ HPO ₄ , ammonium metaphosphate NH ₄ PO ₃ ammonium pyrophosphate (NH ₄ ) ₄ P ₂ O ₇ . At least one selected from the series is used as transition metal compounds: co (nitrate) cobalt nitrate hexahydrate Co (NO ₃ ) ₂ · 6H ₂ O, cobalt acetate tetrahydrate Co (CH ₃ COO) ₂ · 4H ₂ O, cobalt sulfate tetrahydrate CoSO ₄ · 7H ₂ O, cobalt chloride tetrahydrate CoCl ₂ · 4H ₂ O, cobalt citrate dihydrate Co ₃ (C ₆ H ₅ O ₇ ) ₂ · 2H ₂ O, nickel nitrate hexahydrate Ni (NO ₃ ) ₂ · 6H ₂ O, nickel acetate tetrahydrate Ni (CH ₃ COO) ₂ · 4H ₂ O, nickel sulfate tetrahydrate NiSO ₄ · 7H ₂ O, nickel chloride tetrahydrate NiCl ₂ · 4H ₂ O, nickel citrate dihydrate Ni (C ₆ H ₅ O ₇ ) ₂ · 14H ₂ O. B quality compounds noble metal use at least one selected from a number of chloroplatinic acid H ₂ PtCl ₆ tetrachloride geksaamminplatiny [Pt (NH _{3) 6]} Cl _4, dihlorodiamminoplatina (II), [PtCl ₂ (NH _{3) 2]} chloride trihydrate, rhodium, RhCl ₃ · 3H ₂ O, rhodium nitrate dihydrate Rh (NO ₃ ) ₃ · 2H ₂ O, hexa-amminrodium trichloride [Rh (NH ₃ ) ₆ ] Cl ₃ , ruthenium chloride pentahydrate RuCl ₄ · 5H ₂ O, ruthenium nitrate hexahydrate Ru (NO ₃ ) ₃ · 6H ₂ O, hexa-aminrutination trichloride [Ru (NH ₃ ) ₆ ] Cl ₃ .

A method of preparing a catalyst for the deep hydrotreating of hydrocarbon feedstock by impregnating the carrier in terms of moisture capacity or with an excess of a solution of the precursors of the active component is that the carrier is once impregnated with an aqueous solution having a pH of 1.5-3.0, containing at least one of the heteropolyanions of the series [CO ₂ Mo ₁₀ O ₃₈ H ₄ ] ^6- , [Co (OH) ₆ Mo ₆ O ₁₈ ] ^4- , [Ni (OH) ₆ Mo ₆ O ₁₈ ] ^4- , [Ni ₂ Mo ₁₀ O ₃₈ H ₄ ] ^6- , [P ₂ Mo ₅ O ₂₃ ] ^6- , [SiMo ₁₂ O ₄₀ ] ^4- , [PMo ₁₂ O ₄₀ ] ^3- , one of the cobalt hydroxide series Co (OH) ₂ · nH ₂ O, cobalt is used as a cobalt compound carbonate CoCO _3, cobalt y ekisly main 2CoCO ₃ · 3So (OH) ₂ · nH ₂ O, as the nickel compound used is one of a number of nickel hydroxide Ni (OH) ₂ · nH ₂ O, nickel carbonate NiCO _3, nickel carbonate main NiCO ₃ · nNi (OH) ₂ · mH ₂ O, a carboxylic acid containing at least one carboxyl group and 1-20 carbon atoms is used as a stabilizer for the impregnating solution. The heteropolyanion [P ₂ Mo ₅ O ₂₃ ] ^6- or [PMo ₁₂ O ₄₀ ] ^3- can be formed by sequentially dissolving the molybdenum oxide MoO ₃ or molybdenum acid H ₂ MoO ₄ in 85% phosphoric acid H ₃ PO ₄ and adding 30 % solution of H ₂ O ₂ , at a temperature of 50-90 ° C and a pH of 1.0-1.5 in ratios corresponding to stoichiometry in a heteropolyanion. One of the heteropolyanions [CO ₂ Mo ₁₀ O ₃₈ H ₄ ] ^6- , [Co (OH) ₆ Mo ₆ O ₁₈ ] ^4- , [Ni (OH) ₆ Mo ₆ O ₁₈ ] ^4- , [Ni ₂ Mo ₁₀ O ₃₈ H ₄ ] ^6- can be formed by sequentially dissolving molybdenum oxide MoO ₃ or molybdenum acid H ₂ MoO ₄ in a 30% hydrogen peroxide solution at a temperature of 50-90 ° C, followed by the addition of a Co or Ni salt in proportions corresponding to stoichiometry in the heteropolyanion. To prepare the catalyst, citric acid is used as a stabilizer. To prepare the catalyst, either the impregnation of the carrier by moisture capacity or from excess solution is used. The carrier granules are impregnated after creating a vacuum in a vessel containing the carrier. The impregnation of the carrier granules after creating a vacuum is carried out with an impregnating solution at temperatures of 20-50 ° C. After impregnation, the catalyst is dried at a temperature of 120-180 ° C in a stream of air or nitrogen.

The carrier, and therefore the catalyst, is mainly made in the form of extrudates of cylinders or trefoils, with a diameter of 1.0-1.5 mm and a length of 3-5 mm. The use of extrudates in the form of a “trefoil” also allows increasing the efficiency of hydrodesulfurization of oil fractions.

The starting compounds for the preparation of a joint impregnation solution, the composition and texture characteristics of the support, as well as the drying conditions of the catalysts are given in Table 1.

The catalysts were tested in the form of particles 0.25-0.50 mm in size, prepared by grinding and dispersing the initial granules of the calcined catalyst.

The catalytic activity in the hydrodesulfurization reaction (DDS) of dibenzothiophene (DBT) was determined in a laboratory flow unit with a microreactor. The reactor was loaded with a catalyst in an amount of 0.3000 ± 0.0005 g (fraction 0.25-0.50 mm), diluted with SiC to a total volume of 1 cm ³ . The GDS reaction was studied under the following conditions: temperature 300 ° C, hydrogen pressure 3.0 MPa, hydrogen / feed ratio 600 nl / l, bulk feed rate 50.0 h ^-1 . The raw material used was a model mixture of DBT (1500 ppm sulfur) in heptane with the addition of an internal standard, n-hexadecane (1.0 wt.%). Every hour, catalysis was carried out to analyze its composition on a Crystal-5000 gas chromatograph. The reaction products were separated on an OV-101 grafted quartz capillary column.

The activity of the catalysts in the GDS of the DBT was estimated by the constant velocity of the GDS calculated by the equation of the 1st order

where F is the flow rate of DBT, mol / h;

W is the mass of the catalyst, g;

x is the conversion of DBT,%.

The main products of GDS DBT were biphenyl (BF), formed along the direct desulfurization (DS) route of DBT, cyclohexylbenzyl (CHB) and dicyclohexyl (DCG) along the hydrogenation route (HYD) of DBT. Traces of products of incomplete hydrogenation of DBT (tetrahydrodibenzothiophene (TGDBT)) were observed in the reaction products of all catalysts. Relative HYD / DS selectivity was calculated using the following equation:

where C _CHB, C _DCC, C _BF - content cyclohexylbenzene, biphenyl, dicyclohexyl and the reaction products, respectively (wt.%).

The results of the catalytic tests are presented in table.2.

Catalysts were also tested during hydrotreatment of diesel fractions. 15 cm ^{3 of} catalyst diluted with SiC were charged into a tubular reactor to a total volume of 30 cm ³ . Sulfidation was carried out with a mixture of dimethyl disulfide and a kerosene fraction at 240 ° C for 10 hours and at 340 ° C for 8 hours. The raw materials for these test tests were a mixture of straight-run diesel fraction (hereinafter PDF) and light catalytic cracking gas oil (hereinafter LGCC) in a mass ratio of 90/10% wt. and had the following characteristics: ρ ₄ ²⁰ = 0.848; n _D ²⁰ = 1.479; sulfur content 1.14% wt. (11400 ppm); boiling point 180 ° C; boiling point 96% of the volume 360 ° C. Test conditions: hydrogen pressure 4.0 MPa, the hydrogen circulation rate of 500 nl / l of raw materials, the volumetric feed rate of 1.6-2.0 h ^-1 , the temperature in the reactor 340-350 ° C.

The stability of the catalysts was evaluated under severe conditions by the accelerated deactivation rate: for this, the hydrotreatment process was carried out using mixed raw materials consisting of 70% straight-run diesel fraction, 16% light catalytic cracking gas oil and 14% delayed coking gas oil, under the following conditions: reactor temperature 370 ° C, pressure 3.5 MPa, bulk feed rate 2.0 h ^-1 , the hydrogen / feed circulation rate 350 nl / l, duration 50 hours

The stability of the catalyst was evaluated by the degree of accelerated deactivation and calculated by the formula:

- содержание серы в стабильном гидрогенизате, полученном при 340°C до ускоренной дезактивации, ppm; $$S_{ГГ\_340}^{После\_УД}$$

- содержание серы в стабильном гидрогенизате, полученном при 340°C после ускоренной дезактивации, ppm.Where $$S_{GG\_340}^{D\mathrm{about}\_\mathrm{At}D}$$

- sulfur content in stable hydrogenated obtained at 340 ° C until accelerated deactivation, ppm; $$S_{GG\_340}^{P\mathrm{about}\mathrm{from}le\_\mathrm{At}D}$$

- sulfur content in stable hydrogenate obtained at 340 ° C after accelerated deactivation, ppm.

Hydrogenates were separated from hydrogen in high and low pressure separators, then they were treated with 10% NaOH solution for 15 minutes, washed with distilled water until the washings were neutral, dried over calcined CaCl ₂ during the day. Sulfur content was determined using x-ray fluorescence energy and wave dispersion analyzers. The content of individual groups of aromatic hydrocarbons was determined by the method of quasinormal-phase HPLC in isothermal mode.

The test results of the catalysts are presented in table.2.

The invention is illustrated by the following examples.

Example 1

The composition of the catalyst and the method of its preparation according to the well-known technical solution - the prototype.

To prepare the impregnation solution, to 5.89 g of cobalt carbon dioxide CoCO ₃ add 42 cm ³ distilled water and heated to 80 ° C. Then, 6.93 g of citric acid monohydrate, C ₆ H ₈ O ₇ · H ₂ O, are added in portions with stirring, while an intense evolution of CO ₂ is observed. After waiting for the complete dissolution of the precipitate, add 12.14 g of molybdenum oxide MoO ₃ and 4 cm ^{3 of} 80% lactic acid C ₃ H ₆ O ₃ . Stir the solution at 80 ° C until completely dissolved. After dissolution, the volume of the solution is 50 ml, the pH is 2.5. As a carrier, extrudates of aluminum oxide are used, with a diameter of 1.3-1.4 mm and a length of 4-5.2 mm, having a specific surface area of 280 m ² / g, a pore volume of 0.62 cm ³ / g and a pore diameter of 11, 9 nm, determined from nitrogen adsorption isotherms. The pore size of 70-130 Å accounts for 65% of the total pore volume. To 30 g of calcined extrudates add 27 cm ³ impregnation solution and incubated for 15 minutes The impregnated extrudates are dried at room temperature in a stream of nitrogen and subjected to heat treatment in a stream of nitrogen at 150 ° C for 10 hours. After calcining in air for 2 hours at 550 ° C, the catalyst contains 16.4% wt. MoO ₃ , 4.7% wt. NiO (Table 1).

Example 2

For the preparation of modified alumina, gamma alumina granules with a specific surface area of 230 m ² / g, a pore volume of 0.81 cm ³ / g and a pore diameter of 12.2 nm are used. 2.50 g of ammonium hydrogen phosphate (NH ₄ ) ₂ HPO _{4 are} dissolved in 85 cm ^{3 of} distilled water at 20-50 ° C, then the resulting solution is poured into 100 g of gamma-alumina. The obtained phosphorus-containing support is dried at 60, 80 and 120 ° C for 2 hours in air, and then calcined at a rate of 1 ° C / min to 500 ° C and incubated for 2 hours. 7.95 g of nickel nitrate Ni (NO ₃ ) ₂ · 6H ₂ O is dissolved in 85 cm ^{3 of} water, and then poured onto a phosphorus-containing carrier. The resultant modified support was dried at 60, 80 and 120 ° C for 2 hours in air, and then calcined at 1 ° C / min to 500 ° C and held for 4 hours. After calcination, the modified carrier granules have a specific surface area of 225 m ² / g, pore volume 0.79 cm ³ / g and an average pore diameter of 12.1 nm.

To prepare an impregnating solution, 26.90 g of hexamolybdone-nickel heteropoly acid H ₄ [Ni (OH) ₆ Mo ₆ O ₁₈ ] and 7.45 g of nickel hydroxocarbonate NiCO ₃ · nNi (ОН) ₂ · mH ₂ O are dissolved in 65 cm ^{3 of} water at 40 -60 ° C and with stirring. After the completion of the CO ₂ evolution, 11.7 g of citric acid monohydrate C ₆ H ₈ O ₇ · H ₂ O are added to the resulting solution, and the volume is adjusted to 85 cm ³ with water. The pH of the impregnation solution is 2.0-3.0.

A modified carrier weighing 100 g is kept in vacuum for 30 minutes, then pour in an impregnating solution having a temperature of 40 ° C. The carrier is kept in an impregnating solution for 15 minutes. The resulting catalyst was dried in air at room temperature, and then at 120 ° C for 8 hours

After calcination in air for 2 hours at 550 ° C, the catalyst contains 16.5% wt. MoO ₃ , 5.8% wt. NiO (Table 1).

Example 3

The modified carrier is prepared according to example 2.

To prepare an impregnating solution, 26.06 g of hexamolybdocobalt heteropoly acid H ₄ [Co (OH) ₆ Mo ₆ O ₁₈ ] and 6.31 g of cobalt carbonate CoCO ₃ · nH ₂ O are dissolved in 65 cm ^{3 of} water at 40-60 ° C with stirring . After the completion of the CO ₂ evolution, 11.3 g of citric acid monohydrate C ₆ H ₈ O ₇ · N ₂ O are added to the resulting solution, and the volume is adjusted to 85 cm ³ with water. The pH of the impregnation solution is 2.0-3.0.

A modified carrier weighing 100 g is kept in vacuum for 30 minutes, then pour in an impregnating solution having a temperature of 40 ° C. The carrier is kept in an impregnating solution for 15 minutes. The resulting catalyst was dried in air at room temperature, and then at 120 ° C for 8 hours

After calcination in air for 2 hours at 550 ° C, the catalyst contains 16.1% wt. MoO ₃ , 5.7% wt. CoO and NiO (Table 1).

Example 4

For the preparation of modified alumina, gamma alumina granules with a specific surface area of 230 m ² / g, a pore volume of 0.81 cm ³ / g and a pore diameter of 12.2 nm are used. 2.50 g of ammonium hydrogen phosphate (NH ₄ ) ₂ HPO _{4 are} dissolved in 85 cm ^{3 of} distilled water at 20-50 ° C, then the resulting solution is poured into 100 g of gamma-alumina. The obtained phosphorus-containing support is dried at 60, 80 and 120 ° C for 2 hours in air, and then calcined at a rate of 1 ° C / min to 500 ° C and incubated for 2 hours. 10.00 g of nickel nitrate Ni (NO ₃ ) ₂ · 6H ₂ O is dissolved in 85 cm ^{3 of} water, and then poured onto a phosphorus-containing carrier. The resultant modified support was dried at 60, 80 and 120 ° C for 2 hours in air, and then calcined at 1 ° C / min to 500 ° C and held for 4 hours. After calcination, the modified carrier granules have a specific surface area of 218 m ² / g, pore volume 0.77 cm ³ / g and an average pore diameter of 12.0 nm.

To prepare an impregnating solution, 36.30 g of decamolybdicobaltic heteropoly acid H ₆ [CO ₂ Mo ₁₀ O ₃₈ H ₄ ] and 8.38 g of cobalt carbonate CoCO ₃ · nH ₂ O are dissolved in 65 cm ^{3 of} water at 40-60 ° C with stirring. After the evolution of CO _{2 has been completed} , 15.0 g of citric acid monohydrate C ₆ H ₈ O ₇ · H ₂ O are added to the resulting solution and the volume is adjusted to 85 cm ³ with water. The pH of the impregnation solution is 2.0-3.0.

A modified carrier weighing 100 g is kept in vacuum for 30 minutes, then pour in an impregnating solution having a temperature of 40 ° C. The carrier is kept in an impregnating solution for 15 minutes. The resulting catalyst was dried in air at room temperature, and then at 120 ° C for 8 hours

After calcining in air for 2 hours at 550 ° C, the catalyst contains 21.0% wt. MoO ₃ , 6.9% wt. CoO and NiO (Table 1).

Example 5

The modified carrier is prepared according to example 4.

To prepare an impregnating solution, 28.67 g of cobalt salt of the decamolybdodicobalt heteropoly acid Co ₃ [Co ₂ Mo ₁₀ O ₃₈ H ₄ ] and 10.1 g of citric acid monohydrate C ₆ H ₈ O ₇ · H ₂ O are dissolved in 75 cm ^{3 of} water at 40 -60 ° C and with stirring. The pH of the impregnation solution is 2.0-3.0.

A modified carrier weighing 100 g is kept in vacuum for 30 minutes, then pour in an impregnating solution having a temperature of 40 ° C. The carrier is kept in an impregnating solution for 15 minutes. The resulting catalyst was dried in air at room temperature, and then at 120 ° C for 8 hours

After calcining in air for 2 hours at 550 ° C, the catalyst contains 16.3% wt. MoO ₃ , 5.7% wt. CoO and NiO (Table 1).

Example 6

For the preparation of modified alumina, gamma alumina granules with a specific surface area of 230 m ² / g, a pore volume of 0.81 cm ³ / g and a pore diameter of 12.2 nm are used. 2.50 g of ammonium hydrogen phosphate (NH ₄ ) ₂ HPO _{4 are} dissolved in 85 cm ^{3 of} distilled water at 20-50 ° C, then the resulting solution is poured into 100 g of gamma-alumina. The obtained phosphorus-containing support is dried at 60, 80, and 120 ° C for 2 hours in air, and then calcined at a rate of 1 ° C / min to 500 ° C and held for 2 hours.

The phosphorus-containing carrier is impregnated with a water capacity of 85 cm ³ with a solution of platinum hydrochloric acid H ₂ PtCl ₆ with a platinum concentration of 5.9 mg / cm ³ . The obtained modified carrier is dried at 60, 80 and 120 ° C for 2 hours in air, and then calcined at a rate of 1 ° C / min to 500 ° C and incubated for 4 hours. After calcination, the granules of the modified carrier have a specific surface area of 230 m ² / g, a pore volume of 0.78 cm ³ / g and an average pore diameter of 12.2 nm.

To prepare an impregnating solution, 25.76 g of decamolybdicobaltic heteropoly acid H ₆ [Co ₂ Mo ₁₀ O ₃₈ H ₄ ] and 6.17 g of cobalt carbonate CoCO ₃ · nH ₂ O are dissolved in 65 cm ^{3 of} water at 40-60 ° C with stirring. After the completion of the CO ₂ evolution, 11.1 g of citric acid monohydrate C ₆ H ₈ O ₇ · H ₂ O are added to the resulting solution, and the volume is adjusted to 85 cm ³ with water. The pH of the impregnation solution is 2.0-3.0.

A modified carrier weighing 100 g is kept in vacuum for 30 minutes, then pour in an impregnating solution having a temperature of 40 ° C. The carrier is kept in an impregnating solution for 15 minutes. The resulting catalyst was dried under nitrogen at room temperature, and then at 150 ° C for 8 hours.

After calcination in air for 2 hours at 550 ° C, the catalyst contains 16.1% wt. MoO ₃ , 4.4% wt. CoO (Table 1).

Example 7

101 g of a phosphorus-containing support obtained according to Example 6 are impregnated with a moisture capacity of 85 cm ³ with a solution of ruthenium nitrate Ru (NO ₃ ) ₃ with a ruthenium concentration of 5.9 mg / cm ³ . The obtained modified carrier is dried at 60, 80 and 120 ° C for 2 hours in air, and then calcined at a rate of 1 ° C / min to 500 ° C and incubated for 4 hours. After calcination, the granules of the modified carrier have a specific surface area of 230 m ² / g, a pore volume of 0.78 cm ³ / g and an average pore diameter of 12.2 nm.

To prepare an impregnating solution, 25.21 g of decamolybdicobaltic heteropoly acid H ₆ [CO ₂ Mo ₁₀ O ₃₈ H ₄ ] and 6.27 g of cobalt carbonate CoCO ₃ · nH ₂ O are dissolved in 65 cm ^{3 of} water at 40-60 ° C with stirring. After the completion of the CO ₂ evolution, 11.2 g of citric acid monohydrate C ₆ H ₈ O ₇ · H ₂ O are added to the resulting solution and the volume is adjusted to 85 cm ³ with water. The pH of the impregnation solution is 2.0-3.0.

A modified carrier weighing 100 g is kept in vacuum for 30 minutes, then pour in an impregnating solution having a temperature of 40 ° C. The carrier is kept in an impregnating solution for 15 minutes. The resulting catalyst was dried under nitrogen at room temperature, and then at 150 ° C for 8 hours.

After calcining in air for 2 hours at 550 ° C, the catalyst contains 15.8% wt. MoO ₃ , 4.5% wt. CoO (Table 1).

Example 8

101 g of the phosphorus-containing carrier obtained according to Example 6 was impregnated by incipient wetness with a solution of 85 cm ³ Rhodium chloride RhCl ₃ with rhodium concentration 5.9 mg / cm ^3. The obtained modified carrier is dried at 60, 80 and 120 ° C for 2 hours in air, and then calcined at a rate of 1 ° C / min to 500 ° C and incubated for 4 hours. After calcination, the granules of the modified carrier have a specific surface area of 230 m ² / g, a pore volume of 0.78 cm ³ / g and an average pore diameter of 12.2 nm.

To prepare an impregnating solution, 20.2 g of molybdenum oxide is dissolved in 70 cm ^{3 of} water with the addition of 3.8 g of an 85% phosphoric acid solution at a temperature of 60-90 ° C. Further, the resulting solution was added 7.01 g of cobalt carbonate CoCO ₃ · nCo (OH) ₂ · mH ₂ O and 11.0 g of monohydrate citric acid C ₆ H ₈ O ₇ · H ₂ O. After the CO ₂ discharge volume of the resulting solution adjusted with water to 85 cm ³ . The pH of the impregnation solution is 2.0-3.0.

A modified carrier weighing 100 g is kept in vacuum for 30 minutes, then pour in an impregnating solution having a temperature of 40 ° C. The carrier is kept in an impregnating solution for 15 minutes. The resulting catalyst was dried under nitrogen at room temperature, and then at 150 ° C for 8 hours.

After calcining in air for 2 hours at 550 ° C, the catalyst contains 16.3% wt. MoO ₃ , 4.4% wt. CoO (Table 1).

Example 9

For the preparation of modified alumina, gamma alumina granules with a specific surface area of 230 m ² / g, a pore volume of 0.81 cm ³ / g and a pore diameter of 12.2 nm are used. 3.80 g of ammonium metaborate ammonium metaborate NH ₄ BO ₂ · 2H ₂ O is dissolved in 85 cm ^{3 of} distilled water at 20-50 ° C, then the resulting solution is poured into 100 g of gamma-alumina. The resulting boron-containing support is dried at 60, 80 and 120 ° C for 2 hours in air, and then calcined at a rate of 1 ° C / min to 500 ° C and incubated for 2 hours. 10.00 g of cobalt nitrate Co (NO ₃ ) ₂ · 6H ₂ O is dissolved in 85 cm ^{3 of} water, and then poured onto a boron-containing support. The obtained modified carrier is dried at 60, 80 and 120 ° C for 2 hours in air, and then calcined at a rate of 1 ° C / min to 500 ° C and incubated for 4 hours. After calcination, the granules of the modified carrier have a specific surface area of 220 m ² / g, pore volume 0.77 cm ³ / g and an average pore diameter of 12.0 nm.

To prepare an impregnating solution, 33.67 g of cobalt salt of pentamolybdodiphosphoric acid Co ₃ [P ₂ Mo ₅ O ₂₃ ] is dissolved in 70 cm ^{3 of} water with the addition of 9.3 g of tartaric acid C ₄ H ₆ O ₆ . Next, the volume of the resulting solution was adjusted with water to 85 cm ³ . The pH of the impregnation solution is 1.5-2.5.

A modified carrier weighing 100 g is kept in vacuum for 30 minutes, then pour in an impregnating solution having a temperature of 40 ° C. The carrier is kept in an impregnating solution for 15 minutes. The resulting catalyst was dried under nitrogen at room temperature, and then at 150 ° C for 8 hours.

After calcining in air for 2 hours at 550 ° C, the catalyst contains 16.4% wt. MoO ₃ , 5.8% wt. CoO (Table 1).

Example 10

The modified carrier is prepared according to example 9.

To prepare an impregnating solution, 34.41 g of dodecamolybdophosphoric acid H ₃ [PMO ₁₂ O ₄₀ ] is dissolved in 60 cm ^{3 of} water with the addition of 7.30 g of cobalt bicarbonate CoCO ₃ · nCo (OH) ₂ · mH ₂ O and 10.2 g of tartaric acids C ₄ H ₆ O ₆ at 40-70 ° C. Next, the volume of the resulting solution was adjusted with water to 85 cm ³ . The pH of the impregnation solution is 1.5-2.5.

A modified carrier weighing 100 g is kept in vacuum for 30 minutes, then pour in an impregnating solution having a temperature of 40 ° C. The carrier is kept in an impregnating solution for 15 minutes. The resulting catalyst was dried in air at room temperature, and then at 120 ° C for 8 hours

After calcining in air for 2 hours at 550 ° C, the catalyst contains 19.5% wt. MoO ₃ , 5.9% wt. CoO (Table 1).

Example 11

101 g of the boron-containing support obtained according to Example 9 are impregnated with a moisture capacity of 85 cm ³ with a solution of platinum hydrochloric acid H ₂ PtCl ₆ with a platinum concentration of 10.6 mg / cm ³ . The obtained modified carrier is dried at 60, 80 and 120 ° C for 2 hours in air, and then calcined at a speed of 1 ° C / min to 500 ° C and maintained for 4 hours. After calcination, the granules of the modified carrier have a specific surface area of 223 m ² / g, pore volume 0.75 cm ³ / g and an average pore diameter of 12.1 nm.

To prepare an impregnating solution, 33.53 g of decamolybdicobaltic heteropoly acid H ₆ [Co ₂ Mo ₁₀ O ₃₈ H ₄ ] and 8.80 g cobalt bicarbonate CoCO ₃ · nCo (OH) ₂ · mH ₂ O are dissolved in 70 cm ^{3 of} water at 40- 60 ° C and stirring. After the completion of the CO ₂ evolution, 12.3 g of tartaric acid C ₄ H ₆ O ₆ are added to the resulting solution and the volume is adjusted to 85 cm ³ with water. The pH of the impregnation solution is 2.0-3.0.

A modified carrier weighing 100 g is kept in vacuum for 30 minutes, then pour in an impregnating solution having a temperature of 40 ° C. The carrier is kept in an impregnating solution for 15 minutes. The resulting catalyst was dried in air at room temperature, and then at 120 ° C for 8 hours

After calcining in air for 2 hours at 550 ° C, the catalyst contains 19.8% wt. MoO ₃ , 5.4% wt. CoO (Table 1).

Example 12

The modified carrier is prepared according to example 11.

To prepare an impregnating solution, 25.6 g of MoO _{3 are} dissolved in 77 g of a 30% solution of H ₂ O ₂ with vigorous stirring and a temperature of 70-90 ° C. Then, 8.77 g of cobalt bicarbonate CoCO ₃ · nCo (OH) ₂ · mH ₂ O is added to the resulting solution. After the completion of the CO ₂ evolution, 12.3 g of tartaric acid C ₄ H ₆ O ₆ are added to the resulting solution and the volume is adjusted with water to 85 cm ³ . The pH of the impregnation solution is 2.0-3.0.

A modified carrier weighing 100 g is kept in vacuum for 30 minutes, then pour in an impregnating solution having a temperature of 40 ° C. The carrier is kept in an impregnating solution for 15 minutes. The resulting catalyst was dried in air at room temperature, and then at 140 ° C for 8 hours

After calcining in air for 2 hours at 550 ° C, the catalyst contains 19.6% wt. MoO ₃ , 5.4% wt. CoO (Table 1).

The catalysts of the claimed composition and method of preparation have a high catalytic activity and provide products with a low sulfur content of less than 50 and 10 ppm (table 2). The use of a transition or noble metal carrier as a modifier provides higher catalytic stability.

table 2 Catalytic properties in the reaction of GDS DBT and hydrotreatment of diesel fractions No. Hydrogenolysis of Dibenzothiophene (DBT) Hydrotreating of diesel fractions DBT conversion,% Speed constant k _HDS , [mol / (h × g)], × 10 ⁵ Selectivity S _{HYD / DS} Process conditions Stable Hydrogenate Content Accelerated decontamination of UD,% T, ° C ISPS, h ^-1 R, MPa VSG / raw materials, nl / l sulfur ppm aromatic hydrocarbons UIA BAU TAU one 14.2 24.4 0.25 340 2.0 4.0 500 235 23.1 2.9 0.5 31.1 2 21.1 37.8 0.44 340 2.0 4.0 500 73 20.8 1,5 0.2 12.5 3 18.9 33,4 0.25 340 2.0 4.0 500 49 21.8 1.7 0.3 14.5 four 32,7 63.1 0.32 340 2.0 4.0 500 34 20,2 1,1 0.2 10,2 348 1,6 4.0 500 7 19.0 0.8 0,0 5 24.0 43.7 0.27 340 2.0 4.0 500 42 21.5 1.3 0.4 9.8 6 29.8 56.4 0.33 340 2.0 4.0 500 26 18.2 0.5 0,0 5.1 7 28.7 53.9 0.31 340 2.0 4.0 500 29th 19,4 0.8 0,0 7.2 350 1.8 4.0 500 6 18.5 0.2 0,0 8 29.0 54.6 0.31 340 2.0 4.0 500 32 19.1 0.8 0,0 7.4 9 23.7 43.1 0.24 340 2.0 4.0 500 42 20,4 1.4 0.3 16,4 10 31,0 59.1 0.24 340 2.0 4.0 500 45 20.5 1,2 0.3 11.1 eleven 39.5 80.1 0.34 340 2.0 4.0 500 eighteen 17,2 0.3 0,0 6.1 12 36.8 73.1 0.33 340 2.0 4.0 500 25 18,4 0.4 0,0 6.5

Claims (15)

1. The catalyst for the deep hydrotreatment of hydrocarbons, consisting of compounds of metals of the VIII and VIB groups, deposited on an alumina carrier, characterized in that it contains one or more bimetallic complex compounds of metals of the VIII and VIB groups, deposited on a modified carrier, which consists of a gamma- aluminum oxide, non-metal oxides: phosphorus and / or boron, transition metal oxides: nickel and / or cobalt, or one of the noble metal oxides: platinum, rhodium, ruthenium, with the following content, wt.%: 0.5-1.3 ksidy nonmetal, oxides or transition metal oxides 0.5-5.0 0.3-0.8 noble metal, alumina 93,5-99,0; the catalyst has a specific surface area of 180-350 m ² / g, a pore volume of 0.3-0.6 cm ³ / g, an average pore diameter of 8.5-13.0 nm. 2. The catalyst according to claim 1, characterized in that in the catalyst calcined at 550 ° C. the MoO ₃ is 14.0-23.0 wt.%, CoO and / or NiO is 4.0-6.5 wt.%. 3. The catalyst according to claim 1, characterized in that it has the form of cylinders or trefoils. 4. A catalyst carrier for deep hydrotreating hydrocarbons, which consists of a composition of gamma-alumina, non-metal oxides: phosphorus and / or boron, characterized in that it contains a transition metal oxide: nickel and / or cobalt, or one of the noble metal oxides : platinum, rhodium, ruthenium, with the following content, wt.%: non-metal oxides 0.5-1.3, transition metal oxides 0.5-5.0 or noble metal oxides 0.3-0.8, aluminum oxide 99 0-93.5; has a specific surface area of 200-370 m ² / g, pore volume 0.5-1.0 cm ³ / g, average pore diameter 8.5-13.5 nm. 5. A method of obtaining a carrier for a catalyst for the deep hydrotreatment of hydrocarbons according to claim 4, characterized in that gamma-alumina is impregnated with compounds of boron and / or phosphorus, a transition metal (nickel and / or cobalt) or a noble metal (one of a number of platinum, rhodium, ruthenium), followed by drying at 80-120 ° C (5 h) and calcination at 300 ° C (2 h). 6. The method of producing a carrier according to claim 5, characterized in that at least one orthoboric acid H ₃ BO ₃ , pyroboric acid H ₂ B ₄ O ₇ , ammonium metaborate NH ₄ BO ₂ , borate is used as boron compounds ammonium (NH ₄ ) ₃ BO ₃ , ammonium tetraborate (NH ₄ ) ₂ B ₄ O ₇ , phosphorus compounds - orthophosphoric acid H ₃ PO ₄ , metaphosphoric acid HPO ₃ , pyrophosphoric acid H ₄ P ₂ O ₇ , ammonium hydrogen phosphate ( NH ₄ ) ₂ HPO ₄ , ammonium metaphosphate NH ₄ PO ₃ , ammonium pyrophosphate (NH ₄ ) ₄ P ₂ O ₇ . 7. The method of producing a carrier according to claim 5, characterized in that at least one selected from the range of cobalt nitrate hexahydrate Co (NO ₃ ) ₂ · 6H ₂ O, cobalt acetate tetrahydrate Co (CH ₃ COO) is used as a transition metal compound ₂ · 4H ₂ O, cobalt sulfate tetrahydrate CoSO ₄ · 7H ₂ O, cobalt chloride tetrahydrate CoCl ₂ · 4H ₂ O, cobalt citrate dihydrate Co ₃ (C ₆ H ₅ O ₇ ) ₂ · 2H ₂ O, nickel nitrate hexahydrate Ni ( NO ₃ ) ₂ · 6H ₂ O, nickel acetate tetrahydrate Ni (CH ₃ COO) ₂ · 4H ₂ O, nickel sulfate tetrahydrate NiSO ₄ · 7H ₂ O, nickel chloride tetrahydrate NiCl ₂ · 4H ₂ O, nickel citrate dihydrate Ni (C ₆ H ₅ O ₇ ) ₂ · 14H ₂ O. 8. The method of producing a carrier according to claim 5, characterized in that at least one selected from the range of platinum chloride hydrochloric acid H ₂ PtCl ₆ , hexaammineplatinum tetrachloride [Pt (NH ₃ ) ₆ ] Cl ₄ , dichlorodiammaminoplatin (II) is used as the noble metal compound ), [PtCl ₂ (NH ₃ ) ₂ ], rhodium chloride trihydrate RhCl ₃ · 3H ₂ O, rhodium nitrate dihydrate Rh (NO ₃ ) ₃ · 2H ₂ O, hexa-amminrodium trichloride [Rh (NH ₃ ) ₆ ] Cl ₃ , pentahydrate ruthenium chloride RuCl ₄ · 5H ₂ O, ruthenium nitrate hexahydrate Ru (NO ₃ ) ₃ · 6H ₂ O, hexa-amminruthenium trichloride [Ru (NH ₃ ) ₆ ] Cl ₃ . 9. A method of preparing a catalyst for the deep hydrotreatment of hydrocarbon feedstock according to claim 1 by impregnating the carrier by moisture capacity or with an excess of a solution of the precursors of the active component, characterized in that the carrier is once impregnated with an aqueous solution having a pH of 1.5-3.0, containing at least one of heteropolyanions of the series [CO ₂ Mo ₁₀ O ₃₈ H ₄ ] ^6- , [Co (OH) ₆ Mo ₆ O ₁₈ ] ^4- , [Ni (OH) ₆ Mo ₆ O ₁₈ ] ^4- , [Ni ₂ Mo ₁₀ O ₃₈ H ₄ ] ^6- , [P ₂ Mo ₅ O ₂₃ ] ^6- , [SiMo ₁₂ O ₄₀ ] ^4- , [PMo ₁₂ O ₄₀ ] ^3- , one of a number of cobalt hydroxide, cobalt carbon dioxide CoCO ₃ is used as a cobalt compound cobalt carbon sly core, as the nickel compound used is one of a number of nickel hydroxide, nickel carbonate NiCO _3, basic nickel carbonate as the stabilizer impregnation solution a carboxylic acid containing at least one carboxyl group and 1-20 carbon atoms. 10. The method of preparation of the catalyst according to claim 9, characterized in that the heteropolyanion [P ₂ Mo ₅ O ₂₃ ] ^6- or [PMo ₁₂ O ₄₀ ] ^3- is formed by sequentially dissolving the molybdenum oxide MoO ₃ or molybdenum acid H ₂ MoO ₄ in 85% phosphoric acid H ₃ PO ₄ and the addition of a 30% solution of H ₂ O ₂ at a temperature of 50-90 ° C and a pH of 1.0-1.5 in ratios corresponding to stoichiometry in the heteropolyanion. 11. A method of preparing the catalyst according to claim 9, characterized in that one of heteropolyanions [CO ₂ Mo ₁₀ O ₃₈ H _4] ^6-, [Co (OH) ₆ Mo ₆ O _18] ^4-, [Ni (OH) ₆ Mo ₆ O ₁₈ ] ^4- , [Ni ₂ Mo ₁₀ O ₃₈ H ₄ ] ^6- is formed by sequentially dissolving molybdenum oxide MoO ₃ or molybdenum acid H ₂ MoO ₄ in a 30% hydrogen peroxide solution at a temperature of 50-90 ° C , followed by the addition of a salt of Co or Ni in proportions corresponding to stoichiometry in the heteropolyanion. 12. A method of preparing a catalyst according to any one of claims 9, 10 or 11, characterized in that citric acid is used as a stabilizer for the preparation of the catalyst. 13. A method of preparing a catalyst according to any one of claims 9, 10 or 11, characterized in that the impregnation of the carrier granules is carried out after creating a vacuum in the vessel containing the carrier. 14. The method of preparation of the catalyst according to any one of claims 9, 10 or 11, characterized in that the impregnation of the carrier granules after creating a vacuum is carried out with an impregnating solution at temperatures of 20-50 ° C. 15. The method of preparing the catalyst according to any one of claims 9, 10 or 11, characterized in that after impregnation, the catalyst is dried at a temperature of 120-180 ° C in a stream of air or nitrogen.