RU2573561C2 - Hydrodesulphurisation catalyst, method for its preparation and process of deep hydropurification of hydrocarbon raw material - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: invention relates to catalyst of hydrodesulphurisation of hydrocarbon raw material, consisting of heteropolycompound, containing as minimum one of the following heteropolyanions [Co₂Mo₁₀O₃₈H₄]^6-, [Co(OH)₆Mo₆O₁₈]^3-, [Ni(OH)₆Mo₆O₁₈]^2-, [Ni₂Mo₁₀O₃₈H₄]^6-, [P₂Mo₅O₂₃]^6-, [PMo₁₂O₄₀]^3-, [SiMo₁₂O₄₀]^4-, [Co(OH)₆W₆O₁₈]^3-, [PW₁₂O₄₀]^3-, [SiW₁₂O₄₀]^4-, [PMo_nW_12-nO₄₀]^3- (wherein n=1-11), [PV_nMo_12-nO₄₀]^(3+n)- (wherein n=1-4), and organic additive, representing compound, which contains, at least one carboxylic group and 2-20 carbon atoms, with content of organic additive constituting 5-15 wt % of catalyst weight, applied on porous carrier, with content in calcined at 550°C catalyst MoO₃ and/or WO₃ constituting 14.0-23.0 wt %, CoO and/or NiO - 4.0-6.5 wt %. The invention also relates to method for catalyst manufacturing and process of deep hydropurification of hydrocarbon raw material, consisting in conversion of oil distillates in presence of heterogeneous catalyst.

EFFECT: creation of novel hydrodesulphurisation catalyst.

8 cl, 2 tbl, 14 ex

Description

The invention relates to the field of chemistry, in particular to catalysts for deep hydrotreating oil fractions, 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 will remain hydrotreating, and its role will increase due to the tightening of sulfur standards in gasoline and diesel fuel, as well as an increase in the depth of oil refining and the involvement of non-traditional 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 CoMoS phase of type II significantly exceeds the activity of the phase of type I and is characterized by a weak interaction of the active components with the carrier, and, consequently, a greater completeness 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 Co (Ni) Mo (W) S type II phase on the surface of a porous support by using 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 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 are synthesized, with the proportion of pores measuring 75-350 размером 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 accessibility of sulfur-containing compounds to the surface of the active component, but also reduces the possibility of coking of pores.

2. 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 №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. .).

3. 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, reducing 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.

4. 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.

5. Introduction to the active component of additives with 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, July 31, 2001). The main disadvantage of this method is the expensive technology for the synthesis of modified alumina supports, due to the combined use of modified carriers of acidic additives, so that the concentration of the Brainsted centers is at least 50 μmol / g and platinum group metals.

6. 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 oxide-oxide interaction, especially at the thermal stages of preparation.

7. The use of organic additives that reduce the formation of crystallized phases 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 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.). The disadvantage of these catalysts is the interaction of organic additives with the Mo (W) precursor, which reduces the rate of its sulfidation.

A common drawback for the above catalysts and methods for their preparation is that with their use it is not possible to achieve an ultralow residual sulfur content in the resulting products under mild conditions for the hydrotreatment of oil fractions, as well as decontamination caused by coke deposits.

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 introduced. 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 solution of the present invention is the use as predecessors of the active phase of heteropoly compounds of a given chemical composition, structure and degree of polymerization and organic additives containing hydroxyl groups. The combined use of heteropoly compounds and organic additives in the composition of the impregnating solution prevents the dissociation of molecules of heteropoly compounds in the pores of the carrier, reduces the degree of interaction of heteropoly compounds with the surface of the carrier, increases the depth of sulfidation of metals (Mo, W, Co and Ni), the amount and dispersion of the active phase Co (Ni ) Mo (W) S type II.

The technical result of the present invention is the creation of a new hydrodesulfurization catalyst, a method for its preparation and a process for the deep hydrotreatment of hydrocarbon feedstocks. The technical result is achieved by introducing a heteropoly compound of metals of groups VIII and VIB groups and an organic additive on a porous carrier. The heteropoly 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 ] ^3- , [Ni (OH) ₆ Mo ₆ O ₁₈ ] ^4- , [ Ni ₂ Mo ₁₀ O ₃₈ H ₄ ] ^6- , [P ₂ Mo ₅ O ₂₃ ] ^6- , [PMo ₁₂ O ₄₀ ] ^3- , [SiMo ₁₂ O ₄₀ ] ^4- [Co (OH) ₆ W ₆ O ₁₈ ] ^3- , [PW ₁₂ O ₄₀ ] ^3- , [SiW ₁₂ O ₄₀ ] ^4- , [PMo _n W _12-n O ₄₀ ] ^3- (where n = 1-11), [PV _n Mo _12-n O ₄₀ ] ^{(3 + n) -} (where n = 1-4), while the content in the MoO ₃ and / or WO ₃ catalyst calcined at 550 ° C is 14.0-23.0 wt.%, CoO and / or NiO - 4.0 -6.5 wt.% Organic additive is a compound containing at least one carboxyl group and 2-20 carbon atoms and / or a compound containing at least one hydroxyl group and 2-20 carbon atoms, while the content of the organic additive is 5-15 wt.% by weight of the catalyst.

The porous support is one of the following oxides or composites alumina, silica, titanium oxide, zirconia, magnesium oxide, zeolite, aluminosilicate, aluminophosphate, and combinations thereof. The carrier has a specific surface area of 140-700 m ² / g, a pore volume of 0.3-1.6 cm ³ / g, an average pore diameter of 4.0-13.0 nm.

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 method of preparation of the catalyst consists in impregnating the carrier with a solution of the precursor of the active component and drying, characterized in that the carrier is once impregnated with an aqueous solution having a pH of 1.5-5.0, 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 ] ^3- [Ni (OH) ₆ Mo ₆ O ₁₈ ] ^4- [Ni ₂ Mo ₁₀ O ₃₈ H ₄ ] ^6- [P ₂ Mo ₅ O ₂₃ ] ^6- [PMo ₁₂ O ₄₀ ] ^3- [SiMo ₁₂ O ₄₀ ] ^4- , [Co (OH) ₆ W ₆ O ₁₈ ] ^3- , [PW ₁₂ O ₄₀ ] ^3- [SiW ₁₂ O ₄₀ ] ^4- [PMo _n W _{12 -n} O ₄₀ ] ^3- (where n = 1-11), [PV _n Mo _12-n O ₄₀ ] ^{(3 + n) -} (where n = 1-4), one of the series hydroxide is used as a cobalt compound cobalt Co (OH) ₂ · nH ₂ O (n = 0-5), cobalt glekisly CoCO _3, basic cobalt carbonate CoCO ₃ · 1.5So (OH) ₂ · nH ₂ O (n = 0.5-5), cobalt acetate Co (CH ₃ COO) ₂ as a nickel compound used is one of a number of nickel hydroxide Ni ( OH) ₂ · nH ₂ O (n = 0-5), nickel carbonate NiCO ₃ , basic nickel carbonate NiCO ₃ · nNi (OH) ₂ · mH ₂ O (n = 1-3, m = 0.5-5), acetate nickel Ni (CH ₃ COO) ₂ , as an organic additive, a compound containing at least one carboxyl group and 2-20 carbon atoms and / or a compound containing at least one hydroxyl group and 2-20 carbon atoms is used.

To prepare the catalyst, either the impregnation of the carrier by moisture capacity or from excess solution is used. The carrier granules may be impregnated after creating a vacuum in a vessel containing the carrier. Impregnation of the carrier granules after creating a vacuum is carried out with an impregnating solution at temperatures of 20-80 ° C. After impregnation, the catalyst is dried at a temperature of 100-180 ° C in a stream of air or nitrogen.

The above-described method of preparing the proposed catalyst allows to increase the activity of Co (Ni) -Mo (W) of the hydrodesulfurization catalyst and to use it in the process of deep hydrotreating of hydrocarbon feed, which is carried out at a temperature of 280-420 ° C, a pressure of 0.4-10 MPa, a volumetric flow rate of 0.5 -5 h ^-1, volume ratio of hydrogen / feedstock of 100-1500 nm ^3/3 m.

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.

Catalysts were tested during hydrotreatment of diesel fractions in a flow unit. 15 cm ^{3 of} catalyst diluted with SiC were charged into a tubular reactor to a total volume of 30 cm ³ . Sulphidation 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 straight run diesel fraction (PDF) with the following characteristics: density at 20 ° C 847 kg / m ³ ; sulfur content 1.01 wt.% (10 100 ppm); the content of polycyclic aromatic hydrocarbons (PAHs) 6.5 wt.%; boiling point 180 ° C; boiling point 96% of the volume 360 ° C. Also, a mixture of PDF and light gas oil of catalytic cracking (hereinafter referred to as LHCC) in a weight ratio of 80/20 wt.% (Raw material denoted as “PDF + LHCC”) was used as raw material and had the following characteristics: density at 20 ° C 853 kg / m ³ ; sulfur content 1.33 wt.% (13 300 ppm); PAH content of 7.7 wt.%; boiling point 180 ° C; boiling point 96% of the volume of 359 ° C. Test conditions: hydrogen pressure 4.0 MPa, hydrogen / feed 500 nl / l of feed, bulk feed rate of 2.0 h ^-1 , temperature in the reactor 340-350 ° C.

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.

Catalysts were also tested during hydrotreatment of vacuum gas oil. The raw material for conducting these test tests was a vacuum gas oil having a boiling point of 350-535 ° C, and had the following characteristics: density at 20 ° C 921 kg / m ³ ; sulfur content of 2.07 wt.%, PAH content of 10.4 wt.%. Test conditions: hydrogen pressure 5.0 MPa, hydrogen / feed 800 nl / l of feed, bulk feed rate 1.0 h ^-1 , temperature in the reactor 360-380 ° C. Hydrogen sulfide dissolved in hydrogenates was removed by treatment with nitrogen gas at 70 ° C for 15 minutes. The content of sulfur and aromatic hydrocarbons was determined by methods similar to the hydrogenates obtained in the hydrotreatment of diesel fractions.

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 an impregnating 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 C ₇ · H ₂ O are added in portions with stirring, while an intensive 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 12.0 nm, determined from nitrogen adsorption isotherms . Pore size 70-130 Ǻ 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 heat treated in a stream of nitrogen at 150 ° C for 10 hours. After calcination in air for 2 hours at 550 ° C, the catalyst contains 16.4 wt.% MoO ₃ , 4.7 wt.% CoO (table 1).

Example 2

To prepare an impregnating solution, 24.9 g of hexamolybdone-nickel heteropoly acid H ₄ [Ni (OH) ₆ Mo ₆ O ₁₈ ] and 6.3 g of nickel hydroxocarbonate NiCO ₃ · Ni (OH) ₂ · 2H 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, 9.8 g of citric acid monohydrate C ₆ H ₈ O ₇ · H ₂ O, 3.2 g of ethylene glycol C ₂ H ₄ (OH) ₂ are added to the resulting solution, and the volume is adjusted to 85 cm ³ with water. The pH of the impregnation solution is 1.5-3.0.

A gamma-alumina support having texture characteristics as in Example 1, 100 g in weight is kept in vacuum for 30 minutes, then it is filled with 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 in a nitrogen atmosphere at 110 ° C for 8 hours.

After calcining in air for 2 h at 550 ° C, the catalyst contains 16.5 wt.% MoO ₃ , 4.5 wt.% NiO (Table 1).

Example 3

To prepare an impregnating solution, 23.8 g of hexamolybdocobalt heteropoly acid H ₃ [Co (OH) ₆ Mo ₆ O ₁₈ ] and 5.9 g of cobalt carbonate CoCO _{3 are} dissolved in 65 cm ^{3 of} water at 40-60 ° C with stirring. After the completion of the CO ₂ evolution, 8.9 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 gamma-alumina support having texture characteristics as in Example 1, 100 g in weight is kept in vacuum for 30 minutes, then it is filled with 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 in a nitrogen atmosphere at 150 ° C for 5 hours.

After calcining in air for 2 hours at 550 ° C, the catalyst contains 16.1 wt.% MoO ₃ , 4.2 wt.% CoO (Table 1).

Example 4

To prepare an impregnating solution, 36.7 g of decamolybdicobaltic heteropoly acid H ₆ [Co ₂ Mo ₁₀ O ₃₈ H ₄ ] and 6.9 g of cobalt carbonate CoCO _{3 are} dissolved in 65 cm ^{3 of} water at 40-60 ° C with stirring. After the completion of the CO ₂ emission, 10.5 g of citric acid monohydrate C ₆ H ₈ O ₇ · H ₂ O, 3.4 g of ethylene glycol C ₂ H ₄ (OH) ₂ 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 gamma-alumina carrier having a specific surface area of 350 m ² / g, a pore volume of 0.78 cm ³ / g and a pore diameter of 10.1 nm, determined from nitrogen adsorption isotherms of 100 g, is kept in a vacuum for 30 minutes, then it is filled with an impregnating solution having a temperature 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 110 ° C for 8 hours

After calcining in air for 2 h at 550 ° C, the catalyst contains 20.0 wt.% MoO ₃ , 5.2 wt.% CoO (Table 1).

Example 5

To prepare an impregnating solution, 31.8 g of cobalt salt of decamolybdodicobalt heteropoly acid Co ₃ [Co ₂ Mo ₁₀ O ₃₈ H ₄ ] and 10.0 g of ethylene glycol are dissolved in 75 cm ^{3 of} water at 40-50 ° C with stirring. The pH of the impregnation solution is 4.0-5.0.

A gamma-alumina carrier containing 10 wt.% BETA zeolite and having a specific surface area of 382 m ² / g, a pore volume of 0.82 cm ³ / g and a pore diameter of 10.0 nm, determined from nitrogen adsorption isotherms, weighing 100 g, is kept in vacuum for 30 minutes , then fill in with 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 100 ° C for 12 hours

After calcining in air for 2 hours at 550 ° C, the catalyst contains 20.1 wt.% MoO ₃ , 5.4 wt.% CoO (Table 1).

Example 6

To prepare an impregnating solution, 23.9 g of decamolybdicobaltic heteropoly acid H ₆ [Co ₂ Mo ₁₀ O ₃₈ H ₄ ] and 5.7 g of cobalt carbonate CoCO _{3 are} dissolved in 65 cm ^{3 of} water at 40-60 ° C with stirring. After the completion of the CO ₂ evolution, 6.9 g of tartaric acid C ₄ H ₆ O ₆ , 1.7 g of glycerol C ₃ H ₅ (OH) ₃ 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 gamma-alumina carrier containing 10 wt.% Titanium oxide and having a specific surface area of 301 m ² / g, a pore volume of 0.69 cm ³ / g and a pore diameter of 10.0 nm, determined from nitrogen adsorption isotherms, weighing 100 g, was kept in vacuum for 30 minutes , then fill in with 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 16.1 wt.% MoO ₃ , 4.4 wt.% CoO (Table 1).

Example 7

To prepare an impregnating solution, 21.8 g of decamolybdicobaltic heteropoly acid H ₆ [Co ₂ Mo ₁₀ O ₃₈ H ₄ ] and 5.0 g of cobalt carbonate CoCO _{3 are} dissolved in 50 cm ^{3 of} water at 40-60 ° C with stirring. After the completion of the CO ₂ evolution, 6.0 g of tartaric acid C ₄ H ₆ O ₆ are added to the resulting solution and the volume is adjusted with water to 62 cm ³ . The pH of the impregnation solution is 2.0-3.0.

A titanium oxide support (crystalline form of anatase) having a specific surface area of 140 m ² / g, a pore volume of 0.52 cm ³ / g and a pore diameter of 6.0 nm, determined from nitrogen adsorption isotherms, is kept at 100 g in a vacuum for 30 minutes, then it is filled with 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 h at 550 ° C, the catalyst contains 15.0 wt.% MoO ₃ , 4.0 wt.% CoO (Table 1).

Example 8

To prepare an impregnating solution, 53.9 g of tungsten phosphoric heteropoly acid H ₃ [PW ₁₂ O ₄₀ ] · 2H ₂ O is dissolved in 70 cm ^{3 of} water with the addition of 13.4 g of nickel hydrogen carbonate NiCO ₃ · Ni (OH) ₂ · 2H ₂ O and 15.1 g of monohydrate citric acid C ₆ H ₈ O ₇ · H ₂ O at 40-70 ° C. After the completion of the CO ₂ extraction, the volume of the resulting solution was adjusted with water to 85 cm ³ . The pH of the impregnation solution is 2.0-3.0.

The gamma-alumina carrier (Example 4), weighing 100 g, was kept in vacuum for 30 minutes, then filled with 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 in a nitrogen atmosphere at 150 ° C for 6 hours

After calcining in air for 2 h at 550 ° C, the catalyst contains 32.0 wt.% WO ₃ , 5.2 wt.% NiO (Table 1).

Example 9

To prepare an impregnating solution, 39.1 g of cobalt salt of pentamolybdodiphosphoric acid Co ₃ [P ₂ Mo ₅ O ₂₃ ] is dissolved in 90 cm ^{3 of} water with the addition of 13.8 g of tartaric acid C ₄ H ₆ O ₆ and 3.4 g of glycerol C ₃ H ₅ (OH) ₃ at 40-70 ° C. Next, the volume of the resulting solution was adjusted with water to 130 cm ³ . The pH of the impregnating solution is 1.5-2.5.

A silica support having a specific surface area of 352 m ² / g, a pore volume of 1.1 cm ³ / g and a pore diameter of 9.1 nm, determined from nitrogen adsorption isotherms, weighing 100 g is kept in vacuum for 30 minutes, then it is filled with 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 in a nitrogen atmosphere at 110 ° C for 12 hours

After calcining in air for 2 h at 550 ° C, the catalyst contains 19.5 wt.% MoO ₃ , 5.2 wt.% CoO (Table 1).

Example 10

To prepare an impregnating solution, 32.2 g of molybdophosphoric heteropoly acid H ₃ [PMo ₁₂ O ₄₀ ] · 18H ₂ O is dissolved in 65 cm ^{3 of} water with the addition of 11.3 g of cobalt bicarbonate СОСО ₃ · 1.5Со (ОН) ₂ · H ₂ O, 13.5 g of tartaric acid C ₄ H ₆ O ₆ and 3.3 g of glycerol C ₃ H ₅ (OH) ₃ at 40-70 ° C. After the completion of the CO ₂ extraction, the volume of the resulting solution was adjusted with water to 85 cm ³ . The pH of the impregnation solution is 2.0-3.0.

The gamma-alumina carrier (Example 4), weighing 100 g, was kept in vacuum for 30 minutes, then filled with 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 in a nitrogen atmosphere at 110 ° C for 12 hours

After calcining in air for 2 hours at 550 ° C, the catalyst contains 19.5 wt.% MoO ₃ , 5.1 wt.% CoO (Table 1).

Example 11

To prepare an impregnating solution, 31.1 g of decamolybdicobaltic heteropoly acid H ₆ [Co ₂ Mo ₁₀ O ₃₈ H ₄ ] and 6.7 g of cobalt bicarbonate CoCO ₃ · 1.5Со (ОН) ₂ · H ₂ O are dissolved in 65 cm ^{3 of} water at 40-60 ° C and stirring. After the completion of the CO ₂ evolution, 10.2 g of citric acid monohydrate C ₆ H ₈ O ₇ · H ₂ O, 4.0 g of triethylene glycol C ₆ H ₁₄ O ₄ 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.

Carrier aluminosilicate containing 25 wt.% SiO ₂ and 75 wt.% Al ₂ O ₃ , having a specific surface area of 364 m ² / g, a pore volume of 0.91 cm ³ / g and a pore diameter of 9.8 nm, determined from nitrogen adsorption isotherms with a mass of 100 g is kept in vacuum for 30 minutes, then fill in with 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 h at 550 ° C, the catalyst contains 19.8 wt.% MoO ₃ , 5.1 wt.% CoO (Table 1).

Example 12

To prepare an impregnating solution, 18.3 g of molybdophosphoric heteropoly acid H ₃ [PMo ₁₂ O ₄₀ ] · 18H ₂ O, 24.6 g of phosphor-tungsten heteropoly acid H ₃ [PW ₁₂ O ₄₀ ] · 2H ₂ O are dissolved in 65 cm ^{3 of} water with the addition of 12.2 g of hydrogen carbonate nickel NiCO ₃ Ni (OH) ₂ · 2H ₂ O, 19.1 g of citric acid monohydrate C ₆ H ₈ O ₇ · H ₂ O and 6.3 g of ethylene glycol C ₂ H ₄ (OH) ₂ at 40-70 ° C. After the completion of the CO ₂ extraction, the volume of the resulting solution was adjusted with water to 85 cm ³ . The pH of the impregnation solution is 2.0-3.0.

The gamma-alumina carrier (Example 4), weighing 100 g, was kept in vacuum for 30 minutes, then filled with 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 10 hours

After calcining in air for 2 h at 550 ° C, the catalyst contains 10.1 wt.% MoO ₃ , 16.0% WO ₃ and 5.2 wt.% NiO (Table 1).

Example 13

To prepare an impregnating solution, 41.2 g of hexamolybdohexavungsten heteropoly acid H ₃ [PMo ₆ W ₆ O ₄₀ ] · 4H ₂ O is dissolved in 65 cm ^{3 of} water with the addition of 12.5 g of nickel hydrogen carbonate NiCO ₃ · Ni (OH) ₂ · 2H ₂ O, 19.5 g of monohydrate citric acid C ₆ H ₈ O ₇ · H ₂ O at 40-70 ° C. After the completion of the CO ₂ extraction, the volume of the resulting solution was adjusted with water to 85 cm ³ . The pH of the impregnation solution is 2.0-3.0.

Impregnation and drying are carried out according to example 12.

After calcining in air for 2 h at 550 ° C, the catalyst contains 10.3 wt.% MoO ₃ , 15.8 wt.% WO ₃ and 5.3 wt.% NiO (Table 1).

Example 14

To prepare an impregnating solution, 38.6 g of octamolybdotetra-tungsten heteropoly acid H ₃ [PMo ₈ W ₄ O ₄₀ ] · 6H ₂ O is dissolved in 65 cm ^{3 of} water with the addition of 12.0 g of nickel hydrogen carbonate NiCO ₃ · Ni (OH) ₂ · 2H ₂ O, 18.7 g of monohydrate citric acid C ₆ H ₈ O ₇ · H ₂ O at 40-70 ° C. After the completion of the CO ₂ extraction, the volume of the resulting solution was adjusted with water to 85 cm ³ . The pH of the impregnation solution is 2.0-3.0.

The impregnation of the carrier according to example 5 and the subsequent drying of the catalyst is carried out according to example 12.

After calcining in air for 2 h at 550 ° C, the catalyst contains 14.0 wt.% MoO ₃ , 10.9 wt.% WO ₃ and 5.2 wt.% NiO (Table 1).

The inventive catalysts have a high catalytic activity in the hydrodesulfurization of sulfur-containing compounds and the hydrogenation of PAHs (table 2). The process of deep hydrotreating hydrocarbon feeds provides products with a low sulfur content of less than 50 and 10 ppm (Table 2).

Claims (8)

1. Hydrodesulfurization catalyst for hydrocarbons, consisting of a heteropoly compound containing at least one of the following heteropolyanions [Co ₂ Mo ₁₀ O ₃₈ H ₄ ] ^6- , [Co (OH) ₆ Mo ₆ O ₁₈ ] ^3- , [Ni (OH) ₆ Mo ₆ O ₁₈ ] ^2- , [Ni ₂ Mo ₁₀ O ₃₈ H ₄ ] ^6- , [P ₂ Mo ₅ O ₂₃ ] ^6- , [PMO ₁₂ O ₄₀ ] ^3- , [SiMo ₁₂ O ₄₀ ] ^4- , [Co (OH) ₆ W ₆ O ₁₈ ] ^3- , [PW ₁₂ O ₄₀ ] ^3- , [SiW ₁₂ O ₄₀ ] ^4- , [PMo _n W _12-n O ₄₀ ] ^3- (where n = 1 -11), [PV _n Mo _12-n O ₄₀ ] ^{(3 + n) -} (where n = 1-4), and an organic additive, which is a compound containing at least one carboxyl group and 2-20 carbon atoms while the content of organic additives is 5-15 wt.% by weight catalysis an atom deposited on a porous support, while the content of MoO ₃ and / or WO _{3 in the} catalyst calcined at 550 ° C is 14.0–23.0 wt.%, CoO and / or NiO is 4.0–6.5 wt. .%. 2. A method of preparing a catalyst according to claim 1, comprising impregnating the carrier with a solution of the precursor of the active component and drying, characterized in that the carrier is once impregnated with an aqueous solution having a pH of 1.5-5.0, one of the following is used as a cobalt compound: cobalt hydroxide Co (OH ) ₂ · nH ₂ O (n = 0-5), cobalt carbon dioxide CoCO ₃ , basic carbonic cobalt CoCO ₃ · 1.5Со (ОН) ₂ · nH ₂ O (n = 0.5-5), cobalt acetate Co (СН ₃ СОО ) ₂ , one of the series is used as a nickel compound: nickel hydroxide Ni (OH) ₂ · nH ₂ O (n = 0-5), carbon nickel NiCO ₃ , nickel carbon basic acid NiCO ₃ · nNi (OH) ₂ · mH ₂ O (n = 1-3, m = 0.5-5), nickel acetate Ni (CH ₃ COO) ₂ . 3. The method according to p. 2, characterized in that for the preparation of the catalyst, the carrier is impregnated either by moisture capacity or from excess solution. 4. The method according to p. 2, characterized in that the impregnation of the granules of the carrier is carried out after creating a vacuum in the vessel containing the carrier. 5. The method according to p. 2, characterized in that the impregnation of the granules of the carrier after creating a vacuum is carried out by an impregnating solution at temperatures of 20-80 ° C. 6. The method according to any one of paragraphs. 2-5, characterized in that after impregnation, the catalyst is dried at a temperature of 100-180 ° C in a stream of air or nitrogen. 7. The process of deep hydrotreatment of hydrocarbons, which consists in the conversion of petroleum distillates in the presence of a heterogeneous catalyst, characterized in that they use a catalyst prepared according to any one of paragraphs. 2, 3, 4, 5 or 6. 8. The process according to p. 7, characterized in that it is carried out at a temperature of 280-420 ° C, a pressure of 0.4-10 MPa, a volumetric flow of raw materials of 0.5-5.0 h ^-1 , a volumetric ratio of hydrogen / raw material of 100-1500 nm ³ / m ³ .