RU2747053C1 - Method for producing catalyst for deep hydrotreatment of hydrocarbon raw materials, catalyst and method for hydrotreatment of hydrocarbon raw materials with use of it - Google Patents

Abstract

FIELD: catalyst production.SUBSTANCE: invention relates to the production of hydrotreatment, hydrofining and hydrodesulfurization catalysts and methods of deep hydrotreatment of hydrocarbon raw materials. A method for obtaining a catalyst for deep hydrotreatment of hydrocarbon raw materials containing an active component in the form of mixed Mo and Co sulfides is described. The method includes the preparation of an impregnating solution containing active metal precursors and organic additives, the impregnation of a carrier, for which a thermally stable mesoporous aluminum oxide with a specific surface area of at least 260 m2/g, a specific pore volume of 0.75 to 1.2 cm3/g, an average pore radius of 3.5-5.5 nm and a mechanical strength of at least 2.0 kg/mm is used (for the application of active metals, the impregnating solution is prepared by dissolving molybdenum trioxide or molybdenum acid in an aqueous solution of hydroperoxide with a volume concentration of H2O2from 12 to 26% at a temperature of 35-45ºC for 4-6 hours, followed by the addition of acetate, or carbonate, or cobalt acetylacetonate and organic additives), maturation of the impregnated catalyst, drying and activation of the dried catalyst. The invention also relates to a catalyst for deep hydrotreatment of hydrocarbon raw materials obtained by the above method, and to a method for hydrofining hydrocarbon raw materials using the above catalyst.EFFECT: proposed is production of diesel fuel components that meet the quality of modern regulatory requirements.17 cl, 6 tbl, 26 ex

Description

The invention relates to the field of production of catalysts for hydroprocessing, hydrotreating and hydrodesulfurization and methods of deep hydroprocessing of hydrocarbon raw materials.

At present, in order to increase the depth of processing and obtain additional quantities of commercial petroleum products, an increasing number of hydrocarbon fractions of secondary origin are subjected to deep hydroprocessing. Due to the high content of stubborn sulfur compounds of cyclic structure, polycyclic aromatic hydrocarbons (PAHs) and resinous substances, secondary distillates undergo hydrogenation processing more difficult than straight-run fractions.

The problem is aggravated by the tightening environmental requirements, primarily related to the reduction of sulfur content in motor fuels. According to the requirements of the Technical Regulations of the Customs Union [TP CU 013/2011 Technical Regulations of the Customs Union "On Requirements for Automobile and Aviation Gasoline, Diesel and Marine Fuel, Jet Fuel and Fuel Oil" (as amended on December 2, 2015)] sulfur content in marketable petroleum products should be at a level of less than 10 mg / kg in motor gasolines and diesel fuel.

To obtain motor fuels with an ultra-low sulfur content in the process of catalytic purification, it is necessary to remove sulfur compounds by more than 99%, including the most difficult to remove alkyl-substituted dibenzothiophene derivatives. The described problem is solved at oil refineries by two methods. The first is a significant tightening of the technological parameters of the hydro-processing of hydrocarbon raw materials, as a result of which the period between regeneration cycles at the unit is reduced and the annual downtime is increased. The second, and most effective, is the use of more active hydroprocessing catalysts for a more complete removal of sulfur-containing compounds from the processed hydrocarbon fractions.

Various heterogeneous catalysts for the hydroprocessing of hydrocarbon raw materials are known, however, a common disadvantage for them is their low activity in hydrodesulfurization reactions and a high residual content of sulfur-containing compounds in the hydrogenated products obtained with their help.

Most often, for the hydroprocessing of hydrocarbon feedstock, catalysts containing cobalt and / or nickel and molybdenum or tungsten in the form of oxides or sulfides supported on a porous, heat-resistant support, most often aluminum oxide, are used.

Thus, a catalyst for the hydrotreating of crude oil and a method for its preparation is known [patent RU 2137541, IPC B01J 23/88, B01J 37/03, C10G 45/08, publ. 09/20/1999], which is based on the deposition of aluminum hydroxide by the sulfate method, the introduction of ammonium paramolybdate and nickel nitrate into aluminum hydroxide, extrusion molding, drying, calcination, characterized by heat treatment of aluminum hydroxide and its treatment with a monobasic mineral acid (nitric or hydrochloric) to the pH of the medium within 4-6.

A known method of preparing an alumo-cobalt-molybdenum catalyst for hydrotreating petroleum fractions [patent RU 2189860, IPC B01J 37/04, B01J 23/882, publ. September 27, 2002]. According to this method, the catalyst is obtained by introducing molybdenum and cobalt salts into a mass of aluminum hydroxide, pre-peptized with nitric acid, followed by evaporation and re-treatment of the catalyst mass with a monobasic organic acid to obtain aluminum hydroxide modified with molybdenum and cobalt compounds with close packing of particles, which allows the subsequent stages of catalyst production - molding, drying, calcining, to obtain a catalyst, 60-80% of the pore volume of which are pores with a radius of 20-70 Å. The main disadvantage of these methods for preparing a catalyst is the low availability of active components in finished catalysts. A significant proportion of active metals is isolated in the walls of the support and does not participate in hydrodesulfurization reactions. This results in a high sulfur content in the products obtained during hydrotreating using catalysts obtained by the described methods.

Methods for preparing hydrotreating catalysts based on the deposition of active components on a porous heat-resistant support make it possible to avoid the loss of the availability of active metals in the walls of the support. Thus, methods for preparing hydrotreating catalysts are known [patent RU 2286846, IPC B01J 23/78, B01J 23/83, B01J 27/19, B01J 21/02, C10J 45/08, publ. 10.11.2006; patent RU 2306978, IPC B01J 23/88, B01J 23/83, B01J 37/02, publ. September 27, 2007; patent RU 2536965, IPC B01J 37/02, B01J 23/88, B01J 23/882, B01J 23/883, publ. 05/22/2013], based on the impregnation of an alumina carrier with an aqueous solution of compounds of active components: nitrate cobalt and / or nickel and ammonium paramolybdate. The main disadvantage of these methods is the low activity of the catalysts obtained from them, which does not allow obtaining deeply purified motor fuel with a sulfur content of less than 10 mg / kg. This is due both to the limited solubility of ammonium paramolybdate, which leads to limitations on the amount of metals that can be applied in one impregnation, and to the presence in the impregnating solution, and then on the catalyst surface, nitrogen-containing anions, which negatively affect the catalytic properties of the formed active phases of catalysts for hydroprocessing of hydrocarbon raw materials.

The disadvantage of the known method for producing a catalyst [patent RU 2536965, IPC B01J 37/02, B01J 23/88, B01J 23/882, B01J 23/883, publ. 05/22/2013] is a two-stage introduction of active ingredients. In addition, the use of an ammonia solution in the synthesis reduces the strength of the finished catalyst, leads to an uncontrolled change in the porous structure and, as a result, to a decrease in the activity of the catalyst.

To increase the activity of catalysts for the hydroprocessing of hydrocarbon feedstock, orthophosphoric acid is introduced into the impregnating solution [patent RU 2387475, IPC B01J 21/04, B01J 27/19, B01J 27/24, C01G 45/08, publ. 04/27/2010; patent RU 2306978, IPC B01J 23/88, B01J 23/83, B01J 37/02, publ. September 27, 2007; patent RU 2286846, IPC B01J 23/78, B01J 23/83, B01J 27/19, B01J 21/02, C10G 45/08, publ. 10.11.2006], which allows to obtain and stabilize highly concentrated solutions of molybdenum salts, allowing the synthesis of catalysts with high concentrations of active metals. The disadvantage of these methods is the increased acidity of the finished catalysts due to the presence of phosphoric acid in the impregnating solution, which as a result promotes the occurrence of side cracking reactions and a decrease in the yield of target products, together with more intensive deactivation of the catalyst. The larger amount of metals in the catalyst also leads to an undesirable decrease in the available specific surface area.

In patents [patent RU 2562607, IPC B01J 27/051, B01J 37/02, B01J 37/04, B01J 37/08, B01J 37/20, C10G 45/08, publ. 09/10/2015; patent RU 2661866, IPC B01J 37/02, B01J 27/185, B01J 21/04, B01J 27/19, B01J 23/882, B01J 23/883, C10G 45/08, publ. 07/20/2018; patent RU 2678578, IPC B01J 37/20, B01J 37/00, B01J 37/02, B01J 27/19, B01J 23/883, B01J 37/28, B01J 35/10, B01J 35/00, B01J 31/04, publ. 01/30/2019; patent RU 2402380, IPC B01J 23/882, B01J 23/883, B01J 21/02, B01J 21/04, B01J 37/02, C10G 45/08, B01J 38/62, publ. 10/27/2010 and others] describe methods for preparing catalysts using impregnating solutions additionally containing organic additives, often organic acids, for example, citric acid. Organic additives perform the function of reducing the interaction of the precursors of the active phase with the support and the likelihood of the formation of undesirable cobalt-containing phases Co ₃ O ₄ and CoAl ₂ O ₄ . The disadvantage of these methods is the intense formation of carbon deposits on the catalyst surface during sulfonation due to the decomposition of organic additives. The resulting carbon can block the active sites of the catalyst during the initial period of operation. The interaction of organic additives with the precursor of molybdenum reduces the rate of its sulfidation.

Described is a catalyst for hydrotreating heavy oil fractions and a method for its preparation [patent RU 2414963, IPC 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, publ. 07.07.2008], according to which heteropoly compounds of silicon and phosphorus, the promoter of the active component nickel oxide NiO, carrier modifiers V ₂ O ₅ and SnO ₂ are used as precursors of active metals. The main disadvantage of this catalyst is the method of introducing tungsten, which is a component of the active phase.

Complex compounds, including polyoxometalates, can be used as precursors of active metals along with salts. Thus, a hydrotreating catalyst is known [patent RU 2387475, IPC B01J 21/04, B01J 27/19, B01J 27/24, C10G 45/08, publ. 04/27/2010], having a pore volume of 0.3-0.7 ml / g, a specific surface area of 200-350 m ² / g and an average pore diameter of 9-13 nm, characterized in that it contains a bimetallic complex compound [M (H ₂ O) ₂ (H ₂ N) ₂ CO] ₂ [P ₂ Mo ₅ O ₂₃ ] × 0.5M (H ₂ O) ₆ - 20-30 wt. %, which corresponds to the content in the catalyst calcined at 550 ° C, wt. %: MoO ₃ - 12.0-18.0; M - 3.0-4.6; P ₂ O ₅ - 2.3-3.6 Al ₂ O ₃ - the rest, as M, the catalyst contains Co ²⁺ or Ni ²⁺ or their mixture. The main disadvantage of this catalyst is the complexity of obtaining the starting compounds for preparation, the presence of an ammonium ion in the impregnating solution, which has a negative effect on the catalytic activity and a high sulfur content in the products obtained during hydrotreating with its use.

In the patent [patent RU 2573561, IPC B01J 23/882, publ. 01/20/2016] describes a catalyst for hydrodesulfurization of hydrocarbon feedstock, consisting of HPS 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 the organic additive is 5-15 wt. % of the weight of the catalyst supported on a porous support (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 - 4.0-6.5 wt%). As a cobalt compound, one of the following is used: cobalt hydroxide Co (OH) ₂ ⋅nH ₂ O (n = 0-5), cobalt carbonate CoCO ₃ , cobalt carbonate basic CoCO ₃ ⋅1.5Co (OH) ₂ ⋅nH ₂ O (n = 0.5-5.0), cobalt acetate Co (CH ₃ COO) ₂ . One of the following is used as a nickel compound: nickel hydroxide Ni (OH) ₂ ⋅nH ₂ O (n = 0-5), nickel carbonate NiCO ₃ , nickel carbonate basic NiCO ₃ ⋅nNi (OH) ₂ ⋅mH ₂ O (n = 1-3, m = 0.5-5.0), nickel acetate Ni (CH ₃ COO) ₂ . The porous support is alumina, silicon oxide, titanium oxide, zirconium oxide, magnesium oxide, zeolite, aluminosilicate, aluminophosphate, and combinations thereof. The main disadvantage of the method for preparing the described catalyst is the presence of citric and / or tartaric acids in the impregnating solution, which, interacting with the alumina carrier, significantly reduce the strength of the finished catalyst. The presence of phosphorus in the catalyst increases acidity and promotes undesirable cracking reactions of hydrocarbon feedstock.

A common disadvantage for the above methods for preparing catalysts is that the obtained catalysts do not allow obtaining purified products with an ultra-low sulfur content under mild conditions for conducting the process of hydroprocessing of petroleum fractions, the occurrence of side cracking reactions due to increased acidity, as well as deactivation caused by coke deposits.

The closest in technical essence to the claimed method for preparing a catalyst is a method for producing a catalyst for hydrodesulfurization of diesel fractions [patent RU 2314154, IPC B01J 23/882, B01J 23/883, publ. 10.01.2008], which uses an alumina carrier, including modified with acid additives and an impregnating solution containing complex compounds of molybdenum and cobalt (nickel), stabilized with a mixture of complexing organic acids (citric, lactic, malonic, acetic, formic).

The presence in the impregnating solution of complexing organic acids, especially citric acids, including in the form of cobalt monohydrate and / or citrate, affects the alumina support, reduces the strength of the catalyst, leads to an uncontrolled change in the porous structure and, as a result, to a decrease in the activity of the catalyst. The complex compounds of molybdenum and cobalt described in the method are not stable in the entire range of the proposed synthesis conditions, tend to change their composition, especially the intramolecular molar ratio Co (Ni) / Mo, due to the formation of polymolybdates, which leads to the formation of an oxide precursor of non-optimal composition and, as the result is a decrease in the catalytic activity of the resulting catalysts. The use of alumina carriers modified with acid additives and / or the presence of orthophosphoric acid in the impregnating solution leads to an increase in the acidity of the obtained catalysts and a decrease in the yield of the target purified products.

The main disadvantage of this method for preparing a catalyst is that the catalysts obtained with its use do not allow obtaining purified products with a residual sulfur content of less than 10 mg / kg.

The objective of this invention is to develop a method for producing a catalyst for deep hydroprocessing of hydrocarbon feedstock, a catalyst and a method for hydrotreating hydrocarbon feedstock using it, which makes it possible to obtain diesel fuel components that meet the quality of modern regulatory requirements.

The problem is solved by means of a method for preparing a catalyst for deep hydroprocessing of hydrocarbon feedstock containing an active component in the form of mixed sulfides of Mo and Co, including the stages of preparing an impregnating solution containing precursors of active metals and organic additives, impregnating a carrier, which is used as a thermally stable mesoporous alumina with a specific surface area of at least 260 m ² / g, a specific pore volume of 0.75 to 1.2 cm ³ / g, an average pore radius of 3.5-5.5 nm and a mechanical strength of at least 2.0 kg / mm , for the application of active metals, the impregnating solution is prepared by dissolving molybdenum trioxide or molybdic acid in an aqueous solution of hydroperoxide with a volume concentration of H ₂ O ₂ from 12 to 26%, at a temperature of 35-45 ° C for 4-6 hours, followed by the addition of acetate or cobalt carbonate or acetylacetonate and organic additives, maturation of the impregnated catalyst, drying and activation of the dried atalizator.

Preferably, the concentration of Co in the impregnating solution is not less than 85 and not more than 165 g / l, and the concentration of Mo is not less than 195 and not more than 495 g / l.

Preferably, the total molar concentration of organic additives in the finished impregnating solution is from 2.0 to 10.0 mol / l.

Preferably, the finished impregnating solution has a pH in the range of 0.9 to 2.5.

Preferably, the finished impregnating solution contains heteropolyanions of the composition [Co ₂ Mo ₁₀ O ₃₈ H ₄ ] ^6- and [Co (OH) ₆ Mo ₆ O ₁₈ ] ^3- in a molar ratio of 7: 2 to 11: 1 mol / mol.

Preferably, the impregnation of the carrier in the form of extrudates in the form of a trefoil or a cylinder with a circumscribed diameter of 1.1-1.5 mm with the finished solution is carried out in a rotating vacuum impregnator by supplying the impregnating solution to the carrier at a temperature of 20-45 ° C with constant stirring for 20 minutes ...

Preferably, the maturation of the impregnated catalyst is carried out directly in a rotating vacuum impregnator for 4-8 hours at a temperature of 20-45 ° C with periodic stirring once an hour by rotating the impregnator at 520 °.

Preferably, the impregnating solution for preparing the catalyst contains organic additives: hydroxycarboxylic acids, polyhydric alcohols or hydroxycarboxylic acids, organic esters of 2-hydroxybutanoic acid, sulfur-containing organic complexones or polyhydric alcohols, organic esters of 2-hydroxybutanoic acid, sulfur-containing organic complexones.

Preferably, hydroxyethane, 2,3-dihydroxypropanoic, 2-hydroxybutanoic acids or mixtures thereof with a molar ratio of hydroxy acid: molybdenum in solution from 0.25: 1 to 1: 1 are used as hydroxycarboxylic acids.

Preferably, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol with a molecular weight of 200 to 600 g / mol or mixtures thereof with a molar ratio in solution of polyhydric alcohol: molybdenum from 0.1: 1 to 0.5: 1 are used as polyhydric alcohols.

Preferably, 2-mercaptoethanol, 2,3-dimercaptopropanol-1, dithioglycolic acid or mixtures thereof with a molar ratio of chelator: molybdenum in solution from 0.1: 1 to 0.5: 1 are used as sulfur-containing organic chelating agents.

Preferably, methyl, ethyl, dimethyl or diethyl ester of 2-hydroxybutanoic acid is used as organic esters of 2-hydroxybutanoic acid with a molar ratio of ether: molybdenum in solution from 0.25: 1 to 0.5: 1.

Preferably, drying of the impregnated catalyst is carried out for 8 hours at temperatures of 65-130 ° C with a stepwise increase in temperature.

Preferably, the activation of the dried catalyst is carried out in situ stepwise over 36 hours according to the following program: 2 hours at 140 ° C, 12 hours at 240 ° C, 12 hours at 340 ° C in a stream of hydrogen (total pressure 2.5-3.0 MPa , the frequency of circulation of WAG / raw material 400-600 nm ³ / m ^{3 of} raw material) with a uniform increase in temperature between the stages (at a rate of 15-25 ° C / h) and the supply of a mixture of dimethyl disulfide-oil fraction (OSPS = 3 h ^-1 ), having temperatures of the beginning and end of boiling in the range 120-240 ° C, with a total sulfur content of 0.5-1.5 wt. %.

The problem is also solved with the help of a catalyst for deep hydroprocessing of hydrocarbon raw materials obtained by this method, containing the active component in the form of mixed sulfides of Mo and Co, in amounts equal to 10.5-17.5 wt. % and 3.3-5.5 wt. %, Respectively, based on the calcined at 550 ° C for 2 hours oxide catalyst deposited from the impregnating solution onto the thermally stable mesoporous alumina having a specific surface area of at least 260 m ² / g, a pore volume of 0.75 to 1, 2 cm ³ / g, with an average pore radius of 3.5-5.5 nm and a mechanical strength of at least 2.0 kg / mm.

The problem is also solved using the method of hydrotreating hydrocarbon feedstock using the specified catalyst obtained by the specified method, realized at temperatures of 320-380 ° C, a total pressure of 3.4-4.6 MPa, a space velocity of the feedstock 1.2-2.6 h ^-1 , the partial pressure of hydrogen at the inlet to the reactor is not less than 2.9 MPa.

Preferably, the diesel fraction is hydrotreated with the total content of light gas oils of catalytic cracking and / or coking in the mixture not exceeding 30 wt. %.

The technical result of this invention is a method for producing a catalyst for deep hydro-processing of hydrocarbon feedstock, a catalyst and a method for hydrotreating hydrocarbon feedstock with its use, which makes it possible to obtain diesel fuel components that meet the quality of modern regulatory requirements.

The inventive preparation method provides for the production of a catalyst, the chemical composition and properties of the active phase of which determine its high catalytic activity in the target reactions of hydroprocessing of hydrocarbon feedstock.

The use of molybdenum trioxide or molybdic acid, hydroperoxide, acetate or carbonate or acetylacetonate of cobalt and organic additives from among: hydroxycarboxylic acids, polyhydric alcohols or hydroxycarboxylic acids, organic esters of 2-hydroxybutanoic acid, sulfur-containing organic complexones or polyhydric alcohols, organic esters of 2-hydroxybutanoic acid , sulfur-containing organic complexones provides an optimal interaction of the precursors of active metals with the carrier, as well as the formation of an optimal mixed sulfide active phase.

Use of a heat-resistant mesoporous alumina support with a specific surface area of at least 260 m ² / g, a pore volume of 0.75 to 1.1 cm ³ / g, average pore radius of 5.5-8.5 nm and a mechanical strength of not less than 2 , 0 kg / mm, as well as the absence of acid modifiers in the carrier and mineral acids, especially orthophosphoric acids, in the impregnating solution provides a low acidity of the carrier and a catalyst based on it and a high selectivity of the catalyst with respect to the target reactions of hydro-processing of hydrocarbon feedstock. The absence of acid modifiers in the support provides the total acidity of the support according to NH3 TPD at a level of less than 850 μmol / g. The absence of phosphorus, boron, and silicon in the catalyst makes it possible to increase the selectivity of the catalyst with respect to the target reactions of hydrogenolysis of heteroatomic compounds and the stability of the catalyst to blocking the porous structure with coke deposits and components of diesel fractions.

In the examples, the extrudates are in the shape of a trefoil or a cylinder with a circumscribed diameter of 1.1-1.4 mm. If necessary, the carrier can also have a different shape.

The use for the preparation of an impregnating solution of molybdenum trioxide or molybdic acid, dissolved in an aqueous solution of hydroperoxide with moderate heating, followed by the addition of acetate or carbonate or cobalt acetylacetonate and specific organic additives, makes it possible to obtain an impregnating solution containing anions of the composition [Co ₂ Mo ₁₀ O ₃₈ H ₄ ] ^6- and [Co (OH) ₆ Mo ₆ O ₁₈ ] ^3- in a molar ratio from 7: 2 to 11: 1 mol / mol, the use of which ensures the optimal interaction of the precursors of active metals with each other and the selective formation of a highly active active phase.

The carrier is impregnated with a ready-made solution in a rotating vacuum impregnator. It is possible to use other impregnation devices known from the prior art.

The implementation of impregnation, maturation of the impregnated catalyst, drying and activation of the dried catalyst under the stated conditions, ensures the formation of a mixed sulfide active phase with optimal characteristics and, as a result, optimal physicochemical characteristics of a catalyst for deep hydroprocessing of hydrocarbon raw materials with maximum activity in target reactions of hydrogenolysis of heteroatomic compounds of petroleum fractions.

The impregnating solution is prepared by dissolving in specified amounts of molybdenum trioxide or molybdic acid in an aqueous solution of hydroperoxide with a volume concentration of H ₂ O ₂ from 12 to 26%, at a temperature of 35-45 ° C for 4-6 hours, followed by the addition of acetate or carbonate, or cobalt acetylacetonate and organic additives from among: hydroxycarboxylic acids, polyhydric alcohols or hydroxycarboxylic acids, organic esters of 2-hydroxybutanoic acid, sulfur-containing organic complexones or polyhydric alcohols, organic esters of 2-hydroxybutanoic acid, sulfur-containing organic complexones, followed by stirring until a homogeneous solution composition. The concentration of Co in the impregnating solution is not less than 85 and not more than 165 g / l, and the concentration of Mo is not less than 195 and not more than 495 g / l; the total molar concentration of organic additives in the finished impregnating solution is from 2.0 to 10.0 mol / l; the impregnating solution has a pH in the range from 0.9 to 2.5 and differs in that it contains heteropolyanions of the composition [Co ₂ Mo ₁₀ O ₃₈ H ₄ ] ^6- and [Co (OH) ₆ Mo ₆ O ₁₈ ] ^3- in molar ratio from 7: 2 to 11: 1 mol / mol. Impregnation with a ready-made solution of a pre-dried carrier with an internal pore volume freed from air is carried out in a rotating vacuum impregnator by supplying the impregnating solution to the carrier at a temperature of 20-45 ° C with constant stirring for 20 minutes. The maturation of the impregnated catalyst is carried out directly in a rotating vacuum impregnator for 4-8 hours at a temperature of 20-45 ° C with periodic stirring once an hour by rotating the impregnator at 520 °. The impregnated catalyst is dried for 8 hours at temperatures of 65-130 ° C with a stepwise temperature rise. The activation of the dried catalyst is carried out in situ stepwise for 36 hours according to the following program: 2 hours at 140 ° C, 12 hours at 240 ° C, 12 hours at 340 ° C in a stream of hydrogen (total pressure 2.5-3.0 MPa, the frequency of circulation of WAG / raw material 400-600 nm ³ / m ^{3 of} raw material) with a uniform increase in temperature between the stages (at a rate of 15-25 ° C / h) and the supply of a mixture of dimethyl disulfide-oil fraction (OSPS = 3 h ^-1 ), having a temperature beginning and end of boiling in the range 120-240 ° C, with a total sulfur content of 0.5-1.5 wt. %. Hydroprocessing of hydrocarbon feedstock - hydrotreating of a diesel fraction using the above catalyst is carried out at temperatures of 320-380 ° C, a total pressure of 3.4-4.6 MPa, a volumetric feed rate of 1.2-2.6 h ^-1 , a partial pressure of hydrogen at inlet to the reactor not less than 2.9 MPa. The total content of secondary gas oils LGKK and LGZK in the mixture does not exceed 30 wt. %.

To prepare the impregnating solution, precursors and organic additives were used, according to Table 1, in the amounts indicated in Table 2. The properties of the finished impregnating solutions are shown in Table 3. The characteristics of the carriers used for the preparation of the catalysts are presented in Table 4. The content of active metals in the finished catalysts , as well as the synthesis conditions at each of the stages of preparation are shown in Table 5. The conditions of the process of hydroprocessing of hydrocarbon feedstock in the presence of the obtained catalysts, the characteristics of the feedstock and the obtained hydrogenates are presented in Table 6.

The process of hydroprocessing of hydrocarbon feedstock for testing the catalysts was carried out on a flow-through pilot plant under hydrogen pressure. The resulting hydrogenates were stabilized by separating gaseous products in a separator under a pressure equal to the operating pressure of the unit and a temperature of 25 ° C. The degassed hydrogenates were treated with a 15% NaOH alkali solution for 10 min and washed with distilled water until the wash water was neutral. The hydrogenates freed from dissolved hydrogen sulfide were dried over calcined CaCl2. The residual sulfur content in hydrogenated products was determined according to GOST R EN ISO 20846-2006.

Example 1. An impregnating solution is prepared by dissolving molybdenum trioxide in the amount of 277.2 g in an aqueous solution of hydroperoxide weighing 315 g with a volume concentration of H ₂ O ₂ 24%, at a temperature of 45 ° C for 4 hours, followed by the addition of 213.3 g of acetate cobalt and hydroxyethanic acid in the amount of 104.4 g, 2,3-dihydroxypropanoic acid in the amount of 72.8 g and ethylene glycol in the amount of 35.5 g with constant stirring until a homogeneous solution is obtained. The concentration of Co in the impregnating solution is 76 g / l, and the concentration of Mo is 323 g / l; the molar ratio of organic additives to molybdenum in the finished impregnating solution is 3.1 mol / mol; the impregnating solution has a pH of 2.0 and differs in that it contains heteropolyanions of the composition [Co ₂ Mo ₁₀ O ₃₈ H ₄ ] ^6- and [Co (OH) ₆ Mo ₆ O ₁₈ ] ^3- in a molar ratio of 10: 1 mol / mol ...

Impregnation with a ready-made solution of a pre-dried carrier with an internal pore volume freed from air in an amount of 1000 g and the following texture characteristics: specific surface area 264 m ² / g, pore volume 0.85 cm ³ / g, average pore radius 4.4 nm, c the form of extrudates in the form of a cylinder with a diameter of 1.2 mm and a mechanical strength of 2.6 kg / mm, is carried out in a rotating vacuum impregnator by supplying the impregnating solution to the carrier at a temperature of 45 ° C with constant stirring for 20 minutes. The maturation of the impregnated catalyst is carried out directly in a rotating vacuum impregnator for 4 hours at a temperature of 45 ° C with periodic stirring once an hour by rotating the impregnator at 520 °. Drying of the impregnated catalyst is carried out for 8 hours at a temperature of 65-130 ° C with a stepwise rise in temperature.

The stage of activation (sulfonation) of the catalyst is carried out by passing the prepared raw material through a catalyst preheated to 120 ° C and kept at this temperature for 2 hours - a straight-run middle distillate fraction with the beginning of boiling in the temperature range 110-140 ° C and the end of boiling in the range 260-340 ° C, additionally containing 1.6 wt. % sulfur in the form of dimethyl disulfide. The passage of the prepared raw material was carried out at a constant temperature until the appearance of a liquid product at the outlet of the reactor. Then, simultaneously with the passage of the specified raw material through the catalyst, the temperature in the reactor was changed. Heating from 120 to 320 ° C was carried out at a rate of 15-20 ° C / hour, followed by holding the catalyst at 320 ° C for 10 hours. Throughout the catalyst activation procedure, the volumetric feed rate of the prepared feed was maintained at 2 h ^-1 , the volume ratio of hydrogen-containing gas / feed was 500 nm ³ / m ³ , and the pressure in the system was 35 atm.

Hydroprocessing of hydrocarbon feedstock - hydrotreating of a diesel fraction using a prepared and activated catalyst was carried out at a temperature of 320 ° C, a total pressure of 3.8 MPa, a space velocity of the feedstock of 2.6 h ^-1 , a partial hydrogen pressure at the reactor inlet of at least 3.5 MPa. Secondary gas oils were not added to the feed. The characteristics of the obtained hydrogenates are presented in table 6.

Examples 2-26 are similar to example 1 in essence, but differ in the specific conditions of the synthesis, the composition of the impregnating solution, the composition and properties of the carrier and catalyst, as well as the parameters of the hydrotreating process, which are given in the corresponding tables. The line numbers in Tables 1-6 containing the data required for the preparation, activation and carrying out of the hydrotreating process correspond to the numbers of the examples. The compounds required for the preparation of the impregnating solution and the catalyst are shown in Table 1, the weights of the starting compounds - in Table 2. Table 3 reflects the characteristics of the finished impregnating solutions. The properties of the alumina supports used for the preparation of the catalysts are shown in Table 4, and the synthesis parameters and the composition of the finished catalysts are in Table 5, the parameters of the process of hydroprocessing of hydrocarbon feedstock and the results achieved are presented in Table 6.

* HES - hydroxyethanic acid; DHPA - 2,3-Dihydroxypropanoic acid; GBK - 2-hydroxybutanoic acid; EG - ethylene glycol; DEG - diethylene glycol; TEG - triethylene glycol; TetEG - tetraethylene glycol; PEG200 - polyethylene glycol (M = 200); PEG600 - polyethylene glycol (M = 600); ME - 2-mercaptoethanol; DMP - 2,3-dimercaptopropanol-1; DTHC - dithioglycolic acid; M-GBK - 2-hydroxybutanoic acid methyl ester; DM-GBK - dimethyl ester of 2-hydroxybutanoic acid; E-GBK - ethyl ester of 2-hydroxybutanoic acid; DE-GBK - diethyl ether of 2-hydroxybutanoic acid.

Claims (17)

1. A method of obtaining a catalyst for deep hydroprocessing of hydrocarbon feedstock containing an active component in the form of mixed sulfides of Mo and Co, including the stages of preparing an impregnating solution containing precursors of active metals and organic additives, impregnating a carrier, which is used as a thermally stable mesoporous alumina with a specific area surface not less than 260 m ² / g, specific pore volume from 0.75 to 1.2 cm ³ / g, average pore radius 3.5-5.5 nm and mechanical strength not less than 2.0 kg / mm, for application active metals, the impregnating solution is prepared by dissolving molybdenum trioxide or molybdic acid in an aqueous solution of hydroperoxide with a volume concentration of H ₂ O ₂ from 12 to 26% at a temperature of 35-45 ° C for 4-6 hours, followed by the addition of acetate, or carbonate, or cobalt acetylacetonate and organic additives, maturation of the impregnated catalyst, drying and activation of the dried catalyst. 2. The method according to claim 1, characterized in that the concentration of Co in the impregnating solution is not less than 85 and not more than 165 g / l, and the concentration of Mo is not less than 195 and not more than 495 g / l. 3. The method according to claim 1, characterized in that the total molar concentration of organic additives in the finished impregnating solution is from 2.0 to 10.0 mol / l. 4. The method according to claim 1, characterized in that the finished impregnating solution has a pH in the range from 0.9 to 2.5. 5. The method according to claim 1, characterized in that the finished impregnating solution contains heteropolyanions of the composition [Co ₂ Mo ₁₀ O ₃₈ H ₄ ] ^6- and [Co (OH) ₆ Mo ₆ O ₁₈ ] ^3- in a molar ratio of 7: 2 to 11: 1 mol / mol. 6. The method according to claim 1, characterized in that the impregnation of the carrier in the form of extrudates in the form of a trefoil or a cylinder with a circumscribed circle diameter of 1.1-1.5 mm with the finished solution is carried out in a rotating vacuum impregnator by supplying the impregnating solution to the carrier at a temperature of 20 -45 ° C with constant stirring for 20 minutes. 7. A method according to claim 1, characterized in that the maturation of the impregnated catalyst is carried out directly in a rotating vacuum impregnator for 4-8 hours at a temperature of 20-45 ° C with periodic stirring once an hour by rotating the impregnator by 520 °. 8. The method according to claim 1, characterized in that the impregnating solution for preparing the catalyst contains organic additives: hydroxycarboxylic acids, polyhydric alcohols or hydroxycarboxylic acids, organic esters of 2-hydroxybutanoic acid, sulfur-containing organic complexones or polyhydric alcohols, organic esters of 2-hydroxybutanoic acid , sulfur-containing organic complexones. 9. The method according to claim 8, characterized in that hydroxyethanic, 2,3-dihydroxypropanoic, 2-hydroxybutanoic acids or their mixtures with a molar ratio of hydroxyacid: molybdenum in solution from 0.25: 1 to 1: 1 are used as hydroxycarboxylic acids ... 10. The method according to claim 8, characterized in that ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol with a molecular weight of 200 to 600 g / mol or mixtures thereof with a molar ratio in solution of polyhydric alcohol: molybdenum from 0 , 1: 1 to 0.5: 1. 11. The method according to claim 8, characterized in that 2-mercaptoethanol, 2,3-dimercaptopropanol-1, dithioglycolic acid or mixtures thereof with a molar ratio in the solution of a chelator: molybdenum from 0.1: 1 to 0.5: 1. 12. The method according to claim 8, characterized in that methyl, ethyl, dimethyl or diethyl ester of 2-hydroxybutanoic acid is used as organic esters of 2-hydroxybutanoic acid with a molar ratio of ether: molybdenum in solution from 0.25: 1 to 0, 5: 1. 13. The method according to claim 1, characterized in that the impregnated catalyst is dried for 8 hours at temperatures of 65-130 ° C with a stepwise temperature rise. 14. The method according to any one of claims. 1-13, characterized in that the activation of the dried catalyst is carried out in situ stepwise for 36 hours according to the following program: 2 hours at 140 ° C, 12 hours at 240 ° C, 12 hours at 340 ° C in a stream of hydrogen (total pressure 2 , 5-3.0 MPa, circulation rate of WGS / raw material 400-600 nm / m of raw material) with a uniform increase in temperature between the stages (at a rate of 15-25 ° C / h) and feeding a mixture of dimethyl disulfide-oil fraction (OSPS = 3 h ^-1 ), having temperatures of the beginning and end of boiling in the range 120-240 ° C, with a total sulfur content of 0.5-1.5 wt.%. 15. Catalyst deep hydroprocessing of hydrocarbon raw materials obtained by the method according to any one of paragraphs. 1-14, containing the active component in the form of mixed sulfides Mo and Co in amounts equal to 10.5-17.5 wt.% And 3.3-5.5 wt.%, Respectively, based on calcined at 550 ° C in for 2 hours, an oxide catalyst deposited from an impregnating solution on a thermally stable mesoporous alumina with a specific surface area of at least 260 m ² / g, a specific pore volume of 0.75 to 1.2 cm ³ / g, an average pore radius of 3.5 -5.5 nm and mechanical strength not less than 2.0 kg / mm. 16. A method for hydrotreating a hydrocarbon feed using a catalyst according to claim 15, obtained by a method according to any one of claims. 1-14, implemented at temperatures of 320-380 ° C, a total pressure of 3.4-4.6 MPa, a volumetric feed rate of 1.2-2.6 h ^-1 , a partial pressure of hydrogen at the reactor inlet not less than 2, 9 MPa. 17. The hydrotreating method according to claim 16, characterized in that the diesel fraction with the total content of light gas oils from catalytic cracking and / or coking in the mixture is not more than 30 wt%.