RU2478428C1 - Catalyst for hydrofining hydrocarbon material, hydrofining catalyst support, method of making support, method of making catalyst and method of hydrofining hydrocarbon material - Google Patents

Abstract

FIELD: chemistry.SUBSTANCE: invention relates to hydrofining catalysts, methods of making said catalysts, catalyst supports, methods of making supports and methods of obtaining petroleum products with low content of sulphur. Described is a catalyst which contains the following, wt %: Mo - 8.0-15.0; Co or Ni - 2.0-5.0; S - 5.0-15.0; C - 0.2-8.0; Ti - 0.3-4.1; B - 0.2-2.2; AlO-the balance and a support which contains the following, wt %: TiO- 1.0-10.0; BO- 1.0-10.0; AlO- the balance, and having specific surface area of 150-300 m/g, pore volume of 0.5-0.95 cm/g and average pore diameter of 7-22 nm, and which is in form of particles with a cross-section in form of a three-leafed figure with diameter of the circumscribed circle of 1.0-1.6 mm and length of up to 20 mm. The support is obtained by moulding a paste, which is obtained by mixing aluminium hydroxide powder AlOOH, at least one powder of titanium dioxide, at least one boron compound, water and a peptising additive at pressure of up to 10 MPa, followed by drying and calcination at temperature of up to 600°C. The catalyst is prepared by saturating a support with an aqueous solution containing molybdenum and cobalt or nickel in form of complexes, for example, [M(HO)(L)][MoO(CHO)], where: M=Coand/or Ni; L is a partially deprotonated form of citric acid CHOor ammonia NH, x=0 or 2; y=0, 1 or 2; and at least one oxygen-containing organic compound, dried and sulphided. Hydrofining of hydrocarbon material is carried out in the presence of the catalyst described above at temperature of 320-400°C, pressure of 0.5-10 MPa, mass flow rate of material of 0.5-5 h, volume ratio hydrogen/material equal to 100-1000 m/m.EFFECT: obtaining a catalyst having maximum activity in target reactions occurring when hydrofining hydrocarbon material.20 cl, 9 ex, 1 tbl

Description

The invention relates to catalysts for the production of low sulfur oil products, methods for preparing such catalysts, carriers and methods for producing carriers for hydrotreating catalysts, as well as hydrocarbon hydrotreating processes.

In connection with the transition of Russian oil refining to the production of motor fuels, in terms of sulfur content corresponding to the EURO-4 and EURO-5 standards and similar to Russian ones [GOST R 52368-2005. (EH 590-2004). Diesel fuel EURO. Technical conditions; GOST R 51866-2002. (EH 228-1999). Unleaded gasoline], there is an urgent need for highly active domestic hydrotreating catalysts, which make it possible to obtain either directly motor fuels with a low residual sulfur content or low-sulfur feedstock for their production, for example, vacuum gas oil containing not more than 500 ppm sulfur. At the same time, the conditions for hydrotreating processes should be feasible at Russian refineries without their radical reconstruction.

There are various catalysts for hydrotreating petroleum distillates, methods for their preparation, carriers and methods for preparing carriers for these catalysts, as well as methods for hydrotreating various hydrocarbon feedstocks, but a common disadvantage for them is the high residual sulfur content in the resulting products.

Most often, catalysts containing cobalt or nickel and molybdenum oxides supported on alumina are used for hydrodesulfurization of petroleum feedstocks. Thus, a hydrodesulfurization catalyst is known [RF Application No. 2002124681, C10G 45/08, B01J 23/887, 09.16.2002], which contains cobalt oxide, molybdenum oxide and alumina, characterized in that it has a ratio of components, wt.% : cobalt oxide 3.0-9.0, molybdenum oxide 10.0-24.0 wt.%, aluminum oxide the rest, the specific surface area of 160-250 m ² / year In this case, the hydrotreating process is carried out at a temperature of 310-340 ° C, a pressure of 3.0-5.0 MPa, with a hydrogen / feed ratio of 300-500 nm ³ / m ³ and a bulk feed rate of 1.0-4.0 h ^{- 1} . The main disadvantage of such a catalyst and method of carrying out the hydrotreatment process is the high sulfur content in the resulting products.

Reducing the residual sulfur content in the resulting petroleum products is achieved by using catalysts with increased activity. Previously, hydrotreating catalysts were most often prepared by wet mixing of aluminum hydroxide with compounds of active metals, followed by molding, drying and calcination. Such catalysts are described in RF patents No. 1774555, 2073566, 2103065, 2137541, 2147256, 2189860, 2271861. A common disadvantage for these catalysts is the low activity in hydrotreating.

In recent years, the method of depositing active metals on an already formed support has been used to prepare hydrotreating catalysts. As a carrier, alumina with a certain size and shape of granules and certain texture characteristics is most often used. The carrier is often modified with various additives, including boron compounds and titanium compounds, however, in all cases, a separate modification is used with either boron or titanium. There is no information in the scientific and patent literature on the joint modification of carriers by boron and titanium compounds.

Separately, boron or titanium compounds are introduced into the support either prior to its formation by coprecipitation of modifiers and aluminum from co-solutions [Journal of Catalysis 115 (1989) 441-451, Microporous and Mesoporous Materials 23 (1998) 265-275], or by mixing aluminum hydroxide with a modifying compound at the stage of preparation of the paste for molding [Pat. US No. 6147432, Catal. Today 65 (2-4) (2001) 225], or the additive is introduced by impregnation into a molded carrier, followed by drying and calcination [Catalysis Today 107-108 (2005) 551-558, Pat. US No. 6383975].

The introduction of active metals, most often Co, Ni, and Mo, into the catalyst is carried out by impregnating the formed support with aqueous solutions of their salts. In this case, they can be used as separate deposition of active metals by impregnation in several stages [RF No. 2242501, 2246987], and their application from joint solutions stabilized by various agents [RF No. 2073567, 2216404, 2306978].

Hydrotreating catalysts can also be prepared using complex metal salts. So, a known method of producing a catalyst for hydrotreating oil fractions, [RF No. 2074025, B01J 21/04, 02.27.1997] containing, wt.%: 14-21 MoO ₃ ; 3-8 NiO or CoO; 0.5-6 P ₂ O ₅ , Al ₂ O ₃ - the rest, by applying the compounds of the active components to alumina by coprecipitation of metal salts of groups VIII and VI of the Periodic system, as well as phosphorus, followed by molding the catalytic mass in the form of extrudates, drying and laying granules obtained, characterized in that in order to obtain a catalyst with increased activity in the reactions of hydrodesulfurization of oil fractions, during the synthesis of the catalyst, the active components are introduced into aluminum hydroxide in the form of a complex solution of metal salts of groups VIII and VI p stabilized with phosphoric acid, provided that the pH of the phosphoric acid solution is 0.5-2.5 at a temperature of 40-60 ° C.

A common disadvantage for the above catalysts and methods for their preparation is that with their use it is not possible to achieve a low residual sulfur content in the resulting products.

The closest in their technical essence and the achieved effect to the claimed catalyst and the method of its preparation is a catalyst for hydrodesulfurization of the diesel fraction and the method of its preparation [RF No. 2313392, B01J 37/02, B01J 21/02, C10G 45/08, 10/13/2006]. The known catalyst has 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, contains the following components, wt.%: Cobalt compounds with a concentration of 2.5- 7.5 in terms of CoO, molybdenum compounds with a concentration of 12-25 in terms of MoO ₃ , citric acid with a concentration of 15-35, boron compounds 0.5-3.0 in terms of B ₂ O ₃ , alumina Al ₂ O ₃ - the rest, while cobalt, molybdenum, citric acid and boron can be included in complex compounds of various stoichiometry. The method of preparation of the catalyst consists in a one-stage impregnation of the carrier with an impregnating solution obtained by dissolving in water or an aqueous solution of ammonia the following compounds: citric acid, ammonium paramolybdate (NH ₄ ) ₆ Mo ₇ O ₂₄ × 4H ₂ O, at least one cobalt compound, at least one boron compounds, in this case, the order and conditions of dissolution of the components are used to ensure the formation of complex compounds in the solution, and the concentrations of the components in the solution are selected so that after drying, the catalyst contained components with the above concentrations.

The main disadvantage of the prototype, as well as other known catalysts prepared by known methods, is the high sulfur content in hydrotreated products.

Closest to the claimed carrier and method for preparing the carrier is the method described in US patent No. 6174432, C10G 45/04; B01J 21/04, 01.16.2001. According to the well-known solution, aluminum hydroxide is first prepared according to the following multistage scheme: stage 1 — precipitation of an aqueous solution of sodium aluminate with a solution of aluminum sulfate at pH 7 and 60 ° C; stage 2 — filtration; stage 3 — washing with a 0.3% aqueous ammonia solution; 4 stage - adding a 10% aqueous solution of ammonia to pH 11, stage 5 - stirring at 90 ° C for 25 hours, stage 6 - adding 5N. an aqueous solution of nitric acid to pH 2, stage 7 - stirring for 15 minutes, stage 8 - adding a 10% aqueous solution of ammonia to pH 11, stage 9 - filtering and washing with water. Next, the obtained aluminum hydroxide is mixed with a certain amount of an aqueous solution of boric acid, formed, dried at 110 ° C for 10 hours, and calcined for 2 hours at 800 ° C. The result is a carrier containing 1-12% boron in terms of oxide. After the carrier was impregnated with a solution of ammonium paramolybdate and nickel nitrate, dried at 110 ° C and calcined at 500 ° C, a catalyst was obtained having a specific surface area of 70-130 m ² / g, an average pore diameter of 19-25 nm, a pore volume of 0.65- 0.8 ml / g. The described method for preparing the carrier is technologically very complex and leads to the formation of a large amount of wastewater, while the resulting carrier has non-optimal texture characteristics - low specific surface area and oversized pore diameter. As a result, the catalyst prepared on its basis has a low activity in hydrotreating.

The present invention solves the problem of creating an improved hydrotreating catalyst and a method for its preparation, a catalyst support and a method for preparing a carrier, as well as a method for hydrotreating hydrocarbon feedstocks characterized by:

1. The optimal chemical composition of the catalyst and its optimal texture characteristics, providing oil products with low sulfur content.

2. A carrier having a predetermined granule size and predetermined texture characteristics that provide catalysts with optimal texture characteristics and a given chemical composition by a technologically simple single impregnation method.

3. A carrier modified with boron and titanium, which leads to the further preparation of a catalyst with an optimal structure of the active component having an increased activity in hydrotreating.

4. A simple and non-waste method of preparation of the carrier, allowing to obtain a carrier with the optimal chemical composition, texture characteristics and granule size for the hydrotreating catalysts.

5. The method of preparation of the catalyst, which consists in introducing active metals into the composition of the catalyst by the method of one-stage impregnation of the carrier with an aqueous solution containing both molybdenum and cobalt or nickel in the form of complex compounds. This method combines technological simplicity with the ability to reliably obtain catalysts with desired properties having increased activity in hydrotreating.

6. The low sulfur content in the resulting petroleum products, achieved through the use of the inventive catalyst on the inventive carrier, prepared by the inventive methods.

The problem is solved by a hydrocarbon hydrotreating catalyst, which contains, wt.%: Mo - 8.0-15.0; Co or Ni - 2.0-5.0; S - 5.0-15.0; C 0.2-8.0; Ti - 0.3-4.1; B 0.2-2.2; Al ₂ O ₃ - the rest, having a pore volume of 0.3-0.7 cm ³ / g, a specific surface area of 130-280 m ² / g, an average pore diameter of 6-20 nm and representing particles with a cross section in the form of a trefoil with a diameter the circumference described is 1.0-1.6 mm and a length of up to 20 mm.

The problem is also solved by the media for the hydrotreating catalyst, containing, wt.%: TiO ₂ - 1,0-10,0; B ₂ O ₃ - 1.0-10.0; Al ₂ O ₃ - the rest; having a specific surface area of 150-300 m ² / g, a pore volume of 0.5-0.95 cm ³ / g, an average pore diameter of 7-22 nm, and representing particles with a cross section in the form of a trefoil with a diameter of the circumscribed circle of 1.0- 1.6 mm and up to 20 mm long.

The problem is also solved by a method of preparing a carrier for a hydrocarbon hydrotreating catalyst, which consists in preparing a paste from AlOOH aluminum hydroxide powder with a boehmite or pseudoboehmite structure with a crystal size of 30-100 Å and with an average particle size of 30-60 microns of at least one titanium dioxide powder of at least one boron compound, water and a peptizing additive, which are used aqueous solutions of ammonia, nitric or acetic acids, molding the resulting paste through a die in the mold trefoil at pressures up to 10 MPa, drying and calcination.

As a powder of aluminum hydroxide AlOOH, boehmite or pseudoboehmite can be used that meets the above requirements for the size of crystals and agglomerates obtained by any of the industrial technologies for producing aluminum hydroxide: alkaline deposition of aluminum salts or acid deposition of alkali metal aluminates, see, for example, [Z. R. Ismagilov, R. A. Shkrabin, N. A. Koryabkina. Alumina carriers: production, properties and application in catalytic processes of environmental protection. Novosibirsk, 1998, 82 p. - (Ser. Ecology. Issue 50)]; thermochemical activation of gibbsite with subsequent plasticization and spray drying [Smirnov V.K., Usmanov I.F., Ponyatkova Z.Yu., Bodryy AB, Irisova KN, Talisman EL Production of hydrotreating catalysts using wasteless and non-waste technology at Sterlitamak Catalyst Plant LLC. - The world of petroleum products. 2008 No. 3. - s.16-18.]; according to the technology of hydrolysis of aluminum alcoholates [F. Alber. Variationen der physikalisch-chemischen Eigenschaften von Alkoxid-basierten Tonerden. Materials Valley Workshop Heterogene Katalyse - Einfluss des Designs von Tragerwerkstoffen auf den katalytischen Effekt Hanau, 26. Marz 2009].

As titanium dioxide powder, TiO ₂ with a rutile or anatase structure obtained by any known industrial technology can be used.

At least one compound selected from the series can be used as a boron compound: boron oxide B ₂ O ₃ , boric acid (ortho) H ₃ BO ₃ , boric acid (pyro) H ₂ B ₄ O ₇ , ammonium boric acid ( tetra) (NH ₄ ) ₂ B ₄ O ₇ × 4H ₂ O, ammonium boric acid (tetra) acid NH ₄ HB ₄ O ₇ × 3H ₂ O, ammonium boric acid (penta) NH ₄ B ₅ O ₈ × 4H ₂ O.

In the preparation of the paste, the components are taken in the following weight ratios: aluminum hydroxide: titanium dioxide: boron compound: water: peptizing additive = 1: 0.008-0.095: 0.008-0.17: 0.6-1.0: 0.01-0, 07.

Next, the paste is mixed in a mixer with Z-shaped blades at a temperature of 15-95 ° C for 10-480 minutes and formed through a die, which provides particles in the form of a trefoil with a diameter of the circumscribed circle of 1.0-1.6 mm, molding is carried out at pressure of 0.5-10.0 MPa, the obtained granules are dried at a temperature of 100-150 ° C and calcined at a temperature of 500-600 ° C.

The problem is also solved by a method for preparing a hydrocarbon hydrotreating catalyst, which consists in impregnating a carrier containing boron and titanium with an aqueous solution containing molybdenum and cobalt or nickel in the form of complex compounds, for example, in the form of a bimetallic complex compound [M (H ₂ O) _x ( L) _y ] ₂ [Mo ₄ O ₁₁ (C ₆ H ₅ O ₇ ) ₂ ], where: M = Co ²⁺ and / or Ni ²⁺ ; L is a partially deprotonated form of citric acid C ₆ H ₆ O ₇ or ammonia NH ₃ , x = 0 or 2; y = 0; 1 or 2; and at least one oxygen-containing organic compound. The application is carried out by the method of impregnation by moisture capacity or by impregnation from the excess solution, followed by drying and sulfidation.

In this case, the concentrations of molybdenum and cobalt or nickel in the form of complex compounds, and an oxygen-containing organic compound in solution, as well as the drying and sulfidation conditions, are such as to provide the following components in the finished catalyst, wt.%: Mo - 8.0-15.0 ; Co or Ni - 2.0-5.0; S - 5.0-15.0; C 0.2-8.0; Ti - 0.3-4.1; B 0.2-2.2; Al ₂ O ₃ - the rest.

At least one compound selected from the series is used as an oxygen-containing organic compound: ethylene glycol, glycerin, pentaerythritol, diethylene glycol, triethylene glycol, polyethylene glycol or polyethylene oxide with a molecular weight of 200-10000, as well as methyl and ethyl esters of the above alcohols.

The catalyst is impregnated at a temperature of 15-90 ° C for 5-60 minutes, then, if impregnation was used from the excess solution, the excess solution is drained, after impregnation, the catalyst is dried in air at a temperature of 100-250 ° C and sulfidized by processing in hydrogen sulfide, or in a mixture of hydrogen sulfide and hydrogen at temperatures up to 450 ° C.

The task of obtaining low-sulfur oil products is solved by hydrotreating hydrocarbon raw materials at a temperature of 320-400 ° C, a pressure of 0.5-10 MPa, a mass flow rate of 0.5-5 h ^-1 , a volumetric ratio of hydrogen / feedstock 100-1000 m ³ / m ³ in the presence of a catalyst containing, wt.%: Mo - 8.0-15.0; Co or Ni - 2.0-5.0; S - 5.0-15.0; C 0.2-8.0; Ti - 0.3-4.1; B 0.2-2.2; Al ₂ O ₃ - the rest having a pore volume of 0.3-0.7 cm ³ / g, a specific surface area of 130-280 m ² / g, an average pore diameter of 6-20 nm and representing particles with a cross section in the form of a trefoil with a diameter the circumference described is 1.0-1.6 mm and a length of up to 20 mm.

A distinctive feature of the proposed catalyst in comparison with the prototype is that the catalyst contains, wt.%: Mo - 8.0-15.0; Co or Ni - 2.0-5.0; S - 5.0-15.0; C 0.2-8.0; Ti - 0.3-4.1; B 0.2-2.2; Al ₂ O ₃ - the rest. The output of the content of the catalyst components over the claimed boundaries leads to a decrease in the activity of the catalyst.

A distinctive feature of the proposed carrier in comparison with the prototype is that the carrier contains, wt.%: TiO ₂ - 1,0-10,0; B ₂ O ₃ - 1.0-10.0; Al ₂ O ₃ - the rest, has a specific surface area of 150-300 m ² / g, pore volume 0.5-0.95 cm ³ / g, average pore diameter of 7-22 nm, and is a particle with a cross section in the form of a trefoil with the diameter of the circumscribed circle is 1.0-1.6 mm and a length of up to 20 mm.

The main distinguishing feature of the method of preparation of the carrier in comparison with the prototype is that for the preparation of the paste for molding, AlOOH aluminum hydroxide powder is used, having a boehmite or pseudoboehmite structure with a crystal size of 30-100 Å, with an average size of agglomerates of 30-60 micrometers, titanium dioxide powder, at least one boron compound and a peptizing agent.

Also a hallmark of the method of preparation of the carrier compared with the prototype is that the paste for molding is prepared by mixing the powder of aluminum hydroxide, at least one titanium dioxide powder, which is used as TiO ₂ with the structure of rutile or anatase; at least one boron compound selected from the series: boron oxide B ₂ O ₃ , boric acid (ortho) H ₃ BO ₃ , boric acid (pyro) H ₂ B ₄ O ₇ , ammonium boric acid (tetra) (NH ₄ ) ₂ B ₄ O ₇ × 4H ₂ O, ammonium boric acid (tetra) acid NH ₄ HB ₄ O ₇ × 3H ₂ O, ammonium boric acid (penta) NH ₄ B ₅ O ₈ × 4H ₂ O and a peptizing agent, which is used as aqueous solutions ammonia, nitric or acetic acids.

A distinctive feature of the method of preparation of the carrier in comparison with the prototype is that for the preparation of the paste the components are taken in the following weight ratios - aluminum hydroxide: titanium dioxide: boron compound: water: peptizing additive = 1: 0.008-0.095: 0.008-0.17: 0.6-1.0: 0.01-0.07.

A distinctive feature of the method of preparation of the carrier is also that the paste is mixed at a temperature of 15-95 ° C for 10-480 minutes, molded at a pressure of 0.5-10.0 MPa through a die, providing particles in the form of a trefoil with a diameter of the circumference described 1.0-1.6 mm, the obtained granules are dried at a temperature of 100-150 ° C and calcined at a temperature of 500-600 ° C.

The main distinguishing feature of the proposed method for the preparation of the catalyst compared with the prototype is that the carrier containing boron and titanium is impregnated with an aqueous solution containing molybdenum and cobalt or nickel in the form of complex compounds.

A distinctive feature of the catalyst preparation method is that at least one oxygen-containing organic compound is added to the impregnating solution containing molybdenum and cobalt or nickel in the form of complex compounds, while the concentrations of molybdenum and cobalt or nickel in the form of complex compounds, and an oxygen-containing organic compound in the solution, as well as the drying and sulfidation conditions of the catalyst, are such as to provide the following content of components wt.% in the finished catalyst: Mo - 8.0-15.0; Co or Ni - 2.0-5.0; S - 5.0-15.0; C 0.2-8.0; Ti - 0.3-4.1; B 0.2-2.2; Al ₂ O ₃ - the rest.

Also a hallmark of the proposed method for the preparation of the catalyst in comparison with the prototype is that as a complex compound of molybdenum and cobalt or Nickel use the bimetal complex compound [M (H ₂ O) _x (L) _y ] ₂ [Mo ₄ O ₁₁ (C ₆ H ₅ O ₇ ) ₂ ], where: M = Co ²⁺ and / or Ni ²⁺ ; L is a partially deprotonated form of citric acid C ₆ H ₆ O ₇ or ammonia NH ₃ , x = 0 or 2; y = 0; 1 or 2; and as an oxygen-containing organic compound, at least one compound selected from the series is used: ethylene glycol, glycerin, pentaerythritol, diethylene glycol, triethylene glycol, polyethylene glycol or polyethylene oxide with a molecular weight of 200-10000, as well as methyl and ethyl esters of the above alcohols.

A distinctive feature of the catalyst preparation method is that the carrier is impregnated by moisture capacity or from excess solution at a temperature of 15-90 ° C for 5-60 minutes with periodic stirring, in case of impregnation from the excess solution after impregnation, the excess solution is drained from the catalyst and used for the preparation of the following batches of catalyst.

A distinctive feature of the method of preparation of the catalyst is also that after impregnation, the wet catalyst containing supported complex compounds of molybdenum and cobalt or nickel, and an oxygen-containing organic compound, are dried and sulfidized under conditions providing a catalyst with the required content of components, namely, they are dried in air at at a temperature of 100-250 ° C and then sulfidized by heating first to 150-250 ° C, and then to 350-450 ° C in a stream of hydrogen sulfide, or its mixture with hydrogen containing 2 vol.% and olee hydrogen sulfide.

A distinctive feature of the proposed method for hydrotreating hydrocarbons is that the hydrotreating process is carried out at a temperature of 320-400 ° C, a pressure of 0.5-10 MPa, a mass flow rate of 0.5-5 h ^-1 , a volumetric ratio of hydrogen / feedstock 100-1000 m ³ / m ³ in the presence of a catalyst containing, wt.%: Mo - 8.0-15.0; Co or Ni - 2.0-5.0; S - 5.0-15.0; C 0.2-8.0; Ti - 0.3-4.1; B 0.2-2.2; Al ₂ O ₃ - the rest having a pore volume of 0.3-0.7 cm ³ / g, a specific surface area of 130-280 m ² / g, an average pore diameter of 6-20 nm and representing particles with a cross section in the form of a trefoil with a diameter the circumference described is 1.0-1.6 mm and a length of up to 20 mm.

The technical effect of the proposed catalyst, carrier, method of preparation of the catalyst and method of preparation of the carrier, as well as the method of hydrotreatment of hydrocarbons is composed of the following components:

1. The proposed chemical composition of the catalyst and its texture determine the maximum activity in the target reactions occurring during hydrotreatment of hydrocarbons. The presence of titanium, boron and carbon in the proposed intervals in the composition of the catalyst minimizes the undesirable chemical interaction of the supported metals with the surface functional groups of aluminum oxide and ensures the formation of surface compounds of cobalt / nickel, molybdenum and sulfur, which are optimal for catalysis of the structure and morphology, which provides an increased level of catalyst activity .

2. The use of a carrier having the proposed chemical composition, the proposed particle size and texture characteristics, leads to a catalyst with a chemical composition and texture characteristics that are optimal for hydrotreating catalysts, providing access for almost all sulfur-organic compounds of the hydrotreated hydrocarbon feed to the active component localized in the pores of the carrier , and thereby, provides products with a minimum residual sulfur content.

3. The use of a carrier containing the required amount of titanium and boron eliminates the need for introducing titanium and boron into the catalyst in another way, makes it possible to use impregnating solutions with a high concentration of complex compounds of molybdenum, cobalt or nickel and oxygen-containing organic compounds for the preparation of the catalyst, minimizes the formation of inactive in catalysis compounds of cobalt / Nickel and molybdenum with the carrier and provides maximum catalyst activity.

4. The use of the proposed method for preparing the carrier, including the preparation of molding pastes of the proposed composition, the proposed conditions of molding, drying and calcination, allows you to obtain a carrier that combines optimal texture characteristics and optimal chemical composition, which ensures the subsequent production of a catalyst having maximum activity.

5. The proposed methods for producing a carrier and a catalyst are characterized by the complete absence of wastewater requiring treatment and disposal.

6. A method of preparing a catalyst by impregnating a carrier containing titanium and boron with aqueous solutions containing complex compounds of molybdenum and cobalt or nickel and oxygen-containing organic compounds allows one to obtain a catalyst having an optimal chemical composition, a uniform distribution of the active component over the granule, and an optimal structure and morphology particles of the active component, which leads to a catalyst having increased activity in hydrotreatment reactions.

7. The use of bimetallic complex compounds and oxygen-containing organic compounds having a high solubility in water allows one to obtain catalysts with the required mass content of elements, while almost all supported metals are part of the bimetallic sulfide active centers of hydrotreatment - Co (Ni) MoS phase.

8. The application of active metals on a carrier containing boron and titanium by a single impregnation method significantly simplifies the preparation of the catalyst and eliminates the formation of any waste and effluent.

9. Drying the catalyst in the temperature range 100-250 ° C, in addition to obtaining a highly active catalyst having the proposed chemical composition, leads to significant savings in fuel or coolants.

10. Sulfidation of the catalyst under the proposed conditions provides a catalyst with the desired chemical composition and texture characteristics, with maximum activity in hydrotreating.

11. Hydrotreating hydrocarbon feeds under the proposed conditions in the presence of a catalyst prepared by the inventive method on the proposed carrier, prepared by the proposed method, allows to obtain oil products with low sulfur content.

Description of the proposed technical solution.

First, an alumina support is prepared containing titanium and boron. To a sample of AlOOH aluminum hydroxide powder having a boehmite or pseudoboehmite structure with a crystal size of 30-100 Å, with an average agglomerate size of 30-60 μm with continuous stirring in a mixer with Z-shaped blades, the calculated quantities of titanium dioxide powders with anatase or rutile structure ; boron compounds selected from the series: boron oxide B ₂ O ₃ , boric acid (ortho) H ₃ BO ₃ , boric acid (pyro) H ₂ B ₄ O ₇ , ammonium boric acid (tetra) (NH ₄ ) ₂ B ₄ O ₇ × 4H ₂ O, ammonium boric acid (tetra) acid NH ₄ HB ₄ O ₇ × 3H ₂ O, ammonium boric acid (penta) NH ₄ B ₅ O ₈ × 4H ₂ O and peptizing additive, which is an aqueous solution of ammonia, nitric or acetic acids.

The components are taken in the following weight ratios - aluminum hydroxide: titanium dioxide: boron compound: water: peptizing additive = 1: 0.008-0.095: 0.008-0.17: 0.6-1.0: 0.01-0.07.

Stirring is continued for 10-480 minutes at a temperature of 15-95 ° C. The result is a uniform plastic paste. The resulting paste is extruded through a die with holes, the shape and dimensions of which provide granules with a cross section in the shape of a trefoil with a diameter of the circumscribed circle of 1.0-1.6 mm. Extrusion is carried out at a pressure of 0.5-10.0 MPa. The obtained wet carrier is dried at a temperature of 100-150 ° C and calcined at a temperature of 500-600 ° C. Next, the carrier is crushed in length to particles of the desired size.

The result is a homogeneous carrier of white color, representing granules with a cross section in the form of a trefoil with a diameter of the circumscribed circle of 1.0-1.6 mm and a length of 2-20 mm. The carrier contains, wt.%: TiO ₂ - 1.0-10.0; B ₂ O ₃ - 1.0-10.0; Al ₂ O ₃ - the rest and has a specific surface area of 150-300 m ² / g, pore volume 0.5-0.95 cm ³ / g and an average pore diameter of 7-22 nm, and is a particle with a cross section in the form of a trefoil with the diameter of the circumscribed circle is 1.0-1.6 mm and a length of up to 20 mm.

Next, an impregnation solution is prepared with a given concentration of complex compounds of molybdenum and cobalt or nickel and at least one oxygen-containing organic compound. To do this, the required amount of citric acid C ₆ H ₈ O ₇ or citric acid monohydrate C ₆ H ₈ O ₇ × H ₂ O is dissolved in water with stirring. The required amount of at least one molybdenum compound from the series is added to the resulting solution with stirring and heating: ammonium paramolybdate (NH ₄ ) ₆ Mo ₇ O ₂₄ × 4H ₂ O, ammonium molybdenum acid (NH ₄ ) ₂ MoO ₄ , molybdenum trioxide MoO ₃ , molybdenum acid H ₂ MoO ₄ . Stirring is continued until the components are completely dissolved and a clear solution forms. In this case, the complex compound H _xy (NH ₄ ) _y [Mo ₄ O ₁₁ (C ₆ H ₅ O ₇ ) ₂ ] is formed in solution, where x = 4, y = 0; one; 2; 3 or 4.

Then, with continued stirring, add the required amount of at least one cobalt compound from the series: cobalt nitrate Co (NO ₃ ) ₂ × 6H ₂ O, cobalt acetic Co (CH ₃ COO) ₂ × 4H ₂ O, cobalt formic acid Co (CHOO ) ₂ × 2H ₂ O, cobalt citrate Co ₃ (C ₆ H ₅ O ₇ ) ₂ × 2H ₂ O, cobalt hydroxide Co (OH) ₂ , carbon cobalt CoCO ₃ , basic carbon cobalt 2CoCO ₃ × 3Co (OH) ₂ × H ₂ O; or nickel compounds from the series: nickel nitrate Ni (NO ₃ ) ₂ × 6H ₂ O, nickel acetic acid Ni (CH ₃ COO) ₂ × 4H ₂ O, nickel formate Ni (CHOO) ₂ × 2H ₂ O, nickel hydroxide Ni (OH ) ₂ , nickel carbonate NiCO ₃ , basic nickel carbonate 2NiCO ₃ × 3Ni (OH) ₂ × 4H ₂ O or NiCO ₃ × 2Ni (OH) ₂ × 4H ₂ O. Stirring is continued until it is completely dissolved and a solution containing no suspended particles. The result is a solution of bimetallic complex compounds

[M (H ₂ O) _x (L) _y ] ₂ [Mo ₄ O ₁₁ (C ₆ H ₅ O ₇ ) ₂ ], where: M = Co ²⁺ and / or Ni ²⁺ ; L is a partially deprotonated form of citric acid C ₆ H ₆ O ₇ or ammonia NH ₃ , x = 0 or 2; y = 0; 1 or 2.

Next, to the solution of the bimetallic complex compound, with continued stirring and heating, the required amount of an oxygen-containing organic compound selected from the series is added: ethylene glycol, glycerin, pentaerythritol, diethylene glycol, triethylene glycol, polyethylene glycol or polyethylene oxide with a molecular weight of 200-10000, methyl and ethyl ether above.

Further, by adding water, the concentration of the components of the solution is adjusted to a value that provides a catalyst containing the components in the proposed concentrations.

The resulting solution is impregnated with a carrier containing titanium and boron, and either the impregnation of the carrier by moisture capacity or from excess solution is used. The impregnation is carried out at a temperature of 15-90 ° C for 5-60 minutes with periodic stirring, in the case of impregnation from the excess solution after impregnation, the excess solution is poured from the catalyst and used to prepare the following batches of catalyst.

After impregnation, the catalyst is dried in air at a temperature of 100-250 ° C. Next, the catalyst is sulfidized by heating it first to 150-250 ° C, and then to 350-450 ° C in a stream of hydrogen sulfide, or its mixture with hydrogen containing 2 vol.% Or more of hydrogen sulfide.

The result is a catalyst whose characteristics are fully consistent with the proposed intervals.

Straight-run gasoline fraction with a sulfur content of 0.3% and an end of boiling of 210 ° C, straight-run diesel fuel with a sulfur content of 2.2% S and an end of boiling of 360 ° C, vacuum gas oil with a sulfur content of 2.12 wt. % S and the end of boiling 500 ° C. Hydrotreating gasoline is carried out at a temperature of 320 ° C, a pressure of 2.0 MPa, a mass flow rate of gas 5 h ^-1 , a volume ratio of hydrogen / gasoline 200. The process of hydrotreating diesel fuel is carried out at a temperature of 340 ° C, a pressure of 3.5 MPa, a mass flow rate of diesel fuel 2 h ^-1 , the volume ratio of hydrogen / diesel fuel 300. Hydrotreating of vacuum gas oil is carried out at 380 ° C, a pressure of 5.0 MPa, the mass flow rate of vacuum gas oil 1 h ^-1 , the volume ratio of hydrogen / raw material 400.

The invention is illustrated by the following examples.

Example 1. According to a known technical solution (RF №2313392)

18 g of aluminum oxide, molded as extrudates with a diameter of not more than 2 mm and a length of not more than 10 mm and having a specific surface of 330 m ² / g, a pore volume of 0.7 cm ³ / g and an average pore diameter of 120 Å are impregnated with an excess of solution, which prepared as follows.

10.4 g of ammonium paramolybdate (NH ₄ ) ₆ Mo ₇ O ₂₄ × 4H ₂ O are dissolved in 20 cm ^{3 of} distilled water by heating to 60 ° C and stirring. After it is completely dissolved, it is added to the solution with stirring and heating at the same temperature. 11.28 g of citric acid C ₆ H ₈ O ₇ , stirring is continued until complete dissolution and formation of a yellowish solution. Next, 8.51 g of cobalt nitrate Co (NO ₃ ) ₂ × 6H ₂ O was added in portions to the resulting solution, and stirring was continued until it was completely dissolved. After that, 1.18 g of boron oxide B ₂ O _{3 is} added to the solution, stirring and heating are continued until there are no visible suspended particles in the solution. Next, the volume of the solution was adjusted with distilled water to 40 cm ² .

The impregnating solution and the carrier are contacted for 30 minutes, then the excess solution is drained, the resulting catalyst is transferred to a Petri dish, in which it is dried for 12 hours. Next, the catalyst is dried in a stream of air at 175 ° C for 2 hours.

The resulting catalyst has the following composition, wt.%: Cobalt compounds with a concentration of 4.0 in terms of CoO, molybdenum compounds with a concentration of 15.4 in terms of MoO ₃ , citric acid compounds with a concentration of 20.5 in terms of citric acid, compounds boron 2.0 in terms of B ₂ O ₃ , aluminum oxide Al ₂ O ₃ - the rest.

Before testing, the catalyst is sulfidized at 400 ° C and atmospheric pressure in a stream of hydrogen sulfide, flowing at a rate of 1 l / h, for 2 hours

Examples 2-9 illustrate the proposed technical solution.

Example 2

To 100 g of AlOOH aluminum hydroxide powder having a boehmite structure with an average crystal size of 30 Å, with an average powder particle size of 30 μm, with continuous stirring in a mixer with Z-shaped blades, 0.8 g of TiO ₂ powder with anatase structure, 0, 8 g of powder B ₂ O ₃ , 55 ml of water and 5 g of a 20% aqueous solution of ammonia. The weight ratio of the components of the mixture is aluminum hydroxide: titanium dioxide: boron compound: water: peptizing additive = 1: 0.008: 0.008: 0.6: 0.01.

The resulting paste is stirred at 15 ° C for 480 min, then formed through a die with a cross section in the form of a trefoil with a diameter of the circumscribed circle of 1.1 mm at a pressure of 10.0 MPa. The obtained granules are dried in an oven at 100 ° C for 2 hours, then calcined at 600 ° C for 4 hours.

The result is a carrier containing, wt.%: TiO ₂ - 1.0; B ₂ O ₃ - 1.0; Al ₂ O ₃ - the rest; having a specific surface area of 300 m ² / g, a pore volume of 0.5 cm ³ / g, an average pore diameter of 7 nm, which is a particle with a cross section in the form of a trefoil with a diameter of the circumscribed circle of 1.0 mm, a length of up to 20 mm.

Then a bimetallic compound corresponding to the formula [Co (H ₂ O) ₂ (C ₆ H ₅ O ₇ )] ₂ [Mo ₄ O ₁₁ (C ₆ H ₅ O ₇ ) ₂ ] is synthesized in solution, for which 70 ml of distilled water with stirring, 53.5 g of citric acid C ₆ H ₈ O _{7 are} successively dissolved; 71.0 g of ammonium paramolybdate (NH ₄ ) ₆ Mo ₇ O ₂₄ × 4H ₂ O and 17.3 g of cobalt hydroxide Co (OH) ₂ . 15 ml of polyethylene glycol-300 are added to the resulting solution, and then, by adding distilled water, the volume of the solution is brought to 150 ml.

Next, 20 g of the support are contacted at a temperature of 90 ° C. with 50 ml of a solution containing the bimetallic compound [Co (H ₂ O) ₂ (C ₆ H ₅ O ₇ ) ₂ [Mo ₄ O ₁₁ (C ₆ H ₅ O ₇ ) ₂ ] and polyethylene glycol for 60 minutes. The excess solution is drained, the catalyst is dried in air at 100 ° C and sulfidized by heating it first to 150-250 ° C for 1 h, and then to 350-450 ° C for 1 h in a stream of hydrogen sulfide at a volumetric flow rate of 500 h ^{- 1} .

The resulting catalyst has a pore volume of 0.3 cm ³ / g; specific surface area 280 m ² / g, average pore diameter of 6 nm, and contains, wt.%: Mo - 15.0; Co - 5.0; S - 15.0; C is 8.0; Ti - 0.3; B 0.2; Al ₂ O ₃ - the rest.

The test results of the catalyst in hydrotreatment are shown in the table.

Example 3

To 100 g of AlOOH aluminum hydroxide powder having a pseudoboehmite structure with a crystal size of 45-60 Å, with an average agglomerate size of 30-40 μm, with continuous stirring in a mixer with Z-shaped blades, 5 g of rutile titanium dioxide powder with a structure of 10 g are added boric acid H ₃ BO ₃ , 70 ml of water and 10 g of a 30% solution of nitric acid. The weight ratio of the components of the mixture is aluminum hydroxide: titanium dioxide: boron compound: water: peptizing additive = 1: 0.05: 0.10: 0.8: 0.03.

The resulting paste is stirred at 95 ° C for 10 minutes, then formed through a die with a cross section in the form of a trefoil with a diameter of the circumscribed circle of 1.6 mm at a pressure of 5.0 MPa. The obtained granules are dried in an oven at 150 ° C for 2 hours, then calcined at 500 ° C for 4 hours.

The result is a carrier containing, wt.%: TiO ₂ - 5.8; B ₂ O ₃ - 6.6; Al ₂ O ₃ - the rest; having a specific surface of 230 m ² / g, a pore volume of 0.75 cm ³ / g, an average pore diameter of 10 nm, which is a particle with a cross section in the form of a trefoil with a diameter of the circumscribed circle of 1.6 mm, a length of up to 20 mm.

20 g of the obtained carrier are impregnated with a moisture capacity of 10 ml of a solution containing 7.6 g of a complex bimetallic compound of the composition [Co (H ₂ O) ₂ (C ₆ H ₅ O ₇ )] ₂ [Mo ₄ O ₁₁ (C ₆ H ₅ O ₇ ) ₂ ], synthesized analogously to example 2, and 0.5 g of dimethyl ether of ethylene glycol. The catalyst is dried in air at 250 ° C for 2 h and sulfidized by heating it first to 150-250 ° C for 1 h, and then to 350-450 ° C for 1 h in a stream of a mixture of hydrogen sulfide and hydrogen (2 vol.% H ₂ S) at a volumetric flow rate of the mixture of 2000 h ^-1 .

The resulting catalyst has a pore volume of 0.6 cm ³ / g; specific surface area 210 m ² / g, average pore diameter 9 nm, contains, wt.%: Mo - 8.0; Co - 2.0; S is 5.0; C is 0.5; Ti 2.9; B 1.75; Al ₂ O ₃ - the rest.

The test results of the catalyst in hydrotreatment are shown in the table.

Example 4

To 100 g of AlOOH aluminum hydroxide powder having a pseudoboehmite structure with a crystal size of 80-100 Å, with an average agglomerate size of 50-60 μm, with continuous stirring in a mixer with Z-shaped blades, 10 g of TiO ₂ powder with anatase structure, 17 g boric acid H ₃ BO ₃ , 100 ml of water and 7 g of concentrated acetic acid. The weight ratio of the components of the mixture is aluminum hydroxide: titanium dioxide: boron compound: water: peptizing additive = 1: 0.1: 0.17: 1.0: 0.07.

The resulting paste is stirred at 20 ° C for 60 minutes, then formed through a die with a cross section in the form of a trefoil with a diameter of the circumscribed circle of 1.4 mm at a pressure of 0.5 MPa. The obtained granules are dried in an oven at 120 ° C for 2 hours, then calcined at 550 ° C for 4 hours.

The result is a carrier containing, wt.%: TiO ₂ - 10.0; B ₂ O ₃ - 10.0; Al ₂ O ₃ - the rest; having a specific surface area of 150 m ² / g, a pore volume of 0.95 cm ³ / g, an average pore diameter of 22 nm, which is a particle with a cross section in the form of a trefoil with a diameter of the circumscribed circle of 1.3 mm, a length of up to 20 mm.

20 g of the obtained carrier are contacted for 5 min at 90 ° C with 40 ml of the solution from example 2 containing a bimetallic compound

[Co (H ₂ O) ₂ (C ₆ H ₅ O ₇ )] ₂ [Mo ₄ O ₁₁ (C ₆ H ₅ O ₇ ) ₂ ] and polyethylene glycol-300, to which 1 g of glycerol was added. The excess solution is drained, the catalyst is dried in air at 120 ° C, then sulfidized as in example 2.

The resulting catalyst has a pore volume of 0.7 cm ³ / g; specific surface area 130 m ² / g, average pore diameter 20 nm, contains, wt.%: Mo - 12.0; Co - 4.0; S - 10.0; C is 5.0; Ti - 4.1; B 2.2; Al ₂ O ₃ - the rest.

The test results of the catalyst in hydrotreatment are shown in the table.

Example 5

To 100 g of AlOOH aluminum hydroxide powder having a boehmite structure with a crystal size of 70 Å, with an average agglomerate size of 50 μm, with continuous stirring in a mixer with Z-shaped blades, 6 g of TiO ₂ powder with a rutile structure, 7 g of ammonium boric acid (penta) are added NH ₄ B ₅ O ₈ × 4H ₂ O, 80 ml of water and 15 g of a 30% solution of nitric acid. The weight ratio of the components of the mixture is aluminum hydroxide: titanium dioxide: boron compound: water: peptizing additive = 1: 0.06: 0.07: 0.8: 0.05.

The resulting paste is stirred at 40 ° C for 120 minutes, then formed through a die with a cross section in the form of a trefoil with a diameter of the circumscribed circle of 1.3 mm at a pressure of 5.0 MPa. The obtained granules are dried in an oven at 120 ° C for 2 hours, then calcined at 550 ° C for 4 hours.

The result is a carrier containing wt.%: TiO ₂ - 6.0; B ₂ O ₃ - 4.5; Al ₂ O ₃ - the rest; having a specific surface area of 220 m ² / g, a pore volume of 0.65 cm ³ / g, an average pore diameter of 12 nm, which is a particle with a cross section in the form of a trefoil with a diameter of the circumscribed circle of 1.2 mm, up to 20 mm long.

A bimetallic compound of the composition, [Ni (H ₂ O) ₂ ] ₂ [Mo ₄ O ₁₁ (C ₆ H ₅ O ₇ ) ₂ ] is synthesized, for which 40.5 g of citric acid C _{0 are} successively dissolved in 70 ml of distilled water with stirring H ₈ O ₇ ; 71.0 g of ammonium paramolybdate (NH ₄ ) ₆ Mo ₇ O ₂₄ × 4H ₂ O and 17.3 g of nickel hydroxide Ni (OH) ₂ . 15 ml of ethylene glycol was added to the resulting solution, and the volume of the solution was adjusted to 160 ml by adding water.

20 g of the carrier are impregnated with a moisture capacity of 16 ml of an aqueous solution

[Ni (H ₂ O) ₂ ] ₂ [Mo ₄ O ₁₁ (C ₆ H ₅ O ₇ ) ₂ ] and ethylene glycol. The catalyst is dried in air at 100 ° C and sulfidized analogously to example 2.

The resulting catalyst has a pore volume of 0.55 cm ³ / g; specific surface area 200 m ² / g, average pore diameter 11 nm and contains, wt.%: Mo - 13.0; Ni - 3.4; S 9.6; C 6.7; Ti - 2.42; B - 0.95; Al ₂ O ₃ - the rest.

The test results of the catalyst in hydrotreatment are shown in the table.

Example 6

A bimetallic compound is synthesized in a solution

[Ni (H ₂ O) ₂ (C ₆ H ₅ O ₇ )] ₂ [Mo ₄ O ₁₁ (C ₆ H ₅ O ₇ ) ₂ ], for which 53.5 g of lemon are successively dissolved in 70 ml of distilled water with stirring acids C ₆ H ₈ O ₇ ; 71.0 g of ammonium paramolybdate (NH ₄ ) ₆ Mo ₇ O ₂₄ × 4H ₂ O and 17.3 g of nickel hydroxide Ni (OH) ₂ . 15 ml of ethylene glycol ethyl ether are added to the resulting solution, and then the volume of the solution is adjusted to 150 ml by adding distilled water.

20 g of the carrier of Example 3 are contacted at 15 ° C. for 60 minutes with 40 ml of the resulting solution. The excess solution is drained, the catalyst is dried and sulfidized analogously to example 2.

The resulting catalyst has a pore volume of 0.65 cm ³ / g; specific surface area 215 m ² / g, average pore diameter 9 nm and contains, wt.%: Mo - 11.0; Ni - 3.7; S 9.5; C 6.0; Ti - 2.43; B 1.45; Al ₂ O ₃ - the rest.

The test results of the catalyst in hydrotreatment are shown in the table.

Example 7

A bimetallic compound [Co (C ₆ H ₅ O ₇ )] ₂ [Mo ₄ O ₁₁ (C ₆ H ₅ O ₇ ) ₂ ] is synthesized, for which 60 is successively dissolved in 70 ml of distilled water with stirring and heating to 90 ° C. 0 g of citric acid C ₆ H ₈ O ₇ ; 17.3 g of cobalt hydroxide Co (OH) ₂ and 71.0 g of ammonium paramolybdate (NH ₄ ) ₆ Mo ₇ O ₂₄ × 4H ₂ O. 10 g of diethylene glycol-300 and 5 g of polyethylene oxide-1500 are added to the resulting solution, followed by distilled water the volume of the solution was adjusted to 150 ml.

50 ml of the resulting solution is contacted with 20 g of the carrier of Example 5 at 50 ° C. for 20 minutes. Next, the excess solution is drained, the catalyst is dried and sulfidized analogously to example 3.

The resulting catalyst has a pore volume of 0.5 cm ³ / g; specific surface area 205 m ² / g, average pore diameter 11 nm and contains, wt.%: Mo - 12.5; Co - 4.1; S - 10.0; C is 5.5; Ti - 2.44; B 0.96; Al ₂ O ₃ - the rest.

The test results of the catalyst in hydrotreatment are shown in the table.

Example 8

The bimetallic compound [Co (H ₂ O) ₂ (NH ₃ ) ₂ ] ₂ [Mo ₄ O ₁₁ (C ₆ H ₅ O ₇ ) ₂ ] is synthesized, for which it is successively dissolved in 70 ml of distilled water with stirring and 20 ° С 55 , 0 g of citric acid C ₆ H ₈ O ₇ ; 17.3 g of cobalt hydroxide Co (OH) ₂ and 71.0 g of ammonium paramolybdate (NH ₄ ) ₆ Mo ₇ O ₂₄ × 4H ₂ O. To the resulting solution was added 5 ml of a 20% aqueous ammonia solution and 10 g of triethylene glycol, followed by addition distilled water the volume of the solution was adjusted to 150 ml.

20 g of the carrier of Example 3 are soaked in a water capacity of 15 ml of the resulting solution. The catalyst is dried and sulfidized analogously to example 2.

The resulting catalyst has a pore volume of 0.6 cm ³ / g; specific surface area 216 m ² / g, average pore diameter 9 nm and contains, wt.%: Mo - 12.7; Co - 3.6; S - 11.5; C 6.6; Ti 2.28; B 1.36; Al ₂ O ₃ - the rest.

The test results of the catalyst in hydrotreatment are shown in the table.

Example 9

The bimetallic compound [Ni (H ₂ O) ₂ (NH ₃ ) ₂ ] ₂ [Mo ₄ O ₁₁ (C ₆ H ₅ O ₇ ) ₂ ] is synthesized, for which it is successively dissolved in 70 ml of distilled water with stirring and 20 ° С 55 , 0 g of citric acid C ₆ H ₈ O ₇ ; 17.3 g of nickel hydroxide Ni (OH) ₂ and 71.0 g of ammonium paramolybdate (NH ₄ ) ₆ Mo ₇ O ₂₄ × 4H ₂ O. To the resulting solution was added 5 ml of a 20% aqueous ammonia solution, 1 g of pentaerythritol and 1 g diethylene glycol methyl ether, then by adding distilled water the volume of the solution was adjusted to 150 ml.

20 g of the carrier of example 2 are soaked in moisture capacity 10 ml of the resulting solution. The catalyst is dried and sulfidized analogously to example 3.

The resulting catalyst has a pore volume of 0.4 cm ³ / g; specific surface area 280 m ² / g, average pore diameter 6 nm, contains, wt.%: Mo - 9.6; Ni - 2.7; S 9.3; C is 3.7; Ti 0.45; B 0.23; Al ₂ O ₃ - the rest.

The test results of the catalyst in hydrotreatment are shown in the table.

Residual sulfur content during hydrotreating various raw materials The catalyst of the example 1 (prototype) 2 3 four 5 6 7 8 9 Residual sulfur content, ppm Hydrotreating gasoline ^* 105 35 45 55 fifty 45 55 fifty 35 Hydrotreating diesel fuel ^** 500 280 280 300 310 300 295 290 315 Hydrotreating vacuum gas oil ^*** 700 550 530 500 540 530 520 25 560

* - Hydrotreating straight-run gasoline (0.3% sulfur, c.k. 210 ° C) is carried out at a temperature of 320 ° C, a pressure of 2.0 MPa, a mass flow rate of gasoline of 5 h ^-1 , a volume ratio of hydrogen / gasoline of 200.

** - Hydrotreating of diesel fuel (2.2% sulfur, c.k. 360 ° C) is carried out at a temperature of 340 ° C, a pressure of 3.5 MPa, a mass flow rate of diesel fuel of 2 h ^-1 , a volume ratio of hydrogen / diesel fuel of 300 .

*** - Hydrotreating of vacuum gas oil (2.12% sulfur, c.k. 500 ° C) is carried out at 380 ° C, a pressure of 5.0 MPa, a mass flow rate of vacuum gas oil of 1 h ^-1 , a volume ratio of hydrogen / feed 400.

Thus, as can be seen from the above examples, the proposed catalyst due to its chemical composition and texture, due to the use of a carrier containing titanium and boron prepared by the present method, and the inventive method of preparation of the catalyst has a high activity significantly exceeding the activity of the prototype catalyst in hydrotreating hydrocarbon feed.

Claims (20)

1. The catalyst for hydrotreating hydrocarbons, comprising cobalt or nickel, molybdenum and a carrier containing aluminum oxide and boron, characterized in that it contains, wt.%: Mo - 8.0-15.0; Co or Ni - 2.0-5.0; S - 5.0-15.0; C 0.2-8.0; Ti - 0.3-4.1; B 0.2-2.2; Al ₂ O ₃ - the rest, while the carrier contains, wt.%: TiO ₂ - 1,0-10,0; In ₂ About ₃ - 1.0-10.0; Al ₂ O ₃ - the rest and has a specific surface area of 150-300 m ² / g, a pore volume of 0.5-0.95 cm ³ / g and an average pore diameter of 7-22 nm. 2. The catalyst according to claim 1, characterized in that it is a particle with a cross section in the form of a trefoil with a diameter of the circumscribed circle of 1.0-1.6 mm and a length of up to 20 mm. 3. The catalyst according to claim 1, characterized in that it has a pore volume of 0.3-0.7 cm ³ / g, a specific surface area of 130-280 m ² / g, an average pore diameter of 6-20 nm. 4. A carrier for a hydrocarbon hydrotreating catalyst, comprising alumina and boron, characterized in that it contains, wt.%: TiO ₂ - 1.0-10.0; B ₂ O ₃ - 1.0-10.0; Al ₂ O ₃ - the rest and has a specific surface area of 150-300 m ² / g, pore volume of 0.5-0.95 cm ³ / g, average pore diameter of 7-22 nm. 5. The carrier according to claim 4, characterized in that it is a particle with a cross section in the form of a trefoil with a diameter of the circumscribed circle of 1.0-1.6 mm and a length of up to 20 mm. 6. A method of preparing a carrier for a hydrocarbon feed hydrotreating catalyst containing alumina and boron oxide, characterized in that the paste obtained by mixing AlOOH alumina powder having a boehmite or pseudoboehmite structure with a crystal size of 30-100 U and an average particle size of 30 -60 μm of at least one titanium dioxide powder, at least one boron compound, water and peptizing additive are molded, dried and calcined at temperatures up to 500-600 ° C, resulting in a carrier according to any one of .4 and 5. 7. A method of preparing a carrier according to claim 6, characterized in that titanium dioxide with an anatase or rutile structure is used as titanium dioxide powder. 8. A method of preparing a carrier according to claim 6, characterized in that a compound selected from the series is used as a boron compound: boron oxide B ₂ O ₃ , boric acid (ortho) H ₃ BO ₃ , boric acid (pyro) H ₂ B ₄ O ₇ , ammonium boric acid (tetra) (NH ₄ ) ₂ B ₄ O ₇ · 4H ₂ O, ammonium boric acid (tetra) acid NH ₄ HB ₄ O ₇ · 3H ₂ O, ammonium boric acid (penta) NH ₄ B ₅ O ₈ · 4H ₂ O. 9. A method of preparing a carrier according to claim 6, characterized in that nitric, acetic acid or aqueous ammonia is used as the peptizing additive. 10. The method of preparing the carrier according to claim 6, characterized in that for the preparation of the paste, the components are taken in the following weight ratios: aluminum hydroxide: titanium dioxide: boron compound: water: peptizing additive = 1: 0.008-0.095: 0.008-0.17: 0.6-1.0: 0.01-0.07. 11. The method of preparing the carrier according to claim 6, characterized in that the paste is stirred at a temperature of 15-95 ° C for 10-480 minutes, molded at a pressure of 0.5-10.0 MPa, the obtained granules are dried at a temperature of 100-150 ° C and calcined at a temperature of 500-600 ° C. 12. A method of preparing a catalyst for hydrotreating a hydrocarbon feedstock, comprising cobalt or nickel, molybdenum and a carrier, characterized in that the carrier containing, wt.%: TiO ₂ - 1.0-10.0; B ₂ O ₃ - 1.0-10.0; Al ₂ O ₃ - the rest and having a specific surface area of 150-300 m ² / g, a pore volume of 0.5-0.95 cm ³ / g and an average pore diameter of 7-22 nm, is impregnated with an aqueous solution containing molybdenum and cobalt or nickel in the form of complex compounds, an oxygen-containing organic compound is added to the impregnating solution containing molybdenum and cobalt or nickel in the form of complex compounds, then the catalyst is dried and sulfidized, whereby the catalyst according to any one of claims 1 to 3 is obtained. 13. The method of preparation of the catalyst according to item 12, characterized in that as the complex compounds of molybdenum and cobalt or nickel, use the bimetallic complex compound [M (H ₂ O) _x (L) _y ] ₂ [Mo ₄ O ₁₁ (C ₆ H ₅ O ₇ ) ₂ ], where M = Co ²⁺ and / or Ni ²⁺ ; L is a partially deprotonated form of citric acid C ₆ H ₆ O ₇ or ammonia NH ₃ , x = 0 or 2; y = 0; 1 or 2. 14. The catalyst preparation method according to claim 12, characterized in that at least one compound selected from the series is used as the oxygen-containing organic compound: ethylene glycol, glycerin, pentaerythritol, diethylene glycol, triethylene glycol, polyethylene glycol or polyethylene oxide with a molecular weight of 200-10000 as well as methyl and ethyl esters of the above alcohols. 15. The method of preparation of the catalyst according to item 12, characterized in that the concentration of molybdenum, cobalt or nickel in the form of complex compounds and the concentration of oxygen-containing organic compounds in the impregnating solution are such as to provide components in the finished catalyst, wt.%: Mo - 8, 0-15.0; Co or Ni -2.0-5.0; S - 5.0-15.0; C 0.2-8.0; Ti - 0.3-4.1; B 0.2-2.2; Al ₂ O ₃ - the rest. 16. The method of preparation of the catalyst according to item 12, characterized in that for the preparation of the catalyst using either the impregnation of the carrier for moisture capacity, or from an excess of solution, while the excess solution after impregnation is drained from the catalyst and used to prepare subsequent portions of the impregnating solution in the preparation of the following batches catalyst. 17. The method of preparation of the catalyst according to item 12, characterized in that the impregnation of the excess solution is carried out at a temperature of 15-90 ° C for 5-60 minutes, after which the excess solution is drained from the catalyst. 18. The method of preparation of the catalyst according to item 12, characterized in that after the impregnation of the catalyst is dried at a temperature of 100-250 ° C. 19. The method of preparation of the catalyst according to item 12, characterized in that after impregnation and drying, the catalyst is sulfidized by heating it first to 150-250 ° C, and then to 350-450 ° C in a stream of hydrogen sulfide or its mixture with hydrogen containing 2 vol.% or more of hydrogen sulfide. 20. The method of hydrotreating hydrocarbon feeds at a temperature of 320-400 ° C, a pressure of 0.5-10 MPa, a flow rate of feedstock of 0.5-5 h ^-1 , a volume ratio of hydrogen / feedstock of 100-1000 m ³ / m ³ in the presence of heterogeneous a catalyst that contains cobalt or nickel, molybdenum and a carrier containing aluminum oxide and boron, characterized in that they use the catalyst according to any one of claims 1 to 3 or prepared according to any one of claims 12-19.