WO2019059807A1

WO2019059807A1 - Catalyst for hydrotreatment of hydrocarbon feedstocks

Info

Publication number: WO2019059807A1
Application number: PCT/RU2018/000374
Authority: WO
Inventors: Олег Владимирович Климов; Владимир Владимирович ДАНИЛЕВИЧ; Ирина Геннадьевна ДАНИЛОВА; Галина Ивановна КОРЯКИНА; Юлия Витальевна ВАТУТИНА; Игорь Петрович ПРОСВИРИН; Александр Степанович НОСКОВ
Original assignee: Акционерное Общество "Газпромнефть-Омский Нпз" (Ао "Газпромнефть-Онпз")
Priority date: 2017-09-25
Filing date: 2018-06-07
Publication date: 2019-03-28
Also published as: RU2663904C1

Abstract

The invention relates to catalysts for hydrotreatment of hydrocarbon feedstocks. The invention relates to a catalyst comprising: 33.0-43.0 wt% [Co(H2O)2(C6H5O7)]2[Mo4O11(C6H5O7)2]; 0.4-1.6 wt% boron in the form of surface compounds; and the remainder a support. The support comprises: 5.0-25.0 wt% aluminium borate Al3BO6 having the norbergite structure; no more than 0.03 wt% sodium; and the remainder γ-Al2O3. The aluminium borate Al3BO6 having the norbergite structure is in the form of particles having a size of 10 to 200 nm, which are characterized by interplanar spacings of 3.2 and 2.8 Å, with an angle between them of 53.8°. The boron in the form of surface compounds is characterized by IR absorption bands of 930-1040, 1230, 1385-1450 and 3695 cm-1. The catalyst comprises strong Brønsted acid sites and moderate-strength Brønsted acid sites. After sulfidation, the catalyst comprises: 10.0-14.0 wt% Мо; 3.0-4.3wt% Со; 6.7-9.4 wt% S; 0.5-2.0 wt% boron in the form of surface compounds; and the remainder a support. The dispersity of the applied metals, as determined using X-ray photoelectron spectroscopy (XPS) data, for the IMo3d/IA12p intensity ratio lies in the range of 1.45-1.55, and for the 1Co2p/1A12p intensity ratio lies in the range of 1.14-1.18.

Description

Catalyst

hydrocarbon hydrotreatment

The invention relates to Hydrotreating catalysts for the production of petroleum products with a low content of sulfur and nitrogen.

At present, Russian refineries have switched to the production of motor fuels, which, according to the residual sulfur content, meet the new Russian and European standards. Although the nitrogen content in motor fuels is not regulated, it is known that organic nitrogen compounds have a strong negative effect on the activity of catalysts in the conversion of organic sulfur compounds during hydrotreating. Accordingly, an increase in the diazotization activity of catalysts leads to a parallel sharp decrease in the residual sulfur content in hydrotreated products.

Since the known catalysts do not allow to drastically reduce the sulfur and nitrogen content in the resulting products without tightening the conditions of the hydrotreating process, it is an extremely urgent task to create new catalysts that can produce motor fuels with a low residual sulfur and nitrogen content under the conditions of the processes carried out at refineries without their radical reconstruction.

Various applied catalysts for hydrotreating hydrocarbon feedstocks are known; however, a common drawback for them is the high residual content of sulfur and nitrogen in the resulting products.

Most often for carrying out the hydrotreatment of crude oil, catalysts containing cobalt and molybdenum oxides supported on alumina are used.

So known catalyst [RF Application Mb 2002124681, C10G45 / 08, B01J23 / 887, 16.09.2002], containing in its composition cobalt oxide, molybdenum oxide and aluminum oxide, characterized in that it has the ratio components, May. %: cobalt oxide 3.0-9.0, molybdenum oxide 10.0-24.0 May. %, aluminum oxide else, specific surface 160-250 m ² / g, mechanical crushing strength 0.6-0.8 kg / mm ² . In this case the hydrotreating process is carried out at a temperature of 310-340 ° C, pressure 3.0-5.0 MPa, with a ratio hydrogen / feedstock 300-500 Nm ³ / m ³ and a feed space velocity of 1.0-4.0 h ^{' 1} . The main disadvantage of such a hydrotreating catalyst is the high sulfur content in the resulting products.

In recent years, for the preparation of hydrotreating catalysts use the method of deposition of active metals on an already formed carrier. As a carrier, aluminum oxide is most often used with a certain size and shape of granules and certain textural characteristics. The carrier is often modified with various additives, including boron compounds. In this case, modifying additives are introduced into the carrier either prior to the stage of its formation, by co-precipitating modifiers and aluminum from joint solutions [Journal of Catalysis 115 (1989) 441-451], or by mixing aluminum hydroxide with a modifying compound at the stage of preparing a paste for molding [US N ° 6147432, RF N ° 2472585], or enter the additive by impregnation in a molded carrier, followed by drying and calcining [Catalysis Today 107-108 (2005) 551-558].

The introduction of active metals, most often Co, Ni, Mo and W into the catalyst, is carried out by impregnation of the molded carrier with aqueous solutions of their salts. This can be used as a separate application of the active metals by impregnation in several stages [RF N ° N ° 2242501, 2246987], and their application from joint solutions, stabilized by various agents [RF N ° N ° 2073567, 2216404, 2306978].

In order to increase the activity of catalysts in hydrotreating, when preparing them, a carrier with improved textural characteristics is used, while the specific surface of the catalyst reaches 300 m g, and the average pore diameter lies in the range of 8-11 nm, which ensures good access of the heteroatomic molecules of the raw material to be converted catalyst centers. Thus, a catalyst is known [RF Ν ° 2192923, C10G45 / 08, B01J27 / 188, 11.20.2002] based on alumina, which contains, calculated on the weight content of oxide: 2-10 May. % cobalt oxide Soo, 10-30 May. % molybdenum oxide MOOS and 4-10 May. % phosphorus oxide Ρ ₂ 0 ₅ , with a surface area according to the BET method in the range of 100–300 m / g and an average pore diameter in the range of 8–11 nm.

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

Closest to the proposed technical solution is the catalyst described in [US Pat. RF JV ”2626398, B01J23 / 00, C10G48 / 08, 07.27.17] containing, May. %: [Co (H ₂ 0) ₂ (C ₆ H ₅ 0 ₇ )] 2 [Mo ₄ Op (C ₆ H ₅ 0 ₇ ) 2] 33.0- 43.0; carrier - the rest; however, the carrier contains, May. %: aluminum borate A1 ₃ B0 ₆ with the structure of norbergite - 5.0-25.0; sodium - not more than 0.03; γ-Α1 ₂ 0 ₃ - the rest. After sulphidation, the known catalyst contains, in wt.%: Mo - 10.0-14.0; Co - 3.0-4.3; S - 6.7-9.4; carrier - the rest; however, the carrier contains, May. %: aluminum borate A1 ₃ B0 ₆ with the structure of norbergite - 5.0-25.0; sodium - not more than 0.03; γ-Α1 ₂ 0 ₃ - the rest. At the same time, the aluminum borate A1 ₃ B0 ₆ with the structure of norbergite, which is part of the catalyst, consists of particles with sizes from 10 to 200 nm, characterized by interplanar spacings of 3.2 and 2.8 A, with an angle of 53.8 ° between them.

The catalyst has a specific surface of 130-180 m ² / g, a pore volume of 0.35-0.65 cm / g, an average pore diameter of 7-12 nm, and consists of particles with a cross section in the form of a circle, a trefoil or a four leaf clover with a diameter of the circumscribed circle 1.0-1.6 mm and a length of up to 20 mm.

After sulphidation, it contains, in wt.%: Mo - 10.0-14.0; Co - 3.0-4.3; S

- 6.7-9.4; carrier - the rest; however, the carrier contains, May. %: aluminum borate A1 ₃ B0 ₆ with the structure of norbergite - 5.0-25.0; sodium - not more than 0.03; γ-Α1 ₂ 0 ₃ - the rest.

The main disadvantage of the known catalyst is that it has a non-optimal chemical composition, which causes its low activity in the reactions of diazotization and desulfurization. The known catalyst contains boron in the form of aluminum borate A1 ₃ B0 ₆ with the structure of norbergite, which represents particles with sizes from 10 to 200 nm. In this case, borate of aluminum with the structure of norbergite, which is formed at the stage of calcining a granular carrier, contributes to obtaining a carrier, the volume and pore size of which provide access to all active hydrocarbon molecules to be converted. In addition, borate of aluminum with the structure of norbergite helps to minimize undesirable chemical interaction between the active metals (Co and Mo) and the carrier.

However, due to the fact that aluminum borate A1 ₃ B0 ₆ with the structure of norbergite, is contained in the carrier and further in the catalyst in the form of sufficiently large particles with sizes from 10 to 200 nm, the surface of which is completely blocked by aluminum oxide at the stages of granulation and deposition of active metals compounds of cobalt and molybdenum, boron does not affect the acid characteristics of the finished catalyst and does not participate in catalysis. In recent years, it has been established that an increase in the surface acidity of catalysts contributes to an increase in the diazotization and desulfurization activity [Catalysis Today 292 (2017) 58-66; Applied Catalysis A: General 530 (2017) 132-144]. An increase in the acidity of the catalyst leads to an increase in its activity, both due to the participation of surface Brønsted centers in the catalysis of the diazotization reactions, and due to an increase in the dispersity of sulfide particles and an increase in their activity in desulfurization.

Accordingly, the known catalyst has a low acidity and, as a consequence, a relatively low activity in the diazotization and desulfurization.

The present invention solves the problem of creating an improved Hydrotreating catalyst, characterized by:

1. The optimal chemical composition of the catalyst, which contains boron in the form of two different types of chemical compounds - part of the carrier with a concentration of 5.0-25.0% aluminum borate A1 ₃ B0 ₆ with the structure of norbergite, representing particles with sizes from 10 to 200 nm, characterized by interplanar distances of 3.2 and 2.8 A, with an angle between them 53.8 ° and boron with a concentration of 0.4-1.6% in the form surface compounds characterized by absorption bands 930-1040, 1230, 1385-1450 and 3695 cm ^"1 in the IR spectra.

2. Increased surface acidity, in particular the presence of strong Bronsted acid centers (BCCs), determined by IR from the data of low-temperature adsorption of CO, 2-6 μmol / g (RA (affinity for proton) = 1180-1200 kJ / mol) and Bronsted acid centers of medium strength, 30–60 µmol / g (PA = 1250–1260 kJ / mol), providing an increase in the diazotizing activity.

3. The presence on the surface of the catalyst of dispersed boron compounds, contributing to the increase in the dispersion of the deposited compounds of cobalt and molybdenum, which leads to an increase in the desulfurizing activity.

4. Optimal textural characteristics, due to the presence of aluminum borate particles A1 ₃ B0 ₆ in the catalyst with the structure of norbergite, which are particles with sizes from 10 to 200 nm, contributing to the preparation of the catalyst, the volume and pore size of which provides access to all active molecules of the raw material component.

The technical result is to obtain a catalyst having maximum activity in the target reactions of diazotisation and desulfurization that occur during the hydrotreating of hydrocarbons.

The problem is solved by a catalyst for Hydrotreating of hydrocarbons, which contains, wt%: [Co (H ₂ 0) 2 (C ₆ H ₅ 0 ₇ )] 2 [Mo ₄ 0 ₁ i (C ₆ H ₅ 0 ₇ ) ₂ ] 33, 0-43.0; boron in the form of surface compounds - 0.4-1.6%, the carrier - the rest; however, the carrier contains, May. %: aluminum borate A1 ₃ B0 ₆ with the structure of norbergite - 5.0-25.0; sodium - not more than 0.03; γ-Α1 ₂ 0 ₃ - the rest.

The catalyst has a specific surface of 130-180 m / g, a pore volume of 0.35-0.65 cm ³ / g, an average pore diameter of 7-12 nm, and consists of particles with a cross section in the form of a circle, trefoil or tetrafole with a diameter of the circumcircle 1.0-1.6 mm and a length of up to 20 mm.

After sulphidation by known methods, it contains, in wt.%: Mo - 10.0-14.0; Co - 3.0-4.3; S - 6.7-9.4; boron in the form of surface compounds - 0.5-2.0; carrier - the rest; however, the carrier contains, May. %: borate aluminum A1 ₃ B0 ₆ with the structure of norbergite - 5.0-25.0; sodium - not more than 0.03; γ-Α1 ₂ 0 ₃ - the rest.

A distinctive feature of the proposed catalyst in comparison with the prototype is its chemical composition, namely, that the inventive catalyst contains, May. %: [Co (H ₂ 0) ₂ (C ₆ H ₅ 0 ₇ )] ₂ [Mo ₄ O _p (C ₆ H ₅ 0 ₇ ) ₂ ] 33.0- 43.0%; boron in the form of surface compounds - 0.4-1.6%, the carrier - the rest; however, the carrier contains, May. %: aluminum borate A1 ₃ B0 ₆ with the structure of norbergite - 5.0-25.0; sodium - not more than 0.03; γ-Α1 ₂ 0 ₃ - the rest. The output of the content of the catalyst components for the claimed limits leads to a decrease in the activity of the catalyst. An increase in the boron content in the form of surface compounds of more than 1.6% is unattainable due to the limited solubility of boric acid in water.

The second distinguishing feature of the proposed catalyst in comparison with the prototype is that it contains dispersed surface boron compounds, characterized by absorption bands 930-1040, 1230, 1385-1450 and 3695 cm ^-1 in the IR spectra.

The third distinguishing feature of the proposed catalyst in comparison with the prototype is that surface boron compounds provide an increase in the acidity of the catalyst due to the formation of strong Brønsted acid sites, determined by the IR method from low-temperature adsorption of CO, 2-6 µmol / g (PA (affinity to proton) = 1180-1200 kJ / mol) and Bronsted acid centers of medium strength, 30-60 µmol / g (PA = 1250-1260 kJ / mol).

The fourth distinguishing feature of the proposed catalyst compared with the prototype is that after sulfiding it has a dispersion of supported metals, determined according to XPS data of the intensity of IMo3d / IA12p lines in the interval 1.45-1.55, and by the ratio of intensities of 1Со2р / 1А12р lines in the range of 1.14-1.18.

The technical result consists of the following components: 1. The claimed chemical composition of the catalyst determines the maximum activity in the target reactions of deazorization and desulfurization occurring during the hydrotreatment of hydrocarbon raw materials. The presence of boron catalyst in the form of two different types chemical compounds - part of the carrier with a concentration of 5.0–25.0% aluminum borate A1 ₃ B0 ₆ with the structure of norbergite, and boron with a concentration of 0.4–1.6% in the form of surface compounds, provides an optimal combination of textural and acidic characteristics of the carrier and catalyst.

2. The presence in the catalyst of aluminum borate A1 ₃ B0 ₆ with the structure of norbergite with the claimed concentration contributes to minimizing undesirable chemical interaction between the active metals (Co and Mo) and the carrier, and selectively obtaining the most active in the hydrotreating sulfide component - CoMoS phase type P.

3. The presence in the catalyst of aluminum borate A1 ₃ B0 ₆ with the structure of norbergite representing particles with sizes from 10 to 200 nm, characterized by interplanar distances of 3.2 and 2.8 A, with an angle between them 53.8 ° contributes to the achievement of the textural characteristics of the catalyst, providing access to all the transformation of raw material molecules to the active component.

4. The presence of boron in the catalyst composition with a concentration of 0.4-1.6% in the form of surface compounds, characterized by absorption bands by absorption bands 930-1040, 1230, 1385-1450 and 3695 cm ^"1 in the IR spectra, provides a catalyst that after sulphidation, it has a dispersion of deposited metals, determined according to XPS data by the ratio of the intensities of the IMo3d / IA12p lines in the interval of 1.45-1.55, and by the ratio of the intensities of the 1Co2p / 1A12p lines in the interval of 1.14-1.18. increased activity of the sulfide component in target reactions of desulfurization and diazotization.

5. The presence in the composition of the catalyst of surface boron compounds, which increase the acidity of the catalyst due to the formation of strong Bronsted acid sites, determined by the IR method from the data of low-temperature adsorption of CO, 2–6 µmol / g (PA (affinity for proton) = 1180-1200 kJ / mol) and Bronsted acidic centers of medium strength, 30-60 µmol / g (PA = 1250-1260 kJ / mol). Such acid sites promote an increase in the diazotization activity of the catalyst.

Description of the proposed technical solution. Prepare a carrier containing aluminum borate A1 ₃ B0 ₆ with the structure of norbergite and γ-Α1 ₂ 0 ₃ .

Take a sample of the product of thermal activation of hydrargillite (PTH), prepared according to the technology of centrifugal thermo-activation or any other technology providing production of PTH with the following characteristics: mass fraction of X-ray amorphous phase,%, not less than 80; the proportion of mass loss during calcination at (900 ± 20) ° С,% - 10-12; specific surface, m / g, not less than 120; total pore volume (capacity), cm / g, not less than 0.1; mass fraction of gibbsite (hydrargillite),%, not more than 5; mass fraction of sodium oxide,%, not more than 0.5. A portion is ground in a planetary mill to particles with an average size of 20 microns.

A portion of the crushed powder is hydrated with stirring for 2 hours in low-concentrated solutions of nitric acid heated to 50 ° C (acid module 0.03). After that, the resulting suspension is filtered under vacuum and repeatedly washed with distilled water. The result is a wet sediment. Hydrothermal treatment of the washed precipitate is carried out in an autoclave in aqueous solutions of nitric acid with the addition of a specified amount of boric acid at a solution temperature above 100 ° C. After completion of the hydrothermal treatment, the solution is cooled to room temperature, the autoclave is discharged, and the contents of the vessel are repulped with distilled water until a suspension is suitable for spray drying. Next, carry out the drying in a spray dryer at an air temperature at the entrance to the dryer 280 ° C and continuous stirring of the suspension. The finished boron-containing aluminum hydroxide powder is discharged from the glass of the spray dryer cyclone dust collector.

Next, prepare the molding material by mixing and peptizing the obtained powder in a laboratory mixer with образ-shaped blades in the presence of an aqueous solution of ammonia. The ammonia solution is prepared in such a way that the amount of ammonia aqueous 25% is 1.5 ml per 40 g of powder after spray drying.

The finished plastic mass is transferred from the mixer to the molding cylinder of the laboratory extruder and is forced through the die hole, providing extrudates finished media with a cross-section in the shape of a circle, trefoil or chetyrehlistnik with size from the top of the trefoil to the middle of the base from 1.0 to 1.6 mm.

This is followed by heat treatment of the extrudates, including drying and calcining. The extrudates are dried in a drying oven at a temperature of (110 ± 10) ° C for 2 hours. Heat treatment is carried out in a muffle furnace with compressed air fed into the furnace. The extrudates in a porcelain dish are placed in an oven and calcined at a temperature of (550 ± 10) ° C for 4 hours.

Ready media contains May. %: aluminum borate A1 ₃ B0 ₆ with the structure of norbergite - 5.0-25.0; sodium - not more than 0.03; γ-Α1 ₂ 0 ₃ - the rest, and has a specific surface of 200-280 m / g, a pore volume of 0.6-0.8 cm / g, an average pore diameter of 7-12 nm, and is a particle with a cross section in the form of a circle , trefoil or chetyrehlistnika with a diameter of the circumscribed circle 1.0-1.6 mm and a length of up to 20 mm.

The aluminum borate A1 ₃ B0 ₆ with the structure of norbergite, which is part of the carrier, consists of particles with sizes from 10 to 200 nm, characterized by interplanar distances of 3.2 and 2.8 A, with an angle of 53.8 ° between them.

Using this carrier, a supported catalyst is prepared.

First, prepare an impregnating solution containing bimetallic complex compound [Co (H ₂ 0) ₂ (C _b H ₅ 0 ₇ )] ₂ [Mo ₄ Oz (C ₆ H ₅ 0 ₇ ) ₂ ]. For this purpose, the specified amounts of ammonium paramolybdate (ΝΗ ₄ ) ₆ Μ θ ₇ θ ₂₄ · 4 Η ₂ 0, cobalt (II) basic carbonate CoCO3 ^, tCO (OH) ₂ ”pN ₂ 0, citric monohydrate are weighed. Measured cylinder measure the specified amount of distilled water. A measured amount of water is poured into the flask and an anchor of the magnetic stirrer is placed. The flask is placed on the heating surface of a heated magnetic stirrer. Set the rotation speed of the stirrer 300 rpm and the temperature of the solution 60 ° C. A measured amount of citric acid is loaded into the flask and stirred under visual inspection. Then, a portion of ammonium paramolybdate is added to the flask to a solution of citric acid with constant stirring and maintaining the solution temperature (60 ± 5) ° C. Solution mix to form a homogeneous transparent solution containing the complex compound molybdenum citrate (VI) (NH ₄ ) ₄ [Mo ₄ (C ₆ H ₅ 0 ₇ ) ₂ On]. A portion of cobalt (I) basic carbonate is added to the previously obtained aqueous solution of molybdenum citrate (VI). In this case, the liquid foams, and its temperature rises to 70 ° C. Stirring is continued at (65-70) ° C until a homogeneous transparent solution of dark cherry color, not containing turbidity, bubbles and foam. The solution contains cobalt and molybdenum in the form of a bimetallic complex compound [Co (H ₂ 0) 2 (C ₆ H ₅ 0 ₇ )] ₂ [Mo ₄ 0 ₁₁ (C ₆ H ₅ 0 ₇ ) ₂ ].

Further, to the solution with stirring and continued heating, boric acid H3BO3 is added in an amount to obtain a catalyst containing 0.4-1.6% boron in the form of surface compounds, stirring is continued until complete dissolution of boric acid.

The prepared solution is poured into a calibrated measuring cylinder, after which the volume of the solution is adjusted to the specified amount by adding distilled water.

The resulting solution is impregnated with boron-containing carrier, using either the impregnation of the carrier according to moisture capacity, or from an excess of solution. The impregnation is carried out at a temperature of 15-90 ° C for 5-60 minutes with occasional stirring, in the case of impregnation from the excess solution after impregnation, the excess solution is drained from the catalyst and used to prepare the following catalyst batches. After impregnation, the catalyst is dried in air at a temperature of 100-200 ° C.

As a result, get the catalyst containing wt.%:

[Co (H ₂ 0) ₂ (C ₆ H ₅ 0 ₇ )] ₂ [Mo ₄ 0 ₁₁ (C ₆ H ₅ 0 ₇ ) ₂ ] 33.0-43.0%; boron in the form of surface compounds - 0.4-1.6%, the carrier - the rest; however, the carrier contains, May. %: aluminum borate A1 ₃ B0 ₆ with the structure of norbergite - 5.0-25.0; sodium - not more than 0.03; γ-Α1 ₂ 0 ₃ - the rest. To confirm the presence or absence of surface boron compounds in the composition of the catalyst, the catalyst is studied by IR spectroscopy. To confirm the presence of aluminum borate catalyst A1 ₃ B0 ₆ with the structure of norbergite, catalysts are studied by the transmission electron method. high resolution microscopy (HRTEM), during which particles of A1 ₃ B0 ₆ , interplanar distances and the angle between them are determined.

After sulphidation by known methods, the catalyst contains, in wt.%: Mo - 10.0-14.0; Co - 3.0-4.3; S - 6.7-9.4; boron in the form of surface compounds - 0.5-2.0; carrier - the rest; however, the carrier contains, May. %: aluminum borate A1 ₃ B0 ₆ with the structure of norbergite - 5.0-25.0; sodium - not more than 0.03; γ-Α1 ₂ 0 ₃ - the rest.

The invention is illustrated by the following examples.

Example 1. According to the well-known decision [Pat. RF JV "2626398].

First, prepare the carrier, for which 150 g of the product of thermal activation of hydrargillite is ground in a planetary mill to particles in the range of 20-50 microns. Next, the powder is hydrated with stirring and heated in a solution of nitric acid with a concentration of 0.5%. Then the suspension on a funnel with a paper filter is washed with distilled water until the residual sodium content in the powder is not more than 0.03%. The washed and pressed pellet is transferred to an autoclave, to which is added a solution of 2.3 g of boric acid in 1 liter of a 1.5% aqueous solution of nitric acid, having a pH of 1.4. The autoclave is heated to 150 ° C and held for 12 hours. Next, the autoclave is cooled to room temperature and the resulting suspension is dried on a spray dryer at air inlet to the dryer 155 ° C and the suspension is continuously stirred, and the dried powder is collected in the receiving container of the dryer. A weighed 150 g of powder is placed in a mixer trough with Ζ-shaped blades, peptized with 2.5% aqueous ammonia solution, and then extruded at a pressure of 60.0 MPa, through a spinneret, providing particles with a trefoil cross-section with a diameter of circumscribed 1.6 mm. Molded granules are dried at a temperature of 120 ° C and calcined at a temperature of 550 ° C. The result is a carrier containing May. %: aluminum borate A1 ₃ B0 ₆ with the structure of norbergite - 5.0; sodium - 0.03; γ-Α1 ₂ 0 ₃ - the rest.

Next, prepare a solution of the bimetallic complex compound [Co (H ₂ 0) ₂ (C ₆ H ₅ 0 ₇ )] ₂ [Mo ₄ O (C ₆ H ₅ 0 ₇ ) ₂ ], for which, under stirring, 100 ml of distilled water are successively dissolved 73.3 g of citric acid C ₆ H ₈ 0 ₇ ; 89.87 g of ammonium paramolybdate (ΝΗ ₄ ) ₆ ο ₇ θ2 ₄ χ4Η ₂ 0 and 30.1 g cobalt (II) carbonic basic aqueous CoC0 ₃ ^" tCo (OH) ₂ " pN ₂ 0. After complete dissolution of all the components, the solution is made up to 200 ml by adding distilled water.

100 g of the obtained carrier is impregnated with a capacity of 67 ml of a bimetallic complex compound solution

[Co (H ₂ 0) ₂ (C ₆ H ₅ 0 ₇ )] ₂ [Mo ₄ 0 ₁₁ (C ₆ H ₅ 0 ₇ ) 2] at 20 ° C for 60 min. Then the catalyst is dried in air at 100 ° C.

The catalyst contains, may. %: [Co (H ₂ 0) ₂ (C ₆ H ₅ 0 ₇ )] ₂ [Mo ₄ Ots (C ₆ H ₅ 0 ₇ ) ₂ ] 38.4%; carrier - the rest; however, the carrier contains, May. %: aluminum borate A1 ₃ B0 ₆ with the structure of norbergite - 5.0; sodium - 0.03; γ-Α1 ₂ 0 ₃ - the rest.

The catalyst has a specific surface of 150 m ² / g, a pore volume of 0.55 cm ³ / g, an average pore diameter of 13 nm, and consists of particles with a trefoil-shaped cross-section with a diameter of 1.6 mm and a length of 20 mm. The aluminum borate catalyst A1 ₃ B0 ₆ with the structure of norbergite, which is a part, consists of particles with sizes from 10 to 200 nm, characterized by interplanar spacings of 3.2 and 2.8 A, with an angle of 53.8 ° between them.

The catalyst was dried in air at 250 ° C for 2 hours. Next, IR spectra were recorded, which were recorded on a Shimadzu FTIR-8300 spectrometer in the spectral range 700-6000 cm ^"1 with a resolution of 4 cm ¹ , 300 scans were conducted for signal accumulation. Data IR spectroscopy are shown in table 1.

PEMV images were taken on a JEM-2010 electron microscope (JEOL, Japan) with a lattice resolution of 0.14 nm with an accelerating voltage of 200 kV. According to TEMP, the catalyst contains particles of aluminum borate A1 ₃ B0 ₆ with the structure of norbergite with sizes from 10 to 200 nm, characterized by interplanar spacings of 3.2 and 2.8 A, with an angle of 53.8 ° between them.

Next, the catalyst is sulfided by one of the known methods. In this case, the catalyst is sulfided with a straight-run diesel fraction containing an additional 1.5 May. % sulfidizing agent - dimethyl disulfide (DMDS), at volumetric feed rate sulfidiruyuschey mixture of 2 h ^"1 and the ratio of hydrogen / raw materials = 300 according to the following program:

- drying the catalyst in the Hydrotreating reactor in a stream of hydrogen at 140 ° C for 2 h;

- wetting of the catalyst with a straight-run diesel fraction for 2 h;

- supply of sulfiding mixture and increase in temperature up to 240 ° С with a temperature rise rate of 25 ° С / h;

- sulfidization at a temperature of 240 ° C for 8 h (low-temperature stage);

- an increase in the temperature of the reactor to 340 C at a rate of temperature rise of 25 ° C / h;

sulphidation at 340 ° С for 8 h.

The result is a catalyst that contains, may. %: Mo - 12.5; Co — 3.85; S - 8.3; carrier - the rest; however, the carrier contains, May. %: aluminum borate A1 ₃ B0 ₆ with the structure of norbergite - 5.0; sodium - 0.03; γ-Α1 ₂ 0 ₃ - the rest.

Next, the catalyst is characterized by the method of x-ray photoelectron spectroscopy (XPS). XPS spectra were recorded using a SPECS spectrometer (Germany) using a hemispherical energy analyzer PHOIBOS-150 and A1 K and irradiation (hv = 1486.6 eV, 200 W). The IMo3d / IA12p and 1Co2p / 1A12p surface atomic ratios were calculated using VG Eclipse software after processing the non-linear Shirley background and the contribution of the S2 s signal to Mo3d. Data on the dispersion of Mo and Co are given in Table 2.

The catalyst is tested in hydrotreatment of diesel fuel containing 0.37% sulfur, 250 ppm of nitrogen, having a density of 0.86 g / cm ³ , a boiling range of 210-360 ° C, T 5 - 356 ° C. Hydrotreating conditions: volumetric feed rate - 2.5 h ^"1 , H ₂ / raw material ratio = 500 nm ³ H ₂ / m ³ raw material, pressure 3.8 MPa, temperature 350 ° С.

The catalyst is also tested in the hydrotreatment of vacuum gas oil. Hydrotreating of vacuum gas oil (2.5% sulfur, 1500 ppm of nitrogen, kk 560 ° C) is carried out at 375 ° C, pressure of 7.0 MPa, mass flow rate of vacuum gas oil 0.85 h ^"1 , volume ratio hydrogen / raw material 500

The results of catalyst testing in hydrotreating are shown in table 3.

Examples 2-7 illustrate the proposed technical solution.

Example 2

First, prepare the carrier, similarly to example 1. The result is a carrier containing, may. %: aluminum borate A1 ₃ B0 ₆ with the structure of norbergite - 5.0; sodium - 0.03; γ-Α1 ₂ 0 ₃ - the rest.

Next, prepare a solution that simultaneously contains a bimetallic complex compound [Co (H ₂ 0) ₂ (C ₆ H50)] 2 [Mo ₄ Op (C ₆ H ₅ 0 ₇ ) 2] and boric acid, for which in 100 ml of distilled water with by stirring and heating to 70 ° C, 73.3 g of citric acid C ₆ H ₈ 0 _{7 are} successively dissolved; 89.87 g of ammonium paramolybdate (ΝΗ ₄ ) 6Μο ₇ 0 ₂₄ χ4Η ₂ 0, 30.1 g of cobalt (II) carbonate basic aqueous CoC0 ₃ "tCO (OH) ₂ " pN ₂ 0. Then the temperature of the solution is raised to 90 ° С and dissolve in it 44.63 g of boric acid H ₃ B0 ₃ . After complete dissolution of all components, the solution is adjusted to 200 ml by adding distilled water heated to 90 ° C.

[Co (H ₂ 0) ₂ (C ₆ H ₅ 0 ₇ )] ₂ [Mo ₄ 0 ₁₁ (C ₆ H ₅ 0) ₂ ] and boric acid at 90 ° C for 60 minutes. Then the catalyst is dried in air at 100 ° C.

The catalyst contains, may. %: [Co (H ₂ 0) ₂ (C ₆ H ₅ 0 ₇ )] ₂ [Mo ₄ Op (C ₆ H ₅ 0 ₇ ) ₂ ] - 38.4; boron in the form of surface compounds - 1.6, the carrier - the rest; however, the carrier contains, May. %: aluminum borate A1 ₃ B0 ₆ with the structure of norbergite - 5.0; sodium - 0.03; γ-Α1 ₂ 0 ₃ - the rest. Next, they record the IR spectra and make the HRTEM images as in Example 1. The data of IR spectroscopy are shown in Table 1.

The catalyst has a specific surface of 145 m / g, a pore volume of 0.50 cm / g, an average pore diameter of 13 nm, and consists of particles with a trefoil-shaped cross-section with a circumferential diameter of 1.6 mm and a length of up to 20 mm. The aluminum borate A1 ₃ B0 ₆ with the structure of norbergite, which is part of the catalyst, consists of particles with sizes from 10 to 200 nm, characterized by interplanar distances of 3.2 and 2.8 A, with an angle of 53.8 ° between them.

Next, the catalyst is sulfided similarly to example 1. The result is a catalyst that contains, may. %: Mo - 12.5; Co — 3.85; S - 8.3; boron in the form of surface compounds - 2.0, the carrier - the rest; however, the carrier contains, May. %: aluminum borate A1 ₃ B0 ₆ with the structure of norbergite - 5.0; sodium - 0.03; γ-Α1 ₂ 0 ₃ - the rest. The catalyst is characterized by the method of x-ray photoelectron spectroscopy (XPS), analogously to example 1. Data on the dispersion of Mo and Co are given in table 2.

The catalyst is tested in the hydrotreatment of diesel fuel and vacuum gas oil as in Example 1. The results of testing the catalyst in hydrotreating are shown in Table 3.

Example 3

Prepare the carrier according to the method similar to example 2, with the difference that the washed and pressed pellet is transferred to an autoclave, to which is added a solution of 5.98 g of boric acid in 1 liter of 1.5% aqueous solution of nitric acid. The remaining operations and loading components in the preparation of media similar to example 2.

The result is a carrier containing May. %: aluminum borate A1 ₃ VO _b with the structure of norbergite - 12.0; sodium - 0.028; γ-Α1 ₂ 0 ₃ - the rest.

Next, prepare a solution that simultaneously contains a bimetallic complex compound [Co (H ₂ 0) ₂ (C ₆ H ₅ 0 ₇ )] ₂ [Mo ₄ O (C ₆ H ₅ 0 ₇ ) ₂ ] and boric acid, in 100 ml distilled water with stirring and heating to 70 ° C. consistently dissolve 73.3 g of citric acid C ₆ H ₈ 0 ₇ ; 89.87 g of ammonium paramolybdate (NH ₄ ) ₆ Mo ₇ 0 ₂ 4x4H ₂ 0, 30.1 g of cobalt (II) carbonate basic water CoCO3 ^" tCO (OH) ₂ ^" pN ₂ 0 and 22.32 g of boric acid H ₃ B0 ₃ . After complete dissolution of all components, the solution is adjusted to 200 ml by adding distilled water heated to 70 ° C.

100 g of the obtained carrier is impregnated at 70 ° C according to the moisture capacity of 67 ml of a solution of a bimetallic complex compound [Co (H20) ₂ (C ₆ H ₅ 0 ₇ )] ₂ [Mo ₄ 0 ₁₁ (C ₆ H ₅ 0 ₇ ) ₂ ] and boric acid. Then the catalyst is dried in air at 100 ° C.

The catalyst contains, may. %: [Co (H ₂ 0) ₂ (C ₆ H ₅ 0 ₇ )] ₂ [Mo ₄ Ots (C ₆ H ₅ 0 ₇ ) ₂ ]

- 38.4%; boron in the form of surface compounds - 0.8, the carrier - the rest; however, the carrier contains, May. %: aluminum borate A1 ₃ B0 ₆ with the structure of norbergite - 12.0; sodium - 0.028; γ-Α1 ₂ 0 ₃ - the rest. The catalyst is characterized by the methods of IR-spectroscopy and HRTD similarly to example 1. The data of IR-spectroscopy are shown in table 1.

Next, the catalyst is sulfided similarly to example 1. The result is a catalyst, which contains May. %: Mo - 12.5; Co — 3.85; S - 8.3; boron in the form of surface compounds - 1.0; carrier - the rest; however, the carrier contains, May. %: aluminum borate A1 ₃ B0 ₆ with the structure of norbergite

- 12.0; sodium - 0.028; γ-Α1 ₂ 0 ₃ - the rest. The catalyst is characterized by the method of x-ray photoelectron spectroscopy (XPS), analogously to example 1. Data on the dispersion of Mo and Co are given in table 2.

Next, carry out the Hydrotreating of hydrocarbons as in example 1. The results of testing the catalyst in Hydrotreating are shown in table 3.

Example 4

Prepare the media according to the method similar to example 2, with the difference that the washed and pressed pellet is transferred to an autoclave, to which is added a solution of 14.63 g of boric acid in 1 liter of 1.5% aqueous solution of nitric acid. The remaining operations and loading components in the preparation of media similar to example 2.

The result is a carrier containing May. %: aluminum borate A1 ₃ B0 ₆ with the structure of norbergite - 25.0; sodium - 0.023; γ-Α1 ₂ 0 ₃ - the rest.

100 g of the obtained carrier is impregnated with a capacity of 67 ml of a solution of a bimetallic complex compound.

[Co (H20) ₂ (C ₆ H50 ₇ )] ₂ [Mo ₄ Oi (C ₆ H ₅ 0 ₇ ) 2] and boric acid from Example 3. Then the catalyst is dried in air at 200 ° C.

The catalyst contains, may. %: [Co (H ₂ 0) 2 (C ₆ H 0 ₇ )] ₂ [Mo40ii (C ₆ H ₅ 07) 2]

- 38.4; boron in the form of surface compounds - 0.8; carrier - the rest; however, the carrier contains, May. %: aluminum borate A1 ₃ B0 ₆ with structure Norbergite - 25.0; sodium - 0.023; γ-Α1 ₂ 0 ₃ - the rest. The catalyst is characterized by the methods of IR-spectroscopy and HRTD similarly to example 1. The data of IR-spectroscopy are shown in table 1.

The catalyst has a specific surface of 180 m ² / g, a pore volume of 0.55 cm ³ / g, an average pore diameter of 7 nm, and consists of particles with a trefoil-shaped cross-section with a diameter of 1.6 mm and a length of 20 mm.

The aluminum borate A1 ₃ B0 ₆ with the structure of norbergite, which is part of the catalyst, consists of particles with sizes from 10 to 200 nm, characterized by interplanar distances of 3.2 and 2.8 A, with an angle of 53.8 ° between them.

Next, the catalyst is sulfided similarly to example 1. The result is a catalyst, which contains May. %: Mo - 12.5; Co — 3.85; S - 8.3; boron in the form of surface compounds - 1.0; carrier - the rest; however, the carrier contains, May. %: aluminum borate A1 ₃ B0 ₆ with the structure of norbergite - 25.0; sodium - 0.023; γ-Α1 ₂ 0 ₃ - the rest.

The catalyst is characterized by the method of x-ray photoelectron spectroscopy (XPS), analogously to example 1. Data on the dispersion of Mo and Co are given in table 2.

Example 5

Prepare the media in example 3.

A solution of the bimetallic complex compound [Co (H ₂ 0) ₂ (C ₆ H ₅ 0 ₇ )] ₂ [Mo ₄ Oz (C _b H ₅ 0 ₇ ) ₂ ] is prepared, for which, in 100 ml of distilled water, the solution is sequentially dissolved with stirring 63 , 27 g of citric acid With ₆ H ₈ 0 ₇ ; 77.58 g of ammonium paramolybdate (Η ₄ ) ₆ Μο ₇ 0 ₂₄ χ4Η ₂ 0, 26.0 g of cobalt (II) carbonate basic aqueous CoC0 ₃ ^" tCO (OH) ₂ " pN ₂ 0 and 11.16 g of boric acid H ₃ V ₃ . After complete dissolution of all components, the solution is made up to 200 ml by adding distilled water.

100 g of the obtained carrier is impregnated at room temperature with the capacity of 67 ml of a solution of a bimetallic complex compound. [Co (H ₂ 0) ₂ (C ₆ H50 ₇ )] 2 [Mo ₄ Op (C ₆ H50 ₇ ) 2]. Then the catalyst is dried in air at 120 ° C.

The catalyst contains, may. %: [Co (H ₂ 0) 2 (C ₆ H ₅ 0 ₇ )] ₂ [Mo Op (C ₆ H ₅ 0 ₇ ) ₂ ] - 32.7; boron in the form of surface compounds - 0.4; carrier - the rest; however, the carrier contains, May. %: aluminum borate A1 ₃ B0 ₆ with the structure of norbergite - 12.0; sodium - 0.028; γ-Α1 ₂ 0 ₃ - the rest. The catalyst is characterized by the methods of IR-spectroscopy and HRTD similarly to example 1. The data of IR-spectroscopy are shown in table 1.

The catalyst has a specific surface area of 180 m ² / g, a pore volume of 0.65 cm ³ / g, an average pore diameter of 14 nm, and is a trefoil-shaped particle with a circumferential diameter of 1, 6 mm and a length of up to 20 mm.

Next, the catalyst is sulfided similarly to example 1. The result is a catalyst that contains, may. %: Mo - 10.0; Co - 3.0; S — 6.7; boron in the form of surface compounds - 0.5; carrier - the rest; however, the carrier contains, May. %: aluminum borate A1 ₃ B0 ₆ with the structure of norbergite - 12.0; sodium - 0.028; γ-Α1 ₂ 0 ₃ - the rest.

Example 6

Prepare the media according to example 3, with the difference that the molding paste extruded at a pressure of 60.0 MPa, through a die plate, providing particles with a cross section in the form of a circle with a diameter of 1.0 mm.

Prepare a solution of the bimetallic complex compound [Co (H20) ₂ (C ₆ H ₅ 0 ₇ )] 2 [Mo ₄ Op (CfH ₅ 0 ₇ ) 2], for which 100 ml of distilled water is heated to 90 ° C and stirred sequentially dissolve 85.3 g of citric acid C ₆ H 0 ₇ ; 104.53 g of ammonium paramolybdate (ΝΗ ₄ ) ₆ Μο ₇ 0 ₂₄ χ4Η ₂ θ and 35.05 g of cobalt (II) carbonate basic water CoC0 ₃ "tCO (OH) ₂ " pN ₂ 0 and 44.63 g of boric acid H3BO3 . After complete dissolution of all components, the solution is made up to 200 ml by adding distilled water.

Next, use the impregnation of the carrier from the excess solution. 100 g of the obtained carrier is loaded into a flask placed in a water bath heated to 90 ° C, 200 ml of a solution of the bimetallic complex compound [Co (H ₂ 0) ₂ (C ₆ H ₅ 0 ₇ )] ₂ [Mo ₄ Op (SbH ₅ 0 ₇ ) ₂ ], also heated to 90 ° C. The impregnation is continued for 20 minutes with occasional stirring, after which the excess solution is separated from the wet catalyst. Then the catalyst is dried in air at 200 ° C. The catalyst is characterized by the methods of IR-spectroscopy and HRTD similarly to example 1. The data of IR-spectroscopy are shown in table 1.

The catalyst contains, may. %: [Co (H ₂ 0) ₂ (C ₆ H ₅ 0 ₇ )] ₂ [Mo ₄ Op (C ₆ H ₅ 0 ₇ ) ₂ ] -

42.95%; boron in the form of surface compounds - 1.6; carrier - the rest; however, the carrier contains, May. %: aluminum borate A1 ₃ B0 ₆ with the structure of norbergite - 12.0; sodium - 0.028; γ-Α1 ₂ 0 ₃ - the rest.

The catalyst has a specific surface of 130 m / g, a pore volume of 0.35 cm / g, an average pore diameter of 10 nm, and is a particle with a cross section in the form of a circle with a diameter of 1.0 mm and a length of up to 20 mm.

Next, the catalyst is sulfided similarly to example 1. The result is a catalyst that contains, may. %: Mo - 14.0; Co — 4.3; S — 9.4; boron in the form of surface compounds - 2.0; carrier - the rest; however, the carrier contains, May. %: aluminum borate A1 ₃ B0 ₆ with the structure of norbergite - 12.0; sodium - 0.028; γ-Α1 ₂ 0 ₃ - the rest.

The catalyst is characterized by the method of x-ray photoelectron spectroscopy (XPS), analogously to example 1. Data on the dispersion of Mo and Co are given in table 2. Next, carry out the Hydrotreating of hydrocarbons as in example 1. The results of testing the catalyst in Hydrotreating are shown in table 3.

Example 7

Prepare the media according to example 3, with the difference that the molding paste extruded at a pressure of 60.0 MPa, through the die plate, providing particles with a cross section in the form of chetyrehlistnik with a diameter of 1, 6 mm.

Next, use the impregnation of the carrier from the excess solution. 100 g of the obtained carrier is loaded into a flask placed in a water bath heated to 30 ° C, 133 ml of a solution of the bimetallic complex compound [Co (H ₂ 0) ₂ (C ₆ H ₅ 0 ₇ )] ₂ [Mo ₄ Op (C _b H ₅ 0 ₇ ) ₂ ] from example 5, also heated to 30 ° C. The impregnation is continued for 60 minutes with occasional stirring, after which the excess solution is separated from the wet catalyst. Then the catalyst is dried in air at 120 ° C.

The resulting catalyst contains, may. %:

[Co (H ₂ 0) 2 (C ₆ H ₅ 0 ₇ )] ₂ [Mo ₄ Ots (C _b H ₅ 0 ₇ ) ₂ ] - 35.9; boron in the form of surface compounds - 0.4; carrier - the rest; however, the carrier contains, May. %: aluminum borate A1 ₃ B0 ₆ with the structure of norbergite - 12.0; sodium - 0.028; γ- A1 ₂ 0 ₃ - the rest. The catalyst is characterized by the methods of IR-spectroscopy and HRTD similarly to example 1. The data of IR-spectroscopy are shown in table 1.

The catalyst has a specific surface of 175 m / g, a pore volume of 0.6 cm / g, an average pore diameter of 14 nm, and is a particle with a cross section in the form of a four-leaf with a circumferential diameter of 1.6 mm and a length of 20 mm.

Next, the catalyst is sulfided similarly to example 1. The result is a catalyst, which contains May. %: Mo - 11.7; Co — 3.6; S - 7.9; boron in the form of surface compounds - 0.5; carrier - the rest; wherein media contains, may. %: aluminum borate A1 ₃ B0 ₆ with the structure of norbergite - 12.0; sodium - 0.028; γ-Α1 ₂ 0 ₃ - the rest.

Table 1.

IR spectroscopic data of catalysts

Dispersity of deposited metals according to XPS data

Table 3.

Residual sulfur and nitrogen content in hydrotreating products

Thus, as can be seen from the above examples, the proposed catalyst due to its chemical composition, dispersion of the active component, texture and acidity, has a high activity, significantly exceeding the activity of the prototype catalyst in the desulfurization and diazotization of hydrocarbon raw materials.

Claims

Claim

1. A catalyst for hydrotreating hydrocarbon feedstock, including cobalt, molybdenum, boron and a carrier in its composition, characterized in that it contains, in wt.%: [Co (H ₂ 0) ₂ (C ₆ H ₅ 0 ₇ )] ₂ [Mo ₄ 0 ₁₁ (C ₆ H ₅ 0 ₇ ) ₂ ] 33.0-43.0%; boron in the form of surface compounds - 0.4-1.6%, the carrier - the rest; however, the carrier contains, May. %: aluminum borate A1 ₃ B0 ₆ with the structure of norbergite - 5.0-25.0; sodium - not more than 0.03; γ-Α1 ₂ 0 ₃ - the rest.

2. The catalyst according to claim 1, characterized in that it contains boron in the form of two different types of chemical compounds - part of the carrier of aluminum borate A1 ₃ B0 ₆ with the structure of norbergite, which are particles with sizes from 10 to 200 nm, characterized by interplanar distances 3.2 and 2.8 A, with an angle between them of 53.8 ° and boron in the form of surface compounds characterized by absorption bands of 930-1040, 1230, 1385-1450 and 3695 cm ^"1 in the IR spectra.

3. The catalyst according to claim 1, characterized in that it contains strong

Bronsted acid sites, determined by IR method from CO low-temperature adsorption data, 2-6 µmol / g (PA (affinity for proton) = 1180-1200 kJ / mol) and Bronsted acid centers of average strength, 30-60 µmol / g (PA = 1250-1260 kJ / mol).

4. The catalyst according to claim 1, characterized in that it has a specific surface of 130-180 m ² / g, a pore volume of 0.35-0.65 cm ³ / g, an average pore diameter of 7-14 nm, and represents particles with a cross-section in the form of a circle, trefoil or chetyrehlistnik with a circumference of 1.0-1.6 mm and a length of up to 20 mm.

5. The catalyst according to claim 1, characterized in that after sulphidation, it contains, wt%: Mo - 10.0-14.0; Co - 3.0-4.3; S - 6.7-9.4; boron in the form of surface compounds - 0.5-2.0; carrier - the rest; however, the carrier contains, May. %: aluminum borate A1 ₃ B0 ₆ with the structure of norbergite - 5.0-25.0; sodium - not more than 0.03; γ-Α1 ₂ 0 ₃ - the rest.

6. The catalyst according to claim 1, characterized in that after sulfiding, it has a dispersion of deposited metals, determined according to XPS data by the ratio of the intensities of the IMo3d / IA12p lines in the range of 1.45-1.55, and by the ratio of the intensities of the 1Со2р / 1А12р lines the range of 1.14-1.18.