WO2018088938A1

WO2018088938A1 - A catalyst for hydrotreatment of hydrocracking feedstocks

Info

Publication number: WO2018088938A1
Application number: PCT/RU2017/000834
Authority: WO
Inventors: Олег Владимирович Климов; Владимир Владимирович ДАНИЛЕВИЧ; Евгений Юрьевич ГЕРАСИМОВ; Максим Олегович КАЗАКОВ; Ксения Александровна НАДЕИНА; Александр Степанович НОСКОВ
Original assignee: Акционерное Общество "Газпромнефть-Омский Нпз" (Ао "Газпромнефть-Онпз")
Priority date: 2016-11-09
Filing date: 2017-11-08
Publication date: 2018-05-17
Also published as: RU2629358C1; EA201900236A1; EA038249B1

Abstract

The invention relates to catalysts for preliminary hydrotreatment of oil fractions with an onset of boiling temperature above 360°C for producing feedstocks with a low sulfur content, which feedstocks are further processed by hydrocracking. A catalyst comprising (wt%): [Ni(H₂O)₂]₂[Mo₄O₁₁(C₆H₅O₇)₂] - 29.0-36.0%; a substrate - the remainder, is described; wherein the substrate comprises (wt%): aluminium borate Al₃BO₆ having the norbergite structure – 5.0-25.0; sodium – no more than 0.03; γ-Al₂O₃ - the remainder. The aluminium borate Al₃BO₆ with the norbergite structure is in the form of particles having the 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 catalyst has a specific surface area in the range of 130 to 180 m²/g, a pore volume in the range of 0.35 to 0.65 cm³/g, an average pore diameter in the range of 10 to 15 nm, and is in the form of particles having a circular, trefoil or quatrefoil cross-sectional shape with a diameter of a circumscribed circle in the range of 1.0-1.6 mm and a length up to 20 mm. Post-sulfidation, the catalyst comprises (wt%): Mo – 10.0-14.0; Ni – 3.0-4.3; S – 6.7-9.4; the substrate – the remainder; wherein the substrate comprises (wt%): aluminium borate Al₃BO₆having the norbergite structure – 5.0-25.0; sodium – no more than 0.03; γ-Al₂O₃ - the remainder. The technical result is the maximized activity of desulfurization and denitrogenation in the hydrotreatment of oil fractions with an onset of boiling temperature above 360°C for producing quality feedstocks for hydrocracking.

Description

Catalyst

Hydrotreating Hydrocracking Raw Materials

The invention relates to catalysts for preliminary hydrotreatment of oil fractions with a boiling point above 360 ° C to obtain raw materials with a low content of sulfur and nitrogen, which is further processed in the process of hydrocracking.

At present, the hydrocracking process is the most dynamically developing catalytic oil refining process, since it allows increasing the depth of oil refining and improving the quality of the resulting product by converting heavy oil fractions into low-sulfur middle distillates, from which high-quality aviation kerosene and diesel fuels are obtained. Since the characteristics of specific variants of hydrocracking processes and the quality of the products obtained are largely determined by the properties of the catalysts used, the development of improved hydrocracking catalysts, including catalysts for the preparation of raw materials for hydrocracking, is an extremely important and urgent task.

Modern hydrocracking processes, as a rule, include several successive stages, in the first of which preliminary hydrotreating of fractions with a boiling point above 360 ° C is carried out to obtain raw materials with a low content of sulfur, nitrogen and polycyclic aromatic compounds. The need for the maximum possible reduction in the content of these components in the feed is due to the fact that they are catalytic poisons for catalysts of subsequent stages. Further, such hydrotreated feed is fed to hydrocracking carried out on zeolite-containing catalysts. Most typical examples of multi-stage processes are described in patents [Pat. RF j4 ° 2470989, 11/27/2011; Pat. RF We 2565669, 10.20.2015; Pat. RF N ° 2595041, 08/20/2016]. In these process options, the first stage uses well-known catalysts containing metals of groups VI6 and VIII of the Periodic system supported on an alumina or aluminosilicate carrier. The main disadvantage of these catalysts is their low desulfurization and deazotizing activity.

In this regard, the world is actively developing catalysts and methods for the preparation of catalysts designed for hydrotreating or hydrotreating hydrocarbons, combining high desulfurization and deazotizing activity.

Thus, a catalyst is known [RF Application Jfe 2012154275, B01J31 / 02, 07/10/14], the composition of which includes at least one metal of group 6 of the Periodic Table of the Elements, at least one metal of groups 8-10 of the Periodic Table of the Elements and the product a reaction formed by a first organic compound containing at least one amino group and at least 10 carbon atoms, or a second organic compound containing at least one carboxylic acid group and at least 10 carbon atoms, but not both compounds in which second reaction product comprising additional unsaturated carbon atoms with respect to the first organic compound or the second organic compound, a catalyst precursor composition located in the metal lattice and the reaction product is not localized in the crystal lattice.

A known method of producing a catalyst for hydroprocessing [RF Application N °

2010102058, B01J27 / 185, 07.27.2011], comprising the following stages: a) at least one step of impregnating a dry and / or calcined catalyst precursor containing at least one element of group VIII and / or at least one element of group VIB and an amorphous carrier, using an impregnating solution consisting of at least one phosphorus-containing compound, dissolved in at least one polar solvent with a dielectric constant higher than 20; B) at least one stage of maturation of the specified impregnated catalyst precursor obtained in stage a); moreover, the specified the ripening stage is carried out at atmospheric pressure, at a temperature in the range from ambient temperature to 60 ° C during the ripening period from 12 to 340 hours; c) a drying step without a subsequent calcining step of said catalyst precursor obtained in step b).

There is also a method of producing a catalyst [RF Application N ° 2014130016, B01J37 / 02, 02/10/2016]. This method, based on a catalyst precursor containing a carrier based on alumina and / or silica-alumina and / or zeolite and containing at least one element of group VIB and, possibly, at least one element of group VIII, wherein said method comprises impregnating said precursor with a solution of (C1-C4) dialkyl succinate, characterized in that it comprises the following steps:

1) impregnation (stage 1) of the specified dried, calcined or regenerated precursor with at least one solution containing at least one carboxylic acid other than acetic acid, then incubation and drying at a temperature less

200 ° C, possibly followed by heat treatment at a temperature less than

350 ° C; 2) subsequent impregnation (stage 2) with a solution containing at least one (C _! -C ₄ ) dialkyl succinate, then exposure and drying at a temperature of less than 200 ° C without a subsequent calcination step;

and the fact that the catalyst precursor and / or the solution of stage 1 and / or the solution of stage 2 contains phosphorus.

A common disadvantage for the described catalysts, or catalysts prepared by known methods, is the high residual sulfur and nitrogen content in the hydrotreated products obtained using them.

Closest to the proposed technical solution is described in [Pat. RF J s 2472585, B01J23 / 882, 01/20/2013] a catalyst containing, May. %: Mo - 8.0-15.0; Co or Ni - 2.0-5.0; S - 5.0-15.0; B - 0.5-2.0; C - 0.5-7.0; A1 ₂ 0z - the rest, while the medium contains May. %: B - 0.7-3.0; AI2O3 - the rest and has a specific surface area of 170-300 m ² / g, a pore volume of 0.5-0.95 cm / 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 a diameter of the circumscribed circle 1 , 0-1.6 mm and up to 20 mm long, having a mechanical strength of 2.0-2.5 kg / mm.

The main disadvantage of the known catalyst is that it has a non-optimal chemical composition, which leads to its low activity in hydrotreatment and a high content of sulfur and nitrogen in the products obtained during hydrotreatment.

The present invention solves the problem of creating an improved catalyst for hydrotreating oil fractions with a boiling point above 360 ° C, characterized by:

1. The optimal chemical composition of the catalyst, the carrier of which contains as a component that determines the catalytic properties, aluminum borate A1 ₃ B0 ₆ with the structure of norbergite with a concentration of 5.0-25.0 may. % This component provides a level of acidity that helps minimize undesirable chemical interaction between active metals (Ni and Mo) and the support, and selectively produces the most active sulfide component in hydrotreatment, type II NiMoS phase.

2. Optimum textural characteristics of the support and catalyst, the volume and pore size of which provide access to all active molecules to be converted to the active component. The achievement of these characteristics is ensured, on the one hand, by the presence in the catalyst of aluminum borate particles A1 ₃ B0 ₆ with a norbergite structure, which is particles with sizes from 10 to 200 nm, on the other hand, by peptization of the molding paste at an increased concentration of ammonia.

3. The presence in its composition of a nickel compound, which has an increased desulfurizing, hydrogenating and deazotizing activity under the process conditions used for hydrotreating oil fractions with a boiling point above 360 ° C.

The problem is solved by a hydrotreating catalyst for hydrocracking feed, which contains May. %: [Ni (H ₂ 0) 2] 2 [o ₄ On (C ₆ H ₅ 0 ₇ ) 2] 29.0-36.0%; the carrier is the rest; wherein the medium contains May. %: aluminum borate A1 ₃ B0 ₆ with the structure of norbergite - 5.0-25.0; sodium - not more than 0.03; у-А1г0 ₃ - the rest. In this case, the aluminum borate catalyst A1 ₃ B0 ₆ with the structure of norbergite, which is part of the catalyst, represents particles with sizes from 10 to 200 nm, characterized by interplanar distances of 3.2 and 2.8 A, with an angle between them of 53.8 °. The catalyst has a specific surface area of 130-180 m ² / g, a pore volume of 0.35-0.65 cm / g, an average pore diameter of 10-15 nm, and is a particle with a cross section in the form of a circle, trefoil or four-leaf with a diameter of the circumscribed circle 1.0-1.6 mm and up to 20 mm long.

After sulfidation by known methods, the catalyst contains, may. %: Mo - 10.0-14.0; Ni 3.0-4.3; S 6.7-9.4; the carrier is the rest; wherein the medium contains May. %: aluminum borate A1 ₃ B0 ₆ with the structure of norbergite - 5.0-25.0; sodium - not more than 0.03; y-A1 ₂ 0z - 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. %: [Ni (H ₂ 0) 2] ₂ [Mo40n (C ₆ H ₅ 07) 2] 29.0-36.0%; the carrier is the rest; wherein the medium contains May. %: aluminum borate A1zB0 ₆ with the structure of norbergite - 5.0-25.0; sodium - not more than 0.03; y-A1 ₂ 0z - 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.

The second distinguishing feature of the proposed catalyst in comparison with the prototype is that it has a specific surface area of 130-180 m / g, a pore volume of 0.35-0.65 cm / g, an average pore diameter of 10-15 nm, and represents particles with section in the form of a circle, trefoil or four-leaf with a diameter of the circumscribed circle of 1.0-1.6 mm and a length of up to 20 mm. The output of the average pore diameter beyond the claimed framework leads to a decrease in the activity of the catalyst.

The third distinguishing feature of the proposed catalyst in comparison with the prototype is that the aluminum borate A1zB0 ₆ with the structure of norbergite, which is part of the catalyst, is particles with sizes from 10 to 200 nm, characterized by interplanar distances of 3.2 and 2.8 A, with an angle between them of 53.8 °.

The technical effect of the proposed catalyst consists of the following components:

1. The claimed chemical composition of the catalyst determines the maximum activity in the target reactions occurring during hydrotreating of oil fractions with a boiling point above 360 ° C. The presence in the composition of the catalyst of aluminum borate A1zB0 ₆ with the structure norbergite with the claimed concentration provides a level of acidity that helps minimize undesirable chemical interaction between active metals (Ni and Mo) and the support, and selectively produces the most active sulfide component in hydrotreatment - NiMoS phase type I.

2. The presence in the composition of 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 of 53.8 °, helps to achieve optimal texture characteristics of the catalyst, in in particular, the average pore diameter in the range of 10-15 nm, providing access to all active molecules to be converted to the active component.

3. The presence of the bimetallic complex compounds [Ni (H ₂ 0) ₂ ] ₂ [Mo ₄ On (C6H ₅ 0 ₇ ) 2] in the catalyst ensures the further formation in the catalyst during its hydrotreatment of the most active component — NiMoS type II phase optimal particle shape for catalysis morphology, localized in accessible for all to be converted molecules included in the oil fractions with a boiling point above 360 ° C.

Description of the proposed technical solution.

A support is prepared containing aluminum borate A1 ₃ B0 ₆ with the structure of norbergite and y-A Oz.

Take a portion of the product of thermal activation of hydrargillite (PTAG) prepared by centrifugal thermal activation technology, or any other technology that provides PTAG with the following characteristics: mass fraction of the X-ray amorphous phase,%, not less than 80; the proportion of weight loss during calcination at (900 ± 20) ° C,% - 10-12; specific surface, m / g, not less than 120; total pore volume (moisture 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 crushed in a planetary mill to particles with an average size of 20 microns.

A weighed sample of powdered powder is hydrated with stirring for two hours in weakly concentrated solutions heated to 50 ° С nitric acid (acid module 0.03). Then the resulting suspension is filtered under vacuum and washed repeatedly with distilled water. The result is a wet cake. Hydrothermal treatment of the washed precipitate is carried out in an autoclave in aqueous solutions of nitric acid with the addition of a predetermined 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 unloaded, the contents of the vessel are repulped with distilled water to obtain a suspension suitable for spray drying. Next, drying is carried out on a spray dryer at an air temperature at the inlet of the dryer of at least 150 ° C and continuous stirring of the suspension. The finished powder of boron-containing aluminum hydroxide is discharged from a glass of a cyclone dust collector of a spray dryer.

Then, the molding mass is prepared by mixing and peptizing the obtained powder in a laboratory mixer with Ζ-shaped blades in the presence of a 2.5% aqueous ammonia solution. The finished plastic mass is transferred from the mixer into the molding cylinder of the laboratory extruder and pressed through the hole of the die, providing extrudates of the finished carrier with a cross section in the shape of a circle, trefoil or four-leaf with a size from the top of the trefoil to the middle of the base from 1.0 to 1.6 mm.

Then heat treatment of the extrudates is carried out, including drying and calcining. Extrudates are dried in an oven at a temperature of (110 ± 10) ° С for 2 hours. Heat treatment is carried out in a muffle furnace with compressed air supplied to the furnace. The extrudates in a porcelain cup are placed in an oven and calcined at a temperature of (550 ± 10) ° C for 4 hours.

The finished carrier contains May. %: aluminum borate A1 ₃ VO _b 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 area of 200-280 m ² / g, pore volume 0.6-0.8 cm ³ / g, average pore diameter 10-15 nm, and is a particle with a cross section of in the form of a circle, trefoil or four-leafed with a diameter of the circumscribed circle of 1.0-1.6 mm and a length of up to 20 mm

The aluminum borate A1 ₃ B0 ₆ included in the carrier norbergite is a particle with sizes from 10 to 200 nm, characterized by interplanar distances of 3.2 and 2.8 A, with an angle between them of 53.8 °.

Using this support, a supported catalyst is prepared. First, an impregnation solution is prepared containing the bimetallic complex compound [Ni (H20) 2] 2 [Mo4011 (C6H507) 2]. For this, the specified quantities of ammonium paramolybdate (ΝΗ ₄ ) ₆ Μο ₇ θ2 ₄ · 4Η ₂ 0, nickel (II) carbonic acid, basic aqueous NiC0 ₃ m mNi (OH) 2 ^, nH ₂ 0, citric acid monohydrate are weighed out. A measured cylinder measures the specified amount of distilled water. A measured amount of water is poured into the flask and the anchor of the magnetic stirrer is placed. The flask is placed on the heating surface of a heated magnetic stirrer. The rotation speed of the stirrer is set at 300 rpm and the solution temperature is 60 ° C. The metered amount of citric acid is charged into the flask and mixed under visual inspection. Then, a weighed portion of ammonium paramolybdate is added to the solution of citric acid with constant stirring and maintaining the solution temperature (60 ± 5) ° С. The solution is stirred until a homogeneous transparent solution is obtained containing the complex compound molybdenum citrate (VI) (MH ₄ ) 4 [Mo ₄ (C _b H ₅ 0 ₇ ) 20p]. A portion of nickel (II) carbon dioxide basic water is added to the previously obtained aqueous solution of molybdenum (VI) citrate. In this case, the liquid foams, and its temperature rises to 70 ° C. Stirring is continued at (75-80) ° C until a homogeneous transparent solution of bright green color is obtained, free of turbidity, bubbles and foam. The solution contains nickel and molybdenum in the form of a bimetallic complex compound

[Ni (H20) 2] 2 [Mo4011 (C6H507) 2].

The prepared solution is poured into a calibrated graduated cylinder, after which the volume of the solution is adjusted to a predetermined amount by the addition of distilled water.

The resulting solution is impregnated with a boron-containing support, and either the impregnation of the support by moisture capacity or from excess solution is used. The impregnation is carried out at a temperature of 20-80 ° C for 20-60 minutes with periodic stirring, in the case of impregnation from the excess solution after impregnation, the excess solution is drained from the catalyst and used for preparation of the following batches of catalyst. After impregnation, the catalyst is dried in air at a temperature of 100-200 ° C.

As a result, a catalyst is obtained containing P ^y (H20) 2 H o40 ₁₁ (SbH5C ^, 7) 2] 29.0-36.0%; the carrier is the rest; wherein the medium 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. In this case, the aluminum borate catalyst A1 ₃ B0 ₆ with the structure of norbergite is a particle with sizes from 10 to 200 nm, characterized by interplanar distances of 3.2 and 2.8 A, with an angle between them of 53.8 °.

The catalyst has a specific surface area of 130-180 m ² / g, pore volume 0.35-

0.65 cm / g, the average pore diameter of 10-15 nm, and represents particles with a cross section in the form of a circle, trefoil or four-leaf with a diameter of the circumscribed circle of 1.0-1.6 mm and a length of up to 20 mm.

After sulfidation by known methods, the catalyst contains, May. %: Mo - 10.0-14.0; Ni 3.0-4.3; S 6.7-9.4; the carrier is the rest; wherein the medium 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 a well-known solution [Pat. RF Ν ° 2472585].

To 100 g of aluminum hydroxide powder A100H, having a boehmite structure with a crystal size of 60-80 A, with an average size of agglomerates of 40-50 microns, containing impurities in quantity, May. %, no more: Na ₂ 0 - 0.002; Fe ₂ 0 ₃ - 0.01; Si0 ₂ - 0.015, with continuous stirring in a mixer with Z-shaped blades, 2 ml of concentrated nitric acid, 70 ml of an aqueous solution containing 5 g of boric acid H ₃ B0 ₃ and 3 g of ethylene glycol are added. The weight ratio of the components of the mixture is aluminum hydroxide: water: nitric acid: boric acid: ethylene glycol = 1: 0.7: 0.02: 0.05: 0.03.

The resulting paste is stirred at room temperature for 40 minutes, then formed through a die with a cross section in the form of a trefoil with a diameter of the circumscribed circle of 1.5 mm at a pressure of 6.0 MPa. The obtained granules are dried in an oven at 110 ° C for 2 hours, then calcined at 550 ° C for 4 hours.

As a result, a carrier containing B is 1.0 May. %, A1 ₂ 0 ₃ - rest; having a specific surface of 250 m ² / g, a pore volume of 0.95 cm ³ / g, an average pore diameter of 13 nm, which is a particle with a cross section in the form of a trefoil with a diameter of the circumscribed circle 1.4 mm, length up to 20 mm.

A bimetallic compound of the composition, [Ni (H20) ₂ ] ₂ [Mo ₄ On (C6H ₅ 0 ₇ ) ₂ ] is synthesized, for which 40.5 g of citric acid C ₆ H ₈ 0 _{7 are} successively dissolved in 70 ml of distilled water; 71.0 g of ammonium paramolybdate (ΝΗ ₄ ) ₆ 7ο ₇ θ ₂₄ χ4Η ₂ θ and 17.3 g of nickel hydroxide M (OH) g. 15 ml of ethylene glycol are added to the resulting solution and the volume of the solution is 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

[1 (Н20) ₂ ] ₂ [о ₄ Оц (СНН ₅ 0 ₇ ) ₂ ] and ethylene glycol. The catalyst is dried in air at 100 ° C for 2 hours and sulfidized according to one of the known methods.

In this case, the catalyst is sulfidized by a straight-run diesel fraction containing an additional 1.5 May. % sulfidizing agent - dimethyldisulfide (DMDS), with a volumetric feed rate of sulfidizing mixture of 2 h ^"1 and a hydrogen / feed ratio = 300 according to the following program:

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

- wetting the catalyst straight run diesel fraction for 2 hours;

- supply of a sulfidizing mixture and an increase in temperature to 240 ° C at a rate of temperature rise of 25 ° C / h;

- sulfidation at a temperature of 240 ° C for 8 hours (low temperature stage);

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

sulfidation is carried out at a temperature of 340 ° C for 8 hours. The resulting catalyst contains May. %: Mo - 13.0; Ni - 3.4; S 9.6; B - 0.5; C - 6.7; A1 ₂ 0 ₃ - the rest.

Next, hydrotreating the hydrocracking feed is carried out, using vacuum gas oil having a boiling range of 360-570 ° C, containing 3.5% sulfur and 0.2% nitrogen. Hydrotreating is carried out at a pressure of 10.0 MPa, a feed rate of 0.7 h ^"1 , a volume ratio of hydrogen / feed 1200 nm ³ / m ³ , a temperature of 380 ° C. The test results of the catalyst in hydrotreatment are shown in the table.

Examples 2-7 illustrate the proposed technical solution.

Example 2

First, a carrier is prepared, for which 150 g of the product of thermal activation of hydrargillite is crushed in a planetary mill to particles ranging in size from 20-50 microns. Next, the powder is hydrated with stirring and heating 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 to a residual sodium content in the powder of not more than 0.03%. The washed and squeezed cake is transferred to an autoclave, to which a solution of 2.3 g of boric acid in 1 l of a 1.5% solution of nitric acid having a pH of 1.4 is added. The autoclave is heated to 150 ° C and incubated for 12 hours. Next, the autoclave is cooled to room temperature and the resulting suspension is dried on a spray dryer at an air temperature of 155 ° C at the inlet of the dryer and the suspension is continuously stirred; the dried powder is collected in the receiving container of the dryer. A weighed portion of 150 g of powder is placed in a trough of a mixer with лоп-shaped blades, peptized with a 2.5% aqueous ammonia solution, and then extruded at a pressure of 60.0 MPa through a die, providing particles with a cross section in the form of a trefoil with a diameter of the circumference described 1.6 mm. The formed 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 A1zB0 ₆ with a norbergite structure - 5.0; sodium - 0.03; y-A ^ Oz - the rest.

Next, a solution of the bimetallic complex compound [Ni (H20) 2] 2 [Mo4011 (C6H507) 2] is prepared, for which 48.91 g of citric acid C ₆ Hg0 _{7 are} successively dissolved in 100 ml of distilled water; 89.87 g of ammonium paramolybdate (ΝΗ ₄ ) ₆ Μο ₇ θ ₂₄ χ Η ₂ θ and 31.4 g of basic nickel carbonate Ν-СОz · mNi (OH) ₂ * nH ₂ 0. After complete dissolution of all components, adding distilled water the volume of the solution is adjusted to 200 ml.

100 g of the obtained support are impregnated with a moisture capacity of 67 ml of a solution of the bimetallic complex compound [Ni (H ₂ 0) ₂ ] ₂ [Mo40n (C ₆ H50 ₇ ) ₂ ] at 20 ° C for 60 min. Then the catalyst is dried in air at 100 ° C. The resulting catalyst contains May. %: [Ni (H20) 2] 2 [o ₄ 0n (C6H50 ₇ ) 2] - 32.4%; the carrier is the rest; wherein the medium contains May. %: aluminum borate A1zB0 ₆ with a norbergite structure - 5.0; sodium - 0.03; γ-Α1 ₂ 0 ₃ - the rest.

The catalyst has a specific surface area of 150 m ² / g, a pore volume of 0.55 cm ³ / g, an average pore diameter of 13 nm, and represents particles with a cross section in the form of a trefoil with a diameter of the circumscribed circle of 1.6 mm and a length of up to 20 mm. The aluminum borate A1 ₃ VO _b included in the catalyst with the structure of norbergite is a particle with sizes from 10 to 200 nm, characterized by interplanar distances of 3.2 and 2.8 A, with an angle between them of 53.8 °.

Next, the catalyst is sulfidized analogously to example 1.

The result is a catalyst that contains May. %: Mo - 12.5; Ni - 3.85; S is 8.3; the carrier is the rest; wherein the medium 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, hydrotreating the hydrocracking feed is carried out analogously to example 1.

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

Example 3

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

The result is a carrier containing May. %: aluminum borate A1 ₃ VO _b with norbergite structure - 12.0; sodium - 0.028; γ-Α1 ₂ 0 ₃ - the rest. 100 g of the obtained support are impregnated with a moisture capacity of 67 ml of a solution of the bimetallic complex compound [Νί (Η2θ) 2] 2 [θ4θι ι (0 ₆ Η ₅ Ο ₇ ) 2] from Example 2. Then, the catalyst is dried in air at 100 ° C.

The resulting catalyst contains May. %:

[Ni (H20) 2] ₂ [Mo40n (C ₆ H50 ₇ ) 2] - 32.4%; the carrier is the rest; wherein the medium contains May. %: aluminum borate Α1 ₃ Β0 ₆ with norbergite structure - 12.0; sodium - 0.028; u-oz - the rest.

Next, the catalyst is sulfidized analogously to example 1. The result is a catalyst that contains May. %: Mo - 12.5; Ni - 3.85; S is 8.3; the carrier is the rest; wherein the medium contains May. %: aluminum borate A1zB0 ₆ with the structure of norbergite - 12.0; sodium - 0.028; γ-A1 ₂ 0z - the rest.

Next, hydrotreating the hydrocracking feed is carried out analogously to Example 1. The results of testing the catalyst in hydrotreating are shown in the table.

Example 4

A support is prepared analogously to Example 2, with the difference that the washed and pressed cake is transferred to an autoclave, to which a solution of 14.63 g of boric acid in 1 liter of a 1.5% solution of nitric acid is added. The remaining operations and loading of components in the preparation of the media are similar to example 2.

The result is a carrier containing May. %: aluminum borate A1 ₃ VO _b with norbergite structure - 25.0; sodium - 0.023; γ-Α1 ₂ 0 ₃ - the rest. 100 g of the obtained support are impregnated with a moisture capacity of 66 ml of a solution of the bimetallic complex compound M1 (H ₂ 0) 2] 2 [o ₄ Op (C _b H ₅ 0 ₇ ) ₂ ] from Example 2. Then, the catalyst is dried in air at 200 ° C.

The resulting catalyst contains May. %:

[Ni (H ₂ 0) 2] 2 [Mo ₄ On (C ₆ H ₅ 0 ₇ ) 2] - 32.4%; the carrier is the rest; wherein the medium 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.

Next, the catalyst is sulfidized analogously to example 1.

The result is a catalyst that contains May. %: Mo - 12.5; Ni - 3.85; S is 8.3; the carrier is the rest; wherein the medium contains May. %: aluminum borate A1 ₃ B0 ₆ with the structure of norbergite - 25.0; sodium - 0.023; γ-A1g0 ₃ - the rest.

Example 5

Prepare the media as in example 3.

Then a solution of the bimetallic complex compound [Ni (H20) 2] 2 [Mo4011 (C6H507) 2] is prepared, for which 42.23 g of citric acid are successively dissolved in 100 ml of distilled water with stirring C ₆ H ₈ 07; 77.58 g of ammonium paramolybdate (NH ₄ ) ₆ Mo ₇ 0 ₂₄ x 4H ₂ 0 and 27.1 g of basic nickel carbonate NiCCV mNi (OH) 2 * nH ₂ 0. After complete dissolution of all components by adding distilled water, the solution volume is adjusted to 200 ml.

At room temperature, 100 g of the obtained support are impregnated with a moisture capacity of 67 ml of a solution of the bimetallic complex compound [Ni (H20) 2] 2 [Mo4011 (C6H507) 2]. Then the catalyst is dried in air at 120 ° C.

The resulting catalyst contains May. %: ^r i (H ₂ 0) 2] 2 [o ₄ 0 ₁₁ (C ₆ H ₅ 0 ₇ ) ₂ ] - 29.3%; the carrier is the rest; wherein the medium contains May. %: aluminum borate A1zB0 ₆ with the structure of norbergite - 12.0; sodium - 0.028; γ-Α1 ₂ 0 ₃ - the rest.

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 15 nm, and represents particles with a cross section in the form of a trefoil with a diameter of the circumscribed circle of 1.6 mm and a length of up to 20 mm.

The aluminum borate catalyst A1 ₃ B0 ₆ with the structure of norbergite, which is a 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 between them of 53.8 °.

Next, the catalyst is sulfidized analogously to example 1.

The result is a catalyst that contains May. %: Mo - 10.0;

Ni is 3.0; S 6.7; the carrier is the rest; wherein the medium contains May. %: aluminum borate A1 ₃ BEP with the structure of norbergite - 12.0; sodium - 0.028; γ-

ΑΙ2Ο3 - the rest.

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

Example 6

The carrier is prepared in the same manner as in Example 3, with the difference that the molding paste is extruded at a pressure of 60.0 MPa through a die, which provides particles with a cross-section in the form of a circle with a diameter of 1.0 mm.

Then a solution of the bimetallic complex compound [Ni (H20) 2] 2 [Mo4011 (C6H507) 2] is prepared, for which 56.9 g are successively dissolved in 100 ml of distilled water while heating to 80 ° C and with stirring. citric acid C ₆ H ₈ 0 ₇ ; 104.53 g of ammonium paramolybdate (NH4) ₆ Mo ₇ 0 ₂₄ x4H ₂ 0 and 36.5 g of basic nickel carbonate NiC0 ₃ ^» mNi (OH) 2 ^# nH ₂ 0. After all components are completely dissolved, the volume of the solution is adjusted by adding distilled water up to 200 ml.

Next, impregnation of the carrier from the excess solution is used. 100 g of the obtained carrier are loaded into a flask placed in a water bath heated to 80 ° C, 200 ml of a solution of the bimetallic complex compound [Ni (H20) 2] 2 [Mo4011 (C6H507) 2], also heated to 80 ° C, is poured into the flask . The impregnation is continued for 20 minutes with periodic stirring, after which the excess solution is separated from the wet catalyst. Then the catalyst is dried in air at 200 ° C.

The resulting catalyst contains May. %:

[Ni (H20) 2] 2 [Mo40n (C6H ₅ 0 ₇ ) ₂ ] - 35.8%; the carrier is the rest; wherein the medium contains May. %: aluminum borate ABBO _b with the structure of norbergite - 12.0; sodium - 0.028; y-A ^ Oz - the rest.

The catalyst has a specific surface area of 130 m / g, a pore volume of 0.35 cm / g, an average pore diameter of 10 nm, and represents particles 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. The aluminum borate Α1 ₃ Β0 ₆ with norbergite structure, which is part of the catalyst, is a particle with sizes from 10 to 200 nm, characterized by interplanar distances of 3.2 and 2.8 A, with an angle between them of 53.8 °.

Next, the catalyst is sulfidized analogously to example 1.

The result is a catalyst that contains May. %: Mo - 14.0; Ni - 4.3; S 9.4; the carrier is the rest; wherein the medium contains May. %: aluminum borate A1 ₃ B0 ₆ with the structure of norbergite - 12.0; sodium - 0.028; γ-A1 ₂ 0z - the rest.

Example 7

The carrier is prepared in the same manner as in Example 3, with the difference that the molding paste is extruded at a pressure of 60.0 MPa through a die, providing particles with a four-leaf cross-section with a diameter of 1.6 mm.

Next, impregnation of the carrier from the excess solution is used. 100 g of obtained the carrier is loaded into a flask placed in a water bath heated to 30 ° C, and 133 ml of a solution of the bimetallic complex compound ^ (НгОЭГЫ-пПСС _б Н _б С ^ г] from Example 5, also heated to 30 ° С, are poured into the flask. continue for 60 minutes with periodic 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. %:

[Ni (H20) 2] 2 [Mo40n (C ₆ H ₅ 0 ₇ ) 2] - 30.6%; the carrier is the rest; wherein the medium contains May. %: aluminum borate A1 ₃ B0 ₆ with the structure of norbergite - 12.0; sodium - 0.028; y-A ^ Oz - the rest.

The catalyst has a specific surface area of 175 m / g, a pore volume of 0.6 cm / g, an average pore diameter of 14 nm, and represents particles with a four-leaf cross-section with a diameter of the circumscribed circle of 1.6 mm and a length of up to 20 mm. The aluminum borate A1 ₃ B0 ₆ included in the catalyst with the structure of norbergite is a particle with sizes from 10 to 200 nm, characterized by interplanar distances of 3.2 and 2.8 A, with an angle between them of 53.8 °.

Next, the catalyst is sulfidized analogously to example 1.

The result is a catalyst that contains May. %: Mo - 1 1.7; Ni - 3.6; S 7.9; the carrier is the rest; wherein the medium contains May. %: aluminum borate A1 ₃ B0 ₆ with the structure of norbergite - 12.0; sodium - 0.028; γ-A1g0 ₃ - the rest.

Table. Residual sulfur and nitrogen in hydrotreated products

Thus, as can be seen from the above examples, the proposed catalyst, which contains, may. %: [Ni (H ₂ 0) 2] 2 [o ₄ On (C ₆ H50 ₇ ) 2] 29.0- 36.0, carrier — the rest; wherein the medium contains May. %: aluminum borate A1 ₃ VO _b with the structure of norbergite - 5.0-25.0; sodium - not more than 0.03; y-A ^ Oz - the rest; allows you to get raw materials for hydrocracking with a much lower sulfur and nitrogen content than using the prototype catalyst.

Claims

Claim

1. The catalyst for the hydrotreating of hydrocracking feedstocks, comprising nickel, molybdenum and a carrier, characterized in that it contains May. %: [Ni (H ₂ 0) 2] 2 [o ₄ 0n (C6H ₅ 0 ₇ ) ₂ ] 29.0-36.0%; the carrier is the rest; wherein the medium 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 the aluminum borate catalyst A1 ₃ B0 ₆ with the structure of norbergite is particles with sizes from 10 to 200 nm, characterized by interplanar distances of 3.2 and 2.8 A, with an angle between them of 53.8 ° .

3. The catalyst according to claim 1, characterized in that it has a specific surface area of 130-180 m ² / g, a pore volume of 0.35-0.65 cm ³ / g, an average pore diameter of 10-15 nm, and is a particle with a cross-section in the form of a circle, trefoil or four-leaf with a diameter of the circumscribed circle of 1.0-1.6 mm and a length of up to 20 mm.

4. The catalyst according to claim 1, characterized in that after sulfidation it contains, May. %: Mo - 10.0-14.0; Ni 3.0-4.3; S 6.7-9.4; the carrier is the rest; wherein the medium 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.