RU2633967C1 - Method of producing carrier for hydrotreating catalyst - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: method of producing a carrier containing, wt %: aluminium borate Al₃BO₆ with the structure of norbergite - 5.0-25.0; sodium - not more than 0.03; γ-Al₂O₃ - the rest, while aluminium borate Al₃BO₆ with the structure of norbergite is a particle with dimensions from 10 to 200 nm, characterized by interplanar distances of 3.2 and 2.8 Å, with an angle between them of 53.8°. The carrier has a specific surface area of 200-280 m²/g, a pore volume of 0.6-0.8 cm³/g, the average pore diameter is 7-12 nm and is a particle with a section in the form of a circle, trefoil, or quatrefoil with a diameter of the circumscribed circle of 1.0-1.6 mm and a length of up to 20 mm. The method of producing a carrier includes the following steps: grinding the thermal activation product of hydrargillite (gibbsite) Al(OH)₃ up to particles with an average size of 20-50 mcm; hydrating; washing to a residual sodium content of not more than 0.03 wt %; hydrothermal treating the suspension; spray drying; peptizing; extruding, drying and calcining at a temperature of not more than 600°C.

EFFECT: increasing the catalyst activity in the targeted reactions occurring during the hydrotreatment of hydrocarbon feedstocks.

10 cl, 1 tbl, 1 dwg, 7 ex

Description

The invention relates to methods for preparing carriers for hydrotreating catalysts designed to produce low sulfur oil products.

In connection with the transition of Russian oil refining to the production of motor fuels, in terms of sulfur content corresponding to EURO-5 standards and similar to Russian ones [GOST R 52368-2005 (EN 590-2004). Diesel fuel EURO. Technical conditions; GOST R 51866-2002 (EN 228-1999). Unleaded gasoline], there is an urgent need for highly active domestic supported 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 200 ppm sulfur. At the same time, the conditions for hydrotreating processes should be feasible at Russian refineries without their radical reconstruction.

Currently, the main method for the preparation of hydrotreating catalysts is the deposition of active metals, most often Co, Ni, and Mo on finished granular supports, while the properties of hydrotreating catalysts are largely determined by the preparation methods and the properties of the supports on the basis of which the supported catalysts are prepared [S. Eijsbouts, Hydrotreating catalysts, in: K.P. de Jong (Ed.), Synthesis of Solid Catalysts, VILEY-VCH Verlag GmbH & Co, KGa A, Weinheim, 2009, p. 302].

There are many different methods for the preparation of carriers for hydrotreating catalysts for petroleum distillates, which make it possible to obtain supports that are both pure alumina and containing various modifying additives, but a common disadvantage for them is the high residual sulfur content in the products obtained on catalysts prepared using carriers prepared by known methods.

The carrier is often modified with various additives, including boron compounds, using various methods of preparing the carrier — boron is introduced into the carrier by mixing aluminum hydroxide with a boron compound [Studies in Surface Science and Catalysis, Volume 91, 1995, Pages 833-842 ], either by coprecipitation from joint solutions [Journal of Catalysis 115 (1989) 441-451], or boron is introduced by impregnation into the molded alumina, followed by drying and calcination [Catalysis Today 107-108 (2005) 551-558].

A known carrier and a method of preparing a carrier described in the patent [US No. 6174432, C10G 45/04; B01J 21/04, 01/16/2001], according to which, first, aluminum hydroxide is produced 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, stage 4 — adding a 10% aqueous ammonia solution to pH = 11, stage 5 — stirring at 90 ° C for 25 hours, stage 6 — adding a 5n aqueous nitric acid solution to pH = 2, Stage 7 - mixing for 15 minutes, stage 8 - adding 10% aqueous ammonia solution 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 carrier and the method of preparation of the carrier are technologically very complex, while the resulting carrier has non-optimal texture characteristics — low specific surface area and pore diameter that is too high than necessary. As a result, the catalyst prepared on its basis has a low activity in hydrotreating.

и со средним размером частиц порошка 30-60 мкм, с водой, азотной или уксусной кислотой, соединением бора и как минимум одним кислородсодержащим органическим соединением, формуют через фильеру в форме трилистника при давлении до 10 МПа, сушат и прокаливают при температуре до 600°C, в результате чего получают носитель, содержащий, мас. %: В - 0,7-3,0; Al₂O₃ - остальное; имеющий удельную поверхность 170-300 м²/г, объем пор 0,5-0,95 см³/г и средний диаметр пор 7-22 нм, и представляющий собой частицы с сечением в виде трилистника с диаметром описанной окружности 1,0-1,6 мм и длиной до 20 мм.Closest to the proposed technical solution is described in [Pat. RF №2472585, B01J 23/882, 06/20/202013] the method of preparation of the medium. The method consists in the fact that the paste obtained by mixing AlOOH aluminum hydroxide powder having a boehmite or pseudoboehmite structure with a crystal size of 45-100

and with an average powder particle size of 30-60 μm, with water, nitric or acetic acid, a boron compound and at least one oxygen-containing organic compound, they are formed through a trefoil shaped die at a pressure of up to 10 MPa, dried and calcined at temperatures up to 600 ° C resulting in a carrier containing, by weight. %: B - 0.7-3.0; Al ₂ O ₃ - the rest; having a specific surface area of 170-300 m ² / g, a pore volume of 0.5-0.95 cm ³ / g and 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 main disadvantage of this method of preparation of the carrier is that the result is a carrier having a non-optimal chemical composition, which further leads to a catalyst having a low hydrotreatment activity.

The invention solves the problem of creating an improved method for preparing a carrier for a hydrotreating catalyst, characterized by the possibility of obtaining a carrier having:

1. Optimum chemical composition;

2. Optimum texture characteristics for hydrotreating catalysts;

3. The given size and shape of the granules.

EFFECT: obtaining a carrier, further use of which leads to a catalyst having maximum activity in target reactions occurring during hydrotreatment of hydrocarbon feedstocks.

The problem is solved by the method of preparation of the medium, which contains, by weight. %: Al ₃ BO ₆ - 5.0-25.0; sodium - not more than 0.03; γ-Al ₂ O ₃ - the rest, and has a specific surface area of 200-280 m ² / g, a pore volume of 0.6-0.8 cm ³ / g, an average pore diameter of 7-12 nm, and is a particle with a cross section of in the form of a circle, a trefoil or a four-leaf with a diameter of the circumscribed circle of 1.0-1.6 mm and a length of up to 20 mm.

- ПТАГ, измельчают до частиц со средним размером 20-50 мкм, затем гидратируют, промывают, подвергают гидротермальной обработке и распылительной сушке, проводят пептизацию при перемешивании водным раствором аммиака с аммиачным модулем не менее 0,075; экструдируют и после термообработки получают носитель, содержащий, мас. %: борат алюминия Al₃BO₆ со структурой норбергита - 5,0-25,0; натрий - не более 0,03; γ-Al₂O₃ - остальное. Входящий в состав носителя борат алюминия Al₃BO₆ со структурой норбергита представляет собой частицы с размерами от 10 до 200 нм, характеризующиеся межплоскостными расстояниями 3.2 и 2.8

, с углом между ними 53.8°.The carrier is prepared as follows: the product of thermal activation of hydrargillite -

- PTAG, crushed to particles with an average size of 20-50 microns, then hydrated, washed, subjected to hydrothermal treatment and spray drying, peptization is carried out with stirring with an aqueous solution of ammonia with an ammonia module of at least 0.075; extruded and after heat treatment receive a carrier containing, by weight. %: aluminum borate Al ₃ BO ₆ with norbergite structure - 5.0-25.0; sodium - not more than 0.03; γ-Al ₂ O ₃ - the rest. The aluminum borate Al ₃ BO _{6, which} is part of the support, 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

, with an angle between them of 53.8 °.

A product with the following characteristics is used as the initial PTAG: mass fraction of the X-ray amorphous phase,%, not less than 80; fraction of weight loss during calcination at (900 ± 20) ° C,% - 10-12; specific surface, m ² / g, not less than 120; total pore volume (moisture capacity), cm ³ / g, not less than 0.1; mass fraction of hydrargillite%, not more than 5; mass fraction of sodium,%, not more than 0.5.

PTH, crushed to particles with an average size of 20-50 microns, is hydrated with stirring in heated, weakly concentrated solutions of nitric acid.

PTH, after grinding to particles with an average size of 20-50 microns and hydration, are washed to a residual sodium content of not more than 0.03%.

PTH, after grinding to particles with an average size of 20-50 microns, hydration and washing to a residual sodium content of not more than 0.03%, is subjected to hydrothermal treatment in the form of a suspension in an aqueous solution of nitric and boric acids at a pH of more than 1.3, at a temperature at least 150 ° C for at least 4 hours in a sealed autoclave.

PTH, after grinding, hydration, washing and hydrothermal treatment, is spray dried at a temperature of the heat carrier gas of at least 150 ° C.

PTH, after grinding, hydration, washing, hydrothermal treatment, spray drying and peptization, is extruded at a pressure of not more than 10.0 MPa, through a die, providing particles with a cross-section in the form of a circle, trefoil or four-leaf with a circle diameter of 1.0- 1.6 mm.

The formed granules are dried at a temperature of not more than 120 ° C and calcined at a temperature of not more than 600 ° C.

The main distinguishing feature of the proposed method for the preparation of the carrier in comparison with the prototype is the chemical composition of the obtained carrier, namely the presence in the composition of the carrier of aluminum borate Al ₃ BO ₆ with norbergite structure with a concentration of 5.0-25.0 wt. % The output of the content of aluminum borate Al ₃ BO ₆ in the carrier beyond the claimed framework leads to the further production of a catalyst with reduced activity.

(ПТАГ), включающая измельчение, гидратацию, промывку, гидротермальную обработку, распылительную сушку, пептизацию, экструдирование и термообработку, обеспечивающая получение носителя, содержащего, мас. %: борат алюминия Al₃BO₆ со структурой норбергита - 5,0-25,0; натрий - не более 0,03; γ-Al₂O₃ - остальное; имеющего удельную поверхность 200-280 м²/г, объем пор 0,6-0,8 см³/г, средний диаметр пор 7-12 нм, и представляющего собой частицы с сечением в виде круга, трилистника или четырехлистника с диаметром описанной окружности 1,0-1,6 мм и длиной до 20 ммThe second distinguishing feature of the proposed method of preparation of the carrier in comparison with the prototype is the set of stages of processing the starting reagent - the product of thermal activation of hydrargillite (gibbsite)

(PTAG), including grinding, hydration, washing, hydrothermal treatment, spray drying, peptization, extrusion and heat treatment, providing a carrier containing, by weight. %: aluminum borate Al ₃ BO ₆ with norbergite structure - 5.0-25.0; sodium - not more than 0.03; γ-Al ₂ O ₃ - the rest; having a specific surface area of 200-280 m ² / g, a pore volume of 0.6-0.8 cm ³ / g, an average pore diameter of 7-12 nm, and representing particles with a cross-section in the form of a circle, trefoil or four-leaf with a diameter of the described circle 1.0-1.6 mm and up to 20 mm long

The technical result of the proposed method for preparing a carrier for a hydrotreating catalyst consists of the following components:

носителя, имеющего определенный химический состав, мас. %: борат алюминия Al₃BO₆ со структурой норбергита - 5,0-25,0; натрий - не более 0,03; γ-Al₂O₃ - остальное. Данный состав обеспечивает уровень кислотности носителя, способствующий минимизации нежелательного химического взаимодействия между активными металлами (Со и Мо) и дальнейшему селективному получению наиболее активного в гидроочистке сульфидного компонента - CoMoS фазы типа II.1. The inventive method leads to obtaining from the product of thermal activation of hydrargillite (gibbsite)

a carrier having a specific chemical composition, wt. %: aluminum borate Al ₃ BO ₆ with norbergite structure - 5.0-25.0; sodium - not more than 0.03; γ-Al ₂ O ₃ - the rest. This composition provides a level of acidity of the support, which helps minimize undesirable chemical interaction between active metals (Co and Mo) and further selectively produce the most active sulfide component in hydrotreatment — CoMoS type II phase.

(ПТАГ), включающие измельчение, гидратацию, промывку, гидротермальную обработку, распылительную сушку, пептизацию, экструдирование и термообработку, приводят к получению носителя, имеющего размер и форму гранул, обеспечивающие диффузию сырья по всему сечению гранулы при минимальном перепаде давления по реактору, а также текстурные характеристики, обеспечивающие доступ всех серосодержащих молекул сырья к сульфидному активному компоненту.2. The inventive combination and conditions of successive stages of processing the product of thermal activation of hydrargillite (gibbsite)

(PTAG), including grinding, hydration, washing, hydrothermal treatment, spray drying, peptization, extrusion and heat treatment, lead to the formation of a carrier having the size and shape of granules, ensuring the diffusion of raw materials over the entire cross section of the granule with a minimum pressure drop across the reactor, as well as textural characteristics that ensure access of all sulfur-containing raw material molecules to the sulfide active component.

Description of the proposed technical solution.

A support is prepared containing aluminum borate Al ₃ BO ₆ with the structure of norbergite and γ-Al ₂ O ₃ .

Take a portion of the product of thermal activation of hydrargillite (gibbsite) (PTAG) prepared by the centrifugal thermal activation technology (IC SB RAS, TU 2175-040-03533913-2007), or any other technology providing PTAG with the following characteristics: mass fraction of the X-ray amorphous phase, %, not less than 80; fraction of weight loss during calcination at (900 ± 20) ° C,% - 10-12; specific surface, m ² / g, not less than 120; total pore volume (moisture capacity), cm ³ / g, not less than 0.1; mass fraction of hydrargillite (gibbsite),%, 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 20-50 microns.

A weighed portion of the ground powder is hydrated with stirring for two hours in weakly concentrated nitric acid solutions heated to 50 ° C (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 nitric acid solutions 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 in a stream of hot air with continuous stirring of the feed suspension. The finished powder of boron-containing aluminum hydroxide is discharged from a glass of a cyclone dust collector of a spray dryer.

Next, prepare the molding mass by mixing and peptizing the obtained powder in a laboratory mixer with Z-shaped blades in the presence of an aqueous solution of ammonia. An ammonia solution was prepared so that the amount of 25% aqueous ammonia was 1.5 ml per 40 g of powder after spray drying.

The finished plastic mass is loaded 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 form of a trefoil or a four-leaf with a size from 1.0 to 1.6 mm from the top of the trefoil to the middle of the base.

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) ° C 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 were placed in an oven and calcined at a temperature of (550 ± 10) ° C for 4 hours.

The finished carrier contains, by weight. %: Al ₃ BO ₆ - 5.0-25.0; sodium - not more than 0.03; γ-Al ₂ O ₃ - the rest, and has a specific surface area of 200-280 m ² / g, a pore volume of 0.6-0.8 cm ³ / g, an average pore diameter of 7-12 nm, and is a particle with a cross section of in the form of a shamrock or four-leaf with a diameter of the circumscribed circle of 1.0-1.6 mm and a length of up to 20 mm

, угол между ними составляет 53.8°, что соответствует системам плоскостей (201) и (121) в кристаллической решетке Al₃BO₆.The presence in the composition of the carrier of aluminum borate Al ₃ BO ₆ with the structure of norbergite, sodium and γ-Al ₂ O ₃ in the claimed concentration range is confirmed by the data of elemental analysis, X-ray phase analysis (XRD) and high-resolution transmission electron microscopy (HRTEM). According to XRD data, the radiographs of the carrier contain characteristic peaks of γ-Al ₂ O ₃ 37.2; 39.5; 45.7 and 67.1 °; due to its high intensity, overlapping peaks of 37.5; 43.5; 63 and 68 °, characteristic for aluminum borate Al ₃ BO ₆ with a norbergite structure [Ceramic International, 32 (2006) 365], which are present on the X-ray diffraction patterns in the form of low-intensity lines, slightly exceeding the noise level. The presence of aluminum borate Al ₃ BO ₆ with a norbergite structure in the carrier is confirmed by TEMP data (Fig. TEMP image of the microstructure of an Al ₃ BO ₆ particle). On particles of Al ₂ O ₃ observed agglomerates of lamellar particles with sizes from 10 to 200 nm. When measuring interplanar distances, these particles belong to the Al ₃ BO ₆ phase (PDF Number: 26-8). So, according to the FFT image (presented in the tab on the drawing), distances 3.2 and 2.8 are observed on the TEMVR image

, the angle between them is 53.8 °, which corresponds to the systems of planes (201) and (121) in the Al ₃ BO ₆ crystal lattice.

Using this support, a supported catalyst is prepared. First, an impregnation solution is prepared containing the bimetallic complex compound [Co (H ₂ O) ₂ (C ₆ H ₅ O ₇ )] ₂ [Mo ₄ O ₁₁ (C ₆ H ₅ O ₇ ) ₂ ]. For this, the specified amounts of ammonium paramolybdate (NH ₄ ) ₆ Mo ₇ O⋅4Н ₂ O, cobalt (II) of the main carbonate CoCO ₃ ⋅mСо (OH) ₂ ⋅nН ₂ O, and 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. Set the speed of rotation of the stirrer 300 rpm and the temperature of the solution 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 temperature of the solution (60 ± 5) ° C. The solution is stirred until a uniform transparent solution is obtained containing the complex compound molybdenum (VI) citrate (NH ₄ ) ₄ [Mo ₄ (C ₆ H ₅ O ₇ ) ₂ O ₁₁ ]. A portion of cobalt (II) basic carbonate is added to the previously prepared aqueous solution of molybdenum (VI) citrate. In this case, the liquid foams, and its temperature rises to 70 ° C. Stirring is continued at (65-70) ° C until a homogeneous clear dark cherry solution is obtained that does not contain turbidity, bubbles and foam. The solution contains cobalt and molybdenum in the form of a bimetallic complex compound [Co (H ₂ O) ₂ (C ₆ H ₅ O ₇ )] ₂ [Mo ₄ O ₁₁ (C ₆ H ₅ O ₇ ) 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 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 drained from the catalyst and used to prepare the following batches of catalyst. After impregnation, the catalyst is dried in air at a temperature of 100-200 ° C.

As a result, get a catalyst containing, by weight. % [Co (H ₂ O) ₂ (C ₆ H ₅ O ₇ )] ₂ [Mo ₄ O ₁₁ (C ₆ H ₅ O ₇ ) ₂ ] 33.0-43.0%; the carrier is the rest; wherein the carrier contains, by weight. %: Al ₃ BO ₆ - 5.0-25.0; sodium - not more than 0.03; γ-Al ₂ O ₃ - the rest.

After sulfidation by known methods, the catalyst contains, by weight. %: Mo - 10.0-14.0; Co - 3.0-4.3; S 6.7-9.4; the carrier is the rest; wherein the carrier contains, by weight. %: Al ₃ BO ₆ - 5.0-25.0; sodium - not more than 0.03; γ-Al ₂ O ₃ - the rest.

The invention is illustrated by the following examples:

Example 1. According to a well-known solution [Pat. RF №2472585].

, со средним размером агломератов 30-40 мкм, содержащего примеси в количестве, мас. %, не более: Na₂O - 0,002; Fe₂O₃ - 0,01; SiO₂ - 0,015 при непрерывном перемешивании в смесителе с Z-образными лопастями добавляют 3 мл концентрированной азотной кислоты, 80 мл водного раствора, содержащего 7 г оксида бора В₂О₃ и 5 г кислородсодержащих соединений, в качестве которых используют смесь 2,5 г триэтиленгликоля и 2,5 г пентаэритрита. Весовые отношения компонентов смеси - гидроксид алюминия : вода : азотная кислота : оксид бора : кислородсодержащие соединения = 1:0,8:0,03:0,07: 0,05.To 100 g of AlOOH aluminum hydroxide powder having a boehmite structure with a crystal size of 45-60

, with an average agglomerate size of 30-40 microns, containing impurities in an amount, wt. %, no more: Na ₂ O - 0.002; Fe ₂ O ₃ - 0.01; SiO ₂ - 0.015 with continuous stirring in a mixer with Z-shaped blades add 3 ml of concentrated nitric acid, 80 ml of an aqueous solution containing 7 g of boron oxide B ₂ About ₃ and 5 g of oxygen-containing compounds, which use a mixture of 2.5 g triethylene glycol and 2.5 g of pentaerythritol. The weight ratio of the components of the mixture is aluminum hydroxide: water: nitric acid: boron oxide: oxygen-containing compounds = 1: 0.8: 0.03: 0.07: 0.05.

The resulting paste is stirred at 95 ° C for 10 min, then formed through a die with a cross section in the form of a trefoil with a diameter of the circumscribed circle of 1.6 mm at a pressure of 0.5 MPa. The obtained granules are dried in an oven at 150 ° C for 2 hours, then calcined at 600 ° C for 4 hours.

The result is a carrier containing B - 3.0 wt. %, 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, representing particles 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, having mechanical strength 2.0 kg / 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, 17.3 g of cobalt hydroxide Co (OH) ₂ , 7.5 g of ethylene glycol dimethyl ether. Then, by adding distilled water, the volume of the solution was adjusted to 150 ml.

20 g of the obtained carrier are impregnated with a moisture capacity of 10 ml of a solution containing 7.6 g of a 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 ] and 0.5 g of ethylene glycol dimethyl ether. The catalyst was dried in air at 250 ° C for 2 hours and sulfidized according to one of the known methods. In this case, the catalyst is sulfidated by straight-run diesel fraction containing an additional 1.5 wt. % 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 with a rate of temperature rise of 25 ° C / h;

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

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

- sulfidation at a temperature of 340 ° C for 8 hours

The resulting catalyst contains, by weight. %: Mo - 8.0; Co - 2.0; S is 5.0; B - 2.0; C is 0.5; Al ₂ O ₃ - the rest.

The catalyst is tested in hydrotreating diesel fuel containing 0.32% sulfur, 200 ppm nitrogen, having a density of 0.847 g / cm ³ , a boiling range of 210-360 ° C, T ₉₅ - 352 ° C. Hydrotreating conditions: the volumetric feed rate of 2.5 h ^-1 , the ratio of H ₂ / feed = 500 nm ³ N ₂ / m ^{3 of} feedstock, a pressure of 3.8 MPa, a temperature of 350 ° C.

The catalyst is also tested in hydrotreating a vacuum gas oil. Hydrotreating of vacuum gas oil (3.0% sulfur, 1200 ppm nitrogen, KK 560 ° C) is carried out at 370 ° C, a pressure of 9.0 MPa, a mass flow rate of vacuum gas oil of 1 h ^-1 , a volume ratio of hydrogen / feedstock of 500.

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 pressed cake is transferred to an autoclave, to which a solution of 2.3 g of boric acid in 1 liter 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 suspension obtained is dried on a spray dryer at an air temperature at the inlet of the dryer 155 ° C and the suspension is continuously stirred, the dried powder is collected in the receiving tank of the dryer. A sample of 150 g of powder is placed in a trough of a mixer with Z-shaped blades, peptized with a 2.5% aqueous solution of ammonia, 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, by weight. %: aluminum borate Al ₃ BO ₆ with the structure of norbergite - 5.0; sodium - 0.03; γ-Al ₂ O ₃ - the rest. Next, a solution of the bimetallic complex compound [Co (H ₂ O) ₂ (C ₆ H ₅ O ₇ )] ₂ [Mo ₄ O ₁₁ (C ₆ H ₅ O ₇ ) ₂ ] is prepared, for which in 100 ml of distilled water with stirring successively Dissolve 73.3 g of citric acid C ₆ H ₈ O ₇ , 89.87 g of ammonium paramolybdate (NH ₄ ) ₆ Mo ₇ O ₂₄ × 4H ₂ O and 30.1 g of cobalt (II) carbonic basic aqueous CoCO ₃ ⋅mСо ( OH) ₂ ⋅nH ₂ O. After complete dissolution of all components by adding distilled water, the volume of the solution was adjusted to 200 ml. 100 g of the obtained carrier are impregnated with a moisture capacity of 67 ml of a solution of the bimetallic complex compound [Co (H ₂ O) ₂ (C ₆ H ₅ O ₇ )] ₂ [Mo ₄ O ₁₁ (C ₆ H ₅ O ₇ ) ₂ ] at 20 ° C for 60 minutes. Then the catalyst is dried in air at 100 ° C.

The catalyst contains, by weight. %: [Co (H ₂ O) ₂ (C ₆ H ₅ O ₇ )] ₂ [Mo ₄ O ₁₁ (C ₆ H ₅ O ₇ ) ₂ ] - 38.4%; the carrier is the rest; wherein the carrier contains, by weight. %: aluminum borate Al ₃ BO ₆ with the structure of norbergite - 5.0; sodium - 0.03; γ-Al ₂ O ₃ - the rest.

, с углом между ними 53.8°.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 catalyst Al ₃ BO ₆ included in the composition with norbergite structure is a particle with sizes from 10 to 200 nm, characterized by interplanar distances of 3.2 and 2.8

, with an angle between them of 53.8 °.

Next, the catalyst is sulfidized analogously to example 1. The result is a catalyst that contains, by weight. %: Mo - 12.5; Co - 3.85; S is 8.3; the carrier is the rest; wherein the carrier contains, by weight. %: aluminum borate Al ₃ BO ₆ with the structure of norbergite - 5.0; sodium - 0.03; γ-Al ₂ O ₃ - the rest.

Next, carry out hydrotreating of hydrocarbon feeds analogously to example 1.

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

Example 3

The carrier is prepared according to a method similar 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, by weight. %: aluminum borate Al ₃ BO ₆ with a norbergite structure of -12.0; sodium - 0.028; γ-Al ₂ O ₃ - the rest. 100 g of the obtained carrier are impregnated with a moisture capacity of 67 ml of a solution of the bimetallic complex compound [Co (H ₂ O) ₂ (C ₆ H ₅ O ₇ )] ₂ [Mo ₄ O ₁₁ (C ₆ H ₅ O ₇ ) ₂ ] from Example 2. Then the catalyst is dried in air at 100 ° C.

The catalyst contains, by weight. %: [Co (H ₂ O) ₂ (C ₆ H ₅ O ₇ )] ₂ [Mo ₄ O ₁₁ (C ₆ H ₅ O ₇ ) ₂ ] - 38.4%; the carrier is the rest; wherein the carrier contains, by weight. %: aluminum borate Al ₃ BO ₆ with a norbergite structure of -12.0; sodium - 0.028; γ-Al ₂ O ₃ - the rest.

Next, the catalyst is sulfidized analogously to example 1. The result is a catalyst that contains, by weight. %: Mo - 12.5; Co - 3.85; S is 8.3; the carrier is the rest; wherein the carrier contains, by weight. %: aluminum borate Al ₃ BO ₆ with the structure of norbergite - 12.0; sodium - 0.028; γ-Al ₂ O ₃ - the rest.

Next, carry out hydrotreating of hydrocarbon feeds analogously to example 1.

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

Example 4

The carrier is prepared according to a method similar 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, by weight. %: aluminum borate Al ₃ BO ₆ with the structure of norbergite - 25.0; sodium - 0.023; γ-Al ₂ O ₃ - the rest. 100 g of the obtained carrier are impregnated with a moisture capacity of 66 ml of a solution of the bimetallic complex compound [Co (H ₂ O) ₂ (C ₆ H ₅ O ₇ )] ₂ [Mo ₄ O ₁₁ (C ₆ H ₅ O ₇ ) ₂ ] from Example 2. Then the catalyst is dried in air at 200 ° C.

The catalyst contains, by weight. %: [Co (H ₂ O) ₂ (C ₆ H ₅ O ₇ )] ₂ [Mo ₄ O ₁₁ (C ₆ H ₅ O ₇ ) ₂ ] - 38.4%; the carrier is the rest; wherein the carrier contains, by weight. %: aluminum borate Al ₃ BO ₆ with the structure of norbergite - 25.0; sodium - 0.023; γ-Al ₂ O ₃ - the rest.

Next, the catalyst is sulfidized analogously to example 1. The result is a catalyst that contains, by weight. %: Mo - 12.5; Co - 3.85; S is 8.3; the carrier is the rest; wherein the carrier contains, by weight. %: aluminum borate Al ₃ BO ₆ with the structure of norbergite - 25.0; sodium - 0.023; γ-Al ₂ O ₃ - the rest.

Next, carry out hydrotreating of hydrocarbon feeds analogously to example 1.

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

Example 5

The carrier is prepared in the same manner as in Example 3. A solution of the bimetallic complex compound [Co (H ₂ O) ₂ (C ₆ H ₅ O ₇ )] ₂ [Mo ₄ O ₁₁ (C ₆ H ₅ O ₇ ) ₂ ] is prepared, for which, in 100 ml of distilled water, 63.27 g of citric acid C ₆ H ₈ O _{7 are} successively dissolved with stirring; 77.58 g of ammonium paramolybdate (NH ₄ ) ₆ Mo ₇ O ₂₄ × 4H ₂ O and 26.0 g of cobalt (II) carbonic basic aqueous CoCO ₃ * mСо (ОН) ₂ НnН ₂ O. After complete dissolution of all components by adding distilled water the volume of the solution was adjusted to 200 ml.

100 g of the obtained carrier at room temperature are impregnated with a moisture capacity of 67 ml of a solution of the bimetallic complex compound [Co (H ₂ O) ₂ (C ₆ H ₅ O ₇ )] ₂ [Mo ₄ O ₁₁ (C ₆ H ₅ O ₇ ) ₂ ]. Then the catalyst is dried in air at 120 ° C.

The catalyst contains, by weight. %: [Co (H ₂ O) ₂ (C ₆ H ₅ O ₇ )] ₂ [Mo ₄ O ₁₁ (C ₆ H ₅ O ₇ ) ₂ ] - 32.7%; the carrier is the rest; wherein the carrier contains, by weight. %: aluminum borate Al ₃ BO ₆ with the structure of norbergite - 12.0; sodium - 0.028; γ-Al ₂ O ₃ - the rest.

, с углом между ними 53.8°.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 Al ₃ BO ₆ included in the composition with norbergite structure is a particle with sizes from 10 to 200 nm, characterized by interplanar distances of 3.2 and 2.8

, with an angle between them of 53.8 °.

Next, the catalyst is sulfidized analogously to example 1. The result is a catalyst that contains, by weight. %: Mo - 10.0; Co - 3.0; S 6.7; the carrier is the rest; wherein the carrier contains, by weight. %: aluminum borate Al ₃ BO ₆ with the structure of norbergite - 12.0; sodium - 0.028; γ-Al ₂ O ₃ - the rest.

Next, carry out hydrotreating of hydrocarbon feeds analogously to example 1.

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, providing particles with a cross-section in the form of a circle with a diameter of 1.0 mm.

A solution of the bimetallic complex compound [Co (H ₂ O) ₂ (C ₆ H ₅ O ₇ )] ₂ [Mo ₄ O ₁₁ (C ₆ H ₅ O ₇ ) ₂ ] is prepared, for which 100 ml of distilled water is heated to 80 ° C and with stirring, 85.3 g of citric acid C ₆ H ₈ O _{7 are} successively dissolved; 104.53 g of ammonium paramolybdate (NH) ₆ Mo ₇ O ₂₄ × 4H ₂ O and 35.05 g of cobalt (II) carbonic basic aqueous CoCO ₃ ⋅mСо (ОН) ₂ ⋅nН ₂ O. After complete dissolution of all components by addition of distilled water, the solution volume is adjusted to 200 ml.

Next, impregnation of the carrier from 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 [Co (H ₂ O) ₂ (C ₆ H ₅ O ₇ )] ₂ [Mo ₄ O ₁₁ (C ₆ H ₅ O ₇ ) ₂ ], also heated to 80 ° C. 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 catalyst contains, by weight. %: [Co (H ₂ O) ₂ (C ₆ H ₅ O ₇ )] ₂ [Mo ₄ O ₁₁ (C ₆ H ₅ O ₇ ) ₂ ] 42.95%; the carrier is the rest; wherein the carrier contains, by weight. %: aluminum borate Al ₃ BO ₆ with the structure of norbergite - 12.0; sodium - 0.028; γ-Al ₂ O ₃ - the rest.

, с углом между ними 53.8°.The catalyst has a specific surface area of 130 m ² / g, a pore volume of 0.35 cm ³ / 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 catalyst Al ₃ BO ₆ included in the composition with norbergite structure is a particle with sizes from 10 to 200 nm, characterized by interplanar distances of 3.2 and 2.8

, with an angle between them of 53.8 °.

Next, the catalyst is sulfidized analogously to example 1. The result is a catalyst that contains, by weight. %: Mo - 14.0; Co - 4.3; S 9.4; the carrier is the rest; wherein the carrier contains, by weight. %: aluminum borate Al ₃ BO ₆ with the structure of norbergite - 12.0; sodium - 0.028; γ-Al ₂ O ₃ - the rest.

Next, carry out hydrotreating of hydrocarbon feeds analogously to example 1.

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

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 cross section in the form of a four-leaf with a diameter of 1.6 mm.

Next, impregnation of the carrier from excess solution is used. 100 g of the obtained carrier are 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 O) ₂ (C ₆ H ₅ O ₇ )] ₂ [Mo ₄ O ₁₁ (C ₆ H ₅ O ₇ ) ₂ ] from Example 5, also heated to 30 ° C. The impregnation is continued 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 catalyst contains, by weight. %: [Co (H ₂ O) ₂ (C ₆ H ₅ O ₇ )] ₂ [Mo ₄ O ₁₁ (C ₆ H ₅ O ₇ ) ₂ ] - 35.9%; the carrier is the rest; wherein the carrier contains, by weight. %: aluminum borate Al ₃ BO ₆ with the structure of norbergite - 12.0; sodium - 0.028; γ-Al ₂ O ₃ - the rest.

, с углом между ними 53.8°.The catalyst has a specific surface area of 175 m ² / g, a pore volume of 0.6 cm ³ / 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 catalyst Al ₃ BO ₆ included in the composition with norbergite structure is a particle with sizes from 10 to 200 nm, characterized by interplanar distances of 3.2 and 2.8

, with an angle between them of 53.8 °.

Next, the catalyst is sulfidized analogously to example 1. The result is a catalyst that contains, by weight. %: Mo - 11.7; Co - 3.6; S 7.9; the carrier is the rest; wherein the carrier contains, by weight. %: aluminum borate Al ₃ BO ₆ with the structure of norbergite - 12.0; sodium - 0.028; γ-Al ₂ O ₃ - the rest.

Next, carry out hydrotreating of hydrocarbon feeds analogously to example 1.

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

, с углом между ними 53.8°, имеет высокую активность в гидроочистке углеводородного сырья, значительно превосходящую активность катализатора, в процессе приготовления которого использовался носитель, приготовленный по способу-прототипу.Thus, as can be seen from the above examples, the catalyst, in the process of preparation of which the carrier is used, prepared by the claimed method, due to its chemical composition and texture due to the presence in the composition in the given concentrations of aluminum borate Al ₃ BO ₆ with the structure of norbergite, which is a particle with sizes from 10 to 200 nm, characterized by interplanar distances of 3.2 and 2.8

, with an angle between them of 53.8 °, has a high activity in the hydrotreatment of hydrocarbons, significantly superior to the activity of the catalyst, in the process of preparation of which was used a carrier prepared by the prototype method.

Claims (10)

1. A method of preparing a carrier for a hydrotreating catalyst containing alumina and a boron compound, characterized in that the thermal activation product of hydrargillite — Al (OH) ₃ — PTAG — is crushed to particles with an average size of 20-50 microns, then hydrated, washed, subjected hydrothermal treatment and spray drying, peptization is carried out with stirring with an aqueous solution of ammonia with an ammonia module of at least 0.075; extruded and after heat treatment receive a carrier containing, wt.%: aluminum borate Al ₃ BO ₆ with the structure of norbergite - 5.0-25.0; sodium - not more than 0.03; γ-Al ₂ O ₃ - the rest. 2. The method according to p. 1, characterized in that the resulting carrier has a specific surface area of 200-280 m ² / g, a pore volume of 0.6-0.8 cm ³ / 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 four-leaf with a diameter of the circumscribed circle of 1.0-1.6 mm and a length of up to 20 mm. 3. The method according to p. 1, characterized in that the aluminum borate Al ₃ BO ₆ included in the support with the structure of norbergite is particles with sizes from 10 to 200 nm, characterized by interplanar distances of 3.2 and 2.8

, with an angle between them of 53.8 °. 4. The method according to p. 1, characterized in that as the initial PTAG use a product with the following characteristics: mass fraction of the X-ray amorphous phase,%, not less than 80; fraction of weight loss during calcination at (900 ± 20) ° C,% - 10-12; specific surface, m ² / g, not less than 120; total pore volume (moisture capacity), cm ³ / g, not less than 0.1; mass fraction of hydrargillite,%, not more than 5; mass fraction of sodium,%, not more than 0.5. 5. The method according to p. 1, characterized in that the PTAG, crushed to particles with an average size of 20-50 microns, is hydrated with stirring in heated, weakly concentrated solutions of nitric acid. 6. The method according to p. 1, characterized in that the CTAG after grinding to particles with an average size of 20-50 microns and hydration is washed to a residual sodium content of not more than 0.03%. 7. The method according to p. 1, characterized in that the CTAG after grinding to particles with an average size of 20-50 microns, hydration and washing to a residual sodium content of not more than 0.03% is subjected to hydrothermal treatment in the form of a suspension in an aqueous solution of nitrogen and boric acids at a pH of more than 1.3, at a temperature of at least 150 ° C for at least 4 hours in a sealed autoclave. 8. The method according to p. 1, characterized in that the CTAG after grinding, hydration, washing and hydrothermal treatment is spray dried at a temperature of the carrier gas of at least 150 ° C. 9. The method according to p. 1, characterized in that the CTAG after grinding, hydration, washing, hydrothermal treatment, spray drying and peptization is extruded at a pressure of not more than 10.0 MPa through a die, providing particles with a cross section in the form of a circle, trefoil or a four leaf with a diameter of the circumscribed circle of 1.0-1.6 mm. 10. The method according to p. 1, characterized in that the formed granules are dried at a temperature of not more than 120 ° C and calcined at a temperature of not more than 600 ° C.

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