RU2846439C1 - Use of catalyst containing aluminium oxide spheroidal particles in heterogeneous processes - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: invention can be used in chemical engineering during catalytic reforming and dehydrogenation of gaseous hydrocarbons. Invention discloses use of a catalyst in heterogeneous processes, said catalyst containing, based on the total weight of the catalyst, 0.1–4.5 wt. % of group VIII element of periodic table; from 0.1 wt. % to 6.0 wt. % of group I and/or II element of periodic table; from 0.2 wt. % to 6.0 wt. % of halogen and spheroidal particles of aluminium oxide with specific pore volume from 0.50 cm³/g to 0.75 cm³/g, specific surface area from 85 m²/g to 125 m²/g, calculated pore diameter from 12 nm to 28 nm and crushing strength of at least 35 N/granule and spheroidality criterion of at least 0.92.

EFFECT: higher crushing strength and wear resistance.

17 cl, 2 dwg, 1 tbl, 13 ex

Description

Field of technology to which the invention relates

The present invention relates to the use of a catalyst containing spheroidal particles of aluminum oxide in various heterogeneous processes, such as catalytic reforming, dehydrogenation of gaseous hydrocarbons, etc.

State of the art

Light olefins (ethylene, propylene and butene) are valuable components of the petrochemical industry. Such olefins are used especially actively in the polymer industry. Products containing polypropylene, polyethylene, as well as copolymers of propylene, ethylene and butene, have good performance characteristics and are used everywhere, for example, in the production of cables, household appliances, pipes, etc.

One of the common methods for producing light olefins in industry is the dehydrogenation of gaseous C ₂ -C ₄ hydrocarbons in the presence of catalysts. Heterogeneous catalysts containing an element of group VIII of the Periodic Table of D.I. Mendeleyev (hereinafter referred to as the Periodic Table) as an active component are widely used as dehydrogenation catalysts. The active component is applied to a carrier, which is aluminum oxide, aluminosilicate, or another synthetic carrier. In addition to the active component, other components are applied to the carrier that are not active in the catalytic dehydrogenation process, but allow improving the performance characteristics of the catalyst, in particular, the service life of the catalyst. Some of such components are elements of group IV of the Periodic Table, for example, tin. Such components, as is known from the prior art, incl. from documents US3998900 (published 21.12.1976, applicant UNIVERSAL OIL PROD CO [US]) and US3909451 (published 30.09.1975, applicant UNIVERSAL OIL PROD CO [US]), prevent the formation of large platinum nanoparticles during operation. The introduction of additional components into the catalyst composition allows maintaining high dispersion of the active component on the surface of the corresponding carrier and, therefore, maintaining high catalyst activity over time. In addition to group IV elements, other components are applied to the carrier: alkali metals, alkaline earth metals, lanthanides, halogens, etc.

One of the important components of the catalyst for the dehydrogenation of gaseous _C2 - _C4 hydrocarbons is the carrier.

When using spheroidal aluminum oxide particles as a carrier, they must have not only a developed porous structure and a large specific surface area, but also high mechanical strength.

Mechanical strength, in particular crushing strength and abrasion resistance, is a key parameter to be taken into account for the considered application of aluminum oxide particles in catalysis. When used, for example, in a fluidized or moving bed, the particles are subject to impacts and friction phenomena that can cause the formation of fine particles that pose a risk of clogging of installations or filters and that also contribute to the loss of part of the catalyst.

Therefore, it is important to obtain aluminum oxide particles that have both low density and good mechanical strength.

In addition, especially when used in fluidized bed catalysis, uniformity of the size and shape of the aluminum oxide particles is also important to ensure the fluidity of the catalyst.

Thus, application CN115364837 (published on 22.11.2022 by CHINA PETROLEUM & CHEM CORP [CN]; SINOPEC CORP RES INST PETROLEUM PROCESSING [CN]) proposes macroporous spherical aluminum oxide particles with a specific surface area of 223-260 ^m2 /g, a pore volume of 0.7-0.9 ^cm3 /g, characterized by a sphericity index of more than 0.95 based on more than 90 vol.% of all particles. The invention also relates to a method for producing spherical aluminum oxide particles, comprising the following steps:

1) peptization of pseudoboehmite with an acid solution to obtain an aluminum oxide sol;

2) feeding aluminum oxide sol dropwise into the oil/ammonia column to form gel beads;

3) unloading of gel beads from the bottom of the oil/ammonia column, dynamic washing with washing liquid until the disappearance of the residual oil phase and ammonia in the washing liquid at a temperature of 20-50°C;

4) aging the balls in fatty alcohol for 4-36 hours at a temperature from 60°C to the boiling point of the alcohol;

5) unloading of granules followed by drying and calcination.

The disadvantage of the proposed method is the high energy costs for heating the washing liquid and fatty alcohol, as well as the long stage of keeping the spherical particles in fatty alcohol, which reduces the overall productivity of the process.

Since the dehydrogenation catalyst is used in a moving bed mode (pneumatic lifting), it is important to obtain a catalyst carrier that has high mechanical crushing strength, i.e., capable of maintaining its shape when exposed to various significant impact and shear loads.

Disclosure of the Invention

The objective of the present invention is to use a catalyst containing spheroidal particles of aluminum oxide for a new purpose, namely as a catalyst in heterogeneous processes.

The technical result of the present invention is the use of a catalyst containing spheroidal particles of aluminum oxide, characterized by high mechanical crushing strength and wear resistance when moving in a moving bed mode, in heterogeneous processes.

Highly porous, mechanically strong spheroidal particles of aluminum oxide with a mesoporous structure and a pore diameter range from 12 to 28 nm are suitable for use as a catalyst carrier in various catalytic processes, such as catalytic reforming, dehydrogenation of gaseous hydrocarbons, etc. In turn, the catalyst obtained on the basis of the described spheroidal particles of aluminum oxide has high catalytic characteristics, has high wear resistance when conducting abrasion tests in a moving bed.

Description of figures

FIG. 1 illustrates a schematic diagram of a setup for testing the wearability index of a carrier.

FIG. 2 illustrates the results of determining the wear index of the carrier.

Detailed description of the invention

The following is a detailed description of various aspects and embodiments of the present invention.

The present invention relates to the use of a catalyst containing spheroidal particles of aluminum oxide in heterogeneous processes, for example, in processes of catalytic reforming, hydrocracking, hydrogenation, dehydrogenation, dehydrocyclization of hydrocarbons or other organic compounds. More preferably, the use of said catalyst for processes of catalytic reforming and dehydrogenation of C ₂ -C ₄ gaseous hydrocarbons.

The catalyst contains, based on the total mass of the catalyst:

- from 0.1 to 4.5 mass% of an element of group VIII of the Periodic Table;

- from 0.1 to 6.0 mass% of an element of group I and/or II of the Periodic Table;

- from 0.2 to 6.0 mass% halogen;

- spheroidal particles of aluminum oxide.

In some embodiments, the catalyst comprises from 0.15 to 2 wt.%, preferably from 0.15 to 0.8 wt.%, of an element of Group VIII of the Periodic Table, based on the total weight of the catalyst.

In some embodiments, the content of an element of group I and/or II of the Periodic Table in the catalyst according to the invention may be from 0.2 to 3 wt.%, preferably from 0.5 to 2 wt.%.

In some embodiments, the halogen content of the catalyst according to the invention may be from 0.2 to 3 wt.%, preferably from 0.2 to 2 wt.%.

Preferably, the catalyst contains, based on the total weight of the catalyst:

- from 0.15 to 2 mass% of an element of group VIII of the Periodic Table;

- from 0.2 to 3 mass% of an element of group I and/or II of the Periodic Table;

- from 0.2 to 3% by weight of halogen;

- spheroidal particles of aluminum oxide - the rest, where the spheroidal particles of aluminum oxide contain from 0.05 to 0.40 mass% of an element of group IV of the Periodic Table.

Most preferably, the catalyst contains, based on the total weight of the catalyst:

- from 0.15 to 0.8 mass% of an element of group VIII of the Periodic Table;

- from 0.5 to 2 mass% of an element of group I and/or II of the Periodic Table;

- from 0.2 to 2 mass% halogen;

- spheroidal particles of aluminum oxide - the rest, where the spheroidal particles of aluminum oxide contain from 0.15 to 0.25 mass% of an element of group IV of the Periodic Table.

The catalyst may also contain other components that further increase its service life, activity, or selectivity. Examples of such additives include, but are not limited to: rhenium, gallium, cerium, lanthanum, europium, indium, phosphorus, nickel, iron, tungsten, molybdenum, zinc, cadmium, and others. Catalytically effective amounts of these components typically range from 0.01 to 5 wt.% and may be added to the catalyst by any suitable method during or after catalyst preparation, either separately or in a mixture.

The following elements may be used as the element of Group VIII of the Periodic Table: platinum, palladium, ruthenium, rhodium, iridium, osmium or mixtures thereof. In the catalyst, the element of Group VIII may be present as a compound such as an oxide, sulfide, halide, or oxyhalide, in chemical combination with one or more other ingredients of the composite or as an elemental metal. The preferred element of Group VIII is platinum.

In some embodiments, the catalyst comprises from 0.15 to 2 wt.%, preferably from 0.15 to 0.8 wt.%, of an element of Group VIII of the Periodic Table, based on the total weight of the catalyst.

The following elements can be used as elements of groups I and II of the Periodic Table: calcium, potassium, sodium, magnesium, lithium, strontium, barium, beryllium or mixtures thereof. The preferred element is potassium.

In some embodiments, the content of an element of group I and/or II of the Periodic Table in the catalyst may be from 0.2 to 3 wt.%, preferably from 0.5 to 2 wt.%.

An element of group VII of the Periodic Table, such as chlorine, bromine, is used as a halogen; chlorine is preferably used.

In some embodiments, the halogen content of the catalyst may be from 0.2 to 3 wt.%, preferably from 0.2 to 2 wt.%.

According to the present invention, a catalyst based on spheroidal particles of aluminum oxide with an average diameter of from about 0.2 to about 10 mm, preferably from about 0.5 to about 5 mm, most preferably from about 1 to about 3 mm is used.

The term "spheroidal" means that the majority of the catalyst particles are spheroidal in shape with minor variations, where "majority" means at least more than 80% of the particles, preferably more than 90% of the particles, more preferably more than 95% of the particles.

The spheroidal particles of aluminum oxide have a specific pore volume of 0.50 to 0.75 ^cm3 /g, a specific surface area of 85 to 125 ^m2 /g, a calculated pore diameter of 12 to 28 nm and a crushing strength of at least 35 N/granule, and are also characterized by a spheroidality criterion of at least 0.80.

The spheroidal aluminum oxide particles have a specific pore volume of from 0.50 to 0.75 ^cm3 /g, preferably from 0.55 to 0.70 ^cm3 /g, more preferably from 0.60 to 0.65 ^cm3 /g.

The spheroidal aluminum oxide particles have a specific surface area of 85 to 125 ^m2 /g, preferably 90 to 110 ^m2 /g, more preferably 95 to 105 ^m2 /g.

The spheroidal alumina particles are characterized by a calculated pore diameter of 12 to 28 nm, preferably 15 to 25 nm, more preferably 18 to 21 nm.

The spheroidal particles of aluminum oxide are characterized by a mechanical crushing strength of at least 35 N/granule, preferably at least 40 N/granule, more preferably at least 45 N/granule.

The spheroidal particles of aluminum oxide are characterized by a bulk density of from 0.50 to 0.75 g/ ^cm3 , preferably from 0.55 to 0.70 g/ ^cm3 , more preferably from 0.60 to 0.65 g/ ^cm3 .

The spheroidal alumina particles have an average diameter of from about 0.2 to about 10 mm, preferably from about 0.5 to about 5 mm, most preferably from about 1 to about 3 mm.

The aluminum oxide particles used are spheroid, i.e. have a shape close to a sphere. Thus, the majority of the aluminum oxide particles have a spheroid shape with minor deviations, where "the majority" means at least more than 80% of the particles, preferably more than 90% of the particles, more preferably more than 95% of the particles.

The spheroidal aluminum oxide particles used are characterized by a spheroidality criterion of at least 0.80, preferably at least 0.90, more preferably at least 0.92.

The spheroidality criterion is understood as the ratio of the maximum and minimum Feret diameters (K _sph = d _Fmax / d _Fmin ).

The Feret diameter (d _F ) is the distance between two parallel tangents that touch the projection of the particle on opposite sides of it. The tangents must not intersect the edge of the projection of the particle at any point.

The maximum d _Fmax and minimum d _Fmin Feret diameters are measured by rotating the tangents from 0 to 360° (relative to any direction of the particle). The measurements are carried out using an optical method, for example, on the Analysette 28 Imagesizer device. A sample of calcined spheroidal particles of aluminum oxide is poured into a specialized chamber of the device and the length of the sides of the granules and the number of granules are measured using the camera. Then the program calculates the percentage of spheroidal particles in the sample from the data obtained.

The spheroidal particles of aluminum oxide contain an element of group IV of the Periodic Table in an amount of from 0.05 to 0.50 mass%, preferably from 0.10 to 0.40 mass%, most preferably from 0.15 to 0.25 mass%.

The following elements can be used as elements of group IV of the Periodic Table: tin, germanium, lead or mixtures thereof. Preferably, tin is used. In addition to elements of group IV of the Periodic Table, other elements known from the prior art as elements improving the performance characteristics of the catalyst, such as gallium, indium, zinc, manganese or mixtures thereof, can also be present in the spheroidal particles according to the present invention, in a total amount of up to 1.5 wt.% of the catalyst mass.

Implementation of the invention

The present invention is more particularly described in the following examples, which are given solely to illustrate the present invention and do not limit it.

In accordance with the present invention, the mechanical crushing strength is determined using a single-column benchtop universal testing machine Lloyd Instruments LS1 (LFPlus) in accordance with the method described in the standard ASTM D4179-11. The average crushing strength is determined based on the results of crushing at least 100 particles of the sample. It is possible to analyze a larger number of particles in order to increase the accuracy of determining the mechanical crushing strength.

Example 1 (comparative). Obtaining spheroidal particles of aluminum oxide by the hydrocarbon-ammonia molding method.

The acquisition included the following stages:

a) The molding solution was obtained by adding 2 g of tin chloride, 50 g of hydrochloric acid to 2000 g of water;

b) The solution was stirred until completely dissolved using a planetary mixer at a stirring speed of 100 rpm;

c) 300 g of pseudoboehmite was added to the molding solution and the molding mixture was dispersed to a homogeneous state using a planetary mixer with a mixing speed of 300 rpm. The pH of the molded mass was 3.0;

d) Then the molding mixture was pumped into the column using a peristaltic pump through a special flow distributor into uniform drops. The upper part of the column was filled with a 10 cm high layer of petroleum solvent, the lower part of the column was filled with a 0.6 wt.% solution of Tween-80 in a water-ammonia mixture containing 25 wt.% ammonia. The obtained precursors of spheroidal particles were left in the column for 4 hours. Then the solution was displaced with petroleum solvent;

e) The petroleum solvent was displaced with distilled water, then the particles were washed with water for 180 minutes;

f) After washing, the particles were dried stepwise at 40°C for 8 h, then at 150°C for 6 h. After drying, the particles were calcined stepwise at 450°C for 2 h, then at 1000°C for 2 h, heating rate 3°C/min.

Spheroidal particles of aluminum oxide with a specific surface area of 80 ^m2 /g, a specific pore volume of 0.52 ^cm3 /g, a pore diameter of 10 nm, and a mechanical crushing strength of 25 N/granule were obtained. The spheroidality criterion of the obtained particles was 0.80. The mass fraction of spheroidal particles was 50%. The remaining particles were rough, non-spheroidal particles.

Example 2. Obtaining spheroidal particles of aluminum oxide by the method of cold hydrocarbon-ammonia molding.

The acquisition included the following stages:

a) The molding solution was prepared by adding 2 g of tin chloride, 50 g of hydrochloric acid and 1.5 g of citric acid to 2000 g of water;

b) The solution was stirred until completely dissolved using a planetary mixer at a stirring speed of 100 rpm;

c) 400 g of pseudoboehmite was added to the molding solution and the molding mixture was dispersed to a homogeneous state using a planetary mixer with a mixing speed of 300 rpm. The pH of the molded mass was 3.0;

d) Then the molding mixture was pumped into the column through a special flow distributor into uniform drops using a peristaltic pump. The upper part of the column was filled with a 10 cm high layer of kerosene, the lower part of the column was filled with a 0.1 wt.% solution of stearic acid in an aqueous ammonia mixture containing 10 wt.% ammonia. The obtained precursors of spheroidal particles were left to stand in a solution of fatty acid in an aqueous ammonia mixture for 15 hours. Then the solution was displaced with hydraulic oil;

e) The hydraulic oil was displaced with a 6 wt% aqueous solution of polyethylene oxide, and then the particles were washed with this solution for 240 minutes;

f) After washing, the particles were dried stepwise at a temperature of 40°C for 8 h, then at a temperature of 150°C for 6 h. After drying, the particles were calcined stepwise at a temperature of 450°C for 2 h, then at a temperature of 1000°C for 2 h, heating rate 3°C min.

Spheroidal particles of aluminum oxide with a specific surface area of 100 ^m2 /g, a specific pore volume of 0.70 ^cm3 /g, a pore diameter of 23 nm, and a mechanical crushing strength of 40 N/granule were obtained. The spheroidality criterion of the obtained particles was 0.96. The mass fraction of spheroidal particles was 98%.

Example 3

In this example, unlike Example 2, at stage a) citric acid was replaced with oxalic acid, and at stage e) 6 wt.% polyethylene oxide solution was replaced with 4 wt.% polyacrylamide solution.

Spheroidal particles of aluminum oxide with a specific surface area of 105 ^m2 /g, a specific pore volume of 0.68 ^cm3 /g, a pore diameter of 20 nm, and a mechanical crushing strength of 50 N/granule were obtained. The spheroidality criterion of the obtained particles was 0.96. The mass fraction of spheroidal particles was 98%.

Example 4

In this example, in contrast to Example 2, at stage a) hydrochloric acid was replaced with nitric acid, at stage e) the precursors of spheroidal particles were washed for 120 min, at stage d) kerosene was replaced with dodecane.

Spheroidal particles of aluminum oxide with a specific surface area of 105 ^m2 /g, a specific pore volume of 0.65 ^cm3 /g, a pore diameter of 18 nm, and a mechanical crushing strength of 55 N/granule are obtained. The spheroidality criterion of the obtained particles is 0.96. The mass fraction of spheroidal particles was 98%.

Example 5

In comparison with Example 2, the method for obtaining spheroidal particles differed in step f) by calcination. After drying, the particles were calcined stepwise at a temperature of 450°C for 2 h, then at a temperature of 950°C for 1 h, the heating rate was 3°C/min.

Spheroidal particles of aluminum oxide with a specific surface area of 125 ^m2 /g, a specific pore volume of 0.52 ^cm3 /g, a pore diameter of 12 nm, and a mechanical crushing strength of 40 N/granule were obtained. The spheroidality criterion of the obtained particles was 0.96. The mass fraction of spheroidal particles was 98%.

Thus, the proposed carriers can be used to prepare catalysts for the processes of dehydrogenation of _C2 - _C4 hydrocarbons and catalytic reforming, taking place in a moving bed, since they have high mechanical strength and a spheroidality criterion of more than 0.98.

Example 6 (comparative). Obtaining catalyst A (composition 0.3% Pt - 1.0% K - 1.0% Cl/Sn(0.2%)-Al ₂ O ₃ ).

10.0 g of spheroidal particles prepared according to the procedure described in Example 1 were impregnated with a solution containing 0.965 ml of a chloroplatinic acid solution H ₂ PtCl ₆ with a Pt concentration of 31.87 mg/ml and 6.84 ml of distilled water. The wet particles were kept in air at room temperature for 2 h, dried in a drying oven at 60 °C for 1 h and at 120 °C for 2 h. The Pt-containing catalyst was placed in a reactor and impregnated with a solution containing 4.1 ml of a potassium chloride solution KCl with a K concentration of 25.0 ml/ml in 3.7 ml of distilled water. The wet particles were kept in air at room temperature for 2 h, then in a drying oven at 60°C for 1 h and at 120°C for 2 h. The particles were calcined in a muffle furnace at 550°C for 2 h. The temperature was raised to the specified values at a rate of 10°C/min.

The resulting catalyst was reduced in the following manner: the system was purged with argon at a rate of 50 ^cm3 /min for 20 min, then hydrogen was fed into the reactor instead of argon at a rate of 50 ^cm3 /min. The reactor was heated in a hydrogen flow at a rate of 15°C/min to 550 °C and maintained at this temperature for 2 h.

Example 7. Obtaining catalyst B (composition 0.3% Pt - 1.0% K - 1.0% Cl/Sn(0.2%)-Al ₂ O ₃ ).

The carrier was obtained by the method described in Example 2. The application of platinum, potassium, chlorine and subsequent reduction of the catalyst were carried out by the same method as in Example 6. The difference consisted in the addition of a stage of calcination of the dried carrier after applying chloroplatinic acid H ₂ PtCl ₆ from the solution to it. The dried granules of the Pt-containing catalyst were calcined in a muffle furnace at 550°C for 2 h. The temperature was raised to the specified values at a rate of 10°C/min.

Example 8. Obtaining catalyst B (composition 0.3% Pt - 1.0% K - 1.0% Cl/Sn(0.2%)-Al ₂ O ₃ ).

The carrier was obtained using the method described in Example 3. The application of platinum, potassium, chlorine and subsequent reduction of the catalyst was carried out using the same method as in Example 7. The difference consisted in adding hydrochloric acid HCl to the solution of chloroplatinic acid H ₂ PtCl ₆ at a rate of 5 mol of HCl per 1 mol of chloroplatinic acid H ₂ PtCl ₆ .

Example 9. Obtaining catalyst G (composition 0.3% Pt - 1.0% K - 1.0% Cl/Sn(0.2%)-Al ₂ O ₃ ).

The carrier was obtained using the method described in Example 3. The application of platinum, potassium, chlorine and subsequent reduction of the catalyst was carried out using the same method as in Example 8. The difference consisted in adding hydrochloric acid HCl to the potassium chloride KCl solution at a rate of 1 mol HCl per 1 mol potassium chloride KCl.

Example 10. Obtaining catalyst D (composition 0.3% Pt - 1.0% K - 1.0% Cl/Sn(0.2%)-Al2O3).

The support was obtained by the procedure described in Example 4. The deposition of platinum, potassium, chlorine and subsequent reduction of the catalyst were carried out by the same procedure as in Example 9. The difference consisted in the deposition of potassium on the support from a solution of potassium hydroxide KOH. For this purpose, the Pt-containing catalyst precursor was placed in a reactor and impregnated with a solution containing 4.1 ml of a solution of potassium hydroxide KOH with a concentration of K equal to 25.0 ml/ml in 3.7 ml of distilled water. The wet granules were kept in air at room temperature for 2 hours, then in a drying oven at 60°C for 1 hour and at 120°C for 2 hours. The granules were calcined in a muffle furnace at 550°C for 2 hours. The temperature was raised to the specified values at a rate of 10°C/min.

The resulting catalyst was reduced in the following manner: the system was purged with argon at a rate of 50 ^cm3 /min for 20 min, then hydrogen was fed into the reactor instead of argon at a rate of 50 ^cm3 /min. The reactor was heated in a hydrogen flow at a rate of 15°C/min to 550°C and maintained at this temperature for 2 hours.

Example 11 illustrates the use of the obtained catalysts in the propane dehydrogenation reaction (PDH).

The obtained catalysts A, B, C, D and D were studied in the propane dehydrogenation reaction. The studies on comparative testing of catalysts in the propane dehydrogenation reaction were carried out according to the following procedure. At the initial stage, the reactor was heated at a rate of 20 °C/min to 110 °C and maintained at this temperature for 1 hour. The catalyst was reduced in a hydrogen stream while heating at a rate of 15 °C/min to 650 °C and maintained at this temperature for 2 hours. The propane dehydrogenation reaction was carried out at 650 °C for 2 hours with the following gas feed mode: C ₃ H ₈ - 30 cm ³ /min, H ₂ - 6.0 cm ³ /min.

The propane conversion on catalyst A at the beginning of the test is 63% and decreases to 50% after 4 hours. On catalysts B, C, G and D, the propane conversion smoothly decreases from 63% to 59% during the 4-hour test. The propylene selectivity for catalyst A increases from 75% to 90% after 4 hours. For catalysts B, C, G and D, the propylene selectivity is in the range of 83-88%. It can be said that the intermediate calcination of the Pt-containing catalyst helps to stabilize the catalytic properties of the resulting catalyst, allowing the propane conversion and propylene selectivity to be maintained within a narrow range.

Example 12. Obtaining a reforming catalyst based on the particles obtained in Example 5.

The catalyst was obtained according to the method described in document RU2767882, testing was carried out according to the method specified in the same document. As a result, a spheroidal reforming catalyst with a specific surface of 120 ^m2 /g, a specific pore volume of 0.50 ^cm3 /g, a pore diameter of 11 nm, and a crushing strength of 40 N/granule was obtained. The spheroidality criterion of the obtained particles is 0.96. The mass fraction of spheroidal particles is 98%.

Thus, the obtained catalysts based on the supports prepared according to examples 2, 3, 4 and 5 have high activity and selectivity, high mechanical strength, and a spheroidality criterion of more than 0.98.

Example 13 illustrates the abrasion resistance of carrier and catalyst samples as a function of their spheroidality.

Samples of the spheroidal aluminum oxide particles obtained in Example 3 and commercial samples of the carrier and catalyst were tested for resistance to abrasion in a moving bed using a setup including a glass tube 1 of variable cross-section, an absorber 2 and a gas flow controller 3. The setup diagram (A) and a drawing of the glass tube (B) are shown in Fig. 1.

The glass tube included the following sections:

• Nitrogen introduction through the branch pipe and its distribution on the mesh wad 4 (cell size 1 mm);

• Working part with an internal diameter of 18 mm and a length of 900 mm;

• Conical expansion to 46mm internal diameter to trap spherical media and prevent it from being carried away from the tube.

Additionally, a mesh wad 5 with a cell size of 1 mm is installed at the exit of the tube.

Nitrogen was supplied to the bottom of the tube through a gas flow regulator with a supply range of 200-1600 l/h. At the exit of the tube, the gas passed through a bubbler filled with water to trap dust particles.

The abrasion resistance of the carriers was tested according to the procedure below:

1. The test sample weighing 50 g was calcined in a muffle furnace at a temperature of 370°C for 3 hours to remove sorbed moisture.

2. After cooling in the oven to a temperature of 150°C, the sample was placed in a desiccator to cool to room temperature.

3. The cooled sample was weighed to an accuracy of 0.01 g.

4. The test sample was placed in glass tube 1. To do this, the nitrogen outlet tube was disconnected at the top of the glass tube, mesh wad 5 was removed and the sample was poured into the tube through a funnel.

5. Installed wad 5 and the outlet pipe in place.

6. Set the nitrogen flow rate to 1000-1200 l/h on the gas flow regulator. Make sure that the spheroidal particles of the test sample began to move in portions up the tube with a gradual fall down. Also check that no particles slipped through the conical part of the tube. If necessary, change the gas flow rate at the tube inlet.

7. The test was carried out for a specified period of time: from 20 to 120 hours. The duration of the test could be changed based on the properties of a specific sample.

8. After the test time had elapsed, the supply of nitrogen to the tube was stopped.

9. Disconnect the gas inlet tube at the bottom of glass tube 1 and remove the rubber seal with polytetrafluoroethylene tape.

10. Place a large polyethylene bag (gripper) under the lower end of the tube and remove the mesh wad 4 with tweezers so that the tested carrier would spill into the bag. It is important not to lose a single particle of the tested sample.

11. Removed the bag with the collected material.

12. If it was necessary to collect dust for analysis, a small gripper was attached to the lower end of the tube with tape and the dust was poured into a bag by tapping on the upper part of the tube. If necessary, the tube can be blown from top to bottom with nitrogen.

13. The gripper with the collected dust sample was disconnected.

14. The tube was purged with nitrogen to remove residual dust. A brush should be used to remove dust particles that had settled on the walls in the expanded part of the tube. The recommended nitrogen flow rate for purging was 1200 l/hour, and the purging duration was about 5 minutes.

15. The extracted sample was calcined in a muffle furnace at a temperature of 370°C for three hours to remove sorbed moisture.

16. After cooling in the oven to a temperature of 150°C, the sample was placed in a desiccator to cool to room temperature.

17. The cooled sample was weighed with an accuracy of 0.01 g.

The relative mass loss of the studied sample was calculated using the formula:

(1),

Where - relative mass loss,

M ₀ - initial mass of the sample,

M ₁ - final mass of the sample,

The results of the comparative test of the abrasion resistance of the carriers are presented in Fig. 2, the results of the test of the abrasion resistance of the samples for 96 hours are presented in Table 1.

Table 1. Value of relative mass loss of the carrier during abrasion for 96 hours

Commercial sample of catalyst Commercial sample of the carrier Carrier according to Example 3 Crushing strength, N/granule 30 30 55 The meaning of the spheroidality criterion 0.85 0.87 0.96 Relative mass loss, % 6.93 6.70 4.64

It is evident from the results of the tests that the sample of spheroidal aluminum oxide particles prepared according to Example 3 is more resistant to abrasion in a moving bed than the commercial samples of the carrier and catalyst due to the high degree of spheroidality. It is also evident from the data of FIG. 2 that the particles according to Example 3 achieve the same weight loss as the commercial samples only after 144 hours of testing.

Thus, the proposed spheroidal carriers have good abrasion resistance.

Claims (22)

1. The use of a catalyst containing, based on the total mass of the catalyst, - from 0.1 to 4.5 mass % of an element of group VIII of the Periodic Table; - from 0.1 to 6.0 mass % of an element of group I and/or II of the Periodic Table; - from 0.2 to 6.0 mass % halogen; - spheroidal particles of aluminum oxide having a specific pore volume of 0.50 to 0.75 ^cm3 /g, a specific surface area of 85 to 125 ^m2 /g, a calculated pore diameter of 12 to 28 nm and a crushing strength of at least 35 N/granule and a spheroidality criterion of at least 0.92, in heterogeneous processes. 2. Use of a catalyst according to claim 1, wherein the heterogeneous process is a process of reforming or dehydrogenating gaseous hydrocarbons. 3. Use of a catalyst according to claim 1, wherein the catalyst contains from 0.15 to 2 mass %, preferably from 0.15 to 0.8 mass % of an element of group VIII of the Periodic Table, based on the total mass of the catalyst. 4. Use of a catalyst according to claim 1, wherein the catalyst contains an element of group I and/or II of the Periodic Table in an amount of from 0.2 to 3 mass %, preferably from 0.5 to 2 mass %. 5. Use of a catalyst according to claim 1, wherein the catalyst contains halogen in an amount of from 0.2 to 3 mass %, preferably contains halogen in an amount of from 0.2 to 2 mass %. 6. Use of a catalyst according to claim 1, wherein platinum, palladium, ruthenium, rhodium, iridium, osmium or mixtures thereof are used in the catalyst as an element of Group VIII of the Periodic Table, preferably platinum is used. 7. Use of a catalyst according to claim 1, wherein calcium, potassium, sodium, magnesium, lithium, strontium, barium, beryllium or mixtures thereof are used in the catalyst as elements of group I and/or II of the Periodic Table, preferably potassium is used. 8. Use of a catalyst according to claim 1, wherein chlorine is used as a halogen in the catalyst. 9. Use of a catalyst according to claim 1, wherein the catalyst comprises spheroidal particles of aluminum oxide having a specific pore volume of from 0.55 to 0.70 ^cm3 /g, preferably from 0.60 to 0.65 ^cm3 /g. 10. Use of a catalyst according to claim 1, wherein the catalyst comprises spheroidal particles of aluminum oxide having a specific surface area of 90 to 110 ^m2 /g, preferably 95 to 105 ^m2 /g. 11. Use of a catalyst according to claim 1, wherein the catalyst comprises spheroidal particles of aluminum oxide characterized by a calculated pore diameter of 15 to 25 nm, preferably 18 to 21 nm. 12. Use of a catalyst according to claim 1, wherein the catalyst comprises spheroidal particles of aluminium oxide characterized by a mechanical crushing strength of at least 40 N/granule, preferably at least 45 N/granule. 13. Use of a catalyst according to claim 1, wherein the catalyst comprises spheroidal particles of aluminum oxide characterized by a bulk density of from 0.50 to 0.75 g/ ^cm3 , preferably from 0.55 to 0.70 g/ ^cm3 , more preferably from 0.60 to 0.65 g/ ^cm3 . 14. Use of a catalyst according to claim 1, wherein the catalyst comprises spheroidal particles of aluminum oxide characterized in that they have an average diameter of from 0.2 to 10 mm, preferably from 0.5 to 5 mm, most preferably from 1 to 3 mm. 15. Use of a catalyst according to claim 1, wherein the catalyst comprises spheroidal particles of aluminum oxide, characterized in that they contain an element of group IV of the Periodic Table in an amount of from 0.05 to 0.50 mass %, preferably from 0.10 to 0.40 mass %, most preferably from 0.15 to 0.25 mass %. 16. Use of a catalyst according to claim 1, wherein the catalyst contains spheroidal particles of aluminum oxide, characterized in that tin, germanium, lead or mixtures thereof are used as an element of Group IV of the Periodic Table, preferably tin is used. 17. Use of a catalyst according to claim 1, wherein the catalyst contains spheroidal particles of aluminum oxide, characterized in that they additionally contain gallium, indium, zinc, manganese or mixtures thereof.