RU2675629C1 - Catalyst for reforming gasoline fractions, method for its obtaining and application of catalyst - Google Patents

Abstract

FIELD: chemistry.SUBSTANCE: catalyst for the reforming of gasoline fractions, hydrogenation of the benzene fraction or aromatic hydrocarbons containing aluminum oxide, platinum, zeolite with ZSM-5 or ZSM-11 structure is proposed. As a zeolite, the catalyst contains crystalline ferroaluminosilicate or ferrogallium aluminosilicate with ZSM-5 or ZSM-11 structure of zeolite, and has the following composition, wt. %: platinum 0.1–0.5, specified zeolite 1–75, alumina – the rest. Invention also discloses a method for producing a catalyst as described above, a method for reforming gasoline fractions and a method for hydrogenating a benzene fraction or aromatic hydrocarbons.EFFECT: decrease in the temperature of complete burning of the catalyst coke at the stage of catalyst regeneration, as well as an increase in the yield of aromatic hydrocarbons and the octane number of the gasoline fraction obtained.17 cl, 32 ex, 2 tbl, 3 dwg

Description

The invention relates to catalysts for reforming gasoline fractions for producing high-octane gasoline fractions and / or aromatic hydrocarbons, as well as to methods for using this catalyst in reforming processes and in the hydrogenation of aromatic hydrocarbons and their fractions. The invention can be used in the refining and petrochemical industries.

The main process for producing high-octane gasoline fractions and C ₆ -C ₁₀ aromatic hydrocarbons from low-octane gasoline fractions is the catalytic reforming process, which is carried out using catalysts containing at least one metal from the platinum group (Gureev A.A., Zhorov Yu.M. , Smidovich EV, “Production of high-octane gasolines”, M., Chemistry, 1981, 224 pp .; Maslyansky G.N., Shapiro R.N., “Catalytic reforming of gasolines”, L., Chemistry, 1985, 222 from.). To increase the efficiency of the reforming process, the catalysts used are constantly being improved by changing the nature and concentration of metals used as active components and / or promoters, as well as by changing the ratio of dehydrogenating and acid functions.

One way to change the ratio of dehydrogenating and acidic functions of the reforming catalyst is to introduce a zeolite component into its composition, and for this, zeolites of various structural types are used. Known methods for various options for reforming gasoline fractions using zeolite-containing catalysts, for example, containing broad-porous zeolites of type L (US Pat. No. 4,645,586, C10G 59/02, 1987; US Pat. No. 4,985,132, C10G 59/02, 1991; Russian Patent No. 2108153, B01J 29/62; B01J 23/34; C10G 61/06, 1998; RF Pat. No. 2123382, B01J 29/62; C10G 35/09, 1998) and ZSM-12 (US Pat. No. 4,653,360, C10G 35 / 095, 1987) or narrow-pore zeolites with the structure of erionite, ferrierite and filipsite (US Pat. RF No. 2458103, C10G 35/085; B01J 29/54; B01J 29/67; B01J 21/04; B01J 21/12; B01J 32 / 00; B01J 37/04, 2012; pat. Of the Russian Federation No. 2471854, C10G 35/085; C10G 35/095; B01J 23/42; B01J 23/36; B01J 21/04; B01J 29/00; B01J 27/047; B01J 37/02, 2013).

The use of narrow-porous zeolites, which include erionite, ferrierite, phillipsite, etc., as part of reforming catalysts, leads to additional processing of n-paraffins unreacted on the metal oxide catalyst, however, this does not affect weakly branched monomethyl paraffins, which have low octane numbers, which leads to fractions with relatively low octane numbers. If wide-pore zeolites, such as L, beta, omega, etc. zeolites, are used in reforming catalysts, highly octane highly branched isoparaffins are involved in the processing, which, as a result of side reactions of hydrocracking, leads to a decrease in the yield of gasoline fractions. Catalysts containing environmentally porous zeolites with the ZSM-5 and ZSM-11 structure, involving monomethyl and n-paraffins in the processing, and not affecting highly branched isoparaffins due to the molecular sieve effect, are deprived of such drawbacks.

A known method of preparing reforming catalysts containing 0.01-10% by weight. Group VIII metals and zeolites ZSM-5, ZSM-11, ZSM-12, ZSM-35 and ZSM-38 (US Pat. No. 4,653,360, C10G 35/095, 1987). According to this method, the catalyst is prepared by calcining the sodium form of the zeolite at a temperature of 200-600 ° C, its subsequent impregnation or ion exchange with an aqueous solution containing platinum or palladium compounds or platinum in combination with group VIII metal compounds, calcining a metal-containing zeolite at a temperature of 150 -550 ° C, subsequent ion exchange with a solution containing alkali metal compounds, washing with water and drying at a temperature of 110 ° C. As the second metal of group VIII, iridium or rhodium can be used. The reforming process is carried out at a temperature of 375-575 ° C and a mass feed rate of 0.2-5 h ^-1 .

A known catalyst and method of reforming (US Pat. US No. 4276151, C10G 35/095, 1981). According to this method, the process of reforming gasoline fractions is carried out at a temperature of 427-565 ° C, a pressure of 0.6-3.4 MPa, a mass feed rate of 0.5-50 h ^-1 (preferably 1-20 h ^-1 ) and a molar ratio hydrogen / hydrocarbons 1-10 on a catalyst containing platinum or a mixture of platinum and rhenium on alumina and 1-15% wt. zeolite ZSM-5 in ammonia (NH ₄ -) form.

A known method of preparing a zeolite-containing catalyst for reforming gasoline fractions (US Pat. RF No. 2108154, B01J 37/02; B01J 29/40; C10G 35/095, 1998). According to this method, a zeolite-containing reforming catalyst is obtained by impregnation under an excess pressure of 0.02-0.3 MPa of a previously calcined zeolite-containing carrier with a solution of a mixture of platinum ammonia, a promoter compound and a sodium or potassium salt at a pH of 8.5-12 and an atomic ratio of sodium or potassium: platinum - (1-50): 1, subsequent drying and calcination of the resulting material. Alumina is used as a carrier in a mixture with the sodium form of zeolite ZSM-5, ZSM-8, ZSM-11 in a mass ratio (35-45) :( 55-65), and tungsten and molybdenum are used as a promoter.

The closest in its technical essence and the achieved effect is a catalyst for reforming gasoline fractions and a method for its preparation (US Pat. RF No. 2043149, B01J29 / 44; C10G35 / 09, 1995). According to the selected prototype, the catalyst contains a carrier - alumina, 0.2-1.2% wt. platinum or a mixture of platinum and a promoter selected from the group: Re, Ir, Rh, W, Mo in a weight ratio (0.5-12): 1, zeolite type ZSM-5 or ZSM-8, or ZSM-11 in an amount of 50 -75% and 0.4-6.8% of alkali metal oxide - Li or Na or K. The catalyst is prepared in several stages. Initially, a zeolite-containing carrier is prepared, for which aluminum hydroxide is mixed with zeolite in sodium form and nitric acid is added as a peptizer, the resulting mixture is formed into extrudates, dried and calcined in an air stream at a temperature of 500 ° C. The resulting extrudates are impregnated with a solution of platinum ammonia or a mixture of platinum ammonia with a promoter compound at a temperature of 80-90 ° C and pH = 10, after which the excess solution is drained, and the extrudates are impregnated at 80-90 ° C with an aqueous solution of an alkali metal salt (Li, Na or K), after which the excess solution is drained, the resulting catalyst is dried and calcined in a stream of air at a temperature of 500 ° C.

The main disadvantages of the prototype and the above analogues are the relatively high temperature of the burning of coke formed on the zeolite component of the catalyst and the incomplete depth of its burning at moderate temperatures of catalyst regeneration.

The objective of the invention is the development of a catalyst for reforming gasoline fractions with a reduced temperature for the complete burning of coke formed on the zeolite component of the catalyst under the process conditions while maintaining a high level of catalyst activity, as well as a method for preparing such a catalyst, a method for reforming gasoline fractions and a method for using this catalyst in processes hydrogenation of the benzene fraction and aromatic hydrocarbons.

The problem is achieved in that the reforming catalyst for gasoline fractions contains 1-75% wt. crystalline ferroaluminosilicate or ferrogallium aluminosilicate with a zeolite structure of ZSM-5 or ZSM-11, 0.1-0.5% platinum, 0-1.6% rhenium and / or tin, possibly 0.5-2.0% chlorine, and the rest - gamma alumina.

The task is also achieved by the fact that a catalyst for reforming gasoline fractions is prepared by mixing a powder or paste of aluminum hydroxide and crystalline ferroaluminosilicate or ferrogallium aluminosilicate, possibly with a tin-containing reagent, then adding a solution of mineral and / or organic acid as a peptizer, molding the resulting mixture, and neutralizing molded granules with ammonia solution, drying and calcining the molded granules of the carrier, impregnation of calcined granules with compounds platinum, possibly with tin or rhenium compounds, possibly in acid solutions, subsequent drying and calcination of the catalyst granules, and the ferroaluminosilicate or ferrogallium aluminosilicate used has the structure of zeolite ZSM-5 or ZSM-11.

The problem is achieved in the same way that the ferroaluminosilicate has a molar ratio of SiO ₂ / Al ₂ O ₃ in the range of 38-310 and contains 0.1-1.5% wt. iron, and ferrogallium aluminum silicate has a molar ratio of SiO ₂ / Al ₂ O ₃ in the range of 61-320 and contains 0.1-1.2% iron and 0.1-1.5% gallium.

The used catalyst contains 0.1-0.5% wt. platinum, 0-1.6% tin and / or rhenium and may contain 0.1-1.6% chlorine.

The task is also achieved by the fact that the reforming of gasoline fractions is carried out by contacting them at elevated temperatures and pressure in the presence of a hydrogen-containing gas with the aforementioned catalyst containing gamma alumina, platinum, possibly rhenium and / or tin, and containing 1-75% wt. . crystalline ferroaluminosilicate or ferrogallium aluminosilicate with a zeolite structure of ZSM-5 or ZSM-11.

The task is also achieved by the fact that the aforementioned catalyst is used for hydrogenation of a benzene fraction or aromatic hydrocarbons by contacting the feed in the presence of a hydrogen-containing gas at excess pressure with a catalyst containing gamma alumina, platinum, possibly rhenium and / or tin, and containing 1-75% wt. crystalline ferroaluminosilicate or ferrogallium aluminosilicate with a zeolite structure of ZSM-5 or ZSM-11.

The main distinguishing feature of the proposed method is the use of crystalline ferroaluminosilicate or ferrogallium aluminosilicate with the structure of zeolite ZSM-5 or ZSM-11 as a catalyst.

The catalyst is prepared as follows. Aluminum hydroxide obtained by aluminate technology by single-stream or continuous precipitation is mixed with crystalline ferroaluminosilicate or ferrogallium aluminosilicate, possibly mixed with a soluble tin compound, an aqueous solution of mineral and / or organic acid is added as a peptizing agent, granulated by known methods in the form of extrudates or spheres, dried at temperatures up to 200 ° C and calcined in a stream of air at a temperature of 500-650 ° C. Calcined granules after cooling are impregnated with known methods p solutions containing platinum compounds or a mixture of platinum and rhenium compounds, possibly a mineral and / or organic acid. Pretreatment with tin compounds is possible. After the impregnation step, the solution is separated from the catalyst granules, the catalyst is dried and calcined in a stream of air at a temperature of 450-550 ° C. The crystalline ferroaluminosilicate or ferrogallium aluminosilicate used in the preparation of the catalyst has the structure of zeolite ZSM-5 or ZSM-11 and is used in cationic Na form or in cation-decationated HNa form, or in decationic acid H form.

To add an additional amount of chlorine to the catalyst, the step of impregnating the granules with platinum compounds or with a mixture of platinum and promoter compounds is carried out with a solution containing hydrochloric acid.

The reforming of gasoline fractions is carried out by contacting the feedstock with the above-described catalyst in the presence of a hydrogen-containing gas at a temperature of 440-560 ° C, an overpressure of 0.3-4.0 MPa, a volumetric feed rate of liquid feedstock of 0.5-10 h ^-1 and a molar ratio of hydrogen to hydrocarbons 1-10.

Before using the catalyst in the reforming process, it is reduced with hydrogen at a temperature of 450-550 ° C. After hydrogen reduction, the catalyst can be pre-sulfurized with hydrogen sulfide and / or organosulfur compounds at the rate of 0.01-0.07% wt. sulfur on the catalyst.

Hydrogenation of the benzene fraction or aromatic hydrocarbons is carried out by contacting the feed with the catalyst described above in the presence of a hydrogen-containing gas at a temperature of 220-400 ° C, an overpressure of 0.5-5.0 MPa, a volumetric feed rate of liquid feed of 0.5-10 h ^-1 and the molar ratio of hydrogen to hydrocarbons 4-15. Before using the catalyst in the hydrogenation process, it is reduced with hydrogen at a temperature of 400-500 ° C. As a result of hydrogenation, benzene is converted to cyclohexane, which is then partially isomerized to methylcyclopentane. Varying the process conditions, further opening of 6 and 5-membered hydrocarbon rings is possible with the formation of C ₆ paraffins - n-hexane, methyl pentanes and dimethyl butanes. In the hydrogenation of alkylbenzenes, the primary product is the corresponding alkylcyclohexane, which, depending on the process conditions, can be further converted similarly to the above scheme.

During the processing of hydrocarbon raw materials, a gradual coking of the catalyst occurs, leading to a decrease in its catalytic activity, which in turn leads to a decrease in the yield of aromatic hydrocarbons and to a decrease in the octane number of the obtained gasoline fractions. To restore the initial level of activity of the catalyst, its regeneration is carried out, which consists in the controlled burning of coke deposits from the surface of the catalyst with a regenerating gas with a certain oxygen content. However, the burning of coke on the metal component of the catalyst located on alumina occurs more fully and at lower temperatures than the burning out of coke formed inside the crystals of the aluminosilicate (zeolite) component, since polyvalent metal cations (Pt, Re etc.) do not penetrate into zeolite crystals of the ZSM-5 and ZSM-11 type and therefore do not affect the burning process of catalyst coke inside zeolite channels. As a result of this, coke deposits inside zeolite crystals may not completely burn out at moderate regeneration temperatures and gradually accumulate from regeneration to regeneration, leading to a decrease in the level of activity and / or to a reduction in the inter-regeneration run of the catalyst. At the stage of hydrothermal synthesis, the introduction of iron and gallium atoms into the zeolite crystalline framework during the synthesis of ferroaluminosilicate or ferrogallium aluminosilicate with the structure of ZSM-5 and ZSM-11 leads to the formation of active centers in the volume of their crystals that accelerate the reactions of burnout of catalyst coke, which in turn leads to lower temperature and increase the depth of burning of coke in the zeolite component of the catalyst while maintaining a high level of activity of the catalyst.

The essence of the proposed method and its practical applicability is illustrated by the following examples. Examples No. 1-12 describe the preparation of the catalyst according to the proposed method, example No. 13 - the preparation of the catalyst is similar to the prototype; the compositions of the resulting catalysts are additionally presented in table 1. To illustrate the attainability of the goal - to reduce the temperature of coke burnout formed on the zeolite component of the catalyst and increase the completeness of its burnout, examples No. 14-16 and FIG. 1-3 - example No. 14 (Fig. 1) shows the burnup depth of coke formed on the zeolite component of the catalyst prepared similarly to the prototype, and examples No. 15 and 16 (Fig. 2 and 3) illustrate the burnout of coke on the zeolite component of the proposed catalyst. Examples No. 17-28 illustrate the method of application of the proposed catalyst in the reforming process of gasoline fractions, and example No. 29 - the use of a catalyst prepared similar to the prototype and is given for comparison; The test results of the catalysts are shown in table 2. Examples No. 30-32 illustrate the method of using the catalyst in the process of hydrogenation of the benzene fraction and aromatic hydrocarbons.

Example 1

и объемом пор 0,6 см³/г.As a raw material for the preparation of the catalyst carrier, aluminum hydroxide of single-stream deposition with a total humidity of 75% is used. Aluminum hydroxide in an amount of 1000 g at a temperature of 20 ° C is plasticized with 36 ml of 46% acetic acid based on the acid module (molar ratio of acid to aluminum oxide in hydroxide) M _k = 0.12 and 28 g of crystalline ferroaluminosilicate powder with structure is added with stirring zeolite ZSM-5 in decationic acid H-form, having a molar ratio of SiO ₂ / Al ₂ O ₃ = 86 and containing 0.4% wt. gland. The obtained fluid thixotropic mixture is formed into spherical granules by the drop method in the diesel fraction and neutralized in an 18% aqueous ammonia solution. The formed granules are dried in air for 24 hours, dried at a temperature of 120 ° C for 4 hours and calcined at a temperature of 550 ° C for 2 hours in a stream of air with a space velocity of 500 h ^-1 . The obtained spherical granules of the carrier based on γ-A1 ₂ O ₃ contain 10% wt. zeolite and have a diameter of 1.6-2.0 mm, a crushing strength of 25 MPa, a specific surface area of 220 m ² / g. The porous structure of alumina is represented by pores with an average diameter of 70

and a pore volume of 0.6 cm ³ / g.

The cooled granules of the prepared carrier, taken in an amount of 200 g, moisten 290 ml of an aqueous solution of 0.5% acetic acid at a temperature of 25 ° C for 0.5 hours, then 75 ml of platinum nitrate solution (IV ) with a concentration of platinum of 15 g / l and the granules are treated with the resulting solution at a temperature of 60 ° C for 2 hours, after which the mixture is decanted, the catalyst granules are dried in air for 10 hours, dried at 110 ° C for 2 hours and calcined at 500 ° C for e 2 hours. The obtained granules of the catalyst contain 10% wt. ferroaluminosilicate with the structure of zeolite ZSM-5 and 0.5% platinum.

Example 2

As a raw material for the preparation of the catalyst carrier, aluminum hydroxide of single-stream deposition with a total moisture content of 73% is used. Aluminum hydroxide in an amount of 1000 g is plasticized with a solution of 31 g of oxalic acid in 124 ml of water at 45 ° C in the calculation of obtaining M _to = 0.13. The obtained thixotropic mass is mixed with stirring with 30 g of crystalline ferrogallium aluminum silicate powder with the structure of ZSM-5 zeolite in decationated H-form having a molar ratio of SiO ₂ / Al ₂ O ₃ = 92 and containing 0.3% wt. iron and 0.1% gallium. Granulation of the resulting mixture is carried out by the drop method in the diesel fraction, and the formed granules are neutralized in a 15% aqueous ammonia solution. The formed granules are held in air for 10 hours, dried at a temperature of 110 ° C for 4 hours and calcined at a temperature of 600 ° C in a stream of dry air at a feed rate of 1000 h " ¹ for 2 hours. The obtained spherical granules of the carrier based on γ -A1 ₂ O ₃ contain 10% by weight of zeolite and have a diameter of 1.6-1.9 mm, crushing strength of 22 MPa and a specific surface of 250 m ² / g.

The cooled granules of the prepared carrier, taken in an amount of 200 g, moisturize 290 ml of an aqueous solution of 0.5% acetic acid at a temperature of 20 ° C for 0.5 hours, then 45 ml of a solution of platinum chloride with a concentration are added to the solution with granules of the carrier with stirring platinum 15 g / l and the granules are treated with the resulting solution at a temperature of 60 ° C for 2 hours, after which the mixture is decanted, the catalyst granules are dried in air for 10 hours, dried at 110 ° C for 2 hours and calcined at 500 ° C for 2 hours. The obtained granules of the catalyst contain 10% wt. ferrogallium aluminum silicate with the structure of zeolite ZSM-5, 0.3% platinum and 0.5% chlorine.

Example 3

.As raw materials for the preparation of the catalyst carrier using aluminum hydroxide cold deposition with a total humidity of 80%. Aluminum hydroxide in an amount of 1000 g is plasticized at a temperature of 22 ° C with a solution of 56.5 g of citric acid in 45 ml of water, based on the preparation of the acid module M _k = 0.15. To the resulting mixture, with stirring, add a solution of 2 g of tin penta tetrachloride in 10 ml of water and 50 g of crystalline ferroaluminosilicate powder with a ZSM-5 zeolite structure in cationic Na form having a molar ratio of SiO ₂ / Al ₂ O ₃ = 310 and containing 1, 5% wt. gland. Granulation of the resulting mixture is carried out by the drop method in the diesel fraction, and the granules are neutralized in a 15% aqueous ammonia solution. The formed granules are dried in air for 4 hours, dried at a temperature of 110 ° C for 2 hours and calcined at 500 ° C in a stream of air at a volumetric feed rate of 1000 h ^-1 for 2 hours. The obtained spherical granules of the carrier based on γ-Al ₂ About ₃ contain 20% wt. zeolite and 0.2% tin; granules have a diameter of 1.6-1.8 mm, crushing strength 21 MPa and an average pore diameter of alumina 100

.

The cooled granules of the prepared carrier, taken in an amount of 200 g, moisten 320 ml of an aqueous solution of 1% citric acid at a temperature of 20 ° C for half an hour, then 25 ml of an aqueous solution of rhenium acid with a rhenium concentration of 35 g are added to the solution with granules of the carrier with stirring l, 30 ml of a solution of platinum chloride with a platinum concentration of 15.0 g / l and the granules are treated with the resulting solution at 60 ° C for 2 hours, after which the mixture is decanted, the catalyst granules are dried in air for 10 hours, dried at a temperature of 120 ° C for 2 hours and calcined at 500 ° C for 2 hours. The obtained granules of the catalyst contain 20% wt. ferroaluminosilicate with the structure of zeolite ZSM-5, 0.2% platinum, 0.3% rhenium and 0.4% chlorine.

Example 4

.As the raw material for the preparation of the catalyst carrier, aluminum hydroxide of mixed precipitation is used at a ratio of aluminum hydroxides of cold and hot precipitation of 1: 1 wt. Mixed aluminum hydroxide is dried at 110 ° C to a total moisture content of 25%, milled in a ball mill to a powder state with a particle size of not more than 50 microns. The obtained aluminum hydroxide powder in an amount of 1000 g with a total moisture content of 25% is mixed with 2.7 l of deionized water, 38 ml of a solution of 69% nitric acid to obtain M _k = 0.08, after which 40 g of crystalline ferroaluminosilicate powder with the structure is added zeolite ZSM-5 in decationated H-form having a molar ratio of SiO ₂ / Al ₂ O ₃ = 38 and containing 0.1% wt. gland. The stage of plasticization and mixing with zeolite powder is carried out at a temperature of 28 ° C until the content in the mass of 248 g Al ₂ O ₃ / kg of the mixture. The obtained plasticized mass is kept for 24 hours at a temperature of 22 ° C and formed into spherical granules by the drop method in a diesel fraction, followed by neutralization in a 15% aqueous ammonia solution. The formed granules are dried in air at a temperature of 20 ° C for 24 hours, then dried at 110 ° C for 2 hours and calcined at a temperature of 650 ° C for 4 hours in a stream of dry air with a volumetric feed rate of 600 h ^-1 . The obtained spherical granules of the carrier based on γ-A1 ₂ O ₃ contain 5% wt. zeolite, have a diameter of 1.4-1.8 mm, a crushing strength of 28 MPa and an average pore diameter of aluminum oxide of 65

.

The cooled granules of the prepared carrier in an amount of 700 g moisten 1000 ml of an aqueous solution of 0.3 n hydrochloric acid at a temperature of 20 ° C for 0.5 hours, then 21 ml of an aqueous solution of 0.5% acetic is successively added to the solution with granules of the carrier with stirring acid, 105 ml of a solution of platanoic hydrochloric acid with a concentration of platinum of 15 g / l and the granules are treated with the resulting solution at 60 ° C for 2 hours, after which the mixture is decanted, the catalyst granules are dried in air for 10 hours, dried at a temperature ature 120 ° C for 2 hours and calcined at 500 ° C for 2 hours. The obtained granules of the catalyst contain 5% wt. ferroaluminosilicate with the structure of zeolite ZSM-5, 0.2% platinum, 0.3% tin and 1.4% chlorine.

Example 5

.As a raw material for the preparation of the catalyst carrier, aluminum hydroxide of continuous deposition with a total humidity of 85% is used. Aluminum hydroxide in an amount of 500 g kneaded at a temperature of 20 ° C with a mixture of acid, adding 3.8 ml of 69% nitric acid and 3.6 ml of 46% acetic acid, based obtain the total acid value of M _k = 0.12, and mixed with 8.4 g of crystalline ferrogallium aluminosilicate powder with a zeolite structure of ZSM-11 in a decationized H form having a molar ratio of SiO / Al ₂ O ₃ = 61 and containing 0.1% wt. iron and 0.3% gallium. Granulation of the mixture into spherical granules is carried out by the liquid method in the kerosene fraction, and the hardening and neutralization of the granules is carried out in an 18% aqueous ammonia solution. The formed granules are dried at a temperature of 110 ° C for 2 hours and calcined in a stream of dry air with a space velocity of 1000 h ' ¹ at a temperature of 550 ° C for 4 hours. The obtained spherical granules of the carrier based on γ-A1 ₂ O ₃ contain 10% wt. zeolite and have a diameter of 1.6-2.0 mm, crushing strength of 20 MPa, a specific surface of 270 m ² / g and an average pore diameter of alumina 65

.

Chilled granules of the prepared carrier, taken in an amount of 70 g, moisten 150 ml of an aqueous solution of 0.5% acetic acid at a temperature of 20 ° C for 0.5 hours, then 10 ml of a solution of rhenium acid are added successively to the solution with granules of the carrier with stirring with with a rhenium concentration of 35 g / l, 20 ml of a platinum (IV) nitrate solution with a platinum concentration of 15 g / l and granules are treated with the resulting solution at 80 ° C for 2 hours, after which the mixture is decanted, the catalyst granules are dried in air for 10 hours, dried at t temperature of 120 ° C for 2 hours and calcined at 500 ° C for 2 hours. The obtained granules of the catalyst contain 10% wt. ferrogallium aluminum silicate with the structure of zeolite ZSM-11, 0.2% platinum and 0.4% rhenium.

Example 6

As a raw material for the preparation of the catalyst carrier, aluminum hydroxide of single-stream deposition with a total moisture content of 73% is used. Aluminum hydroxide in an amount of 1000 g is plasticized with a solution of 31 g of oxalic acid in 124 ml of water at 45 ° C in the calculation of obtaining M _to = 0.13. The obtained thixotropic mass is mixed with the addition of 30 g of crystalline ferrogallium aluminum silicate powder with the structure of zeolite ZSM-11 in cation-decationized HNa form having a molar ratio of SiO ₂ / Al ₂ O ₃ = 320 and containing 1.1% wt. iron and 1.5% gallium. Granulation of the resulting mixture is carried out by the drop forming method in the diesel fraction, and the granules are neutralized in an 18% aqueous ammonia solution. The formed granules are kept in air for 10 hours, dried at a temperature of 110 ° C for 4 hours and calcined at a temperature of 600 ° C in a stream of dry air at a feed rate of 1000 h ^-1 for 2 hours. The obtained spherical granules of the carrier based on γ-A1 ₂ O ₃ contain 10% wt. zeolite and 0.5% tin, the granules have a diameter of 1.6-1.9 mm, a crushing strength of 15 MPa and a specific surface area of 250 m ² / g.

Chilled granules of the prepared carrier in an amount of 250 g moisten 360 ml of an aqueous solution of 0.5% hydrochloric acid at a temperature of 20 ° C for 0.5 hours, then a solution of 4.5 g of tin penta tetrachloride in 50 ml of water is added to the solution with granules of the carrier and the granules are treated with the resulting solution for one hour at a temperature of 60 ° C, after which the mixture is decanted, the granules are dried at a temperature of 110 ° C for 2 hours and calcined at 500 ° C for 2 hours. The cooled granules are moistened at a temperature of 20 ° C with deionized water, then 55 ml of a solution of platinum hydrochloric acid with a concentration of platinum of 15 g / l are added to the solution with granules and the granules are treated with the resulting solution initially at 20 ° C, and then at 70 ° C. after which the mixture is decanted, the catalyst granules are dried in air for 10 hours, dried at a temperature of 120 ° C for 2 hours and calcined at 500 ° C for 2 hours. The obtained granules of the catalyst contain 10% wt. ferrogallium aluminum silicate with the structure of zeolite ZSM-11, 0.3% platinum, 0.5% tin and 0.9% chlorine.

Example 7

и объемом пор 0,55 см³/г.As a raw material for the preparation of the catalyst carrier, aluminum hydroxide of continuous deposition with a total humidity of 79% is used. A paste of this aluminum hydroxide in an amount of 600 g at a temperature of 25 ° C is peptized with 9.5 ml of a solution of 69% nitric acid based on the preparation of the acid module M _k = 0.10 and mixed with stirring with 0.4 g of tin tetrachloride in 5 ml of water and 1.3 g of crystalline ferroaluminosilicate powder with a ZSM-11 zeolite structure in cationic Na form having a molar ratio of SiO ₂ / Al ₂ O ₃ = 88 and containing 0.1% wt. gland. The obtained fluid thixotropic mixture is formed by the drop forming method in a diesel fraction and neutralized in a 20% aqueous ammonia solution. The formed granules are dried in air for 10 hours and dried initially at a temperature of 60 ° C for 2 hours, and then at a temperature of 110 ° C for 4 hours, after which they are calcined for 3 hours at a temperature of 550 ° C dry air flow with a volumetric feed rate of 1000 h ^-1 . The obtained granules γ-A1 ₂ O ₃ contain 1% wt. zeolite and 0.1% tin, have a size of 1.6-1.8 mm, crushing strength of 31 MPa, specific surface area of 210 m ² / g and a porous structure with an average pore diameter of 90

and a pore volume of 0.55 cm ³ / g.

The cooled granules of the prepared carrier in an amount of 100 g are moistened in 200 ml of deionized water at a temperature of 20 ° C for 0.5 hours, then 16 ml of a rhenium acid solution with a rhenium concentration of 35 g / l, 22 ml are added to the solution with granules of the carrier with stirring a platinum (IV) nitrate solution with a platinum concentration of 15.0 g / l and the granules are treated with the resulting solution at 20 ° C for 2 hours, after which the mixture is decanted, the catalyst granules are dried in air for 10 hours, dried at 120 ° C for 2 hours, etc. calcined at 500 ° C for 2 hours. The obtained granules of the catalyst contain 1% wt. ferroaluminosilicate with the structure of zeolite ZSM-11, 0.3% platinum, 0.5% rhenium and 0.1% tin.

Example 8

и объемом пор 0,8 см³/г.As a raw material for the preparation of the catalyst carrier, aluminum hydroxide of continuous deposition with a total humidity of 79% is used. A paste of this aluminum hydroxide in an amount of 500 g is plasticized with 5.1 ml of a solution of 69% nitric acid based on the preparation of the acid module M _k = 0.08. The obtained thixotropic mass of aluminum hydroxide is mixed with 3 g of tin penta tetrachloride in 30 ml of water and with 3.2 g of crystalline ferrogallium aluminum silicate powder with a ZSM-5 zeolite structure in a decationated H form having a molar ratio of SiO ₂ / Al ₂ O ₃ = 212 and containing 0.6% wt. iron and 1.1% gallium. The mixture is formed into spherical granules by droplet molding in a kerosene fraction, and the formed granules are neutralized in a 15% aqueous ammonia solution. The formed granules are dried in air for 10 hours and dried at a temperature of 110 ° C for 4 hours, after which they are calcined for 3 hours at a temperature of 550 ° C in a stream of dry air with a space velocity of 600 h ^-1 . The obtained granules of the carrier - γ-A1 ₂ O _{3 with a} size of 1.6-1.8 mm have a crushing strength of 20 MPa, a specific surface area of 250 m ² / g and contain 3% wt. zeolite and 1% tin. The porous structure of alumina is represented by pores with an average diameter of 90

and a pore volume of 0.8 cm ³ / g.

The cooled granules of the prepared carrier, taken in an amount of 100 g, moisten 150 ml of an aqueous solution of 1% hydrochloric acid at a temperature of 20 ° C for 0.5 hours, then 3 ml of an aqueous solution of 0.5% acetic acid are added to the solution with granules of the carrier with stirring acid, 35 ml of an aqueous solution of rhenium acid with a rhenium concentration of 20.0 g / l, 33 ml of a solution of platinum hydrochloric acid with a concentration of platinum of 15.0 g / l and granules are treated with the resulting solution at 20 ° C for half an hour, and then at 80 ° C for 1 hour, after which the solution ekantiruyut catalyst pellets provyalivayut in air for 10 hours and dried at 110 ° C for 2 hours and calcined at 500 ° C for 2 hours. The obtained granules of the catalyst contain 3% wt. ferrogallium aluminum silicate with the structure of zeolite ZSM-5, 0.4% platinum, 0.6% rhenium, 1% tin and 1.6% chlorine.

Example 9

и содержат 10% мас. цеолита и 1% олова.As a raw material for the preparation of the catalyst carrier, aluminum hydroxide of continuous deposition with a total humidity of 85% is used. Aluminum hydroxide in an amount of 1500 g is plasticized at a temperature of 20 ° C with a mixture of acids, adding 11 ml of 69% nitric acid and 46% acetic acid, based on the calculation of the total value of the acid module M _k = 0.12. The obtained thixotropic mass of aluminum hydroxide is mixed with a solution of 7 g of tin penta tetrachloride in 60 ml of water and with 25 g of crystalline ferrogallium aluminum silicate powder with a zeolite structure ZSM-11 in a decationated H form having a molar ratio SiO ₂ / Al ₂ O ₃ = 186 and containing 1.2% wt. iron and 0.3% gallium. Granulation of the mixture into spherical granules is carried out by the liquid method in the kerosene fraction, and the hardening and neutralization of the granules is carried out in an 18% aqueous ammonia solution. The formed granules are dried at a temperature of 120 ° C for 2 hours and calcined in a stream of dry air with a space velocity of 800 h ^-1 at a temperature of 550 ° C for 4 hours. The obtained spherical granules of the carrier based on γ-A1 ₂ O ₃ have a diameter of 1.6-1.9 mm, crushing strength 22 MPa, specific surface 260 m ² / g, average pore diameter of alumina 70

and contain 10% wt. zeolite and 1% tin.

The cooled granules of the prepared carrier in an amount of 200 g are moistened in 400 ml of deionized water at a temperature of 20 ° C for 0.5 hours, then 40 ml of a solution of ammonium perrenate with a rhenium concentration of 35 g / l, 15 ml are added to the solution with granules of the carrier with stirring a platinum (IV) nitrate solution with a platinum concentration of 15.0 g / l and the granules are treated with the resulting solution at 20 ° C for 2 hours, after which the mixture is decanted, the catalyst granules are dried in air for 10 hours, dried at 120 ° C for 2 hours and p roasted at 500 ° C for 2 hours. The obtained granules of the catalyst contain 10% wt. ferrogallium aluminum silicate with the structure of zeolite ZSM-5, 0.1% platinum, 0.6% rhenium and 1.0% tin.

Example 10

As a raw material for the preparation of the catalyst carrier, aluminum hydroxide of continuous deposition with a total humidity of 80% is used. 3.0 kg of a paste of aluminum hydroxide is loaded into a mixer with Z-shaped blades and 19 ml of 69% nitric acid are added with constant stirring. After stirring for 15 minutes, 1.4 kg of crystalline ferroaluminosilicate powder with a ZSM-5 zeolite structure in decationated H-form having a molar ratio of SiO ₂ / Al ₂ O ₃ = 96 and containing 0.5 wt% is added to the plasticized mass with stirring. . gland. The resulting mass with a total humidity of 50% is formed on an extruder in cuttings with a diameter of 3-4 mm and a length of 5-7 mm. The extrudates were held in air for 10 hours, dried at 110 ° C for 4 hours and calcined at 500 ° C for 4 hours. The obtained granules of the carrier contain 30% wt. γ-A1 ₂ O ₃ and 70% zeolite, have a crushing strength of 7.1 MPa and a specific surface area of 340 m ² / g.

Chilled granules of the prepared carrier in an amount of 2.0 kg moisten 3.3 l of an aqueous solution of 0.5% acetic acid at a temperature of 20 ° C for 0.5 hours, then 420 ml of platinum nitrate solution is added to the solution with carrier granules during the circulation of the solution (IV) with a platinum concentration of 15.0 g / l and the granules are treated with the resulting solution initially at 20 ° C for 0.5 hours, and then at 70 ° C for 1 hour, after which the mixture is decanted, the catalyst granules are dried on air for 10 hours, dried at a temperature of 120 ° C for 2 hours s and calcined at 500 ° C for 2 hours. The obtained granules of the catalyst contain 70% wt. ferroaluminosilicate with the structure of zeolite ZSM-5 and 0.3% platinum.

Example 11

As a raw material for the preparation of the catalyst carrier, aluminum hydroxide of mixed precipitation is used with a ratio of aluminum hydroxide of cold precipitation and hot 1: 1 wt. Mixed aluminum hydroxide is dried at 110 ° C to a total moisture content of ~ 25%, milled in a ball mill to a powder state with a particle size of not more than 50 microns. The obtained powder of aluminum hydroxide in an amount of 3 kg with a total moisture content of 25% is placed in a mixer with Z-shaped blades and mixed with constant stirring with 1.5 kg of crystalline ferrogallium aluminum silicate powder with a ZSM-5 zeolite structure in a decationated H-form having a molar ratio of SiO ₂ / Al ₂ O ₃ = 145 and containing 0.2% wt. iron and 0.6% gallium. To the resulting mixture of powders, a nitric acid solution containing 114 ml of 69% nitric acid was added with constant stirring to obtain an acid module M _k = 0.08 and 1930 ml of water. The resulting mass is stirred for 20 minutes and add 25 g of tin tetrachloride pentachydrate in 140 ml of water. A mixture with a total moisture content of 46% is molded into extrudates with a diameter of 4-5 mm and a length of 5-8 mm. The granules are kept in air for 10 hours and dried at a temperature of 120 ° C for 4 hours. Calcination of the granules is carried out at a temperature of 550 ° C in a stream of dry air at its volumetric feed rate of 1000 h ^-1 for 4 hours. The obtained granules of extrudates based on γ-A1 ₂ O ₃ contain 40% wt. zeolite and 0.2% tin, granules have a crushing strength of 8.9 MPa and a specific surface area of 310 m ² / g.

The cooled granules of the prepared carrier in an amount of 3.5 kg moisturize 5.5 l of an aqueous solution of 0.1 n hydrochloric acid at a temperature of 20 ° C for 0.5 hours, then 130 ml of a solution of platinum chloride with a concentration of 15 g of platinum are added / l and the granules are treated with the resulting solution initially at 20 ° C for 0.5 hours, and then at 70 ° C for 1 hour, after which the mixture is decanted, the catalyst granules are dried in air for 10 hours, dried at 120 ° C for 2 hours and calcination m at 500 ° C for 2 hours. The obtained granules of the catalyst contain 40% wt. ferrogallium aluminum silicate with the structure of zeolite ZSM-5, 0.1% platinum, 0.2% tin and 0.9% chlorine.

Example 12

As a raw material for the preparation of the catalyst carrier, aluminum hydroxide of continuous deposition with a total humidity of 75% is used. 2.0 kg of aluminum hydroxide paste was charged into a mixer with Z-shaped blades and 222 ml of 69% nitric acid were added with constant stirring. After mixing the plasticized mass for 15 minutes, 4.0 kg of mixed aluminum hydroxide powder, obtained after drying the wet cake of mixed aluminum hydroxide at 110 ° C to a moisture content of ~ 25% and grinding it in a ball mill to particles with a size, is added to it with constant stirring. less than 50 microns. After 30 minutes of stirring, 10.5 kg of crystalline ferrogallium aluminosilicate powder with a ZSM-11 zeolite structure in decationated H form having a molar ratio of SiO ₂ / Al ₂ O ₃ = 105 and containing 0.4% wt. Is introduced into the obtained plasticized mass. iron and 0.1% gallium. The obtained plasticized mass of aluminum hydroxide with a total moisture content of 50% is extruded into granules with a diameter of 5-7 mm and a length of 7-10 mm. The extruded granules are kept in air at room temperature for 10 hours, dried at 110 ° C for 4 hours and calcined in a stream of air at a volumetric feed rate of 500 h ^-1 at a temperature of 550 ° C for 2 hours. The obtained granules of the carrier contain 25% wt. γ-A1 ₂ O ₃ and 75% zeolite, granules have a crushing strength of 4.8 MPa and a specific surface area of 350 m ² / g.

The cooled granules of the prepared carrier in an amount of 14.0 kg are moistened with vacuum 25 l of deionized water at a temperature of 20 ° C for 0.5 hours, then when the solution is circulated add 1.4 l of rhenium acid solution with a concentration of rhenium of 35 g / l and 2 1 l of a solution of platinum (IV) nitrate with a concentration of platinum of 15.0 g / l and granules are treated with the resulting solution at 20 ° C for 2 hours, after which the mixture is decanted, the catalyst granules are dried in air for 10 hours, dried at temperature of 110 ° C for 2 hours and calcined at 500 ° C for 2 hours. The obtained granules of the catalyst contain 75% wt. ferrogallium aluminum silicate with the structure of zeolite ZSM-11, 0.2% platinum and 0.3% rhenium.

Example 13 (for comparison).

The catalyst carrier and the catalyst itself are prepared similar to their preparation according to the prototype. To prepare the carrier, an aluminum hydroxide paste with a moisture content of 30% is used. The paste of aluminum hydroxide in an amount of 43 g was mixed with 70 g of ZSM-5 zeolite in the decationized H form having a molar ratio SiO ₂ / Al ₂ O ₃ = 91, and a solution of 57% nitric acid as a peptizing agent to give an acid of M _to = 0.05. The mixture is molded on an extruder in cuttings with a diameter of 3-4 mm and a length of 5-7 mm, dried in air for 10 hours and calcined in a stream of air at a temperature of 500 ° C for 4 hours. The obtained granules of the carrier have a crushing strength of 5.1 MPa and a specific surface area of 340 m ² / g and contain 30% wt. γ-A1 ₂ O ₃ and 70% zeolite.

An impregnation of 100 g of the obtained carrier with 200 ml of a solution of platinum (IV) nitrate with a platinum content of 2 g / l is carried out at a temperature of 85 ° C for 3 hours, the excess solution is drained, the catalyst is dried in air for 10 hours and calcined in an air stream at a temperature 500 ° C for 4 hours. The obtained granules of the catalyst contain 70% wt. zeolite ZSM-5 and 0.3% platinum.

Example 14 (for comparison).

The study of the burning process of catalyst coke of a coked sample is carried out by controlling the change in mass of 0.2 g of sample in a reactor close to isothermal. Coke burning is carried out by contacting with a catalyst a regenerating gas containing 1.3% vol. oxygen in a mixture with nitrogen, which is carried out at atmospheric pressure, a temperature of 500-600 ° C and a gas flow rate of 50 l / h.

Coke is burned out by the support of Example 13, which has worked for 15 hours as a catalyst for processing the C ₆ -C ₈ hydrocarbon fraction and containing 5.1% wt. coke.

Coke burning starts at a constant temperature of 500 ° C and is carried out for 60 minutes until the mass of the catalyst sample is stabilized; As a result of the oxidative treatment of the catalyst, 39% of the initial coke content was removed. After raising the regeneration temperature to 520 ° C and subsequent burning of coke for 60 min until the mass stabilization of the catalyst sample, another 22% of the initial coke content was removed. At a temperature of 550 ° C another 8% of coke was removed. Residual coke in the amount of 31% of the initial coke content burned out at a temperature of 600 ° C in 70 minutes. The total coke burning time was ~ 250 min. The curves of sample weight loss over time due to coke burnout in a coked catalyst are shown in FIG. one.

Example 15

Similar to example 14 with the difference that the coke is burned by the support of example 10, which worked for 15 hours as a catalyst for processing the hydrocarbon fraction C ₆ -C ₈ and containing 5.2% wt. coke.

Coke burning starts at a constant temperature of 500 ° C and is conducted for 85 minutes until the mass of the catalyst sample is stabilized; As a result of the oxidative treatment of the catalyst, 62% of the initial coke content was removed. After raising the regeneration temperature to 520 ° C and subsequent burning of coke for 75 min until the mass stabilization of the catalyst sample, another 28% of the initial coke content was removed. Residual coke in the amount of 10% of the initial coke content burned out at a temperature of 550 ° C for 20 minutes. The control temperature increase to 600 ° C did not lead to a further change in the mass of the sample, which confirms the complete removal of coke at a temperature of 550 ° C. The total coke burning time was ~ 180 min. The curves of sample weight loss over time due to coke burnout in a coked catalyst are shown in FIG. 2.

Example 16

Similar to example 14 with the difference that the coke is subjected to burning the carrier of example 12, which worked for 100 hours as a catalyst for processing the hydrocarbon fraction C ₆ -C ₈ and containing 10.2% wt. coke.

Coke burning starts at a constant temperature of 500 ° C and lasts 80 minutes until the mass of the catalyst sample is stabilized; As a result of the oxidative treatment of the catalyst, 81% of the initial coke content was removed. After raising the regeneration temperature to 520 ° C and subsequent burning of coke for 60 min until the mass stabilization of the catalyst sample, another 13% of the initial coke content was removed. Residual coke in the amount of 6% of the initial coke content burned out at a temperature of 550 ° C for 20 minutes. The control temperature increase to 600 ° C did not lead to a further change in the mass of the sample, which confirms the complete removal of coke at a temperature of 550 ° C. The total coke burning time was ~ 160 min. The curves of sample weight loss over time due to coke burnout in a coked catalyst are shown in FIG. 3.

Example 17

The test of the catalyst in the reforming process is carried out in a laboratory installation with a tubular isothermal reactor. When testing the catalyst, the model fraction of C ₆ -C ₈ hydrocarbons containing naphthenes, n-paraffins and isoparaffins in a weight ratio of 1: 1: 1 is used as a feedstock for the reforming process. The catalyst used is the catalyst of Example 10. Before the test, the catalyst is activated in an air stream for 1 hour at 450 ° C, then purged with nitrogen and reduced in a stream of hydrogen at a temperature of 480 ° C for 4 hours. The reforming of the hydrocarbon fraction C ₆ -C _{8 is} carried out at a temperature of 480 ° C, an excess pressure of 1.0 MPa, a volumetric feed rate of liquid feed of 2.0 h ^-1 and a molar ratio of hydrogen to hydrocarbons of H ₂ / CH = 5. Under these conditions, the resulting gasoline fraction C ₅₊ contains,% wt .: n-paraffins - 11.4; isoparaffins - 29.6; naphthenes - 6.2; aromatic hydrocarbons - 52.8; and has an octane rating of 83.6 MM.

Examples 18-28.

Similar to example 17. The conditions of the reforming process and the test results of the catalysts are shown in table 2. The compositions of the catalysts are shown in table 1.

Example 29 (for comparison).

Similar to example 17. As the catalyst using the catalyst of example No. 13, prepared similarly to the prototype. The composition of the catalyst are shown in table 1. The conditions of the reforming process and the test results of the catalysts are shown in table 2.

Example 30

The test of the catalyst in the hydrogenation reactions is carried out in a laboratory setup with a tubular isothermal reactor. The catalyst is tested in the process of hydrogenation of a benzene fraction containing% wt.: Paraffins C ₆ - 24.6, naphthenes C ₆ - 4.1, benzene - 34.8, paraffins C ₇ - 36.5. The catalyst used is the catalyst of Example 10. Before testing the catalyst, it is activated in a stream of air for 1 hour at 450 ° C, then purged with nitrogen and reduced in a stream of hydrogen at a temperature of 500 ° C for 2 hours. The test of the catalyst is carried out at a temperature of 380 ° C, an excess pressure of 3.0 MPa, a volumetric feed rate of liquid raw materials of 5.0 h ^-1 and a molar ratio of hydrogen to hydrocarbons of H ₂ / CH = 5. Under these conditions, the conversion of benzene is 83%, the yield of the C ₅₊ fraction is 65% by weight. Fraction C ₅₊ contains 75.9% wt. C ₅ -C ₇ paraffins, 12.9% C ₆ naphthenes, 9.1% benzene, 1.3% toluene and 0.8% xylenes.

Example 31

Similar to example 30. As a raw material of the hydrogenation process, a mixture of benzene and toluene in a ratio of 2: 1 wt. Is used. As a catalyst, the catalyst of example 1 is used. The conversion of raw materials is carried out at a temperature of 300 ° C, a pressure of 3.0 MPa, and a bulk feed rate 2.0 h ^-1 and a molar ratio of H ₂ / CH = 15. Under these conditions, the conversion of benzene is 84%, the conversion of toluene is 98%, the yield of the C ₅₊ fraction is 96% by weight. Fraction C ₅₊ contains 0.1% wt. paraffins C ₆ , 94.9% naphthenes C ₆ -C ₇ and 5.0% benzene with toluene.

Example 32

Similar to example 30. Benzene is used as the raw material of the hydrogenation process, the catalyst of Example 12 is used as the catalyst. The feed is converted at a temperature of 280 ° C, a pressure of 5.0 MPa, a bulk feed rate of 1.7 h ^-1 and a molar ratio of N ₂ / CH = 10. Under these conditions, the conversion of benzene is 96%, the yield of the C ₅₊ fraction is 97% by weight. Fraction C ₅₊ contains 0.1% wt. paraffins C ₆ , 24.9% methylcyclopentane, 71.2% cyclohexane and 3.8% benzene.

As can be seen from the above examples No. 13-15 and FIG. 1-3, the proposed catalyst has the ability to remove coke deposits from the surface of the zeolite component of the regenerated catalyst under milder conditions, consisting in lowering the temperature of complete burning of coke from 600 ° C to 550 ° C and reducing the total regeneration time. Moreover, it is highly active in the reforming of gasoline fractions and the hydrogenation of aromatic hydrocarbons. In addition, under the same conditions of the reforming process as the prototype, the proposed catalyst produces a C ₅₊ gasoline fraction with a high content of aromatic hydrocarbons and a high octane number than the prototype catalyst (see, respectively, examples 17 and 29 in table 2).

Claims (18)

1. The catalyst for reforming gasoline fractions, hydrogenation of the benzene fraction or aromatic hydrocarbons containing aluminum oxide, platinum, zeolite with a structure of ZSM-5 or ZSM-11, characterized in that the catalyst contains zeolite crystalline ferroaluminosilicate or ferrogallium aluminosilicate with a structure of zeolite ZSM- 5 or ZSM-11 and has the following composition, wt.%: platinum 0.1-0.5 specified zeolite 1-75 aluminium oxide rest 2. The catalyst according to claim 1, characterized in that the ferroaluminosilicate has a molar ratio of SiO ₂ / Al ₂ O ₃ in the range of 38-310 and contains 0.1-1.5 wt.% Iron. 3. The catalyst according to claim 1, characterized in that the ferrogallium aluminum silicate has a molar ratio of SiO ₂ / Al ₂ O ₃ in the range of 61-320 and contains 0.1-1.2% wt. iron and 0.1-1.5% gallium. 4. The catalyst according to any one of paragraphs. 1-3, characterized in that it further includes a promoter - rhenium and / or tin in an amount of 0.1-1.6 wt.%. 5. The catalyst according to claim 1, characterized in that the catalyst contains 0.1-1.6 wt.% Chlorine. 6. A method of producing a catalyst according to claims 1-5 for reforming gasoline fractions, hydrogenating a benzene fraction or aromatic hydrocarbons by mixing a powder or paste of aluminum hydroxide and zeolite with a structure of ZSM-5 or ZSM-11, adding a solution of mineral and / or organic acid to as a peptizer, molding the resulting mixture, neutralizing the formed granules with ammonia solution, drying and calcining the formed granules, impregnating the calcined granules of the carrier with platinum compounds, drying and calcining the granules and characterized in that the crystalline zeolite is used ferroalyumosilikat or ferrogalliyalyumosilikat zeolite structure with ZSM-5 or ZSM-11. 7. The method according to p. 6, characterized in that the ferroaluminosilicate has a molar ratio of SiO ₂ / Al ₂ O ₃ in the range of 38-310 and contains 0.1-1.5 wt.% Iron. 8. The method according to p. 6, characterized in that the ferrogallium aluminum silicate has a molar ratio of SiO ₂ / Al ₂ O ₃ in the range of 61-320 and contains 0.1-1.2 wt.% Iron and 0.1-1.5% Gaul. 9. The method according to p. 6, characterized in that in addition, rhenium and / or tin are used as a promoter. 10. The method according to p. 6, characterized in that the impregnation of the calcined carrier granules with platinum compounds is carried out in a solution of mineral and / or organic acid. 11. The method according to p. 9, characterized in that the mixing of aluminum hydroxide with a powder or zeolite paste is carried out with a promoter representing a tin compound. 12. The method according to p. 9, characterized in that the impregnation of the calcined carrier granules with platinum compounds and compounds of rhenium and / or tin promoters is carried out in a solution of mineral and / or organic acid. 13. The method according to any one of paragraphs. 6-12, characterized in that the calcination of the carrier is carried out at a temperature of 500-650 ° C, the calcination of the catalyst is carried out at a temperature of 450-550 ° C. 14. A method of reforming gasoline fractions by contacting them in the presence of a hydrogen-containing gas at elevated temperatures and overpressure with a catalyst, characterized in that the catalyst used in accordance with any one of paragraphs is used as a catalyst. 1-5. 15. The method according to p. 14, characterized in that the reforming of gasoline fractions is carried out at a temperature of 440-560 ° C, an excess pressure of 0.3-4.0 MPa, a volumetric feed rate of liquid raw materials of 0.5-10 h ^-1 and molar the ratio of hydrogen to hydrocarbons 1-10. 16. The method of hydrogenation of a benzene fraction or aromatic hydrocarbons by contacting the feedstock with a catalyst in the presence of a hydrogen-containing gas at an overpressure, characterized in that the catalyst according to any one of paragraphs is used. 1-5. 17. The method according to p. 16, characterized in that the hydrogenation of the benzene fraction or aromatic hydrocarbons is carried out at a temperature of 220-400 ° C, a pressure of 0.5-5.0 MPa, a volumetric feed rate of liquid raw materials of 0.5-10 h ^-1 and a molar ratio of hydrogen to hydrocarbons of 4-15.

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