RU2333035C2 - Zeolite-containing catalyst, method for obtaining same and method of transformation of c2-c12 aliphatic hydrocarbon into aromatic hydrocarbons or high-octane gasoline component - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: invention describes zeolite-containing catalyst for transformation of aliphatic hydrocarbons C₂-C₁₂ to a mix of aromatic hydrocarbons or high-octane gasoline component containing zeolite ZSM-5 with silicate module SiO₂/Al₂O₃=60-80 mol/mol and 0.02-0.05 wt % of residual sodium oxide content, zeolite structural element, promoter and binding component, with zirconium or zirconium and nickel oxides as zeolite structural component, and zinc oxide as promoter, at the following component ratio (wt %): zeolite 65.00-80.00; ZrO₂ 1.59-4.00; NiO 0-1.00; ZnO 0-5.00; Na₂O 0.02-0.05, the rest being binding component. Also, a method for obtaining zeolite-containing catalyst is described, which involves mixing reagents, hydrothermal synthesis, flushing, drying and calcinations of sediment. The reaction mix of water solutions of aluminum, zirconium and nickel salts, sodium hydroxide, silicagel and/or aqueous silicate acid, inoculating zeolite crystals with ZSM-5 structure in Na or H-form, and structure-former, such as n-butanol, is placed in an autoclave, where hydrothermal synthesis is performed at 160-190°C for 10-20 hours with continuous stirring; the hydrothermal synthesis over, Na-form pulp of the zeolite is filtered; the obtained sediment is flushed with domestic water and transferred to salt ion exchange by processing by water ammonium chloride solution with heating and stirring of the pulp; the pulp obtained from salt ion exchange is filtered and flushed with demineralised water with residual sodium oxide content of 0.02-0.05 wt % on the basis of dried and calcinated product; flushed sediment of ammonium zeolite form proceeds to zinc promoter introduction and preparation of catalyst mass by mixing of ammonium zeolite form modified by zinc and active aluminum hydroxide; obtained catalyst mass is extruded and granulated; the granules are dried at 100-110°C and calcinated at 550-650°C; calcinated granules of zeolite-containing catalyst are sorted, ready fraction of zeolite-containing catalyst is separated, while the granule fraction under 2.5 mm is milled into homogenous powder and returned to the stage of catalyst mass preparation. The invention also describes method of transformation of aliphatic hydrocarbons to high-octane gasoline component or a mix of aromatic hydrocarbons (variants), involving heating and passing raw material (gasoline oil fraction direct sublimation vapours or gas mix of saturated C₂-C₄ hydrocarbons) through stationary layer of the aforesaid catalyst.

EFFECT: reduced number of components and synthesis stages of zeolite-containing catalyst; increased transformation degree of raw material; improved quality and yield of target products with the said catalyst.

4 cl, 8 tbl, 12 ex

Description

The invention relates to the field of oil refining and petrochemical industries and is devoted to the creation of catalysts used in the processing of aliphatic hydrocarbons C ₂ -C ₁₂ into a mixture of aromatic hydrocarbons or high-octane gasoline component.

A known zeolite-containing catalyst and a method for producing high octane gasolines and aromatic hydrocarbons with its use (RF patent No. 2087191, 1997). The catalyst includes a zeolite of the pentasil group, zinc oxide, rare earth oxide (REE), a binder component and additionally contains boron oxide and fluorine, and as a rare earth element two or more oxides selected from the group of lanthanides: lanthanum oxide, cerium oxide, neodymium oxide , praseodymium oxide, and has the following content of components, wt.%: zeolite 20-70, zinc oxide 1.0-4.0, REE oxides 0.1-2.0, boron oxide 0.1-3.0, fluorine 0.1-3.0, the binder component is the rest. The method of converting aliphatic hydrocarbons C ₂ -C ₁₂ to high-octane gasoline and aromatic hydrocarbons is carried out by contacting them with a catalyst at 280-550 ° C, a pressure of 0.5-3.0 MPa and a bulk feed rate of 0.5-3.0 h ^-1 .

A known zeolite-containing catalyst for the conversion of aliphatic hydrocarbons C ₂ -C ₁₂ into high-octane gasoline enriched in aromatic hydrocarbons (RF patent No. 2092240, 1997). The catalyst contains a zeolite of the pentasil group with a silicate module SiO ₂ / Al ₂ O ₃ = 20-80 mol / mol and a residual Na ₂ O content of 0.1-0.4 wt.%, A binder component, zinc and a mixture of rare earth oxides in the following the ratio of components, wt.%: zeolite 25.0-50.0, zinc 1.0-3.0, the sum of REE oxides 0.1-2.0, which is a mixture of the following composition, wt.%: CeO ₂ 40, 0-55,0 sum La ₂ O _3, Pr ₂ O _3, Nd ₂ O ₃ 60,0-45,0, a binder component - the rest. The method of converting aliphatic hydrocarbons C ₂ -C ₁₂ into a high-octane component of motor gasoline with an octane rating of at least 76 points or an aromatic hydrocarbon concentrate is carried out by contacting the catalyst with the feed at a temperature of 280-550 ° C, a pressure of 0.2-2.0 MPa and volumetric feed rates of 0.5-5.0 h ^-1 .

A zeolite-containing catalyst is known for converting C ₂ -C ₁₂ aliphatic hydrocarbons into a high-octane gasoline component with an octane rating of at least 76 points or into an aromatic hydrocarbon concentrate (RF patent No. 2100075, 1997). The catalyst contains a zeolite of the pentasil group with a silicate module SiO ₂ / Al ₂ O ₃ = 20-80 mol / mol and a residual Na ₂ O content of not more than 0.2 wt.%, A binder component, zinc oxides and rare earth elements as promoters, and characterized in that it additionally contains phosphorus pentoxide when two or more of the following are used as REE oxides: CeO ₂ , La ₂ O ₃ , Nd ₂ O ₃ , Pr ₂ O ₃ , etc. with the following content of components, wt.%: zeolite 50-75, ZnO 0.5-3.0, sum (REE) ₂ O ₃ 0.5-3.0, P ₂ O ₅ 0.5-2.0, the connecting component is the rest. The method of converting aliphatic hydrocarbons C ₂ -C ₁₂ into a high-octane component of motor gasoline with an octane rating of at least 76 points or an aromatic hydrocarbon concentrate on this zeolite-containing catalyst is carried out by contacting the catalyst with the feed at a temperature of 280-550 ° C, pressure 0.2-2, 0 MPa and a volumetric feed rate of 0.5-5.0 h ^-1 .

Known methods for producing motor fuels from gas condensate (RF patents No. 20088323, 1994 and 2030446, 1995). The straight run gasoline fraction is contacted at 300-480 ° C and 0.2-4.0 MPa with a zeolite-containing catalyst. The resulting products are fractionated with the release of gaseous and liquid fractions, the liquid fraction is rectified with the release of high octane and residual fractions. The straight run residual fraction or its mixture with gaseous contact products is subjected to pyrolysis. The resulting products are fractionated with the release of pyrocondensate and pyrogas, followed by mixing of the pyrogas with a straight-run gasoline fraction and their joint contact with the catalyst. The pyrocondensate is combined with liquid contact products and subjected to their joint distillation with the release of the target gasoline and the residual fraction. As a catalyst, systems based on zeolites with ZSM-5 or ZSM-11 structures are used, including those modified by elements of groups I, II, III, V, VI, and VIII of the periodic system of elements.

The disadvantages of the above methods for producing zeolite-containing catalysts are their complex composition and the presence of harmful effluents in the production process, as well as the need for fluorine synthesis (RF patent No. 2087191, 1997), high residual content of sodium oxide and low mass fraction of the active part of the catalyst (RF patent No. 2092240, 1997), which significantly reduces its productivity in the target product, the high cost of catalysts containing expensive rare earth oxides. In addition, a significant drawback of most zeolite-containing catalysts is the inability to implement with their help a method for converting gaseous aliphatic hydrocarbons of composition C ₂ -C ₄ into a condensed liquid phase of aromatic hydrocarbons.

Closest to the claimed catalyst is a zeolite-containing catalyst, a method for its preparation and a method for converting aliphatic hydrocarbons into an aromatic hydrocarbon concentrate or high-octane gasoline component (RF patent, 2221643, 2004). The zeolite-containing catalyst contains a pentasil group zeolite with a silicate module SiO ₂ / Al ₂ O ₃ = 55-102 mol / mol and a residual content of sodium oxide of 0.02-0.07 wt.%, Zinc, tin and lanthanum oxides as structural elements of the zeolite and, as a promoter, chromium oxide with the following content of components, wt.%: zeolite 65.0-80.0; ZnO 0.0-4.0; SnO ₂ 0.0-2.5; La ₂ O ₃ 0.0-0.8; Cr ₂ O ₃ 0.0-5.0; Na ₂ O 0.02-0.07, the binder component is the rest. Methods are also described for converting aliphatic hydrocarbons into an aromatic hydrocarbon concentrate or high-octane gasoline component (options) by passing a gaseous mixture of low molecular weight saturated hydrocarbons or straight-run gasoline fraction of oil through a layer of zeolite-containing catalyst at a temperature of 500-600 ° C and 300-380 ° C, respectively, catalyst for raw materials 100-400 h ^-1 and 2 h ^-1 . The yield of the target product in the processing of gaseous hydrocarbons and straight-run gasoline fraction of oil is 49.0-60.2% and not less than 67%, respectively.

The main disadvantages of this zeolite-containing catalyst are its complex component composition, the use of expensive rare earth oxide (lanthanum oxide) and a large number of stages of preparation. This zeolite-containing catalyst, its production method and method of use is selected as a prototype. The output, octane numbers and group composition of gasolines obtained by the prototype method from a straight-run gasoline fraction of oil, as well as the conversion of a mixture of C ₂ -C ₄ alkanes, the yield and selectivity of the formation of aromatic hydrocarbons on this catalyst are shown in tables 2 and 8.

The proposed zeolite-containing catalyst, a method for its preparation and a method for converting C ₂ -C ₁₂ aliphatic hydrocarbons into a mixture of aromatic hydrocarbons or a high-octane gasoline component with its use eliminates these disadvantages.

The objective of the invention is to reduce the cost of the catalyst, simplifying the method of its production, increasing the degree of conversion of raw materials, quality and yield of target products.

The technical result of the invention is to reduce the number of components and stages of the synthesis of a zeolite-containing catalyst, increasing the degree of conversion of raw materials, quality and yield of target products on the claimed catalyst.

The technical result regarding the method of producing a zeolite-containing catalyst is achieved by the fact that the zeolite-containing catalyst contains a pentasil group zeolite with a silicate module SiO ₂ / Al ₂ O ₃ = 60-80 mol / mol and zirconium and nickel oxides as zeolite structure elements and oxide as a promoter zinc in the following ratio of components, wt.%: zeolite 65.00-80.00; ZrO ₂ 0-4.00; NiO 0-1.00; ZnO 0-5.00; Na ₂ O 0.02-0.05; the connecting component is the rest.

The technical result regarding the method based on the use of the proposed zeolite-containing catalyst for the conversion of aliphatic hydrocarbons C ₂ -C ₁₂ into a high-octane gasoline component is achieved by passing the vapors of the straight-run gasoline fraction of oil (feedstock) through a stationary catalyst bed heated to a temperature of 300-420 ° C, when the catalyst load for raw materials is 2 h ^-1 and with the yield of the target product of at least 53%.

The technical result in relation to the method based on the use of the proposed zeolite-containing catalyst to obtain a mixture of aromatic hydrocarbons is achieved by passing the vapors of a gaseous mixture of saturated hydrocarbons C ₂ -C ₄ (raw materials) through a stationary catalyst bed heated to a temperature of 550-600 ° C, under load catalyst for raw materials 100-200 h ^-1 , with the degree of conversion of raw materials 99-100% and the yield of aromatic hydrocarbons 42.0-61.1%.

The advantages of the proposed zeolite-containing catalyst are the use of cheaper and more affordable compounds for its synthesis, in the absence of an expensive rare-earth oxide - lanthanum, and in reducing the number of components and stages of catalyst synthesis.

In the future, the invention is illustrated by specific examples of its implementation.

Example 1. To obtain a zeolite-containing catalyst of a given composition containing, as an active component, a zeolite of the pentasil group in the H-form (65-80 wt.%) And a carrier in the form of γ-Al ₂ O ₃ (15-30 wt.%), First By hydrothermal synthesis, the Na-form of the zeolite is obtained, modified at the stage of synthesis by zirconium and nickel. For this, in intermediate containers, aqueous solutions of aluminum nitrate, nickel nitrate and sodium hydroxide are prepared. 28.7 g of zirconium sulfate of the 4th water grade “h” (99.5% of the main substance in the reagent), 400.0 g, are introduced into a 3.5-liter capacity tank made of stainless steel and equipped with a vane-type mechanical stirrer. acids of the “chda” silica water mark (mass fraction of loss of calcination PP ₄₀₀ = 15.56%) and 1430 ml of household drinking water. The stirrer is turned on and with vigorous stirring, 133.9 ml of an aqueous solution of aluminum nitrate with an aluminum concentration of 28.2 g / l, 637.6 ml of a solution of sodium hydroxide with a concentration of sodium hydroxide of 128.4 g / l, 12.0 are successively added to the mixture g of seed crystals of zeolite in Na or H-form and 123.0 ml of n-butanol. After mixing the mixture for 5 minutes, turn off the stirrer and pour the resulting mixture into a 5.0 L autoclave equipped with a mechanical stirrer with blades. The vacated container is rinsed in 2-3 doses of 714 ml of household drinking water, which is poured into an autoclave. The autoclave mixer is turned on and the prepared reaction mixture is autoclaved at 160-190 ° С for 10-20 hours. After completion of hydrothermal synthesis, the Na-form zeolite pulp is filtered, the resulting precipitate is washed with household drinking water until the pH = 8.5-7.0 (the ratio of liquid to solid phase during washing is 22: 1). The washed precipitate of Na-form is sent to conduct salt ion exchange.

In a 3.5 liter container made of stainless steel and equipped with a mechanical stirrer, the precipitate of the Na-form of zeolite in 1.8 liter of a 25% aqueous solution of ammonium chloride is pulped. The resulting pulp is maintained at a temperature of 90-100 ° C and with constant stirring for 4-6 hours

The pulp obtained after salt-ion exchange is filtered, washed with household drinking water at a ratio of liquid and solid phases W: T = 18: 1, and then washed with demineralized water at a ratio of liquid and solid phases W: T = 2: 1.

The washed precipitate of the ammonium form of the zeolite is dried in an oven at a temperature of 100-110 ° C for 6-8 hours and sent to the operation of preparing the catalyst mass.

The washed and dried precipitate of the ammonium form of zeolite is mixed with 125 ml of demineralized water, 176.6 g of active aluminum hydroxide in the form of a wet paste (with a residual moisture mass fraction of 26.7%) and 80 ml of nitric acid solution with a concentration of nitric acid are added to the resulting mixture. 76.7 g / l.

The resulting mixture is stirred until a homogeneous plastic catalyst mass suitable for extrusion and granulation of the catalyst (if necessary, kept in a vacuum oven to obtain a consistency suitable for extrusion and molding of catalyst granules).

The wet catalyst granules obtained after extrusion and granulation are dried in a vacuum oven at a temperature of 100-110 ° C for 4-6 hours and calcined in a muffle furnace at a temperature of 550-650 ° C for 1 hour.

The calcined catalyst pellets are screened for classification. The finished catalyst fraction is separated, and the granule fraction <2.5 mm is sent to the grinding operation in a ball mill to obtain a homogeneous powder, which is subsequently used as a charge component in the preparation of the catalyst mass.

Example 2. Straight-run gasoline fraction of oil (25.44 wt.% N-paraffins, 39.24 wt.% I-paraffins, 29.34 wt.% Naphthenes, 5.98 wt.% Aromatic hydrocarbons, octane 51 and 44 according to research and motor methods, respectively) is subjected to contact with a zeolite-containing catalyst placed in a reactor with a volume of 5 cm ³ at a temperature of 300-420 ° C, a volumetric feed rate of liquid raw materials of 2 h ^-1 and atmospheric pressure. The catalyst consists of 80.38 wt.% Zeolite of the structural type ZSM-5, containing in its structure 1.59 wt.% Zirconium, and 19.62 wt.% Γ-Al ₂ About ₃ used as a binder.

The zeolite-containing catalyst was prepared according to the method described in example 1, only crushed silica gel (KSKG grade, fraction less than 50 μm) was used as the silicon-containing component. The qualitative and quantitative composition of the obtained catalyst are shown in table 1. The output, group composition and octane numbers of the obtained gasolines are given in table 2.

Example 3. Similar to example 1, only the zeolite component of the zeolite-containing catalyst is used zeolite structure ZSM-5, containing in its structure 1.99 wt.% Zirconium and obtained using crushed silica gel (brand KSKG, fraction less than 50 microns).

The qualitative and quantitative composition of the zeolite-containing catalyst is presented in table 1. The yield, group composition and octane numbers of the obtained gasolines are given in table 3.

Example 4. Similar to example 1, only as a zeolite component of a zeolite-containing catalyst is used a zeolite structure ZSM-5, containing in its structure 2.42 wt.% Zirconium.

The qualitative and quantitative composition of the zeolite-containing catalyst is presented in table 1. The yield, group composition and octane numbers of the obtained gasolines are given in table 3.

Example 5. Similar to example 1, only as a zeolite component of a zeolite-containing catalyst is used a zeolite structure ZSM-5, containing in its structure 3.21 wt.% Zirconium.

The qualitative and quantitative composition of the zeolite-containing catalyst are presented in table 1. The yield, group composition and octane numbers of the obtained gasolines are given in table 4.

Example 6. Similar to example 4, only as a zeolite component of a zeolite-containing catalyst is used a zeolite structure ZSM-5, promoted with zinc.

The qualitative and quantitative composition of the zeolite-containing catalyst are presented in table 1. The yield, group composition and octane numbers of the obtained gasolines are given in table 4.

Example 7. Analogously to example 4, only as a zeolite component of a zeolite-containing catalyst is used a zeolite structure ZSM-5, different in silicate modulus.

The qualitative and quantitative composition of the zeolite-containing catalyst are presented in table 1. The yield, group composition and octane numbers of the obtained gasolines are given in table 5.

Example 8. Similar to example 7, only as a zeolite component of a zeolite-containing catalyst is used a zeolite structure ZSM-5, promoted with zinc.

The qualitative and quantitative composition of the zeolite-containing catalyst are presented in table 1. The yield, group composition and octane numbers of the obtained gasolines are given in table 5.

Example 9. Similar to example 7, only as a zeolite component of the zeolite-containing catalyst is used a zeolite structure ZSM-5, containing in its structure 0.08 wt.% Nickel.

The qualitative and quantitative composition of the zeolite-containing catalyst are presented in table 1. The yield, group composition and octane numbers of the obtained gasolines are given in table 6.

Example 10. Similar to example 7, only as a zeolite component of the zeolite-containing catalyst is used a zeolite structure ZSM-5, containing in its structure 0.39 wt.% Nickel.

The qualitative and quantitative composition of the zeolite-containing catalyst are presented in table 1. The yield, group composition and octane numbers of the obtained gasolines are given in table 6.

Example 11. Samples of the zeolite-containing catalyst were prepared according to the method described in example 1. As a result, eight samples of the zeolite-containing catalyst were obtained, differing in the amount in the structure of the zirconium, the silicate module of the zeolite component and the presence of zinc as a promoter. All obtained samples were tested in the process of converting a mixture of saturated C ₂ -C ₄ hydrocarbons into a mixture of aromatic hydrocarbons under equal conditions: raw materials of the following composition, wt.%: 2.2 ethane, 73.7 propane, 24.1 i- and n-butane were subjected to contact with samples of a zeolite-containing catalyst at a temperature of 600 ° C, a space velocity of 100 h ^-1 and atmospheric pressure. After the end of the process, the degree of conversion of the raw material to the final product (X,%), the selectivity of the formation of aromatic hydrocarbons (S _ap , wt.%) And the mass content of aromatic hydrocarbons in the final product (ω _ar , wt.%) Were analyzed. The results are presented in table 7.

As follows from the data presented in table 7, the high catalytic activity (X,%) and selectivity (S _ap , wt.%) Of the zeolite-containing catalyst is typical for samples containing 2.42 wt.% Zirconium and promoted with zinc. Moreover, an increase in the silicate module from 60 to 80 mol / mol leads to an increase in the mass content of aromatic hydrocarbons in the final product (ω _ap , wt.%).

Example 12. A sample of a zeolite-containing catalyst was prepared according to the method described in example 1. The content of the catalyst components was, wt.%: SiO ₂ 75.76; Al ₂ O ₃ 1,60; ZrO ₂ 2.39; ZnO 1.00; Na ₂ O 0.05; binder component 19.20. To compare the activity of the prepared zeolite-containing catalyst, the activity data of the zeolite-containing catalyst according to the prototype are given. Samples were tested during the conversion of a mixture of saturated C ₂ -C ₄ hydrocarbons into a mixture of aromatic hydrocarbons under equal conditions: raw materials of the following composition, wt.%: 2.2 ethane, 73.7 propane, 24.1 i- and n-butane, subjected contacting samples of a zeolite-containing catalyst at a temperature of 600 ° C, a space velocity of 100 and 200 h ^-1 and atmospheric pressure. After the end of the process, the degree of conversion of the raw material to the final product (X,%), the selectivity of the formation of aromatic hydrocarbons (S _ap , wt.%) And the mass content of aromatic hydrocarbons in the final product (ω _ar , wt.%) Were analyzed. The results are presented in table 8.

From the data presented in table 8, it is seen that the claimed zeolite-containing catalyst is not inferior to the prototype in terms of activity (X,%), yield (ω _ap , wt.%) And selectivity (S _ap , wt.%) Of the formation of aromatic hydrocarbons. At different bulk feed rates, the degree of conversion on the compared zeolite-containing catalysts was 100%. The mass content of aromatic hydrocarbons in the final product as a result of the conversion of raw materials in the presence of the inventive zeolite-containing catalyst at bulk speeds of 100 and 200 h ^-1 varied from 61.1 to 57.1%. The mass content of aromatic hydrocarbons in the final product when using another zeolite-containing catalyst at a space velocity of 100-200 h ^-1 varied from 60.2 to 56.3%, which is slightly less than the values obtained for the inventive zeolite-containing catalyst.

Table 1 Qualitative and quantitative composition of zeolite-containing catalysts Example The structural type of zeolite The content of components, wt.% Structure elements ZnO promoter Binder γ-Al ₂ O ₃ SiO ₂ Al ₂ O ₃ ZrO ₂ Nio Na ₂ O 2 ZSM-5 76.62 2.15 1,59 - 0.02 - 19.62 3 ZSM-5 75.44 2.15 1.99 - 0.02 - 20.40 four ZSM-5 76.73 1,61 2.42 - 0.04 - 19,20 5 ZSM-5 75.07 1.84 3.21 - 0,03 - 19.85 6 ZSM-5 75.84 1,50 2.42 - 0.04 1.00 19,20 7 ZSM-5 76.49 1,61 2.40 - 0.05 - 19.45 8 ZSM-5 75.76 1,60 2,39 - 0.05 1.00 19,20 9 ZSM-5 74.83 1,66 2.29 0.08 0.04 - 21.10 10 ZSM-5 74.41 1.65 1.96 0.39 0.04 - 21.55 table 2 The yield and group composition of the liquid reaction products * Example According to the prototype 2 Temperature ° C 300 340 360 380 300 340 380 420 Gasoline output 88 75 73 67 91 82 75 70 Product Output: Alkanes C ₃ -C ₄ 9.6 8.6 6.9 6.1 9,4 4.4 4.0 3,7 Alkenes C ₃ -C ₄ 0.6 0.8 0.8 0.6 0.4 0.3 0.4 0.6 n-alkanes C ₅₊ 8.9 6.7 6.0 5.7 9.5 8.1 7.5 8.1 i-Alkanes C ₅₊ 36.5 34.9 33.3 33,2 37.8 41.3 37,2 34.7 Alkenes C ₅₊ 3.0 2,8 2,8 2,8 2,4 3,1 3.0 3.0 Naphthenes C ₅₊ 8.0 8.2 7.4 7.7 9.2 8.1 8.4 9.7 Arenas 33,4 38,0 42.8 43.9 31.3 34.7 39.5 40,2 Octane number 81 83 84 84 77 81 83 84 * - values are indicated in wt.%. Table 3 The yield and group composition of the liquid reaction products * Example 3 four Temperature ° C 300 340 380 420 300 340 380 420 Gasoline output 89 80 71 65 85 70 65 60 Product Output: Alkanes C ₃ -C ₄ 8.5 6.2 4.4 3,1 1.7 1.7 1,1 0.6 Alkenes C ₃ -C ₄ 0.3 0.4 0.4 0.5 0.3 0.4 0.2 0.1 n-alkanes C ₅₊ 7.7 6.8 5.7 6.7 11,4 3.4 5,4 4,5 i-Alkanes C ₅₊ 37.7 38,2 36.6 33.8 38.7 28.5 26.2 25.1 Alkenes C ₅₊ 2.6 2.2 2.1 2.6 2.0 2,5 0.6 0.6 Naphthenes C ₅₊ 9.3 7.3 6.6 7.5 12.1 5,6 5,0 5,0 Arenas 33.9 38.9 44,2 45.8 33.8 57.9 61.5 64.1 Octane number 78 83 86 87 78 90 92 93 * - values are indicated in wt.%.

Table 4 The yield and group composition of the liquid reaction products * Example 5 6 Temperature ° C 300 340 380 420 300 340 380 420 Gasoline output 91 80 70 65 85 66 59 60 Product Output: Alkanes C ₃ -C ₄ 7.9 5,0 5,6 3.0 2,5 1,1 0.5 0.7 Alkenes C ₃ -C ₄ 0.3 0.3 0.5 0.5 0.1 0.1 0.1 0.1 n-alkanes C ₅₊ 8.6 7.5 6.9 6.2 11,4 4.6 3,5 3.3 i-Alkanes C ₅₊ 37.6 36,2 35.0 33.6 35,4 20.5 18.2 19.5 Alkenes C ₅₊ 2.7 2,8 2.0 2.2 0.1 0.4 0.3 0.3 Naphtha ₅₊ 9.7 7.0 7.3 6.8 11.8 7.7 5,4 7.4 Arenas 33,2 41.2 42.7 47.7 38.7 65.6 72.0 68.7 Octane number 77 84 85 87 82 92 96 95 * - values are indicated in wt.%. Table 5 The yield and group composition of the liquid reaction products * Example 7 8 Temperature ° C 300 340 380 420 300 340 380 420 Gasoline output 75 67 60 58 68 63 55 53 Product Output: Alkanes C ₃ -C ₄ 2,8 0.7 0.8 0.9 0.8 0.2 0.2 0.2 Alkenes C ₃ -C ₄ 0.2 0.1 0.3 - - - - - n-alkanes C ₅₊ 5,6 4.2 3,1 2,3 4,5 3.6 3,7 3.2 i-Alkanes C ₅₊ 27.7 22.0 22.1 21.9 22.0 20,4 18.5 17.7 Alkenes C ₅₊ 1.3 0.7 0.8 0.7 0.2 0.2 0.5 0.6 Naphthenes C ₅₊ 6.7 4.9 5.1 6.0 5.1 3,1 3.4 3.6 Arenas 55.7 67.4 67.8 68,2 67.4 72.5 73.7 74.7 Octane number 89 94 95 96 93 96 97 97 * - values are indicated in wt.%. Table 6 The yield and group composition of the liquid reaction products * Example 9 10 Temperature ° C 300 340 380 420 300 340 380 420 Gasoline output 73 65 57 54 70 64 55 53 Product Output: Alkanes C ₃ -C ₄ 9.8 6.9 4.2 2.1 1,2 0.9 1,0 1.3 Alkenes C ₃ -C ₄ 0.2 0.1 0.2 0.2 0.1 0.1 0.1 0.2 n-alkanes C ₅₊ 6.6 6.7 6.2 4.9 6.0 4.6 4.8 4.7 i-Alkanes C ₅₊ 32.6 35.1 28.7 28,2 26.2 20.6 18.7 20.3 Alkenes C ₅₊ 2,4 2,4 1.4 1.4 1,6 0.8 0.9 1,5 Naphtha ₅₊ 7.1 6.1 5.1 5,6 4,5 2.9 3.0 3,7 Arenas 41.3 42.7 54,2 57.6 60,4 70.1 71.5 68.3 Octane number 83 84 89 90 89 95 96 94 * - values are indicated in wt.%

Table 7 The dependence of the activity of the zeolite-containing catalyst on the silicate module of the zeolite component and the content of zirconium in its structure Sample No. one 2 3 four 5 6 7 8 Silicate module SiO ₂ / Al ₂ O ₃ , mol / mol 60 60 60 60 60 60 80 80 The concentration of Zr, wt.% 1,59 1.99 2.42 3.21 2.42 2.40 2,39 The concentration of Zn, wt.% 1,0 1,0 X% 96 97 99 one hundred 95 one hundred 99 one hundred S _ap , wt.% 27.3 27.0 28.9 30.8 32.9 43.0 50.7 61.1 ω _ap , wt.% 26.2 26.2 28.6 30.8 31,2 43.0 50,2 61.1 Table 8 The activity of zeolite-containing catalysts at different volumetric feed rates Zeolite-containing catalyst Obtained by the method described in example 1 According to the prototype Volumetric feed rate, h ^-1 one hundred 200 one hundred 200 X% one hundred one hundred one hundred one hundred S _ap , wt.% 61.1 57.1 60,2 56.3 ω _ar , wt.% 61.1 57.1 60,2 56.3

Claims (4)

1. The zeolite catalyst for the conversion of aliphatic hydrocarbons C ₂ -C ₁₂ aromatic hydrocarbon or a mixture of high-octane gasoline component comprising zeolite ZSM-5 with the silicate modulus SiO ₂ / Al ₂ O ₃ = 60-80 mol / mol and a residual content of sodium oxide 0 , 02-0.05 wt.%, A zeolite structure element, a promoter and a binder component, characterized in that, as a zeolite structure element, the catalyst contains zirconium oxide or zirconium and nickel oxides, zinc oxide as a promoter in the following components, wt. %: zeolite 65.00-80.00 ZrO ₂ 1.59-4.00 Nio 0-1.00 Zno 0-5.00 Na ₂ O 0.02-0.05 binder component rest 2. The method of producing a zeolite-containing catalyst according to claim 1, including the operation of mixing the reagents, hydrothermal synthesis, washing, drying and calcining the precipitate, characterized in that the reaction mixture obtained by mixing aqueous solutions of aluminum, zirconium, nickel, sodium hydroxide, silica gel and / or aqueous silicic acid, seed crystals of a zeolite with a ZSM-5 structure in Na or H form, a structurant, for example n-butanol, is loaded into an autoclave in which hydrothermal synthesis is carried out at a temperature of 160-190 ° C in t for 10–20 h with constant stirring, after completion of hydrothermal synthesis, the Na-form zeolite pulp is filtered, the resulting precipitate is washed with drinking water and sent to conduct ion-salt exchange by treating it with an aqueous solution of ammonium chloride while heating and stirring the pulp obtained after saline the ion exchange of the pulp is filtered, washed with drinking water and then washed with demineralized water to a residual content of sodium oxide of 0.02-0.05 wt.% in terms of dried and the calcined product, the washed precipitate of the ammonium zeolite form is directed to the operation of introducing the zinc promoter and preparing the catalyst mass by mixing the ammonium form of the zeolite modified with zinc with active aluminum hydroxide, the resulting catalyst mass is extruded and granulated, the granules are dried at a temperature of 100-110 ° C and calcined at 550-650 ° C, calcined zeolite-containing catalyst pellets are classified, the finished zeolite-containing catalyst fraction is separated, and the granule fraction <2.5 mm is crushed ayut to a uniform powder and recycled to the step of preparation of the catalyst mass. 3. A method of converting aliphatic hydrocarbons into a high-octane gasoline component using a zeolite-containing catalyst, comprising heating and passing the feed through a zeolite-containing catalyst, characterized in that straight-run gasoline fractions of oil are used as feedstock, which are passed through a stationary zeolite-containing catalyst layer according to claim 1, heated to a temperature of 300-420 ° C, with a catalyst load of raw materials of 2 h ^-1 . 4. A method of converting aliphatic hydrocarbons into a mixture of aromatic hydrocarbons using a zeolite-containing catalyst, comprising heating and passing a feed through a zeolite-containing catalyst, characterized in that a gaseous mixture of saturated C ₂ -C ₄ hydrocarbons is used as feed, which is passed through a stationary layer of a zeolite-containing catalyst according to claim 1, heated to a temperature of 550-600 ° C, with a load of the zeolite-containing catalyst for raw materials 100-200 h ^-1 .