RU2478429C1 - Catalyst, method for production thereof and method for transalkylation of benzene with diethylbenzenes using said catalyst - Google Patents

Abstract

FIELD: chemistry.SUBSTANCE: invention relates to transalkylation catalysts. Described is a catalyst for transalkylation of benzene with diethylbenzenes in form of cylindrical granules with a regular shape, which contains zeolite Y in an acidic Hform, which contains 100 wt % zeolite with degree of substitution of Naions with Hions of not less than 0.95 and more than 80% of volume of the transported pores of the granules is made up of pores with diameter larger than 100 nm. Described is a method of producing said catalyst, which involves preparation of cylindrical granules with a regular shape, involving drying and calcination of the granules, wherein to obtain the catalyst, zeolite NaY, which is granulated with binding material and has high phase purity, wherein more than 80% of the volume of the transported pores is made up of pores with a diameter larger than 100 nm, is successively treated with aqueous solutions of ammonium salts with concentration of 20-25 g/dm(with respect to NH?) with the ratio of mass of granules to volume of the solution of (1:6)-(1:7) and temperature of 80-90°C for 1.0-1.5 hours, alternating three or four steps of said treatment with two or three intermediate calcinations, respectively, at temperature of 540-600°C for 3-4 hours, drying at temperature of 120-150°C for 3-4 hours and calcining for 3-4 hours at temperature of 540-600°C. Described is a method for transalkylation of benzene with diethylbenzenes, involving reaction of benzene with diethylbenzenes in liquid phase at high temperature and pressure using said catalyst, wherein content of water in the material is less than 200 ppm.EFFECT: high conversion of diethylbenzenes.3 cl, 2 tbl, 10 ex

Description

The present invention solves the important task of the petrochemical industry - the production of ethylbenzene by processing by-products formed during the alkylation of benzene with ethylene, namely diethylbenzenes in the presence of a zeolite-containing catalyst.

The well-known "alkylation Catalyst and method for its preparation" (US Pat. US 5036033 from 30/07/1991). The catalyst is used in the alkylation and transalkylation of aromatic hydrocarbons with C ₂ -C ₄ olefins and contains ultra-stable type Y zeolite in an acid H ⁺ form with a molar ratio of SiO ₂ / Al ₂ O _{3 of} less than or equal to 20. The catalyst contains from 70 to 95 wt. .% zeolite and 5-30 wt.% binder - aluminum oxide. Sodium oxide content less than 0.6 wt.%

A known method of producing ethylbenzene (US Pat. US 4169111 from 25/09/1979). As the active component of the catalyst, parastabilized type Y zeolite in an acid H ⁺ form with a molar ratio of SiO ₂ / Al ₂ O ₃ of 4 to 12 is used. The catalyst contains 90 wt.% Zeolite and 10 wt.% Binder - alumina (however, most often the binder content is 30 wt.%, and the zeolite is 70 wt.%). The preferred diameter of the meso and macropores in the granules of the catalyst is from 30 to 100 nm. Sodium oxide content less than 0.5 wt.%

A known method of alkylation and transalkylation using zeolite-containing catalysts (US Pat. US 5324877 from 28/06/1994). The patent describes a method for preparing a catalyst that contains 90 wt.% Ultra-stable type Y zeolite in acid H ⁺ form and 10 wt.% Binder - alumina. The molar ratio of SiO ₂ / Al ₂ O ₃ in the zeolite is from 6 to 12. The content of Na ₂ O in the catalyst is less than or equal to 0.6 wt.%

The well-known "Processes of liquid-phase alkylation and transalkylation" (US Pat. US 4459426 from 12/07/1982) of aromatic hydrocarbons by C ₂ -C ₄ olefins. The catalyst for these processes contains type Y zeolite in an acid H ⁺ form and a binder — alumina in a weight ratio of 75/25 to 90/10. The preferred diameter of the meso and macropores in the granules of the catalyst is from 30 to 100 nm. The content of Na ₂ O in the catalyst is less than or equal to 0.7 wt.%, In addition, the catalysts contain 0.5-5.0 wt.% Metal oxides of group II.

Known methods for the preparation of granular zeolite-containing catalyst for the alkylation of benzene with ethylene (A.S. SU 1401678 from 26/06/1986) and a method for preparing a ball zeolite-containing catalyst for the alkylation of benzene with Ethylene (A.S. SU 1576194 from 28/09/1988). The basis of these methods is the method of producing spherical granules containing 50 wt.% Type Y zeolite in rare earth-calcium form and 50 wt.% Binder - aluminum oxide, by means of hydrocarbon-ammonia molding of granules, their drying and calcination.

A known method of preparation of a zeolite-containing catalyst for the alkylation of benzene with ethylene (and.with. SU 1803179 from 16/07/1990). According to this method, a zeolite-containing pseudo sol of aluminum hydroxide is obtained, which is converted into a gel. The gel is formed by extrusion into granules, which are then dried and calcined. The content of type Y zeolite in rare earth-calcium form is 50-70 wt.%, And the rest is a binder (alumina).

Other catalysts are used as catalysts for liquid-phase alkylation or transalkylation of aromatic hydrocarbons, the active components of which are beta or mordenite zeolites.

A known method of liquid phase alkylation or transalkylation on a catalyst containing a zeolite type beta (US Pat. US 5081323 from 14/01/1992). The catalyst contains 60-80 wt.% Zeolite with a molar ratio of SiO ₂ / Al ₂ O ₃ from 5 to 50 in an acid H ⁺ form and the binder is alumina.

Known "Catalytic composition for the alkylation of aromatic compounds, the method of their alkylation and transalkylation" (US Pat. RU 2147929 from 15/06/1995), "Catalytic composition and method of alkylation and / or transalkylation of the aromatic compounds" (US Pat. RU 2189859 from 11/12 / 1997). The catalysts contain 50-90 wt.% Beta-type zeolite in the acid H ⁺ form, and the rest is a binder (alumina). In this case, the extraceolite (meso- and macro-) porosity of the granules — the pore volume with a radius of more than 10 nm — is at least 35% of the total pore volume. In the methods of alkylation and transalkylation of aromatic compounds, the same catalyst is used. In US Pat. RU 2189859 shows a typical block diagram of the preparation of a transalkylation catalyst consisting of a zeolite and a binder.

The well-known "catalyst for the processes of alkylation and transalkylation of aromatic hydrocarbons" (US Pat. US 4849570 from 11/03/1988). The catalyst contains from 75 to 90 wt.% Zeolite of the mordenite type in acid H ⁺ form and a binder (alumina) - the rest. The catalyst is produced in the form of spherical, extruded or granular granules. The examples describe the method of preparation of the catalyst.

Despite the apparent diversity, all considered inventions have similar disadvantages.

one). All catalytic compositions shown in the analogues are granular products consisting of a catalytically active part - zeolite and an inactive binder material, the role of which is to give the granules of the catalysts a certain shape, parameters of the secondary porous structure (size and volume of transport - meso and macropores) and mechanical strength. The fact that the zeolite content in such catalysts is not more than 90 wt.% (Often 75-80 wt.%) Leads to their low activity (yield of the target product ethylbenzene) in the transalkylation of benzene with diethylbenzenes.

2). The desire of the authors of the inventions (analogues) to maximize the content of the active base (up to 90-95 wt.%) In the catalytic compositions leads to a decrease in the mechanical strength of the granules of the catalysts, the formation of dust and crumbs at the stages of production, transportation, as well as during operation and regeneration of the catalysts.

3). The considered catalytic compositions (analogues) have an insufficiently developed secondary porous structure of granules, namely, the volume of transport - meso- and macropores, whose radius is more than 100 nm, does not exceed 35% of the total volume of transport pores. This complicates the delivery of reactants to the active sites of the catalyst and the removal of reaction products in the transalkylation of benzene with diethylbenzenes.

four). The complexity, complexity and multi-stage method for producing catalytic compositions (analogues), which includes: mixing in a certain ratio of powdered zeolite with a binder; peptization of the resulting mixture with acid; molding the resulting mass by extrusion; drying and calcining the granules.

A known catalyst for the transalkylation of benzene with diethylbenzenes, including zeolites of the types UZM-5, UZM-5P and UZM-6, containing organic cations, which can be made in the form of granules of various shapes, such as pills, balls, extrudates, spheres, etc. with or without a binder, and a method for producing it (US Pat. RF No. 2273602 dated 10/04/2006), and it is preferable to use a binder in an amount of at least 10%.

A disadvantage of the known catalyst is that molding without binding granules of zeolite types UZM-5, UZM-5P and UZM-6 leads to a deterioration in its properties compared with molding with a binder, as it allows you to get durable granules.

The closest in technical essence and the achieved result to the proposed invention is the "Catalytic composition and method of transalkylation of aromatic hydrocarbons" (US Pat. RU 2351393 from 15/12/2003, CL B01J 29/04; B01J 35/10; B01J 37/04; С07С 6/12; C10G 29/20), which was chosen as the prototype.

According to the prototype, the catalytic composition contains dealuminated zeolite type Y in an acid H ⁺ form with a molar ratio of SiO ₂ / Al ₂ O ₃ from 11 to 17 and a binder γ - alumina. The mass ratio of zeolite / binder exceeds 1: 1 and, as a rule, is 4: 1, i.e. the catalyst contains 80 wt.% zeolite and 20 wt.% a binder.

The catalytic composition is a cylindrical granules of regular shape with a diameter of at least 1.8 mm The granules have a developed structure of transport pores and at least 30% of the volume of meso- and macropores falls on pores whose diameter is greater than 100 nm.

The strength of such granules is 1.7 kg / mm (crushing strength / granule length) or 0.8 kg / mm ² (crushing strength / granule cross-sectional area).

A method of preparing a catalyst composition in accordance with the prototype includes the following stages:

- preparation of a mixture consisting of type Y zeolite in an acid H ⁺ form and a binder precursor selected from boehmite or pseudoboehmite by mechanical mixing of the components in a high-speed mixer;

- slow addition to this mixture (with constant stirring) of acetic acid solution with a concentration of not more than 0.5 wt.% in such an amount that the final ratio of the mass of acid to the total mass of the mixture is from 0.25 to 0.50%;

- extrusion molding of the mixture;

- drying the obtained granules in a stream of air at a temperature of not higher than 30 ° C for at least 48 hours;

- stepwise rise in temperature (22 hours) to the final calcination temperature (550-600 ° C) and holding at this temperature for 8 hours

The method of transalkylation of aromatic hydrocarbons involves the interaction of benzene with diethylbenzenes in the presence of a catalytic composition containing not more than 80 wt.% Type Y zeolite in an acid H ⁺ form with a molar ratio of SiO ₂ / Al ₂ O ₃ in the range from 11 to 17. The reaction is carried out in liquid or gas-liquid phase at a temperature of 150-300 ° C; pressure of 20-50 atm; the volumetric feed rate of 0.5-10 h ^-1 , the molar ratio benzene: diethylbenzene, equal to (3-30): 1, and the water content in the transalkylation feed is not more than 50 ppm.

Known catalytic composition (prototype), the method of its production and the method of transalkylation of aromatic hydrocarbons with its use have the following disadvantages:

one). The low content of type Y zeolite in the acid H ⁺ form (not more than 80 wt.%) In the composition of the catalyst, which leads to insufficient catalyst activity in the transalkylation of benzene with diethylbenzenes, namely, low conversion of diethylbenzenes and the yield of the target product ethylbenzene.

2). The catalytic composition has an insufficiently developed secondary porous structure of the granules, which complicates the delivery of reacting substances to the active centers of the catalyst and the removal of reaction products and, ultimately, reduces the activity of the compositions due to their premature deactivation.

3). Low mechanical strength of the catalyst composition, which leads to the formation of dust and crumbs at the stages of production, transportation, as well as during operation and regeneration of catalysts.

four). The large diameter of the catalyst granules obtained by mechanical mixing impairs the delivery of raw materials to the active centers of the catalyst and the removal of the products of the transalkylation reaction.

5). The complexity, complexity and multi-stage method for producing catalytic compositions, which includes: mixing powdered ultra-stable type Y zeolite in an acid H ⁺ form with a binder - boehmite or pseudoboehmite in a high-speed mixer (stirrer speed from 900 to 1100 rpm); peptization of the resulting mixture with acid at a certain mass ratio of acid to the total weight of the mixture; molding the resulting mass by extrusion; prolonged (at least 48 hours) drying of the granules at 25-30 ° C; a slow rise in temperature (22 h) to the final calcination temperature (550-600 ° C) and holding at this temperature for 8 hours

6). The need for deep drying of transalkylation feeds to a water content of less than 50 ppm (50 ppm), which leads to an increase in energy consumption at the unit for rectification of aromatic hydrocarbons. An increase in water content above the specified value causes a decrease in the activity of the catalyst in the transalkylation of benzene with diethylbenzenes.

The purpose of the invention is to improve the method of liquid-phase transalkylation of benzene with diethylbenzenes, namely increasing the conversion of diethylbenzenes, ethylbenzene yield, eliminating the formation of crumbs and dust during the production, transportation, operation and regeneration of catalysts by changing the process conditions and using high-strength granular catalyst without a binder containing 100 wt.% zeolite type Y.

) при соотношении масса гранул : объем раствора, равном (1:6)÷(1:7), и температурах 80-90°С в течение 1,0-1,5 ч, чередуя три или четыре стадии обработки с двумя или тремя промежуточными прокалками соответственно при температурах 540-600°С в течение 3-4 ч. Затем катализатор высушивают при температурах 120-150°С в течение 3-4 ч и прокаливают 3-4 ч при температурах 540-600°С.This goal is achieved due to the use in the method of transalkylation of the catalyst in the form of mechanically strong granules containing 100 wt.% Type Y zeolite in an acid H ⁺ form with a degree of substitution of Na ⁺ ions for H ^{+ of} at least 0.95. In the catalyst, more than 80% of the volume of transport pores (which include meso- and macropores) are in pores with a diameter greater than 100 nm. In the transalkylation feed, the water content is less than 200 ppm (200 ppm). To obtain a catalyst, use is made of a granular non-binder zeolite of the NaY type of high phase purity synthesized according to the invention “A method of producing a granular non-binder zeolite of the type NaY of high phase purity” (US Pat. RU 2412903 from 03/08/2009, CL 01/39), which is sequentially treated with aqueous solutions of ammonium salts with a concentration of 20-25 g / dm ³ (in terms of

) when the ratio of the mass of granules: the volume of the solution equal to (1: 6) ÷ (1: 7), and temperatures of 80-90 ° C for 1.0-1.5 hours, alternating three or four stages of processing with two or three intermediate calcinations, respectively, at temperatures of 540-600 ° C for 3-4 hours. Then, the catalyst is dried at temperatures of 120-150 ° C for 3-4 hours and calcined for 3-4 hours at temperatures of 540-600 ° C.

A comparative analysis of the claimed catalyst with the prototype allows us to conclude that the claimed catalyst differs from the known composition and physico-chemical properties. Namely, the fact that the catalyst granules are single intergrowths of type Y zeolite crystals; contain 100 wt.% zeolite with a degree of exchange of Na ⁺ to H ⁺ ions of at least 0.95; have a mechanical strength of not less than 2.1 kg / mm ² and more than 80% of the transport pore volume of the catalyst falls on pores with a diameter of more than 100 nm.

) при соотношении масса гранул : объем раствора, равном (1:6)÷(1:7), и температурах 80-90°С в течение 1,0-1,5 ч, чередуя три или четыре стадии обработки с двумя или тремя промежуточными прокалками при температурах 540-600°С в течение 3-4 ч. Затем катализатор высушивают при температурах 120-150°С в течение 3-4 ч и прокаливают 3-4 ч при температурах 540-600°С.The inventive method for producing a catalyst differs from the known one by using high phase purity granular granules without a zeolite of NaY type as feedstock in the form of mechanically strong granules, in which the pore volume with a diameter of more than 100 nm is more than 80% of the total volume of transport pores (US Pat. RU 2412903 from 08/03/2009, CL 01B 39/24). A NaY-type zeolite granulated without a binder is sequentially treated with aqueous solutions of ammonium salts with a concentration of 20-25 g / dm ³ (in terms of

) when the ratio of the mass of granules: the volume of the solution equal to (1: 6) ÷ (1: 7), and temperatures of 80-90 ° C for 1.0-1.5 hours, alternating three or four stages of processing with two or three intermediate calcinations at temperatures of 540-600 ° C for 3-4 hours. Then, the catalyst is dried at temperatures of 120-150 ° C for 3-4 hours and calcined for 3-4 hours at temperatures of 540-600 ° C.

A comparative analysis of the proposed method for the transalkylation of benzene with diethylbenzenes with the prototype indicates that the claimed method differs in the use of a catalyst containing 100 wt.% Type Y zeolite with a degree of substitution of Na ⁺ ions for Н ^{+ of} at least 0.95, in which more than 80% of the transport volume pores are pores with diameters greater than 100 nm, and the water content of the transalkylation feed is less than 200 ppm (200 ppm). This achieves a higher conversion of diethylbenzenes and a higher yield of ethylbenzene in the method of transalkylation of benzene with diethylbenzenes.

The essence of the invention is as follows. The catalyst granules are single intergrowths of zeolite crystals, contain 100% type Y zeolite with a degree of substitution of Na ⁺ for H ^{+ of} at least 0.95, and more than 80% of the transport (meso- and macro-) pore volume of the granules are pores with a diameter of more than 100 nm A restriction on the size of transport pores is necessary to ensure a long catalyst life, namely, to reduce the rate of catalyst deactivation.

), при соотношении масса гранул : объем раствора, равном (1:6)÷(1:7), и температурах 80-90°С в течение 1,0-1,5 ч. Три или четыре таких обработки чередуются с двумя или тремя промежуточными прокалками при температурах 540-600°С в течение 3-4 ч. Затем катализатор высушивают при температурах 120-150°С в течение 3-4 ч и прокаливают 3-4 ч при температурах 540-600°С. Полученный катализатор содержит 100 мас.% цеолита типа Y со степенью замещения ионов Na⁺ на Н⁺ не менее 0,95; имеет диаметр гранул 1,5-1,7 мм; обладает механической прочностью не менее 2,1 кг/мм² и, по меньшей мере, 80% объема транспортных пор катализатора составляют поры диаметром больше 100 нм.The essence of the catalyst preparation method consists in sequential processing of NaY type granular without a binder zeolite of high phase purity in the form of mechanically strong granules, in which the pore volume with a diameter of more than 100 nm is more than 80% of the total volume of transport pores, with aqueous solutions of ammonium salts (sulfate, chloride or nitrate) with a concentration of 20-25 g / DM ³ (in terms of

), with the ratio of the mass of granules: the volume of the solution equal to (1: 6) ÷ (1: 7), and temperatures of 80-90 ° С for 1.0-1.5 hours. Three or four such treatments alternate with two or three intermediate calcinations at temperatures of 540-600 ° C for 3-4 hours. Then the catalyst is dried at temperatures of 120-150 ° C for 3-4 hours and calcined for 3-4 hours at temperatures of 540-600 ° C. The resulting catalyst contains 100 wt.% Type Y zeolite with a degree of substitution of Na ⁺ ions on H ⁺ not less than 0.95; has a diameter of granules of 1.5-1.7 mm; has a mechanical strength of at least 2.1 kg / mm ² and at least 80% of the transport pore volume of the catalyst are pores with a diameter greater than 100 nm.

The essence of the transalkylation of benzene with diethylbenzenes consists in the interaction of benzene with diethylbenzenes in the liquid phase on a zeolite-containing catalyst at elevated temperature and pressure, and granules representing single intergrowths of type Y zeolite crystals containing 100 wt.% Zeolite with a degree of substitution of Na ions are used as a catalyst ⁺ H ⁺ at least 0.95, wherein more than 80% of the volume of transport pores granules is in pores with a diameter greater than 100 nm, and the water content of the transalkylation feed is m her 200 parts per million (200 ppm).

The following are examples of compositions and methods for preparing benzene transalkylation catalysts with diethylbenzenes, as well as their physicochemical and catalytic properties in a method for transalkylating benzene with diethylbenzenes, illustrating the invention.

Example 1 (prototype).

80 g (in terms of absolutely dry matter) of zeolite Y CBV 712 (molar ratio SiO ₂ / Al ₂ O ₃ = 12) in powder form and 20 g (in terms of absolutely dry substance) of pseudoboehmite Versal V-250 in powder form into the turbomixer (the number of revolutions of the mixer is 1000 rpm). Then add 58 cm ³ 0.5 wt.% An aqueous solution of glacial acetic acid with a constant speed for 36 minutes at a speed of rotation of the mixer 400 rpm The final ratio of the mass of acid to the total mass of the mixture before adding acid is 0.288. The mixture is then further stirred at a stirrer speed of 400 rpm for 12 minutes. The resulting mass is extruded. The extruded product in the form of regular cylinders with a diameter of 2.1 mm was placed in a drying oven and dried at a temperature of 25 ° C for 48 hours. Then, the granules were calcined according to a stepwise temperature regime. The temperature is raised from room temperature to 120 ° C for 360 minutes, kept at this temperature for 120 minutes, from 120 to 350 ° C for 360 minutes, kept at this temperature for 240 minutes, from 350 to 550 ° C for 240 min, maintained at this temperature for 480 min. The finished catalyst is analyzed.

The phase composition and the unit cell parameter of the zeolite is determined by X-ray diffraction (XRD) analysis on a PHILIPS PW 1800 automatic diffractometer. X-ray diffraction patterns are identified by known diffraction data. The lattice module of zeolites (M) is calculated according to the Breck-Flanigen equation, based on the calculated unit cell parameters:

where n _Al is the number of aluminum atoms in the unit cell, calculated by the formula:

n _Al = 115.2 · (a _x -24.191);

a _x is the cell parameter, Å.

The content of sodium oxide is determined by transferring it to the solution with hydrofluoric acid and then by flame photometry using a PLAPHO-4 device.

The degree of substitution (K) of Na ⁺ ions on H ⁺ in the catalysts is determined by the formula:

- содержание оксида натрия в исходном цеолите, мас.%;Where

- the content of sodium oxide in the initial zeolite, wt.%;

- содержание оксида натрия в катализаторе, мас.%

- the content of sodium oxide in the catalyst, wt.%

Determination of mechanical crushing strength is carried out according to OST 38.01134-77. Catalysts and adsorbents. - 1978.

The porous structure of the granules was examined by mercury porosimetry on a Porosimeter-2000 mercury poromer by measuring mercury indentation curves. Penetration of mercury into pores with a diameter of from 8 to 2000 nm is carried out at a pressure of from 0.1 to 200 MPa. The properties of the catalyst are shown in tables 1, 2.

Example 2

100 g granulated without a binder zeolite of the NaY type of high phase purity with a diameter of granules equal to 1.7 mm (obtained in accordance with US Pat. RU 2412903) is treated with 0.7 dm ^{3 of an} aqueous solution of ammonium sulfate with a concentration of 20 g / dm ³ ( in terms of NH ₄ ⁺ ) with the ratio of the mass of granules: the volume of the solution equal to 1: 7, and a temperature of 80 ° C for 1.5 hours. Four such treatments are carried out, alternating them with three intermediate calcinations at a temperature of 540 ° C for 4 hours. Then the catalyst is dried at a temperature of 120 ° C for 3 hours and calcined for 4 hours at a temperature f 540 ° C. The properties of the catalyst are shown in tables 1, 2.

Example 3

100 g granulated without a binder zeolite of the NaY type of high phase purity with a diameter of granules equal to 1.5 mm (obtained in accordance with US Pat. RU 2412903) is treated with 0.6 dm ^{3 of an} aqueous solution of ammonium nitrate with a concentration of 25 g / dm ³ ( in terms of NH ₄ ⁺ ) with the ratio of the mass of granules: the volume of the solution equal to 1: 6 and a temperature of 90 ° C for 1.0 h. Three such treatments are carried out, alternating them with two intermediate calcinations at a temperature of 600 ° C for 3 hours Then the catalyst is dried at a temperature of 150 ° C for 4 hours and calcined for 3 hours at a temperature of 600 ° FROM. The properties of the catalyst are shown in tables 1, 2.

Example 4

100 g of granular granule without a NaY type zeolite of high phase purity with a granule diameter of 1.0 mm (obtained in accordance with US Pat. RU 2412903) is treated with 0.7 dm ^{3 of an} aqueous solution of ammonium sulfate with a concentration of 20 g / dm ³ ( in terms of NH ₄ ⁺ ) with the ratio of the mass of granules: the volume of the solution equal to 1: 7, and a temperature of 80 ° C for 1.5 hours. Four such treatments are carried out, alternating them with three intermediate calcinations at a temperature of 540 ° C for 4 hours. Then the catalyst is dried at a temperature of 120 ° C for 3 hours and calcined for 4 hours at a temperature f 540 ° C. The properties of the catalyst are shown in tables 1, 2.

Example 5

100 g of granular granule without a NaY type zeolite of high phase purity with a diameter of granules of 3.2 mm (obtained in accordance with US Pat. RU 2412903) is treated with 0.6 dm ^{3 of an} aqueous solution of ammonium nitrate with a concentration of 25 g / dm ³ ( in terms of NH ₄ ⁺ ) with the ratio of the mass of granules: the volume of the solution equal to 1: 6, and a temperature of 90 ° C for 1.0 h. Three such treatments are carried out, alternating them with two intermediate calcinations at a temperature of 600 ° C for 3 hours. Then the catalyst is dried at a temperature of 150 ° C for 4 hours and calcined for 3 hours at a temperature of 600 S. The properties of the catalyst are shown in tables 1, 2.

Example 6 (comparative).

100 g granulated without a binder zeolite of the NaY type of high phase purity with a diameter of granules of 1.6 mm (obtained in accordance with US Pat. RU 2412903) is treated with 0.7 dm ^{3 of an} aqueous solution of ammonium sulfate with a concentration of 20 g / dm ³ ( in terms of NH ₄ ⁺ ) with the ratio of the mass of granules: the volume of the solution equal to 1: 7, and a temperature of 80 ° C for 1.5 hours. Two such treatments are carried out with one intermediate calcination at a temperature of 540 ° C for 4 hours. Then the catalyst is dried at a temperature of 120 ° C for 3 hours and calcined for 4 hours at a temperature of 540 ° C. A decrease in the number of zeolite treatments with a solution of ammonium sulfate to two, while reducing the number of intermediate calcinations to one, leads to a decrease in the degree of substitution of Na ⁺ ions for H ⁺ less than 0.95. This causes a deterioration in catalytic properties, namely, a decrease in the conversion of diethylbenzenes and the yield of ethylbenzene. The properties of the catalyst are shown in tables 1, 2.

Example 7 (comparative).

100 g of high purity granulated without a binder zeolite of the NaY type with a granule diameter of 1.6 mm (obtained in accordance with US Pat. RU 2412903) is treated with 0.7 dm ^{3 of an} aqueous solution of ammonium sulfate with a concentration of 20 g / dm ³ (in in terms of NH ₄ ⁺ ) with the ratio of the mass of granules: the volume of the solution equal to 1: 7, and a temperature of 80 ° C for 1.5 hours. Five such treatments are carried out, alternating them with four intermediate calcinations at a temperature of 540 ° C for 4 o'clock Then the catalyst is dried at a temperature of 120 ° C for 3 hours and calcined for 4 hours at a temperature of 540 ° C. An increase in the number of zeolite treatments with a solution of ammonium sulfate to five with a simultaneous increase in the number of intermediate calcinations from three to four leads to almost complete replacement of Na ⁺ ions by H ⁺ . However, four intermediate calcinations at a temperature of 540 ° C cause partial amorphization of the zeolite. The zeolite content in the composition of the granules of the catalyst is reduced from 100 to 92 wt.%. This leads to a deterioration in catalytic properties, namely, a decrease in the conversion of diethylbenzenes and the yield of ethylbenzene. The properties of the catalyst are shown in tables 1, 2.

Example 8 (comparative).

100 g granulated without a binder zeolite of the NaY type of high phase purity with a diameter of granules of 1.6 mm (obtained in accordance with US Pat. RU 2412903) is treated with 0.7 dm ^{3 of an} aqueous solution of ammonium sulfate with a concentration of 20 g / dm ³ ( in terms of NH ₄ ⁺ ) with the ratio of the mass of granules: the volume of the solution equal to 1: 7, and a temperature of 80 ° C for 1.5 hours. Four such treatments are carried out, alternating them with three intermediate calcinations at a temperature of 500 ° C for 4 hours. Then the catalyst is dried at a temperature of 120 ° C for 3 hours and calcined for 4 hours at a temperature f 540 ° C. A decrease in the temperature of intermediate calcinations from 540 to 500 ° C causes a decrease in the degree of substitution of Na ⁺ ions for H ⁺ less than 0.95. This leads to a deterioration in catalytic properties, namely, a decrease in the conversion of diethylbenzenes and the yield of ethylbenzene. The properties of the catalyst are shown in tables 1, 2.

Example 9 (comparative)

100 g granulated without a binder zeolite of the NaY type of high phase purity with a diameter of granules of 1.6 mm (obtained in accordance with US Pat. RU 2412903) is treated with 0.6 dm ^{3 of an} aqueous solution of ammonium nitrate with a concentration of 25 g / dm ³ ( in terms of NH ₄ ⁺ ) with the ratio of the mass of granules: the volume of the solution equal to 1: 6, and a temperature of 90 ° C for 1.0 h. Three such treatments are carried out, alternating them with two intermediate calcinations at a temperature of 650 ° C for 3 hours. Then the catalyst is dried at a temperature of 150 ° C for 4 hours and calcined for 3 hours at a temperature of 600 S. An increase in the temperature of intermediate calcinations from 600 to 650 ° C leads to partial amorphization of the zeolite. The zeolite content in the composition of the catalyst granules is reduced from 100 to 88 wt.%. This causes a deterioration in catalytic properties, namely, a decrease in the conversion of diethylbenzenes and the yield of ethylbenzene. The properties of the catalyst are shown in tables 1, 2.

Treatment of zeolite with solutions of ammonium salts at a temperature below 80 ° C, as well as a decrease in concentration of less than 20 g / dm ³ (in terms of NH ₄ ⁺ ), a decrease in the ratio of the mass of granules: volume of the solution (less than 1: 6) and a decrease in the processing time ( less than 1 h) is impractical, since the ion exchange conditions are worsened, which leads to a decrease in the degree of substitution of Na ⁺ ions for H ⁺ .

Processing zeolite with solutions of ammonium salts at temperatures above 90 ° C, as well as increasing the concentration of the solution over 25 g / dm ³ (in terms of NH ₄ ⁺ ), increasing the ratio of the mass of granules: the volume of the solution (more than 1: 7) and increasing the processing time (more than 1.5 hours) technologically and economically impractical.

Example 10

The catalytic properties of the known and synthesized catalysts (examples 1-9) are evaluated in isothermal mode on a flow-through installation. 30 cm ^{3 of} catalyst are loaded into the reactor, which is preliminarily crushed to obtain a uniform (granule length) fraction of 2.5-3 mm. The space under and above the catalyst layer is filled with broken quartz (packing) of a fraction of 2.5-3 mm. The height of the loaded catalyst bed and nozzle is 75-80 mm, the inner diameter of the reactor is 25 mm.

Before testing, the system is sealed. Turn on the heating of the furnace and raise the temperature in the reactor to 150-160 ° C at a speed of not more than 20 deg / h. At this temperature, the catalyst is dried in a stream of nitrogen for 3-4 hours, then the temperature is raised to 220 ° C and at this temperature the catalyst is additionally held for 1 hour. The reaction temperature is maintained automatically. Set the pressure in the reactor of 0.3 MPa and begin the flow of raw materials with a space velocity of 1 h ^-1 . The duration of one experiment is 56 hours.

A mixture of benzene according to GOST 9572-93 and diethylbenzenes according to TU 2414-135-05766575-2007 is used as raw material.

The composition of the raw material, which is used to determine the catalytic properties of the catalysts obtained in examples 1-9, contains (wt.%):

benzene - 84.6;

∑ diethylbenzenes - 15.4;

Water - 40 ppm; 195 ppm; 225 ppm.

The test conditions of the catalysts obtained in examples 1-9:

temperature, ° С 220 pressure, MPa 3.0 feed space velocity, h ^-1 1,0 mass ratio benzene / diethylbenzenes 5/1 experiment duration, h 56

The composition of the raw materials and reaction products are analyzed by chromatographic method on a Crystallux-4000M instrument on a 60 m long capillary column processed by ZB WAX in the programmed temperature rise mode using a flame ionization detector. Components are identified by comparing their retention times with reference individual substances. Calculation of chromatograms is carried out by the method of "internal normalization".

The conversion of diethylbenzenes (DEB) is calculated by the formula, (X),%:

- массовая доля ДЭБ в катализате, мас.%;Where

- mass fraction of DEB in the catalysis, wt.%;

- массовая доля ДЭБ в сырье, мас.%

- mass fraction of DEB in raw materials, wt.%

The yield of ethylbenzene (wt.%) Is taken from these chromatograms. The catalytic properties of the catalysts obtained in examples 1-9 are shown in table 2.

Claims (3)

1. The catalyst for the transalkylation of benzene with diethylbenzenes in the form of cylindrical granules of the correct form with certain characteristics of the porous structure, including type Y zeolite in an acid H ⁺ form, characterized in that the catalyst contains 100 wt.% Zeolite with a degree of substitution of Na ⁺ ions for H ⁺ not less than 0.95 and more than 80% of the volume of transport pores of the granules are pores with a diameter of more than 100 nm. 2. A method of producing a catalyst for transalkylation of benzene with diethylbenzenes according to claim 1, including the preparation of cylindrical granules of the correct form with certain characteristics of the porous structure by mixing zeolite type Y in an acid H ⁺ form and a binder, drying and calcining the granules, characterized in that to obtain catalyst, granular without a binder, a zeolite of the NaY type of high phase purity, in which more than 80% of the transport pore volume falls on pores with a diameter of more than 100 nm, are sequentially treated with aqueous ammonium salts proof operation with a concentration of 20-25 g / ^dm3 (based on

) with the ratio of the mass of granules: the volume of the solution equal to (1: 6) - (1: 7) and temperatures of 80-90 ° C for 1.0-1.5 hours, alternating three or four stages of the indicated treatment with two or three intermediate calcinations, respectively, at temperatures of 540-600 ° C for 3-4 hours, dried at temperatures of 120-150 ° C for 3-4 hours and calcined for 3-4 hours at temperatures of 540-600 ° C. 3. The method of transalkylation of benzene with diethylbenzenes, comprising reacting benzene with diethylbenzenes in the liquid phase on a zeolite-containing catalyst at elevated temperature and pressure, characterized in that the catalyst according to claim 1 is used, and the water content in the transalkylation feed is less than 200 ppm (200 ppm )