RU2288034C1 - Hydrocarbon conversion process, micro-mesoporous-structure catalyst for accomplishment thereof and catalyst preparation process - Google Patents

Abstract

FIELD: petrochemical process catalysts.

SUBSTANCE: group of inventions relates to conversion of hydrocarbons using micro-mesoporous-structure catalysts. A hydrocarbon conversion process is provided involving bringing hydrocarbon raw material, under hydrocarbon conversion conditions, into contact with micro-mesoporous-structure catalyst containing microporous crystalline zeolite-structure silicates composed of T₂O₃(10-1000)SiO₂, wherein T represents elements selected from group III p-elements and group IV-VIII d-elements, and mixture thereof, micro-mesoporous structure being characterized by micropore fraction between 0.03 and 0.40 and mesopore fraction between 0.60 and 0.97. Catalyst is prepared by suspending microporous zeolite-structure crystalline silicates having above composition in alkali solution with hydroxide ion concentration 0.2-1.5 mole/L until residual content of zeolite phase in suspension 3 to 40% is achieved. Thereafter, cationic surfactant in the form of quaternary alkylammonium of general formula C_nH_2n+1(CH₃)₃NAn (where n=12-18, An is Cl, Br, HSO₄ ^-) is added to resulting silicate solution suspension and then acid is added formation of gel with pH 7.5-9.0. Gel is then subjected to hydrothermal treatment at 100-150°C at atmospheric pressure or in autoclave during 10 to 72 h to produce finished product.

EFFECT: enlarged assortment of hydrocarbons and increased selectivity of formation thereof.

16 cl, 2 dwg, 2 tbl

Description

The present invention relates to methods for the conversion of hydrocarbons using catalysts with a micro-mesoporous structure. The invention can be used in the processes of petrochemistry, oil refining and organic synthesis.

Microporous molecular sieves, such as zeolites and zeolite-like materials, are known to be catalysts in various hydrocarbon conversion processes. They have strong acidity, high thermal and thermocouple stability, as well as a developed system of pores of a certain size.

Zeolites of the type LTL, MAZ, MEI, EMT, OFF, BEA, MOR, MEL, MTW, MTT, MFI, FER, TON are widely used in hydrocarbon conversion reactions, such as cracking hydrocarbons, isomerization, transalkylation and disproportionation of alkyl aromatic compounds, alkylation of aromatic hydrocarbons the conversion of naphtha, paraffins and / or olefins to aromatic hydrocarbons, the conversion of oxygen-containing substances to aromatic hydrocarbons (US 6160191).

It is known to use in the alkylation and transalkylation reactions of aromatic compounds zeolites of the type BEA (US 4891458, US 6034291), ultrastable zeolite Y (patent US 4169111), ZSM-5, ZSM-11, ZSM-12, ZSM-23, ZSM-35, ZSM -38, ZSM-48 (US 4577048), mordenite (US 5243116), as well as MCM-22 for paraffin isomerization (US 5107054), H-ZSM-5 in the processes of aromatization of hydrocarbons (US 5574199).

US 6194616 proposes the use of ZSM-4, L, ZSM-12, ZSM-22, ZSM-23, ZSM-48, Y, X, - ZSM-5, Beta, ZSM-11, offretite, chabazite, clinoptilolite, erionite, mordenite, phillipsite in the acylation of aromatic compounds.

All of the above traditional zeolites, both natural and synthetic, have a micropore system with a diameter of less than 2 nm, which leads to difficulties in the mass transfer of reagent molecules to the active centers of the zeolite located inside its channels, as well as reaction products from the reaction zone, which reduces the efficiency of the zeolite when it is used in hydrocarbon conversion processes. In addition, zeolites do not catalyze reactions involving large organic molecules (K. Tanabe, W. F. Holderich. // Applied Catalysis A: General, 181 (1999), 399-434).

With the advent of mesoporous molecular sieves, first obtained in 1992, great prospects for heterogeneous catalysis have been associated, since it was assumed that they will be widely used as catalysts in the conversion of large molecules (US 5098684, JSBeck, JCVartuli, WHRoth et al. // J. Am. Chem. Soc. 114 (1992) 10834). In particular, it was planned to use mesoporous catalysts both in oil refining processes for deep catalytic cracking and in the fine organic synthesis and pharmaceutical industry (D.Trong On, D.Desplantier-Giscard, C.Danumah, S.Kaliaguine. // Applied Catalysis A: General, 222 (2001) 299-357).

It is known to use mesoporous catalysts modified with heteroatoms selected from the group Al, Ti, V, Cr, Zn, Fe, Sn, Mo, Ga, Ni, Co, In, Zr, Mn, Cu, Mg, Pd, Pt or W, in hydrocarbon conversion processes such as alkylation, acylation, oligomerization, selective oxidation, hydroprocessing, isomerization, demetallation, catalytic dewaxing, hydroxylation, hydrogenation, dehydrogenation and cracking (US 6,930,219).

However, the use of mesoporous materials as catalysts, characterized by a large pore diameter (from 2 to 50 nm), leads to the formation of a large number of reaction by-products, which greatly reduces the selectivity of the formation of the target products. In addition, as subsequent studies have shown, mesoporous molecular sieves have low resistance to water vapor and relatively low acidity. This has led to the fact that mesoporous catalysts have not received real distribution.

It is known to use a micro-mesoporous catalyst in cracking, alkylation and isomerization reactions in which a microporous zeolite (Beta, Y or ZSM-5) is introduced into an inorganic oxide having mesopores with a diameter of 3 to 25 nm (US 6,762,143).

The named catalyst is characterized, firstly, by the presence of two phases: zeolite and inorganic oxide, each of which has inherent disadvantages of micro- and mesoporous catalysts, and secondly, a wide range of mesopore sizes (from 3 to 25 nm), which leads to low selectivity by target products.

US 6,558,647 proposes a Beta zeolite micro-mesoporous catalyst for alkane hydrocracking.

The catalyst has a limited scope due to the presence of only the structure of the zeolite Beta.

The present invention is based on the technical task to develop a method for the conversion of hydrocarbons, which, through the use of a catalyst with a micro-mesoporous structure, would provide an expanded assortment of hydrocarbons with good selectivity for their formation.

The technical result is achieved by the fact that the proposed method for the conversion of hydrocarbons, including the introduction of hydrocarbon materials under the conditions of conversion of hydrocarbons in contact with a catalyst with a micro-mesoporous structure containing microporous crystalline silicates with a zeolite structure having the composition of the anionic framework T ₂ O ₃ (10-1000) SiO ₂ , where T is the elements selected from the group consisting of p-elements of group III or d-elements of group IV-VIII, or mixtures thereof, while the micro-mesoporous structure is characterized by a fraction of micropores from 0.03 to 0 , 40 and mesopore fractions from 0.60 to 0.97.

The use of a catalyst that combines the advantages of zeolites and mesoporous molecular sieves allows one to achieve greater catalytic activity and stability compared to microporous and mesoporous catalysts by increasing the access of reactants and reaction products to the active sites of the catalyst.

The named catalyst is versatile and can be successfully used for various hydrocarbon production processes selected from a number of processes, including cracking hydrocarbons, alkylation of aromatic compounds, transalkylation of aromatic hydrocarbons, aromatization of paraffinic hydrocarbons, acylation of aromatic compounds, isomerization of paraffinic hydrocarbons and oligomerization of olefinic hydrocarbons.

These processes are characterized by a fairly high selectivity for the formation of target products.

It is advisable to carry out the conversion of hydrocarbons at a temperature of from 220 to 550 ° C, a gauge pressure of 0.1 to 1 MPa, a feed rate of 0.5 to 5 g / g · h.

The implementation of the conversion at lower temperatures and pressures and at higher feed rates of the reagents leads to a noticeable decrease in the conversion of the feedstock. Conducting the conversion at higher temperatures and pressures and at lower feed rates of the reagents leads to a noticeable increase in the formation of reaction by-products, and therefore to a decrease in selectivity for the target reaction products.

It is advisable to use silicates with the structure of zeolites FAU, LTL, FER, MAZ, MOR, BEA, MFI, MEL, MTW as microporous crystalline silicates.

It is advisable to further modify the catalysts with metals selected from d-elements of groups II and VIII, for example zinc or platinum. The content of metals selected from d-elements of groups II and VIII is from 0.1 to 2 wt.%.

This provides catalysts with bifunctionality for use in reactions such as isomerization and / or aromatization of alkanes.

It is advisable to use a catalyst with a micro-mesoporous crystalline structure of the initial microporous silicate with acid sites with an activation energy of ammonia desorption of 140-190 kJ / mol, the proportion of which is at least 0.5, in the conversion process.

The invention is also based on the technical task of creating a catalyst with a micro-mesoporous structure and a method for its preparation, which would have high catalytic activity and ensure high selectivity for the formation of target products in various hydrocarbon conversion processes by preserving the crystal structure of the initial microporous crystalline silicate, as well as due to the presence of a regular mesopore system.

The technical result is achieved by the fact that the proposed catalyst for the conversion of hydrocarbons with a micro-mesoporous structure, which according to the invention includes microporous crystalline silicate with a zeolite structure having the composition of the anionic framework T ₂ O ₃ (10-1000) SiO ₂ , where T are the elements selected from the group consisting of p-elements of group III or d-elements of group IV-VIII, or a mixture thereof, while the micro-mesoporous structure is characterized by a micropore fraction of 0.03 to 0.40 and a mesopore fraction of 0.60 to 0, 97.

Along with silicon atoms, forming a silicate crystal lattice, Al or Ga, or B, or Fe, or Zn, or Ti, or Zr, or V, or Cr, or a mixture thereof are used.

The technical result is also achieved by the fact that the proposed method for producing a catalyst with a micro-mesoporous structure, including the suspension of microporous crystalline silicates with a zeolite structure having the composition of the anionic framework T ₂ O ₃ (10-1000) SiO ₂ , where T are elements selected from the group consisting of p-elements of group III or d-elements of group IV-VIII, or a mixture thereof in an alkaline solution with a concentration of hydroxide ions of 0.2-1.5 mol / l to achieve a residual content of the zeolite phase in a suspension of 3-40 wt. .%, the introduction of a suspension of sily ata solution of cationic surfactant in the form of a quaternary alkylammonium salt composition C _n H _{2n + 1} (CH _{3) 3} NAn, where n = 12-18, An - Cl, Br, HSO ₄ ^-, followed by the addition of acid to form a gel with a pH of 7.5-9.0 and hydrothermal treatment of the gel at 100-150 ° C at atmospheric pressure or in an autoclave for 10-72 hours with the release of the finished product, which is characterized by a fraction of micropores from 0.03 to 0.40 and fractions mesopore from 0.60 to 0.97.

The obtained micro-mesoporous catalyst has the structure of a microporous crystalline silicate with a zeolite structure of the type FAU, LTL, FER, MAZ, MOR, BEA, MFI, MEL, MTW.

If necessary, the resulting catalyst can additionally be modified by ion exchange or impregnation with metal salts selected from d-elements of groups II and VIII, mainly zinc or platinum salts. The amount of applied modifier (metal selected from d-elements of groups II and VIII) is from 0.1 to 2 wt.%.

The invention will be further described in detail in the description and examples of its implementation with reference to the accompanying drawings, in which, according to the invention

figure 1 depicts powder diffraction patterns of the source and the resulting catalysts;

figure 2 depicts the isothermal low-temperature adsorption-desorption of nitrogen source and the resulting catalysts.

A catalyst with a micro-mesoporous structure according to the invention is obtained by suspending microporous crystalline silicates with a zeolite structure having the composition of an anionic framework of T ₂ O ₃ (10-1000) SiO ₂ in an alkaline solution until the residual zeolite phase content in the suspension is 3-40 wt. %, introducing into the silicate suspension a solution of a cationic surfactant, followed by adding acid to form a gel, and hydrothermally treating the gel to isolate the finished product.

The obtained micro-mesoporous catalyst retains the crystalline structure of the starting microporous crystalline silicate, as can be seen in FIG. where curve 1 depicts a diffractogram of a microporous aluminosilicate with a MOR structure, curve 2 shows a diffractogram of a catalyst with a micro-mesoporous structure obtained from an aluminosilicate with a MOR structure, and curve 3 shows a diffractogram of an aluminosilicate with a known mesoporous structure that is not crystalline.

Suspension of microporous crystalline silicates is carried out in an alkaline solution with a concentration of hydroxide ions of 0.2-1.5 mol / l, after which the alkaline suspension of zeolite is mixed with a solution of cationic surfactant and acid is added until a gel is formed with pH = 7.5- 9.0. Hydrothermal treatment of the gel is carried out at a temperature of 100-150 ° C at atmospheric pressure or in an autoclave for 10-72 hours.

As cationic surfactants, quaternary alkylammonium salts of the composition С _n Н _{2n + 1} (СН ₃ ) ₃ NAn are used, where n = 12-18, An - Cl, Br, HSO ₄ ^- , which provide electrostatic interaction between negatively charged (in as a result of adsorption of hydroxide ions) with highly dispersed crystal fragments of the initial silicate and silicate ions and positively charged micelles of a surfactant. As a result of this interaction, a mesoporous phase is formed.

Pore volume, micropore fraction and mesopore fraction are calculated from isotherms of low-temperature nitrogen adsorption, as shown in Fig. 2, where curve 4 depicts the isotherm of low-temperature nitrogen adsorption-desorption for microporous silicate with the MFI zeolite structure, curve 5 shows the isotherm of low-temperature nitrogen adsorption-desorption material with a micro-mesoporous structure, obtained on the basis of microporous silicate with a MFI zeolite structure, curve 6 - isotherm of low-temperature nitrogen adsorption-desorption for a known silicate with mesoporis oh structure. As follows from figure 2, the adsorption isotherm of the micro-mesoporous catalyst (curve 5) is similar to the isotherm of the mesoporous catalyst (curve 6), which indicates the formation of a developed regular structure. The location of the isotherms of the micro-mesoporous catalyst (curve 5) and microporous silicate (curve 6) indicates a 2.5-fold increase in pore volume.

A feature of the catalyst with a micro-mesoporous structure is the presence of two types of pores - micropores (whose share in the total pore volume of the material is 0.03-0.40) and mesopores (whose share in the total pore volume of the material is 0.60-0.97) . The presence of micropores is due to the presence of highly dispersed fragments of microporous crystalline silicates homogeneously distributed in the bulk of the mesoporous phase formed by the stereoregular mesopore system. As a result, a catalyst with a micro-mesoporous structure combines the advantages of microporous crystalline zeolites (the presence of acid centers with an activation energy of ammonia desorption of 140-190 kJ / mol, whose share in the total acidity spectrum is at least 0.5) and mesoporous molecular sieves (developed regular porous structure with a pore volume of at least 0.45 cm ³ / g).

To obtain micro-mesoporous catalysts, microporous crystalline silicates of different crystal structures and different chemical compositions were used, the properties of which are presented in table 1.

Table 1 Structure Structure Pore volume, cm ³ / g The proportion of micropores α * one Mor Al ₂ O ₃ · 97 SiO ₂ 0.195 1,0 0.53 2 BEA Al ₂ O ₃ 84SiO ₂ 0.184 1,0 0.70 3 Mfi Al ₂ O ₃ · 80 SiO ₂ 0.164 1,0 0.70 * α is the fraction of acid sites with an activation energy of ammonia desorption of 140-190 kJ / mol in the total acidity spectrum

The starting microporous zeolites are commercially available mordenite with a ratio of SiO ₂ / Al ₂ O ₃ = 97 (MOR), beta with a ratio of SiO ₂ / Al ₂ O ₃ = 84 (BEA) and ZSM-5 with a ratio of SiO ₂ / Al ₂ O ₃ = 80 (MFI). The synthesis of the mesoporous catalyst MCM-41 with the ratio SiO ₂ / Al ₂ O ₃ = 90 was carried out using cetyltrimethylammonium bromide as a template at 105 ° C for 48 hours under hydrothermal conditions in accordance with CTKresge, MELeonowicz et al. // Nature, 359 (1992) 710.

The conversion of hydrocarbons is carried out under continuous flow conditions in a reactor with a fixed catalyst bed of the composition according to the invention in the temperature range from 220 to 550 ° C at gauge pressure from 0.1 to 1 MPa, feed rate from 0.5 to 5 g / g · h in the presence of an inert gas. Hydrocarbon conversion is selected from a number of processes including the cracking of 1,3,5-triisopropylbenzene; alkylation of polynuclear aromatic compounds such as biphenyl; transalkylation of biphenyl and diisopropylbenzene; benzene acylation with dodecanoic acid; octane isomerization; oligomerization of propylene and conversion of propane to aromatic compounds. The composition of the reaction products was determined chromatographically.

The following examples illustrate the invention, but do not limit it.

Example 1

A micro-mesoporous catalyst (ReMOR) is prepared as follows: 5 g of a microporous crystalline aluminosilicate with a mordenite structure are added to 30 ml of a 0.2 mol / L NaOH solution. The resulting suspension was stirred at room temperature for 2 hours, after which it was mixed with a solution of 7.76 g of hexadecyltrimethylammonium bromide (C ₁₆ H ₃₃ (CH ₃ ) ₃ NBr) in 48 ml of H ₂ O. 10 ml of 2 mol / L was added to the resulting mixture. hydrochloric acid to form a gel with pH = 7.5. After homogenizing the gel for 1 h, it is transferred to an autoclave, which is closed and heated for 24 h at 110 ° C. At the end of the hydrothermal treatment, the material is separated on the filter, washed with distilled water, dried at 100 ° C for 24 hours, calcined at 550 ° C for 24 hours. As a result, a micro-mesoporous catalyst with a zeolite mordenite structure with a pore volume of 0.823 cm ^{3 is} obtained / g, with fractions of micropores and mesopores in the pore volume of 0.03 and 0.97, respectively.

Example 2

The cracking of 1,3,5-triisopropylbenzene is carried out as follows: the micro-mesoporous catalyst described in example 1 is placed in a flow reactor, purged with nitrogen at 550 ° C, then the temperature is reduced to 300 ° C and 1,3,5- triisopropylbenzene at a pressure of 0.1 MPa, a feed rate of 1 g / g · h, dilution with nitrogen in the ratio of 1,3,5-triisopropylbenzene: N ₂ = 1: 5 (mol). The experimental results are presented in table 2.

Example 3

Similar to example 2, the difference is that they use a microporous catalyst MOR. The experimental results are presented in table 2.

Example 4

Similar to example 2, the difference is that they use a mesoporous catalyst MCM-41. The experimental results are presented in table 2.

Example 5

The catalyst is prepared analogously to example 1, but 5 g of a microporous crystalline aluminosilicate with a mordenite structure are added to 30 ml of a 0.5 mol / L NaOH solution. The result is a micro-mesoporous catalyst with a mordenite zeolite structure, pore volume 0.365 cm ³ / g, with fractions of micropores and mesopores in pore volumes of 0.40 and 0.60, respectively.

Example 6

Transalkylation of biphenyl with p-diisopropylbenzene is carried out as follows: the micro-mesoporous catalyst described in Example 5 is placed in a flow reactor, purged with nitrogen at a temperature of 400 ° C, then the temperature is reduced to 220 ° C and biphenyl with p-diisopropylbenzene is fed at a pressure of 1 MPa the feed rate of biphenyl 0.5 g / g · h, the molar ratio of biphenyl: p-diisopropylbenzene: N ₂ = 1: 6: 10. The experimental results are presented in table 2.

Example 7

Similar to example 6, the difference is that they use a microporous catalyst MOR. The experimental results are presented in table 2.

Example 8

Similar to example 6, the difference is that they use a mesoporous catalyst MCM-41. The experimental results are presented in table 2.

Example 9

Alkylation of biphenyl with propylene is carried out as follows: the micro-mesoporous catalyst described in example 5 is placed in a flow reactor, purged with nitrogen at a temperature of 400 ° C, then the temperature is reduced to 220 ° C and biphenyl with propylene is fed at a pressure of 1 MPa, biphenyl feed rate 0.5 g / g · h, a molar ratio of biphenyl: propylene: N ₂ = 1: 6: 10. The experimental results are presented in table 2.

Example 10

Similar to example 9, the difference is that they use a microporous catalyst MOR. The experimental results are presented in table 2.

Example 11

Similar to example 9, the difference is that they use a mesoporous catalyst MCM-41. The experimental results are presented in table 2.

Example 12

Alkylation of benzene with dodecene-1 is carried out as follows: the micro-mesoporous catalyst described in example 5 is placed in a flow reactor, purged with nitrogen at a temperature of 550 ° C, then the temperature is reduced to 230 ° C and a mixture of benzene with dodecene-1 at a pressure of 0 , 1 MPa, feed rate of 3.7 g / g · h, the molar ratio of benzene: dodecene-1 = 1: 8. The diluent gas speed N ₂ 10 ml / min. The experimental results are presented in table 2.

Example 13

Similar to example 9, the difference is that they use a microporous catalyst MOR. The experimental results are presented in table 2.

Example 14

Similar to example 9, the difference is that they use a mesoporous catalyst MCM-41. The experimental results are presented in table 2.

Example 15

The acylation of benzene with dodecanoic acid is carried out as follows: the micro-mesoporous catalyst described in example 5 is placed in a flow reactor, purged with nitrogen at a temperature of 550 ° C, then the temperature is reduced to 230 ° C and a solution of dodecanoic acid in benzene with a molar ratio of benzene is supplied: acid = 30: 1 at a rate of 5 g / g · h at a pressure of 0.1 MPa. Speed N ₂ 10-30 ml / min. The experimental results are presented in table 2.

Example 16

Similar to Example 12, the difference is that a microporous MOR catalyst is used. The experimental results are presented in table 2.

Example 17

Similar to example 12, the difference is that they use a mesoporous catalyst MCM-41. The experimental results are presented in table 2.

Example 18

A micro-mesoporous catalyst (ReBEA) is prepared as follows: 5 g of a microporous crystalline aluminosilicate with a BEA structure are added to 30 ml of a 0.75 mol / L NaOH solution. The resulting suspension was stirred at room temperature for 1 h, after which it was mixed with a solution of 6.56 g of dodecyl trimethylammonium bromide (C ₁₂ H ₂₅ (CH ₃ ) ₃ HBr) in 48 ml of H ₂ O. 10 ml of 2 mol / L was added to the resulting mixture. hydrochloric acid to form a gel with a pH of 9.0. After homogenizing the gel for 1 h, it is transferred to an autoclave, which is closed and heated for 72 h at 100 ° C. At the end of the hydrothermal treatment, the material is separated on the filter, washed with distilled water, dried at 100 ° C for 24 hours, calcined at 550 ° C for 24 hours. As a result, a micro-mesoporous catalyst with a BEA zeolite structure with a pore volume of 0.415 cm ^{3 is} obtained / g, with fractions of micropores and mesopores in the pore volume of 0.34 and 0.66, respectively.

Examples 19-21 illustrate the catalytic properties of catalysts during isomerization of n-octane. To carry out the isomerization process, platinum must be present in the composition of the catalyst, which creates additional active centers. Modification of microporous, micro-mesoporous and mesoporous catalysts was carried out by ion exchange in a solution of [Pt (NH ₃ ) ₄ ] Cl ₂ salt taken in the amount of 1/580 of the catalyst mass for 3 days at room temperature, followed by washing, drying at 100 ° C, calcination and reduction with hydrogen at 400 ° C. All catalysts contain 0.1 wt.% Pt.

Example 19

Isomerization of n-octane is carried out in the presence of the micro-mesoporous catalyst described in example 15 containing 0.1 wt.% Pt, as follows: the catalyst is placed in a flow reactor, purged in a stream of hydrogen at a temperature of 400 ° C for 1 h, then reduce the temperature to 230 ° C and serves octane at a speed of 2 g / g · h at a pressure of 0.1 MPa and a molar ratio of H ₂ : octane = 5: 1. The experimental results are presented in table 2.

Example 20

Similar to example 16, the difference is that they use a microporous catalyst BEA containing 0.1 wt.% Pt. The experimental results are presented in table 2.

Example 21

Similar to example 16, the difference is that they use a mesoporous catalyst MCM-41 containing 0.1 wt.% Pt. The experimental results are presented in table 2.

Example 22

A micro-mesoporous catalyst (ReBEA) is prepared as follows: 5 g of a microporous crystalline aluminosilicate with a BEA structure are added to 30 ml of a 1.5 mol / L NaOH solution. The resulting suspension was stirred at room temperature for 1 h, after which it was mixed with a solution of 7.16 g of octadecyltrimethylammonium bromide (C ₁₈ H ₃₇ (CH ₃ ) ₃ NBr) in 48 ml of H ₂ O. To the resulting mixture was added 10 ml of 2 mol / L hydrochloric acid to form a gel with pH = 8. After homogenizing the gel for 1 h, it is transferred to an autoclave, which is closed and heated for 10 h at 150 ° C. At the end of the hydrothermal treatment, the material is separated on the filter, washed with distilled water, dried at 100 ° C for 24 hours, calcined at 550 ° C for 24 hours. As a result, a micro-mesoporous catalyst with a pore volume of 0.427 cm ³ / g, s fractions of micropores and mesopores in the pore volume of 0.27 and 0.73, respectively.

Example 23

The propylene oligomerization is carried out as follows: the micro-mesoporous catalyst described in example 19 is placed in a flow reactor, purged in a stream of nitrogen at a temperature of 500 ° C, then the temperature is reduced to 350 ° C and propylene is fed at a rate of 3 g / g · h at pressure of 0.1 MPa. The experimental results are presented in table 2.

Example 24

Similar to example 20, the difference is that they use a microporous catalyst BEA. The experimental results are presented in table 2.

Example 25

Similar to example 20, the difference is that they use a mesoporous catalyst MCM-41. The experimental results are presented in table 2.

Example 26

A micro-mesoporous catalyst (ReMFI) is prepared as follows: 5 g of a microporous crystalline aluminosilicate with an MFI structure are added to 30 ml of a 0.5 mol / L NaOH solution. The resulting suspension was stirred at room temperature for 1 h, after which it was mixed with a solution of 7.76 g of hexadecyltrimethylammonium bromide (C ₁₆ H ₃₃ (CH ₃ ) ₃ HBr) in 48 ml of H ₂ O. 10 ml of 2 mol / L was added to the resulting mixture. hydrochloric acid to form a gel with pH = 8. After homogenizing the gel for 1 h, it is transferred to an autoclave, which is closed and heated for 24 h at 110 ° C. At the end of the hydrothermal treatment, the material is separated on the filter, washed with distilled water, dried at 100 ° C for 24 hours, calcined at 550 ° C for 24 hours. As a result, a micro-mesoporous catalyst with an MFI zeolite structure with a pore volume of 0.510 cm is obtained ³ / g, with fractions of micropores and mesopores in the pore volume of 0.20 and 0.80, respectively.

Examples 27-29 illustrate the catalytic properties of the catalysts in the process of aromatization of propane. To carry out the isomerization process, zinc must be present in the composition of the catalyst, which creates additional active centers. Modification of microporous, micro-mesoporous and mesoporous catalysts was carried out by impregnating the catalysts with a solution of Zn (NO ₃ ) ₂ · 6H ₂ O salt, taken in the amount of 1 / 2.1 by weight of the catalyst, at room temperature, followed by drying at 100 ° С and calcination at 500 ° C. All catalysts contain 2 wt.% Zn.

Example 27

Aromatization of propane is carried out as follows: the micro-mesoporous catalyst described in example 23, containing 2 wt.% Zn, is placed in a flow reactor, purged in a stream of dried air at a temperature of 550 ° C and propane is supplied at a rate of 2 g / g · h at pressure of 0.1 MPa. The experimental results are presented in table 2.

Example 28

Similar to example 24, the difference is that they use a microporous catalyst MFI containing 2 wt.% Zn. The experimental results are presented in table 2.

Example 29

Similar to example 24, the difference is that they use a mesoporous catalyst MCM-41 containing 2 wt.% Zn. The experimental results are presented in table 2.

Example 30

A micro-mesoporous catalyst (ReMOR) is prepared as follows: 5 g of a microporous crystalline iron silicate with a MOR structure are added to 30 ml of a 1.0 mol / L NaOH solution. The resulting suspension was stirred at room temperature for 2 hours, after which it was mixed with a solution of 7.76 g of dodecyl trimethylammonium bromide (C ₁₂ H ₂₅ (CH ₃ ) ₃ NBr) in 48 ml of H ₂ O. To the resulting mixture was added 15 ml of 2 mol / L hydrochloric acid to form a gel with pH = 8. After homogenizing the gel for 1 h, it is transferred to an autoclave, which is closed and heated for 48 h at 110 ° C. At the end of hydrothermal treatment, the catalyst is separated on a filter, washed with distilled water, dried at 100 ° C for 24 hours, calcined at 550 ° C for 24 hours. As a result, a material with a MOR zeolite structure of SiO ₂ / Fe ₂ O ₃ = 20, pore volume 0.50 cm ³ / g, with fractions of micropores and mesopores in the pore volume 0.20 and 0.80, respectively. The share of acid sites with an activation energy of ammonia desorption of 140-190 kJ / mol in the total acidity spectrum is 0.70.

Example 31

Similar to example 2, the difference is that they use the micro-mesoporous catalyst described in example 30. The results of the experiment are presented in table 2.

Example 32

Similar to example 2, the difference is that they use a microporous iron-containing catalyst with a MOR structure (FeMOR). The experimental results are presented in table 2.

Example 33

Similar to example 2, the difference is that they use a mesoporous iron-containing catalyst with the structure of MCM-41 (FeMCM-41). The experimental results are presented in table 2.

Example 34

The micro-mesoporous material is prepared as follows: 5 microporous crystalline iron aluminum silicate with a MOR zeolite structure is added to 30 ml of a 10 mol / L NaOH solution. The resulting suspension was stirred at room temperature for 2 hours, then mixed with a solution of 7.76 g of cetyltrimethylammonium bromide (C ₁₆ H ₃₃ (CH ₃ ) ₃ NBr) in 48 ml of H ₂ O. 10 ml of 2 mol / L was added to the resulting mixture. hydrochloric acid to form a gel with pH = 8. After homogenizing the gel for 1 h, it is transferred to an autoclave, which is closed and heated for 24 h at 110 ° C. At the end of hydrothermal treatment, the catalyst is separated on a filter, washed with distilled water, dried at 100 ° C for 24 hours, calcined at 550 ° C for 24 hours. As a result, a catalyst with a mordenite zeolite structure (MOR) of the composition Al ₂ O ₃ · Fe ₂ O ₃ · 50SiO ₂ with a pore volume of 0.65 cm ³ / g, with fractions of micropores and mesopores in the pore volume of 0.30 and 0.70, respectively. The share of acid sites with an activation energy of ammonia desorption of 140-190 kJ / mol in the total acidity spectrum is 0.70.

Example 35

Similar to example 2, the difference is that they use the micro-mesoporous catalyst described in example 34. The results of the experiment are presented in table 2.

Example 36

Similar to example 2, the difference is that they use a microporous iron-containing catalyst with the structure of MOR (Fe, AlMOR). The experimental results are presented in table 2.

Example 37

Similar to example 2, the difference is that a mesoporous iron-containing catalyst with the structure of MCM-41 (Fe, AlMCM-41) is used. The experimental results are presented in table 2.

Example 38

A micro-mesoporous catalyst is prepared as follows: 5 g of a microporous crystalline gallosilicate with a BEA zeolite structure are added to 30 ml of a 1.5 mol / L NaOH solution. The resulting suspension was stirred at room temperature for 2 hours, after which it was mixed with a solution of 8.40 g of octadodecyl trimethylammonium bromide (C ₁₈ H ₃₇ (CH ₃ ) ₃ NBr) in 48 ml of H ₂ O. 10 ml of 2 mol / L was added to the resulting mixture. hydrochloric acid to form a gel with pH = 8. After homogenizing the gel for 1 h, it is transferred to an autoclave, which is closed and heated for 24 h at 110 ° C. At the end of the hydrothermal treatment, the catalyst is separated on the filter, washed with distilled water, dried at 150 ° C for 24 hours, calcined at 550 ° C for 24 hours. As a result, a catalyst with a BEA zeolite structure with a SiO ₂ / Ga ₂ O ratio is obtained ₃ = 50, pore volume 0.45 cm ³ / g, with fractions of micropores and mesopores in the pore volume 0.38 and 0.62, respectively. The share of acid sites with an activation energy of ammonia desorption of 140-190 kJ / mol in the total acidity spectrum is 0.60.

Example 39

Similar to example 2, the difference is that they use the micro-mesoporous catalyst described in example 38. The experimental results are presented in table 2.

Example 40

Similar to example 2, the difference is that they use a microporous iron-containing catalyst with the structure of the zeolite BEA (GaBEA). The experimental results are presented in table 2.

Example 41

Similar to example 2, the difference is that they use a mesoporous iron-containing catalyst with the structure of MCM-41 (GaMCM-41). The experimental results are presented in table 2.

Example 42

A micro-mesoporous catalyst is prepared as follows: 5 g of a microporous crystalline titanoaluminosilicate with a BEA structure are added to 30 ml of a 1.5 mol / L KOH solution. The resulting suspension was stirred at room temperature for 2 hours, after which it was mixed with a solution of 7.76 g of cetyltrimethylammonium bromide (C ₁₆ H ₃₃ (CH ₃ ) ₃ NBr) in 48 ml of H ₂ O. 15 ml of 2 mol / L was added to the resulting mixture. hydrochloric acid to form a gel with pH = 8. After homogenizing the gel for 1 hour, it is transferred to an autoclave, which is closed and heated for 24 hours at 150 ° C. At the end of hydrothermal treatment, the catalyst is separated on a filter, washed with distilled water, dried at 100 ° C for 24 hours, calcined at 550 ° C for 24 hours. As a result, a catalyst with a BEA zeolite structure of Al ₂ O ₃ · TiO ₂ · 70SiO ₂ , with a pore volume of 0.65 cm ³ / g, with fractions of micropores and mesopores in the pore volume of 0.15 and 0.85, respectively. The share of acid sites with an activation energy of ammonia desorption of 140-190 kJ / mol in the total acidity spectrum is 0.50.

Example 43

Similar to example 2, the difference is that they use the micro-mesoporous catalyst described in example 42. The experimental results are presented in table 2.

Example 44

Similar to example 2, the difference is that they use a microporous titanium-aluminum-containing catalyst with a BEA structure (Ti, AlBEA). The experimental results are presented in table 2.

Example 45

Similar to example 2, the difference is that they use a mesoporous titanium-aluminum-containing catalyst with the structure of MCM-41 (Ti, AlMCM-41). The experimental results are presented in table 2.

table 2 Example No. Catalyst Properties of the catalyst with a micro-mesoporous structure Conversion% Selectivity, mol.% pore volume, cm ³ / g micropore fraction mesopore fraction 2 Remor 0.823 0.15 0.85 36.8 ¹ 23.1 ² 3 Mor 0.195 1.0 0 7.1 ¹ 7.5 ² four MSM-41 0.970 0 1.0 20.7 ¹ 38.8 ² 6 Remor 0.365 0.40 0.60 32.1 ³ 19.3 ⁴ 7 Mor 0.195 1.0 0 12.3 ³ 6.1 ⁴ 8 MSM-41 0.970 0 1.0 14.0 ³ 3.3 ⁴ 9 Remor 0.365 0.40 0.60 96.1 ³ 62.9 ⁴ 10 Mor 0.195 1.0 0 90.0 ³ 56.0 ⁴ eleven MSM-41 0.970 0 1.0 95.2 ³ 20.4 ⁴ 12 Remor 0.365 0.40 0.60 99.1 ⁵ 10.0 ⁶ 13 Mor 0.195 1.0 0 99.5 ⁵ 6.4 ⁶ fourteen MSM-41 0.970 0 1.0 74.4 ⁵ 3.3 ⁶ fifteen Remor 0.365 0.40 0.60 7.8 ⁷ 4.3 ⁸ 16 Mor 0.195 1.0 0 5.1 ⁷ 3.8 ⁸ 17 MSM-41 0.970 0 1.0 1.3 ⁷ 1.3 ⁸ 19 Pt / ReBEA 0.415 0.34 0.66 72.7 ⁹ 63.6 ¹⁰ twenty Pt / bea 0.184 1.0 0 44.2 ⁹ 50.2 ¹⁰ 21 Pt / MCM-41 0.970 0 1.0 0 ⁹ 0 ¹⁰ 23 Pt / ReBEA 0.427 0.27 0.73 70.6 ¹¹ 32.1 ¹² 24 Pt / bea 0.184 1.0 0 65.4 ¹¹ 28.7 ¹² 25 Pt / MCM-41 0.970 0 1.0 48.0 ¹¹ 24.0 ¹² 27 Zn / ReMFI 0.510 0.20 0.80 98.1 ¹³ 36.9 ¹⁴ 28 Zn / MFI 0.164 1.0 0 82.5 ¹³ 28.1 ¹⁴ 29th Zn / MCM-41 0.970 0 1.0 2.4 ¹³ 0.1 ¹⁴ 31 FeReMOR 0.500 0.60 0.40 26.3 ¹ 28.0 ² 32 FeMOR 0.475 1.0 0 5.2 ¹ 6.8 ² 33 FeMCM-41 0.980 0 1.0 14.0 ¹ 25.0 ² 35 FeAlReMOR 0.460 0.60 0.40 31.4 ¹ 25.6 ² 36 FeAlMOR 0.430 1.0 0 6.3 ¹ 6.1 ² 37 FeAlMCM-41 0.860 0 1.0 18.2 ¹ 21.5 ² 39 GaRebea 0.450 0.38 0.62 29.2 ¹ 25.0 ² 40 GaBEA 0.450 1.0 0 6.1 ¹ 6.4 ² 41 GaMCM-41 0.960 0 1.0 15.2 ¹ 23.6 ² 43 TiAlReBEA 0.650 0.15 0.85 17.9 ¹ 18.0 ² 44 TiAlBEA 0.480 1.0 0 3.4 ¹ 3.6 ² 45 TiAlMCM-41 0.890 0 1.0 14.4 ¹ 14.6 ^{2 1} - conversion of 1,3,5-triisopropylbenzene, ² - selectivity for the formation of diisopropylbenzenes, ³ - conversion of biphenyl, ⁴ - selectivity for the formation of diisopropylbiphenyls, ⁵ - conversion for dodecene-1, ⁶ - selectivity for the formation of dodecanylbenzenes, ⁷ - conversion for dodecanoic acid, ⁸ - yield 1-phenyl-1-dodecanone, ⁹ - octane conversion, ¹⁰ - selectivity for the formation of isomerization products, ¹¹ - propylene conversion, ¹² - hexene yield, ¹³ - propane conversion, ¹⁴ - aromatic hydrocarbon selectivity.

Claims (16)

1. The method of conversion of hydrocarbons, including the introduction of hydrocarbon materials under the conditions of conversion of hydrocarbons in contact with a catalyst with a micro-mesoporous structure, including microporous crystalline silicates with a zeolite structure of the composition T ₂ O ₃ (10-1000) SiO ₂ , where T are the elements selected from the group consisting of p-elements of group III or d-elements of group IV-VIII, or a mixture thereof, while the micro-mesoporous structure is characterized by a fraction of micropores from 0.03 to 0.40 and a fraction of mesopores from 0.60 to 0, 97. 2. The method according to claim 1, characterized in that the conversion of hydrocarbons is selected from a number of processes, including cracking hydrocarbons, alkylation of aromatic compounds, transalkylation of aromatic hydrocarbons, aromatization of paraffinic hydrocarbons, acylation of aromatic compounds, isomerization of paraffinic hydrocarbons and oligomerization of olefinic hydrocarbons. 3. The method according to claim 1, characterized in that the conversion of hydrocarbons is carried out under conditions including a temperature of from 220 to 550 ° C, gauge pressure from 0.1 to 1 MPa, feed rate from 0.5 to 5 g / g hours 4. The method according to claim 1, characterized in that the catalyst with a micro-mesoporous structure includes a microporous crystalline silicate with a zeolite structure of the type FAU, LTL, FER, MAZ, MOR, BEA, MFI, MEL, MTW. 5. The method according to claim 1, characterized in that the catalyst is modified with metals selected from d-elements of groups II and VIII. 6. The method according to claim 5, characterized in that the content of metals selected from d-elements of groups II and VIII is from 0.1 to 2 wt.%. 7. The method according to claim 1, characterized in that the micro-mesoporous structure has acid centers with an activation energy of ammonia desorption of 140-190 kJ / mol, the proportion of which from the total number of acid centers is at least 0.5. 8. A catalyst for the conversion of hydrocarbons with a micro-mesoporous structure, including a microporous crystalline silicate with a zeolite structure of the composition T ₂ O ₃ (10-1000) SiO ₂ , where T are elements selected from the group consisting of p-elements of group III or d -elements of groups IV-VIII, or mixtures thereof, while the micro-mesoporous structure is characterized by a micropore fraction of 0.03 to 0.40 and a mesopore fraction of 0.60 to 0.97. 9. The catalyst according to claim 8, characterized in that the catalyst with a micro-mesoporous structure includes a microporous crystalline silicate with a zeolite structure of the type FAU, LTL, FER, MAZ, MOR, BEA, MFI, MEL, MTW. 10. The catalyst of claim 8, characterized in that it is modified with metals selected from d-elements of groups II and VIII. 11. The catalyst of claim 10, characterized in that the content in it of metals selected from d-elements of groups II and VIII is from 0.1 to 2 wt.%. 12. The catalyst according to claim 8, characterized in that the micro-mesoporous structure has acid sites with an activation energy of ammonia desorption of 140-190 kJ / mol, the proportion of which from the total number of acid sites is at least 0.5. 13. A method of producing a catalyst with a micro-mesoporous structure, comprising suspending microporous crystalline silicates with a zeolite structure having a composition of T ₂ O ₃ (10-1000) SiO ₂ , where T are elements selected from the group consisting of p-elements of group III or d-elements of group IV-VIII, or a mixture thereof in an alkaline solution with a concentration of hydroxide ions of 0.2-1.5 mol / l to achieve a residual content of the zeolite phase in a suspension of 3-40 wt.%, the introduction of a suspension of silicate solution cationic surfactant in the form of a Quaternary salt th alkylammonium composition C _n H _{2n + 1} (CH _{3) 3} NAn, where n = 12-18, An - Cl, Br, HSO ₄ ^-, followed by the addition of acid to form a gel with pH 7.5-9.0 and hydrothermal gel treatment at 100-150 ° C at atmospheric pressure or in an autoclave for 10-72 hours with the release of the finished product according to claim 8. 14. The method according to item 13, wherein FAU, LTL, FER, MAZ, MOR, BEA, MFI, MEL, MTW are used as microporous crystalline silicate with a zeolite structure. 15. The method according to 14, characterized in that the resulting catalyst is further modified by ion exchange or impregnation with metal salts selected from d-elements of groups II and VIII. 16. The method according to p. 15, characterized in that they use a modifier in the form of metal salts in an amount that provides in the catalyst the content of metals selected from d-elements of groups II and VIII, in an amount of from 0.1 to 2 wt.%.

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