RU2393992C1 - Micro-mesoporous crystalline material and method of making said material - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: invention relates to production of crystalline materials with a micro-mesoporous structure. The method of making micro-mesoporous crystalline material involves reacting microporous crystalline material with a solution of a water-soluble base and a surfactant, drying and calcination of the obtained material. The reaction takes place in a single step in a solution containing 0.07-0.7 mol/l of a water-soluble base and 0.02-0.40 mol/l of a surfactant at 20-100°C for 1-24 hours. The obtained material has high crystallinity and has a bimodal porous structure which has zeolite micropores with diametre of 0.4-1.0 nm and mesopores with diametre of 2-30 nm, localised in the volume of a zeolite crystal. The fraction of micropores in the total pore volume may vary from 0.4 to 0.85, while the fraction of mesopores in the total pore volume may vary from 0.15 to 0.60.

EFFECT: invention improves quality of micro-mesoporous material, simplifies the production method and widens the range of crystalline materials with a micro-mesoporous structure.

7 cl, 2 tbl, 23 ex, 6 dwg

Description

The invention relates to inorganic chemistry, in particular to methods for producing crystalline zeolite and zeolite-like materials with a micro-mesoporous structure.

A known method of producing zeolite with an increased volume of mesopores, in which, in order to increase the volume of mesopores with a diameter of 2 to 60 nm, hydrothermal treatment of the zeolite is carried out in an aqueous solution containing one or more salts, acids, bases and / or water-soluble organic compounds at a temperature exceeding the atmospheric boiling point of the solution (RU 2127227, 03/10/1999).

The disadvantages of this method are:

- the possibility of implementing the method only for zeolite U;

- insignificant depth of influence on the porous structure of zeolite U, at which the volume of mesopores in the resulting material is only 5-10% higher than the volume of mesopores in the initial zeolite;

- a decrease in the crystallinity of the sample due to the transformation of the crystalline microporous zeolite phase into an amorphous mesoporous phase;

- the need for hydrothermal treatment at temperatures from 115 to 250 ° C, which requires the use of special equipment for working under pressure.

A known method for producing a bicomponent inorganic material with combined micro- and mesoporosity, including heating a mixture containing water, a source of inorganic oxide, crystalline zeolite beta and an organic compound capable of binding to the inorganic oxide by hydrogen bonds, keeping the mixture boiling until water and the organic compound evaporate, calcining the mixture at a temperature exceeding 300 ° C (US 6814950, 09/09/2004).

There is also known a method of producing a material containing zeolite and porous inorganic oxide, in which 97% of the volume is occupied by microporous zeolite from the series: zeolite Beta, U, mordenite, ZSM, MCM, ITQ, SAPO, AlPO, etc., while the zeolite particles are surrounded by mesoporous channels (US 7470645, 12/30/2008).

A disadvantage of the known materials is that the combined micro-mesoporous structure refers to only one of the components of the material, namely the inorganic oxide, while the zeolite component remains only microporous.

A known method for producing a zeolite composite material, including pretreatment of a zeolite with a layered structure, mixing the zeolite with an inorganic oxide or its precursor in the presence of at least one organic compound forming mesopores, drying the mixture, heating it at a temperature of from 100 to 250 ° C to form a mesoporous structure of an inorganic oxide, calcining the mixture at 300-1000 ° C to remove water and an organic compound (US 7084087, 08/01/2006).

The disadvantage of this method is that in the process of preparing the material, mesopores are formed only in inorganic oxide.

The closest in technical essence and the achieved result is a method according to which a suspension of microporous crystalline silicates with a zeolite structure is carried out, 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 group d-elements of group IV-VIII, or a mixture thereof, in an alkaline solution until a residual zeolite content in the suspension of 1-60% by weight is achieved, introducing a solution of a cationic surfactant into the silicate suspension, followed by adding leniem acid to gel formation and the hydrothermal treatment of the gel with the release of the finished product. The invention provides a material having a crystalline structure of the starting silicate and having a developed regular porous structure with a pore volume of at least 0.45 cm ³ / g (RU 2282587, 08.27.2006).

The disadvantage of this method is its multi-stage and recrystallization of only part of the zeolite material in the mesoporous phase, while in the resulting material, the proportion of micropores is 0.01-0.60, and the proportion of mesopores is 0.10-0.85.

The present invention is the creation of a new type of crystalline material having a bimodal porous structure, including micropores with a diameter of 0.4-1.0 nm and homogeneous mesopores with a diameter of 2-30 nm, which are localized in the volume of the zeolite crystal, and the development of a method for producing crystalline material with bimodal porosity, which allows the formation of mesopores of a given diameter.

The problem is solved by the described method for producing a micro-mesoporous crystalline material, including the interaction of a microporous crystalline material with a solution of a water-soluble base and a surfactant, washing, drying and calcining the obtained material, in which the interaction is carried out in one stage in a solution containing 0 , 07-0.7 mol / L water-soluble base and 0.02-0.40 mol / L surfactant at a temperature of 20-100 ° C for 1-24 hours

The method provides that crystalline microporous aluminosilicates with a structure of FAU, CHA, LTL, FER, MAZ, MOR, BEA, MFI, MEL, MTN, MTT, MTW, MWW, TON, crystalline microporous metal silicates with a structure of BEA, MFI, MEL are fed into the interaction , MTN, MTT, MTW, MWW or crystalline microporous silica-aluminum phosphates with the structure of FAU, CHA, AEI, AFI, AFO.

Quaternary alkylammonium salts are preferably fed into the interaction as a surfactant, the cation size of which is selected depending on the given mesopore size.

The problem is also solved by the described micro-mesoporous crystalline material obtained by the claimed method, as described above, while the material has a bimodal porous structure, including zeolite micropores with a diameter of 0.4-1.0 nm, the proportion of which in the total pore volume is from 0.15 to 0.60, and mesopores with a diameter of 2-30 nm, the proportion of which in the total pore volume is from 0.4 to 0.85.

The following are specific examples describing the claimed method, as well as the properties of the obtained materials.

To obtain micro-mesoporous materials, microporous crystalline materials of different zeolite structure and different chemical composition were used, the properties of which are presented in Table 1.

Figure 1-6 presents the results of the analysis of the porous and crystalline structure of the obtained materials.

Table 1 Properties of the source crystalline microporous materials N Crystal structure Chemical composition Pore volume, cm ³ / g The proportion of micropores in the total pore volume one Bea aluminosilicate, Si / Al-53 0.450 0.40 2 Bea aluminosilicate, Si / Al = 40 0.270 0.80 3 Bea aluminosilicate, Si / Al = 30 0.350 0.50 four Mor aluminosilicate, Si / Al = 45 0.225 0.75 5 FAU aluminosilicate, Si / Al = 42 0.427 0.57 6 Fer aluminosilicate, Si / Al = 10 0.190 0.80 7 Mfi aluminosilicate, Si / Al = 24 0.210 0.75 8 Mfi iron-aluminum silicate, Si / Al / Fe = 75 / 0.5 / 0.5 0.220 0.70 9 MEL titanosilicate, Si / Ti = 15 0.210 0.80 Cha silicoaluminophosphate, Si / Al / P = 0.3 / 1/1 0.220 0.75

Example 1

Micro-mesoporous material is prepared as follows. In 78 ml of water, 0.55 g of NaOH and 7.76 g of hexadecyl trimethylammonium bromide C ₁₆ H ₃₃ (CH ₃ ) ₃ NBr (GDMA) are dissolved, in the resulting solution, the concentration of NaOH is 0.18 mol / l, the concentration of GDMA is 0.3 mol / l 5 g of a microporous crystalline aluminosilicate with a BEA structure are added to the resulting solution (sample 1, table 1). The resulting suspension was stirred at room temperature for 7 hours, after which the material was separated on a filter, washed with distilled water, dried at 100 ° C for 24 hours and calcined at 550 ° C for 24 hours. As a result, a material with the structure of BEA zeolite was obtained , Si / Al ratio = 34, pore volume 0.7 cm ³ / g, with fractions of micropores and mesopores 0.2 and 0.8, respectively. The average mesopore diameter is 3 nm.

Example 2

The material is obtained analogously to example 1, but dodecyl trimethylammonium bromide C ₁₂ H ₂₅ (CH ₃ ) ₃ NBr is used as a quaternary alkylammonium salt. The properties of the obtained material are presented in table.2.

Example 3

The material is obtained analogously to example 1, but benzyltriethylammonium bromide is used as a quaternary alkylammonium salt. The properties of the obtained material are presented in table.2.

Example 4

The material is obtained analogously to example 1, but tetramethylammonium hydroxide is used as a water-soluble base. Ion exchange for this material is not carried out. The properties of the obtained material are presented in table.2.

Examples 1-4 illustrate the preparation of a micro-mesoporous structure with different mesopore diameters by changing combinations of a water-soluble base and a quaternary alkylammonium salt. Figure 1 depicts nitrogen adsorption isotherms (1a), pore volume distribution curves for diameter (1b) and IR spectra (1c) of crystalline aluminosilicates with a BEA structure (sample 1, table 1, examples 1-4, table 2). In accordance with the IUPAC nomenclature, the presence of a jump on the nitrogen adsorption isotherms indicates the presence of mesopores in the porous structure of the synthesized materials (1a). The distribution curves of pore volume over the diameter demonstrate the presence of mesopores of a strictly defined diameter (1b). The preservation of the set of absorption bands in the region of 500-650 cm ^-1 on the IR spectra of micro-mesoporous materials confirms the preservation of high crystallinity of the samples, and an increase in the intensity of these absorption bands (examples 1/2, 3/2, 4/2) indicate an increase in crystallinity (1c).

Example 5

Micro-mesoporous material is prepared as follows. In 78 ml of water, 0.85 g of NaOH and 7.76 g of hexadecyltrimethylammonium bromide C ₁₆ H ₃₃ (CH ₃ ) ₃ NBr (GDMA) are dissolved, in the resulting solution, the concentration of NaOH is 0.28 mol / L, the concentration of GDMA is 0.3 mol / l 5 g of a microporous crystalline aluminosilicate with a BEA structure are added to the resulting solution (sample 2, table 1). The resulting suspension was stirred at room temperature for 7 hours, after which the material was separated on a filter, washed with distilled water, dried at 100 ° C for 24 hours, and calcined at 550 ° C for 24 hours. As a result, a material with a BEA zeolite structure was obtained , the ratio Si / Al = 36, the pore volume of 0.68 cm ³ / g, with fractions of micropores and mesopores of 0.15 and 0.85, respectively. The average mesopore diameter is 3 nm.

Example 6

The material is obtained analogously to example 5, but 0.67 g of NaOH and 7.76 g of hexadecyltrimethylammonium bromide C ₁₆ H ₃₃ (CH ₃ ) ₃ NBr (GDMA) are dissolved in 78 ml of water, and the NaOH concentration in the resulting solution is 0.22 mol / l, the concentration of HDTMA is 0.3 mol / l. The properties of the obtained material are presented in table.2.

Example 7

The material is obtained analogously to example 5, but 0.48 g of NaOH and 7.76 g of hexadecyltrimethylammonium bromide C ₁₆ H ₃₃ (CH ₃ ) ₃ NBr (GDMA) are dissolved in 78 ml of water, and the NaOH concentration in the resulting solution is 0.16 mol / l, the concentration of HDTMA is 0.3 mol / l. The properties of the obtained material are presented in table.2.

Examples 5-7 illustrate the regulation of the proportion of mesopores of a certain diameter by changing the concentration of water-soluble base. Figure 2 depicts nitrogen adsorption isotherms (2a), pore volume distribution curves for diameter (26) and IR spectra (2c) of crystalline aluminosilicates with a BEA structure (sample 2, table 1, examples 5-7, table 2). In accordance with the IUPAC nomenclature, an increase in the intensity at nitrogen adsorption isotherms indicates an increase in the proportion of mesopores in the porous structure of the synthesized materials (2a). The distribution curves of pore volume over the diameter confirm the presence of mesopores with a strictly defined diameter (26), and the peak height on the distribution curves is proportional to the intensity of the jump on the isotherms. The set of absorption bands in the region of 500-650 cm ^-1 in the IR spectra of micro-mesoporous materials confirms the preservation of high crystallinity of the samples, and an increase in the intensity of the mentioned absorption bands (examples 6/2, 7/2) indicate an increase in crystallinity (2c).

Example 8

The material is obtained analogously to example 7, but 5 g of microporous crystalline aluminosilicate with a BEA structure are added to the resulting solution (sample 3, table 1). The properties of the obtained material are presented in table.2.

Examples 1, 7, 8 illustrate the possibility of the formation of a micro-mesoporous structure for zeolites with the same crystalline structure, but different chemical composition. Figure 3 depicts the distribution curves of pore volume in diameter (Fig. 3, a), confirming the presence of mesopores in the porous structure of the synthesized materials, and IR spectra (Fig. 3, b), confirming the high crystallinity of the synthesized materials, for crystalline aluminosilicates with a structure BEA (examples 1, 7, 8, table 2).

Example 9

The material is obtained analogously to example 1, but in this case, 5 g of microporous crystalline aluminosilicate with a MOR structure is added to the resulting solution (sample 4, table 1). The properties of the obtained material are presented in table.2.

Example 10

The material is obtained analogously to example 9, but benzyltriethylammonium bromide is used as the quaternary alkylammonium salt. The properties of the obtained material are presented in table.2.

Example 11

The material is obtained analogously to example 9, but the resulting suspension is stirred for 7 hours at 100 ° C. The properties of the obtained material are presented in table.2.

Example 12

The material is obtained analogously to example 9, but the resulting suspension is stirred at room temperature for 24 hours. The properties of the obtained material are presented in table.2.

Examples 9, 11, 12 illustrate the preparation of a micro-mesoporous structure under standard mild conditions (example 9), conditions of elevated temperature (example 11, 100 ° C) and increased processing time (example 12, 24 hours). Figure 4 depicts the distribution curves of pore volume over the diameter (Fig. 4, a) and IR spectra (Fig. 4, b) of crystalline aluminosilicates with the MOR structure (sample 4, table 1, examples 9, 11, 12, table. 2). The curves of the distribution of pore volume in diameter confirm the formation of mesopores in materials obtained under different conditions. IR spectra confirm that the implementation of the method at elevated temperature and increased processing time does not lead to a decrease in the crystallinity of materials. A decrease in the intensity of absorption bands in the region of 950 cm ^- 1, as well as an increase in intensity and a clearer separation of absorption bands of about 600 cm ^- 1 indicate an increase in the crystallinity of the samples during the process at an elevated processing temperature (100 ° C, example 11, table 2) or with an increased processing time (24 hours, example 12, table 2).

Example 13

Micro-mesoporous material is prepared as follows. In 78 ml of water, 7.6 g of a 25% solution of NH ₄ OH and 7.76 g of hexadecyltrimethylammonium bromide C ₁₆ H ₃₃ (CH ₃ ) ₃ NBr (GDMA) are dissolved; in the resulting solution, the concentration of NH ₄ OH is 0.7 mol / L the concentration of HDTMA is 0.3 mol / L. To the resulting solution was added 5 g of microporous crystalline aluminosilicate with an FAU structure (sample 5, table 1). The resulting suspension was stirred at room temperature for 7 hours, after which the material was separated on a filter, washed with distilled water, dried at 100 ° C for 24 hours and calcined at 550 ° C for 24 hours. As a result, a material with the structure of the zeolite FAU was obtained. the ratio Si / Al = 36, the pore volume of 0.45 cm ³ / g, with fractions of micropores and mesopores of 0.4 and 0.6, respectively. The average mesopore diameter is 3 nm.

Example 14

The material is obtained analogously to example 13, but 1.85 g of a 35% solution of TMAOH and 7.76 g of hexadecyltrimethylammonium bromide C ₁₆ H ₃₃ (CH ₃ ) ₃ NBr (GDMA) are dissolved in 78 ml of water, the concentration of TMAON in the resulting solution is 0 , 07 mol / L, HDTMA concentration of 0.3 mol / L. The properties of the obtained material are presented in table.2.

Example 15

Micro-mesoporous material is prepared as follows. 1.22 g of NaOH and 10.3 hexadecyltrimethylammonium bromide C ₁₆ H ₃₃ (CH ₃ ) ₃ NBr (GDMA) are dissolved in 78 ml of water, in the resulting solution, the concentration of NaOH is 0.4 mol / l, the concentration of HDTM is 0.4 mol / l 5 g of a microporous crystalline aluminosilicate with the FER structure are added to the resulting solution (sample 6, table 1). The resulting suspension was stirred at room temperature for 7 hours, after which the material was separated on a filter, washed with distilled water, dried at 100 ° C for 24 hours and calcined at 550 ° C for 24 hours. As a result, a material with the structure of zeolite FER was obtained , the ratio Si / Al = 12, pore volume 0.25 cm ³ / g, with fractions of micropores and mesopores of 0.6 and 0.4, respectively. The average mesopore diameter is 4 nm.

Example 16

Micro-mesoporous material is prepared as follows. In 78 ml of water, 0.83 g of NaOH and 10.3 g of hexadecyltrimethylammonium bromide C ₁₆ H ₃₃ (CH ₃ ) ₃ NBr (GDMA) are dissolved, in the resulting solution, the concentration of NaOH is 0.24 mol / L, the concentration of GDMA is 0.4 mol / l 5 g of microporous crystalline aluminosilicate with the MFI structure are added to the resulting solution (sample 7, table 1). The resulting suspension was stirred at room temperature for 7 hours, after which the material was separated on a filter, washed with distilled water, dried at 100 ° C for 24 hours and calcined at 550 ° C for 24 hours to obtain a material with an MFI zeolite structure. the ratio Si / Al = 32, the pore volume of 0.34 cm ³ / g, with fractions of micropores and mesopores of 0.25 and 0.75, respectively. The average mesopore diameter is 5 nm.

Example 17

The material is obtained analogously to example 15, but in 78 ml of water 0.83 g of NaOH and 7.76 g of hexadecyltrimethylammonium bromide C ₁₆ H ₃₃ (CH ₃ ) ₃ NBr (GDMA), in the resulting solution, the concentration of NaOH is 0.24 mol / l, the concentration of HDMA 0.3 mol / l. The properties of the obtained material are presented in table.2.

Example 18

The material is obtained analogously to example 15, but in 78 ml of water 0.83 g of NaOH and 2.33 g of hexadecyltrimethylammonium bromide C ₁₆ H ₃₃ (CH ₃ ) ₃ NBr (GDMA), in the resulting solution, the concentration of NaOH is 0.24 mol / l, the concentration of GDMA 0.09 mol / l. The properties of the obtained material are presented in table.2.

Example 19

The material is obtained analogously to example 15, but in 78 ml of water 0.83 g of NaOH and 0.52 g of hexadecyltrimethylammonium bromide C ₁₆ H ₃₃ (CH ₃ ) ₃ NBr (GDMA), in the resulting solution, the concentration of NaOH is 0.24 mol / l, the concentration of GDMA 0.02 mol / L. The properties of the obtained material are presented in table.2.

Examples 16-19 illustrate the formation of a micro-mesoporous structure and the regulation of the proportion of mesopores during the implementation of the method in the range of surfactant concentrations from 0.02 to 0.4 mol / L. Figure 5 depicts the distribution curves of pore volume in diameter (Fig. 5, a) and IR spectra (Fig. 5, b) of crystalline aluminosilicates with the MFI structure (sample 6, Table 1, examples 16-19, Table 2) . The curves of the distribution of pore volume over diameter confirm the formation of mesopores in materials obtained in the range of surfactant concentrations from 0.02 to 0.4 mol / L. IR spectra confirm that the implementation of the method in the claimed range of surfactant concentrations does not lead to a deterioration in the crystallinity of micro-mesoporous materials: similar to the IR spectrum of the initial crystalline aluminosilicate with the MFI structure, the high intensity of the absorption band of 550 cm ^-1 and a high value of the ratio of this intensity to the intensity of the absorption band of 450 cm ^-1 , which is evidence of the high crystallinity of the materials.

Example 20

Micro-mesoporous material is prepared as follows. In 78 ml of water, 1.1 g of NaOH and 7.76 g of hexadecyltrimethylammonium bromide C ₁₆ H ₃₃ (CH ₃ ) ₃ NBr (GDMA) are dissolved, in the resulting solution, the concentration of NaOH is 0.36 mol / l, the concentration of GDMA is 0.3 mol / l To the resulting solution was added 5 g of microporous crystalline iron aluminosilicate with the MFI structure (sample 8, table 1). The resulting suspension was stirred at room temperature for 7 hours, after which the material was separated on a filter, washed with distilled water, dried at 100 ° C for 24 hours and calcined at 550 ° C for 24 hours. As a result, an MFI zeolite structure material was obtained , the ratio Si / Al / Fe = 75 / 0.2 / 0.6, pore volume 0.30 cm ³ / g, with fractions of micropores and mesopores 0.35 and 0.65, respectively. The average mesopore diameter is 5 nm.

Example 21

Micro-mesoporous material is prepared as follows. 1.1 g of NaOH and 7.3 g of tetrabutylammonium bromide (C ₄ H ₉ ) ₄ NBr (TBA) are dissolved in 78 ml of water, in the resulting solution, the concentration of NaOH is 0.36 mol / L, the concentration of TBA 0.3 mol / L . To the resulting solution was added 5 g of microporous crystalline iron aluminosilicate with the MFI structure (sample 8, table 1). The resulting suspension was stirred at room temperature for 7 hours, after which the material was separated on a filter, washed with distilled water, dried at 100 ° C for 24 hours and calcined at 550 ° C for 24 hours. As a result, an MFI zeolite structure material was obtained , the ratio Si / Al / Fe = 75 / 0.15 / 0.65, pore volume 0.28 cm ³ / g, with fractions of micropores and mesopores of 0.4 and 0.6, respectively. The average mesopore diameter is 30 (C ₄ H ₉ ) ₄ NBr nm.

Example 22

Micro-mesoporous material is prepared as follows. 1.28 g of NaOH and 7.76 g of hexadecyl trimethylammonium bromide C ₁₆ H ₃₃ (CH ₃ ) ₃ NBr (GDMA) are dissolved in 78 ml of water, in the resulting solution, the concentration of NaOH is 0.42 mol / L, the concentration of GDMA 0.3 mol / l 5 g of microporous crystalline titanosilicate with the MEL structure are added to the resulting solution (sample 9, table 1). The resulting suspension was stirred at room temperature for 7 hours, after which the material was separated on a filter, washed with distilled water, dried at 100 ° C for 24 hours, and calcined at 550 ° C for 24 hours. As a result, a material with a MEL zeolite structure was obtained , the ratio Si / Ti = 12, the pore volume of 0.30 cm ³ / g, with fractions of micropores and mesopores of 0.4 and 0.6, respectively. The average mesopore diameter is 4 nm.

Example 23

Micro-mesoporous material is prepared as follows. 1.95 g of a 35% solution of TMAOH and 7.76 g of hexadecyltrimethylammonium bromide C ₁₆ H ₃₃ (CH ₃ ) ₃ NBr (GDMA) are dissolved in 78 ml of water, the concentration of TMAON in the resulting solution is 0.07 mol / L, and the concentration of GDMA 0 , 3 mol / L. 5 g of microporous crystalline silica-aluminum phosphate with a CHA structure are added to the resulting solution (sample 10, table 1). The resulting suspension was stirred at room temperature for 7 hours, after which the material was separated on a filter, washed with distilled water, dried at 100 ° C for 24 hours and calcined at 550 ° C for 24 hours. As a result, a material with a CHA zeolite structure was obtained , the ratio Si / Al / P = 0.2 / 1/1, the pore volume of 0.30 cm ³ / g, with fractions of micropores and mesopores of 0.4 and 0.6, respectively. The average mesopore diameter is 4 nm.

Thus, as can be seen from the above examples, a new type of crystalline materials is obtained having a bimodal porous structure, including micropores with a diameter of 0.4-1.0 nm, determined by the type of the initial crystalline microporous structure, and homogeneous mesopores with a diameter of 2-30 nm localized in the volume of the zeolite crystal. The diameter of the mesopores varies from 2 to 30 nm, depending on the combination of a water-soluble base and a surfactant.

Figure 6a shows a TEM image of the material obtained by the proposed method (Example 9, Table 2), from which the absence of an isolated mesoporous phase and localization of the mesopores in the volume of the zeolite crystal obviously follow, whereas the TEM image of the material obtained according to the prototype method (Fig.6, b), there are two phases - microporous and mesoporous.

As can be seen from the above examples, a significant increase in the pore volume of micro-mesoporous materials was achieved compared to the starting microporous materials due to the formation of mesopores uniform in diameter. The proportion of mesopores in the pore volume of the micro-mesoporous material varies from 0.4 to 0.85 depending on the process conditions.

As can be seen from the above examples, a simplification of the method for producing crystalline material with bimodal porosity was achieved, in which the process is carried out in one stage while ensuring high quality of the synthesized products. The resulting materials retain high crystallinity of the initial zeolites, and in some cases, crystallinity increases.

Figure 4, b depicts the IR spectra of crystalline aluminosilicates with the MOR structure: starting material, sample 4, table 1, examples 11 and 12, table 2. The decrease in the intensity of the absorption bands in the region of 950 cm ^-1 , as well as the increase in intensity and a clearer separation of the absorption bands of about 600 cm ^-1 indicate an increase in the crystallinity of the samples obtained by the present method in the most severe conditions - at an elevated processing temperature (example 11, table .2) or increased processing time (example 12, table 2).

As can be seen from the above examples, the expansion of the spectrum of crystalline structures obtained by the claimed method was achieved, while crystalline aluminosilicates with the structure FAU, CHA, LTL, FER, MAZ, MOR, BEA, MFI, MEL, MTN, MTT were used as starting microporous materials. , MTW, MWW, TON, crystalline metal silicates with the structure BEA, MFI, MEL, MTN, MTT, MTW, MWW or silicoaluminophosphates with the structure FAU, CHA, AEI, AFI, AFO.

The resulting materials are suitable for various sorption and catalytic processes as sorbents, carriers, catalysts, filter materials.

Claims (7)

1. A method of obtaining a micromesoporous crystalline material, including the interaction of a microporous crystalline material with a solution of a water-soluble base and a surfactant, washing, drying and calcining the obtained material, characterized in that the interaction is carried out in one stage in a solution containing 0.07-0, 7 mol / L water-soluble base and 0.02-0.40 mol / L surfactant, at a temperature of 20-100 ° C for 1-24 hours 2. The method according to claim 1, characterized in that the interaction serves microporous crystalline aluminosilicates with the structure of FAU, CHA, LTL, FER, MAZ, MOR, BEA, MFI, MEL, MTN, MTT, MTW, MWW, TON. 3. The method according to claim 1, characterized in that the interaction serves microporous crystalline metal silicates with the structure of BEA, MFI, MEL, MTN, MTT, MTW, MWW. 4. The method according to claim 1, characterized in that the interaction serves microporous crystalline silica-aluminum phosphates with the structure of FAU, CHA, AEI, AFI, AFO. 5. The method according to claim 1, characterized in that the quaternary alkylammonium salt, the cation size of which is selected depending on the given diameter of the mesopores, is supplied as a surfactant for the interaction. 6. A micromesoporous crystalline material obtained by the method described in claim 1, having a bimodal porous structure, including zeolite micropores with a diameter of 0.4-1.0 nm and mesopores with a diameter of 2-30 nm, localized in the volume of the zeolite crystal. 7. The material according to claim 6, characterized in that the proportion of micropores in the total pore volume is from 0.15 to 0.60, and the proportion of mesopores in the total pore volume is from 0.4 to 0.85.

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