PL238641B1 - Method for preparation of zeolite monolithic catalyst - Google Patents

Description

Description of the invention

The subject of the invention is a method of preparing zeolite monolithic catalyst on a non-porous monolith based on alumina (a-AbOa), obtained with the use of three-dimensional structure-forming patterns printed by DLP (Digital Light Processing) technique.

One of the difficulties encountered in the production of heterogeneous zeolite catalysts in a particulate form (e.g. powder or granules) is the necessity to separate them from the post-reaction mixture. This involves additional operations, such as filtering, and losses of both catalyst and reagents. This results in an increase in the overall production costs.

The above-mentioned problem can be reduced by bonding the zeolite to a monolithic support, which allows the production process to be carried out in a continuous manner, without the need for catalyst separation.

The main method of producing monolithic structures (carriers) is now extruding them in devices called extruders. This process is based on the use of specially constructed matrices reflecting the assumed spatial structure of the manufactured monolith and is extensively described in the literature, e.g. Nijhuis T.A., Beers A.E.W., Vergunst T., Hoek I., Kapteijn F., Moulijn J.A., Catal. Rev, Sci. Eng. 43 (2001) 345; US3790654; US4741792; US5070588; JPH03281306.

The production of monoliths by extrusion requires the preparation of a mixture of powdered ceramic raw materials and a binder, its plasticization with a solvent (usually water) and organic or inorganic additives (e.g. plasticizers, surfactants, temporary binders, reinforcing fibers), squeezing the paste through dies of the desired shape, and then drying the extruded shapes and calcining them.

The properties of the monoliths depend on the type and properties of the materials used, additives, pH, water content and the pressure used in extrusion.

Low surface area monolithic supports are prepared from cordierite or a mixture of three or more of its precursors to provide a SiO2: Al2O3: MgO molar ratio close to that corresponding to cordierite. Typically the raw materials are: talc, kaolin, clay, hydroxide and / or alumina, magnesium hydroxide [US4448833; US4279849; US3930522].

In Tubio C.R., Azuaje J., Escalante L., Coelho A., Guitian F., Sotelo E., Gil A., J. Catal. 334 (2016) 110, the possibility of using a 3D printer, operating on the principle of extruding the material, for the synthesis of catalysts was indicated. However, the proposed printing method does not allow for any design of the monolith architecture (i.e. the shape, size and structure of the channels).

Such a possibility is provided by the method of producing monoliths using polymer templates, printed in the 3D printing technology - DLP, which is described in the publication of P. Michorczyk, E. Hędrzak, A. Węgrzyniak, J. Mater. Chem. A, 4 (48) (2016) 18753. The method in question involves the use of a high-resolution polymer 3D printout made in DLP technology as a structure-forming template for a monolithic carrier, which is poured over with a liquid ceramic mass. After drying the ceramic mass and firing the polymer template (usually at 850 ° C) in the air atmosphere, a monolithic support with the desired architecture is obtained.

The literature describes a number of methods of applying homogeneous zeolite layers on the surfaces of extruded monolithic supports, e.g. made on the basis of a-AbO3 [incl. G.B.F. Seijger, O.L. Oudshoorn, W.E.J. van Kooten, J.C. Jansen, H. van Bekkum, C.M. van den Bleek, H.P.A. Calis Microporous and Mesoporous Materials 39 (2000) 195], y-AbO3 [M.R. Othman, S.C. Tan, S. Bhatia Microporous and Mesoporous Materials 121 (2009) 138] or Teflon [T. Sano, Y. Kiyozumi, M. Kawamura, F. Mizukami, H. Takaya, T. Mouri, W. Inaoka, Y. Toida, M. Watanabe, K. Toyoda Zeolites 11 (1991) 842].

However, little information is still devoted to the methods of depositing zeolite layers on the surface of 3D-printed structures. So far, only the method of applying the ZSM-5 zeolite layer on ceramic meshes printed with the 3DFD (Three-Dimentional Fiber Deposition) technique, containing aluminum and titanium oxide in its composition, has been described in the literature [J. van Noyen, A. de Wilde, M. Schroeven, S. Mullens, J. Luyten, Int. J. Appl. Ceram. Technol. 9 (2012) 902]. The zeolite deposition process disclosed in this publication is a multi-stage process in which a gel is obtained in the first stage, in which nucleation of the zeolite takes place under hydrothermal conditions. Then, the gel prepared in this way is diluted in another gel, from which the crystallization process is carried out on the surface of ceramic meshes. The process of crystal growth is carried out, according to the authors, by the hydrothermal method, in autoclaves under isothermal conditions.

PL 238 641 B1

The object of the present invention is to develop such a method for the preparation of a zeolite catalyst on a non-porous monolith based on alumina, obtained with the use of DLP printed structure-forming templates, in which the zeolite layer is deposited on the monolith in one step in the process of direct zeolite synthesis.

According to the invention, a method for preparing a zeolite monolithic catalyst on a non-porous monolith based on alumina, obtained with the use of three-dimensional structure-forming templates printed with the DLP technique, in which the structure-forming template for the monolithic support is flooded with a liquid ceramic mass containing a-AbO3 mixture, water glass, sodium hydroxide and water, and after drying the ceramic mass and firing the polymer template, the zeolite layer is applied to the monolith thus produced by the hydrothermal method, characterized by the fact that the zeolite is applied to the monolithic catalyst support in the process of direct zeolite synthesis from an alkaline gel in which the monolith is immersed.

The zeolite synthesis is carried out, preferably in an autoclave, at a temperature of 110-240 ° C for 3 to 36 hours.

In the zeolite synthesis process, a gel is used, obtained by mixing colloidal silica (SiO2), sodium aluminate (NaAIO2), a structure-forming template which is tetrapropylammonium bromide (TPABr), sodium hydroxide (NaOH) and water, preferably deionized, in such amounts, that the molar ratios of the gel components are in the following ranges: Al / Si = 0 - 0.067, H2O / SiO2 = 20 - 100, OH ^- / SiO2 = 0.05 - 1 and TPA + / OH ^- = 0.1 - 10, where TPA + represents a tetrapropylammonium cation.

After the synthesis is completed, the monolithic support with the deposited layer of zeolite crystals is rinsed in water, preferably deionized, dried at a temperature below 100 ° C and subjected to first calcination at 450-800 ° C for 5-12 hours and then cooled. This calcination is to remove occluded molecules of the structure-forming template (tetrapropylammonium bromide) from the inside of the pores of zeolite crystals.

Then, ion exchange is carried out in the sodium forms of the zeolite by immersing the monolithic carrier with a deposited layer of zeolite crystals at least once in a 0.5 molar ammonium nitrate (V) solution for a period of 3 - 48 h at a temperature of 20 - 90 ° C. This allows the removal of extra-network sodium ions from the zeolite structure and their replacement by ammonium cations.

Finally, the monolith with the deposited layer of zeolite crystals is dried and subjected to a second calcination to break down the ammonium ions and generate catalytically active acid sites. The second calcination is carried out at the temperature of 350-800 ° C for 6-12 hours, after which the catalyst prepared in this way is cooled down.

Preferably, before starting the zeolite synthesis on the surface of the monolithic support, the gel obtained by mixing its components is homogenized for 60 minutes. at a temperature of 20 - 80 ° C.

Preferably, the synthesis of zeolite on the surface of the monolithic support is carried out at a temperature of 120 - 180 ° C for 5 to 25 h.

Preferably, the drying process of the monolithic carrier with the deposited layer of zeolite crystals is carried out at a temperature of 60-80 ° C.

Preferably, the first calcination of the monolithic support with the deposited layer of zeolite crystals is carried out at a temperature of 500-650 ° C for 8 hours.

Preferably, the second calcination of the monolithic support with the deposited layer of zeolite crystals is carried out at a temperature of 400-650 ° C for 8 hours.

Preferably, the ion exchange in the sodium forms of the zeolite is carried out by a 3 to 4-fold exchange of the ammonium nitrate solution in which the monolithic support with the deposited layer of zeolite crystals is immersed.

The developed preparation method enables the application of a uniform layer of ZSM-5 crystals with a thickness of 15-50 microns and a Si / Al silicon module of at least 15, preferably 30-70, on the carrier monolith, in one technological operation. This significantly simplifies the preparation and reduces the production costs of the catalyst compared to the solutions known from the state of the art.

Due to the fact that the zeolite is synthesized as a layer on the monolith in one operation, it is possible to easily control the catalytic properties of the prepared catalysts by changing the thickness of the zeolite crystal layer.

The invention is illustrated in several examples of practical implementation below.

PL 238 641 B1

In each of the examples, zeolite layers were applied to alumina-based monoliths obtained using high resolution 3D printing. The exact method of monolith preparation and source files for polymer models of structure-forming templates can be found in the work of: P. Michorczyk, E. Hędrzak, A. Węgrzyniak, J. Mater. Chem. A, 4 (48) (2016), p. 18753 et seq.

The monoliths were prepared by mixing a-Al2O3 with water glass (containing 50 - 70% Na2SiO3,> 10% NaOH) in a 2: 1 weight ratio. The printed templates were filled with the paste-like consistency obtained in this way. Thereafter, the mass-filled templates were dried at room temperature and 120 ° C (using a temperature increase of 2 ° C / min) for 4 hours.

Hardening of the ceramic mass and removal of the template were carried out by calcining the templates filled with the mass at the temperature of 850 ° C (temperature increase 2 ° C / min) for 4 hours with free air access.

Based on the monoliths obtained in this way, obtained with the use of 3D printing - DLP, examples of catalysts containing zeolite layers with Si / Al modulus = 30, 50, 70 and comparatively silicon analog of zeolite ZSM-5 - silicalite-1 (without aluminum) were prepared.

In each of the examples, zeolite was applied from a gel which was poured over the monoliths placed in the autoclave.

After pouring the monoliths with gel, the autoclave was tightly closed and heated, conducting the zeolite synthesis process and its simultaneous deposition on the monolith.

After synthesis, monoliths with a layer of zeolite crystals deposited on the surface were cooled, rinsed several times with deionized water, dried and then calcined in the flow of air.

In the final stage of catalyst preparation, sodium forms of zeolite were subjected to ion exchange, which was carried out with a 0.5 molar solution of ammonium nitrate (V).

The ion exchange procedure was performed four times. After its completion, the monolithic catalysts were dried at room temperature and again subjected to thermal treatment in the flow of air.

P r z k ł a d 1

The corundum carrier with a defined shape and geometry of the channels was placed in an autoclave equipped with a Teflon insert.

A gel was made of 1.196 g colloidal silica (e.g. based on SigmaAldrich), 89.16 mg sodium aluminate, 0.87 g tetrapropylammonium bromide, 130 mg sodium hydroxide and 47.075 g distilled water. The ingredients were combined and mixed for 30 min. on a magnetic stirrer at room temperature, then introduced into the autoclave.

The zeolite synthesis was carried out in an autoclave at 180 ° C for 24 hours. After its completion, a monolith with a layer of zeolite crystals with Si / Al = 30 module was obtained, which was dried for 24 hours at 80 ° C, and then calcined at 550 ° C. for 8 h. Calcination conditions were selected in such a way that the temperature increase did not exceed 1 ° C / min. After the calcination was completed and the monolithic shaped body had cooled down, the zeolite was subjected to ion exchange, which was carried out with a 0.5-molar ammonium nitrate solution at room temperature. The ion exchange was repeated 4 times, each time exchanging the nitrate solution.

The catalyst was then dried and re-soaked (calcined) at 450 ° C while maintaining the temperature increase of 1 ° C / min.

P r z k ł a d 2

As in example 1, the corundum support with a defined shape and geometry of the channels was placed in an autoclave equipped with a Teflon insert.

A gel was introduced into the autoclave, which was obtained by dissolving 130 mg of sodium hydroxide in 47.075 g of distilled water. Then 0.87 g of tetrapropylammonium bromide was added to the thus prepared solution. The mixture was thoroughly mixed, then 53.50 mg of sodium aluminate was added while stirring. In a final step, 1.196 g of silica was added. The obtained gel was left for 30 min. on a magnetic stirrer for homogenization.

The zeolite synthesis was carried out in an autoclave at 180 ° C for 24 hours.

After its completion, a monolith with a layer of zeolite crystals with Si / Al = 50 modulus was obtained, which was dried for 24 hours at 80 ° C, and then calcined at 550 ° C for 8 hours. The temperature increase in the case of calcination was 1 ° C / min.

PL 238 641 Β1

After the calcination was completed and the shaped pieces had cooled down, the zeolite deposited on it was subjected to ion exchange, which was carried out with a 0.5 molar solution of ammonium nitrate (V) at room temperature. The ion exchange was repeated 4 times, each time exchanging the nitrate solution.

The catalyst was then dried and re-heated (calcined) at 450 ° C assuming a temperature increase of 1 ° C / min.

Example 3

The gel from which the zeolite crystal layer was synthesized was prepared by dissolving 38.20 mg of sodium aluminate in 47.075 g of distilled water. The solution was mixed and then 0.13 g of sodium hydroxide and 0.87 g of tetrapropylammonium bromide were introduced with continued stirring. In the final reaction step, 1.196 g of colloidal comminuted silica was added to the solution. The obtained gel was left on the magnetic stirrer for another 30 min.

The gel prepared in this way was introduced into an autoclave equipped with a Teflon cartridge in which a corundum monolith had previously been placed.

The further steps of the procedure were as in examples 1 and 2. A monolithic zeolite catalyst with a modulus of Si / Al = 70 was obtained.

Example 4 (comparative)

The alumina support, as in Example 1, was placed in an autoclave equipped with a Teflon cartridge, and then a gel obtained by mixing a silicon source, a structure-forming template (tetrapropylammonium bromide), sodium hydroxide and water was introduced into the autoclave.

A gel was prepared by mixing 0.98 g of tetrapropylammonium bromide, 150 mg of sodium hydroxide and 53.26 g of water. The resulting solution was left on the stirrer until complete homogenization. After the components had dissolved, 5.18 g of an alkaline solution in which 2.22 g of silica was dissolved were taken up. After dissolving the silica, the two solutions were mixed and the gel thus obtained was stirred for 30 min. on a magnetic stirrer and then introduced into the autoclave.

The synthesis was carried out in an autoclave at 180 ° C for 24 hours. After its completion, a monolith with a layer of ZSM-5 analogue crystals (Silicalite-1) was obtained, which was dried for 24 hours at 80 ° C, and then calcined at 550 ° C. C for 8 h. Calcination conditions were selected in such a way that the temperature increase did not exceed 1 ° C / min.

After the calcination was completed and the shaped pieces had cooled down, the silicalite-1 deposited thereon was subjected to an ion exchange process, which was carried out with a 0.5 molar ammonium nitrate solution at room temperature. This process, as in the previous examples, was repeated 4 times.

After its completion, the catalyst was dried and calcined again at a temperature of 450 ° C, assuming a temperature increase of 1 ° C / min.

The exemplary monolithic catalysts obtained as described above were characterized by various physicochemical techniques to identify the phase composition, morphology, porosity and specific surface area.

The results of sorption tests of the produced catalysts and the comparative analysis of the monolith itself are presented in Table 1, which summarizes the specific surface area, volume and pore diameter determined by the low-temperature nitrogen sorption method.

Table 1

Catalyst Sbet [m ² / g] V pores [cm ³ / g] avg [nm] ZSM-5 Si / AI = 30 34.87 0.007 3.39 ZSM-5 Si / AI = 50 52.23 0.009 3.11 ZSM-5 Si / AI = 70 66.17 0.011 2.96 Silicalite-1 72.79 0.013 3.10 Monolith (a-AI ₂ O ₃ ) 0.17 0.001> 6.00

It can be seen that depending on the modulus of silica (Si / AI) the specific surface area was varied from approx. 35 m ² / g Si / Al = 30 to more than 72 m ² / g for the analog czystokrzemowego

ZSM-5 zeolite (silicalite-1). At the same time, the obtained monoliths covered with a layer of zeolite crystals had a much larger surface compared to the pure monolith with a-AbOa.

It was also found that the determined pore volumes for the tested catalysts are small, which proves that zeolite crystals are densely packed on the monolith surface.

The surface micro-images and cross-sections of corundum monoliths covered with a layer of ZSM-5 zeolite crystals and its pure silicon analog, i.e. silicalite-1, are shown in the attached drawing, in which:

Fig. 1a shows the surface of the catalyst of example 1, fig. 1b shows the cross section of the monolith and zeolite layer of the catalyst of example 1, fig. 1c shows the surface of the catalyst of example 2, fig. 1d shows the cross-section of the monolith and zeolite layer of the catalyst of example 2, fig. 1e shows the surface of the catalyst of example 3, fig. 1f shows the cross section of the monolith and zeolite layer of the catalyst of example 3, fig. 1g shows the surface of the catalyst of example 4, fig. 1h shows the cross-section of the monolith and zeolite layer of the catalyst of example 4.

Scanning electron microscopy (SEM) studies have confirmed that the zeolite crystals formed on the surface of alumina monoliths form densely packed and continuous layers with a thickness of 15-50 microns.

Structural studies by powder diffraction method have shown that monolithic catalysts consist of three phases: zeolite phase with MFI structure - (ZSM-5, silicalite-1), corundum phase (a-AbOa) and nepheline - crystalline aluminosilicate that is a binder of alumina monoliths.

Diffractograms for individual catalysts are presented in the attached drawing, where:

Fig. 2a relates to the diffraction patterns for the zeolite coated monoliths according to example 1;

Fig. 2b relates to the diffraction patterns for the zeolite coated monoliths according to example 2;

Fig. 2c relates to the diffraction patterns for the zeolite coated monoliths according to example 3;

Fig. 2d relates to the diffraction patterns for the zeolite coated monoliths according to example 4.

These diffractograms indicate which line refers to the zeolites deposited on the carrier, and which line refers to pure ZSM-5 zeolites deposited on the walls of the autoclave during the syntheses carried out.

The activity of the prepared exemplary monolithic catalysts with zeolite layers was checked in the isomerization reaction of a-pinene (terpene). This process was carried out in the gas phase.

The isomerization reaction of a-pinene to typical transformation products, such as camphene and limonene, carried out at a temperature of 200 ° C for 15 hours for catalytic systems containing a heteropolyacid deposited on silicon, niobium, titanium or zirconium oxides, is described in the publication: A. Alsalme, EF Kozhevnikova, I.V. Kozhevnikov, Appl. Catal. A: Gen. 390 (2010) 219. All the catalytic systems examined by the authors of this publication were characterized by high activity and values of α-pinene conversion degrees in the range between 80 and 100%. A decrease in the value of the conversion degree of a-pinene from a few to a dozen or so percent (depending on the catalyst used) was observed with the passage of time. The degree of deactivation of the catalysts used in the above work depended on the acidity of the catalytic system, obtained as a result of depositing heteropolyacids on oxide supports. It was revealed that the acidity of the catalytic system influenced not only the degree of conversion of α-pinene, but also the selectivity of obtaining the main reaction products, namely camphene and limonene.

Tests of the catalytic properties of the exemplary catalysts of the invention in the isomerization of α-pinene were performed under flow conditions in an experimental reactor that contained a catalyst monolith inside a quartz tube.

The experimental reactor was annealed in a helium atmosphere at 250 ° C for 1 hour in order to remove mainly water vapor and other volatile impurities that could interfere with the test reaction.

PL 238 641 Β1

Thereafter, helium, as inert gas, containing α-pinene in an amount of 1 ml / hour was passed through the experimental reactor at 250 ° C. The catalytic test for each of the tested catalysts was carried out for 4 hours. The obtained reaction products were collected at regular intervals (every 30 minutes) and analyzed using a Bruker GC430 gas chromatograph equipped with a FID detector and a VX column.

The results of these measurements are presented in Table 2, in which the values of the α-pinene conversion degree for the tested catalytic systems after 30 minutes and 2 hours for the process carried out at 250 ° C were collected.

Table 2

Catalyst ZSM-5 (70) on a monolith ZSM-5 (50) on a monolith ZSM-5 (30) on a monolith Thirty minutes 4 hours Thirty minutes 4 hours Thirty minutes 4 hours A-pinene conversion rate 33.3% 22.8% 76.1% 59.4% 82.6% 69.7%

As can be seen from this table, the degree of α-pinene conversion decreases with increasing process time. This is due to the gradual deactivation of the catalyst (unlike in the case of the liquid phase process, where the batch method is usually used).

The degree of α-pinene conversion also decreases with increasing aluminum content in the ZSM-5 zeolite coating (i.e. decreasing the value of the so-called silicon module).

For the purposes of comparison, for the selected catalyst, which was ZSM-5 (30) on the monolith, an α-pinene isomerization reaction was additionally carried out at the temperature of 225 and 200 ° C.

The method of preparing the experimental reactor for the isomerization process and the implementation of the process were analogous to those described above.

The test results are presented in Table 3, where the values of the α-pinene conversion degree for the above-mentioned catalytic system after 30 minutes and 4 hours for the process carried out at 200, 225 and 250 ° C were collected.

Table 3

Catalyst A-pinene conversion rate 250 ° C 225 ° C 200 ° C Thirty minutes 4 hours Thirty minutes 4 hours Thirty minutes 4 hours ZSM5 (30) on the monolith 82.6% 69.7% 74.9% 41.9% 37.6% 17.9%

Regardless of the applied temperature of the α-pinene isomerization reaction, a decrease in the degree of conversion was observed along with the duration of the process, with the only difference that the decrease in the value of the conversion degree was the lowest at the highest temperature.

Additionally, in order to test the stability of operation of the selected catalyst system, several cycles were performed: isomerization reaction - catalyst regeneration. In each of these cycles, after the catalytic test, the investigated ZSM-5 catalyst system (30) was regenerated on a monolith at the temperature of 700 ° C for 30 minutes in the flow of air, and then the process of isomerization of a-pinene was performed again.

PL 238 641 Β1

The test results are presented in Table 4, where the values of the α-pinene conversion degree for the selected catalyst system after 30 minutes and 4 hours for the fresh catalyst and after several regenerations were collected.

Table 4

Catalyst A-pinene conversion rate Fresh catalyst After the first regeneration After the 2nd regeneration After the 3rd regeneration Thirty minutes 4 hours Thirty minutes 4 hours thirty minutes 4 hours Thirty minutes 4 hours ZSM-5 (30) on a monolith 82.6% 69.7% 77.6% 47.1% 78.4% 44.0% 55.9% 31.4%

The conducted research showed that the repeated application of the selected catalyst system results in a gradual decrease of the initial activity of the tested catalyst.

The results presented in Tables 2 to 4 show that the catalysts prepared according to the invention show high activity in the α-pinene isomerization reaction, comparable to the catalyst systems described in the literature.

It should be mentioned that the test results presented above show that the catalysts prepared according to the invention have the advantage that their activity can be restored to a satisfactory level in a relatively easy way, without the need for additional operations, such as e.g. filtration (necessary when conducting process in the liquid phase, the task of which is to separate the solid catalyst from the post-reaction mixture).

Additionally, carrying out the process of isomerization of α-pinene with the use of the catalysts according to the invention makes it possible to limit the participation of subsequent reactions; which the resulting reaction products may undergo.

Claims (7)

1. The method of preparing zeolite monolithic catalyst on a non-porous monolith based on alumina, obtained with the use of three-dimensional structure-forming templates printed with the DLP technique, in which the structure-forming template for the monolithic support is flooded with a liquid ceramic mass containing a-Al ₂ C> 3 mixture, water glass , sodium hydroxide and water, and after drying the ceramic mass and firing the polymer template, the monolith thus produced is applied with a hydrothermal zeolite layer, characterized in that the zeolite is applied to the monolithic catalyst carrier in the process of direct zeolite synthesis from an alkaline gel, in which the monolith is immersed, the synthesis of which is carried out at a temperature of 110 - 240 ° C for a period of 3 to 36 hours, while the zeolite synthesis uses a gel obtained by mixing colloidal silica, sodium aluminate, tetrapropylammonium bromide, sodium hydroxide and water, in such quantities as to make a ratio k and molar components of the gel were in the following ranges: Al / Si = 0 - 0.067, H ₂ O / SiO ₂ = 20 - 100, OH7SiO ₂ = 0.05 - 1 and TPA7OH '= 0.1 - 10, where TPA ⁺ is a cation tetrapropylammonium, and after the synthesis is completed, the monolithic support with a deposited layer of zeolite crystals is washed in deionized water, dried at a temperature below 100 ° C and subjected to the first calcination at the temperature of 450 - 800 ° C for 5 - 12 hours, then cooled and the exchange is carried out ions in sodium forms of zeolite by at least once immersing the monolithic carrier with a deposited layer of zeolite crystals in a 0.5 molar solution of ammonium nitrate (V) for a period of 3 - 48 hours at a temperature of 20 - 90 ° C, and The end of the monolith with the deposited layer of zeolite crystals is dried and subjected to a second calcination at the temperature of 350-800 ° C for 6-12 hours, after which the catalyst thus prepared is cooled down. 2. The method according to p. The method of claim 1, characterized in that, before starting zeolite synthesis on the surface of the monolithic support, the gel obtained by mixing its components is homogenized for 5-60 minutes. at a temperature of 20 - 80 ° C. 3. The method according to p. The method of claim 1, characterized in that the synthesis of zeolite on the surface of the monolithic support is carried out at a temperature of 120 - 180 ° C for 5 - 25 h. 4. The method according to p. The method of claim 1, wherein the drying process of the monolithic support with a deposited layer of zeolite crystals is carried out at a temperature of 60-80 ° C. 5. The method according to p. The method of claim 1, characterized in that the first calcination of the monolithic support with the deposited layer of zeolite crystals is carried out at a temperature of 500 - 650 ° C for 8 hours. 6. The method according to p. The process of claim 1, wherein the second calcination of the monolithic support with the deposited layer of zeolite crystals is carried out at a temperature of 400 - 650 ° C for 8 hours. 7. The method according to p. The method of claim 1, characterized in that the ion exchange in the sodium forms of the zeolite is carried out by a 3-4-fold exchange of the ammonium nitrate solution in which a monolithic support with a deposited layer of zeolite crystals is immersed.