Catalyst materials and method of producing said materials

FIELD: chemistry.

SUBSTANCE: present invention relates to catalyst material which is a mesoporous molecular sieve with zeolite solid support. The mesoporous molecular sieve is selected from the M41S group. The zeolite is an average-porous zeolite selected from MFI, MTT, TON, AEF, MWW and FER zeolites, or a coarse-porous zeolite selected from BEA, FAU, MOR zeolites. The catalyst material is heat-resistant at temperature not below 900°C. The invention also relates to a catalyst, a method of making a mesoporous molecular sieve with a zeolite solid support and use of the catalyst material and the catalyst.

EFFECT: invention enables to obtain heat-resistant catalyst material having high catalytic activity.

16 cl, 52 ex, 7 tbl, 9 dwg

 

The technical field to which the invention relates

The present invention relates to mesoporous catalysts and, in particular, to a new mesoporous molecular sieves with the incorporation of the zeolite having a high heat resistance, and to a method for catalytic materials. These catalytic materials are suitable for applications in the field of hydrocarbon processing.

Description of prototype

Mesoporous molecular sieves as catalyst materials have attracted the attention of scientists due to their unique properties such as large uniform pores having a very high surface area, the size of which can vary from 2 to 50 nm. However, mesoporous molecular sieves, known in the art, are often not very heat-resistant and hydrothermolysis, the walls of the pores are amorphous and they have a weak acid properties. In addition, regeneration of the spent catalyst after processing of the hydrocarbon structure of mesoporous molecular sieves may deteriorate.

Crystalline materials having a pore size in the microporous region (d<2 nm), are used as catalysts and as carriers of catalysts on an industrial level. Zeolites are well-known examples of such materials. Zeolites are widely and which are due to their special properties, such as large surface area, high adsorption capacity and the ability to adjust adsorption capacity. You can create active sites in the zeolite structure, build active centers and regulate the strength and number of acid sites. The pore size of the zeolites is usually in the range of 0.4-1.2 nm, and both thermal and chemical stability of the zeolites is high. However, the ability of zeolites to process molecules with larger molecular size than the pore size of the zeolites is limited, and, in addition, zeolites relatively quickly deactivated in some reactions.

US 5198203 considers a family of ordered mesoporous molecular sieves designated as M41S and developed in the early 90-ies. M41S is a group of mesoporous molekularsiebe materials formed in aqueous solution precursors of silicon oxide and aluminum oxide with CiH2i(CH3)N+cations (i>7) in hydrothermal conditions. The most well-known representatives of this group are of hexagonal MCM-41, cubic MCM-48 and plate structure of MCM-50. The pore size of mesoporous molecular sieves can be adjusted in the range from 2 to 10 nm, and the composition may contain pure silicon oxide and the oxide metallocene (for example, Al-, V - and T-substituted silicon oxide). Mesoporous MOLEKULYaRNAYa materials of the M41S groups are amorphous in nature, and their porous system is ordered.

Synthetic composition material containing ultracapacity crystalline phase is seen in US 5246689 and US 5334368. This material is inorganic, porous and non-sliced, with pore sizes in the range from 1.3 to 20 nm. The distribution of the pore size in a single phase is somewhat regular. At least one peak on the x-ray is at the d-a distance of more than 1.8 nm.

EP 0748652 considers the group mesoporous materials (MSA), having a narrow distribution of the pore size. This material is amorphous and the completely disordered. The surface area of the material by BET method is in the range 672-837 m2/year

Synthetically derived mesoporous materials are non-acidic, or their acidity is limited. The number of acid sites in mesoporous materials increases with the introduction of aluminum into the structure of the silicon oxide mesoporous material. The strength of the acidity of mesoporous materials, described above, is, however, less power acidity of zeolites.

Different ways of obtaining mesoporous materials known in the art. Attempts have been made to increase thermal and GI is rotaries firmness and acidity of mesoporous molecular sieves, for example, the introduction of catalytically active particles in mesoporous structure. In principle, the synthesis methods include obtaining a solution of a source of silicon with an organic agent or agents, adjusting the pH of the solution to the value when there is precipitation, with subsequent extraction and calcination of the precipitate. The source of aluminum is introduced into the solution at any stage before the beginning of the synthesis at elevated temperature. Some surfactants and templates (organic agents), composition, solvents and reaction conditions.

US 5942208 describes a method of obtaining a mesoporous material having improved hydrothermal stability compared to MCM-41. The method uses a variety of salts and pH of the solution is adjusted with weak acids.

EP 0795517 provides a method for the synthesis of mesoporous materials using a mixture of silicon source and an organic template containing fluorine.

US 5942208 describes obtaining a mesoporous molecular sieve having thermal and hydrothermal stability, which are better than conventional mesoporous molecular sieves. The material can be boiled in water for 12 h without significant changes in the structure.

An alternative approach to obtaining stable and active mesoporous materials is the introduction the of the zeolites in the walls of the mesopores. US 09/764686 considers the synthesis of mesoporous materials using germ Y-zeolite, germ MFI zeolite and germ beta zeolite.

CN 1349929 describes obtaining MSA-3 and MAS-8 using solutions of the precursor L-zeolite.

In the work Kloetstra et al.,Micropor. Mesopor. Mater.,6 (1996), 287 discusses education in the place of poasito and MCM-41. Their method is based on sequential synthesis of zeolites and MCM-41.

In the work of Karlsson et al.,Micropor. Mesopor. Mater.,27 (1999), 181 discusses the use of mixed formulaic approach for the simultaneous synthesis phase zeolite/MCM-41.

Materials may be mixtures of two or more phases, or freely associated zeolite and mesoporous material in the case of methods of synthesis must grow and precipitate MSM-41 on top of the zeolite, or the germ of the zeolite can be introduced into the gel.

Two different types of template used in the synthesis of mesoporous materials. The reproducibility of these methods of obtaining can be difficult. In addition, in the absence of chemical interaction between the zeolite and mesoporous molecular sieve thermal and hydrothermal stability of the obtained materials are likely to be low.

In accordance with the present technique mesoporous molecular sieves have a wide range of applications in catalysis as the active phase or as carriers. Some of the reactions the AI conversion of hydrocarbons are kislotosoderjasimi. On the basis of their function, acid catalysis zeolites are known for their activity in the isomerization of the double bond and the structural isomerization of olefins, isomerization of paraffins, cracking, dimerization of olefins, oligomerization of olefins, the disclosure ring naphthenes, alkylation, transalkylation aromatic substances, flavoring, etc. Bifunctional catalyst having a metal or metal oxide, or sulfide phase is applicable in such reactions as reforming, isomerization of paraffins, hydrocracking, catalytic deparafineerimine, dehydrochlorinated, digidroksikhinolina, dehydrohydrocortisone and some of the reactions of gidrogenizirovanii. The main disadvantages in the use of zeolites is their relatively high capacity for decontamination and limited ability to process massive molecules.

On the basis of the above, you can see that there is a need for thermally and hydrothermally stable catalytic materials based on mesoporous molecular sieves and method of obtaining such thermally and hydrothermally stable catalyst materials. It is also clear that there is a need for a catalyst having an active center of the zeolite type, but also has high accessibility to the active centers of reagents, real now with a small length of the diffusion path and products limiting secondary reactions and gumming.

The purpose of the invention

The aim of the present invention is to provide a new and active catalytic material having a mesoporous molecular sieve with the incorporation of the zeolite, in particular, for the reactions of conversion of hydrocarbons.

Another objective of the present invention is mechanically, thermally and hydrothermally stable mesoporous molecular sieve with the incorporation of the zeolite with the acidity of the zeolite type.

Another objective of the present invention is a method of obtaining a specified catalytic material having a mesoporous molecular sieve with the incorporation of the zeolite structure.

Another objective of the present invention is the use of this catalytic material having a mesoporous molecular sieve with the incorporation of the zeolite structure, in the conversion reactions of hydrocarbons.

Distinctive features of mesoporous molecular sieves with the incorporation of the zeolite, method of its production and application of mesoporous molecular sieves with the incorporation of the zeolite defined in the claims.

Brief description of the invention

Without the desire to have a restriction in the following explanations and theoretical considerations, dealing with the synthesis of new catalytic material having a mesoporous molecule is RNA the sieve with the incorporation of the zeolite structure, which is particularly suitable for reactions conversion of hydrocarbons, the essential features of the invention are discussed as follows.

The present invention relates to a new and active catalytic material having a mesoporous molecular sieve with the incorporation of the zeolite structure. The invention relates also to a method for producing mesoporous molecular sieves with the incorporation of the zeolite, resulting in easier and reproduced synthesis, and product shows high catalytic activity.

Catalytic material having a mesoporous molecular sieve with the incorporation of the zeolite structure is appropriate for the reactions of conversion of hydrocarbons and, in particular, for the processing of high molecular weight hydrocarbons. Specified new catalytic material can be used as a component of the catalyst in the cracking, hydrocracking, the disclosure of ring hydrogenation of aromatic compounds and, especially, multirelational compounds, the dimerization of olefins, oligomerization, isomerization of olefins and paraffins, the alkylation of aromatic compounds, esterification, hydrodesulfurization and reforming process, either as such or with modifications known in the technique.

Detailed description of the invention

Now it is established that issues related to zeoli the major mesoporous catalysts and the catalysts in accordance with the prototype, you can avoid or at least significantly reduce new catalytic material according to the present invention, which is a mesoporous molecular sieve with the incorporation of the zeolite having the mechanical, thermal and hydrothermal stability. New mesoporous molecular sieve with the incorporation of the zeolite is heat resistant at temperatures below 900°C in the presence of air.

The present invention provides a group of new mesoporous molecular sieves with the incorporation zeolites, which are mechanically, thermally and hydrothermally stable. The materials are very well reproducible, as can be seen in the examples, and they show the best properties in some reactions the conversion of hydrocarbons. The group of new mesoporous molecular sieves with the incorporation zeolites is called mesoporous materials (MM). Mesoporous here means materials having pores 2-15 nm, and the pore system is regular.

Mesoporous molecular sieve with the incorporation of the zeolite contains mesoporous molecular sieve selected from the group M41S, which is defined on page 2 and contains mesoporous materials with ordered porous system. Preferably, the mesoporous molecular sieve selected from mesoporous aluminosilicates known as the group of MSM-41.

Mesopo the East of the molecular sieve has a sealing zeolite, selected from crednerite zeolites, which are 10-tier circular zeolites, such structures MFI, MTT, TON, ΛEF, MWW and FER, and macroporous zeolites, which are 12-tier circular zeolites, such structures BEA, FAU and MOR. Examples of this group of zeolites are ZSM-5, ZSM-23, ZSM-22, SAPO-11, MCM-22, periera, beta, Y - and X-zeolites and mordenite. Preferably, the zeolite is MFI, MTT, AEF, MWW, MOR and BEA zeolite.

The catalytic material contains 0.01 to 10 wt.% aluminum (Al).

The catalyst which is particularly suitable for industrial and commercial applications, contains mesoporous molecular sieve with the incorporation of the zeolite according to the present invention, and a carrier selected from alumina, silica, clay and any other media according to the prototype and their combinations. Preferably, the medium contains aluminum oxide or silicon oxide. The number of media varies in the range from 10 to 90 wt.% in relation to the total weight of the catalyst.

A new group of catalytic materials with mesoporous molecular sieve with the incorporation of the zeolite structure according to the present invention has a high specific surface area (by BET method) in the range 1400-500 m2/g, preferably 1200-600 m2/year

X-ray powder catalytic material according to the present invention shows the structure of mesoporous molecular sieves and zeolite. The size of the unit cell of zeolite varies with the amount of Al in the catalytic material. The size of the unit cell decreases with the number of Al from 1,982 nm in the catalytic material containing 0.2 wt.% Al, to 1,972 nm in the catalytic material containing 3.9 wt.% Al, when the type of zeolite is MFI (material code M). Changing the size of the unit cell is the reverse of the changes observed in zeolites at all.

The dimensions of the unit cell are 1,428 1,430 nm and nm, when the type of zeolite is WEAH (code material MWE), the dimensions of the unit cell are 1,406 nm and 1,436 nm, when the type of MWW zeolite is (material code MMMW22), and the dimensions of the unit cell are 1,800 nm and 1,806 nm, when the type of zeolite is MOR (code material MMO).

The distance d100in mesoporous molecular sieve MCM-41 decreases with increase in the content of the zeolite. The distance d100varies from 4.4 to 3.8 nm in MM, and the distance d100varies from 4.1 to 4.0 nm in MWE, MMO and from 4.0 to 4.2 nm in MMMW.

The size of the unit cell and the values of d100in phases of pure zeolite and MCM-41 are the same as in their mechanical mixtures.

Changes the distance d100and dimensions of the unit cell are obvious evidence of a true chemical bond between the mesoporous molecular sieve embedded with a zeolite in to delicious.com material according to the present invention.

The distinctive characteristics of the catalytic material according to the present invention, mesoporous molecular sieves with the incorporation of the zeolite, determined by x-ray diffraction powder, scanning electron microscopy, transmission electron microscopy, determination of specific surface area using nitrogen adsorption (BET method) and a determination of acidity using desorption of ammonia with programming temperature ((TPD)(PTA)and infrared spectroscopy with Fourier-transform ((IXFP)(FTIR)pyridine.

The total number of acid sites can be defined by the ability of the catalytic material to bind the molecules of a strong base, such as ammonia or pyridine. The total acidity is determined by the desorption of ammonia with programming temperature (TA), and the acidity of the acids Bronsted and Lewis IR spectroscopy of pyridine (IXFP).

The acidity of the catalytic material can be set by the amount of Al is introduced into the structure, and modification of the content of aluminum (Al) in the zeolite, MCM-41 MM and phases. On figa and 1b presents the correlation between acidity and aluminium content in the catalytic material according to the present invention. Figa shows linearity total acidity as a function of Al-content in different MM catalytic material is, and fig.1b shows how zeolite and MCM-41 catalytic materials are rejected total acidity MM from the catalytic materials. Zeolites show a greater number of acid sites as a function of Al content than the samples MM, MVE and MMMW, MCM-41 is less acidic with a similar Al-content.

Because there is no international standard methods applicable to determine the acidity, the methods used here are described below.

The definition of pH is carried out using NH3-The PTA. The total acidity of the catalyst materials is determined by desorption with the programming of the temperature of ammonia (NH3-PTA) with the use of device Altamira AMI-100. The sample size is 40 mg of Total acidity is determined by the desorption of NH3as a function of temperature. The acidity of the samples are calculated according to the number of NH3adsorbed at 200°C and desorbed in the range from 100 to 500°C. NH3-PTA-the instrument is equipped with a thermal conductivity detector ((RTA)(TCD)), manufactured by Gow Mac. The temperature increase with a linear speed of 20°C/min up to 500°C with exposure for 30 min at this value. Conduct quantitative determination using launches a known volume of 10% NH3Not.

The acidity is determined also using IXFP pyridine. The acidity of the samples opredelaetsa the infrared spectroscopy (ATI Mattson IXFP) using pyridine (≥99,5%, HC) as a molecule probe for qualitative and quantitative determination of acids Branstad, and Lewis acids. The samples are pressed into a thin self-supporting plate (10-12 mg/cm2). Pyridine initially adsorb for 30 min at 110°C and then was stripped during removal at different temperatures (250, 300 and 450°C) to obtain the concentration of acid centers. All spectra were recorded at 100°C with a spectral resolution of 2 cm-1. Spectral band at 1545 cm-1and 1450 cm-1respectively used to identify the centers of acids Branstad ((CCB)(BAS)) and Lewis acids ((CKL)(LAS)). The number of CCB and CCL calculated using intensities of spectral bands using molar ratios of decay.

The acid sites located on the surface of the catalytic material. The total surface area and pore volume are determined using the adsorption and desorption of nitrogen. The average surface area of mesopores and the diameter of the mesopores is determined by the desorption of nitrogen using BCH-equation (Barrera-Joyner-Halenda). The diameter of pores is nasmerovanie effect on the reagents and products. The size of micropores depends on the structure of the zeolite. In accordance with IUPAC pores with diameter less than 2 nm are defined as micropores, pores and diametral from 2 to 50 nm are defined as mesopores.

Isotherms of nitrogen adsorption/desorption of MMVE shown in figure 2. The diameter of the mesopores remains similar (2,4-2,7 nm) in sealed material compared with 2.6 nm in mesoporous molecular sieve.

BCH-desorption illustrating the distribution of the diameter of MMVE shown on the attached figure 3.

The surface area and total pore volume decrease when the zeolite is closed up in the mesoporous molecular sieve, as can be seen from table 1 below, representing the values of surface area, pore volume and pore size for MM, MVE and MMMW, and for comparison included data for MCM-41, MFI, BEA.

Table 1
Surface area and porosity
SampleSurface area by BET method (m2/g)The surface area of the mesopores by the method of BCH (m2/g)Total pore volume (cm3/g)The diameter of pores according to the method of BCH (nm)
Na-MCM-41-209499470,8292,6
Na-MM5-2ZS89611450,814Na-MM5-4ZS82010090,7132,6
Na-MM5-4ZS-2A186710690,7942,5
Na-MM5-4ZS-2A1257335990,6562,4
MFI ZSM-53601000,35120*
Na-MMBE-4B8798840,6922,7
Na-MMBE-4B-2A18448590,7422,7
Na-MMBE-4B-2A1357936840,8352,6
BEA585850,254no
H-MM-MW22 8548380,7552,5
H-MM-MW22-2A18087720,7032,5
H-MM-MW22-2A1-357286390,8342,5
* - the size of the voids between long

Zeolite is identified by x-ray diffraction ((XRD)(XRD)). On radiographs can be defined the size of the unit cell of the zeolite and MCM-41 phases, when using appropriate internal standards. As internal standard used α-Al2O3or TiO2(rutile).

The size of the unit cell MFI determined by the method of ASTM D 3942-97 using α-Al2O3as an internal standard.

The size of the unit cell WEAH determined by the modified method of ASTM D 3942-97 using TiO2as an internal standard and [302] reflection at 22°2 θ.

The size of the unit cell MWW determined by the modified method of ASTM D 3942-97 using α-Al2O3as an internal standard and [100] reflections when 7,2° 2 θ.

The size of the elementary cell which IMO is determined according to the provisions of the peak without internal standard. The value is a0=2∙d[100]/√3.

The size of the unit cell mesoporous molecular sieves (MCM-41) is determined by the method described in J.S.Becker et al.,SoC.,114 (1992) 10834.

The size of the unit cell of zeolite corresponds to the number of Al introduced in the zeolite structure. The Al atom is more Si atoms, thus, the size of the unit cell generally increases with increasing amount of Al in most zeolites. On the contrary, in sealed zeolite dimensions of the unit cell decreases with increasing amount of Al in the catalytic material M, as can be seen from table 2 (values and0MFI, BEA, MWW and MOR). Change the size of the unit cell(RAY)(UCD)) MCM-41 does not correlate with the amount of Al, it decreases slightly with increasing intensity MFI phase. Change the dimensions of the unit cell are clear evidence of the actual chemical bond between the mesoporous molecular sieve embedded with a zeolite.

The Al content and the size of the unit cell MCM-41 and zeolite MFI, BEA, MWW and MOR, embedded in mesoporous molecular sieve (MCM-41), shown in the following table 2.

Table 2
The aluminium content and the size of the unit cell
The way the Al (%)MCM-41 (a0(nm)MFI, BEA, MWW and MOR a0(nm)
MCM-412,53,5-
Na-MM5-2ZS0,24,41,982
Na-MM5-4ZS0,44,21,981
Na-MM5-4ZS-2A11,54,31,979
Na-MM5-4ZS-2A135a 3.9the 3.81,972
MFI ZSM-51,4-1,978
Na-MM-BE-4B1,04,01,428
Na-MM-BE-4B-2A12,44,11,428
Na-MM-BE-4ZS-2A1356,04,11,430
Na-MMMW22-2Al 2,24,21,426
H-MM-MW220,84,11,406
H-MM-MW22-2A12,24,11,436
H-MM-MW22-2A1-353,74,01,427
MCM-222,4-1,405
Na-MM-MO1,04,11,800
Na-MM-MO-2Al4,64,11,800
H-MM-MO1,04,01,806
Pt/H-MM-MO1,14,11,806

The temperature of the catalytic material according to the present invention determines if the shutter speed is clamped material at a temperature of 1000°C in air. Radiograph prokalennom MM presented in figure 4. After heat treatment at 1000°C it turns out the same radiograph as shown in figure 5. This observation provides evidence that the catalytic material according to the present invention is heat-resistant at a temperature of not lower than 1000°C.

Nanostructure catalyst materials according to the present invention are examined using high-resolution transmission electron microscopy ((WRTEN) (HRTEM)) (transmission electron microscope Philips CM-200FEG with a resolution of 0.24 nm). The composition determines the energy dissipation spectrometry ((earth)(EDS)) (energy dissipating spectrometer NORAN Voyager). On figa shows WRTEN-snapshot mesoporous material, sealed beta zeolite according to the present invention. For comparison on fig.6b shows WRTEN-snapshot ordered MCM-41 material.

The method of obtaining mesoporous molecular sieves with the incorporation of the zeolite described in more detail below.

The method of obtaining mesoporous molecular sieves with the incorporation of the zeolite contains the following stages:

a) obtaining a germ of zeolite from a source of silicon and a source of aluminum and struktureerimisega agent (template R) or silicate or aluminosilicate precursor germ zeolite and optional removal of the pattern operation stage calcination;

b) obtaining a gel MCA and mesoporous molecular sieves from a source of silicon, optional source of aluminum and surfactant (S);

C) introduction of germs zeolite or silica or aluminosilicate precursor obtained in stage (a), as reagents in the gel mixture mesoporous molecular sieve obtained in stage b), and homogenization and dispersion of the embryo zeolite or silica or aluminosilicate precursor gel molecular sieve;

(d) conducting maturation of the gel mixture of stage (C) under stirring;

e) performing hydrothermal synthesis of a mixture of stage (C) during curing of the mixture in sufficient conditions including a temperature from about 100°C to about 200°C under static or dynamic version of stirring, until then, until crystals are formed;

f) removing the crystals;

g) washing the solid product;

h) drying the solid product; and

i) removing the surfactant (S) partially or fully operation stage calcination and, optionally, the template (R), if he had not been removed at the stage a),

resulting in a mesoporous molecular sieve with the incorporation of the zeolite.

At the stage a) embryos zeolite obtained from a source of silicon and a source of aluminum and struktureerimisega agent (template R). The source of silicon is selected from oxides of silicon, preferably, colloidal diox is Yes silicon, solid silicon dioxide and fume silica. The source of aluminum is selected from aluminum sulfate (Al2(SO4)3·18H2O), hydrated aluminum hydroxides, aluminates, of aluminum isopropylate and aluminum oxide.

In order to obtain the desired zeolite structure, select the appropriate template. Examples of commonly used templates are alkilammonievymi, alkylhalogenide, acylaminoacyl and alkylhalogenide, such as tetrapropylammonium, Tetramethylammonium, tetraethylammonium, Tetramethylammonium, tetraethylammonium, piperidine, pyrrolidone, octylamine, Ethylenediamine, 1,6-diamino-hexane, hexamethylenimine.

The temperature of stage a) is in the range from 40 to 200°C, and receiving can take place in a static or dynamic form. Finally, in stage a) optional template is removed by heat treatment operation, known as operation stage of annealing. Temperature removal treatment is in the range of 350-900°C. alternative Template can be removed at stage i), if it was not removed at the stage a), but, preferably, the template is removed at the stage a).

At the stage b) gel mesoporous molecular sieve is obtained from sources of silicon, an optional source of aluminum and a surface-active ve is esta (S). The source of silicon is selected from silicon compounds having an organic group, and inorganic sources of silicon. These sources of silicon, having an organic group, are tetraethoxysilane ((TEOC)(TEOS)), silicate of Tetramethylammonium, silicate of tetraethylammonium etc. Inorganic sources of silicon are sodium silicate, liquid glass, colloidal silicon dioxide, particulate silicon dioxide and steaming silicon dioxide. The source of aluminum is selected from aluminum sulfate (Al2(SO4)3·18H2O), hydrated aluminum hydroxides, aluminates, of aluminum isopropylate and aluminum oxide. Surfactant selected in order to obtain the desired mesoporous phase. Suitable surfactants are alkyltrimethylammonium compounds of General formula CnH2n+1(CH3)3∙NX, where n=12-18, X represents Cl, Br. Preferably, the surfactant is selected from the group consisting of n-hexadecyltrimethylammonium, n-hexadecyltrimethylammonium, cetyltrimethylammonium bromide and cetyltrimethylammoniumbromide. The temperature of stage (b) is in the range from 20 to 100°C, and receiving takes place with stirring.

On stage) embryos zeolite or silica or aluminosilicate precursor obtained in stage a), are introduced into the gel mesoporous molecular sieves under stirring. Formed mixture is homogenized and dispersed embryos zeolite or silica or aluminosilicate precursor. To adjust the acidity of the product may be an additional source of aluminum. Specified additional source of aluminum is a source of aluminum, having an organic ligand selected from aluminum alcoholate, preferably, isopropyl aluminum. The mixing speed at the stage (C) is in the range from 50 to 1000 Rev/min processing Time is in the range from 10 to 500 minutes

At stage d) gel Matures under stirring. The mixing speed is 200-1000 rpm, and the time of maturation of the gel is 30-1800 minutes

At stage e) hydrothermal synthesis is carried out at a temperature in the range of 100-200°C. hydrothermal synthesis can vary from 10 h to 300 h depending on the desired material. Hydrothermal synthesis is carried out in a dynamic variant in terms of the mixing process until until crystals are formed.

At stage f) the crystals from step (e) is retrieved, for example, by filtration or other means known in the art. If necessary, before removing, such as filtration, the pH of the mixture is adjusted to 6-8.

At stage g) of the solid product is t, obtained in stage f), carefully washed using, for example, water as a drilling fluid. The water temperature ranges from room temperature to 60°C. Washing is finished, when all the unwanted solid materials removed from the solid product.

At stage h) of the solid product is dried to remove the solvent by methods known in the art.

At stage i) surfactant (S) partially or completely removed by heat treatment operation, known as operation stage of annealing. Template (R) can be optionally removed at stage i) simultaneously with the removal of surfactants. Treatment temperature is in the range of 350-900°C. the heating Rate is in the range from 0.2 to 10°C/min Atmosphere processing is oxidative, and at the final stage the material is usually processed in air. Get mesoporous molecular sieve with the incorporation of the zeolite.

In the method of obtaining of mesoporous molecular sieves get gel solution, then in suitable synthesis conditions imposed zeolite a nucleating agent, and the source of aluminum is substituted zeolite a nucleating agent. Eligible source of aluminum alcoholate is aluminum and, preferably, isopropyl aluminum.

Preferably, surface-active substances the your is n-hexadecyltrimethylammonium, n-hexadecyltrimethylammonium, cetyltrimethylammonium bromide and cetyltrimethylammoniumbromide.

The solvent and washing of the material, preferably, use distilled water or deionized water.

Zeolite nucleating are aluminosilicate precursors that do not contain strukturodinamike agents, and they may be partially or fully crystalline. Due to the change of crystal size, they can be determined or cannot be determined by the method of DRL. However, their morphology can be observed in scanning electron microscopy. The germ of the zeolite have a metastable phase, which in the presence of surfactants in the synthesis of catalytic material according to the present invention provides a chemical link with the walls of a mesoporous molecular sieve.

After an intense dispersion of silica-alumina nuclei in the gel solution mesoporous molecular sieves in the presence of surfactants and in the maturation process of the mesophase gel is formed complex germ-surfactant, which strengthens and improves the chemical linking and crystallinity of the walls of the mesoporous material.

Aluminosilicate precursor germ zeolite can be obtained from the La these types of zeolite structure, as MFI, BEA, TON, MOR, MWW, AEF and FAU of the known in the art (EP 23089, USP 3308069, EP 102716, EP 23089). Here are two examples of obtaining aluminosilicate precursors of germ zeolite structures MFI and BEA. However, it is obvious that other specified zeolites are equally suitable.

The germ of the zeolite obtained from aluminosilicate precursor, suitably used in the preparation of a gel. In the period of maturation of the gel are chemical interaction and binding through the process of nucleation. Maturation of the gel speeds up the process of nucleation, and the germ of the zeolite may also occur secondary nucleation with the formation of the complex germ zeolite-mesophase surfactant", which improves the chemical nature of the relationship between micro - and mesophases. Microphases are responsible for the formation of zeolite structure and mesophase for the formation of a microporous structure.

The formation of the complex germ zeolite-mesophase surfactant is favorable when the germ of the zeolite is introduced after the introduction of surfactant in the alkaline medium or soaking germ zeolite in an aqueous solution of surfactant prior to its introduction and subsequent maturation of the gel.

The order of introduction of the reagents, especially the o surface-active substances and germs zeolite, pre-processing and maturation process of the gel is important to create the chemical nature of the connection between microporous and mesoporous molecularity material. In order to get a new high acidity of mesoporous molekulyarnoe sieve with the incorporation of the zeolite materials, the source of aluminum is introduced after the introduction of the germ of the zeolite, but before the period of maturation of the gel.

Intensive mixing of embryos zeolite in the process of obtaining the gel is important to increase the homogeneity and dispersion of germs zeolite gel solution.

The obtained catalytic materials can be optionally converted into the corresponding proton form by ammonium ion exchange and calcination. A suitable starting material for ammonium ion is the ammonium salt such as ammonium nitrate or ammonium chloride. Catalytic materials are processed in aqueous solution ammonium salt at temperatures in the range of 25-80°C for a suitable time interval, for example, 1-6 p.m Ammonium cations displace the alkali or alkaline cations of materials during processing. The degree of ion exchange may vary when changing the processing time, the ammonium concentration of the solution and the temperature After the ion-exchange treatment, the resulting material is dried and calcined to decompose ammonium ions on proton and ammonia.

Modification of the catalytic material according to the present invention, a new mesoporous molecular sieves with the incorporation of the zeolite can be carried out by methods selected from the group consisting of deposition, coating, encapsulation and selective removal. As impregnation and ion-exchange processing are the methods of application. The impregnation deposition is performed from the liquid phase and adsorption, ion exchange and selective reaction can take place on or from the surface of the substrate. In the process of removing the liquid surfaces are formed to a greater extent crystallites than monolayers. In ion-exchange processing is used diluted solution, and the desired metal cation is transferred from solution into the material, replacing cation or proton solid material. Methods and choice of method modifications depend on the given reactions. Typically, the method of ion-exchange processing is preferred that require low maintenance and high dispersion of metal.

Removal of surfactants after synthesis it is necessary to obtain mesoporous molecular sieves with the incorporation of the zeolite having a high surface area and acidity. The temperature of annealing, the degree and duration of heating can affect the surface area, pore size and position brand the Oia in the frame. A very large surface area determined by nitrogen adsorption, and changing strong acidity, determined PTA ammonia synthesized mesoporous molecular sieves with the incorporation of the zeolite confirm that the operation stage of annealing is a very suitable method for removal of surface-active substances.

Remove template from mesoporous molecular sieves with the incorporation of the zeolite is also carried out by operation stage ignition.

Synthesis of mesoporous material may be conducted with or without additional sources of aluminum. In the synthesis of catalytic material, you only need one template.

The catalytic material may be introduced into or onto the carrier using any of the methods known in the art.

The method of synthesis results in increased crystallinity of the walls of the pores by chemical binding of the zeolite material in the mesoporous material and therefore the introduction of the desired properties of the zeolite and at the same time maintaining a solid mesoporous structure. In this way you only need one template type in a gel solution for synthesis of the product.

Small crystals of the zeolite are used as a "germ" in the synthesis of mesoporous material, and it is possible to vary the concentration of "germs" and the size of the zeolite crystals. This results in an increase in the end of the ation germ zeolite and sealing a large number of microporous structure in the mesoporous molecular sieve and increased crystallinity of mesoporous walls. This also affects thermal and hydrothermal stability and acidic properties of the material. Change the size of the germ of the zeolite may affect the characteristic selectivity for the shape of the material.

X-rays powder, the results of scanning electron microscopy and nitrogen adsorption confirm the high thermal and hydrothermal stability of mesoporous molecular sieves with the incorporation of the zeolite according to the present invention, such as the structure of MFI, BEA, MWW and MOR.

In addition, complete or almost complete regeneration of used catalysts from various conversion reactions of hydrocarbons such as the isomerization of n-butane and 1-butene and oligomerization of 1-mission and the preservation of catalytic activity also indicate the stability of the catalytic material.

The way to obtain makes it possible to create your own acid properties of mesoporous molecular sieves. Own acidic properties of mesoporous molekularsiebe materials can be created by using a source of aluminum and varying relations Si|Al of gel solution and various zeolite nuclei. Results characterization of catalysts H-MM5, H-MMBE and H-MMMW PTA ammonia and various test reactions, such as isomerization of n-butane, confirm the success in the development of these materials is within the different acidity.

The walls of the pores of the mesoporous material are amorphous MSM-41, but with the introduction of zeolite they show increased crystallinity. Zeolite unit cell in the product according to the present invention differs from the zeolite unit cell in a mechanical mixture of zeolite and mesoporous molecular sieves, and unit cell of the mesoporous molecular sieve is more than a mechanical mixture.

Another important characteristic of the product is the fact that a large part of the zeolite phase is chemically related to mesoporous molecular sieve. The product is heat resistant at temperatures below 900°C in the presence of air.

Mesoporous molecular sieve with the incorporation of the zeolite according to the present invention and the method of obtaining such material are significantly different from the one considered in the prototype and have some advantages.

As you can see from the x-ray and SEM-images and measurements of the surface area, the new mesoporous molecular sieve MM with the incorporation of the zeolite with MFI structure is heat-resistant up to a temperature of not lower than 1000°C, and MVE - not lower than 900°C.

The conversion of the cationic forms MM5, MMBE, MMMW and MMMO, such as Na-form, represented in the examples, the corresponding proton form MM5, MMBE, MMMW and MMMO ion exchange treatment with an aqueous solution of ammonium nitrate with the settlement of etousa by drying at 100°C and calcination at 500°C does not change the structure, as shown by x-ray, which indicates that the hydrothermal stability of the new material. It is known that the structure of MCM-41 is destroyed by the contact with water at high temperatures.

As shown by x-ray, modification MM5, MMBE, MMMW and MMMO metal, such as modification of noble metal and, in particular, modifications platinum samples obtained using aqueous solutions hexachloroplatinic acid at 80°C for 24 h followed by drying at 100°C and calcination at 450°C do not affect the structure M, MMVI. This indicates that the material is stable in an acid environment.

Proton form mesoporous molecular sieves with the incorporation MFI structure shows very high activity in reactions of isomerization of n-butane and 1-butene. Catalysts H-M show an increase in the conversion of n-butane with increasing acidity.

Proton form mesoporous molecular sieves with sealing structures MFI and BEA show a very high activity in the dimerization of 1-olefins. Catalysts H-M and N-MMVA show an increase in the conversion of 1-mission with increasing acidity. Proton form mesoporous molecular sieves with the incorporation MFI structure shows very high activity in the dimerization of isobutene, and the catalyst is not deactivated.

The catalytic materials of the N-M and N-M IS VE fully regenerated in the presence of air. Recycled materials show almost the same catalytic activity in the isomerization of n-butane and 1-butene as fresh catalyst. It is well known that one of the main problems of catalyst MCM-41 is regeneration, i.e. mesoporous structure is destroyed after regeneration. Conservation of the catalytic activity of the new mesoporous molecular sieves with the incorporation of zeolite materials in both reactions clearly shows that the structure after the regeneration is stable.

Pt-M shows a very high conversion in the isomerization of n-butane, and the catalytic material after regeneration retains its catalytic activity.

Pt-MVE shows high selectivity to the product disclosure rings.

Thus, for mesoporous materials MM, MMVE not require modification after synthesis to increase their thermal and hydrothermal stability. High thermal and hydrothermal stability due to the incorporation of the zeolite, such as the structure of the MFI, BEA, walls of mesoporous molecular sieves by using method as described above.

Specified new group mesoporous materials can be applied as catalysts for the dimerization of olefins, oligomerization of olefins, the cracking of hydrocarbons, alkylation of aromatic compounds, aromatical the light hydrocarbons, the esterification, the reaction degidrirovaniya and disclosure rings without additional modification of the active material. Material modified with metal, shows high activity in the isomerization of light paraffins. Similarly, the materials modified with metals, may also be active in the isomerization of long-chain paraffins, hydrogenation, hydrocracking, hydrodesulfurization, hydrodeoxygenation, hydrodenitrogenation, dehydrophenylalanine, the reforming process, the reactions of Fischer-Tropsch and oxidized with modifications known in the art methods. The metal catalyst may be a metal, oxide or sulfide form or in any other form with modifications known in the art methods.

The materials according to the present invention can also be used in various separation technologies, such as adsorption, absorption or selective deletion.

The following illustrative examples provide a better understanding of the present invention and variants of its implementation, however, the specialist in the art will understand that the scope of the present invention is in no way limited to these examples.

Examples

Example 1 (comparative)

Obtaining zeolite ZSM-5 in accordance with US 3926784

The source materials are silicate al the MINIA, aluminum sulfate, triisopropylsilane ((TPABr) (Tpabr)), sodium chloride, sulfuric acid and water.

A solution obtained by mixing 3.5 g of the aluminosilicate with a 4.4 liter of water. The solution is To get a mixture of 107 g of aluminum sulfate, 438 g Tpabr, 1310 g NaCl, 292 g H2SO4and 6 l of water. The solution injected into the reactor under stirring with a stirring speed of 250 rpm, the Temperature is gradually increased to 100°C, and pressure is increased to 8 bar. The reaction is carried out under stirring for 6 days. The reactor is cooled. Formed solid product (ZSM-5) was filtered, washed with warm water and dried at 110°C until the morning. The product is calcined to remove the template, conduct an ion-exchange treatment with ammonium nitrate and calcined to obtain the proton form of the zeolite (H-ZSM-5).

Examples 2-4

Obtaining materials of type MSA in accordance with EP 0784652

Source materials used in the synthesis of materials of type MSA are isopropylate aluminum (Al-i-C3H7O)3tetraethylorthosilicate (Si(C2H5O)4) and an aqueous solution of hydroxide of tetrapropylammonium (TRA).

TRA-HE (Al-i-C3H7O)3and water are mixed at 60°C for 40 minutes the resulting solution was heated to 85°C, and formed a clear solution. Then, using a dropping funnel add liquid Si(C2H5O)4. The resulting mixture peremeci is up for 3 hours The reaction mixture is cooled with continuous stirring for 20 hours After cooling, the formed alcohol and water are evaporated, and the solid gel is dried at 100°C. the Dry solid material is pulverized and calcined at 550°C for 8 hours

In the following table 3 presents the preparation and properties of the obtained catalysts of type MSA.

Table 3
The synthesis parametersExample 2 MSA-1Example 3 MSA-2Example 4 MSA-3
Si/Al (mol/mol)50125
TRA-HE/water (mol/mol)0,180,180,18
Properties of product
Si/Al (mol/mol)5411,54,8
Surface area by BET method (m2/g)650440310
The surface area of micropores (m2/g)380340210
The average pore size (nm)1,41,41,4
The surface area of mesopores (m2/g)27010080

Example 5 (comparative)

Obtaining mesoporous molecular sieves H-MCM-41

Synthesis of Na-MCM-41 is conducted upon receipt of the solutions a, b and C. a Solution obtained by mixing fuming silica with distilled water with continuous stirring for 15 minutes the Solution produced by adding silicate of Tetramethylammonium to the sodium silicate with continuous stirring, and the mixture is stirred for 20 minutes the Solution obtained when dissolving tetradecyltrimethylammonium in distilled water with stirring for 20 minutes the Solution slowly (over 15 min) is added to solution a with stirring, and after adding the solution In the mixture is stirred for additional 20 minutes the Solution slowly (within 20 min) add to the mixture a and b with stirring, and after adding a solution of the mixture of the additive is about is stirred for 20 minutes Then isopropylate aluminum is added to the gel solution (a+b+C) under stirring, and the resulting mixture is a gel, ripened for 2 h with stirring. Adjust the pH, and the gel is loaded into a Teflon Cup, which is established in the autoclave. Synthesis is carried out for 48 h at 100°C. After completion of the synthesis reactor is cooled, and the mesoporous material is filtered and washed with distilled water. The obtained Na-MCM-41 is dried at 110°C and calcined at 550°C for 10 h Sodium form Na-MCM-41 is subjected to ion exchange treatment 1M aqueous solution of ammonium nitrate for 2 h at 80°C, and then the NH4-MCM-41 was washed with distilled water, dried and calcined.

Examples 6-8

Mesoporous molecular sieve with the incorporation of the zeolite with MFI structure

Obtaining embryos zeolite MFI

To obtain embryos of zeolite MFI receive three different solution a, b and C. a Solution obtained by addition of 10.5 g of fuming silica to 81,2 ml of distilled water. A solution obtained by dissolving 2.2 g of NaOH and 0.3 g of Al(OH)39.4 ml of distilled water. The solution is added to the solution and the resulting gel mixture is stirred for 20 minutes a Solution obtained by dissolving 3.7 g of tetrapropylammonium 3.8 ml of water with stirring for 20 minutes the Solution is added to the gel mixture (AB) and stirred for 15 min, and add 55 ml of water. The obtained gel mixture is additionally stirred for 20 minutes Synthesis is carried out for 18 h at 150°C. After completion of the synthesis, the product was filtered, washed with distilled water, dried and calcined to obtain embryos of zeolite MFI.

Example 6A

Synthesis of mesoporous molecular sieves with the incorporation of the zeolite with MFI structure Na-MM5-96h-4ZS without a source of aluminum

Synthesis of Na-MM5-96h-4ZS conduct upon receipt of the solutions a, b and C. a Solution obtained by mixture of 8.3 g of fume silica with 51.7 g of distilled water with continuous stirring (196 rpm) for 20 minutes the Solution produced by adding to 18.1 g of silicate of Tetramethylammonium to an 11.7 g of sodium silicate with continuous stirring (180 rpm), and the mixture is stirred for 20 minutes, the Solution obtained by dissolution of 26.3 g of tetradecyltrimethylammonium in 174,3 ml of distilled water with intensive stirring (336 rpm) for 20 minutes The solution slowly (over 15 min) is added to the solution with intensive stirring (320 rpm), and after adding the solution In the mixture is stirred for additional 20 minutes the Solution slowly (over 20 min) add to the mixture (a+b) with intensive stirring (336 rpm), and after adding a solution of the mixture is additionally stirred for 20 minutes

Then of 4.2 g zero is ISA MFI, obtained as described above was dispersed in a gel solution (a+b+C) under vigorous stirring (340 rpm) for 20 minutes Homogenization dispersed germ MFI carried out with intensive stirring (340 rpm) gel for 35 minutes Then provide the maturation of the gel solution for 3 h at ambient temperature with stirring (180 rpm). Adjust the pH of the gel, and the gel is loaded into a Teflon Cup, which is then installed in the autoclave. Synthesis is carried out for 96 h at 100°C. After completion of the synthesis reactor is cooled for 30 min, and the resulting material is mesoporous molecular sieves with the incorporation of the MFI structure is mixed with distilled water, filtered and washed thoroughly with distilled water for 3 hours Obtained Na-MM5-96h-4ZS dried and calcined at 450°C using the operation stage of annealing for 10 h in a muffle furnace.

Example 6b

Obtaining H-MM5-96h-4ZS, proton form of the material of example 6A

10 g of Na-MM5-96h-4ZS (sodium form, obtained as described above) is subjected to ion exchange treatment 1M aqueous solution of ammonium nitrate or ammonium chloride for 24 h at ambient temperature. After the ion-exchange processing, NH4-MM5-96h-4ZS thoroughly washed with distilled water, dried and calcined used is of the operation stage calcination in a muffle furnace at 450°C.

Radiograph obtained H-MM5-96h-4ZS is similar to the x-ray Na-MM5-96h-4ZS, showing that the water treatment of the new mesoporous material and subsequent heat treatment does not affect the stability of the structure.

Example 7

Synthesis of mesoporous molecular sieves with the incorporation of the zeolite with MFI structure - Na-MM5-96h-4ZS-2Al using a source of aluminum

Example 7a

Synthesis of Na-MM5-96h-4ZS-2Al

Synthesis of Na-MM5-96h-4ZS-2Al conduct upon receipt of the solutions a, b and C. a Solution obtained by mixture of 8.3 g of fume silica with 51.7 g of distilled water with continuous stirring (196 rpm) for 20 minutes the Solution produced by adding to 18.1 g of silicate of Tetramethylammonium to an 11.7 g of sodium silicate with continuous stirring (180 rpm), and the resulting mixture is stirred for 20 minutes, the Solution obtained by dissolution of 26.3 g of tetradecyltrimethylammonium in 174,3 ml of distilled water with intensive stirring (336 rpm) for 20 minutes the Solution slowly (over 15 min) is added to the solution with intensive stirring (320 rpm), and after adding the solution In the mixture is stirred for additional 20 minutes the Solution slowly (over 20 min) add to the mixture (a+b) with intensive stirring (336 rpm), and after adding a solution of the mixture is additionally stirred over their 20 minutes

Then of 4.2 g of embryos MFI is dispersed in the gel solutions (a+b+C) under vigorous stirring (340 rpm) for 20 minutes Homogenization dispersed germ MFI carried out with intensive stirring (340 rpm) gel for 35 minutes Then add 2.3 g of aluminum isopropylate and stirred for 20 minutes to Provide the maturation of the obtained gel for 3 h with agitation (180 rpm). Adjust the pH of the gel, and the gel is loaded into a Teflon Cup, which is then installed in the autoclave. Synthesis is carried out for 96 h at 100°C. After completion of the synthesis reactor is cooled, and the resulting mesoporous material was filtered and washed thoroughly with distilled water. The obtained Na-MM5-96h-4ZS-2Al dried and calcined using the operation stage calcination in a muffle furnace.

Example 7b

Synthesis of H-MM5-96h-4ZS-2Al

10 g of Na-MM5-96h-4ZS-2Al (obtained as above) is subjected to ion exchange treatment 1M aqueous solution of ammonium nitrate for 24 h at room temperature. After ion-exchange treatment mesoporous material is thoroughly washed, dried and calcined for 4 h using the operation stage calcination in a muffle furnace at 450°C.

Radiograph obtained H-MM5-96h-4ZS-2Al is similar to the x-ray Na-MM5-96h-4ZS-2Al, showing that water treatment new m is zaporizkogo material and subsequent heat treatment does not affect the stability of the structure.

Example 8

Synthesis of mesoporous molecular sieves with the incorporation of the zeolite with MFI structure - Na-MM5-96h-4ZS-2Al-35 with a source of aluminum

Example 8A

Synthesis of Na-MM5-96h-4ZS-2Al-35

Synthesis of Na-MM5-96h-4ZS-2Al-35 spend upon receipt of the solutions a, b and C. a Solution obtained by mixing 4.5 g of steaming silicon dioxide with 51.7 g of distilled water with continuous stirring (196 rpm) for 20 minutes the Solution produced by adding to 18.1 g of silicate of Tetramethylammonium to an 11.7 g of sodium silicate with continuous stirring (180 rpm) and the resulting mixture is stirred for 20 minutes, the Solution obtained by dissolution of 26.3 g of tetradecyltrimethylammonium in 174,3 ml of distilled water with intensive stirring (336 rpm) within 20 minutes the Solution slowly (over 15 min) is added to the solution with intensive stirring (320 rpm) and after addition of the solution In the mixture is stirred for additional 20 minutes the Solution slowly (over 20 min) add to the mixture (a+b) with intensive stirring (336 rpm) and after adding a solution of the mixture is additionally stirred for 20 minutes

Then of 4.2 g of embryos MFI obtained in example 6, was dispersed in the gel mixture (a+b+C) under vigorous stirring (340 rpm) for 20 minutes Homogenization dispersed germ MFI wire is t with additional intensive stirring (340 rpm) gel for 35 minutes Then 2.3 g of aluminum isopropylate are added to the mixture and stirred for 20 minutes Then provide the maturation of the obtained gel for 3 h with agitation (180 rpm). Adjust the pH of the gel and the gel is loaded into a Teflon Cup, which is then installed in the autoclave. Synthesis is carried out for 96 h at 100°C. After completion of the synthesis reactor is cooled and the resulting mesoporous material was filtered and washed thoroughly with distilled water. The obtained Na-MM5-96h-4ZS-2Al-35 is dried and calcined using the operation stage calcination in a muffle furnace at 450°C.

Example 8b

Obtaining H-MM5-96h-4ZS-2Al-35

10 g of Na-MM5-96h-4ZS-2Al-35 (obtained as above) is subjected to ion exchange treatment 1M aqueous solution of ammonium nitrate for 24 h at room temperature. After ion-exchange treatment mesoporous material is thoroughly washed, dried and calcined for 4 h using the operation stage calcination in a muffle furnace at 450°C.

The x-ray H-MM5-96h-4ZS-2Al-35 is similar to the x-ray Na-MM5-96h-4ZS-2Al-35, showing that the water treatment of the new mesoporous material and subsequent heat treatment does not affect the stability of the structure.

Example 9

Material MM modified platinum - Pt-H-MM5-96h-4ZS-2Al

5 g H-MM5-96h-4ZS-2Al enter 2 wt.% Pt using way about the threads. The above impregnation is carried out in a rotary evaporator at 80°C for 24 h using an aqueous solution hexachloroplatinic acid. MM5-96h-2Al impregnated with 2 wt.% Pt is dried at 100°C and calcined at 450°C.

Radiograph of Pt-H-MM5-96h-4ZS-2Al presented on figure 5, is similar to the x-ray Na-MM5-96h-4ZS-2Al, indicating hydrothermal stability of the new mesoporous molecular sieves with the incorporation of the zeolite.

Example 10

Material MM modified platinum - Pt-H-MM5-96h-4ZS-2Al-35

5 g H-MM5-96h-4ZS-2Al-35 enter 2 wt.% Pt using impregnation method. The above impregnation is carried out in a rotary evaporator at 80°C for 24 h using an aqueous solution hexachloroplatinic acid. MM5-96h-2Al-35 impregnated with 2 wt.% Pt is dried at 100°C and calcined at 450°C.

Radiograph of Pt-H-MM5-96h-4ZS-2Al-35 is similar to the x-ray Na-MM5-96h-4ZS-2Al-35, indicating hydrothermal stability of the new mesoporous molecular sieves with the incorporation of the zeolite.

Examples 11-13

Obtaining mesoporous materials with the incorporation of zeolite BEA-structure

Obtaining embryos BEA-zeolite

7,8 g NaAlO2mixed with 60 ml of distilled water under stirring for 10 min, and to this solution was added 74 g of a hydroxide of tetraethylammonium (TE-HE, 40%) and stirred for 20 minutes To the above races the thief add 145,4 g of colloidal silicon dioxide and stirred for 25 minutes The obtained gel is loaded into a Teflon Cup and place it in the autoclave. The synthesis is carried out at 150°C for 65 h in a static version. After completion of the synthesis, the product was filtered, washed with distilled water, dried at 110°C and calcined at 550°C for 7 h with obtaining zeolite BEA.

Example 11a

Synthesis of mesoporous molecular sieves with the incorporation of the zeolite structure, BEA - Na-MMBE-96h-4B without a source of aluminum

Synthesis of Na-MMBE-96h-4ZS-4V conduct upon receipt of the solutions a, b and C. a Solution obtained by mixture of 8.3 g of fume silica with 51.7 g of distilled water with continuous stirring (196 rpm) for 20 minutes the Solution produced by adding to 18.1 g of silicate of Tetramethylammonium to an 11.7 g of sodium silicate with continuous stirring (180 rpm), and the resulting mixture is stirred for 20 minutes, the Solution obtained by dissolution of 26.3 g of tetradecyltrimethylammonium in 174,3 ml of distilled water with intensive stirring (336 rpm) for 20 minutes the Solution slowly (over 15 min) is added to the solution with intensive stirring (320 rpm) and after addition of the solution In the mixture is stirred for additional 20 minutes the Solution slowly (over 20 min) add to the mixture (a+b) with intensive stirring (336 rpm) and after addition of a solution With a mix of facilities is but stirred for 20 minutes

Then 3.7 g of precursor germ zeolite BEA, obtained as described above is introduced into the gel mixture (a+b+C) under vigorous stirring (340 rpm) and gel ripening for 3 h with agitation (180 rpm). Adjust the pH of the gel and the gel is loaded into a Teflon Cup, which is then installed in the autoclave.

Synthesis is carried out for 96 h at 100°C. After completion of the synthesis reactor is cooled, and the resulting mesoporous material was filtered and washed thoroughly with distilled water. The obtained Na-MMBE-96h-4B dried and calcined using the operation stage of calcination.

Example 11b

Obtaining NMMBE-96h-4ZS-4B

10 g of Na-MMBE-96h-4B (obtained as above) is subjected to ion exchange treatment 1M aqueous solution of ammonium nitrate for 24 h at room temperature. After ion-exchange treatment mesoporous material is thoroughly washed, dried and calcined using the operation stage of calcination.

The x-ray H-MMBE-96h-4B is similar to the x-ray Na-MMBE-96h-4B, showing that the water treatment of the new mesoporous material and subsequent heat treatment does not affect the stability of the structure.

Example 12

Synthesis of mesoporous molecular sieves with the incorporation of the zeolite structure, BEA - Na-MMBE-96h-4B-2Al source of aluminum

Example 12A

Synthesis of Na- MMBE-96h-4B-2Al

Synthesis of Na-MMBE-96h-4B-2Al conduct upon receipt of the solutions a, b and C. a Solution obtained by mixture of 8.3 g of fume silica with 51.7 g of distilled water with continuous stirring (196 rpm) for 20 minutes the Solution produced by adding to 18.1 g of silicate of Tetramethylammonium to an 11.7 g of sodium silicate with continuous stirring (180 rpm), and the resulting mixture is stirred for 20 minutes, the Solution obtained by dissolution of 26.3 g of tetradecyltrimethylammonium in 174,3 ml of distilled water with intensive stirring (336 rpm) for 20 minutes the Solution slowly (over 15 min) is added to the solution with intensive stirring (320 rpm), and after adding the solution In the mixture is stirred for additional 20 minutes the Solution slowly (over 20 min) add to the mixture (a+b) with intensive stirring (336 rpm), and after adding a solution of the mixture is additionally stirred for 20 minutes

Then 3.7 g of precursor germ zeolite BEA (obtained as described above) is introduced into the gel mixture (a+b+C) under vigorous stirring (350 rpm) and stirred for 25 min and then added to 1.9 g of aluminum isopropylate and stirred for 20 minutes to Provide the maturation of the obtained gel for 3 h with agitation (180 rpm). Adjust the pH of the gel, and the gel is loaded into teplo the new Cup, which is then installed in the autoclave. Synthesis is carried out for 96 h at 100°C. After completion of the synthesis reactor is cooled, and the mesoporous material is filtered and washed thoroughly with distilled water. The obtained Na-MMBE-96h-4B-2Al dried and calcined using the operation stage calcination for 10 hours

Example 12b

Obtaining NMMBE-96h-4B-2Al

10 g of Na-MMBE-96h-4B-2Al (obtained as above) is subjected to ion exchange treatment 1M aqueous solution of ammonium nitrate for 24 h at ambient temperature. After the ion-exchange processing material mesoporous molecular sieve thoroughly washed, dried and calcined in a muffle furnace using the operation stage of calcination.

The x-ray H-MMBE-96h-4B-2Al is similar to the x-ray Na-MMBE-96h-4B-2Al, showing that the water treatment of the new mesoporous material and subsequent heat treatment does not affect the stability of the structure.

Example 13

Synthesis of mesoporous molecular sieves with the incorporation of zeolite BEA-structure - Na-MMBE-96h-4B-2Al-35 with a source of aluminum

Example 13A

Synthesis of Na-MM5-96h-4ZS-2Al-35

Synthesis of Na-MM5-96h-4ZS-2Al-35 spend upon receipt of the solutions a, b and C. a Solution obtained by mixing 4.4 g fume silica with 51.7 g of distilled water with continuous stirring (about 196/mi is within 20 minutes The solution produced by adding to 18.1 g of silicate of Tetramethylammonium to an 11.7 g of sodium silicate with continuous stirring (180 rpm), and the resulting mixture is stirred for 20 minutes, the Solution obtained by dissolution of 26.3 g of tetradecyltrimethylammonium in 174,3 ml of distilled water with intensive stirring (336 rpm) for 20 minutes the Solution slowly (over 15 min) is added to the solution with intensive stirring (320 rpm), and after adding the solution In the mixture is stirred for additional 20 minutes the Solution slowly (over 20 min) add to the mixture (a+b) with intensive stirring (336 rpm), and after adding a solution of the mixture is additionally stirred for 20 minutes

Then 3.7 g of precursor germ zeolite BEA (obtained as described above) is introduced into the gel mixture (a+b+C) under vigorous stirring (350 rpm) and stirred for 25 minutes Then added to 1.9 g of aluminum isopropylate and stirred for 20 minutes Then provide the maturation of the obtained gel for 3 h with agitation (180 rpm). Adjust the pH of the gel, and the gel is loaded into a Teflon Cup, which is then installed in the autoclave. Synthesis is carried out for 96 h at 100°C. After completion of the synthesis reactor is cooled, and the mesoporous material is filtered and washed thoroughly with distilled water. According to the scientists Na-MMBE-96h-4B-2Al-35 is dried and calcined using the operation stage of calcination.

Example 13b

Obtaining NMMBE-96h-4B-2Al-35

10 g of Na-MMBE-96h-4B-2Al-35 (obtained as above) is subjected to ion exchange treatment 1M aqueous solution of ammonium nitrate for 24 h at ambient temperature. After the ion-exchange processing material mesoporous molecular sieves washed thoroughly with distilled water, dried and calcined using the operation stage of calcination.

The x-ray H-MMBE-96h-4B-2Al-35 is similar to the x-ray Na-MMBE-96h-4B-2Al-35, showing that the water treatment of the new mesoporous material and subsequent heat treatment does not affect the stability of the structure.

Example 14

Material MMVE modified platinum - Pt-N-MMBE-96h-4B-2Al

5 g H-MMBE-96h-4B-2Al (obtained as above) enter 2 wt.% Pt using impregnation method. The above impregnation is carried out in a rotary evaporator at 80°C for 24 h using an aqueous solution hexachloroplatinic acid. H-MMBE-96h-2Al impregnated with 2 wt.% Pt is dried and calcined.

Radiograph of Pt-H-MMBE-96h-4B-2Al is similar to the x-ray Na-MMBE-96h-4B-2Al, indicating hydrothermal stability of the new mesoporous molecular sieves. In addition, modification of the H-MMBE-96h-2Al platinum does not affect the original structure.

Example 15

Obtaining material MMVE modified is Latino - Pt-H-MMBE-96h-4B-2Al-35

5 g H-MMBE-96h-4B-2Al-35 enter 2 wt.% Pt using impregnation method. The above impregnation is carried out in a rotary evaporator at 80°C for 24 h using an aqueous solution hexachloroplatinic acid. H-MMBE-96h-2Al-35 impregnated with 2 wt.% Pt is dried and calcined.

Radiograph of Pt-H-MMBE-96h-4B-2Al-35 is similar to the x-ray Na-MMBE-96h-4B-2Al-35, indicating hydrothermal stability of the new mesoporous molecular sieves. In addition, modification of the H-MMBE-96h-2Al-35 platinum does not affect the original structure.

Examples 16-18

Obtaining Pt-H-MMBEion exchange process

2 g each of N-MWE-materials: H-MMBE-96h-4B (example 16), H-MMBE-96h-4B-2Al (example 17) and H-MMBE-96h-4B-2Al-35 (example 18) weighed in 2 l flasks. Add 1 l of ion-exchange water. On the upper part of the flask establish a reflux condenser. The flask placed in a water bath temperature of 70°C and shaking 110. The flask was kept in these conditions for 1 h Then reflux condenser replace the drip funnel with air release. 52 ml of 0.01 M Pt solution is metered into the addition funnel. Pt-solution slowly (about 15 drops per minute) dripped into the flask, the temperature 70°C, shaking 110. Introduction platinum is 53 minutes addition funnel is replaced by a reflux condenser, and the flask was left under these conditions for 24 hours

The reaction mixture from the filter flask with from what asianam using a crucible made of tempered glass. The resulting material is washed into the flask 1 l of ion exchange water and filtered again. Do this twice. After a second washing step, the crucible is made of tempered glass with the material placed in an oven at a temperature of 80°C for 16 hours

After 16 hours of drying material overload in the crucible and calcined in a furnace. The temperature was raised from 21 to 300°C at a rate of 0.2°C/min

Examples 19-28

Mesoporous molecular sieve with the incorporation of the zeolite structure MWW

Obtaining embryos zeolite MWW

To obtain embryos of MWW zeolite prepared two solutions a and B. Solution produced by adding 87,58 g of sodium silicate to 42 ml of distilled water under stirring for 15 min, and to this solution is added dropwise 16.7 g of hexamethylene over a period of 25 min, and the solution is stirred for 20 minutes the Solution produced by adding to 7.35 g of concentrated sulfuric acid to 224 ml of distilled water and stirring for 10 minutes, then add the 8.9 g of aluminum sulfate and stirred for 20 minutes the Solution is added slowly to the solution with intensive stirring. The gel is loaded into a Teflon Cup and set in 300 ml autoclaves. The synthesis is carried out at 150°C for 96 h in a rotary version. After completion of the synthesis, the product was filtered, washed with distilled water, dried at 110°C and calcined at 550°C in those who tell 8 h with the generation of precursor germ of MWW zeolite.

Example 19a

Synthesis of mesoporous molecular sieves with the incorporation of the zeolite structure MWW Na-MM-4MW22 without a source of aluminum

Synthesis of Na-MM-4MW22 conduct upon receipt of the solutions a, b and C. a Solution obtained by mixture of 8.3 g of fume silica with 51.7 g of distilled water with continuous stirring (196 rpm) for 20 minutes the Solution produced by adding to 18.1 g of silicate of Tetramethylammonium to an 11.7 g of sodium silicate with continuous stirring (180 rpm), and the mixture is stirred for 20 minutes, the Solution obtained by dissolution of 26.3 g of tetradecyltrimethylammonium in 174,3 ml of distilled water with intensive stirring (336 rpm) for 20 minutes the Solution In slowly (over 15 min) is added to the solution with intensive stirring (320 rpm), and after adding all of the solution In the mixture is stirred for additional 20 minutes the Solution slowly (over 20 min) add to the mixture (a+b) with intensive stirring (336 rpm), and after adding a solution of the mixture is additionally stirred for 20 minutes

After that 4,22 g of precursor germ zeolite MWW obtained as described above is introduced into the gel solution (a+b+C) under vigorous stirring (340 rpm). Homogenization dispersed MWW spend with additional stirring (340 rpm) gel for 35 minutes After e the CSOs provide the maturation of the gel for 3 h with agitation (180 rpm) at ambient temperature. Adjust the pH of the gel, and the gel is loaded into a Teflon Cup, which is then installed in the autoclave. Synthesis is carried out for 96 h at 100°C.

After completion of the synthesis reactor is cooled for 30 min, and the material is mesoporous molecular sieves with the incorporation of the zeolite of the MWW structure is mixed with distilled water, filtered and washed thoroughly with distilled water for 3 hours Synthesized thus Na-MM-4MW22 dried at 110°C and calcined at 550°C using the operation stage of annealing for 10 h in a muffle furnace.

Example 19b

Obtaining H-MM-4MW22

10 g of Na-MM-4MW22 (sodium form, obtained as described above) is subjected to ion exchange treatment 1M aqueous solution of ammonium nitrate or ammonium chloride for 24 h at ambient temperature. After the ion-exchange processing of the material obtained mesoporous molecular sieves NH4-MM-4MW22 thoroughly washed with distilled water, dried at 110°C for 12 h and calcined at 450°C for 4 h in a muffle furnace using the operation stage of calcination.

Example 20

Synthesis of mesoporous molecular sieves with the incorporation of the zeolite structure MWW - Na-MM-4MW22-2Al using a source of aluminum

Example 20A

Synthesis of Na-MM-4MW22-2Al

Synthesis of Na-MM-4MW22-2Al conduct in obtaining solutions, and a Solution obtained by mixture of 8.3 g of fume silica with 51.7 g of distilled water with continuous stirring (196 rpm) for 20 minutes The solution produced by adding to 18.1 g of silicate of Tetramethylammonium to an 11.7 g of sodium silicate with continuous stirring (180 rpm), and the resulting mixture is stirred for 20 minutes, the Solution obtained by dissolution of 26.3 g of tetradecyltrimethylammonium in 174,3 ml of distilled water with intensive stirring (336 rpm) for 20 minutes the Solution slowly (over 15 min) is added to the solution with intensive stirring (320 rpm), and after adding the solution In the mixture is stirred for additional 20 minutes the Solution slowly (over 20 min) add to the solutions (a+b) with intensive stirring (336 rpm), and after adding all of the solution mixture is additionally stirred for 20 minutes

4,2 g germ of MWW zeolite, obtained as above, is added to the gel solution (a+b+C) under vigorous stirring (350 rpm) for 20 minutes Homogenization dispersed MWW carried out with intensive stirring (340 rpm) gel for 35 minutes Then add 2.3 g of aluminum isopropylate and stirred for 20 minutes then provide the maturation of the obtained gel for 3 h with agitation (180 rpm) at ambient temperature. Adjust the pH of the gel, and the gel is loaded into a Teflon Cup, which is then set in 300 ml autoclaves. The synthesis is carried out in t the value of 96 h at 100°C.

After completion of the synthesis reactor is cooled, and the material is mesoporous molecular sieves with the incorporation of the zeolite structure MWW filtered and washed thoroughly with distilled water for 3 hours Synthesized thus Na-MM-4MW22-2Al dried at 110°C and calcined at 550°C using the operation stage calcination for 10 hours

Example 20b

Obtaining H-MM-4MW22-2Al

10 g of Na-MM-4MW22-2Al (sodium form, obtained as described above) is subjected to ion exchange treatment 1M aqueous solution of ammonium nitrate or ammonium chloride for 24 h at ambient temperature. After the ion-exchange processing of the material obtained mesoporous molecular sieves NH4-MM-4MW22-2Al thoroughly washed with distilled water, dried at 110°C for 12 h and calcined at 450°C for 4 h in a muffle furnace using the operation stage of calcination.

Chest x-ray N-MM-4MW22-2Al is similar to the x-ray Na-MM-4MW22-2Al, showing that the water treatment of the new mesoporous material and subsequent heat treatment does not affect the stability of the structure.

Example 21

Synthesis of mesoporous molecular sieves with the incorporation MWW zeolite-structure - Na-MM-4MW22-2Al-35 with a source of aluminum

Example 21A

Synthesis of Na-MM-4MW22-2Al-35

Synthesis of Na-MM-4MWW22-2Al-35 spend upon receipt of the RA the solutions And, B and C. a Solution obtained by mixing 4.5 g of steaming silicon dioxide with 51.7 g of distilled water with continuous stirring (196 rpm) for 20 minutes the Solution produced by adding to 18.1 g of silicate of Tetramethylammonium to an 11.7 g of sodium silicate with continuous stirring (180 rpm), and the resulting mixture is stirred for 20 minutes, the Solution obtained by dissolution of 26.3 g of tetradecyltrimethylammonium in 174,3 ml of distilled water with intensive stirring (336 rpm) for 20 minutes the Solution slowly (over 15 min) is added to the solution And with intensive stirring (320 rpm), and after adding all of the solution In the mixture is stirred for additional 20 minutes the Solution slowly (over 20 min) add to the solutions (a+b) with intensive stirring (336 rpm), and after adding a solution of the mixture is additionally stirred for 20 minutes

4,2 g germ of MWW zeolite obtained in example 19, is introduced into the gel mixture (a+b+C) under vigorous stirring (340 rpm) for 20 minutes Homogenization dispersed MWW carried out with intensive stirring (340 rpm) gel for 35 minutes Then 2.3 g of aluminum isopropylate are added to the mixture and stirred for 20 minutes then provide the maturation of the obtained gel for 3 h with agitation (180 rpm) at temperatures of the environment. Adjust the pH of the gel, and the gel is loaded into a Teflon Cup, which is then set in 300 ml autoclaves. Synthesis is carried out for 96 h at 100°C.

After completion of the synthesis reactor is cooled, and the resulting material is mesoporous molecular sieves with the incorporation of the zeolite of the MWW structure is mixed with distilled water, filtered and washed thoroughly with distilled water for 3 hours Synthesized thus Na-MM-4MW22-2Al-35 dried at 110°C and calcined at 550°C in a muffle furnace using the operation stage calcination for 10 hours

Example 21b

Obtaining H-MM-4MW22-2Al-35

10 g of Na-MM-4MW22-2Al-35 (sodium form, obtained as described above) is subjected to ion exchange treatment 1M aqueous solution of ammonium nitrate for 24 h at ambient temperature. After the ion-exchange processing of the material obtained mesoporous molecular sieves NH4-MM-4MW22-2Al-35 washed thoroughly with distilled water, dried at 110°C for 12 h and calcined at 450°C for 4 h in a muffle furnace using the operation stage of calcination.

Radiograph obtained N-MM-4MW22-2Al-35 is similar to the x-ray Na-MM-4MW22-2Al-35, showing that the water treatment of the new mesoporous material and subsequent heat treatment does not affect the stability of the structure.

Example 22

Receiving the material N-MM-4MW22-2Al, modified platinum

5 g N-MM-4MW22-2Al enter 2 wt.% Pt using impregnation method. The above impregnation is carried out in a rotary evaporator at 80°C for 24 h using an aqueous solution hexachloroplatinic acid. H-MM-4MW22-2Al impregnated with 2 wt.% Pt is dried at 100°C and calcined at 450°C.

Radiograph obtained Pt-H-MM-4MW22-2Al is similar to the x-ray Na-MM-4MW22-2Al, indicating hydrothermal stability of the new mesoporous molecular sieves with the incorporation of the zeolite of the MWW structure.

Example 23

Obtaining material N-MM-4MW22-2Al-35 modified platinum

5 g N-MM-4MW22-2Al-35 enter 2 wt.% Pt using impregnation method. The above impregnation is carried out in a rotary evaporator at 80°C for 24 h using an aqueous solution hexachloroplatinic acid. H-MM-4MW22-2Al-35 impregnated with 2 wt.% Pt is dried at 100°C and calcined at 450°C.

Radiograph of Pt-H-MM-4MW22-2Al-35 is similar to the x-ray Na-MM-4MW22-2Al-35, indicating hydrothermal stability of the new mesoporous molecular sieves with the incorporation of the zeolite of the MWW structure.

Examples 24-28

Mesoporous molecular sieve with the incorporation of the zeolite structure MOR

Obtaining embryos zeolite MOR

To obtain embryos of MOR zeolite prepared two solutions a and B. Solution a obtained when the addition of 37.8 g of Ludox S30 to 6.7 g of piperidine and stirring for 15 minutes The solution produced by adding 44 ml of distilled water to 4.6 g of sodium hydroxide and stirring for 10 min, and then added 5.9 g of aluminum sulfate and additionally stirred for 15 minutes the Solution is added slowly to the solution with intensive stirring for 15 minutes the Gel is loaded into a Teflon Cup and set in 300 ml autoclaves. The synthesis is carried out at 200°C for 48 h in a rotary version. After completion of the synthesis, the product was filtered, washed with distilled water, dried at 110°C and calcined at 550°C for 19 h with the generation of precursor germ zeolite MOR.

Example 24A

Synthesis of mesoporous molecular sieves with the incorporation of the zeolite structure MOR - Na-MM-MO-4MO-96h without a source of aluminum

Synthesis of Na-MM-MO-4MO-96h conduct upon receipt of the solutions a, b and C. a Solution obtained by mixture of 8.3 g of fume silica with 51.7 g of distilled water with continuous stirring (196 rpm) for 20 minutes the Solution produced by adding to 18.1 g of silicate of Tetramethylammonium to an 11.7 g of sodium silicate with continuous stirring (180 rpm), and the mixture is stirred for 20 minutes, the Solution obtained by dissolution of 26.3 g of tetradecyltrimethylammonium (Fluka) in 174,3 ml of distilled water with intensive stirring (336 rpm within 20 minutes the Solution slowly (over 15 m is n) are added to the solution with intensive stirring (320 rpm), and after adding all of the solution In the mixture is stirred for additional 20 minutes the Solution slowly (over 20 min) add to the mixture (a+b) with intensive stirring (336 rpm), and after adding all of the solution mixture is additionally stirred for 20 minutes

Then 3.7 g of precursor germ of MOR zeolite obtained as described above is introduced into the gel mixture (a+b+C) under vigorous stirring (340 rpm) for 20 minutes Homogenization dispersed patterns MOR carried out with intensive stirring (350 rpm) the gel for 30 minutes then provide the maturation of the gel for 3 h with agitation (180 rpm) at ambient temperature. Adjust the pH of the gel, and the gel is loaded into a Teflon Cup, which is then set in a 300 ml autoclave. Synthesis is carried out for 96 h at 100°C.

After completion of the synthesis reactor is cooled, and the resulting material is mesoporous molecular sieves with the incorporation of the zeolite structure MOR mixed with distilled water, filtered and washed thoroughly with distilled water for 3 hours Synthesized thus Na-MM-MO-4MO-96h dried at 110°C and calcined at 550°C using the operation stage calcination for 10 hours

Example 24b

Obtaining H-MM-MO-4MO-96h

10 g of Na-MM-MO-4MO-96h (sodium form received, to the to above) is subjected to ion exchange treatment 1M aqueous solution of ammonium nitrate or ammonium chloride for 24 h at ambient temperature. After the ion-exchange processing of the material obtained mesoporous molecular sieves NH4-MM-MO-4MO-96h thoroughly washed with distilled water, dried at 110°C for 12 h and calcined at 450°C for 4 h in a muffle furnace using the operation stage of calcination.

Radiograph obtained N-MM-MO-4MO-96h is similar to the x-ray Na-MM-MO-4MO-96h, showing that the water treatment of the new mesoporous material and subsequent heat treatment does not affect the stability of the structure.

Example 25

Synthesis of mesoporous molecular sieves with the incorporation of the zeolite structure MOR - Na-MM-MO-4MO-96h-2Al using a source of aluminum

Example 25A

Synthesis of Na-MM-MO-4MO-96h-2Al

Synthesis of Na-MM-MO-4MO-96h-2Al conduct upon receipt of the solutions a, b and C. a Solution obtained by mixture of 8.3 g of fume silica with 51.7 g of distilled water with continuous stirring (196 rpm) for 20 minutes the Solution produced by adding 18,10 g of silicate of Tetramethylammonium to an 11.7 g of sodium silicate with continuous stirring (180 rpm), and the resulting mixture is stirred for 20 minutes, the Solution obtained by dissolution of the 26,34 g tetradecyltrimethylammonium in 174,3 ml of distilled water with intensive stirring (336 rpm within 20 minutes the Solution slowly (over 15 min) is added to the solution And with the intense the main mixing (320 rpm), and after adding all of the solution In the mixture is stirred for additional 20 minutes the Solution slowly (over 20 min) add to the mixture (a+b) with intensive stirring (336 rpm), and after adding all of the solution mixture is additionally stirred for 20 minutes

3.7 g of precursor germ of MOR zeolite obtained in example 23, is introduced into the gel mixture (a+b+C) under vigorous stirring (350 rpm) for 25 min, and then the gel is added to 1.9 g of aluminum isopropylate in the presence of intensive peremeshivanii (350 rpm), and the gel is stirred for 30 minutes then provide the maturation of the gel for 3 h with agitation (180 rpm) at ambient temperature. Adjust the pH of the gel, and the gel is loaded into a Teflon Cup, which is then set in 300 ml autoclaves. Synthesis is carried out for 96 h at 100°C.

After completion of the synthesis reactor is cooled for 30 min, and the material is mesoporous molecular sieves with the incorporation of the zeolite structure MOR mixed with distilled water, filtered and washed thoroughly with distilled water for 3 hours Synthesized thus Na-MM-MO-4MO-96h-2Al dried at 110°C and calcined at 550°C using the operation stage calcination for 10 hours

Example 25b

Obtaining H-MM-MO-4MO-96h-2Al

10 g of Na-MM-MO-4MO-96h-2Al (sodium form, obtained as the criminal code is shown above) is subjected to ion exchange treatment 1M aqueous solution of ammonium nitrate or ammonium chloride for 24 h at ambient temperature. After the ion-exchange processing of the material obtained mesoporous molecular sieves NH4-MM-MO-4MO-96h-2Al thoroughly washed with distilled water, dried at 110°C for 12 h and calcined at 450°C for 4 h in a muffle furnace using the operation stage of calcination.

Radiograph obtained N-MM-MO-4MO-96h-2Al is similar to the x-ray Na-MM-MO-4MO-96h-2Al, showing that the water treatment of the new mesoporous material and subsequent heat treatment does not affect the stability of the structure.

Example 26

Synthesis of mesoporous molecular sieves with the incorporation of the zeolite structure MOR - Na-MM-MO-4MO-96h-2Al-35 with a source of aluminum

Example 26a

Synthesis of Na-MM-MO-4MO-96h-2Al-35

Synthesis of Na-MM-MO-4MO-96h-2Al-35 spend upon receipt of the solutions a, b and C. a Solution obtained by mixing 4.4 g fume silica with 51.7 g of distilled water with continuous stirring (196 rpm) for 20 minutes the Solution produced by adding 18,10 g of silicate of Tetramethylammonium to an 11.7 g of sodium silicate with continuous stirring (180 rpm), and the mixture is stirred for 20 minutes, the Solution obtained by dissolution of 26.3 g of tetradecyltrimethylammonium in 174,3 ml of distilled water with intensive stirring (about 336/min) for 20 minutes the Solution slowly (over 15 min) is added to the solution And with the intense the main mixing (320 rpm), and after adding all of the solution In the mixture is stirred for additional 20 minutes the Solution slowly (over 20 min) add to the mixture (a+b) with intensive stirring (336 rpm), and after adding all of the solution mixture is additionally stirred for 20 minutes

3.7 g of precursor germ of MOR zeolite obtained in example 45, injected into the gel mixture (a+b+C) under vigorous stirring (320 rpm) for 25 minutes Then added to 1.9 g of aluminum isopropylate and stirred for 20 minutes then provide the maturation of the gel for 3 h with agitation (180 rpm) at ambient temperature. Adjust the pH of the gel, and the gel is loaded into a Teflon Cup, which is then set in a 300-ml autoclave. Synthesis is carried out for 96 h at 100°C.

After completion of the synthesis reactor is cooled for 30 min, and the material is mesoporous molecular sieves with the incorporation of the zeolite structure MOR mixed with distilled water, filtered and washed thoroughly with distilled water for 3 hours Synthesized thus Na-MM-MO-4MO-96h-2Al-35 dried at 110°C and calcined at 550°C using the operation stage calcination for 10 hours

Example 26b

Obtaining H-MM-MO-4MO-96h-2Al-35

10 g of Na-MM-MO-4MO-96h-2Al-35 (sodium form, obtained as described above) is subjected to ion exchange treatment 1M in denim solution of ammonium nitrate or ammonium chloride for 24 h at ambient temperature. After the ion-exchange processing of the material obtained mesoporous molecular sieves NH4-MM-MO-4MO-96h-2Al-35 washed thoroughly with distilled water, dried at 110°C for 12 h and calcined at 450°C for 4 h in a muffle furnace using the operation stage of calcination.

Example 27

Obtaining material N-MM-MO-4MO-96h-2Al modified platinum

5 g N-MM-MO-4MO-96h-2Al enter 2 wt.% Pt using impregnation method. The above impregnation is carried out in a rotary evaporator at 80°C for 24 h using an aqueous solution hexachloroplatinic acid. H-MM-MO-4MO-96h-2Al impregnated with 2 wt.% Pt is dried at 100°C and calcined at 450°C.

Radiograph obtained Pt-H-MM-MO-4MO-96h-2Al is similar to the x-ray Na-MM-MO-4MO-96h-2Al, indicating hydrothermal stability of the new mesoporous molecular sieves with the incorporation of the zeolite structure MOR.

Example 28

Obtaining material N-MM-MO-4MO-96h-2Al-35 modified platinum

5 g N-MM-MO-4MO-96h-2Al-35 enter 2 wt.% Pt using impregnation method. The above impregnation is carried out in a rotary evaporator at 80°C for 24 h using an aqueous solution hexachloroplatinic acid. H-MM-MO-4MO-96h-2Al-35 impregnated with 2 wt.% Pt is dried at 100°C and calcined at 450°C.

Radiograph of Pt-H-MM-MO-4MO-96h-2Al-35 is similar to the x-ray Na-MM-MO-4MO-96h-2Al-35, is kasiva on the hydrothermal stability of the new mesoporous molecular sieves with the incorporation of the zeolite structure MOR.

Example 29

Test resistance

Test the resistance carried out by heating the materials according to the present invention at temperatures of 700°C, 800°C, 900°C and 1000°C in air for 24 hours After this treatment the material analyzed by the methods of BET and XRD. An example of XRD diagrams of samples processed at 1000°C, are presented in figure 5. Methods BET or DRL is not the difference in the structure of materials.

Example 30

Test for mechanical strength

Test the mechanical strength of the materials according to the present invention is carried out at a pressing of the powder material at a pressure of 20,000 H. Molded tablets are crushed and scatter into different particle sizes. The different fractions of the scattered powder analyze the methods of XRD and BET. Differences in DRL-charts and surface area by BET method is not observed. The results are presented in the following table 4, where examples are given of the definition of N2-adsorption and the results of tests on the mechanical strength.

Table 4
Surface area and porosity by the method of N2-adsorptionSurface area by BET method (m2/g) Surface area method BCH (m2/g)Pore volume by BET method (cm3/g)Pore volume according to the method of BCH (cm3/g)The pore diameter by BET method (Ǻ)The diameter of pores according to the method of BCH (Ǻ)
H-MM5-96h-4ZS from 0.6 to 0.857757310,5940,5133228
H-MM5-96h-4ZS <0,0077486820,5630,4893129

Example 31

The reproducibility of the methods

The same method of obtaining materials according to the present invention (example 8) is repeated at different scales. Party show very similar properties, as shown in table 5, representing the results of determination of reproducibility.

Table 5
Si wt.%Al (wt.%)Si/AlMCM-41 (a0E) MFI a0(E)
Example 842,3a 3.910,438of 19.72
Example 8
(10 times greater)
42,7the 3.810,93619,73

Examples 32-41

Oligomerization of 1-mission using the materials according to the present invention as catalysts

Oligomerization of 1-mission using the materials according to the present invention as the catalyst shows high activity, low decontamination and Regenerist catalysts according to the present invention. Catalytic materials according to the present invention and comparative catalysts according to the prototype of experience in the oligomerization of 1-mission. Testing is carried out in a batch reactor, the under stirring. The reaction temperature is 200°C. the reaction Time is 24 hours, the reactor Pressure is 20 bar.

The reaction products analyzed by the methods of GC and GC-distillation, and the peaks are identified in relation to the number of carbon atoms of the molecule. Molecules with the number of the carbon atoms is higher than 20 in GC-analysis identified as lubricating components. Molecules boiling above 343°C, identified in GC-distillation as a lubricant molecule.

The catalysts used in the experiments, regenerate in a muffle furnace in air at a temperature of 540°C.

The test results on the reaction of oligomerization of 1-mission are summarized in the following table 6.

Table 6
ExampleCatalyst% conversionThe selectivity to lubrication, %Out of grease, %
32ZSM-5 (example 1)2030,5
33MSA-1 (example 2)0,5870,4
34MSA-3 (example 4)1870,9
35MCM-41 (example 5)459729
36 H-MM5-96h-4ZS2A135 (example 9)719769
37H-MMBE-96h-4B-2Al (example 12)789473
38H-MMBE-96-4B-2A135 (example 13)809374
39H-MM5-96h-4ZS2A135 Regenerated709869
40H-MMBE-96h-4B-2Al Regenerated769673
41H-MMBE-96-4B-2A135 Regenerated799372

Examples 42 and 43

The reaction isobutene with materials according to the present invention as catalysts

Test the reaction of isobutene carried out with the materials according to the present invention as catalysts, the results of which show high activity and low deactivation of the catalysts with the according to the present invention. The catalysts tested in a reactor with a fixed bed at the reaction temperature of 100°C at 20 bar and with the mass time volume rate(MCOS)(WHSV)) 20. There is a high activity and a lack of deactivation of the catalysts. As an example, the reaction of isobutene the catalyst of example 8 is compared with the comparative catalyst (example 1) figure 7 in the dimerization of isobutene.

Examples 44-47

Tests for the isomerization of paraffins with materials according to the present invention as catalysts

In order to test the reaction of isomerization of n-butane is the confirmation of the chemical nature of interaction in the mesoporous molecular sieve with the incorporation of the zeolite with MFI structure according to the present invention, the formation of centers of strong acids Branstad and hydrothermal stability of the new material. Isomerisation of n-butane is used as a test reaction for the evaluation of the acidity of the catalysts. Isomerization of n-butane is carried out with a proton form of new mesoporous molekularsiebe catalysts with assessment of acid properties. It is noted that N-form (H-MM5-96h-4ZS-2Al-35) of the catalyst with the lowest ratio of Si/Al shows the highest conversion of n-butane, clearly indicating the formation of centers of strong acids Branstad and the formation of a new mesoporous molecular sieves with what adelai zeolite with MFI structure with true chemical binding.

The regeneration of N-forms and Pt-H-MM5 catalysts is carried out in the presence of air at 450°C for 2 hours the Purpose of regeneration is to assess whether you can restore the catalytic activity and, in addition, to assess the hydrothermal stability of the catalyst during regeneration of the catalyst, as in the regeneration process turns the water. It was confirmed that as the H-form and catalysts modified Pt, almost completely retain their catalytic activity, confirming the hydrothermal stability of the structure.

Isomerization of n-butane to isobutane investigate proton form of the catalyst and catalysts H-MM5-96h-4ZS-2Al, modified 2 wt.% Pt, in a quartz micro-reactor with a fixed bed. Experiments carried out at a pressure close to atmospheric, and the used amount of the catalyst amount from 0.3 to 1.0, the Reagent n-butane fed into the reactor using hydrogen as the carrier gas. Analysis of the product is performed on-line using a gas chromatograph equipped with a flame ionization detector (FID)(FID)and capillary column. The results of the test reactions of isomerization of n-butane are shown in table 7, representing the isomerization of n-butane at a temperature of 450°C, MCOS 1,23 h-1, the ratio of n-butane/hydrogen is 1:1.

Table 7
Conversion of n-butane
# exampleCatalystConversion
(wt.%)
44H-MM5-96h-4ZS-2AI40
45H-MM5-96h-4ZS-2AI-3570
46Pt-H-MM5-96h-4ZS-2AI-35-C χ87
47Pt-H-MM5-96h-4ZS-2AI-35-C regenerated85

Examples 48 and 49

Experiments on the isomerization of 1-butene with materials according to the present invention as catalysts

In order to test the reaction of isomerization of 1-butene is the confirmation of the chemical nature of interaction in the mesoporous molecular sieve with the incorporation of the zeolite with MFI structure according to the present invention, the formation of centers of strong acids Branstad and hydrothermal stability of the new material.

The isomerization of 1-butane is also used as a test reaction for the study of isomerization of 1-butene to isobutene. In addition, the aim is to investigate the possibility of regeneration of used catalyst and assessment of Sokh is anal whether the catalyst for its catalytic activity after regeneration. It was found that the regenerated catalyst shows almost the same conversion (97,2 mol.%) 1-butene as the corresponding fresh catalyst (97 mol.%), pointing also to the hydrothermal stability of the catalyst.

Isomerization of 1-butene to isobutene investigate proton form of the catalyst H-MM5-96h-4ZS-2Al in a quartz micro-reactor with a fixed bed. Experiments carried out at a pressure close to atmospheric at a temperature of 350°C with MCOS 10 h-1.

Reagent 1-butene fed into the reactor using hydrogen as the carrier gas at a ratio of 1:1. Analysis of the product is performed on-line using a gas chromatograph equipped with a flame ionization detector (FID) (FID)and capillary column. After GC install the refrigerator to facilitate sampling of liquid product of the heavy compounds. The first sample taken after 10 minutes of time on stream (TOS)(GNP)). The first 10 samples taken 1 h intervals, and follow-up samples every 3 hours

Example 50

Experiment by ring opening with materials according to the present invention as catalysts

The activity and selectivity of the catalyst according to the present invention in response to the disclosure decalogo rings define a 50 ml autoclave at 250°C at a hydrogen pressure of 20 bar. Decalin (10 ml, ≈9.0 g) enter s and room temperature in the reactor, containing 1 g of the catalyst reduced at 250°C. the Pressure increase with hydrogen to 10 bar. Then the reactor was placed in an oil bath at 250°C. When the temperature in the reactor reaches 250°C, the hydrogen pressure adjusting up to 20 bar. The reaction time is 5 hours and Then the reactor was quickly cooled to -10°C. After cooling, the reactor was weighed. The pressure in the reactor dropped. The product-containing catalyst selected from the sampler and GC-sample is taken by needle from the filter. For the catalyst according to the present invention obtained in accordance with example 16, the conversion of decalin is 81%, and the selectivity to reaction products of the disclosure ring is 32%.

Examples 51 and 52

Experiments on hydrocracking with the material according to the present invention as catalyst

The activity and selectivity of the catalyst according to the present invention (catalyst of example 17) in the hydrocracking reaction is determined in an autoclave at 300°C (example 51) and 350°C (example 52) at a hydrogen pressure of 30 bar. Paraffin mixture (about 80 g) was injected at room temperature into the reactor containing 2 g of the catalyst reduced at 400°C. the Pressure increase by up to 30 bar hydrogen. When the temperature in the reactor reaches 300°C (example 51) or 350°C (example 52), the hydrogen pressure adjusting up to 30 bar. The reaction time for example the t 65 h After cooling, the reactor was weighed. The pressure in the reactor dropped. The product is analyzed by GC method. The conversion of paraffins is 60% (example 51) and 65% (example 52), and the selectivity to products of cracking in both cases is 100%.

1. The catalytic material, wherein the catalytic material is a mesoporous molecular sieve with the incorporation of the zeolite, where the mesoporous molecular sieve selected from the group M41S, and the zeolite is srednepolny zeolite is selected from zeolite MFI, MTT, TON, AEF, MWW and PER, or macroporous zeolite is selected from zeolite BEA, FAU, MOR, and the catalytic material is heat-resistant at a temperature of not lower than 900°C.

2. The catalytic material according to claim 1, characterized in that the catalytic material has a specific surface area in the range 1400-500 m2/g, preferably 1200-600 m2/year

3. The catalytic material according to claim 1, characterized in that the catalytic material contains a mesoporous molecular sieve is selected from MCM-41 or MCM-48.

4. The catalytic material according to claim 1, characterized in that the catalytic material contains a zeolite selected from the MFI, MTT, AEF, BEA, MWW or MOR.

5. The catalytic material according to claim 4, wherein the mesoporous molecular sieve is MCM-41 or MCM-48 and zeolite is an MFI zeolite or BEA or MWW, or MOR.

6. Ka is Litichevsky material according to claim 1, characterized in that the catalytic material is in the proton form, the cation form or modified by the metal.

7. The catalyst, wherein the catalyst contains 90-10 wt.% the catalytic material according to any one of claims 1 to 6 and 10-90 wt.% media.

8. The method of obtaining mesoporous molecular sieves with the incorporation of the zeolite according to claim 1, characterized in that the method comprises the following stages:
a) obtaining embryos zeolite from a source of silicon and a source of aluminum and struktureerimisega agent or silicate or aluminosilicate precursor germ zeolite and, optionally, removing struktureerimisega agent operation stage calcination;
b) obtaining a gel mixture of mesoporous molecular sieves from a source of silicon, an optional source of aluminum and a surfactant;
c) introduction of germs zeolite or silica or aluminosilicate precursor obtained in stage a), the gel mixture mesoporous molecular sieve obtained in stage b), and homogenization and dispersion in the gel, molecular sieves germ zeolite or silica or aluminosilicate precursor;
d) implementation of the maturation of the gel mixture of stage (C) under stirring;
e) carrying out hydrothermal synthesis of a mixture of stage (d) while maintaining the mixture in sufficient the conditions including a temperature from about 100°to about 200°C in a static or dynamic version of stirring, until then, until crystals are formed;
f) removing the crystals;
g) washing the solid product;
h) drying the solid product; and
i) removing the surfactant (S) partially or fully operation stage calcination and, optionally, struktureerimisega agent, if he had not been removed at the stage a), resulting in a mesoporous molecular sieve with the incorporation of the zeolite catalyst.

9. The method of obtaining mesoporous molecular sieves with the incorporation of the zeolite of claim 8, wherein the source of silicon at the stage a) is selected from oxides of silicon, preferably of colloidal silicon dioxide, particulate silicon dioxide and fume silica.

10. The method of obtaining mesoporous molecular sieves with the incorporation of the zeolite of claim 8 or 9, characterized in that the source or sources of silicon at the stage b) is selected from compounds of silicon having an organic group, and inorganic sources of silicon, and preferably a source of silicon, having an organic group is tetraethoxysilane, tetraethylorthosilicate or tetraethylorthosilicate, and inorganic source of silica is sodium silicate, liquid glass, colloidal dioxide is Rennie, solid silicon dioxide or fume silica.

11. The method of obtaining mesoporous molecular sieves with the incorporation of the zeolite of claim 8, wherein the source of aluminum is selected from aluminum sulfate (Al2(SO4)3·18H2O), hydrated aluminum hydroxides, aluminates, of aluminum isopropylate and aluminum oxide.

12. The method of obtaining mesoporous molecular sieves with the incorporation of the zeolite of claim 8, wherein the surfactant is selected from alkyltrimethylammonium compounds with the General formula
CnH2n+1(CH3)3·NX, where n=12-18, X represents Cl, Br, and preferably the surfactant is an n-hexadecyltrimethylammonium, n-hexadecyltrimethylammonium, cetyltrimethylammonium bromide and cetyltrimethylammoniumbromide.

13. The method of obtaining mesoporous molecular sieves with the incorporation of the zeolite of claim 8, wherein the additional source of aluminum is selected from aluminum alcoholate, preferably of aluminum isopropylate add on stage).

14. The application of catalytic material according to any one of claims 1 to 6 or of a catalyst according to claim 7 for the processing of hydrocarbons, preferably in the dimerization of olefins, oligomerization of olefins, isomerization of olefins, the cracking of hydrocarbons, alkyl is the formation of aromatic compounds, aromatization of light hydrocarbons, esterification, dehydration and reactions to the disclosure of the ring.

15. The application of catalytic material according to claim 6 in the isomerization of light paraffins, isomerization of long-chain paraffins, hydrogenerating, hydrocracking, hydrodesulfurization, hydrodeoxygenation, hydrodenitrogenation, dehydrophenylalanine, the reforming process, the reactions of Fischer-Tropsch and oxidized.

16. The application 14 in the oligomerization of 1-mission dimerization of isobutene, isomerization of n-butane isomerization of 1-butene and the ring opening of decalin.



 

Same patents:

The invention relates to the catalytic substance and the method of its production

FIELD: chemistry.

SUBSTANCE: invention relates to a method of producing a mixture of hexacyclo[8.4.0.02.17.03.14.04.8.09.13]tetradecene-5 and hexacyclo[6.6.0.02.6.05.14.07.12.09.13]tetradecene-3 through isomerisation of binor-S at high temperature on a platinum catalyst Pt/SiO2, characterised by that, the reaction is carried out on a platinum catalyst which is obtained by saturating wide-pore silica gel balls with diametre ranging from 2.5 to 3.5 mm with an aqueous solution of chloroplatinic acid H2PtCl6 until platinum content of 0.25 to 0.5%. Binor-S is fed into the reactor in form of a 20 to 40% solution in benzene or toluene with bulk speed of 50 to 60 ml/h at temperature ranging from 240 to 250°C.

EFFECT: increased output of mixture of olefins.

1 cl, 8 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a benzene hydrogenation and ring opening method and isomerisation of C5-C6 paraffins of starting paraffin material, which contains normal paraffins C5-C6 and at least 1 wt % benzene, involving: (a) feeding starting material, without tapping or condensing hydrogen, into a drier for removing water and obtaining dried starting material containing not less than 0.5 wt % water; (b) combination of dried starting material with a hydrogen-rich gas stream with formation of a mixed load; (c) feeding the mixed load at temperature ranging from 38 to 232°C into the hydrogenation zone, and bringing the said mixed load into contact with a hydrogenation catalyst under hydrogenation conditions in order to saturate benzene and form a stream of products, removed from the hydrogenation zone, with temperature ranging from 149 to 288°C and containing less than 1.5 wt % benzene; hydrogenation conditions include excess pressure from 1400 kPa to 4800 kPa, hourly space velocity for feeding the load from 1 to 40 h-1 and ratio of contained hydrogen to hydrocarbons ranging from 0.1 to 2; (d) regulation of temperature of the stream of product removed from the hydrogenation zone in the interval from 104 to 204°C through at least heat exchange of the product removed from the hydrogenation zone with the mixed load; (e) feeding at least part of the product removed from the hydrogenation zone into the isomerisation zone and bringing the stream of the said load into contact with an isomerisation catalyst under isomerisation and ring opening conditions at excess pressure ranging from 1380 to 4830 kPa; and (f) extraction of the isomerisation product obtained in the isomerisation zone. The invention also relates to a device for realising the proposed method.

EFFECT: use of the proposed invention provides for economisation by reducing the number of units of the equipment used and equipment expenses, and also reduces amount of hydrogen required for carrying the process.

9 cl, 1 tbl, 1 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to a method of producing a mixture of hexacyclo[8.4.0.02,7.03,14.04,8.09,13]tetradecene-5 and hexacyclo[6.6.0.02,6.05,14.07,12.09,13]tetradecene-3 through isomerisation of binor-S under the effect of phosphoric anhydride P2O5 (P4O10), characterised by that the reaction is carried out in a dichloromethane medium at temperature ranging from 25 to 35°C with addition of aluminium oxide Al2O3 to P2O5 in the following ratio of reagents : [Al2O3]: [P2O5]: [binor-S]=0.2-0.3:0.2-0.3:1. Use of this method allows for 80% olefin output without using tetrachloromethane.

EFFECT: reduced energy consumption, duration of reaction and reduced consumption of P2O5.

1 cl, 5 ex

FIELD: chemistry.

SUBSTANCE: invention relates to method of obtaining bicyclo-[3,3,0]-octane-2 by isomerisation of cyclooctadiene-1,5 on catalyst system based on nickel complexes, characterised by the following: as catalyst system bis[1,2:5,6-η-cyclooctadiene-1,5] nickel is used in combination with boron trifluoride etherate with mole ratio Ni: BF3·OEt2=1:2.

EFFECT: simplification of bicyclo-[3,3,0]-octane-2 obtaining and increase of its output.

1 cl, 4 ex, 1 tbl

FIELD: chemistry.

SUBSTANCE: invention relates to method of polymerisation of raw material flow containing C5-C6 hydrocarbons, which includes: loading of hydrogen and raw material, containing at least, normal C5-C6 hydrocarbons into isomerisation zone and contacting of hydrogen and raw material with isomerisation catalyst in conditions that favour increase of degree of hydrocarbons branching in raw material flow and ensuring formation of outgoing flow from isomerisation zone, which contains, at least, butane, normal pentane, normal hexane, methylbutane, dimethylbutane, methylpentanes and hydrocarbons which have seven or more carbon atoms, isomerisation conditions including temperature from 40° to 235°C and pressure 70 kPa abs. to 7000 kPa abs; passing outgoing flow from isomerisation zone through deisohexanizer zone in order to divide it into four flows, flow outgoing from upper part of deisohexaniser zone, containing, at least, butane, first side flow from deisohexaniser zone, containing, at least, methylbutane and dimethylbutanes, second side flow from deisohexaniser zone, containing, at least, methylpentanes and normal hexane, and lower flow from deisohexaniser zone, containing, at least, hydrocarbons, consisting of seven and more carbon atoms; and supply of first side flow from deisohexaniser zone into zone of isomerizate stripping in order to separate upper flow from isomerisate desorber which contains, at least, butane, from product flow from zone of isomerisate stripping, containing methylbutane and dimethylbutanes.

EFFECT: application of claimed method allows to reduce capital outlays and reduce cost of energy supply due to excluding of column-stabiliser.

9 cl, 4 dwg

FIELD: chemistry.

SUBSTANCE: catalyst includes carrier, which contains tungsten oxide or hydroxide of at least one element from grope IVB ("ИЮПАК 4"), first component from at least one element from lanthanide line, yttrium and their mixture, and second component, which contains at least one component of metal from platinum group or their mixture. Also described is method of hydrocarbons transformation by contacting of raw material with solid acid catalyst, described above, with transformed product formation. Described is method of paraffin raw material isomerisation by its contacting with said catalyst at temperature from 25 to 300°C, pressure from 100 kPa to 10 MPa and volumetrical speed of liquid feeding from 0.2 to 15 hour-1 , with further product release, enriched by isoparaffins.

EFFECT: stability in hydrocarbons transformation process, increase of isoparaffins content.

10 cl, 1 tbl, 2 ex, 8 dwg

FIELD: chemistry.

SUBSTANCE: invention pertains to a catalyst and a method for selective increase in quality of paraffin raw material, with the aim of obtaining concentrated isoparaffin product as a benzine component. Description is given of the catalyst, which consists of a carrier from a sulphated oxide or hydroxide of group IVB (IUPAC 4) metals. The first component is, at least, from one lanthanide element or an yttric component, which is mainly ytterbium, and at least, one metal of the platinum group, which is mainly platinum, and a fireproof oxide binding substance, on which is dispersed at least, one metal of the platinum group. Description is given of the method of making the above mentioned catalyst, including a sulphated oxide or hydroxide of a group 1VB metal, depositing of the first component, mixing the sulphated carrier with the fireproof inorganic oxide of the oxide carrier, burning, depositing of the second component and subsequent burning. Description is given of the method of converting hydrocarbons through contacting with raw materials with the catalyst described above.

EFFECT: selective increase in quality of paraffin raw materials.

12 cl, 2 tbl, 2 dwg, 7 ex

FIELD: organic synthesis.

SUBSTANCE: invention pertains to obtaining branched alkanes with general formula CnH2n+2, where n = 4-10. CCI4 is gradually added to a mixture of hexane, triethylaluminium - Et3Al and a catalyst - PdCl2, in an argon atmosphere at atmospheric pressure and temperature of 10-60°C for a period of 0.5-2 hours. The molar ratio of hexane: Et3Al : CCl4 : PdCl2 is 75:10:20:0.1.

EFFECT: obtaining of a mixture of branched alkanes with high output.

1 tbl, 1 ex

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 CnH2n+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

FIELD: petrochemical processes.

SUBSTANCE: feedstock is brought into contact with preliminarily activated zeolite-containing catalyst, namely mordenite-supported Pt, at 250-300°C, pressure 1.5-3.5 MPa, hydrogen-containing gas-to-feedstock ratio 300-1000 nm3/m3, and feed flow rate 1.0-4.0 h-1. Preliminary activation of zeolite-containing isomerization catalyst is conducted in two successive steps: drying catalyst in inert gas flow; reducing catalyst in hydrogen-containing gas flow; and supplying feedstock and setting steady-state isomerization process. Drying of zeolite-containing catalyst in inert gas flow is effected under conditions of gradually raised temperature from 120°C at temperature raise rate 10-15°C/h and ageing for 2-5 h at 120°C to 350°C followed by ageing at this temperature, whereupon temperature is lowered to 130°C. Reduction of zeolite-containing catalyst in hydrogen-containing gas flow is effected at gradually raised temperature to 220-350°C at temperature rise rate 15-25°C/h and ageing for 2-6 h at 220-350°C, whereupon temperature is lowered to 180°C. Initial feedstock is supplied at 180°C in circulating hydrogen-containing gas flow, aged for 4 h at 180°C and then gradually heated to 250°C at heating rate 5°C/h, after which further heated at heating rate 5°C a day to achieve process characteristics meeting product quality requirements.

EFFECT: increased catalyst activity, selectivity, and working stability.

2 cl, 2 tbl, 17 ex

FIELD: chemistry.

SUBSTANCE: linear sterol dimer (trans-1,3-diphenylbut-1-ene) is produced by sterol oligomerisation with ceolite catalyst added in solvent and characterised by that catalyst is Beta ceolite in N-form in amount 8-15 wt %. Reaction is enabled in chlorbenzene in ratio sterol:chlorbenzene=1:4 (vol) and temperature 100-115°C.

EFFECT: simplified linear sterol dimer production process.

1 tbl, 5 ex

FIELD: chemistry.

SUBSTANCE: present invention pertains to the method of producing linear styrene dimers (cis- and trans-1.3-diphenylbut-1enes) through oligomerisation of styrene in the presence of zeolite catalyst. The method is characterised by that, the catalyst used in ZSM-12 type zeolite in H-form, in quantity of 10-20 wt %. The reaction is carried out at 95-110°C temperature.

EFFECT: use of this method makes easier the production of unsaturated linear styrene dimers.

5 ex, 1 tbl

FIELD: chemistry.

SUBSTANCE: present invention pertains to the method of producing linear styrene dimers (cis- and trans-1.3-diphenylbut-1-enes) through oligomerisation of styrene in the presence of zeolite catalyst in a solvent. The method is characterised by that, the catalyst used is ZSM-12 type zeolite in H-form, in quantity of 5-20 wt %. The reaction is carried out in nonane with ratio styrene:nonane = 1:2-4 (vol.) and 80-110°C temperature.

EFFECT: use of this method simplifies the method of producing linear styrene dimers.

1 tbl, 6 ex

FIELD: chemistry.

SUBSTANCE: method involves oligomerisation of α-methylstyrene, in the presence of a zeolite catalyst. The catalyst used is a zeolite series of pentasils Fe-ZSM-5 (1.8÷2.2% mass content of Fe3+) with molar ratio SiO2/(Al2O3+Ee2O3)=60, in H form in percentage mass content of 5÷10% α-methylstyrene. The reaction is carried out in a neutral medium (nitrogen, argon) at 80-120°C.

EFFECT: simplification of the process of obtaining linear dimmers of α-methylstyrene and increased efficiency of the process.

1 tbl, 1 ex

FIELD: industrial organic synthesis.

SUBSTANCE: invention provides process for producing linear α-methylstyrene dimers useful as polymer molecular mass regulator, varnish solvents, dielectric liquids, and base for production of synthetic lubricating oils. Process is accomplished through dimerization of α-methylstyrene in presence of 0.5-4% of BETA-type zeolite in H form at 20-40°C for 2 to 8 h.

EFFECT: increased selectivity and improved technology.

7 ex

FIELD: industrial organic synthesis.

SUBSTANCE: process is accomplished by dimerization of styrene in presence of Y-type zeolite with molar ratio SiO2/Al203 = 6-7 in H-form and with ion exchange degree 94-97% undergone heat treatment and utilized in amount of 5-10 wt % based on styrene. Reaction is carried out at 80-120°C in pseudocumene solvent used in (1-2):1 proportion to styrene.

EFFECT: simplified process and increased yield of end product.

1 tbl, 9 ex

FIELD: chemical industry; methods of production of the linear dimmers of a-methylsterene.

SUBSTANCE: the invention is pertaining to the methods of production of the linear dimmers of a-methylsterene, which are used in the capacity of the modifiers in production of polymers. The method is exercised by dimerization of α- methylsterene in the presence of zeolite Y with the molar ratio of SiO2/Al2O3 = 6.2, with the stage of the ionic exchange of Na+ for Н+ - 40÷60 % containing 0.5÷2.0 mass % of copper (II). The catalyst amount makes 1÷4 mass %, the temperature of the reaction is 80÷100°С. The output of the dimmers compounds - 92.8÷94.8 % at conversion of the raw of 96.3÷99.4 %. The technical result of the invention is the raise of the selectivity of formation and output of the linear unsaturated dimmers of α- methylsterene.

EFFECT: the invention ensures the increased selectivity of formation and output of the linear unsaturated dimmers of α- methylsterene.

9 ex, 1 tbl

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to a method for synthesis of linear unsaturated dimmers of α-methylstyrene that are used as modifying agents in manufacturing polymers. Method is carried out by the dimerization reaction in the presence of zeolite Y at the mole ratio SiO2/Al2O3 = 6.2-7.0 in NaH-form and ionic exchange degree 40-60%. The amount of catalyst is 1-5 wt.-%, the reaction temperature is 40-800C. Invention provides increasing working time of catalyst and improving indices of the process.

EFFECT: improved method of synthesis.

9 ex

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