RU2499631C1 - Aluminosilicate zeolite uzm-37 - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: present invention relates to a family of aluminosilicate zeolites, a method of producing zeolites and a method of converting hydrocarbons. Described is a novel family of microporous crystalline aluminosilicate zeolites, having a space frame of at least tetrahedral AlO₂ and SiO₂ units, wherein the empirical composition of the zeolite in anhydrous state is expressed by the following formula: $$M_m^{+}{R}_r^{+}A{l}_{1-x}{E}_{x}S{i}_y{O}_z,$$

where M is sodium or a combination of potassium and sodium cations capable of exchange, m is the molar ratio of M to (Al+E) and varies from 0.05 to 2, R denotes a single-charge propyl trimethylammonium cation, r is the molar ratio of R to (Al+E) and varies from 0.25 to 3.0, and E is an element selected from a group consisting of gallium, iron, boron and mixtures thereof, x is the molar fraction or H and varies from 0 to 1.0, y is the molar ratio of Si to (Al+E) and varies from more than 8 to 40, and z is the molar ratio of O to (Al+E) and has a value defined by the equation: z=(m+r+3+4y)/2.

EFFECT: said zeolites are characterised by a unique X-ray diffraction pattern and composition, and have catalytic activity for carrying out various hydrocarbon conversion processes.

10 cl, 5 tbl, 4 ex

Description

Prioritization for previously submitted national applications

The pending application claims priority for US patent applications 12/750911, 12/750923 and 12/750939, which were filed March 31, 2010.

FIELD OF THE INVENTION

The present invention relates to a new family of aluminosilicate zeolites, a method for producing zeolites and methods for using zeolites. These zeolites are designated UZM-37. They are represented by the empirical formula:

, $$M_m^{n+}{R}_r^{+}A{l}_{\mathrm{one}-x}{E}_{x}S{i}_y{O}_z$$

,

where M is sodium or a combination of exchangeable sodium / potassium or lithium / strontium cations, R is a singly charged organo-ammonium cation, such as propyltrimethylammonium hydroxide, and E is a framework element, such as gallium. These zeolites can be used in hydrocarbon conversion processes, such as catalytic cracking.

State of the art

Zeolites are aluminosilicate compositions that are microporous and which are formed when the angles of AlO ₂ and SiO ₂ tetrahedra are shared. Numerous zeolites, both of natural origin and synthetically obtained, are used in various industrial processes. Synthetic zeolites are prepared by hydrothermal synthesis using suitable sources of Si, Al and structurally oriented agents such as alkali metals, alkaline earth metals, amines or organo-ammonium cations. Structurally oriented agents are located in the pores of the zeolite, and they are mainly responsible for the specific structure, which is finally formed. These particles compensate for the charge of the frame associated with aluminum, and can also play the role of a filler of voids. Zeolites are characterized in that they have the same pore mouths, have significant ion-exchange capacity, and are capable of reversibly desorbing the adsorbed phase, which is dispersed over all the internal cavities of the crystal, without significant replacement of any atoms that make up the zeolite’s constant crystalline structure. Topological zeolites can be used as catalysts for hydrocarbon conversion processes that can occur on the outer surface, as well as on the inner surface inside the pores.

US Pat. No. 4,528,171 describes EU-4 zeolite. In the synthesis of EU-4, a molecular template is used - propyltrimethylammonium hydroxide. However, the ratio of silica to alumina in the resulting EU-4 zeolite is more than 49.1.

U.S. Pat. No. 6,892,511 describes another zeolite, UZM-15. In the synthesis of UZM-15, a template is used - propyltrimethylammonium hydroxide, but only as an additive to another template; and not as the only template.

In US patent 7575737, another zeolite is synthesized - UZM-27, with a template - propyltrimethylammonium hydroxide, in combination with calcium.

Applicants have successfully synthesized a new family of materials designated UZM-37. The topology of these materials is the same as that observed for MWW zeolite. These materials are obtained by using a simple, industrially available structurally orienting agent, such as propyltrimethylammonium hydroxide, using the “Charge density mismatch” approach in zeolite synthesis (US Pat. No. 7,578,993). The organo ammonium compounds used in preparing the UZM-37 zeolite are not cyclic and do not contain cyclic substituents, and are usually very simple. Examples of the used organomonium compounds in the preparation of UZM-37 include propyltrimethylammonium cations (PTMA) and isopropyltrimethylammonium cations (i-PTMA).

SUMMARY OF THE INVENTION

As set forth, the present invention relates to a new aluminosilicate zeolite designated UZM-37. Accordingly, one embodiment of the invention is a microporous crystalline zeolite having a spatial framework of at least tetrahedral blocks of AlO ₂ and SiO ₂ , wherein the empirical composition of the synthesized zeolite in the anhydrous state is expressed by the empirical formula:

, $$M_m^{+}{R}_r^{+}A{l}_{\mathrm{one}-x}{E}_{x}S{i}_y{O}_z$$

,

where M is sodium or a combination of sodium / potassium or lithium / strontium cations capable of exchange, "m" means the molar ratio of M to (Al + E) and varies from 0.05 to 2, R is a singly charged organomonium cation - propyltrimethylammonium hydroxide , "r" means the molar ratio of R to (Al + E) and has a value of from 0.25 to 5.0, E is an element selected from the group consisting of gallium, iron, boron and mixtures thereof, "x" means molar fraction of E and has a value from 0 to 1.0, "y" is the molar ratio of Si to (Al + E) and varies from more than 7 to 20, and "z" means molar elations O to (Al + E) and has a value determined by the equation:

z = (m + r + 3 + 4 · y) / 2

and differs in that the zeolite has an X-ray diffraction pattern in which there are at least interplanar distances (d) and intensities (I) shown in Table A:

Table a 2θ d (Å) I / Io% 3.22-3.48 25.35-27.44 wed 6.62-6.92 12.76-13.34 wed 7.12-7.39 11.93-12.4 s-o 7.92-8.32 10.61-11.15 wed 8.64-8.81 10.01-10.22 wed 9.71-9.85 8.97-9.09 wed 12.75-12.78 6.92-6.93 cl 13.39-13.72 6.44-6.6 cl 14.34-14.5 6.1-6.17 cl 20,13-20,2 4.39-4.4 wed 21.56-21.64 4.1-4.11 wed 22.14-22.28 3.98-4.01 wed 23.09-23.35 3.8-3.84 wed 23.95-23.97 3.7-3.71 wed 24.92-25.19 3.53-3.57 wed 25.92-26.21 3.39-3.43 very good 26.7-26.77 3.32-26.7 wed 28.99-29.32 3.04-3.07 wed 31.51-31.64 2.82-2.83 cl 33.3-33.69 2.65-2.68 cl 37.68-37.94 2.36-2.38 cl 46.05-46.29 1.95-1.96 cl 48.78-48.94 1.85-1.86 cl

and is thermally stable to temperatures higher than 600 ° C in one embodiment and 700 ° C in another embodiment.

Another embodiment of the invention is a method for producing crystalline microporous zeolite described above. The specified method includes the formation of a reaction mixture containing reactive sources of M, R, Al, Si and optionally E, and heating the reaction mixture at a temperature of from 150 ° C to 200 ° C, or from 165 ° C to 185 ° C, over time, sufficient for the formation of zeolite, and the reaction mixture has a composition expressed on the basis of molar ratios of oxides:

aM ₂ O: bR _{2 / p} O: (1-c) Al ₂ O ₃ : cE ₂ O ₃ : dSiO ₂ : eH ₂ O

where "a" has a value from 0.05 to 25, "b" has a value from 1.5 to 80, "c" has a value from 0 to 1.0, "d" has a value from 8 to 40, "e" has a value from 25 to 4000.

Another embodiment of the invention is a method for converting hydrocarbons using the zeolite described above. The method includes contacting a hydrocarbon with a zeolite under conversion conditions to obtain a converted hydrocarbon.

Detailed Disclosure of Invention

Applicants synthesized aluminosilicate zeolite whose topological structure is similar to that of MWW zeolite, as described in the Atlas of Zeolite Frame Types, maintained by the International Zeolite Association Structure Commission at http://topaz.ethz.ch/IZA-SC/StdAtlas.htm, which designated UZM-37. As will be shown later, the UZM-37 differs from MWW in the number of characteristics. The present microporous crystalline zeolite (UZM-37) has an empirical composition in a synthesized form and in an anhydrous state, expressed by the empirical formula:

$$M_m^{+}{R}_r^{+}A{l}_{\mathrm{one}-x}{E}_{x}S{i}_y{O}_z$$

where M is sodium or a combination of sodium / potassium or lithium / strontium cations capable of exchange. R is a singly charged organo-ammonium cation, examples of which include, but are not limited to, a propyltrimethylammonium cation, an isopropyltrimethylammonium cation, a dimethyldipropylammonium cation, (DMDPA ⁺ ), choline [(CH ₃ ) ₃ N (CH ₂ ) ₂ OH] ⁺ , ETMA ⁺ , DEDMA ⁺ , trimethylbutylammonium, dimethyldiethanolammonium, methyltripropylammonium, TEA ⁺ , TPA ⁺ and mixtures thereof and "r" means the molar ratio of R to (Al + E) and has a value of from 0.25 to 2.0, while "m" means molar the ratio of M to (Al + E) and varies from 0.05 to 3. The molar ratio of silicon to (Al + E) is denoted by "y" and changes etsya from 8 to 40. E is an element with tetrahedral coordination, which is located in the frame and which is selected from the group consisting of gallium, iron and boron. The molar fraction E is designated as "x" and has a value from 0 to 1.0, while "z" means the molar ratio of O to (Al + E), which is determined from the equation:

z = (mn + r + 3 + 4y) / 2.

и средневзвешенная валентность (n) определяются из уравнений:When M is the only metal, then the weighted average valency is the valency of that one metal, i.e. +1 or +2. However, when more than one metal M is present in zeolite, the total amount $$\left(M_m^{n+}\right)$$

and weighted average valency (n) are determined from the equations:

$$M_m^{n+}=M_{m\mathrm{one}}^{\left(n\mathrm{one}\right)+}+M_{m2}^{\left(n2\right)+}+M_{m3}^{\left(n3\right)+}+...$$

and

$$n=\frac{m_{\mathrm{one}}\cdot n_{\mathrm{one}}+m_2\cdot n_2+m_3\cdot n_3+...}{m_{\mathrm{one}}+m_2+m_3...}$$

A microporous crystalline zeolite, UZM-37, is obtained by hydrothermal crystallization of a reaction mixture prepared by combining reactive sources of M, R, aluminum, silicon, and optionally E. Sources of aluminum include, but are not limited to, aluminum alkoxides, precipitated aluminum oxides, metal aluminum, aluminum salts and alumina sols. Specific examples of aluminum alkoxides include, but are not limited to, ortho-secondary aluminum butoxide and ortho-aluminum isopropoxide. Sources of silica include, but are not limited to, tetraethylorthosilicate, colloidal silica, precipitated silica, and alkali metal silicates. Sources of elements E include, but are not limited to, alkali metal borates, boric acid, precipitated gallium oxyhydroxide, gallium sulfate, iron sulfate, and iron chloride. Sources of metals M, potassium and sodium include halide salts, nitrate salts, acetate salts and hydroxides of the corresponding alkali metals. R is an ammonium cation which is selected from the group consisting of propyltrimethylammonium, isopropyltrimethylammonium, dimethyldipropylammonium, choline, ETMA, DEDMA, TEA, TPA, trimethylbutylammonium, dimethyldiethanolammonium and mixtures thereof, and bromides, iodides, chlorides, iodides, and chlorides, - Specific examples include, but are not limited to, propyltrimethylammonium hydroxide, propyltrimethylammonium chloride, propyltrimethylammonium bromide, propyltrimethylammonium isohydroxide, isopropyltrimethylammonium bromide, isopropyltrimethylmethyldimethyltropyltrimethylammonium hydroxide, dimethylmethyldimethylmethyldimethyltropyltrimethylammonium hydroxide

A reaction mixture containing reactive sources of the desired components can be described based on molar ratios of oxides using the formula:

aM ₂ O: bR ₂ / _p O: (1-s) Al ₂ O ₃ : cE ₂ O ₃ : dSiO ₂ : eH ₂ O

where "a" varies from 0.05 to 1.25, "b" varies from 1.5 to 80, "c" has a value from 0 to 1.0, "d" varies from 8 to 40, and "e" has a value of from 25 to 4000. If alkoxides are used, the distillation or evaporation of the reaction mixture is preferably used in order to remove alcohol hydrolysis products. The reaction mixture is then reacted at a temperature of from 150 ° C to 200 ° C, from 165 ° C to 185 ° C, or from 170 ° C to 180 ° C, for a period of 1 day to 3 weeks, and preferably for a time of 5 to 12 days in a sealed reaction vessel at autogenous pressure. After crystallization is complete, the solid product is isolated from the heterogeneous mixture by a method such as filtration or centrifugation, and then washed with deionized water and dried in air at room temperature to 100 ° C. It should be noted that it is not possible to add UZM-37 seed to the reaction mixture in order to accelerate the formation of zeolite.

In a preferred synthesis approach to UZM-37, the concept of charge density mismatch is used, which is disclosed in US Pat. No. 7,578,993 and in Studies in Surface Science and Catalysis, (2004), Volume 154A, pp. 344-372. The process described in US Pat. No. 7,578,993 uses quaternary ammonium hydroxides to solubilize the aluminosilicate particles, although crystallization inducing agents, such as alkali and alkaline earth metal cations and stronger ammonium cations, are often introduced in a separate step. Sometimes some UZM-37 seed crystals are formed using this approach, the seed can be used at a single stage of UZM-37 synthesis using, for example, a combination of propyltrimethylammonium hydroxide and alkali metal cations. The use of commercially available propyltrimethylammonium hydroxide to obtain UZM-37 provides a significant economic advantage over previously used structurally oriented agents, such as hexamethylimine, used for the synthesis of aluminosilicates with MWW topology. In addition, using the concept of charge density mismatch, propyltrimethylammonium hydroxide can be used as hydroxide or chloride in combination with other inexpensive organo-ammonium hydroxides in order to further reduce costs.

The aluminosilicate zeolite UZM-37, which is obtained in the synthesis described above, is characterized by an X-ray diffractogram, in which there are at least interplanar distances (d) and relative intensities shown in Table A below.

Table a 2θ d (Å) I / Io% 3.22-3.48 25.35-27.44 wed 6.62-6.92 12.76-13.34 wed 7.12-7.39 11.93-12.4 s-o 7.92-8.32 10.61-11.15 wed 8.64-8.81 10.01-10.22 wed 9.71-9.85 8.97-9.09 wed 12.75-12.78 6.92-6.93 cl 13.39-13.72 6.44-6.6 cl 14.34-14.5 6.1-6.17 cl 20,13-20,2 4.39-4.4 wed 21.56-21.64 4.1-4.11 wed 22.14-22.28 3.98-4.01 wed 23.09-23.35 3.8-3.84 wed 23.95-23.97 3.7-3.71 wed 24.92-25.19 3.53-3.57 wed 25.92-26.21 3.39-3.43 very good 26.7-26.77 3.32-26.7 wed 28.99-29.32 3.04-3.07 wed 31.51-31.64 2.82-2.83 cl 33.3-33.69 2.65-2.68 cl 37.68-37.94 2.36-2.38 cl 46.05-46.29 1.95-1.96 cl 48.78-48.94 1.85-1.86 cl

As will be shown in detail in the examples, the UZM-37 material is thermally stable to a temperature of at least 600 ° C and, in another embodiment, up to 700 ° C. Characteristics of diffraction lines corresponding to typical calcined UZM-37 samples are shown in Table B.

Table B 2and d (Å) I / Io% 7.28-7.45 11.84-12.1 s-o 8.04-8.18 10.79-10.98 wed 10.02-10.21 8.64-8.82 wed 12.91-13.15 6.72-6.81 wed 14.52-14.69 6.02-6.08 wed 19-19,16 4.62-4.66 cl 19.79-19.92 4.45-4.48 wed 20.36-20.53 4.32-4.33 wed 22.03-22.15 4-4,03 wed 22.8-22.9 3.88-3.89 s-o 23.82-24.02 3.7-3.73 wed 25.24-25.3 3.51-3.52 wed 26.2-26.36 3.37-3.39 very good 27.06-27.24 3.27-3.29 wed 27.88-27.97 3.18-3.19 wed 28.15-28.33 3.14-3.16 wed

The synthesized material UZM-37 may contain in its pores a certain amount of cations capable of exchange or compensating for the charge. These exchangeable cations can be replaced by other cations or, in the case of organic cations, they can be removed by heating under controlled conditions. Zeolite UZM-37 can be modified in many ways in order to adapt the zeolite to a specific application. Modifications include calcination, ion exchange, steaming, various acid extraction processes, treatment with ammonium hexafluorosilicate, or any combination thereof, as summarized for UZM-4M in US Pat. No. 6,776,975 B1, the disclosure of which is incorporated herein by reference. Modified characteristics include porosity, adsorption, Si / Al ratio, acidity, thermal stability, etc.

The composition of UZM-37, which is modified using one or more methods and is indicated in patent 6776975 (hereinafter UZM-37HS), in the anhydrous state is described by the empirical formula:

$$M{\mathrm{one}}_a^{n+}A{l}_{\left(\mathrm{one}-x\right)}{E}_{x}S{i}_{y\text{'}\text{'}}{O}_{z\text{'}\text{'}\text{'}\text{'}}$$

where M1 is at least one exchangeable cation selected from the group consisting of alkali metals, alkaline earth metals, rare earth elements, ammonium ion, hydrogen ion and mixtures thereof, “a” means the molar ratio of M1 to (Al + E ) and varies from 0.05 to 50, “n” means the weighted average valency of M1 and has a value from +1 to +3, E is an element that is selected from the group consisting of gallium, iron, boron and mixtures thereof, “x” means the molar fraction of the element E and varies from 0 to 1.0, y 'is the molar ratio of Si to (Al + E) and and varies from greater than 4 to virtually pure silica and z 'is the mole ratio of O to (Al + E) and has a value determined by the equation:

z '= (an + 3 + 4y') / 2

The expression “substantially pure silica” means that virtually all of the aluminum and / or metals E have been removed from the framework. It is well known that it is practically impossible to remove all aluminum and / or metal E. Numerically, the zeolite is substantially pure silica when y 'has a value of at least 3000, preferably 10,000, and most preferably 20,000. Thus, the range of y' is from 4 to 3000, preferably more than 10 to 3000; from 4 to 10,000, preferably 10 to 10,000, and from 4 to 20,000, preferably from more than 10 to 20,000.

When determining in the invention the ratios of the starting materials for the zeolite or the adsorption characteristics of the zeolite product and the like, the “anhydrous state” of the zeolite will be implied, unless otherwise indicated. The term “anhydrous state” as used in the invention refers to a zeolite in which physically adsorbed as well as chemically adsorbed water is practically absent.

The crystalline zeolite UZM-37 of the present invention can be used to separate mixtures at the molecular level, to remove contaminants by ion exchange, and for catalytic conversions of hydrocarbons in various processes. Separation at the molecular level can be based either on the size of the molecules (kinetic diameter) or on the degree of polarity of the species of molecules.

In addition, the UZM-37 zeolite of the present invention can be used as a catalyst or catalyst support in various hydrocarbon conversion processes. Hydrocarbon conversion processes are well known in the art and include cracking, hydrocracking, alkylation of aromatic as well as isoparaffin hydrocarbons, isomerization of paraffins and polyalkylbenzenes such as xylene, transalkylation of polyalkylbenzenes with benzene or monoalkylbenzenes, disproportionation of monoalkylbenzenes, polymerization, hydrogenation, polymerization dealkylation, hydration, dehydration, alkylation of olefins with an isoparaffin hydrocarbon, dimerization of olefins, oligomers ation of olefins catalytic cracking and dewaxing. The specific process conditions and types of raw materials that can be used in these processes are indicated in US Pat. Nos. 4,310,440 and 4,440,871, the disclosures of which are incorporated herein by reference.

One hydrocarbon conversion process that can be carried out using UZM-37 as a catalyst or catalyst carrier is a catalytic cracking process using feedstocks such as gas oil, heavy naphtha, deasphalted crude oil residues, etc., the main desired product is gasoline. Suitable conditions are: temperature from 454 ° C to 593 ° C (from 850 ° F to 1100 ° F), a volumetric fluid flow rate (OSJ) of 0.5 to 10 h ^-1 and an overpressure of 0 to 344 kPa (0 -50 psi).

Another hydrocarbon conversion process that can be carried out using UZM-37 as a catalyst or catalyst carrier is the alkylation of aromatic hydrocarbons, which usually involves the interaction of aromatics (C ₂ to C ₁₂ ), especially benzene, with a monoolefin to produce aromatics, substituted by linear alkyl. The specified process is carried out at a ratio of aromatic hydrocarbon: olefin (for example, benzene: olefin) between 1: 1 and 30: 1, OSL of olefin from 0.3 to 10 hours ^-1 , temperature from 80 ° to 300 ° C and overpressure from 1379 up to 6895 kPa (200 to 1000 psi). Additional installation details can be found in US Pat. No. 4,870,222, which is incorporated herein by reference.

Another hydrocarbon conversion process that can be carried out using UZM-37 as a catalyst or catalyst support is the alkylation of isoparaffin hydrocarbons with olefins in order to obtain alkylates used as components of motor fuel, which is carried out at a temperature of from -30 ° to 100 ° C, atmospheric pressure to 6895 kPa (1000 psi) and a mass feed rate (ICP) of 0.1 to 120 hour ^-1 . Details of the paraffin alkylation process can be found in US Pat. Nos. 5,157,196 and 5,157,197, which are incorporated herein by reference.

The structure of the zeolite UZM-37 of the present invention is determined using x-ray analysis. The X-ray diffraction patterns presented in the following examples were obtained using a standard X-ray powder diffraction technique. The radiation source was a high-intensity X-ray tube operating at 45 kV and 35 mA. The diffraction pattern of the copper radiation K _{α was} recorded using a computer and appropriate software. Flat samples of pressed powders were continuously scanned in the range of angles from 2 ° to 56 ° (2θ). Interplanar distances (d) in Angstrom units are calculated from the position of the diffraction peaks, expressed by the angle θ, which means the Bragg angle, measured from data in digital form. The intensity values are determined from the integral area of the diffraction peaks, minus the background, with "I ₀ " means the intensity of the strongest line or peak, and "I" is the intensity of each of the following peaks.

As will be understood by those skilled in the art, in determining the parameter 2θ, a subjective error appears, as well as an instrument error, which in combination can impose an uncertainty of ± 0.4 ° for each reduced value of 2θ. Of course, this uncertainty also manifests itself in the given values of interplanar distances, which are calculated from the values of 2θ. The specified error is common for the whole prior art and is not sufficient to prevent the establishment of differences between the crystalline materials according to the invention among themselves, as well as from compositions of the prior art. In some X-ray patterns given, for the relative intensities of interplanar spacings, the designations are indicated: o.s, s, av, and s, which respectively mean: very strong, strong, medium and weak. Based on the rating of “100 · I / Io,” the above designations are defined as:

cl = 0-15; avg = 15-60: s = 60-80 and v.s = 80-100

In some cases, the purity of the synthesized product can be estimated based on its x-ray powder diffraction pattern. Thus, for example, if it is claimed that the sample is clean, it is assumed that the lines of the crystal are not present in the X-ray diffraction pattern of the sample, but amorphous materials are possible.

In the following examples, BET surface area and micropore volume of materials are determined using UOP method 964-98.

In order to better illustrate the invention, the following examples are presented. It should be understood that the examples are given for illustration only and are not intended to inappropriately limit the broad scope of the invention that is set forth in the appended claims.

EXAMPLE 1

A solution of aluminosilicate is prepared by first mixing 39.81 g of aluminum hydroxide (28.22% Al) and 1371.36 g of a solution of propyltrimethylammonium hydroxide (21.9%), with vigorous stirring. After thorough mixing, 952.5 g of Ludox ™ AS-40 reagent (39.8% SiO ₂ ) is added. The reaction mixture is further homogenized for one hour using a high speed mechanical stirrer and placed overnight in a dryer at 100 ° C. According to the analysis, the resulting aluminosilicate solution contains 7.58 wt.% Si and 0.49 wt.% Al, which corresponds to a Si / Al ratio of 14.86.

An aqueous NaCl solution containing 21.16 g NaCl (98%) dissolved in 100.0 g distilled water was added to a portion (1000 g) of the aluminosilicate solution prepared in Example 1 with vigorous stirring, and the reaction mixture was further homogenized for 30 min A portion (1067 g) of the reaction mixture was transferred to a stainless steel Parr autoclave (volume 2000 ml), which was heated to 175 ° C and held at this temperature for 168 hours. The solid product is recovered by filtration, washed with deionized water and dried at 100 ° C.

The product is identified as UZM-37 by X-ray diffraction (XRD). The characteristic diffraction lines observed for the product are shown in Table 1. The composition of the product, determined by elemental analysis, corresponds to the following molar ratios: Si / Al = 13.02, Na / Al = 0.57, N / A1 = 1.32, C / N = 5.94. Part of the material is calcined by linearly raising the temperature to 600 ° C in air for 2 hours, followed by exposure to air for 2 hours. It was found that the BET surface area is 378 m ² / g and the micropore volume is 0.16 ml / g.

Table 1 2θ d (Å) I / I ₀ % 3.37 26.12 wed 6.77 13.03 wed 7.26 12.16 from 8.16 10.82 wed 8.64 10.22 wed 9.71 9.09 wed 12.75 6.93 cl 14.44 6.12 cl 20.15 4.4 wed 21.64 4.1 wed 22.14 4.01 wed 23.3 3.81 wed 23.95 3.71 wed 25.08 3,54 wed 26.07 3.41 very good 26.72 3.33 wed 29.26 3.04 cl 31.62 2.82 cl 33.69 2.65 cl 37.88 2,37 cl 46.15 1.96 cl 48.83 1.86 cl 51.3 1.77 cl

Using scanning electron microscopy (SEM), crystals with a plate-shaped morphology of approximately 400 nm × 600 nm were detected. The specified sample is calcined in air at 600 ° C for 2 hours. Typical diffraction lines observed for the product are shown in table 2.

table 2 2and d (Å) I / I ₀ % 4.06 21.74 cl 7.28 12,13 S 8.12 10.87 wed 10.04 8.8 wed 12.91 6.84 wed 14.52 6.09 wed 16.03 5.52 wed 19.16 4.62 cl 20.36 4.35 wed 22.06 4.02 wed 22.8 3.89 from 24.02 3,7 wed 25.3 3,51 wed 26.2 3.39 very good 27.09 3.28 wed 27.97 3.18 cl 46.54 1.94 cl

EXAMPLE 2

To a portion (1000 g) of the aluminosilicate solution prepared in Example 1, an aqueous solution of NaCl containing 15.87 g of NaCl (98%) dissolved in 100.0 g of distilled water was added with vigorous stirring, and the reaction mixture was further homogenized for 30 min A portion (1050 g) of the reaction mixture was transferred to a stainless steel Parr autoclave (volume 2000 ml), which was heated to 175 ° C and held at this temperature for 168 hours. The solid product is recovered by filtration, washed with deionized water and dried at 100 ° C.

The product is identified as UZM-37 by XRD. The characteristic diffraction lines observed for the product are shown in Table 3. The product composition determined by elemental analysis corresponds to the following molar ratios: Si / Al = 13.21, Na / Al = 0.45, N / A1 = 1.37, C / N = 5.90. Part of the material is calcined by linearly raising the temperature to 600 ° C in air for 2 hours, followed by exposure to air for 2 hours. It was found that the BET surface area is 401 m ² / g and the micropore volume is 0.164 ml / g. Using scanning electron microscopy (SEM), crystals with a platelet morphology of approximately 500 nm × 600 nm were detected.

Table 3 2and d (Å) I / I ₀ % 3.31 26.59 wed 6.77 13.02 wed 7.24 12.19 very good 8.12 10.87 wed 8.81 10.01 wed 9.28 9.52 wed 12.78 6.92 cl 13.58 6.51 cl 15.84 5.58 cl 20.19 4.39 wed 21.63 4.1 wed 22.18 four wed 22.76 3.9 wed 23.35 3.8 wed 23.53 3.77 wed 23.77 3.73 cp 23.97 3,7 cl 25.11 3,54 cp 26.07 3.41 very good 26.76 3.32 cp 28,99 3.07 cl 31.64 2.82 cl 33.69 2.65 cl 37.82 2,37 cl 46.29 1.95 cl 48.94 1.85 cl 51.62 1.76 cl

EXAMPLE 3

The aluminosilicate solution is prepared by first mixing 13.27 g of aluminum hydroxide (28.22% Al) and 457.12 g of propyltrimethylammonium hydroxide solution (21.9%), with vigorous stirring. After thorough mixing, add 317.50 g of Ludox ™ AS-40 reagent (39.8% SiO ₂ ). The reaction mixture is further homogenized for one hour using a high speed mechanical stirrer and placed overnight in a dryer at 100 ° C. According to the analysis, the resulting aluminosilicate solution contains 7.71 wt.% Si and 0.49 wt.% Al, which corresponds to a Si / Al ratio of 15.15.

A part (790 g) of the aluminosilicate solution was placed in a container, and with vigorous stirring, an aqueous NaCl solution containing 16.71 g of NaCl (98%) dissolved in 80.0 g of distilled water was added, and the reaction mixture was further homogenized for 30 minutes. A portion (850 g) of the reaction mixture was transferred to a stainless steel Parr autoclave (volume 2000 ml), which was heated to 175 ° C and held at this temperature for 144 hours. The solid product is recovered by filtration, washed with deionized water and dried at 100 ° C.

The product is identified as UZM-37 by XRD. The characteristic diffraction lines observed for the product are shown in Table 4. The product composition determined by elemental analysis corresponds to the following molar ratios: Si / Al = 12.86, Na / Al = 0.55, N / A1 = 1.40, C / N = 5.7. Part of the material is calcined by linearly raising the temperature to 600 ° C in air for 2 hours, followed by exposure to air for 2 hours. It was found that the BET surface area is 342 m ² / g and the micropore volume is 0.14 ml / g.

Table 4 2and d (Å) I / I ₀ % 3.22 27.44 wed 6.62 13.34 wed 7.12 12.40 from 7.92 11.15 wed 8.79 10.04 wed 9.85 8.97 wed 13.39 6.60 cl 14.34 6.17 cl 20,13 4.40 wed 21.56 4.11 wed 22.18 4.00 wed 23.25 3.82 wed 24.92 3.57 wed 25.92 3.43 very good 26.7 3.33 wed 29.01 3.07 wed 31.51 2.83 cl 33.65 2.68 cl 37.68 2,38 cl 46.05 1.96 cl 48.78 1.86 cl

EXAMPLE 4

The aluminosilicate solution is prepared by first mixing 13.27 g of aluminum hydroxide (28.22% Al) and 457.12 g of propyltrimethylammonium hydroxide solution (21.9%), with vigorous stirring. After thorough mixing, add 317.50 g of Ludox ™ AS-40 reagent (39.8% SiO ₂ ). The reaction mixture is further homogenized for one hour using a high speed mechanical stirrer and placed overnight in a dryer at 100 ° C. According to the analysis, the obtained aluminosilicate solution contains 7.47 wt.% Si and 0.47 wt.% Al, which corresponds to the ratio Si / Al 15.3.

A part (55 g) of the aluminosilicate solution was placed in a container, and with vigorous stirring, an aqueous solution of NaOH and KOH containing 0.19 g of NaOH (98%) and 0.26 g of KOH dissolved in 10.0 g of distilled water was added, the reaction mixture homogenize further for 30 minutes. A portion (20 g) of the reaction mixture was transferred to a stainless steel Parr autoclave (volume 45 ml), which was heated to 175 ° C and held at this temperature for 240 hours. The solid product is recovered by filtration, washed with deionized water and dried at 100 ° C.

The product is identified as UZM-37 by XRD. The characteristic diffraction lines observed for the product are shown in Table 5. The product composition determined by elemental analysis corresponds to the following molar ratios: Si / Al = 12.68, Na / Al = 0.10, K / Al = 0.07, N / A1 = 1.13; C / N = 6.0. Part of the material is calcined by linearly raising the temperature to 600 ° C in air for 2 hours, followed by exposure to air for 2 hours. It was found that the BET surface area is 352 m ² / g and the micropore volume is 0.14 ml / g.

Table 5 2and d (Å) I / I ₀ % 3.48 25.35 wed 6.92 12.76 wed 7.39 11.93 from 8.32 10.61 wed 9.83 8.98 wed 13.72 6.44 cl 14.50 6.10 cl 20,20 4.39 wed 22.28 3.98 wed 23.09 3.84 wed 23.95 3.71 wed 25.19 3.53 wed 26.21 3.39 very good 26.77 3.32 wed 29.32 3.04 cl 33.3 2.68 cl 37.94 2,36 cl

Claims (10)

1. A microporous crystalline zeolite having a spatial framework of at least tetrahedral blocks of AlO ₂ and SiO ₂ , while the empirical composition of the synthesized zeolite in the anhydrous state is expressed by the empirical formula
$$M_m^{+}{R}_r^{+}A{l}_{\mathrm{one}-x}{E}_{x}S{i}_y{O}_z,$$

where M is sodium or a combination of potassium and sodium cations exchangeable, m is the molar ratio of M to (Al + E) and varies from 0.05 to 2, R is a singly charged propyltrimethylammonium cation, r is the molar ratio of R to (Al + E) and has a value from 0.25 to 3.0, E is an element selected from the group consisting of gallium, iron, boron and mixtures thereof, x means the mole fraction of E and has a value from 0 to 1.0, y - the molar ratio of Si to (Al + E) and varies from more than 8 to 40 and z is the molar ratio of O to (Al + E) and has a value determined from the equation
z = (m + r + 3 + 4 · y) / 2,
and characterized in that the zeolite has an X-ray diffraction pattern in which there are at least interplanar distances (d) and intensities (I) shown in Table A:
Table a 2θ d (Å) I / Io% 3.22-3.48 25.35-27.44 cp 6.62-6.92 12.76-13.34 cp 7.12-7.39 11.93-12.4 s-o 7.92-8.32 10.61-11.15 wed 8.64-8.81 10.01-10.22 cp 9.71-9.85 8.97-9.09 cp 12.75-12.78 6.92-6.93 cl 13.39-13.72 6.44-6.6 cl 14.34-14.5 6.1-6.17 cl 20,13-20,2 4.39-4.4 cp 21.56-21.64 4.1-4.11 cp 22.14-22.28 3.98-4.01 cp 23.09-23.35 3.8-3.84 cp 23.95-23.97 3.7-3.71 wed 24.92-25.19 3.53-3.57 cp 25.92-26.21 3.39-3.43 very good 26.7-26.77 3.32-26.7 cp 28.99-29.32 3.04-3.07 wed 31.51-31.64 2.82-2.83 cl 33.3-33.69 2.65-2.68 cl 37.68-37.94 2.36-2.38 cl 46.05-46.29 1.95-1.96 cl 48.78-48.94 1.85-1.86 cl
and is thermally stable up to a temperature of at least 600 ° C and has a BET surface area of less than 420 m ² / g. 2. The zeolite according to claim 1, in which the volume of zeolite micropores is from 0.12 to 0.18 ml / g 3. The zeolite according to claim 1, in which the value of x is zero. 4. The zeolite according to claim 1, which is thermally stable up to a temperature of at least 700 ° C. 5. The method of producing zeolite according to one of claims 1 to 4, comprising forming a reaction mixture containing reactive sources of M, R, Al, Si and optionally E, and heating the reaction mixture at a temperature of from 150 to 200 ° C, over time, sufficient for the formation of zeolite, while the reaction mixture has a composition expressed as a molar ratio of oxides:
aM ₂ O: bR _{2 / p} O: (1-c) Al ₂ O ₃ : cE ₂ O ₃ : dSiO ₂ : eH ₂ O,
where a has a value from 0.05 to 1.25, b from 1.5 to 40, c from 0 to 1.0, d from 4 to 40, e from 25 to 4000. 6. The method according to claim 5, where the reaction mixture interacts at a temperature of from 150 to 185 ° C for a time from 1 day to 3 weeks. 7. The method according to claim 5, where R is a combination of propyltrimethylammonium hydroxide and at least one singly charged organo-ammonium cation, which is selected from the group consisting of TEA, TPA, ETMA, DEDMA, dimethyldipropylammonium, isopropyltrimethylammonium, trimethylbutylammonethylammonium dimethylammonium dimethyl ammonium dimethyl ammonium . 8. The method according to claim 5, which further includes adding a seed UZM-37 to the reaction mixture. 9. A method for converting a hydrocarbon, which comprises contacting a hydrocarbon stream with a catalyst under conditions of hydrocarbon conversion to obtain a converted product, the catalyst containing a zeolite according to one of claims 1 to 4. 10. The method according to claim 9, where the hydrocarbon conversion process is selected from the group consisting of alkylation, dealkylation, trans-alkylation of aromatic hydrocarbons, isomerization of aromatic hydrocarbons, alkylation of olefins with isoparaffin hydrocarbons, dimerization of olefins, oligomerization of olefins, catalytic cracking and dewaxing.