RU2273602C2 - Uzm-5, uzm-5p, and uzm-6: crystalline aluminosilicate zeolites and processes involving them - Google Patents

Abstract

FIELD: various-destination catalysts.

SUBSTANCE: invention provides a novel crystalline aluminosilicate zeolite family depicted by general formula M_mR_rAl_(1-x)E_xSi_yO_z, where M represents alkali or alkali-earth metal such as lithium or strontium, R is nitrogen-containing organic cation such as tetramethylammonium, and E structural element such as gallium. Zeolites are characterized by unique x-ray diffraction pattern and show catalytic properties in hydrocarbon conversion processes, especially in isomerization and alkylation of aromatic compounds.

EFFECT: extended assortment of zeolite-type catalysts.

18 cl, 18 tbl, 18 ex

Description

Zeolites are microporous crystalline aluminosilicate compositions that have a three-dimensional skeleton oxide structure formed by AlO ₂ angles and SiO ₂ tetrahedra. Numerous zeolites, both natural and synthetically prepared, are used in various industrial processes. Zeolites are characterized by the presence of open pores of the same size, have significant ability to ion exchange and are capable of creating a reversible desorbed and adsorbed phase, which is distributed throughout the inner space of the crystal without significant displacement of any of the atoms that make up the constant crystalline zeolite structure.

The number of synthetic zeolites has exceeded far over a hundred, as follows from the Atlas of Types of Zeolite Structures published by the International Zeolite Association (IZA). As is well known, zeolites differ from each other in composition, crystal structure, and adsorption properties. One of the methods that are commonly used in the art for determining differences between zeolites is x-ray diffraction.

The applicants synthesized a family of crystalline zeolite compositions that have unique x-ray diffraction patterns and have an empirical formula on an anhydrous basis, expressed in terms of molar ratios:

where M is at least one ion exchange cation selected from the group consisting of alkali and alkaline earth metals, "m" defines the molar ratio of M to (Al + E) and varies from 0 to 1.2, R is a nitrogen-containing organic cation selected from the group consisting of Quaternary ammonium ions, protonated amines, protonated diamines, protonated alkanolamines, Quaternary alkanolammonium ions, double Quaternary ammonium ions and mixtures thereof, "r" determines the molar ratio of R to (Al + E) and has the value from 0.25 to 3.0, E is an element selected from the group consisting of Ga, Fe, In, Cr, and B, "x" determines the mole fraction of E and varies from 0 to 0.5, "n" determines the weight average valence of M and has a value from +1 to +2, "p" determines the weight average valency of R and has a value from +1 to +2, "y" determines the molar ratio of Si to (Al + E) and varies from 5 to 12 and "z" determines the molar ratio About to (Al + E) and has a value defined by the equation:

z = (m • n + r • p + 3 + 4 • y) / 2.

Special members of this family of zeolites are: UZM-5, UZM-5P and UZM-6 zeolites. These zeolites can be catalysts for various hydrocarbon conversion processes, such as benzene alkylation and xylene isomerization.

Applicants synthesized a new family of zeolites. In its directly synthesized form, this family of zeolites has an anhydrous composition, which is represented by the formula:

where M is an ion exchange cation selected from the group consisting of alkali and alkaline earth metals. Specific examples of M cations include, but are not limited to, lithium, sodium, potassium, cesium, strontium, calcium, magnesium, barium, and mixtures thereof. The value of "m", which determines the molar ratio of M to (Al + E), varies from 0 to 1.2. R is a nitrogen-containing organic cation and is selected from the group consisting of protonated amines, protonated diamines, protonated alkanolamines, quaternary ammonium ions, double quaternary ammonium ions, quaternary alkanolammonium ions and mixtures thereof. The value of "r", which determines the molar ratio of R to (Al + E), varies from 0.25 to 3.0. The value of "n", which is the weight average valency of M, varies from +1 to +2. The p value, which is the weight average valency of the organic cation, ranges from +1 to +2. E is an element that is present in the structure and is selected from the group consisting of gallium, iron, boron, chromium, indium and mixtures thereof. The value of "x", which determines the mole fraction of E, varies from 0 to 0.5. The ratio of silicon to (Al + E) is represented by "y", which varies from 5 to 12, while the molar ratio of O to (Al + E) is determined using "z" and has a value that is determined by the equation:

Z = (m • n + r • p + 3 + 4 • y) / 2.

When M is only one metal, then the weight average valency is the valency of this particular metal, i.e. +1 or +2. However, when more than one metal M is present, the total amount:

and the weight average valency "n" is determined by this equation:

Similarly, when only one organic cation R is present, the weight average valency is the valency of one cation R, i.e., +1 or +2. When more than one R cation is present, the total number of R cations is determined by the following equation:

and the weight average valency "p" is determined by this equation:

These aluminosilicate zeolites are obtained by hydrothermal crystallization of a reaction mixture obtained by combining reactive sources of R, aluminum, optionally E and / or M and silicon in an aqueous medium. Accordingly, aluminum sources include, but are not limited to, aluminum alkoxides, precipitated alumina, aluminum hydroxide, aluminum salts, and aluminum metal. Specific examples of aluminum alcoholates include, but are not limited to, ortho-secondary butoxide and ortho-isopropoxide aluminum. Sources of silica include, but are not limited to, tetraethylorthosilicate, solid silica, precipitated silica, and colloidal silica. Sources of M metals include, but are not limited to, halide salts, nitrates, acetates, and hydroxides of the corresponding alkali or alkaline earth metals. Sources of E elements include, but are not limited to, alkaline borates, boric acid, gallium oxyhydroxide powder, gallium sulfate, ferric sulfate, ferric chloride, chromium chloride, chromium nitrate, indium chloride and indium nitrate. When R is a quaternary ammonium cation, the sources include, but are not limited to, hydroxide and halide compounds. Specific examples include, but are not limited to, tetramethylammonium hydroxide, tetraethylammonium hydroxide, hexonium bromide, tetramethylammonium chloride, methyltriethylammonium hydroxide. R can also be neutral amines, diamines and alkanolamines. Specific examples are triethanolamine, triethylamine and N, N, N ′, N′-tetramethyl-1,6-hexanediamine.

The reaction mixture containing chemically active sources of the desired components can be described through molar ratios of oxides of the formula:

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

where "a" is the molar concentration of oxide M and has a value from 0 to 2, "b" is the molar concentration of oxide R and has a value from 1.5 to 30, "d" is the molar concentration of silicon oxide and has a value from 5 to 30, " c "is the molar concentration of oxide E and has a value from 0 to 0.5 and" e "is the molar concentration of water and has a value from 30 to 6000. The reaction mixture thus reacts under the reaction conditions, including a temperature of from 100 ° C to 175 ° C, preferably from 140 ° C to 160 ° C, for a period of time from 12 hours to 14 days, preferred But over a period of time from 2 days to 5 days, in a hermetically sealed reaction vessel under autogenous pressure. After crystallization is complete, the solid product is isolated from the heterogeneous mixture by filtration or centrifugation and then washed with deionized water and dried in air at a temperature selected in the range from ambient temperature to 100 ° C.

In the case of synthesis, zeolites will contain a certain amount of ion-exchange or charge-balanced cations in their pores. These ion exchange cations can be replaced by other cations or, in the case of organic cations, they can be removed by heating under controlled conditions. All of these methods are well known in the art.

Crystalline zeolites are characterized by a three-dimensional skeleton structure formed by at least SiO ₂ and AlO ₂ tetrahedral elements. In addition, these zeolites are characterized by a unique x-ray diffraction pattern. The X-ray diffraction pattern has at least two peaks: one peak for d-interplanar spacings in the crystal lattice is 3.9 ± 0.12 Å and one peak for d-interplanar spacings is 8.6 ± 0.20 Å. Various types of structures and compositions of crystalline zeolites are given an arbitrary designation UZM-h, where "h" is an integer starting from one, and where, for example, "1" denotes a framework structure of type "1". That is, one or more zeolite compositions with different empirical formulas can have the same structure of type "h", for example, "1".

In this regard, the following species can be identified using x-ray diffraction patterns, which have at least d-interplanar spacings and relative intensities, which are presented in tables A and C.

Table a UZM-5 2-θ D (Å) I / I ₀ % 6.31-5.89 14.00-15.00 w-m 7.96-7.58 11.10-11.65 m-s 10.40-10.01 8.50-8.83 w-m 12.11-11.59 7.30-7.63 m 10.16-15.53 5.50-5.70 m-vs 19.28-18.55 4.60-4.78 w-m 22.26-21.60 3.99-4.11 m 23.20-22.43 3.83-3.96 w-s 24.16-23.33 3.68-3.81 vs 30.48-29.55 2.93-3.02 w-m 31.94-30.92 2.80-2.89 w-m 44.83-43.47 2.02-2.08 w

Table B UZM-5P 2-θ D (Å) I / I ₀ % 6.31-5.19 14.00-17.00 w-vs 7.96-7.56 11.10-11.70 w-m 10.52-10.04 8.40-8.80 m-s 16.56-15.67 5.35-5.65 w-m 19.49-18.87 4.55-4.70 w-m 23.52-22.09 3.78-4.02 w-vs 03.24-23.39 3.70-3.80 w-vs 30.81-29.76 2.90-3.00 w-m 31.94-30.81 2.80-2.90 w-m 45.30-43.04 2.00-2.10 w-m Table C UZM-6 2-θ

I / I ₀ % 6.31-5.89 14.00-15.00 w-m 7.96-7.58 11.10-11.65 m-s 10.40-10.01 8.50-8.83 w-m 12.11-11.59 7.30-7.63 m 10.16-15.53 5.50-5.70 m-vs 19.28-18.55 4.60-4.78 w-m 22.26-21.60 3.99-4.11 m 23.20 -22.43 3.92-4.00 m-vs 24.16-23.33 3.83-3.96 w-s 30.48 -29.55 3.68-3.81 s-vs 31.94-30.92 2.80-2.89 m 44.83-43.47 2.02-2.08 w

The zeolites of the present invention are capable of separating mixtures of compounds with different molecules depending on the size of the molecule (kinetic diameter) or depending on the degree of polarity of the various molecules. When the separation of various molecules is based on their size, it is achieved using smaller molecules that enter the intracrystalline void, while larger molecules are eliminated. The kinetic diameters of various molecules, such as oxygen, nitrogen, carbon dioxide, carbon monoxide, are given in D.W. Breck, Zeolite Molecular Sieves, John Wiley and Sons (1974), p.636.

The crystalline microporous compositions of the present invention, either synthesized or after calcination, can be used as catalysts or catalyst supports in hydrocarbon conversion processes. Hydrocarbon conversion methods are well known in the art and include cracking, hydrocracking, alkylation of both aromatic compounds and isoparaffins, isomerization, polymerization, reforming, dewaxing, hydrogenation, dehydrogenation, transalkylation, dealkylation, hydration, dehydration, hydrotreating, hydrodenite hydrodesulfurization; conversion of carbon oxides in the presence of hydrogen to methane; and a synthesis gas conversion process. The specific reaction conditions and starting materials that can be used in these processes are well known in the art. Preferred hydrocarbon conversion processes are aromatic alkylation and xylene isomerization.

These crystalline microporous compositions may be catalysts for other reactions, including base-catalyzed reactions, such as alkylation of the side chain of alkyl aromatic compounds, aldol condensations, isomerization of double olefinic bonds and isomerization of acetylenes, dehydrogenation of alcohols and dimerization of olefins, oligomerization and conversion of alcohol to olefins. Suitable ion exchange forms of these products can catalyze the reduction of NO _x to N ₂ in automotive exhaust and industrial exhaust gases. Some of the reaction conditions and types of starting materials that can be used in these processes are described in US-A-5015796 and H. Pines, THE CHEMISTRY OF CATALYTIC HYDROCARBON CONVERSIONS, Academic Press (1981), pp. 123-154 and links in this publication.

Although zeolites can be used on their own, it is preferable that the zeolite be mixed with a binder to conveniently form catalyst particles in a proportion of 5 to 100% by weight. zeolite and from 0 to 95% of the mass. a binder component, preferably with a zeolite inclusion of from 10 to 90% of the mass. from the composition. The binder component should preferably be porous, have a surface area of 5 to 800 m ² / g and be relatively resistant to the hydrocarbons used in the conversion process. Non-limiting examples of binders are aluminum oxides, titanium dioxide, zirconium dioxide, zinc oxide, magnesium oxide, boron oxide, aluminum oxide - silicon dioxide, magnesium oxide - silicon dioxide, chromium oxide - aluminum oxide, aluminum oxide - boron oxide, dioxide zirconium - silicon dioxide, silicon dioxide, silica gel and clay. Preferred binders are amorphous silica and alumina, including gamma, eta and theta alumina with gamma and eta alumina being particularly preferred.

Zeolite with or without a binder can be made in various forms, such as pills, balls, extrudates, spheres, etc. Preferred forms are extrudates and spheres. The extrudates are obtained by conventional means, which include mixing the zeolite either first or after adding metal components with a binder and a suitable peptizer, which allows the formation of a homogeneous thick mass or a thick paste having sufficient moisture, which would allow the formation of extrudates with acceptable integrity, capable of resist direct calcination. Then the thick mass is extruded through the mold, which gives the extrudate a shape. Many different forms of extrudate may exist, which include, but are not limited to, cylinders, shamrocks, weight-like, symmetrical, and asymmetric polyfoils. It is also within the scope of the present invention that extrudates can be further imparted by any means known in the art to any desired shape, such as, for example, a sphere.

Spheres can be prepared by the well-known oil-drop method, which is described in US-A-2620314, incorporated by reference. The method includes dropping a mixture of zeolite and, for example, an alumina sol and a thickener in an oil bath maintained at elevated temperature. The droplets of the mixture remain in the oil bath until they solidify in the form of hydrogel spheres. The spheres are then sequentially removed from the oil bath and are usually subjected to special aging treatments in oil and ammonia solution to further improve their physical characteristics. The resulting aged and gelled particles are then washed and dried at a relatively low temperature in the range of 50 ÷ 200 ° C, and then calcined at a temperature in the range of 450 ÷ 700 ° C for a period of 1 to 20 hours. Such treatment leads to the conversion of the hydrogel into the corresponding crystalline alumina.

A platinum group of metals, including one or more metals such as platinum, palladium, rhodium, ruthenium, osmium and iridium, is an optional component of the present catalyst, but is necessary for isomerization and alkylation processes. A preferred platinum group metal is platinum. The platinum group metal component may be present within the final composition in the form of a compound, such as an oxide, sulfide, halogen, oxysulfide, and so on, or as a metal as an element or in combination with one or more other ingredients of the catalyst composition. It was verified that the best results were obtained when essentially all the components of the platinum group metals are in a reduced state. The platinum group metal component is generally contained in an amount of from 0.01 to 5% by weight. and preferably from 0.1 to 2%, based on the total elemental composition of the composition.

The platinum group metal component can be incorporated into the catalyst composition by any suitable method. One way to obtain a catalyst involves the use of a water-soluble degradable compound of a platinum group metal to impregnate a calcined composition containing a sieve / binder. Alternatively, a platinum group metal compound may be added during the preparation of the zeolite composition and the binder. Another way of distributing a suitable metal is to obtain a composition of the metal component with a binder prior to the process of coextruding the zeolite and the binder. Complexes of platinum group metals which may be employed in accordance with the aforementioned or other known methods include chloroplatinic acid, hlorpalladievuyu acid, ammonium chloroplatinate, bromplatinovuyu acid trichloride, platinum, hydrate tetrachloride platinum dihlorkarbonildihlorid platinum tetraaminohloridplatiny, dinitrodiaminoplatinum, sodium tetranitroplatinate (II) , palladium chloride, palladium nitrate, palladium sulfate, diaminopalladium (II) hydroxide, tetraaminopalladium (II) chloride and the like .

It is within the scope of the present invention that the catalyst composition may contain other metal components known as modifiers of the action of the platinum group metal component. Such metal modifiers may include rhenium, tin, germanium, lead, cobalt, nickel, indium, gallium, zinc, uranium, dysprosium, thallium, and mixtures thereof. Catalytically effective amounts of such metal modifiers can be incorporated into the catalyst by any means known in the art to allow for a homogeneous or layered distribution.

The catalyst composition of the present invention may contain halogen as a component. The halogen component may be fluorine, chlorine, bromine or iodine, or mixtures thereof, chlorine is preferred. The halogen component is typically present in combination with an inorganic oxide carrier. Preferably, the optional halogen component is well dispersed throughout the catalyst, and may be contained in an amount of more than 0.2 to 15% by weight, based on the elemental final composition of the catalyst. The halogen component may be incorporated into the catalyst composition by any suitable method, either during the preparation of the inorganic oxide carrier or first, during or after other catalyst components have been incorporated.

The catalyst composition is dried at a temperature of from 100 ° to 320 ° C for a period of time from 2 to 24 hours or more hours and is usually calcined at a temperature of from 400 ° to 650 ° C in air for a period of time from 1 to 10 hours, until the incoming metal compounds are mostly converted into oxide form. If desired, the optional halogen component may be selected by incorporating a halogen or halogen-containing compound in air.

The resulting calcined composition is optimally subjected to substantial reduction under anhydrous conditions to ensure uniform and finally distributed dispersion of the optional metal components. Recovery may optionally be carried out in situ. At this stage, substantially pure and dry hydrogen (i.e., less than 20 vol. Ppm H ₂ O) is preferably used as the reducing agent. The reducing agent is contacted with the catalyst at a temperature of from 200 ° to 650 ° C for a period of time from 0.5 to 10 hours in order to recover essentially all of the metal components of group VIII to metals. In some cases, the resulting reduced catalytic composition can also be successfully subjected to preliminary sulfonation using a method known in the art for incorporation of from 0.05 to 1.0% by weight into the catalytic composition. sulfur, calculated on the total elemental composition.

The feedstock in the case of the process of isomerization of aromatic compounds includes isomerizable alkylaromatic hydrocarbons of the general formula C ₆ H _(6-n) R _n , where n is an integer from 1 to 5 and R is CH ₃ , C ₂ H ₅ , C ₃ H ₇ or C ₄ H ₉ , in any combination and including all their isomers, to obtain more valuable isomers of alkyl aromatic hydrocarbons. Suitable alkyl aromatic hydrocarbons include, but are not limited to, ortho-xylene, meta-xylene, para-xylene, ethylbenzene, ethyltoluenes, trimethylbenzenes, diethylbenzenes, triethylbenzenes, methylpropylbenzenes, ethylpropylbenzenes, di-isopropylbenzenes and mixtures thereof.

A particularly preferred application for the zeolites of the present invention is the isomerization of a C ₈ aromatic mixture containing ethylbenzene and xylenes. Typically, such a mixture has an ethylbenzene content that is approximately in the range of 5 to 50 wt.%, The ortho-xylene content is approximately in the range of 0 to 35% by mass, and the meta-xylene content is approximately in the range of 20 to 95 % of the mass. and the content of para-xylene is approximately in the range from 0 to 15% of the mass. It is preferable that the above C ₈ aromatic compounds contain a nonequilibrium mixture, that is, at least one C ₈ aromatic isomer is present in a concentration that is significantly different (as defined here as a difference of at least 5% of the mass. from the total mass of C ₈ aromatic compounds) from the thermodynamic equilibrium concentration of this isomer under isomerization conditions. Typically, a nonequilibrium mixture is obtained by removing para- and / or ortho-xylene from a fresh C ₈ aromatic mixture obtained in the process of producing aromatic compounds, and preferably, the nonequilibrium mixture contains less than 5% of the mass. para-xylene.

Alkylaromatic hydrocarbons that can be used in the present invention relate to those contained in suitable fractions from various refined oil streams, for example, as separate components or as certain fractions boiling in the range obtained by selective fractionation and distillation of hydrocarbons after catalytic cracking or reforming. Isomerizable aromatic hydrocarbons do not need to be concentrated; the process of the present invention allows isomerization of streams containing alkyl aromatic compounds, such as catalytic reforming products, with or without subsequent extraction of aromatic compounds, to obtain certain xylene isomers and, in particular, to obtain para-xylene. The starting C ₈ aromatic compounds according to the present method may contain non-aromatic hydrocarbons, i.e. naphthenes and paraffins, in an amount up to 30% by weight. Preferably, the isomerizable hydrocarbons are essentially composed of aromatics, however, nevertheless, they provide pure products from the downflows of the recycle.

In accordance with the method of the present invention, the initial mixture of alkylaromatic hydrocarbons, preferably in admixture with hydrogen, is contacted with a catalyst as defined below in an alkylaromatic hydrocarbon isomerization zone. Contacting can be accomplished using the catalyst in a fixed bed system, in a moving bed system, in a fluidized bed system, or in a batch process. In view of the danger of losing valuable catalyst due to abrasion and to simplify the process, a fixed bed system is preferably used. In this system, the hydrogen-enriched gas and the feed mixture are preheated using suitable heating means to achieve the desired process temperature, and then passed into the isomerization zone containing the fixed catalyst bed. The conversion zone may have one or more separate reactors with suitable adapters between them, which ensure the maintenance of the desired temperature of isomerization at the entrance to each zone. Upon contact, the reactants can contact the catalyst bed in any upward, downward or radial advancement of the streams, and the reactants can be in a liquid phase, a mixed liquid vapor phase or vapor phase.

The starting alkyl aromatic mixture, preferably a nonequilibrium mixture of C ₈ aromatic compounds, is contacted with an isomerization catalyst under conditions suitable for the isomerization of alkyl aromatic hydrocarbons. Such conditions include a temperature in the range of 0 ° to 600 ° C. or more, and preferably in the range of 100 ° to 500 ° C. The pressure, as a rule, has a value of from 101 to 10132 kPa (1-100 abs. Atmospheres), preferably less than 5066 kPa (50 atmospheres). The amount of catalyst contained in the isomerization zone should be sufficient to provide an hourly volumetric rate of liquid in relation to the initial hydrocarbon mixture from 0.1 to 30 h ^-1 and, preferably, from 0.5 to 10 h ^-1 . The initial hydrocarbon-containing mixture reacts optimally in a mixture with hydrogen at a hydrogen / hydrocarbon molar ratio of 0.5: 1 to 25: 1 or more. Other inert diluents, such as nitrogen, argon, and light hydrocarbons, may be present.

The reaction proceeds through the xylene isomerization mechanism described above during the interaction of ethylbenzene with the formation of a xylene mixture through conversion and reconversion from naphthenes. The xylene yield in the product accordingly increases due to the formation of xylenes from ethylbenzene. The loss of C ₈ aromatic compounds during the reaction is accordingly low: usually less than 4% of the mass. in one pass C ₈ aromatic compounds when fed into the reactor, preferably 3% of the mass. or less and most preferably not more than 2.5% of the mass.

The particular scheme employed, including isolating the isomerization product from the reaction streams of the isomerization zone, is not essential in the present invention, and any effective isolation scheme known in the art can be applied. Typically, the reaction stream is condensed and hydrogen and light hydrocarbon components are removed from it by contact degassing. The condensed liquid product is then fractionated to remove light and / or heavy by-products and to obtain an isomerization product. In some cases, certain types of products, such as ortho-xylene, can be isolated from the isomerization product by selective fractionation. The isomerization product of C ₈ aromatic compounds is usually subjected to selective isolation of the para-xylene isomer, optionally by crystallization. Selective adsorption is preferred when using crystalline aluminosilicates in accordance with US-A-3201491. Improvements and alternatives to the preferred adsorption process during isolation are described in US-A-3626020, US-A-3696107, US-A-4039599, US-A-4184943, US-A-4381.419 and US-A-4402832.

When combining the separation / isomerization processes according to the method for processing the ethylbenzene / xylene mixture, the initial fresh mixture of C ₈ aromatic compounds is combined with the isomerization product containing C ₈ aromatic compounds and naphthenes from the isomerization reaction zone and fed to the para-xylene separation zone; a depleted para-xylene stream containing a nonequilibrium mixture of C ₈ aromatic compounds is fed to the isomerization reaction zone in which C ₈ aromatic isomers are isomerized to near equilibrium levels to obtain an isomerization product. In accordance with this method scheme, non-secreted C ₈ aromatic isomers are preferably recycled to decay, until all of them are either converted to paraxylene or lost due to adverse reactions. The separation of ortho-xylene, preferably by fractionation, can also be carried out from the fresh starting C ₈ aromatic product, or from the isomerization product, or from both of them in combination, to the separation of para-xylene.

Alkylation and preferably monoalkylation of aromatic compounds involves reacting the aromatic compound with an olefin using the zeolite catalyst described above. The olefins that can be used in the process are any of those that contain from 2 to 20 carbon atoms. Said olefins may be branched or linear olefins, and the double bond may be either at the end or inside the olefin. Preferred olefins are ethylene, propylene, and those olefins that are known as serial detergent olefins. Serial detergent olefins are linear olefins containing from 6 to 20 carbon atoms, which have either internal or terminal double bonds. Linear olefins containing from 8 to 16 carbon atoms are preferred, and those containing from 10 to 14 carbon atoms are particularly preferred.

Alkylated aromatic compounds may be selected from the group consisting of benzene, naphthalene, anthracene, phenanthrene and their substituted derivatives, with benzene and its derivatives being the most preferred aromatic compounds. Alkylated means that an aromatic compound can be alkylated with an olefinic compound. Alkylated aromatic compounds may have one or more substituents selected from the group consisting of alkyl groups (having from 1 to 20 carbon atoms), hydroxyl groups and alkoxy groups, whose alkyl groups also contain from 1 to 20 carbon atoms. In case the substituent is an alkyl or alkoxy group, the phenyl group may also be substituted on the alkyl chain. Although unsubstituted and monosubstituted benzenes, naphthalenes, anthracenes and phenanthrenes are most commonly used in the practice of the present invention, polysubstituted aromatic compounds can also be used. Examples of suitable alkylating aromatic compounds in addition to those cited above include diphenyl, toluene, xylene, ethylbenzene, propylbenzene, butylbenzene, phenylbenzene, hexylbenzene, heptylbenzene, octylbenzene, etc .; phenol, cresol, anisole, ethoxy, propoxy, butoxy, pentoxy, hexoxybenzene, etc.

The specific conditions under which the monoalkylation reaction proceeds depends on the aromatic compound and olefin used. One of the necessary conditions is that the reaction is carried out at least partially in the liquid phase. Thus, the pressure in the reaction is controlled so as to keep the olefin at least partially dissolved in the liquid phase. In the case of higher olefins, the reaction can be carried out under autogenous pressure. For practical use, the pressure is usually set between 1379 and 6985 kPa (200-1000 psi), but it is usually between 2069-4137 kPa (300-600 psi). Alkylation of alkylated aromatic compounds with olefins within the range of C ₂ -C ₃₀ can be carried out at a temperature of from 60 ° C to 400 ° C and preferably from 90 ° C to 250 ° C, for a time sufficient to form the desired product. In a continuous process, this time can vary significantly, but usually it is from 0.1 to 3 hours ^-1 hourly average feed rate relative to the olefin. In particular, the alkylation of benzene with ethylene can be carried out at a temperature of from 200 ° C to 250 ° C and the alkylation of benzene with propylene at a temperature of from 90 ° C to 200 ° C. The ratio of the alkylated aromatic compound to the olefin used in the present process will depend on the desired degree of selectivity of the monoalkylation, as well as on the comparative cost of the aromatic and olefin components of the reaction mixture. For the alkylation of benzene with propylene, the ratios of benzene to olefin can be as low as 1 and as high as 10, with a ratio of 2.5-8 being preferred. If benzene is alkylated with ethylene, a benzene to olefin ratio between 1: 1 and 8: 1 is preferred. For a detergent series of C ₆ -C ₂₀ olefins, the ratio of benzene to olefin between 5: 1 up to as high as 30: 1 is usually sufficient to provide the desired selectivity of monoalkylation with an interval between 8: 1 and 20: 1, which is most preferred.

The zeolites of the present invention can also be used to catalyze the transalkylation reaction. By "transalkylation" is meant a process in which an alkyl group from one aromatic nucleus of a molecule is transferred to a second aromatic nucleus. A preferred transalkylation process is a process in which one or more alkyl groups of a polyalkylated aromatic compound is transferred to an unalkylated aromatic compound, as illustrated by the reaction of diisopropylbenzene with benzene to give two cumene molecules. Thus, transalkylation is often used to increase the selectivity of the desired selective monoalkylation by reacting the polyalkylated compounds constantly formed during the alkylation process with the non-alkylated aromatic compound to form additional monoalkylated products. From the point of view of this process, polyalkylated aromatic compounds are those which are formed by the alkylation of alkylated aromatic compounds with olefins, as described above, and non-alkylated aromatic compounds are benzene, naphthalene, anthracene and phenanthrene. The reaction conditions for transalkylation are similar to those applicable for alkylation, with temperatures ranging from 100 to 250 °, pressures ranging from 6985 to 3447 kPa (100-750 psi) and a molar ratio of non-alkylated aromatic compound to polyalkyl aromatic compound in ranges from 1 to 10. Examples of polyalkylated aromatic compounds that can react with, for example, benzene as a non-alkylated aromatic compound include diethylbenzene, diisopropylbenzene, dibutylbenzene, triethylbenzene, three zopropylbenzene, etc.

X-ray diffraction patterns presented in the following examples (and the above tables) were obtained using standard methods of x-ray powder diffraction. The radiation source is a high-intensity X-ray tube operating at 45 kV and 35 mA. The diffraction pattern from copper K-alpha radiation was obtained using appropriate computer technology. Flat pressed powder samples were continuously scanned at 2 ° (2θ) per minute from 2 ° to 70 ° (2θ). The interplanar distances (d) in Angstroms were obtained based on the position of the diffraction peaks expressed as 2θ, where θ is the Bragg angle observed from the digitized data. Interplanar intervals were determined from the combined region of the diffraction peaks after subtracting the background, “I ₀ ” is the intensity of the strongest spectral line or peak, and “I” is the intensity of each other peak.

As will be understood by a person skilled in the art, the determination of the parameter 2θ admits a subjective error and an error of the device, which in total is ± 0.4 for each indicated value of 2θ and up to ± 0.5 for the values indicated for nanocrystalline materials. The specified error is also valid for the specified d-distances, which are calculated depending on 9 values. Such an error is generally accepted in the art and does not prevent the establishment of differences between existing crystalline materials from each other and from compositions known from the technical field. In some of the radiographs described, the relative intensities of the d-distances are indicated by the conventional signs vs, c, m and w, which mean very strong, strong, medium and weak intensities, respectively. In terms of 100 X I / I _0, the designations described above are defined as w = 0-15; m = 15-60; c = 60-80 and vs = 80-100. In some samples, the purity of the synthesized product can be evaluated with reference to its x-ray powder. Thus, for example, if it is claimed that the sample is clean, it means only that the X-ray diffraction pattern of the sample does not contain spectral lines related to crystalline impurities, and not that there are no amorphous substances.

To more fully illustrate the invention, the following examples are provided. It should be understood that the examples are merely illustrative and are not intended to limit the broad scope of the invention as set forth in the appended claims.

Example 1

The aluminosilicate reaction mixture is obtained in the following manner. Second-aluminum butoxide (95 +%), 58.75 g is added to 836.34 g of TEAOH (35%) with vigorous stirring. To this mixture was added 294.73 g of colloidal silicon dioxide (Ludox AS-40, 40% SiO ₂ ), then an additional 10.18 g of distilled water. The reaction mixture is homogenized for one hour using a high-speed mechanical stirrer, and then kept in Teflon vessels overnight at a temperature of 95 ° C. After the aging step, the reaction mixture is recombined and analyzed; analysis shows a silicon content of 4.67%.

A charge of 500 g from the resulting reaction mixture was treated with vigorous stirring with TMACI with a solution consisting of 11.77 g of TMACI (97%) dissolved in 23.0 g of distilled water. After half an hour, the homogenized reaction mixture was partitioned between 8 Teflon-coated autoclaves. Autoclaves are placed in thermostats at a temperature of 150 ° C, where the reaction mixtures are kept for 4 days at autogenous pressure. Solid products are separated by centrifugation, washed and dried at a temperature of 95 ° C.

The composition of the isolated products is characterized by a molar ratio of Si / Al = 6.88, N / Al = 0.83, and C / N = 6.05. Scanning electron microscopy (SEM) shows that the crystals consist of grouped plates approximately 100-300 nm wide. The determination of the parameters using X-ray powder diffraction (PRD) shows the presence in the sample of spectral lines that are characteristic of the material designated UZM-5. Table 1 below shows the spectral lines characteristic of this phase. Part of the sample is calcined by heating it to 540 ° C at a speed of 2 ° C / min in an atmosphere of N ₂ , kept at a temperature of 540 ° C in an atmosphere of N ₂ for an hour, followed by 7-hour exposure at a temperature of 540 ° C in air. The surface area of BET is 530 m ² / g and the micropore volume is 0.2 cm ³ / g.

Table 1 2-θ d (Å) I / I ₀ % 6.24 14.15 m 7.90 11.18 m 10.32 8.57 w-m 12.00 7.37 m 15.80 5.60 m-s 16.34 5.42 m 05/19 4.66 w-m 10 p.m. 4.04 m 22.86 3.89 m 23.80 3.74 vs 27.40 3.25 w 30.14 2.96 w 30.90 2.89 w 31.60 2.83 m 33.20 2.70 w 34.56 2.59 w 36.64 2.45 w 44.32 2.04 w

Example 2

The aluminosilicate reaction mixture is prepared as follows. 876.65 g of distilled water is used to dilute 846.25 g of TEAOH solution (35%). With vigorous stirring, sec-aluminum butoxide (95 +%) was added in an amount of 49.54 g, followed by an additional 427.57 g TEOS (98%). The reaction mixture was heated to 85 ° C. overnight and then distilled, raising the temperature to 95 ° C. for 2 hours to remove the solvent. The reaction mixture was allowed to cool, after which it was found by elemental analysis that the mixture contained 3.34% Si. A portion of the indicated reaction mixture weighing 300 g is placed in a Teflon beaker and vigorously stirred. A solution is prepared containing 3.8 g of TMACI (97%), 0.3 g of LiCI and 1.1 g of Sr (NO ₃ ) ₂ in 25 g of distilled water, which is slowly added with stirring to the aluminosilicate concentrate. After addition, the reaction mixture is homogenized for 2 hours, and then partitioned between four Teflon-lined autoclaves. Autoclaves are placed in a thermostat at a temperature of 150 ° C, where the reaction mixtures are incubated for 5 days at a temperature of 150 ° C under autogenous pressure. The products are recombined, solids are isolated by centrifugation, washed and dried at 95 ° C.

Powder X-ray diffraction analysis shows that the product has a UZM-5 structure. Part of the product is calcined in a stream of nitrogen for 7 hours at a temperature of 580 ° C. The composition of the calcined product has the following molar ratios determined by elemental analysis: Si / Al = 7.6, Sr / Al = 0.11, Li / Al = 0.06. The BET surface area of the calcined product is 500 m ² / g and the micropore volume is 0.19 cm ³ / t. The SEM of the product shows that the crystals have a rosette morphology, usually the beam bundles are of the order of 0.3 to 0.8 microns wide. The characteristic lines found on the radiograph are illustrated in Table 2 below.

table 2 2-θ d (Å) I / I ₀ % 6.12 14.43 m 7.84 11.27 m 10.18 8.68 w-m 11.90 7.43 m 15.78 5.61 m-s 04/19 4.66 w-m 20.38 4.35 w 21.90 4.05 m 22.80 3.90 m 23.70 3.75 vs 25.22 3.53 w 26.26 3.39 w 06/30 2.97 w 31.40 2.85 w-m 33.18 2.70 w 44.13 2.05 w

Example 3

The aluminosilicate reaction mixture was obtained by adding, with vigorous stirring, 17.22 g of Al (Osec-Bu) ₃ (95 +%) to 470.69 g of TEAOH (35%). Then add 8.41 g of deionized water and an additional -103.67 g of colloidal silicon dioxide brand Ludox AS-40. First, the reaction mixture is homogenized for one hour using a high-speed mixer, then the mixture is placed in a Teflon vessel and kept at a temperature of 95 ° C for 2 days. Then the reaction mixture is cooled and, using elemental analysis, it is established that the reaction mixture contains 3.46% Si. A portion of the resulting reaction mixture weighing 50 g was treated with a solution of TMACI (97%) 0.71 g in 10 g of deionized water. The mixture is homogenized for 30 minutes using a high-speed mixer, and then divided between 3 Teflon-clad autoclaves and incubated for 2, 4, and 6 days at a temperature of 150 ° C under autogenous pressure. Solid products are isolated by centrifugation, washed with distilled water and dried at 95 ° C.

As X-ray powder diffraction showed, the products of the reaction mixture, which were held for 4 and 6 days, turned out to be products of the UZM-5 structure. The characteristic lines found on the x-ray for the 6-day exposure product are presented in Table 3.

Table 3 2-θ d (Å) I / I ₀ % 5.90 14.97 m 7.66 11.53 m 10.06 8.78 w-m 11.70 7.56 m 15.70 5.64 m-s 16.36 5.41 w-m 18.74 4.73 w-m 20.36 4.36 w 21.84 4.07 m 22.72 3.91 w-m 23.56 3.77 vs 26.20 3.40 w 27.26 3.27 w 29.94 2.98 w 31.26 2.86 w-m 08/33 2.71 w 43.92 2.06 w

Example 4

This example demonstrates the substitution in the structure of gallium for a certain amount of aluminum. Two separate reaction mixtures are obtained — Mixture A, an aluminosilicate composition, and Mixture B, a gallosilicate composition. Mixture A was prepared by adding, with vigorous stirring, 116.06 g of Al (OsecBu) ₃ (95 +%) to 1982.41 g of TEAOH (35%). 2.92 g of deionized water was added to the stirred reaction mixture along with 698.62 g of Ludox AS-40 grade colloidal silica. The resulting mixture was homogenized for one hour using a high-speed mixer, then it was placed in Teflon vessels and kept at a temperature of 95 ° C for one day. This aluminosilicate composition is a Mixture A, which according to the analysis contains 4.96% Si and has a Si / Al ratio of 9.53. Mixture B was prepared by diluting 275.23 g TEAOH (35%) 275.23 g deionized water. To this vigorously stirred solution was added 107.77 g of Ludox AS-40 brand colloidal silicon dioxide and 36.2 g of freshly precipitated Ga (OH) ₃ • xH ₂ O, 13.8% Ga. After an hour, the homogenized reaction mixture was placed in a Teflon vessel and kept at 95 ° C for three days. This gallosilicate composition. Mixture B, according to the analysis, contains 3.21% Si.

Substituted aluminosilicate is prepared with vigorous stirring in a Teflon beaker 45 g of Mixture A and 5 g of Mixture B. The solution is obtained by dissolving 1.17 g of TMACI (97%) in 10.0 g of deionized water added to the stirred mixture. After half an hour, the homogenized reaction mixture was distributed between three autoclaves and incubated for 4, 6, and 8 days at a temperature of 150 ° C under autogenous pressure. Solid products are isolated by centrifugation, washed with deionized water and dried at 95 ° C.

As X-ray powder diffraction showed, the three products have a UZM-5 structure. Elemental analysis shows that the six-day sample has the following molar ratios: Si / (Al + Ga) = 7.35; N / (Al + Ga) = 1.11; Si / Ga = 78.3; Al / Ga = 15.0 and C / N = 5.44. The characteristic lines found in the x-ray are presented in Table 4.

Table 4 2-θ d (Å) I / I ₀ % 6.06 14.57 m 7.80 11.33 m 10.16 8.70 w-m 11.84 7.46 m 15.72 5.63 m-s 04/19 4.66 w-m 20.38 4.35 w 21.822 4.07 m 22.76 3.90 w-m 23.66 3.76 vs 26.22 3.40 w 06/30 2.97 w 31.44 2.84 w-m 33.14 2.70 w-m 34.50 2.60 w 44.04 2.05 w

Example 5

The aluminosilicate reaction mixture was obtained by adding 197.31 g of Al (Osec-Bu) ₃ to 2808.74 g of TEAOH (35%), followed by the introduction of 989.82 g of colloidal silicon dioxide (Ludox AS-40) while maintaining vigorous stirring. The reaction mixture was kept at 95 ° C. for 16 hours and then allowed to cool. The resulting aluminosilicate reaction mixture is designated as Mixture C and is used again in Example 7.

Elemental analysis shows that Mixture C contains 4.79% Si. A portion of the resulting reaction mixture, in an amount of 110 g, was placed in a Teflon beaker equipped with a high-speed stirrer. Separately, a solution is obtained by dissolving 1.27 g of TMACI (97%) and 0.68 g of NaCI in 6 g of deionized water. This solution is added to the stirred aluminosilicate reaction mixture. After half an hour, the homogenized reaction mixture was partitioned between 4 Teflon-lined autoclaves, which were held under various conditions. The solid products are filtered off, washed with deionized water and dried at 95 ° C.

The X-ray diffraction pattern shows that all reaction products have a UZM-5 structure. The characteristic lines found on the x-ray obtained for a sample kept at 150 ° C for 4 days are shown in Table 5. Scanning electron microscopy shows that the sample, being very homogeneous, consists of small rosettes similar to plate crystals with values parameters for measuring outlets from 0.5 to 2 microns wide. The BET surface area for this product is 553 m / g with a micropore volume of 0.22 cm / g. Elemental analysis shows the following ratios: Si / Al = 5.97, Na / Al = 0.19, N / A1 = 0.97, and C / N = 5.59. The characteristic lines found on the x-ray obtained for this product are presented in Table 5.

Table 5 2-θ d (Å) I / I ₀ % 6.16 14.33 m 7.76 11.39 s 10.12 8.73 m 11.82 7.48 m 15.74 5.63 vs 04/19 4.66 m 20.36 4.36 w 21.84 4.07 m 22.68 3.92 s 23.56 3.77 vs 26.18 3.40 w 02.27 3.30 m 29.98 2.98 m 31.32 2.85 m 12/33 2.70 m 44.10 2.05 w

Example 6

The aluminosilicate reaction mixture is obtained by performing the following procedure: 987.54 g of sec-butoxide of aluminum (95 +%) is added with vigorous stirring to 14058 g of TEAOH (35%), then 4954 g of colloidal silicon dioxide of the brand Ludox AS-40 is additionally introduced. The reaction mixture was kept, stirring at a temperature of 95 ° C for 16 hours. After aging, the resulting reaction mixture was found to contain 4.72% Si. This aluminosilicate reaction mixture was identified as Mixture D and used again in Example 9. A portion of Mixture D, in an amount of 47.01 g, was placed in a beaker equipped with a stirrer. Separately, a solution is obtained by dissolving 1.12 g of TMACI (97%) in 1.87 g of deionized water. While stirring the aluminosilicate reaction mixture, a TMACI solution was added and the resulting mixture was then homogenized for 20 minutes. Then the reaction mixture was placed in a Parra autoclave with a volume of 100 ml with a stirrer. The temperature of the reaction mixture was changed from room temperature to 150 ° C. over a period of 3 hours, and then the mixture was kept at 150 ° C. for 24 hours. Then the reaction mixture is maintained at autogenous pressure. The solid reaction product is isolated by centrifugation, washed with deionized water and dried at a temperature of 100 ° C.

The X-ray diffraction pattern of the product indicates that the sample has a UZM-5P structure. The characteristic lines found in the x-ray obtained for this product are shown in Table 6. below. A reaction mixture of the same composition, but aged for 72 hours instead of 24 hours, leads to a well crystallized product UZM-5. The morphology of UZM-5P is a plate-like crystals having submicron sizes, as determined by scanning electron microscopy. Elemental analysis shows the following ratios: Si / Al = 6.0, N / Al = 1.00 and C / N = 6.07.

Table 6 2-θ d (Å) I / I ₀ % 6.16 14.33 vs 7.62 11.60 m 10.26 8.61 s 16.23 5.46 m 06/19 4.65 m 22.86 3.89 vs 30.38 2.94 m 44.22 2.05 w

Example 7

A UZM-5P composition similar to that disclosed in Example 6 is prepared as follows: 40 g of mixture C (see Example 5) is used as a source of aluminum and silicon and placed in a beaker equipped with a stirrer. Separately, 0.92 g of TMACI (97%) is dissolved in 40 g of deionized water. This solution was added to Mix C with vigorous stirring. After stirring for 20 minutes, the reaction mixture was placed in a Teflon-lined autoclave and kept at 150 ° C for 4 days under autogenous pressure. Solid products are isolated by centrifugation, washed with deionized water and dried at a temperature of 95 °.

The X-ray diffraction pattern of the product indicates the presence of a UZM-5P structure. The characteristic lines found on the x-ray obtained for this product are presented in Table 7. Elemental analysis shows that the product has the following ratios: Si / Al = 6.03, N / Al = 1.07 and C / N = 6.11. Scanning electron microscopy shows that the sample consists of clusters of curved plate-shaped crystals that form rosettes with a size of 400-800 nm in width.

Table 7 2-θ d (Å) I / I ₀ % 5.80 15.23 s 7.77 11.37 m 10.22 8.65 m 11.66 7.58 m 16.15 5.48 m 21.93 4.05 w 22.84 3.89 m 23.54 3.78 vs 30.00 2.98 w 33.02 2.71 w 44.04 2.05 w

Example 8

The aluminosilicate reaction mixture was prepared as follows: TEAOH (35%), 846.25 g diluted with 876.65 g of deionized water. 49.54 g of Al (O-secBu) ₃ (95 +%) was added to the hydroxide solution with vigorous stirring, then additionally TEOS (98%), 427.57 g. After 2 hours, the homogenized reaction mixture was placed in a flask and kept at a temperature of 75 ° C. with gentle stirring overnight. After aging, the flask is equipped with a reflux condenser and some alcohol hydrolysis products are distilled off. After removal of solvent, the reaction mixture contains 3.34% Si. A portion of the aluminosilicate reaction mixture weighing 1200 g is placed in a beaker equipped with a high-speed stirrer. Separately, a solution is obtained by dissolving 15 g of TMACI (97%) in 30 g of deionized water. This solution is pinned to the aluminosilicate reaction mixture and then homogenized for half an hour. The reaction mixture is then placed in a Parra 2 liter static autoclave equipped with a Teflon lining. The reaction mixture was kept at a temperature of 150 ° C for 90 hours at autogenous pressure. The solid product is isolated by centrifugation, washed with deionized water and dried at a temperature of 95 ° C.

The X-ray diffraction pattern of the product shows that it has a UZM structure in which the most noticeable peaks are observed at d = 8.68 Å and 3.89 Å. Elemental analysis shows that the ratio Si / Al = 10.05, the surface area is 601 m ² / g and the micropore volume is 0.21 cm ³ / g. Scanning electron microscopy shows that the product consists of uniform clusters of plate-like crystals forming a socket, which have a diameter of 0.25 to 0.5 microns. The characteristic lines found on the x-ray obtained for a sample of this product are presented in Table 8 below.

Table 8 2-θ d (Å) I / I ₀ % 7.58 11.65 m 10.18 8.68 m 16.36 5.41 m 22.84 3.89 m 23.60 3.77 vs

Example 9

A number of zeolites are obtained under conditions similar to the conditions for the preparation of zeolite described in Example 6. 47.01 g of mixture D are placed in a beaker (see Example 6) and 1.12 g of a TMACI solution (97%) in 1.87 g of deionized water is added to it with stirring. The resulting mixture was homogenized for 20 minutes, and then transferred to a Parra autoclave with a volume of 100 ml with a stirrer. Four other mixtures are obtained in a similar way, the mixture is heated to a temperature of 150 ° C and kept at a temperature of 150 ° C for 12 hours, 18 hours, 24 hours, 36 hours and 72 hours at autogenous pressure. Each solid reaction product is isolated by centrifugation, washed with deionized water, and then dried at a temperature of 100 ° C.

The X-ray data obtained for the five samples are presented in Table 9. The data show that additional spectral lines are observed in the case of an increase in the exposure time in the autoclave. It is clear that peaks at d≈8.6 Å and d≈3.9 Å (in bold) are common to all synthesized products, i.e. structures.

Without relying on any particular theory, the following explanation was proposed. UZM-5 can be indexed as a tetragonal cell with a≈12.4 Å and с≈28.6 Å. The 8.6 Å and 3.9 Å peaks located on tetragonal cells have indices 110 and 310, respectively. This suggests that the distribution first appears in the a and b directions, and then in the c direction. It seems that a large number of structures can be obtained by stopping the reaction at various times up to 36 hours, when the formation of the UZM-5 structure is achieved. By stopping the synthesis at different times, it is possible to obtain zeolites with different surface areas, acidity and adsorption properties.

Example 10

The aluminosilicate reaction mixture was prepared as follows: 116.09 g of Al (Osec-Bu) ₃ (95 +%) was added to 1983.17 g of TEAOH (35%) and 1.86 g of deionized water with vigorous stirring. Then, while stirring, 698.88 g of Ludox AS-40 are added. After an hour, the homogenized aluminosilicate reaction mixture was placed in several Teflon vessels and kept at a temperature of 95 ° C for 3 days. After the aging step, elemental analysis shows that the mixture contains 5.01% Si and has a Si / Al ratio of 10.03. This reaction mixture is designated as Mixture E. A portion of this aluminosilicate reaction mixture, in an amount of 40.0 g, is placed in a beaker, where it is vigorously stirred. Separately, 0.78 g of TMACI (97%) was dissolved in 15.0 g of deionized water. This solution is pinned to a stirred aluminosilicate reaction mixture. The mixture then gives an opportunity to homogenize within an hour. The reaction mixture is then placed in a Teflon-lined autoclave and kept at 150 ° C. for 6 days under autogenous pressure. The solid product is isolated by centrifugation, washed with deionized water and dried at a temperature of 95 ° C.

The product, according to x-ray data, has a UZM-6 structure. Scanning electron microscopy (SEM) shows that the product consists of plate-shaped crystals 0.1-0.4 microns wide and less than 0.05 microns thick. The Si / Al ratio for the product UZM-6 in accordance with the data of elemental analysis is 8.34. The surface area of the BET sample is 520 m ² / g with a micropore volume of 0.21 cm ³ / t. The characteristic lines found on the x-ray obtained for the sample are presented in Table 10.

Table 10 2-θ d (Å) I / I ₀ % 6.14 14.38 m 7.76 11.38 m 10.12 8.73 m 11.82 7.48 m 15.68 5.65 S 16.30 5.43 m 18.98 4.67 m 20.32 4.37 w 21.86 4.06 m 22.42 3.96 s 22.78 3.90 m 23.68 3.75 vs 25.24 3.53 w 26.28 3.39 w 26.88 3.31 m 27.34 3.26 m 29.64 3.01 m 08/30 2.97 w 31.44 2.84 w 33.20 2.70 w 44.14 2.05 w

Example 11

The aluminosilicate reaction mixture is obtained under conditions identical to the conditions for obtaining the Mixture E described in Example 10. However, the resulting reaction mixture according to the analysis is slightly different in its characteristics: Si content = 4.79% by weight. and the ratio Si / Al = 9.59. A portion of this aluminosilicate reaction mixture, in an amount of 1100 g, is placed in a large beaker equipped with a high-speed stirrer. Separately, a solution of 4.14 g of LiCI and 21.43 g of TMACI (97%) in 65 g of deionized water is obtained. This solution is pinned to the aluminosilicate reaction mixture with stirring and homogenized for one hour. The reaction mixture is then transferred to a static Parr reactor with a volume of 2 l and kept at a temperature of 150 ° C for 3 days at autogenous pressure. The solid product is isolated by filtration, washed with deionized water and dried at a temperature of 95 ° C.

According to x-ray data obtained on the powder, the product has the structure of UZM-6. The Si / Al ratio is 7.58. The surface area is 512 m ² / g, the micropore volume is 0.18 cm ³ / g. The SEM of the calcined product shows that it consists of curved plate crystals, sometimes folded to 0.1-0.4 microns wide and less than 0.05 microns thick. The characteristic lines found on the x-ray obtained for the sample are presented in Table 11.

Table 11 2-θ d (Å) I / I ₀ % 6.28 07/14 m 7.84 11.27 s 10.22 8.65 m 11.92 7.42 m 15.93 5.56 m 18.98 4.67 m 21.98 4.04 w 22.52 3.95 vs 22.92 3.88 m 23.76 3.74 vs 26.33 3.38 w 26.92 3.31 m 31.36 2.85 m 33.26 2.69 m 44.24 2.05 w

Example 12

Zeolites are known to provide various hydrocarbon conversion processes and are of great utility in this regard. This example demonstrates the ability of zeolites UZM-5, UZM-5P and UZM-6 to convert heptane into a number of products. Calcined samples of these products and, for comparison, Y vapor resistant zeolite (SSY) are tested in a microreactor operating at atmospheric pressure. Sample UZM-5 from Example 5 and sample UZM-6 from Example 11 are subjected to ammonium ion exchange after calcination to remove alkali and obtain the zeolite in acid form. The feedstock is heptane, saturated at a temperature of 0 ° C H ₂ . The catalyst charge is 250 mg per 40-60 mesh particles. Samples are pretreated with H ₂ at a temperature of 550 ° C for 60 minutes. The feed is introduced at a constant flow rate of 125 cm ³ / min. The products are hydrogenated before being sent to a gas chromatograph. In this variable temperature regime, the product stream is taken at the following temperature / time ratios in the stream: 25 ° C / 0 hours, 450 ° C / 0.33 hours, 500 ° C / 1.10 hours and 1.45 hours and 550 ° C / 2.20 hours and 2.55 hours . The selectivity for the main products for each sample is given in Table 12, the latest data are given for the sampling point at a temperature of 550 ° C. The data show that UZM-5 and UZM-5P are comparable to SSY in their ability to provide heptane conversion, while it is clear that UZM-6 is much more active than SSY in providing heptane conversion. UZM-6 shows a much greater ability to provide the conversion of aromatic compounds than other catalysts.

Table 12 Sample SSY Example 1 UZM-5 Example 5 UZM-5 Example 8 UZM-5P Example 11 UZM-6 Temperature 550 ° C 550 ° C 550 ° C 550 ° C 550 ° C Flow time (hours) 2.55 2.55 2.55 2.55 2.55 Methane 0.58 1.35 1.67 0.44 3.27 Ethane 3.21 3.90 5.33 1.78 10.22 Propane 17.14 17.15 22.98 8.69 30.88 Isobutane 9.9 5.12 7.04 4.61 14.23 n-butane 8.61 8.40 10.25 5.13 11.35 Isopentane 1.72 1.16 1.43 1.37 1.52 n-Pentane 1.18 1.24 1.45 0.65 1.26 Benzene 0.19 0.12 0.29 0.17 1.66 Heptane 55.58 60.73 48.31 75.98 19.9 Toluene 1.75 0.46 0.88 0.75 4.19

Example 13

Another distinguishing feature of zeolites is their ability to adsorb molecules into their micropores. Such properties ensure the suitability of zeolites for adsorption, separation, and as a selective catalyst. Adsorption is evaluated using standard Mac Bain-Bakr gravimetric adsorption apparatus. Samples are calcined at 560 ° C to remove organic impurities before being loaded into tubes. They are then activated at 350 ° C. overnight to remove adsorbed water from the pores. Then the samples are exposed to gas at several specific partial pressures and the amount of adsorbed gas is expressed in units of mass percent of the sample. The data presented in the tables below demonstrate the ability of UZM-5 and UZM-5P to adsorb n-butane, isobutane, O ₂ , and SF ₆ .

Adsorption of O ₂ (T = -183 ° C) R / ro Example 1 Example 5 Example 8 (Partial UZM-5 UZM-5 UZM-5P pressure) % weight O ₂ % weight O ₂ % weight O ₂ 0.13 24.8 26.1 17.4 0.39 28.3 28.7 25.4 0.92 37.1 34.2 39.2 Adsorption of n-butane T = 22 ° C R / ro Example 1 Example 5 Example 8 (Partial UZM-5 UZM-5 UZM-5P pressure) % weight nC ₄ N ₁₀ % weight n-C ₄ H ₁₀ % weight n-C ₄ H ₁₀ 0.04 7.9 9.4 4.6 0.12 9.6 11.0 7.1 0.30 11.7 12.7 11.4

Isobutane Adsorption T = 22 ° C R / ro Example 1 Example 5 Example 8 (Partial UZM-5 UZM-5 UZM-5P pressure) % weight iC ₄ H ₁₀ % weight iC ₄ H ₁₀ % weight iC ₄ H ₁₀ 0.04 1.7 1.5 3.1 0.12 2.6 2.0 5.7 0.30 4.1 2.8 9.3 Adsorption of SF ₆ T = 22 ° C R / ro Example 1 Example 5 Example 8 (Partial UZM-5 UZM-5 UZM-5P Pressure) % the weight. Sf ₆ % the weight. Sf ₆ % the weight. Sf ₆ 0.92 3.3 1.8 5.6

Example 14

Another way to study the adsorption properties is to use TGA or Thermal gravimetric analysis. In such devices, data on adsorption at elevated temperatures can easily be obtained, just as the release of adsorption gases is controlled. This is especially convenient for larger, less volatile adsorbates, which are more easily studied and processed at higher temperatures. The tests are carried out on calcined samples. Approximately 50 mg of the sample is placed in a TGA sample holder. Then the sample is activated for 2 hours at a temperature of 500 ° C in a stream of N ₂ at a speed of 127 cm ³ / minute. After pre-treatment, the temperature of the sample was brought to 120 ° C and diluted with additional raw materials consisting of N ₂ saturated with cis-1,2-dimethylcyclohexane at a temperature of 25 ° C, with a flow rate of 72 cm / min. Therefore, the total flow rate passing through the sample is 200 cm ³ / min. The adsorption of cis-1,2-dimethylcyclohexane is then monitored by TGA at a temperature of 120 ° C for an additional 250 minutes. Adsorption of cis-1,2-dimethylcyclohexane after 5 and 250 minutes is presented in units of% of the mass. sample in Table 14. The table shows that UZM-6 adsorb the total amount of cis-1,2-dimethylcyclohexane much more easily than UZM-5.

Table 14 Adsorption of cis-1,2-dimethylcyclohexane (DMC), T = 120 ° C Example 1, UZM-5% of the mass. CIS 1,2-DMC Example 10, UZM-6% of the mass. CIS 1,2-DMC 5 minutes 0.59 2.08 250 minutes 1.18 2.59

Example 15

Samples obtained in examples 1-3 were tested for alkylating activity in the method of disproportionation of ethylbenzene. Before testing, the products were converted to H ⁺ form. UZM-6 obtained in example 3 was calcined in air at a temperature of 350 ° C for 1.5 hours, at a temperature of 450 ° C for 1.5 hours and at a temperature of 580 ° C for 7 hours and carried out ion exchange three times with ammonium chloride at a temperature of 80 ° C for 2 hours. UZM-6 obtained in Example 2 was calcined at a temperature of 520 ° C for an hour in N ₂ , then for 19 hours in air. UZM-5 obtained in Example 1 was calcined at a temperature of 520 ° C for 10 hours. The calcined samples were sorted up to 40-60 mesh and loaded (250 mg) into a quartz tube (11 mm inner diameter) reactor located in the furnace. The outlet pressure of the reactor input was equal to atmospheric pressure. Samples were pretreated at a temperature of 250 ° C in a stream of N ₂ . The temperature was reduced to 150 ° C, and then the feed was supplied. The feed consisted of a stream of N ₂ passing through an ethylbenzene saturator, maintained at a temperature of 0 ° C, and a stream of N ₂ directed at a speed of 150 cm ³ / minute. While the flow rate remained constant, the sample was exposed to raw materials and the reaction products were investigated at a temperature of 150 ° C, 150 ° C, 125 ° C, 175 ° C, 200 ° C, 230 ° C and 175 ° C. Waste products were analyzed by online gas chromatography to measure activity and selectivity. The results of the study of products at a second temperature of 150 ° C and a temperature of 230 ° C are presented in Table 15.

Table 15 UZM-5 Example 1 UZM-6 Example 2 UZM-6 Example 3 Temperature (° C) 150 230 150 230 150 230 Flow rate (cm ³ / min) 150 150 150 150 150 150 Methane / ethane 0.02 0 0.03 0.06 0 0.08 C ₄ 0 0 0.02 0.07 0.1 0.11 Benzene 0.09 0.18 0.39 1.21 0.64 2.63 Ethylcyclohexane 0 0 0 0 0 0 Toluene 0 0 0.04 0.04 0.04 0.05 Ethylbenzene 99.72 99.46 98.69 96.02 97.86 91.97 p-xylene 0 0 0 0 0 0 m-xylene 0 0 0 0 0 0 o-xylene 0 0 0 0 0 0 1E4MBZ 0 0 0 0 0 0 1E3MBZ 0 0 0 0 0 0 1E2MBZ 0 0 0 0 0 0 13DEBZ 0.09 0.22 0.41 1.63 0.76 3.24 14DEBZ 0.08 0.13 0.4 0.82 0.55 1.6 12DEBZ 0 0 0.03 0.15 0.05 0.28 14DIPBZ 0 0 0 0 0 0.02 135TEBZ 0 0 0 0 0 0 124TEBZ 0 0 0 0 0 0 EV CONV 0.28 0.54 1.31 3.98 2.14 8.03

Example 16

This example demonstrates the ability of UZM-6 to catalyze the synthesis of ethylbenzene from benzene and ethylene. The zeolite obtained in Example 3 is protonated in the same manner as in Example 15. The zeolite is then bonded to Plural SB grade alumina in the composition of 70% zeolite / 30% alumina formed in the form of an extrudate of 1/16 '' diameter. The extrudates are then calcined at 550 ° C. for 2 hours. In the test, a 7/8 '' diameter stainless steel reactor is used, into which 40 cubic centimeters of catalyst are loaded. Benzene and ethylene are mixed online in a ratio of 3/1 benzene / ethylene, and then preheated before entering the reactor. LHSV brand olefin is added at a rate of 0.45 hours ^-1 . The test is conducted with recycle of the effluent to control the free olefin at the inlet of the reactor. The reaction is carried out at 500 psi. Data on activity and selectivity are recorded at temperatures of 200 ° C and 230 ° C. Selectivities for alkylated products are shown in Table 16.

Table 16 Synthesis of ethylbenzene in the presence of UZM-6 Flow time 60 271 Inlet temperature 200 ° C 230 ° C Ethylbenzene 80.31 74.95 Diethylbenzenes 16.26 19.95 Triethylbenzenes 2.46 3.92 Tetraethylbenzenes 0.22 0.37 Alkylated Products 99.25 99.19

Example 17

The aluminosilicate reaction mixture was obtained under conditions identical to the conditions for the preparation of Mixture B described in Example 3. Nevertheless, as analysis showed, the obtained reaction mixture slightly differed in its characteristics: Si content = 4.79% by weight. and the ratio Si / Al = 9.59. A portion of the obtained aluminosilicate reaction mixture, in an amount of 1100 g, is placed in a large beaker equipped with a high-speed stirrer. Separately, a solution of 4.14 g of LiCI and 21.43 g of TMACI (97%) in 65 g of deionized water is obtained. This solution was added dropwise with stirring to the aluminosilicate reaction mixture and homogenized for one hour. The reaction mixture is then transferred to a static Parr reactor with a volume of 2 l and kept at a temperature of 150 ° C for 3 days at autogenous pressure. The solid product is filtered off, washed with deionized water and dried at 95 ° C.

X-ray powder diffraction shows that the obtained data are consistent with the data known for the UZM-6 structure. The Si / Al ratio is 7.58. The surface area of the BET is 512 m ² / g, the micropore volume is 0.18 cm ³ / t. SEM of the calcined product shows that it consists of curved plate-like crystals, sometimes stacked up to 0.1-0.4 microns wide and less than 0.05 microns thick. The characteristic lines found on the x-ray obtained for the sample are presented in Table 17.

Table 17 2-θ d (Å) I / I ₀ % 6.28 07/14 m 7.84 11.27 s 10.22 8.65 m 11.92 7.42 m 15.93 5.56 m 18.98 4.67 m 21.98 4.04 w 22.52 3.95 vs 22.92 3.88 m 23.76 3.74 vs 26.33 3.38 w 26.92 3.31 m 31.36 2.85 m 33.26 2.69 m 44.24 2.05 w

Example 18

The zeolites obtained in examples 1-3 and 17 are tested for their ability to isomerize xylene. Before checking the products are converted into acid form. The product obtained in accordance with the method described in Example 1 was tested after calcination for 5 hours at a temperature of 550 ° C. This sample is designated as UZM-5 in Example 1. Before calcination at 550 ° C. for 5 hours, part of the same product is washed with acid (9 g of sample, 2 g of H2S04 (98%) in 60 g of deionized water, at a temperature of 90 ° C, for 2 hours), then washed with water and conduct ammonium ion exchange (1N NH ₄ CI, at a temperature of 90 ° C, for 1.5 hours). This sample is designated as UZM-5 from Example 1-AW. The product of Example 2 is calcined at 550 ° C for 5 hours, ammonium ion exchange (1N NI-UCI, 75 ° C) is carried out three times and then calcined at 550 ° C for 2 hours. This sample is designated as UZM-5, Example 2. UZM-6 from Example 3 is calcined in an atmosphere of N ₂ for an hour and 19 hours in air at a temperature of 520 ° C and designated as UZM-6, Example 3. UZM-6 from Example 17 is obtained in protonated form by calcination at a temperature of 350 ° C for 1.5 hours, then at a temperature of 450 ° C for 1.5 hours and at a temperature of 580 ° C for an hour in an atmosphere of N ₂ , then it is calcined for 6 hours on in the air. Then, for 85 g of the calcined product, ion exchange is carried out three times in 2 L of a 10% NH ₄ CI solution at a temperature of 80 ° C for 2 hours. Finally, the sample is calcined for 2 hours at a temperature of 500 ° C in air. This sample is designated as UZM-6, Example 17. For testing in a small reactor, the samples are sorted by size 40-60 mesh and activated in a muffle furnace in an air stream at a temperature of 550 ° C for 2 hours. Sifted samples, in an amount of 125 mg, are loaded into a quartz reactor with an internal diameter of 11 mm in the furnace; the outlet of the reactor is at atmospheric pressure. Samples are preheated to a temperature of 375 ° C in a stream of H ₂ . The H ₂ stream is then directed through a saturator, where it is saturated with either m-xylene or o-xylene at 0 ° C. The stream of H ₂ direct with a speed of 50 cm ³ / minute. The furnace temperature is then stepwise changed, setting the following temperature values: 375 ° C, 400 ° C, 425 ° C, 450 ° C, 475 ° C and 425 ° C. Exiting products at each temperature are routinely sent for gas chromatography to measure activity and selectivity. The m-xylene and o-xylene isomerization data are shown in Tables 18a and 18b, respectively.

Table 18A M-xylene isomerization data Isomerization of m-xylene UZM-5 Example 1 UZM-5 Example 1-AW Temperature (° C) 375 425 475 375 425 475 Flow rate (cm ³ / min) fifty fifty fifty fifty fifty fifty Methane 0.05 0.21 0.23 0.17 0.22 0.21 Benzene 0.09 0.09 0.1 0.1 0.1 0.1 Toluene 0.78 0.57 0.51 1.18 0.9 0.92 Ethylbenzene 0 0 0 0 0 0 p-xylene 20.69 24.27 24.36 12/24 24.14 23.97 m-xylene 62.58 54.19 51.78 53.92 51.57 50.95 o-xylene 06/15 20.45 22.77 19.25 22.15 22.93 135TMBZ 0.18 0 0 0.31 0.22 0.21 124TMBZ 0.5 0.22 0.24 0.83 0.6 0.6 123TMBZ 0.07 0 0 0.11 0.09 0.1 1235TTMBZ 0 0 0 0 0 0 1234TTMBZ 0 0 0 0 0 0 1245TTMBZ 0 0 0 0 0 0 Common Unknowns 0 0 0 0 0 0 M-xylene Conversion 37.42 45.81 48.22 46.08 48.43 49.05 Temperature (° C) 375 425 475 375 425 475 Flow rate (cm ³ / min) fifty fifty fifty fifty fifty fifty Methane 0.12 0.16 0.18 0.12 0.32 0.65 Benzene 0.12 0.1 0.12 0.14 0.12 0.22 Toluene 8.06 5.53 5.3 10.57 6.76 9.08 Ethylbenzene 0 0 0 0 0 0 p-xylene 19.85 21.31 21.49 18.41 20.7 19.21 m-xylene 43.21 45.63 45.56 40.01 44.27 40.89 o-xylene 09/18 19.89 20.55 16.81 19.33 18.51 135TMBZ 2.56 1.75 1.55 3.35 2.01 2.51 124TMBZ 6.57 4.67 4.33 8.55 5.37 6.97 123TMBZ 0.92 0.7 0.69 1.2 0.8 1.11 1235TTMBZ 0.25 0.14 0.13 0.4 0.18 0.3 1234TTMBZ 0.06 0 0 0.09 0 0.08 1245TTMBZ 0.2 0.11 0.1 0.32 0.13 0.22 Common Unknowns 0 0 0 0 0 0.25 M-xylene conversion 56.69 54.37 54.44 59.99 45.73 59.11

Table 18B. O-Xylene Isomerization Data O-xylene isomerization UZM-5 Example 1-AW UZM-5 Example 2 Temperature (° C) 375 425 475 375 425 475 Flow rate (cm ³ / min) fifty fifty fifty fifty fifty fifty METHANE 0.00 0.00 0.00 0.00 0.00 0.00 ETHANE 0.06 0.07 0.20 0.09 0.13 0.19 PROPANE 0.00 0.00 0.00 0.00 0.00 0.00 Ethylcyclohexane 0.11 0.10 0.07 0.11 0.09 0.00 BENZENE 0.13 0.13 0.13 0.15 0.15 0.16 TOLUENE 0.12 0.13 0.22 0.29 0.34 0.50 ETHYLBENZENE 0.00 0.00 0.00 0.12 0.11 0.10 P-XYLOL 6.18 14.60 20.61 14.19 04/21 06/23 m-XYLOL 30.68 43.71 49.52 45.15 50.51 51.16 o-XYLOL 62.55 41.06 29.00 39.52 27.19 09/24 135-TM-BENZENE 0 0 0 0.10 0.12 0.17 124-TM-BENZENE 0 0 0 0.28 0.31 0.47 123-TM-BENZENE 0.13 0.19 0.25 0.00 0.00 0.08 1245-TETPAM-BENZ 0 0 0 0.00 0.00 0.00 1235-TETPAM-BENZ 0 0 0 0.00 0.00 0.00 1234-TETPAM-BENZ 0 0 0 0.00 0.00 0.00 O-xylene conversion 37.45 58.84 71.00 60.48 72.81 75.91

Claims (18)

1. Microporous crystalline zeolite having a composition on an anhydrous basis, expressed through the molar ratios of the elements:

where M is at least one ion exchange cation selected from the group consisting of alkali and alkaline earth metals, m is a molar ratio of M to (Al + E) and varies from 0 to 1.2, R is a nitrogen-containing organic cation selected from the group consisting of protonated amines, protonated diamines, protonated alkanolamines, quaternary ammonium ions, double quaternary ammonium ions, quaternary alkanolamines and mixtures thereof, r is a molar ratio of R to (Al + E) and co ranges from 0.25 to 3.0, E represents an element selected from the group consisting of Ga, Fe, B, Cr, In and B, x represents the molar fraction of E and varies from 0 to 0.5, n is the weight average valency value of M and has a value from +1 to +2, p is the weight average valency value and has a value from +1 to +2, y is the molar ratio of Si to (Al + E) and varies from 5 to 12 and z is the molar ratio of O to (Al + E) and has a value determined by the equation: z = (mn + rp + 3 + 4y) / 2, The zeolite is characterized in that it has at least two peaks in the X-ray diffraction pattern: one with a d-distance of 3.9 ± 0.12 Å and one with a d-distance of 8.6 ± 0.20 Å. 2. The zeolite according to claim 1, characterized in that it has an X-ray powder diffraction pattern that has at least the d-distance and relative intensities given in one of the tables from A to C. 3. The zeolite according to claim 1 or 2, where M is at least one of the metals selected from the group consisting of lithium, cesium, sodium, potassium, strontium, barium, calcium, magnesium, and R is a quaternary ammonium cation . 4. The method of producing microporous crystalline zeolite according to any one of claims 1 to 3, which includes the formation of a reaction mixture containing chemically active sources of R, Al, Si and optionally E and / or M and the reaction of the reaction mixture having a composition expressed in units molar ratios of oxides: aM _{2 / n} 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 to 2, b has a value from 1.5 to 30, c has a value from 0 to 0.5, d has a value from 5 to 30 and e has a value from 30 to 6000 under reactive conditions, which include temperature from 100 ° C to 175 ° C for a period of time from 12 hours to 2 weeks. 5. The method according to claim 4, where the source E is selected from the group consisting of alkaline borates, boric acid, precipitated gallium oxyhydroxide, gallium sulfate, ferric chloride, chromium chloride, chromium nitrate, indium chloride and indium nitrate. 6. The method according to claim 4, where the aluminum source is selected from the group consisting of isopropoxide aluminum, sec-butoxide aluminum, precipitated alumina, Al (OH) ₃ , aluminum metal and aluminum salts. 7. The method according to claim 4, where the reaction conditions include a temperature of from 140 ° C to 160 ° C for a period of time from 2 days to 5 days. 8. The use of a microporous crystalline zeolite according to any one of claims 1 to 3 in a hydrocarbon conversion process comprising contacting a hydrocarbon stream with a microporous crystalline zeolite under conditions of a hydrocarbon conversion to form a conversion product. 9. The method of isomerization of a nonequilibrium initial mixture containing xylenes and ethylbenzene, comprising contacting the initial mixture in the presence of hydrogen in the isomerization zone with a catalytic composition containing an effective amount of at least one component representing a platinum group metal and a crystalline aluminosilicate zeolite according to any one of claims 1-3 under the conditions of the isomerization process to obtain an isomerization product containing p-xylene in a larger ratio than in the initial mixture. 10. The method according to claim 9, where the component, which is a metal of the platinum group, is present in an amount of from 0.01 to 5 wt.% In the calculation of the elemental composition. 11. The method according to claim 9, where ortho-xylene is isolated from the product of isomerization and / or fresh raw mix. 12. The method according to claim 9, further comprising isolating para-xylene by selective adsorption from the isomerization product and fresh feed mixture. 13. The method according to claim 9, where the conditions of the isomerization process include a temperature of from 100 ° C to 500 ° C, a pressure of from 1 to 50 atmospheres and an hourly average fluid flow rate of from 0.5 to 10 h ^-1 . 14. The method of monoalkylation of aromatic compounds, comprising reacting an olefin with an alkylated aromatic compound in the presence of a catalyst containing a crystalline aluminosilicate zeolite according to any one of claims 1 to 3, to obtain an alkylated compound. 15. The method according to 14, where the olefin contains from 2 to 20 carbon atoms. 16. The method according to 14, which is carried out at least partially in liquid phase conditions. 17. A method of producing cumene by alkylation of benzene with propylene, comprising reacting propylene with benzene at a temperature selected in the range of 90 ° C-200 ° C, under a pressure sufficient to maintain at least partially the liquid phase in the presence of a catalyst containing crystalline aluminosilicate zeolite according to any one of claims 1 to 3. 18. A transalkylation process comprising reacting a polyalkylated aromatic compound with a non-alkylated aromatic compound, wherein at least one alkyl group moves from the polyalkylated aromatic compound to the non-alkylated aromatic compound in the presence of the microporous crystalline zeolite according to any one of claims 1 to 3, under reaction conditions transalkylation.