RU2340552C2 - Uzm-16: crystalline alumo-silicate zeolite material - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: microporous crystalline zeolite and its substituted version designated UZM-16 have been synthesized. Said zeolites are obtained by means of benzyltrimethylammonium cation (BzTMA) or combination of (BzTMA) with one other quaternary ammonium cation. Said zeolites have structure related to structure of offretite, but demonstrate structural and other differences. Zeolites UZM-15 can be dealuminated with formation of zeolites UZM-16HS, which have different acidity, porosity and ion-exchange properties.

EFFECT: obtained products ate efficient in different processes of hydrocarbon conversion.

9 cl, 3 tbl, 2 dwg, 3 ex

Description

State of the art

The present invention relates to an aluminosilicate zeolite material identified as UZM-16. This material can be dealuminated with the formation of UZM-16HS, which allows to obtain materials with different acidity, porosity and ion-exchange properties. UZM-16 and UZM-16HS can be used in hydrocarbon conversion processes.

Zeolites are aluminosilicate compositions that are microporous and which are formed from common angles of AlO ₂ and SiO ₂ tetrahedra. Numerous zeolites, both of natural origin and synthetically prepared, are used in various industrial processes. Synthetic zeolites are prepared by hydrothermal synthesis using suitable sources of Si, Al, as well as structuring agents such as alkali metals, alkaline earth metals, amines, or organosubstituted ammonium cations. Structuring agents are located in the pores of the zeolite and are largely responsible for the resulting concrete structure. These agents compensate the aluminum charge of the lattice and can also play the role of spatial fillers. Zeolites are characterized by uniform sizes of feather holes, having a significant exchange capacity and the ability to reversibly desorb the adsorbed phase, which is dispersed along the internal voids of the crystal without significant displacement of any atoms that make up the constant structure of the zeolite crystal. Zeolites can be used as catalysts for the conversion of hydrocarbons, which is carried out both on the outer surfaces and on the inner surfaces inside the pore.

A synthetic zeolite called zeolite T was obtained in the Na, K system and disclosed by Breck and Acara in US-A-2950952. A subsequent crystallographic study using electron diffraction (J.M. Bennett and J.A. Guard, Nature, 214, 1005 (1967)) revealed differences and uniqueness of the lattices of offretite and erionite, classifying zeolite T as an intergrowth of two structures. A synthetic zeolite with an offretite structure that does not contain fused erionite was obtained in the systems Na, K, TMA and K, TMA (R. Aiello and R. Barrer, J. Chem. Soc. (A), 1470, (1970)). Rubin and Rosinsky were able to obtain erionite-related material in the benzyltrimethylammonium system (BzTMA), Na, K (US-A-3699139). In the same system, an offretitis sample was prepared that did not have X-ray diffraction lines related to erionite (M.L. Ocelli, R. A. Innes, S. S. Pollack, and J. V. Sanders, Zeolites, 7, 265 (1987)). The electron diffraction study of offretite, erionite and offretite-erionite structures obtained by synthesis, including six organic matrix systems, including BzTMA, characterize many types of defects that arise in this system (JVSanders, MLOccelli, RAInnes, SSPollack, Studies in Surface Sciences and Catalysis, Ed. Y. Murakami, A. Iijima, and JWWard, Elsevier, New York, 28, 429 (1986)).

In the present work, the applicants obtained zeolite designated UZM-16, which has some similarities with offretitis, but also has significant differences, which makes it a unique new structure. UZM-16 can be obtained in the system of benzyltrimethylammonium (BzTMA) with a small amount of added potassium. The X-ray diffraction pattern is similar to the x-ray of offretitis, without having lines associated with erionite, but which contains a broad line in the spectrum with a center at d = 21.5 Å, which includes unresolved peaks located between d = 18 to 27 Å. This feature is observed in the electron diffraction diagrams of crystals and in the form of interference fringes in images of high-resolution gratings. In addition, in the electron diffraction diagrams (electron diffraction patterns) of UZM-16, a unique periodicity is observed observed in the a-b plane, which is not known for offretitis and erionite. UZM-16 is more mesoporous than offretite.

Brief Description of the Drawings

Figure 1 represents the electron diffraction pattern of offretitis (figa) and UZM-16 (figv) from example 1, each of which is taken along the plane [110].

Figure 2 is an image of a lattice obtained using high resolution electron microscopy for UZM-16 from example 1.

The implementation of the invention

Applicants synthesized a new family of zeolites designated UZM-16. In its freshly synthesized form, UZM-16 zeolite has a composition represented by the formula based on the anhydrous form:

where M is an exchangeable 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, but potassium and sodium are preferred. The value "m", which represents the molar ratio of M to (Al + E), varies from 0 to 0.75. R denotes a benzyltrimethylammonium cation (BzTMA) or a combination of BzTMA with at least one organosubstituted cation from the group consisting of quaternary ammonium cations, protonated amines, protonated diamines, protonated alkanolamines, dimertinate quaternary ammonium cations, and quaternized mixtures. The value of "r", which represents the molar ratio of R to (Al + E), varies from 0.25 to 5.0. The value of "n", which represents the weighted average valency of M, varies from +1 to +2. The p value, which represents the weighted average valency of the organic cation, ranges from +1 to +2. E denotes an element that is present in the lattice and is selected from the group consisting of gallium, iron, boron, chromium, indium and mixtures thereof. The value of "x", which represents the mole fraction of E, varies from 0 to 1.0. The ratio of silicon to (Al + E) is represented by the symbol "y", which varies from 3 to 25, while the molar ratio of O to (Al + E) is represented by the symbol "z" and has the value given by the equation:

z = (mn + rp + 3 + 4y) / 2

When M represents only one metal, 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, the total amount:

and the weighted average valency "n" is given by the equation:

Similarly, when only one organic cation R is present, the weighted average valency is the valency of that one cation R, i.e. +1 or +2. When more than one R cation is present, the total amount of R is given by the equation:

and the weighted average valency "p" is given by the equation:

These aluminosilicate zeolites are obtained by hydrothermal crystallization of a reaction mixture prepared by combining sources of R, aluminum, possibly E and / or M and silicon in aqueous media. Accordingly, aluminum sources include, but are not limited to, aluminum alkoxides, precipitated alumina, aluminum hydroxide, aluminum salts, and aluminum metal. Specific examples of aluminum alkoxides include, but are not limited to, aluminum ortho-sec-butoxide and aluminum ortho-isopropoxide. Sources of silica include, but are not limited to, tetraethylorthosilicate, a fine, highly porous silica powder, precipitated silica, and colloidal silica. The preferred silica source is Ultrasil VN SP (89% SiO ₂ ). Sources of metal M include, but are not limited to, halide salts, nitrate salts, acetate salts and hydroxides of the corresponding alkali and alkaline earth metals. In particular, metals M can appear in impurities in some sources of organosubstituted ammonium hydroxides, as well as in some sources of silicon oxide. For example, Ludox AS-40 colloidal silica may contain about 0.05% Na, while Aldrich Chemical Company benzyltrimethylammonium hydroxide has 0.5% K as an impurity. Sources of elements E include (but are not limited to) alkali metal borates , boric acid, precipitated gallium oxyhydroxide, gallium sulfate, iron (III) sulfate, iron (III) chloride, chromium chloride, chromium nitrate, indium chloride and indium nitrate. As indicated, when R is benzyltrimethylammonium, the sources contain (but are not limited to) hydroxide, chloride, bromide, iodide and fluoride compounds. R may also be a combination of benzyltrimethylammonium and at least one of some other organosubstituted ammonium compounds. In the case where R is a quaternary ammonium cation or a quaternized alkanolammonium cation, the sources may be hydroxide, chloride, bromide, iodide and fluoride compounds. Specific examples include, but are not limited to, diethyl dimethyl ammonium hydroxide, tetraethyl ammonium hydroxide, hexamethonium bromide, tetramethyl ammonium chloride, and methyl triethyl ammonium hydroxide. The source of R may also be neutral amines, diamines, and alkanolamines. Specific examples are triethanolamine, triethylamine, and N, N, N ′, N′-tetramethyl-1,6-diaminohexane. In some cases, a reagent in the form of a solution of aluminosilicate raw materials can be used. These solutions consist of one or more organosubstituted ammonium hydroxides and sources of silicon and aluminum and are treated to form a clear, homogeneous solution, which is usually stored and used as a reagent. This reagent contains aluminosilicate molecules, which, as a rule, are not found in zeolite reaction mixtures obtained from separate sources of silicon and aluminum. The reagent usually does not contain alkali or contains alkali at the level of impurities coming from sources of silicon, aluminum and organosubstituted ammonium hydroxide. In the synthesis of zeolite, one or more such solutions can be used. In the case of replacing Al with E, a silicate of the corresponding metal can also be used in the synthesis.

The reaction mixture containing the reactive sources of the desired components can be described using the formula in which the molar ratios of the oxides are given:

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" denotes the molar coefficient of oxide M and has a value from 0 to 5, "b" denotes a molar coefficient of oxide R and has a value from 1 to 120, "d" denotes a molar coefficient of silicon oxide and has a value from 5 to 100, " c "denotes the molar coefficient of oxide E and has a value of from 0 to 1.0 and" e "denotes the molar coefficient of water and has a value of from 50 to 15000. In the present study, the reaction mixture is maintained under reaction conditions including a temperature of from 80 to 160 ° C , mainly from 95 to 125 ° C, during the time from 2 to 30 days, pre uschestvenno for a time from 5 to 15 days in a sealed reaction vessel under autogenous pressure. After crystallization is complete, the solid product is isolated from the heterogeneous mixture by, for example, filtration or centrifugation, washed with deionized water and dried in air at room temperature to 100 ° C.

Crystalline zeolites are characterized by a three-dimensional skeletal structure formed by at least tetrahedral SiO ₂ and Al ₂ O ₃ cells. In addition, these zeolites are characterized by their roentgenogram. The X-ray diffraction pattern has at least diffraction lines with d-distances and relative intensities shown in Table A.

Table a 2-θ d (Å) I / I _o % 3.86-4.22 22.87-20.92 w-m 7.60-7.84 11.62-11.27 s-vs 11.58-11.86 7.64-7.46 w-m 13.29-13.54 6.65-6.53 m 13.90-14.20 6.36-6.23 w 15.34-15.68 5.77-5.65 m 19.30-19.65 4.60-4.51 m 20.37-20.73 4.35-4.28 m-s 23.18-23.54 3.83-3.78 m-s 23.57-23.89 3.77-3.72 s-vs 24.68-25.03 3.60-3.55 m-s 26.84-27.23 3.32-3.27 m 28.15-28.58 3.17-3.12 m 31.25-31.71 2.86-2.82 vs 33.37-33.76 2.68-2.65 w 35.89-36.36 2,50-2,47 m 48.05-48.52 1.89-1.87 w-m 51.38-51.90 1.78-1.76 w-m 55.35-56.04 1.66-1.64 w-m 58.08-58.64 1.59-1.57 w

Freshly synthesized zeolite contains in its pores some cations that can exchange or compensate 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. Ion exchange involves contacting zeolites with a solution containing the desired cation (in molar excess) under exchange conditions. Exchange conditions include a temperature of 15 to 100 ° C. and a time of 20 minutes to 50 hours. Calcination conditions include a temperature of 300 to 600 ° C. and a time of 2 to 24 hours.

A special treatment to remove organic cations, which leads to the ammonium form of the zeolite, is ammonia calcination. Calcination in an atmosphere of ammonia can destroy organic cations, presumably to a proton form, which can be neutralized by ammonia to form an ammonium cation. The obtained ammonium form of the zeolite can then be subjected to ion exchange in order to obtain any other desired form. Ammonia calcination conditions include treatment in an ammonia atmosphere at a temperature of from 250 to 600 ° C and more preferably from 250 to 450 ° C for a time of 10 minutes to 5 hours. If necessary, the processing can be performed in several stages, carried out in the same temperature range, so that the total residence time in the ammonia atmosphere does not exceed 5 hours. At temperatures above 500 ° C, the treatment should be short-term - less than half an hour and more preferably over a period of about 5-10 minutes. Prolonged calcination at temperatures above 500 ° C can lead to undesired dealumination along with targeted ion exchange for ammonium and proceeds under harsh conditions, since most organosubstituted ammonium decomposes at lower temperatures.

The form of UZM-16 after ion exchange can be described by the empirical formula:

where R, x, y, and E are described above and m ′ is from 0 to 5.75, M ′ is a cation selected from the group consisting of alkali metals, alkaline earth metals, rare earth metals, hydrogen ion, ammonium ion, and mixtures thereof , n ′ denotes the weighted average valency of M ′ and varies from 1 to 3, r ′ has a value from 0 to 5.75, r ′ + m ′> 0 and p denotes the weighted average valency of R and varies from +1 to +2. The value of z ′ is given by the formula:

z ′ = (m ′ · n ′ + r ′ · p + 3 + 4 · y) / 2

The UZM-16 zeolites represented by equation (2) can be further processed to remove aluminum and possibly introduce silicon, as a result of which the Si / Al ratio increases and the acidity and ion-exchange properties of zeolites change accordingly. Such operations include: a) contacting with a fluorosilicate solution or suspension; b) calcination or steaming followed by acid extraction or ion exchange; c) acid extraction; or d) any combination of these operations in random order.

Fluorosilicate treatment is known in the art and is described in US-A-6,200,463 B1, which cites US-A-4,711,770, which describes a process for treating a zeolite with a fluorosilicate salt. Typical conditions for this treatment are to contact the zeolite with a solution containing a fluorosilicate salt, such as ammonium fluorosilicate (AFS) at a temperature of from 20 to 90 ° C.

Acids that can be used in carrying out acid extraction include, but are not limited to, mineral acids, carboxylic acids, and mixtures thereof. Examples of these acids include sulfuric acid, nitric acid, ethylenediaminetetraacetic acid (EDTA), citric acid, oxalic acid, etc. The concentration of acid that can be used is not critical, but it is convenient to operate at a concentration of from 1 to 80 wt.% And preferably from 5 to 40 wt.%. Acid extraction conditions include a temperature of from 10 to 100 ° C. over a period of 10 minutes to 24 hours. After acid treatment, the UZM-16 zeolite is isolated, for example, by filtration, washed with deionized water and dried at room temperature to 100 ° C. UZM-16 zeolites subjected to one or more treatments, whereby aluminum is removed and, possibly, silicon is introduced into the skeleton, hereinafter referred to as UZM-16HS.

The degree of dealumination achieved as a result of acid extraction depends on the form of the cation of the starting UZM-16, as well as on the acid concentration, time and temperature at which the extraction is carried out. For example, if the original UZM-16 contains organic cations, the dealumination rate will be small compared to UZM-16, from which the organic cations were removed. This can be an advantage if the chain is dealumination only on the surface of the UZM-16. As noted above, convenient methods for removing organic cations include calcination, ammonia calcination, steaming and ion exchange. The conditions of calcination, ammonia calcination and ion exchange are defined above. Steaming conditions include a temperature of 400 to 850 ° C. with 1-100% steam over a period of 10 minutes to 48 hours and preferably at a temperature of 500 to 600 ° C., a steam concentration of 5 to 50% and a time of 1 to 2 hours

It should be emphasized that calcination and steaming operations not only remove organic cations, but can also dealuminate zeolite. Thus, alternative embodiments for dealumination include: an calcination operation followed by acid extraction and steaming followed by acid extraction. Another embodiment for dealumination involves calcining or steaming the initial zeolite UZM-16, followed by ion exchange treatment. Needless to say, acid extraction can be carried out simultaneously, before or after ion exchange.

The ion exchange conditions are the same as defined above, namely the temperature is from 15 to 100 ° C and the time is from 20 minutes to 50 hours. The ion exchange can be carried out with a solution comprising a cation (M1 ′) selected from the group consisting of alkali metals, alkaline earth metals, rare earth metals, hydrogen ion, ammonium ion and mixtures thereof. During this ion exchange, the cation M1 is exchanged for a secondary or different cation M1 ′. In one preferred embodiment, the UZM-16HS composition is contacted after the steps of steaming or calcining with an ion exchange solution containing an ammonium salt. Examples include, but are not limited to, ammonium nitrate, ammonium chloride, ammonium bromide, and ammonium acetate. A solution containing ammonium ion may in some cases contain mineral acid, such as (but not limited to) nitric, hydrochloric, sulfuric, or mixtures thereof. The concentration of mineral acid is such that its amount provides a ratio of H ⁺ to NH ₄ ⁺ from 0 to 1. This exchange for ammonium ion helps to remove possible contaminants remaining in the pores after steaming and / or calcining.

From the foregoing, it is clear that from the point of view of the efficiency of the process conditions, it is desirable that the integrity of the structure of the zeolite crystal is substantially preserved during the entire dealumination process and that the zeolite retains at least 50%, preferably at least 70% and more preferably at least 90% of its initial crystallinity. A convenient way to assess the crystallinity of products in comparison with the crystallinity of the starting material is to compare the relative intensities of the d-distances in the corresponding x-ray powder diffraction patterns. As a standard, the sum of the intensities (in arbitrary units) of the peaks of the starting material over the background is used, which is compared with the corresponding intensities of the product peaks. When, for example, the numerical sum of the peak heights of the molecular sieve product is 85% of the sum of the peak intensities of the initial zeolite, this means that 85% crystallinity is retained. In practice, it is customary to use only part of the peaks for this purpose, for example, five or six of the strongest peaks. Other indicators of crystallinity conservation are surface area and adsorption capacity. These tests may be preferred when the substituted metal changes significantly, for example enhances, the absorption of X-rays by the sample or when the peaks undergo significant shifts, such as during dealumination.

After any of the dealumination operations described above, the UZM-16HS is usually dried and can be used in various processes, as described below. Applicants have discovered that the properties of UZM-16HS can be further modified using one or more additional steps. These operations include steaming, calcination or ion exchange, which can be carried out separately or in any combination. These operations include (but are not limited to):

steaming → calcination → ion exchange

calcination → steaming → ion exchange

ion exchange → calcination → steaming

ion exchange → steaming → calcination

steaming → calcination

In order to form the zeolites of the invention, although not necessarily with the same result, the dealumination operation described above can be combined in any order. It should be emphasized that a certain sequence of operations, for example, treatment with ammonium fluorosilicate, acid extraction, steaming, calcination, etc., can be repeated as many times as necessary to obtain the desired properties. It goes without saying that one of the operations can be repeated without repeating the others, for example, repeating the treatment with ammonium fluorosilicate two or more times before steaming or calcining, etc. Finally, the sequence and / or repetition of operations will determine the properties of the final UZM-16HS composition.

The UZM-16HS obtained above is described by the empirical formula (for the anhydrous form):

where M1 denotes at least one exchangeable cation selected from the group consisting of alkali, alkaline earth metals, rare earth metals, ammonium ion, hydrogen ion and mixtures thereof, and represents a molar ratio of M1 to (Al + E) and varies from 0.01 to 50, n denotes the weighted average valency of M1 and has a value from +1 to +3, E denotes an element selected from the group consisting of gallium, iron, boron, chromium, indium and mixtures thereof, x denotes the mole fraction of E and varies from 0 to 1.0, y ′ denotes the molar ratio of Si to (Al + E) and varies from more than 3.0 to practically pure silicon oxide and z ″ denotes the molar ratio of O to (Al + E) and has a value that is determined by the equation:

z ′ ′ = (a · n + 3 + 4 · y ') / 2;

moreover, the zeolite is characterized in that it has an x-ray having at least d-distances and relative intensities shown in table B.

Table B 2-θ d (Å) I / I _o % 7.70-8.40 11.47-10.52 m-vs 11.70-12.10 7.56-7.31 w 13.35-14.56 6.63-6.08 s-vs 20.60-21.70 4.31-4.09 w 24.60-25.65 3.62-3.47 m-s

By practically pure silicon oxide is meant such silicon oxide from which almost all aluminum and / or metals E are removed from the lattice. It is well known that it is practically impossible to remove all aluminum and / or metal E. In numerical terms, zeolite is almost pure silicon oxide when y ′ has a value of at least 3000, preferably 10000 and most preferably 20,000. Thus, the limits for y ′ are from 3 to 3000, preferably from more than 10 to 3000; from 3 to 10,000, preferably from more than 10 to 10,000 and from 3 to 20,000, preferably from more than 10 to 20,000.

When specifying here the proportions of the starting material for the zeolite or the adsorption properties of the zeolite product, etc., unless otherwise specified, a “anhydrous state” of the zeolite will be assumed. The expression “anhydrous state” is used here with respect to a zeolite, which to a large extent does not contain both physically adsorbed and chemically adsorbed water.

The zeolites of the present invention (both UZM-16 and UZM-16HS) are able to separate mixtures of molecular particles by the size of the molecules (kinetic diameter) or by the degree of polarity of the molecular particles. When the separation of molecular particles is based on the size of the molecules, the separation is due to the fact that smaller molecular particles enter the intracrystalline empty space into which larger particles cannot enter. The kinetic diameters of various molecules, such as oxygen, nitrogen, carbon dioxide, carbon monoxide, are given in D.W. Breck, Zeolite Molecular Sieves (zeolite molecular sieves), John Wiley and Sons (1974), p.636.

Crystalline microporous compositions of the present invention (both UZM-16 and UZM-16HS), freshly synthesized, after calcination, or after any of the above treatments, can be used as catalysts or catalyst supports in hydrocarbon conversion processes. Hydrocarbon conversion processes are well known in the art and include ring opening reactions, cracking, hydrocracking, alkylation of both aromatic compounds and isoparaffins, isomerization, polymerization, reforming, dewaxing, hydrogenation, dehydrogenation, transalkylation, dealkylation, hydration, dehydration, hydrotreating, hydrodesulfurization, methanation, and synthesis gas conversion process. The specific reaction conditions and types of raw materials that can be used in these processes are given in US-A-4,310,440 and US-A-4,440,871. A preferred hydrocarbon conversion process is a ring opening process in which cyclic hydrocarbons are converted to non-cyclic hydrocarbons, i.e. linear or branched hydrocarbons.

These crystalline microporous compositions can also catalyze other reactions, including base-catalyzed alkylation of the side chains of alkyl aromatic compounds, aldol condensation reactions, isomerization of the olefin double bond and isomerization of acetylenes, dehydrogenation of alcohols and dimerization of olefins, oligomerization and conversion of alcohols to olefins. Forms of these materials with exchanged ions can successfully catalyze the reduction of NO _x to N ₂ in automobile and industrial exhausts. Some of the reaction conditions and the types of feed that can be used in these processes are given in US-A-5015796 and H. Pines, THE CHEMISTRY OF CATALYTIC HYDROCARBON CONVERSIONS (Chemistry of catalytic conversion of hydrocarbons). Academic Press (1981), pp. 123-124 and the references therein.

The X-ray patterns shown in the following examples (and, moreover, in the tables) were obtained using powder X-ray diffraction analysis methods. The radiation source was a high-intensity X-ray tube operating at 45 kV and 35 mA. The diffraction pattern from the K-α radiation of copper was obtained using appropriate computer methods. Flat pressed powder samples were continuously scanned at a speed of 2 ° (2θ) per minute from 2 ° to 70 ° (2θ). Interplanar distances (d) in angstroms are obtained based on the position of the diffraction peaks expressed in 2θ, where θ means the Bragg angle, as it is presented from the digitized data. The intensities were determined based on the integrated area of the diffraction peaks after subtracting the background, where “I _o ” is the intensity of the strongest line or peak, and “I” is the intensity of each of the other peaks.

As is known to specialists in this field, the determination of the parameter 2θ is associated with human and mechanical errors, which in total can lead to errors of ± 0.4 for each given value of 2θ and up to ± 0.5 for the reduced values of nanocrystalline materials. This error also manifests itself naturally in the reducible values of d-distances, which are calculated from the values of θ. This error is common to the entire field and therefore does not interfere with distinguishing the crystalline materials of the present invention from one another and from compositions of the prior art. In some radiographs, the relative intensities of the d-distances are indicated using the notation vs, s, m, and w, which mean “very strong”, “strong”, “medium” and “weak”, respectively. Expressed in units of 100 × I / I _{o, the} above designations are evaluated as: w = 0-15, m = 15-60, s = 60-80 and vs = 80-100. In some cases, the purity of the synthesized product can be estimated based on a powder x-ray. So, for example, if it is believed that the sample is clean, then it is only assumed that in the X-ray diffraction pattern of the sample there are no lines attributed to crystalline impurities, but this does not mean the absence of amorphous materials.

To more fully illustrate the invention, the following examples are provided. It should be borne in mind that these examples are only illustrative and are not intended to inappropriately limit the wide scope of the invention, which is given in the attached claims.

EXAMPLE 1

The aluminosilicate reaction mixture was prepared by adding 2.33 g of Al (O-sec-Bu) ₃ (95 +%) to 63.35 g of BzTMAOH (40%) with vigorous stirring, after which 28 g of colloidal silica (LUDOX ™ AS-40 , 40% SiO ₂ ). Next, 6 g of water was slowly added to the aluminosilicate reaction mixture with continuous stirring. The mixture is homogenized for another 30 minutes using a high-speed stirrer and placed in three Teflon-lined autoclaves, which are placed in an oven at 125 ° C and the mixtures are autoclaved there for 3, 6 and 10 days under spontaneous pressure. Solid products are isolated by filtration, washed with deionized water and dried at 95 ° C.

The products of the three reactions showed an x-ray characteristic of the zeolite designated UZM-16. Representative diffraction lines of a 3-day sample are shown in Table 1 below. The surface area of the BET of the calcined material, determined by N ₂ adsorption, was 523 m ² / g and the micropore volume was 0.26 cm ³ / g.

Table 1 2-θ d (Å) I / I _o % 4.10 21.49 m 7.68 11.50 s 11.66 7.58 w 13.38 6.61 m 14.00 6.32 w 15.48 5.72 m 19.46 4,56 m 20.56 4.32 s 23.36 3.80 s 23.72 3.75 vs 24.80 3,59 s 27.02 3.30 m 28.32 3.15 m 30.65 2.91 w 31,42 2.84 vs 33.52 2.67 w 36.08 2.49 m 41.00 2.20 w 42.92 2.11 w 43.68 2.07 w 45.92 1.97 w 48.28 1.88 m 49.86 1.83 w 51.62 1.77 w 54.14 1,69 w 55.90 1,64 m 58.42 1,58 w 61.69 1,50 w 63.76 1.46 w 65.40 1.43 w 69.00 1.36 w

. Ясно, что периодичность в направлениях

у UZM-16 отличается от той же периодичности у оффретита и что межплоскостное расстояние больше в три раза. Представленная здесь электронограмма соответствует электронограммам, приводимым в литературе для той же самой ориентации (J.V.Sanders, M.L.Ocelli, R.A.Innes, S.S.Pollack, Studies in Surface Sciences and Catalysis, Ed. Y.Murakami, A.Iijima, and J.W.Ward, Elsevier, New York, 28, 429 (1986)).The difference between UZM-16 and the structure of offretitis is also detected by electron diffraction. Figure 1 shows a comparison of electron diffraction patterns of UZM-16 (Fig. 1B) and offretitis (Fig. 1A) taken along the [110] plane and shown in the indicated plane in the (001) directions and

. Clearly, the frequency in the directions

UZM-16 differs from the same frequency for offretitis and that the interplanar spacing is three times greater. The electron diffraction pattern presented here corresponds to electron diffraction patterns cited in the literature for the same orientation (JV Sanders, MLOcelli, RAInnes, SSPollack, Studies in Surface Sciences and Catalysis, Ed. Y. Murakami, A. Iijima, and JWWard, Elsevier, New York, 28, 429 (1986)).

на фиг.1b. Это расстояние втрое больше

расстояния, которое можно ожидать у оффретита и которое было бы равным 6,65 Å.Greater interplanar spacings can be easily observed on images of the UZM-16 grating. Figure 2 shows a lattice image taken along [110]. The edges of the grating in the vertical direction in the image correspond to 19.3 Å indicated by reflection at 1/3

on fig.1b. This distance is three times greater

the distance that can be expected from offretitis and which would be equal to 6.65 Å.

EXAMPLE 2

This example demonstrates the preparation of UZM-16, its modification by calcination, ion exchange and steaming to form UZM-16HS, followed by further modification by acid extraction, resulting in another variant of UZM-16HS. The aluminosilicate reaction mixture was prepared by adding 35.21 g of Al (O-sec-Bu) ₃ (95 +%) to 927.47 g of BzTMAOH (40%) with vigorous stirring. After dissolving the aluminum reagent, 416.45 g of colloidal silica (LUDOX ™ AS-40, 40% SiO ₂ ) is added and the resulting mixture is homogenized for 30 minutes using a high-speed stirrer. The mixture was crystallized at 125 ° C. for 6 days in a stirred 2 L PARR ™ reactor under spontaneous pressure. Solid products are isolated by filtration, washed with deionized water and dried at 95 ° C. Using powder x-ray analysis, the product is identified as UZM-16. The diffraction lines characteristic of the X-ray diffraction pattern are presented in Table 2 below. Elemental analysis showed that this related UZM-16 material is characterized by a Si / Al ratio of 5.83. A portion of 62.5 g of UZM-16 is first calcined in a stream of nitrogen, gradually raising the temperature to 250 ° C at a rate of 1 ° C / min with holding at 250 ° C for 2 hours, after which the temperature is gradually raised to 500 ° C at a speed 1 ° C / min, incubated for 3 hours at 500 ° C, replace the atmosphere with an air current and incubated at 500 ° C for another 3 hours. The BET surface area of the calcined material was 676 m ² / g, and the micropore volume was 0.33 cm ³ / g. A portion of 51 g of calcined material is exchanged for ammonium, suspending it in a solution containing 52 g of NH ₄ NO ₃ dissolved in 500 g of deionized water. The suspension is heated for 7 hours to 85 ° C and then isolated by filtration and washed thoroughly with deionized water. The ion exchange is repeated two more times, but for only 2.5 hours at 85 ° C.

A portion of 40 g of calcined UZM-16 exchanged for ammonium is steamed for 2 hours at 600 ° C. with 50% steam using a horizontal steamer. The product is identified as UZM-16HS by X-ray powder analysis. The characteristic diffraction lines of this product are shown in Table 2 below. Nitrogen adsorption measurements were obtained for the steamed UZM-16HS exchanged ammonium material for a BET surface area of 424 m ² / g and a micropore volume of 0.20 cm ³ / g.

A portion of 20 g of the obtained steaming UZM-16HS is further treated with acid. An acidic solution is prepared by dissolving 19.7 g of HNO ₃ (69%) in 350 g of deionized water. Before adding steamed UZM-16, the solution is heated to 90 ° C. The resulting suspension is stirred for 1 hour at 90 ° C. The product was isolated by filtration, washed with deionized water and dried at 98 ° C. A modified product is defined as UZM-16HS using X-ray powder diffraction analysis. Characteristic diffraction lines are shown in Table 2 below. Elemental analyzes of the steamed, acid-washed product gave a Si / Al value of 14.76.

table 2 UZM-16 UZM-16HS (steamed exchanged for ammonium calcined UZM-16) UZM-16HS (acid extracted, exchanged for ammonium calcined UZM-16) 2-θ d (Å) I / I _o % 2-θ d (Å) I / I _o % 2-θ d (Å) I / I _o % 4.04 21.85 m 7.72 11.44 vs 7.94 11.13 vs 8.18 10.80 m 11.72 7.55 w 11.86 7.46 w 11.96 7.39 w 13.40 6.60 M 13.64 6.48 s 14.04 6.30 W 14.30 6.19 m 14.26 6.21 vs 15,52 5.71 M 19.48 4,55 M 19.18 4.62 w 20.58 4.31 S 20.98 4.23 w 21.32 4.16 w 23.38 3.80 M 23.67 3.76 w 23.76 3.74 vs 23.98 3.71 w 24.34 3.65 w 24.86 3,58 s 25.02 3.56 m 25.25 3.52 m 27.06 3.29 m 28.34 3.15 m 30.62 2.92 w 31.46 2.84 vs 31.84 2.81 m 33.56 2.67 w 36.08 2.49 m 41.08 2.20 w 42.92 2,4 w 43.60 2.07 w 45.88 1.98 w 48.26 1.88 m 48,99 1.86 w 49.92 1.83 w 51.64 1.77 m 54.14 1,69 w 55.80 1.65 m 58.40 1,58 w 61.66 1,50 w 63.68 1.46 w 65.52 1.42 w 67,99 1.38 w 68.91 1.36 w

EXAMPLE 3

The aluminosilicate reaction mixture was prepared by adding 35.21 g of Al (O-sec-Bu) ₃ (95 +%) to 927.47 g of BzTMAOH (40%) with vigorous stirring. After dissolving the aluminum reagent, 416.45 g of colloidal silica (LUDOX ™ AS-40, 40% SiO ₂ ) is added and the resulting mixture is homogenized for 30 minutes using a high-speed stirrer. The mixture was crystallized at 105 ° C. for 12 days in a 2 L stirred PARR ™ reactor under spontaneous pressure. The solid product is isolated by filtration, washed with deionized water and dried at 95 ° C. Using powder x-ray analysis, the product is identified as UZM-16. The diffraction lines characteristic of the X-ray diffraction pattern are presented in Table 3 below. Elemental analysis showed that this related UZM-16 composition is characterized by a Si / Al ratio of 5.7. The product is first calcined in a nitrogen atmosphere, gradually raising the temperature to 350 ° C at a rate of 1 ° C / min with exposure at 350 ° C for 1 hour, after which the temperature is gradually raised to 500 ° C at a speed of 1 ° C / min 6 hours at 500 ° C, replace the atmosphere with air and incubated at 500 ° C for another 6 hours. The BET surface area of the calcined material was 574 m ² / g and the micropore volume was 0.24 cm ³ / g. A portion of 98 g of calcined material is exchanged for ammonium, suspending it in a solution containing 100 g of NH ₄ NO ₃ dissolved in 1000 g of deionized water. The suspension is heated for 5 hours to 80 ° C, the product is isolated by filtration and washed thoroughly with deionized water. Ion exchange is repeated 3 more times.

A portion of 18 g of calcined UZM-16 exchanged for ammonium was steamed for 2 hours at 600 ° C. with 50% steam using a horizontal steamer. 12 g of this steamed material is further extracted with acid. An acidic solution is prepared by diluting 10 g of HNO ₃ (69%) in 300 g of deionized water. Before adding steamed, exchanged for ammonia UZM-16, the solution is heated to 90 ° C. The product was isolated by filtration, washed with deionized water and dried at 98 ° C. A modified product is defined as UZM-16HS using X-ray powder diffraction analysis. The characteristic diffraction lines of the product are shown in Table 3. Elemental analyzes showed that the dealuminated product was characterized by a Si / Al ratio of 11.56. Measurements of nitrogen adsorption showed that the BET surface area is 466 m ² / g and the micropore volume is 0.19 cm ³ / g.

Table 3 UZM-16 UZM-16HS (acid extracted, steamed and exchanged for ammonium calcined UZM-16) 2-θ d (Å) I / I _o ,% 2-θ d (Å) I / I _o % 3.93 22.49 w 7.66 11.53 s 8.08 10.93 m 11.70 7.56 w 11.84 7.47 w 13.38 6.61 m 13.84 6.39 vs 14.00 6.32 w 15.44 5.73 m 19.44 4,56 m 19.88 4.46 w 20.56 4.32 m 21.08 4.21 w 23.32 3.81 s 23.76 3.74 s 24.82 3,58 vs 25.06 3,55 m 27.05 3.29 m 28.32 3.15 m 31.48 2.84 vs 31.80 2.81 w 33.58 2.67 w 36.22 2.48 w 48.24 1.89 w 49.83 1.83 w 51.64 1.77 m 55.58 1.65 m 58.34 1,58 w 61.58 1,50 w 63.69 1.46 w 65,43 1.43 w 68.02 1.38 w 68.83 1.36 w

Claims (9)

1. Microporous crystalline zeolite having a composition in a freshly synthesized anhydrous form, expressed in molar ratios of elements:

, where M denotes at least one exchangeable cation selected from the group consisting of alkali and alkaline earth metals; m represents the molar ratio of M to (A1 + E) and varies from 0 to 0.75; R denotes a benzyltrimethylammonium cation (BzTMA) or a combination of BzTMA with at least one organosubstituted cation from the group consisting of quaternary ammonium cations, protonated amines, protonated diamines, protonated alkanolamines, dimertinate quaternary ammonium cations, and quaternized mixtures; r represents a molar ratio of R to (Al + E) and has a value of from 0.25 to 5.0; E denotes an element selected from the group consisting of Ga, Fe, In, Cr, B and mixtures thereof; x represents the molar fraction E and varies from 0 to 1.0; n represents the weighted average valency of M and has a value from +1 to +2; p represents the weighted average valency of R and has a value from +1 to +2; y represents the molar ratio of Si to (Al + E) and varies from more than 3 to 25 and z represents the molar ratio of O to (A1 + E) and has a value that is determined by the equation z = (m · n + r · p + 3 + 4 · y) / 2; while the zeolite is characterized in that it has an x-ray having at least d-distances and relative intensities shown in table A: Table a 2-θ d (Å) I / I _o % 3.86-4.22 22.87-20.92 w-m 7.60-7.84 11.62-11.27 s-vs 11.58-11.86 7.64-7.46 w-m 13.29-13.54 6.65-6.53 m 13.90-14.20 6.36-6.23 w 15.34-15.68 5.77-5.65 m 19.30-19.65 4.60-4.51 m 20.37-20.73 4.35-4.28 m-s 23.18-23.54 3.83-3.78 m-s 23.57-23.89 3.77-3.72 s-vs 24.68-25.03 3.60-3.55 m-s 26.84-27.23 3.32-3.27 m 28.15-28.58 3.17-3.12 m 31.25-31.71 2.86-2.82 vs 33.37-33.76 2.68-2.65 w 35.89-36.36 2,50-2,47 m 48.05-48.52 1.89-1.87 w-m 51.38-51.90 1.78-1.76 w-m 55.35-56.04 1.66-1.64 w-m 58.08-58.64 1.59-1.57 w 2. The zeolite according to claim 1, in which m is equal to zero. 3. The method of producing microporous crystalline zeolite according to claim 1, comprising preparing a reaction mixture containing sources of R, Al, Si and, optionally, E and / or M and heating the reaction mixture at a temperature of from 80 to 160 ° C, and the reaction mixture has composition expressed in molar ratios of oxides:

, where a has a value from 0 to 5.0, b has a value from 1 to 120, c has a value from 0 to 1.0, d has a value from 5 to 100 and e has a value from 50 to 15000. 4. A microporous crystalline zeolite having an empirical composition for an anhydrous form, expressed in molar ratios of the elements:

, where Ml is at least one exchangeable cation selected from the group consisting of alkali metals, alkaline earth metals, rare earth metals, ammonium ion, hydrogen ion and mixtures thereof, and represents the molar ratio of Ml to (Al + E) and varies from 0.01 to 50, E denotes an element selected from the group consisting of gallium, iron, boron, chromium, indium and mixtures thereof, x denotes the mole fraction of E and varies from 0 to 1.0, n represents the weighted average valency of Ml and has a value from +1 to +3, y ′ indicates the molar ratio of Si to (Al + E) and has a value greater than 3.0 and z ′ ′ denotes the molar ratio of O to (Al + E) and has a value that is determined by the equation z ′ ′ = (a · n + 3 + 4 · y ′) / 2, however, the zeolite is characterized in that it has an x-ray having at least d-distances and relative intensities shown in table B: Table B 2-θ d (Å) I / I _o % 7.70-8.40 11.47-10.52 m-vs 11.70-12.10 7.56-7.31 w 13.35-14.56 6.63-6.08 s-vs 20.60-21.70 4.31-4.09 w 24.60-25.65 3.62-3.47 m-s 5. The zeolite according to claim 4, in which y ′ has a value from 3 to 20,000. 6. A method of producing a microporous crystalline zeolite according to claim 5, comprising treating the initial zeolite under processing conditions, which removes at least part of the aluminum in the lattice and, optionally, silicon is introduced into the lattice with the formation of microporous crystalline zeolite, and the initial zeolite has an empirical formula (for anhydrous form):

, where M ′ denotes an exchangeable cation selected from the group consisting of ammonium ion, hydrogen ion, alkali metals, alkaline earth metals, rare earth metals and mixtures thereof, n denotes a weighted average valency of M ′ and varies from 1 to 3, m ′ denotes a molar ratio M ′ k (Al + E) and ranges from 0 to 5.75, R denotes a benzyltrimethylammonium cation (BzTMA) or a combination of BzTMA with at least one organosubstituted cation from the group consisting of protonated amines, protonated diamines, protonated alkanol ins, diquaternary ammonium ions, quaternized alkanolammonium ions and mixtures thereof; p represents the weighted average valency of the organic cation and varies from +1 to +2; r ′ represents the molar ratio of R to (Al + E) and varies from 0 to 5.75; r ′ + m ′> 0; y ′ represents the ratio of Si to (Al + E) and varies from 3 to 25; and z ′ represents the molar ratio of O to (Al + E) and has a value which is determined by the equation z ′ = (m ′ · n + r ′ · p + 3 + 4 · y ′) / 2, wherein the initial zeolite has an x-ray having at least d-distances and relative intensities shown in table A. 7. The method according to claim 6, in which the processing step is selected from the group consisting of treatment with a fluorosilicate solution or suspension, extraction with a weak, strong or complex acid, calcination plus ion exchange, calcination plus acid extraction, steaming plus ion exchange, steaming plus acid extraction and combinations thereof. 8. A method of converting hydrocarbons, comprising bringing a hydrocarbon stream into contact with a catalytic composite under conditions of hydrocarbon conversion, whereby a converted product is obtained, the catalytic composite containing the microporous crystalline zeolite according to claim 1 or 4, or mixtures thereof. 9. The method of claim 8, wherein the hydrocarbon conversion process is selected from the group consisting of alkylation of aromatic compounds, xylene isomerization, naphtha cracking, ring opening reaction, transalkylation, isoparaffins alkylation and ethylbenzene isomerization.

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