RU2328445C2 - Microporous crystalline zeolitic material (zeolite itq-22), method for producing and application as catalyst - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: invention relates to the microporous crystalline material of zeolite origine (ITQ-22) which in tempered condition has the empiric formula x (M_1/nXO₂): y YO₂ - z GeO₂ : (1 - z) SiO₂ where M is H⁺ or at least one inorganic cation with +n charge; X is at least one chemical element with the oxidation rate +3 chosen preferably from the group that consists of Al, Ga, B, Fe and Cr; Y is at least one chemical element with the oxidation rate +4, different from Si and Ge, and chosen preferably from the group that consists of Ti, Sn and V; x has the value less than 0.2, preferably less than 0.1 and can be equal to zero, y has the value less than 0.1, preferably less than 0.05 and can be equal to zero, z has the value less than 0.8, preferably between 0.005 and 0.5 and can be equal to zero. In accordance with the invention, the material has the typically X-ray diffraction pattern.

EFFECT: invented material can recommended as catalyst in processes which include separation and transformation of organic compounds.

40 cl, 2 dwg, 18 ex

Description

FIELD OF THE INVENTION

This invention relates to the field of zeolite microporous crystalline materials of nature used as catalysts or catalyst components for the separation and conversion of organic compounds.

State of the art

Zeolites are microporous crystalline materials built on the basis of the crystal lattice of TO ₄ tetrahedra, in which all vertices are socialized, forming a three-dimensional structure containing channels and / or cavities of molecular size. The composition of zeolites is variable, and usually T represents atoms having a formal oxidation state of +3 or +4, such as, for example, Si, Ge, Ti, Al, B, Ga, and the like. When any of the T atoms has an oxidation state of less than +4, the resulting crystal lattice carries a negative charge, which is compensated by the presence of organic or inorganic cations in the channels or cavities. In addition, organic molecules and H ₂ O can be located in these channels and cavities, and thus, in the general case, the chemical composition of zeolites can be represented using the following empirical formula:

x (M _{1 / n} XO ₂ ): yYO ₂ : zR: wH ₂ O

in which M represents one or more organic or inorganic cations having a charge + n; X is one or more trivalent elements; Y is one or more tetravalent elements, typically Si; and R represents one or more organic compounds. Although due to the processing after synthesis, the nature of M, X, Y, and R and the values of x, y, z, and w may vary, the chemical composition of the zeolite (after synthesis or after calcination) has a number of differences characteristic of each zeolite and the method of its preparation.

The crystal structure of each zeolite with a specific system of channels and cavities leads to a specific X-ray diffraction pattern, with which zeolites can be distinguished from each other.

A large number of zeolites are synthesized in the presence of organic molecules that act as a structure-determining agent. Organic molecules that perform the function of a structure-determining agent (AOC) usually contain nitrogen atoms and can be the source of organic cations in the reaction medium.

The mobilization of the precursor particles during the synthesis of zeolites can be carried out in the presence of OH ^- groups and a basic medium, which can be introduced as hydroxide of MA itself, for example, such as tetrapropylammonium hydroxide in the case of zeolite ZSM-5. Fluoride ions can also act as mobilizing agents in the synthesis of zeolites, for example, EP-A-337479 describes the use of HF in H ₂ O at low pH as an agent that mobilizes silicon dioxide in the synthesis of ZSM-5 zeolite. Nevertheless, from an industrial point of view, the use of fluoride ions in the synthesis of zeolites is less desirable than OH ^- ions, since in the presence of fluoride ions it is necessary to use special materials in the synthesis equipment, as well as special treatment of wastewater and gases.

Catalytic fluid cracking (CPK), or its modification - deep catalytic cracking (GKK), along with cracking with steam, are the processes that make the greatest contribution to the production of C3-C5 olefins. In addition, KFK provides approximately 30% of the gasoline volume at oil refineries. Propylene production in the CPC process can be increased by changing the technological conditions of the installation, such as, for example, increasing the temperature in the reactor. However, this solution leads to a significant increase in the yield of gases and especially undesirable dry gas. Better results are obtained using new catalyst compositions, including the use of a mixture of zeolites. The use of zeolite ZSM-5 as an additive in CPA catalysts also leads to an increase in the yield of C3 and C4 olefins (see, for example, US Pat. and US $ 437,458 and Buchanan, JS and Adewuyi, YG., Applied Catalysis: A General, 134, 247 (1996); Madon, RJ, Journal of Catalysis 129 (1), 275 (1991)). Nevertheless, it is known (Studies in Surface Science and Catalysis, vol. 76, 499 (1993)) that the addition of ZSM-5 zeolite leads to a decrease in the yield of dry gas and an increase in the proportion of aromatic compounds in gasoline. From the point of view of obtaining an increased yield of C3-C5 olefins, and especially propylene, as well as obtaining high-octane marketable gasoline with a low content of aromatic compounds, it is especially important to find other zeolites, alternative to ZSM-5, which, acting as an additive to zeolite faujasite Y, could ensure the release of light olefins with minimal loss of gasoline. For this purpose, numerous zeolites have been investigated, such as zeolite MCM-22, Omega, L, mordenite BEA and ITQ-7 (see, for example, articles in J. Catal. 165, 102 (1997); Stud. Surf. Sci. and Catal. 46, 115 (1989); patents: US 5314612; EP 489324; US 474292; US 4137152; EP 350331; FR 2661621; WO 0170905).

However, there continues to be a need to improve known methods through the use of new catalysts with better properties in the cracking process.

Regarding the use of zeolites as catalysts in the alkylation processes of aromatic compounds, cumene is of particular interest as the starting compound for the production of phenol and acetone. Numerous works have been performed using acid catalysts. General information on the catalysts and processes used can be found in the book: Encyclopedia of Chemical Processing and Design, J. J. McKetta and W. A. Cunningham Editors, V.14, pp. 33-55 (1982). To achieve high propylene conversion and high selectivity for the monoalkylated product isopropylbenzene (cumene) during the alkylation of benzene with propylene, it is also necessary to minimize the amount of n-propylbenzene (NPB) formed. Since it is known that the separation of cumene and NPB by traditional methods, such as distillation, is difficult, it can be understood that the yield of NPB during the alkylation of benzene with propylene should always be kept at the lowest possible level.

Zeolites are used as catalysts in the alkylation of aromatic compounds, for example, in patent US 429457 zeolite ZSM-5 is described as a catalyst for the alkylation of benzene with propylene.

Nevertheless, it is likely that, due to the small diameter of the channels in the zeolite, a low selectivity for the desired product is observed in this process. There are also numerous patents describing the use of faujasite and modified faujasites as catalysts for the production of cumene by alkylation of benzene with propylene. Zeolite Y can be used as a catalyst, but it is necessary to maintain a high benzene / propylene ratio in the feed. This leads to an increase in the cost of recycling benzene. Zeolite Beta was also patented as a catalyst for the alkylation of benzene with propylene in various patents, such as, for example, US 4,891,458, US 5,030,786, EP 432814, EP 439632; EP 629599. This zeolite gives good results in terms of activity and selectivity, however, its properties should be improved both in terms of selectivity for NPB, and in connection with the stability of the catalyst. Recently, the use of a new zeolite (MSM-22) has been patented.

The purpose of the present invention is to develop a natural material that can be expediently used in the processes of separation and conversion of organic compounds, and, more specifically, this material is used as an active zeolite compound for cracking organic compounds and, in particular, hydrocarbon fractions obtained from natural or artificial oil, as well as in the process of alkylation of aromatic compounds.

The pore topology of this new zeolite gives it the properties of an active additive to zeolite faujasite Y in catalysts for catalytic fluid cracking (CPK) plants; this ensures a high yield of light olefins, production of high-octane marketable gasoline, as well as a decrease in the content of aromatic compounds in gasoline, in comparison with the base catalyst.

Disclosure of invention

In the present invention, the objectives stated above are achieved thanks to the microporous crystalline material of zeolite nature, which is also defined as "ITQ-22" or "ITQ-22 zeolite, the method of its preparation in the absence of fluoride ions and the use of the material. This material, both in a calcined form and in a non-calcined form after synthesis, has an X-ray diffraction pattern that differs from the diffraction patterns of other known zeolite materials, and therefore this diffraction pattern is a characteristic of this material.

An X-ray diffraction pattern of the synthesized ITQ-22 material is recorded for a powder sample using the method with a fixed slit of the beam divergence of K _α radiation of copper. This diffraction pattern is characterized by 2θ angles (in degrees) and relative intensity values (I / I ₀ ) of the most intense reflections, which are shown in Table I, in which I ₀ represents the intensity of the most intense peak to which 100 is assigned. To express the relative intensity use the following terms: cf. - average intensity (between 20 and 40%); forces. - strong intensity (between 40 and 60%) and very strong. - very strong intensity (between 60 and 100%).

Table I Angle 2θ (degrees) ± 0.5 Intensity (I / I ₀ ) 8.02 very strong 8.43 very strong 9.31 Wed 10.64 very strong 20.26 Wed 21.81 forces. 22.53 very good

After calcination and in an anhydrous state, this material corresponds to the general formula:

x (M _{1 / n} XO ₂ ): yYO ₂ : zGeO ₂ : (1-z) SiO ₂

in which "x" has a value of less than 0.2, preferably less than 0.1, and may be zero; “y” has a value of less than 0.1, preferably less than 0.05, and may be zero; “z” has a value of less than 0.8, preferably between 0.005 and 0.5, and may be zero; M represents one or more inorganic cations with a charge + n; X means one or more chemical elements with an oxidation state of +3 (Al, Ga, B, Fe, Cr) and Y means one or more chemical elements with an oxidation state of +4, different from Si and Ge (Ti, Sn, V).

Nevertheless, depending on the synthesis method and on calcination or subsequent treatments, defects in the crystal lattice may appear, which appear as the presence of Si-OH silanol groups. The empirical formula above does not take into account such defects.

Table II shows the values of 2θ angles (degrees) and relative intensities (I / I ₀ ) of the most intense reflections in the X-ray powder diffraction pattern of ITQ-22 zeolite after calcination in order to remove organic compounds adsorbed inside the zeolite, where the shorten . and very good have the meanings indicated in table I.

Table II Angle 2θ (degrees) ± 0.5 Intensity (I / I ₀ ) 6.97 Wed 8.00 very strong

Angle 2θ (degrees) ± 0.5 Intensity (I / I ₀ ) 8.40 very good 9.28 Wed 10.62 very strong 20.18 Wed 21.74 Wed 22.54 very good

The position, width, and relative intensities of the peaks to a certain extent depend on the chemical composition of the material, as well as on the degree of hydration and the size of the crystals. In particular, when the lattice consists exclusively of silicon and germanium oxides with a ratio of Si / Ge = 3.8 and the material is synthesized using quaternary ammonium cation 1,5-bis (methylpyrrolidinium) pentane as a structure determining agent, the X-ray diffraction pattern of the synthesized material has view similar to that shown in figure 1. This diffraction pattern is characterized by 2θ angles (degrees) and relative intensity (I / I ₀ ), which are shown in Table III. The following terms are used to express relative intensity: - low intensity (between 0 and 20%); Wed - average intensity (between 20 and 40%); forces. - strong intensity (between 40 and 60%) and very strong. - very strong intensity (between 60 and 100%).

Table III Angle 2θ (degrees) ± 0.5 Intensity (I / I ₀ ) 6.96 next 7.12 next 8.02 very strong 8.43 very good 9.31 Wed 10.64 very good 10.95 next 13.83 next 16.11 next 16.31 next 18.68 next 19.58 next 19.95 next 20.11 Wed 20.26 Wed 20.68 next 21.54 next 21.81 forces. 22.27 next 22.53 very good 22.70 Wed 22.91 next 23.03 next 23.18 next 24.22 next 24.33 next 25.30 next 26.44 next 27.65 next 28.14 next 28.52 next 29.03 next 29.69 next 29.90 next 32.28 next 33.26 next 35.98 next

An X-ray diffraction pattern of the above ITQ-22 sample after calcination at 580 ° C. in order to remove organic compounds adsorbed inside the zeolite is shown in FIG. 2. This diffraction pattern is characterized by the values of the angles 2θ (degrees) and relative intensity (I / I ₀ ), which are shown in table IV, where the abbreviations of sr, cf. force. and very good have the meanings indicated in Table III. When comparing x-ray diffraction patterns corresponding to zeolite ITQ-22 after synthesis and after calcination, we can conclude that the thermal stability of this material.

Table IV Angle 2θ (degrees) ± 0.5 Intensity (I / I ₀ ) 6.97 Wed 7.12 next 8.00 very good 8.40 very good 9.28 Wed 9.97 next 10.62 very good 10.92 next 11.62 next 13.81 next 15.04 next 15.04 next 16.04 next 16.14 next 16.26 next 18.63 next 19.52 next 20.18 Wed 20.63 next 21.48 next 21.74 next 22.21 Wed 22.54 next 23.04 very good 24.17 next 25.23 next 26.33 next 27.58 next 28.02 next 28.22 next 28.42 next 28.92 next 29.62 next 32.24 next

The present invention also relates to a method for producing ITQ-22. The preparation of zeolite is carried out in a basic medium in the absence of fluoride ions, the method comprising heat treatment at a temperature between 80 and 200 ° C, preferably between 130 and 200 ° C, of a reaction mixture containing a source of SiO ₂ (such as, for example, tetraethylorthosilicate, colloidal silicon dioxide, crystalline silicon dioxide), optionally a GeO ₂ source, one or more (different) organic cations, which may include 1,5-bis (methylpyrrolidinium) pentane, and water. Organic cations are added to the reaction mixture in the form of a salt (for example, a halide, preferably chloride or bromide) or hydroxide, and in addition, a source of alkali or alkaline earth metal ions can also be added as a hydroxide or as a salt.

Optionally, a source of a tetravalent element or elements Y other than Si and Ge, preferably Ti, V, Sn and / or trivalent elements X, preferably Al, B, Ga, Fe, Cr, can be added. The addition of this element or elements can be carried out before heating the reaction mixture or at an intermediate moment during this heating. In addition, it may be appropriate from time to time to add ITQ-22 crystals (between 0.01 and 20 wt.% Based on inorganic oxides taken as a whole, preferably between 0.05 and 10 wt.%) As a crystallization seed ( sowing) at some stage of preparation of the zeolite. The composition of the reaction mixture corresponds to the general empirical formula:

rROH: sM _{1 / n} OH: tX ₂ O _3: YO _2, and: νGeO _2: SiO _2: wH ₂ O,

in which M represents one or more inorganic cations with a charge + n; X is one or more trivalent elements, preferably Al, B, Ga, Fe, Cr; Y represents one or more tetravalent elements other than Si and Ge, preferably Ti, Sn, V; R is an organic cation, preferably 1,5-bis (methylpyrrolidinium) pentane; and the values of r, s, t, and, ν and w vary in the ranges:

r = ROH / SiO ₂ = 0.01-1.0, preferably 0.1-1.0

s = M _{1 / n} OH / SiO ₂ = 0-1.0, preferably 0-0.2

t = X ₂ O ₃ / SO ₂ = 0-0.1, preferably 0-0.05

u = YO ₂ / SiO ₂ = 0-0.1, preferably 0-0.05

ν = GeO ₂ / SiO ₂ = 0-4, preferably 0.005-1

w = H ₂ O / SiO ₂ = 1-100, preferably 1-50.

Heat treatment of the reaction mixture can be carried out statically or by stirring the mixture. Upon completion of crystallization, the solid product is separated by filtration or centrifugation and dried. During subsequent calcination at temperatures above 350 ° C, preferably between 400 and 900 ° C, decomposition and desorption of the organic matter remaining adsorbed inside the zeolite takes place, and the channels of the zeolite become free. The calcination operation can be carried out in the presence of N ₂ followed by calcination in air, or direct calcination in air can be carried out, or the organic substance can be extracted with mineral or organic acid, or the organic material can be removed by treatment with ozone.

After calcination, the material is granulated. The methods by which the catalyst is granulated are well known in the literature, using diluents, for example, such as SiO ₂ or Al ₂ O ₃ or clay, zirconium, magnesium oxides, or mixtures thereof, in a zeolite / diluent ratio between 20 and 95 %, preferably between 40 and 90 wt.%.

In an alternative embodiment, the calcined catalyst may be treated with an aqueous solution of a mineral acid, for example, such as HNO ₃ , H ₂ SO ₄ , H ₃ PO ₄ , HClO ₄ .

As a result of treatment with this aqueous solution of mineral acid, the pH value is set between 0 and 1.5 at a temperature between 20 and 100 ° C for a time between 10 and 400 minutes, depending on the concentration of the acid and the processing temperature. The ratio of catalyst / aqueous acid solution is between 0.05 and 1, preferably between 0.1 and 0.5 by weight.

The resulting material, treated (or untreated) with acid, but containing acid sites in its structure, after calcination at a temperature between 450 and 700 ° C, is used as a catalyst.

ITQ-22 may have the following applications:

- as an additive to catalysts for catalytic cracking of hydrocarbons, and in general organic compounds,

- as a component of catalysts for hydrocracking and soft hydrocracking,

- as a component or additive to light paraffin isomerization catalysts,

- as a component of catalysts for dewaxing and isodeparaffinization,

- as a catalyst for the alkylation of isoparaffins with olefins and the alkylation of aromatic compounds and substituted aromatic compounds with olefins, alcohols or polyalkylated aromatic compounds, and more particularly as a catalyst for the alkylation of benzene with propylene,

- as a catalyst in acylation reactions, preferably in the acylation reactions of substituted aromatic compounds using acids, acid chlorides or organic acid anhydrides as acylating agents,

- as catalysts in oxidation reactions, preferably reactions of the Meerwein-Pondorf-Verley type.

Particularly preferred is the use of hydrocarbons and generally organic compounds as additives to catalytic cracking catalysts. Zeolite ITQ-22 has a three-dimensional topology with a system of pores whose sizes differ from those in any other zeolite used so far in catalysts of the CPK process. This zeolite contains pores formed by linked 8-, 10- and 12-membered rings, and it is this topology that determines the specific properties of cracking catalysts.

When used as a cracking catalyst, the ITQ-22 zeolite material may be the only zeolite component of the catalyst embedded in the matrix, or it may be combined with at least one second zeolite component, both components embedded in the matrix.

When ITQ-22 is combined with another zeolite component or components, said second zeolite component can be formed by zeolite structures selected from: zeolite structures containing pores delimited by 14-membered rings, for example, such as SSZ-24, CIT-5, UTD -one; zeolite structures containing pores delimited by 12-membered rings, for example, such as Beta zeolite, ITQ-7, zeolite faujasite Y, SSZ-33; zeolite structures containing pores delimited by 11-membered rings, for example, such as NU-86; zeolite structures containing pores delimited by 10-membered rings, for example, such as ITQ-13, ZSM-5, SAPO-11, MSM-22, and mixtures thereof.

In addition, for the cracking process, the catalyst may consist, in whole or in part, of the same particles of ITQ-22 material, said at least second component being present in the catalyst in the same particles embedded in the matrix. These particles preferably include at least two zeolite components that are ITQ-22 and zeolite faujasite Y in one or more embodiments selected from the group consisting of zeolite faujasite Y, ultra-stable zeolite faujasite Y, zeolite faujasite Y, subjected to complete ion exchange with rare earth metals, zeolite faujasite Y, subjected to partial ion exchange with rare earth metals, ultra-stable zeolite faujasite Y, subjected to complete ion exchange with re dc-earth metals, ultrastable zeolite faujasite Y, subjected to partial ion exchange with rare-earth metals, and mixtures thereof. Preferably, said second zeolite component of the type of faujasite Y is present in an amount of between 0.1 and 99.9% by weight, based on the total weight of the zeolite components, wherein the weight of ITQ-22 zeolite is between 0.1 and 60% by weight on the total mass of zeolite components. The remainder of the catalyst composition is constituted by components containing a matrix that are well known in the art, such as kaolin, alumina and silica, and, in addition, it may contain P ₂ O ₅ .

When zeolite ITQ-22 is used in the cracking process, together with at least one other zeolite component, the zeolite components embedded in the same particles, at least some particles of the catalytic cracking catalyst preferably contain:

0.1-40 wt.% Zeolite material ITQ-22 based on the total weight of zeolite components,

0.1-99.9 wt.% Zeolite faujasite Y calculated on the total weight of zeolite components.

When used in cracking processes, ITQ-22 zeolite can form part of a catalyst that is partially or fully constructed from at least two types of particles in which ITQ-22 zeolite material and at least one second zeolite material are embedded in the matrix moreover, the ITQ-22 zeolite material and said second zeolite component are in different particles, and the catalyst is a physical mixture of particles of different nature. Thus, in this case, each zeolite will be separately introduced into the matrix. The final mixed catalyst will be formed from a mixture of at least two types of particles, with particles of each type introduced into different zeolite components. The final mixture will preferably be formed from particles of the type whose matrix includes ITQ-22, and from particles of the second type that include zeolite faujasite Y in any other form other than the forms of faujasite Y embedded in the second matrix. The CPK process catalyst may be formed from said mixture of particles of this type; particles with ITQ-22; and particles with zeolite faujasite Y in any of its two forms.

When zeolite ITQ-22 is used in the cracking process with another zeolite component or components, the zeolite components embedded in various types of particles, the catalytic cracking catalyst preferably contains:

0.1-40 wt.% Particles containing zeolite ITQ-22, calculated on the sum of the zeolite components, in which each particle includes 10-70 wt.% Zeolite ITQ-22;

0.1-99.9 wt.% Particles containing a conventional catalytic cracking catalyst based on a faujasite type zeolite, in which percentages are calculated based on the sum of the zeolite components.

In the case where the catalyst for the cracking process includes ITQ-22 and another zeolite component or components contained in particles of a different type, said catalyst may have a composition in which at least a third type of particles exists in which the third zeolite can be included in the matrix. This third zeolite is preferably ZSM-5.

Of course, and this is known from the prior art, the final catalyst may also contain other particles, for example, for the purpose of (but without limitation): improving fluidization, trapping contaminants (for example, such as metals, nitrogen, Na ⁺ ), bed circulation, trapping SOx In particular, the CPK catalyst may contain these mentioned types of additional particles.

In the described catalytic cracking catalyst, which contains ITQ-22, zeolite faujasite Y and ZSM-5, a physical mixture of individual particles in which the zeolite components will be in the following proportions: not less than 20 wt.% Zeolite faujasite Y, calculated on the total mass of zeolite components; and not more than 80 wt.% the sum of zeolites (ITQ-22 + ZSM-5), and the value of the ratio of the mass of zeolite ZSM-5 to the mass of zeolite ITQ-22 is between 10 and 0.

When the catalyst contains ITQ-22 zeolite and at least two other zeolite components present in different types of particles, the third component is preferably ZSM-5 zeolite.

For use in the cracking process, the catalyst may include more than three types of different particles, in particular CPK catalysts, which, in addition, may contain other particles to improve fluidization, etc.

Particles of the catalyst include components that are not active in the catalytic process, but they are necessary in order to modify the catalyst, such as binders and / or traditional additives, such as clays, as well as others.

Zeolite components may include one or more T ^IV elements, for example, such as Si, as well as other T ^III elements or elements preferably selected from the group consisting of Al, Fe, Ge, Ga, Zn, Ti, B and mixtures thereof. In addition, they may include phosphorus. Moreover, they can exchange with divalent and / or trivalent ions or with rare earth metals. In addition, they may optionally contain vanadium compounds and optionally cerium, which are added in the next step after zeolite synthesis.

In both cases, when the zeolite components must be in the same particles and when the zeolite components must be in different particles, zeolite faujasite Y can be added to the cracking catalyst in various forms, such as zeolite HY, ultrastable zeolite faujasite Y (USY) , zeolite faujasite Y, with complete exchange for rare earth ions (REY) or with rare earth metals, protons H ⁺ (HREY), zeolite USY, a partial exchange for ions of rare earth metals (REUSY), or zeolite type Y, exchanged with rare-earth ions metal and calcined (CREY).

When the catalytic cracking catalyst includes ITQ-22 with at least two other zeolite components in different particles, each type of catalyst particle may include one or more zeolite components.

In both cases, when the catalyst contains ITQ-22 as the only zeolite component and when the catalyst contains another zeolite component or components, a matrix containing at least one binder material such as silica, alumina, aluminosilicate is used to form the catalyst particles , P ₂ O ₅ and mixtures thereof. In addition, the final catalyst particles may contain additives conventional for catalytic cracking, such as clays.

In particular, CPK catalysts may contain any conventional material, such as, for example, kaolin, so that the catalysts can take the form of particles of various sizes. Upon receipt of the catalyst CPK prepare and grind the suspension in order to form catalyst particles. In the case of CPK reactors, particles between 60 and 200 micrometers are preferred.

Other zeolitic components of the ITQ-22 zeolite material that form part of the catalyst used in the cracking process may include one or more T ^IV elements, such as, for example, Si and Ge, and also include at least one T ^III element. The specified T ^III element is preferably selected from the group consisting of Al, Fe, Ge, Ga, Zn, Ti, B and mixtures thereof.

In the case of catalytic cracking in CPK reactors, ITQ-22 zeolite can be modified by the addition of phosphorus. In the original composition, the molar ratio between T ^IV and T ^III is between 8 and 10000 and preferably between 20 and 1000. In addition, the cracking catalyst may contain one or more alkali metals. However, if they are used, the amount of alkali metals in no case may exceed 0.25 wt.% Na ₂ O.

Zeolite components that can form part of a cracking catalyst, including the ITQ-22 zeolite material, as noted above, may contain phosphorus. The amount of phosphorus present is preferably from 0 to 8 wt.%, Calculated on zeolite ITQ-22. Phosphorus can be introduced by impregnation, for example, in an aqueous solution of at least one acid or salt selected from the group consisting of H ₃ PO ₄ , (NH ₄ ) ₂ PO ₄ , (NH ₄ ) ₂ HPO ₄ , ( NH ₄ ) H ₂ PO ₄ . The resulting product is calcined at a temperature between 350 and 700 ° C.

The zeolite components that can form part of the cracking catalyst, including the ITQ-22 zeolite material, can be ion exchanged with divalent and / or trivalent ions, or they can be fully or partially exchanged with rare earth ions.

The catalyst used in the cracking process may contain vanadium compounds and optionally cerium added in the post-synthesis phase of ITQ-22 zeolite.

The particles of the catalyst used in the cracking process may have a size between 20 and 400 micrometers. In a preferred embodiment, the catalyst is formed from particles between 60 and 200 micrometers in size.

Zeolite ITQ-22 can be used in the process of cracking KFK and in the process of deep catalytic cracking (GKK), which includes contacting the feedstock with the catalyst in the reactor for a time between 0.1 and 80 s and the selection of the resulting product.

As a result of using ITQ-22 zeolite, gasoline with a reduced content of aromatic compounds, with a high content of olefins and isoparaffins, with an increased octane number is obtained, and less dry gas and an increased propylene / propane ratio are obtained, compared to using a catalyst that does not contain ITQ zeolite -22.

In addition, the use of ITQ-22 zeolite as a catalyst in the alkylation process is particularly preferred. In the indicated process for the alkylation of aromatic compounds, an appropriate amount of catalyst is used along with an alkylating agent selected from olefins, alcohols, polyalkylated aromatic compounds and mixtures thereof.

Preferably, said alkylation process is carried out at a molar ratio of the alkylating agent to the starting aromatic compound in the range between 2 and 20 in the presence of a catalyst.

When the alkylating agent is selected from olefins, alcohols and mixtures thereof, said olefin and said alcohol preferably contain from 2 to 20 carbon atoms.

In a preferred embodiment, the starting aromatic compound is selected from the group consisting of benzene, naphthalene, anthracene, phenanthrene and their substituted derivatives, and even more preferably, the starting aromatic compound is benzene.

In addition, the starting aromatic compound may be selected from alkylbenzene, alkylanthracene, alkylphenanthrene, hydroxybenzene, hydroxynaphthalene, hydroxyanthracene, hydroxyphenanthrene, alkoxybenzene, alkoxynaphthalene, alkoxyanthracene and alkoxyphenanthrene.

Preferably, the alkylating agent is a polyalkylated aromatic compound and the starting aromatic compound is a non-alkylated aromatic compound, thus, during the alkylation, at least one alkyl group is transferred from the polyalkylated aromatic compound to the starting aromatic compound.

When the alkylating agent is a polyalkylated aromatic compound, the alkyl group or alkyl groups of said polyalkylating agent may contain a different number of carbon atoms. In a preferred embodiment, said alkyl group or groups may contain from 2 to 20 carbon atoms, preferably from 6 to 20 carbon atoms.

When the alkylating agent is a polyalkylated aromatic compound and the starting aromatic compound is a non-alkylated aromatic compound, said starting aromatic compound is preferably selected from benzene, naphthalene, anthracene, phenanthrene, substituted benzene, substituted naphthalene, substituted anthracene and substituted phenanthrene.

Preferably, the alkylating agent is a polyalkylated aromatic agent and the starting aromatic compound is benzene. Even more preferably, said polyalkylated aromatic compound is polyisopropylbenzene and the starting aromatic compound is benzene, thus benzene is alkylated with propylene (from polyisopropylbenzene) to form cumene.

Therefore, a preferred use of ITQ-22 relates to the alkylation of benzene with an alkylating agent selected from propylene, ethylene, ethyl alcohol, propyl alcohol and mixtures thereof.

According to the use of ITQ-22 zeolite in the alkylation process, this alkylation reaction is carried out at a temperature between 60 and 350 ° C., preferably between 80 and 300 ° C.

The alkylation process is carried out under pressure, which is sufficient at least to partially preserve the liquid phase, preferably in the range between 1.4 and 7.0 MPa, more preferably between 1.4 and 4.1 MPa.

The alkylation process is carried out at a feed rate (weight feedrate VSP) reagents between 0.2 and 150 hours ^-1 and preferably between 0.5 and 10 h ^-1.

Preferably, the alkylation of benzene with propylene is carried out under the following conditions: the reaction temperature is between 60 and 350 ° C, preferably between 80 and 300 ° C; the process is carried out under pressure, which is sufficient at least to partially preserve the liquid phase, preferably in the range between 1.4 and 7.0 MPa, more preferably between 1.4 and 4.1 MPa; feed rate (VSP) of reagents is between 0.2 and 150 h ^-1, preferably between 0.5 and 10 h ^-1; the benzene / propylene molar ratio is between 2 and 20, preferably between 2 and 15.

When zeolite ITQ-22 is used in acid form during the alkylation of aromatic compounds with olefins or alcohols, more specifically, when zeolite is used as a catalyst for the alkylation of benzene with propylene, it turns into a highly active catalyst that has an unexpectedly low selectivity for the formation of NPBs. In addition, cumene selectivity can be increased by introducing appropriate amounts of alkali or alkaline earth metals or metal cations by ion exchange with a zeolite. Selectivity can also be increased by eliminating acid sites on the surface by extraction of trivalent cations from the lattice, such as, for example, Al and / or B, by treatment with mineral acids or other chemical agents capable of extracting these elements. Processing by cation exchange or the above leaching can reduce the yield of polyalkylated products.

When ITQ-22 contains Ti, it is a particularly effective catalyst in processes: epoxidation of olefins, oxidation of alkanes, oxidation of alcohols and oxidation of thioethers to sulfoxides and sulfones using organic or inorganic hydroperoxides, such as, for example, H ₂ O, as oxidizing agents ₂ , tert-butyl hydroperoxide, cumene hydroperoxide; the amoxidation of ketones, more specifically, the oxidation of cyclohexanone to cyclohexanone oxime by NH ₃ and H ₂ O ₂ . When ITQ-22 contains Sn, it is very convenient as a catalyst in Bayer-Williger oxidation reactions in which H ₂ O _{2 is} used as an oxidizing agent.

Brief Description of the Drawings

Figure 1 presents the x-ray diffraction pattern of the synthesized sample ITQ-22, in which the lattice consists exclusively of oxides of germanium and silicon, with a ratio of Si / Ge = 3.8 and which is synthesized using a quaternary ammonium cation, 1,5-bis (methylpyrrolidinium) pentane, as a structure determining agent.

Figure 2 presents the x-ray diffraction pattern of the same ITQ-22 sample after calcination at 580 ° C in order to remove organic compounds adsorbed inside the zeolite.

EXAMPLES

Example 1

This example illustrates the preparation of 1,5-bis (methylpyrrolidinium) pentane dihydroxide.

In a 500 ml flask, 18.7 g of 1,5-dibromopentane, 20 g of 1-methylpyrrolidine and 300 ml of acetone are stirred. The mixture was kept at the boil under reflux for 24 hours, after which the precipitated solid was separated by decantation and then washed several times with acetone. The material is finally dried in vacuo to give 31.9 g of a white solid. The elemental analysis and nuclear magnetic resonance spectrum in D ₂ O indicate that this solid is the target product, namely 1,5-bis (methylpyrrolidinium) pentane dibromide.

The dihydroxide form of the structure-determining agent is obtained by anion exchange using a Dowex SBR resin (in molar excess). This exchange is carried out with stirring in a fluidized bed of resin in hydroxide form and an aqueous solution of cation bromide for one night. The resulting solution was titrated with aqueous HCl (hydrochloric acid) using phenolphthalein as an indicator and it was determined that the exchange efficiency was 95%. This solution can be concentrated in a rotary evaporator, for example to a concentration of 0.5-1 N., for use in the synthesis of molecular sieves.

Example 2

This example illustrates the preparation of ITQ-22 by using the 1,5-bis (methylpyrrolidinium) pentane cation.

6.17 g of tetraethylorthosilicate (TEOS) are added in 23.14 g of a solution of 1,5-bis (methylpyrrolidinium) pentane dihydroxide, (R (OH) ₂ ) containing 0.96 equivalents of hydroxide in 1000 g of solution. 1.55 g of germanium oxide was added to this mixture, and the mixture was allowed to evaporate with stirring until the ethanol formed during the hydrolysis of TEOS was completely removed and the required amount of water was removed; thus, the final composition of the gel is:

0.67 SiO ₂ : 0.33 GeO ₂ : 0.25R (OH) ₂ : 3.5H ₂ O.

The resulting mixture was loaded into an autoclave, which was internally lined with polytetrafluoroethylene, and heated at 175 ° C for 14 days. Then the autoclave is cooled, its contents are filtered, the solid is washed with water and dried at 100 ° C. An X-ray diffraction pattern of the substance is shown in FIG. 1, and a list of the most typical peaks is presented in Table III. Annealing a solid at 580 ° C in air for 3 days allows you to remove adsorbed organic compounds from it. An X-ray diffraction pattern of the calcined ITQ-22 zeolite is shown in FIG. 2, and a list of the most typical peaks is presented in Table IV, it follows from these data that this material is stable during this treatment.

Example 3

The following example illustrates the preparation of ITQ-22 of various compositions.

12 g of tetraethylorthosilicate (TEOS) are added to 27.3 g of a solution of 1,5-bis (methylpyrrolidinium) pentane dihydroxide (R (OH) ₂ ) containing 1.16 equivalents of hydroxide in 1000 g of solution. 0.6 g of germanium oxide is dissolved in this mixture, and the mixture is left to evaporate with stirring until the ethanol formed is completely removed and the required amount of water is removed, so the final gel composition is:

0.91 SiO ₂ : 0.09 GeO ₂ : 0.25R (OH) ₂ : 3.5H ₂ O.

The resulting mixture is heated in an autoclave, which is internally lined with polytetrafluoroethylene, at 175 ° C for 14 days. The solid obtained after filtration, washing with distilled water and drying at 100 ° C. is ITQ-22.

Example 4

This example illustrates the synthesis of Al-ITQ-22.

Add 0.097 g of aluminum isopropoxide to 9 g of tetraethylorthosilicate (TEOS). After that, 20.68 g of a solution of 1,5-bis (methylpyrrolidinium) pentane dihydroxide, (R (OH) ₂ ) containing 1.16 equivalents of hydroxide 1000 g of a solution are added, and then 0.5 g of germanium oxide is dissolved. The mixture is left to evaporate with stirring until the ethanol formed during the hydrolysis of TEOS is completely removed and the required amount of water is removed in order to obtain the indicated final composition. This gel has the following composition: 0.91 SiO ₂ : 0.09 GeO ₂ : 0.005 Al ₂ O ₃ : 0.25R (OH) ₂ : 3.5H ₂ O.

The resulting mixture was loaded into an autoclave which was internally lined with polytetrafluoroethylene and heated at 175 ° C for 12 days.

The X-ray diffraction pattern of the solid obtained after filtration, washing with distilled water and drying at 100 ° C indicates that the substance is ITQ-22.

Example 5

This example illustrates the preparation of an Al-ITQ-22 sample having a chemical composition different from that in Example 4.

0.325 g of aluminum isopropoxide is added to 11.05 g of tetraethylorthosilicate (TEOS). After that, 34.2 g of a solution of 1,5-bis (methylpyrrolidinium) pentane dihydroxide, (R (OH) ₂ ) containing 1.2 equivalents of hydroxide per 1000 g of solution are added, and then 2.77 g of germanium oxide are dissolved. The mixture is left to evaporate with stirring until the ethanol formed during the hydrolysis of TEOS is completely removed and the required amount of water is removed in order to obtain the indicated final composition. This gel has the following composition: 0.67 SiO ₂ : 0.33 GeO ₂ : 0.01 Al ₂ O ₃ : 0.25R (OH) ₂ : 15H ₂ O.

The resulting mixture was loaded into an autoclave which was internally lined with polytetrafluoroethylene and heated at 175 ° C for 12 days.

The X-ray diffraction pattern of the solid obtained after filtration, washing with distilled water and drying at 100 ° C indicates that this substance is ITQ-22. The resulting solid was calcined at 580 ° C. for 3 hours, and it follows from the X-ray diffraction pattern that the structure of the zeolite is preserved. Chemical analysis of the calcined zeolite shows that it has a composition corresponding to the values of the molar ratio Si / Ge = 5 and (Si + Ge) / Al = 30.

Example 6

This example illustrates the synthesis of Ti-ITQ-22.

0.3 g of titanium (IV) tetraethoxide is added to 9.26 g of tetraethylorthosilicate (TEOS). After this, 39.97 g of a solution of 1,5-bis (methylpyrrolidinium) pentane dihydroxide, (R (OH) ₂ ) containing 0.85 equivalents of hydroxide in 1000 g of solution are added, and then 2.32 g of germanium oxide are dissolved. The mixture is left to evaporate with stirring until the ethanol formed during the hydrolysis of TEOS is completely removed and the required amount of water is removed in order to obtain the indicated final composition. This gel has the following composition: 0.67 SiO ₂ : 0.33 GeO ₂ : 0.02 TiQ ₂ : 0.25R (OH) ₂ : 3.5H ₂ O.

The resulting mixture was loaded into an autoclave, which was internally lined with polytetrafluoroethylene, and heated at 175 ° C for 16 days.

The X-ray diffraction pattern of the solid obtained after filtration, washing with distilled water and drying at 100 ° C indicates that this substance is ITQ-22.

Example 7

This example illustrates the synthesis of Sn-ITQ-22.

15.12 g of solution of 1,5-bis (methylpyrrolidinium) pentane dihydroxide, (R (OH) ₂ ) containing 1.20 equivalent of hydroxide in 1000 g of solution is added to 5.00 g of tetraethylorthosilicate (TEOS), and then 1, 26 g of germanium oxide. After this, a solution of 0.105 g of tin (IV) tetrachloride pentahydrate in 2 g of water is added. The mixture is left to evaporate with stirring until the ethanol formed during the hydrolysis of TEOS is completely removed and the required amount of water is removed in order to obtain the indicated final composition. This gel has the following composition: 0.67 SiO ₂ : 0.33 GeO ₂ : 0.0083 SnO ₂ : 0.25R (OH) ₂ : 3.5H ₂ O.

The resulting mixture was loaded into an autoclave which was internally lined with polytetrafluoroethylene and heated at 175 ° C for 23 days.

The X-ray diffraction pattern of the solid obtained after filtration, washing with distilled water and drying at 100 ° C indicates that this substance is ITQ-22.

Example 8

This example illustrates the preparation of a catalytic cracking catalyst component containing an ITQ-22 type zeolite that is preactivated at 580 ° C. in air in order to obtain an acid form of the zeolite.

In order to study the activity and selectivity of ITQ-22 zeolite in the process of catalytic cracking of industrial oil fractions, a catalyst is prepared by mixing the ITQ-22 type zeolite in acid form as described in Example 5 with silica (BASF D1111), both in the form of powders, and with a mixture of 23% zeolite type ITQ-22 and 77 wt.% SiO ₂ , respectively. This mixture is thoroughly homogenized to obtain a cake, which is ground in a mortar, and sieved, selecting a fraction of particles with a diameter between 0.59 and 0.84 mm.

Example 9

This example illustrates the preparation of a catalytic cracking catalyst component containing USY zeolite for laboratory testing.

The catalyst is prepared by mixing USY zeolite (CBV760 from Zeolyst Intl.) With silica (BASF D1111), both in powder form, and with a composition of 67% USY and 33 wt.% SiO ₂ , respectively. This mixture is thoroughly homogenized to obtain a cake, which is ground in a mortar, and sieved, selecting a fraction of particles with a diameter between 0.59 and 0.84 mm.

Example 10

This example illustrates the use of ITQ-22 zeolite as an additive to a vacuum gas oil catalytic cracking catalyst.

The catalytic components described in example 8 are used as an additional catalytic component described in example 9 during the catalytic cracking of vacuum gas oil, the properties of which are shown in table V. Both catalysts are placed in the reactor in two different layers, as described in Journal of Catalysis 1997, 165 (1), p. 102. 1.5 g of the catalyst of Example 9 was placed in the upper reaction zone, and 1.34 g of the catalyst of Example 8 was placed in the lower zone.

Table v
Properties of Vacuum Gas Oil Density (15 ° С) g · cm ^-3 0.9172 Aniline point (° C) 79.2 Content: sulfur (wt.%) 1.65 nitrogen (ppm) 1261 Na (ppm) 0.18 Cu (ppm) <0.1 Fe (ppm) 0.30 Ni (ppm) 0.2 V (ppm) 0.40 Distillation according to ASTM D-1160 (° C): 5% 319 10% 352 thirty% 414 fifty% 436 70% 459 90% 512 VABP (° C) ¹⁾ 435 K (UOP) 11.82 Average molecular weight 407 Aromatic carbon (wt.%) 22.96 Naphthenic carbon (wt.%) 15.16 Paraffin carbon (wt.%) 61.88 ¹⁾ VABP - medium temperature (by volume)

The process is carried out under conditions: temperature 520 ° C, reaction time 30 s, catalyst weight 2.34 g, with catalyst / feed ratios (by weight) equal to 0.59, 0.73, 0.95, 1.35 and 2 , 38, while the amount of supplied gas oil feed is 3.76, 3.07, 2.35, 1.65 and 0.94 g. The gas obtained is analyzed by gas chromatography, for liquid products, simulated distillation is carried out (according to ASTM D-2887 ) and coke are determined by IR analysis of CO ₂ formed during the combustion of coke. The conversion value is defined as the sum of the values of the output of gases (H ₂ and C ₁ -C ₄ ), coke and gasoline (boiling point <235.4 ° C).

The composition (PIONA: Paraffinic, Isoparaffinic, Olefin, Naphthenic and Aromatic hydrocarbons) and quality (OR m. = Octane number by research method; OR m. M. - by motor method) of the gasoline fraction is determined by gas chromatography using computer the Detailed hydrocarbons analysis program provided by VARIAN and the correlation coefficients given in the publication: Lugo, HJ, Ragone, G., and Zambrano, J., Ind. Eng. Chem. Res. 38, 2171 (1999). The results obtained by interpolation with a total conversion of 80% are shown in table VI. The use of zeolite ITQ-22 as an additive to zeolite USY (catalyst USY / ITQ-22) leads to an increase in the yield of olefins C3 and C4 calculated on the main catalyst (USY), with a slight decrease in the yield of gasoline. In addition, the resulting gasoline has a reduced aromatic content when the catalyst contains an ITQ-22 additive.

It is important to note that when using ITQ-22 as an additive, a higher propylene / propane ratio is obtained, and this result is very advantageous from the point of view of a possible industrial process.

Table VI
The values of selectivity and ratios of importance in the process of catalytic cracking of gas oil at 520 ° C and a feed time of 30 s. Fresh supplement. CATALYST USY USY / ITQ-22 Cat / Hydrocarbon (g / g) 1,50 1.37 Conversion% 80 80 Gasoline% 45.9 40.3 Gases,% 28.1 33.0 Coke,% 6.0 6.7 Fraction C ₁ -C ₄ : Hydrogen,% 0.12 0.10 Methane% 0.88 0.88 Ethane,% 1,04 1,04 Ethylene,% 1.99 2.21 Propane% 3.42 3.75 Propylene,% 5.18 7.09 Isobutane,% 8.89 9.25 n-Bhutan,% 2.23 2.41 n-butenes,% 3.28 4.07 Isobutene,% 1,08 2.22 Ratios: butene / butane 0.39 0.54 propylene / propane 1.51 1.89 isobutane / n-butane 3.99 3.84 H ₂ + C1 + C2 3.92 4.14 isobutene / n-butenes 0.33 0.55 isobutene / isobutane 0.12 0.24 H ₂ + C1 + C2 / isobutane 0.44 0.45 C3 / C4 0.56 0.60 isobutene + isobutane / amount C4 0.64 0.64 isobutane / n-butane 0.08 0.14 H ₂ + C1 + C2 / (isobutene + isobutane) 0.39 0.36 ethylene / ethane 1.91 2.12 ethylene / propylene 0.39 0.31 The composition of gasoline, wt.%: aromatic hydrocarbons,% 75.81 77.63 isoparaffins,% 11.85 9.13 naphthenes,% 6.90 5.62 olefins,% 3.43 3.71 paraffins,% 2.02 3.91 Very good 90.68 91.04 OCH m.m. 86.31 86.80 Very good (in a barrel) 41.6 36.7 OCH m.m. (in a barrel) 39.6 35.0 Isoamylene,% 0.91 0.94

Example 11

This example illustrates the use of the material prepared according to example 5 and activated by calcination in air at 580 ° C for 3 hours, as a catalyst for the alkylation of benzene with propylene.

A sample of the activated material prepared according to Example 5 is obtained in the form of a cake, particles between 0.25 and 0.42 mm in size are taken in order to carry out the reaction. Zeolite (0.55 g) is diluted with silicon carbide (particles 0.59-0.84 mm) in a ratio of SiC / zeolite equal to 5 (by weight). The diluted catalyst is charged into a tubular steel reactor 1 cm in diameter and passed N ₂ flow rate of 100 ml · min ^-1 under standard conditions at 150 ° C for 1.5 hours. Then reduce the temperature to 20 ° C and close the flow of N ₂ . At this point, benzene (1200 μl · min ⁻¹ ) is supplied and the pressure is increased to 3.5 MPa. When the pressure reaches 3.5 MPa, increase the temperature to 125 ° C and begin to supply propylene (270 μl · min ^-1 ), and the molar ratio of benzene / propylene (B / P) is 3.4.

The results of the conversion of propylene are shown in table VII.

Table VII
Conversion and selectivity in the alkylation of benzene with propylene at 125 ° C, B / P = 3.4 mol · mol ^-1 , VSP propylene = 6 h ^-1 , P = 3.5 MPa for the Al-ITQ-22 catalyst prepared according to example 5 Reaction time (min) Conversion (%) Selectivity based on propylene (%) by: Cumene DIPB Airbag Other fifteen 95.62 93.09 6.70 0.04 0.17 60 98.02 93.01 6.73 0.05 0.22 one hundred 97,23 93.89 5.75 0,03 0.33 140 96.30 95.83 3.83 0,03 0.31 180 97.94 95.55 4.27 0,03 0.15

In this example, very high cumene selectivity values can be noted along with very low NPB and diisopropylbenzene (DIPB) selectivity values, which are lower than the selectivity values obtained using Beta zeolite as a catalyst under the same process conditions. The results obtained with industrial Beta zeolite with a Si / Al ratio of 13, supplied by Zeolyst (code CP811), are shown in Table VIII.

Table VIII
The conversion and selectivity of an industrial catalyst is Beta zeolite (Si / Al = 13) during the alkylation of benzene with propylene at 125 ° C, B / P = 3.4 mol · mol ^-1 , VSP propylene = 6 h ^-1 , P = 3, 5 MPa Reaction time (min) Conversion (%) Selectivity based on propylene (%) by: Cumene DIPB Airbag Other twenty 98.07 91.35 8.45 0.04 0.16 90 97.36 92.41 7.35 0.05 0.19 160 98.54 90.84 8.85 0.05 0.26 210 99.65 93.28 6.49 0.05 0.18

From a comparison of the results presented in Tables VI and VIII, it can be seen that ITQ-22 zeolite has higher cumene selectivity and less n-propylbenzene selectivity than Beta zeolite, which is the zeolite catalyst that is currently most commonly used in the production of cumene.

Example 12

This example shows the effect of the process temperature on the conversion and selectivity in the alkylation of benzene with propylene using the same catalyst as in example 11, and the other process conditions coincided with the conditions in example 11.

The results of the change in conversion during the reaction are presented in table IX.

Table IX
Conversion and selectivity in the alkylation of benzene with propylene on an Al-ITQ-22 catalyst prepared according to Example 5 at 150 ° C, B / P = 3.4 mol / mol, VSP propylene = 6 h ^-1 , P = 3.5 MPa Reaction time (min) Conversion (%) Selectivity based on propylene (%) by: Cumene DIPB Airbag Other twenty 99.51 97.25 2.62 0.06 0,07 60 98.70 94.17 5.62 0,07 0.14 one hundred 99.41 96.10 3.77 0.06 0,07 180 99.31 95.04 4.74 0.06 0.16

Example 13

This example illustrates the use of the material prepared according to example 5 and activated by calcination in air at 580 ° C for 3 hours, as a catalyst for the alkylation of benzene with ethylene.

A sample of the activated material prepared according to Example 5 is obtained in the form of a cake, particles between 0.25 and 0.42 mm in size are taken in order to carry out the reaction. Thus, zeolite (0.55 g) is diluted with silicon carbide (1.57 g, particles 0.59-0.84 mm). The diluted catalyst is loaded into a 1 cm diameter tubular steel reactor. The catalyst is activated in the same manner as in Example 11. In the present example, the process temperature is 220 ° C., with a supply of benzene and ethylene of 2.90 and 0.30 mmol, respectively, and pressure the process is 3.5 MPa. The results are shown in table X.

Table X
Conversion and selectivity in the alkylation of benzene with ethylene (E) at 220 ° C, B / E = 9.6 mol mol ^-1 , VSP ethylene = 1.0 h ^-1 , P = 3.5 MPa, on an Al-ITQ catalyst -22 prepared according to example 5 Reaction time (min) Ethylene Conversion (%) Selectivity (%) by: ethylbenzene butylbenzene diethylbenzene triethylbenzene thirty 99.40 98.20 0.09 1.71 0.00 120 99,20 98.10 0.10 1.80 0.00 210 99.10 97.47 0.16 2,37 0.00 300 99.18 98.54 0.09 1.36 0.01 420 99.52 97.67 0.12 2.19 0.02

Example 14

This example illustrates the use of a Ti-ITQ-22 sample prepared according to Example 6 and activated by calcining in air at 580 ° C. for 3 hours as a catalyst in the epoxidation of hexene-1 with hydrogen peroxide.

A solution of 1.420 g of hexene-1 and 0.412 g of hydrogen peroxide (35% in water) in 12.00 g of methanol is charged into a glass reactor. The reaction mixture is heated to 60 ° C. and 0.100 g of activated Ti-ITQ-22 catalyst is added. After 3 hours of reaction at this temperature with stirring, an olefin conversion of 15% is achieved relative to the maximum possible, taking into account the olefin / oxidizing agent molar ratio used in this example.

Example 15

This example illustrates the use of Ti-ITQ-22 as a catalyst prepared according to Example 6 and activated by calcining in air at 580 ° C. for 3 hours for the epoxidation reaction of dodecene-1 with hydrogen peroxide.

A solution of 2.780 g of dodecene-1 and 0.440 g of hydrogen peroxide (35% in water) in 60.00 g of methanol is charged into a glass reactor. The reaction mixture is heated to 60 ° C. and 0.100 g of activated Ti-ITQ-22 catalyst is added. After 7 hours of reaction at this temperature with stirring, an olefin conversion of 5% is achieved relative to the maximum possible, taking into account the olefin / oxidizing agent molar ratio used in this example.

Example 16

This example illustrates the use of a Ti-ITQ-22 sample prepared according to Example 6 and activated by calcining in air at 580 ° C. for 3 hours as a catalyst for the epoxidation of cyclohexene with tert-butyl hydroperoxide.

9.270 g of cyclohexene and 3.180 g of tert-butyl hydroperoxide are charged into a glass reactor. The reaction mixture was heated to 60 ° C and 0.600 g of activated Ti-ITQ-22 catalyst was added. After 5 hours of reaction at this temperature with stirring, an olefin conversion of 4% is achieved relative to the maximum possible, taking into account the olefin / oxidizing agent molar ratio used in this example.

Example 17

This example illustrates the use of Sn-ITQ-22 as the catalyst prepared according to Example 7 and activated by calcining in air at 580 ° C for 3 hours in the Bayer-Williger reaction between cyclohexanone and hydrogen peroxide.

A solution of 0.063 g of cyclohexanone and 0.078 g of hydrogen peroxide (35% in water) in 1.520 g of dioxane are charged into a glass reactor. The reaction mixture is heated to 70 ° C. and 0.025 g of activated Sn-ITQ-22 catalyst is added. After 7 hours of reaction at this temperature with stirring, a conversion of ketone of 47% is achieved relative to the maximum possible, taking into account the ketone / oxidizing agent molar ratio used in this example.

Example 18

This example illustrates the use of Sn-ITQ-22 as the catalyst prepared according to Example 7 and activated by calcining in air at 580 ° C for 3 hours in the Bayer-Williger reaction between adamantanone and hydrogen peroxide.

A solution of 0.250 g of adamantanone and 0.259 g of hydrogen peroxide (35% in water) in 1.530 g of dioxane is charged into a glass reactor. The reaction mixture was heated to 90 ° C. and 0.025 g of activated Sn-ITQ-22 catalyst was added. After 7 hours of reaction at this temperature with stirring, a conversion of ketone of 22% is achieved relative to the maximum possible, taking into account the ketone / oxidizing agent molar ratio used in this example.

Claims (40)

1. A microporous crystalline material of a zeolite nature, which in the calcined state and in the absence of defects in the crystal lattice, which are manifested as the presence of silanol groups, has the empirical formula x (M _{1 / n} XO ₂ ): yYO ₂ : zGeO ₂ : (1-z) SiO ₂ , in which M represents H ⁺ or at least one inorganic cation with a charge + n; X means at least one chemical element with an oxidation state of +3, preferably selected from the group consisting of Al, Ga, B, Fe and Cr; Y means at least one chemical element with an oxidation state of +4, different from Si and Ge, preferably selected from the group consisting of Ti, Sn and V, characterized in that x has a value of less than 0.2, preferably less than 0.1, and may be zero; y has a value less than 0.1, preferably less than 0.05, and can take a zero value; z has a value less than 0.8, preferably between 0.005 and 0.5, and take a zero value; and the fact that the material after synthesis has an X-ray diffraction pattern with the corresponding values of the angle 2θ (in degrees) and relative intensity values (I / I ₀ ) 2θ (degrees) ± 0.5 Intensity (I / I ₀ ) 8.02 very good 8.43 very good 9.31 Wed 10.64 very good 20.26 Wed 21.81 forces. 22.53 very good where cf. mean average relative intensity between 20 and 40%; forces. means a strong relative intensity between 40 and 60%, and very strong. means a very strong relative intensity between 60 and 100%. 2. The microporous crystalline material of zeolite nature according to claim 1, characterized in that in the calcined state it has an X-ray diffraction pattern with corresponding values of angles 2θ (degrees) and relative intensity (I / I ₀ ) 2θ (degrees) ± 0.5 Intensity (I / I ₀ ) 6.97 Wed 8.00 very good 8.40 very good 9.28 Wed 10.62 very good 20.18 Wed 21.74 Wed 22.54 very good where cf. mean average relative intensity between 20 and 40%; forces. means strong relative intensity between 40 and 60%, and very strong means a very strong relative intensity between 60 and 100%. 3. A method of obtaining a microporous crystalline material according to claim 1 or 2, in which the reaction mixture containing source of SiO ₂ , optional source of GeO ₂ , optional source of another tetravalent element or elements Y, preferably Ti, V, Sn, optionally a source of another trivalent element or elements X, preferably Al, B, Ga, Fe, Cr, optional source of inorganic cations M with a charge + n, one or more sources of 1,5-bis (methylpyrrolidinium) pentane (R), and water subjected to heating with stirring (or without stirring) at a temperature between 80 and 200 ° C, preferably between 130 and 200 ° C, until crystallization is achieved, characterized in that the reaction mixture has a composition, in units molar ratios of oxides in the ranges ROH / SiO ₂ = 0.01-1.0, preferably 0.1-1.0; M _{1 / n} OH / SiO ₂ = 0-1.0, preferably 0-0.2; X ₂ O ₃ / SiO ₂ = 0-0.1, preferably 0-0.05; YO ₂ / SiO ₂ = 0-0.1, preferably 0-0.05; GeO ₂ / SiO ₂ = 0-4, preferably 0.005-1; H ₂ O / SiO ₂ = 1-100, preferably 1-50. 4. The method according to claim 3, characterized in that the organic cation 1,5-bis (methylpyrrolidinium) pentane is added as a dihydroxide or as a mixture of a hydroxide and another salt, preferably a halide. 5. The method according to claim 4, characterized in that a certain amount of crystalline material is added to the reaction mixture, preferably having material properties according to one of claims 1 and 2, as a crystallization promoter, said amount being in the range from 0.01 to 20 wt.% Based on the amount of added inorganic oxides, preferably between 0.05 and 10%. 6. The use of microporous crystalline material according to one of claims 1 and 2, characterized in that this material is used as a catalyst component in a process selected from cracking, hydrocracking, soft hydrocracking of hydrocarbons and / or functionalized hydrocarbons, isomerization of light paraffins, dewaxing process or isodeparaffinization, the process of alkylation of isoparaffins with olefins, the process of alkylation of aromatic compounds and substituted aromatic compounds with olefins, alcohols , Polyalkylated aromatics or mixtures thereof, an acylation process, and the oxidation process. 7. The use according to claim 6 in the process of catalytic cracking of organic compounds, in which the catalyst includes zeolite ITQ-22 as the only zeolite component embedded in the matrix, or zeolite material ITQ-22, at least one second zeolite component embedded into the matrix. 8. The use according to claim 7, in which the specified at least one second zeolite component is formed from zeolite structures containing pores delimited by 14-membered rings, 12-membered rings, 11-membered rings, 10-membered rings, and their mixtures. 9. The use according to claim 7, in which at least part of the catalyst particles contains a second zeolite component selected from one or more groups, including zeolite faujasite Y, ZSM-5 and Beta. 10. The use of claim 7, wherein said catalyst partially or completely consists of particles of the same type with ITQ-22 zeolite material, wherein said at least one second zeolite component is present in the same particle. 11. The use of claim 10, in which the specified second zeolite component is a zeolite faujasite Y in the form of one or more options selected from the group consisting of zeolite faujasite Y, ultrastable zeolite faujasite Y, zeolite faujasite Y, subjected to complete ion exchange with rare earth metals, zeolite faujasite Y, partially ion exchanged with rare earth metals, ultrastable zeolite faujasite Y, subjected to total ion exchange with rare earth metals, ultras partial zeolite faujasite Y, subjected to partial ion exchange with rare earth metals, and mixtures thereof, wherein said ITQ-22 zeolite is present in an amount of between 0.1 and 60 wt.%, calculated on the total weight of zeolite components and zeolite faujasite Y is present in an amount between 0.1 and 99.9 wt.%, calculated on the total weight of the zeolite components, and the rest of the catalyst composition up to 100% is a matrix. 12. The use according to claim 11, in which at least a portion of the catalyst particles contains 0.1-40 wt.% Zeolite material ITQ-22 based on the total weight of the zeolite components, and 0.1-99.9 wt.% Zeolite faujasite Y calculated on the total weight of zeolite components. 13. The use according to claim 7, wherein said catalyst consists, in whole or in part, of at least two types of particles, wherein ITQ-22 and said at least one second zeolite component are in different particles. 14. The application of item 13, in which the catalytic cracking catalyst includes 0.1-40 wt.% Particles containing zeolite ITQ-22, based on the amount of zeolite components, where each particle includes 10-70 wt.% Zeolite ITQ-22; 0.1-99.9 wt.% Particles of a traditional catalytic cracking catalyst based on zeolite faujasite Y, and the percentage is calculated based on the sum of the zeolite components. 15. The application of item 13, in which the specified catalytic cracking catalyst, in addition, includes particles containing zeolite ZSM-5, and the composition of the catalyst zeolite faujasite Y in an amount of at least 20 wt.%, calculated on the total weight of zeolite components, ITQ-22 and ZSM-5 zeolites in a maximum amount of 80 wt.%, calculated on the total weight of zeolite components, and the ratio zeolite mass ZSM-5 zeolite - ITQ-22 lies between 10 and 0. 16. The use according to claim 7, in which the matrix contains at least one binder material selected from silica, aluminosilicate, alumina, P ₂ O ₅ and combinations thereof, and in addition, optionally a traditional catalytic cracking additive. 17. The use according to claim 7, in which any zeolite components also contain no more than 8 wt.% Phosphorus. 18. The use of claim 7, wherein the zeolite components are exchanged with ions selected from divalent ions, trivalent ions, divalent and trivalent ions, and rare earth ions. 19. The use according to claim 7, in which any zeolite component contains vanadium compounds introduced in the stage after synthesis. 20. The use according to claim 7, in which any zeolite component contains cerium introduced in the stage after synthesis. 21. The use according to claim 7, in which the catalyst is formed from particles having a size between 20 and 400 micrometers. 22. The use according to claim 7, in which the catalytic process is selected among the process of catalytic cracking with a fluid layer (KFK) and the process of deep catalytic cracking (GKK). 23. The use according to claim 6, in which the organic compounds are hydrocarbons obtained from fractions of natural or synthetic oil. 24. The use of microporous crystalline material according to one of claims 1 and 2 as a catalyst component in the alkylation of an aromatic compound with an alkylating agent selected from olefins, alcohols, polyalkylated aromatic compounds or mixtures thereof. 25. The application of paragraph 24, in which the starting aromatic compound is selected from the group consisting of benzene, naphthalene, anthracene, phenanthrene and their substituted derivatives. 26. The application of paragraph 24, in which the starting aromatic compound is selected from alkylbenzene, alkylanthracene, alkylphenanthrene, hydroxybenzene, hydroxynaphthalene, hydroxyanthracene, hydroxyphenanthrene, alkoxybenzene, alkoxynaphthalene, alkoxyanthracene and alkoxyphenanthrene. 27. The application of paragraph 24, in which the alkylating agent is selected among olefins, alcohols and mixtures thereof, said olefins and said alcohols containing from 2 to 20 carbon atoms. 28. The use of claim 26, wherein the alkylating agent is a polyalkylated aromatic compound, the starting aromatic compound is a non-alkylated aromatic compound, and in which at least one alkyl group is transferred from the polyalkylated aromatic compound to the starting aromatic compound during alkylation . 29. The use of claim 28, wherein said polyalkylated aromatic compound contains at least one alkyl group that includes from 2 to 20 carbon atoms. 30. The application of claim 28, wherein the starting aromatic compound is selected from benzene, naphthalene, anthracene, phenanthrene, substituted benzene, substituted naphthalene, substituted anthracene, and substituted phenanthrene. 31. The use of claim 28, wherein the polyalkylated aromatic compound is polyisopropylbenzene and the starting aromatic compound is benzene. 32. The use of claim 24, wherein the starting aromatic compound is benzene, the alkylating agent is propylene, and in which cumene is formed as an alkylated aromatic compound during the alkylation process. 33. The application of paragraph 24, in which the alkylation process is carried out at a temperature between 60 and 350 ° C. 34. The application of paragraph 24, in which the alkylation process is carried out at pressure between 1.4 and 7.0 MPa. 35. The application of paragraph 24, in which the alkylating agent and the starting aromatic compound are in a ratio between 2 and 20, in the presence of a catalyst. 36. The use of claim 24, wherein the starting aromatic compound is benzene and the alkylating agent is propylene, and the resulting alkylated aromatic compound is cumene; the alkylation process is carried out at a temperature between 60 and 350 ° C; the pressure at which the alkylation process is carried out is between 1.4 and 7.0 MPa; the feed rate (VSP) of the reactants is between 0.2 and 10 hours and the benzene / propylene molar ratio is between 2 and 20. 37. The use according to claim 6, characterized in that the material contains Ti and is used as a catalyst in the processes selected among the processes of selective oxidation of organic compounds using an oxidizing agent selected among H ₂ O ₂ or peroxides, hydroperoxides or organic peracids. 38. The use according to claim 6, characterized in that the material contains Sn and is used as a catalyst in the process selected from the Bayer-Williger type oxidation processes. 39. The use according to claim 6, characterized in that the material is used as a catalyst in a process selected from among the oxidation processes of the Meerwein-Pondorf-Verley type. 40. The use according to claim 6, characterized in that the material is used as a catalyst in the process selected among the processes of hydroisomerization of olefins, alkylation of olefins with isoparaffins and alkylation of aromatic compounds with olefins or alcohols. The priority is set as follows: paragraphs 1-6 and 37-40 of 05/23/2002, according to the initial application ES P200201249; paragraphs 7-23 have priority from 05/23/2002, according to the application ES P20021249 regarding the use of ITQ-22 as a catalyst or catalyst component of catalytic cracking and hydrocracking; on points 7-23 they take priority from 02/14/2003, according to the application of ES P200300444 regarding other features not disclosed in ES 20021249; paragraphs 24-36 take priority from 05/23/2002, according to the application ES P200201249 regarding the use of ITQ-22 as a catalyst for the alkylation of aromatic or substituted aromatic compounds with olefins, alcohols, or polyalkylated aromatic compounds; on points 24-36 take priority from 04/30/2003, according to the application of ES P200301058 regarding all other features not disclosed in ES 200201249.

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