WO2012049344A1

WO2012049344A1 - Itq-45 material, method for obtaining same and use thereof

Info

Publication number: WO2012049344A1
Application number: PCT/ES2011/070650
Authority: WO
Inventors: Avelino CORMA CANÓS; Fernando REY GARCÍA; María Teresa NAVARRO VILLALBA; Raquel Simancas Coloma; Noemí VELAMAZÁN CIRUJEDA; Ángel CANTÍN SANZ; José Luis JORDÁ MORET
Original assignee: Consejo Superior De Investigaciones Científicas (Csic); Universidad Politécnica De Valencia
Priority date: 2010-10-13
Filing date: 2011-09-19
Publication date: 2012-04-19
Also published as: ES2380471A1; ES2380471B1

Abstract

The invention relates to a microporous crystalline material and to the method for preparing same, which has the composition: x X203 : z Z02 : y Y0₂where X is a trivalent element such as Al, B, Fe, In, Ga or Cr or mixtures thereof, wherein (y+z)/x can be between 9 and infinity; Z is a tetravalent element selected from Si and Ge or mixtures thereof; and Y is a tetravalent element such as Ti, Sn, Zr or V or mixtures thereof, wherein z/y is between 10 and infinity.

Description

ITQ-45 material, its procedure for obtaining and its use

Field of the Invention

This patent refers to a zeolitic material called ITQ-45 and its method of preparation.

State of the art prior to the invention

Zeolites are porous crystalline aluminosilicates that have found important applications as catalysts, adsorbents and ion exchangers. These zeolitic materials have well-defined structures that form channels and cavities in their interior of uniform size and shape that allow the adsorption of certain molecules, while preventing the passage into the glass of other molecules of size too large to diffuse through pores This characteristic gives these materials molecular sieve properties. These molecular sieves may include in the network, in addition to Si, other elements of the NIA group of the periodic system, all of them tetrahedrally coordinated. The negative charge generated by the elements of the MIA group tetrahedrally coordinated in network positions is compensated by the presence in the cation crystal, such as alkaline or alkaline earth cations. These cations can be totally or partially exchanged for other types of cations by ion exchange techniques, thus being able to vary the properties of a given silicate by selecting the desired cations.

Many zeolites have been synthesized in the presence of an organic molecule that acts as a structure directing agent. Organic molecules that act as structure directing agents (ADE) generally contain nitrogen in their composition, and can give rise to stable organic cations in the reaction medium. From a point of view of their possible applications, zeolites containing channel systems with different pore openings are especially desirable since they provide selectivities in catalytic processes that cannot be obtained with materials with channels with identical openings in all of them. That is why, an important scientific activity has been developed in this regard.

Description of the invention In the present invention, a synthetic microporous crystalline material called ITQ-45 is described. The structure of this material has a microporous network consisting of channels with openings formed by 8 and 10 T0 ₄ tetrahedra that intersect each other giving rise to non-spherical cavities, which are accessed through two windows formed by 8 tetrahedra and others two of 10 tetrahedra, these cavities being accessible to molecules of interest in catalysis, in adsorption or separation processes. The space not occupied by these cavities is completed with other smaller ones with a distorted dodecahedron shape, which are accessible only through windows formed by five tetrahedra, and therefore cannot be occupied by molecules of interest.

The structure of the ITQ-45 zeolite can be described by its unit cell, which is the smallest structural unit that contains all the structural elements of this material. Table 1 shows the list of atomic positions of all atoms in tetrahedral coordination in a unit cell. All these atoms are connected to each other through bridge oxygen that bind contiguous tetrahedral atoms two to two. In total, each unit cell contains 92 atoms in tetrahedral coordination, called T1, T2, T3, T4 up to T92, other than oxygen, which are located in the crystallographic positions with Cartesian atomic coordinates x, yyz shown in Table 1. Table 1

Coordinates a (A) b (A) C (A) atomic

T1 7.1 2.2 5.0

T2 8.5 4.6 12.3

T3 8.8 7.1 10.5

T4 10.6 2.1 2.3

T5 10.7 2.4 13.0

S6 7.0 5.1 1.1

T7 6.1 3.1 7.8

T8 7.2 2.2 10.7

S9 16.1 13.4 11.9

T10 17.5 15.8 5.4

T11 17.8 18.3 3.6

T12 1.6 13.3 9.2

T13 1.7 13.6 6.0

T14 15.9 16.3 8.1

T15 15.0 14.3 0.9

T16 16.2 13.4 3.7

T17 10.8 20.3 5.0

T18 9.3 17.9 12.3

T19 9.1 15.4 10.5

T20 7.3 20.3 2.3

T21 7.2 20.0 13.0

T22 10.9 17.4 1.1

T23 11.8 19.3 7.8

T24 10.7 20.2 10.7

T25 1.8 9.0 11.9

T26 0.4 6.6 5.4

T27 0.1 4.1 3.6

T28 16.2 9.1 9.2 T29 16.1 8.8 6.0

T30 2.0 6.1 8.1

T31 2.9 8.1 0.9

T32 1.7 9.0 3.7

T33 16.1 20.3 5.0

T34 17.5 17.9 12.3

T35 17.8 15.4 10.5

T36 1.6 20.3 2.3

T37 1.7 20.0 13.0

T38 15.9 17.4 1.1

T39 15.0 19.3 7.8

T40 16.2 20.2 10.7

T41 7.1 9.0 11.9

T42 8.5 6.6 5.4

T43 8.8 4.1 3.6

T44 10.6 9.1 9.2

T45 10.7 8.8 6.0

T46 7.0 6.1 8.1

T47 6.1 8.1 0.9

T48 7.2 9.0 3.7

T49 1.8 2.2 5.0

T50 0.4 4.6 12.3

T51 0.1 7.1 10.5

T52 16.2 2.1 2.3

T53 16.1 2.4 13.0

T54 2.0 5.1 1.1

T55 2.9 3.1 7.8

T56 1.7 2.2 10.7

T57 10.8 13.4 11.9

T58 9.3 15.8 5.4

T59 9.1 18.3 3.6 T60 7.3 13.3 9.2

T61 7.2 13.6 6.0

T62 10.9 16.3 8.1

T63 11.8 14.3 0.9

T64 10.7 13.4 3.7

T65 8.9 0.0 4.0

T66 8.9 0.0 1 1.8

T67 0.0 1 1.2 1 1.0

T68 0.0 1 1.2 4.9

T69 0.0 0.0 4.0

T70 0.0 0.0 1 1.8

T71 8.9 1 1.2 1 1.0

T72 8.9 1 1.2 4.9

T73 4.5 3.3 0.9

T74 4.5 1.9 3.6

T75 4.5 1.5 12.2

T76 13.4 14.5 7.8

T77 13.4 13.1 10.6

T78 13.4 12.7 5.2

T79 13.4 19.2 0.9

T80 13.4 20.6 3.6

T81 13.4 20.9 12.2

T82 4.5 7.9 7.8

T83 4.5 9.4 10.6

T84 4.5 9.7 5.2

T85 13.4 1.4 13.0

T86 13.4 1.1 2.4

T87 4.5 12.6 6.1

T88 4.5 12.3 9.3

T89 4.5 21.1 13.0

T90 4.5 21.3 2.4 T91 13.4 9.8 6.1

T92 13.4 10.1 9.3

Each of the T atoms in Table 1 is surrounded by four oxygen atoms as first neighbors and four other T atoms as second neighbors, so that the T atoms are connected two by two through bridge oxygen forming TOT bonds . The presence of cations or depending on the nature of the T atoms can modify the values presented in Table 1, so that each crystallographic coordinate can be modified up to 0.5 A of the value given in Table 1.

The ITQ-45 zeolite has in its uncalcrated form an X-ray diffraction diagram whose most important diffraction peaks are given in Table 2, and in Table 3 for its calcined form.

Table 2

Intensity

26 ^a

Relative

6.3 m

7.5 f

7.9 md

9.9 md

1 1, 3 md

12.7 d

15.0 m

15.5 d

15.8 m

16.2 mf

16.8 d

17.8 d

18.1 mf 18.7 md

19.1 d

19.5 d

20.4 md

21.3 d

22.6 md

22.7 md

23.0 d

23.7 md

24.2 md

24.7 md

25.6 m

26.4 d

28.1 md

28.7 d

28.9 d

29.1 md

29.4 md

31.1 md

31.9 md

34.3 md ^a (± 0.4)

Table 3

Intensity

2Θ ³

Relative

6.3 mf

7.5 f

7.9 md

9.9 md

11.3 d 12.7 md

12.8 md

13.5 md

14.3 md

15.0 md

15.4 md

15.8 md

16.2 md

16.7 md

17.8 md

18.0 d

18.1 md

18.7 md

19.0 md

19.6 md

20.0 md

20.4 md

21.3 md

21.4 md

22.7 md

23.0 md

23.7 md

24.1 md

24.7 md

25.2 md

25.5 md

25.7 md

25.8 md

26.5 md

27.7 md

28.0 md 28.3 md

28.6 md

28.9 md

29.2 md

29.5 md

30.0 md

a (± 0.4)

These X-ray diffractograms were obtained with a Panalytical X'Pert Pro diffractometer equipped with a fixed divergence slit using the K «radiation of copper. The relative intensity of the lines is calculated as the percentage with respect to the most intense peak, and is considered very strong (mf) = 80-100, strong (f) = 60-80, average (m) = 40-60, weak ( d) = 20-40, and very weak (md) = 0-20. It should be borne in mind that the diffraction data listed for these samples as single or single lines, can be formed by multiple overlaps or overlapping reflections that, in certain conditions, such as differences in chemical composition, may appear as resolved or partially resolved lines. Generally, changes in the chemical composition can cause variations in the parameters of the unit cell and / or changes in the symmetry of the crystal, without a change in the structure. These modifications, which also include changes in relative intensities may also be due to differences in the type and amount of compensation cations, network composition, crystal size and shape thereof, preferred orientation or the type of thermal or hydrothermal treatments suffered.

The present invention relates to a microporous crystalline material called ITQ-45, which may have a chemical composition:

x X ₂ 0 ₃ : y Y0 ₂ : z Z0 ₂

where: - X is a trivalent element selected from Al, B, Fe, In, Ga, Cr, or mixtures thereof;

- Y is a tetravalent element selected from Ti, Sn, Zr, V or mixtures thereof, preferably between Ti, Sn, Zr, or mixtures thereof;

- Z is a tetravalent element selected from Si, Ge or mixtures thereof, preferably Si;

- the value of (y + z) / x is between 9 and infinity, preferably between 20 and infinity;

- the value of z / y is between 10 and infinity, preferably between 15 and infinity.

It is clear from the values given that the ITQ-45 crystalline material can be obtained in the absence of added trivalent elements.

According to a particular embodiment of the present invention, the value of x can be equal to zero, so it can have a chemical composition:

and Y0 ₂ : z Z0 ₂

According to another particular embodiment, the value of y is equal to zero, so it can have a chemical composition:

x X ₂ 0 ₃ : z Z0 ₂

where:

- the value of z / x is between 9 and infinity, and more preferably between 20 and infinity.

According to a preferred embodiment, the material of the present invention, ITQ-45, has a chemical composition:

t P2O5: x X2O3: y Y0 ₂ : z Z0 ₂

where:

- X is a trivalent element selected from Al, B, Fe, In, Ga, Cr, or mixtures thereof;

- Y is a tetravalent element selected from Ti, Sn, Zr, V or mixtures thereof, preferably between Ti, Sn, Zr, or mixtures thereof; - Z is a tetravalent element selected from Si, Ge or mixtures thereof, preferably Si;

- P refers to phosphorus from the structure managing agent;

- the value of t / (x + y + z) can be between 1 and 0. It is clear from the values given that the crystalline material

ITQ-45 can be synthesized in the absence of added trivalent elements. The X-ray diffractogram of the zeolite in its calcined form presents the diffraction peaks listed in Table 3. According to a particular embodiment, x may be 0 and the ITQ-45 material may have a chemical composition:

t P ₂ 0 ₅ : y Y0 ₂ : z Z0 ₂

where:

- t / (y + z) can be between 1 and 0.

According to another particular embodiment, and it can be 0 and the ITQ-45 material can have a chemical composition:

where:

- the value of z / x is between 9 and infinity, preferably between 20 and infinity.

- t / (x + z) can be between 1 and 0.

The calcined crystalline material ITQ-45 can be subjected to one or several chemical extraction processes or washing in aqueous, alcoholic, organic or mixture thereof to eliminate P2O5 inorganic residues from the elimination of the structure directing agent. This extraction or washing treatment can be performed in acid, neutral or alkaline medium. According to another preferred embodiment, the material of the present invention, ITQ-45, has a chemical composition:

n R: x X ₂ 0 ₃ : z Z0 ₂ : y Y0 ₂

where:

- R is a structure directing agent, preferably said R contains P, more preferably R contains P-N bonds, and more preferably is selected from tert-butyl-imino-tris (di-methyl-amino) -phosphorane and its protonated derivative;

- the value of n / (x + y + z) is between 1 and 0.001.

It is clear from the values given that the ITQ-45 crystalline material can be synthesized in the absence of added trivalent elements. The n / z ratio may be between 1 and 0.001 in the ITQ-45 material as synthesized. The X-ray diffractogram of the zeolite in its synthesized form presents the diffraction peaks listed in Table 2.

According to a particular embodiment, x may be 0 and the ITQ-45 material may have a chemical composition:

n R: and YO ₂ : z ZO ₂

where:

- the value of n / (y + z) is between 1 and 0.001. According to another particular embodiment, and it can be 0 and the ITQ-45 material can have a chemical composition

n R: x X ₂ 0 ₃ : z Z0 ₂

where:

- the value of n / (x + z) is between 1 and 0.001. The calcined and / or calcined and washed ITQ-45 crystalline material may be subjected to one or more post-synthesis processes of incorporation or exchange of trivalent elements using solutions containing trivalent elements X that may be selected from Al, Ga, B, Cr , Fe, In and mixtures thereof in aqueous, alcoholic, organic or mixture thereof. In this process, inorganic P2O5 residues from the elimination of the structure directing agent and / or incorporating the trivalent elements of the solutions can be eliminated. This treatment of incorporation of trivalent metals and / or washing can be carried out in acid, neutral or alkaline medium. The crystalline material with trivalent metals incorporated by post-synthesis treatments has a molar composition in its anhydrous state that is given by the equation:

x X ₂ 0 ₃ : y Y0 ₂ : z Z0 ₂

wherein X is a trivalent element such as Al, B, Fe, In, Ga, Cr or mixtures thereof, Y is a tetravalent element such as Ti, Sn, Zr, V or mixtures thereof, and Z corresponds to a element selected from Si or Ge, or mixtures of them. The value of (y + z) / x is at least 9, and can be between 20 e∞ and the value z / y is at least 10. From the given values it is clear that the ITQ-45 crystalline material is can synthesize in the absence of added trivalent elements. The X-ray diffractogram of the zeolite after post-synthesis treatment to incorporate trivalent elements in its structure presents the diffraction peaks listed in Table 4. The organic component present in the ITQ-45 material as synthesized can be removed, for example by extraction and / or by heat treatment by heating at a temperature above 200 ^δ C for a period of time that can be between 2 minutes and 25 hours.

The compensation cations in the material in its uncalcined form, or after thermal treatment, can be exchanged in the case of being present, by other cations such as metal ions, H ⁺ and H ⁺ precursors such as NH ⁺ ₄ . Among the cations that can be introduced by ion exchange, those that can have a positive role in the activity of the material as a catalyst are preferred, and more specifically cations such as H ⁺ , rare earth cations, and group VIII metals are preferred, as well as from the NA, MIA, IVA, Va, IB, NB, IIIB, IVB, VB, VIIB group of the periodic table of the elements.

It is also possible to introduce cations in the ITQ-45 zeolite network through post-synthesis treatments. These treatments consist in suspending the calcined or calcined ITQ-45 sample and washed in an aqueous, alcoholic, organic solution or mixtures of both containing the trivalent element that is to be incorporated at a temperature between 0 and 200 ⁹ C for periods between 1 hour and 15 days

In order to prepare catalysts, the crystalline material of the present invention can be intimately combined with hydrogenating-dehydrogenating components such as platinum, palladium, nickel, rhenium, cobalt, tungsten, molybdenum, vanadium, chromium, manganese, iron and combinations thereof. The introduction of these elements can be carried out in the crystallization stage, by exchange (if applicable), and / or by impregnation or by physical mixing. These elements can be introduced in their cathonic form and / or from salts or other compounds that by decomposition generate the metal component or oxide in its appropriate catalytic form. In addition, the present invention relates to the procedure for obtaining the ITQ-45 matenal described above.

According to the present invention, the ITQ-45 material preparation process may comprise at least a first step of preparing a mixture containing H ₂ 0, an oxide or other source of the tetravalent material Z and a structure directing agent (R) , a source of the trivalent element X, an oxide or other source of the tetravalent material Y, where the synthesis mixture has a molar composition of oxides in the following ranges:

{Y0 ₂ + Z0 ₂ ) / X20 ₃ greater than 2, preferably greater than 5 H ₂ 0 / (Y0 ₂ + Z0 ₂ ) 1 -50, preferably 2-30.

R / (Y0 ₂ + Z0 ₂ ) 0.05-3.0, preferably between 0.05-1.

OH7 (Y0 ₂ + Z0 ₂ ) 0.05-3.0, preferably between 0.05-1.

Z0 ₂ / Y0 ₂ greater than 5, preferably between 8-25.

Si0 ₂ / Ge0 ₂ greater than 2, preferably greater than 5

A second step in which the mixture can be maintained at a temperature between 80 and 200 ^Q C until crystals of the material and a subsequent step of recovering the crystalline material form.

According to a preferred embodiment of the present invention, Z is Si.

According to another preferred embodiment, the structure directing agent R can be a compound containing P, preferably R contains PN bonds, and more preferably is selected from tert-butyl-imino-tris (di-methyl-amino) -phosphorane and its derivative proton cationic.

The method of preparation of this material can be carried out in basic medium and absence of added fluoride ions.

This material can be prepared according to a particular embodiment, from a reaction mixture containing H ₂ 0, optionally an oxide or a source of the trivalent element X, such as Al and / or B, an oxide or a source of the tetravalent element or elements Y, such as Si, a source of Ge, such as Ge02 and an organic structure directing agent (R ) generally an organic cation, which may contain atoms other than C, H and N in its composition. Compositions of the phosphazene base type characterized by the presence of PN bonds in its structure can be used as structure directing agents, and more preferably it is the tert-butyl-imino-tris (di-methyl-amino) -phosphorane compound or its cationic derivative protonated

The composition of the reaction mixture has the following composition in terms of molar ratios of oxides:

Reagents Useful Preferred

(Y0 ₂ + Z0 ₂ ) / X ₂ 0 ₃ greater than 2 greater than 5

H ₂ 0 / (Y0 ₂ + Z0 ₂ ) 1 -50 2-30

R / (Y0 ₂ + Z0 ₂ ) 0.05-3.0 0.05-1.0

OH7 {Y0 ₂ + Z0 ₂ ) 0.05-3.0 0.05-1.0

ZO ₂ / YO ₂ greater than 5 8-25

Si0 ₂ / Ge0 ₂ greater than 2 greater than 5

The crystallization of the material can be carried out under stirring, in autoclaves at a temperature between 80 and 200 ° C, at times sufficient to achieve crystallization, for example between 12 hours and 30 days. At the end of the crystallization stage, the crystals of the material are separated from the mother liquors, and recovered. It should be taken into account that the components of the synthesis mixture can come from different sources, and depending on these, crystallization times and conditions may vary. In order to facilitate synthesis, crystals of the same material or of this calcined material can be added as seeds, in amounts of up to 15% by weight with respect to the total oxides, to the synthesis mixture. These can be added before or during crystallization. According to a particular embodiment, the ITQ-45 material preparation process may comprise a step of calcining the crystalline material obtained, calcination that can be carried out under vacuum, in air, nitrogen, hydrogen, argon, helium or any other gas already a temperature greater than 200 ^e C and less than 1200 ^S C, preferably between 200 and 1000 ^S C for a time that can be between 2 minutes and 25 hours. The ITQ-45 material after calcination, has a pore system free of organic matter, whose X-ray diffractogram presents the peaks listed in Table 2. During this calcination they can remain inside the channels or on the surface of inorganic waste material from the structure director. These residues can be eliminated by a subsequent treatment of washing with water, any alcohol with less than six carbons or mixtures thereof, as well as by aqueous or alcoholic solutions of inorganic salts.

According to a particular embodiment, said washing process or processes may comprise at least the following stage: a) suspension of the material in a solution of a compound selected from an acid, a base, an ammonium salt, a sodium salt, of any alkali metal , any alkaline earth metal or mixtures thereof. Preferably said solution is an aqueous, alcoholic, organic solution or mixture of both. The washing process is carried out at a temperature preferably between 0 ^S C and 200-C. The diffraction diagram of the resulting material presents the diffraction peaks listed in Table 3.

In addition, the calcined ITQ-45 material or the calcined and washed ITQ-45 material may be subjected to one or more post-synthesis treatments. Such treatments may preferably consist of treating the ITQ-45 with aqueous, alcoholic, organic solutions or mixtures thereof containing trivalent elements X, preferably selected from Al, Ga, B, Cr, Fe In, and mixtures thereof in order to incorporate them into the zeolitic network. This post-synthesis treatment can be carried out at alkaline, acidic or neutral pHs at temperatures preferably between 0 and 200 ^QC for a preferred time between 1 hour to 15 days. The resulting material presents the diffraction peaks shown in Table 4 and contains elements from the treatment solution incorporated into the network.

Subsequently, it can be recovered from the washed solid by filtration, centrifugation or any liquid solids separation technique and can subsequently be activated by calcination at temperatures above 200 ⁹ C.

The present invention also relates to the use of the ITQ-45 material obtained according to the procedure described above, as a component of catalytic cracking catalysts of hydrocarbons, catalytic hydro-cracking of hydrocarbons, aromatic alkylation processes with alcohols or olefins and in esterification, acylation, reaction of aniline with formaldehyde in its acid form and / or exchanged with suitable cations as well as to convert feeds formed by organic compounds to products of higher added value. The produced ITQ-45 material can be pasted according to known techniques.

Examples

Example 1- Preparation of tert-butylimino-tris (dimethylamine »no) phosphorane. 13.8 g of PCI5 are dissolved in 100 ml of anhydrous CH2CI2 under a nitrogen atmosphere. To this solution is slowly added a mixture consisting of 1.1 g of a 2M solution in dimethylamine tetrahydrofuran at -50 ^S C and 26.3 g of triethylamine. The mixture is vigorously stirred at low temperature for 1 hour and the reaction is allowed to end at room temperature for 12 hours.

To this mixture 33.0 g of tertbutylamine are added ^and -50 C. The resulting mixture was filtered and the filtrate solvent removed under vacuum. The resulting solid product is dissolved in water and precipitated as a tetrafluoroborate salt by adding an excess of sodium tetrafluoroborate. The resulting crystals are recovered by filtration, being recrystallized from ethyl acetate. The crystals obtained are transformed into the desired tert-butylimino-tris (dimethylamino) phosphorane by treatment with methanolic potash, separating the unwanted solid residue from the supernatant. The resulting solution is brought to dryness by evacuation under high vacuum, and the solid is treated with 0.5 g of barium oxide, the tert-butyliminotris (dimethylamino) phosphorane distilled under high vacuum.

Example 2- Preparation of ITQ-45 Zeolite

To 7,063 g (0.030 mol) of tert-butylimino-tris (dimethylamino) phosphorane prepared as described in example 1, 7,875 g (0.4375 mol) of H ₂ 0 are added, keeping the mixture under stirring for fifteen minutes. To this mixture is added 13,084 g (0.063 mol) of tetraethylorthosilicate, 1,309 g (0.0125 mol) of Ge0 ₂ and 0.180 g (0.0029 mol) of H ₃ B0 ₃ . The mixture is kept under stirring at room temperature until the total evaporation of the ethanol formed during the hydrolysis of the tetraethylorthosilicate. Subsequently, 6,971 g (0.387 mol) of H ₂ 0 are added until the ratio H ₂ 0 / Si + Ge of 10 is reached.

The gel obtained is transferred to Teflon coated steel autoclaves and placed in an oven at 160-C for 10 days. After the synthesis time, the solid obtained is washed with 100 ml of an aqueous solution of tert-butylamino-tris (dimethylamino) phosphorane of pH = 1 1 .5. It is subsequently washed with 2000 ml of distilled water and dried at 100 ^e C for 10 hours. The resulting solid presents an X-ray diffraction diagram that contains all the peaks indicated in Table 6.

Table 6

Intensity

2Θ

Relative

6.34 41

7.45 99

7.90 12

9.93 12

1 1, 27 12

12.70 22

14.97 43

15.45 28

15.82 46

16.15 97

16.75 28

17.78 36 18.10 100

18.70 15

19.10 21

19.50 29

20.35 10

21, 32 34

22.73 1 1

23.02 21

23.73 15

24.14 13

24.68 9

25.58 41

26.36 37

28.06 12

Example 3- Preparation of zeolite ITQ-45 in its calcined form.

A solid prepared as described in Example 2 is introduced into a muffle furnace and calcined in air at 700 ^Q C for 5 hours to decompose organic matter retained therein.

The resulting solid presents an X-ray diffraction diagram that contains all the peaks indicated in Table 7.

Table 7

Intensity

2Θ

Relative

6.34 100

7.52 75

7.90 10

9.90 13 1 1, 31 34

12.67 12

12.79 10

13.45 1

14.28 3

15.04 15

15.39 3

15.82 9

16.19 20

16.73 6

17.77 8

18.04 21

18.14 16

18.68 5

19.04 3

19.62 6

20.03 1

20.40 1

21, 26 7

21, 37 6

22.68 4

22.98 4

23.69 5

24.14 3

24.73 3

25.17 2

25.46 5

25.65 4

25.83 2

26.48 7

27.65 1 28.02 4

28.32 1

28.58 5

28.90 8

29.17 2

29.48 3

29.95 1

Example 4- Washing of a calcined ITQ-45 zeolite.

0.25 g of the solid prepared as described in example 3 are treated with 16 ml of a solution of 3M ammonium acetate at 75 ^e C for 1 hour, and 3 hours at 90 ^S C. The solid is recovered by filtration and is Wash thoroughly with boiling water. The solid is dried at 100 ^S C for 10 hours.

The resulting solid presents an X-ray diffraction diagram that contains all the peaks indicated in Table 8.

Table 8

Intensity

29 ^a

Relative

6.34 79

7.51 100

7.9 9

9.92 12

11, 3 32

12.78 19

13.47 1

14.27 5

15.03 25 15.43 4

15.82 13

16.19 33

16.74 6

17.78 1 1

18.14 24

18.66 4

19.09 3

19.6 1 1

20.39 2

21, 28 9

22.68 4

23.06 6

23.71 8

24.13 5

24.77 4

25.68 10

26.48 18

26.93 2

28.08 5

28.84 12

29.53 4

30.07 2

38.14 4

Example 5- Post-synthesis treatment of a calcined ITQ-45 zeolite to obtain AI-ITQ-45. 0.501 g of the solid prepared as described in example 3 are added to 25 ml of an 8% aluminum nitrate solution. The mixture is transferred to Teflon coated steel autoclaves and placed in a stove at 140 ^Q C for 3 days. The solid obtained is washed with 2000 ml of distilled water and dried at 100 ⁹ C for 10 hours.

The resulting solid presents a characteristic X-ray diffraction diagram of the ITQ-45 zeolite.

Example 6- Post-synthesis treatment of a calcined ITQ-45 zeolite to obtain ITQ-45 without trivalent elements in its composition. 0.42 g of the solid prepared as described in example 3 are added to 30 ml of a 0.01 N hydrochloric acid solution. The mixture is kept at room temperature for 24 h. The solid obtained is washed with 2000 ml of distilled water and dried at 100 ⁹ C for 10 hours. The resulting solid presents a characteristic X-ray diffraction diagram of the ITQ-45 zeolite.

Example 7- Preparation of ITQ-45 zeolite At 2,554 g (0.01 1 mol) of tert-butylimino-tris (dimethylamino) phosphorane prepared as described in example 1, 4,281 g (0.238 mol) of H ₂ O is added , keeping the mixture under stirring for fifteen minutes. To this mixture is added 6.378 g (0.031 mol) of tetraethylorthosilicate, 0.316 g (0.003 mol) of Ge0 ₂ and 0.079 g (0.0013 mol) of H ₃ B0 ₃ . The mixture is kept under stirring at room temperature until the total evaporation of the ethanol formed during the hydrolysis of the tetraethylorthosilicate. Subsequently 2,792 g (0.155 mol) of H ₂ 0 are added until the ratio H ₂ 0 / Si + Ge of 10 is reached.

The gel obtained is transferred to Teflon coated steel autoclaves and placed in an oven at 160 ^S C for 18 days. After the synthesis time, the solid obtained is washed with 100 ml of an aqueous solution of tert-butylamino-tris {dimethylamino) phosphorane of pH = 1 1 .5. It is subsequently washed with 2000 ml of distilled water and dried at 100 ^QC for 10 hours.

Example 8- Preparation of zeolite ITQ-45

To 2,932 g (0.013 mol) of tert-butylimino-tris (dimethylamino) phosphorane prepared as described in example 1, 3,254 g (0.181 mol) of H ₂ 0 are added, keeping the mixture under stirring for fifteen minutes. To this mixture is added 4,326 g (0.021 mol) of tetraethylorthosilicate, 1,100 g (0.01 1 mol) of Ge0 ₂ and 0.060 g (0.001 mol) of H ₃ B0 ₃ . The mixture is kept under stirring at room temperature until the total evaporation of the ethanol formed during the hydrolysis of the tetraethylorthosilicate. Subsequently, 2,376 g (0.132 mol) of H ₂ 0 are added until the H ₂ 0 / Si + Ge ratio of 10 is reached. The gel obtained is transferred to Teflon coated steel autoclaves and placed in an oven at 160 ^S C during 25 days.

After the synthesis time, the solid obtained is washed with 100 ml of an aqueous solution of tert-butylimino-tris (dimethylamino) phosphorane of pH = 1 1 .5. It is subsequently washed with 2000 ml of distilled water and dried at 100 ^QC for 10 hours.

The resulting solid presents a characteristic X-ray diffraction diagram of the ITQ-45 zeolite. Example 9- Preparation of ITQ-45 zeolite

To 2,578 g (0.01 1 mol) of tert-butylamino-tris (dimethylamino) phosphorane prepared as described in Example 1, 3,971 g (0.221 mol) of H ₂ 0 is added, keeping the mixture under stirring for fifteen minutes To this mixture is added 5,217 g (0.025 mol) of tetraethylorthosilicate. The mixture is kept under stirring at room temperature until the total evaporation of the ethanol formed during the hydrolysis of the tetraethylorthosilicate. Subsequently, 0.075 g of ITQ-45 zeolite seed dispersed in 1.068 g (0.059 mol) of H ₂ 0 are added until reaching the H ₂ 0 / Si ratio of 10.

The gel obtained is transferred to teflon coated steel autoclaves and placed in an oven at 160 ^S C for 30 days. After the synthesis time, the solid obtained is washed with 100 ml of an aqueous solution of tert-butylimino-tris (dimethylamino) phosphorane of pH = 1 1 .5. It is subsequently washed with 2000 ml of distilled water and dried at 100 ^QC for 10 hours. The resulting solid presents an X-ray diffraction diagram that presents characteristic diffraction lines of the ITQ-45 zeolite.

Example 10- Preparation of the ITQ-45 zeolite At 4,690 g (0.020 mol) of tert-butylimino-tris (dimethylamine) phosphorane prepared as described in example 1, 7.529 g (0.418 mol) of H ₂ 0 are added, keeping the mixture under stirring for fifteen minutes. To this mixture is added 9,480 g (0.0455 mol) of tetraethylorthosilicate, 0.474 g (0.0045 mol) of Ge0 ₂ and 0.126 g (0.002 mol) of H ₃ B0 ₃ . The mixture is kept under stirring at room temperature until the total evaporation of the ethanol formed during the hydrolysis of the tetraethylorthosilicate. Later they are added 0.136 g of ITQ-45 zeolite planting dispersed in 3,134 g (0.174 mol) of H ₂ 0 until reaching the ratio H ₂ 0 / Yes + Ge of 10.

The gel obtained is transferred to teflon coated steel autoclaves and placed in an oven at 160 ⁹ C for 10 days.

The resulting solid presents a characteristic X-ray diffraction diagram of the ITQ-45 zeolite. Example 11- Refinement of the ITQ-45 structure according to the Rietveld method.

The structure of the ITQ-45 zeolite can be satisfactorily refined using the Rietveld method applied to an X-ray diffraction diagram obtained from a sample prepared as described in example 3. The fit between the experimental and the simulated diagram is shown in Figure 1. The spatial group, refinement parameters and atomic positions of the ITQ-45 zeolite are shown in Table 5. Table 5

Space Group:

i m to 2

Unit cell parameters:

a = 17.8896 (8) angstroms

b = 22.4278 (10) angstroms

c = 13.8626 (6) angstroms

alpha = beta = gamma = 90 ^e Atomic positions:

Yes1 0.3972 (5) 0.0967 (3) 0.3615 (6)

Si2 0.4774 (5) 0.2036 (4) 0.8896 (5)

Si3 0.4941 (4) 0.3153 (4) 0.7583 (7)

Si4 0.5918 (5) 0.0944 (4) 0.1639 (5)

S¡5 0.5974 (4) 0.1065 (4) 0.9352 (6)

Si6 0.3900 (4) 0.2258 (3) 0.0822 (6)

Si7 0.3384 (4) 0.1386 (4) 0.5654 (6)

Si8 0.4029 (5) 0.0973 (4) 0.7692 (6)

Si9 0.5000 0.0000 0.2905 (9)

YES10 0.5000 0.0000 0.8521 (8)

Si1 1 0.2500 0.1458 (4) 0.0657 (7)

SM 2 0.2500 0.0825 (4) 0.2620 (6)

Si13 0.2500 0.0669 (4) 0.8784 (7)

YES14 0.7500 0.0613 (4) 0.9408 (6)

YES15 0.7500 0.0484 (5) 0.1736 (7)

01 0.552 (3) 0.0478 (13) 0.906 (3)

02 0.4398 (17) 0.0336 (9) 0.3541 (19)

03 0.4204 (9) 0.1558 (1 1) 0.304 (3)

04 0.449 (3) 0.9543 (16) 0.231 (3)

05 0.6850 (6) 0.1082 (10) 0.920 (3)

06 0.5497 (12) 0.1665 (8) 0.923 (3)

07 0.5071 (14) 0.2515 (12) 0.81 1 (3)

08 0.3151 (9) 0.0761 (15) 0.3388 (17)

09 0.5687 (10) 0.3533 (13) 0.734 (2)

010 0.5801 (13) 0.1023 (13) 0.0480 (5)

01 1 0.380 (2) 0.1 13 (2) 0.4714 (12)

012 0.3296 (7) 0.1767 (8) 0.056 (3)

013 0.4499 (12) 0.2192 (19) 0.9967 (12)

014 0.3552 (12) 0.2083 (5) 0.578 (5)

015 0.541 (2) 0.9595 (13) 0.7744 (13)

016 0.4460 (17) 0.1515 (14) 0.823 (3) 017 0.4341 (16) 0.291 (2) 0.6808 (16)

018 0.8205 (8) 0.4078 (13) 0.688 (3)

019 0.377 (2) 0.390 (2) 0.1600 (12)

O20 0.3321 (10) 0.4259 (15) 0.330 (2) 021 0.2500 0.0929 (9) 0.9870 (1 1)

022 0.2500 0.1244 (14) 0.572 (7)

023 0.2500 -0.0039 (4) 0.8712 (13)

024 0.2500 0.0120 (6) 0.2405 (20)

025 0.2500 0.4059 (8) 0.6470 (8) 026 0.7500 0.0606 (16) 0.0576 (6)

Claims

1. - A microporous crystalline material, characterized in that it has a chemical composition:

x X ₂ 0 ₃ : y Y0 ₂ : z Z0 ₂

where:

- Y is a tetravalent element selected from Ti, Sn, Zr, V or mixtures thereof;

- Z is a tetravalent element selected from Si, Ge or mixtures thereof;

- the value of (y + z) / x is between 9 and infinity;

- the value of z / y is between 10 and infinity;

and because it has an X-ray diffraction pattern represented in table 3.

2. - A microporous crystalline material according to claim 1, characterized in that

- And it is selected from Ti, Sn, Zr, or mixtures thereof;

- the value of (y + z) / x is between 20 and infinity;

- the value of z / y is between 15 and infinity;

3. - A microporous crystalline material according to any of claims 1 and 2, characterized in that Z is Si.

4. A microporous crystalline material according to any of claims 1 to 3, characterized in that x is equal to zero and has a chemical composition:

and Y0 ₂ : z Z0 ₂

5. A microporous crystalline material according to any of claims 1 to 3, characterized in that it is equal to zero and has a chemical composition:

x X2O3: z Z0 ₂ where:

- the value of z / x is between 9 and infinity.

6. - A microporous crystalline material according to claim 5, characterized in that the value of z / x is between 20 and infinity.

7. - A microporous crystalline material according to any of claims 1 to 3, characterized in that it has a chemical composition:

t P ₂ 0 ₅ : x X2O3: y Y0 ₂ : z Z0 ₂

where:

- the value of t / (x + y + z) is between 1 and 0.

and because it has an x-ray pattern represented in table 2.

8. - A microporous crystalline material according to claim 7, characterized in that it has a chemical composition:

where:

- t / (y + z) can be between 1 and 0.

9. - A microporous crystalline material according to claim 7, characterized in that it has a chemical composition:

t P ₂ 0 ₅ : x X ₂ 0 ₃ : z Z0 ₂

where:

- the value of z / x is between 9 and infinity;

- t / (x + z) can be between 1 and 0.

10. - A microporous crystalline material according to claim 9, characterized in that the value of z / x is between 20 and infinity.

11. A microporous crystalline material according to one of claims 1 to 3, characterized in that it has a chemical composition:

n R: x X ₂ 0 ₃ : z Z0 ₂ : y Y0 ₂ where:

- R is a structure managing agent;

- the value of n / (x + y + z) is between 1 and 0.001.

and because it has an x-ray pattern represented in table 1.

12. A microporous crystalline material according to claim 1, characterized in that the structure directing agent R contains P.

13. A microporous crystalline material according to claim 12, characterized in that R contains P-N bonds.

14. - A microporous crystalline material according to claim 13, characterized in that R is selected from tert-butyl-imino-tris (di-methyl-amine) -phosphorane and its protonated derivative.

15. - A microporous crystalline material according to any of claims 1 to 14, characterized by the following chemical composition:

n R: y Y0 ₂ : z Z0 ₂

where:

- the value of n / (y + z) is between 1 and 0.001.

16. - A microporous crystalline material according to any of claims 1 1 to 14, characterized by the following chemical composition:

n R: x X ₂ 0 ₃ : z Z0 ₂

where:

- the value of z / x is between 9 and infinity;

- the value of n / (x + z) is between 1 and 0.001.

17. A microporous crystalline material according to claim 16, characterized in that the value of z / x is between 20 and infinity.

18. An isostructural microporous crystalline material according to any one of the preceding claims, characterized in that it has tetrahedral coordination atoms linked through bridging oxygen atoms that connect contiguous tetrahedral coordination atoms, containing 92 tetrahedral coordination atoms in its unit cell, called T1, T2, T3, T4 through T92, which are located in the crystallographic positions with Cartesian atomic coordinates x, yyz, which are shown in Table 5.

19. A process for preparing the material described according to any of claims 1 to 18, characterized in that it comprises at least the following steps:

a) preparation of a mixture containing H ₂ 0, an oxide or other source of the tetravalent material Z and a structure directing agent (R), a source of the trivalent element X, an oxide or other source of the tetravalent material Y, where the Synthesis mixture has a molar composition of oxides in the following ranges:

(Y0 ₂ + Z0 ₂ ) / X ₂ 0 ₃ greater than 2

H ₂ 0 / (Y0 ₂ + Z0 ₂ ) 1 -50

R / (Y0 ₂ + Z0 ₂ ) 0.05-3.0

OH7 (Y0 ₂ + Z0 ₂ ) 0.05-3.0

Z0 ₂ / Y0 ₂ greater than 5

Yes0 ₂ / Ge0 ₂ greater than 2

b) keep the mixture at a temperature between 80 and 200 ⁹ C until the crystals of the material form;

c) recovery of the crystalline material.

20. Procedure for obtaining a material according to claim 19, characterized in that Z is Si.

21. Process for obtaining a material according to any of claims 19 and 20, characterized in that the structure directing agent R is a compound containing P.

22. - Method of obtaining a material according to claim 21, characterized in that R contains P-N bonds.

23. - Method of obtaining a material according to claim 22, characterized in that R is selected from tert-butyl-imino-tris (dí-methyl-amino) -phosphorane and its protonated cationic derivative.

24. - Method of obtaining a material according to any of claims 19 to 23, characterized in that it further comprises the calcination of the crystalline material obtained.

25. - Method of obtaining a material according to claim 24, characterized in that the calcination is carried out at a temperature between 200 and 1000 ⁹ C.

26. - Method of obtaining a material according to any of claims 24 and 25, characterized in that it also comprises at least one process of washing the calcined material.

27.- Procedure for obtaining a material according to claim 26, characterized in that said washing process or processes comprises at least the following stage:

a) suspension of the material in a solution of a compound selected from an acid, a base, an ammonium salt, a sodium salt, of any alkali metal, any alkaline earth metal or mixtures thereof.

28.- Method of obtaining a material according to claim 27, characterized in that said solution is selected from an aqueous, alcoholic, organic solution or mixture thereof.

29.- Procedure for obtaining a material according to any of claims 26 to 28, characterized in that said washing is carried out at a temperature between 0 and 200 ^e C.

30.- Procedure for obtaining a material according to any of claims 19 to 29, characterized in that it also comprises one or more post-synthesis processes.

31. - Method of obtaining a material according to claim 30, characterized in that said post-synthesis treatment comprises at least: a) suspending in a solution containing at least one trivalent element X selected from Al, Ga, B, Cr, Fe , In or mixtures thereof;

b) recovery of the solid by filtration, centrifugation or any liquid solids separation technique;

c) activation of the material by calcination at temperatures above 200 ^QC .

32. - Method of obtaining a material according to claim 31, characterized in that the solution is selected from an aqueous, alcoholic, organic solution or mixture of both.

33. - Procedure for obtaining a material according to any of claims 31 and 32, characterized in that the post-synthesis treatment is carried out at a temperature between 0 and 200 ^QC .

34. - Use of a material described according to claims 1 to 18, and obtained according to the method of obtaining described in claims 19 to 33, to convert feeds formed by organic compounds to products of greater added value.

35.- Use of a material described according to claims 1 to 18, and obtained according to the method of obtaining described in claims 19 to 33, in processes of catalytic cracking of hydrocarbons.

36.- Use of a material described according to claims 1 to 18, and obtained according to the method of obtaining described in claims 19 to 33, in processes of alkylation of aromatic compounds with alcohols or olefins.