ES2380471B1 - ITQ-45 MATERIAL, ITS PROCESSING PROCEDURE AND ITS USE. - Google Patents

Abstract

ITQ-45 material, its method of obtaining and its use. # In the present invention, a microporous crystalline material and its method of preparation is presented, which has a composition: #xX {sub, 2} O {sub, 3}: zZO {sub, 2}: yYO {sub, 2} # in which X is a trivalent element such as Al, B, Fe, In, Ga, Cr, or mixtures thereof, where (y + z) / x can take values between 9 and infinity; Z corresponds to a tetravalent element selected from Si and Ge or mixtures thereof; And corresponds to corresponds to a tetravalent element such as Ti, Sn, Zr, V or mixtures thereof, where z / y can take values 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 can include, in addition to Si, other elements of group IIIA of the periodic system, all of them tetrahedrally coordinated. The negative charge generated by the tetrahedrally coordinated group IIIA elements 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 TO4 tetrahedra that intersect each other giving rise to non-spherical cavities, which are accessed through two windows formed by 8 tetrahedra and two others 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 to T92, other than oxygen, which are located in the crystallographic positions with Cartesian atomic coordinates x, y and z shown in Table 1.

Table 1

Atomic coordinates

to (Å) b (Å) c (Å)

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

T6

7.0  5.1  1.1

T7

6.1  3.1  7.8

T8

 7.2 2.2 10.7

T9

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 11.8

T67

 0.0 11.2 11.0

T68

 0.0 11.2 4.9

T69

0.0  0.0  4.0

T70

 0.0 0.0 11.8

T71

 8.9 11.2 11.0

T72

 8.9 11.2 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 each crystallographic coordinate can be modified up to 0.5 Å from 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

2Sa

Relative

6.3

 m

7.5

 F

7.9

md

9.9

md

11.3

 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

to (0.4)

Table 3

Intensity

2Sa

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

to (0.4)

These X-ray diffractograms were obtained with a Panalytical X’Pert Pro diffractometer equipped with a fixed divergence slit using the Ka 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 noted that the diffraction data listed for these samples as single or single lines, may be formed by multiple overlaps or overlapping reflections that, under certain conditions, such as differences in chemical composition, may appear as partially or resolved lines. resolved. 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 X2O3: y YO2: z ZO2

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 from 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

may have a chemical composition: and YO2: z ZO2

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

x X2O3: z ZO2

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 YO2: z ZO2

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 from 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 (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.

-

The value of t / (x + y + z) can be between 1 and 0.

It is clear from the values given that the ITQ-45 crystalline material 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 P2O5: and YO2: z ZO2

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:

t P2O5: x X2O3: z ZO2

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 X2O3: z ZO2: and YO2

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 from 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.

-

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-methylamino) -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 YO2: z ZO2

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 X2O3: z ZO2

where:

-

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

-

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 X2O3: y YO2: z ZO2

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 and 0 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 ° C for a period of time that can be between 2 minutes and 25 hours .

Compensation cations in the material in its uncalcined form, or after heat treatment, can be exchanged, if present, for 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 Group IIA, IIIA, VAT, Va, IB, IIB, IIIB, IVB, VB, VIIB 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 sample of calcined or calcined ITQ-45 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 ° 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 cationic 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 process for obtaining the ITQ-45 material described above.

According to the present invention, the process for preparing the ITQ-45 material may comprise at least a first step of preparing a mixture containing H2O, 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:

(YO2 + ZO2) / X2O3 greater than 2, preferably greater than 5.

H2O / (YO2 + ZO2) 1-50, preferably 2-30.

R / (YO2 + ZO2) 0.05-3.0, preferably between 0.05-1.

OH - / (YO2 + ZO2) 0.05-3.0, preferably between 0.05-1.

ZO2 / YO2 greater than 5, preferably between 8-25.

SiO2 / GeO2 greater than 2, preferably greater than 5.

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

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 (dimethyl-amino) -phosphorane and its protonated cationic derivative .

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 H2O, optionally an oxide or a source of the trivalent element X, such as Al and / or B, an oxide or a source of the element or elements tetravalent Y, such as Si, a source of Ge, such as GeO2 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

(YO2 + ZO2) / X2O3 greater than 2 greater than 5

H2O / (YO2 + ZO2) 1-50 2-30

R / (YO2 + ZO2) 0.05-3.0 0.05-1.0

OH - / (YO2 + ZO2) 0.05-3.0 0.05-1.0

ZO2 / YO2 greater than 5 8-25

SiO2 / GeO2 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 previously

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 ° C and less than 1200 ° C, preferably between 200 and 1000 ° C for a time that may be between 2 minutes and 25 hours. The ITQ45 material after calcination, has a system of pores 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 the material inorganic waste from the structure director. These residues can be eliminated by a subsequent water wash treatment, 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 ° 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 with the in order to incorporate them into the zeolitic network. This post-synthesis treatment can be performed at alkaline, acidic or neutral pHs at temperatures preferably between 0 and 200 ° C 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 ° 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 acidic form and / or exchanged with suitable cations as well as to convert feeds formed by organic compounds to products of greater added value. The produced ITQ-45 material can be pasted according to known techniques.

Examples

Example 1- Preparation of tert-butylimino-tris (dimethylamino) phosphorane.

13.8 g of PCl5 are dissolved in 100 ml of anhydrous CH2Cl2 under a nitrogen atmosphere. To this solution is slowly added a mixture consisting of 11.7 g of a 2M solution in dimethylamine tetrahydrofuran at -50 ° 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 at -50 ° C. The resulting mixture is filtered and the solvent is removed from the filtrate in vacuo.

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-butylimino-tris (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 H2O is 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 GeO2 and

0.180 g (0.0029 mol) of H3BO3. 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 H2O are added until the H2O / Si + Ge ratio 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-butylimino-tris (dimethylamino) phosphorane of pH = 11.5. It is subsequently washed with 2000 ml of distilled water and dried at 100 ° 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

2S

Relative

6.34

 41

7.45

 99

7.90

 12

9.93

 12

11.27

 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

 fifteen

19.10

 twenty-one

19.50

 29

20.35

 10

21.32

 3. 4

22.73

 eleven

23.02

 twenty-one

23.73

 fifteen

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 ° C for 5 hours to decompose the retained organic matter inside.

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

Table 7

2S

Relative Intensity

6.34

 100

7.52

 75

7.90

 10

9.90

 13

11.31

 3. 4

12.67

 12

12.79

 10

13.45

 one

14.28

 3

15.04

 fifteen

15.39

 3

15.82

 9

16.19

 twenty

16.73

 6

17.77

 8

18.04

 twenty-one

18.14

 16

18.68

 5

19.04

 3

19.62

 6

20.03

 one

20.40

 one

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

 one

28.02

 4

28.32

 one

28.58

 5

28.90

 8

29.17

 2

29.48

 3

29.95

 one

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 ° C for 1 hour, and 3 hours at 90 ° C. The solid is recovered by filtration and washed thoroughly with boiling water. The solid is dried at 100 ° C for 10 hours.

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

Table 8

2Sa

Relative Intensity

6.34

 79

7.51

 100

7.9

 9

9.92

 12

11.3

 32

12.78

 19

13.47

 one

14.27

 5

15.03

 25

15.43

 4

15.82

 13

16.19

 33

16.74

 6

17.78

 eleven

18.14

 24

18.66

 4

19.09

 3

19.6

 eleven

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 Al-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

5 stove at 140 ° C for 3 days. The solid obtained is washed with 2000 ml of distilled water and dried at 100 ° 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.

10 0.42 g of the solid prepared as described in example 3 are added to 30 ml of a 0.01N 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 ° 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

To 2,554 g (0.011 mol) of tert-butylimino-tris (dimethylamino) phosphorane prepared as described in Example 1, 4,281 g (0.238 mol) of H2O 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 GeO2 and 0.079 g (0.0013 mol) of H3BO3. 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 H2O are added until

20 reach the H2O / Si + Ge ratio of 10.

The obtained gel is transferred to Teflon coated steel autoclaves and placed in an oven at 160 ° C for 18 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 = 11.5. It is subsequently washed with 2000 ml of distilled water and dried at 100 ° C for 10 hours.

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

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 H2O 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 (0.011 mol) of GeO2 and 0.060 g (0.001 mol) of H3BO3. 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 H2O are added until the H2O / Si + Ge ratio of 10 is reached.

The gel obtained is transferred to Teflon coated steel autoclaves and placed in an oven at 160 ° C for 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 = 11.5. It is subsequently washed with 2000 ml of distilled water and dried at 100 ° C 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 (0.011 mol) of tert-butylimino-tris (dimethylamino) phosphorane prepared as described in Example 1, 3,971 g (0.221 mol) of H2O 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 H2O are added until the H2O / Si ratio of 10 is reached.

The gel obtained is transferred to teflon coated steel autoclaves and placed in an oven at 160 ° 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 = 11.5. It is subsequently washed with 2000 ml of distilled water and dried at 100 ° C 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 ITQ-45 zeolite

To 4,690 g (0.020 mol) of tert-butylimino-tris (dimethylamino) phosphorane prepared as described in example 1, 7,529 g (0.418 mol) of H2O is 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 GeO2 and 0.126 g

(0.002 mol) of H3BO3. The mixture is kept under stirring at room temperature until the total evaporation of the ethanol formed during the hydrolysis of the tetraethylorthosilicate. Subsequently, 0.136 g of ITQ-45 zeolite seed dispersed in 3,134 g (0.174 mol) of H2O are added until the H2O / Si + Ge ratio 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-butylimino-tris (dimethylamino) phosphorane of pH = 11.5. It is subsequently washed with 2000 ml of distilled water and dried at 100 ° C for 10 hours.

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 a 2 Unit cell parameters: a = 17.8896 (8) angstroms b = 22.4278 (10) angstroms c = 13.8626 (6) angstroms alpha = beta = gamma = 90º Atomic positions:

Si1 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)

Si5 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)

Si10 0.5000 0.0000 0.8521 (8)

Si11 0.2500 0.1458 (4) 0.0657 (7)

Si12 0.2500 0.0825 (4) 0.2620 (6)

Si13 0.2500 0.0669 (4) 0.8784 (7)

Si14 0.7500 0.0613 (4) 0.9408 (6)

Si15 0.7500 0.0484 (5) 0.1736 (7)

O1 0.552 (3) 0.0478 (13) 0.906 (3)

O2 0.4398 (17) 0.0336 (9) 0.3541 (19)

O3 0.4204 (9) 0.1558 (11) 0.304 (3)

O4 0.449 (3) 0.9543 (16) 0.231 (3)

O5 0.6850 (6) 0.1082 (10) 0.920 (3)

O6 0.5497 (12) 0.1665 (8) 0.923 (3)

O7 0.5071 (14) 0.2515 (12) 0.811 (3)

O8 0.3151 (9) 0.0761 (15) 0.3388 (17)

O9 0.5687 (10) 0.3533 (13) 0.734 (2)

O10 0.5801 (13) 0.1023 (13) 0.0480 (5)

O11 0.380 (2) 0.113 (2) 0.4714 (12)

O12 0.3296 (7) 0.1767 (8) 0.056 (3)

O13 0.4499 (12) 0.2192 (19) 0.9967 (12)

O14

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

O15

0.541 (2)   0.9595 (13) 0.7744 (13)

O16

0.4460 (17) 0.1515 (14)  0.823 (3)

O17

0.4341 (16) 0.291 (2) 0.6808 (16)

5

O18 0.8205 (8)  0.4078 (13)  0.688 (3)

O19

0.377 (2) 0.390 (2)   0.1600 (12)

O20

0.3321 (10) 0.4259 (15)  0.330 (2)

O21

0.2500 0.0929 (9) 0.9870 (11)

O22

0.2500   0.1244 (14) 0.572 (7)

10

O23 0.2500 -0.0039 (4)    0.8712 (13)

O24

0.2500 0.0120 (6) 0.2405 (20)

O25

0.2500 0.4059 (8) 0.6470 (8)

O26

0.7500   0.0606 (16) 0.0576 (6)

Claims (12)

1.-A microporous crystalline material, characterized in that it has a chemical composition: x X2O3: y YO2: z ZO2 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;

-

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 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 one of claims 1 to 3, characterized in that x is equal

to zero and has a chemical composition: and YO2: z ZO2 5.-A microporous crystalline material according to any of claims 1 to 3, characterized in that y is zero and has a chemical composition: x X2O3: z ZO2 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 P2O5: x X2O3: y YO2: z ZO2 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 composition

chemistry: t P2O5: and YO2: z ZO2 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 P2O5: x X2O3: z ZO2 where:

-

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

-

t / (x + z) may 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 X2O3: z ZO2: and YO2 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 11, characterized in that the directing agent of

R structure 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-amino) -phosphorane and its protonated derivative. 15. A microporous crystalline material according to any of claims 11 to 14, characterized by the following chemical composition: n R: and YO2: z ZO2 wherein:

-

 the value of n / (y + z) is between 1 and 0.001. 16. A microporous crystalline material according to any of claims 11 to 14, characterized by the following chemical composition:

n R: x X2O3: z ZO2 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 H2O, 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 mixture of Synthesis has a molar composition of oxides in the following ranges: (YO2 + ZO2) / X2O3 greater than 2 H2O / (YO2 + ZO2) 1-50 R / (YO2 + ZO2) 0.05-3.0 OH - / (YO2 + ZO2) 0.05-3.0 ZO2 / YO2 greater than 5 SiO2 / GeO2 greater than 2 b) keep the mixture at a temperature between 80 and 200 ° 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. Procedure 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.- Procedure for obtaining a material according to claim 21, characterized in that R Contains PN links. 23. Process for obtaining a material according to claim 22, characterized in that R is selected from tert-butyl-imino-tris (di-methyl-amino) -phosphorane and its protonated cationic derivative. 24. Method for 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 for obtaining a material according to claim 24, characterized in that the calcination is carried out at a temperature between 200 and 1000 ° C. 26.- Procedure for 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.- Method of obtaining a material according to claim 26, characterized in that said washing process or processes comprises at least the following step: a) suspension of the material in a solution of a compound selected from an acid, a base, a salt ammonium, 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 ° 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 ° C. 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 ° C. 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.  FIG. one   SPANISH OFFICE OF PATENTS AND BRANDS SPAIN REPORT ON THE STATE OF THE TECHNIQUE 51 Int. Cl.: C01B39 / 48 (2006.01) C01B39 / 04 (2006.01) twenty-one N.O request: 201031513 22 Date of submission of the application: 13.10.2010 32 Date of priority: RELEVANT DOCUMENTS

Category

Documents cited Claims Affected

TO

US 4992250 A (FLANIGEN et al.) 12.02.1991, 1-36

column 1, lines 10-25; column 3, lines 59-68; column 8, lines 1-19; claims 1.73.

TO

US 4880611 A (VON BALLMOOS et al.) 14.11.1989, 1-36

claims 1-8.

TO

US 6379646 B1 (MILLER) 04/30/2002, 1-36

column 3, lines 55-66; column 4, lines 1-30.

TO

US 20080069769 A1 (CAO) 03.20.2008, 1-36

paragraph [0033]; claims 10-17.

Category of the documents cited X: of particular relevance Y: of particular relevance combined with other / s of the same category A: reflects the state of the art O: refers to unwritten disclosure P: published between the priority date and the date of priority submission of the application E: previous document, but published after the date of submission of the application

This report has been produced • for all claims • for claims No:

Date of realization of the report 22.11.2011

Examiner V. Balmaseda Valencia Page 1/4

TECHNICAL STATUS REPORT Application NO .: 201031513 Minimum documentation sought (classification system followed by classification symbols) C01B Electronic databases consulted during the search (name of the database and, if possible, terms of search used) INVENES, EPODOC, WPI, NPL, XPESP, HCAPLUS State of the Art Report Page 2/4  WRITTEN OPINION Application NO .: 201031513 Date of Written Opinion: 22.11.2011 Statement

Novelty (Art. 6.1 LP 11/1986)

Claims 1-36 Claims IF NOT

Inventive activity (Art. 8.1 LP11 / 1986)

Claims 1-36 Claims IF NOT

The application is considered to comply with the industrial application requirement. This requirement was evaluated during the formal and technical examination phase of the application (Article 31.2 Law 11/1986).  Opinion Base.- This opinion has been made on the basis of the patent application as published. State of the Art Report Page 3/4  WRITTEN OPINION Application NO .: 201031513  1. Documents considered.- Below are the documents pertaining to the state of the art taken into consideration for the realization of this opinion.

Document

Publication or Identification Number publication date

D01

US 4992250 A (FLANIGEN et al.) 12.01.1991

D02

US 4880611 A (VON BALLMOOS et al.) 11/14/1989

D03

US 6379646 B1 (MILLER) 04/30/2002

D04

US 20080069769 A1 (CAO) 03.20.2008

 2. Statement motivated according to articles 29.6 and 29.7 of the Regulations for the execution of Law 11/1986, of March 20, on Patents on novelty and inventive activity; quotes and explanations in support of this statement The object of the present invention is a microporous crystalline material characterized by its chemical composition and its corresponding X-ray diffraction pattern, a method of obtaining said material and the use thereof in the conversion of organic compounds. Document D01 describes a composition for a molecular sieve of microporous structure based on the formula mR: (GewAlxPySiz) O2, where R represents a directing agent of organic structure (a quaternary ammonium or phosphonium compound). Said composition is characterized by its X-ray diffraction pattern and is used as a catalyst or adsorbent material (column 1, lines 10-25; column 3, lines 59-68; column 8, lines 1-19; claims 1, 73) . A composition for a crystalline molecular sieve with ionic and catalytic exchange properties is described in document D02. Said composition is characterized by the formula, on its anhydrous basis, Mmfx / m: (XO2) -1-y: (YO2) f1-x: (ZO2) xfy: Nn-y / n and an X-ray diffraction pattern ( claims 1-8). Document D03 discloses a molecular sieve comprising a phosphorus oxide, a first silicon oxide, germanium or mixture of sides and a second aluminum oxide, boron or mixture of both. It also has a pore diameter greater than 5 A and is useful as a catalyst in the conversion of hydrocarbons (column 3, lines 55-66; column 4, lines 1 30.) Document D04 describes a method of obtaining a porous crystalline material with a pore size greater than 6 A. Said material is constituted by one or several tetravalent elements (silicon, germanium or combinations), optionally trivalent elements (aluminum, boron, iron , indium, gallium, chromium and combinations) and optionally pentavalent (phosphorus) (paragraph [0033]; claims 10-17). None of documents D01-D04 or any relevant combination thereof discloses a composition with the same X-ray diffraction pattern of the claimed composition, as well as a method of obtaining it comprising the use of tert-butyl -imino-tris (di-methyl-amino) -phosphorane as the structure directing agent. In addition, it would not be obvious to a person skilled in the art such composition from the cited documents. Consequently, the object of claims 1-36 is considered to be new and involves inventive activity (Articles 6.1 and 8.1 of the L.P). State of the Art Report Page 4/4