ITQ-49 material, method for the production thereof and use of same

Abstract

The present invention refers to a microporous crystalline material, to the method for the production thereof and to the use of same, the material having a composition:
xX.sub.2O.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 have values of between 9 and infinity; Z corresponds to a tetravalent element selected from Si, Ge or mixtures thereof; and Y corresponds to a tetravalent element such as Ti, Sn, Zr, V or mixtures thereof, where z/y can have values of between 10 and infinity.

Claims

1. A microporous crystalline material, having a chemical composition:
xX.sub.2O.sub.3:yYO.sub.2:zZO.sub.2 wherein: X is a trivalent element selected from Al, B, Fe, In, Ga, Cr, or mixtures thereof; Y is a tetravalent element tetravalent selected from Ti, Sn, Zr, V or mixtures thereof; Z is a tetravalent element tetravalent selected from Si, Ge and mixtures thereof; the value of (y+z)/x is comprised between 9 and infinity; the value of z/y is comprised between 10 and infinity; and an X-ray diagram shown in Table 3.

2. The microporous crystalline material according to claim 1, wherein Y is selected from Ti, Sn, Zr, or mixtures thereof; the value of (y+z)/x is comprised between 20 and infinity; and the value of z/y is comprised between 15 and infinity.

3. The microporous crystalline material according to claim 1, wherein Z is Si.

4. The microporous crystalline material according to claim 1, wherein x is zero and having a chemical composition:
yYO.sub.2:zZO.sub.2.

5. The microporous crystalline material according to claim 1, wherein y is zero and having a chemical composition:
xX.sub.2O.sub.3:zZO.sub.2 wherein: the value of z/x is comprised between 9 and infinity.

6. The microporous crystalline material according to claim 5, wherein the value of z/x is comprised between 20 and infinity.

7. The microporous crystalline material according to claim 6, wherein y is zero and having a chemical composition:
tP.sub.2O.sub.5:xX.sub.2O.sub.3:zZO.sub.2 wherein: the value of z/x is comprised between 9 and infinity; t/(x+z) is comprised between 1 and 0.

8. The microporous crystalline material according to claim 7, wherein the value z/x is comprised between 20 and infinity.

9. The microporous crystalline material according to claim 1, that has a chemical composition:
tP.sub.2O.sub.5:xX.sub.2O.sub.3:yYO.sub.2:zZO.sub.2 wherein: the value of t/(x+y+z) is comprised between 1 and 0; and it has an X ray diagram shown in Table 3.

10. The microporous crystalline material according to claim 9, wherein x is zero and having a chemical composition:
tP.sub.2O.sub.5:yYO.sub.2:zZO.sub.2 wherein: t/(y+z) is comprised between 1 and 0.

11. The microporous crystalline material according to claim 1, having a chemical composition:
nR:xX.sub.2O.sub.3:zZO.sub.2:yYO.sub.2 wherein: R is a structure directing agent; the value of n/(x+y+z) is comprised between 1 and 0.001; and having an X-ray diffraction diagram shown in Table 2.

12. The microporous crystalline material according to claim 11, wherein the structure directing agent, R, contains P.

13. The microporous crystalline material according to claim 12, wherein R is a salt of an alkylphosphonium cation.

14. The microporous crystalline material according to claim 13, wherein R is 1,4-butanediyl-bis(tritertbutyl)phosphonium hydroxide.

15. The microporous crystalline material according to claim 11 wherein x is zero and it has the following chemical composition:
nR:yYO.sub.2:zZO.sub.2 wherein: the value of n/(y+z) is comprised between 1 and 0.001.

16. The microporous crystalline material according to claim 11, wherein y is zero and it has the following chemical composition:
nR:xX.sub.2O.sub.3:zZO.sub.2 wherein: the value of z/x is comprised between 9 and infinity; the value of n/(x+z) is comprised between 1 and 0.001.

17. The microporous crystalline material according to claim 16, wherein the value of z/x is comprised between 20 and infinity.

18. The microporous crystalline material according to claim 1, wherein it has atoms in tetrahedral coordination linked through through oxygen bridging atoms that connect adjacent atoms with tetrahedral coordination, containing 92 atoms in tetrahedral coordination in its unit cell, designated T1, T2, T3, T4 until T92, that are located in the crystallographic positions with cartesian coordinates x, y y z shown in Table 1.

Description

DESCRIPTION OF FIGURES

(1) FIG. 1.—View of the zeolite ITQ-49 structure along a-axis (oxygen atoms are omitted for the shake of clarity).

(2) FIG. 2.—View of the zeolite ITQ-49 structure along b-axis (oxygen atoms are omitted for the shake of clarity).

(3) FIG. 3.—View of the zeolite ITQ-49 structure along c-axis (oxygen atoms are omitted for the shake of clarity).

(4) FIG. 4.—Rietveld refining of the X-ray diffraction diagram of a ITQ-49 sample, calcined at 923K, measured using the K alpha radiation of copper. The spots show the experimental diagram. The line along the spots shows the calculated diagram for the proposed structure. The difference between both is shown below. The vertical lines under the diagrams depict the positions of Bragg's reflections.

EXAMPLES

Example 1—Preparation of 1,4-butanediyl-bis(tritertbutyl)phosphonium hydroxide

(5) 20.2 g of tri-tertbutylphosphine are dissolved in 250 mL of acetonitrile. To this solution a solution of 61.5 g of 1,4-diiodobutane in 150 mL of acetonitrile was slowly added. The mixture was kept under stirring at 90° C. for 12 hours and then it is cooled down to room temperature.

(6) The resulting mixture is filtered, the obtained solid is sequentially washed with acetonitrile and ethyl ether, and dried under vacuum. This solid, after being dissolved in methanol, was transformed into the corresponding hydroxide using an anionic exchange resin, with stirring, for 12 hours.

Example 2—Preparation of the ITQ-49 Zeolite

(7) To 28.69 g of a 0.7 M aqueous solution of 1,4-butanediyl-bis(tritertbutyl)phosphonium hydroxide, 1.9 g of GeO.sub.2 and 13 g of tetraethyl orthosilicate are added. The mixture is kept under stirring at room temperature until the total evaporation of the ethanol formed during the hydrolysis of tetraethyl orthosilicate. Then, 1.67 g of HF (48%) are added and the enough amount of water to achieve a H.sub.2O/Si of 7.

(8) The obtained gel was homogenized and transferred to teflon-coated steel autoclaves and they were put in a furnace with stirring at 125° C. for 16 days.

(9) After the synthesis period, the solid is washed with distilled water at 85° C., it is centrifugated to separate the solid and dried at 100° C. for 12 hours.

(10) The resulting solid has a X-ray diffraction diagram that contains the characteristic peaks of the ITQ-49 material.

Example 3—Preparation of the Zeolite ITQ-49 in its Calcined Form

(11) A solid prepared according to example 2 was put in a muffle furnace and it was calcined in air at 700° C. for 5 hours to decompose the organic matter retained in its interior.

(12) The resulting solid has a X-ray diffraction diagram that contains the characteristic peaks of the calcined ITQ-49 material.

Example 4—Preparation of the ITQ-49 Zeolite

(13) To 28.69 g of a 0.7 M aqueous solution of 1,4-butanediyl-bis(tritertbutyl)phosphonium hydroxide, 1.4 g of GeO.sub.2 and 14 g of tetraethyl orthosilicate are added. The mixture is kept under stirring at room temperature until the total evaporation of the ethanol formed during the hydrolysis of tetraethyl orthosilicate. Then, 1.67 g of HF (48%) are added and the enough amount of water to achieve a H.sub.2O/Si of 7.

(14) The obtained gel was homogenized and transferred to teflon-coated steel autoclaves and they were put in a furnace with stirring at 125° C. for 16 days.

(15) After the synthesis period, the solid is washed with distilled water at 85° C., it is centrifugated to separate the solid and dried at 100° C. for 12 hours.

(16) The resulting solid has a X-ray diffraction diagram that contains the characteristic peaks of the ITQ-49 material.

Example 5—Refining of the Structure of ITQ-49 According Rietveld Method

(17) The structure of a sample of the zeolite ITQ-49 can be satisfactorily refined using Rietveld method applied to a X-ray diffraction diagram obtained from a sample prepared according to example 3. The matching between the experimental and the simulated diagrams is shown in FIG. 4. The space group, the refining parameters and the atomic positions of zeolite ITQ-49 are shown in Table 4.

(18) TABLE-US-00006 TABLE 4 Space group: l m m m Parameters of unit cell: a = 19.6007(8) angstroms b = 18.3274(7) angstroms c = 16.5335(6) angstroms alpha = beta = gamma = 90°
Atomic Positions:

(19) TABLE-US-00007 Position x y z Ocupation Si1 0.2357(3) 0.1189(3) 0.1786(4) 0.78(1) Ge1 0.2357(3) 0.1189(3) 0.1786(4) 0.22(1) Si2 0.1640(3) 0.3802(4) 0.1797(4) 0.77(1) Ge2 0.1640(3) 0.3802(4) 0.1797(4) 0.23(1) Si3 0 0.1436(4) 0.0908(5) 0.89(1) Ge3 0 0.1436(4) 0.0908(5) 0.11(1) Si4 0.1389(4) 0.2365(4) 0.0960(4) 0.91(1) Ge4 0.1389(4) 0.2365(4) 0.0960(4) 0.09(1) Si5 0.0812(4) ½ 0.2575(5) 0.83(1) Ge5 0.0812(4) ½ 0.2575(5) 0.17(1) Si6 0.2487(4) 0 0.4062(4) 0.66(1) Ge6 0.2487(4) 0 0.4062(4) 0.34(1) Si7 0.1481(4) 0 0.2636(4) 0.78(1) Ge7 0.1481(4) 0 0.2636(4) 0.22(1) Si8 0.1806(4) ½ 0.4067(4) 0.90(1) Ge8 0.1806(4) ½ 0.4067(4) 0.10(1) Si9 0 0 0.2061(6) 0.92(1) Ge9 0 0 0.2061(6) 0.08(1) O1 0.2854(10) 0.1493(7) 0.2501(10) 1.0 O2 0.1695(7) 0.0724(7) 0.2126(11) 1.0 O3 0.2005(7) 0.1898(7) 0.1354(11) 1.0 O4 0.2665(7) 0.0671(6) 0.1070(8) 1.0 O5 0.0965(6) 0.4320(7) 0.1950(9) 1.0 O6 0.2144(8) 0.4210(6) 0.1153(9) 1.0 O7 0.1245(8) 0.3199(6) 0.1240(10) 1.0 O8 0 0.1096(11) 0 1.0 O9 0.0698(6) 0.1891(8) 0.1079(11) 1.0 O10 0 0.0663(7) 0.1392(10) 1.0 O11 0.1468(13) 0.2247(13) 0 1.0 O12 0.1151(8) ½ 0.3473(8) 1.0 O13 0 ½ 0.268(2) 1.0 O14 0.1749(7) 0 0.3581(7) 1.0 O15 0.2169(11) 0 ½ 1.0 O16 0.0655(4) 0 0.2650(10) 1.0 O17 0.1596(14) ½ ½ 1.0