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 process for the preparation of a material, comprising at least the following steps: a) preparing a mixture containing H.sub.2O, a source of fluoride ions, an oxide or another 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, wherein the synthesis mixture has a molar composition of oxides within the following ranges: TABLE-US-00007 (YO.sub.2 + ZO.sub.2)/X.sub.2O.sub.3 higher than 2 H.sub.2O/(YO.sub.2 + ZO.sub.2) 1-50 R/(YO.sub.2 + ZO.sub.2) 0.05-3.0 F.sup./(YO.sub.2 + ZO.sub.2) 0.01-3.0 ZO.sub.2/YO.sub.2 higher than 5 SiO.sub.2/GeO.sub.2 higher than 1 b) maintaining the mixture at a temperature between 80 and 200 C. until crystals of the material are formed; c) recovering the crystalline material; wherein the microporous crystalline material has the following chemical composition: x X.sub.2O3 : 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 process for the preparation of a material according to claim 1, wherein Z is Si, Ge or a mixture of both.

3. The process for the preparation of a material according to claim 1, wherein the strucure directing agent R is a compound that contains P.

4. The process for the preparation of a material according to claim 3, wherein R is an alkylphosphonium salt.

5. The process for the preparation of a material according to claim 4, wherein R is 1,4-butanediyl-bis(tritertbutyl)phosphonium hydroxide or one of its salts.

6. The process for the preparation of a material according to claim 1, that further comprises the calcination of the crystalline material obtained.

7. The process for the preparation of a material according to claim 6, wherein the calcination is carried out at a temperature between 200 and 1200 C.

8. The process for the preparation of a material according to claim 1, that further comprises one or more post-synthesis processes.

9. The process for the preparation of a material according to claim 8, wherein said post-synthesis treatment comprises at least: a) suspending the material in a solution that contains at least a trivalent element X selected from the group consisting of Al, Ga, B, Cr, Fe, In and mixtures thereof; b) recovering of the solid through filtration, centrifugation or any other technique for solids-liquids separation; c) activating the material through calcination at temperatures higher than 200 C.

10. The process for the preparation of a material according to claim 9, wherein the solution is selected from the group consisting of an aqueous solution, an alcoholic solution, an organic solution and mixtures thereof.

11. The process for the preparation of a material according to claim 9, wherein the post-synthesis treatment is carried out at a temperature between 0 and 200 C.

12. Method of catalysing a reaction comprising subjecting the reagents to a catalyst comprising 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.

13. Method of catalysing according to claim 12, wherein said material was obtained through a process comprising at least the following steps: a) preparing a mixture containing H.sub.2O, a source of fluoride ions, an oxide or another 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, wherein the synthesis mixture has a molar composition of oxides within the following ranges: TABLE-US-00008 (YO.sub.2 + ZO.sub.2)/X.sub.2O.sub.3 higher than 2 H.sub.2O/(YO.sub.2 + ZO.sub.2) 1-50 R/(YO.sub.2 + ZO.sub.2) 0.05-3.0 F.sup./(YO.sub.2 + ZO.sub.2) 0.01-3.0 ZO.sub.2/YO.sub.2 higher than 5 SiO.sub.2/GeO.sub.2 higher than 1 b) maintaining the mixture at a temperature between 80 and 200 C. until crystals of the material are formed; c) recovering the crystalline material.

14. Method of converting hydrocarbons comprising subjecting the hydrocarbons to a catalyst comprising the material described in claim 12.

15. Method of dewaxing hydrocarbons comprising subjecting the hydrocarbons to a catalyst comprising the material described in claim 12.

16. Method of converting hydrocarbons comprising subjecting the alcohols to a catalyst comprising the material described in claim 12.

17. Method for converting alcohols with less than four carbon atoms, into olefins comprising subjecting said alcohols to a catalyst comprising the material described in claim 12.

18. Method for removing nitrogenated pollutants in gaseous or liquid streams comprising subjecting said gaseous or liquid streams to a catalyst comprising the material described in claim 12.

19. Method for removing nitrogen oxides in gaseous streams comprising subjecting said gaseous stream to a catalyst comprising the material described in claim 12.

20. Method for removing nitrogen oxides in gaseous streams in the presence of reducing gases comprising subjecting said gaseous streams to a catalyst comprising the material described in claim 12.

21. Method for removing nitrogen oxides in gaseous streams in the presence of ammonia as a reducing agent comprising subjecting said gaseous streams to a catalyst comprising the material described in claim 12.

22. Method for removing nitrogen oxides in gaseous streams in the presence of hydrocarbons as reducing agents comprising subjecting said gaseous streams to a catalyst comprising the material described in claim 12.

23. Method of adsorbing a substance comprising putting said substance into contact with 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, as an adsorbent.

24. Method of adsorbing a substance according to claim 23, wherein said material was obtained through a process comprising at least the following steps: a) preparing a mixture containing H.sub.2O, a source of fluoride ions, an oxide or another 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, wherein the synthesis mixture has a molar composition of oxides within the following ranges: TABLE-US-00009 (YO.sub.2 + ZO.sub.2)/X.sub.2O.sub.3 higher than 2 H.sub.2O/(YO.sub.2 + ZO.sub.2) 1-50 R/(YO.sub.2 + ZO.sub.2) 0.05-3.0 F.sup./(YO.sub.2 + ZO.sub.2) 0.01-3.0 ZO.sub.2/YO.sub.2 higher than 5 SiO.sub.2/GeO.sub.2 higher than 1 b) maintaining the mixture at a temperature between 80 and 200.degree. C. until crystals of the material are formed; c) recovering the crystalline material.

25. The method according to claim 23 wherein the adsorbent is a selective adsorbent and wherein CO.sub.2 and methane are separated.

26. The method according to claim 23 wherein the adsorbent is a selective adsorbent and wherein propane and propene are separated.

27. The method according to claim 23 wherein the adsorbent is a selective adsorbent and wherein linear olefins are separated from the C4 fraction.

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 1Preparation 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 2Preparation 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 3Preparation 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 4Preparation 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 5Refining 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: 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) 0.2575(5) 0.83(1) Ge5 0.0812(4) 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) 0.4067(4) 0.90(1) Ge8 0.1806(4) 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) 0.3473(8) 1.0 O13 0 0.268(2) 1.0 O14 0.1749(7) 0 0.3581(7) 1.0 O15 0.2169(11) 0 1.0 O16 0.0655(4) 0 0.2650(10) 1.0 O17 0.1596(14) 1.0