CRYSTALLINE ZEOLITE-TYPE MATERIAL

Abstract

The present invention relates to a microporous material of the zeolite type, known as IDM-1, the method for preparing same, and applications thereof. Said material may be entirely silicon-based or may include different elements at either the reticular or non-reticular positions. The present invention falls within the fields of crystalline silicas, zeolites and catalysts.

Claims

1. A crystalline material wherein a zeolite has a general chemical formula SiO(.sub.2-x)(OH).sub.2x, wherein x is equal to a value between 0.02 and 0.12; and presents an X-ray diffractogram recorded with a Bragg-Brentano geometry diffractometer with a fixed divergence slit and using Kα.sub.1 and Kα.sub.2 radiation of Cu, and comprising the following angle values 2θ (°), and relative intensities (I/Io).Math. 100, wherein the relative intensities are represented by e, f, m, j and d, with values of e= 0-100, f = 80-100, m = 20-80, j=0-80 and d = 0-20: TABLE-US-00009 2θ (°) ± 0.30 (°) (I/Io).Math. 100 5.00 d 7.06 e 7.92 f 8.31 j 8.79 m 9.01 d 9.16 d 9.38 d 9.84 d 10.05 j 10.96 d 11.28 d 11.60 d 11.86 d 12.48 12.48 d 12.84 d 13.22 d 13.94 j 14.20 d 14.80 j 14.95 d 15.12 d 15.42 d 15.64 d 15.91 d 16.12 d 16.5 d 16.64 d 17.23 d 17.66 d 17.89 d 18.39 d 18.92 d 19.25 d 19.43 d 19.57 d 20.08 d 20.24 d 20.37 d 20.58 d 20.87 d 21.03 d 21.46 d 21.80 d 22.14 d 22.34 d 22.69 d 23.14 m 23.35 j 23.73 j 23.99 m 24.15 j 24.43 j 24.77 j 25.38 d 25.6 d 26.02 d 26.36 d 26.69 d 27.04 d 27.48 d 27.65 d 27.93 d 28.16 d 28.45 d 28.73 d 28.94 d 29.37 d 29.67 d 29.98 d .

2. The crystalline material according to claim 1, comprising a micropore volume, measured from the value of the volume of N.sub.2 adsorbed to a relative pressure of 0.3 and a density in liquid state, between 0.15 ml/g and 0.25 ml/g.

3. The crystalline material according to claim 1, comprising a mesopore volume measured from the value of the volume of N.sub.2 adsorbed at relative pressure 0.3 and a density in liquid state, between 0.060 ml/g and 0.250 ml/g.

4. The crystalline material according to claim 1, wherein silicon is isomorphically substituted by an element selected from Al, B, Ga, Fe, Ti, Sn, Zn, V, and any combination thereof.

5. The crystalline material according to claim 4, wherein silicon is substituted by Al in a Si/Al ratio of more than 12 .

6. The crystalline material according to claim 4, wherein silicon is substituted by Ti in a Si/Ti ratio of more than 10 .

7. A method for obtaining the crystalline material as described in claim 1 comprising the following steps.sub.: a) adding at least one source of silica to an aqueous solution of a halide of the dication (p-phenylenedimethylene)bis(tripropylammonium); b) adding to the mixture obtained in step (a) a source of fluorine F.sup.- selected from hydrofluoric acid and a fluorine salt,, up to a pH between 12 and 5, homogenising, wherein the molar ratio of the mixture is SiO.sub.2: a TF.sub.2: b H.sub.2O, wherein T represents the cation (p-Phenylenedimethylene)bis(tripropylammonium) and a=0.05-2 and wherein b=2-100 ; c) introducing the mixture obtained in (b) in a digestion bomb and leaving with or without stirring in an oven at a temperature between 80 and 200° C., for a period of time between 1 h and 50 days; d) cooling the mixture obtained in (c) and obtaining the solid by filtration or by centrifugation, washing with water and drying; and e) calcining in the presence of an oxidising agent the dry product obtained in step (d) at a temperature between 300° C. and 1000° C. for a period of time between 0.5 h and 2 days.

8. The method according to claim 7, wherein the halide of the dication (p-Phenylenedimethylene)bis(tripropylammonium) is found as (p-Phenylenedimethylene)bis(tripropylammonium) hydroxide, and is obtained by anion exchange from the corresponding halide.

9. The method according to claim 7, wherein after step (a) and before step (b) the mixture obtained is left to rest for a period of time between 1 h and 5 days, rest, up to a ratio of H.sub.2O:SiO.sub.2 between 2 and 100, by evaporation of the solvents.

10. The method according to claim 7, wherein the heating in a digestion bomb of step (c) is selected from a static autoclave or a stirring autoclave.

11. The method according to claim 7, wherein to obtain the halide of the dication (p-Phenylenedimethylene)bis(tripropylammonium) of step (a) it comprises adding tripropylamine dropwise to a solution of 1,4-bis(chloromethyl)benzene in an ice bath, leaving under reflux and stirring for a period of time between 3 h and 7 days and separating the solvent to obtain a solid and wash it.

12. The method according to claim 7,wherein in step (b) a precursor of an element selected from among Al, B, Ga, Fe, Ti, Sn, Zn, V and any combination thereof is also added in a molar ratio between said element and silicon between 0.001 and 0.2000 .

13. The method according to claim 12, wherein the precursor is aluminium and wherein said precursor is selected from aluminium isopropoxide, aluminium nitrate or any other aluminium salt, in a molar ratio between the precursor in an equivalent oxide form, Al.sub.2O.sub.3 and SiO.sub.2 between 0.0005 and 0.1000.

14-17. (canceled)

18. A catalyst comprising the crystalline material described according to claim 1.

19. A molecular sieve comprising the crystalline material described according to claim 1.

Description

BRIEF DESCRIPTION OF THE FIGURES

[0044] FIG. 1. Cation used as structure-directing agent in the synthesis of the zeolite IDM-1.

[0045] FIG. 2. Diffractograms of the IDM-1 materials obtained in the experiments of the zeolites in examples (from top to bottom) 2, 3 and 4. The reflection at 28.44 corresponds to Si, used as internal standard.

[0046] FIG. 3. Adsorption and desorption isotherms of the IDM-1 solids calcined at 550° C. prepared in examples 2 and 3 (above and below, respectively).

[0047] FIG. 4. SEM images of the IDM-1 zeolites obtained in examples 2, 3 and 4.

[0048] FIG. 5. Diffractograms of the calcined solids obtained in the experiments of example 6.

EXAMPLES

[0049] Next, the invention will be illustrated by means of assays carried out by the inventors that demonstrate the effectiveness of the product of the invention.

Example 1

[0050] This example illustrates the preparation of (p-Phenylenedimethylene)bis(tripropylammonium) hydroxide (FIG. 1).

[0051] 5 g of g of 1,4-bis(chloromethyl)benzene, 300 g of ethanol are introduced in a 500 ml flask. About 24.5 g of tripropylamine is added to this mixture with stirring, dropwise and in an ice bath. After 3 days under reflux and stirring, the mixture is evaporated in a rotary evaporator until a white solid is obtained. After washing the obtained solid with acetone, the final mass of product obtained is 13.1 g. The nuclear magnetic resonance spectrum indicates that the solid obtained is the chloride of the dication (p-Phenylenedimethylene)bis(tripropylammonium).

[0052] The hydroxide form of the dication is obtained by anion exchange using an exchange resin (Dowex Monosphere 550A hydroxide form, Sigma-Aldrich)

[0053] 100 g of resin are added to a solution of 13 g of the previous product in 194.02 g of water and it is left under stirring for about 12 hours. After filtering the resin, the solution is titrated with HCI (aq.) using phenolphthalein as indicator, finding an efficiency in the exchange of 82%. This solution can be concentrated in a rotary evaporator for use in the synthesis of IDM-1, and its final concentration is obtained by a new titration.

Example 2

[0054] This example illustrates the preparation of purely siliceous IDM-1, using (p-Phenylenedimethylene)bis(tripropylammonium) hydroxide as the organic structure-directing agent.

[0055] 3.47 g of tetraethyl orthosilicate (TEOS) are added to 7.17 of a solution containing 1.16 mmol of (p-Phenylenedimethylene)bis(tripropylammonium) hydroxide per gram of solution, obtained in the manner described in example 1, and stirred, allowing the evaporation of the ethanol produced in the hydrolysis of TEOS together with water.

[0056] When the evaporation loss is 5.51 g, 0.35 g of HF (aq.) (48%, Aldrich) is added and homogenised by hand with the spatula. The paste obtained is introduced into an autoclave lined internally with polytetrafluoroethylene and remains at 150° C. for 10 days. As such, the autoclave cools down, the solid produced is separated by filtration, it is washed with water and it is dried at 60° C.

[0057] Lastly, the product obtained and characterised is calcined at 550° C. for 5 hours, thus obtaining a white solid that indicates that the calcination has dislodged the host agents from the lattice and has provided empty space for the corresponding applications and that is characterised by X-ray diffraction, bottom diagram of FIG. 2, where it presents an X-ray diffractogram recorded with a Bruker diffractometer with Bragg-Brentano geometry with a fixed divergence slit and using Kα.sub.1 and Kα.sub.2 radiation of Cu comprising the following angle values 2θ (°), and relative intensities (l/lo).Math.100, wherein the relative intensities are represented by f, m and d, with values of f .sub.= 80-100, m .sub.= 20-80 and d = 0-20:

TABLE-US-00002 2θ (°) ± 0.30 (°) (l/lo).Math.100 4.87 d 7.06 d 7.88 f 8.33 d 8.75 m 9.03 d 9.73 d 10.93 d 11.84 d 12.45 d 13.17 d 13.89 d 14.73 d 15.43 d 15.85 d 16.46 d 17.22 d 17.6 d 17.79 d 18.16 d 18.86 d 19.19 d 19.97 d 20.31 d 20.81 d 21.25 d 21.74 d 22.13 d 23.03 m 23.38 d 23.89 m 24.28 d 24.5 d 25.48 d 25.79 d 26.59 d 26.95 d 27.39 d 28.12 d 29.3 d 29.86 d 30.22 d 30.5 d 31.24 d 32.64 d 33.4 d 33.7 d 34.53 d

Example 3

[0058] This example illustrates the preparation of purely siliceous IDM-1, using the dication of (p-Phenylenedimethylene)bis(tripropylammonium) as organic structure-directing agent in its hydroxide form of (p-Phenylenedimethylene)bis(tripropylammonium).

[0059] It follows example 2 exactly, except that the mass evaporation loss is 5.81 g and the reaction time in the autoclave is 17 days at 150° C.

[0060] It is characterised by X-ray diffraction, middle diagram of FIG. 2, where it presents an X-ray diffractogram recorded with a Bruker diffractometer with Bragg-Brentano geometry with a fixed divergence slit and using Kα.sub.1 and Kα.sub.2 radiation of Cu comprising the following angle values 2θ (°), and relative intensities (l/lo).Math.100, wherein the relative intensities are represented by f, m and d, with values of f = 80-100, m = 20-80 and d = 0-20:

TABLE-US-00003 2theta i/io.sup.∗100 4.93 32 3.20 d 7.05 182 18.20 d 7.9 1000 100.00 f 8.35 63 6.30 d 8.77 466 46.60 m 9.03 110 11.00 d 9.92 69 6.90 d 10.95 14 1.40 d 11.86 6 0.60 d 13.2 63 6.30 d 13.92 132 13.20 d 14.19 11 1.10 d 14.76 147 14.70 d 15.01 28 2.80 d 15.49 31 3.10 d 15.89 86 8.60 d 16.51 12 1.20 d 17.22 7 0.70 d 17.62 25 2.50 d 17.81 17 1.70 d 18.91 22 2.20 d 19.23 16 1.60 d 19.57 5 0.50 d 20.07 22 2.20 d 20.37 33 3.30 d 20.85 31 3.10 d 21.38 13 1.30 d 21.79 23 2.30 d 22.18 14 1.40 d 23.1 392 39.20 m 23.44 92 9.20 d 23.66 77 7.70 d 23.95 253 25.30 m 24.25 43 4.30 d 24.47 37 3.70 d 25.62 33 3.30 d 25.94 25 2.50 d 26.22 9 0.90 d 26.64 41 4.10 d 27 44 4.40 d 27.44 20 2.00 d 28.2 16 1.60 d 29.4 24 2.40 d 29.9 47 4.70 d 30.26 23 2.30 d 30.63 13 1.30 d 31.23 6 0.60 d 31.58 6 0.60 d 32.68 10 1.00 d 33.45 4 0.40 d 33.74 2 0.20 d 34.62 16 1.60 d

Example 4

[0061] This example illustrates the preparation of purely siliceous IDM-1, using (p-Phenylenedimethylene)bis(tripropylammonium) hydroxide as the organic structure-directing agent.

[0062] It follows example 2 exactly, except that the evaporation loss is 6.11 g and the reaction time is 10 days in the autoclave at 150° C.

[0063] It is characterised by X-ray diffraction, top diagram of FIG. 2, where it presents an X-ray diffractogram recorded with a Bruker diffractometer with Bragg-Brentano geometry with a fixed divergence slit and using Kα.sub.1 and Kα.sub.2 radiation of Cu comprising the following angle values 2θ (°), and relative intensities (l/lo).Math.100, wherein the relative intensities are represented by f, m and d, with values of f = 80-100, m = 20-80 and d = 0-20:

TABLE-US-00004 2θ (°) ± 0.30 (°) (l/lo).Math.100 5.00 d 7.06 m 7.92 f 8.31 d 8.79 m 9.01 d 9.16 d 9.38 d 10.05 d 10.96 d 11.28 d 11.60 d 12.84 d 13.22 d 13.94 d 14.20 d 14.80 d 14.95 d 15.12 d 15.42 d 15.64 d 15.91 d 16.12 d 16.64 d 17.2 3 d 17.66 d 17.89 d 18.39 d 18.92 d 19.25 d 19.43 d 19.57 d 20.08 d 20.24 d 20.37 d 20.58 d 20.87 d 21.03 d 21.46 d 21.80 d 22.14 d 22.34 d 22.69 d 23.14 m 23.73 m 23.99 m 24.15 d 24.53 d 25.38 d 25.60 d 26.02 d 26.36 d 26.69 d 27.04 d 27.48 d 27.65 d 27.93 d 28.16 d 28.73 d 28.94 d 29.37 d 29.67 d 29.98 d

Example 5

[0064] N.sub.2 adsorption isotherms in the calcined samples of examples 2 and 3.

[0065] The isotherms (FIG. 3) show the characteristics of the presence of the microporous space of zeolites at low pressures. However, they also show a hysteresis loop at relatively high pressures, suggesting the presence of mesoporous space. This mesoporous space is probably related to the presence of sheets of a few tens of nanometres thick that make up the particles thereof, as can be seen in FIG. 4, wherein additionally, a single morphology is shown in each image, which supports the fact that the IDM-1 material is not a mixture of particles with different structures. Table 1 summarises the information obtained from the isotherms.

TABLE-US-00005 Micro and mesopore volumes of the calcined solids obtained in the corresponding examples. example V.sub.micro (ml/g) V.sub.meso (ml/g) 2 0.20 0.07 3 0.21 0.09

Example 6

[0066] The same method is followed as to prepare the zeolite IDM-1 in example 2 except for the addition of aluminium isopropoxide (Al(Oi-Pr)3 together with tetraethyl orthosilicate (TEOS) in the amounts shown below:

TABLE-US-00006 Relevant amounts in the preparation of the zeolite IDM-1 in the presence of aluminium. example m(dis OH)(g) c(OH) (mmol/g) m(TEOS) (g) m(AI(O-i-Pr).sub.3) (g) Δm(g) m(dis HF 48%) (g) IDM-1-AI1 12.46 0.57 2.77 0.091 9.70 0.28 IDM-1-AI2 12.07 0.57 2.77 0.045 9.30 0.28

[0067] They are characterised by X-ray diffraction, diagrams of FIG. 5 (IDM-1-AI top and IDM-1-Al2 bottom), wherein each of the materials presents an X-ray diffractogram recorded with a Bruker diffractometer with Bragg-Brentano geometry with a fixed divergence slit and using Kα.sub.1 and Kα.sub.2 radiation of Cu and comprising the following angle values 2θ (°), and relative intensities (l/lo).Math.100, wherein the relative intensities are represented by e, f, m, j and d, with values of e= 0-100, f = 80-100, m = 20-80, j=0-80 and d = 0-20:

TABLE-US-00007 IDM-1-AI1 • • 5.01 8 • 0.8 • d 7.07 71 • 7.1 • d 7.95 1000 • 100 • f 8.35 26 • 2.6 • d 8.85 535 • 53.5 • m 9.12 117 • 11.7 • d 9.91 18 • 1.8 • d 10.17 14 • 1.4 • d 11 5 • 0.5 • d 11.96 17 • 1.7 • d 12.58 7 • 0.7 • d 13.3 51 • 5.1 • d 14.03 118 • 11.8 • d 14.28 5 • 0.5 • d 14.9 141 • 14.1 • d 15.62 56 • 5.6 • d 16.03 96 • 9.6 • d 16.65 17 • 1.7 • d 17.4 16 • 1.6 • d 17.8 34 • 3.4 • d 17.93 27 • 2.7 • d 18.36 5 • 0.5 • d 19.07 7 • 0.7 • d 19.41 30 • 3 • d 19.66 3 • 0.3 • d 20.15 11 • 1.1 • d 20.54 46 • 4.6 • d 21.06 68 • 6.8 • d 21.65 7 • 0.7 • d 21.97 15 • 1.5 • d 22.39 29 • 2.9 • d 23.31 538 • 53.8 • m 23.5 214 • 21.4 • m 23.91 144 • 14.4 • d 24.18 258 • 25.8 • m 24.64 155 • 15.5 • d 25.03 16 • 1.6 • d 25.51 6 • 0.6 • d 25.83 32 • 3.2 • d 26.15 44 • 4.4 • d 26.48 12 • 1.2 • d 26.64 15 • 1.5 • d 26.91 42 • 4.2 • d 27.06 24 • 2.4 • d 27.25 44 • 4.4 • d 27.72 22 • 2.2 • d 28.37 14 • 1.4 • d 28.74 16 • 1.6 • d 29.19 4 • 0.4 • d 29.56 47 • 4.7 • d 30.23 68 • 6.8 • d 30.66 31 • 3.1 • d 31.08 4 • 0.4 • d 31.56 14 • 1.4 • d 31.91 3 • 0.3 • d 32.22 4 • 0.4 • d 32.47 6 • 0.6 • d 32.89 4 • 0.4 • d 33.11 18 • 1.8 • d 33.78 3 • 0.3 • d 34.06 4 • 0.4 • d 34.74 20 • 2 • d

TABLE-US-00008 IDM-1-AI2 • • 4.95 24 • 2.4 • d 6.98 208 • 20.8 • m 7.83 1000 • 100 • f 8.28 68 • 6.8 • d 8.72 472 • 47.2 • m 8.99 111 • 11.1 • d 9.34 14 • 1.4 • d 9.8 29 • 2.9 • d 10.03 40 • 4 • d 10.9 11 • 1.1 • d 11.8 15 • 1.5 • d 12.42 7 • 0.7 • d 12.77 5 • 0.5 • d 13.15 63 • 6.3 • d 13.86 158 • 15.8 • d 14.14 21 • 2.1 • d 14.73 186 • 18.6 • d 15.42 40 • 4 • d 15.84 124 • 12.4 • d 16.48 23 • 2.3 • d 17.2 16 • 1.6 • d 17.61 51 • 5.1 • d 17.8 11 • 1.1 • d 18.14 5 • 0.5 • d 18.32 5 • 0.5 • d 18.84 25 • 2.5 • d 19.19 30 • 3 • d 19.48 9 • 0.9 • d 19.97 31 • 3.1 • d 20.31 64 • 6.4 • d 20.79 65 • 6.5 • d 21.35 20 • 2 • d 21.73 33 • 3.3 • d 22.13 27 • 2.7 • d 23.07 738 • 73.8 • m 23.61 183 • 18.3 • d 23.89 395 • 39.5 • m 24.32 141 • 14.1 • d 24.73 12 • 1.2 • d 25.19 14 • 1.4 • d 25.52 50 • 5 • d 25.85 48 • 4.8 • d 26.2 22 • 2.2 • d 26.61 83 • 8.3 • d 26.94 70 • 7 • d 27.38 26 • 2.6 • d 28.03 23 • 2.3 • d 28.41 18 • 1.8 • d 28.79 13 • 1.3 • d 29.18 50 • 5 • d 29.58 23 • 2.3 • d 29.86 90 • 9 • d 30.27 53 • 5.3 • d 30.67 12 • 1.2 • d 31.17 14 • 1.4 • d 31.53 8 • 0.8 • d 31.87 7 • 0.7 • d 32.1 6 • 0.6 • d 32.53 12 • 1.2 • d 32.7 16 • 1.6 • d 33.42 5 • 0.5 • d 33.71 4 • 0.4 • d 34.33 25 • 2.5 • d 34.61 17 • 1.7 • d 34.83 14 • 1.4 • d