ENANTIOENRICHED CHIRAL MICROPOROUS MATERIAL, PREPARATION METHOD AND USES

Abstract

The present invention relates to a new chiral zeolite material of composition a SiO.sub.2:b GeO.sub.2:c X.sub.2O.sub.3:d YO.sub.2, with an ITV structure, prepared with a specific chiral organic structure-directing agent, (1S,2S)—N-ethyl-N-methyl-pseudoephedrine or its enantiomer, (1R,2R)—N-ethyl-N-methyl-pseudoephedrine, which means that the material is rich in one of the crystalline forms; a method whereby said material is obtained, and the use thereof in adsorption and catalysis processes.

Claims

1. A GTM-3 crystalline microporous material, characterized by: having a chemical composition in its anhydrous calcined form a SiO.sub.2:b GeO.sub.2:c X.sub.2O.sub.3:d YO.sub.2, wherein X is one or more trivalent elements, Y is one or more tetravalent elements other than Si or Ge, the b/a ratio takes any value greater than 0, c/(a+b) takes any value between 0 and 0.2, both included, and d/(a+b) takes any value between 0 and 0.2, both included; having an ITV structure; and being enantio-enriched in either one of the enantiomorphic crystalline forms of the ITV structure.

2. The material according to claim 1, wherein the ITV structure in its non-calcined form is defined by having an X-ray diffraction pattern characteristic thereof, recorded with a Philips X'PERT diffractometer using copper Kα radiation with a Ni filter, and comprising the following values of angles 2θ (°) and distance d (Å): TABLE-US-00014 Angle 2θ Distance d (±0.50) (°) (±0.500) (Å) 4.77 18.532 5.83 15.150 7.53 11.740 8.25 10.708 10.11 8.753 10.65 8.304 11.18 7.917 12.15 7.284 12.62 7.017 13.98 6.327 14.31 6.190 14.70 6.025 15.83 5.600 17.22 5.151 17.55 5.053 18.18 4.879 18.57 4.775 19.12 4.642 20.57 4.317 20.85 4.260 21.67 4.102 22.46 3.959 22.97 3.873 23.02 3.861 23.95 3.715 24.21 3.676 24.67 3.608 24.93 3.572 25.83 3.450 26.07 3.418 26.73 3.336 27.16 3.284 28.23 3.162 29.05 3.074 29.26 3.052 29.84 2.994 30.44 2.936 31.02 2.883 31.58 2.833 32.34 2.768 33.06 2.710 33.42 2.682 33.78 2.653 34.45 2.603 34.99 2.565 35.44 2.531 35.68 2.517 36.54 2.459 37.02 2.428 37.73 2.385 37.86 2.375 38.78 2.322 39.45 2.284.

3. The material according to claim 2, wherein it comprises, for the values of angles 2θ (°) and distance d (Å), relative intensity values (I/I.sub.0).Math.100 of: TABLE-US-00015 Angle 2θ Distance d Relative (±0.20) (°) (±0.500) (Å) intensity 4.77 18.532 e 5.83 15.150 d 7.53 11.740 d 8.25 10.708 d 10.11 8.753 d 10.65 8.304 d 11.18 7.917 d 12.15 7.284 d 12.62 7.017 d 13.98 6.327 d 14.31 6.190 d 14.70 6.025 d 15.83 5.600 d 17.22 5.151 d 17.55 5.053 d 18.18 4.879 d 18.57 4.775 d 19.12 4.642 b 20.57 4.317 d 20.85 4.260 d 21.67 4.102 e 22.46 3.959 d 22.97 3.873 d 23.02 3.861 d 23.95 3.715 f 24.21 3.676 m 24.67 3.608 d 24.93 3.572 d 25.83 3.450 d 26.07 3.418 d 26.73 3.336 d 27.16 3.284 d 28.23 3.162 d 29.05 3.074 d 29.26 3.052 d 29.84 2.994 d 30.44 2.936 d 31.02 2.883 d 31.58 2.833 d 32.34 2.768 d 33.06 2.710 d 33.42 2.682 d 33.78 2.653 d 34.45 2.603 d 34.99 2.565 d 35.44 2.531 d 35.68 2.517 d 36.54 2.459 d 37.02 2.428 d 37.73 2.385 d 37.86 2.375 d 38.78 2.322 d 39.45 2.284 d and wherein relative intensities are represented by “e”=40-100, “f”=60-100, “m”=40-60, “b”=0-60, and “d”=0-40.

4. The material according to claim 1, wherein X is at least one trivalent element selected from the group consisting of Al, B, In, Ga, Fe, Cr, Ti, V, and combinations thereof.

5. The material according to claim 4, wherein X is Al, B, or any combinations thereof.

6. The material according to claim 1, wherein Y is at least one tetravalent element selected from the group consisting of Sn, Ti, V, and combinations thereof.

7. The material according to claim 1, wherein c/(a+b) and d/(a+b) are 0.

8. The material according to claim 1, wherein the pores of the material are empty due to the removal of the organics.

9. A catalyst, characterized in that it comprises the GTM-3 crystalline microporous material according to claim 8, together with at least one hydrogenating-dehydrogenating component.

10. A method for preparing the GTM-3 crystalline microporous material according to claim 1, characterized in that it comprises the following steps: a) preparing a synthesis gel by mixing at least one source of Si, a source of Ge, a source of water, a source of the (1R,2R)—N-ethyl-N-methyl-pseudoephedrinium cation or a source of the (1S,2S)—N-ethyl-N-methyl-pseudoephedrinium cation, and a source of fluoride; b) subjecting the synthesis gel obtained in step (a) to a temperature of between 58° C. and 130° C. for a time of between 6 hours and 1 month until the crystalline microporous material is formed, and c) recovering the GTM-3 crystalline microporous material obtained in step (b); and further comprises, optionally, an additional step (d), after recovery step (c), of removing occluded organic matter from the material recovered in step (c), performed by thermal treatment or extraction.

11. The method according to claim 10, characterized in that the source of organic cation of step (a) is in the form of hydroxide or halide.

12. The method according to claim 10, characterized in that the source of silicon of step (a) is selected from tetraethylorthosilicate, Aerosil SiO.sub.2, and colloidal SiO.sub.2.

13. The method according to claim 10, wherein the source of Ge of step (a) is Ge dioxide.

14. The method according to claim 10, characterized in that the preparation of the synthesis gel of step (a) further comprises adding variable amounts of other trivalent elements (X), which is selected from Al, B, In, Ga, Fe, Cr, Ti, V, and combinations thereof, and/or of tetravalents (Y) other than Si or Ge, which is selected from Sn, Ti, V, and combinations thereof.

15. The method according to claim 10, wherein the source of fluoride of step (a) is hydrofluoric acid or ammonium fluoride.

16. The method according to claim 10, wherein previously obtained GTM-3 material crystals, which acts as seeds, are added after step (a) and before step (b).

17. An adsorbent of organic compounds comprising the GTM-3 crystalline microporous material according to claim 1.

18. A catalyst in reactions with organic compounds comprising the GTM-3 crystalline microporous material according to claim 1.

19. The method according to claim 10, wherein the step of removing occluded organic matter from the material recovered in step (c) by thermal calcination treatment at a temperature of between 250° C. and 600° C. for a time of between 1 h and 48 h.

Description

BRIEF DESCRIPTION OF THE FIGURES

[0075] FIG. 1. Molecular structure of the organic agent that has given rise to the ITV structure in the present invention (in its two enantiomeric forms ADE5-SS and ADE5-RR), and of other very similar organic compounds that do not give rise to the ITV structure (ADE6-8), which demonstrates the high specificity of ADE5 to the ITV structure.

[0076] FIG. 2. Molecular structure of the organic agents that have given rise to the ITV structure to date, reported in the bibliography.

[0077] FIG. 3. Detail of the synthesis scheme of the chiral structure-directing agent shown for the (1S,2S) enantiomer, the synthesis scheme for the (1R,2R) enantiomer being exactly the same.

[0078] FIG. 4. Characteristic X-ray diffraction pattern of the GTM-3 material prepared at 100° C. with a Si/Ge ratio in the gel of 5.

[0079] FIG. 5. .sup.27Al solid state nuclear magnetic resonance at the magic angle of the Al-GTM-3(SS) material obtained as indicated in Example 10.

[0080] FIG. 6. X-ray diffraction patterns from enantioselective crystallization experiments. Top: using a GTM-3(SS) seeding, using the same enantiomer (SS) for the synthesis gel (gray, case A in Example 14) or the opposite enantiomer (RR) (black, case B in Example 14). Bottom: using a GTM-3(RR) seeding, using the opposite enantiomer (SS) for the synthesis gel (gray, case C in Example 15) or the same enantiomer (RR) (black, case D in Example 15).

[0081] FIG. 7. .sup.13C solid state nuclear magnetic resonance at the magic angle of the GTM-3(SS) material obtained according to Example 3 (black line), and of a (1S,2S)—N-ethyl-N-methyl-pseudoephedrinium cation solution in D.sub.2O (gray line), as explained in Example 16.

[0082] FIG. 8. X-ray diffraction patterns of the GTM-3 material (prepared at 100° C. with a Si/Ge ratio in the gel of 5 according to Example 3) recorded in-situ during the calcination process (as explained in Example 17): bottom: original GTM-3(SS) (black line); middle: GTM-3(SS) at 550° C. (gray line); top: GTM-3(SS) subjected to calcination at 550° C. and subsequently cooled to room temperature (light gray line).

[0083] FIG. 9. X-ray diffraction pattern of the GTM-3 material, prepared at 100° C. with a Si/Ge ratio in the gel of 5, as indicated in Example 3, after air calcination at 500° C. for 4 hours, as explained in Example 18.

[0084] FIG. 10. N.sub.2 adsorption/desorption isotherm of the calcined GTM-3(SS) material, as explained in Example 18.

EXAMPLES

[0085] The following describes several examples illustrating the details of the preparation of the chiral organic agents, several GTM-3 materials object of the present invention in different compositions, as well as the evidence for the enrichment of GTM-3 in one enantiomorphic crystalline form or another depending on the use of one enantiomer of the organic agent or another. However, these examples do not limit the present invention. Hereinafter, the GTM-3 material obtained in the presence of the (1S,2S)—N-ethyl-N-methyl-pseudoephedrinium enantiomer will be referred to as GTM-3(SS), and the material obtained in the presence of the (1R,2R)—N-ethyl-N-methyl-pseudoephedrinium enantiomer will be referred to as GTM-3(RR).

Example 1: Synthesis of the Structure-Directing Agent: (1S,2S)—N-ethyl-N-methyl-pseudoephedrinium hydroxide

[0086] The synthesis of the structure-directing agent starts from the alkaloid (1S,2S)-pseudoephedrine or (1R,2R)-pseudoephedrine; the choice of the starting enantiomer of the precursor determines the final absolute configuration of the structure-directing agent. The synthesis consists of three steps, a first addition of a methyl group, a second addition of an ethyl group (FIG. 3), and a final ion exchange of iodide to the corresponding hydroxide.

[0087] In a typical synthesis of (1S,2S)—N-ethyl-N-methyl-pseudoephedrinium hydroxide, 15.10 g of formaldehyde (37 wt % in aqueous solution) and 23.00 g of formic acid (95 wt %) are mixed in a flask under magnetic stirring. The flask is cooled in an ice bath, and then 25.00 g of (1S,2S)-pseudoephedrine are added very slowly. The mixture is refluxed overnight. Next, 18.20 g of hydrochloric acid (37 wt %) are added, keeping the flask with the mixture in an ice bath. Next, successive extractions of the product are performed by washing with diethyl ether. The aqueous phase is then collected to which an aqueous sodium hydroxide solution (25 wt %) is added until reaching a pH of 12, giving rise to the formation of an oily product. Lastly, the product is extracted in a decantation funnel with diethyl ether, collecting the organic phase. Next, traces of water are removed from the organic phase with potassium carbonate (K.sub.2CO.sub.3), and the solvent is removed on a rotary evaporator. An oil containing (1S,2S)—N-methyl-pseudoephedrine is thus obtained, with a yield of about 80%.

[0088] In the second step of the reaction, 20.00 g of (1S,2S)—N-methyl-pseudoephedrine are dissolved in 400 ml of acetonitrile, and 34.85 g of iodoethane is added little by little while keeping the mixture under stirring and cooling with an ice bath. The mixture is allowed to warm to room temperature and is thus kept under stirring for 5 days. The solvent is then evaporated in a rotary evaporator, yielding a precipitate which is washed with diethyl ether. The product, (1S,2S)—N-ethyl-N-methyl-pseudoephedrinium iodide, is obtained with yields of about 90%.

[0089] The last step of the synthesis consists of the anionic exchange of iodide for hydroxide using an anion resin (Amberlite IRN-78). 34.30 g of (1S,2S)—N-ethyl-N-methyl-pseudoephedrinium iodide are dissolved in 400 ml of water under stirring and at a temperature of 50° C. Then, 102 g of anionic resin is added and it is kept under stirring for 7 days at room temperature. Once the exchange has completed, the resulting aqueous solution is concentrated by evaporating part of the water in a rotary evaporator at 40° C. until reaching the desired concentration (between 25 and 30 wt %).

Example 2: Synthesis of the Structure-Directing Agent: (1R,2R)—N-ethyl-N-methyl-pseudoephedrinium hydroxide

[0090] The synthesis of (1R,2R)—N-ethyl-N-methyl-pseudoephedrinium hydroxide is carried out in exactly the same way as in Example 1, but starting in this case from the enantiomer (1R,2R)-pseudoephedrine.

[0091] In a typical synthesis of (1R,2R)—N-ethyl-N-methyl-pseudoephedrinium hydroxide, 15.10 g of formaldehyde (37 wt % in aqueous solution) and 23.00 g of formic acid (95 wt %) are mixed in a flask under magnetic stirring. The flask is cooled in an ice bath, and then 25.00 g of (1R,2R)-pseudoephedrine are added very slowly. The mixture is refluxed overnight. Next, 18.20 g of hydrochloric acid (37 wt %) are added, keeping the flask with the mixture in an ice bath. Next, successive extractions of the product are performed by washing with diethyl ether. The aqueous phase is then collected to which an aqueous sodium hydroxide solution (25 wt %) is added until reaching a pH of 12, giving rise to the formation of an oily product. Lastly, the product is extracted in a decantation funnel with diethyl ether, collecting the organic phase. Next, traces of water are removed from the organic phase with potassium carbonate (K.sub.2CO.sub.3), and the solvent is removed on a rotary evaporator. An oil containing (1R,2R)—N-methyl-pseudoephedrine is thus obtained, with a yield of about 80%.

[0092] In the second step of the reaction, 20.00 g of (1R,2R)—N-methyl-pseudoephedrine are dissolved in 400 ml of acetonitrile, and 34.85 g of iodoethane is added little by little while keeping the mixture under stirring and cooling with an ice bath. The mixture is allowed to warm to room temperature and is thus kept under stirring for 5 days. The solvent is then evaporated in a rotary evaporator, yielding a precipitate which is washed with diethyl ether. The product, (1R,2R)—N-ethyl-N-methyl-pseudoephedrinium iodide, is obtained with yields of about 90%.

[0093] The last step of the synthesis consists of the anionic exchange of iodide for hydroxide using an anion resin (Amberlite IRN-78). 34.30 g of (1R,2R)—N-ethyl-N-methyl-pseudoephedrinium iodide are dissolved in 400 ml of water under stirring and at a temperature of 50° C. Then, 102 g of anionic resin is added and it is kept under stirring for 7 days at room temperature. Once the exchange has completed, the resulting aqueous solution is concentrated by evaporating part of the water in a rotary evaporator at 40° C. until reaching the desired concentration (between 25 and 30 wt %).

[0094] The following Examples 3 to 13 include different preparations of the GTM-3 material using various synthesis conditions.

Example 3: Preparation of the GTM-3 Material with a Si/Ge Ratio in the Gel of 5 from (1S,2S)—N-ethyl-N-methyl-pseudoephedrinium

[0095] This example shows a typical preparation of GTM-3 with a Si/Ge ratio in the gel of 5, and using the (1S,2S)—N-ethyl-N-methyl-pseudoephedrinium enantiomer as the organic agent.

[0096] 0.57 g of GeO.sub.2 are dissolved in 6.36 g of aqueous (1S,2S)—N-ethyl-N-methyl-pseudoephedrinium hydroxide solution with a concentration of 28.8 wt %. Next, 5.76 g of tetraethylorthosilicate are added, leaving the mixture under stirring to remove ethanol.

[0097] Finally, 0.34 g of hydrofluoric acid (48 wt %) are added and stirred until homogeneous with the help of a spatula. The prepared gel has the following composition: 0.25 ROH: 0.833 SiO.sub.2: 0.167 GeO.sub.2: 0.25 HF: 6.5 H.sub.2O, wherein ROH is (1S,2S)—N-ethyl-N-methyl-pseudoephedrinium hydroxide.

[0098] The gel is transferred to Teflon sleeves which are inserted into steel autoclaves and heated at 100° C. for 6 days under static conditions. The obtained solid is filtered, washed with ethanol and water, and dried. The solid obtained, GTM-3(SS), presents the characteristic X-ray diffraction pattern of the ITV structure, showing the main diffraction maxima listed below:

TABLE-US-00003 Angle 2θ Distance d Relative (±0.20) (°) (±0.500) (Å) intensity 4.78 18.485 f 5.84 15.126 d 7.54 11.726 d 8.27 10.677 d 10.08 8.772 d 10.64 8.317 d 11.14 7.941 d 12.12 7.301 d 12.58 7.038 d 13.96 6.338 d 14.26 6.210 d 14.65 6.045 d 15.79 5.611 d 17.13 5.177 d 17.48 5.075 d 18.12 4.896 d 18.48 4.797 d 19.05 4.659 m 20.47 4.340 d 20.77 4.273 d 21.58 4.117 f 22.32 3.982 d 22.99 3.865 d 23.87 3.728 f 24.13 3.688 f 24.57 3.623 m 24.81 3.588 m 25.71 3.465 d 25.97 3.431 d 26.65 3.393 d 27.04 3.298 m 28.08 3.175 d 28.92 3.088 d 29.14 3.063 d 29.67 3.009 d 30.32 2.948 d 30.94 2.888 d 31.39 2.850 d 32.20 2.780 d 32.97 2.715 d 33.27 2.693 d 33.72 2.658 d 34.33 2.610 d 34.84 2.575 d 35.52 2.525 d 35.60 2.520 d 36.33 2.473 d 36.84 2.440 d 37.53 2.396 d 38.60 2.333 d 39.22 2.295 d

[0099] This material has an average Si/Ge ratio of 2.8, measured by SEM-EDX (scanning electron microscopy with energy dispersive X-ray analyzer), giving a Ge content significantly lower than that of zeolite ITQ-37. In turn, it has a C/N ratio of 12.8 (13 being the theoretical value of the organic cation), and an organic content of 19.3% (measured by CHN elemental analysis). The complete incorporation of the organic cation in the GTM-3 material is verified by means of nuclear magnetic resonance in Example 16, and the resistance of the GTM-3 material to the removal of the organic material in Examples 17 and 18.

Example 4: Preparation of the GTM-3 Material from (1R,2R)—N-ethyl-N-methyl-pseudoephedrinium with a Si/Ge Ratio in the Gel of 5

[0100] In this example, the (1R,2R)—N-ethyl-N-methyl-pseudoephedrinium enantiomer is used as the organic agent, under the same synthesis conditions as in Example 3.

[0101] 0.57 g of GeO.sub.2 are dissolved in 6.25 g of aqueous (1R,2R)—N-ethyl-N-methyl-pseudoephedrinium hydroxide solution with a concentration of 29.3 wt %. Next, 5.76 g of tetraethylorthosilicate are added, leaving the mixture under stirring to remove ethanol. Finally, 0.34 g of hydrofluoric acid (48 wt %) are added and stirred until homogeneous with the help of a spatula. The prepared gel has the following composition: 0.25 ROH: 0.833 SiO.sub.2: 0.167 GeO.sub.2: 0.25 HF: 6.5 H.sub.2O, wherein ROH is (1R,2R)—N-ethyl-N-methyl-pseudoephedrinium hydroxide.

[0102] The gel is transferred to Teflon sleeves which are inserted into steel autoclaves and heated at 100° C. for 6 days under static conditions. The obtained solid is filtered, washed with ethanol and water, and dried. The solid obtained, GTM-3(RR), presents the characteristic X-ray diffraction pattern of the ITV structure, showing the main diffraction maxima listed below:

TABLE-US-00004 Angle 2θ Distance d Relative (±0.20) (°) (±0.500) (Å) intensity 4.71 18.765 f 5.78 15.303 d 7.43 11.892 d 8.18 10.800 d 10.04 8.815 d 10.58 8.359 d 11.08 7.985 d 12.04 7.350 d 12.51 7.068 d 13.88 6.377 d 14.21 6.232 d 14.63 6.056 d 15.73 5.632 d 17.10 5.186 m 17.39 5.099 d 18.11 4.896 d 18.97 4.677 d 20.47 4.338 d 20.67 4.295 d 21.54 4.125 m 22.36 3.973 d 22.87 3.886 d 23.82 3.736 f 24.07 3.697 f 24.56 3.624 m 25.90 3.440 d 26.95 3.309 m 29.03 3.076 d 30.28 2.952 d 31.29 2.859 d 32.06 2.792 d 33.24 2.694 d 33.70 2.660 d 34.78 2.580 d 35.20 2.547 d 36.28 2.476 d 36.75 2.443 d 37.43 2.402 d 38.53 2.337 d 39.16 2.299 d

Example 5: Preparation of the GTM-3 Material with a Si/Ge Ratio in the Gel of 5 from (1S,2S)—N-ethyl-N-methyl-pseudoephedrinium, with a Water Content in the Gel of 3

[0103] In this example, the water content in the molar composition of the gel is reduced from 6.5 (such as in Examples 3 and 4) to 3.

[0104] 0.67 g of GeO.sub.2 are dissolved in 7.56 g of aqueous (1S,2S)—N-ethyl-N-methyl-pseudoephedrinium hydroxide solution with a concentration of 28.8 wt %. Next, 6.84 g of tetraethylorthosilicate are added, leaving the mixture under stirring for the time necessary to remove ethanol and water required to obtain the desired composition. Finally, 0.40 g of hydrofluoric acid (48 wt %) are added and stirred until homogeneous with the help of a spatula. The prepared gel has the following composition: 0.25 ROH: 0.833 SiO.sub.2: 0.167 GeO.sub.2: 0.25 HF: 3.0 H.sub.2O, wherein ROH is (1S,2S)—N-ethyl-N-methyl-pseudoephedrinium hydroxide.

[0105] The gel is transferred to Teflon sleeves which are inserted into steel autoclaves and heated at 100° C. for 14 days under static conditions. The obtained solid is filtered, washed with ethanol and water, and dried. The solid obtained, GTM-3(SS), presents the characteristic X-ray diffraction pattern of the ITV structure, showing the main diffraction maxima listed below:

TABLE-US-00005 Angle 2θ Distance d Relative (±0.20) (°) (±0.500) (Å) intensity 4.77 18.532 f 5.83 15.150 d 7.53 11.740 d 8.25 10.708 d 10.11 8.753 d 10.65 8.304 d 11.18 7.917 d 12.15 7.284 d 12.62 7.017 d 13.98 6.327 d 14.31 6.190 d 14.70 6.025 d 15.83 5.600 d 16.90 5.242 d 17.22 5.151 d 17.55 5.053 d 18.18 4.879 d 18.57 4.775 d 19.12 4.642 m 20.57 4.317 d 20.85 4.260 d 21.67 4.102 m 21.95 4.047 d 22.46 3.959 d 22.97 3.873 d 23.02 3.861 d 23.53 3.778 d 23.95 3.715 f 24.21 3.676 m 24.67 3.608 d 24.93 3.572 d 25.83 3.450 d 26.07 3.418 d 26.73 3.336 d 27.16 3.284 d 27.44 3.248 d 28.23 3.162 d 29.05 3.074 d 29.26 3.052 d 29.84 2.994 d 30.44 2.936 d 31.02 2.883 d 31.58 2.833 d 32.34 2.768 d 33.06 2.710 d 33.42 2.682 d 33.78 2.653 d 34.45 2.603 d 34.99 2.565 d 35.44 2.531 d 35.68 2.517 d 36.54 2.459 d 37.02 2.428 d 37.73 2.385 d 37.86 2.375 d 38.78 2.322 d 39.45 2.284 d

Example 6: Preparation of the GTM-3 Material with a Si/Ge Ratio in the Gel of 5 from (1S,2S)—N-ethyl-N-methyl-pseudoephedrinium, Using Aerosil SiO.SUB.2 .as Source of Si

[0106] In this example, Aerosil SiO.sub.2 is used as a source of Si (instead of tetraethylorthosilicate such as in the preceding examples).

[0107] 0.82 g of GeO.sub.2 are dissolved in 9.21 g of aqueous (1S,2S)—N-ethyl-N-methyl-pseudoephedrinium hydroxide solution with a concentration of 28.8 wt %. Next, 2.36 g of Aerosil SiO.sub.2 and 0.12 g of water (miliQ) are added, leaving the mixture under stirring until homogeneous. Finally, 0.49 g of hydrofluoric acid (48 wt %) are added and stirred until homogeneous with the help of a spatula. The prepared gel has the following composition: 0.25 ROH: 0.833 SiO.sub.2: 0.167 GeO.sub.2: 0.25 HF: 6.5 H.sub.2O, wherein ROH is (1S,2S)—N-ethyl-N-methyl-pseudoephedrinium hydroxide.

[0108] The gel is transferred to Teflon sleeves which are inserted into steel autoclaves and heated at 100° C. for 7 days under static conditions. The obtained solid is filtered, washed with ethanol and water, and dried. The solid obtained, GTM-3(SS), presents the characteristic X-ray diffraction pattern of the ITV structure, showing the main diffraction maxima listed below:

TABLE-US-00006 Angle 2θ Distance d Relative (±0.20) (±0.500) (Å) intensity 4.67 18.934 m 5.73 15.428 d 7.41 11.935 d 8.08 10.927 d 9.96 8.884 d 10.51 8.417 d 11.01 8.035 d 12.00 7.378 d 12.46 7.101 d 14.12 6.274 d 14.53 6.097 d 15.60 5.681 d 17.00 5.215 d 17.32 5.119 d 17.96 4.939 d 18.89 4.698 m 20.34 4.366 d 20.60 4.307 d 21.43 4.147 f 22.21 4.003 d 23.22 3.828 d 23.69 3.756 f 23.95 3.716 f 24.41 3.647 m 24.64 3.612 m 25.55 3.486 m 25.77 3.457 m 26.49 3.363 d 26.87 3.318 m 28.84 3.096 d 29.55 3.021 d 30.14 2.966 d 30.73 2.907 d 31.21 2.866 d 31.95 2.801 d 33.12 2.703 d 33.52 2.674 d 34.65 2.589 d 35.39 2.535 d 36.18 2.483 d 36.68 2.450 d 37.33 2.409 d 38.39 2.345 d 38.91 2.313 d 39.86 2.262 d

Example 7: Preparation of the GTM-3 Material with a Si/Ge Ratio in the Gel of 5 from (1S,2S)—N-ethyl-N-methyl-pseudoephedrinium, Using NH.SUB.4.F as a Source of Fluoride

[0109] In this example, ammonium fluoride is used as the source of fluoride (instead of hydrofluoric acid such as in the preceding examples).

[0110] 0.47 g of GeO.sub.2 are dissolved in 5.33 g of aqueous (1S,2S)—N-ethyl-N-methyl-pseudoephedrinium hydroxide solution with a concentration of 28.8 wt %. Next, 4.83 g of tetraethylorthosilicate and 0.11 g of water (MilliQ) are added, leaving the mixture under stirring for the time necessary to remove ethanol. Finally, 0.26 g of ammonium fluoride are added and stirred until homogeneous with the help of a spatula. The prepared gel has the following composition: 0.25 ROH: 0.833 SiO.sub.2: 0.167 GeO.sub.2: 0.25 NH.sub.4F: 6.5 H.sub.2O, wherein ROH is (1S,2S)—N-ethyl-N-methyl-pseudoephedrinium hydroxide.

[0111] The gel is transferred to Teflon sleeves which are inserted into steel autoclaves and heated at 100° C. for 7 days under static conditions. The obtained solid is filtered, washed with ethanol and water, and dried. The solid obtained, GTM-3(SS), presents the characteristic X-ray diffraction pattern of the ITV structure, showing the main diffraction maxima listed below:

TABLE-US-00007 Angle 2θ Distance d Relative (±0.20) (°) (±0.500) (Å) intensity 4.74 18.651 f 5.80 15.226 d 7.50 11.795 d 10.06 8.794 d 10.61 8.335 d 11.14 7.945 m 12.10 7.308 d 12.56 7.051 d 14.28 6.205 d 14.66 6.041 d 15.79 5.612 d 16.24 5.452 d 17.17 5.165 d 17.50 5.069 d 19.07 4.655 m 19.91 4.460 d 20.53 4.324 d 21.62 4.111 f 22.41 3.967 d 22.90 3.880 d 23.90 3.723 f 24.16 3.684 f 24.60 3.618 m 24.85 3.580 d 25.83 3.447 d 26.00 3.428 d 27.09 3.292 m 28.48 3.134 m 29.20 3.059 d 30.34 2.946 d 31.48 2.839 d 32.33 2.769 d 32.88 2.724 d 33.34 2.685 d 33.79 2.652 d 34.38 2.606 d 34.94 2.568 d 36.40 2.469 d 36.96 2.432 d 37.60 2.390 d 38.73 2.325 d

Example 8: Preparation of the GTM-3 Material with a Si/Ge Ratio in the Gel of 5 from (1S,2S)—N-ethyl-N-methyl-pseudoephedrinium, at a Temperature of 60° C.

[0112] In this example, the temperature of the hydrothermal crystallization treatment is reduced to 60° C. (instead of 100° C. such as in the preceding examples), thereby allowing the use of Pyrex jars instead of autoclaves.

[0113] 0.57 g of GeO.sub.2 are dissolved in 6.36 g of aqueous (1S,2S)—N-ethyl-N-methyl-pseudoephedrinium hydroxide solution with a concentration of 28.8 wt %. Next, 5.76 g of tetraethylorthosilicate are added, leaving the mixture under stirring to remove ethanol. Finally, 0.34 g of hydrofluoric acid (48 wt %) are added and stirred until homogeneous with the help of a spatula. The prepared gel has the following composition: 0.25 ROH: 0.833 SiO.sub.2: 0.167 GeO.sub.2: 0.25 HF: 6.5 H.sub.2O, wherein ROH is (1S,2S)—N-ethyl-N-methyl-pseudoephedrinium hydroxide.

[0114] The gel is transferred to Pyrex jars which are heated at 60° C. for 14 days under static conditions. The obtained solid is filtered, washed with ethanol and water, and dried. The solid obtained, GTM-3(SS), presents the characteristic X-ray diffraction pattern of the ITV structure, showing the main diffraction maxima listed below:

TABLE-US-00008 Angle 2θ Distance d Relative (±0.20) (°) (±0.500) (Å) intensity 4.70 18.805 f 5.79 15.269 d 7.42 11.918 d 10.01 8.840 d 10.56 8.380 d 11.07 7.989 d 12.01 7.368 d 12.51 7.072 d 14.57 6.080 d 15.64 5.661 d 17.06 5.196 d 17.43 5.085 d 18.98 4.676 d 20.39 4.356 d 21.49 4.134 m 23.88 3.726 f 24.51 3.629 d 25.80 3.454 d 26.83 3.323 d 28.91 3.089 d 30.10 2.969 d 31.21 2.864 d 31.90 2.805 d 33.58 2.669 d 34.74 2.582 d 36.17 2.483 d 36.59 2.454 d 38.30 2.350 d 38.93 2.312 d

Example 9: Preparation of the GTM-3 Material with a Si/Ge Ratio in the Gel of 3 from (1S,2S)—N-ethyl-N-methyl-pseudoephedrinium

[0115] In this example, the Ge content is increased to a Si/Ge ratio in the gel of 3 (instead of 5 such as in the preceding examples).

[0116] 0.74 g of GeO.sub.2 are dissolved in 5.38 g of aqueous (1S,2S)—N-ethyl-N-methyl-pseudoephedrinium hydroxide solution with a concentration of 29.7 wt %. Next, 4.52 g of tetraethylorthosilicate are added, leaving the mixture under stirring to remove ethanol. Finally, 0.30 g of hydrofluoric acid (48 wt %) are added and stirred until homogeneous with the help of a spatula. The prepared gel has the following composition: 0.25 ROH: 0.75 SiO.sub.2:0.25 GeO.sub.2: 0.25 HF: 6.5 H.sub.2O, wherein ROH is (1S,2S)—N-ethyl-N-methyl-pseudoephedrinium hydroxide.

[0117] The gel is transferred to Teflon sleeves which are inserted into steel autoclaves and heated at 100° C. for 6 days under static conditions. The obtained solid is filtered, washed with ethanol and water, and dried. The solid obtained, GTM-3(SS), presents the characteristic X-ray diffraction pattern of the ITV structure, showing the main diffraction maxima listed below:

TABLE-US-00009 Angle 2θ Distance d Relative (±0.20) (°) (±0.500) (Å) intensity 4.68 18.900 f 5.73 15.415 d 7.43 11.898 d 8.04 10.995 d 9.96 8.882 d 10.51 8.415 d 11.03 8.020 d 12.02 7.366 d 12.46 7.107 d 14.14 6.263 d 14.54 6.091 d 15.65 5.662 d 17.04 5.204 m 17.36 5.108 m 17.99 4.932 d 18.92 4.690 d 20.35 4.365 d 21.45 4.143 m 22.19 4.006 d 23.71 3.752 f 24.39 3.650 m 25.56 3.486 d 25.79 3.454 d 26.91 3.313 d 27.93 3.194 d 28.88 3.092 d 30.11 2.968 d 31.20 2.867 d 31.94 2.802 d 33.09 2.705 d 33.62 2.666 d 34.66 2.588 d 36.15 2.485 d 36.66 2.452 d 37.37 2.407 d 38.44 2.342 d 39.02 2.308 d 39.84 2.261 d

Example 10: Preparation of the Al-GTM-3 Material with a Si/Ge Ratio in the Gel of 3, and a T/Al Ratio of 70, from (1S,2S)—N-ethyl-N-methyl-pseudoephedrinium, and with Seedings

[0118] This example demonstrates the possibility of obtaining the material object of the invention in the presence of aluminum in the synthesis gel, in this particular case which does not limit the scope of the invention, Al is introduced to the gel in a T/Al ratio in the gel equal to 70. Furthermore, seedings of previously prepared GTM-3 material are also introduced into the gel to favor crystallization, although the presence thereof is not essential to form the material in the presence of Al.

[0119] 0.60 g of GeO.sub.2 are dissolved in 4.21 g of aqueous (1S,2S)—N-ethyl-N-methyl-pseudoephedrinium hydroxide solution with a concentration of 30.8 wt %. Next, 3.67 g of tetraethylorthosilicate and 0.07 g of Al isopropoxide are added, leaving the mixture under stirring to remove ethanol, isopropanol, and water required to obtain the desired composition. Then, 1.15 g of hydrofluoric acid (10 wt %) are added. Lastly, 0.16 g of the previously prepared GTM-3 material (according to Example 9) are added and stirred until homogeneous. The prepared gel has the following composition: 0.25 ROH: 0.75 SiO.sub.2: 0.25 GeO.sub.2: 0.007 Al.sub.2O.sub.3: 0.25 HF: 3.68 H.sub.2O, wherein ROH is (1S,2S)—N-ethyl-N-methyl-pseudoephedrinium hydroxide, and with 10% seeding (by weight with respect to the sum of SiO.sub.2 and GeO.sub.2) of previously prepared solid GTM-3(SS).

[0120] The gel is transferred to Teflon sleeves which are inserted into steel autoclaves and heated at 100° C. for 9 days under static conditions. The obtained solid is filtered, washed with ethanol and water, and dried. The solid obtained, Al-GTM-3(SS), presents the characteristic X-ray diffraction pattern of the ITV structure, showing the main diffraction maxima listed below:

TABLE-US-00010 Angle 2θ Distance d Relative (±0.20) (°) (±0.500) (Å) intensity 4.66 18.956 m 5.72 15.450 d 7.41 11.935 d 9.98 8.860 d 10.53 8.402 d 11.05 8.010 d 12.04 7.351 d 12.47 7.100 d 14.17 6.249 d 14.57 6.081 d 15.67 5.655 d 17.08 5.192 d 17.43 5.088 d 18.02 4.922 d 18.98 4.677 d 20.41 4.351 d 20.73 4.282 d 21.51 4.130 m 22.29 3.988 d 22.81 3.898 d 23.81 3.737 f 24.07 3.698 f 24.51 3.632 d 24.77 3.594 d 25.67 3.471 d 25.93 3.436 d 26.61 3.347 d 26.99 3.304 m 28.05 3.181 d 29.10 3.069 d 29.71 3.005 d 30.28 2.952 d 30.92 2.890 d 31.38 2.851 d 32.06 2.792 d 33.31 2.688 d 33.71 2.659 d 34.29 2.615 d 34.85 2.575 d 35.56 2.525 d 36.34 2.472 d 36.90 2.436 d 37.51 2.398 d 38.61 2.332 d 39.24 2.296 d

[0121] The incorporation of Al into the Al-GTM-3(SS) material is demonstrated by solid-state NMR of .sup.27Al (FIG. 5), in which the presence of a single signal at 50 ppm proves the incorporation of Al in tetrahedral positions of the ITV structure.

Example 11: Preparation of the B-GTM-3 Material with a Si/Ge Ratio in the Gel of 5, and a T/B Ratio of 70, from (1S,2S)—N-ethyl-N-methyl-pseudoephedrinium

[0122] This example demonstrates the possibility of obtaining the material object of the invention in the presence of boron in the synthesis gel, in this particular case which does not limit the scope of the invention, B is introduced to the gel in a T/B ratio in the gel equal to 70.

[0123] 0.35 g of GeO.sub.2 are dissolved in 3.68 g of aqueous (1S,2S)—N-ethyl-N-methyl-pseudoephedrinium hydroxide solution with a concentration of 30.6 wt %. Next, 3.54 g of tetraethylorthosilicate, 0.018 g of boric acid, and 0.20 g of water (miliQ) are added, leaving the mixture under stirring to remove ethanol. Finally, 0.21 g of hydrofluoric acid (48 wt %) are added and stirred until homogeneous with the help of a spatula. The prepared gel has the following composition: 0.25 ROH: 0.833 SiO.sub.2: 0.167 GeO.sub.2: 0.007 B.sub.2O.sub.3: 0.25 HF: 6.5 H.sub.2O, wherein ROH is (1S,2S)—N-ethyl-N-methyl-pseudoephedrinium hydroxide.

[0124] The gel is transferred to Teflon sleeves which are inserted into steel autoclaves and heated at 100° C. for 14 days under static conditions. The obtained solid is filtered, washed with ethanol and water, and dried. The solid obtained, B-GTM-3(SS), presents the characteristic X-ray diffraction pattern of the ITV structure, showing the main diffraction maxima listed below:

TABLE-US-00011 Angle 2θ Distance d Relative (±0.20) (°) (±0.500) (Å) intensity 4.69 18.836 f 5.77 15.319 d 7.45 11.869 d 10.03 8.823 d 10.64 8.311 d 11.05 8.008 d 12.05 7.342 d 12.52 7.064 d 14.33 6.177 d 14.61 6.064 d 15.65 5.661 d 17.09 5.188 d 17.46 5.076 d 18.10 4.897 d 18.99 4.674 d 20.56 4.320 d 21.59 4.116 m 22.28 3.988 d 23.89 3.725 f 24.76 3.596 m 25.79 3.454 m 27.03 3.299 d 29.01 3.078 d 30.16 2.964 d 32.01 2.796 d 33.59 2.668 d 34.90 2.571 d 36.36 2.471 d 36.92 2.433 d 37.77 2.380 d 38.69 2.327 d

Example 12: Preparation of the Sn-GTM-3 Material with a Si/Ge Ratio in the Gel of 5, and a T/Sn Ratio of 140, from (1S,2S)—N-ethyl-N-methyl-pseudoephedrinium

[0125] This example demonstrates the possibility of obtaining the material object of the invention in the presence of tin in the synthesis gel, in this particular case which does not limit the scope of the invention, Sn is introduced to the gel in a T/Sn ratio in the gel equal to 140.

[0126] 0.35 g of GeO.sub.2 are dissolved in 4.03 g of aqueous (1S,2S)—N-ethyl-N-methyl-pseudoephedrinium hydroxide solution with a concentration of 27.9 wt %. Next, 3.53 g of tetraethylorthosilicate and 0.038 g of tin tetrachloride are added, leaving the mixture under stirring to remove ethanol. Finally, 0.21 g of hydrofluoric acid (48 wt %) are added and stirred until homogeneous with the help of a spatula. The prepared gel has the following composition: 0.25 ROH: 0.833 SiO.sub.2: 0.167 GeO.sub.2: 0.007 SnO.sub.2: 0.25 HF: 6.5 H.sub.2O, wherein ROH is (1S,2S)—N-ethyl-N-methyl-pseudoephedrinium hydroxide.

[0127] The gel is transferred to Teflon sleeves which are inserted into steel autoclaves and heated at 100° C. for 6 days under static conditions. The obtained solid is filtered, washed with ethanol and water, and dried. The solid obtained, Sn-GTM-3(SS), presents the characteristic X-ray diffraction pattern of the ITV structure, showing the main diffraction maxima listed below:

TABLE-US-00012 Angle 2θ Distance d Relative (±0.20) (°) (±0.500) (Å) intensity 4.73 18.673 f 5.80 15.247 d 7.48 11.814 d 8.29 10.653 d 10.04 8.808 d 10.58 8.364 d 11.09 7.977 d 12.06 7.341 d 12.54 7.057 d 13.79 6.417 d 14.20 6.239 d 14.60 6.069 d 15.69 5.647 d 17.07 5.194 d 17.40 5.098 d 18.10 4.897 d 18.98 4.676 m 20.44 4.345 d 20.77 4.274 d 21.50 4.133 m 22.28 3.991 d 23.76 3.745 f 24.07 3.698 f 24.50 3.634 m 25.86 3.445 m 26.93 3.310 m 27.98 3.189 d 29.07 3.072 d 30.21 2.959 d 31.36 2.853 d 32.06 2.792 d 33.26 2.692 d 33.63 2.665 d 34.78 2.580 d 35.58 2.522 d 36.19 2.482 d 36.79 2.443 d 37.48 2.399 d 38.39 2.345 d 39.06 2.304 d 39.99 2.255 d

Example 13: Preparation of the Ti-GTM-3 Material with a Si/Ge Ratio in the Gel of 5, and a T/Ti Ratio of 140, from (1S,2S)—N-ethyl-N-methyl-pseudoephedrinium

[0128] This example demonstrates the possibility of obtaining the material object of the invention in the presence of titanium in the synthesis gel, in this particular case which does not limit the scope of the invention, Ti is introduced to the gel in a T/Ti ratio in the gel equal to 140.

[0129] 0.35 g of GeO.sub.2 are dissolved in 4.02 g of aqueous (1S,2S)—N-ethyl-N-methyl-pseudoephedrinium hydroxide solution with a concentration of 27.9 wt %. Next, 3.53 g of tetraethylorthosilicate and 0.04 g of titanium (IV) isopropoxide are added, leaving the mixture under stirring to remove ethanol. Finally, 0.21 g of hydrofluoric acid (48 wt %) are added and stirred until homogeneous with the help of a spatula. The prepared gel has the following composition: 0.25 ROH: 0.833 SiO.sub.2: 0.167 GeO.sub.2: 0.007 TiO.sub.2: 0.25 HF: 6.5 H.sub.2O, wherein ROH is (1S,2S)—N-ethyl-N-methyl-pseudoephedrinium hydroxide.

[0130] The gel is transferred to Teflon sleeves which are inserted into steel autoclaves and heated at 100° C. for 42 days under static conditions. The obtained solid is filtered, washed with ethanol and water, and dried. The solid obtained, Ti-GTM-3(SS), presents the characteristic X-ray diffraction pattern of the ITV structure, showing the main diffraction maxima listed below:

TABLE-US-00013 Angle 2θ Distance d Relative (±0.20) (°) (±0.500) (Å) intensity 4.72 18.730 f 5.79 15.275 d 7.47 11.831 d 8.24 10.718 d 9.60 9.209 d 10.05 8.806 d 10.59 8.357 d 11.11 7.967 d 12.08 7.327 d 12.55 7.056 d 14.22 6.228 d 14.62 6.060 d 15.73 5.633 d 17.12 5.180 d 17.46 5.081 d 18.10 4.898 d 19.04 4.662 m 20.48 4.337 d 20.77 4.274 d 21.56 4.121 f 22.42 3.962 d 23.38 3.802 d 23.86 3.730 f 24.12 3.689 m 24.61 3.614 d 24.82 3.587 d 25.84 3.448 d 26.62 3.346 d 27.05 3.296 d 28.96 3.084 d 30.30 2.949 d 30.88 2.894 d 31.34 2.854 d 32.20 2.780 d 32.91 2.719 d 33.35 2.685 d 33.74 2.657 d 34.35 2.609 d 34.85 2.574 d 35.65 2.516 d 36.38 2.469 d 36.95 2.433 d 37.59 2.393 d 38.73 2.325 d 39.17 2.298 d

[0131] The following Examples 14 and 15 represent conclusive evidence that the GTM-3 material is enriched in one enantiomorphic crystalline form or another depending on whether one enantiomer of the organic agent or another, i.e., (1S,2S)—N-ethyl-N-methyl-pseudoephedrinium or (1S,2S)—N-ethyl-N-methyl-pseudoephedrinium, is used. Said evidence is given by the fact that, if the same enantiomer of the organic agent is used to prepare the seeding and for the synthesis gel, crystallization is significantly faster than in the case of preparing the seeding and the synthesis gel with different enantiomers. This verifies that the GTM-3 seeding crystals are capable of recognizing the different enantiomers of the synthesis gel.

Example 14: Enantioselective Crystallization of the GTM-3 Material with a Si/Ge Ratio in the Gel of 8 from (1S,2S)—N-ethyl-N-methyl-pseudoephedrinium or (1R,2R)—N-ethyl-N-methyl-pseudoephedrinium, with GTM-3(SS) Seedings

[0132] A) 0.26 g of GeO.sub.2 are dissolved in 4.07 g of aqueous (1S,2S)—N-ethyl-N-methyl-pseudoephedrinium hydroxide solution with a concentration of 30.6 wt %. Next, 4.18 g of tetraethylorthosilicate and 0.27 g of water (milliQ) are added, leaving the mixture under stirring to remove ethanol. Next, 0.23 g of hydrofluoric acid (48 wt %) are added and stirred.

[0133] Lastly, 0.073 g of seedings of the GTM-3(SS) material previously prepared (with the enantiomer (1S,2S)—N-ethyl-N-methyl-pseudoephedrinium, according to Example 3) are added and stirred until homogeneous. The prepared gel has the following composition: 0.25 ROH: 0.89 SiO.sub.2: 0.11 GeO.sub.2: 0.25 HF: 6.5 H.sub.2O, wherein ROH is (1S,2S)—N-ethyl-N-methyl-pseudoephedrinium hydroxide, and with 5% seeding (by weight with respect to the sum of SiO.sub.2 and GeO.sub.2) of GTM-3(SS) solid prepared with the enantiomer which is the same as that used in the gel.

[0134] B) Moreover, the same experiment is performed using the same GTM-3(SS) seedings, but in this case by adding the other enantiomer, (1R,2R)—N-ethyl-N-methyl-pseudoephedrinium, in the gel. 0.26 g of GeO.sub.2 are dissolved in 4.26 g of aqueous (1R,2R)—N-ethyl-N-methyl-pseudoephedrinium hydroxide solution with a concentration of 29.3 wt %. Next, 4.18 g of tetraethylorthosilicate and 0.08 g of water (milliQ) are added, leaving the mixture under stirring to remove ethanol. Next, 0.23 g of hydrofluoric acid (48 wt %) are added and stirred. Lastly, 0.073 g of seedings of the GTM-3(SS) material previously prepared (with the enantiomer (1S,2S)—N-ethyl-N-methyl-pseudoephedrinium, according to Example 3) are added and stirred until homogeneous. The prepared gel has the following composition: 0.25 ROH: 0.89 SiO.sub.2: 0.11 GeO.sub.2: 0.25 HF: 6.5 H.sub.2O, wherein ROH is (1R,2R)—N-ethyl-N-methyl-pseudoephedrinium hydroxide, and with 5% seeding (by weight with respect to the sum of SiO.sub.2 and GeO.sub.2) of GTM-3(SS) solid prepared with the enantiomer which is opposite to that used in the gel.

[0135] The gels are transferred to Teflon sleeves which are inserted into steel autoclaves and heated at 100° C. for 3 days under static conditions. The obtained solids are filtered, washed with ethanol and water, and dried. If the enantiomer used in the synthesis gel (1S,2S) is the same as the one used in the seeding preparation (1S,2S) (case A), the obtained solid, GTM-3(SS), presents the characteristic X-ray diffraction pattern of GTM-3, crystallizing significantly faster due to the seeding prepared with the same enantiomer. On the contrary, if the enantiomer used in the synthesis gel (1R,2R) is opposite to that used in the seeding preparation (1S,2S) (case B), the crystallization of the GTM-3 material is much slower (see the top part of FIG. 6).

Example 15: Enantioselective Crystallization of the GTM-3 Material with a Si/Ge Ratio in the Gel of 8 from (1S,2S)—N-ethyl-N-methyl-pseudoephedrinium or (1R,2R)—N-ethyl-N-methyl-pseudoephedrinium, with GTM-3(RR) Seedings

[0136] Next, the enantioselective crystallization experiments of the GTM-3 material of Example 14 are repeated, but in this case using GTM-3 seedings previously prepared with the enantiomer, (1R,2R)—N-ethyl-N-methyl-pseudoephedrinium.

[0137] C) 0.26 g of GeO.sub.2 are dissolved in 3.60 g of aqueous (1S,2S)—N-ethyl-N-methyl-pseudoephedrinium hydroxide solution with a concentration of 34.6 wt %. Then, 4.18 g of tetraethylorthosilicate and 0.74 g of water (MilliQ) are added, leaving the mixture under stirring to remove ethanol. Next, 0.23 g of hydrofluoric acid (48 wt %) are added and stirred. Lastly, 0.073 g of seedings of the GTM-3(RR) material previously prepared (with the opposite enantiomer, (1R,2R)—N-ethyl-N-methyl-pseudoephedrinium, according to Example 4) are added and stirred until homogeneous. The prepared gel has the following composition: 0.25 ROH: 0.89 SiO.sub.2: 0.11 GeO.sub.2: 0.25 HF: 6.5 H.sub.2O, wherein ROH is (1S,2S)—N-ethyl-N-methyl-pseudoephedrinium hydroxide, and with 5% seeding (by weight with respect to the sum of SiO.sub.2 and GeO.sub.2) of solid GTM-3(RR) prepared with the enantiomer contrary to that used in the gel.

[0138] D) Moreover, the same experiment is performed using the same GTM-3(RR) seedings, but in this case by adding the same enantiomer, (1R,2R)—N-ethyl-N-methyl-pseudoephedrinium, in the gel. 0.26 g of GeO.sub.2 are dissolved in 4.25 g of aqueous (1R,2R)—N-ethyl-N-methyl-pseudoephedrinium hydroxide solution with a concentration of 29.3 wt %. Then, 4.18 g of tetraethylorthosilicate and 0.09 g of water (milliQ) are added, leaving the mixture under stirring to remove ethanol. Next, 0.23 g of hydrofluoric acid (48 wt %) are added and stirred. Lastly, 0.073 g of seedings of the GTM-3(RR) material previously prepared (with the enantiomer (1R,2R)—N-ethyl-N-methyl-pseudoephedrinium, according to Example 4) are added and stirred until homogeneous. The prepared gel has the following composition: 0.25 ROH: 0.89 SiO.sub.2: 0.11 GeO.sub.2: 0.25 HF: 6.5 H.sub.2O, wherein ROH is (1R,2R)—N-ethyl-N-methyl-pseudoephedrinium hydroxide, and with 5% seeding (by weight with respect to the sum of SiO.sub.2 and GeO.sub.2) of GTM-3(RR) solid prepared with the enantiomer which is the same as that used in the gel.

[0139] The gels are transferred to Teflon sleeves which are inserted into steel autoclaves and heated at 100° C. for 3 days under static conditions. The obtained solids are filtered, washed with ethanol and water, and dried. If the enantiomer used in the synthesis gel (1R,2R) is the same as the one used in the seeding preparation (1R,2R) (case D), the obtained solid, GTM-3(RR), presents the characteristic X-ray diffraction pattern, crystallizing significantly faster due to the seeding prepared with the same enantiomer. On the contrary, if the enantiomer used in the synthesis gel (1S,2S) is opposite to that used in the seeding preparation (1R,2R) (case C), the crystallization of the GTM-3 material is much slower (see the bottom part of FIG. 6).

[0140] The same experiments of Examples 14 and 15 were repeated increasing seeding to 10% (by weight with respect to the sum of SiO.sub.2 and GeO.sub.2), giving rise to similar enantioselective crystallization results. In that sense, this clearly demonstrates that the GTM-3(SS) and GTM-3(RR) materials are at least enriched in either one of the enantiomorphic crystalline forms.

Example 16: Characterization of the GTM-3(SS) Material Prepared According to Example 3, with a Si/Ge Ratio of 5, by Means Solid State Nuclear Magnetic Resonance at the Magic Angle

[0141] The GTM-3(SS) material prepared as described in Example 3 was characterized by means of .sup.13C solid state nuclear magnetic resonance at the magic angle to confirm the integrity of the chiral organic species, (1S,2S)—N-ethyl-N-methyl-pseudoephedrinium. In the GTM-3(SS) material, bands, which are very similar to the bands observed for a solution in D.sub.2O of the cation, (1S,2S)—N-ethyl-N-methyl-pseudoephedrinium (FIG. 7—gray line), are observed at 8.5, 13.9, 50.3, 64.7, 70.1, 74.8, 130.2 and 141.7 ppm (FIG. 7—black line), which demonstrates the complete incorporation thereof inside the GTM-3 material.

Example 17: X-Ray Diffraction Experiment at Controlled Temperature of the GTM-3(SS) Material Prepared According to Example 3, with a Si/Ge Ratio of 5: Thermal Stability of the Material

[0142] An X-ray diffraction experiment at increasing temperature is performed for the GTM-3 material obtained according to the method described in Example 3 (black line-bottom) for monitoring the in situ air calcination process (FIG. 8). It is observed that the structure is maintained at 550° C. (the diffraction maxima remain in the same positions, with only the relative intensities varying due to the removal of the organic material) (gray line-middle). Once the GTM-3 material is subjected to calcination and cooled to room temperature (light gray line-top), the structure of the material is also maintained.

Example 18: Air Calcination and Characterization of the GTM-3(SS) Material Prepared According to Example 9, with a Si/Ge Ratio of 3: Stability and Resistance to the Removal of Organic

[0143] The GTM-3(SS) material prepared with a Si/Ge ratio of 3 was subjected to air calcination at 500° C. for 4 hours. X-ray diffraction of this calcined material (FIG. 9) again demonstrates the resistance of the structure to removal of the organics. Likewise, the N.sub.2 adsorption/desorption isotherm (FIG. 10) demonstrates the high porosity of the material, with a micropore volume of 0.31 cm.sup.3/g and an external area (BET) of 866 m.sup.2/g.