Title of Invention	POROUS CRYSTALLINE MATERIAL (ZEOLITE ITQ-24), PREPARATION METHOD THEREOF AND USE OF SAME IN THE CATALYTIC CONVERSION OF ORGANIC COMPOUNDS
Abstract	The invention relates to a porous crystalline material (zeolite ITQ-24), the preparation method thereof and the use of same in the catalytic conversion of organic compounds. More specifically, the invention relates to a synthetic porous crystalline material which is characterised in that it is formed by tetrahedrally-coordinated atoms which are interconnected by means of oxygens. Said material, which comprises a unit cell containing 56 tetrahedrally-coordinated atoms, is known as ITQ-24. Moreover, in the calcined anhydrous state, the material has chemical formula nM1/pXO2: YO2, wherein: X is at least one trivalent element, Y is at least one tetravalent element, n is between 0 and 0.2 and M is at least one charge compensation cation in oxidation state p.

Title of Invention

POROUS CRYSTALLINE MATERIAL (ZEOLITE ITQ-24), PREPARATION METHOD THEREOF AND USE OF SAME IN THE CATALYTIC CONVERSION OF ORGANIC COMPOUNDS

Abstract

The invention relates to a porous crystalline material (zeolite ITQ-24), the preparation method thereof and the use of same in the catalytic conversion of organic compounds. More specifically, the invention relates to a synthetic porous crystalline material which is characterised in that it is formed by tetrahedrally-coordinated atoms which are interconnected by means of oxygens. Said material, which comprises a unit cell containing 56 tetrahedrally-coordinated atoms, is known as ITQ-24. Moreover, in the calcined anhydrous state, the material has chemical formula nM1/pXO2: YO2, wherein: X is at least one trivalent element, Y is at least one tetravalent element, n is between 0 and 0.2 and M is at least one charge compensation cation in oxidation state p.

Full Text	2 Title Porous crystalline material (zeolite ITQ-24), preparation method thereof and use of same in the catalytic conversion of organic compounds 5 Field of the art The invention comes within crystalline zeolitic materials and their use in the catalytic conversion of organic compounds. 10 Prior art Zeolites are porous crystalline materials which have found important applications as catalysts, adsorbents and ion exchangers. Many of these zeolitic materials have 15well-defined structures which form channels and cavities in their interior, of uniform size and shape that permit the adsorption of certain molecules, whereas they prevent other molecules of a size too large for diffusing through the pores, from passing into the interior of the crystal. 20This characteristic confers molecular sieve properties on these materials. These molecular sieves can include Si and other elements of groups IIIA and IVA of the periodic table in their lattice, and/or transition metals such as Ti, V, etc., all of them tetrahedrally coordinated, the 25tetrahedrons being bound by their vertices via oxygens forming a three-dimensional lattice. In the case of containing elements corresponding to IIIA group tetrahedrally coordinated in lattice positions, the negative charge that is generated is compensated by the 30presence of cations, such as alkalis or alkaline earths for example, which are sited in the channels and/or cavities of these materials. One type of cation can be totally or partially exchanged for another type of cation by means of ion exchange techniques, thereby being able 35to vary the properties of a given silicate by selecting 3 the desired cations. In the event of these cations being protons, the resulting materials have a high degree of acidity which confers interesting catalytic properties on them. 5 The use of organic catalysts as structure directing agents has so far been a highly effective method for obtaining novel zeolitic structures. It has recently been proven that the incorporation of heteroatoms other than silicon . can play an important role as structure lOdirectors, since they promote the formation of certain secondary construction subunits. So, for example, the incorporation of Ge promotes the formation four-member double rings in the final zeolites, while the incorporation of Be or Zn promotes the appearance of 15three-member rings in the final materials. As a consequence of the work done in the field of zeolite synthesis, more than 140 zeolitic structures have so far been described wherein the shape, size and connectivity of their channels and/or cavities vary, 20conferring on them different adsorption/diffusion properties, and therefore displaying different catalytic properties. It is thus evident that obtaining novel zeolites is an important field of development, since the possibility of having a high number of zeolites means 25that a selection can be made of the structure best suited to the processes sought to be catalysed. Description of the Invention The present invention relates to a synthetic porous 30crystalline material characterised in that it is formed by tetrahedrally coordinated atoms bound together by means of oxygens, which comprises a unit cell containing 56 tetrahedrally coordinated atoms, known as ITQ-24, whose chemical formula in the calcined anhydrous state is 35given by 4 M1/PXO2: Y02 wherein: 5X is at least one trivalent element, Y is at least one tetravalent element, the value of n is between 0 and 0.2 and M is at least one charge compensation cation in oxidation state p. which possesses an X-ray .diffractogram in the 10calcined anhydrous state whose most representative reflections appear at the spacings given in table 1: Table 1 29 d(± 0.5 A) 100 Io/Inax 7.1400 12.4012 W 7.8650 11.2596 vs 11.0150 8.0457 w 20.2900 4.3840 vw 21.4200 4.1552 vw 22.0450 4.0388 vw 22.7350 3.9178 vw 22.9300 3.8849 vw 15wherein the interplanar spacings, d, were calculated in Angstroms and the relative intensity of the lines is calculated as the percentage with respect to the most intense peak, and are regarded as very strong (vs) = 80- 100, strong (s) = 60-80, medium (m) = 40-60, weak (w) = 2020-40 and very weak (vw) = 0-20. Examples of trivalent elements in the formula given above for ITQ-24 are Al, B, Fe, In, Ga, Cr and mixtures thereof. Examples of tetravalent elements in the formula given 25above for ITQ-24 are Si, Ti, Sn; Ge and mixtures thereof. Examples of compensation cations in the formula 5 given above for ITQ-24 are a proton, H+ precursors such as NH4+ for example, metallic ions such as alkaline or alkaline earth metals, rare earth cations, and metals of group VIII, and also of group IIA, IIIA, IVA, Va, IB, 5IIB, IIIB, IVB, VB, VIIB of the periodic table of elements, or mixtures thereof. From the given values, it can be deduced that the crystalline material ITQ-24 can be synthesised in the absence of added trivalent elements and/or compensation locations. In a preferred embodiment of ITQ-24, X is selected from among B, Al and combinations thereof, and Y is Si, Ge, Ti and combinations thereof. The synthetic porous crystalline material, ITQ-24, 15as prepared prior to calcining, possesses an X-ray diffractogram, whose most representative reflections appear at the spacings given in table 2: Table 2 29 d(± 0.5 A) 100 Io/Imax 7.1000 12.4709 vw 7.9400 11.1534 vs 10.5950 8.3637 w 11.0150 8.0457 m 19.4800 4.5644 vw 19.5700 4.5436 vw 20.6050 4.3177 m 21.5450 4.1314 vw 22.1750 4.0154 m 22.6550 3.9314 w 22.8650 3.8958 m 22.9550 3.8807 m 26.9400 3.3150 w 27.0100 3.3066 w wherein the relative intensity is as defined above. These diffractograms were obtained with a Philips X'Pert diffractometer equipped with a graphite 25monochromator and an automatic divergence slit using Kot radiation from copper. The diffraction data was registered by means of steps of 29 of 0.01° wherein 9 is - the Bragg angle and with a count time of 10 seconds per step. 30 It has to be borne in mind that the diffraction data for this sample listed as single lines can consist of overlapping multiples or superpositions of reflections which, under certain conditions, such as differences in crystallographic changes, can appear as resolved or 35partially resolved lines. In general, the crystallographic changes can include small variations in the parameters of the unit cells and/or changes in the symmetry of the crystal, without any change talcing place in the connectivity among the atoms of the structure. 40These modifications, which also include changes in relative intensities, can also be due to differences in the type and quantity of compensation cations, lattice composition and shape thereof, preferred orientation or the type of thermal and hydrothermal treatment undergone. 45 The porous crystalline material ITQ-24 to which this invention refers is a single crystalline phase possessing a three-directional system of channels which intersect with each other. In particular, zeolite ITQ-24 possesses a first system of channels defined by 12-member rings of 50tetrahedrally coordinated atoms with a channel opening of 7.7 x 5.6 A, a second system of sinusoidal channels also defined by channel openings formed by 12 tetrahedrally coordinated atoms with a channel opening of 7.2 x 6.2 A, and finally a third system of channels with a channel 7 opening of 10 tetrahedrally coordinated atoms with a channel opening of 5.75 x 4.8 A. These three systems are interconnected to each other. The structure of zeolite ITQ-24 can be defined by 5its unit cell, which is the smallest structural unit displaying all the symmetry elements of the material. Table 3 shows the list of positions of all the tetra- coordinated atoms contained in the unit cell for a particular embodiment of . ITQ-24. Each tetra-coordinated lOatom is bonded to its four neighbours via oxygen bridges. Given that the position of the tetra-cooordinated atoms can vary slightly depending on the presence of organic matter or water in its pores, on the chemical composition of the material or any other modification, each position 15coordinate given in table 3 can be modified by ± 0.5 A without any change taking place in the connectivity of the atoms forming the structure of the zeolite ITQ-24. Table 3 Site Atom coordinates (9) X Y Z Tl 1.61 1.60 4.71 T2 12.24 8.36 4.71 T3 19.65 11.92 4.71 T4 9.02 5.16 4.71 T5 1.61 11.92 7.90 T6 12.24 5.16 7.90 T7 19.65 1.60 7.90 T8 9.02 8.36 7.90 T9 19.65 11.92 7.90 T10 9.02 5.16 7.90 Til 1.61 1.60 7.90 T12 12.24 8.36 7.90 8 T13 19.65 1.60 4.71 T14 9.02 8.36 4.71 T15 1.61 11.92 4.71 T16 12.24 5.16 4.71 T17 3.19 2.61 2.31 T18 13.82 9.37 2.31 T19 18.06 10.91 2.31 T20 7.43 4.15 2.31 T21 3.19 10.91 10.30 T22 13.82 4.15 10.30 T23 18.06 2.61 10.30 T24 7.43 9.37 10.30 T25 18.06 10.91 10.30 T26 7.43 4.15 10.30 T27 3.19 2.61 10.30 T28 13.82 9.37 10.30 T29 18.06 2.61 2.31 T30 7.43 9.37 2.31 T31 3.19 10.91 2,31 T32 13.82 4.15 2.31 T33 16.63 8.26 1.61 T34 6.00 1.50 1.61 T35 4.63 5.27 1.61 T36 15.26 12.03 1.61 T37 16.63 5.27 11.00 T38 6.00 12.03 11.00 T39 4.63 8.26 11.00 T40 15.26 1.50 11.00 T41 4.63 5.27 11.00 T42 15.26 12.03 11.00 T43 16.63 8.26 11.00 T44 6.00 1.50 11.00 T45 4.63 8.26 1.61 T46 15.26 1.50 • 1.61 T47 16.63 5.27 1.61 9 T48 6. 00 12.03 1.61 T49 1. 62 1.54 0.00 T50 12 .25 8.30 0.00 T51 19 .63 11.98 0.00 T52 9. 01 5.22 0.00 T53 1. 62 11.98 0.00 T54 12 .25 5.22 0.00 T55 19 .63 1.54 0.00 T56 9. 01 8.30 0.00 A second object of the present invention is a process for synthesising a crystalline material ITQ-24, which comprises at least: 25 a first stage wherein a synthesis mixture comrpising at least the following: - H2O, - a source of at least one tetravalent element, Y, - a structure directing agent (R), and 30 - a source of hydroxide ions M', is made to react, a second stage comprising keeping the synthesis mixture at a temperature of between 80 and 200°C until crystals of said crystalline material form; and 35 a third stage comprising recovering said crystalline material. In certain cases, the source of hydroxide ions can be the structure directing agent itself. The synthesis process can furthermore comprise 40 a fourth stage wherein organic matter occluded in the interior of the crystalline material is eliminated by means of a treatment selected from among extraction treatments, thermal treatments at temperatures above 250°C for a period of time between 2 minutes and 25 45hours, and combinations thereof. According to a preferred embodiment of the process, 10 the synthesis mixture can furthermore comprise a source of the trivalent element X. According to a preferred embodiment of the 5invention, the source of the tetravalent element Y is an oxide, the source of the trivalent element X is an oxide, and the synthesis mixture has a composition, in terms of molar ratios of oxides, of YO2/X2O3 > 5 10 H2O/YO2 = between 1 and 50 R/YO2 = between 0.05 and 3.0 OH/YO2 = between 0.05 and 6.0 M'2/jO/X203 = between 0 and 1.0 wherein j is the oxidation state of the cation M' and can 15be one or two. According to a more preferred embodiment of the invention, the source of the tetravalent element Y is an oxide, the source of the trivalent element X is an oxide, 20and the synthesis mixture has a composition, in terms of molar ratios of oxides, of YO2/X2O3 > 7 H2O/YO2 = between 2 and 20 R/YO2 = between 0.05 and 1.0 25 OH/YO2 = between 0.1 and 2.0 M'2/jO/X2O3 = between 0 and 1.0 wherein j is the oxidation state of the cation M' and can be one or two. 30 According to the process of the present invention, the hydroxide source M' can be selected from among a source of at least a compensation cation M, the anion of the structure directing agent and a mixture of the two. A preferred example of structure directing agent is 35a salt of the dication hexamethylene-bis 10 11 (trimethylammonium). An additional preferred example of structure directing agent is a salt of the dihydroxide of hexamethylene-bis(trimethylammonium). 5 A preferred source of the tetravalent element Y is an oxide. A preferred source of the trivalent element X is an oxide. A preferred source of the compensation cation M is a lOhydroxide or an oxide. According to a particular embodiment of the process, fluoride ions are added to the synthesis mixture in a molar ratio F~/YO2 equal to or less than 0.02. For example, in a particular embodiment, ammonium fluoride 15can be added in a molar ratio F-/ SiO2 less than 0.01, in the case in which Y is Si. The zeolite ITQ-24 can essentially be prepared as a pure phase or with very small amounts of impurities which can even be undetectable by X-ray diffraction. 20 In the synthesis process of ITQ-24, hydroxide ions can be used as mobilising agents of the trivalent and tetravalent element oxides, which are introduced in the synthesis means as the hydroxide of an organic cation, inorganic cation or mixtures thereof, being able to be 25occluded in the interior of the organic species structure, which can be eliminated by conventional means. So, the organic component can be eliminated by, for example, extraction, or by thermal treatment by heating to a temperature of above 250 °C for a- period of time 30between 2 minutes and 25 hours. The compensation cations in the material in its uncalcined form, or following thermal treatment, can, if present, be exchanged for other cations such as metallic ions, H+ and H+ precursors such as NH4+. Among the cations 35that can be introduced by ion exchange, those which can 12 play a positive role in the activity of the material as a catalyst are preferred, and more specifically, cations such as H+, cations of rare earths and metals of group VIII, as well as of group IIA, IIIA, IVA, Va, IB, IIB, 5IIIB, IVB, VB, VIIB of the periodic table of elements are preferred. The crystallisation of ITQ-24 can be carried out statically or with stirring, in autoclaves at a temperature between 80 and 200 °C, at a sufficient length lOof time for achieving the crystallisation, for example between 12 hours and 60 days. It must be borne in mind that the components of the synthesis mixture can come from different sources, and depending on them the crystallisation times and 15conditions can vary. With the aim of facilitating the synthesis, crystals of ITQ-24 can be added as seeds to the synthesis mixture, in amounts of up to 15% by weight with respect to the total components constituting the source of the elements X, Y and M. These can be added to 20the synthesis mixture in advance, during the first stage of the process, or during the crystallisation of ITQ-24, in other words, during the second stage of the process. In order to facilitate the synthesis, fluoride ions can also be added, in the form of, for example, ammonium 25fluoride, in F-/SiO2 ratios of less than 0.01. On completion of the crystallisation stage, the crystals of ITQ-24 are separated from the mother liquor and recovered. According to a particular embodiment, the ITQ-24 30material containing Al can also be prepared starting from the form containing boron using well-known post-synthesis methods (Chen et al., Studies in Surface Science and Catalysis (2001), 135, 1710-1717), such as for example the exchange in the aqueous phase of the material with 35boron for a source of aluminium ions among which 13 preference is given to nitrate, chloride or halide in general, sulphate, carbonate, citrate, oxide and hydroxide. Also, the zeolite B-Ti-ITQ-24 can be converted into the Ti-ITQ-24 analogue by means of post-synthesis 5treatments permitting the selective elimination of atoms of B from the zeolite lattice using processs similar to those described previously in the literature (Tatsumi et al., J. , Phys. Chem., B., 105, 2897 (2001) , J. Catal, 202, 245 (2000) and PCT WO2003/074422). 10 A third object of the present invention refers to a method for converting a feed formed from at least one organic compound consisting of placing the feed in contact with a catalytically active quantity of the crystalline material known as ITQ-24. 15 An additional object of the present invention is a method for converting a feed formed from at least one organic compound consisting of placing the feed in contact with a catalytically active quantity of the crystalline material obtained in accordance with the 20process described above. With the aim of preparing catalysts, the crystalline material of the present invention can also be intimately combined with hydrogenating-deoxygenating components such as platinum, palladium, nickel, rhenium, cobalt, 25tungsten, molybdenum, chromium, vanadium, manganese, iron and mixtures thereof. The introduction of these elements can be carried out in the crystallisation stage, by exchange {if appropriate), and/or by impregnation or physical mixing. These elements can be introduced in 30their cationic form and/or starting from salts or other compounds which, by decomposition, generate the metallic compound or oxide in its suitable catalytic form. The zeolite ITQ-24 produced by means of this invention can, when it contains trivalent elements in its 35composition, and once pelletised, be used as a component 14 of catalysts in acid catalytic cracking processes, such as for example processes of catalytic cracking of hydrocarbons, catalytic hydro-cracking of hydrocarbons, reforming of hydrocarbons, alkylation of aromatics with 5olefins and in processes of esterification, acylation, aniline reaction with formaldehyde in its acid form and/or exchanged with suitable cations. Likewise, when it contains tetravalent elements in its composition, such as Ti and/or Sn, zeolite ITQ-24 can lObe used as a heterogeneous catalyst in oxidation processes of olefins with organic or inorganic peroxides in reactions of the Bayer-Villiger type or Meerwein- Pondorf type, among others. 15Brief description of the figures Figure 1 shows the projection of a first system of channels defined by 12-member rings of tetrahedrally coordinated atoms with a channel opening of 7.7 x 5.6 A. Figure 2 shows a second system of sinusoidal channels 20also defined by channel openings formed by 12 tetrahedrally coordinated atoms with a channel opening of 7.2 x 6.2 A. Figure 3 shows a third system of channels with a channel opening of 10 tetrahedrally coordinated atoms with a 25channel opening of 5.75 x 4.8 A. Figure 4 shows the unit cell of ITQ-24. Figure 5 shows the structure of the dication hexamethylene-bis(trimethylammonium). In order to illustrate the nature of the invention 30and the manner of preparing and using it, the following examples are presented: EXAMPLES Example 1.- Preparation of hexamethylene-bis 35(trimethylammonium) bromide 15 37.38 g of 1,6-dibromohexane (purity = 96%) and 82.35 g of trimethylamine solution (31-35% by weight in ethanol) are added to a 500 ml flask, and the necessary ethanol is immediately added for obtaining a suitable 5mixture of the different products that have been added while they are homogenised by magnetic stirring. The resulting mixture is kept at room temperature with constant stirring for 48 hours, and the solid that is formed is recovered by means of filtration and is lOthoroughly washed with ethyl acetate and diethyl ether. The white solid obtained is dried at room temperature for 12 hours. Example 2.- Preparation of hexamethylene-bis 15(trimethylammonium) dihydroxide Hexamethonium dihydroxide is prepared by direct anion exchange, using a resin, Amberlite IRN-78 (Supelco), as a source of hydroxide anions, having previously washed the resin with distilled water up to pH 20= 7. The process consists of dissolving 9 g of hexamethonium dibromide obtained according to example 1 in 250 g of Milli Q water (Millipore) . The resulting solution is made to pass through an Amberlite IRN-78 washed resin column, with the flow velocity being 25adjusted in order to achieve an exchange level greater than 95%. The resulting solution of hexamethylene-bis (trimethylammonium) dihydroxide is collected in a precipitates jar. This solution is concentrated at 50 °C and vacuum until reaching a concentration of 30hexamethylene-bis(trimethylammonium) dihydroxide of approximately 0.5 mol/kg. Example 3.- Synthesis of the material ITQ-24 with aluminium 35 1.46 g of GeO2 are dissolved in 42.0 g of a solution 16 of hexamethylene-bis(trimethylammonium) dihydroxide with a concentration of 0.4 99 mols/kg. In the solution obtained, 14.54 g of tetraethylorthosilicate and 0.856 g of aluminium triisopropoxide are hydrolysed, and it is 5kept stirring allowing all the ethanol and isopropoxide formed in the hydrolysis to evaporate until the reaction mixture reaches a final composition: 5 SiO2 : 1 GeO2 : 1.50 R(0H)2 : 30 H20 : 0.15 A12O3 10 wherein R{OH2) is of hexamethylene-bis (trimethylammonium) dihydroxide. The gel is heated at 175°C with stirring for 15 days in steel autoclaves with an internal Teflon lining. The 15solid obtained after filtering, washing with distilled water and drying at 100 °C is ITQ-24 and whose list of diffraction peaks is included in table 4. Table 4 20 dA 100 Io/I»ax 7.1000 12.4709 9 7.9400 11.1534 100 10.5950 8.3637 17 11.0150 8.0457 41 16.4350 5.4026 6 19.4800 4.5644 13 19.5700 4.5436 16 20.1450 4.4152 7 20.6050 4.3177 54 21.5450 4.1314 17 22.1750 4.0154 50 22.6550 3.9314 24 22.8650 3.8958 56 22.9550 3.8807 49 17 25.1600 3.5454 6 25.3350 3.5213 10 26.3500 3.3879 6 26.9400 3.3150 22 27.0100 3.3066 19 28.4350 3.1441 7 28.8050 3.1045 7 29.2100 3.0624 22 30.4950 2.9362 8 32.0750 2.7951 8 32.2100 2.7837 6 32.7300 2.7407 6 33.2450 2.6994 8 35.6600 2.5219 6 37.3550 2.4113 11 The material is calcined following the heating ramp described below. The temperature is increased from 25 °C to 300 °C with a speed of 1 °C/min, maintaining the 25temperature for 3 hours, and then finally raising the temperature up to 580 °C at a speed of 1 °C/min, with the temperature being maintained for an additional three hours. ; The calcined sample displays a diffraction diagram 30characteristic of ITQ-24, whose list of peaks is shown in table 5. Table 5 29 d(± 0.5 A) 100 Io/Imax 7.1400 12.4012 15 7.8650 11.2596 100 8.4300 10.5062 6 10.5800 8.3755 3 11.0150 8.0457 24 13.2300 6.7032 2 18 14.2200 6.2387 2 16.4850 5.3863 3 16.8100 5.2829 2 20.2900 4.3840 6 21.4200 4.1552 2 22.0450 4.0388 8 22.7350 3.9178 4 22.9300 3.8849 7 35Example 4. - Synthesis of the material ITQ-24 with aluminium 1.115 g of GeO2 are dissolved in 125 g of a solution of hexamethylene-bis(trimethylammonium) dihydroxide with a concentration of 0.128 mols/kg. In the solution 40obtained, 11.10 g of tetraethylorthosilicate and 0.435 g of aluminium triisopropoxide are hydrolysed, and it is kept stirring allowing all the ethanol and isopropanol formed in the hydrolysis to evaporate until the reaction mixture reaches a final composition: 45 5 SiO2 : 1 GeO2 : 1.50 R(OH)2 : 30 H2O : 0.10 A12O3 wherein R(OH2) is of hexamethylene-bis(trimethylammonium) dihydroxide. 50 The gel is heated at 175°C with stirring for 15 days in steel autoclaves with an internal Teflon lining. The solid obtained after filtering, washing with distilled water and drying at 100°C is ITQ-24. The material is calcined following the heating ramp 55described below. The temperature is increased from 25°C to 300°C with a speed of 1 °C/min, maintaining the temperature for 3 hours, and then finally raising the temperature up to 580°C at a speed of l°C/min, with the temperature being maintained for an additional three 60hours. 19 The calcined sample displays a diffraction diagram characteristic of ITQ-24. Example 5.- Synthesis of the material ITQ-24 with boron 5 1.13 g of GeO2 are dissolved in 42.0 g of a solution of hexamethylene-bis(trimethylammonium) dihydroxide with a concentration of 0.1505 mol/kg. In the solution obtained, 11.28 g of tetraethylorthosilicate and 0.160 g of boric acid are hydrolysed, and it is kept stirring lOallowing all the ethanol formed in the hydrolysis to evaporate until the reaction mixture reaches a final composition: 5 SiO2 : 1 GeO2 : 1.50 R(OH)2 : 30 H2O : 0.12 B2O3 15 where R(OH)2 is of hexamethylene-bis(trimethylammonium) dihydroxide. The gel is heated at 175°C with stirring for 15 days in steel autoclaves with an internal Teflon lining. The 20solid obtained after filtering, washing with distilled water and drying at 100°C is ITQ-24. The material is calcined following the heating ramp described below. The temperature is increased from 25°C to 300°C with a speed of 3°C/min, maintaining the 25temperature for 3 hours, and then finally raising the temperature up to 580°C at a speed of 3°C/min, with the temperature being maintained for an additional three hours. The calcined sample displays a diffraction diagram 30characteristic of ITQ-24. Example 6.- Synthesis of the material ITQ-24 containing titanium 1.177g of GeO2 are dissolved in 56.0 g of a solution 35of hexamethylene-bis(trimethylammonium) dihydroxide with 20 a concentration of 0.301 mol/kg. In the solution obtained, 11.72 g of tetraethylorthosilicate, 0.154 g of titanium tetraoxide and 0.167 g of boric acid are hydrolysed, and it is kept stirring allowing all the 5ethanol formed in the hydrolysis to evaporate until the reaction mixture reaches a final composition: 5 SiO2 : 1 GeO2 : 1.50 R{OH)2 : 30 H2O : 0.12 B2O3 : 0.06 TiO2 10 wherein R(OH)2 is hexamethylene-bis(trimethylammonium) dihydroxide. The gel is heated at 175°C with stirring for 30 days in steel autoclaves with an internal Teflon lining. The 15solid obtained after filtering, washing with distilled water and drying at 100°C is ITQ-24. The material is calcined following the heating ramp described below. The temperature is increased from 25°C to 300°C with a speed of l°C/min, maintaining the 20temperature for 3 hours, and then finally raising the temperature up to 580°C at a speed of l°C/min, with the temperature being maintained for additional three hours. The calcined sample displays a diffraction diagram characteristic of ITQ-24. 25 Example 7.- Post-synthesis treatment of a zeolite ITQ-24 containing Ti in its composition A gram of zeolite prepared as described in example 6 is suspended in 30 ml of a 2 M solution of nitric acid at 3090 °C for 16 hours. The solid is recovered by filtration and washed with distilled water up to neutrality and absence of chloride ions in the wash water, and is dried at 80°C for 12 hours. The resulting solid displays diffraction peaks characteristic of zeolite ITQ-24 and 35the content in B lies below the detection level of the 20 21 usual analysis techniques. Also, this solid presents a band in the ultraviolet-visible spectrum at around 210 run, which is assigned to the presence of Ti incorporated into the zeolite lattice. 5 22 CLAIMS 1. A synthetic porous crystalline material characterised in that it is formed by tetrahedrally coordinated atoms 5which are interconnected by means of oxygens, which presents a unit cell containing 56 tetrahedrally coordinated atoms, known as ITQ-24, whose chemical formula in the calcined anhydrous state is given by nMi/pXO2: Y02 lOwherein: X is at least one trivalent element, Y is at least one tetravalent element, the value of n is between 0 and 0.2 and M is at least one charge compensation cation in oxidation state p. 15 which possesses an X-ray diffractogram in the calcined anhydrous state whose most representative reflections appear at the spacings given in table 1: Table 1 26 d(± 0.5 A) 100 Io/Imax 7.1400 12.4012 w 7.8650 11.2596 vs 11.0150 8.0457 w 20.2900 4.3840 vw 21.4200 4.1552 vw 22.0450 4.0388 vw 22.7350 3.9178 vw 22.9300 3.8849 vw 20 wherein the relative intensity of the lines is calculated as the percentage with respect to the most intense peak, and where (vs) = 80-100 signifies very strong, (s) = 60- 80 strong, (m) = 40-60 medium, (w) - 20-40 weak and (vw) 25= 0-20 very weak. 23 2. A synthetic porous crystalline material according to claim 1, characterised in that, as prepared prior to calcining, it possesses an X-ray diffractogram, whose most representative reflections appear at the spacings 5given in table 2: Table 2 29 d(± 0.5 A) 100 Io/Imax 7.1000 12.4709 vw 7.9400 11.1534 vs 10.5950 8.3637 w 11.0150 8.0457 m 19.4800 4.5644 vw 19.5700 4.5436 vw 20.6050 4.3177 m 21.5450 4.1314 vw 22.1750 4.0154 m 22.6550 3.9314 w 22.8650 3.8958 m 22.9550 3.8807 m 26.9400 3.3150 w 27.0100 3.3066 w 29.2100 3.0624 w lOwherein the relative intensity of the lines is calculated as the percentage with respect to the most intense peak, and where (vs) = 80-100 signifies very strong, (s) = 60- 80 strong, (m) = 40-60 medium, (w) = 20-40 weak and (vw) = 0-20 very weak. 15 3. A synthetic porous crystalline material according to claim 1, characterised in that Y is a tetravalent element selected from among Si, Ge, Ti, Sn; and mixtures thereof. 24 4. A synthetic porous crystalline material according to claim 1, characterised in that X is a trivalent element selected from among Al, B, Fe, In, Ga, Cr and mixtures thereof. 5 5. A synthetic porous crystalline material according to claim 1, characterised in that X is selected from among B, Al and combinations thereof, and Y is selected from among Si, Ti and combinations thereof. 10 6. A synthetic porous crystalline. material according to claim 1, characterised in that it possesses certain atom coordinates shown below 15Table 3 Site Atom coordinates (9) X Y Z Tl 1.61 1.60 4.71 T2 12.24 8.36 4.71 T3 19.65 11.92 4.71 T4 9.02 5.16 4.71 T5 1.61 11.92 7.90 T6 12.24 5.16 7.90 T7 19.65 1.60 7.90 T8 9.02 8.36 7.90 T9 19.65 11.92 7.90 T10 9.02 5.16 7.90 Til 1.61 1.60 7.90 T12 12.24 8.36 7.90 T13 19.65 1.60 4.71 T14 9.02 8.36 4.71 T15 1.61 11.92 4.71 T16 12.24 5.16 4.71 25 T17 3.19 2.61 2.31 T18 13.82 9.37 2.31 T19 18.06 10.91 2.31 T20 7.43 4.15 2.31 T21 3.19 10.91 10.30 T22 13.82 4.15 10.30 T23 18.06 2.61 10.30 T24 7.43 9.37 10.30 T25 18.06 10.91 10.30 T26 7.43 4.15 10.30 T27 3.19 2.61 10.30 T28 13.82 9.37 10.30 T29 18.06 2.61 2.31 T30 7.43 9.37 2.31 T31 3.19 10.91 2.31 T32 13.82 4.15 2.31 T33 16.63 8.26 1.61 T34 6.00 1.50 1.61 T35 4.63 5.27 1.61 T36 15.26 12.03 1.61 T37 16.63 5.27 11.00 T38 6.00 12.03 11.00 T39 4.63 8.26 11.00 T40 15.26 1.50 11.00 T41 4.63 5.27 11.00 T42 15.26 12.03 11.00 T43 16.63 8.26 11.00 T44 6.00 1.50 11.00 T45 4.63 8.26 1.61 T46 15.26 1.50 1.61 T47 16.63 5.27 1.61 T48 6.00 12.03 1.61 T49 1.62 1.54 0.00 T50 12.25 8.30 0.00 T51 19.63 11.98 0.00 26 T52 9.01 5.22 0.00 T53 1.62 11.98 0.00 T54 12.25 5.22 0.00 T55 19.63 1.54 0.00 T56 9.01 8.30 0.00 being able to be modified by ± 0.5 A without any change taking place in the connectivity of the atoms forming the 20structure. 7. A process for synthesising the crystalline material of any of claims 1 to 6, characterised in that it comprises at least: 25 a first stage wherein a synthesis mixture comprising at least the following: - H2O, - a source of at least one tetravalent element, Y, - a structure directing agent (R), and 30 - a source of hydroxide ions M' , is made to react a second stage comprising keeping the synthesis mixture at a temperature of between 80 and 200 °C until crystals of said crystalline material form; and 35 a third stage comprising recovering said crystalline material. 8. A process according to claim 7, characterised in that it comprises at least: 40 a first stage wherein a synthesis mixture consisting of at least the following: - a source of at least one trivalent element X, - H20, - a source of at least one tetravalent element, Y, 45 - a structure directing agent (R), and - a source of hydroxide ions M', 27 is made to react a second stage comprising keeping the synthesis mixture at a temperature of between 80 and 200 °C until crystals of said crystalline material form; and 5 a third stage comprising recovering said crystalline material. 9. A process according to claim 7 or 8, characterised in that it furthermore comprises a fourth stage wherein lOorganic matter occluded in the interior of the crystalline material is eliminated by means of a treatment selected from among extraction treatments, thermal treatments at temperatures above 250°C for a period of time between 2 minutes and 25 hours, and 15combinations thereof. 10. A process according to claim 8, characterised in that the source of the tetravalent element Y is an oxide, the source of the trivalent element X is an oxide, and the 20synthesis mixture has a composition, in terms of molar ratios of oxides, of YO2/X2O3 > 5 H2O/YO2 = between 1 and 50 25 R/YO2 = between 0.05 and 3.0 OH/YO2 = between 0.05 and 6.0 M'2/jO/X2O3 = between 0 and 1.0 wherein j is the oxidation state of the cation M' and can be one or two. 30 11. A* process according to claim 8, characterised in that the source of the tetravalent element Y is an oxide, the source of the trivalent element X is an oxide, and the synthesis mixture has a composition, in terms of molar 35ratios of oxides, of 28 YO2/X2O3 > 7 H2O/YO2 = between 2 and 20 R/YO2 = between 0.05 and 1.0 5 OH/YO2 = between 0.1 and 2.0 M'2/jO/X2O3 = between 0 and 1.0 wherein j is the oxidation state of the cation M' and can be one or two. 1012. A process according to claim 7, characterised in that the structure directing agent is a salt of the (hexamethylene-bis(trimethylammonium) dication. 13.A process according to claim 7, characterised in that 15the structure directing agent is the (hexamethylene-bis (trimethylammonium) dihydroxide. 14. A process according to claim 7, characterised in that the source of the hydroxide M' is selected from between a 20at least one compensation cation M, the organic structure directing cation and a mixture of the two. 15. A process according to claim 7, characterised in that seeds of ITQ-24 are added during the first stage, or 25during the second stage of the process. 16. A process according to one of claims 7 to 15, characterised in that fluoride ions are added to the synthesis mixture in a molar ratio F~/YO2 equal to or 301ess than 0.02. 17. A method for converting a feed formed from at least one organic compound characterised in that it comprises placing the feed in contact with a 35catalytically active quantity of a crystalline material 29 known as ITQ-24 defined in any of claims 1 to 6, for the conversion of said organic compound. 18. A method for converting a feed formed from at least 5one organic compound characterised in that it comprises placing the feed in contact with a catalytically active quantity of a crystalline material obtained according to the method claimed in any of claims 7 to 16. 1019. A method according to claim 17 or 18, characterised in that the crystalline material is used combined with hydrogenating-deoxygenating components. 20. A method according to claim 17 or 18, characterised 15in that the crystalline material is used combined with hydrogenating-deoxygenating components selected from among platinum, palladium, nickel, rhenium, cobalt, tungsten, molybdenum, chromium, vanadium, manganese, iron. 20 21. A method according to claim 17 or 18, characterised in that the crystalline material contains trivalent elements in its composition and is used as a pelletised component of catalysts in a conversion selected from 25among a process of catalytic cracking of hydrocarbons, catalytic hydro-cracking of hydrocarbons, reforming of hydrocarbons, alkylation of aromatics with olefins, esterification, acylation and aniline reaction with formaldehyde. 30 22. A method according to claim 16 or 17, characterised in that the crystalline material contains tetravalent elements in its composition, selected from among Ti, Sn and a mixture of both, and is used as a heterogeneous 35catalyst in a conversion selected from among an oxidation 30 process of olefins with organic or inorganic peroxides, a Bayer-Villiger type process, and a Meerwein-Pondorf reaction. 523. A method according to claim 21, characterised in that the crystalline material is used in a form selected from among an acid form, exchanged with cations, and in acid form and exchanged with cations. The invention relates to a porous crystalline material (zeolite ITQ-24), the preparation method thereof and the use of same in the catalytic conversion of organic compounds. More specifically, the invention relates to a synthetic porous crystalline material which is characterised in that it is formed by tetrahedrally-coordinated atoms which are interconnected by means of oxygens. Said material, which comprises a unit cell containing 56 tetrahedrally-coordinated atoms, is known as ITQ-24. Moreover, in the calcined anhydrous state, the material has chemical formula nM1/pXO2: YO2, wherein: X is at least one trivalent element, Y is at least one tetravalent element, n is between 0 and 0.2 and M is at least one charge compensation cation in oxidation state p.

Full Text

2
Title
Porous crystalline material (zeolite ITQ-24), preparation
method thereof and use of same in the catalytic
conversion of organic compounds
5
Field of the art
The invention comes within crystalline zeolitic
materials and their use in the catalytic conversion of
organic compounds.
10
Prior art
Zeolites are porous crystalline materials which have
found important applications as catalysts, adsorbents and
ion exchangers. Many of these zeolitic materials have
15well-defined structures which form channels and cavities
in their interior, of uniform size and shape that permit
the adsorption of certain molecules, whereas they prevent
other molecules of a size too large for diffusing through
the pores, from passing into the interior of the crystal.
20This characteristic confers molecular sieve properties on
these materials. These molecular sieves can include Si
and other elements of groups IIIA and IVA of the periodic
table in their lattice, and/or transition metals such as
Ti, V, etc., all of them tetrahedrally coordinated, the
25tetrahedrons being bound by their vertices via oxygens
forming a three-dimensional lattice. In the case of
containing elements corresponding to IIIA group
tetrahedrally coordinated in lattice positions, the
negative charge that is generated is compensated by the
30presence of cations, such as alkalis or alkaline earths
for example, which are sited in the channels and/or
cavities of these materials. One type of cation can be
totally or partially exchanged for another type of cation
by means of ion exchange techniques, thereby being able
35to vary the properties of a given silicate by selecting

3
the desired cations. In the event of these cations being
protons, the resulting materials have a high degree of
acidity which confers interesting catalytic properties on
them.
5 The use of organic catalysts as structure directing
agents has so far been a highly effective method for
obtaining novel zeolitic structures. It has recently been
proven that the incorporation of heteroatoms other than
silicon . can play an important role as structure
lOdirectors, since they promote the formation of certain
secondary construction subunits. So, for example, the
incorporation of Ge promotes the formation four-member
double rings in the final zeolites, while the
incorporation of Be or Zn promotes the appearance of
15three-member rings in the final materials.
As a consequence of the work done in the field of
zeolite synthesis, more than 140 zeolitic structures have
so far been described wherein the shape, size and
connectivity of their channels and/or cavities vary,
20conferring on them different adsorption/diffusion
properties, and therefore displaying different catalytic
properties. It is thus evident that obtaining novel
zeolites is an important field of development, since the
possibility of having a high number of zeolites means
25that a selection can be made of the structure best suited
to the processes sought to be catalysed.
Description of the Invention
The present invention relates to a synthetic porous
30crystalline material characterised in that it is formed
by tetrahedrally coordinated atoms bound together by
means of oxygens, which comprises a unit cell containing
56 tetrahedrally coordinated atoms, known as ITQ-24,
whose chemical formula in the calcined anhydrous state is
35given by

4
M1/PXO2: Y02
wherein:
5X is at least one trivalent element,
Y is at least one tetravalent element,
the value of n is between 0 and 0.2 and M is at least one
charge compensation cation in oxidation state p.
which possesses an X-ray .diffractogram in the
10calcined anhydrous state whose most representative
reflections appear at the spacings given in table 1:
Table 1
29 d(± 0.5 A) 100 Io/Inax
7.1400 12.4012 W
7.8650 11.2596 vs
11.0150 8.0457 w
20.2900 4.3840 vw
21.4200 4.1552 vw
22.0450 4.0388 vw
22.7350 3.9178 vw
22.9300 3.8849 vw
15wherein the interplanar spacings, d, were calculated in
Angstroms and the relative intensity of the lines is
calculated as the percentage with respect to the most
intense peak, and are regarded as very strong (vs) = 80-
100, strong (s) = 60-80, medium (m) = 40-60, weak (w) =
2020-40 and very weak (vw) = 0-20.
Examples of trivalent elements in the formula given
above for ITQ-24 are Al, B, Fe, In, Ga, Cr and mixtures
thereof.
Examples of tetravalent elements in the formula given
25above for ITQ-24 are Si, Ti, Sn; Ge and mixtures thereof.
Examples of compensation cations in the formula

5
given above for ITQ-24 are a proton, H+ precursors such
as NH4+ for example, metallic ions such as alkaline or
alkaline earth metals, rare earth cations, and metals of
group VIII, and also of group IIA, IIIA, IVA, Va, IB,
5IIB, IIIB, IVB, VB, VIIB of the periodic table of
elements, or mixtures thereof.
From the given values, it can be deduced that the
crystalline material ITQ-24 can be synthesised in the
absence of added trivalent elements and/or compensation
locations.
In a preferred embodiment of ITQ-24, X is selected
from among B, Al and combinations thereof, and Y is Si,
Ge, Ti and combinations thereof.
The synthetic porous crystalline material, ITQ-24,
15as prepared prior to calcining, possesses an X-ray
diffractogram, whose most representative reflections
appear at the spacings given in table 2:
Table 2

29 d(± 0.5 A) 100 Io/Imax
7.1000 12.4709 vw
7.9400 11.1534 vs
10.5950 8.3637 w
11.0150 8.0457 m
19.4800 4.5644 vw
19.5700 4.5436 vw
20.6050 4.3177 m
21.5450 4.1314 vw
22.1750 4.0154 m
22.6550 3.9314 w
22.8650 3.8958 m
22.9550 3.8807 m
26.9400 3.3150 w
27.0100 3.3066 w

wherein the relative intensity is as defined above.
These diffractograms were obtained with a Philips
X'Pert diffractometer equipped with a graphite
25monochromator and an automatic divergence slit using Kot
radiation from copper. The diffraction data was
registered by means of steps of 29 of 0.01° wherein 9 is
- the Bragg angle and with a count time of 10 seconds per
step.
30 It has to be borne in mind that the diffraction data
for this sample listed as single lines can consist of
overlapping multiples or superpositions of reflections
which, under certain conditions, such as differences in
crystallographic changes, can appear as resolved or
35partially resolved lines. In general, the
crystallographic changes can include small variations in
the parameters of the unit cells and/or changes in the
symmetry of the crystal, without any change talcing place
in the connectivity among the atoms of the structure.
40These modifications, which also include changes in
relative intensities, can also be due to differences in
the type and quantity of compensation cations, lattice
composition and shape thereof, preferred orientation or
the type of thermal and hydrothermal treatment undergone.
45 The porous crystalline material ITQ-24 to which this
invention refers is a single crystalline phase possessing
a three-directional system of channels which intersect
with each other. In particular, zeolite ITQ-24 possesses
a first system of channels defined by 12-member rings of
50tetrahedrally coordinated atoms with a channel opening of
7.7 x 5.6 A, a second system of sinusoidal channels also
defined by channel openings formed by 12 tetrahedrally
coordinated atoms with a channel opening of 7.2 x 6.2 A,
and finally a third system of channels with a channel

7
opening of 10 tetrahedrally coordinated atoms with a
channel opening of 5.75 x 4.8 A. These three systems are
interconnected to each other.
The structure of zeolite ITQ-24 can be defined by
5its unit cell, which is the smallest structural unit
displaying all the symmetry elements of the material.
Table 3 shows the list of positions of all the tetra-
coordinated atoms contained in the unit cell for a
particular embodiment of . ITQ-24. Each tetra-coordinated
lOatom is bonded to its four neighbours via oxygen bridges.
Given that the position of the tetra-cooordinated atoms
can vary slightly depending on the presence of organic
matter or water in its pores, on the chemical composition
of the material or any other modification, each position
15coordinate given in table 3 can be modified by ± 0.5 A
without any change taking place in the connectivity of
the atoms forming the structure of the zeolite ITQ-24.
Table 3

Site Atom coordinates
(9)
X Y Z
Tl 1.61 1.60 4.71
T2 12.24 8.36 4.71
T3 19.65 11.92 4.71
T4 9.02 5.16 4.71
T5 1.61 11.92 7.90
T6 12.24 5.16 7.90
T7 19.65 1.60 7.90
T8 9.02 8.36 7.90
T9 19.65 11.92 7.90
T10 9.02 5.16 7.90
Til 1.61 1.60 7.90
T12 12.24 8.36 7.90

8

T13 19.65 1.60 4.71
T14 9.02 8.36 4.71
T15 1.61 11.92 4.71
T16 12.24 5.16 4.71
T17 3.19 2.61 2.31
T18 13.82 9.37 2.31
T19 18.06 10.91 2.31
T20 7.43 4.15 2.31
T21 3.19 10.91 10.30
T22 13.82 4.15 10.30
T23 18.06 2.61 10.30
T24 7.43 9.37 10.30
T25 18.06 10.91 10.30
T26 7.43 4.15 10.30
T27 3.19 2.61 10.30
T28 13.82 9.37 10.30
T29 18.06 2.61 2.31
T30 7.43 9.37 2.31
T31 3.19 10.91 2,31
T32 13.82 4.15 2.31
T33 16.63 8.26 1.61
T34 6.00 1.50 1.61
T35 4.63 5.27 1.61
T36 15.26 12.03 1.61
T37 16.63 5.27 11.00
T38 6.00 12.03 11.00
T39 4.63 8.26 11.00
T40 15.26 1.50 11.00
T41 4.63 5.27 11.00
T42 15.26 12.03 11.00
T43 16.63 8.26 11.00
T44 6.00 1.50 11.00
T45 4.63 8.26 1.61
T46 15.26 1.50 • 1.61
T47 16.63 5.27 1.61

9

T48 6. 00 12.03 1.61
T49 1. 62 1.54 0.00
T50 12 .25 8.30 0.00
T51 19 .63 11.98 0.00
T52 9. 01 5.22 0.00
T53 1. 62 11.98 0.00
T54 12 .25 5.22 0.00
T55 19 .63 1.54 0.00
T56 9. 01 8.30 0.00
A second object of the present invention is a
process for synthesising a crystalline material ITQ-24,
which comprises at least:
25 a first stage wherein a synthesis mixture comrpising
at least the following:
- H2O,
- a source of at least one tetravalent element, Y,
- a structure directing agent (R), and
30 - a source of hydroxide ions M',
is made to react,
a second stage comprising keeping the synthesis
mixture at a temperature of between 80 and 200°C until
crystals of said crystalline material form; and
35 a third stage comprising recovering said crystalline
material.
In certain cases, the source of hydroxide ions can
be the structure directing agent itself.
The synthesis process can furthermore comprise
40 a fourth stage wherein organic matter occluded in
the interior of the crystalline material is eliminated by
means of a treatment selected from among extraction
treatments, thermal treatments at temperatures above
250°C for a period of time between 2 minutes and 25
45hours, and combinations thereof.
According to a preferred embodiment of the process,

10
the synthesis mixture can furthermore comprise a source
of the trivalent element X.
According to a preferred embodiment of the
5invention, the source of the tetravalent element Y is an
oxide, the source of the trivalent element X is an oxide,
and the synthesis mixture has a composition, in terms of
molar ratios of oxides, of
YO2/X2O3 > 5
10 H2O/YO2 = between 1 and 50
R/YO2 = between 0.05 and 3.0
OH/YO2 = between 0.05 and 6.0
M'2/jO/X203 = between 0 and 1.0
wherein j is the oxidation state of the cation M' and can
15be one or two.
According to a more preferred embodiment of the
invention, the source of the tetravalent element Y is an
oxide, the source of the trivalent element X is an oxide,
20and the synthesis mixture has a composition, in terms of
molar ratios of oxides, of
YO2/X2O3 > 7
H2O/YO2 = between 2 and 20
R/YO2 = between 0.05 and 1.0
25 OH/YO2 = between 0.1 and 2.0
M'2/jO/X2O3 = between 0 and 1.0
wherein j is the oxidation state of the cation M' and can
be one or two.
30 According to the process of the present invention,
the hydroxide source M' can be selected from among a
source of at least a compensation cation M, the anion of
the structure directing agent and a mixture of the two.
A preferred example of structure directing agent is
35a salt of the dication hexamethylene-bis

10 11
(trimethylammonium).
An additional preferred example of structure
directing agent is a salt of the dihydroxide of
hexamethylene-bis(trimethylammonium).
5 A preferred source of the tetravalent element Y is
an oxide.
A preferred source of the trivalent element X is an
oxide.
A preferred source of the compensation cation M is a
lOhydroxide or an oxide.
According to a particular embodiment of the process,
fluoride ions are added to the synthesis mixture in a
molar ratio F~/YO2 equal to or less than 0.02. For
example, in a particular embodiment, ammonium fluoride
15can be added in a molar ratio F-/ SiO2 less than 0.01, in
the case in which Y is Si.
The zeolite ITQ-24 can essentially be prepared as a
pure phase or with very small amounts of impurities which
can even be undetectable by X-ray diffraction.
20 In the synthesis process of ITQ-24, hydroxide ions
can be used as mobilising agents of the trivalent and
tetravalent element oxides, which are introduced in the
synthesis means as the hydroxide of an organic cation,
inorganic cation or mixtures thereof, being able to be
25occluded in the interior of the organic species
structure, which can be eliminated by conventional means.
So, the organic component can be eliminated by, for
example, extraction, or by thermal treatment by heating
to a temperature of above 250 °C for a- period of time
30between 2 minutes and 25 hours.
The compensation cations in the material in its
uncalcined form, or following thermal treatment, can, if
present, be exchanged for other cations such as metallic
ions, H+ and H+ precursors such as NH4+. Among the cations
35that can be introduced by ion exchange, those which can

12
play a positive role in the activity of the material as a
catalyst are preferred, and more specifically, cations
such as H+, cations of rare earths and metals of group
VIII, as well as of group IIA, IIIA, IVA, Va, IB, IIB,
5IIIB, IVB, VB, VIIB of the periodic table of elements are
preferred.
The crystallisation of ITQ-24 can be carried out
statically or with stirring, in autoclaves at a
temperature between 80 and 200 °C, at a sufficient length
lOof time for achieving the crystallisation, for example
between 12 hours and 60 days.
It must be borne in mind that the components of the
synthesis mixture can come from different sources, and
depending on them the crystallisation times and
15conditions can vary. With the aim of facilitating the
synthesis, crystals of ITQ-24 can be added as seeds to
the synthesis mixture, in amounts of up to 15% by weight
with respect to the total components constituting the
source of the elements X, Y and M. These can be added to
20the synthesis mixture in advance, during the first stage
of the process, or during the crystallisation of ITQ-24,
in other words, during the second stage of the process.
In order to facilitate the synthesis, fluoride ions
can also be added, in the form of, for example, ammonium
25fluoride, in F-/SiO2 ratios of less than 0.01.
On completion of the crystallisation stage, the
crystals of ITQ-24 are separated from the mother liquor
and recovered.
According to a particular embodiment, the ITQ-24
30material containing Al can also be prepared starting from
the form containing boron using well-known post-synthesis
methods (Chen et al., Studies in Surface Science and
Catalysis (2001), 135, 1710-1717), such as for example
the exchange in the aqueous phase of the material with
35boron for a source of aluminium ions among which

13
preference is given to nitrate, chloride or halide in
general, sulphate, carbonate, citrate, oxide and
hydroxide. Also, the zeolite B-Ti-ITQ-24 can be converted
into the Ti-ITQ-24 analogue by means of post-synthesis
5treatments permitting the selective elimination of atoms
of B from the zeolite lattice using processs similar to
those described previously in the literature (Tatsumi et
al., J. , Phys. Chem., B., 105, 2897 (2001) , J. Catal,
202, 245 (2000) and PCT WO2003/074422).
10 A third object of the present invention refers to a
method for converting a feed formed from at least one
organic compound consisting of placing the feed in
contact with a catalytically active quantity of the
crystalline material known as ITQ-24.
15 An additional object of the present invention is a
method for converting a feed formed from at least one
organic compound consisting of placing the feed in
contact with a catalytically active quantity of the
crystalline material obtained in accordance with the
20process described above.
With the aim of preparing catalysts, the crystalline
material of the present invention can also be intimately
combined with hydrogenating-deoxygenating components such
as platinum, palladium, nickel, rhenium, cobalt,
25tungsten, molybdenum, chromium, vanadium, manganese, iron
and mixtures thereof. The introduction of these elements
can be carried out in the crystallisation stage, by
exchange {if appropriate), and/or by impregnation or
physical mixing. These elements can be introduced in
30their cationic form and/or starting from salts or other
compounds which, by decomposition, generate the metallic
compound or oxide in its suitable catalytic form.
The zeolite ITQ-24 produced by means of this
invention can, when it contains trivalent elements in its
35composition, and once pelletised, be used as a component

14
of catalysts in acid catalytic cracking processes, such
as for example processes of catalytic cracking of
hydrocarbons, catalytic hydro-cracking of hydrocarbons,
reforming of hydrocarbons, alkylation of aromatics with
5olefins and in processes of esterification, acylation,
aniline reaction with formaldehyde in its acid form
and/or exchanged with suitable cations.
Likewise, when it contains tetravalent elements in
its composition, such as Ti and/or Sn, zeolite ITQ-24 can
lObe used as a heterogeneous catalyst in oxidation
processes of olefins with organic or inorganic peroxides
in reactions of the Bayer-Villiger type or Meerwein-
Pondorf type, among others.
15Brief description of the figures
Figure 1 shows the projection of a first system of
channels defined by 12-member rings of tetrahedrally
coordinated atoms with a channel opening of 7.7 x 5.6 A.
Figure 2 shows a second system of sinusoidal channels
20also defined by channel openings formed by 12
tetrahedrally coordinated atoms with a channel opening of
7.2 x 6.2 A.
Figure 3 shows a third system of channels with a channel
opening of 10 tetrahedrally coordinated atoms with a
25channel opening of 5.75 x 4.8 A.
Figure 4 shows the unit cell of ITQ-24.
Figure 5 shows the structure of the dication
hexamethylene-bis(trimethylammonium).
In order to illustrate the nature of the invention
30and the manner of preparing and using it, the following
examples are presented:
EXAMPLES
Example 1.- Preparation of hexamethylene-bis
35(trimethylammonium) bromide

15
37.38 g of 1,6-dibromohexane (purity = 96%) and
82.35 g of trimethylamine solution (31-35% by weight in
ethanol) are added to a 500 ml flask, and the necessary
ethanol is immediately added for obtaining a suitable
5mixture of the different products that have been added
while they are homogenised by magnetic stirring. The
resulting mixture is kept at room temperature with
constant stirring for 48 hours, and the solid that is
formed is recovered by means of filtration and is
lOthoroughly washed with ethyl acetate and diethyl ether.
The white solid obtained is dried at room temperature for
12 hours.
Example 2.- Preparation of hexamethylene-bis
15(trimethylammonium) dihydroxide
Hexamethonium dihydroxide is prepared by direct
anion exchange, using a resin, Amberlite IRN-78
(Supelco), as a source of hydroxide anions, having
previously washed the resin with distilled water up to pH
20= 7. The process consists of dissolving 9 g of
hexamethonium dibromide obtained according to example 1
in 250 g of Milli Q water (Millipore) . The resulting
solution is made to pass through an Amberlite IRN-78
washed resin column, with the flow velocity being
25adjusted in order to achieve an exchange level greater
than 95%. The resulting solution of hexamethylene-bis
(trimethylammonium) dihydroxide is collected in a
precipitates jar. This solution is concentrated at 50 °C
and vacuum until reaching a concentration of
30hexamethylene-bis(trimethylammonium) dihydroxide of
approximately 0.5 mol/kg.
Example 3.- Synthesis of the material ITQ-24 with
aluminium
35 1.46 g of GeO2 are dissolved in 42.0 g of a solution

16
of hexamethylene-bis(trimethylammonium) dihydroxide with
a concentration of 0.4 99 mols/kg. In the solution
obtained, 14.54 g of tetraethylorthosilicate and 0.856 g
of aluminium triisopropoxide are hydrolysed, and it is
5kept stirring allowing all the ethanol and isopropoxide
formed in the hydrolysis to evaporate until the reaction
mixture reaches a final composition:
5 SiO2 : 1 GeO2 : 1.50 R(0H)2 : 30 H20 : 0.15 A12O3
10
wherein R{OH2) is of hexamethylene-bis (trimethylammonium)
dihydroxide.
The gel is heated at 175°C with stirring for 15 days
in steel autoclaves with an internal Teflon lining. The
15solid obtained after filtering, washing with distilled
water and drying at 100 °C is ITQ-24 and whose list of
diffraction peaks is included in table 4.
Table 4

20 dA 100 Io/I»ax
7.1000 12.4709 9
7.9400 11.1534 100
10.5950 8.3637 17
11.0150 8.0457 41
16.4350 5.4026 6
19.4800 4.5644 13
19.5700 4.5436 16
20.1450 4.4152 7
20.6050 4.3177 54
21.5450 4.1314 17
22.1750 4.0154 50
22.6550 3.9314 24
22.8650 3.8958 56
22.9550 3.8807 49

17

25.1600 3.5454 6
25.3350 3.5213 10
26.3500 3.3879 6
26.9400 3.3150 22
27.0100 3.3066 19
28.4350 3.1441 7
28.8050 3.1045 7
29.2100 3.0624 22
30.4950 2.9362 8
32.0750 2.7951 8
32.2100 2.7837 6
32.7300 2.7407 6
33.2450 2.6994 8
35.6600 2.5219 6
37.3550 2.4113 11
The material is calcined following the heating ramp
described below. The temperature is increased from 25 °C
to 300 °C with a speed of 1 °C/min, maintaining the
25temperature for 3 hours, and then finally raising the
temperature up to 580 °C at a speed of 1 °C/min, with the
temperature being maintained for an additional three
hours. ;
The calcined sample displays a diffraction diagram
30characteristic of ITQ-24, whose list of peaks is shown in
table 5.
Table 5
29 d(± 0.5 A) 100 Io/Imax
7.1400 12.4012 15
7.8650 11.2596 100
8.4300 10.5062 6
10.5800 8.3755 3
11.0150 8.0457 24
13.2300 6.7032 2

18

14.2200 6.2387 2
16.4850 5.3863 3
16.8100 5.2829 2
20.2900 4.3840 6
21.4200 4.1552 2
22.0450 4.0388 8
22.7350 3.9178 4
22.9300 3.8849 7
35Example 4. - Synthesis of the material ITQ-24 with
aluminium
1.115 g of GeO2 are dissolved in 125 g of a solution
of hexamethylene-bis(trimethylammonium) dihydroxide with
a concentration of 0.128 mols/kg. In the solution
40obtained, 11.10 g of tetraethylorthosilicate and 0.435 g
of aluminium triisopropoxide are hydrolysed, and it is
kept stirring allowing all the ethanol and isopropanol
formed in the hydrolysis to evaporate until the reaction
mixture reaches a final composition:
45
5 SiO2 : 1 GeO2 : 1.50 R(OH)2 : 30 H2O : 0.10 A12O3
wherein R(OH2) is of hexamethylene-bis(trimethylammonium)
dihydroxide.
50 The gel is heated at 175°C with stirring for 15 days
in steel autoclaves with an internal Teflon lining. The
solid obtained after filtering, washing with distilled
water and drying at 100°C is ITQ-24.
The material is calcined following the heating ramp
55described below. The temperature is increased from 25°C
to 300°C with a speed of 1 °C/min, maintaining the
temperature for 3 hours, and then finally raising the
temperature up to 580°C at a speed of l°C/min, with the
temperature being maintained for an additional three
60hours.

19
The calcined sample displays a diffraction diagram
characteristic of ITQ-24.
Example 5.- Synthesis of the material ITQ-24 with boron
5 1.13 g of GeO2 are dissolved in 42.0 g of a solution
of hexamethylene-bis(trimethylammonium) dihydroxide with
a concentration of 0.1505 mol/kg. In the solution
obtained, 11.28 g of tetraethylorthosilicate and 0.160 g
of boric acid are hydrolysed, and it is kept stirring
lOallowing all the ethanol formed in the hydrolysis to
evaporate until the reaction mixture reaches a final
composition:
5 SiO2 : 1 GeO2 : 1.50 R(OH)2 : 30 H2O : 0.12 B2O3
15
where R(OH)2 is of hexamethylene-bis(trimethylammonium)
dihydroxide.
The gel is heated at 175°C with stirring for 15 days
in steel autoclaves with an internal Teflon lining. The
20solid obtained after filtering, washing with distilled
water and drying at 100°C is ITQ-24.
The material is calcined following the heating ramp
described below. The temperature is increased from 25°C
to 300°C with a speed of 3°C/min, maintaining the
25temperature for 3 hours, and then finally raising the
temperature up to 580°C at a speed of 3°C/min, with the
temperature being maintained for an additional three
hours.
The calcined sample displays a diffraction diagram
30characteristic of ITQ-24.
Example 6.- Synthesis of the material ITQ-24 containing
titanium
1.177g of GeO2 are dissolved in 56.0 g of a solution
35of hexamethylene-bis(trimethylammonium) dihydroxide with

20
a concentration of 0.301 mol/kg. In the solution
obtained, 11.72 g of tetraethylorthosilicate, 0.154 g of
titanium tetraoxide and 0.167 g of boric acid are
hydrolysed, and it is kept stirring allowing all the
5ethanol formed in the hydrolysis to evaporate until the
reaction mixture reaches a final composition:
5 SiO2 : 1 GeO2 : 1.50 R{OH)2 : 30 H2O : 0.12 B2O3 : 0.06
TiO2
10
wherein R(OH)2 is hexamethylene-bis(trimethylammonium)
dihydroxide.
The gel is heated at 175°C with stirring for 30 days
in steel autoclaves with an internal Teflon lining. The
15solid obtained after filtering, washing with distilled
water and drying at 100°C is ITQ-24.
The material is calcined following the heating ramp
described below. The temperature is increased from 25°C
to 300°C with a speed of l°C/min, maintaining the
20temperature for 3 hours, and then finally raising the
temperature up to 580°C at a speed of l°C/min, with the
temperature being maintained for additional three hours.
The calcined sample displays a diffraction diagram
characteristic of ITQ-24.
25
Example 7.- Post-synthesis treatment of a zeolite ITQ-24
containing Ti in its composition
A gram of zeolite prepared as described in example 6
is suspended in 30 ml of a 2 M solution of nitric acid at
3090 °C for 16 hours. The solid is recovered by filtration
and washed with distilled water up to neutrality and
absence of chloride ions in the wash water, and is dried
at 80°C for 12 hours. The resulting solid displays
diffraction peaks characteristic of zeolite ITQ-24 and
35the content in B lies below the detection level of the

20 21
usual analysis techniques. Also, this solid presents a
band in the ultraviolet-visible spectrum at around 210
run, which is assigned to the presence of Ti incorporated
into the zeolite lattice.
5

22
CLAIMS
1. A synthetic porous crystalline material characterised
in that it is formed by tetrahedrally coordinated atoms
5which are interconnected by means of oxygens, which
presents a unit cell containing 56 tetrahedrally
coordinated atoms, known as ITQ-24, whose chemical
formula in the calcined anhydrous state is given by
nMi/pXO2: Y02
lOwherein:
X is at least one trivalent element,
Y is at least one tetravalent element,
the value of n is between 0 and 0.2 and M is at least one
charge compensation cation in oxidation state p.
15 which possesses an X-ray diffractogram in the
calcined anhydrous state whose most representative
reflections appear at the spacings given in table 1:
Table 1
26 d(± 0.5 A) 100 Io/Imax
7.1400 12.4012 w
7.8650 11.2596 vs
11.0150 8.0457 w
20.2900 4.3840 vw
21.4200 4.1552 vw
22.0450 4.0388 vw
22.7350 3.9178 vw
22.9300 3.8849 vw
20
wherein the relative intensity of the lines is calculated
as the percentage with respect to the most intense peak,
and where (vs) = 80-100 signifies very strong, (s) = 60-
80 strong, (m) = 40-60 medium, (w) - 20-40 weak and (vw)
25= 0-20 very weak.

23
2. A synthetic porous crystalline material according to
claim 1, characterised in that, as prepared prior to
calcining, it possesses an X-ray diffractogram, whose
most representative reflections appear at the spacings
5given in table 2:
Table 2

29 d(± 0.5 A) 100 Io/Imax
7.1000 12.4709 vw
7.9400 11.1534 vs
10.5950 8.3637 w
11.0150 8.0457 m
19.4800 4.5644 vw
19.5700 4.5436 vw
20.6050 4.3177 m
21.5450 4.1314 vw
22.1750 4.0154 m
22.6550 3.9314 w
22.8650 3.8958 m
22.9550 3.8807 m
26.9400 3.3150 w
27.0100 3.3066 w
29.2100 3.0624 w
lOwherein the relative intensity of the lines is calculated
as the percentage with respect to the most intense peak,
and where (vs) = 80-100 signifies very strong, (s) = 60-
80 strong, (m) = 40-60 medium, (w) = 20-40 weak and (vw)
= 0-20 very weak.
15
3. A synthetic porous crystalline material according to
claim 1, characterised in that Y is a tetravalent element
selected from among Si, Ge, Ti, Sn; and mixtures thereof.

24
4. A synthetic porous crystalline material according to
claim 1, characterised in that X is a trivalent element
selected from among Al, B, Fe, In, Ga, Cr and mixtures
thereof.
5
5. A synthetic porous crystalline material according to
claim 1, characterised in that X is selected from among
B, Al and combinations thereof, and Y is selected from
among Si, Ti and combinations thereof.
10
6. A synthetic porous crystalline. material according to
claim 1, characterised in that it possesses certain atom
coordinates shown below
15Table 3

Site Atom coordinates
(9)
X Y Z
Tl 1.61 1.60 4.71
T2 12.24 8.36 4.71
T3 19.65 11.92 4.71
T4 9.02 5.16 4.71
T5 1.61 11.92 7.90
T6 12.24 5.16 7.90
T7 19.65 1.60 7.90
T8 9.02 8.36 7.90
T9 19.65 11.92 7.90
T10 9.02 5.16 7.90
Til 1.61 1.60 7.90
T12 12.24 8.36 7.90
T13 19.65 1.60 4.71
T14 9.02 8.36 4.71
T15 1.61 11.92 4.71
T16 12.24 5.16 4.71

25

T17 3.19 2.61 2.31
T18 13.82 9.37 2.31
T19 18.06 10.91 2.31
T20 7.43 4.15 2.31
T21 3.19 10.91 10.30
T22 13.82 4.15 10.30
T23 18.06 2.61 10.30
T24 7.43 9.37 10.30
T25 18.06 10.91 10.30
T26 7.43 4.15 10.30
T27 3.19 2.61 10.30
T28 13.82 9.37 10.30
T29 18.06 2.61 2.31
T30 7.43 9.37 2.31
T31 3.19 10.91 2.31
T32 13.82 4.15 2.31
T33 16.63 8.26 1.61
T34 6.00 1.50 1.61
T35 4.63 5.27 1.61
T36 15.26 12.03 1.61
T37 16.63 5.27 11.00
T38 6.00 12.03 11.00
T39 4.63 8.26 11.00
T40 15.26 1.50 11.00
T41 4.63 5.27 11.00
T42 15.26 12.03 11.00
T43 16.63 8.26 11.00
T44 6.00 1.50 11.00
T45 4.63 8.26 1.61
T46 15.26 1.50 1.61
T47 16.63 5.27 1.61
T48 6.00 12.03 1.61
T49 1.62 1.54 0.00
T50 12.25 8.30 0.00
T51 19.63 11.98 0.00

26

T52 9.01 5.22 0.00
T53 1.62 11.98 0.00
T54 12.25 5.22 0.00
T55 19.63 1.54 0.00
T56 9.01 8.30 0.00
being able to be modified by ± 0.5 A without any change
taking place in the connectivity of the atoms forming the
20structure.
7. A process for synthesising the crystalline material of
any of claims 1 to 6, characterised in that it comprises
at least:
25 a first stage wherein a synthesis mixture comprising
at least the following:
- H2O,
- a source of at least one tetravalent element, Y,
- a structure directing agent (R), and
30 - a source of hydroxide ions M' ,
is made to react
a second stage comprising keeping the synthesis
mixture at a temperature of between 80 and 200 °C until
crystals of said crystalline material form; and
35 a third stage comprising recovering said crystalline
material.
8. A process according to claim 7, characterised in that
it comprises at least:
40 a first stage wherein a synthesis mixture consisting
of at least the following:
- a source of at least one trivalent element X,
- H20,
- a source of at least one tetravalent element, Y,
45 - a structure directing agent (R), and
- a source of hydroxide ions M',

27
is made to react
a second stage comprising keeping the synthesis
mixture at a temperature of between 80 and 200 °C until
crystals of said crystalline material form; and
5 a third stage comprising recovering said crystalline
material.
9. A process according to claim 7 or 8, characterised in
that it furthermore comprises a fourth stage wherein
lOorganic matter occluded in the interior of the
crystalline material is eliminated by means of a
treatment selected from among extraction treatments,
thermal treatments at temperatures above 250°C for a
period of time between 2 minutes and 25 hours, and
15combinations thereof.
10. A process according to claim 8, characterised in that
the source of the tetravalent element Y is an oxide, the
source of the trivalent element X is an oxide, and the
20synthesis mixture has a composition, in terms of molar
ratios of oxides, of
YO2/X2O3 > 5
H2O/YO2 = between 1 and 50
25 R/YO2 = between 0.05 and 3.0
OH/YO2 = between 0.05 and 6.0
M'2/jO/X2O3 = between 0 and 1.0
wherein j is the oxidation state of the cation M' and can
be one or two.
30
11. A* process according to claim 8, characterised in that
the source of the tetravalent element Y is an oxide, the
source of the trivalent element X is an oxide, and the
synthesis mixture has a composition, in terms of molar
35ratios of oxides, of

28
YO2/X2O3 > 7
H2O/YO2 = between 2 and 20
R/YO2 = between 0.05 and 1.0
5 OH/YO2 = between 0.1 and 2.0
M'2/jO/X2O3 = between 0 and 1.0
wherein j is the oxidation state of the cation M' and can
be one or two.
1012. A process according to claim 7, characterised in that
the structure directing agent is a salt of the
(hexamethylene-bis(trimethylammonium) dication.
13.A process according to claim 7, characterised in that
15the structure directing agent is the (hexamethylene-bis
(trimethylammonium) dihydroxide.
14. A process according to claim 7, characterised in that
the source of the hydroxide M' is selected from between a
20at least one compensation cation M, the organic structure
directing cation and a mixture of the two.
15. A process according to claim 7, characterised in
that seeds of ITQ-24 are added during the first stage, or
25during the second stage of the process.
16. A process according to one of claims 7 to 15,
characterised in that fluoride ions are added to the
synthesis mixture in a molar ratio F~/YO2 equal to or
301ess than 0.02.
17. A method for converting a feed formed from at
least one organic compound characterised in that it
comprises placing the feed in contact with a
35catalytically active quantity of a crystalline material

29
known as ITQ-24 defined in any of claims 1 to 6, for the
conversion of said organic compound.
18. A method for converting a feed formed from at least
5one organic compound characterised in that it comprises
placing the feed in contact with a catalytically active
quantity of a crystalline material obtained according to
the method claimed in any of claims 7 to 16.
1019. A method according to claim 17 or 18, characterised
in that the crystalline material is used combined with
hydrogenating-deoxygenating components.
20. A method according to claim 17 or 18, characterised
15in that the crystalline material is used combined with
hydrogenating-deoxygenating components selected from
among platinum, palladium, nickel, rhenium, cobalt,
tungsten, molybdenum, chromium, vanadium, manganese,
iron.
20
21. A method according to claim 17 or 18, characterised
in that the crystalline material contains trivalent
elements in its composition and is used as a pelletised
component of catalysts in a conversion selected from
25among a process of catalytic cracking of hydrocarbons,
catalytic hydro-cracking of hydrocarbons, reforming of
hydrocarbons, alkylation of aromatics with olefins,
esterification, acylation and aniline reaction with
formaldehyde.
30
22. A method according to claim 16 or 17, characterised
in that the crystalline material contains tetravalent
elements in its composition, selected from among Ti, Sn
and a mixture of both, and is used as a heterogeneous
35catalyst in a conversion selected from among an oxidation

30
process of olefins with organic or inorganic peroxides, a
Bayer-Villiger type process, and a Meerwein-Pondorf
reaction.
523. A method according to claim 21, characterised in that
the crystalline material is used in a form selected from
among an acid form, exchanged with cations, and in acid
form and exchanged with cations.

The invention relates to a porous crystalline material (zeolite ITQ-24), the preparation method thereof and the use of same in the catalytic conversion of organic compounds. More specifically, the invention relates to a synthetic porous crystalline material which is characterised in that it is formed by tetrahedrally-coordinated atoms which are interconnected by means of oxygens. Said material, which comprises a unit cell containing 56 tetrahedrally-coordinated atoms, is known as ITQ-24. Moreover, in the calcined anhydrous state, the material has chemical formula nM1/pXO2: YO2, wherein: X is at least one trivalent element, Y is at least one tetravalent element, n is between 0 and 0.2 and M is at least one charge compensation cation in oxidation state p.

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Patent Number

222149

Indian Patent Application Number

01818/KOLNP/2005

PG Journal Number

30/2008

Publication Date

25-Jul-2008

Grant Date

23-Jul-2008

Date of Filing

13-Sep-2005

Name of Patentee

CONSEJO SUPERIOR DE INVESTIGACIONES CIENTIFICAS

Applicant Address

C/SERRANO, 117, 28006 MADRID

Inventors:

#	Inventor's Name	Inventor's Address
1	CORMA CANOS, AVELINO	INSTITUTO DE TECNOLOGIA QUIMICA, CONSEJO SUPERIOR DE INVESTIGACIONES CIENTIFICAS, AVDA, LOS NARANJOS, S/N 46022 VALENCIA
2	CASTANEDA SANCHEZ, RAFAEL	INSTITUTO DE TECNOLOGIA QUIMICA, CONSEJO SUPERIOR DE INVESTIGACIONES CIENTIFICAS, AVDA, LOS NARANJOS, S/N 46022 VALENCIA
3	FORNES SEGUI, VICENTE	INSTITUTO DE TECNOLOGIA QUIMICA, CONSEJO SUPERIOR DE INVESTIGACIONES CIENTIFICAS, AVDA, LOS NARANJOS, S/N 46022 VALENCIA
4	REY GARCIA FERNANDO	INSTITUTO DE TECNOLOGIA QUIMICA, CONSEJO SUPERIOR DE INVESTIGACIONES CIENTIFICAS, AVDA, LOS NARANJOS, S/N 46022 VALENCIA

PCT International Classification Number

C01B 39/48

PCT International Application Number

PCT/ES2004/070006

PCT International Filing date

2004-02-10

PCT Conventions:

#	PCT Application Number	Date of Convention	Priority Country
1	P200300445	2003-02-14	Spain