ZEOLITE ITQ-3

Abstract: The present invention refers to a microporous crystalline material of zeolitic nature named ITQ-3, to the process of preparation thereof and to the use thereof in processes of separation and transformation of organic compounds. In its calcined anhydrous state, the chemical composition of the material corresponds to the empirical formula: wherein x has a value lower than 0.15; it may be equal to zero; and y has a value lower than 0, 1; it may be equal to zero; M is H + or an inorganic cation of charge +n; X is a chemical element with oxidation state (Al, Ge, B, Cr) and Y is a chemical element with oxidation state +4 (Ti, Ge, V), when x=0 and y=0 the material can be described as a new polymorphous of silica of microporous nature. The material of this invention is also characterized by its characteristic X-ray diffraction pattern and its microporous properties. The process of preparation is characterized by the use of one or several organic additives in a reaction mixture that is made to crystallize by heating.

Description: TECHNICAL FIELD Microporous crystalline materials BACKGROUND Zeolites are microporous crystalline materials of variable composition characterized by a TO 4 tetrahydra crystalline lattice (wherein T represents atoms in the formal oxidation state of +3 or +4, such as for example Si, Ti, Al, Ge, B, Ga) which all share their vertexes giving rise to a three-dimensional structure containing channels and/or cavities of molecular dimensions. When some of the atoms T have an oxidation state lower than +4, the crystalline lattice formed has negative charges which are compensated by the presence of organic or inorganic cations in the channels or cavities. Organic molecules and H 2 O can also be located in these channels and cavities, so in general, the chemical composition of zeolites can be represented by the following empirical formula: x(M 1/n xO 2 ):yYO 2 :SiO 2 wherein M is one or several organic or inorganic cations with charge +n; X is one or several trivalent elements; Y is one or several tetravalent elements, generally Si; and R is one or several organic substances. Although the nature of M, X, Y and R and the values of x, y, z and w can, in general, be varied by means of post-synthesis treatments, the chemical composition of a zeolite (just as it is synthesized or after calcination thereof) has a range characteristic of each zeolite and its preparation method. On the other hand, a zeolite is also characterized by its crystalline structure, which defines a system of channels and cavities and gives rise to a specific X-ray diffraction pattern. In this way, zeolites are differentiated from each other by their range of chemical composition plus their X-ray diffraction pattern. Both characteristics (crystalline structure and chemical composition) also determine the physicochemical properties of each zeolite and the applicability thereof in different industrial processes. DESCRIPTION OF THE INVENTION The present invention refers to a microporous crystalline material of zeolitic nature named ITQ-3, to its method of obtainment and to its applications. The material is characterized by its chemical composition and its X-ray diffraction pattern. In its anhydrous and calcined form, the chemical composition of ITQ-3 may be represented by the empirical formula: X(M 1/n XO 2 ):yYO 2 :SiO 2 wherein x has a value lower than 0.15; it may be equal to zero; and y has a value lower than 0,1; it may be equal to zero; M is H + or an inorganic cation of charge +n; X is a chemical element with oxidation state +3 (Al, Ge, B, Cr). and Y is a chemical element with oxidation state +4 (Ti, Ge, V), when x=0 and y=0 the material can be described as a new polymorphous of silica of microporous nature. In the preferred embodiment of the present invention, ITQ-3 has the composition, in a calcined and anhydrous state x(HXO 2 ):SiO 2 wherein X is a trivalent element and x has a value lower than 0.1 and may be equal to zero, in which case the material may be described by means of the formula SiO 2 . However, it is possible, in terms of the synthesis method and the calcination or subsequent treatments, the existence of defects in the crystalline lattice, manifested by the presence of Si-OH groups (silanols). These defects have not been included in the above empirical formulae. In a preferred embodiment of the present invention, ITQ-3 has a very low concentration of this type of defect (silanol concentration lower than 15% with respect to the total Si atoms, preferably lower than 6%, measured by nuclear magnetic resonance spectroscopy of 29 Si in spinning angle). The X-ray diffraction pattern of ITQ-3 just as synthesized as obtained by the powder method using a variable divergence slit and the Cu Kα radiation, is characterized by the following values of 2  angles and relative intensities (I/I 0 ) : 2(°) I/I o (%) 8.54 100 9.28 85 10.07 15 11.04 5 12.41 5 13.60 7 14.17 3 15.70 14 17.02 11 17.58 15 18.10 85 18.84 20 19.29 30 19.56 30 20.20 65 20.35 70 20.94 25 22.08 5 22.25 5 22.93 5 23.21 5 23.73 60 23.90 20 24.07 35 24.11 25 24.47 25 25.04 90 25.49 45 26.12 10 26.63 8 27.14 10 27.83 10 28.23 10 28.85 10 29.08 10 30.33 20 31.53 25 32.43 15 32.84 20 34.37 5 The positions and relative intensities of the peaks depend to a certain degree on the chemical composition of the material (the pattern represented in Table I refers to the material whose lattice is exclusively comprised of silicon oxide, SiO 2 and synthesized using a quaternary ammonium cation as a structure-directing agent). The relative intensities may also be affected by phenomena of preferred orientation of the crystals, produced during preparation of the sample, while the precision in the interplanar spacing measurement depends on the quality of alignment of the goniometer. Moreover, calcination can yield significant changes in the X-ray diffraction pattern, due to the removal of organic compounds retained during synthesis in the zeolite pores, so that Table II represents the X-ray diffraction pattern of ITQ-3 of calcined ITQ-3 of composition SiO 2 is represented: 2 I/I o (%) 8.66 100 9.10 82 10.14 32 11.08 4 12.51 6 15.87 4 16.93 6 17.26 5 17.81 7 18.27 46 18.81 9 19.51 17 20.10 21 20.38 11 20.74 10 22.17 9 22.26 8 23.90 9 24.04 12 24.17 15 24.27 11 24.42 10 24.84 10 25.12 40 25.52 7 25.62 7 27.23 8 27.53 5 27.91 4 28.12 4 28.27 5 28.48 4 28.67 6 30.54 10 30.83 6 31.13 7 31.79 13 32.48 6 32.84 4 33.06 8 33.46 3 33.48 3 34.15 4 34.26 4 34.64 3 34.77 3 The present invention also reters to the method or preparation of ITQ-3. This comprises thermal treatment at temperatures between 80 and 200ºC, preferably between 130 and 180ºC, of a reaction mixture that contains a source of SiO 2 (such as, for example, tetraethylorthosilicate, colloidal silica, amorphous silica), an organic cation in hydroxide form, preferably N,N-dimethyl-6-azonium-1,3,3-trimethylbicyclo(3.2.1)octane (I) hydroxide, hydrofluoric acid and water. Alternatively, it is possible to use the organic cation as a salt (for example, a halide, preferably chloride) and to substitute hydrofluoric acid by a fluoride salt, preferably NH 4 F. The reaction mixture is characterized by its relatively low pH<12, preferably <11, and which may also be neutral or slightly acidic. Optionally, it is possible to add a source of another tetravalent element Y and/or trivalent element X, preferably Ti or Al. The addition of this element may be done before heating the reaction mixture or in an intermediate time during said heating. Occasionally, it may be convenient to add also in a certain time during the preparation of ITQ-3 crystals (up to 15% by weight with respect to the total inorganic oxides, preferably up to 10% by weight) as cryst6allizer promoters (seeding). The composition of the reaction mixture in oxide form responds to the general formula rR 2 O:aHF:xHXO 2 :yYO 2 :SiO 2 :wH 2 O wherein X is one or several trivalent elements, preferably Al; Y is one or several tetravalent elements; R is an organic cation, preferably N,N-dimethyl-6-azonium-1,3,-trimethyl-6-bicyclo(3.2.1) octane, and the values of r,a,x,y and w are in the ranges r =0.05-1.0, preferably 0.1-0-75 a = 0-1.5, preferably 0.1-1.5 x = 0-0.15 y = 0-0.1 w = 3-100, preferably 5-50, more preferably 7-50 The thermal treatment of the reaction mixture may be done in static or with stirring of the mixture. Once the crystallization is finished the solid product is separated and dried. Subsequent calcination at temperatures between 400 and 650ºC, preferably between 450 and 600º C, produces the decomposition of the organic residue occluded in the zeolite and renders the free zeolitic channels. This method of synthesis of ITQ-3 zeolite has the peculiarity that it does not require introduction of alkali cations in the reaction medium. As a consequence the organic cation R is the only cation that balances the lattice charges when the zeolite contains a trivalent element in its crystalline lattice. Therefore, simple calcination to decompose the organic cation leaves the zeolite in acid form, without the need to resort to cation exchange processes. Besides, the absence of alkali cations in the reaction mixture allows synthesis of the material containing elements such as Ti(IV), which would not be possible to introduce in the lattice in the presence of these cations (see, for example, M.A. Camblor, A. Corma, J. Pérez-Pariente, Zeolites, vol. 13, 82-87, 1993). Thus, once calcined the material has the general formula x(HXO 2 ):yYO 2 :SiO 2 wherein x is lower than 0.15, and may be equal to 0; y is lower than 0.1, and may also be zero; X is a chemical element with oxidation state of +3 and Y is a chemical element with an oxidation state of +4. The crystalline material of the present invention may be used in several applications, such as, for example, in processes for the separation of linear and branched paraffin compounds. Hence, a mixture of isobutane and n-butane or isopentane and n-pentane may be enriched in the more branched isomer by selective adsorption of the linear paraffin by the microporous material of the present invention. Said material is particularly suitable for use in this type of process due to its high adsorption capacity (micropore volume determined by adsorption of N 2 = 0.23 cm 3 /g) and its small pore size (maximum opening ≤ 5.5Å, determined by adsorption of Ar, using the Horvath-Kawazoe formalism). Likewise and preferably using the pure silica polymorph, it is possible to separate by selective adsorption the n-olefins of mixtures containing normal and isoolefins, enriching the final stream in isoolefins. In general, this material would allow the separation of organic compounds, which may or may not contain heteroatoms, with sizes smaller than 5-5.5 Å present in mixtures also containing organic compounds of larger sizes. Due to the hydrophobic characteristics of the silica polymorph, ITQ-3 would permit selective adsorption of organic compounds with kinetic diameter smaller than 5-5.5 Å present in polar media, such as, for example, in aqueous media. From the view point of its use as a catalyst, this material, when prepared in the acid form and which may or may not contain supported transition metals such as Pt, Pd or Ni, allows the selective cracking and hydrocracking of linear alkanes with respect to the branched ones or to larger hydrocarbons, thus being adequate as a catalyst or catalytic cracking aditive and as a catalyst in the "selectoforming" type process that involves hydrocracking of the stream coming from the reformed unit for the purpose of removing n-paraffins. Likewise, ITQ-3 gives good results as an alkane and alkene catalyst for the purpose of producing high yields of ethylene, propylene and butene, thus being suitable as a catalyst for production processes of short olefins by catalytic steam cracking. Moreover, its possibilities of selectively cracking linear paraffins makes it a good catalyst for dewaxing processes. Finally, this material is a good catalyst in processes of transformation of methanol into olefins. EXAMPLES Example 1: This example illustrates the preparation of N,N-dimethyl-6-azonium-1,3,3-trimethylbicyclo(3.2.1) octane hydroxide. 38.32 of 1,3,3-trimethyl-6-azabicyclo (3.2.1) octane (Aldrich), 220 g of CHCl 3 (SDS synthesis grade) and 82.50g of potassium carbonate sesquihydrate (99%, Aldrich) are introduced in a 500ml flask. To this mixture 31 ml of CH 3 I (99% Aldrich) are added dropwise and under stirring in an ice bath. After seven days of stirring at room temperature the mixture is filtered and the liquid is evaporated in a rotovap. After washing the obtained solid with ethyl acetate and drying it, 71.37 g of a solid is obtained, whose nuclear magnetic resonance spectrum in CDCl 3 indicates that it is a nucleophilic substitution product, namely, the iodide of the organic cation corresponding to the dimethylation of the amine. Chemical analysis of the product 45.5% C, 4.42% N, 7.54% H, Theoretical: 46.51% C, 4.53% N, 7.82% H) confirms this result. The hydroxide form of the structure-directing agent is obtained by anion exchange using Dowex 1 (Sigma) resin, previously washed with distilled water until pH = 7. To a solution of 9.27g of the former product in 194.02 g of water, 221.73 g of resin were added and left under stirring for about 12 hours. After filtering the resin, the solution was titrated with HCl (aq) using phenolphthalein as indicator, and finding an efficiency of 96.62% in the exchange. This solution could be concentrated in the rotovap for use in the synthesis of ITQ-3, and its final concentration is obtained by means of further titration. Example 2: This example illustrates the preparation of pure silica ITQ-3, using N,N-dimethyl-5-azonium-1,3,3-trimethylbicyclo(3.2.1) octane hydroxide as the organic structure-directing agent. 12.08 g of tetraethylorthosilicate (TEOS) were added to 23.02 g. Of a solution containing 1.26 moles of N,N-dimethyl-6-azonium-1,3,3-trimethylbicyclo(3.2.1)octane hydroxide per 1000 g, obtained in the way described in Example 1, and the mixture was stirred, allowing evaporation of the ethanol produced in the hydrolysis of TEOS, along with some water. After 6 hours of stirring (weight loss: 18.99 g) 0.57 g of water and 1.21 g. Of HF (aq) (48% Aldrich) were added. The paste obtained is introduced in a polytetrafluoroethylene lined autoclave and kept at 150º C under rotation (60 rpm) for 19 days. Then, the autoclave was cooled down, the contents were filtered and the solid washed with water and dried at 100ºC. Its X-ray diffraction pattern is shown in Table 1. After calcination at 580ºC the white solid obtained has the diffractogram of Table 2. Chemical analysis by atomic absorption spectroscopy of the calcined material reveals that, within the detection limits of the technique and the experimental error, the obtained product is silica (SiO 2 ). 29 Si MAS NMR spectroscopy measurements indicate that the calcined material contains a very low proportion of connectivity defects, as inferred from the ratio of SiOH to total Si (calculated as the quotient between the area of the peak centered at 101ppm and the total area of all of the peaks). N 2 adsorption measures indicate a surface area of 455 m 2 /g (B.E.T. method) and a micropore volume of 0.23 cc/g. The solid state 13 NMR spectrum of the material just as it was made clearly shows the presence of the organic cation occluded in the inorganic crystalline lattice, as well as the elemental analysis which gives molar ratios that are practically those of the organic cation (C/N=11.8, H/N=23.4). Examples 3-6 These examples illustrate the preparation of pure silica of Al-containing ITQ-3, whether in the presence or absence of seeds. The same experimental procedure of example 2 was followed. The synthesis conditions are listed in Table 3. In examples 4 and 5 metal aluminum and aluminum nitrate nonahydrate were used, respectively, as an aluminum source. The OH ef formalism is defined as the difference between the added OH moles and those employed by the aluminum to reach tetrahedral coordination. All the crystallizations were carried out under stirring (60 r.p.m.). In all cases high crystallinity ITQ-3 was obtained. Molar ratios seeds example SiO 2 /Al 2 O 3 T/SiO 2 OH ef /F H 2 O/SiO 2 %(SiO 2 ) T(°C) t(days) Si/Al(solid) 3 0.48 1 14.6 2.7 135 14 4 60 0.52 1 15 - 150 35 38.8 5 104 0.55 1 17.4 4.7 135 14 55.8 6 53 0.69 1 16.5 4.7 135 13 32.7

Claims: A microporous crystalline material of zeolitic nature with an X-ray diffraction pattern substantially in accordance with that which is established in Tables I and II for the material as it is synthesized and after calcination, respectively and with a chemical composition in the calcined and anhydrous state that may be represented by the following empirical formula x(M 1/n XO 2 ):yYO 2 :SiO 2 wherein x has a value lower than 0.15; it may be equal to zero; and y has a value lower than 0,1; it may be equal to zero; M is H + or an inorganic cation of charge +n; X is a chemical element with oxidation statet +3 (Al, Ge, B, Cr) and Y is a chemical element with oxidation state +4 (Ti, Ge, V). A zeolite according to claim 1 whose chemical composition in the calcined and anhydrous state may be represented by the following empirical formula x(HXO 2 ):yYO 2 :SiO 2 wherein X is a trivalent element (Al, B, Ga, Cr), Y is a tetravalent element different from Si(Ti, Ge, V), x has a value lower than 0.15, and it may be equal to zero, y has a value lower than 0.1, it may also be equal to zero, and wherein the cation H + may be exchanged by other mono-, di- or trivalent organic or inorganic cations. A zeolite in accordance with claim 1 whose chemical composition in the calcined and anhydrous state may be represented by the following empirical formula x(HalO 2 ):SiO 2 wherein x has a value lower than 0.15, it may also be equal to zero and wherein the H ± cation may be exchanged by other mono-, di- or trivalent organic or inorganic cations. A zeolite in accordance with claim 1 whose chemical compound in the calcined and anhydrous state may be represented by SiO 2 . A method for synthesizing the zeolite of the above claims wherein a reaction mixture that contains a source of SiO 2 , an organic cation R + (preferably N,N-dimethyl-6-azonium-1,1,3-trimethylbicyclo(3.2.1) octane), a source of F - , a source of one or several tetravalent elements Y different from Si, a source of one or several tetravalent elements X and water subjected to heating with or without stirring at a temperature between 80 and 200º C, preferably between 130 and 180ºC, until achieving crystallization thereof and wherein the reaction mixture has a composition, in terms of molar ratios of oxides, comprised between the ranges X 2 O 3 /SiO 2 =0-0.1, preferably 0-0.5 ROH/SiO 2 =0.05-2.0, preferably 0.2-1.50 F - /Si=0-2, preferably 0.2-1.50 YO 2 /SiO 2 =0-0.1 H 2 O/SiO 2 =3-100, preferably 5-50, more preferably 7-50. A method for synthesizing the zeolite of the above claims wherein a reaction mixture that contains a source of SiO 2 , an organic cation R + (preferably), a source of fluoride anions, a source of one or several trivalent elements X and water is subjected to heating with or without stirring at a temperature between 80 and 200º C, preferably between 130 and 180ºC, until achieving crystallization, and wherein the reaction mixture has a composition in terms of molar ratios of oxides, comprised between the ranges X 2 O 3 /SiO 2 =0-0.1, preferably 0-0.5 ROH/SiO 2 =0.05-2.0, preferably 0.2-1.5 F - /Si=0-2, preferably 0.2-1.5 H 2 O/SiO 2 =3-100, preferably 5-50, more preferably 7-50. A method for synthesizing the zeolite of claims 1 and 3 wherein the reaction mixture that contains a source of SiO 2 , an organic cation R + (preferably N,N-dimethyl-6-azonium-1,1,3-trimethylbicyclo(3.2.1) octane), a source of fluoride anions, a source of Al and water is subjected to heating with or without stirring at a temperature between 80 and 200ºC, preferably between 130 and 180ºC, until achieving its crystallization, and wherein the reaction mixture has a composition, in terms of molar ratios of oxides, comprised between the ranges Al 2 O 3 /SiO 2 =0-0.1, preferably 0-0.5 ROH/SiO 2 =0.05-2.0, preferably 0.2-1.5 F - /Si=0-2, preferably 0.2-1.5 H 2 O/SiO 2 =3-100, preferably 5-50, more preferably 7-50. A method for synthesizing the zeolite of claims 1 and 4 wherein a reaction mixture that contains a source of SiO 2 , an organic cation R + (preferably N,N-dimethyl-6-azonium-1,1,3-trimethylbicyclo(3.2.1) octane, a source of fluoride anions and water is subjected to heating with or without stirring at a temperature between 80 and 200º C, preferably between 130 and 180º C, until achieving its crystallization, and wherein the reaction mixture has a composition, in terms of molar ratios of oxides, comprised between the ranges ROH/SiO 2 =0.05-2.0, preferably 0.2-1.5 F - /Si=0-2, preferably 0.2-1.50 H 2 O/SiO 2 =3-100, preferably 5-50, more preferably 7-50. A method for synthesizing the zeolite of claims 1 and 2 wherein a reaction mixture that contains a source of SiO 2 , an organic cation R + (preferably N,N-dimethyl-6-azonium-1,3,3-trimethylbicyclo(3.2.1) octane, a source of fluoride anion, a source of one or several tetravalent elements Y different from Si, and water is subjected to heating with or without stirring at a temperature between 80 and 200º C, preferably between 130 and 180º C, until achieving its crystallization, and wherein the reaction mixture has a composition, in terms of molar ratios of oxides, comprised between the ranges ROH/SiO 2 =0.05-2.0, preferably 0.2-1.5 F - /Si=0-2, preferably 0.2-1.5 YO 2 /SiO 2 =0-0.1 H 2 O/SiO 2 =3-100, preferably 5-50, more preferably 7-50. A method for synthesizing the crystalline material of claims 1-4 in accordance with claims 5-9 wherein the organic cation is added in hydroxide form or in the form of a mixture of hydroxide and another salt, preferably a halide, and the fluoride anion is added in the form of ammonium fluoride, in such a way that the pH of the mixture is equal to or lower than 12, preferably lower than 11, and may even be neutral or slightly acidic. A method for synthesizing a microporous crystalline material in accordance with claim 10 and the previous ones, so that the crystalline material has an X-ray diffraction pattern substantially in accordance with what is established in tables I and II for the material just as synthesized and after calcination, respectively, and with a chemical composition in the calcined and anhydrous state that may be represented by the following empirical formula x(M 1/n XO 2 ):yYO 2 :SiO 2 wherein x has a value lower than 0.15, it may likewise be equal to zero; y has a value lower than 0.04, and may likewise be equal to zero; M is H + or an inorganic cation of charge +n; X is a chemical element in an oxidation state +3 (such as, for example, Al, Ga, B, Cr) and Y is a chemical element with an oxidation state +4 (such as, for example, Ti, Ge, V). A method for synthesizing the zeolite of claims 1-4 and 11 according to the process of claims 5-10 wherein to the reaction mixture is added an amount of crystalline material (preferably with the characteristics of the material of claims 1-4 and 11) as crystallization promoter, said amount being comprised in the range of 0 to 15% by weight with regard to the total silica added, preferably 0.05 to 5%. A method for synthesizing the zeolite of claims 1-4 and 11 according to the process of claims 5-10 and 12 wherein the reaction mixture is essentially free of alkali cations, the only limitation to this condition being the possible content of alkali impurities of the reagents used. A method for synthesizing the zeolite of the claims 1-3 and 11 according to the process of claims 5, 6, 7, 9, 10 and 12, wherein a source of a tetravalent element different than Si is added or a trivalent element is added in an intermediate step during the heating of the reaction. Use of the microporous crystalline material of claims 1-4 and 11 in processes of separation of iso- and normal paraffins, by selective adsorption of the normal paraffins. Use of the microporous crystalline material of claims 1-4 and 11 in process of separation of isobutane and n-butane by selective adsorption of n-butane. Use of the microporous crystalline material of claims 1-4 and 11 in processes of separation of isopentane and n-pentane by selective adsorption of n-pentane. Use of the microporous crystalline material of claims 1-4 and 11 in processes of separation of iso- and normal olefins, by selective adsorption of n-olefins. Use of the microporous crystalline material of claims 1-4 and 11 in process of separation of isobutene and normal butene, by selective adsorption of n-butene. Use of the microporous crystalline material of claims 1-4 and 11 in process of separation of isopentene and normal pentene, by selective adsorption of n-pentene. Use of the microporous material of claims 1-4 and 11 in processes of separation of organic compounds which may or may not contain heteroatoms and with a kinetic diameter smaller than 5-5.5 Å, by selective adsorption of the same in mixtures containing compounds with a kinetic diameter larger than 5-5.5 Å. Use of the microporous crystalline material of claim 4 in processes of separation of organic compounds with a kinetic diameter smaller than 5.5 Å. Present in polar streams and especially aqueous ones, for the purpose of purifying said streams. Use of the microporous crystalline material of claims 1-4 and 11 as a catalyst for selective cracking and hydrocracking of linear paraffins and/or olefins. Use of microporous crystalline material of claims 1-4 and 11 as a catalyst of "postreformate" of gasoline. Use of the microporous crystalline material of claims 1-4 and 11 as catalyst to produce streams with a high content of ethylene, propylene and butene by cracking in the presence or absence of steam. Use of the microporous crystalline material of claims 1-4 and 11 as a catalyst in dewaxing processes by selective cracking of n-paraffins. Use of the microporous crystalline material of claims 1-4 and 11 as a catalysts in processes of conversion of methanol into olefins.

Inventors: CAMBLOR FERNANDEZ MIGUEL-ANGEL, CORMA CANOS AVELINO, VILLAESCUSA ALONSO LUIS-ANGEL-, CAMBLOR FERNANDEZ, MIGUEL-ANGEL, CORMA CANOS, AVELINO, VILLAESCUSA ALONSO, LUIS-ANGEL-INSTITUTO DE TECN., CAMBLOR FERNANDEZ, MIGUEL-ANGEL,INSTITUTO DE TECN., CORMA CANOS, AVELINO-INSTITUTO DE TECNOLOGIA QUIM.
Applicants: CONSEJO SUPERIOR DE BR INVESTI, UNIV VALENCIA POLITECNICA, CONSEJO SUPERIOR DE<BR>INVESTIGACIONES CIENTIFICAS, UNIVERSIDAD POLITECNICA DE VALENCIA
Application year: 1998
Main classification: C01B37
IPC codes: C07C1, C10G45, C07C11, C10G3, C01B39, C07C4, C10G25, C10G11, C07C7, B01J29, C10G35, B01J20, C01B37