Resumen
This invention refers to a new zeolitic material included under the ITQ-16 denomination, to the method for obtaining them and their use as catalysts. This material, ITQ-16 zeolite, is characterized by having different ratios of the different polymorphs A, B and C described as possible intergrowths in Beta zeolite and which, therefore, show different X-ray diffraction patterns to that described for Beta zeolite, showing the X-ray diffraction pattern for ITQ-16, as it is synthesised, diffraction peaks at 2theta angles of 6.9°, 7.4°, and 9.6°, simultaneously. ITQ-16 zeolite in its calcinated form has the following empiric formula: <?in-line-formulae description="In-line Formulae" end="lead"?>x(M<SUB>1/n</SUB>XO<SUB>2</SUB>):tTO<SUB>2</SUB>:gGeO<SUB>2</SUB>:(1-g)SiO<SUB>2</SUB><?in-line-formulae description="In-line Formulae" end="tail"?> where T is one or various elements with +4 oxidation status, different of Ge and Si; X is one or various elements with +3 oxidation status and M can be H<SUP>+</SUP> or one or various inorganic cations with charge +n, t is comprised between 0 and 0.1, g is comprised between 0.001 and 0.33 and x is comprised between 0 and 0.2.
Reivindicaciones
1. A group of microporous materials, denominated ITQ-16, characterised in that in its calcinated form it has the following empirical formula: x (M<1/n> XO<2> ) :t TO<2> :g GeO<2> : (1-g )SiO<2> wherein: - T represents one or various elements different of Ge and Si, with +4 oxidation status; - X represents one or various elements with +3 oxidation status and - M represents H<+> or one or various inorganic cations with charge +n, and in that , as synthesised, its X-ray diffraction pattern presents diffraction peaks at angles 2θ of 6.9º, 7.4º and 9.6º simultaneously. 2. A group of microporous materials according to claim 1, characterised in that the relative intensity of the peaks at 6.9º and 9.6º with regard to the peak at 7.4º complies with the I<9.6º> /I<7.4º> ratio being greater than zero and less than ∞. 3. A group of microporous materials according to claim 1 or 2, characterised in that it has an X-ray diffraction pattern, as synthesised, with the following values of angle 2θ and relative intensities, I/Io, 6.93 v 7.44 v 9.58 v 19.32 d 21.12 m 21.93 f 22.19 mf 25.12 d 27.15 d 27.94 d 28.43 d 29.46 d 29.99 d 32.98 d 33.11 d 34.68 d 35.76 d 37.12 d where d means an intensity of between 0 and 20%; m means medium intensity, between 20 and 40%; f means strong intensity, between 40 and 60%, mf means very strong intensity, between 60 and 100% and v means variable intensity. 4. A group of microporous materials according to claim 1, characterised in that T represents one or various elements in +4 oxidation status selected between Ti, V and Sn. 5. A group of microporous materials according to claim 1, characterised in that X represents one or various elements in +3 oxidation status selected from among Al, Ga, B, Cr and Fe. 6. A group of microporous materials according to claim 1, characterised in that M represents a mono or divalent cation in +3 oxidation status selected from among H<+> , Li<+> , Na<+> , Ca<2+> and Mg<2+> . 7. A process for the synthesis of a group of microporous materials denominated ITQ-16, which in calcinated form has the following empirical formula: x (M<1/n> XO<2> ) : tTO2 : gGeO2 : (1-g )SiO<2> wherein: - T is one or various elements different of Ge and Si, with +4 oxidation status; - X is one or various elements with +3 oxidation status and - M can be H<+> or one or various inorganic cations with charge +n. according to claim 1, characterised in that it comprises preparing a reaction mixture comrpising at least: - fluoride anions as a mineralising agent, - water, - a cation selected from among TEA, DABCO-benzyl, Q-benzyl and mixtures thereof as structure directing agents, at a pH between 5 and 8.5, and subjecting it to heating at a temperature of between 110ºC and 200ºC. 8. A synthesis process according to claim 7, characterised in that the reaction mixture is at a pH between 6 and 8. 9. A synthesis process according to claim 7, characterised in that the reaction mixture is subjected to heating at a temperature of between 130ºC and 175ºC. 10. A synthesis process according to claim 7, characterised in that the reaction mixture has a composition in terms of molar ratios within the following ranges: H<2> O/(SiO<2> + GeO<2> ) = between 1000 and 0.5, HF/SiO<2> +GeO<2> ) = between 3 and 0.01, SiO<2> +GeO<2> /TO<2> = between 10 and ∞, (SiGe)/X is between 5 and ∞, where X represents an element in its trivalent oxidation state, and T represents an element in its tetravalent oxidation state, other than Si and Ge. 11. A synthesis process according to claim 10, characterised in that the ratio H<2> O/(SiO<2> + GeO<2> ) is between 100 and 2. 12. A synthesis process according to claim 10, characterised in that the ratio HF/SiO<2> + GeO<2> ) is between 1 and 0.03. 13. A synthesis process according to claim 10, characterised in that the ratio SiO<2> + GeO<2> /TO<2> is between 10 and 10000. 14. A synthesis process according to claim 10, characterised in that the ratio SiO<2> + GeO<2> /TO<2> ) is between 20 and 1000. 15. A synthesis process according to claim 10, characterised in that the ratio (Si + Ge) /X is greater than 15. 16. A synthesis process according to claim 10, characterised in that the ratio (Si + Ge) /X is greater than 20. 17. A synthesis process according to any claim from 7 to 16, characterised in that the DABCO-benzyl cation is used as a structure directing agent, and in that the reaction mixture has a composition in terms of molar ratios within the following ranges: DABCO-benzyl/(SiO<2> + GeO<2> ) between 3 and 0.01, GeO<2> /(SiO<2> + GeO<2> ), defined as g, between 0.17 and 0.001 18. A synthesis process according to claim 17, characterised in that the ratio DABCO-benzyl/(SiO<2> + GeO<2> ) is between 1 and 0.03. 19. A synthesis process according to claim 17, characterised in that the ratio GeO<2> /(SiO<2> +GeO<2> ), defined as g, is between 0.032 and 0.001. 20. A synthesis process according to any claim from 7 to 16, characterised in that the Q-benzyl cation is used as structure directing agent and in that the reaction mixture has a composition in terms of molar ratios within ranges: Q-benzyl/(SiO<2> + GeO<2> ) between 3 and 0.01, GeO<2> /(SiO<2> + GeO<2> ), defined as g; between 0.2 and 0.001 21. A synthesis process according to claim 20, characterised in that the ratio Q-benzyl/(SiO<2> + GeO<2> ) is between 1 and 0.03. 22. A synthesis process according to claim 20, characterised in that the ratio GeO<2> /(SiO<2> + GeO<2> ), defined as g, is between 0.134 and 0.001. 23. A synthesis process according to claim 20, characterised in that the ratio GeO<2> /(SiO<2> + GeO<2> ), defined as g, is between 0.134 and 0.01. 24. A synthesis process according to any claim from 7 to 16, characterised in that the TEA cation is used as structure directing agent and because the synthesis mixture has a composition in terms of molar ratios within ranges: TEA/(SiO<2> + GeO<2> ) between 3 and 0.01, and GeO<2> /(SiO<2> + GeO<2> ), defined as g, between 0.33 and 0.001 25. A synthesis process according to claim 24, characterised in that the ratio TEA/(SiO<2> + GeO<2> ) is between 1 and 0.03. 26. A synthesis process according to claim 24, characterised because the ratio GeO<2> /(SiO<2> + GeO<2> ), defined as g, is between 0.33 and 0.01. 27. Synthesis procedure according to any claim from 7 to 16, characterised in that mixtures of DABCO-benzyl and Q-benzyl cations are used as structure directing agent, and in that the reaction mixture has a composition in terms of molar ratios within ranges: (DABCO-benzyl+Q-benzyl)/(SiO<2> + GeO<2> ) between 3 and 0.01, GeO<2> /(SiO<2> +GeO<2> ), defined as g, between 0.2 and 0.001, and DABCO-benzyl/(DABCO-benzyl+Q-benzyl) between 0 and 1, both excluded. 28. A synthesis process according to claim 27, characterised in that the ratio (DABCO-benzyl+Q-benzyl)/(SiO<2> +GeO<2> ) is between 1 and 0.03. 29. A synthesis process according to claim 27, characterised in that the ratio GeO<2> /(SiO<2> +GeO<2> ), defined as g, is between 0.134 and 0.001. 30. A synthesis process according to claim 27, characterised in that the ratio GeO<2> /(SiO<2> +GeO<2> ), defined as g, is between 0.134 and 0.01. 31. The use of a group of microporous materials defined according to any claim from 1 to 6, as a catalyst of a process selected from among a cracking process, hydro-cracking process, hydrocarbon and/or functionalised hydrocarbon soft hydro-cracking process, olefin hydroisomerization process, a process of alkylation of olefins with isoparaffins and a process of aromatic alkylation with olefins or alcohols. 32. The use of a group of microporous materials according to claim 31, characterised in that said aromatic alkylation with olefins is a process of alkylation of benzene with propylene. 33. The use of a group of microporous materials defined according to any claim from 1 to 6, as a catalyst in processes of selective oxidation of organic compounds using H<2> O, peroxides or organic hydro-peroxides as oxidants. 34. The use of a group of microporous materials defined according to any claim from 1 to 6, as a catalyst in a Baeyer-Villiger type oxidation process. 35. The use of a group of microporous materials defined according to any claim from 1 to 6, as a catalyst in a Meerwein-Pondorf-Verley type reduction process. 36. The use of a group of microporous materials defined according to any claim from 1 to 6, as a catalyst in a Oppenauer type oxidation process. 37. The use of a group of microporous materials defined according to any claim from 1 to 6, as a component of catalysts for the elimination of organic vapours (VOC). 38. The use of a group of microporous materials defined according to any claim from 1 to 6 that includes Ti, as a catalyst for the epoxidation of olefins, using organic or inorganic hydroperoxide, such as for example H<2> O, tertbutylhydroperoxide, cumene hydroperoxide, as oxidating agents. 39. The use of a group of microporous materials defined according to any claim from 1 to 6 containing Ti, as a catalyst in an oxidation process selected from an alkane oxidation process, a process of alcohol oxidation and a process of oxidation of thioethers to sulphoxides and sulphones. 40. The use of a group of microporous materials defined according to any claim from 1 to 6 containing Sn, as a catalyst in a Bayer-Villiger oxidation process using H<2> O<2> as an oxidating agent. 41. The use of a group of microporous materials defined according to any claim from 1 to 6 containing Sn, as a catalyst in the ammoximation from cyclohexanone to cyclohexanone oxime with NH<3> and H<2> O<2> .
