Patent EA-004784-B1 (EA)
Title: High surface microporous materials which are active in oxidation reactionstiq-6 and metiq-6
Inventor: CORMA CANOS AVELINO
IPC: C07D301/12
Filed: 2000-11-24
Abstract: 1. A zeolitic material, TIQ-6 whose chemical composition corresponds to the formula, expressed as oxides, SiO2:zZo2:mMO2:xX2O3:aH2O, wherein Z is Ge, Sn, z is between 0 and 0.25 mol.mo<-1>, M is Ti or Zr, m has a value between 0.00001 and 0.25, preferably between 0.001 and 0.1, X is Al, Ga or B, x has a value between 0 and 1, and a has a value between 0 and 2. 2. A zeolitic material according to claim 1, wherein the material has a specific external area higher than 500 m<2>g<-1>, a pore volume over 0.5 cm<3>g<-1> and a load transfer band in the visible ultraviolet spectrum in the range between 200 and 230 nm. 3. A microporous METIQ-6 material with a chemical composition represented by the formula SiO2:yYRpO2-p/2:zZO2:mMO2:xX2O3:aH2O, wherein R is selected among hydrogen, alkyl groups with 1 to 22 carbon atoms, aryl groups with 6 to 36 carbon atoms, aromatic groups with 6 to 36 carbon atoms, polyaromatic groups with 6 to 36 carbon atoms and these groups are selected among non functionalized groups and functionalized groups with functional groups selected among acid, amino, thiol, sulphonic and tetra-alkyl ammonium groups, Y is Si, Ge, Sn or Ti and is directly joined to atoms making up a structure by means of C-Y bonds, p has a value between 1 and 3, y has a value between 0.0001 and 1, Z is Ge or Sn, z has a value between 0 and 0.25 mol.mol<-1>, M is Ti or Zr, m has a value between 0.00001 and 0.25, preferably between 0.001 and 0.1, X is Al, Ga or B, x has a value between 0 and 1, and a has a value between 0 and 2. 4. A microporous material according to claim 3, wherein the material has a specific external area higher than 500 m<2>g<-1>, a pore volume over 0.5 cm<3>g<-1> and a load transfer band in the visible ultraviolet spectrum in the range between 200 and 230 nm. 5. A process for preparing the zeolitic TIQ-6 material of claim 1, comprising: a first step wherein a laminar precursor of ferrieritic type with a structure comprising at least one of Ti and Zr is synthesised; a second step wherein the laminar precursor is subjected to swelling with a long chain organic compound to obtain a swollen laminar material; a third step wherein the swollen laminar material is at least partially delaminated using mechanical stirring techniques, ultrasounds, spray drying, liophilisation and combinations thereof; a fourth step wherein the at least partially delaminated material is subjected to an acid treatment; a fifth step wherein the at least partially delaminated material is subjected to calcination until removing of at least part of the organic matter present in the material to obtain a calcinated material. 6. A process according to claim 5 wherein the laminar precursor is prepared by a mixing step comprising mixing in an autoclave a silica source, a titanium and/or zirconium source, a salt and fluoride acid, a structure director organic compound and water until a mixture is obtained; a heating step wherein the mixture is heated at autogenous pressure, between 100 and 200 degree C., with stirring for 1 to 30 days until a synthesis material is obtained; and a final step wherein the synthesis material is filtered, washed and dried at a temperature below 300 degree C. until the laminar precursor is obtained. 7. A process according to claim 6, wherein the silica source is selected among sources of SiO2, tetraethylorthosilicate (TEOS) and combinations thereof. 8. A process according to claim 6 wherein the titanium source is selected between TiCl4, tetraethylorthotitanate (TEOTi) and combinations thereof. 9. A process according to claim 6, wherein the zirconium source is selected among ZrCl4, zirconile chloride and combinations thereof. 10. A process according to claim 6, wherein the salt and fluoride acid are selected between ammonium fluoride, hydrogen fluoride and combinations thereof. 11. A process according to claim 6, wherein the structure director organic compound is selected among 1,4-diaminobutane, ethylenediamine, 1,4-dimethylpiperazine, 1,4-diaminocyclohexane, hexamethylenimine, pyrrolidine, pyridine and preferably 4-amino-2,2,6,6-tetramethylpiperidine and combinations thereof. 12. A process according to claim 6, wherein the heating step lasts between 2 and 15 days. 13. A process according to claim 6, wherein the final step is carried out at a temperature below 200 degree C. 14. A process according to claim 5, wherein the acid treatment is carried out at a pH below 2. 15. A method for preparing the microporous material according to any one of claims 3 and 4, which comprises subjecting the zeolitic material defined in claim 1 to a reaction with reagents selected among organogermanes, organosilanes, organometals and combinations thereof, in order to generate organic species anchored on the surface of the described materials. 16. A method for preparing the METIQ-6 microporous material according to any one of claims 3 and 4, which comprises subjecting the zeolitic material obtained according to claims 5-14 to a process to produce organic species anchored on the surface, by means of a reaction with reagents selected among organogermanes, organosilanes and organometallics selected between organotitanium and organotin. 17. A method according to any one of claims 15 and 16, wherein the material is subjected to a process to produce organic species anchored on the surface, at a reaction temperature between 0 and 400 degree C., using an agent selected between R1R2R3(R')Y, R1R2(R')2Y, R1(R')3Y, R1R2R3Y-NH-YR1R2R3 and combinations thereof, wherein R1, R2 and R3 are selected among hydrogen, alkyl groups with 1 to 22 carbon atoms, aryl groups with 6 to 36 carbon atoms, aromatic groups with 6 to 36 carbon atoms, polyaromatic groups with 6 to 36 carbon atoms and these groups are selected among identical groups and groups different to each other and selected, in turn, between non functionalised groups and groups functionalised with functional groups selected among acid, amino, thiol, sulphonic and tetra-alkyl ammonium groups, R' is a group hydrolysable at the reaction temperature, selected among alkoxide, halide and trimethylsilylamino groups, Y is at least an element selected among Si, Ge, Sn, Ti. 18. A method according to claim 17, wherein said process to produce organic species anchored on the surface is carried out by dissolving the material in a solvent selected between organic and inorganic solvents. 19. A method according to claim 17 or 18, wherein said process to produce organic species anchored on the surface is carried out in the presence of at least one catalyst which favours a reaction of an alkylsilane, alkylgermane or organometallic compound in general with Si- groups. 20. A method according to any one of claims 15-19, wherein said process to produce organic species anchored on the surface is carried out in a gas phase and the reaction temperature is from 50 to 200 degree C. 21. Use a material, wherein an olefin is subjected to epoxidation with a hydroperoxide selected between organic and inorganic hydroperoxides, and the catalyst comprises a material according to any one of claims 1-4. 22. Use according to claim 21, wherein the olefin is selected between propylene, ethylene, isoprene, norbonene, limonene, [alpha]-pinene, terpinolene, longifolene, cariofilene, [alpha]-cedrene, styrene, substituted styrenes, fatty esters and acids, alphylic alcohols and vinylic alcohols, and the hydroperoxides are selected among tertbutylhydroxiperoxides, cumene hydroperoxide and hydrogen peroxide. 23. Use a material for the oxidation of alcohols, wherein an alcohol is subjected to oxidation with a hydroperoxide selected between organic and inorganic hydroperoxides, and the catalyst comprises a material according to any one of claims 1-4. 24. Use according to claim 23, wherein the alcohol is oxidated to ketone. 25. Use according to claim 23, wherein the alcohol is oxidated to aldehyde. 26. Use according to claim 23, wherein the alcohol is oxidated to acid. 27. Use a material for the oxidation of organic thiols to the corresponding sulphoxides and sulphons with a hydroperoxide selected between organic and inorganic hydroperoxides, and the catalyst comprises a material according to any one of claims 1-4. 28. Use a material for the hydroxylation of aromatic compounds with a hydroperoxide selected between organic and inorganic hydroperoxides, and the catalyst comprises a material according to any one of claims 1-4. 29. Use a material A method for the ammoximation of ketones comprising treating said ketones with a hydroperoxide selected between organic and inorganic hydroperoxides, and a catalyst comprising a material according to any one of claims 1-4.