WO2002030821A1 - Zeolita itq-16 - Google Patents
Zeolita itq-16 Download PDFInfo
- Publication number
- WO2002030821A1 WO2002030821A1 PCT/ES2001/000387 ES0100387W WO0230821A1 WO 2002030821 A1 WO2002030821 A1 WO 2002030821A1 ES 0100387 W ES0100387 W ES 0100387W WO 0230821 A1 WO0230821 A1 WO 0230821A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- benzyl
- family
- ratio
- synthesis
- microporous materials
- Prior art date
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- 239000010457 zeolite Substances 0.000 title abstract description 48
- 229910021536 Zeolite Inorganic materials 0.000 title abstract description 47
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 title abstract description 46
- 230000003647 oxidation Effects 0.000 claims abstract description 33
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 33
- 238000000034 method Methods 0.000 claims abstract description 31
- 239000003054 catalyst Substances 0.000 claims abstract description 22
- 229910052732 germanium Inorganic materials 0.000 claims abstract description 18
- 238000002441 X-ray diffraction Methods 0.000 claims abstract description 17
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 15
- 150000001767 cationic compounds Chemical class 0.000 claims abstract 2
- 229910001411 inorganic cation Inorganic materials 0.000 claims abstract 2
- 239000000203 mixture Substances 0.000 claims description 43
- 230000015572 biosynthetic process Effects 0.000 claims description 30
- 238000003786 synthesis reaction Methods 0.000 claims description 30
- 239000003795 chemical substances by application Substances 0.000 claims description 27
- LCMQZFKHBPYYAE-UHFFFAOYSA-N 3-benzyl-1,4-diazabicyclo[2.2.2]octane Chemical compound C1N(CC2)CCN2C1CC1=CC=CC=C1 LCMQZFKHBPYYAE-UHFFFAOYSA-N 0.000 claims description 19
- 150000001768 cations Chemical class 0.000 claims description 19
- 239000012229 microporous material Substances 0.000 claims description 19
- -1 benzyl-DABCO cation Chemical class 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- 229910052719 titanium Inorganic materials 0.000 claims description 13
- 229910052782 aluminium Inorganic materials 0.000 claims description 12
- 229910052718 tin Inorganic materials 0.000 claims description 12
- 229910052720 vanadium Inorganic materials 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 10
- 229910052796 boron Inorganic materials 0.000 claims description 9
- 150000001336 alkenes Chemical class 0.000 claims description 8
- 238000005804 alkylation reaction Methods 0.000 claims description 7
- 229910052804 chromium Inorganic materials 0.000 claims description 7
- 229910052733 gallium Inorganic materials 0.000 claims description 7
- 229910052742 iron Inorganic materials 0.000 claims description 7
- 239000011541 reaction mixture Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- 230000029936 alkylation Effects 0.000 claims description 5
- 239000007800 oxidant agent Substances 0.000 claims description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 4
- 238000004517 catalytic hydrocracking Methods 0.000 claims description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 4
- VEZUQRBDRNJBJY-UHFFFAOYSA-N cyclohexanone oxime Chemical compound ON=C1CCCCC1 VEZUQRBDRNJBJY-UHFFFAOYSA-N 0.000 claims description 4
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims description 4
- 150000001298 alcohols Chemical class 0.000 claims description 3
- 229930195733 hydrocarbon Natural products 0.000 claims description 3
- 150000002430 hydrocarbons Chemical class 0.000 claims description 3
- 150000002894 organic compounds Chemical class 0.000 claims description 3
- 241001292274 Eumenes Species 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- 238000006735 epoxidation reaction Methods 0.000 claims description 2
- 230000001089 mineralizing effect Effects 0.000 claims description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 2
- 150000003457 sulfones Chemical class 0.000 claims description 2
- 150000003462 sulfoxides Chemical class 0.000 claims description 2
- 150000003568 thioethers Chemical class 0.000 claims description 2
- 238000001308 synthesis method Methods 0.000 claims 12
- 238000006220 Baeyer-Villiger oxidation reaction Methods 0.000 claims 1
- 238000005336 cracking Methods 0.000 claims 1
- 230000008030 elimination Effects 0.000 claims 1
- 238000003379 elimination reaction Methods 0.000 claims 1
- 150000002432 hydroperoxides Chemical class 0.000 claims 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims 1
- 150000002978 peroxides Chemical class 0.000 claims 1
- 238000011946 reduction process Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 8
- 239000000377 silicon dioxide Substances 0.000 abstract description 2
- 229910052681 coesite Inorganic materials 0.000 abstract 1
- 229910052906 cristobalite Inorganic materials 0.000 abstract 1
- 230000001747 exhibiting effect Effects 0.000 abstract 1
- 235000012239 silicon dioxide Nutrition 0.000 abstract 1
- 229910052682 stishovite Inorganic materials 0.000 abstract 1
- 229910052905 tridymite Inorganic materials 0.000 abstract 1
- 229910005793 GeO 2 Inorganic materials 0.000 description 21
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 21
- 229910004298 SiO 2 Inorganic materials 0.000 description 13
- 239000010936 titanium Substances 0.000 description 11
- 239000000499 gel Substances 0.000 description 8
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 7
- 238000001704 evaporation Methods 0.000 description 7
- 230000007062 hydrolysis Effects 0.000 description 7
- 238000006460 hydrolysis reaction Methods 0.000 description 7
- 239000004810 polytetrafluoroethylene Substances 0.000 description 7
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 239000010703 silicon Substances 0.000 description 4
- 229910000577 Silicon-germanium Inorganic materials 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 2
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000005917 acylation reaction Methods 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- OGHBATFHNDZKSO-UHFFFAOYSA-N propan-2-olate Chemical compound CC(C)[O-] OGHBATFHNDZKSO-UHFFFAOYSA-N 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
- C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
- C10G47/10—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used with catalysts deposited on a carrier
- C10G47/12—Inorganic carriers
- C10G47/16—Crystalline alumino-silicate carriers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/86—Borosilicates; Aluminoborosilicates
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/89—Silicates, aluminosilicates or borosilicates of titanium, zirconium or hafnium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/023—Preparation of physical mixtures or intergrowth products of zeolites chosen from group C01B39/04 or two or more of groups C01B39/14 - C01B39/48
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/06—Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/06—Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis
- C01B39/08—Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis the aluminium atoms being wholly replaced
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/06—Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis
- C01B39/12—Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis the replacing atoms being at least boron atoms
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/46—Other types characterised by their X-ray diffraction pattern and their defined composition
- C01B39/48—Other types characterised by their X-ray diffraction pattern and their defined composition using at least one organic template directing agent
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/54—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition of unsaturated hydrocarbons to saturated hydrocarbons or to hydrocarbons containing a six-membered aromatic ring with no unsaturation outside the aromatic ring
- C07C2/64—Addition to a carbon atom of a six-membered aromatic ring
- C07C2/66—Catalytic processes
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/29—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of hydroxy groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/29—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of hydroxy groups
- C07C45/294—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of hydroxy groups with hydrogen peroxide
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
- C07C45/33—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/45—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation
- C07C45/46—Friedel-Crafts reactions
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
- C10G11/04—Oxides
- C10G11/05—Crystalline alumino-silicates, e.g. molecular sieves
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G29/00—Refining of hydrocarbon oils, in the absence of hydrogen, with other chemicals
- C10G29/20—Organic compounds not containing metal atoms
- C10G29/205—Organic compounds not containing metal atoms by reaction with hydrocarbons added to the hydrocarbon oil
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/58—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins
- C10G45/60—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used
- C10G45/64—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/30—Capture or disposal of greenhouse gases of perfluorocarbons [PFC], hydrofluorocarbons [HFC] or sulfur hexafluoride [SF6]
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Definitions
- Zeolite Beta is a microporous material with channels formed by 12-member rings, which has a characteristic diffraction pattern shown in Figure 1 (Pérez-Pariente, J., Martens, J.A., Jacobs, P.A.,
- This zeolite is formed by an inter-growth of different polymorphs related to each other, as has been described in the literature (J.M. Newsam, M.M.J. Treacy, W.T. Koetsier, C.B. de Gruyter, Proc. R. Soc.
- polymorphs A and B are the ones that fundamentally make up the intercreation called Zeolite Beta (Zeolites, 5/6, (1996), 641) while Polymorph C (whose diffractogram calculated from the proposed structure in JM Newsam, MMJ Treacy, WT Koetsier, CB de Gruyter,
- zeolite ITQ-16 a family of materials are presented that are included under the denomination of zeolite ITQ-16, and that is characterized by its X-ray diffractogram, which seems to indicate that the materials of this family have different relationships of the different polymorphs A , B and C described as possible inter-growths in the Beta zeolite and therefore have different X-ray diffraction patterns to that described for the Beta zeolite.
- the present invention relates to a new family of zeolitic materials that are encompassed within the ITQ-16 designation, its method of production, and its catalytic applications.
- the ITQ-16 zeolite is related to the Beta zeolite, but it has a different X-ray diffractogram, shown in Figure 3, which may be due to the presence of a different proportion of the different polymorphs found in the Beta zeolite, whose diffractogram is shown in Figure 1.
- the ITQ-16 zeolite could be constituted, in addition to the polymorphs A and B characteristic of the Beta zeolite, by another polymorph that could correspond to the polymorph C proposed by Newsam (JM Newsam, MMJ Treacy, WT Koetsier, CB de Gruyter, Proc. R. Soc. London A, 420 (1998) 375). Therefore, the presence of this other polymorph, gives the ITQ-16 material an X-ray diffraction pattern different from that of the Beta zeolite.
- the X-ray diffraction pattern for the ITQ-16 zeolite, as synthesized, shows following 2 ⁇ angle values and relative intensities, I / lo,;
- d means intensity 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%
- v indicates that the relative intensity of these peaks may vary depending on the proportion of polymorphs.
- the positions, widths and relative intensities of the diffraction peaks can be modified according to the chemical composition of the material (type of structure directing agent, Si / Ge ratio, presence of other trivalent and / or tetravalent heteroatoms (one or more) in the network , in addition to silicon and / or germanium, such as: aluminum, boron, titanium, vanadium, etc.), as well as the degree of hydration and crystal size.
- Table 2 shows the values of angle 2 ⁇ and relative intensities (l / l 0 ) of the reflections of the powder X-ray diffractogram of the previous sample of ITQ-16 after being calcined at 580 ° C to remove the organic compounds occluded inside the zeolite, where d, m, f and mf have the same meanings as in table I.
- the X-ray diffraction pattern of the ITQ-16 zeolite differs mainly, from that of the Beta zeolite, in that at low angles it presents, in addition to a wide peak around a 2 ⁇ value of 7.4 °, two peaks at angles 2 ⁇ of 6 9 o and 9 6 °, which generally show a smaller width at half height than the peak at 7 4 o
- the present invention relates to a family of materials having as extreme limits the Beta zeolite and another polymorph that could be polymorph C in the Beta zeolite and in the possible polymorph C, contrary to what occurs in the ITQ zeolite -16 peaks are not found simultaneously at angles 6 9 °, 7 4 ° and 9 6 °
- the material in its calcined form has the following empirical formula x (M 1 / n XO 2 ) fTO 2 gGeO 2 (1 -g) S ⁇ O 2 where T is one or several elements with oxidation state +4 other than Ge and Si such and since Ti, V, Sn, X is one or several elements with oxidation state +3 such as Al, Ga, B, Cr, Fe and M can be H + or one or inorganic charge cations + n as per example L ⁇ + , Na + , K + , Ca 2+ , Mg 2+ , etc.
- the synthesis composition necessary to synthesize the ITQ-16 zeolite depends on the structure directing agent used, the range of the chemical composition of the ITQ-16 material for particular embodiments of the invention is described below, according to the structure directing agent.
- the ITQ zeolite -16 is achieved when the Si + Ge / AI ratio, equivalent to 1 / x, is between 5 and ⁇ , and preferably greater than 15
- the SiO 2 + Ge0 2 / T0 ratio must have a value between 10 and ⁇ , and preferably between 20 and 1000.
- the value of g must be between 0.17 and 0.001, and preferably between 0.032 and 0.001, and more preferably between 0.032 and 0.01.
- the Si + Ge / AI ratio is between 5 and oo, and preferably greater than 15, and more preferably greater than 20.
- the SiO 2 + GeO / T0 2 ratio must have a value between 10 and ⁇ , and preferably between 20 and 1000.
- the Si + Ge / AI ratio is between 5 and ⁇ , and preferably greater than 15, and more preferably greater than 20.
- the SiO + GeO 2 / TO 2 ratio must have a value between 10 and ⁇ , and preferably between 20 and 1000.
- the present invention relates to the process for obtaining the material called ITQ-16, characterized by a synthesis medium with a pH between 5 and 8.5 and preferably between 6 and 8 and the use of fluoride anions as a mineralizing agent, and TEA cations, benzyl-DABCO and benzyl-Q as structure managing agents.
- the preparation method is based on heating at temperatures between 110 ° C and 200 ° C and preferably between 130 ° C and 175 ° C of a reaction mixture containing a source of Si, among which amorphous silica, silica are preferred. colloidal, silica gel, tetraalkylortosilicate, and a source of germanium such as oxide, halides or alkoxides of germanium.
- the synthesis mixture contains one or more of the following cations as structure directing agents: TEA, benzyl-DABCO, benzyl-Q, and a source of F ions.
- trivalent cations such as Al, B, Ga, Fe or Cr
- tetravalent cations such as Ti, V or Sn
- composition of the synthesis mixture is characterized by the following ranges of molar ratios when the benzyl-DABCO cation is used as the structure directing agent.
- benzyl-DABCO / (SiO 2 + GeO 2 ) between 3 and 0.01, and preferably between 1 and
- H 2 O / (SiO 2 + Ge0 2 ) between 1000 and 0.5, and preferably between 100 and 2.
- GeO / (SiO 2 + GeO 2 ), defined as g; between 0J 7 and 0.001, and preferably between 0.032 and 0.001, and more preferably between 0.032 and 0.01.
- SiO 2 + GeO 2 / T0 2 between 10 and oo, and preferably between 20 and 1000.
- X represents an element in its trivalent oxidation state such as Al, B, Fe, Ga or Cr; and T is an element in its tetravalent oxidation state such as Ti, Sn or V.
- HO / (SiO 2 + Ge0 2 ) between 1000 and 0.5, and preferably between 100 and 2.
- GeO 2 / (S ⁇ O 2 + Ge0 2 ), defined as g, between 0.33 and 0.001, preferably between 0.33 and 0.01.
- (Si + Ge) / X between 5 and oo, and preferably greater than 15.
- SiO 2 + GeO 2 / TO 2 between 10 and ⁇ , and preferably between 20 and 1000.
- X represents an element in its trivalent oxidation state such as Al, B, Fe, Ga or Cr
- T is an element in its tetravalent oxidation state such as Ti, Sn or V.
- H 2 O / (S ⁇ O 2 + GeO 2 ) between 000 and 0.5, and preferably between 100 and 2.
- HF / SiO 2 + GeO 2 between 3 and 0.01, and preferably between 1 and 0.03.
- GeO 2 / (S ⁇ O 2 + GeO), defined as g, between 0.2 and 0.001, and preferably
- SiO 2 + GeO 2 / TO 2 between 10 and ⁇ , and preferably between 20 and 1000.
- X represents an element in its trivalent oxidation state such as Al, B, Fe, Ga or Cr; and T is an element in its tetravalent oxidation state such as Ti, Sn or V.
- composition of the synthesis mixture is characterized by the following ranges of molar ratios:
- H 2 O / (SiO 2 + GeO 2 ) between 1000 and 0.5, and preferably between 100 and 2.
- HF / SiO 2 + GeO 2 ) between 3 and 0.01, and preferably between 1 and 0.03.
- GeO 2 / (S ⁇ O 2 + GeO 2 ), defined as g, between 0.2 and 0.001, and preferably between 0J 34 and 0.001, and more preferably between 0.134 and 0.01.
- SiO + GeO 2 / TO 2 between 10 and ⁇ , and preferably between 20 and 1000.
- benzyl-DABCO / (benzyl-DABCO + benzyl-Q) between 0 and 1 both excluded.
- X represents an element in its trivalent oxidation state such as Al, B, Fe, Ga or Cr; and T is an element in its tetravalent oxidation state such as Ti, Sn or V.
- the solids are separated from the mother liquors by filtration and / or by centrifugation. As a result, a highly crystalline solid containing occluded organic material is obtained.
- the solid product obtained has a characteristic diffraction pattern (CuK ⁇ radiation) as presented in Figure 3 and Table 1, and that bears some similarity with that of the Beta zeolite (US Patent Re28341) at a high angle 2 ⁇ > 20 ° , where ⁇ is the Bragg angle, and little similarity at low angles.
- Organic matter and occluded fluoride anions are removed by calcination under vacuum, air, N 2 or other inert gas, at temperatures above
- the calcined ITQ-16 zeolite has a diffraction peak around 7.4 °, characterized by a half-height width of about 1 ° and characteristic of the Beta zeolite (Newsam et al., Proc. R. Soc. London A , 1988, 420, 375) with an intercreation of the polymorphs A and B determined, but also presents two peaks at 6.9 ° and 9.6 ° corresponding to the presence of another polymorph that could be polymorph C.
- the ITQ- zeolite 16 shows an intercreation different from that of Beta zeolite.
- alkylation catalyst for isoparaffins with olefins and alkylation of aromatics and aromatics substituted with olefins or alcohols and more specifically as a catalyst for the alkylation of benzene with propylene.
- VOC organic vapors
- Figure 1 represents an X-ray diffractogram of the Beta zeolite.
- Figure 2 represents the calculated diffractogram of polymorph C
- Figure 4 represents the formulas of the cations used as the structure director. The diffraction pattern of calcined ITQ-16 zeolite is shown in Figure 5.
- Example 1 This example illustrates the preparation of ITQ-16 containing Si and Ge, and using the benzyl-DABCO cation as the structure directing agent.
- TEOS tetraethylorthosilicate
- benzyl-DABCO 2.10 "3 moles of benzyl-DABCO (OH) / g) and 0.92g of water.
- GeO 2 0.0684g of GeO 2 are then added The mixture is left stirring and evaporating the ethanol formed in the hydrolysis of the TEOS Finally, 1,334g of HF (aq., 50%) are added. The resulting mixture is heated in autoclaves internally coated with PTFE at 150 ° C. After 13h of heating, the mixture is filtered and 17g of ITQ-16 zeolite are obtained per 100g of synthesis gel. The X-ray diffraction pattern is presented in Figure 3. Example 2.
- TEOS tetraethylorthosilicate
- Example 3 This example illustrates the preparation of ITQ-16 containing Si and Ge, and using the benzyl-Q cation as the structure directing agent.
- TEOS tetraethylorthosilicate
- Example 4 This example illustrates the preparation of ITQ-16 containing Si, Ge and Al, and using benzyl-Q as the structure directing agent.
- tetraethylorthosilicate TEOS
- benzyl-Q (1.39J0 "4m benzyl-Q (OH) / g)
- isopropoxide 0.457g of Ge0 2 and 0.286g of isopropoxide
- the mixture is left stirring and evaporating the ethanol, formed in the hydrolysis of TEOS, and 7g of water.Finally, 1.40g of HF (aq., 50%) are added.
- the resulting mixture is heated in coated autoclaves internally of PTFE at 150 ° C. After 5 days of heating the mixture is filtered and 19g of ITQ-16 zeolite are obtained per 100g of synthesis gel.
- the X-ray diffraction pattern is presented in Figure 8. Example 5 .
- This example illustrates the preparation of ITQ-16 containing Si and Ge, and using the TEA cation as the structure directing agent.
- tetraethylorthosilicate TEOS
- 39.26g of an aqueous solution of tetraethylammonium hydroxide (35%) and 1.5g of water 3.01 g of Ge0 2 are added .
- the mixture is left stirring and evaporating the ethanol formed in the hydrolysis of TEOS.
- 3.89g of HF aq., 48%) are added.
- the resulting mixture is heated in internally coated PTFE autoclaves at 140 ° C in an oven equipped with a rotation system (60 rpm). After 48h of heating, the mixture is filtered and 25g of ITQ-16 zeolite are obtained per 100g of synthesis gel.
- the X-ray diffraction pattern is presented in Figure 9.
- This example illustrates the preparation of ITQ-16 containing Si, Ge and Al, and using the TEA cation as the structure directing agent.
- TEOS tetraethylorthosilicate
- Example 7 This example illustrates the synthesis of ITQ-16 containing Si
- tetraethylorthosilicate TEOS
- 10J g of an aqueous solution of benzyl-DABCO 2J 0 "3 moles of benzyl-DABCO (OH) / g).
- benzyl-DABCO 2J 0 "3 moles of benzyl-DABCO (OH) / g).
- 0.245g of Ge0 2 , 0.0927g of boric acid and 1g of water The mixture is left under stirring and evaporating the ethanol, formed in the hydrolysis of TEOS.Finally, 0.75g of HF (aq., 50%) is added. The resulting mixture is heated in internally coated autoclaves of PTFE a
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Abstract
Description
Claims
Priority Applications (8)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AT01974352T ATE294138T1 (de) | 2000-10-11 | 2001-10-11 | Zeolith itq-16 |
DE60110456T DE60110456T2 (de) | 2000-10-11 | 2001-10-11 | Zeolith itq-16 |
JP2002534214A JP4227805B2 (ja) | 2000-10-11 | 2001-10-11 | ゼオライトitq−16 |
EP01974352A EP1338561B1 (en) | 2000-10-11 | 2001-10-11 | Zeolite itq-16 |
ES01974352T ES2241877T3 (es) | 2000-10-11 | 2001-10-11 | Zeolita itq-16. |
DK01974352T DK1338561T3 (da) | 2000-10-11 | 2001-10-11 | Zeolit ITQ-16 |
AU2001293885A AU2001293885A1 (en) | 2000-10-11 | 2001-10-11 | Zeolite itq-16 |
US10/412,624 US6916459B2 (en) | 2000-10-11 | 2003-04-11 | Zeolite ITQ-16 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
ES200002537A ES2186489B1 (es) | 2000-10-11 | 2000-10-11 | Zeolita itq-16. |
ESP200002537 | 2000-10-11 |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
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US10/412,624 Continuation US6916459B2 (en) | 2000-10-11 | 2003-04-11 | Zeolite ITQ-16 |
Publications (1)
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WO2002030821A1 true WO2002030821A1 (es) | 2002-04-18 |
Family
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PCT/ES2001/000387 WO2002030821A1 (es) | 2000-10-11 | 2001-10-11 | Zeolita itq-16 |
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US (1) | US6916459B2 (es) |
EP (1) | EP1338561B1 (es) |
JP (1) | JP4227805B2 (es) |
AT (1) | ATE294138T1 (es) |
AU (1) | AU2001293885A1 (es) |
DE (1) | DE60110456T2 (es) |
DK (1) | DK1338561T3 (es) |
ES (2) | ES2186489B1 (es) |
WO (1) | WO2002030821A1 (es) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
ES2192967A1 (es) * | 2001-11-20 | 2003-10-16 | Univ Valencia Politecnica | Proceso y catalizadores para la oxidacion de compuestos de azufre de las fracciones gasolina, keroseno y diesel |
ES2192969A1 (es) * | 2001-11-30 | 2003-10-16 | Univ Poletecnica De Valencia C | Proceso y catalizadores para la oxidacion selectiva de compuestos de acufre de las fracciones gasolina, queroseno y diesel. |
WO2014064318A1 (es) | 2012-10-25 | 2014-05-01 | Consejo Superior De Investigaciones Científicas (Csic) | Catalizador y proceso catalítico para la eterificación/reducción de furfuril derivados a tetrahidro-furfuril éteres |
Families Citing this family (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2850099B1 (fr) * | 2003-01-16 | 2005-03-04 | Inst Francais Du Petrole | Solide cristallise im-9 et son procede de preparation |
ES2246704B1 (es) * | 2004-05-28 | 2007-06-16 | Universidad Politecnica De Valencia | Zeolita itq-30. |
US7449168B2 (en) * | 2004-12-27 | 2008-11-11 | Saudi Basic Industries Corporation | Process for making a germanium-zeolite |
US7029650B1 (en) * | 2004-12-27 | 2006-04-18 | Saudi Basic Industries Corporation | Process for making a germanium-zeolite |
WO2007075382A1 (en) * | 2005-12-20 | 2007-07-05 | Exxonmobil Research And Engineering Company | Itq-26, new crystalline microporous material |
CA2584876A1 (en) * | 2007-02-02 | 2008-08-02 | Albemarle Netherlands Bv | A crystalline microporous material of zeolitic nature |
AU2009270971A1 (en) | 2008-07-16 | 2010-01-21 | Schering Corporation | Bicyclic Heterocycle Derivatives and use thereof as GPR119 modulators |
US7922997B2 (en) * | 2008-09-30 | 2011-04-12 | Uop Llc | UZM-35 aluminosilicate zeolite, method of preparation and processes using UZM-35 |
US8865121B2 (en) * | 2009-06-18 | 2014-10-21 | Basf Se | Organotemplate-free synthetic process for the production of a zeolitic material |
US10913053B2 (en) * | 2016-03-04 | 2021-02-09 | California Institute Of Technology | Germanosilicate compositions and methods of preparing the same |
CN105905921A (zh) * | 2016-06-29 | 2016-08-31 | 北京化工大学 | 一种itq-16分子筛的合成方法 |
CN110252281A (zh) * | 2018-11-21 | 2019-09-20 | 湖北工业大学 | 一种能降解染料废水的催化剂及其制备方法和应用 |
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USRE28341E (en) * | 1964-05-01 | 1975-02-18 | Marshall dann | |
US4826667A (en) * | 1986-01-29 | 1989-05-02 | Chevron Research Company | Zeolite SSZ-25 |
ES2137885B1 (es) * | 1997-12-19 | 2000-08-16 | Univ Valencia Politecnica | Zeolita itq-5. |
US6733742B1 (en) * | 2002-12-26 | 2004-05-11 | Chevron U.S.A. Inc. | Molecular sieve SSZ-63 composition of matter and synthesis thereof |
-
2000
- 2000-10-11 ES ES200002537A patent/ES2186489B1/es not_active Expired - Fee Related
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2001
- 2001-10-11 JP JP2002534214A patent/JP4227805B2/ja not_active Expired - Fee Related
- 2001-10-11 DE DE60110456T patent/DE60110456T2/de not_active Expired - Fee Related
- 2001-10-11 ES ES01974352T patent/ES2241877T3/es not_active Expired - Lifetime
- 2001-10-11 WO PCT/ES2001/000387 patent/WO2002030821A1/es active IP Right Grant
- 2001-10-11 EP EP01974352A patent/EP1338561B1/en not_active Expired - Lifetime
- 2001-10-11 AU AU2001293885A patent/AU2001293885A1/en not_active Abandoned
- 2001-10-11 AT AT01974352T patent/ATE294138T1/de not_active IP Right Cessation
- 2001-10-11 DK DK01974352T patent/DK1338561T3/da active
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EP0091049A1 (en) * | 1982-03-29 | 1983-10-12 | Union Carbide Corporation | Zeolite LZ-133 |
ES2133042A1 (es) * | 1996-03-14 | 1999-08-16 | Univ Valencia Politecnica | Sintesis de zeolita y zeotipos isomorfos a la zeolita beta. |
WO1998029338A1 (en) * | 1996-12-31 | 1998-07-09 | Chevron U.S.A. Inc. | Zeolite ssz-45 |
Non-Patent Citations (1)
Title |
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CORMA A. ET AL.: "ITQ-16: A new zeolite family of the beta group with different proportions of polymorphs A,B and C", CHEM. COMMUN., vol. 18, 14 September 2001 (2001-09-14), pages 1720 - 1721, ISSN 1359-7345, XP002953329 * |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
ES2192967A1 (es) * | 2001-11-20 | 2003-10-16 | Univ Valencia Politecnica | Proceso y catalizadores para la oxidacion de compuestos de azufre de las fracciones gasolina, keroseno y diesel |
ES2192969A1 (es) * | 2001-11-30 | 2003-10-16 | Univ Poletecnica De Valencia C | Proceso y catalizadores para la oxidacion selectiva de compuestos de acufre de las fracciones gasolina, queroseno y diesel. |
WO2014064318A1 (es) | 2012-10-25 | 2014-05-01 | Consejo Superior De Investigaciones Científicas (Csic) | Catalizador y proceso catalítico para la eterificación/reducción de furfuril derivados a tetrahidro-furfuril éteres |
Also Published As
Publication number | Publication date |
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DK1338561T3 (da) | 2005-08-08 |
DE60110456T2 (de) | 2006-01-26 |
ES2241877T3 (es) | 2005-11-01 |
AU2001293885A1 (en) | 2002-04-22 |
EP1338561B1 (en) | 2005-04-27 |
JP2004511406A (ja) | 2004-04-15 |
DE60110456D1 (de) | 2005-06-02 |
ES2186489A1 (es) | 2003-05-01 |
US6916459B2 (en) | 2005-07-12 |
ES2186489B1 (es) | 2004-01-16 |
EP1338561A1 (en) | 2003-08-27 |
ATE294138T1 (de) | 2005-05-15 |
JP4227805B2 (ja) | 2009-02-18 |
US20040042958A1 (en) | 2004-03-04 |
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