WO2013156638A1 - Material itq-49, su procedimiento de obtención y su uso - Google Patents
Material itq-49, su procedimiento de obtención y su uso Download PDFInfo
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- WO2013156638A1 WO2013156638A1 PCT/ES2013/000094 ES2013000094W WO2013156638A1 WO 2013156638 A1 WO2013156638 A1 WO 2013156638A1 ES 2013000094 W ES2013000094 W ES 2013000094W WO 2013156638 A1 WO2013156638 A1 WO 2013156638A1
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- microporous crystalline
- crystalline material
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- 239000000463 material Substances 0.000 title claims abstract description 79
- 238000000034 method Methods 0.000 title claims abstract description 46
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 4
- 239000000203 mixture Substances 0.000 claims abstract description 78
- 239000002178 crystalline material Substances 0.000 claims abstract description 33
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 11
- 229910052742 iron Inorganic materials 0.000 claims abstract description 11
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 10
- 229910052796 boron Inorganic materials 0.000 claims abstract description 10
- 229910052733 gallium Inorganic materials 0.000 claims abstract description 10
- 229910052718 tin Inorganic materials 0.000 claims abstract description 10
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 10
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 10
- 229910052738 indium Inorganic materials 0.000 claims abstract description 9
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 7
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims description 24
- 239000000126 substance Substances 0.000 claims description 21
- 238000003786 synthesis reaction Methods 0.000 claims description 18
- 239000007787 solid Substances 0.000 claims description 16
- 239000003054 catalyst Substances 0.000 claims description 15
- 150000001768 cations Chemical class 0.000 claims description 15
- 239000003795 chemical substances by application Substances 0.000 claims description 14
- 238000011282 treatment Methods 0.000 claims description 14
- 125000004429 atom Chemical group 0.000 claims description 12
- 238000000926 separation method Methods 0.000 claims description 11
- 230000008030 elimination Effects 0.000 claims description 10
- 238000003379 elimination reaction Methods 0.000 claims description 10
- 150000003839 salts Chemical group 0.000 claims description 10
- 238000002441 X-ray diffraction Methods 0.000 claims description 9
- 238000001354 calcination Methods 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- ZYKBLOGDCZGSOS-UHFFFAOYSA-L [OH-].[OH-].CC(C)(C)[P+](CCCC[P+](C(C)(C)C)(C(C)(C)C)C(C)(C)C)(C(C)(C)C)C(C)(C)C Chemical group [OH-].[OH-].CC(C)(C)[P+](CCCC[P+](C(C)(C)C)(C(C)(C)C)C(C)(C)C)(C(C)(C)C)C(C)(C)C ZYKBLOGDCZGSOS-UHFFFAOYSA-L 0.000 claims description 8
- 230000001476 alcoholic effect Effects 0.000 claims description 8
- 239000003463 adsorbent Substances 0.000 claims description 7
- 230000015572 biosynthetic process Effects 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 239000013078 crystal Substances 0.000 claims description 7
- 229930195733 hydrocarbon Natural products 0.000 claims description 7
- 150000002430 hydrocarbons Chemical class 0.000 claims description 7
- -1 fluoride ions Chemical class 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- 239000004215 Carbon black (E152) Substances 0.000 claims description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 4
- 150000001336 alkenes Chemical class 0.000 claims description 4
- 239000003638 chemical reducing agent Substances 0.000 claims description 4
- 150000001875 compounds Chemical group 0.000 claims description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 4
- 238000011084 recovery Methods 0.000 claims description 4
- 238000005119 centrifugation Methods 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- 230000004913 activation Effects 0.000 claims description 2
- 150000001298 alcohols Chemical class 0.000 claims description 2
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 2
- 239000001294 propane Substances 0.000 claims description 2
- 239000000356 contaminant Substances 0.000 claims 1
- 239000010457 zeolite Substances 0.000 description 17
- 229910021536 Zeolite Inorganic materials 0.000 description 14
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 14
- 239000000243 solution Substances 0.000 description 13
- 238000010586 diagram Methods 0.000 description 11
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 9
- 239000011651 chromium Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- 238000002425 crystallisation Methods 0.000 description 6
- 230000008025 crystallization Effects 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 238000003991 Rietveld refinement Methods 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 239000004809 Teflon Substances 0.000 description 2
- 229920006362 Teflon® Polymers 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 238000010348 incorporation Methods 0.000 description 2
- 239000010805 inorganic waste Substances 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 150000002892 organic cations Chemical class 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 238000007669 thermal treatment Methods 0.000 description 2
- BWHDROKFUHTORW-UHFFFAOYSA-N tritert-butylphosphane Chemical compound CC(C)(C)P(C(C)(C)C)C(C)(C)C BWHDROKFUHTORW-UHFFFAOYSA-N 0.000 description 2
- ROUYUBHVBIKMQO-UHFFFAOYSA-N 1,4-diiodobutane Chemical compound ICCCCI ROUYUBHVBIKMQO-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000003957 anion exchange resin Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000002447 crystallographic data Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical class 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
-
- 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
- B01J29/047—Germanosilicates; Aluminogermanosilicates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
- B01D53/04—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with stationary adsorbents
- B01D53/0407—Constructional details of adsorbing systems
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
- B01D53/8628—Processes characterised by a specific catalyst
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3078—Thermal treatment, e.g. calcining or pyrolizing
-
- 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
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
- C01B37/005—Silicates, i.e. so-called metallosilicalites or metallozeosilites
-
- 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
- C01B39/54—Phosphates, e.g. APO or SAPO compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
- C07C1/22—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms by reduction
-
- 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
- C10G73/00—Recovery or refining of mineral waxes, e.g. montan wax
- C10G73/02—Recovery of petroleum waxes from hydrocarbon oils; Dewaxing of hydrocarbon oils
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
- B01D2253/10—Inorganic adsorbents
- B01D2253/106—Silica or silicates
- B01D2253/108—Zeolites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/50—Zeolites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
- B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
- B01D53/9404—Removing only nitrogen compounds
- B01D53/9409—Nitrogen oxides
- B01D53/9413—Processes characterised by a specific catalyst
- B01D53/9418—Processes characterised by a specific catalyst for removing nitrogen oxides by selective catalytic reduction [SCR] using a reducing agent in a lean exhaust gas
Definitions
- Zeolites are porous crystalline aluminosilicates that have found important applications as catalysts, adsorbents and ion exchangers. These zeolitic materials have well-defined structures that form channels and cavities in their interior of uniform size and shape that allow the adsorption of certain molecules, while preventing the passage into the glass of other molecules of size too large to diffuse through pores This characteristic gives these materials molecular sieve properties. These molecular sieves may include in the network, in addition to Si, other elements of the MIA group of the periodic system, all of them tetrahedrally coordinated.
- the negative charge generated by the elements of the NIA group tetrahedrally coordinated in network positions is compensated by the presence in the cation crystal, such as alkaline or alkaline earth cations.
- cation crystal such as alkaline or alkaline earth cations.
- These cations can be totally or partially exchanged for other types of cations by ion exchange techniques, thus being able to vary the properties of a given silicate by selecting the desired cations.
- zeolites have been synthesized in the presence of an organic molecule that acts as a structure directing agent.
- Organic molecules that act as structure directing agents (ADE) generally contain nitrogen in their composition, and can give rise to stable organic cations in the reaction medium.
- zeolites containing channel systems with different pore openings are especially desirable since they provide selectivities in catalytic processes that cannot be obtained with materials with channels with identical openings in all of them. That is why, an important scientific activity has been developed in this regard. Description of the invention
- a synthetic microporous crystalline material called ITQ-49 is described.
- the structure of this material has a microporous network consisting of channels with openings formed by 7 and 8 T0 4 tetrahedra that intersect each other giving rise to non-spherical cavities, which are accessed through four windows formed by 7 tetrahedra and others two of 8 tetrahedra, with a narrowing formed by 10 tetrahedra, these cavities being accessible to molecules of interest in catalysis, in adsorption or separation processes.
- the structure of the ITQ-49 zeolite can be described by its unit cell, which is the smallest structural unit that contains all the structural elements of this material and whose projections along the crystallographic axes are shown in Figures 1 to 3.
- Table 1 shows the list of atomic positions of all atoms in tetrahedral coordination in a unit cell. All these atoms are connected to each other through bridge oxygen that bind contiguous tetrahedral atoms two to two.
- each unit cell contains 92 atoms in tetrahedral coordination, called T1, T2, T3, T4 through T92, other than oxygen, which are located in the crystallographic positions with Cartesian atomic coordinates x, y and z shown in Table 1.
- Each of the T atoms in Table 1 is surrounded by four oxygen atoms as first neighbors and four other T atoms as second neighbors, so that the T atoms are connected two by two through bridge oxygen forming TOT bonds .
- the presence of cations or the different nature of atoms T can modify the values presented in Table 1, so each crystallographic coordinate can be modified up to 1 A of the value given in Table 1.
- the ITQ-49 zeolite has in its uncalcined form an X-ray diffraction diagram whose most important diffraction peaks are given in Table 2, and in Table 3 for its calcined form.
- the diffraction data listed for these samples as single or single lines may be formed by multiple overlaps or overlapping reflections that, under certain conditions, such as differences in chemical composition, may appear as partially or resolved lines. resolved.
- changes in the chemical composition can cause variations in the parameters of the unit cell and / or changes in the symmetry of the crystal, without a change in the structure.
- modifications, which also include changes in relative intensities may also be due to differences in the type and amount of compensation cations, network composition, crystal size and shape thereof, preferred orientation or the type of thermal or hydrothermal treatments suffered.
- the present invention relates to a microporous crystalline material called ITQ-49, which may have a chemical composition: x X 2 0 3 : y Y0 2 : z Z0 2
- X is a trivalent element selected from Al, B, Fe, In, Ga, Cr, or mixtures thereof;
- Y is a tetravalent element selected from Ti, Sn, Zr, V or mixtures thereof, preferably from Ti, Sn, Zr, or mixtures thereof;
- Z is a tetravalent element selected from Si, Ge or mixtures thereof, preferably Si;
- the value of (y + z) / x is between 9 and infinity, preferably between 20 and infinity; the value of z / y is between 10 and infinity, preferably between 15 and infinity.
- the value of x can be equal to zero, so it can have a chemical composition:
- the value of y is equal to zero, so it can have a chemical composition: x X 2 0 3 : z Z0 2
- the value of z / x is between 9 and infinity, and more preferably between 20 and infinity.
- the material of the present invention has a chemical composition: t P 2 0 5 : x X 2 0 3 : y Y0 2 : z Z0 2
- X is a trivalent element selected from Al, B, Fe, In, Ga, Cr, or mixtures thereof;
- Y is a tetravalent element selected from Ti, Sn, Zr, V or mixtures thereof, preferably from Ti, Sn, Zr, or mixtures thereof;
- Z is a tetravalent element selected from Si, Ge or mixtures thereof, preferably Si;
- P refers to phosphorus from the structure managing agent; the value of (y + z) / x is between 9 and infinity, preferably between 20 and infinity; the value of z / y is between 10 and infinity, preferably between 15 and infinity.
- t / (x + y + z) can be between 1 and 0. It is clear from the values given that the ITQ-49 crystalline material can be synthesized in the absence of added trivalent elements.
- the X-ray diffractogram of the zeolite in its calcined form has the diffraction peaks listed in Table 3.
- x may be 0 and the ITQ-49 material may have a chemical composition: t P 2 0 5 : y Y0 2 : z Z0 2
- the ITQ-49 material can have a chemical composition: t P 2 0 5 : x X 2 0 3 : z Z0 2
- the value of z / x is between 9 and infinity, preferably between 20 and infinity.
- t / (x + z) can be between 1 and 0.
- the calcined crystalline material ITQ-49 can be subjected to one or several chemical extraction processes or washing in aqueous, alcoholic, organic or mixture thereof to eliminate inorganic residues P 2 0 5 from the elimination of the structure directing agent.
- This extraction or washing treatment can be performed in acid, neutral or alkaline medium.
- the material of the present invention has a chemical composition: n R: x X 2 0 3 : z ZO z : y Y0 2
- X is a trivalent element selected from Al, B, Fe, In, Ga, Cr, or mixtures thereof;
- Y is a tetravalent element selected from Ti, Sn, Zr, V or mixtures thereof, preferably from Ti, Sn, Zr, or mixtures thereof;
- Z is a tetravalent element selected from Si, Ge or mixtures thereof, preferably Si;
- the value of z / y is between 10 and infinity, preferably between 15 and infinity.
- R is a structure directing agent, preferably said R contains P, more preferably R is a salt of an alkylphosphonium cation, and more preferably is selected from 1,4-butanediyl bis (tritertbutyl phosphonium) hydroxide or one of its salts;
- n / (x + y + z) is between 1 and 0.001.
- n R y Y0 2 : z Z0 2
- n / (y + z) is between 1 and 0.001.
- the ITQ-49 material can have a chemical composition n R: x X 2 0 3 : z Z0 2
- the value of z / x is between 9 and infinity, preferably between 20 and infinity. . .
- n / (x + z) is between 1 and 0.001.
- the calcined and / or calcined and washed ITQ-49 crystalline material may be subjected to one or more post-synthesis processes of incorporation or exchange of trivalent elements using solutions containing trivalent elements X that may be selected from Al, Ga, B, Cr , Fe, In and mixtures thereof in aqueous, alcoholic, organic or mixture thereof.
- trivalent elements X may be selected from Al, Ga, B, Cr , Fe, In and mixtures thereof in aqueous, alcoholic, organic or mixture thereof.
- inorganic waste P 2 0 5 from the elimination of the structure directing agent and / or incorporating the trivalent elements of the solutions can be eliminated.
- This treatment of incorporation of trivalent metals and / or washing can be carried out in acid, neutral or alkaline medium.
- the crystalline material with trivalent metals incorporated by post-synthesis treatments has a molar composition in its anhydrous state that is given by the equation: x X 2 0 3 : y Y0 2 : z Z0 2 in which X is a trivalent element such as Al, B, Fe, In, Ga, Cr or mixtures thereof, Y is a tetravalent element such as Ti, Sn, Zr, V or mixtures thereof, and Z corresponds to an element selected from Si or Ge, or mixtures thereof.
- the value of (y + z) / x is at least 9, and can be between 20 and infinity and the value z / y is at least 10.
- the ITQ-49 crystalline material is can synthesize in the absence of added trivalent elements.
- the X-ray diffractogram of the zeolite after post-synthesis treatment to incorporate trivalent elements in its structure presents the characteristic diffraction peaks of the ITQ-49 material
- the organic component present in the ITQ-49 material as synthesized can be removed, for example by extraction and / or by heat treatment by heating at a temperature above 200 ° C for a period of time that can be between 2 minutes and 25 hours.
- the compensation cations in the material in its uncalcined form, or after thermal treatment, can be exchanged in the case of being present, by other cations such as metal ions, H + and H + precursors such as NH + 4 .
- cations that can be introduced by ion exchange those that can have a positive role in the activity of the material as a catalyst are preferred, and more specifically cations such as H + , rare earth cations, and group VIII metals are preferred, as well as from the NA, MIA, IVA, Va, IB, IIB, IIIB, IVB, VB, VIIB group of the periodic table of the elements.
- the crystalline material of the present invention can be intimately combined with hydrogenating-dehydrogenating components such as platinum, palladium, nickel, rhenium, cobalt, tungsten, molybdenum, vanadium, chromium, manganese, iron and combinations thereof.
- hydrogenating-dehydrogenating components such as platinum, palladium, nickel, rhenium, cobalt, tungsten, molybdenum, vanadium, chromium, manganese, iron and combinations thereof.
- the introduction of these elements can be carried out in the crystallization stage, by exchange (if applicable), and / or by impregnation or by physical mixing.
- These elements can be introduced in their cationic form and / or from salts or other compounds that by decomposition generate the metal component or oxide in its appropriate catalytic form.
- the present invention relates to the process for obtaining the ITQ-49 material described above.
- the process for preparing the ITQ-49 material may comprise at least a first step of preparing a mixture containing H 2 0, a source of fluoride ions, an oxide or other source of the tetravalent material Z and an agent structure director (R), a source of the trivalent element X, an oxide or other source of the tetravalent material Y, where the synthesis mixture has a molar composition of oxides in the following ranges:
- F7 (Y0 2 + Z0 2 ) 0.01-3.0, preferably between 0.05-1.
- Si0 2 / Ge0 2 greater than 1, preferably greater than 5.
- Z is a mixture of Si and Ge.
- the structure directing agent R may be a compound containing P, more preferably R is a salt of an alkylphosphonium cation, and more preferably is selected from 1,4-butanediyl-bis (tritertbutyl phosphonium) hydroxide or One of its salts.
- This material can be prepared according to a particular embodiment, from a reaction mixture containing H 2 0, a source of fluoride anions, optionally an oxide or a source of the trivalent element X, such as Al and / or B, a oxide or a source of the tetravalent element or elements Y, such as Si, a source of Ge, such as Ge0 2 and an organic structure directing agent (R) generally an organic cation, which may contain atoms other than C, H and N in its composition.
- Composite structure directing agents of the alkylphosphonium type can be used, and more preferably it is 1,4-butanediyl bis (tritertbutyl phosphonium) hydroxide or one of its salts.
- composition of the reaction mixture has the following composition in terms of molar ratios of oxides: Reagents Useful Preferred (Y0 2 + Z0 2 ) / X 2 0 3 greater than 2 greater than 5 H 2 0 / (Y0 2 + Z0 2 ) 1-50 2-30
- Crystallization of the material can be carried out under stirring, in autoclaves at a temperature between 80 and 200 ° C, at times sufficient to achieve crystallization, for example "between 12 hours and 30 days.
- the crystals of the material are separated from the mother liquors, and recovered. It should be taken into account that the components of the synthesis mixture can come from different sources, and depending on these, crystallization times and conditions may vary. In order to facilitate synthesis, crystals of the same material or of this calcined material can be added as seeds, in amounts of up to 15% by weight with respect to the total oxides, to the synthesis mixture. These can be added before or during crystallization.
- the procedure for preparing the ITQ-49 material may comprise a step of calcining the crystalline material obtained, calcination that can be carried out under vacuum, in air, nitrogen, hydrogen, argon, helium or any other gas already a temperature greater than 200 ° C and less than 1200 ° C, preferably between 200 and 1000 ° C for a time that may be between 2 minutes and 25 hours.
- the ITQ-49 material after calcination has a system of pores free of organic matter, whose X-ray diffractogram presents the peaks listed in Table 2. During this calcination they can remain inside the channels or on the surface of inorganic waste material from the structure director.
- washing process or processes may comprise at least the following stage:
- a solution is an aqueous, alcoholic, organic solution or mixture of both.
- the washing process is carried out at a temperature preferably between 0 ° C and 200 ° C.
- the diffraction diagram of the resulting material presents the characteristic diffraction peaks of this ITQ-49 material.
- the calcined ITQ-49 material or the calcined and washed ITQ-49 material may be subjected to one or more post-synthesis treatments.
- Such treatments may preferably consist of treating the ITQ-49 with aqueous, alcoholic, organic solutions or mixtures thereof containing trivalent elements X, preferably selected from Al, Ga, B, Cr, Fe In, and mixtures thereof with the in order to incorporate them into the zeolitic network.
- This post-synthesis treatment can be carried out at alkaline, acidic or neutral pHs at temperatures preferably between 0 and 200 ° C for a preferred time between 1 hour to 15 days.
- the resulting material has the characteristic diffraction peaks of this ITQ-49 material.
- the present invention relates to a method of obtaining a material that it possesses, in addition a post-synthesis treatment comprises at least:
- the solution is selected from an aqueous, alcoholic, organic solution or mixture of both.
- said post-synthesis treatment is carried out at a preferred temperature between 0 and 200 ° C.
- the ITQ-49 material can be used as a catalyst in processes of conversion of hydrocarbons, alcohols to others of greater added value, in the elimination of nitrogen compounds from gaseous or liquid streams as well as in separation processes.
- the ITQ-49 material can be used as a catalyst in hydrocarbon conversion processes, in hydrocarbon dewaxing processes, in alcohol conversion processes, in alcohol conversion processes with less than four carbons in olefins, in processes of elimination of nitrogen pollutants in gaseous or liquid streams, in processes of elimination of nitrogen oxides from gaseous streams, in processes of elimination of nitrogen oxides from gaseous streams in the presence of reducing gases, in processes of nitrogen oxides removal of gaseous streams in the presence of ammonia as a reducer, in processes of elimination of nitrogen oxides from gaseous streams in the presence of hydrocarbons as reductants and combinations thereof.
- the ITQ-49 material can be used as an adsorbent.
- it can be used as a selective adsorbent in processes of separation of C0 2 and methane, in processes of separation of propane and propene, in processes of separation of linear olefins of fraction C4 and combinations thereof.
- Figure 1. View of the structure of the ITQ-49 zeolite along the a axis (oxygen omitted for clarity.
- Figure 2. View of the structure of the ITQ-49 zeolite along the b-axis (oxygens omitted for clarity).
- Figure 3 View of the structure of the ITQ-49 zeolite along the c axis (oxygens omitted for clarity).
- Figure 4. Rietveld tuning of the X-ray diffraction diagram of an ITQ-49 sample calcined at 923K, measured using the copper's alpha K radiation.
- the dots show the experimental diagram.
- the line along them shows the calculated diagram for the proposed structure. The difference between the two is shown below.
- the vertical lines under the diagrams indicate the positions of the Bragg reflections.
- the resulting solid presents an X-ray diffraction diagram that contains the characteristic peaks of the ITQ-49 material.
- Example 3- Preparation of zeolite ITQ-49 in its calcined form.
- a solid prepared as described in Example 2 is introduced into a muffle furnace and calcined in air at 700 ° C for 5 hours to decompose the retained organic matter inside.
- the resulting solid presents an X-ray diffraction diagram containing the characteristic peaks of the calcined ITQ-49 material.
- the gel obtained is homogenized and transferred to Teflon coated steel autoclaves and placed in an oven with stirring at 125 ° C for 18 days.
- Example 5- Refinement of the ITQ-49 structure according to the Rietveld method.
- the structure of a sample of the ITQ-49 zeolite can be satisfactorily refined using the Rietveld method applied to an X-ray diffraction diagram obtained from a sample prepared as described in example 3.
- the fit between the experimental diagram and the simulated is shown in Figure 4.
- the spatial group, refinement parameters and atomic positions of the ITQ-49 zeolite are shown in Table 4.
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Abstract
Description
Claims
Priority Applications (11)
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RU2014141931A RU2667296C2 (ru) | 2012-04-18 | 2013-04-16 | Материал itq-49, способ его получения и его применение |
KR1020147029223A KR101951217B1 (ko) | 2012-04-18 | 2013-04-16 | Itq-49 재료, 그 제조 방법 및 용도 |
JP2015506267A JP6194352B2 (ja) | 2012-04-18 | 2013-04-16 | Itq−49物質、その製造方法およびその使用 |
BR112014026154-7A BR112014026154B1 (pt) | 2012-04-18 | 2013-04-16 | material itq-49, método para a produção do mesmo e uso do mesmo |
CN201380026350.9A CN104487385B (zh) | 2012-04-18 | 2013-04-16 | Itq‑49材料、其生产方法及其用途 |
CA2870579A CA2870579C (en) | 2012-04-18 | 2013-04-16 | Itq-49 zeolitic material, method for the production thereof and use of same |
EP13778919.4A EP2840064A4 (en) | 2012-04-18 | 2013-04-16 | ITQ-49 MATERIAL, METHOD FOR THE PRODUCTION THEREOF AND USE THEREOF |
SG11201406708XA SG11201406708XA (en) | 2012-04-18 | 2013-04-16 | Itq-49 material, method for the production thereof and use of same |
ZA2014/07558A ZA201407558B (en) | 2012-04-18 | 2014-10-17 | Itq-49 material, method for the production thereof and use of same |
US14/516,743 US9764311B2 (en) | 2012-04-18 | 2014-10-17 | ITQ-49 material, method for the production thereof and use of same |
US15/678,636 US10427140B2 (en) | 2012-04-18 | 2017-08-16 | ITQ-49 material, method for the production thereof and use of same |
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ES201230579A ES2430404B1 (es) | 2012-04-18 | 2012-04-18 | Material ITQ-49, su procedimiento de obtención y su uso |
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EP (1) | EP2840064A4 (es) |
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CN (1) | CN104487385B (es) |
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WO2015196018A1 (en) * | 2014-06-20 | 2015-12-23 | Higher Council Of Scientific Research (Csic) | Material itq-55, method for preparation and use |
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ES2430404B1 (es) | 2012-04-18 | 2014-09-29 | Consejo Superior De Investigaciones Científicas (Csic) | Material ITQ-49, su procedimiento de obtención y su uso |
SG11202007112SA (en) * | 2018-02-20 | 2020-09-29 | Exxonmobil Res & Eng Co | Emm-37 materials and processes and uses thereof |
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AU2015276976B2 (en) * | 2014-06-20 | 2017-07-13 | Exxonmobil Research And Engineering Company | Separation and storage of fluids using ITQ-55 |
AU2015276970B2 (en) * | 2014-06-20 | 2017-07-13 | Exxonmobil Research And Engineering Company | Separation and storage of fluids using ITQ-55 |
AU2015276953B2 (en) * | 2014-06-20 | 2017-07-13 | Exxonmobil Research And Engineering Company | Separation and storage of fluids using ITQ-55 |
JP2017519629A (ja) * | 2014-06-20 | 2017-07-20 | エクソンモービル リサーチ アンド エンジニアリング カンパニーExxon Research And Engineering Company | Itq−55を使用する流体の分離および貯蔵 |
JP2017519628A (ja) * | 2014-06-20 | 2017-07-20 | エクソンモービル リサーチ アンド エンジニアリング カンパニーExxon Research And Engineering Company | Itq−55を使用する流体の分離および貯蔵 |
JP2017521243A (ja) * | 2014-06-20 | 2017-08-03 | エクソンモービル リサーチ アンド エンジニアリング カンパニーExxon Research And Engineering Company | Itq−55を使用する流体の分離および貯蔵 |
US9738539B2 (en) | 2014-06-20 | 2017-08-22 | Exxonmobil Research And Engineering Company | Separation and storage of fluids using ITQ-55 |
JP2017524637A (ja) * | 2014-06-20 | 2017-08-31 | コンセホ・スペリオール・デ・インベスティガシオネス・シエンティフィカス(シーエスアイシー)Consejo Superior De Investigaciones Cientificas | 材料itq−55、調製方法および使用 |
US9856145B2 (en) | 2014-06-20 | 2018-01-02 | Exxonmobil Research And Engineering Company | Material ITQ-55, method for preparation and use |
CN106458617B (zh) * | 2014-06-20 | 2018-09-14 | 埃克森美孚研究工程公司 | 使用itq-55分离流体的方法 |
RU2672424C2 (ru) * | 2014-06-20 | 2018-11-14 | ЭкссонМобил Рисерч энд Энджиниринг Компани | Разделение и хранение текучих сред с использованием itq-55 |
RU2674121C2 (ru) * | 2014-06-20 | 2018-12-04 | ЭкссонМобил Рисерч энд Энджиниринг Компани | Разделение и хранение текучих сред с использованием itq-55 |
RU2675874C2 (ru) * | 2014-06-20 | 2018-12-25 | ЭкссонМобил Рисерч энд Энджиниринг Компани | Разделение и хранение текучих сред с использованием itq-55 |
RU2682600C2 (ru) * | 2014-06-20 | 2019-03-19 | Хайер Каунсил Оф Сайентифик Рисерч (Ксис) | Материал ITQ-55, способ получения и применение |
CN106660011B (zh) * | 2014-06-20 | 2019-09-17 | 科学研究高等委员会 | 材料itq-55、制备方法及用途 |
KR102338470B1 (ko) | 2014-06-20 | 2021-12-15 | 엑손모빌 리서치 앤드 엔지니어링 컴퍼니 | Itq-55를 사용한 유체 분리 및 저장 |
KR102338477B1 (ko) | 2014-06-20 | 2021-12-15 | 엑손모빌 리서치 앤드 엔지니어링 컴퍼니 | Itq-55를 사용한 유체 분리 및 저장 |
KR102360244B1 (ko) | 2014-06-20 | 2022-02-09 | 엑손모빌 리서치 앤드 엔지니어링 컴퍼니 | Itq-55를 사용한 유체 분리 및 저장 |
KR102382437B1 (ko) * | 2014-06-20 | 2022-04-04 | 하이어 카운슬 오브 사이언티픽 리서치 (씨에스아이씨) | Itq-55 물질, 제조 방법 및 용도 |
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Publication number | Publication date |
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CN104487385A (zh) | 2015-04-01 |
KR20150016215A (ko) | 2015-02-11 |
EP2840064A4 (en) | 2016-02-10 |
US10427140B2 (en) | 2019-10-01 |
WO2013156638A8 (es) | 2014-12-18 |
CN104487385B (zh) | 2017-11-14 |
EP2840064A1 (en) | 2015-02-25 |
US9764311B2 (en) | 2017-09-19 |
SG11201406708XA (en) | 2015-04-29 |
CA2870579A1 (en) | 2013-10-24 |
ES2430404B1 (es) | 2014-09-29 |
ZA201407558B (en) | 2016-01-27 |
BR112014026154A2 (pt) | 2017-06-27 |
RU2014141931A (ru) | 2016-05-10 |
RU2667296C2 (ru) | 2018-09-18 |
JP6194352B2 (ja) | 2017-09-06 |
US20150038756A1 (en) | 2015-02-05 |
CA2870579C (en) | 2019-09-03 |
JP2015520715A (ja) | 2015-07-23 |
ES2430404A1 (es) | 2013-11-20 |
BR112014026154B1 (pt) | 2021-01-05 |
US20170368537A1 (en) | 2017-12-28 |
KR101951217B1 (ko) | 2019-02-22 |
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