JP5150485B2 - 高アルミニウム含有量を有するメソ構造化材料 - Google Patents
高アルミニウム含有量を有するメソ構造化材料 Download PDFInfo
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- JP5150485B2 JP5150485B2 JP2008514139A JP2008514139A JP5150485B2 JP 5150485 B2 JP5150485 B2 JP 5150485B2 JP 2008514139 A JP2008514139 A JP 2008514139A JP 2008514139 A JP2008514139 A JP 2008514139A JP 5150485 B2 JP5150485 B2 JP 5150485B2
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- mesostructured
- zeolite
- material according
- solution
- matrix
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- 239000000463 material Substances 0.000 title claims description 200
- 229910052782 aluminium Inorganic materials 0.000 title claims description 46
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims description 44
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 123
- 239000010457 zeolite Substances 0.000 claims description 97
- 229910021536 Zeolite Inorganic materials 0.000 claims description 88
- 239000011159 matrix material Substances 0.000 claims description 77
- 239000002159 nanocrystal Substances 0.000 claims description 70
- 238000002360 preparation method Methods 0.000 claims description 68
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 47
- 238000000034 method Methods 0.000 claims description 45
- 239000002243 precursor Substances 0.000 claims description 45
- 239000004094 surface-active agent Substances 0.000 claims description 37
- 239000011148 porous material Substances 0.000 claims description 31
- 239000012798 spherical particle Substances 0.000 claims description 28
- 239000003795 chemical substances by application Substances 0.000 claims description 27
- 239000000377 silicon dioxide Substances 0.000 claims description 20
- 239000000443 aerosol Substances 0.000 claims description 19
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 15
- 239000013078 crystal Substances 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 14
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- 239000010703 silicon Substances 0.000 claims description 5
- 230000002051 biphasic effect Effects 0.000 claims description 4
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- 239000003463 adsorbent Substances 0.000 claims description 3
- 230000002194 synthesizing effect Effects 0.000 claims description 3
- 238000005507 spraying Methods 0.000 claims description 2
- 239000000243 solution Substances 0.000 description 51
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 40
- 229910000323 aluminium silicate Inorganic materials 0.000 description 33
- 239000002245 particle Substances 0.000 description 29
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 23
- 229910052757 nitrogen Inorganic materials 0.000 description 20
- 238000004458 analytical method Methods 0.000 description 19
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- 229920000233 poly(alkylene oxides) Polymers 0.000 description 12
- 238000002441 X-ray diffraction Methods 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 238000009826 distribution Methods 0.000 description 10
- 239000012071 phase Substances 0.000 description 10
- 229920001577 copolymer Polymers 0.000 description 9
- 238000004448 titration Methods 0.000 description 9
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- 238000004626 scanning electron microscopy Methods 0.000 description 8
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- 238000001179 sorption measurement Methods 0.000 description 8
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 229910004298 SiO 2 Inorganic materials 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000002152 aqueous-organic solution Substances 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000003153 chemical reaction reagent Substances 0.000 description 6
- 238000011161 development Methods 0.000 description 6
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- 238000001704 evaporation Methods 0.000 description 6
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- 238000001338 self-assembly Methods 0.000 description 6
- 238000001308 synthesis method Methods 0.000 description 6
- 238000004627 transmission electron microscopy Methods 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 239000012159 carrier gas Substances 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 230000007935 neutral effect Effects 0.000 description 5
- 239000002736 nonionic surfactant Substances 0.000 description 5
- 238000011017 operating method Methods 0.000 description 5
- -1 aluminum acetylacetone Chemical compound 0.000 description 4
- 229910052796 boron Inorganic materials 0.000 description 4
- 230000000875 corresponding effect Effects 0.000 description 4
- 230000008021 deposition Effects 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 239000012013 faujasite Substances 0.000 description 4
- 230000002209 hydrophobic effect Effects 0.000 description 4
- 239000002563 ionic surfactant Substances 0.000 description 4
- 150000002894 organic compounds Chemical class 0.000 description 4
- 229920001983 poloxamer Polymers 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 3
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000003618 dip coating Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910001657 ferrierite group Inorganic materials 0.000 description 3
- 229910052733 gallium Inorganic materials 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000010335 hydrothermal treatment Methods 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000012229 microporous material Substances 0.000 description 3
- 238000012544 monitoring process Methods 0.000 description 3
- 229910052680 mordenite Inorganic materials 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 230000008520 organization Effects 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- 239000002798 polar solvent Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 238000001988 small-angle X-ray diffraction Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229920000428 triblock copolymer Polymers 0.000 description 3
- 238000012800 visualization Methods 0.000 description 3
- MWRWFPQBGSZWNV-UHFFFAOYSA-N Dinitrosopentamethylenetetramine Chemical compound C1N2CN(N=O)CN1CN(N=O)C2 MWRWFPQBGSZWNV-UHFFFAOYSA-N 0.000 description 2
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000003929 acidic solution Substances 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000011805 ball Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 239000003791 organic solvent mixture Substances 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 241000446313 Lamella Species 0.000 description 1
- 102220500397 Neutral and basic amino acid transport protein rBAT_M41T_mutation Human genes 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 108010039918 Polylysine Proteins 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical group CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 239000004113 Sepiolite Substances 0.000 description 1
- 229910003902 SiCl 4 Inorganic materials 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229920002359 Tetronic® Polymers 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 229920000615 alginic acid Polymers 0.000 description 1
- 235000010443 alginic acid Nutrition 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 229960000892 attapulgite Drugs 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
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- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 239000000412 dendrimer Substances 0.000 description 1
- 229920000736 dendritic polymer Polymers 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 125000005594 diketone group Chemical group 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 230000009881 electrostatic interaction Effects 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000005984 hydrogenation reaction 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
- 238000010348 incorporation Methods 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 238000000696 nitrogen adsorption--desorption isotherm Methods 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052625 palygorskite Inorganic materials 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 238000001637 plasma atomic emission spectroscopy Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000656 polylysine Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052624 sepiolite Inorganic materials 0.000 description 1
- 235000019355 sepiolite Nutrition 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- WOZZOSDBXABUFO-UHFFFAOYSA-N tri(butan-2-yloxy)alumane Chemical compound [Al+3].CCC(C)[O-].CCC(C)[O-].CCC(C)[O-] WOZZOSDBXABUFO-UHFFFAOYSA-N 0.000 description 1
- GPRLSGONYQIRFK-MNYXATJNSA-N triton Chemical compound [3H+] GPRLSGONYQIRFK-MNYXATJNSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 150000003754 zirconium Chemical class 0.000 description 1
Images
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
- C01B39/04—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 using at least one organic template directing agent, e.g. an ionic quaternary ammonium compound or an aminated compound
-
- 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
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
- B01J20/08—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04 comprising aluminium oxide or hydroxide; comprising bauxite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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Description
本発明は、少なくとも2つの単位球状粒子からなり、前記粒子のそれぞれは、酸化アルミニウムをベースとする1.5〜30nmの細孔サイズを有するメソ構造化マトリクスを含み、該メソ構造化マトリクスは、前記マトリクスの質量に対して46重量%超を示す酸化アルミニウムの含有量を有し、メソ構造化マトリクスは、1〜30nm厚さを有する無定形壁を有する、メソ構造化材料であって、前記単位球状粒子は、10μmの最大径を有する、ものに関する。酸化アルミニウムをベースとする前記メソ構造化マトリクスは、好ましくは、前記マトリクスのSi/Alモル比が厳格に1未満であるような比率で酸化ケイ素を含む。
本発明によるメソ構造化材料は、単位球状粒子からなり、該粒子のそれぞれは、高アルミニウム含有量を有するメソ構造化マトリクスを含む、材料である。前記メソ構造化マトリクスはまた、酸化ケイ素を含有し得、これは、この場合、本発明による材料に有利な酸−塩基特性を与える。本発明はまた、混合された多孔度を有し、メソ構造化マトリクス中にゼオライトナノ結晶が捕捉された材料を提供し、このような材料は、ゼオライト族の材料および酸化アルミニウムをベースとする材料、より特定的にはメソ構造化アルミノケイ酸塩材料に特有である構造、組織(textural)および酸−塩基の特性を同時に有しているため、有利である。いわゆるエアロゾル技術によって誘発される蒸発によるミセル化または自己集合の現象に連続的である本発明による材料の秩序のある構造は、ゼオライトナノ結晶の存在を伴ってまたは伴わないで、メソ構造化相の性質にも場合により存在するゼオライト相の性質に損傷を与えないで、メソ構造化材料を容易に発展させることおよびそれらの最初の合成方法とは関係なく広範囲のゼオライトナノ結晶と共に働くことを可能にする。実際に、メソ構造化された/ゼオライト性の混合された多孔度を有する材料の調製のために、300nmよりはるかに大きいサイズのゼオライト結晶を用いることが可能である。それらは、溶液、特に酸性溶液、非常に好ましくは酸性の水性有機溶液中に、300nmに等しい最大ナノメートルサイズのナノ結晶の形態で分散するという特性を有するからである。さらに、メソ構造化された/ゼオライト性の材料のナノメートルスケールでの発展は、同一の球状粒子内のミクロ孔およびメソ孔帯域の好適な接続につながる。
本発明の対象は、メソ構造化材料であって、少なくとも2つの単位球状粒子からなり、前記粒子のそれぞれは、酸化アルミニウムをベースとするメソ構造化マトリクスを含み、該メソ構造化マトリクスは、1.5〜30nmの細孔サイズを有し、かつ、前記マトリクスの質量に対して46重量%超を示す酸化アルミニウム含有量を有し、該マトリクスは、1〜30nmの厚さの無定形壁を有し、前記単位球状粒子は、10μmの最大径を有する、ものである。
3.38gの三塩化アルミニウムが、30gのエタノール、13.6mLの水、0.036mLのHClおよび1.4gのCTAB界面活性剤を含有する溶液に加えられる。全体構成は、室温で、アルミニウム前駆体が完全に溶解するまで攪拌される。1.45gのオルトケイ酸テトラエチル(tetraethyl orthosilicate:TEOS)が次いで処理される。10分間にわたって室温で攪拌した後、全体構成は、エアロゾル発生器の噴散室に送られ、溶液は、上記の説明に記載されたようにして圧力(P=1.5バール)下に導入されたキャリアガス(乾燥空気)の作用の元で微細滴体の形態で噴散させられる。滴体は、上記本発明の説明に記載された操作手順に従って乾燥させられる。乾燥炉の温度は350℃に設定される。次いで、収集された粉体は、空気中で5時間にわたりT=550℃で焼成される。固体は、低角XRD(図1)、窒素による容積分析(図2、横座標上に示されるPOの大きさは、飽和蒸気圧である)、SEMおよびICPによって特徴付けられる。TEM分析により、最終の材料は、バーミキュラ構造によって特徴付けられる組織化されたメソ多孔度を有することが示される。窒素を用いる容積分析による分析は、SBET=780m2/gの最終材料の比表面積およびφ=2.5nmのメソ孔径につながる。小角XRD分析は、角2θ=2.2に相関を有するピークの視覚化につながる。ブラッグの式2d・sin(1.1)=1.5406は、メソ構造化マトリクスの細孔間の相関距離dを計算することを可能にし、すなわち、d=4.0nmである。e=d−φによって規定されるメソ構造化マトリクスの壁の厚さは、したがって、e=1.5nmである。ICP分析は、0.5に等しいSi/Alモル比を提供する。こうして得られた球状単位粒子のSEMブロックにより、これらの粒子は、50〜700nmで変動する径によって特徴付けられるサイズを有し、これらの粒子のサイズ分布は、300nm前後を中心とすることが示される。
2.65gの三塩化アルミニウムが、30gのエタノール、13.8mLの水、0.036mLのHClおよび1.4gの界面活性剤P123を含有する溶液に加えられる。全体構成は、室温で、アルミニウム前駆体が完全に溶解するまで攪拌される。次いで、2gのオルトケイ酸テトラエチル(TEOS)が処理される。18時間にわたって室温で攪拌した後、全体構成は、エアロゾル発生器の噴散室に送られ、溶液は、圧力(P=1.5バール)下に導入されるキャリアガス(乾燥空気)の作用の元で微細滴体の形態で噴散させられる。滴体は、上記本発明の詳説に記載された操作手順に従って乾燥させられる。乾燥炉の温度は、350℃に設定される。次いで、収集された粉体は、空気中5時間にわたってT=550℃で焼成される。固体は、低角XRD(図3)、窒素による容積分析(図4、横座標上に示されるPOの大きさは、飽和蒸気圧である)、SEMおよびICPによって特徴付けられる。TEM分析により、最終材料は、バーミキュラ構造によって特徴付けられる組織化されたメソ多孔度を有することが示される。窒素を用いる容積分析による分析は、SBET=180m2/gの最終材料の比表面積および5.6nmのメソ孔径につながる。小角XRD分析は、角2θ=0.64と相関を有するピークの視覚化につながる。ブラッグの式2d・sin(0.32)=1.5406は、メソ構造化マトリクスの細孔間の相関距離dを計算することを可能にし、すなわち、d=13.1nmである。したがって、e=d−φによって規定されるメソ構造化マトリクスの壁の厚さは、e=7.5nmである。ICP分析は、0.9に等しいSi/Alモル比を提供する。こうして得られた球状単位粒子のSEMブロックにより、これらの粒子は、50〜700nmで変動する径によって特徴付けられるサイズを有し、これらの粒子のサイズ分布は、300nm前後を中心とすることが示される。
0.14gのアルミニウム トリ−sec−ブトキシドが、3.5mLのテトラプロピルアンモニウムヒドロキシド(TPAOH)、0.01gのNaOHソーダおよび4.3mLの水を含有する溶液に加えられる。アルミニウムアルコキシドが溶解させられた後、6gのオルトケイ酸テトラエチル(TEOS)が加えられる。溶液は、室温で5時間にわたり攪拌され、次いで、T=95℃で12時間にわたりオートクレーブ処理に付された。135nmのZSM−5ナノ結晶を含有する白色溶液が得られる。この溶液は、30分間にわたって20,000rpmの遠心分離にかけられる。固体は、水中に再分散させられ、次いで、再度、30分間にわたって20,000rpmの遠心分離にかけられる。この洗浄は、2回行われる。ナノ結晶はゲルを形成し、これは一晩にわたって60℃でオーブンにおいて乾燥させられる。0.461mgのこれらの結晶は、30gのエタノール、13.8mLの水、2gのTEOS、2.65gのAlCl3・6H2O、0.036mLのHClおよび1.4gのP123界面活性剤を含有する溶液中に、24時間にわたって超音波攪拌することによって再分散させられる。全体構成は、エアロゾル発生器の噴散室に送られ、溶液は、上記の本発明の詳説に記載された方法に従って、圧力(P=1.5バール)下に導入されるキャリアガス(乾燥空気)の作用の元で微細滴体の形態で噴散させられる。滴体は、上記本発明の詳説に記載された操作手順に従って乾燥させられる。乾燥炉の温度は、350℃に設定される。次いで、収集された粉体は、空気中5時間にわたりT=550℃で焼成される。固体は、低角XRD(図5)、高角XRD(図6)、窒素による容積分析(図7)、SEMおよびICPによって特徴付けられる。TEM分析により、最終材料は、バーミキュラ構造によって特徴付けられる組織化されたメソ多孔度を有するアルミノケイ酸塩マトリクス中に捕捉されたZSM−5ゼオライトナノ結晶からなることが示される。窒素を用いる容積分析による分析は、SBET=310m2/gの最終材料の比表面積およびφ=5.6nmのアルミノケイ酸塩メソ構造化材料の特徴であるメソ孔径につながる。高角XRD分析は、ZSM−5ゼオライト(0.55nm程度のミクロ孔のサイズ)の特徴であるディフラクトグラムを得ることにつながる。小角XRD分析は、メソ構造化マトリクスのバーミキュラ対称性に関連する相関ピークの視覚化につながる。ブラッグの式は、2d・sin(0.32)=1.5406、すなわちd=13.1nmを提供する。したがって、e=d−φによって規定されるアルミノケイ酸塩メソ構造化材料の無定形壁の厚さは、e=7.5nmである。ICP分析は、0.9に等しいマトリクスのSi/Alモル比を提供する。こうして得られた球状単位粒子のSEMブロックにより、これらの粒子は、50〜700nmで変動する径によって特徴付けられるサイズを有し、これらの粒子のサイズ分布は、300nm前後を中心とすることが示される。
Claims (14)
- 少なくとも2つの単位球状粒子からなるメソ構造化材料であって、該粒子のそれぞれは、酸化アルミニウムをベースとするメソ構造化マトリクスを含み、該メソ構造化マトリクスは1.5〜30nmの細孔サイズを有し、マトリクスの質量に対して46重量%超を示す酸化アルミニウム含有量を有し、該メソ構造化マトリクスは、1〜30nmの厚さの無定形壁を有し、前記単位球状粒子は、10μmの最大径を有する、メソ構造化材料。
- 酸化アルミニウムをベースとする前記メソ構造化マトリクスは、酸化ケイ素を含む、請求項1に記載の材料。
- 前記メソ構造化マトリクスは、厳格に1未満であるSi/Alモル比を有する、請求項2に記載の材料。
- 前記メソ構造化マトリクスは、立方晶系、バーミキュラ、コレステリック、ラメラ、連続二相または六方晶系の構造を有する、請求項1〜3のいずれか1つに記載の材料。
- 100〜1200m2/gの比表面積を有する、請求項1〜4のいずれか1つに記載の材料。
- 前記球状粒子のそれぞれは、0.2〜2nmの細孔サイズを有するゼオライトナノ結晶を含む、請求項1〜5のいずれか1つに記載の材料。
- 前記ゼオライトナノ結晶は、MFI、BEA、FAUおよびLTA構造型のゼオライトの中から選択される少なくとも1種のゼオライトを含む、請求項6に記載の材料。
- 前記ゼオライトナノ結晶は、完全にシリカの少なくとも1種のゼオライトを含む、請求項6または7に記載の材料。
- 前記ゼオライトナノ結晶は、ケイ素およびアルミニウムを含有する少なくとも1種のゼオライトを含む、請求項6または7に記載の材料。
- 請求項1〜9のいずれか1つに記載のメソ構造化材料を調製する方法であって、a)少なくとも1種の界面活性剤、および少なくとも1種のアルミニウム前駆体を溶液中で混合する段階;b)段階a)において得られる溶液をエアロゾル噴散させて、200μm以下の径を有する球状滴体を形成させる段階;c)前記滴体を乾燥させる段階、およびd)前記界面活性剤を除去して、メソ構造化材料を得る段階を包含する、方法。
- a0)少なくとも1種の構造化剤の存在下に、300nmに等しい最大ナノメートルサイズのゼオライトナノ結晶を合成して、前記ナノ結晶が分散させられたコロイド溶液を得る段階;a’)少なくとも1種の界面活性剤、少なくとも1種のアルミニウム前駆体および段階a0)により得られた少なくとも1種のコロイド溶液を溶液中で混合する段階;b’)段階a’)において得られた溶液をエアロゾル噴散させて、200μm以下の径を有する球状滴体を形成させる段階;c’)前記滴体を乾燥させる段階、およびd’)前記界面活性剤および前記構造化剤を除去して、メソ構造化された/ゼオライト性の混合された材料を得る段階を包含する、請求項10に記載のメソ構造化材料の調製方法。
- a”)少なくとも1種の界面活性剤、少なくとも1種のアルミニウム前駆体、および300nmに等しい最大ナノメートルサイズのナノ結晶の形態で溶液中に分散させられたゼオライト結晶を溶液中で混合する段階;b”)段階a”)において得られた前記溶液をエアロゾル噴散させて、200μm以下の径の球状滴体を形成させる段階;c”)前記滴体を乾燥させる段階、およびd”)少なくとも前記界面活性剤を除去して、メソ構造化された/ゼオライト性の混合された材料を得る段階を包含する、請求項10に記載のメソ構造化材料の調製方法。
- 前記段階a)、段階a’)または段階a”)において、さらに少なくとも1種のシリカ前駆体を溶液中に混合する、請求項10〜12のいずれか1つに記載のメソ構造化材料の調製方法。
- 請求項1〜9のいずれか1つに記載のメソ構造化材料または請求項10〜13のいずれか1つに記載された方法により調製されたメソ構造化材料を含む吸着剤。
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FR0505678 | 2005-06-02 | ||
FR0505678A FR2886637B1 (fr) | 2005-06-02 | 2005-06-02 | Materiau mesostructure a forte teneur en aluminium |
PCT/FR2006/001112 WO2006128989A1 (fr) | 2005-06-02 | 2006-05-17 | Materiau mesostructure a forte teneur en aluminium |
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US (1) | US7807598B2 (ja) |
EP (1) | EP1910226B1 (ja) |
JP (1) | JP5150485B2 (ja) |
CN (1) | CN101189187B (ja) |
DE (1) | DE602006008312D1 (ja) |
FR (1) | FR2886637B1 (ja) |
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ZA (1) | ZA200708050B (ja) |
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FR2886636B1 (fr) * | 2005-06-02 | 2007-08-03 | Inst Francais Du Petrole | Materiau inorganique presentant des nanoparticules metalliques piegees dans une matrice mesostructuree |
FR2920756B1 (fr) * | 2007-09-07 | 2010-08-20 | Inst Francais Du Petrole | Materiau amorphe comprenant du silicium a porosite hierarchisee et organisee |
FR2920757B1 (fr) | 2007-09-07 | 2009-11-13 | Inst Francais Du Petrole | Materiau cristallise comprenant du silicium a porosite hierarchisee et organisee |
FR2929265B1 (fr) * | 2008-03-31 | 2016-04-15 | Inst Francais Du Petrole | Materiau aluminosilicate mesostructure forme de particules spheriques de taille specifique |
FR2929264B1 (fr) | 2008-03-31 | 2010-03-19 | Inst Francais Du Petrole | Materiau inorganique forme de particules spheriques de taille specifique et presentant des nanoparticules metalliques piegees dans une matrice mesostructuree |
FR2929266B1 (fr) * | 2008-03-31 | 2010-03-19 | Inst Francais Du Petrole | Materiau mesostructure a forte teneur en aluminium et constitue de particules spheriques de taille specifique |
FR2931706B1 (fr) * | 2008-05-28 | 2010-12-24 | Inst Francais Du Petrole | Catalyseur a base d'un materiau cristallise comprenant du silicium a porosite hierarchisee et organisee et procede ameliore de traitement de charges hydrocarbonees |
FR2931833B1 (fr) * | 2008-05-28 | 2011-06-10 | Inst Francais Du Petrole | Procede de production de distillats moyens par hydrocraquage de charges issues du procede fischer-tropsch avec un catalyseur a base d'un materiau amorphe |
FR2931708B1 (fr) * | 2008-05-28 | 2014-03-14 | Inst Francais Du Petrole | Catalyseur a base d'un materiau cristallise a porosite hierarchisee et organisee et son utilisation en oligomerisation des olefines legeres |
FR2931818B1 (fr) * | 2008-05-28 | 2012-11-30 | Inst Francais Du Petrole | Procede d'oligomerisation des olefines legeres utilisant un catalyseur a base d'un materiau amorphe a porosite hierarchisee et organisee |
FR2931834B1 (fr) * | 2008-05-28 | 2010-07-30 | Inst Francais Du Petrole | Procede de production de distillats moyens par hydrocraquage de charges issues du procede fischer-tropsch avec un catalyseur a base d'un materiau cristallise |
FR2931705B1 (fr) * | 2008-05-28 | 2010-09-03 | Inst Francais Du Petrole | Catalyseur a base d'un materiau amorphe comprenant du silicium a porosite hierarchisee et organisee et procede ameliore de traitement de charges hydrocarbonees |
FR2933088B1 (fr) * | 2008-06-27 | 2010-08-20 | Inst Francais Du Petrole | Procede de preparation d'une alumine a mesoporosite controlee |
FR2969513B1 (fr) | 2010-12-22 | 2013-04-12 | IFP Energies Nouvelles | Procede de preparation d'un materiau spherique a porosite hierarchisee comprenant des particules metalliques piegees dans une matrice mesostructuree |
FR2969511B1 (fr) * | 2010-12-22 | 2012-12-28 | IFP Energies Nouvelles | Materiau spherique comprenant des nanoparticules metalliques piegees dans une matrice oxyde mesostructuree et son utilisation comme catalyseur dans les procedes du raffinage |
US8882993B2 (en) | 2011-03-07 | 2014-11-11 | Exxonmobil Research And Engineering Company | Stabilized aggregates of small crystallites of zeolite Y |
US8852326B2 (en) | 2011-03-07 | 2014-10-07 | Exxonmobil Research And Engineering Company | Aggregates of small particles of synthetic faujasite zeolite |
US8778824B2 (en) | 2011-03-07 | 2014-07-15 | Exxonmobil Research And Engineering Company | Aggregates of small crystallites of zeolite Y |
US8778171B2 (en) | 2011-07-27 | 2014-07-15 | Exxonmobil Research And Engineering Company | Hydrocracking catalysts containing stabilized aggregates of small crystallites of zeolite Y associated hydrocarbon conversion processes |
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US4217240A (en) * | 1976-09-02 | 1980-08-12 | E. I. Du Pont De Nemours And Company | Stable aluminosilicate aquasols having uniform size particles and their preparation |
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WO2001017901A1 (en) * | 1999-09-07 | 2001-03-15 | Technische Universiteit Delft | Inorganic oxides with mesoporosity or combined meso-and microporosity and process for the preparation thereof |
FR2800300B1 (fr) | 1999-11-02 | 2002-12-20 | Rhodia Chimie Sa | Materiau mesostructure integrant des particules de dimension nanometrique |
AU1684101A (en) * | 1999-11-23 | 2001-06-04 | Universite Laval | Mesoporous zeolitic material with microporous crystalline mesopore walls |
FR2802120B1 (fr) * | 1999-12-14 | 2002-02-01 | Inst Francais Du Petrole | Solide silicoaluminate micro et mesoporeux, procede de preparation, utilisation comme catalyseur et en conversion d'hydrocarbures |
FR2803223B1 (fr) * | 1999-12-30 | 2002-06-21 | Rhodia Chimie Sa | Procede de preparation d'un materiau mesostructure a partir de particules de dimensions nanometriques |
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FR2872151B1 (fr) * | 2004-06-24 | 2007-06-29 | Inst Francais Du Petrole | Materiau aluminosilicate mesostructure |
JP2006069864A (ja) * | 2004-09-03 | 2006-03-16 | National Institute Of Advanced Industrial & Technology | ナノポーラス体及びその製造方法 |
CA2604869A1 (en) * | 2005-04-05 | 2006-10-12 | University College Cork - National University Of Ireland, Cork | Mesoporous particles |
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JP2008542178A (ja) | 2008-11-27 |
US7807598B2 (en) | 2010-10-05 |
EP1910226A1 (fr) | 2008-04-16 |
EP1910226B1 (fr) | 2009-08-05 |
ZA200708050B (en) | 2009-01-28 |
DE602006008312D1 (de) | 2009-09-17 |
US20090029847A1 (en) | 2009-01-29 |
WO2006128989A1 (fr) | 2006-12-07 |
CN101189187B (zh) | 2011-03-30 |
CN101189187A (zh) | 2008-05-28 |
FR2886637A1 (fr) | 2006-12-08 |
FR2886637B1 (fr) | 2007-08-03 |
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