JP4673379B2 - ゲルマニウム・ゼオライトを製造する方法 - Google Patents
ゲルマニウム・ゼオライトを製造する方法 Download PDFInfo
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- JP4673379B2 JP4673379B2 JP2007549556A JP2007549556A JP4673379B2 JP 4673379 B2 JP4673379 B2 JP 4673379B2 JP 2007549556 A JP2007549556 A JP 2007549556A JP 2007549556 A JP2007549556 A JP 2007549556A JP 4673379 B2 JP4673379 B2 JP 4673379B2
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- zeolite
- aluminum
- germanium
- silica
- reaction mixture
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- 239000010457 zeolite Substances 0.000 title claims description 70
- 229910021536 Zeolite Inorganic materials 0.000 title claims description 65
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 title claims description 58
- 229910052732 germanium Inorganic materials 0.000 title claims description 19
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 title claims description 19
- 238000004519 manufacturing process Methods 0.000 title description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 48
- 238000000034 method Methods 0.000 claims description 31
- 229910052782 aluminium Inorganic materials 0.000 claims description 20
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 20
- 239000013078 crystal Substances 0.000 claims description 20
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 19
- 239000000377 silicon dioxide Substances 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 239000010703 silicon Substances 0.000 claims description 14
- 239000011541 reaction mixture Substances 0.000 claims description 13
- 229910052710 silicon Inorganic materials 0.000 claims description 13
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium oxide Inorganic materials O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 claims description 12
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 8
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 7
- 229910001868 water Inorganic materials 0.000 claims description 6
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical group [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 235000019253 formic acid Nutrition 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- PVADDRMAFCOOPC-UHFFFAOYSA-N oxogermanium Chemical group [Ge]=O PVADDRMAFCOOPC-UHFFFAOYSA-N 0.000 claims description 4
- 229910001388 sodium aluminate Inorganic materials 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- -1 aluminum-silicon-germanium Chemical compound 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 150000002222 fluorine compounds Chemical class 0.000 claims description 3
- 230000002194 synthesizing effect Effects 0.000 claims description 3
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 2
- 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 claims description 2
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 2
- FNIHDXPFFIOGKL-UHFFFAOYSA-N disodium;dioxido(oxo)germane Chemical compound [Na+].[Na+].[O-][Ge]([O-])=O FNIHDXPFFIOGKL-UHFFFAOYSA-N 0.000 claims description 2
- 239000000706 filtrate Substances 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 229910021485 fumed silica Inorganic materials 0.000 claims description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical group O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 2
- PKLMYPSYVKAPOX-UHFFFAOYSA-N tetra(propan-2-yloxy)germane Chemical compound CC(C)O[Ge](OC(C)C)(OC(C)C)OC(C)C PKLMYPSYVKAPOX-UHFFFAOYSA-N 0.000 claims description 2
- IEXRMSFAVATTJX-UHFFFAOYSA-N tetrachlorogermane Chemical compound Cl[Ge](Cl)(Cl)Cl IEXRMSFAVATTJX-UHFFFAOYSA-N 0.000 claims description 2
- BGQMOFGZRJUORO-UHFFFAOYSA-M tetrapropylammonium bromide Chemical compound [Br-].CCC[N+](CCC)(CCC)CCC BGQMOFGZRJUORO-UHFFFAOYSA-M 0.000 claims description 2
- FBEVECUEMUUFKM-UHFFFAOYSA-M tetrapropylazanium;chloride Chemical compound [Cl-].CCC[N+](CCC)(CCC)CCC FBEVECUEMUUFKM-UHFFFAOYSA-M 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims 1
- 235000012239 silicon dioxide Nutrition 0.000 claims 1
- 239000000243 solution Substances 0.000 description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 11
- 230000015572 biosynthetic process Effects 0.000 description 9
- 239000000203 mixture Substances 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 7
- 229960000583 acetic acid Drugs 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 229910052796 boron Inorganic materials 0.000 description 3
- 239000008119 colloidal silica Substances 0.000 description 3
- QPJSUIGXIBEQAC-UHFFFAOYSA-N n-(2,4-dichloro-5-propan-2-yloxyphenyl)acetamide Chemical compound CC(C)OC1=CC(NC(C)=O)=C(Cl)C=C1Cl QPJSUIGXIBEQAC-UHFFFAOYSA-N 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 229910052814 silicon oxide Inorganic materials 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 2
- 229910005793 GeO 2 Inorganic materials 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 229910000323 aluminium silicate Inorganic materials 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000002178 crystalline material Substances 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 229910052733 gallium Inorganic materials 0.000 description 2
- 239000012362 glacial acetic acid Substances 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
- 229910052742 iron Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000001465 metallisation Methods 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- 239000011135 tin Substances 0.000 description 2
- ZSLUVFAKFWKJRC-IGMARMGPSA-N 232Th Chemical compound [232Th] ZSLUVFAKFWKJRC-IGMARMGPSA-N 0.000 description 1
- 229910002012 Aerosil® Inorganic materials 0.000 description 1
- 239000007848 Bronsted acid Substances 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910052776 Thorium Inorganic materials 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 238000005899 aromatization reaction Methods 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- AJNVQOSZGJRYEI-UHFFFAOYSA-N digallium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ga+3].[Ga+3] AJNVQOSZGJRYEI-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 229910001195 gallium oxide Inorganic materials 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000001089 mineralizing effect Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 238000004846 x-ray emission Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 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
- C01B39/06—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
-
- 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
-
- 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
- C01B39/36—Pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
- C01B39/38—Type ZSM-5
-
- 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
- C01B39/36—Pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
- C01B39/38—Type ZSM-5
- C01B39/40—Type ZSM-5 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/20—After treatment, characterised by the effect to be obtained to introduce other elements in the catalyst composition comprising the molecular sieve, but not specially in or on the molecular sieve itself
-
- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S423/00—Chemistry of inorganic compounds
- Y10S423/22—MFI, e.g. ZSM-5. silicalite, LZ-241
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Catalysts (AREA)
Description
以下の溶液の調製:
・ 溶液1: 37.84gの脱イオン水中に3.80gの水酸化ナトリウムを溶解させた。3.30gの酸化ゲルマニウムを加え、透明な溶液が得られるまで撹拌した。
・ 溶液2: 49.61gの脱イオン水中に0.85gのアルミン酸ナトリウム(57質量%のAl2O3、35質量%のNa2O、8質量%のH2O)を溶解させた。
以下に示すように溶液を調製した:
・ 溶液1: 120.30gの脱イオン水中に12.15gの水酸化ナトリウムを溶解させた。6.89gのGeO2を加え、透明な溶液が得られるまで撹拌した。
・ 溶液2: 108.51gの40質量%のTPAOH溶液を222.29gの脱イオン水で希釈した。1.66gの擬似ベーマイト(アルコア(Alcoa)社からのHiQ−40)を加え、よく撹拌した。
溶液を以下に示したように調製した:
・溶液1: 45.26gの脱イオン水中に4.08gの水酸化ナトリウムを溶解させた。2.31gのGeO2を加え、透明で均質な溶液が得られるまで撹拌した。
・溶液2: 25.13gの脱イオン水中に0.76gのアルミン酸ナトリウム(57質量%のAl2O3、35質量%のNa2O、8質量%のH2O)を溶解させた。
・溶液3: 40.43gの40質量%のTPAOH溶液を58.37gの脱イオン水で希釈した。
Claims (20)
- アルミニウム・ケイ素・ゲルマニウムゼオライトを合成する方法であって、
a) シリカ源、ゲルマニウム源、アルミニウム源、型剤および水を組み合わせてゲルを形成することによって、反応混合物を調製し、
b) 前記反応混合物を混合し、
c) フッ素を含有しない酸を導入し、
d) 前記反応混合物を加熱して、ゼオライト結晶を形成し、
e) 前記反応混合物を冷却し、
f) 前記ゼオライト結晶を前記反応混合物から分離し、
g) 前記ゼオライト結晶を洗浄し、
h) 前記ゼオライト結晶を乾燥させ、
i) 前記ゼオライト結晶をか焼する、
各工程を有してなり、
アルミニウム・ケイ素・ゲルマニウムゼオライトが、反応混合物中においてフッ素化合物を使用しないで合成されることを特徴とする方法。 - 前記反応混合物を、100℃から200℃の範囲の温度に加熱することを特徴とする請求項1記載の方法。
- 前記反応混合物を室温まで冷却することを特徴とする請求項1記載の方法。
- 前記ゼオライト結晶を濾過により分離することを特徴とする請求項1記載の方法。
- 前記洗浄が、濾液のpHが約7.5となるまで、0℃から50℃で脱イオン水により行われることを特徴とする請求項1記載の方法。
- 前記ゼオライト結晶を、4から24時間に亘り90℃から110℃で空気中において乾燥させることを特徴とする請求項1記載の方法。
- 前記ゼオライト結晶を、3から10時間に亘り400℃から600℃で空気中においてか焼することを特徴とする請求項1記載の方法。
- 前記シリカ源が二酸化ケイ素であることを特徴とする請求項1記載の方法。
- 前記シリカ源がシリカゾル、沈降シリカまたはヒュームドシリカであることを特徴とする請求項8記載の方法。
- 前記アルミニウム源がアルミン酸ナトリウム、硝酸アルミニウム、硫酸アルミニウムまたは擬似ベーマイトであることを特徴とする請求項1記載の方法。
- 前記ゲルマニウム源が酸化ゲルマニウム、塩化ゲルマニウム、ゲルマニウムイソプロポキシドまたはゲルマニウム酸ナトリウムであることを特徴とする請求項1記載の方法。
- 前記型剤が水酸化テトラn−プロピルアンモニウム、臭化テトラn−プロピルアンモニウムまたは塩化テトラn−プロピルアンモニウムであることを特徴とする請求項1記載の方法。
- 前記酸が、硫酸、酢酸、硝酸、リン酸、塩化水素酸または蟻酸であることを特徴とする請求項1記載の方法。
- 前記ゼオライトが、MFI、FAU、TON、MFL、VPI、MEL、AEL、AFI、MWWまたはMOR構造を有することを特徴とする請求項1記載の方法。
- 前記ゼオライトがMFI構造を有し、ケイ素対アルミニウムの原子比が10:1より大きいことを特徴とする請求項14記載の方法。
- 前記ケイ素対アルミニウムの原子比が20:1から200:1の範囲にあることを特徴とする請求項15記載の方法。
- 前記ケイ素対アルミニウムの原子比が25:1から100:1の範囲にあることを特徴とする請求項16記載の方法。
- 前記ゼオライトがMFI構造を有し、シリカ対ゲルマニアのモル比が100:1から8:1の範囲にあることを特徴とする請求項14記載の方法。
- 前記シリカ対ゲルマニアのモル比が50:1から10:1の範囲にあることを特徴とする請求項18記載の方法。
- 前記シリカ対ゲルマニアのモル比が25:1から10:1の範囲にあることを特徴とする請求項19記載の方法。
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US11/023,100 US7449168B2 (en) | 2004-12-27 | 2004-12-27 | Process for making a germanium-zeolite |
PCT/US2005/047091 WO2006071871A1 (en) | 2004-12-27 | 2005-12-26 | Process for making a germanium-zeolite |
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US (1) | US7449168B2 (ja) |
EP (1) | EP1848664B1 (ja) |
JP (1) | JP4673379B2 (ja) |
CN (1) | CN101090865B (ja) |
MY (1) | MY140466A (ja) |
WO (1) | WO2006071871A1 (ja) |
ZA (1) | ZA200705155B (ja) |
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KR100670698B1 (ko) * | 2005-09-29 | 2007-01-17 | 주식회사 하이닉스반도체 | 반도체메모리소자 내 파이프 래치장치 |
WO2008153759A2 (en) * | 2007-05-24 | 2008-12-18 | Saudi Basic Industries Corporation | Catalyst for conversion of hydrocarbons, process of making and process of using thereof-bimetallic deposition |
US8993468B2 (en) | 2007-05-24 | 2015-03-31 | Saudi Basic Industries Corporation | Catalyst for conversion of hydrocarbons, process of making and process of using thereof—Ge zeolites |
US9221723B2 (en) * | 2007-05-24 | 2015-12-29 | Saudi Basic Industries Corporation | Catalyst for conversion of hydrocarbons, process of making and process of using thereof—incorporation-1 |
US8969232B2 (en) * | 2007-05-24 | 2015-03-03 | Saudi Basic Industries Corporation | Catalyst for conversion of hydrocarbons, process of making and process of using thereof—incorporation 2 |
WO2009134534A2 (en) * | 2008-05-02 | 2009-11-05 | Exxonmobil Chemical Patents Inc. | Treatment of small pore molecular sieves and their use in the conversion of oxygenates to olefins |
US8545797B2 (en) | 2011-04-28 | 2013-10-01 | Chevron U.S.A. Inc. | Germanosilicate SSZ-75 |
ES2421063B1 (es) * | 2012-01-25 | 2014-06-26 | Consejo Superior De Investigaciones Cientificas (Csic) | Material ITQ-38, su procedimiento de obtención y su uso |
US8772192B2 (en) | 2012-06-29 | 2014-07-08 | Saudi Basic Industries Corporation | Germanium silicalite catalyst and method of preparation and use |
US9180441B2 (en) | 2012-09-20 | 2015-11-10 | Saudi Basic Industries Corporation | Method of forming zeolite shaped body with silica binder |
US10207255B2 (en) | 2013-11-22 | 2019-02-19 | Saudi Basic Industries Corporation | Catalyst with improved activity/selectivity for light naphtha aromatization |
JP2018531208A (ja) | 2015-10-26 | 2018-10-25 | エコラブ ユーエスエイ インク | 高度に均質なゼオライトの前駆体 |
WO2018093469A1 (en) * | 2016-11-17 | 2018-05-24 | Chevron U.S.A. Inc. | Aluminum-substituted molecular sieve cit-13 |
CN110139829B (zh) | 2016-12-02 | 2023-10-13 | 埃科莱布美国股份有限公司 | 聚铝盐及其在制备高纯度胶体铝-二氧化硅复合颗粒和沸石中的用途 |
CN112209403B (zh) * | 2019-07-09 | 2022-07-12 | 中国石油化工股份有限公司 | Scm-25/mfi共结晶分子筛、其制备方法及其用途 |
WO2023244652A1 (en) * | 2022-06-14 | 2023-12-21 | University Of Houston System | Synthesis of nano-sized zeolites |
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- 2005-12-22 MY MYPI20056134A patent/MY140466A/en unknown
- 2005-12-26 WO PCT/US2005/047091 patent/WO2006071871A1/en active Application Filing
- 2005-12-26 CN CN200580044988.0A patent/CN101090865B/zh not_active Expired - Fee Related
- 2005-12-26 EP EP05855617.6A patent/EP1848664B1/en not_active Not-in-force
- 2005-12-26 JP JP2007549556A patent/JP4673379B2/ja not_active Expired - Fee Related
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EP1848664B1 (en) | 2018-12-19 |
US7449168B2 (en) | 2008-11-11 |
ZA200705155B (en) | 2008-09-25 |
EP1848664A4 (en) | 2014-01-22 |
JP2008525306A (ja) | 2008-07-17 |
US20060140854A1 (en) | 2006-06-29 |
MY140466A (en) | 2009-12-31 |
WO2006071871A1 (en) | 2006-07-06 |
EP1848664A1 (en) | 2007-10-31 |
CN101090865A (zh) | 2007-12-19 |
CN101090865B (zh) | 2010-09-01 |
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