CN101090865B - 制造锗-沸石的方法 - Google Patents
制造锗-沸石的方法 Download PDFInfo
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- CN101090865B CN101090865B CN200580044988.0A CN200580044988A CN101090865B CN 101090865 B CN101090865 B CN 101090865B CN 200580044988 A CN200580044988 A CN 200580044988A CN 101090865 B CN101090865 B CN 101090865B
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- 239000010457 zeolite Substances 0.000 title claims abstract description 76
- 229910021536 Zeolite Inorganic materials 0.000 title claims abstract description 73
- 238000000034 method Methods 0.000 title claims abstract description 32
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 63
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910052732 germanium Inorganic materials 0.000 claims abstract description 23
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 22
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000002253 acid Substances 0.000 claims abstract description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 10
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000011737 fluorine Substances 0.000 claims abstract description 9
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 9
- 239000000377 silicon dioxide Substances 0.000 claims abstract 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 abstract description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 5
- 235000019253 formic acid Nutrition 0.000 claims abstract description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 26
- 239000010703 silicon Substances 0.000 claims description 26
- 239000013078 crystal Substances 0.000 claims description 25
- 229910052710 silicon Inorganic materials 0.000 claims description 25
- 239000004411 aluminium Substances 0.000 claims description 18
- 239000011541 reaction mixture Substances 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 238000001354 calcination Methods 0.000 claims description 9
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 7
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium oxide Inorganic materials O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 claims description 7
- PVADDRMAFCOOPC-UHFFFAOYSA-N oxogermanium Chemical group [Ge]=O PVADDRMAFCOOPC-UHFFFAOYSA-N 0.000 claims description 7
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 7
- DYAHQFWOVKZOOW-UHFFFAOYSA-N Sarin Chemical group CC(C)OP(C)(F)=O DYAHQFWOVKZOOW-UHFFFAOYSA-N 0.000 claims description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 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
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 4
- 229910001388 sodium aluminate Inorganic materials 0.000 claims description 4
- GNFTZDOKVXKIBK-UHFFFAOYSA-N 3-(2-methoxyethoxy)benzohydrazide Chemical compound COCCOC1=CC=CC(C(=O)NN)=C1 GNFTZDOKVXKIBK-UHFFFAOYSA-N 0.000 claims description 3
- FGUUSXIOTUKUDN-IBGZPJMESA-N C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 Chemical compound C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 FGUUSXIOTUKUDN-IBGZPJMESA-N 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- 238000005406 washing Methods 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
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-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
- -1 aluminium-silicon-germanium Chemical compound 0.000 claims description 2
- 230000031709 bromination Effects 0.000 claims description 2
- 238000005893 bromination reaction Methods 0.000 claims description 2
- 238000005660 chlorination reaction Methods 0.000 claims description 2
- 239000008367 deionised water Substances 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical group [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- IEXRMSFAVATTJX-UHFFFAOYSA-N tetrachlorogermane Chemical compound Cl[Ge](Cl)(Cl)Cl IEXRMSFAVATTJX-UHFFFAOYSA-N 0.000 claims description 2
- 229910001723 mesolite Inorganic materials 0.000 claims 4
- 229910021641 deionized water Inorganic materials 0.000 claims 1
- 229910021485 fumed silica Inorganic materials 0.000 claims 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 abstract description 10
- 150000002222 fluorine compounds Chemical class 0.000 abstract 2
- BYMMIQCVDHHYGG-UHFFFAOYSA-N Cl.OP(O)(O)=O Chemical compound Cl.OP(O)(O)=O BYMMIQCVDHHYGG-UHFFFAOYSA-N 0.000 abstract 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 23
- 239000000499 gel Substances 0.000 description 18
- 238000003756 stirring Methods 0.000 description 14
- 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
- 239000000203 mixture Substances 0.000 description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 7
- 238000002425 crystallisation Methods 0.000 description 6
- 230000008025 crystallization Effects 0.000 description 6
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 150000001875 compounds Chemical class 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
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-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
- 229910052796 boron Inorganic materials 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 229910052733 gallium Inorganic materials 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000000017 hydrogel 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
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 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
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 229960000583 acetic acid Drugs 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910000323 aluminium silicate Inorganic materials 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000002178 crystalline material Substances 0.000 description 2
- 238000002242 deionisation method Methods 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 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
- 238000011068 loading method Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 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
- 239000000376 reactant Substances 0.000 description 2
- OSBSFAARYOCBHB-UHFFFAOYSA-N tetrapropylammonium Chemical compound CCC[N+](CCC)(CCC)CCC OSBSFAARYOCBHB-UHFFFAOYSA-N 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
- 229910002016 Aerosil® 200 Inorganic materials 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
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-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
- 150000004945 aromatic hydrocarbons Chemical class 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
- 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
- 239000003054 catalyst Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000005242 forging Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 230000003993 interaction Effects 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
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction 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
- 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
- 239000010970 precious metal Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 229960001866 silicon dioxide Drugs 0.000 description 1
- 235000012239 silicon dioxide Nutrition 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
- 238000005507 spraying Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000004846 x-ray emission Methods 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
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- 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)
Abstract
本发明涉及未用氟化合物制造锗-沸石的方法。沸石优选为MFI-型结构，最优选ZSM-5MFI沸石。在不含氟的酸，如硫酸、乙酸、硝酸、磷酸、盐酸或甲酸的存在下，锗-沸石基本上在没有氟化合物的情况下由含硅源、锗源、铝源和结构导向剂的水凝胶合成。
Description
发明背景
发明领域：
本发明涉及制造沸石的方法，该沸石优选MFI-型结构，最优选在骨架中有锗的ZSM-5MFI沸石(在下文中称为“Ge-沸石”，或如果沸石是ZSM-5MFI，称为Ge-ZSM-5)。合成此Ge-沸石不用氟化合物。
现有技术的描述：
沸石是水合结晶的铝硅酸盐，也可含其它金属，如钠、钙、钡和钾，并具有离子交换能力(
世界英语字典【北美版】&(P)2001微软公司)。制备沸石的方法包括(a)制备氧化硅和铝氧化物源的水溶液混合物；和(b)将所述水溶液混合物保持在晶化条件下直到所述沸石的晶体形成。
合成的沸石通常由来自过饱和合成混合物的沸石晶化制备。然后将所得到的晶化产物干燥和煅烧以生成沸石粉末。沸石粉末可用于某种装置和方法，例如流化床反应器。
美国专利第3,702,886号公开了ZSM-5沸石的制备，其通过将含氢氧化四丙铵、氧化钠、铝或镓的氧化物、硅石或锗的氧化物和水的溶液加热到温度为100℃至175℃，经六小时至六天由该反应混合物形成晶体，然后冷却至室温，过滤分离固体产物，洗涤和干燥。实施例和权利要求被限定成铝硅酸盐。
EP0951444公开了大晶体沸石的合成，其通过在苛性碱水溶液如氢氧化钠中溶解铝源，然后将此加入到在水中的硅源的混合物中，将反应混合物混合均匀，加热至成核温度以晶化，通过冷却、过滤分离晶体产物，洗涤和干燥。
美国专利第6,723,300号公开了三价元素如铝、硼、铁、铟和/或镓以及四价元素如硅、锡、钛和/或锗的多孔晶体材料的合成，其用氢氟酸代替碱的氢氧化物作为矿化剂，并使用有机导向剂。
美国专利第5,246,688号公开了硅基MFI沸石的生产，其溶解四价或三价元素如硅(随意地，和锗)和铝的氧化物或氢氧化物，在氢氟酸中，形成沉淀物，分离该沉淀物并煅烧该沉淀物。
美国专利第5,371,307号公开了实质上在无三价元素和有结构助剂的情况下制备硅/锗氧化物沸石，促进微孔的形成并稳定沸石。动员剂如氢氟酸可用于促进提供结合到沸石结构中的硅和锗的反应物的溶解。
美国专利第6,471,941号公开了三价元素如硼、铁、铟、镓、铝或其组合物以及四价元素如硅、锡、钛、锗或其组合物的晶体材料，其使用氟化物，特别是HF，作为合成中的矿化剂。
在结构中有锗的MFI-型沸石的合成被公开在“Synthesis andCharacterization of Ge-ZSM-5 Zeolites，H.Kosslick et al.，J.Phys.Chem.，vol.97，p.5678-5684(1993)。氢氟酸(HF)被用于合成中。
在合成锗沸石中氟化合物的使用产生卤化的催化剂，在高温下加热这些催化剂时(例如，催化加热处理，煅烧或处理条件)，析出少量HCl和/或HF。这产生了会与处理设备中的金属反应的酸性卤化物气体。
具有在合成凝胶中未用氟化合物制造锗沸石-型催化剂的方法将是有利的。
发明概要
本发明提供了基本上在无氟化合物的情况下合成在骨架中含铝、硅和锗的沸石的方法。沸石结构可为MFI、FAU、TON、MFL、VPI、MEL、AEL、AFI、MWW或MOR，但是优选沸石具有MFI结构，更优选是ZSM-5MFI沸石。在不含氟的酸如硫酸、乙酸、硝酸、磷酸、盐酸或甲酸的存在下，由含硅源、锗源、铝源和结构导向剂的水凝胶合成Ge-沸石。将反应混合物凝胶加热以形成沸石晶体，然后冷却。将沸石晶体从凝胶中分离并洗涤，干燥和煅烧。
发明详述
已知沸石是结晶的硅酸盐并包括通过分享氧原子形成三维网络的TO4四面体结构，此处T代表四阶元素如硅，和三价元素如铝。沸石通常结晶自水溶液。合成沸石的典型技术包括使用溶解/再结晶装置，通过水热处理，使硅源、锗源和铝源的水凝胶转换为沸石晶体。反应介质还包含在晶化期间结合在沸石网络的微孔空间中的结构助剂，从而通过与沸石组分的相互作用控制网络的构造并帮助稳定结构。在不含氟的酸如硫酸、乙酸、硝酸、磷酸、盐酸或甲酸的存在下，反应发生。
Ge-沸石由含硅源、锗源、铝源和结构导向剂的水凝胶合成。
具体地，本发明涉及一种合成铝-硅-锗沸石的方法，包括：
a)通过混合硅源、锗源、铝源、结构导向剂和水形成反应混合物；
b)将步骤a)的反应混合物混合；
c)向步骤b)的反应混合物中引入不含氟的酸；
d)将步骤c)的反应混合物加热以形成沸石晶体；
e)将步骤d)的反应混合物冷却；
f)从步骤e)的反应混合物中分离沸石晶体；
g)将步骤f)的沸石晶体洗涤；
h)将步骤g)的沸石晶体干燥；和
i)将步骤h)的沸石晶体煅烧。
硅源的例子是二氧化硅或硅石(SiO2)，它可以各种形式得到，如硅溶胶，商业上可用的如Ludox AS-40TM，沉淀二氧化硅，商业上可用的如Ultrasil VN3SPTM和锻制氧化硅，商业上可用的如Aerosil 200TM。
铝源的例子是铝酸钠、硝酸铝、硫酸铝和假勃姆石。
锗源的例子是氧化锗、氯化锗、异丙醇锗和锗酸钠。
结构导向剂的例子是氢氧化四正丙铵、溴化四丙铵和氯化四丙铵。
酸可以是质子酸或路易斯酸。在本发明中有用的非限制性酸的例子是硫酸、乙酸、硝酸、磷酸、盐酸和甲酸。
将反应混合物搅拌并加热以形成沸石晶体。温度在100℃到200℃的范围内。将反应混合物冷却至室温。从凝胶中分离沸石晶体。为了从沸石晶体中除去水，可通过过滤、蒸发、喷雾干燥或任何其它方法除去凝胶的液体部分。在环境温度下用去离子水清洗沸石晶体，优选0℃到50℃，直到滤液的pH大约是7.5。将沸石晶体于空气中在90℃到110℃下干燥4到24小时，优选大约6小时。沸石晶体可于空气中在400℃到600℃下煅烧，优选大约550℃煅烧3到10小时，优选大约6小时。
MFI沸石的硅与铝原子比(Si∶Al)优选大于10∶1，更优选在从20∶1到200∶1的范围内，最优选在从25∶1到100∶1的范围内。氧化化硅与氧化锗(genmania)的比例优选在从100∶1到8∶1的范围内，更优选在从50∶1到10∶1的范围内和最优选在从25∶1到10∶1的范围内。
沸石平均孔径优选在从2埃到100埃的范围内，更优选在从2埃到50埃的范围内和最优选在从2埃到20埃的范围内。
贵金属，如铂，可沉积在Ge-沸石上(下文中称为Pt/Ge-沸石，或如果沸石是ZSM-5MFI，称为Pt/Ge-ZSM-5)。可煅烧Pt/Ge-沸石以产生Pt/Ge-沸石催化剂，其可用在每分子有2到6个碳原子的烷烃如苯、甲苯和二甲苯芳构化成为芳香烃的方法中。Pt/Ge-沸石可于空气中在200℃到500℃下煅烧，优选大约300℃煅烧1到6小时，优选大约4小时。在贵金属沉积之前或之后，沸石可通过镁、铝、钛、锆、钍、硅、硼的氧化物和其混合物结合。用粘合剂或用贵金属沉积，结合、沉积贵金属以及单独煅烧沸石的方法步骤能以任何一种顺序进行。
已经一般地描述了本发明，给出下列实施例作为本发明的详细具体实施方案以说明其操作和优点。能理解的是，作为说明给出了实施例，但不是为了将说明书或权利要求限制为遵循任何方式。
实施例1
制备下列溶液：
●溶液#1：将3.80g氢氧化钠溶解在37.84g去离子(DI)水中。加入3.30g氧化锗并搅拌直到获得清澈的溶液。
●溶液#2：将0.85g铝酸钠(57wt％Al2O3，35wt％Na2O和8wt％H2O)溶解在49.61gDI水中。
将溶液#1添加到57.66g硅溶胶(Ludox AS-40)中，并在室温下剧烈搅拌以形成均匀的白色凝胶。加入溶液2#并充分混合。向混合物中添加55.60g40wt％的氢氧化四丙铵(TPAOH)并充分搅拌1小时。加入11.42g冰乙酸(AA)并另外搅拌15分钟。合成凝胶的摩尔比显示在表1中。将凝胶装入内衬PTFE的高压釜，并在持续搅拌下将凝胶加热至160℃，保持36小时。由组分计算摩尔比。
表1实施例1的摩尔比
过滤沸石并在有空气流的炉中在550℃下煅烧6小时。
实施例2
制备下列溶液：
●溶液#1：将12.15g氢氧化钠溶解在120.30g DI水中。加入6.89g GeO2并搅拌直到获得清澈均匀的溶液。
●溶液#2：用222.29g DI水稀释108.51g 40wt％的TPAOH溶液。加入1.66g假勃姆石(来自Alcoa的HiQ-40)并搅拌充分。
将溶液#1添加到159.87g硅溶胶(Ludox AS-40)中并充分搅拌成均匀的白色凝胶。加入溶液#2并搅拌充分。添加25.68g冰乙酸并在室温下搅拌凝胶15分钟。凝胶的摩尔组成显示在表2中。将凝胶装入内衬PTFE的高压釜，持续搅拌下在160℃合成36小时。过滤沸石并在有空气流的炉中在550℃下煅烧6小时。由组分计算摩尔比。
表2实施例2中合成凝胶的摩尔比
比较例(未添加酸)
制备下列溶液：
●溶液#1：将4.08g氢氧化钠溶解在45.26g DI水中。加入2.31g GeO2并搅拌直到获得清澈均匀的溶液。
●溶液#2：将0.76g铝酸钠(57wt％Al2O3，35wt％Na2O和8wt％H2O)溶解在25.13g DI水中
●溶液#3：用58.37g DI水稀释40.43g 40wt％的TPAOH溶液。
将溶液#1添加到57.20g硅溶胶(Ludox AS-40)中并充分搅拌成均匀的白色凝胶。加入溶液#2并搅拌充分。加入溶液#3。凝胶的摩尔组成显示在表3中。将凝胶装入内衬PTFE的高压釜，持续搅拌下在160℃合成36小时。过滤沸石并在有空气流的炉中在550℃下煅烧6小时。由组分计算摩尔比。
表3比较例中合成凝胶的摩尔比
通过X-射线荧光光谱分析上面例子中的每个沸石以确定硅、铝、钠和锗的含量。
表4
| 沸石 | Ge(wt％) | Si(wt％) | Al(wt％) |
| 实施例1 | 7.08 | 39.48 | 0.87 |
| 实施例2 | 5.42 | 40.02 | 0.88 |
| 比较例 | 0.44 | 43.94 | 1.08 |
如上面的结果所示，为了更好地使锗结合入沸石的结构中，添加无氟反应物如酸是必须的。
根据以上教导，本发明可进行许多改进和变化。应理解的是，本发明除按具体所述实施之外，可在所附权利要求的范围内实施。
Claims (20)
1.一种合成铝-硅-锗沸石的方法，包括：
a)通过结合和混合硅源、锗源、铝源、结构导向剂和水形成反应混合物；
b)向步骤a)的反应混合物中引入不含氟的酸；
c)将步骤b)的反应混合物加热以形成沸石晶体；
d)将步骤c)的反应混合物冷却；
e)从步骤d)的反应混合物中分离沸石晶体；
f)将步骤e)的沸石晶体洗涤；
g)将步骤f)的沸石晶体干燥；和
h)将步骤g)的沸石晶体煅烧。
2.如权利要求1的方法，其中在步骤c)中反应混合物被加热到100℃到200℃范围内的温度。
3.如权利要求1的方法，其中在步骤d)中反应混合物被冷却到室温。
4.如权利要求1的方法，其中在步骤e)中通过过滤分离沸石晶体。
5.如权利要求1的方法，其中在步骤f)中洗涤是用去离子水在0℃到50℃下进行，直到滤液的pH值大约是7.5。
6.如权利要求1的方法，其中在步骤g)中沸石晶体于空气中在90℃到110℃下干燥4到24小时。
7.如权利要求1的方法，其中在步骤h)中沸石晶体于空气中在400℃到600℃下煅烧3到10小时。
8.如权利要求1的方法，其中硅源是氧化硅。
9.如权利要求8的方法，其中硅源是硅溶胶、沉淀二氧化硅或煅制二氧化硅。
10.如权利要求1的方法，其中铝源是铝酸钠、硝酸铝、硫酸铝或假勃姆石。
11.如权利要求1的方法，其中锗源是氧化锗、氯化锗、异丙醇锗或锗酸钠。
12.如权利要求1的方法，其中结构导向剂是氢氧化四正丙铵、溴化四正丙铵和氯化四正丙铵。
13.如权利要求1的方法，其中酸是硫酸、乙酸、硝酸、磷酸、盐酸或甲酸。
14.权利要求1的方法，其中沸石具有MFI、FAU、TON、MFL、VPI、MEL、AEL、AFI、MWW或MOR的结构。
15.权利要求14的方法，其中沸石具有MFI结构和硅与铝的原子比在从10∶1到200∶1的范围内。
16.权利要求15的方法，其中硅与铝的原子比在从20∶1到200∶1的范围内。
17.权利要求16的方法，其中硅与铝的原子比在从25∶1到100∶1的范围内。
18.权利要求14的方法，其中沸石具有MFI结构和氧化硅与氧化锗的摩尔比例在从100∶1到8∶1的范围内。
19.权利要求18的方法，其中氧化硅与氧化锗的摩尔比例在从50∶1到10∶1的范围内。
20.权利要求19的方法，其中氧化硅与氧化锗的摩尔比例在从25∶1到10∶1的范围内。
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| CN1735451A (zh) * | 2002-11-25 | 2006-02-15 | 亚拉国际有限公司 | 多金属沸石催化剂的制备和活化方法、催化剂组合物和用于减少n2o的应用 |
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- 2004-12-27 US US11/023,100 patent/US7449168B2/en active Active
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2005
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- 2005-12-26 JP JP2007549556A patent/JP4673379B2/ja not_active Expired - Fee Related
- 2005-12-26 EP EP05855617.6A patent/EP1848664B1/en not_active Not-in-force
- 2005-12-26 CN CN200580044988.0A patent/CN101090865B/zh not_active Expired - Fee Related
- 2005-12-26 WO PCT/US2005/047091 patent/WO2006071871A1/en active Application Filing
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| US6784333B2 (en) * | 2002-08-06 | 2004-08-31 | Saudi Basic Industries Corporation | Catalyst for aromatization of alkanes, process of making and using thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2023244652A1 (en) * | 2022-06-14 | 2023-12-21 | University Of Houston System | Synthesis of nano-sized zeolites |
Also Published As
| Publication number | Publication date |
|---|---|
| US7449168B2 (en) | 2008-11-11 |
| EP1848664A1 (en) | 2007-10-31 |
| JP2008525306A (ja) | 2008-07-17 |
| ZA200705155B (en) | 2008-09-25 |
| EP1848664A4 (en) | 2014-01-22 |
| WO2006071871A1 (en) | 2006-07-06 |
| EP1848664B1 (en) | 2018-12-19 |
| JP4673379B2 (ja) | 2011-04-20 |
| CN101090865A (zh) | 2007-12-19 |
| MY140466A (en) | 2009-12-31 |
| US20060140854A1 (en) | 2006-06-29 |
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