WO2013154086A1 - ベータ型ゼオライト及びその製造方法 - Google Patents
ベータ型ゼオライト及びその製造方法 Download PDFInfo
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- WO2013154086A1 WO2013154086A1 PCT/JP2013/060684 JP2013060684W WO2013154086A1 WO 2013154086 A1 WO2013154086 A1 WO 2013154086A1 JP 2013060684 W JP2013060684 W JP 2013060684W WO 2013154086 A1 WO2013154086 A1 WO 2013154086A1
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 title claims abstract description 116
- 239000010457 zeolite Substances 0.000 title claims abstract description 111
- 229910021536 Zeolite Inorganic materials 0.000 title claims abstract description 107
- 238000004519 manufacturing process Methods 0.000 title claims description 20
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 54
- 239000013078 crystal Substances 0.000 claims abstract description 53
- 239000011541 reaction mixture Substances 0.000 claims abstract description 31
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 29
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000003513 alkali Substances 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 14
- 239000002245 particle Substances 0.000 claims description 14
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 13
- 238000010304 firing Methods 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 abstract description 9
- 239000003463 adsorbent Substances 0.000 abstract description 8
- 229910052681 coesite Inorganic materials 0.000 abstract 1
- 229910052593 corundum Inorganic materials 0.000 abstract 1
- 229910052906 cristobalite Inorganic materials 0.000 abstract 1
- 229910052682 stishovite Inorganic materials 0.000 abstract 1
- 229910052905 tridymite Inorganic materials 0.000 abstract 1
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 30
- 239000000047 product Substances 0.000 description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- 229910052757 nitrogen Inorganic materials 0.000 description 15
- 238000003756 stirring Methods 0.000 description 15
- 238000002441 X-ray diffraction Methods 0.000 description 14
- 238000001179 sorption measurement Methods 0.000 description 10
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 9
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical group [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 9
- 239000004110 Zinc silicate Substances 0.000 description 9
- 229910052725 zinc Inorganic materials 0.000 description 9
- 239000011701 zinc Substances 0.000 description 9
- XSMMCTCMFDWXIX-UHFFFAOYSA-N zinc silicate Chemical compound [Zn+2].[O-][Si]([O-])=O XSMMCTCMFDWXIX-UHFFFAOYSA-N 0.000 description 9
- 235000019352 zinc silicate Nutrition 0.000 description 9
- 230000032683 aging Effects 0.000 description 8
- 229910052782 aluminium Inorganic materials 0.000 description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 8
- 239000012535 impurity Substances 0.000 description 8
- 239000011734 sodium Substances 0.000 description 8
- 229910000323 aluminium silicate Inorganic materials 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 238000002425 crystallisation Methods 0.000 description 7
- 230000008025 crystallization Effects 0.000 description 7
- 239000011148 porous material Substances 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- 239000007788 liquid Substances 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 6
- -1 tetraethylammonium ions Chemical class 0.000 description 6
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 6
- 239000006227 byproduct Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 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 4
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 4
- 238000001354 calcination Methods 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 229910001388 sodium aluminate Inorganic materials 0.000 description 4
- 229910001415 sodium ion Inorganic materials 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000002808 molecular sieve Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 3
- BEAZKUGSCHFXIQ-UHFFFAOYSA-L zinc;diacetate;dihydrate Chemical compound O.O.[Zn+2].CC([O-])=O.CC([O-])=O BEAZKUGSCHFXIQ-UHFFFAOYSA-L 0.000 description 3
- 239000004115 Sodium Silicate Substances 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000008204 material by function Substances 0.000 description 2
- 239000012452 mother liquor Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 229910052911 sodium silicate Inorganic materials 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 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 description 1
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 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
- 239000002585 base Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000001784 detoxification Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000002431 foraging effect Effects 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- 230000010534 mechanism of action Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical compound CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 description 1
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- 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
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- 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
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- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
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- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
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- C01B39/06—Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis
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- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Definitions
- the present invention relates to a beta zeolite and a method for producing the same.
- Synthetic zeolite is crystalline aluminosilicate and has uniform angstrom-sized pores due to its crystal structure. Taking advantage of this feature, synthetic zeolite is industrially used as a molecular sieve adsorbent that adsorbs only molecules having a specific size, an adsorbent separation agent that adsorbs molecules with strong affinity, or a catalyst base.
- One of such zeolites, beta-type zeolite is currently used in large quantities all over the world as a catalyst in the petrochemical industry and as an adsorbent for treating automobile exhaust gas.
- beta-type zeolite Various methods for synthesizing beta-type zeolite have been proposed.
- a common method is to use a surfactant such as tetraethylammonium ion as an organic structure directing agent (hereinafter abbreviated as “OSDA”).
- OSDA organic structure directing agent
- compounds containing tetraethylammonium ions are expensive, and most of them are decomposed after the crystallization of beta zeolite is completed, so that they cannot be recovered and reused. Therefore, the beta zeolite produced by this method is expensive.
- tetraethylammonium ions are taken into the crystal, it must be removed by firing when used as an adsorbent or a catalyst.
- the exhaust gas at that time causes environmental pollution and also requires many chemicals for the detoxification treatment of the synthetic mother liquor.
- the synthesis method of beta-type zeolite using tetraethylammonium ions is not only expensive, but also a production method with a large environmental load. Therefore, it has been desired to realize a production method that does not use OSDA.
- mesoporous molecular sieves such as MCM-41 are known as porous crystals having pores in the mesopore region. Since the OSDA is still used for the synthesis of the mesoporous molecular sieve, there are the disadvantages described above.
- An object of the present invention is to provide a beta-type zeolite whose performance is further improved as compared with the above-described conventional beta-type zeolite and a method for producing the same.
- the SiO 2 / Al 2 O 3 ratio is 8 to 30, and the SiO 2 / ZnO ratio is 8 to 1000
- the micropore surface area is 300 to 800 m 2 / g
- the micropore volume is 0.1 to 0.3 cm 3 / g
- the present invention provides a suitable method for producing the beta zeolite, (1) A silica source, an alumina source, an alkali source, and water are mixed so as to be a reaction mixture having a composition represented by a molar ratio shown below.
- a beta zeolite having an SiO 2 / ZnO ratio of 4 to 50, an SiO 2 / Al 2 O 3 ratio of 4 or more, and an average particle diameter of 100 nm or more is seeded without firing.
- the beta zeolite of the present invention has both micropores and mesopores, and is useful as a catalyst, an adsorbent, an ion exchanger, and various functional materials.
- FIG. 1 is an X-ray diffraction pattern of the zinc silicate beta zeolite used in Example 1 in an unfired state.
- FIG. 2 is an X-ray diffraction pattern of the beta zeolite obtained in Example 1.
- FIG. 3 is a nitrogen adsorption isotherm at the liquid nitrogen temperature for the beta zeolite obtained in Example 1.
- FIG. 4 is an X-ray diffraction pattern of the beta zeolite obtained in Example 2.
- FIG. 5 is an X-ray diffraction pattern of the beta zeolite obtained in Example 8.
- FIG. 6 is a nitrogen adsorption isotherm at liquid nitrogen temperature for the beta zeolite obtained in Example 8.
- FIG. 7 is an X-ray diffraction pattern of the beta zeolite obtained in Example 10.
- FIG. 8 is a nitrogen adsorption isotherm at the liquid nitrogen temperature for the beta zeolite obtained in Example 10.
- the beta zeolite of the present invention has one of the characteristics in that it has both micropores and mesopores.
- Conventionally known beta-type zeolites have micropores, but beta-type zeolites that have mesopores in addition to micropores have not been known so far.
- the beta zeolite of the present invention has an aluminosilicate skeleton, and a part of aluminum in the aluminosilicate skeleton is substituted with zinc.
- the beta zeolite of the present invention is a very novel substance that has not been known so far.
- Micropores are pores having a diameter of less than 2 nm
- mesopores are pores having a diameter of 2 nm or more and 50 nm or less.
- the content of zinc contained in the beta zeolite of the present invention is 8 to 1000, preferably 10 to 500, and more preferably 10 to 350, when the content is expressed in terms of SiO 2 / ZnO ratio.
- the content of aluminum in terms of the SiO 2 / Al 2 O 3 ratio is 8 to 30, preferably 10 to 25, and more preferably 10 to 22.
- the amounts of zinc and aluminum contained in the beta zeolite of the present invention are controlled by adjusting the gel composition, the zinc content in the seed crystal, the ratio of addition of the gel and the seed crystal, etc. in the production method described later. it can.
- the beta zeolite of the present invention has both micropores and mesopores.
- the micropores have a volume of 0.1 to 0.3 cm 3 / g. And preferably 0.11 to 0.3 cm 3 / g, and more preferably 0.12 to 0.3 cm 3 / g.
- the surface area of the micropores is 300 to 800 m 2 / g, preferably 300 to 750 m 2 / g, and more preferably 330 to 700 m 2 / g.
- the mesopores have a diameter of 2 to 6 nm, preferably 2 to 5 nm, more preferably 3 to 5 nm, as synthesized.
- the volume of the mesopores is 0.001 to 0.3 cm 3 / g, preferably 0.003 to 0.2 cm 3 / g, more preferably 0.005 to 0 in the as-synthesized state. .1 cm 3 / g.
- the beta-type zeolite of the present invention having micropores and mesopores of the size as described above and containing zinc is an exhaust gas purification catalyst for petrol chemical products such as gasoline engines and diesel engines, and synthesis of petrochemical products. It is useful as a catalyst, a selective synthesis catalyst for structural isomers, an adsorbent in an N 2 / O 2 adsorption separation process, an ion exchanger, and various functional materials.
- the beta zeolite of the present invention is preferably 400 to 800 m 2 / g, more preferably 500 to 800 m 2. / G.
- the beta-type zeolite of the present invention includes sodium-type zeolites and those containing alkali metal ions or divalent metal ions other than sodium, and sodium ions are ion-exchanged with protons to form H + type. Is also included.
- the beta zeolite is of the H + type, the various physical properties are measured after replacing protons with sodium ions.
- the sodium type beta zeolite is dispersed in an aqueous ammonium salt solution such as ammonium nitrate, and sodium ions in the zeolite are replaced with ammonium ions. By calcining this ammonium type beta zeolite, an H + type beta zeolite can be obtained.
- beta zeolite seed crystal is used and grown in a gel having a specific composition to obtain a beta zeolite having a target structure.
- Zinc silicate beta zeolite is used as the seed crystal.
- This special seed crystal is used. By using this seed crystal, it is possible to successfully produce a beta zeolite having both target micropores and mesopores. On the other hand, even if ordinary aluminosilicate beta zeolite is used, a beta zeolite having the target structure cannot be obtained.
- the zincosilicate beta zeolite has a structure in which all or a part of aluminum in the aluminosilicate beta zeolite is substituted with zinc.
- Zinc silicate beta-type zeolite is a substance known in the technical field, and its production method and the like are described in, for example, the following documents 1 to 3. In these documents, zincosilicate beta zeolite is synthesized using, for example, tetraethylammonium hydroxide as OSDA.
- Reference 1 J. Phys. Chem., B 1999, 103, 2674-2679
- Reference 2 Topics in Catalysis 9 (1999), 35-42 Reference 3: Chem. Eur. J. 2002, 8, No. 22, 5153-5160
- the SiO 2 / ZnO ratio is 4 to 50, preferably 5 to 40, more preferably 8 to 30.
- the SiO 2 / Al 2 O 3 ratio is 4 or more, preferably 10 or more, more preferably 13 or more, and still more preferably 20 or more.
- the seed crystal may not contain aluminum.
- the average particle size of the seed crystal is 100 nm or more, preferably 100 to 2000 nm, more preferably 200 to 1000 nm.
- the size of the zeolite crystals obtained by the synthesis is generally not uniform, and it is not difficult to determine the crystal particle size having a certain degree of particle size distribution and having the maximum frequency.
- the average particle diameter refers to the maximum particle diameter of crystals in observation with a scanning electron microscope.
- Beta-type zeolite composed of zinc silicate obtained by the methods described in the above-mentioned documents 1 to 3 generally has an average particle size in the range of 100 nm to 1000 nm. However, the particle diameter is unclear due to the aggregation of small particles, or there are those exceeding 1000 nm.
- beta zeolite having an average particle size of 100 nm or more is used as a seed crystal. Since the beta zeolite obtained by this production method also has an average particle diameter in this range, it can be suitably used as a seed crystal.
- the reaction mixture to which the seed crystal is added is obtained by mixing a silica source, an alumina source, an alkali source, and water so as to have a composition represented by the molar ratio shown below.
- a beta zeolite having the desired micropores and mesopores can be obtained for the first time.
- silica source used for obtaining the reaction mixture having the above molar ratio examples include silica itself and silicon-containing compounds capable of generating silicate ions in water. Specific examples include wet method silica, dry method silica, colloidal silica, sodium silicate, aluminosilicate gel, and the like. These silica sources can be used alone or in combination of two or more. Of these silica sources, the use of silica (silicon dioxide) is preferred in that a beta zeolite can be obtained without unnecessary by-products.
- alumina source for example, a water-soluble aluminum-containing compound can be used. Specific examples include sodium aluminate, aluminum nitrate, and aluminum sulfate.
- Aluminum hydroxide is also a suitable alumina source. These alumina sources can be used alone or in combination of two or more. Of these alumina sources, it is preferable to use sodium aluminate or aluminum hydroxide because a beta zeolite can be obtained without unnecessary by-products (for example, sulfate, nitrate, etc.).
- the alkali source for example, sodium hydroxide can be used.
- sodium silicate is used as the silica source or sodium aluminate is used as the alumina source
- sodium which is an alkali metal component contained therein is simultaneously regarded as NaOH and is also an alkali component.
- NaOH sodium hydroxide
- the method of adding the raw materials when preparing the reaction mixture may be a method that facilitates obtaining a uniform reaction mixture.
- a uniform reaction mixture can be obtained by adding and dissolving an alumina source in an aqueous sodium hydroxide solution at room temperature, then adding a silica source and stirring and mixing.
- the seed crystal is generally added by mixing with the silica source or after the silica source is added, but there is no particular limitation on the timing of addition. Thereafter, stirring and mixing are performed so that the seed crystals are uniformly dispersed.
- the temperature at which the reaction mixture is prepared and generally the reaction may be performed at room temperature (20 to 25 ° C.).
- the reaction mixture containing the seed crystals is placed in a sealed container and heated to react, and the beta zeolite is crystallized under an autogenous pressure.
- This reaction mixture does not contain OSDA. It is important to use the seed crystal as it is obtained by the method described in Documents 1 to 3 described above. That is, this seed crystal is not subjected to firing. Therefore, the OSDA used in the synthesis of the seed crystal remains in the pores of the seed crystal. Even if a beta zeolite made of zinc silicate subjected to calcination is used as a seed crystal, the target beta zeolite having micropores and mesopores cannot be obtained.
- the amount of seed crystals added to the reaction mixture is 0.1 to 20% by weight, preferably 0.5 to 15% by weight, more preferably 1 to 10% by weight, based on the silica component in the reaction mixture. A percentage. By setting the ratio of the seed crystal and the reaction mixture within this range, the target beta-type zeolite having micropores and mesopores can be successfully produced.
- aging refers to an operation of maintaining the temperature at a temperature lower than the reaction temperature for a certain period of time. In aging, it is generally allowed to stand without stirring. It is known that by aging, effects such as preventing by-product impurities, enabling heating under stirring without by-product impurities, and increasing the reaction rate are known. However, the mechanism of action is not always clear. The temperature and time for aging are set so that the above-mentioned effects are maximized. In this production method, aging is preferably carried out at 20 to 100 ° C., more preferably 20 to 80 ° C., more preferably 20 to 60 ° C., and preferably in the range of 2 hours to 1 day.
- the heating temperature is in the range of 80 to 200 ° C., preferably 100 to 200 ° C., more preferably 120 to 180 ° C. in both cases where crystallization is performed under stationary conditions and crystallization is performed under stirring conditions. Range. This heating is under autogenous pressure. If the temperature is less than 80 ° C., the crystallization rate becomes extremely slow, so that the production efficiency of the beta zeolite is deteriorated. On the other hand, when the temperature exceeds 200 ° C., an autoclave having a high pressure resistance is required, which is not economical, and the generation rate of impurities increases.
- the heating time is not critical in the present production method, and it may be heated until a beta zeolite with sufficiently high crystallinity is produced. In general, satisfactory crystalline beta zeolite can be obtained by heating for about 5 to 150 hours.
- Crystals of beta zeolite are obtained by the heating. After completion of the heating, the produced crystal powder is separated from the mother liquor by filtration, then washed with water or warm water and dried. Since the amount of the organic substance substantially contained in the dry state is small, it can be used as an adsorbent or the like if it is dehydrated without firing. However, in order to fully exhibit the characteristics of the obtained beta-type zeolite crystals, it is preferable to perform a calcination treatment. Firing can be easily performed by a method such as heat treatment in air at a temperature of 500 ° C. or higher. When used as a solid acid catalyst, it can be used as an H + type by, for example, calcination after exchanging Na + ions in the crystal with NH 4 + ions.
- Powder X-ray diffractometer manufactured by Mac Science Co., Ltd., powder X-ray diffractometer MO3XHF 22 , using Cuk ⁇ ray, voltage 40 kV, current 30 mA, scan step 0.02 °, scan speed 2 ° / min
- Composition analyzer ICP-AES LIBERTY Series II manufactured by Varian Scanning Electron Microscope: Field Emission Scanning Electron Microscope S-4800, manufactured by Hitachi High- Proceedings S Corporation BET surface area measuring device: AUTOSORB-1 manufactured by Cantachrome Instruments
- Example 1 (1) Synthesis of seed crystal Tetraethylammonium hydroxide (TEAOH) was used as OSDA. Further, zinc diacetate dihydrate was used as a zinc source, and fine powdered silica (Cab-O-Sil, M-5) was used as a silica source. Further, lithium hydroxide and sodium hydroxide were used. Among these raw materials, TEAOH, lithium hydroxide and sodium hydroxide were dissolved in water, zinc diacetate dihydrate was added, and then fine powdered silica was added and stirred for 2 hours.
- TEAOH seed crystal Tetraethylammonium hydroxide
- the composition of the reaction mixture thus obtained was 0.05M lithium hydroxide, 0.65M TEAOH, 0.03M zinc diacetate dihydrate, 1M finely divided silica, and 30M water. It was.
- the reaction mixture was placed in a stainless steel autoclave with a polytetrafluoroethylene lining and heated at 150 ° C. for 96 hours under static conditions. By this heating, a zincosilicate beta zeolite having a SiO 2 / ZnO ratio of 13.1 and an infinite SiO 2 / Al 2 O 3 ratio was synthesized.
- FIG. 1 shows an X-ray diffraction pattern of the beta zeolite before firing. When this beta zeolite was observed with a scanning electron microscope, the average particle size was 640 nm. The beta zeolite crystals were used as seed crystals without firing.
- Beta-type Zeolite 0.036 g of sodium aluminate and 1.284 g of 36% sodium hydroxide aqueous solution were dissolved in 4.759 g of pure water to obtain an aqueous solution.
- a mixture of 0.937 g of finely divided silica (Cab-O-Sil, M-5) and 0.094 g of seed crystals was added little by little to the aqueous solution and mixed with stirring.
- the composition of the gel after mixing was as shown in Table 1.
- the addition amount of the seed crystal was 10% with respect to the silica component in the gel.
- the mixture of the gel and the seed crystal was put in a 23 cc stainless steel sealed container and allowed to stand at 140 ° C.
- Beta-type zeolite was obtained in the same manner as in Example 1 except that the conditions shown in Table 1 were adopted. The obtained beta zeolite was evaluated in the same manner as in Example 1. The results are shown in Table 1.
- an X-ray diffraction pattern of the beta-type zeolite obtained in Example 2 before firing is shown in FIG.
- an X-ray diffraction diagram and a nitrogen adsorption isotherm of the beta zeolite obtained in Example 8 are shown in FIGS. 5 and 6, respectively, and the beta zeolite obtained in Example 10 is not fired.
- X-ray diffraction diagrams and nitrogen adsorption isotherms are shown in FIGS. 7 and 8, respectively.
- Example 1 As a seed crystal, an aluminosilicate beta zeolite calcined product synthesized using TEAOH as OSDA was used. This beta-type zeolite had a SiO 2 / Al 2 O 3 ratio of 24.0 and did not contain ZnO. This seed crystal was added to a reaction mixture (gel) prepared using the same raw materials as those used in Example 1. The composition of the gel is as shown in Table 2. The gel containing the seed crystals was heated under the conditions shown in Table 2 to crystallize the beta zeolite. The obtained product was filtered and washed with water to obtain a white powder.
- this product was a beta zeolite containing no impurities. However, it was confirmed from the nitrogen adsorption isotherm at liquid nitrogen temperature that no mesopores were present.
- Example 4 As a seed crystal, the unsintered zinc silicate beta zeolite fired product used in Example 2 (in air, 550 ° C., 10 hours) was used. Except this, it reacted with the same composition and conditions as Example 2. The obtained product was filtered and washed with water to obtain a white powder. As a result of X-ray diffraction of this product, this product was amorphous.
Abstract
Description
(ii)ミクロ孔表面積が300~800m2/gであり、
(iii)ミクロ孔容積が0.1~0.3cm3/gであり、
(iv)合成したままの状態で直径が2~6nmであり、その容積が0.001~0.3cm3/gであるメソ孔を有する、ことを特徴とするベータ型ゼオライトを提供するものである。
(1)以下に示すモル比で表される組成の反応混合物となるように、シリカ源、アルミナ源、アルカリ源、及び水を混合し、
SiO2/Al2O3=8~300
Na2O/SiO2=0.05~0.6
H2O/SiO2=5~50
(2)SiO2/ZnO比が4~50であり、かつSiO2/Al2O3比が4以上であり、かつ平均粒子径が100nm以上であるベータ型ゼオライトを、焼成することなく種結晶として用い、これを、前記反応混合物中のシリカ成分に対して0.1~20重量%の割合で該反応混合物に添加し、
(3)前記種結晶が添加された前記反応混合物を80~200℃で密閉加熱する、ことを特徴とするベータ型ゼオライトの製造方法を提供するものである。
・文献1:J. Phys. Chem., B 1999, 103, 2674-2679
・文献2:Topics in Catalysis 9 (1999), 35-42
・文献3:Chem. Eur. J. 2002, 8, No.22, 5153-5160
SiO2/Al2O3=8~300
Na2O/SiO2=0.05~0.6
H2O/SiO2=5~50
SiO2/Al2O3=20~300
Na2O/SiO2=0.1~0.5
H2O/SiO2=10~30
組成分析装置:(株)バリアン製、ICP-AES LIBERTY SeriesII
走査型電子顕微鏡:(株)日立ハイテクノロジーズ社製、電界放出型走査電子顕微鏡 S-4800
BET表面積測定装置:(株)カンタクローム インスツルメンツ社製 AUTOSORB-1
(1)種結晶の合成
テトラエチルアンモニウムヒドロキシド(TEAOH)をOSDAとして用いた。また、二酢酸亜鉛二水和物を亜鉛源として用い、微粉状シリカ(Cab-O-Sil、M-5)をシリカ源として用いた。更に水酸化リチウム、水酸化ナトリウムを用いた。これらの原料のうち、TEAOH、水酸化リチウム及び水酸化ナトリウムを水に溶解させた後、二酢酸亜鉛二水和物を添加し、次いで微粉状シリカを添加して2時間撹拌した。このようにして得られた反応混合物の組成は、水酸化リチウムが0.05M、TEAOHが0.65M、二酢酸亜鉛二水和物が0.03M、微粉状シリカが1M、水が30Mであった。この反応混合物をポリ四フッ化エチレンの内張を有するステンレス製のオートクレーブ内に入れ、静止状態下に150℃で96時間にわたり加熱した。この加熱によってSiO2/ZnO比が13.1であり、SiO2/Al2O3比が無限大であるジンコシリケートベータ型ゼオライトを合成した。このベータ型ゼオライトの未焼成でのX線回折図を図1に示す。このベータ型ゼオライトを走査型電子顕微鏡で観察したところ平均粒子径は640nmであった。このベータ型ゼオライトの結晶を未焼成のまま種結晶として使用した。
純水4.759gに、アルミン酸ナトリウム0.036gと36%水酸化ナトリウム水溶液1.284gを溶解して水溶液を得た。微粉状シリカ(Cab-O-Sil、M-5)0.937gと、0.094gの種結晶とを混合したものを、前記の水溶液に少しずつ添加して撹拌混合した。混合後のゲルの組成は、表1に示すとおりであった。また種結晶の添加量は、ゲル中のシリカ成分に対して10%であった。ゲルと種結晶の混合物を23ccのステンレス製密閉容器に入れて、熟成及び撹拌することなしに140℃で2日間、自生圧力下で静置加熱した。密閉容器を冷却後、生成物をろ過、水洗浄して白色粉末を得た。この生成物のX線回折の結果、この生成物は不純物を含まないベータ型ゼオライトであることが確認された。未焼成品のX線回折図を図2に示す。また、液体窒素温度における窒素吸着等温線(図3)から、表1に示すような特徴を有するミクロ孔とメソ孔を併せ持つことが確認された。細孔特性を表す数値を表1に示す。
種結晶として、TEAOHをOSDAとして用いて合成したアルミノシリケートベータ型ゼオライトの焼成品を用いた。このベータ型ゼオライトは、SiO2/Al2O3比が24.0であり、ZnOを含有しないものであった。実施例1で用いたものと同じ原料を用いて調製した反応混合物(ゲル)に、この種結晶を添加した。ゲルの組成は表2に示すとおりである。種結晶を含むゲルを表2に示す条件で加熱してベータ型ゼオライトの結晶化を行った。得られた生成物をろ過、水洗浄して白色粉末を得た。この生成物のX線回折の結果、この生成物は不純物を含まないベータ型ゼオライトであることが確認された。しかし、液体窒素温度における窒素吸着等温線から、メソ孔が全く存在しないことが確認された。
種結晶として、比較例1で用いたアルミノシリケートベータ型ゼオライトの焼成品を用いた。この種結晶を、表2に示す組成の反応混合物(ゲル)に添加し、表2に示す条件で加熱してベータ型ゼオライトの結晶化を行った。得られた生成物をろ過、水洗浄して白色粉末を得た。この生成物のX線回折の結果、この生成物は不純物を含まないベータ型ゼオライトであることが確認された。しかし、液体窒素温度における窒素吸着等温線から、メソ孔が全く存在しないことが確認された。
種結晶として、実施例2で用いた未焼成のジンコシリケートベータ型ゼオライトの焼成品(空気中、550℃、10時間)を用いた。これ以外は実施例2と同じ組成及び条件で反応を行った。得られた生成物をろ過、水洗浄して白色粉末を得た。この生成物のX線回折の結果、この生成物はアモルファスであった。
Claims (4)
- (i)SiO2/Al2O3比が8~30であり、かつSiO2/ZnO比が8~1000であり、
(ii)ミクロ孔表面積が300~800m2/gであり、
(iii)ミクロ孔容積が0.1~0.3cm3/gであり、
(iv)合成したままの状態で直径が2~6nmであり、その容積が0.001~0.3cm3/gであるメソ孔を有する、ことを特徴とするベータ型ゼオライト。 - (1)以下に示すモル比で表される組成の反応混合物となるように、シリカ源、アルミナ源、アルカリ源、及び水を混合し、
SiO2/Al2O3=8~300
Na2O/SiO2=0.05~0.6
H2O/SiO2=5~50
(2)SiO2/ZnO比が4~50であり、かつSiO2/Al2O3比が4以上であり、かつ平均粒子径が100nm以上であるベータ型ゼオライトを、焼成することなく種結晶として用い、これを、前記反応混合物中のシリカ成分に対して0.1~20重量%の割合で該反応混合物に添加し、
(3)前記種結晶が添加された前記反応混合物を80~200℃で密閉加熱する、ことを特徴とするベータ型ゼオライトの製造方法。 - 反応混合物を加熱する前に、20~100℃の温度下に熟成する請求項2に記載の製造方法。
- 密閉加熱する工程で反応混合物を撹拌する請求項1ないし3のいずれか一項に記載の製造方法。
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JP2013234109A (ja) | 2013-11-21 |
US20150086786A1 (en) | 2015-03-26 |
KR102013974B1 (ko) | 2019-08-23 |
JP6034224B2 (ja) | 2016-11-30 |
US9688541B2 (en) | 2017-06-27 |
EP2837596A4 (en) | 2015-05-06 |
KR20150005538A (ko) | 2015-01-14 |
CN104321280A (zh) | 2015-01-28 |
EP2837596A1 (en) | 2015-02-18 |
EP2837596B1 (en) | 2016-05-18 |
CN104321280B (zh) | 2016-09-07 |
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