CN115321555A - Method for synthesizing high-silicon AFX zeolite molecular sieve by using small-molecule organic template agent - Google Patents
Method for synthesizing high-silicon AFX zeolite molecular sieve by using small-molecule organic template agent Download PDFInfo
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 87
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 87
- 229910021536 Zeolite Inorganic materials 0.000 title claims abstract description 61
- 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 61
- 239000010457 zeolite Substances 0.000 title claims abstract description 61
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 59
- 239000010703 silicon Substances 0.000 title claims abstract description 59
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 20
- 238000000034 method Methods 0.000 title claims abstract description 19
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 13
- 150000003384 small molecules Chemical class 0.000 title claims description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 124
- 239000003054 catalyst Substances 0.000 claims abstract description 10
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 99
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 73
- 239000007795 chemical reaction product Substances 0.000 claims description 44
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 42
- 239000000243 solution Substances 0.000 claims description 41
- 238000005406 washing Methods 0.000 claims description 37
- 238000003756 stirring Methods 0.000 claims description 33
- 238000002425 crystallisation Methods 0.000 claims description 27
- 230000008025 crystallization Effects 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical group [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 16
- SGRHVVLXEBNBDV-UHFFFAOYSA-N 1,6-dibromohexane Chemical compound BrCCCCCCBr SGRHVVLXEBNBDV-UHFFFAOYSA-N 0.000 claims description 7
- 239000003957 anion exchange resin Substances 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 238000000967 suction filtration Methods 0.000 claims description 7
- 238000001291 vacuum drying Methods 0.000 claims description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000005342 ion exchange Methods 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 6
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical group O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 6
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 239000011734 sodium Substances 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- AMVQGJHFDJVOOB-UHFFFAOYSA-H aluminium sulfate octadecahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O AMVQGJHFDJVOOB-UHFFFAOYSA-H 0.000 claims description 4
- GNVRJGIVDSQCOP-UHFFFAOYSA-N n-ethyl-n-methylethanamine Chemical compound CCN(C)CC GNVRJGIVDSQCOP-UHFFFAOYSA-N 0.000 claims description 4
- 125000005270 trialkylamine group Chemical group 0.000 claims description 4
- 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 claims description 3
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 3
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims 1
- 230000032683 aging Effects 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 62
- 239000002994 raw material Substances 0.000 description 56
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 33
- 239000012467 final product Substances 0.000 description 31
- 239000000377 silicon dioxide Substances 0.000 description 31
- 239000008367 deionised water Substances 0.000 description 30
- 229910021641 deionized water Inorganic materials 0.000 description 30
- 238000001035 drying Methods 0.000 description 30
- 238000002156 mixing Methods 0.000 description 29
- -1 1-adamantyl Chemical group 0.000 description 27
- 229910001220 stainless steel Inorganic materials 0.000 description 27
- 239000010935 stainless steel Substances 0.000 description 27
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 25
- 239000004810 polytetrafluoroethylene Substances 0.000 description 25
- 239000000047 product Substances 0.000 description 11
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 3
- 238000010335 hydrothermal treatment Methods 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- DAZXVJBJRMWXJP-UHFFFAOYSA-N n,n-dimethylethylamine Chemical compound CCN(C)C DAZXVJBJRMWXJP-UHFFFAOYSA-N 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 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
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- 229910002796 Si–Al Inorganic materials 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- KMWBBMXGHHLDKL-UHFFFAOYSA-N [AlH3].[Si] Chemical group [AlH3].[Si] KMWBBMXGHHLDKL-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- VMOWKUTXPNPTEN-UHFFFAOYSA-N n,n-dimethylpropan-2-amine Chemical compound CC(C)N(C)C VMOWKUTXPNPTEN-UHFFFAOYSA-N 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
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- 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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- 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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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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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)
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a method for synthesizing a high-silicon AFX zeolite molecular sieve by using a small-molecular organic template. The invention utilizes a series of simple and cheap small molecular organic templates to synthesize the high-silicon AFX zeolite molecular sieve, the silicon-aluminum ratio of the product obtained by the method can be about 7, and the method is very suitable for NH 3 -SCR reaction and the obtained product has very excellent hydrothermal stability, maintaining its basic structure even after 16 hours of hydrothermal aging at 850 ℃; the micromolecular organic template agent used in the method has simple structure and low price, greatly reduces the synthesis cost, and solves the problem that the silicon-aluminum ratio of the conventional AFX zeolite molecular sieve is not higher than 5 (Si/Al)<5.0 Poor hydrothermal stability or high production cost caused by the use of a template agent with high price; for the industrial production of AFX zeolite molecular sieves and as a new generation of NH 3 SCR catalyst offers the possibility.
Description
Technical Field
The invention relates to a method for synthesizing a high-silicon AFX zeolite molecular sieve by using a small-molecular organic template, belonging to the technical field of molecular sieves.
Technical Field
The AFX molecular sieve belongs to ABC family, and the framework structure of the AFX molecular sieve is mainly formed by arranging d6r in AABBCCBB order to form a three-dimensional eight-membered ring channel structure and has a larger aft cage (0.55 multiplied by 1.35 nm) and a slightly smaller gme cage (0.34 multiplied by 0.66 nm). This molecular sieve was originally found as an aluminophosphate structure and was designated by Wilson et al as SAPO-56 molecular sieve. Zones et al then succeeded in obtaining a double-headed quaternary ammonium salt 1,4-bis (1-azoniabic [ 2.2.2)]octane) butyl diboride is an organic template agent to synthesize AFX with a silicon-aluminum structure and is named SSZ-16 zeoliteAnd (5) screening the seeds. Exchanging Cu 2+ Post SSZ-16 zeolite molecular sieve in NO x Selective catalytic reduction (NH) 3 -SCR) exhibits excellent NO x And (4) conversion rate. But the product silicon-aluminum ratio is not higher than 5 (Si/Al) due to SSZ-16 zeolite molecular sieve<5.0 And thus has poor hydrothermal stability, and generally loses activity completely after hydrothermal aging at 800 ℃ for 16 hours. Subsequently, zones et al developed a new method for synthesizing SSZ-16 using 1,3-bis (1-adamantyl) imidozolium bromide as an organic template, which resulted in a product with a Si/Al ratio as high as 17, which was less acidic and not suitable for NH 3 -SCR reaction. Corma et Al synthesized nano-sized high-silicon SSZ-16 (Si/Al = 5.2-5.3) by a high-silicon USY (USY) crystallization method using a large-size rigid double-headed quaternary ammonium salt as an organic template, and the organic template used in the method has a complex structure, is expensive and is not easy to synthesize.
Therefore, to better develop AFX in NH 3 Application to SCR reactions, it is necessary to develop a simple and efficient synthesis suitable for NH 3 -SCR reacted high silicon AFX zeolite molecular sieves.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: the silicon-aluminum ratio of the prior AFX zeolite molecular sieve is not high (Si/Al)<5.0 Poor hydrothermal stability, use of expensive templating agents resulting in high production costs or unsuitability for NH 3 SCR reaction and the like.
In order to achieve the above object, the present invention provides a method for synthesizing a high-silicon AFX zeolite molecular sieve by using a small molecule organic template, comprising: firstly, a silicon-aluminum source, a sodium hydroxide solid and an organic template agent OSDA (OH) 2 The aqueous solution and the water are SiO according to the mol ratio 2 :Al 2 O 3 :Na 2 O:OSDA(OH) 2 :H 2 Feeding according to the proportion of O = 25-72; wherein the organic template agent in the organic template agent water solution is N, N ' -dimethyl-N, N, N ', N ' -tetraethyl-1, 6-hexamethylene diammonium hydroxide, N, N,at least one of N ', N' -tetramethyl-N, N '-diethyl-1, 6-hexamethylenediammonium hydroxide, N, N, N', N '-tetramethyl-N, N' -diisopropyl-1, 6-hexamethylenediammonium hydroxide, N, N-dimethyl-N, N ', N', N '-tetraethyl-1, 6-hexamethylenediammonium hydroxide, and N, N, N' -trimethyl-N, N ', N' -triethyl-1, 6-hexamethylenediammonium hydroxide.
Preferably, the preparation method of the organic template aqueous solution comprises the following steps: reacting trialkylamine R 1 N(R 2 ) 2 Dissolving 1, 6-dibromohexane in acetonitrile according to a proportion, heating, refluxing and stirring for reaction; after the reaction is finished, carrying out suction filtration on a reaction product and washing the reaction product with acetonitrile; vacuum drying, and exchanging with hydroxide anion exchange resin to obtain organic template agent water solution with certain concentration; wherein, the trialkylamine R 1 N(R 2 ) 2 Is at least one of N, N-diethylmethylamine, N-dimethylethylamine, N-dimethylisopropylamine and triethylamine.
Preferably, the silica-alumina source is a combination of a silicon source and an aluminum source, and/or at least one of a USY molecular sieve, a ZSM-5 molecular sieve, a ZSM-22 molecular sieve, a ZSM-23 molecular sieve, a ZSM-11 molecular sieve, a MCM-22 molecular sieve and a FER (ZSM-35) molecular sieve, wherein the silicon source is selected from silica sol and/or tetraethyl silicate (TEOS), and the aluminum source is selected from at least one of sodium metaaluminate, aluminum hydroxide, aluminum sulfate octadecahydrate and aluminum isopropoxide.
Preferably, the temperature of the crystallization reaction is 140-160 ℃ and the time is 1-5 days.
The invention also provides the high-silicon AFX zeolite molecular sieve prepared by the method for synthesizing the high-silicon AFX zeolite molecular sieve by using the small-molecule organic template.
The invention also provides a Cu-AFX catalyst, which is prepared by sequentially roasting the high-silicon AFX zeolite molecular sieve, exchanging ammonium ions and Cu 2+ Ion exchange and secondary roasting.
Compared with the prior art, the invention has the following beneficial effects:
1. the method for synthesizing the high-silicon AFX zeolite molecular sieve by using the small-molecular organic template has the advantages that the used organic template is simple in structure and low in price, the production cost is greatly reduced, the yield of the method is high, and the method has important significance in the field of actual chemical production;
2. the silicon-aluminum ratio of the synthesized high-silicon AFX zeolite molecular sieve product can be about 7, and the product with the silicon-aluminum ratio is very suitable for NH 3 SCR reaction, and the product has good hydrothermal stability, even under 10% water and air condition, after hydrothermal aging at 850 deg.C for 16 hr, it can still retain its basic structure, so that it can be used as new generation of NH with high hydrothermal stability 3 -an SCR catalyst.
Drawings
FIG. 1 is an XRD spectrum of a high silicon AFX zeolite molecular sieve product synthesized in example 1;
FIG. 2 is a scanning electron microscope image of the high-silicon AFX zeolite molecular sieve synthesized in example 1;
FIG. 3 is an XRD spectrum of AFX molecular sieve products synthesized from different Si-Al sources in examples 2-8;
FIG. 4 is the XRD spectra of AFX molecular sieve products synthesized from different organic templates in examples 13-16.
Detailed Description
In order to make the invention more comprehensible, preferred embodiments accompanied with figures are described in detail below.
In the following examples, the synthesis of the organic templating agent used was as follows:
n, N ' -dimethyl-N, N, N ', N ' -tetraethyl-1, 6-hexanediammonium hydroxide (OSDA 1 (OH) 2 ): dissolving N, N-diethylmethylamine and 1, 6-dibromohexane in acetonitrile according to a certain proportion, heating, condensing and stirring for 1 day; after the reaction is finished, carrying out suction filtration on a reaction product and washing the reaction product by using a large amount of acetonitrile; vacuum drying, and exchanging with hydroxide anion exchange resin to obtain organic template agent water solution with certain concentration.
N, N, N ', N ' -tetramethyl-N, N ' -diethyl-1, 6-hexanediammonium hydroxide (OSDA 2 (OH) 2 ): dissolving N, N-dimethylethylamine and 1, 6-dibromohexane in acetonitrile according to a certain proportion, and heating, refluxing and stirring for 1 day; after the reaction is finished, carrying out suction filtration on a reaction product and washing the reaction product by using a large amount of acetonitrile; vacuum drying, and exchanging with hydroxide anion exchange resin to obtain organic template agent water solution with certain concentration。
N, N, N ', N ' -tetramethyl-N, N ' -diisopropyl-1, 6-hexanediammonium hydroxide (OSDA 3 (OH) 2 ): dissolving N, N-dimethylisopropylamine and 1, 6-dibromohexane in acetonitrile according to a proportion, and heating, refluxing and stirring for 1 day; after the reaction is finished, carrying out suction filtration on a reaction product and washing the reaction product by using a large amount of acetonitrile; vacuum drying, and exchanging with hydroxide anion exchange resin to obtain organic template agent water solution with certain concentration.
N, N-dimethyl-N, N ', N ', N ' -tetraethyl-1, 6-hexanediammonium hydroxide (OSDA 4 (OH) 2 ): dissolving N, N-dimethylethylamine, triethylamine and 1, 6-dibromohexane in acetonitrile according to a proportion, and heating, refluxing and stirring for 1 day; after the reaction is finished, carrying out suction filtration on a reaction product and washing the reaction product by using a large amount of acetonitrile; vacuum drying, and exchanging with hydroxide anion exchange resin to obtain organic template agent water solution with certain concentration.
N, N, N ' -trimethyl-N, N ', N ' -triethyl-1, 6-hexanediammonium hydroxide (OSDA 5 (OH) 2 ): dissolving N, N-diethylmethylamine, N-dimethylethylamine and 1, 6-dibromohexane in acetonitrile in proportion, and heating, refluxing and stirring for 1 day; after the reaction is finished, carrying out suction filtration on a reaction product and washing the reaction product by using a large amount of acetonitrile; vacuum drying, and exchanging with hydroxide anion exchange resin to obtain organic template agent water solution with certain concentration.
Example 1
First, a certain amount of sodium hydroxide, OSDA1 (OH) 2 Adding the solution (0.53M) and a high-stability Y molecular sieve (USY molecular sieve, si/Al = 12.5) into a proper amount of water, stirring for 2-3 hours to form uniform gel, transferring the reaction raw material into a polytetrafluoroethylene stainless steel reaction kettle, crystallizing for 2.5 days at 160 ℃ to complete crystallization, washing the reaction product with deionized water after the reaction is finished, and drying at 80 ℃ for more than 12 hours. The molar ratio of the reaction raw materials is as follows: 25SiO 2 ：1Al 2 O 3 ：2Na 2 O：6OSDA(OH) 2 ：1000H 2 O; the final product, high-silicon AFX zeolite molecular sieve, had a silica to alumina ratio of 7.1.
It is AFX zeolite molecular sieve (figure 1) by X-ray diffraction analysis, and the synthesized product is shown to be in a spindle-shaped block shape by a scanning electron micrograph (figure 2).
Example 2
Mixing a certain amount of sodium hydroxide, OSDA1 (OH) 2 Adding the solution (0.53M) and a ZSM-5 molecular sieve (Si/Al = 15) into a proper amount of water, stirring for 2-3 hours to form uniform gel, transferring the reaction raw material into a polytetrafluoroethylene stainless steel reaction kettle, crystallizing for 2.5 days at 160 ℃ to complete crystallization, washing the reaction product with deionized water after the reaction is finished, and drying at 80 ℃ for more than 12 hours. The molar ratio of the reaction raw materials is as follows: 30SiO 2 ：1Al 2 O 3 ：4Na 2 O：8OSDA(OH) 2 ：1200H 2 O; the final product, high-silicon AFX zeolite molecular sieve, had a silica to alumina ratio of 5.2.
Example 3
Mixing a certain amount of sodium hydroxide, OSDA1 (OH) 2 Adding the solution (0.53M) and a ZSM-22 molecular sieve (Si/Al = 35.8) into a proper amount of water, stirring for 2-3 hours to form uniform gel, transferring the reaction raw material into a polytetrafluoroethylene stainless steel reaction kettle, crystallizing for 2.5 days at 160 ℃, completely crystallizing, washing the reaction product with deionized water after the reaction is finished, and drying at 80 ℃ for more than 12 hours. The molar ratio of the reaction raw materials is as follows: 72SiO 2 ：1Al 2 O 3 ：16Na 2 O：18OSDA(OH) 2 ：3000H 2 O; the final product, high-silicon AFX zeolite molecular sieve, had a silica to alumina ratio of 5.2.
Example 4
Mixing a certain amount of sodium hydroxide, OSDA1 (OH) 2 Adding the solution (0.53M) and ZSM-23 (Si/Al = 33) into a proper amount of water, stirring for 2-3 hours to form uniform gel, transferring the reaction raw material into a polytetrafluoroethylene stainless steel reaction kettle, crystallizing for 2.5 days at 160 ℃, completely crystallizing, washing the reaction product with deionized water after the reaction is finished, and drying at 80 ℃ for more than 12 hours. The molar ratio of the reaction raw materials is as follows: 66SiO 2 ：1Al 2 O 3 ：15Na 2 O：17OSDA(OH) 2 ：2600H 2 O; the final product, high-silicon AFX zeolite molecular sieve, had a silica to alumina ratio of 5.2.
Example 5
Mixing a certain amount of sodium hydroxide, OSDA1 (OH) 2 Solution (0.53M) and MCM-22 (Si/Al = 13.4) were addedStirring in proper amount of water for 2-3 hr to form homogeneous gel, transferring the reaction material to stainless steel reactor, crystallizing at 160 deg.c for 2.5 days to complete crystallization, washing the reaction product with deionized water, and drying at 80 deg.c for over 12 hr. The molar ratio of the reaction raw materials is as follows: 27SiO 2 ：1Al 2 O 3 ：3Na 2 O：6OSDA(OH) 2 ：1100H 2 O; the final product, high-silicon AFX zeolite molecular sieve, had a silica to alumina ratio of 5.5.
Example 6
Mixing a certain amount of sodium hydroxide, OSDA1 (OH) 2 Adding the solution (0.53M) and FER (Si/Al = 30) into a proper amount of water, stirring for 2-3 hours to form uniform gel, transferring the reaction raw materials into a polytetrafluoroethylene stainless steel reaction kettle, crystallizing at 160 ℃ for 2.5 days to complete crystallization, washing the reaction product with deionized water after the reaction is finished, and drying at 80 ℃ for more than 12 hours. The molar ratio of the reaction raw materials is as follows: 60SiO 2 ：1Al 2 O 3 ：13Na 2 O：15OSDA(OH) 2 ：2400H 2 O; the final product, high-silicon AFX zeolite molecular sieve, had a silica to alumina ratio of 5.5.
Example 7
Mixing a certain amount of sodium hydroxide, OSDA1 (OH) 2 Adding the solution (0.53M) and ZSM-11 (Si/Al = 33.1) into a proper amount of water, stirring for 2-3 hours to form uniform gel, transferring the reaction raw material into a polytetrafluoroethylene stainless steel reaction kettle, crystallizing for 2.5 days at 160 ℃ to complete crystallization, washing the reaction product with deionized water after the reaction is finished, and drying at 80 ℃ for more than 12 hours. The molar ratio of the reaction raw materials is as follows: 66SiO 2 ：1Al 2 O 3 ：15Na 2 O：17OSDA(OH) 2 ：2700H 2 O; the final product, high-silicon AFX zeolite molecular sieve, had a silica to alumina ratio of 5.2.
Example 8
Mixing a certain amount of sodium hydroxide, sodium metaaluminate and OSDA1 (OH) 2 Adding the solution (0.53M) and silica sol (mass fraction is 40%) into a proper amount of water, stirring for 2-3 hours, transferring the reaction raw materials into a polytetrafluoroethylene stainless steel reaction kettle, crystallizing for 2.5 days at 160 ℃, and completely crystallizing to reactAfter completion, the reaction product was washed with deionized water and dried at 80 ℃ for 12 hours or more. The molar ratio of the reaction raw materials is as follows: 25SiO 2 ：1Al 2 O 3 ：2Na 2 O：6OSDA(OH) 2 ：1000H 2 O; the final product, high-silicon AFX zeolite molecular sieve, had a silica to alumina ratio of 7.1.
Example 9
Mixing a certain amount of sodium hydroxide, aluminum hydroxide, OSDA1 (OH) 2 Adding the solution (0.53M) and silica sol (mass fraction: 40%) into appropriate amount of water, crystallizing at 160 deg.C for 2.5 days to obtain complete crystallization, washing the reaction product with deionized water, and drying at 80 deg.C for more than 12 hr. The molar ratio of the reaction raw materials is as follows: 25SiO 2 ：1Al 2 O 3 ：6Na 2 O：6OSDA(OH) 2 ：1000H 2 O; the final product, high-silicon AFX zeolite molecular sieve, had a silica to alumina ratio of 7.1.
Example 10
Mixing a certain amount of sodium hydroxide, aluminum isopropoxide, OSDA1 (OH) 2 Adding the solution (0.53M) and silica sol (mass fraction: 40%) into appropriate amount of water, crystallizing at 160 deg.C for 2.5 days to obtain complete crystallization, washing the reaction product with deionized water, and drying at 80 deg.C for more than 12 hr. The molar ratio of the reaction raw materials is as follows: 25SiO 2 ：1Al 2 O 3 ：6Na 2 O：6OSDA(OH) 2 ：1000H 2 O; the final product, high-silicon AFX zeolite molecular sieve, had a silica to alumina ratio of 7.1.
Example 11
Mixing a certain amount of sodium hydroxide, aluminum sulfate octadecahydrate, OSDA1 (OH) 2 Adding the solution (0.53M) and silica sol (mass fraction: 40%) into appropriate amount of water, crystallizing at 160 deg.C for 2.5 days to obtain complete crystallization, washing the reaction product with deionized water, and drying at 80 deg.C for more than 12 hr. The molar ratio of the reaction raw materials is as follows: 25SiO 2 ：1Al 2 O 3 ：6Na 2 O：6OSDA(OH) 2 ：1000H 2 O; the final product, high-silicon AFX zeolite molecular sieve, had a silica to alumina ratio of 7.1.
Example 12
Will be fixedA quantity of sodium hydroxide, aluminum sulfate octadecahydrate, OSDA1 (OH) 2 Adding the solution (0.53M) and tetraethyl silicate (TEOS) into a proper amount of water, crystallizing at 160 ℃ for 2.5 days to obtain complete crystallization, washing the reaction product with deionized water after the reaction is finished, and drying at 80 ℃ for more than 12 hours. The molar ratio of the reaction raw materials is as follows: 25SiO 2 ：1Al 2 O 3 ：6Na 2 O：6OSDA(OH) 2 ：1000H 2 O; the final product, high-silicon AFX zeolite molecular sieve, had a silica to alumina ratio of 7.1.
Example 13
Mixing a certain amount of sodium hydroxide, OSDA2 (OH) 2 Adding the solution (0.75M) and high-stability Y (Si/Al = 12.5) into a proper amount of water, stirring for 2-3 hours to form uniform gel, transferring the reaction raw material into a polytetrafluoroethylene stainless steel reaction kettle, crystallizing for 3 days at 160 ℃, completely crystallizing, washing the reaction product with deionized water after the reaction is finished, and drying at 80 ℃ for more than 12 hours. The molar ratio of the reaction raw materials is as follows: 25SiO 2 ：1Al 2 O 3 ：1Na 2 O：6OSDA(OH) 2 ：1000H 2 O; the final product, high-silicon AFX zeolite molecular sieve, had a silica to alumina ratio of 7.1.
Example 14
Mixing a certain amount of sodium hydroxide, OSDA3 (OH) 2 Adding the solution (0.51M) and high-stability Y (Si/Al = 12.5) into a proper amount of water, stirring for 2-3 hours to form uniform gel, transferring the reaction raw material into a polytetrafluoroethylene stainless steel reaction kettle, crystallizing for 3 days at 160 ℃ to complete crystallization, washing the reaction product with deionized water after the reaction is finished, and drying at 80 ℃ for more than 12 hours. The molar ratio of the reaction raw materials is as follows: 25SiO 2 ：1Al 2 O 3 ：4Na 2 O：6OSDA(OH) 2 ：1000H 2 O; the final product, high-silicon AFX zeolite molecular sieve, had a silica to alumina ratio of 7.1.
Example 15
Mixing a certain amount of sodium hydroxide, OSDA4 (OH) 2 Adding the solution (0.53M) and high-stability Y (Si/Al = 12.5) into appropriate amount of water, stirring for 2-3 hours to form uniform gel, transferring the reaction raw material into a polytetrafluoroethylene stainless steel reaction kettle, crystallizing at 160 ℃ for 3 days to complete crystallization, and reacting completelyAfter completion, the reaction product was washed with deionized water and dried at 80 ℃ for 12 hours or more. The molar ratio of the reaction raw materials is as follows: 25SiO 2 ：1Al 2 O 3 ：1Na 2 O：6OSDA(OH) 2 ：1000H 2 O; the final product, high-silicon AFX zeolite molecular sieve, had a silica to alumina ratio of 7.1.
Example 16
Mixing a certain amount of sodium hydroxide, OSDA5 (OH) 2 Adding the solution (0.55M) and high-stability Y (Si/Al = 12.5) into a proper amount of water, stirring for 2-3 hours to form uniform gel, transferring the reaction raw material into a polytetrafluoroethylene stainless steel reaction kettle, crystallizing for 3 days at 160 ℃ to complete crystallization, washing the reaction product with deionized water after the reaction is finished, and drying at 80 ℃ for more than 12 hours. The molar ratio of the reaction raw materials is as follows: 25SiO 2 ：1Al 2 O 3 ：1Na 2 O：6OSDA(OH) 2 ：1000H 2 O; the final product, high-silicon AFX zeolite molecular sieve, had a silica to alumina ratio of 7.1.
Example 17
Mixing a certain amount of sodium hydroxide, OSDA1 (OH) 2 Adding the solution (0.53M) and high-stability Y (Si/Al = 12.5) into a proper amount of water, stirring for 2-3 hours to form uniform gel, transferring the reaction raw material into a polytetrafluoroethylene stainless steel reaction kettle, crystallizing for 2.5 days at 160 ℃ to complete crystallization, washing the reaction product with deionized water after the reaction is finished, and drying at 80 ℃ for more than 12 hours. The molar ratio of the reaction raw materials is as follows: 25SiO 2 ：1Al 2 O 3 ：0.6Na 2 O：6OSDA(OH) 2 ：1000H 2 O; the final product, high-silicon AFX zeolite molecular sieve, had a silica to alumina ratio of 7.1.
Example 18
Mixing a certain amount of sodium hydroxide, OSDA1 (OH) 2 Adding the solution (0.53M) and high-stability Y (Si/Al = 12.5) into a proper amount of water, stirring for 2-3 hours to form uniform gel, transferring the reaction raw material into a polytetrafluoroethylene stainless steel reaction kettle, crystallizing for 2.5 days at 160 ℃ to complete crystallization, washing the reaction product with deionized water after the reaction is finished, and drying at 80 ℃ for more than 12 hours. The molar ratio of the reaction raw materials is as follows: 25SiO 2 ：1Al 2 O 3 ：1Na 2 O：6OSDA(OH) 2 ：1000H 2 O; the final product, high-silicon AFX zeolite molecular sieve, had a silica to alumina ratio of 7.1.
Example 19
Mixing a certain amount of sodium hydroxide, OSDA1 (OH) 2 Adding the solution (0.53M) and high-stability Y (Si/Al = 12.5) into a proper amount of water, stirring for 2-3 hours to form uniform gel, transferring the reaction raw material into a polytetrafluoroethylene stainless steel reaction kettle, crystallizing for 2.5 days at 160 ℃ to obtain complete crystallization, washing the reaction product with deionized water after the reaction is finished, and drying at 80 ℃ for more than 12 hours. The molar ratio of the reaction raw materials is as follows: 25SiO 2 ：1Al 2 O 3 ：3Na 2 O：6OSDA(OH) 2 ：1000H 2 O; the final product, high-silicon AFX zeolite molecular sieve, had a silica to alumina ratio of 6.5.
Example 20
Mixing a certain amount of sodium hydroxide, OSDA1 (OH) 2 Adding the solution (0.53M) and high-stability Y (Si/Al = 12.5) into a proper amount of water, stirring for 2-3 hours to form uniform gel, transferring the reaction raw material into a polytetrafluoroethylene stainless steel reaction kettle, crystallizing for 2.5 days at 160 ℃ to complete crystallization, washing the reaction product with deionized water after the reaction is finished, and drying at 80 ℃ for more than 12 hours. The molar ratio of the reaction raw materials is as follows: 25SiO 2 ：1Al 2 O 3 ：4Na 2 O：6OSDA(OH) 2 ：1000H 2 O; the final product, high-silicon AFX zeolite molecular sieve, had a silica to alumina ratio of 5.8.
Example 21
Mixing a certain amount of sodium hydroxide, OSDA1 (OH) 2 Adding the solution (0.53M) and high-stability Y (Si/Al = 12.5) into a proper amount of water, stirring for 2-3 hours to form uniform gel, transferring the reaction raw material into a polytetrafluoroethylene stainless steel reaction kettle, crystallizing for 2.5 days at 160 ℃ to complete crystallization, washing the reaction product with deionized water after the reaction is finished, and drying at 80 ℃ for more than 12 hours. The molar ratio of the reaction raw materials is as follows: 25SiO 2 ：1Al 2 O 3 ：2Na 2 O：5OSDA(OH) 2 ：1000H 2 O; the final product, high-silicon AFX zeolite molecular sieve, had a silica to alumina ratio of 6.8.
Example 22
Mixing a certain amount of sodium hydroxide, OSDA1 (OH) 2 Adding the solution (0.53M) and high-stability Y (Si/Al = 12.5) into a proper amount of water, stirring for 2-3 hours to form uniform gel, transferring the reaction raw material into a polytetrafluoroethylene stainless steel reaction kettle, crystallizing for 2.5 days at 160 ℃ to complete crystallization, washing the reaction product with deionized water after the reaction is finished, and drying at 80 ℃ for more than 12 hours. The molar ratio of the reaction raw materials is as follows: 25SiO 2 ：1Al 2 O 3 ：2Na 2 O：8OSDA(OH) 2 ：1000H 2 O; the final product, high-silicon AFX zeolite molecular sieve, had a silica to alumina ratio of 7.1.
Example 23
Mixing a certain amount of sodium hydroxide, OSDA1 (OH) 2 The solution (0.53M) and high stability Y (Si/Al = 12.5) were added to an appropriate amount of water, stirred for 2-3 hours to form a uniform gel, and then the reaction material was transferred to a teflon stainless steel reaction kettle and dried at 80 ℃ for 12 hours or more. The molar ratio of the reaction raw materials is as follows: 25SiO 2 ：1Al 2 O 3 ：2Na 2 O：10OSDA(OH) 2 ：1000H 2 O; the final product, high-silicon AFX zeolite molecular sieve, had a silica to alumina ratio of 7.1.
Example 24
Mixing a certain amount of sodium hydroxide, OSDA1 (OH) 2 Adding the solution (0.53M) and high-stability Y (Si/Al = 12.5) into a proper amount of water, stirring for 2-3 hours to form uniform gel, transferring the reaction raw material into a polytetrafluoroethylene stainless steel reaction kettle, crystallizing for 2.5 days at 160 ℃ to obtain complete crystallization, washing the reaction product with deionized water after the reaction is finished, and drying at 80 ℃ for more than 12 hours. The molar ratio of the reaction raw materials is as follows: 25SiO 2 ：1Al 2 O 3 ：2Na 2 O：6OSDA(OH) 2 ：500H 2 O; the final product, high-silicon AFX zeolite molecular sieve, had a silica to alumina ratio of 7.1.
Example 25
Mixing a certain amount of sodium hydroxide, OSDA1 (OH) 2 Adding the solution (0.53M) and high-stability Y (Si/Al = 12.5) into a proper amount of water, stirring for 2-3 hours to form uniform gel, transferring the reaction raw materials into a polytetrafluoroethylene stainless steel reaction kettle,crystallizing at 160 deg.C for 2.5 days to obtain complete crystallization, washing the reaction product with deionized water, and drying at 80 deg.C for more than 12 hr. The molar ratio of the reaction raw materials is as follows: 25SiO 2 ：1Al 2 O 3 ：2Na 2 O：6OSDA(OH) 2 ：750H 2 O; the final product, high-silicon AFX zeolite molecular sieve, had a silica to alumina ratio of 7.1.
Example 26
Mixing a certain amount of sodium hydroxide, OSDA1 (OH) 2 Adding the solution (0.53M) and high-stability Y (Si/Al = 12.5) into a proper amount of water, stirring for 2-3 hours to form uniform gel, transferring the reaction raw material into a polytetrafluoroethylene stainless steel reaction kettle, crystallizing for 2.5 days at 160 ℃ to obtain complete crystallization, washing the reaction product with deionized water after the reaction is finished, and drying at 80 ℃ for more than 12 hours. The molar ratio of the reaction raw materials is as follows: 32SiO 2 ：1Al 2 O 3 ：2Na 2 O：8OSDA(OH) 2 ：1300H 2 O; the final product, high-silicon AFX zeolite molecular sieve, had a silica to alumina ratio of 7.1.
Example 27
Mixing a certain amount of sodium hydroxide, OSDA1 (OH) 2 Adding the solution (0.53M) and high-stability Y (Si/Al = 12.5) into a proper amount of water, stirring for 2-3 hours to form uniform gel, transferring the reaction raw material into a polytetrafluoroethylene stainless steel reaction kettle, crystallizing for 2.5 days at 160 ℃ to obtain complete crystallization, washing the reaction product with deionized water after the reaction is finished, and drying at 80 ℃ for more than 12 hours. The molar ratio of the reaction raw materials is as follows: 60SiO 2 ：1Al 2 O 3 ：5Na 2 O：15OSDA(OH) 2 ：2400H 2 O; the final product, high-silicon AFX zeolite molecular sieve, had a silica to alumina ratio of 7.1.
Example 28
Mixing a certain amount of sodium hydroxide, OSDA1 (OH) 2 Adding the solution (0.53M) and high-stability Y (Si/Al = 12.5) into a proper amount of water, stirring for 2-3 hours to form uniform gel, transferring the reaction raw material into a polytetrafluoroethylene stainless steel reaction kettle, crystallizing for 1 day at 160 ℃, washing the reaction product with deionized water after the reaction is finished, and drying for more than 12 hours at 80 ℃. The molar ratio of the reaction raw materials is as follows: 25SiO 2 ：1Al 2 O 3 ：2Na 2 O：6OSDA(OH) 2 ：1000H 2 O; the final product, high-silicon AFX zeolite molecular sieve, had a silica to alumina ratio of 7.1.
Example 29
Mixing a certain amount of sodium hydroxide, OSDA1 (OH) 2 Adding the solution (0.53M) and high-stability Y (Si/Al = 12.5) into a proper amount of water, stirring for 2-3 hours to form uniform gel, transferring the reaction raw material into a polytetrafluoroethylene stainless steel reaction kettle, crystallizing for 2 days at 160 ℃, washing the reaction product with deionized water after the reaction is finished, and drying at 80 ℃ for more than 12 hours. The molar ratio of the reaction raw materials is as follows: 25SiO 2 ：1Al 2 O 3 ：2Na 2 O：6OSDA(OH) 2 ：1000H 2 O; the final product, high-silicon AFX zeolite molecular sieve, had a silica to alumina ratio of 7.1.
Example 30
Mixing a certain amount of sodium hydroxide, OSDA1 (OH) 2 Adding the solution (0.53M) and high-stability Y (Si/Al = 12.5) into a proper amount of water, stirring for 2-3 hours to form uniform gel, transferring the reaction raw material into a polytetrafluoroethylene stainless steel reaction kettle, crystallizing for 5 days at 140 ℃ to complete crystallization, washing the reaction product with deionized water after the reaction is finished, and drying at 80 ℃ for more than 12 hours. The molar ratio of the reaction raw materials is as follows: 25SiO 2 ：1Al 2 O 3 ：2Na 2 O：6OSDA(OH) 2 ：1000H 2 O; the final product, high-silicon AFX zeolite molecular sieve, had a silica to alumina ratio of 7.1.
Example 31
Mixing a certain amount of sodium hydroxide, OSDA1 (OH) 2 Adding the solution (0.53M) and high-stability Y (Si/Al = 12.5) into a proper amount of water, stirring for 2-3 hours to form uniform gel, transferring the reaction raw material into a polytetrafluoroethylene stainless steel reaction kettle, crystallizing for 4 days at 150 ℃ to complete crystallization, washing the reaction product with deionized water after the reaction is finished, and drying at 80 ℃ for more than 12 hours. The molar ratio of the reaction raw materials is as follows: 25SiO 2 ：1Al 2 O 3 ：2Na 2 O：6OSDA(OH) 2 ：1000H 2 O; the final product, high-silicon AFX zeolite molecular sieve, had a silica to alumina ratio of 7.1.
Measurement of Performance
0.5g of the zeolite molecular sieve of example 1 and, as a control, the conventional AFX zeolite molecular sieve having a silica-alumina ratio of 3.5 were calcined in a muffle furnace at 600 ℃ for 5 hours in air; then ammonium ion exchange is carried out in 1.0mol/L ammonium nitrate solution, and then filtration, washing and drying are carried out; repeating for 2-3 times to complete ammonium ion exchange; adding the molecular sieve which finishes ammonium ion exchange into 0.05mol/L cupric nitrate solution, and stirring for 6 hours at 40 ℃; and after filtering, washing and drying, transferring the product to a muffle furnace, and roasting the product for 5 hours at 550 ℃ in the air to obtain the Cu-AFX catalyst and the comparative sample Cu-AFX-con. The mass content of copper ions is 2.5-3.5%. The catalyst is sieved into particles with the size of 40-60 meshes for standby.
Taking 0.2g of sieved Cu-AFX catalyst and a comparative sample Cu-AFX-con, and respectively carrying out hydrothermal treatment in a tubular fixed bed reactor: treating at 850 deg.C for 16 hr in 10% water and air; after treatment, the mixture was cooled to room temperature. The crystallinity (100%) of the catalyst after hydrothermal treatment relative to the catalyst before hydrothermal treatment is as follows:
| sample numbering | Relative degree of crystallinity% |
| Cu-AFX catalyst | 64.8 |
| Cu-AFX-con control | 0 |
The performance tests show that the high-silicon AFX zeolite molecular sieve synthesized by the small-molecule organic template has excellent hydrothermal stability.
The above-described embodiments are intended to be preferred embodiments of the present invention only, and not to limit the invention in any way and in any way, it being noted that those skilled in the art will be able to make modifications and additions without departing from the scope of the invention, which shall be deemed to also encompass the scope of the invention.
Claims (6)
1. A method for synthesizing a high-silicon AFX zeolite molecular sieve by using a small-molecule organic template is characterized by comprising the following steps of: firstly, a silicon-aluminum source, a sodium hydroxide solid and an organic template agent OSDA (OH) 2 The aqueous solution and the water are SiO according to the molar ratio 2 :Al 2 O 3 :Na 2 O:OSDA(OH) 2 :H 2 Feeding according to the proportion of O = 25-72; wherein the organic template agent in the organic template agent aqueous solution is at least one of N, N ' -dimethyl-N, N, N ', N ' -tetraethyl-1, 6-hexamethylene diammonium hydroxide, N, N, N ', N ' -tetramethyl-N, N ' -diethyl-1, 6-hexamethylene diammonium hydroxide, N, N, N ', N ' -tetramethyl-N, N ' -diisopropyl-1, 6-hexamethylene diammonium hydroxide, N, N-dimethyl-N, N ', N ', N ' -tetraethyl-1, 6-hexamethylene diammonium hydroxide and N, N, N ' -trimethyl-N, N ', N ' -triethyl-1, 6-hexamethylene diammonium hydroxide.
2. The method for synthesizing a high-silicon AFX zeolite molecular sieve by using the small-molecule organic template as claimed in claim 1, wherein the preparation method of the organic template aqueous solution comprises the following steps: reacting trialkylamine R 1 N(R 2 ) 2 Dissolving 1, 6-dibromohexane in acetonitrile according to a proportion, heating, refluxing and stirring for reaction; after the reaction is finished, carrying out suction filtration on a reaction product and washing the reaction product with acetonitrile; vacuum drying, and exchanging with hydroxide anion exchange resin to obtain organic template agent water solution with certain concentration; wherein, the trialkylamine R 1 N(R 2 ) 2 Is at least one of N, N-diethylmethylamine, N-dimethylethylamine, N-dimethylisopropylamine and triethylamineAnd (4) seed preparation.
3. The method for synthesizing a high-silicon AFX zeolite molecular sieve by using a small-molecule organic template as claimed in claim 1, wherein the silicon-aluminum source is a combination of a silicon source and an aluminum source, and/or at least one of a USY molecular sieve, a ZSM-5 molecular sieve, a ZSM-22 molecular sieve, a ZSM-23 molecular sieve, a ZSM-11 molecular sieve, an MCM-22 molecular sieve and an FER molecular sieve, wherein the silicon source is selected from silica sol and/or tetraethyl silicate, and the aluminum source is selected from at least one of sodium metaaluminate, aluminum hydroxide, aluminum sulfate octadecahydrate and aluminum isopropoxide.
4. The method for synthesizing the high-silicon AFX zeolite molecular sieve by using the small-molecule organic template as claimed in claim 1, wherein the temperature of the crystallization reaction is 140-160 ℃ and the time is 1-5 days.
5. The high-silicon AFX zeolite molecular sieve prepared by the method for synthesizing the high-silicon AFX zeolite molecular sieve by using the small-molecule organic template as claimed in any one of claims 1 to 4.
6. A Cu-AFX catalyst, characterized in that the high-silicon AFX zeolite molecular sieve of claim 5 is sequentially subjected to calcination, ammonium ion exchange, cu 2+ Ion exchange and secondary roasting.
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| CN116196969A (en) * | 2023-03-07 | 2023-06-02 | 中国科学院城市环境研究所 | Cu-AFX catalyst for ammonia selective catalytic reduction |
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| 吕双春;葛云丽;赵倩;李轩;纪娜;宋春风;马德刚;刘庆岭;: "高硅分子筛的合成及其在VOCs吸附去除领域的应用", 环境化学, no. 07, pages 1 - 8 * |
| 栾慧敏等: "使用四乙基氢氧化铵作为有机模板剂和常规硅铝源直接合成 SSZ-13 沸石分子筛", 《高等学校化学学 报》, pages 1470 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115784255A (en) * | 2022-12-15 | 2023-03-14 | 上海科技大学 | Preparation method and application of SSZ-74 molecular sieve |
| CN116196969A (en) * | 2023-03-07 | 2023-06-02 | 中国科学院城市环境研究所 | Cu-AFX catalyst for ammonia selective catalytic reduction |
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| CN115321555B (en) | 2024-03-15 |
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