CN114804145A - Method for directly synthesizing hydrogen type zeolite - Google Patents
Method for directly synthesizing hydrogen type zeolite Download PDFInfo
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- CN114804145A CN114804145A CN202111385175.5A CN202111385175A CN114804145A CN 114804145 A CN114804145 A CN 114804145A CN 202111385175 A CN202111385175 A CN 202111385175A CN 114804145 A CN114804145 A CN 114804145A
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- 239000010457 zeolite Substances 0.000 title claims abstract description 132
- 229910021536 Zeolite Inorganic materials 0.000 title claims abstract description 120
- 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 120
- 238000000034 method Methods 0.000 title claims abstract description 25
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 16
- 239000001257 hydrogen Substances 0.000 title claims abstract description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 14
- 239000011541 reaction mixture Substances 0.000 claims abstract description 43
- 239000002994 raw material Substances 0.000 claims abstract description 37
- 239000002002 slurry Substances 0.000 claims abstract description 36
- -1 which comprises S1 Substances 0.000 claims abstract description 27
- 238000002360 preparation method Methods 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000005216 hydrothermal crystallization Methods 0.000 claims abstract description 19
- 239000008367 deionised water Substances 0.000 claims abstract description 18
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 18
- 239000000203 mixture Substances 0.000 claims abstract description 18
- 238000001035 drying Methods 0.000 claims abstract description 16
- 238000005406 washing Methods 0.000 claims abstract description 16
- 238000003756 stirring Methods 0.000 claims abstract description 15
- 230000003068 static effect Effects 0.000 claims abstract description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 9
- 238000001914 filtration Methods 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 7
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910001948 sodium oxide Inorganic materials 0.000 claims abstract description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 83
- 239000000377 silicon dioxide Substances 0.000 claims description 45
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 42
- 239000000047 product Substances 0.000 claims description 34
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 24
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 claims description 19
- 238000002425 crystallisation Methods 0.000 claims description 19
- 230000008025 crystallization Effects 0.000 claims description 19
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 claims description 18
- 238000003786 synthesis reaction Methods 0.000 claims description 18
- 239000012065 filter cake Substances 0.000 claims description 13
- 230000007935 neutral effect Effects 0.000 claims description 13
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 12
- 230000015572 biosynthetic process Effects 0.000 claims description 12
- 150000007530 organic bases Chemical class 0.000 claims description 11
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Inorganic materials [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 150000007529 inorganic bases Chemical class 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 2
- 239000007858 starting material Substances 0.000 claims 1
- 229910052710 silicon Inorganic materials 0.000 abstract description 22
- 239000010703 silicon Substances 0.000 abstract description 22
- 239000003513 alkali Substances 0.000 abstract description 12
- 239000003054 catalyst Substances 0.000 abstract description 12
- 150000001412 amines Chemical class 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 238000005341 cation exchange Methods 0.000 abstract description 6
- 238000004904 shortening Methods 0.000 abstract 1
- 239000011734 sodium Substances 0.000 description 24
- 229910052708 sodium Inorganic materials 0.000 description 14
- 238000005303 weighing Methods 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 13
- 239000000243 solution Substances 0.000 description 13
- 239000000843 powder Substances 0.000 description 11
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 11
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 10
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 9
- 239000004810 polytetrafluoroethylene Substances 0.000 description 9
- 229910001220 stainless steel Inorganic materials 0.000 description 9
- 239000010935 stainless steel Substances 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 8
- 229910002027 silica gel Inorganic materials 0.000 description 8
- 239000000741 silica gel Substances 0.000 description 8
- 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 7
- 239000013078 crystal Substances 0.000 description 7
- 238000000967 suction filtration Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 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 6
- 239000012467 final product Substances 0.000 description 6
- VLSDXINSOMDCBK-BQYQJAHWSA-N (E)-1,1'-azobis(N,N-dimethylformamide) Chemical compound CN(C)C(=O)\N=N\C(=O)N(C)C VLSDXINSOMDCBK-BQYQJAHWSA-N 0.000 description 5
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 5
- 229910001388 sodium aluminate Inorganic materials 0.000 description 5
- 239000002585 base Substances 0.000 description 4
- 229910052814 silicon oxide Inorganic materials 0.000 description 4
- 150000003863 ammonium salts Chemical class 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000003973 alkyl amines Chemical class 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 125000001453 quaternary ammonium group Chemical group 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000006467 substitution reaction 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
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- DKNWSYNQZKUICI-UHFFFAOYSA-N amantadine Chemical compound C1C(C2)CC3CC2CC1(N)C3 DKNWSYNQZKUICI-UHFFFAOYSA-N 0.000 description 1
- 229960003805 amantadine Drugs 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 238000010587 phase diagram Methods 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 239000011949 solid catalyst Substances 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
- C01B39/46—Other types characterised by their X-ray diffraction pattern and their defined composition
- C01B39/48—Other types characterised by their X-ray diffraction pattern and their defined composition using at least one organic template directing agent
-
- 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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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/14—Pore volume
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/16—Pore diameter
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Abstract
The invention relates to a method for directly synthesizing hydrogen type zeolite, which comprises S1, raw material proportioning, wherein the raw material proportioning is determined according to the type of zeolite to be prepared; s2, mixing the raw materials according to the proportioning scheme of the step S1, and adding deionized water for stirring; s3, preparing slurry, adding slurry preparation raw materials into the raw material mixture mixed in the step S2, and stirring to prepare reaction mixture slurry; s4, performing hydrothermal crystallization, transferring the slurry mixed in the step S2 into a high-pressure kettle, and performing static hydrothermal crystallization; s5, suction filtering, washing, drying and roasting. The invention directly synthesizes the H-type high-silicon zeolite with sodium oxide less than 0.30 percent by properly adjusting the alkali/silicon ratio and the amine (ammonium)/silicon ratio, and the zeolite can be directly used for preparing a catalyst without cation exchange, thereby reducing the preparation steps of the hydrogen type zeolite and shortening the production period.
Description
Technical Field
The invention relates to the field of preparation of zeolite catalyst materials, in particular to a method for directly synthesizing hydrogen type zeolite.
Background
The zeolite molecular sieve serving as a solid catalyst has extremely important and wide application in the fields of petroleum refining, oil product refining, petrochemical industry, fine chemical industry, environmental protection and the like, and is an indispensable inorganic material in national economy. The catalysts commonly used in these fields are essentially zeolites of the hydrogen type, i.e. zeolites of the hydrogen (H-) type freed from alkali metal cations (sodium or potassium). This is because most catalytic reactions are solid acidic reactions. However, hydrothermal synthesis of zeolites is typically carried out under basic conditions. The reaction mixture is prepared from a silicon source (amorphous silica such as silica gel, white carbon black, silica sol, water glass and the like), an aluminum source (aluminum oxide, aluminum hydroxide, sodium metaaluminate, aluminum sulfate, aluminum chloride and other aluminum salts), alkali (sodium hydroxide, potassium hydroxide and the like) and water according to a certain molar ratio. For most high silica (i.e., silica to alumina molar ratio, SAR, greater than 10) zeolites used as catalysts, it is often necessary to add an organic directing agent (also referred to as a templating agent) to the reaction mixture to promote nucleation and growth of the zeolite to ensure that the product of the hydrothermal synthesis is the target zeolite with a pure crystalline phase and a single structure. The organic directing agent is typically a basic organic containing nitrogen, such as quaternary ammonium base, alkyl amine, and the like.
After hydrothermal reaction of the reaction mixture to produce zeolite with specific structure type and containing organic alkali and sodium (or potassium) type, the product is separated from the mother liquid, washed with water to neutral, filtered to obtain filter cake, and stoved to obtain the zeolite powder. It is known from the composition analysis that the zeolite raw powder obtained by synthesis necessarily contains alkali metal cations and organic ammonium cations in balance with the negative charge of the framework, in addition to silica and alumina composed of the framework, and the whole zeolite exhibits solid basicity. Therefore, after the organic template agent is removed by roasting, inorganic acid (such as hydrochloric acid, sulfuric acid and nitric acid) or ammonium salt (such as ammonium chloride, ammonium sulfate and ammonium nitrate) aqueous solution is used for ion exchange for several times at a certain temperature to remove alkali metal ions contained in the zeolite to prepare hydrogen-type or ammonium-type zeolite, wherein the former can be used as a solid acid catalyst, and the latter can be prepared into the catalyst after the amine ions are removed by roasting to obtain H-type zeolite.
Therefore, in the production process of the zeolite catalyst, basic zeolite raw powder generated by hydrothermal synthesis must be subjected to cation exchange for sodium removal to prepare the catalyst. The multiple cation exchange process increases the treatment process, and simultaneously needs to use chemical raw materials such as acid or salt, etc., which inevitably causes a large amount of industrial wastewater, greatly increases the environmental protection treatment cost, occupies too much equipment, increases the energy consumption, and greatly improves the production period and the production cost.
Disclosure of Invention
Therefore, the invention provides a method for directly synthesizing hydrogen type zeolite, which is used for overcoming the problems of large energy consumption and long production period in the synthesis process in the prior art.
In order to achieve the above objects, the present invention provides a method for directly synthesizing hydrogen type zeolite by controlling the ratio of alkaline substances in a synthesis reaction mixture and preparing hydrogen type zeolite by hydrothermal synthesis, comprising,
s1, determining the raw material ratio according to the type of the zeolite to be prepared;
s2, mixing the raw materials according to the proportioning scheme of the step S1, and adding deionized water for stirring;
s3, preparing slurry, adding slurry preparation raw materials into the raw material mixture mixed in the step S2, and stirring to prepare reaction mixture slurry;
s4, performing hydrothermal crystallization, transferring the slurry mixed in the step S2 into a high-pressure kettle, and performing static hydrothermal crystallization;
s5, suction filtering, washing, drying and roasting. And after crystallization, naturally cooling to room temperature, carrying out suction filtration on the crystallized product, washing until the PH value is close to neutral, and drying and roasting the filter cake.
Further, the hydrogen-type zeolite is one of MFI-type high-silica zeolite, FER-type high-silica zeolite, and CHA-type high-silica zeolite.
Further, the alkaline substance is organic alkali and inorganic alkali, wherein,
the organic base includes alkylamine organic base and organic quaternary ammonium organic base;
the inorganic base includes sodium hydroxide inorganic base and potassium hydroxide inorganic base.
Further, the sodium oxide content of the hydrogen-form zeolite is less than 0.3%.
Further, the content and proportion of the alkaline substance in the synthesis reaction mixture are controlled to be the ratio of the organic base to the silicon oxide or the ratio of the inorganic base to the silicon oxide.
Furthermore, the high-silicon zeolite has a silica-alumina molar ratio value ranging from 10 to 400.
Further, when preparing the MFI type high-silicon zeolite, the raw materials are mixed in a molar ratio of,
SiO 2 :0.016Al 2 O 3 :0.089Na 2 o0.104 n-butylamine 15H 2 O；
Or SiO 2 :0.014Al 2 O 3 :0.079Na 2 O0.104 n-butylamine 15H 2 O；
Or SiO 2 :0.018Al 2 O 3 :0.10Na 2 O0.10 n-butylamine 15H 2 O。
Further, when FER type high silica zeolite is prepared, the raw material mixture ratio in terms of mole ratio,
120SiO 2 :0.13Na2O:0.0025PrNH 2 :Al 2 O 3 :18H 2 O；
or 120SiO 2 :0.025Na2O:0.004PrNH 2 :Al 2 O 3 :21H 2 O；
Or 120SiO 2 :0.030Na2O:0.005PrNH 2 :Al 2 O 3 :22H 2 O。
Further, when preparing the CHA-type high-silica zeolite, the raw materials are mixed in a molar ratio of,
SiO 2 :0.0625Al 2 O 3 :0.45Na 2 O:0.125TMAD:20H 2 O
or SiO 2 :0.0285Al 2 O 3 :0.50Na 2 O:0.20TMAD:18H 2 O；
Or SiO 2 :0.05Al 2 O 3 :0.25Na 2 O:0.20TMAD:22.5H 2 O。
Further, the slurry preparation raw material when preparing the MFI-type high-silica zeolite is an n-butylamine solution, the slurry preparation raw material when preparing the FER-type high-silica zeolite is an n-propylamine solution, and the slurry preparation raw material when preparing the CHA-type high-silica zeolite is a TMAD solution.
Compared with the prior art, the method has the advantages that the method directly synthesizes the H-type high-silicon zeolite with the sodium oxide of less than 0.30 percent by properly adjusting the alkali/silicon ratio and the amine (ammonium)/silicon ratio in the reaction mixture, and the zeolite can be directly used for preparing the catalyst without cation exchange. The preparation steps of the hydrogen type zeolite are reduced, and the production period is shortened.
Drawings
FIG. 1 is a flow diagram of a process for the direct synthesis of hydrogen form zeolite in accordance with the present invention;
FIG. 2 is a XRD powder diffraction pattern of a synthetic zeolite product of the present invention;
FIG. 3 is SEM electron micrograph of synthesized zeolite product of the present invention.
Detailed Description
In order that the objects and advantages of the invention will be more clearly understood, the invention is further described below with reference to examples; it should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Preferred embodiments of the present invention are described below with reference to the accompanying drawings. It should be understood by those skilled in the art that these embodiments are only for explaining the technical principle of the present invention, and do not limit the scope of the present invention.
It should be noted that in the description of the present invention, the terms of direction or positional relationship indicated by the terms "upper", "lower", "left", "right", "inner", "outer", etc. are based on the directions or positional relationships shown in the drawings, which are only for convenience of description, and do not indicate or imply that the device or element must have a specific orientation, be constructed in a specific orientation, and be operated, and thus, should not be construed as limiting the present invention.
Furthermore, it should be noted that, in the description of the present invention, unless otherwise explicitly specified or limited, the terms "mounted," "connected," and "connected" are to be construed broadly, and may be, for example, fixedly connected, detachably connected, or integrally connected; can be mechanically or electrically connected; they may be connected directly or indirectly through intervening media, or they may be interconnected between two elements. The specific meanings of the above terms in the present invention can be understood by those skilled in the art according to specific situations.
FIG. 1 is a flow chart of a process for the direct synthesis of hydrogen form zeolite according to the present invention;
the invention provides a method for directly synthesizing hydrogen type zeolite, which comprises S1, raw material proportioning, wherein the raw material proportioning is determined according to the type of zeolite to be prepared;
s2, mixing the raw materials according to the proportioning scheme of the step S1, and adding deionized water for stirring;
s3, preparing slurry, adding slurry preparation raw materials into the raw material mixture mixed in the step S2, and stirring to prepare reaction mixture slurry;
s4, performing hydrothermal crystallization, transferring the slurry mixed in the step S2 into a high-pressure kettle, and performing static hydrothermal crystallization;
s5, suction filtering, washing, drying and roasting. And after crystallization, naturally cooling to room temperature, carrying out suction filtration on the crystallized product, washing until the PH value is close to neutral, and drying and roasting the filter cake.
Further, the hydrogen-type zeolite is one of MFI-type high-silica zeolite, FER-type high-silica zeolite, and CHA-type high-silica zeolite.
Further, the alkaline substance is organic alkali and inorganic alkali, wherein,
the organic base includes alkylamine organic base and organic quaternary ammonium organic base;
the inorganic base includes sodium hydroxide inorganic base and potassium hydroxide inorganic base.
Further, the sodium oxide content of the hydrogen-form zeolite is less than 0.3%.
Further, the content and proportion of the alkaline substance in the synthesis reaction mixture are controlled to be the ratio of the organic base to the silicon oxide or the ratio of the inorganic base to the silicon oxide.
Furthermore, the high-silicon zeolite has a silica-alumina molar ratio value ranging from 10 to 400.
Further, when preparing the MFI type high-silicon zeolite, the raw materials are mixed in a molar ratio of,
SiO 2 :0.016Al 2 O 3 :0.089Na 2 o0.104 n-butylamine 15H 2 O；
Or SiO 2 :0.014Al 2 O 3 :0.079Na 2 O0.104 n-butylamine 15H 2 O；
Or SiO 2 :0.018Al 2 O 3 :0.10Na 2 O0.10 n-butylamine 15H 2 O。
Further, when FER type high silica zeolite is prepared, the raw material mixture ratio in terms of mole ratio,
120SiO 2 :0.13Na2O:0.0025PrNH 2 :Al 2 O 3 :18H 2 O；
or 120SiO 2 :0.025Na2O:0.004PrNH 2 :Al 2 O 3 :21H 2 O；
Or 120SiO 2 :0.030Na2O:0.005PrNH 2 :Al 2 O 3 :22H 2 O。
Further, when preparing the CHA-type high-silica zeolite, the raw materials are mixed in a molar ratio of,
SiO 2 :0.0625Al 2 O 3 :0.45Na 2 O:0.125TMAD:20H 2 O
or SiO 2 :0.0285Al 2 O 3 :0.50Na 2 O:0.20TMAD:18H 2 O；
Or SiO 2 :0.05Al 2 O 3 :0.25Na 2 O:0.20TMAD:22.5H 2 O。
Further, the slurry preparation raw material when preparing the MFI-type high-silica zeolite is an n-butylamine solution, the slurry preparation raw material when preparing the FER-type high-silica zeolite is an n-propylamine solution, and the slurry preparation raw material when preparing the CHA-type high-silica zeolite is a TMAD solution.
Synthesis of MFI zeolite
Example 1 preparation of a reaction mixture according to the molar ratio SiO 2 :0.016Al 2 O 3 :0.089Na 2 O0.104 n-butylamine 15H 2 O；
Accurately weighing silica gel powder according to the molar ratio, placing the silica gel powder into a beaker, sequentially adding sodium metaaluminate and sodium hydroxide, then adding deionized water, uniformly stirring, and finally adding n-butylamine solution to form reaction mixture slurry. The slurry was stirred at 30 ℃ for 30 to 60 minutes and then transferred to a 250mL stainless steel autoclave lined with PTFE and subjected to static hydrothermal crystallization at 150 ℃ for 28 hours. After crystallization, naturally cooling to room temperature, carrying out suction filtration on the crystallized product, and washing until the PH is close to neutral. And drying the filter cake at 120 ℃ for 2h, and roasting at 550 ℃ for 5h to obtain a final product, namely a sample A. XRD identified as MFI zeolite pure phase (see above fig. 2). The SEM micrograph thereof is shown in FIG. 3. The photographs show that the zeolite is hexagonal rectangular single crystal grains, 0.4nm to 1.5nm in size. XRF determination of SAR of sample A as 49, Na 2 O is 0.18 percent and belongs to H-type MFI zeolite.
Example 2 preparation of a reaction mixture according to the molar ratio SiO 2 :0.014Al 2 O 3 :0.079Na 2 O0.104 n-butylamine 15H 2 O。
Accurately weighing the silica sol according to the molar ratio, sequentially weighing the silica sol, and adding aluminum sulfate and sodium hydroxide into a beaker. Then deionized water is added, the mixture is stirred evenly, and finally n-butylamine solution is added to form reaction mixture slurry. The slurry was stirred at 30 ℃ for 30 to 60min, transferred to a 250mL stainless steel autoclave with a polytetrafluoroethylene liner, and subjected to static hydrothermal crystallization at 120 ℃ for 36 h. Naturally cooling to room temperature after crystallization is finished, carrying out suction filtration on the crystallized product, washing until the PH is close to neutral, drying the filter cake at 120 ℃ for 2h, and roasting at 550 ℃ for 5h to obtain a final product, namely a sample B. XRD identified as MFI zeolite pure phase. XRF determination of SAR of 53, Na for sample B 2 O is 0.20 percent and belongs to H-type MFI zeolite.
Example 3 preparation of a reaction mixture according to the molar ratio SiO 2 :0.018Al 2 O 3 :0.10Na 2 O0.10 n-butylamine 15H 2 O。
Accurately weighing silica sol according to the molar ratio, sequentially weighing the silica sol, adding aluminum sulfate and sodium hydroxide into a beaker, adding deionized water, uniformly stirring, and finally adding n-butylamine solution to form reactant slurryAnd (5) feeding. Stirring the slurry at 30 ℃ for 30-60 min, transferring the slurry into a 250mL stainless steel autoclave with a polytetrafluoroethylene lining, and performing static hydrothermal crystallization at 120 ℃ for 36 h. And after crystallization is finished, naturally cooling to room temperature, carrying out suction filtration on a crystallized product, washing until the pH value is close to neutral, drying a filter cake at 120 ℃ for 2h, and roasting at 550 ℃ for 5h to obtain a final product, namely a sample C. XRD identified as MFI zeolite pure phase. XRF determination of SAR of 41, Na for sample C 2 O is 2.33 percent and belongs to Na and H-type MFI zeolite.
Synthesis of FER zeolite
Example 4A reaction mixture was prepared with the molar ratio 120SiO 2 :0.13Na2O:0.0025PrNH 2 :Al 2 O 3 :18H 2 O
Weighing a certain amount of silica gel powder, sodium hydroxide, sodium aluminate, n-propylamine and deionized water according to the molar ratio, respectively placing the silica gel powder, the sodium hydroxide, the sodium aluminate, the n-propylamine and the deionized water in a polytetrafluoroethylene beaker, mixing and stirring the mixture for 15min, then placing the mixture into a 250mL stainless steel reaction kettle, and carrying out hydrothermal crystallization reaction at 120 ℃ for 48 hours. And after the crystallization reaction is finished, washing the product by deionized water until the pH value is close to neutral, and drying the filter cake to obtain a pure-phase high-silicon FER zeolite-sample D. The XRD pattern is shown in figure 2, and XRD is identified as FER zeolite pure phase. The SEM micrograph is shown in FIG. 3. The photograph shows that the zeolite crystal presents a sheet-shaped single crystal with the thickness of 0.01nm, and a plurality of single crystals are overlapped and aggregated into a polycrystalline structure with the thickness of o.1 nm. XRF determination of SAR of sample D245, Na 2 O is 0.23 percent and belongs to H-type FER zeolite.
Example 5 a reaction mixture was prepared in the following molar ratio:
120SiO 2 :0.025Na2O:0.004PrNH 2 :Al 2 O 3 :21H 2 O
weighing a certain amount of silica gel powder, sodium hydroxide, sodium aluminate, n-propylamine and deionized water according to the molar ratio, respectively placing the silica gel powder, the sodium hydroxide, the sodium aluminate, the n-propylamine and the deionized water in a polytetrafluoroethylene beaker, mixing, stirring for 15min, then placing the mixture into a 250mL stainless steel reaction kettle, and carrying out hydrothermal crystallization reaction at 120 ℃ for 36 hours. After the crystallization reaction is finished, washing the product with deionized water until the pH value is close to neutral, and filtering the product. And drying the filter cake to obtain a pure-phase high-silicon FER zeolite sample E. SAR of sample E determined by XRF is 165, Na 2 O is 0.25%, belongs toIn the H-type FER zeolite.
Example 6A reaction mixture was prepared with the molar ratio 120SiO 2 :0.030Na2O:0.005PrNH 2 :Al 2 O 3 :22H 2 O
Weighing a certain amount of silica gel powder, sodium hydroxide, sodium aluminate, n-propylamine and deionized water according to the molar ratio, mixing in a polytetrafluoroethylene beaker, stirring for 15min, and then putting into a 250mL stainless steel reaction kettle, performing hydrothermal crystallization reaction at 120 ℃ for 36 hours. After the crystallization reaction is finished, washing the product with deionized water until the pH value is close to neutral, and filtering the product. And drying the filter cake to obtain a pure-phase high-silicon FER zeolite sample F. SAR 136, Na of sample F by XRF determination 2 O is 0.40%, and belongs to Na and H-type FER zeolite.
Synthesis of CHA zeolites
Example 7 preparation of a reaction mixture according to the molar ratio SiO 2 :0.0625Al 2 O 3 :0.45Na 2 O:0.125TMAD:20H 2 O
Accurately weighing the silica sol according to the molar ratio, sequentially weighing the silica sol, and adding aluminum sulfate and sodium hydroxide into a beaker. Then deionized water is added, the mixture is stirred evenly, and finally TMAD solution is added to prepare reaction mixture slurry. The slurry was stirred at 30 ℃ for 30 to 60min and then transferred to a 250mL stainless steel autoclave with a polytetrafluoroethylene lining for static hydrothermal crystallization at 150 ℃ for 48 h. And after crystallization is finished, naturally cooling to room temperature, carrying out suction filtration on the crystallized product, washing until the pH value is close to neutral, drying the filter cake at 120 ℃ for 2h, and roasting at 550 ℃ for 5h to obtain a final product, namely a sample G. The product was identified by XRD as CHA zeolite pure phase (see fig. 2 below). The SEM micrograph thereof is shown below in FIG. 3. The product exhibits a cubic single crystalline form with a size of 0.15nm to 0.20 nm. XRF determination of SAR of sample G30, Na 2 O is 0.70%, belonging to Na, H-type CHA zeolite.
Example 8 preparation of a reaction mixture according to the molar ratio SiO 2 :0.0285Al 2 O 3 :0.50Na 2 O:0.20TMAD:18H 2 O
Accurately weighing the silica sol according to the molar ratio, sequentially weighing the silica sol, and adding aluminum sulfate and sodium hydroxide into a beakerThen deionized water is added, the mixture is stirred evenly, and finally TMAD solution is added to prepare reaction mixture slurry. The slurry was stirred at 30 ℃ for 30 to 60min and transferred to a 250mL stainless steel autoclave with a polytetrafluoroethylene liner, and static hydrothermal crystallization was carried out at 160 ℃ for 48 h. After crystallization, naturally cooling to room temperature, and filtering and washing the crystallized product until the PH is close to neutral. And taking out the filter cake, drying for 2H at 120 ℃, and roasting for 5H at 550 ℃ to obtain a final product, namely a sample H. XRD identified the product as CHA zeolite pure phase, XRF determined the SAR of sample H to be 25, Na 2 O is 0.45% belonging to Na, H-type CHA zeolite.
Example 9 preparation of a reaction mixture SiO 2 :0.05Al 2 O 3 :0.25Na 2 O:0.20TMAD:22.5H 2 O
Accurately weighing the silica sol according to the molar ratio, sequentially weighing the silica sol, adding aluminum sulfate and sodium hydroxide into a beaker, adding deionized water, uniformly stirring, and finally adding a TMAD solution to form reaction mixture slurry. The slurry was stirred at 30 ℃ for 30 to 60min and transferred to a 250mL stainless steel autoclave with a polytetrafluoroethylene liner, and subjected to static hydrothermal crystallization at 150 ℃ for 48 h. And after crystallization is finished, naturally cooling to room temperature, carrying out suction filtration and washing on a crystallized product until the pH value is close to neutral, drying a filter cake at 120 ℃ for 2h, and roasting at 550 ℃ for 5h to obtain a final product, namely a sample I. XRD identified as CHA zeolite pure phase, and XRF determined that sample I had an SAR of 18, Na 2 O is 0.20% belonging to the H-type CHA zeolite.
In the 9 examples described above, the synthesis of three different structure types of high silica zeolites, namely MFI (ZSM-5), FER (ZSM-35) and CHA (SSZ-13), was involved. Since the hydrothermal synthesis of zeolites with different structures usually has to be within a certain range defined by a certain reaction mixture composition-product phase composition diagram (so-called "phase diagram"), the reaction mixtures for synthesizing the three kinds of high-silicon zeolites with different structures not only differ fundamentally in the types of organic templates, but also differ greatly in other aspects such as SAR, alkali/silicon ratio, amine (ammonium)/silicon ratio and water/silicon ratio, and the hydrothermal crystallization reaction temperature and time are different. The types of the used synthetic raw materials, the molar ratio of the reaction mixture, the crystallization reaction temperature, the crystallization reaction time and the like are different. In order to observe the synthesis data of the three zeolites with different structures conveniently and statistically, the table one summarizes the organic template type, the type of the silicon-aluminum raw material, the molar ratio of the reaction mixture, the temperature and time of the crystallization reaction, and the like used for synthesizing each zeolite reaction mixture, and the data of the phase of the crystallization reaction product and the main composition thereof. It can be seen that the organic templates used for synthesizing the high-silica zeolites with three different structural types are different from each other, and the organic templates include alkylamine such as n-butylamine and n-propylamine, and quaternary ammonium bases such as trimethyl amantadine ammonium, and the molar ratio (SAR) of the reaction mixture is wide and ranges from 16 to 400. The silica to alumina mole ratio (SAR) of the synthesized product also covers a wide range, from 15 to 245. The reaction mixture for each zeolite synthesis has a suitable base/silica ratio, amine (ammonium)/silica ratio and water/silica ratio. Careful observation revealed that the sodium oxide content in the product was from 0.15% (H-type zeolite) to 2.33% Na, H-type zeolite due to the difference in the alkali/silicon ratio and the amine (ammonium)/silicon ratio in the reaction mixture. The former low-sodium H-type zeolite can be directly used for preparing a catalyst without cation exchange, and the catalyst is the target product of the invention.
In addition to its structure directing effect, the organic base in the reaction mixture can also create the necessary basic environment for zeolite crystallization, under which the amorphous silica and alumina in the reaction mixture hydrolyze into silica tetrahedra and aluminoxy tetrahedra that are further linked to each other to form a quantity of polysiloxy-aluminoxy anions. However, the organic templating agent is often not sufficiently basic to allow the amorphous silica and alumina in the reaction mixture to hydrolyze sufficiently to form siloxy tetrahedra and aluminoxy tetrahedra, which are further linked to each other to form polysiloxy-aluminoxy anions, which surround the organic templating agent molecules at a suitable temperature to form crystalline nuclei of the zeolite and further grow into zeolite crystals of a specific structure. If the amount of organic base in the reaction mixture is too small, the templating effect is insufficient to induce crystallization of the zeolite having the specific structure, whereas if too much, the crystallization of the zeolite is induced, but the organic templating agent is expensive, difficult to recover, and environmentally undesirable. Therefore, the amount of the organic base to be added is generally selected so as to be sufficient to direct the target zeolite crystals when preparing the reaction mixture. The organic base can be used as a template agent in the specific space of the pore channel in the formed target zeolite crystal, and can also be used as a part of cations to play a charge balance role with the negative charge of aluminum atoms on the generated zeolite framework. While the cation, which acts to balance the negative charge of the backbone, is usually provided primarily by an inorganic base. This is the fundamental reason why the hydrothermal crystallization product always contains different amounts of alkali (sodium or potassium ions) in the usual zeolite production processes. When the silica to alumina molar ratio is not too high (e.g., SAR 10-50), such as the MFI zeolite and CHA zeolite listed in Table I, the sodium content of the product is relatively high, reaching 2.33% and 0.70%, respectively, and such zeolite products are Na, H-type MFI zeolite or Na, H-type CHA zeolite. However, the experiments of the present invention demonstrate that by properly adjusting the base/silica ratio and the amine (ammonium)/silica ratio in the reaction mixture, it is possible to directly synthesize H-type high silica zeolite having less than 0.30% sodium oxide, which can be used directly for the preparation of a catalyst without being subjected to cation exchange. The above rules of the present invention apply generally to high silica zeolites of different structure types, regardless of the silica to alumina mole ratio of the product.
Table two summarizes the structure types and low temperature nitrogen adsorption data for all the synthesized products in the synthesis examples of the present invention. It can be seen that the BET surface area and the micropore surface area, and the total pore volume and the micropore volume of the three types of structures synthesized according to the invention, each of which is 3 samples, are not significantly different. This shows that the adsorption properties of the H-type zeolite directly synthesized by the method of the present invention by controlling the appropriate alkali/silicon ratio and amine (ammonium)/silicon ratio of the reaction mixture are consistent with those of the general synthesized product.
TABLE 1 Synthesis reaction mixture molar ratios and product compositions TABLE
TMAD-trimethylamantadine ammonium salt
Table 2 synthetic product zeolite low temperature nitrogen adsorption data
TMAD-trimethylamantadine ammonium salt
So far, the technical solutions of the present invention have been described in connection with the preferred embodiments shown in the drawings, but it is easily understood by those skilled in the art that the scope of the present invention is obviously not limited to these specific embodiments. Equivalent changes or substitutions of related technical features can be made by those skilled in the art without departing from the principle of the invention, and the technical scheme after the changes or substitutions can fall into the protection scope of the invention.
Claims (10)
1. A method for directly synthesizing hydrogen type zeolite is characterized in that the hydrogen type zeolite is prepared by controlling the proportion of alkaline substances in a synthesis reaction mixture and by hydrothermal synthesis, and comprises the following steps,
s1, determining the raw material ratio according to the type of the zeolite to be prepared;
s2, mixing the raw materials according to the proportioning scheme of the step S1, and adding deionized water for stirring;
s3, preparing slurry, adding slurry preparation raw materials into the raw material mixture mixed in the step S2, and stirring to prepare reaction mixture slurry;
s4, performing hydrothermal crystallization, transferring the slurry mixed in the step S2 into a high-pressure kettle, and performing static hydrothermal crystallization;
s5, suction filtering, washing, drying, roasting, naturally cooling to room temperature after crystallization is finished, suction filtering and washing the crystallized product until the PH is close to neutral, and drying and roasting the filter cake.
2. The method of claim 1, wherein the hydrogen-type zeolite is one of MFI-type high-silica zeolite, FER-type high-silica zeolite and CHA-type high-silica zeolite.
3. The method of claim 2, wherein the basic material is an organic base or an inorganic base, wherein,
the organic base includes alkylamine organic base and organic quaternary ammonium organic base;
the inorganic base includes sodium hydroxide inorganic base and potassium hydroxide inorganic base.
4. A process for the direct synthesis of hydrogen zeolite according to claim 3, wherein the hydrogen zeolite has a sodium oxide content of less than 0.3%.
5. The method of claim 4, wherein the content and ratio of the basic substance in the synthesis reaction mixture are controlled to be the ratio of the organic base to the silica or the ratio of the inorganic base to the silica.
6. The method of claim 5, wherein the high-silica zeolite has a silica to alumina molar ratio in the range of 10 to 400.
7. The method of directly synthesizing hydrogen-type zeolite according to claim 2, wherein when preparing MFI-type high-silica zeolite, the raw material mixture ratio in terms of mole ratio is,
SiO 2 :0.016Al 2 O 3 :0.089Na 2 o0.104 n-butylamine 15H 2 O；
Or SiO 2 :0.014Al 2 O 3 :0.079Na 2 O0.104 n-butylamine 15H 2 O；
Or SiO 2 :0.018Al 2 O 3 :0.10Na 2 O0.10 n-butylamine 15H 2 O。
8. The method of directly synthesizing hydrogen-type zeolite according to claim 2, wherein when preparing FER-type high-silica zeolite, the raw material mixture ratio in terms of mole ratio is,
120SiO 2 :0.13Na2O:0.0025PrNH 2 :Al 2 O 3 :18H 2 O；
or 120SiO 2 :0.025Na2O:0.004PrNH 2 :Al 2 O 3 :21H 2 O；
Or 120SiO 2 :0.030Na2O:0.005PrNH 2 :Al 2 O 3 :22H 2 O。
9. The method of claim 2, wherein when preparing the CHA-type high-silica zeolite, the raw materials are mixed in a molar ratio of,
SiO 2 :0.0625Al 2 O 3 :0.45Na 2 O:0.125TMAD:20H 2 O
or SiO 2 :0.0285Al 2 O 3 :0.50Na 2 O:0.20TMAD:18H 2 O；
Or SiO 2 :0.05Al 2 O 3 :0.25Na 2 O:0.20TMAD:22.5H 2 O。
10. The method of directly synthesizing hydrogen-type zeolite according to claim 2, wherein the slurry preparation raw material is n-butylamine solution when preparing MFI-type high silica zeolite and n-propylamine solution when preparing FER-type high silica zeolite. When preparing CHA-type high-silica zeolites the slurry preparation starting material is a trimethylamantadine ammonium (TMAD) solution.
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