CN109678177A - A kind of preparation method of high silica alumina ratio step hole Beta molecular sieve - Google Patents
A kind of preparation method of high silica alumina ratio step hole Beta molecular sieve Download PDFInfo
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- CN109678177A CN109678177A CN201910010035.6A CN201910010035A CN109678177A CN 109678177 A CN109678177 A CN 109678177A CN 201910010035 A CN201910010035 A CN 201910010035A CN 109678177 A CN109678177 A CN 109678177A
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- molecular sieve
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 96
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 78
- 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 78
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 49
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 76
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 63
- 239000010703 silicon Substances 0.000 claims abstract description 63
- 238000002425 crystallisation Methods 0.000 claims abstract description 48
- 230000008025 crystallization Effects 0.000 claims abstract description 48
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000004411 aluminium Substances 0.000 claims abstract description 8
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 60
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 35
- 229910001868 water Inorganic materials 0.000 claims description 33
- 239000013078 crystal Substances 0.000 claims description 24
- 230000032683 aging Effects 0.000 claims description 21
- 229910052731 fluorine Inorganic materials 0.000 claims description 16
- 239000011737 fluorine Substances 0.000 claims description 16
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 14
- 239000000843 powder Substances 0.000 claims description 13
- 229910052681 coesite Inorganic materials 0.000 claims description 10
- 229910052906 cristobalite Inorganic materials 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 229910052682 stishovite Inorganic materials 0.000 claims description 10
- 229910052905 tridymite Inorganic materials 0.000 claims description 10
- 238000010899 nucleation Methods 0.000 claims description 9
- 239000003513 alkali Substances 0.000 claims description 8
- 229910052593 corundum Inorganic materials 0.000 claims description 8
- 239000003921 oil Substances 0.000 claims description 8
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 8
- 239000000017 hydrogel Substances 0.000 claims description 7
- 238000001354 calcination Methods 0.000 claims description 5
- 239000006229 carbon black Substances 0.000 claims description 4
- 235000019353 potassium silicate Nutrition 0.000 claims description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 3
- 239000000741 silica gel Substances 0.000 claims description 2
- 229910002027 silica gel Inorganic materials 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 abstract description 32
- 238000003786 synthesis reaction Methods 0.000 abstract description 31
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 17
- 239000007788 liquid Substances 0.000 abstract description 8
- 230000007246 mechanism Effects 0.000 abstract description 8
- 239000011148 porous material Substances 0.000 abstract description 6
- 239000002699 waste material Substances 0.000 abstract description 6
- 230000008901 benefit Effects 0.000 abstract description 5
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 24
- 230000008569 process Effects 0.000 description 15
- 239000003795 chemical substances by application Substances 0.000 description 10
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 230000007547 defect Effects 0.000 description 6
- 238000011049 filling Methods 0.000 description 5
- 238000009415 formwork Methods 0.000 description 5
- 239000011775 sodium fluoride Substances 0.000 description 5
- 235000013024 sodium fluoride Nutrition 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 4
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 4
- 229910000525 Si/Al2O3 Inorganic materials 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 3
- 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 3
- 230000008859 change Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000002779 inactivation Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000010189 synthetic method Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- 229910004074 SiF6 Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 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 description 2
- SWCIQHXIXUMHKA-UHFFFAOYSA-N aluminum;trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SWCIQHXIXUMHKA-UHFFFAOYSA-N 0.000 description 2
- KVBCYCWRDBDGBG-UHFFFAOYSA-N azane;dihydrofluoride Chemical compound [NH4+].F.[F-] KVBCYCWRDBDGBG-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000006399 behavior Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000004005 microsphere Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 2
- 125000001453 quaternary ammonium group Chemical group 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 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 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- CQBLUJRVOKGWCF-UHFFFAOYSA-N [O].[AlH3] Chemical compound [O].[AlH3] CQBLUJRVOKGWCF-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000001767 cationic compounds Chemical class 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 210000003850 cellular structure Anatomy 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000005216 hydrothermal crystallization Methods 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 229910001411 inorganic cation Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 239000011022 opal Substances 0.000 description 1
- 150000002892 organic cations Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000011698 potassium fluoride Substances 0.000 description 1
- 235000003270 potassium fluoride Nutrition 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/46—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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/85—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by XPS, EDX or EDAX data
Abstract
This patent provides a kind of preparation method of the steam auxiliary synthesizing high-silicon aluminium than step hole Beta molecular sieve, and explains synthesis mechanism in more detail, has certain directive significance to the subsequent method synthesis of molecular sieve.This method can successfully synthesize high-crystallinity Beta molecular sieve of the silica alumina ratio 200 ~ 2000 in 24 hours, and have the advantages such as silica alumina ratio controllable, high-crystallinity, step pore structure abundant.Compared with hydro-thermal method of uniting, crystallization liquid needed for the method is seldom, avoids the emission problem of a large amount of crystallization waste liquids；Template dosage is few, and synthesis cost is low；Raw material availability is high, can reach nearly 100% product yield；Generated time is short, and step is simple, can effectively reduce energy consumption, be conducive to large-scale industrial production.
Description
Technical field
The present invention relates to a kind of preparation methods of molecular sieve with * BEA structure, specifically a kind of to utilize steam
Booster action rapid synthesis high silica alumina ratio, high-crystallinity, Beta molecule with abundant step pore structure under low amounts template
The preparation method of sieve.
Background technique
Beta molecular sieve is unique molecular sieve for intersecting pore canal system with twelve-ring, have unique cellular structure,
Peracidity and good hydrothermal stability.In the 1960s, developing a series of low silica-alumina ratios from Mobile company, the U.S.
Molecular sieve, molecular screen material become most important catalytic core or catalyst carrier in petrochemical industry.Patent CN
106430230 B once pointed out that the thermal stability and hydrothermal stability of low si molecular sieves were relatively low, and reaction process is easy to happen
Carbon distribution inactivation, can not substantially meet industrial catalyst high stability, non-easy in inactivation, durable feature demand, this is greatly
Limit molecular sieve heavy industrialization application.Therefore develop that a kind of high silica alumina ratio, skeleton defect be few, stable structure, while again
With silica alumina ratio, controllable, hierarchical porous structure, nanoscale Beta molecular sieve are critically important to its large-scale industrialization application.
Sial system Beta molecular sieve is grown by uncharged oxygen-octahedron and electronegative aluminum-oxygen tetrahedron intertexture,
Its synthesis needs the organic cation in inorganic base metal ion and template to carry out the negative electrical charge in balance skeleton, to reach stable
The purpose of skeleton structure.Therefore, in Na+Wait one timing of alkali metal ions quantity, the cation in the templates such as quaternary ammonium base
Number is more, and the aluminium content of Beta molecular sieve made of being oriented in an assembling process is higher, and obtained product silica alumina ratio is also got over
It is low, refined (Chemistry of Materials, 20 (2008) 4533-4535) is thanked once under Template-free method using this point
Synthesize Beta molecular sieve with crystal seed guiding, but the silica alumina ratio of the molecular sieve can only be confined to 13.5.From this, whether passing
System hydro-thermal method or steam auxiliary law, the synthesis of superelevation silica alumina ratio Beta molecular sieve must need a certain amount of template.Meanwhile
The Beta molecular sieve of conventional hydrothermal synthesis is mostly micro porous molecular sieve, and traditional sample aperture is confined in 0.67*0.73 nanometer range,
Greatly limit the mass transfer diffusion process of reactants and products.Currently, the preparation process of hydrothermal synthesis Beta molecular sieve is also faced with
Long preparation period, it is at high cost, be easy to produce the problems such as stray crystal, therefore, break through conventional hydrothermal synthesis defect, look in extremely low mould
There is the new side of high silica alumina ratio, high-crystallinity, large aperture, simple, short preparation period the Beta molecular sieve of step under plate agent dosage
Method is a major challenge of molecular sieve heavy industrialization application.
F-It, can be by SiO as a kind of mineralizer2In Si hydrolysis, it is converted to soluble SiF5-Or SiF6 2-, and
It plays to SiO2Carrying and transformation.Meanwhile can be to avoid excessive inorganic cation is introduced, this reduces inorganic sun
Guiding function of the ion pair oxygen-octahedron in polymerization, so that defect (SiO caused when crystal growth-M+) greatly reduce,
To make the thermal stability of product and hydrothermal stability greatly increase.Therefore, in F-Under the conditions of existing, can synthesize has
The perfect cystal or large single crystal of high silica alumina ratio or pure silicon, the excellent effect with molecular sieves stabilized skeleton.
1967, Mobile company, the U.S. synthesized the Beta molecular sieve with * BEA structure with hydro-thermal method for the first time.
108069437 A of CN reports a kind of new method with step hole Beta molecular sieve.The method is simultaneously with tetraethyl
Ammonium hydroxide and enzymolysis xylogen are template, have synthesized Beta points by hydrothermal crystallizing after mixing with silicon source, silicon source, alkali source
Son sieve.But big (the TEAOH/SiO of consumption of template agent needed for the method2Molar ratio is 0.652.5 ~ 5), at high cost, crystallization
Step is complicated, needs two sections of crystallization, crystallization time is up to 80 hours, and under high template consumption, and silica alumina ratio is only in 30 ~ 50 models
Interior modulation is enclosed, silica alumina ratio is low, and product stability is poor, is unfavorable for Product industrialization production.
107416859 A of CN reports a kind of preparation method with step hole Beta molecular sieve.This method is with sub-molten salt
The kaolin or rectorite of activation are whole silicon sources and part silicon source, are then pressed with alkali source, supplement silicon source, crystal seed and deionized water
Certain ratio is uniformly mixed, and hydrothermal synthesis has gone out Beta molecular sieve.The method has synthesized under Template-free method has step hole
Beta molecular sieve, effectively reduce the high cost problem of use bring because of template, but the sample sial synthesized is very low (produces
Product silica alumina ratio≤20), this is the Template-free method method synthesis inevitable defect of Beta molecular sieve.Meanwhile the synthetic method is adhered rigidly to
In traditional hydrothermal synthesis, still unavoidable crystallization low efficiency, raw material availability is low, one-pot yield is low, high discharging of waste liquid band
The problems such as carrying out extensive environmental pollution.
106276949 A of CN reports a kind of multi-stage porous Beta molecular sieve with opal structural.The method is first by silicon
Then sucrose, the polystyrene microsphere, nanometer two of sulfuric acid treatment is added in source, silicon source, tetraethyl ammonium hydroxide, water mixing aging
Silicon oxide microsphere mixing hard mould agent carries out high temperature cabonization twice and handles, finally carries out crystallization again.The patent provides a kind of benefits
With the new method of vapor action synthesis Beta molecular sieve, the drawbacks of conventional hydrothermal synthesizes, but the method organic formwork are effectively prevented
Big (the TEAOH/SiO of agent dosage2Molar ratio introduces hard mould agent in order to which reaming is secondary, not only increases production cost up to 0.65)
Adding, the later period is soft, hard mould agent calcining also brings huge environmental problem, and under conditions of largely using organic formwork agent,
The silica alumina ratio of the Beta molecular sieve of synthesis is not still high, the silica alumina ratio only modulation in 10 ~ 50.
Zhang Junliang is in the current research (Chemical about steam auxiliary law synthesis Beta molecular sieve
Engineering Journal 291 (2016) 82-93) in, it was recently reported that a kind of step hole coexisted with micro--step hole
The synthetic method of Beta molecular sieve, the silica alumina ratio of sample can in 30 ~ 100 ranges modulation, it is opposite to tie but as silica alumina ratio improves
Brilliant degree reduces.
It is all had following defects that in the above-mentioned method about synthesis Beta molecular sieve firstly, synthesizing Beta molecular sieve now
Technique be mostly confined on hydrothermal synthesis method, and there are unavoidable defects for hydrothermal synthesis: (1) product yield is low.Crystallization
Extra siliceous and aluminum cannot be applied sufficiently in waste liquid afterwards；(2) utilization rate of kettle is low.Steam auxiliary law is approximately hydrothermal synthesis
3 times of utilization rate；(3) reaction pressure is high.By a large amount of solvents and high temperature crystallization；(4) high waste, high pollution.Containing siliceous, aluminium
The crystallization residual liquid of matter, template etc. is caused to waste and be polluted；(5) organic formwork agent needed for the molecular sieve of synthesizing high-silicon aluminium ratio is used
Amount is big, at high cost；(6) crystallization water requirement is big, and is not fully utilized, finally with discharging of waste liquid.
Dry gum method emerging in recent years can effectively avoid the problem of above-mentioned hydrothermal synthesis is brought, and be that one kind is more advantageous to reality
The existing industrialized method of Beta molecular sieve.But from the point of view of the progress of current dry gum method synthesis Beta molecular sieve, Beta points
Silica alumina ratio in son sieve product is confined in the range of Si/Al < 100, and the structural stability and hydrothermal stability of sample are also poor,
In addition the molecular sieve of high silica alumina ratio must need a certain amount of template, therefore, superelevation sial be synthesized under low template dosage
The step hole Beta molecular sieve of ratio is always a challenge.
Summary of the invention
The purpose of the present invention is being directed to the deficiency of the above Beta Zeolite synthesis method, it is simple, time-consuming to provide a kind of step
Synthesize high silica alumina ratio, high-crystallinity, high yield, high hydrothermal stability under short, low template consumption while there is step pore structure
Nanometer Beta molecular sieve preparation method, and propose " steam auxiliary law " synthesize the possible synthesis mechanism of Beta molecular sieve, be
The method efficiently synthesizes other kinds of molecular sieve and provides certain directive function.
Method includes the following steps:
1. basic step
1) silicon source is with SiO2Meter, silicon source is with Al2O3Meter, according to silicon source: silicon source: NaOH: template: Fluorine source: water=1:0.0003 ~
0.0056:0.11 ~ 0.245:0.03 ~ 0.1:0.01 ~ 1:20 ~ 80 molar ratio is sufficiently mixed, and is then added and is equivalent to silicon source matter
The crystal seed of amount 0.05% ~ 10%, aging 0.2 ~ 3 hour under conditions of temperature is 20 ~ 70 DEG C.By the hydrogel after aging 30 ~
It is evaporated 12 ~ 48 hours in 90 DEG C of oil bath, obtains the xerogel of templating and seeding；
2) the resulting xerogel of step 1) is ground, according to water: the ratio that dry powder quality ratio is 0.15 ~ 1.5 be respectively placed in kettle and
In small liner, in 110 ~ 160 DEG C crystallization 20 ~ 36 hours, products therefrom is washed to neutrality and after drying, 6 small in 550 DEG C of calcinings
When, obtain Beta molecular sieve.
2. the explanation of synthesis mechanism
About the synthesis mechanism of steaming process synthesis Beta molecular sieve, from the point of view of this experiment, it should which comprehensive solventless method and hydro-thermal are closed
(bibliography: Wang Baoguo, chemical industry and engineering, 22 (2005) 115-119 is comprehensively considered at the synthesis mechanism of method;
Huo Q, Leon R, Mesostructure design with gemini surfactants: supercage
formation in a three-dimensional hexagonal array, Science, 268 (1995) 1324-
1327;Xie Bin, Jilin University's academic dissertation, 2010, no organic formwork crystal seed method synthetic zeolite catalysis material).Recognize herein
For in the synthesis process of xerogel presoma, there are following behaviors for each substance: (1) TEAOH template is dispersed in NaOH
In alkaline solution, hydrophilic group and hydrophobic chain form flakes micella according to the form of " head is met and discussed, shoulder to shoulder ", and are stabilized
In system；(2) silicon source is hydrolyzed into meta-aluminic acid root anion under the action of enough NaOH, and with the slight dissolution of crystal seed.
Meanwhile silicon source, in the environment existing for alkalinity, fluoride, the effect of hydrolysis and fluorine ion through alkaline matter forms SiF5-Or
SiF6 2-Etc. low polyfluorin, and it is present in system；(3) during being evaporated, silicon species, aluminium species, the template of oligomeric state
Micella, seed concentration are gradually increased, and the interaction between each substance gradually increases, and form the primary list for constituting Beta molecular sieve
Meta structure.It is each substance behavior that may be present in presoma under experiment condition of the present invention above.When dry powder presoma enters kettle
When crystallization, it may occur that following crystallization process: (1) in " steam auxiliary law ", each dry powder particle is all equivalent to one
Small crystalline element region, after crystallization water is heated, gradually evaporating-osmosis is into the gap of every dry powder particle；(2) in high temperature
Under the driving of high pressure, the dry powder presoma in each crystal region is able to " activate ", i.e., oligomeric state silicon species and aluminium species with
The electron cloud on surfactant micellar surface is matched, with " head " group bonding of the effect of ionic bond and template, shape
At the oligomeric state species of the sial of a templating and seeding；(3) again with Van der Waals between multiple such oligomeric state species
Power or the form of hydrogen bond bond together, and then form the secondary units structure of Beta molecular sieve；(4) between secondary units structure each other
Interaction, the final Beta molecular sieve for growing into and there is three-dimensional twelve-ring duct that interweaves.
According to the above-mentioned discussion to " steam auxiliary law " synthesis Beta Zeolite synthesis mechanism, it can be deduced that the present invention is able to
Rapid synthesis goes out the reason of high silica alumina ratio Beta molecular sieve: (1) in " steam auxiliary law ", first by silicon source and silicon source seeding
And templating, then carry out subsequent crystallization process.Compared to conventional hydrothermal synthesize, by during hydrothermal crystallization structure disperses it is each
Substance be changed into constitute Beta molecular sieve primary unit structure (primary unit structure is just obtained directly in ageing process, and
Carried out in crystallization process in non-hydrothermal synthesis), this greatly shortens crystallization process；(2) in conventional hydrothermal synthesis process,
In order to maintain the high temperature and high pressure in kettle, need to be added a large amount of crystallization water, the addition for crossing polycrystallization water makes entire crystalline areas
It greatly increases.If crystallization process is compared to the process of one " reaction ", crystalline areas increase is bound to cause each composition species
Bulk phase concentration reduce, forward reaction process is restricted.On the contrary, crystallization water is deposited in vapour form in " steam auxiliary law "
Dry powder forerunner's body space can be quickly and effectively being penetrated into, and then around every dry powder, form unit crystallization small one by one
Area.In this way, the bulk phase concentration of each component greatly increases in each unit crystal region, and the driving force of steam is also remote
Greater than the driving force of liquid water, finally makes entirely to crystallize reaction rate and greatly increase.
This method has following remarkable advantage compared with existing synthesis Beta sieve technology:
This method is the method for synthesizing Beta molecular sieve by " steam auxiliary law ", and the Beta molecular sieve of synthesis has following excellent
Gesture: (1) superelevation silica alumina ratio.Its silica alumina ratio is up to Si/Al2O3=2000, and can in 200 ~ 2000 ranges random modulation；(2) high
Crystallinity.In general, the relative crystallinity of sial system molecular sieve can be gradually decreased with the raising of silica alumina ratio, but specially with this
The Beta molecular sieve of " steam auxiliary law " synthesis that benefit proposes, relative crystallinity maintains always high level, even if silica alumina ratio
Si/Al2O3The relative crystallinity of=2000 sample is also higher by 130% than standard sample；(3) skeleton stability is good, hydrophobic performance is excellent
More.The unstability of skeleton is to limit one of the critically important reason of Beta molecular sieve heavy industrialization, point of low stability
Son sieve is easy to happen carbon distribution, inactivation etc., and Fluorine source is introduced into framework of molecular sieve by the present invention, not only skeleton stability is made to increase greatly
Add, also increases the hydrophobicity of sample；(4) the abundant step pore structure coexisted with micro--step hole.Traditional Beta molecular sieve
Single microporosity limits the path that certain macromolecule reactants reach active site, and which greatly limits the works of Beta molecular sieve
Industry application, and method proposed by the present invention, do not need additionally to add second reaming agent, can one-step synthesis provide step hole
Beta molecular sieve can be significantly expanded the application field of Beta molecular sieve.
From synthesis technology, this method is conducive to industrialized significant advantage: (1) high product yield with following.It passes
The crystallization process of system hydrothermal synthesis needs a large amount of solvents, and after the completion of crystallization, there are still silicate, aluminate, templates in solvent
Deng part " nutriment ", therefore product yield is relatively low, and still, " steam auxiliary law " proposed by the present invention can be by all moulds
The sial " nutriment " of plate is completely used for synthesis Beta molecular sieve, with nearly 100% product yield；(2) inexpensive, low
Pollution.In general, residual substance in a solvent is dissolved under hydrothermal condition directly as pollutant emission, and it is several after present invention reaction
Without extra water, the wasting of resources and environmental pollution are reduced to the maximum extent；(3) low energy consumption, low kettle pressure.Conventional hydrothermal synthesis
A large amount of crystallization solvent makes kettle press through height, and energy consumption is larger, and there are biggish security risks.(4) low template consumption.In the present invention
In, template dosage is only TEA/SiO2<0.1。
In summary it analyzes, " steam auxiliary law " proposed by the present invention, which has, makes Beta molecular sieve realize large-scale industry
The characteristics of change, substantially reduces synthesis cost and carrying capacity of environment, and the application field of Beta molecular sieve greatly improved；It proposes simultaneously
It is fluorine-containing under the conditions of " steam auxiliary law " synthesize the possible crystallization mechanism of Beta molecular sieve, it is synthesized to subsequent " steam auxiliary law "
He has certain directive significance by the molecular sieve of perfect crystal form.
Detailed description of the invention
Fig. 1 is the X-ray powder diffraction figure of the Beta molecular sieve of the embodiment of the present invention.
Fig. 2 is the N of the embodiment of the present invention2Physical absorption desorption figure.
Specific embodiment
The present invention provides the preparation method of high silica alumina ratio step hole Beta a kind of, which is characterized in that this method includes following
Step:
1) silicon source is with SiO2Meter, silicon source is with Al2O3Meter, according to silicon source: silicon source: NaOH: template: Fluorine source: water=1:0.0003 ~
0.0056:0.11 ~ 0.245:0.03 ~ 0.1:0.01 ~ 1:20 ~ 80 molar ratio is sufficiently mixed, and is then added and is equivalent to silicon source matter
The crystal seed of amount 0.05% ~ 10%, aging 0.2 ~ 3 hour under conditions of temperature is 20 ~ 70 DEG C.By the hydrogel after aging 30 ~
It is evaporated 12 ~ 48 hours in 90 DEG C of oil bath, obtains the xerogel of templating and seeding；
2) the resulting xerogel of step 1) is ground, according to water: the ratio that dry powder quality ratio is 0.15 ~ 1.5 be respectively placed in kettle and
In small liner, in 110 ~ 160 DEG C crystallization 20 ~ 36 hours, products therefrom is washed to neutrality and after drying, 6 small in 550 DEG C of calcinings
When, obtain Beta molecular sieve.
According to the method for the present invention, preferably to silicon source in step 1): silicon source: NaOH: template: Fluorine source: water=1:
0.0005 ~ 0.005:0.16 ~ 0.24:0.04 ~ 0.1:0.03 ~ 0.3:30 ~ 80, the additional amount of crystal seed be silicon source quality 0.05% ~
1%。
According to the method for the present invention, described in step 1) without silicon source compound can be well known in the art it is various
The solid silicon source or liquid silicon source of high quality purity.It specifically, can be one in white carbon black, silica gel, waterglass, silica solution
Kind is several, it is demonstrated experimentally that above-mentioned silicon source can be used in synthetic method proposed by the present invention, and relative crystallinity is very high.
According to the method for the present invention, the quaternary ammonium base that template described in step 1) can be well known in the art
Class can be specifically one of tetramethylammonium hydroxide, tetraethyl ammonium hydroxide and tetrapropyl hydrogen-oxygen ammonium salt solution or several
Kind.Preferably tetraethyl ammonium hydroxide solution.
According to the method for the present invention, silicon source described in step 1) is Patent alum, ANN aluminium nitrate nonahydrate, aluminic acid
One or more of sodium.Preferably Patent alum and/or ANN aluminium nitrate nonahydrate.
According to the method for the present invention, Fluorine source described in step 1) is sodium fluoride, in potassium fluoride, ammonium fluoride, ammonium acid fluoride
One or more.Preferably sodium fluoride and/or ammonium acid fluoride.
According to the method for the present invention, crystal seed described in step 1) is preferably technical grade sial system Beta molecular sieve.
According to the method for the present invention, aging temperature described in step 1) is preferably 20 ~ 60 DEG C, and the time is 0.25 ~ 1 hour.
According to the method for the present invention, the evaporated temperature of hydrogel described in step 1) is preferably 50 ~ 70 DEG C, and the time is preferably
20 ~ 40 hours.
According to the method for the present invention, the side known to those skilled in the art of aging method described in the step 1)
Method.
According to the method for the present invention, method side known to those skilled in the art is evaporated described in the step 1)
Method.
According to the method for the present invention, the ratio of crystallization water and dry powder is preferably crystallization water: dry powder=0.2 ~ 0.6 in step 2.
According to the method for the present invention, crystallization temperature is preferably 140 ~ 160 DEG C in step 2, and crystallization time is preferably 22 ~ 25
Hour, and crystallization obtained solid product is washed with deionized to neutrality and after drying, it is calcined 6 hours at 550 DEG C.
According to the method for the present invention, washing described in the step 2, drying, method of roasting are those skilled in the art
Known method.It is 2 ~ 10 hours dry at 110 DEG C after being washed 3 times for example, by using deionized water.
According to the method for the present invention, crystallization process in step 2 crystallization process well known in the art, the crystallization mistake
Journey is static crystallization process.
Below by way of specific embodiment, the present invention will be described in detail, but the present invention is not restricted to following implementations
Example.
In following embodiment, the relative crystallinity of embodiment is according to document (Feng Qing, the dry gel conversion method of the reports such as Feng Qing
Synthesize monoblock type SSZ-13 molecular sieve, Journal of Chemical Industry and Engineering, 68 (2017) 1231-1238), the meter of crystal relative crystallinity (RC)
Calculation method are as follows: the sum of the sum of RC=embodiment characteristic peak peak area/technical grade sample characteristic peak peak area, and be defined as commercially available
Technical grade sample (the Si/Al of hydrothermal synthesis2O3=25) crystallinity is 100%.
Reagent in following embodiment, various silicon sources are purchased from Shanghai Shan Bo Industrial Co., Ltd., and organic formwork agent is purchased from
West Asia reagent Co., Ltd, remaining reagent are purchased from Sinopharm Chemical Reagent Co., Ltd..
The mole of template in following embodiment is with TEA+Meter.
Embodiment 1
The present embodiment is used to illustrate the preparation method of high silica alumina ratio step hole Beta.
First by silicon source (with SiO2Meter), silicon source is (with Al2O3Meter), alkali source, template, Fluorine source and water is according to white carbon black:
Al2(SO4)3·18H2O:NaOH:TEAOH:NaF:H2The molar ratio of O=1:0.0005:0.22:0.08:0.1:50 is sufficiently mixed,
Then the crystal seed for being equivalent to silicon source quality 1% is added, aging 0.5 hour under conditions of temperature is 30 DEG C.By the water-setting after aging
Glue evaporates 24 hours in 60 DEG C of oil bath, obtains the xerogel of templating and seeding.Resulting xerogel is pulverized,
Take 10g to be put in small liner, then put it into the crystallizing kettle for filling 2.5g water, kettle is sealed, in 145 DEG C crystallization 23 hours,
Products therefrom is washed with deionized to neutrality and after drying, and calcines 6 hours at 550 DEG C, obtains product S1.
Embodiment 2
The present embodiment is used to illustrate the preparation method of high silica alumina ratio step hole Beta.
First by silicon source (with SiO2Meter), silicon source is (with Al2O3Meter), alkali source, template, Fluorine source and water is according to silica solution:
Al2(SO4)3·18H2O:NaOH:TEAOH:NaF:H2The molar ratio of O=1:0.00067:0.21:0.1:0.1:60 is sufficiently mixed,
Then the crystal seed for being equivalent to silicon source quality 0.05% is added, aging 0.25 hour under conditions of temperature is 50 DEG C.After aging
Hydrogel evaporates 40 hours in 70 DEG C of oil bath, obtains the xerogel of templating and seeding.Resulting xerogel is ground
Cheng Fen takes 10g to be put in small liner, then puts it into the crystallizing kettle for filling 2.5g water, and kettle is sealed, in 150 DEG C of crystallization 20
Hour, products therefrom is washed with deionized to neutrality and after drying, and calcines 6 hours at 550 DEG C, obtains product S2.
Embodiment 3
The present embodiment is used to illustrate the preparation method of high silica alumina ratio step hole Beta.
First by silicon source (with SiO2Meter), silicon source is (with Al2O3Meter), alkali source, template, Fluorine source and water is according to silica solution: Al
(NO3)3·9H2O:NaOH:TEAOH:NH4HF:H2The molar ratio of O=1:0.001:0.215:0.09:0.1:50 is sufficiently mixed, so
The crystal seed for being equivalent to silicon source quality 1% is added afterwards, aging 1 hour under conditions of temperature is 30 DEG C.Hydrogel after aging is existed
It is evaporated 40 hours in 60 DEG C of oil bath, obtains the xerogel of templating and seeding.Resulting xerogel is pulverized, is taken
10g is put in small liner, then is put it into the crystallizing kettle for filling 5g water, and kettle is sealed, in 145 DEG C crystallization 24 hours, gained
Product is washed with deionized to neutrality and after drying, and calcines 6 hours at 550 DEG C, obtains product S3.
Embodiment 4
The present embodiment is used to illustrate the preparation method of high silica alumina ratio step hole Beta.
First by silicon source (with SiO2Meter), silicon source is (with Al2O3Meter), alkali source, template: Fluorine source and water are according to silicon source: aluminium
Source: NaOH: template: Fluorine source: water=waterglass: Al (NO3)3·9H2O:NaOH:TEAOH:NH4HF:H2O=1:0.00125:
The molar ratio of 0.24:0.06:0.03:80 is sufficiently mixed, and the crystal seed for being equivalent to silicon source quality 1% is then added, and is 30 DEG C in temperature
Under conditions of aging 0.5 hour.Hydrogel after aging is evaporated 24 hours in 70 DEG C of oil bath, obtains templating and crystal seed
The xerogel of change.Resulting xerogel is pulverized, 10g is taken to be put in small liner, then puts it into the crystallization for filling 3g water
In kettle, kettle is sealed, in 140 DEG C crystallization 25 hours, products therefrom is washed with deionized to neutrality and after drying, at 550 DEG C
Calcining 6 hours, obtains product S4.
Embodiment 5
The present embodiment is used to illustrate the preparation method of high silica alumina ratio step hole Beta.
First by silicon source (with SiO2Meter), silicon source is (with Al2O3Meter), alkali source, template: Fluorine source and water are according to white carbon black:
Al2(SO4)3·18H2O:NaOH:TEAOH:NaF:H2The molar ratio of O=1:0.005:0.19:0.08:0.1:50 is sufficiently mixed, so
The crystal seed for being equivalent to silicon source quality 0.5% is added afterwards, aging 0.5 hour under conditions of temperature is 40 DEG C.By the water-setting after aging
Glue evaporates 26 hours in 60 DEG C of oil bath, obtains the xerogel of templating and seeding.Resulting xerogel is pulverized,
Take 10g to be put in small liner, then put it into the crystallizing kettle for filling 2g water, kettle is sealed, in 160 DEG C crystallization 22 hours, institute
It obtains product to be washed with deionized to neutrality and after drying, is calcined 6 hours at 550 DEG C, obtain product S5.
The silica alumina ratio for the Beta molecular sieve that 1 embodiment relative crystallinity of table and ICP elemental analysis measure
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | |
| Relative crystallinity (100%) | 170% | 182% | 170.6% | 175% | 180% |
| Product Si/Al2O3 ICP | 1570 | 60 | 97 | 1110 | 12 |
By above data it is found that there is high silica alumina ratio with the Beta molecular sieve of " steam auxiliary law " provided by the invention synthesis,
Sial ratio can arbitrarily be regulated and controled, and be far more than the crystallinity and purity of standard sample.According to nitrogen physisorption-desorption knot
Fruit, the sample have micropore and the mesoporous step pore structure coexisted, adapt to the reaction molecular disengaging duct of sizes.
In summary it analyzes, " steam auxiliary law " proposed by the present invention, which has, makes Beta molecular sieve realize large-scale industry
The characteristics of change, substantially reduces synthesis cost and carrying capacity of environment, and the application field of Beta molecular sieve greatly improved.Meanwhile this
Invention also discuss in more detail it is fluorine-containing under the conditions of " steam auxiliary law " synthesis the possible crystallization mechanism of Beta molecular sieve, to rear
The molecular sieve that continuous " steam auxiliary law " synthesizes other perfect crystal forms has certain directive significance.
Claims (6)
1. a kind of steam auxiliary synthesizing high-silicon aluminium is than the preparation method of step hole Beta molecular sieve, which is characterized in that this method packet
Include following steps:
1) silicon source is with SiO2Meter, silicon source is with Al2O3Meter, according to silicon source: silicon source: NaOH: template: Fluorine source: water=1:0.0003 ~
0.0056:0.11 ~ 0.245:0.03 ~ 0.1:0.01 ~ 1:20 ~ 80 molar ratio is sufficiently mixed, and is then added and is equivalent to silicon source matter
The crystal seed of amount 0.05% ~ 10%, aging 0.2 ~ 3 hour under conditions of temperature is 20 ~ 70 DEG C.By the hydrogel after aging 30 ~
It is evaporated 12 ~ 48 hours in 90 DEG C of oil bath, obtains the xerogel of templating and seeding；
2) the resulting xerogel of step 1) is ground, according to water: the ratio that dry powder quality ratio is 0.15 ~ 1.5 be respectively placed in kettle and
In small liner, in 110 ~ 160 DEG C crystallization 20 ~ 36 hours, products therefrom is washed to neutrality and after drying, 6 small in 550 DEG C of calcinings
When, obtain Beta molecular sieve.
2. according to the method described in claim 1, wherein, in step 1), silicon source: silicon source: alkali source: template: Fluorine source: water rubs
You are than being silicon source: silicon source: template: Fluorine source: water=1:0.0005 ~ 0.005:0.16 ~ 0.24:0.04 ~ 0.1:0.03 ~ 0.3:30 ~
80, the additional amount of crystal seed is the 0.05% ~ 1% of silicon source quality.
3. in step 1), the aging temperature is 20 ~ 60 DEG C according to the method described in claim 1, wherein, the time is 0.25 ~
1 hour；The temperature being evaporated is 50 ~ 70 DEG C, and the time is 20 ~ 40 hours.
4. according to the method for the present invention, the ratio of crystallization water and dry powder is preferably crystallization water in step 2: the mass ratio of dry powder is
0.2~0.6。
5. in step 2, crystallization temperature is 140 ~ 160 DEG C according to the method described in claim 1, wherein, crystallization time is 22 ~
25 hours.
6. method according to claim 1 or 2, wherein the silicon source is white carbon black, in silica gel, waterglass, silica solution
One or more.
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