CN106698459A - Method for preparing nano zeolite molecular sieve by after-treatment of amorphous precursors - Google Patents
Method for preparing nano zeolite molecular sieve by after-treatment of amorphous precursors Download PDFInfo
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- CN106698459A CN106698459A CN201710029141.XA CN201710029141A CN106698459A CN 106698459 A CN106698459 A CN 106698459A CN 201710029141 A CN201710029141 A CN 201710029141A CN 106698459 A CN106698459 A CN 106698459A
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 33
- 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 33
- 239000010457 zeolite Substances 0.000 title claims abstract description 32
- 238000000034 method Methods 0.000 title claims abstract description 31
- 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 24
- 229910021536 Zeolite Inorganic materials 0.000 title claims abstract description 20
- 239000002243 precursor Substances 0.000 title claims abstract description 20
- 150000003839 salts Chemical class 0.000 claims abstract description 25
- 238000003756 stirring Methods 0.000 claims abstract description 16
- 238000002425 crystallisation Methods 0.000 claims abstract description 13
- 230000008025 crystallization Effects 0.000 claims abstract description 13
- 239000003513 alkali Substances 0.000 claims abstract description 12
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000005406 washing Methods 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 44
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 21
- 239000000243 solution Substances 0.000 claims description 20
- 239000004411 aluminium Substances 0.000 claims description 16
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 16
- 229910052782 aluminium Inorganic materials 0.000 claims description 16
- 238000012805 post-processing Methods 0.000 claims description 13
- 229910021417 amorphous silicon Inorganic materials 0.000 claims description 12
- 239000002105 nanoparticle Substances 0.000 claims description 12
- 239000000377 silicon dioxide Substances 0.000 claims description 8
- 238000005119 centrifugation Methods 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 5
- 239000012266 salt solution Substances 0.000 claims description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- 230000018044 dehydration Effects 0.000 claims description 3
- 238000006297 dehydration reaction Methods 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- 238000012545 processing Methods 0.000 claims description 2
- 238000004062 sedimentation Methods 0.000 claims description 2
- 229910000323 aluminium silicate Inorganic materials 0.000 abstract description 6
- 239000013078 crystal Substances 0.000 abstract description 5
- 229910052751 metal Inorganic materials 0.000 abstract description 4
- 239000002184 metal Substances 0.000 abstract description 4
- 239000002159 nanocrystal Substances 0.000 abstract description 2
- 238000010438 heat treatment Methods 0.000 abstract 1
- 230000015572 biosynthetic process Effects 0.000 description 12
- 238000003786 synthesis reaction Methods 0.000 description 12
- 239000003795 chemical substances by application Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000003643 water by type Substances 0.000 description 6
- 238000009415 formwork Methods 0.000 description 5
- 238000010189 synthetic method Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 238000004108 freeze drying Methods 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 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
- 241001515806 Stictis Species 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- PZZYQPZGQPZBDN-UHFFFAOYSA-N aluminium silicate Chemical compound O=[Al]O[Si](=O)O[Al]=O PZZYQPZGQPZBDN-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 235000021050 feed intake Nutrition 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000006552 photochemical reaction Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000004088 simulation Methods 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
- 238000001228 spectrum Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
Classifications
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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
-
- 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
- C01B39/20—Faujasite type, e.g. type X or Y
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- 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
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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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
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Nanotechnology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The invention relates to a method for preparing a nano zeolite molecular sieve by after-treatment of amorphous precursors. The method comprises the following steps: preparing amorphous aluminosilicate solutions with different silica-alumina ratios at room temperature, and stirring; sublimating in a freeze dryer to obtain amorphous gel solutions; centrifugating or settling and washing the gel solutions, and drying to obtain amorphous aluminosilicate precursors with different silica-alumina ratios; taking the amorphous aluminosilicate precursors, adding alkali liquor, and stirring uniformly; taking the amorphous aluminosilicate precursors, adding metal salts, stirring uniformly, treating at fixed temperature, adding alkali liquor, and stirring uniformly; and putting the solutions into a crystallization kettle, and carrying out two-stage heating to obtain the zeolite molecular sieve. Amorphous aluminosilicates with different silica-alumina ratios are used as precursors and subjected to after-treatment by different after-treatment solutions to controllably synthesize the zeolite molecular sieve nanocrystal with large external surface area and small crystal size; and the method has the advantages of simple reaction conditions, energy saving, environment friendliness and high yield.
Description
Technical field
The present invention relates to a kind of inorganic material technology of preparing, more particularly to a kind of post processing amorphous precursors prepare nanometer
The method of level zeolite molecular sieve.
Background technology
Received because the zeolite molecular sieve of Nano grade has unique property compared with the zeolite molecular sieve of micron level
It is to the favor of researcher, such as logical with active, more active sites of bigger external surface area and Geng Gao and shorter diffusion
Road etc..The synthesis of the zeolite molecular sieve of Nano grade is for understanding molecular sieve crystal nucleation process and growth course, improving catalysis
Application and ultra-thin zeolite molecular sieve film in agent activity and photochemical reaction and the aspect such as preparation of micro- composite received have again
The Research Significance and value wanted.So far, the synthesis report of Nano grade zeolite molecular sieve is few in number, mainly including template
Agent synthetic method, space limitation several synthetic routes such as synthetic method and crystal seed revulsion.However, organic formwork agent and confined space method
Used it is unfriendly to environment and cannot reusable organic formwork agent and polymeric additive, so synthetic route is not only multiple
It is miscellaneous, pollute environment and substantially increase synthesis cost.Furthermore, organic formwork agent is removed by high-temperature roasting and polymer is added
Agent can cause nanocrystal to be agglomerated into big solid particle, and this accumulation process is irreversible.Crystal seed revulsion is due to crystal seed
Synthesis used organic formwork agent, Template-free method method can not be calculated on stricti jurise.Thus develop a kind of green, it is simple
, low cost nanocrystalline Zeolite synthesis method have important research meaning.
The control of crystalline size is a step for key, crystallization temperature mistake for the synthesis of Nano grade zeolite molecular sieve
Overlong time high can cause crystalline size to become big, crystallization temperature too low time too short crystallinity reduction, it is necessary to strict controlling crystallizing
Temperature and time.
The content of the invention
The drawbacks described above that the purpose of the present invention exists aiming at prior art, there is provided one kind post processing amorphous precursors
The method for preparing nano-sized zeolites molecular sieve, with difference feed intake silica alumina ratio amorphous silicon aluminium hydrochlorate as presoma, using difference
Aftertreatment fluid is post-processed, controllable M-FAU zeolite molecular sieve nanometer of the synthesis with big external surface area, small crystalline size
It is brilliant.Aftertreatment fluid includes various variety classeses, the metal salt solution and alkali lye that can serve as duct supporter of various concentrations.
The method that a kind of post processing amorphous precursors that the present invention is mentioned prepare nano-sized zeolites molecular sieve, including it is following
It is prepared by step：
（1）The amorphous silicon aluminium acid salt solution of different silica alumina ratios is configured at room temperature, is stirred, wherein, silicon source is the alkali of 30wt%
Property Ludox, silicon source is aluminium powder, and different silica alumina ratio scopes are：7~25：1；
（2）Will be by step（1）The clear liquid for the treatment of is placed in freeze-dryer and distils, and obtains unformed gel solution：
（3）Will be by step（2）The gel solution centrifugation or sedimentation washing for the treatment of are 8~9 to pH value, are placed in freeze-dryer
Middle drying, obtains different silica alumina ratio amorphous silicon aluminium hydrochlorate presomas；
（4）Learnt from else's experience step（1）、（2）、（3）The amorphous silicon aluminium hydrochlorate presoma for obtaining, addition concentration is 2wt%~7wt%
Alkali lye, stir；
（5）Learnt from else's experience step（1）、（2）、（3）The amorphous silicon aluminium hydrochlorate presoma for obtaining, adds slaine, stirs,
Alkali lye is added after processing after a while under fixed temperature, is stirred；
（6）Will be by step（4）、（5）The solution for obtaining is placed in crystallizing kettle, and nanoscale is obtained by two sections of temperature-raising method crystallization
Other FAU zeolite molecular sieves.
Preferably, in step 2, it is placed in freeze-dryer and distils, makes its dehydration.
Preferably, in step 4, alkali lye is the sodium hydroxide solution that concentration is 2wt%~7wt%.
Preferably, described slaine is the one kind in K salt, Li salt, Fe salt, Ca salt, Cu salt, Eu salt.
Preferably, the concentration of described Fe salt is 0.005M~0.025M.
Preferably, described K salt, Li salt, Ca salt, Cu salt, the concentration of Eu salt are 2wt%~7wt%.
Preferably, in step 5, fixed temperature is 50 DEG C, is for a period of time 6h.
Preferably, described two benches temperature-raising method is then transferred to 100 DEG C of crystallization 10h~48h for 50 DEG C of crystallization 15h, or
50 DEG C of crystallization 15h are then transferred to 120 DEG C of crystallization 10h~24h.
In addition, the rate of charge for preparing of above-mentioned amorphous silicon aluminium hydrochlorate presoma is NaOH:Al:SiO2:H2O=90:2~
7:50:411。
The beneficial effects of the invention are as follows：The invention provides a kind of simple, green, low energy consumption, the synthesis of high yield nanometer
The method of the M-FAU zeolite molecular sieves of rank；Compared with prior synthesizing method, the present invention has advantage following prominent：1st, react
Condition is simple, energy saving, environmental protection, yield are high；2nd, conventional method uses organic formwork agent, expensive and need high-temperature roasting
Removed from product, nanocrystalline reunion can be caused, reduce nanocrystalline advantage, organic-free template of the present invention is greatly reduced
Cost and energy consumption；3rd, using various low concentration aftertreatment fluids, various M-FAU are synthesized nanocrystalline；4th, post-processing stages of the present invention
Using two sections of temperature-raising methods, can very well control nanocrystalline size and improve crystallinity；5th, unformed presoma dehydration is prepared
Journey and drying process are all processed with freeze-dryer, can effectively be controlled nanocrystalline reunion and be kept the hole of molecular sieve to tie
Structure.
Brief description of the drawings
Fig. 1 is the XRD of amorphous silicon aluminium hydrochlorate presoma；
Fig. 2 is the FAU and simulation FAU contrast XRDs of present invention synthesis；
Fig. 3 is the M-FAU XRDs of the hetero atom substitution of present invention synthesis；
Fig. 4 is a kind of FAU SEM figures of present invention synthesis；
Fig. 5 is another FAU SEM figures of present invention synthesis.
Specific embodiment
The preferred embodiments of the present invention are illustrated below in conjunction with accompanying drawing, it will be appreciated that preferred reality described herein
Apply example to be merely to illustrate and explain the present invention, be not intended to limit the present invention.
Embodiment 1：A kind of post processing amorphous precursors that the present invention is mentioned prepare the synthesis of nano-sized zeolites molecular sieve
Method, comprises the following steps：
One be amorphous silicon aluminium silicate material synthetic method it is as follows：
At room temperature, in beaker A, 10g NaOH is dissolved in 20g deionized waters, adds 0.945g aluminium powders, stirred；
In beaker B, 8g NaOH is dissolved in 17g deionized waters, adds 50g Ludox, stirring is clarified until solution becomes.Beaker
A, B are cooled to room temperature, and beaker B is placed in frozen water mixing bath, the solution in beaker A are added drop-wise in beaker B, mixed liquor
24h is stirred at room temperature.Mixed liquor after stirring removes 46-48g water in being put into freeze-drying, and centrifugation to PH is 8-9, removal
Upper strata centrifugate, is put into freeze-dryer and dries 24h.Taking sample segment carries out XRD signs, as shown in Figure 1, it can be seen that sample
Product are unformed states.
At room temperature, in beaker A, 10g NaOH is dissolved in 20g deionized waters, adds 3g aluminium powders, stirred；
In beaker B, 8g NaOH is dissolved in 17g deionized waters, adds 50g Ludox, stirring is clarified until solution becomes.Beaker
A, B are cooled to room temperature, and beaker B is placed in frozen water mixing bath, the solution in beaker A are added drop-wise in beaker B, mixed liquor
24h is stirred at room temperature.Mixed liquor after stirring removes 46-48g water in being put into freeze-drying, and centrifugation to PH is 8-9, removal
Upper strata centrifugate, is put into freeze-dryer and dries 24h.
At room temperature, in beaker A, 10g NaOH is dissolved in 20g deionized waters, adds 0.8g aluminium powders, stirred；
In beaker B, 8g NaOH is dissolved in 17g deionized waters, adds 50g Ludox, stirring is clarified until solution becomes.Burn
Cup A, B are cooled to room temperature, and beaker B is placed in frozen water mixing bath, the solution in beaker A are added drop-wise in beaker B, mixing
Liquid is stirred at room temperature 24h.Mixed liquor after stirring removes 46-48g water in being put into freeze-drying, and centrifugation to PH is 8-9, is gone
Except upper strata centrifugate, it is put into freeze-dryer and dries 24h.
Two be Nano grade FAU zeolite molecular sieves synthetic method it is as follows：
At room temperature, the unformed presomas of 500mg are taken to be dissolved in the sodium hydroxide solution of 10ml 2wt%, is stirred.By solution
It is fitted into the crystallizing kettle that capacity is 50ml, is placed in and is transferred to 10h in 100 DEG C of baking ovens in 50 DEG C of baking ovens after 15h, washing centrifugation 5 times,
It is put into drying in freeze-dryer.Taking sample segment carries out XRD and SEM signs, as illustrated, gained is as schemed and standard FAU types
Zeolite molecular sieve XRD spectra is consistent, as can be seen that crystalline size size is about 20-400nm from SEM spectrum.
Three be hetero atom substitution Nano grade M-FAU zeolite molecular sieves synthetic method it is as follows：
At room temperature, take during the unformed presomas of 500mg are dissolved in the nine water ferric nitrates of 10ml 0.005M as metal salt solution,
Stir, be put into 6h in 50 DEG C of baking ovens, centrifuge washing 3 times.The hydroxide of 10ml 2wt% is dissolved in after removal centrifugate again
In sodium solution, stir.Solution is fitted into the crystallizing kettle that capacity is 50ml, is placed in 50 DEG C of baking ovens and is transferred to 100 after 15h
10h in DEG C baking oven, washing centrifugation 5 times is put into freeze-dryer and dries.
Wherein, metal salt solution uses the LiOH solution and Ca (NO of 2wt%3)2Solution.
The above, is only part preferred embodiment of the invention, and any those of ordinary skill in the art may profit
Equivalent technical scheme is changed or is revised as with the technical scheme of above-mentioned elaboration.Therefore, according to technology of the invention
Any simple modification or substitute equivalents that scheme is carried out, belong to the greatest extent the scope of protection of present invention.
Claims (9)
1. a kind of post processing amorphous precursors prepare the method for nano-sized zeolites molecular sieve, it is characterized in that comprising the following steps system
It is standby：
（1）The amorphous silicon aluminium acid salt solution of different silica alumina ratios is configured at room temperature, is stirred, wherein, silicon source is the alkali of 30wt%
Property Ludox, silicon source is aluminium powder；
（2）Will be by step（1）The clear liquid for the treatment of is placed in freeze-dryer and distils, and obtains unformed gel solution：
（3）Will be by step（2）The gel solution centrifugation or sedimentation washing for the treatment of are 8~9 to pH value, are placed in freeze-dryer
Middle drying, obtains different silica alumina ratio amorphous silicon aluminium hydrochlorate presomas；
（4）Learnt from else's experience step（1）、（2）、（3）The amorphous silicon aluminium hydrochlorate presoma for obtaining, addition concentration is 2wt%~7wt%
Alkali lye, stir；
（5）Learnt from else's experience step（1）、（2）、（3）The amorphous silicon aluminium hydrochlorate presoma for obtaining, adds slaine, stirs,
Alkali lye is added after processing after a while under fixed temperature, is stirred；
（6）Will be by step（4）、（5）The solution for obtaining is placed in crystallizing kettle, and nanoscale is obtained by two sections of temperature-raising method crystallization
Other FAU zeolite molecular sieves.
2. the method that a kind of post processing amorphous precursors according to claim 1 prepare nano-sized zeolites molecular sieve, its
It is characterized in：In step one, different silica alumina ratio scopes are：7~25：1.
3. the method that a kind of post processing amorphous precursors according to claim 1 prepare nano-sized zeolites molecular sieve, its
It is characterized in：In step 2, it is placed in freeze-dryer and distils, makes its dehydration.
4. the method that a kind of post processing amorphous precursors according to claim 1 prepare nano-sized zeolites molecular sieve, its
It is characterized in：In step 4, alkali lye is the sodium hydroxide solution that concentration is 2wt%~7wt%.
5. the method that a kind of post processing amorphous precursors according to claim 1 prepare nano-sized zeolites molecular sieve, its
It is characterized in：Described slaine is the one kind in K salt, Li salt, Fe salt, Ca salt, Cu salt, Eu salt.
6. the method that a kind of post processing amorphous precursors according to claim 5 prepare nano-sized zeolites molecular sieve, its
It is characterized in：The concentration of described Fe salt is 0.005M~0.025M.
7. the method that a kind of post processing amorphous precursors according to claim 5 prepare nano-sized zeolites molecular sieve, its
It is characterized in：Described K salt, Li salt, Ca salt, Cu salt, the concentration of Eu salt are 2wt%~7wt%.
8. the method that a kind of post processing amorphous precursors according to claim 1 prepare nano-sized zeolites molecular sieve, its
It is characterized in：In step 5, fixed temperature is 50 DEG C, is for a period of time 6h.
9. alkali process amorphous precursors according to claim 1 prepare the side of the FAU type zeolite molecular sieves of Nano grade
Method, it is characterized in that：Described two benches temperature-raising method is then transferred to 100 DEG C of crystallization 10h~48h, or 50 for 50 DEG C of crystallization 15h
DEG C crystallization 15h is then transferred to 120 DEG C of crystallization 10h~24h.
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Cited By (6)
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| CN108002403A (en) * | 2017-12-13 | 2018-05-08 | 卓悦环保新材料（上海）有限公司 | A kind of synthetic method of CHA molecular sieves |
| CN113019427A (en) * | 2019-12-25 | 2021-06-25 | 中国石油化工股份有限公司 | Preparation method of hydrotreating catalyst |
| CN113019425A (en) * | 2019-12-25 | 2021-06-25 | 中国石油化工股份有限公司 | Hydrotreating catalyst carrier, hydrotreating catalyst and preparation method thereof |
| CN113019428A (en) * | 2019-12-25 | 2021-06-25 | 中国石油化工股份有限公司 | Preparation method of hydrotreating catalyst carrier |
| CN113019429A (en) * | 2019-12-25 | 2021-06-25 | 中国石油化工股份有限公司 | Preparation method of hydrotreating catalyst |
| CN113582197A (en) * | 2021-08-31 | 2021-11-02 | 青岛大学 | MOR molecular sieve with high silica-alumina ratio and preparation method thereof |
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| CN1737085A (en) * | 2005-06-17 | 2006-02-22 | 朱广山 | LTA and FAU molecular screen nanocrystalline preparation method |
| CN101164883A (en) * | 2007-09-27 | 2008-04-23 | 江西师范大学 | Preparation method for nano T-type molecular sieve |
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| CN108002403A (en) * | 2017-12-13 | 2018-05-08 | 卓悦环保新材料（上海）有限公司 | A kind of synthetic method of CHA molecular sieves |
| CN113019427A (en) * | 2019-12-25 | 2021-06-25 | 中国石油化工股份有限公司 | Preparation method of hydrotreating catalyst |
| CN113019425A (en) * | 2019-12-25 | 2021-06-25 | 中国石油化工股份有限公司 | Hydrotreating catalyst carrier, hydrotreating catalyst and preparation method thereof |
| CN113019428A (en) * | 2019-12-25 | 2021-06-25 | 中国石油化工股份有限公司 | Preparation method of hydrotreating catalyst carrier |
| CN113019429A (en) * | 2019-12-25 | 2021-06-25 | 中国石油化工股份有限公司 | Preparation method of hydrotreating catalyst |
| CN113019427B (en) * | 2019-12-25 | 2022-09-09 | 中国石油化工股份有限公司 | Preparation method of hydrotreating catalyst |
| CN113019428B (en) * | 2019-12-25 | 2022-09-09 | 中国石油化工股份有限公司 | Preparation method of hydrotreating catalyst carrier |
| CN113019429B (en) * | 2019-12-25 | 2022-09-09 | 中国石油化工股份有限公司 | Preparation method of hydrotreating catalyst |
| CN113019425B (en) * | 2019-12-25 | 2022-09-09 | 中国石油化工股份有限公司 | Hydrotreating catalyst carrier, hydrotreating catalyst and preparation method thereof |
| CN113582197A (en) * | 2021-08-31 | 2021-11-02 | 青岛大学 | MOR molecular sieve with high silica-alumina ratio and preparation method thereof |
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| CN109502599A (en) | 2019-03-22 |
| CN106698459B (en) | 2019-01-08 |
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