CN108793185A - A kind of preparation method of nano-ZSM-5 molecular sieve - Google Patents
A kind of preparation method of nano-ZSM-5 molecular sieve Download PDFInfo
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- CN108793185A CN108793185A CN201810781733.1A CN201810781733A CN108793185A CN 108793185 A CN108793185 A CN 108793185A CN 201810781733 A CN201810781733 A CN 201810781733A CN 108793185 A CN108793185 A CN 108793185A
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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
- C01B39/36—Pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
- C01B39/38—Type ZSM-5
- C01B39/40—Type ZSM-5 using at least one organic template directing agent
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- 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
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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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
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
Abstract
The invention belongs to zeolite molecular sieve synthetic technology fields, it is intended to provide a kind of preparation method of green, easy nano-ZSM-5 molecular sieve, it is stirred evenly more particularly to one kind by adding high molecular polymer, silicon source, silicon source, Organic structure directing agent and deionized water in synthetic system, form the collosol and gel of Zeolite synthesis presoma, then dry glue is made in above-mentioned collosol and gel, the method for recycling water vapour auxiliary crystallization method to obtain nano-ZSM-5 molecular sieve.By this method prepare nano-ZSM-5 molecular sieve have the characteristics that higher crystallinity, grain size it is controllable between 10~100nm, containing mesoporous-microporous combined multi-stage pore structure, with larger specific surface area.The preparation method of nano-ZSM-5 molecular sieve provided by the invention, nano molecular sieve is not only avoided to be difficult to that the technological deficiencies such as a large amount of synthesis waste liquids are separated and collected and discharged from mother liquor, combined coefficient can also be improved, it is a kind of simple and effective, environmental-friendly synthetic route, there is certain industrial applications foreground.
Description
Technical field
The present invention relates to zeolite molecular sieve synthetic technology fields, are specifically to provide a kind of green, easy nano-ZSM-5 molecule
The preparation method of sieve.
Background technology
ZSM-5 molecular sieve is Mobile oil companies of the U.S. in a kind of successful aluminosilicate of novel crystallization of research and development in 1972
Salt material.Because having many advantages, such as excellent duct shape selectivity, suitable acid and good hydrothermal stability, it is increasingly becoming stone
One of oil refining most important catalysis material of chemical industry.But because only containing micropore canals, cause mass transfer diffusivity limited, no
Only cannot effective catalyzed conversion macromolecular raw material, be also easy to that catalyst carbon deposit is caused to inactivate.With conventional micron ZSM-5 molecular sieve phase
Than, the grain size of nano-ZSM-5 molecular sieve is generally less than 100nm, thus can significantly shorten micropore diffusion path, also have compared with
The advantages that big external surface area, acidic site accessibility are high and exposure aperture density is high, to make nano molecular sieve have more
High reactivity and stability, shows excellent catalytic performance.
All the time, the technology of preparing of nano molecular sieve is concerned.Patent CN106698463A discloses a kind of synthesis
The synthetic method of nano-ZSM-5 molecular sieve.Specific building-up process is, first by organic formwork agent, silicon source, silicon source, inorganic base and
Deionized water is mixed evenly to obtain gel, is then uniformly mixed gel with macropore carbon, is sieved using macropore carbon restriction molecule
Nano-ZSM-5 molecular sieve is made in crystal growth in the case of relatively low consumption of template agent.Patent CN1958453A is disclosed
A kind of preparation method using -5 molecular sieve of crystal seed method synthesizing small crystal grain ZSM-5 specifically includes silicon source being dissolved in acid solution, then
Template and silicon source are added in above-mentioned silicon source solution successively, then add a small amount of molecular sieve seed, using hydrothermal crystallization method
Prepare small crystal grain molecular sieve.Patent CN101428818B discloses a kind of method using interference nucleus growth, specifically exists
A kind of structure directing agent organic base isopropylamine for synthesizing ZSM-23 molecular screen is added in ZSM-5 molecular sieve synthetic system, leads to
It crosses to control the dosage of above-mentioned isopropylamine and can obtain nano-ZSM-5 molecular sieve in OK range.Patent CN102745714A is carried
A kind of preparation method of ZSM-5 molecular sieve with small crystal grains is supplied.Organic silicon source and alcoholic solvent are uniformly mixed in preparation process, obtained
To the alcoholic solution containing silicon source, then template is dissolved in the aqueous solution of inorganic base, silicon source and alcohol containing silicon source is molten
Liquid is added in the alkaline solution containing template, is thoroughly mixed and is formed uniformly lotion, and above-mentioned emulsion crystallization is obtained small crystalline substance
Grain ZSM-5 molecular sieve.Patent CN101182004B discloses one kind by adding hydro carbons in Zeolite synthesis precursor solution
Component surfactant, forms the super solubilizing systems of oily packet fusant, and regulatory molecule sieves grain size, prepares the conjunction of nano molecular sieve
At method.Patent CN104192859A discloses a kind of method quickly preparing ZSM-5 molecular sieve with small crystal grains.In the preparation method
In, first the sial mixed sols of preparation is placed under cryogenic conditions and is nucleated, is then increasing the obtained little crystal grain of temperature crystallization again
ZSM-5 molecular sieve.
It can be seen that although there are many synthetic technology of existing nano-ZSM-5 molecular sieve, most of is all by synthesizing
The substances such as molecular sieve seed, Organic structure directing agent, induced synthesis nano-ZSM-5 molecular sieve are added in system；Either synthesize
Inorganic salts, Organic Alcohol or surfactant etc. are added in system to adjust zeolite crystal size, prepare nano molecular sieve；Part
Synthetic technology is also by finely regulating crystallization condition and crystallization temperature, especially with low temperature crystallized induced synthesis nano molecular
Sieve.But that often there is processes in above-mentioned building-up process is complicated, combined coefficient is low, nano molecular sieve product is not easy from mother liquor point
From collecting, need the technological deficiencies such as a large amount of structure directing agent synthesis costs are high, a large amount of synthesis waste liquor contamination environment of discharge.This is greatly
Ground limits industrialized production and the application of nano-ZSM-5 molecular sieve.Therefore, it develops a kind of green, simplicity nano molecular sieve
Synthetic route has very necessity and urgency.
Invention content
The present invention be overcome in existing nano-ZSM-5 molecular sieve synthetic technology product to separate and collect difficult, combined coefficient is low
The defects of with pollution environment, provide a kind of simple and effective, preparation method that is environmental-friendly and being easy to industrialized production.Party's legal system
Standby nano-ZSM-5 molecular sieve has higher crystallinity, mesoporous-microporous combined multi-stage pore structure, larger specific surface area, larger
Micropore specific area and Micropore volume the features such as.
The present invention prepares the method for nano-ZSM-5 molecular sieve specifically, by adding high molecular polymerization in synthetic system
Initial synthesis collosol and gel is made in the mixture that object, silicon source, silicon source, Organic structure directing agent and deionized water are formed, and then will
Dry glue is made in above-mentioned collosol and gel, and water vapour auxiliary crystallization method is recycled to obtain nano-ZSM-5 molecular sieve.
The present invention also provides the preparation method of above-mentioned nano-ZSM-5 molecular sieve, specific synthesis step is as follows：
(1) a certain amount of high molecular polymer is dissolved in deionized water, at room temperature stir 2~12h, be made uniformly mix it is molten
Liquid A；
(2) sequentially add a certain amount of silicon source and silicon source, 20~80 DEG C of constant temperature water baths stirrings 0~for 24 hours, obtain uniformly mix it is molten
Liquid B；
(3) under stirring, Organic structure directing agent is added dropwise into above-mentioned mixed solution B, continues 20~80
DEG C constant temperature water bath stirring 0~for 24 hours, collosol and gel mixture is made in abundant aging, and wherein feed molar composition is as follows：50~
100SiO2:0~2Al2O3:5~15SDA:0~5X:4000H2O, wherein X represents high molecular polymer, and SDA represents organic knot
Structure directed agents；
(4) above-mentioned starting sol gel mixture is placed in constant temperature oven, dry 0~48h, obtains at 25~120 DEG C
To Zeolite synthesis dry glue；
(5) and then by above-mentioned Zeolite synthesis dry glue it is transferred in the stainless steel crystallizing kettle of polytetrafluoroethyllining lining, uses
Water vapour auxiliary crystallization method prepares nano molecular sieve, wherein crystallization temperature is 100~200 DEG C, and crystallization time is 8~72h；
(6) after the completion of waiting for crystallization, products obtained therefrom is filtered, is washed, dries and obtains solid product, is i.e. nano-ZSM-5
Molecular screen primary powder；Above-mentioned nano-ZSM-5 molecular sieve original powder is roasted in Muffle furnace at 500~600 DEG C to 4~12h, is removed wherein
Organic matter, obtain nano-ZSM-5 molecular sieve product.
Raw material used in the present invention is specific preferably as follows：
In the above preparation method, the silicon source of use can be glass, silicic acid, Ludox, aerosil, white carbon
Or one kind or the double silicon source systems of tetraethyl orthosilicate；Wherein it is preferred to which silicon source is tetraethyl orthosilicate.
In the above preparation method, the silicon source used can be sodium aluminate, aluminium isopropoxide, aluminum sulfate, aluminium chloride, nitric acid
One or more mixtures in aluminium, aluminium hydroxide, boehmite；Wherein it is preferred to which silicon source is aluminium isopropoxide.
In the above preparation method, the high molecular polymer of use can be polyvinylpyrrolidone, polyacrylamide, gather
One or more mixtures in styrene, polyurethane etc., wherein preferably high molecular polymer is polyvinylpyrrolidone；
In the above preparation method, the Organic structure directing agent SDA used can be tetraethyl ammonium hydroxide, tetrapropyl hydrogen
One or more mixtures in amine-oxides, tetrabutylammonium hydroxide, wherein preferably Organic structure directing agent SDA is 4 third
Base ammonium hydroxide；
Some processes condition is preferred as follows in the present invention：
In the above preparation method, it is preferably 80 that the starting sol gel mixture drying, which prepares the drying temperature of dry glue,
~100 DEG C, drying time is preferably 12~for 24 hours；
In the above preparation method, it is brilliant during the Zeolite synthesis dry glue turns brilliant using water vapour auxiliary crystallization method
It is preferably 120~180 DEG C to change temperature, and crystallization time is preferably 4~72h.
Compared with prior art, the invention has the advantages that.
(1) polyvinylpyrrolidone is a kind of commercial reagents cheap and easy to get, and environmentally safe, industrial use is wide
It is general, it is highly soluble in water, after preparing nano-ZSM-5 molecular sieve experiment, is attached to the excessive poly- of nano molecular sieve surface
Vinylpyrrolidone is easy to remove by washing.
(2) present invention using dry gel conversion method prepares nano-ZSM-5 molecular sieve, by by Zeolite synthesis collosol and gel system
It is standby then to carry out turning crystalline substance by water vapour auxiliary crystallization again, not only reduce the space that aqueous solvent occupies in crystallizing kettle at dry glue,
Also have preparation condition mild, easy to operate, combined coefficient is high, hardly discharge synthesis waste liquid, and is conducive to zeolite product
The advantages that being detached with mother liquor, this green, easy preparation method will be that futurity industry metaplasia production nano molecular sieve is explored
Efficiently, there are certain industrial applications to be worth for safe synthetic route and product.
Description of the drawings
In order to facilitate the understanding of those skilled in the art, the present invention will be further described below with reference to the drawings.
Fig. 1 is the XRD spectra for the nano-ZSM-5 molecular sieve sample that the embodiment of the present invention 1 synthesizes；
Fig. 2 is the SEM figures for the nano-ZSM-5 molecular sieve sample that the embodiment of the present invention 1 synthesizes；
Fig. 3 is the TEM figures for the nano-ZSM-5 molecular sieve sample that the embodiment of the present invention 1 synthesizes；
Fig. 4 is the N for the nano-ZSM-5 molecular sieve sample that the embodiment of the present invention 1 synthesizes2Adsorption and desorption isotherms；
Fig. 5 is the SEM figures for the nano-ZSM-5 molecular sieve sample that the embodiment of the present invention 2 synthesizes；
Fig. 6 is the SEM figures for the nano-ZSM-5 molecular sieve sample that the embodiment of the present invention 3 synthesizes；
Fig. 7 is the SEM figures for the nano-ZSM-5 molecular sieve sample that the embodiment of the present invention 4 synthesizes.
Specific implementation mode
Embodiment 1
The feature of nano-ZSM-5 molecular sieve prepared by the present invention characterizes with the following method：
The phase structure and crystallinity of molecular sieve are characterized using powder x-ray diffraction (XRD).
Molecular sieve can intuitively be observed using scanning electron microscope (SEM) and transmission electron microscope (TEM) very much
Crystal morphology and size.
Using the surface area and adsorption isothermal curve of nitrogen adsorption measuring molecular sieve, pore-size distribution judges that its hole is tied
Structure.
The high molecular polymer polyvinylpyrrolidone of 3.2g is dissolved in by a kind of preparation method of nano-ZSM-5 molecular sieve
In the deionized water of 40.0g, it is stirred at room temperature to being completely dissolved, forms mixed solution A；Sequentially add the silicon source and 10.4g of 0.2g
Silicon source, continue constant temperature stir to be uniformly mixed form solution B；Then the structure directing agent of 3.0g is added dropwise into solution B,
Mixed solution is formed, the 60 DEG C of water bath with thermostatic control stirring agings of above-mentioned mixed solution are formed into collosol and gel for 24 hours；By above-mentioned collosol and gel
Dry glue is made in drying, and the dry glue after grinding is transferred in crystallizing kettle, realizes that molecular sieve turns brilliant mistake using water vapour auxiliary crystallization method
Journey, 180 DEG C of crystallization 36h, products obtained therefrom obtain molecular screen primary powder through filtering, drying.Molecular screen primary powder is placed in 550 in Muffle furnace
DEG C roasting 6h remove organic matter, obtain nano-ZSM-5 molecular sieve.
Fig. 1-4 is seen as it can be seen that by XRD spectra it is found that there is prepared molecular sieve typical MFI skeleton structures, ZSM-5 to divide
The purity and crystallinity of son sieve sample are higher；Schemed it is found that the nano-ZSM-5 molecular sieve crystal morphology is regular, by nano-crystal group by SEM
Fill the microballoon formed；Schemed it is found that nano-ZSM-5 molecular sieve grain size is about 10~20nm by TEM；By N2Adsorption desorption isothermal
Line hysteresis loop occurs it is found that nano-ZSM-5 molecular sieve sample has a certain amount of meso-hole structure.
Embodiment 2
A kind of preparation method of nano-ZSM-5 molecular sieve,：The high molecular polymer polyvinylpyrrolidone of 1.6g is dissolved in
In the deionized water of 40.0g, it is stirred at room temperature to being completely dissolved, forms mixed solution A；Sequentially add the silicon source and 10.4g of 0.2g
Silicon source, continue constant temperature stir to be uniformly mixed form solution B；Then the structure directing agent of 3.0g is added dropwise into solution B,
Mixed solution is formed, the 60 DEG C of water bath with thermostatic control stirring agings of above-mentioned mixed solution are formed into collosol and gel for 24 hours；By above-mentioned collosol and gel
Dry glue is made in drying, and the dry glue after grinding is transferred in crystallizing kettle, realizes that molecular sieve turns brilliant mistake using water vapour auxiliary crystallization method
Journey, 180 DEG C of crystallization 36h, products obtained therefrom obtain molecular screen primary powder through filtering, drying.Molecular screen primary powder is placed in 550 in Muffle furnace
DEG C roasting 6h remove organic matter, obtain nano-ZSM-5 molecular sieve.As shown in figure 5, prepared nano-ZSM-5 molecular sieve sample
Macro morphology is the botryoidalis aggregation being self-assembly of by the crystal grain of many sizes about 50nm.
Embodiment 3
A kind of preparation method of nano-ZSM-5 molecular sieve：The high molecular polymer polyvinylpyrrolidone of 6.4g is dissolved in
In the deionized water of 40.0g, it is stirred at room temperature to being completely dissolved, forms mixed solution A；Sequentially add the silicon source and 10.4g of 0.2g
Silicon source, continue constant temperature stir to be uniformly mixed form solution B；Then the structure directing agent of 3.0g is added dropwise into solution B,
Mixed solution is formed, the 60 DEG C of water bath with thermostatic control stirring agings of above-mentioned mixed solution are formed into collosol and gel for 24 hours；By above-mentioned collosol and gel
Dry glue is made in drying, and the dry glue after grinding is transferred in crystallizing kettle, realizes that molecular sieve turns brilliant mistake using water vapour auxiliary crystallization method
Journey, 180 DEG C of crystallization 36h, products obtained therefrom obtain molecular screen primary powder through filtering, drying.Molecular screen primary powder is placed in 550 in Muffle furnace
DEG C roasting 6h remove organic matter, obtain nano-ZSM-5 molecular sieve；As shown in fig. 6, prepared nano-ZSM-5 molecular sieve sample
Macro morphology is the ellipsoid aggregation being self-assembly of by the crystal grain of many sizes about 10~20nm.
Embodiment 4
The high molecular polymer polyvinylpyrrolidone of 3.2g is dissolved in by a kind of preparation method of nano-ZSM-5 molecular sieve
In the deionized water of 40.0g, it is stirred at room temperature to being completely dissolved, forms mixed solution A；Sequentially add the silicon source and 10.4g of 0.1g
Silicon source, continue constant temperature stir to be uniformly mixed form solution B；Then the structure directing agent of 3.0g is added dropwise into solution B,
Mixed solution is formed, the 60 DEG C of water bath with thermostatic control stirring agings of above-mentioned mixed solution are formed into collosol and gel for 24 hours；By above-mentioned collosol and gel
Dry glue is made in drying, and the dry glue after grinding is transferred in crystallizing kettle, realizes that molecular sieve turns brilliant mistake using water vapour auxiliary crystallization method
Journey, 180 DEG C of crystallization 36h, products obtained therefrom obtain molecular screen primary powder through filtering, drying.Molecular screen primary powder is placed in 550 in Muffle furnace
DEG C roasting 6h remove organic matter, obtain sodium form nano-ZSM-5 molecular sieve.Molecular screen primary powder is placed in 550 DEG C of roastings in Muffle furnace
6h removes organic matter, obtains nano-ZSM-5 molecular sieve.As shown in fig. 7, macroscopical shape of prepared nano-ZSM-5 molecular sieve sample
Looks are the aggregations for the irregular shape being self-assembly of by the crystal grain of many sizes about 20~50nm.
Present invention disclosed above preferred embodiment is only intended to help to illustrate the present invention.There is no detailed for preferred embodiment
All details are described, are not limited the invention to the specific embodiments described.Obviously, according to the content of this specification,
It can make many modifications and variations.These embodiments are chosen and specifically described to this specification, is in order to preferably explain the present invention
Principle and practical application, to enable skilled artisan to be best understood by and utilize the present invention.The present invention is only
It is limited by claims and its full scope and equivalent.
Claims (7)
1. a kind of preparation method of nano-ZSM-5 molecular sieve, which is characterized in that including following synthesis step：：
(1) high molecular polymer, silicon source, silicon source, Organic structure directing agent and deionized water are stirred well to uniformly mixed, shape
At Zeolite synthesis collosol and gel, then above-mentioned collosol and gel is dried, dry glue is made；
(2) dry glue obtained above is fully ground, is transferred in the stainless steel crystallizing kettle of polytetrafluoroethyllining lining, is steamed using water
Vapour auxiliary crystallization method, crystallization temperature is 100-200 DEG C, crystallization time 6-72h, after the completion of waiting for crystallization, detaches solid product, does
Dry, roasting removing organic matter obtains nano-ZSM-5 molecular sieve.
2. a kind of preparation method of nano-ZSM-5 molecular sieve according to claim 1, which is characterized in that specifically include as
Lower synthesis step：
(1) high molecular polymer is dissolved in deionized water, stirs 2~12h at room temperature, homogeneous mixture solotion A is made；
(2) a certain amount of silicon source and silicon source are sequentially added, 20~80 DEG C of constant temperature water baths stirrings 0~for 24 hours, obtain homogeneous mixture solotion B；
(3) under stirring, Organic structure directing agent is added dropwise into above-mentioned mixed solution B, continues in 20~80 DEG C of water
Bath constant temperature stirring 0~for 24 hours, collosol and gel mixture is made in abundant aging, and wherein feed molar composition is as follows：50~
100SiO2:0~2Al2O3:5~15SDA:0~5X:4000H2O, wherein X represents high molecular polymer, and SDA represents organic knot
Structure directed agents；
(4) above-mentioned starting sol gel mixture is placed in constant temperature oven, dry 0~48h, is divided at 25~120 DEG C
Son sieve synthesis dry glue；
(5) and then by above-mentioned Zeolite synthesis dry glue it is transferred in the stainless steel crystallizing kettle of polytetrafluoroethyllining lining, is steamed using water
Vapour auxiliary crystallization method prepares nano molecular sieve, wherein crystallization temperature is 100~200 DEG C, and crystallization time is 8~72h；
(6) after the completion of waiting for crystallization, products obtained therefrom is filtered, is washed, dries and obtains solid product, is i.e. nano-ZSM-5 molecule
Sieve original powder；Above-mentioned nano-ZSM-5 molecular sieve original powder is roasted to 4~8h in Muffle furnace, removing is therein to be had at 500~600 DEG C
Machine object obtains nano-ZSM-5 molecular sieve product.
3. a kind of preparation method of nano-ZSM-5 molecular sieve according to claim 2, which is characterized in that in step (3)
In, be made collosol and gel aging temperature be 20~80 DEG C, ageing time be 0~for 24 hours.
4. a kind of preparation method of nano-ZSM-5 molecular sieve according to claim 1, it is characterised in that：In step (1)
In, the high molecular polymer be one kind in polyvinylpyrrolidone, polyacrylamide, polystyrene, polyurethane etc. or
A variety of mixtures.
5. a kind of preparation method of nano-ZSM-5 molecular sieve according to claim 1, it is characterised in that：In step (1)
In, the Organic structure directing agent is one kind in tetraethyl ammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide
Or a variety of mixtures.
6. a kind of preparation method of nano-ZSM-5 molecular sieve according to claim 1, it is characterised in that：In step (1)
Silicon source used in Zeolite synthesis is one kind or more in tetraethyl orthosilicate, aerosil, white carbon or Ludox
Kind mixture；Silicon source used in Zeolite synthesis is aluminum sulfate, aluminum nitrate, sodium metaaluminate, boehmite, boehmite or different
One or more mixtures in aluminium propoxide.
7. a kind of preparation method of nano-ZSM-5 molecular sieve according to claim 1, it is characterised in that：In step (2)
In, the crystallization method for preparing nano-ZSM-5 molecular sieve is dry gel conversion method.
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Cited By (11)
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| CN109437232A (en) * | 2018-12-13 | 2019-03-08 | 东莞理工学院 | A kind of preparation method of the ZSM-5 molecular sieve of multilevel structure |
| CN110156046A (en) * | 2019-06-25 | 2019-08-23 | 华东理工大学 | The preparation method of SSZ-13 molecular sieve and the application of SSZ-13 molecular sieve |
| CN110304637A (en) * | 2019-08-13 | 2019-10-08 | 黑龙江大学 | A kind of steam auxiliary dry gel conversion method fabricated in situ nanometer Zn/Al-ZSM-5 molecular sieve method |
| CN110316742A (en) * | 2019-07-22 | 2019-10-11 | 黑龙江大学 | A kind of dry gel conversion method synthesizes the nanocrystalline method of ultra-fine HZSM-5 molecular sieve |
| CN112259685A (en) * | 2020-10-30 | 2021-01-22 | 南京工业大学 | High-stability flash-erasing patterned polymer memory and preparation method thereof |
| CN112279263A (en) * | 2020-10-28 | 2021-01-29 | 北京大学深圳研究生院 | Monodisperse molecular sieve microsphere and preparation method thereof |
| CN112591764A (en) * | 2021-02-05 | 2021-04-02 | 福州大学 | Single crystal aluminum-rich cascade hole HZSM-5 molecular sieve and green preparation method thereof |
| CN112875721A (en) * | 2021-01-11 | 2021-06-01 | 中国石油天然气股份有限公司 | Method for rapidly preparing mesoporous ZSM-5 molecular sieve macroscopic body |
| CN113072079A (en) * | 2021-05-26 | 2021-07-06 | 常州大学 | Synthesis method of twist-shaped porous ZSM-5 zeolite assembled by nano square conical particles |
| CN113929110A (en) * | 2021-11-23 | 2022-01-14 | 浙江大学 | Variable pillared ZSM-5 nanosheet molecular sieve and preparation method thereof |
| CN114506857A (en) * | 2022-02-08 | 2022-05-17 | 中国矿业大学 | Steam-assisted crystallization synthesis method of HZSM-5 molecular sieve |
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