CN106698464B - A kind of ZSM-5 microballoon and preparation method thereof - Google Patents
A kind of ZSM-5 microballoon and preparation method thereof Download PDFInfo
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- CN106698464B CN106698464B CN201611270247.0A CN201611270247A CN106698464B CN 106698464 B CN106698464 B CN 106698464B CN 201611270247 A CN201611270247 A CN 201611270247A CN 106698464 B CN106698464 B CN 106698464B
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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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- 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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- 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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- 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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- C01P2004/32—Spheres
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- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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- C01P2006/12—Surface area
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/16—Pore diameter
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- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/16—Pore diameter
- C01P2006/17—Pore diameter distribution
Abstract
The present invention relates to a kind of ZSM-5 particle and preparation method thereof, the ZSM-5 particle is the spherical particle of the hierarchical structure of porous nano-sheet directional assembly, and the porous nano-sheet width is about 100~300nm.Preparation methods steps are 1) to mix sodium hydroxide, tetraethyl ammonium hydroxide and tetrapropylammonium hydroxide, are stirred at room temperature to sodium hydroxide and dissolve, obtain mixed solution；2) silica solution is added into mixed solution obtained by step 1), and is stirred at room temperature to uniform dispersion liquid is obtained, aluminium isopropoxide is then added, stir progress hydro-thermal reaction in thermal response kettle of sufficiently falling back and obtain ZSM-5 particle.The present invention is prepared using hydro-thermal reaction by the ZSM-5 particle of the hierarchical structure of porous nano-sheet directional assembly, provides new approaches to expand the application range of ZSM-5.
Description
Technical field
The invention belongs to inorganic chemical synthesis technical fields, and in particular to a kind of hierarchical structure by nanometer sheet directional assembly
ZSM-5 particle and preparation method thereof.
Background technique
(US3,702,886) ZSM-5 molecular sieve that Mobil company synthesized for the first time in 1972 has special cellular structure
And catalytic performance, thermal stability and hydrothermal stability are preferable, thus both at home and abroad petrochemical industry bound pair this very pay close attention to and payes attention to, section
Extremely currently, ZSM-5 molecular sieve has been used for a variety of courses of industrialization, highly important effect is played wherein, mainly includes
Catalytic cracking, aromatisation, alkylation, disproportionation etc..In petrochemical industry, ZSM-5 is mainly catalysis material, adsorbing separation material
Material, ion exchange material, and play a significant role.
In recent years, in-depth study and discussion are carried out in terms of the raw material and synthesis technology of ZSM-5 synthesis, change synthesis item
Part realizes that the difference of ZSM-5 pattern, main method have hydrothermal synthesis method, non-microwave method, dry gel method, dry powder system hair etc.,
Wherein hydrothermal synthesis method is most classic method, not only economical using water as solvent but also dissolve to ionic and polar compound
Ability is strong.Say have two methods of template and Template-free method that can synthesize ZSM- molecular sieve, wherein template from template angle
The method of agent integrates micella of various shapes using the structural particularity of template, so that sial tetrahedron is around arrangement
Form the corresponding establishment unit of specific skeleton.
The present invention is innovated on the basis of the hydrothermal synthesis method of original classics, it is contemplated that different templates agent structure
Two kinds of templates are successfully combined together by difference, and using water as solvent, two kinds of templates are soluble in water, are gathered into each
The micella of kind shape, oxygen-octahedron arrange to form specific geometry topology knot around single organic formwork agent molecule and micella
Structure provides initial establishment unit for corresponding skeleton structure, and crystallization is precipitated, and the ZSM- for forming certain structure and shape is micro-
Grain, being formed, there is porous nano sheet to accumulate spherical ZSM-5 molecular sieve.
Summary of the invention
The technical problem to be solved by the present invention is to aiming at the above shortcomings existing in the prior art, provide one kind by nanometer
ZSM-5 particle of the hierarchical structure of piece directional assembly and preparation method thereof.
In order to solve the above technical problems, present invention provide the technical scheme that
A kind of ZSM-5 particle is provided, the ZSM-5 particle is that the spherical shape of the hierarchical structure of porous nano-sheet directional assembly is micro-
Grain, the porous nano-sheet width is about 100~300nm.
According to the above scheme, the ZSM-5 particle size is 2~5 μm.
The present invention also provides the preparation methods of above-mentioned ZSM-5 particle, and its step are as follows:
1) sodium hydroxide is mixed with tetraethyl ammonium hydroxide and tetrapropylammonium hydroxide, is stirred at room temperature to sodium hydroxide
Dissolution, obtains mixed solution；
2) silica solution is added into mixed solution obtained by step 1), and is stirred at room temperature to obtaining uniform dispersion
Then aluminium isopropoxide is added in liquid, stir in thermal response kettle of sufficiently falling back and carry out hydro-thermal reaction, then through suction filtration, drying, calcining
After obtain ZSM-5 particle.
According to the above scheme, the step 1) sodium hydroxide, tetraethyl ammonium hydroxide, tetrapropylammonium hydroxide and step 2) institute
State silica solution, the molar ratio of element Na, N, N, Si, Al are 1:2~2.5:1~1.5:11~15:0.7~0.8 in aluminium isopropoxide.
According to the above scheme, dioxide-containing silica is 30wt% in the step 2) silica solution.
According to the above scheme, the step 2) hydrothermal temperature is 180~200 DEG C, and the hydro-thermal reaction time is 1~6 day.
According to the above scheme, step 2) the calcine technology condition are as follows: keep the temperature 2~8 hours at 350~600 DEG C.
The beneficial effects of the present invention are: compared with traditional ZSM- molecular sieve, ZSM-5 particle provided by the invention is not only
Also there is meso-hole structure with microcellular structure, expansion forms hierarchical structure, and the particularity of structure is the application of its shape selective catalysis
Provide a possibility that more.In addition, preparation method is simple, it is at low cost, it is only necessary to be taken out after mixed at room temperature by hydro-thermal reaction
It is product after filter, is suitble to large-scale production.
Detailed description of the invention
Fig. 1 is the SEM figure of ZSM-5 particle prepared by the embodiment of the present invention 1；
Fig. 2 is the XRD diagram of ZSM-5 particle prepared by embodiment 1；
Fig. 3 is the TEM figure of ZSM-5 particle prepared by embodiment 1；
Fig. 4 is the adsorption/desorption curve of ZSM-5 particle prepared by embodiment 1；
Fig. 5 is the graph of pore diameter distribution of ZSM-5 particle prepared by embodiment 1；
Fig. 6 is the SEM figure of ZSM-5 particle prepared by embodiment 2；
Fig. 7 is the XRD diagram of ZSM-5 particle prepared by embodiment 2；
Fig. 8 is the SEM figure of ZSM-5 particle prepared by embodiment 3；
Fig. 9 is the XRD diagram of ZSM-5 particle prepared by embodiment 3.
Specific embodiment
Technical solution in order to enable those skilled in the art to better understand the present invention, with reference to the accompanying drawing to the present invention make into
One step detailed description.
Dioxide-containing silica is 30wt% in silica solution used in the embodiment of the present invention.
Embodiment 1
A kind of preparation method of ZSM-5 particle, steps are as follows:
1) 0.1g sodium hydroxide, 9.45g tetraethyl ammonium hydroxide and 8.16g tetrapropylammonium hydroxide are added in beaker,
It is stirred at room temperature to sodium hydroxide and dissolves, obtain mixed solution；
2) 17.85g silica solution is added into mixed solution obtained by step 1), and is stirred at room temperature uniform to obtaining
Dispersion liquid, then be added 0.366g aluminium isopropoxide, stir sufficiently to unobvious aluminium isopropoxide white particles, be subsequently poured into
In hydrothermal reaction kettle, hydro-thermal reaction 4 days at 180 DEG C, after reaction filtered reaction solution from hydrothermal reaction kettle taking-up,
Drying, then calcined and (keep the temperature 4 hours at 550 DEG C) and obtain ZSM-5 particle.
Be as depicted in figs. 1 and 2 the SEM figure and XRD diagram of ZSM-5 particle prepared by the present embodiment, by SEM figure as it can be seen that
Gained diameter of particle is 2~5 μm, and microstructure is the hierarchical structure for the nanometer sheet directional assembly that width is 100~300nm
Spherical particle (the TEM figure through Fig. 3, the BET graph of pore diameter distribution of Fig. 5 can be seen that a nanometer chip architecture), XRD diagram sufficiently demonstrates institute
Substance is ZSM-5, substantially without dephasign peak, the ZSM-5 illustrated is purer and stable appearance.
Fig. 3 be ZSM-5 particle manufactured in the present embodiment TEM scheme, it can be seen that the ZSM-5 particle by a length of 600nm,
Width is what the flake nano piece of 100nm or so was accumulated, is in close contact and accumulates between nanometer sheet.It is tested from Fig. 4 and Fig. 5
To nitrogen adsorption desorption curve and graph of pore diameter distribution known to ZSM-5 particle specific surface area obtained by the present embodiment reach 312m2/ g,
Micropore in the nanometer chip architecture of ZSM-5 particle, it is mesoporous coexist, and mesoporous pore size has 3.8nm or so.
Embodiment 2
A kind of preparation method of ZSM-5 particle, steps are as follows:
1) 0.1g sodium hydroxide, 9.45g tetraethyl ammonium hydroxide and 8.16g tetrapropylammonium hydroxide are added in beaker,
It is stirred at room temperature to sodium hydroxide and dissolves, obtain mixed solution；
2) 17.85g silica solution is added into mixed solution obtained by step 1), and is stirred at room temperature uniform to obtaining
Dispersion liquid, then be added 0.366g aluminium isopropoxide, stir sufficiently to unobvious aluminium isopropoxide white particles, be subsequently poured into
In hydrothermal reaction kettle, hydro-thermal reaction 1 day at 180 DEG C, after reaction filtered reaction solution from hydrothermal reaction kettle taking-up,
Drying, then calcined and (keep the temperature 4 hours at 550 DEG C), obtain ZSM-5 particle.
Fig. 6 and Fig. 7 is that the SEM figure of ZSM-5 particle manufactured in the present embodiment and XRD diagram keep temperature not as seen from the figure
Become, shortening the hydro-thermal reaction time can be obtained complete particle, and partial size is 2~5 μm, and microstructure is that width is 100~300nm
Nanometer sheet directional assembly hierarchical structure spherical particle, XRD diagram sufficiently demonstrate obtained material be ZSM-5, substantially without
Dephasign peak, the ZSM-5 illustrated is purer and stable appearance.
Embodiment 3
A kind of preparation method of ZSM-5 particle, steps are as follows:
1) 0.1g sodium hydroxide, 9.45g tetraethyl ammonium hydroxide and 8.16g tetrapropylammonium hydroxide are added in beaker,
It is stirred at room temperature to sodium hydroxide and dissolves, obtain mixed solution；
2) 17.85g silica solution is added into mixed solution obtained by step 1), and is stirred at room temperature uniform to obtaining
Dispersion liquid, then be added 0.366g aluminium isopropoxide, stir sufficiently to unobvious aluminium isopropoxide white particles, be subsequently poured into
In hydrothermal reaction kettle, hydro-thermal reaction 3 days at 200 DEG C, after reaction filtered reaction solution from hydrothermal reaction kettle taking-up,
Drying, then calcined and (keep the temperature 4 hours at 550 DEG C), obtain ZSM-5 particle.
Fig. 8 and Fig. 9 is that the SEM figure of ZSM-5 particle manufactured in the present embodiment and XRD diagram change the reaction time as seen from the figure
And complete particle can be obtained in reaction temperature, partial size is 2~5 μm, and microstructure is the nanometer sheet that width is 100~300nm
The spherical particle of the hierarchical structure of directional assembly, it is that ZSM-5 is said substantially without dephasign peak that XRD diagram, which sufficiently demonstrates obtained material,
Bright obtained ZSM-5 is purer and stable appearance.
Claims (5)
1. a kind of preparation method of ZSM-5 particle, the ZSM-5 particle is the ball of the hierarchical structure of porous nano-sheet directional assembly
Shape particle, the porous nano-sheet width are 100 ~ 300nm, and the ZSM-5 particle size is 2 ~ 5 μm, it is characterised in that step
It is as follows:
1) sodium hydroxide is mixed with tetraethyl ammonium hydroxide and tetrapropylammonium hydroxide, is stirred at room temperature molten to sodium hydroxide
Solution, obtains mixed solution；
2) silica solution is added into mixed solution obtained by step 1), and is stirred at room temperature to obtaining uniform dispersion liquid,
Then aluminium isopropoxide is added, stirs in thermal response kettle of sufficiently falling back and carries out hydro-thermal reaction, then after suction filtration, drying, calcining
Obtain ZSM-5 particle.
2. preparation method according to claim 1, it is characterised in that sodium hydroxide described in step 1), tetraethyl hydroxide
Silica solution described in ammonium, tetrapropylammonium hydroxide and step 2, in aluminium isopropoxide element Na, N, N, Si, Al molar ratio be 1:2 ~
2.5:1~1.5:11~15:0.7~0.8。
3. preparation method according to claim 1, it is characterised in that dioxide-containing silica is in silica solution described in step 2
30wt%。
4. preparation method according to claim 1, it is characterised in that hydrothermal temperature described in step 2 is 180 ~ 200
DEG C, the hydro-thermal reaction time is 1 ~ 6 day.
5. preparation method according to claim 1, it is characterised in that calcine technology condition described in step 2 are as follows: 350 ~
2 ~ 8 hours are kept the temperature at 600 DEG C.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102910645A (en) * | 2011-08-01 | 2013-02-06 | 中国石油化工股份有限公司 | Isomorphous phase compound molecular sieve and preparation method thereof |
| CN106006666A (en) * | 2016-04-22 | 2016-10-12 | 宁夏大学 | Hierarchical pore ZSM-5 molecular sieve with nanosheet layer structure and synthesis method thereof |
| CN106219569A (en) * | 2016-07-16 | 2016-12-14 | 太原理工大学 | A kind of method preparing porous zeotile without secondary template one step |
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2016
- 2016-12-31 CN CN201611270247.0A patent/CN106698464B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102910645A (en) * | 2011-08-01 | 2013-02-06 | 中国石油化工股份有限公司 | Isomorphous phase compound molecular sieve and preparation method thereof |
| CN106006666A (en) * | 2016-04-22 | 2016-10-12 | 宁夏大学 | Hierarchical pore ZSM-5 molecular sieve with nanosheet layer structure and synthesis method thereof |
| CN106219569A (en) * | 2016-07-16 | 2016-12-14 | 太原理工大学 | A kind of method preparing porous zeotile without secondary template one step |
Non-Patent Citations (2)
| Title |
|---|
| One-Step Dual Template Mediated Synthesis of Nanocrystalline Zeolites of Different Framework Structures;Poonam Rani,et al.;《Cryst. Growth Des.》;20160506;第16卷;第3323-3333页 |
| Seed-induced synthesis of hierarchical ZSM-5 nanosheets in the presence of hexadecyl trimethyl ammonium bromide;Min Liu，et al.;《RSC Advances》;20141224;第5卷;第9237-9240页 |
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