CN106698464A - ZSM-5 microsphere and preparation method thereof - Google Patents
ZSM-5 microsphere and preparation method thereof Download PDFInfo
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- CN106698464A CN106698464A CN201611270247.0A CN201611270247A CN106698464A CN 106698464 A CN106698464 A CN 106698464A CN 201611270247 A CN201611270247 A CN 201611270247A CN 106698464 A CN106698464 A CN 106698464A
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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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- 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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- 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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- 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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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
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- 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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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
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- 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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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/16—Pore diameter
- C01P2006/17—Pore diameter distribution
Abstract
The invention relates to a ZSM-5 microsphere and a preparation method thereof. The ZSM-5 microsphere is a spherical particle with a grading structure formed by directional assembling of porous nanosheets, and the width of the porous nanosheets is about 100-300 nm. The preparation method comprises the following steps: 1, mixing sodium hydroxide, tetraethylammonium hydroxide and tetrapropylammonium hydroxide, and stirring above substances at room temperature to dissolve the sodium hydroxide in order to obtain a mixed solution; and 2, adding silica sol to the mixed solution obtained in step 1, stirring the silica sol and the mixed solution at room temperature to obtain a uniform dispersion, adding aluminum isopropoxide, fully stirring the uniform dispersion and the aluminum isopropoxide, pouring the obtained dispersion into a hydrothermal reaction kettle, and carrying out a hydrothermal reaction to obtain the ZSM-5 microsphere. The ZSM-5 microsphere with the grading structure formed by directional assembling of porous nanosheets, prepared through adopting the hydrothermal reaction, provides a new ideal for the development of the application range of ZSM-5.
Description
Technical field
The invention belongs to inorganic chemical synthesis technical field, and in particular to a kind of hierarchy by nanometer sheet NW-TFT
ZSM-5 particulates and preparation method thereof.
Background technology
(US3,702,886) ZSM-5 molecular sieve that Mobil companies synthesized first in 1972 has special pore passage structure
And catalytic performance, heat endurance and hydrothermal stability preferably, therefore both at home and abroad petrochemical industry bound pair this extremely pay close attention to and pay attention to, cut
To current, ZSM-5 molecular sieve has been used for various courses of industrialization, and 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 were carried out in terms of the raw material and synthesis technique of ZSM-5 synthesis, changed synthesis bar
Part realizes the difference of ZSM-5 patterns, and main method has hydrothermal synthesis method, non-microwave method, dry gel method, dry powder system hair etc.,
Wherein hydrothermal synthesis method is most classical method, not only economical using water as solvent but also ionic and polar compound are dissolved
Ability is strong.Say there are two methods of template and Template-free method to synthesize ZSM- molecular sieves, wherein template from template angle
The method of agent, using the structural particularity of template, assembles integrated variously-shaped micella so that sial tetrahedron is around arrangement
Form the corresponding establishment unit of specific skeleton.
The present invention is innovated, it is contemplated that different templates agent structure on the basis of original classical hydrothermal synthesis method
, successfully be combined together for two kinds of templates by difference, and using water as solvent, two kinds of templates are soluble in water, is gathered into each
The micella of shape is planted, silicon-oxy tetrahedron arranges to form specific geometry topology knot around single organic formwork agent molecule and micella
Structure, for corresponding skeleton structure provides initial establishment unit, crystallization is separated out, and the ZSM- for forming a fixed structure and shape is micro-
Grain, being formed, there is porous nano sheet to pile up spherical ZSM-5 molecular sieve.
The content of the invention
The technical problems to be solved by the invention are directed to above shortcomings in the prior art, there is provided one kind is by nanometer
ZSM-5 particulates of the hierarchy of piece NW-TFT and preparation method thereof.
In order to solve the above technical problems, the technical scheme that the present invention is provided is：
A kind of ZSM-5 particulates are provided, the ZSM-5 particulates are spherical micro- for the hierarchy of porous nano-sheet NW-TFT
Grain, the porous nano-sheet width is about 100~300nm.
By such scheme, the ZSM-5 particle sizes are 2~5 μm.
The present invention also provides the preparation method of above-mentioned ZSM-5 particulates, and its step is as follows：
1) NaOH is mixed with tetraethyl ammonium hydroxide and TPAOH, is stirred at room temperature to NaOH
Dissolving, obtains mixed solution；
2) to step 1) Ludox is added in gained mixed solution, and be stirred at room temperature to obtaining homogeneous dispersion
Liquid, is subsequently adding aluminium isopropoxide, and stirring fully being fallen back hydro-thermal reaction of carry out in thermal response kettle, then through suction filtration, drying, calcine
After obtain ZSM-5 particulates.
By such scheme, step 1) NaOH, tetraethyl ammonium hydroxide, TPAOH and step 2) institute
The mol ratio for stating element Na, N, N, Si, Al in Ludox, aluminium isopropoxide is 1:2~2.5:1~1.5:11~15:0.7~0.8.
By such scheme, step 2) dioxide-containing silica is 30wt% in the Ludox.
By such scheme, step 2) hydrothermal temperature be 180~200 DEG C, the hydro-thermal reaction time be 1~6 day.
By such scheme, step 2) the calcine technology condition is：2~8 hours are incubated at 350~600 DEG C.
The beneficial effects of the present invention are：Compared with traditional ZSM- molecular sieves, the ZSM-5 particulates that the present invention is provided are not only
Also there is meso-hole structure with microcellular structure, expansion forms hierarchy, and the particularity of its structure is the application of its shape selective catalysis
There is provided more possibilities.In addition, its preparation method is simple, low cost, it is only necessary to taken out by hydro-thermal reaction after mixed at room temperature
It is product after filter, is adapted to large-scale production.
Brief description of the drawings
Fig. 1 is the SEM figures of the ZSM-5 particulates prepared by the embodiment of the present invention 1；
Fig. 2 is the XRD of the ZSM-5 particulates prepared by embodiment 1；
Fig. 3 is the TEM figures of the ZSM-5 particulates prepared by embodiment 1；
Fig. 4 is the adsorption/desorption curve of the ZSM-5 particulates prepared by embodiment 1；
Fig. 5 is the graph of pore diameter distribution of the ZSM-5 particulates prepared by embodiment 1；
Fig. 6 is the SEM figures of the ZSM-5 particulates prepared by embodiment 2；
Fig. 7 is the XRD of the ZSM-5 particulates prepared by embodiment 2；
Fig. 8 is the SEM figures of the ZSM-5 particulates prepared by embodiment 3；
Fig. 9 is the XRD of the ZSM-5 particulates prepared by embodiment 3.
Specific embodiment
To make those skilled in the art more fully understand technical scheme, the present invention is made below in conjunction with the accompanying drawings into
One step is described in detail.
Dioxide-containing silica is 30wt% in Ludox used by the embodiment of the present invention.
Embodiment 1
A kind of preparation method of ZSM-5 particulates, step is as follows：
1) by 0.1g NaOH, 9.45g tetraethyl ammonium hydroxides and 8.16g TPAOHs add beaker in,
It is stirred at room temperature to NaOH dissolving, obtains mixed solution；
2) to step 1) 17.85g Ludox is added in gained mixed solution, and it is stirred at room temperature homogeneous to obtaining
Dispersion liquid, be subsequently adding 0.366g aluminium isopropoxides, stirring fully to without obvious aluminium isopropoxide white particles, is subsequently poured into
In hydrothermal reaction kettle, hydro-thermal reaction 4 days at 180 DEG C, reaction terminate after by reaction solution from hydrothermal reaction kettle take out carry out suction filtration,
Drying, then obtain ZSM-5 particulates through calcining (being incubated 4 hours at 550 DEG C).
The SEM figures and XRD of the ZSM-5 particulates prepared by the present embodiment, are schemed from SEM as depicted in figs. 1 and 2,
Gained diameter of particle is 2~5 μm, and its microstructure is the hierarchy of nanometer sheet NW-TFT that width is 100~300nm
Spherical particle (TEM through Fig. 3 schemes, and the BET graph of pore diameter distribution of Fig. 5 can be seen that a nanometer chip architecture), XRD fully demonstrates institute
Material is ZSM-5, substantially without dephasign peak, illustrate that the ZSM-5 that obtains is purer and stable appearance.
Fig. 3 be ZSM-5 particulates manufactured in the present embodiment TEM figure, it can be seen that the ZSM-5 particulates by a length of 600nm,
The flake nano piece of a width of 100nm or so piles up what is obtained, is in close contact between nanometer sheet and piled up.Tested from Fig. 4 and Fig. 5
To nitrogen adsorption desorption curve and graph of pore diameter distribution understand the present embodiment gained ZSM-5 particulate specific surface areas reach 312m2/ g,
Micropore in the nanometer chip architecture of ZSM-5 particulates, it is mesoporous coexist, and mesoporous pore size has 3.8nm or so.
Embodiment 2
A kind of preparation method of ZSM-5 particulates, step is as follows：
1) by 0.1g NaOH, 9.45g tetraethyl ammonium hydroxides and 8.16g TPAOHs add beaker in,
It is stirred at room temperature to NaOH dissolving, obtains mixed solution；
2) to step 1) 17.85g Ludox is added in gained mixed solution, and it is stirred at room temperature homogeneous to obtaining
Dispersion liquid, be subsequently adding 0.366g aluminium isopropoxides, stirring fully to without obvious aluminium isopropoxide white particles, is subsequently poured into
In hydrothermal reaction kettle, hydro-thermal reaction 1 day at 180 DEG C, reaction terminate after by reaction solution from hydrothermal reaction kettle take out carry out suction filtration,
Drying, then through calcining (being incubated 4 hours at 550 DEG C), obtain ZSM-5 particulates.
Fig. 6 and Fig. 7 are the SEM figures and XRD of ZSM-5 particulates manufactured in the present embodiment, and as seen from the figure, keeping temperature is not
Become, shorten the hydro-thermal reaction time and can obtain complete particulate, particle diameter is 2~5 μm, and its microstructure is that width is 100~300nm
Nanometer sheet NW-TFT hierarchy spherical particle, its XRD fully demonstrate gained material be ZSM-5, substantially without
Dephasign peak, illustrates that the ZSM-5 that obtains is purer and stable appearance.
Embodiment 3
A kind of preparation method of ZSM-5 particulates, step is as follows：
1) by 0.1g NaOH, 9.45g tetraethyl ammonium hydroxides and 8.16g TPAOHs add beaker in,
It is stirred at room temperature to NaOH dissolving, obtains mixed solution；
2) to step 1) 17.85g Ludox is added in gained mixed solution, and it is stirred at room temperature homogeneous to obtaining
Dispersion liquid, be subsequently adding 0.366g aluminium isopropoxides, stirring fully to without obvious aluminium isopropoxide white particles, is subsequently poured into
In hydrothermal reaction kettle, hydro-thermal reaction 3 days at 200 DEG C, reaction terminate after by reaction solution from hydrothermal reaction kettle take out carry out suction filtration,
Drying, then through calcining (being incubated 4 hours at 550 DEG C), obtain ZSM-5 particulates.
Fig. 8 and Fig. 9 are the SEM figures and XRD of ZSM-5 particulates manufactured in the present embodiment, as seen from the figure, change the reaction time
And reaction temperature can obtain complete particulate, particle diameter is 2~5 μm, and its microstructure is nanometer sheet that width is 100~300nm
The spherical particle of the hierarchy of NW-TFT, it is ZSM-5 that its XRD fully demonstrates gained material, substantially without dephasign peak, is said
The bright ZSM-5 for obtaining is purer and stable appearance.
Claims (7)
1. a kind of ZSM-5 particulates, it is characterised in that：The ZSM-5 particulates are the hierarchy of porous nano-sheet NW-TFT
Spherical particle, the porous nano-sheet width is about 100~300nm.
2. ZSM-5 particulates according to claim 1, it is characterised in that：The ZSM-5 particle sizes are 2~5 μm.
3. the preparation method of the ZSM-5 particulates described in a kind of claim 1 or 2, it is characterised in that step is as follows：
1) NaOH is mixed with tetraethyl ammonium hydroxide and TPAOH, is stirred at room temperature molten to NaOH
Solution, obtains mixed solution；
2) to step 1) Ludox is added in gained mixed solution, and be stirred at room temperature to obtaining homogeneous dispersion liquid,
It is subsequently adding aluminium isopropoxide, stirring fully to be fallen back and carry out hydro-thermal reaction in thermal response kettle, then after suction filtration, drying, calcining
Obtain ZSM-5 particulates.
4. preparation method according to claim 3, it is characterised in that step 1) NaOH, tetraethyl hydroxide
Ammonium, TPAOH and step 2) Ludox, the mol ratio of element Na, N, N, Si, Al is 1 in aluminium isopropoxide:2~
2.5:1~1.5:11~15:0.7~0.8.
5. preparation method according to claim 3, it is characterised in that step 2) dioxide-containing silica is in the Ludox
30wt%.
6. preparation method according to claim 3, it is characterised in that step 2) hydrothermal temperature is 180~200
DEG C, the hydro-thermal reaction time is 1~6 day.
7. preparation method according to claim 3, it is characterised in that step 2) the calcine technology condition is：350~
2~8 hours are incubated at 600 DEG C.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201611270247.0A CN106698464B (en) | 2016-12-31 | 2016-12-31 | A kind of ZSM-5 microballoon and preparation method thereof |
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| CN201611270247.0A CN106698464B (en) | 2016-12-31 | 2016-12-31 | A kind of ZSM-5 microballoon and preparation method thereof |
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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 |
|---|
| MIN LIU，ET AL.: "Seed-induced synthesis of hierarchical ZSM-5 nanosheets in the presence of hexadecyl trimethyl ammonium bromide", 《RSC ADVANCES》 * |
| POONAM RANI,ET AL.: "One-Step Dual Template Mediated Synthesis of Nanocrystalline Zeolites of Different Framework Structures", 《CRYST. GROWTH DES.》 * |
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Granted publication date: 20190723 Termination date: 20191231 |