CN107082436B - A kind of preparation method of mesoporous micro porous molecular sieve - Google Patents
A kind of preparation method of mesoporous micro porous molecular sieve Download PDFInfo
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- CN107082436B CN107082436B CN201710244037.2A CN201710244037A CN107082436B CN 107082436 B CN107082436 B CN 107082436B CN 201710244037 A CN201710244037 A CN 201710244037A CN 107082436 B CN107082436 B CN 107082436B
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 69
- 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 69
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000000463 material Substances 0.000 claims abstract description 41
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000011324 bead Substances 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 19
- 239000011148 porous material Substances 0.000 claims abstract description 16
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims abstract description 14
- 230000009977 dual effect Effects 0.000 claims abstract description 12
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 11
- 238000002425 crystallisation Methods 0.000 claims abstract description 10
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 8
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 8
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 8
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 8
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 8
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 5
- 239000010703 silicon Substances 0.000 claims abstract description 5
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 239000000843 powder Substances 0.000 claims description 10
- 239000000725 suspension Substances 0.000 claims description 10
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 9
- 230000008025 crystallization Effects 0.000 claims description 9
- 235000019441 ethanol Nutrition 0.000 claims description 9
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 claims description 8
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 7
- 229940043237 diethanolamine Drugs 0.000 claims description 7
- 238000006460 hydrolysis reaction Methods 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 6
- 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 claims description 5
- 239000013078 crystal Substances 0.000 claims description 5
- 230000007062 hydrolysis Effects 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- 239000011734 sodium Substances 0.000 claims description 5
- 238000007598 dipping method Methods 0.000 claims description 4
- 229920006395 saturated elastomer Polymers 0.000 claims description 4
- 239000012752 auxiliary agent Substances 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 claims 1
- 229910001388 sodium aluminate Inorganic materials 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 abstract description 11
- 238000003786 synthesis reaction Methods 0.000 abstract description 11
- 239000000376 reactant Substances 0.000 abstract description 9
- 238000006555 catalytic reaction Methods 0.000 abstract description 6
- 239000003610 charcoal Substances 0.000 abstract description 3
- 239000000047 product Substances 0.000 description 12
- 239000000243 solution Substances 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 230000003197 catalytic effect Effects 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 238000010586 diagram Methods 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 3
- 230000032683 aging Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 241000790917 Dioxys <bee> Species 0.000 description 1
- 229910003978 SiClx Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 210000003850 cellular structure Anatomy 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
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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
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/617—500-1000 m2/g
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/643—Pore diameter less than 2 nm
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
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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
- C01P2002/01—Crystal-structural characteristics depicted by a TEM-image
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- 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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- C01P2006/17—Pore diameter distribution
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- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The present invention relates to a kind of preparation methods of mesoporous micro porous molecular sieve.A kind of mesoporous micro porous molecular sieve with hierarchical porous structure, the mesoporous micro porous molecular sieve have dual mesoporous and two kinds of pore structures of micropore, and dual mesoporous size is respectively 2-3nm and 40-60nm, by mesoporous SiO2Crystallization is carried out by steam assisting alcohol-hydrothermal method under the action of structure directing agent TPAOH as silicon source and template simultaneously to obtain.Compared with conventional molecular sieves catalysis material, the present invention has synthesized the mesoporous ZSM-5 molecular sieve monocrystalline with counter opal structure, with dual mesoporous and micropore hierarchical porous structure.The opposite mesoporous microporous molecular screen method of conventional synthesis, not using non-reactant such as PS bead, charcoal templates as template, method is simple, and the molecular sieve bore diameter of synthesis is controllable.
Description
Technical field
The invention belongs to technical field of inorganic material, and in particular to the preparation of the mesoporous micro porous molecular sieve of morphology controllable.
Background technique
Because molecular screen material has very high specific surface area, have widely in fields such as adsorption/desorption, separation catalysis
Application prospect, but industrial molecular sieve catalytic efficiency in catalysis is lower at this stage, in catalytic reaction process, intermediate reaction product
Microporous molecular sieve duct can be blocked, the circulation diffusivity of reactant is reduced, causes molecular sieve internal active sites abundant
It utilizes.In other words molecular sieve is being applied to catalytic field still needs to solve the problems, such as be molecular sieve internal circulation divergent question.This
It is that current restriction molecule sieves the bottleneck factor yielded positive results in catalytic field
Mesoporous micro porous molecular sieve material have a catalysis material containing hierarchical porous structure, catalytic process intermediary hole can
To increase the circulation diffusivity of reactant, reactant is made to enter the effect of molecular sieve crystal internal gutter structure, keeps molecular sieve brilliant
Intracorporal active site is fully utilized, and improves molecular sieve catalytic efficiency.
The method of the conventionally employed synthesising mesoporous micro porous molecular sieve material of Metaporous silicon dioxide material is mesoporous to MCM-41 etc.
Material carries out aluminium doping, carries out aging with structure directing agents such as TPAOH, under hydrothermal conditions TPA+Replace the Al of mesoporous wall surface
Element carries out self assembly, and roasting goes after template to form one layer of MFI type topological structure, Jie that this method obtains in mesopore surfaces
Hole-micro porous molecular sieve material only carries out corrosion crystallization in mesoporous wall surface, and inner silica silicon structure is relatively stable, final
To the compound of MCM-41 and 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 a kind of shape rule
The preparation method of whole, morphology controllable mesoporous micro porous molecular sieve.Its molecular sieve synthesized is mono-crystalline structures, has dual mesoporous knot
Structure.
In order to solve the above technical problems, present invention provide the technical scheme that
A kind of mesoporous micro porous molecular sieve with hierarchical porous structure is provided, the mesoporous micro porous molecular sieve have it is dual mesoporous and
Two kinds of pore structures of micropore, dual mesoporous size is respectively 2-3nm and 40-60nm, by mesoporous SiO2It is used as silicon source and mould simultaneously
Plate carries out crystallization by steam assisting alcohol-hydrothermal method under the action of structure directing agent TPAOH and obtains.TPA+ ion in crystallization process
Form skeleton in conjunction with mesoporous silicon oxide bead surface, OH-ion enter mesoporous inside by mesoporous silicon oxide from inside into
Row corrosion, obtains aperture controllable, mesoporous-micro porous molecular sieve material with dual meso-hole structure and microcellular structure.
According to the above scheme, the mesoporous-micro porous molecular sieve pore size is 0.45-0.47nm；The molecular sieve crystal ruler
Very little is 700-900nm.
The present invention also provides the preparation methods of above-mentioned mesoporous micro porous molecular sieve material, will have 2- having a size of 40-60nm, inside
3nm mesoporous mesoporous silicon oxide bead adds water to be thoroughly mixed uniformly to obtain suspension, then dry to obtain by suspension
Then tetrapropylammonium hydroxide dipping is added dropwise on powder, is put into beaker after dry, is then placed in reaction for solid powder
The water for the sufficient amount that air pressure in kettle can be made to reach saturated pressure is added in kettle liner, in inner liner of reaction kettle outside beaker, installs reaction
Steam is carried out after kettle and assists hydro-thermal reaction, is filtered, washed, is dried after reaction, obtains mesoporous-micro porous molecular sieve
Material.
According to the above scheme, the mesoporous SiO2The preparation method of bead: by (hexadecyltrimethylammonium chloride TEOS is (just
Silester) using second alcohol and water as primary solvent, then hydrolysis in the presence of auxiliary agent diethanol amine and pore creating material is located afterwards
Roasting removes what early hole agent obtained after reason.
According to the above scheme, the TEOS (ethyl orthosilicate): diethanol amine: the mass ratio of pore creating material is 30~35:1:10
~15；
Hydrolysising reacting temperature is 20-60 DEG C, 3~6h of hydrolysis time.
According to the above scheme, the concentration of TEOS is 0.3-0.4mol/L in the hydrolysis reaction system；
The pore creating material is CTAC (hexadecyltrimethylammonium chloride).
According to the above scheme, maturing temperature is 550 DEG C, and calcining time is 4~6h.
According to the above scheme, it is 10%~15% that the ethyl alcohol, which accounts for the ratio of second alcohol and water total weight,.
According to the above scheme, mesoporous SiO2The specific preparation method of bead: water is added to be mixed diethanol amine, ethyl alcohol equal
It is even, solution I is obtained, then the aqueous solution of solution I and CTAC (hexadecyltrimethylammonium chloride) are mixed, makes it sufficiently
Dissolution dispersion, is then added TEOS (ethyl orthosilicate) hydrolysis, it filtered, washed, be dried after reaction,
It is then placed in Muffle kiln roasting；
According to the above scheme, mesoporous silicon oxide bead and TPAOH (tetrapropylammonium hydroxide) mass ratio are 0.9~1.3:1.
According to the above scheme, TPAOH concentration is 2mol/L；Drying temperature after dipping is 60 DEG C.
According to the above scheme, sodium metaaluminate is added as needed in the preparation of the suspension, to synthesize Si/Al type molecule
The mass ratio of sieve, mesoporous silicon oxide bead and sodium metaaluminate is 20-50:1.
According to the above scheme, the hydrothermal reaction condition are as follows: in 130-150 DEG C of isothermal reaction 1d~3d.
According to the above scheme, inside liner water content and liner capacity ratio are 4%~10%, and air pressure in kettle is made to reach saturated air
Pressure.
The present invention is with respect to the mesoporous microporous molecular screen method of conventional synthesis, not using non-reactant such as PS bead, charcoal templates
As template, but directlys adopt mesoporous silicon oxide bead and gone out as templated synthesis with the mesoporous of counter opal structure
ZSM-5 monocrystalline molecular sieve exists simultaneously dual mesoporous and micropore canals, mesoporous tool in the mesoporous micro porous molecular sieve material of synthesis
There is channel diameter more biggish than micropore, mesoporous presence can be such that macromolecule reactant rapidly enters inside molecular sieve pore passage, micro-
The presence in hole makes molecular screen material have very bigger serface, thus mesoporous to provide channel for reactant and enter in molecular sieve crystal
In portion's micropore canals, while accelerating the circulation of intermediate product, to greatly enhance the catalytic efficiency of molecular sieve, effectively
The problems such as reactant diffuser efficiency is low when solving molecular sieve as catalyst application.
The present invention relates to a kind of preparation method of hard template method synthesis grade pore structure molecular sieve, first synthesising mesoporous dioxy
SiClx bead, size are about 40-600nm, then mesoporous silicon oxide is carried out dipping aging with TPAOH, then use steam
Assisting alcohol-hydrothermal method carries out crystallization synthesis, TPA+ ion and mesoporous silicon oxide in crystallization process under conditions of high temperature and pressure
Bead surface, which combines, forms skeleton, and OH-ion enters mesoporous inside and corrodes mesoporous silicon oxide from inside, obtains and is situated between
Hole silicon oxide pellets corresponding size it is mesoporous, the mesopore molecular sieve of this method synthesis is compared with general material duct order
It is higher, and due to its special cellular structure, selectivity is also more preferable, solves the circulation of conventional molecular sieve material in the application
Divergent question, and do not needed in the synthesis process using other materials as hard template, method is relatively simple, in removal mould
Too many exhaust gas will not be generated when plate.
The beneficial effects of the present invention are:
Compared with conventional molecular sieves catalysis material, the present invention has synthesized the mesoporous ZSM-5 with counter opal structure points
Son sieve monocrystalline, with dual mesoporous and micropore hierarchical porous structure.The opposite mesoporous microporous molecular screen method of conventional synthesis, does not have
Using non-reactant such as PS bead, charcoal templates as template, method is simple, and the molecular sieve bore diameter of synthesis is controllable.
Detailed description of the invention
Fig. 1 is mesoporous SiO prepared by the embodiment of the present invention 12The SEM photograph of bead；
Fig. 2 is mesoporous SiO prepared by embodiment 12The mesoporous BET of bead schemes；
Fig. 3 is the XRD diagram of mesoporous micro porous molecular sieve material prepared by embodiment 1；
Fig. 4 is the SEM photograph of mesoporous micro porous molecular sieve material prepared by embodiment 1；
Fig. 5 is the TEM photo of mesoporous micro porous molecular sieve material prepared by embodiment 1；
Fig. 6 is the mesoporous BET figure of mesoporous micro porous molecular sieve material prepared by embodiment 1；
Fig. 7 is the micropore BET figure of mesoporous micro porous molecular sieve material prepared by embodiment 1；
Fig. 8 is the Product scan electron microscope picture that 2 step 2) of embodiment obtains；
Fig. 9 is the XRD diagram of 2 products therefrom of embodiment；
Figure 10 is the nitrogen adsorption curve graph and graph of pore diameter distribution of 2 products therefrom of embodiment.
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.
Embodiment 1
Mesoporous micro porous molecular sieve material is prepared, steps are as follows:
1) mesoporous SiO is prepared2Bead: the ethyl alcohol of 0.2g diethanol amine and 9ml is added in 44mL deionized water, mixing
It stirs evenly, obtains solution I, the CTAC of 2.6g is added in 30ml deionized water, be completely dissolved to obtain solution II, then will
Obtained solution II is added in solution I, is stirred under 60 DEG C of environment 30 minutes, and 7.3mlTEOS is then added and continues stirring three
Then a hour is centrifuged, is dried, obtained solid is put into Muffle furnace and roasts 6 hour removal moulds at 550 DEG C
Plate agent obtains mesoporous SiO2Bead；
2) it prepares mesoporous micro porous molecular sieve material: 0.125g mesoporous silicon oxide bead and 6mg sodium metaaluminate and 5ml is gone
Ionized water is added in beaker, is thoroughly mixed uniformly, obtains suspension, then dry suspension in 60 DEG C of baking ovens, obtain
To solid powder, the tetrapropylammonium hydroxide that 0.28ml concentration is 2mol/L is then added dropwise on powder and impregnates one day, to complete
Beaker is put into 100ml reaction kettle after drying, 4ml deionized water is added outside beaker in inner liner of reaction kettle, is put into after closed
140 DEG C of baking ovens react 2d, are filtered, washed, are dried after reaction, gained powder is put into Muffle furnace 550
4 hours are roasted at DEG C, obtain mesoporous-micro porous molecular sieve material.
The product that the present embodiment step 1) obtains is shot through scanning electron microscope determines that silicon oxide dimensions are 50nm, and
And particle size is more uniform, SEM photograph is shown in Fig. 1.(Fig. 2) step 1) products therefrom has as the result is shown for nitrogen adsorption analysis
Up to 767m2The specific surface area of/g, and there are mesopore orbit, channel diameter 2.6nm in product.Fig. 3 is the present embodiment step
2) XRD diagram of products therefrom, can be seen from the chart, which is ZSM-5 molecular sieve, have preferable crystallinity；Fig. 4 is step
The SEM photograph of rapid 2) products therefrom, it is seen that sample is the block of hexagonal prism shape, and size is about 800nm or so, in block
The mesoporous pore size less than 50nm is clear that on body；Fig. 5 is mesoporous micro porous molecular sieve material prepared by the present embodiment
TEM figure can be seen from the chart, sample interior is uniformly dispersed with mesopore orbit structure, and surface is without meso-hole structure, this
Just explaining most of particle surface in SEM figure does not have the phenomenon that mesopore orbit, and second figure is clear that it has
Apparent single crystal diffraction style, it was demonstrated that synthesized mesopore molecular sieve is monocrystalline molecular sieve；Fig. 6 is Jie prepared by the present embodiment
The mesoporous nitrogen adsorption figure of hole micro porous molecular sieve material, can be seen from the chart, the specific surface area of sample is up to 406m2/ g, tool
There is mesopore orbit, and there are double mesopore orbit structures, the first weight mesoporous pore size is 2.2nm, and second focuses on 49.6nm or so,
This size is closely sized to mesoporous silicon oxide bead, is illustrated its crystallization process and is imagined unanimously, molecular sieve is in bead table
Face carries out crystallization, and inner silica silicon, which is corroded, provides silicon source；Fig. 7 is mesoporous micro porous molecular sieve material prepared by the present embodiment
Micropore BET figure, it can be seen that sample have 0.45nm micropore canals diameter.
Embodiment 2
Mesoporous micro porous molecular sieve material is prepared, steps are as follows:
1) it prepares mesoporous SiO2 bead: the ethyl alcohol of 0.2g diethanol amine and 9ml is added in 44mL deionized water, mix
It stirs evenly, obtains solution I, the CTAC of 2.6g is added in 30ml deionized water, be completely dissolved to obtain solution II, then will
Obtained solution II is added in solution I, is stirred under 60 DEG C of environment 30 minutes, and 7.3mlTEOS is then added and continues stirring three
Then a hour is centrifuged, is dried, obtained solid is put into Muffle furnace and roasts 6 hour removal moulds at 550 DEG C
Plate agent obtains mesoporous SiO2 bead；
2) it prepares mesoporous micro porous molecular sieve material: 0.125g mesoporous silicon oxide bead and 3mg sodium metaaluminate and 5ml is gone
Ionized water is added in beaker, is thoroughly mixed uniformly, obtains suspension, then dry suspension in 60 DEG C of baking ovens, obtain
To solid powder, the tetrapropylammonium hydroxide that 0.25ml concentration is 2mol/L is then added dropwise on powder and impregnates one day, to complete
Beaker is put into 100ml reaction kettle after drying, 4ml deionized water is added outside beaker in inner liner of reaction kettle, installs reaction kettle
It is reacted for 24 hours in 140 DEG C of baking ovens afterwards, is filtered, washed, be dried after reaction, gained powder is put into Muffle furnace
In at 550 DEG C roast 4 hours, obtain mesoporous-micro porous molecular sieve material.
The product that the present embodiment step 2) obtains shoots to obtain such as Fig. 8 image through scanning electron microscope, is rendered as marking
Quasi- ZSM-5 hexagonal prism shape, size is about 2~3 μm；Fig. 9 is the XRD diagram of products therefrom, it can be seen that its peak
Shape complies fully with the distinctive peak shape of MFI-type molecular sieve, illustrates that prepared product is ZSM-5 molecular sieve；Figure 10 is the nitrogen of product
The attached curve graph of aspiration and graph of pore diameter distribution, from nitrogen adsorption analysis result can be seen that its with apparent meso-hole structure, it is mesoporous
Pore-size distribution is in two regions 2~4nm and 30~50nm.
As can be seen that all may be used in certain crystallization temperature time range and under TPAOH content from the above analysis data
To obtain the mesoporous micropore ZSM-5 molecular sieve material with dual meso-hole structure.
Claims (7)
1. the preparation method of mesoporous micro porous molecular sieve material, it is characterised in that: with mesoporous SiO2It is being tied simultaneously as silicon source and template
Crystallization is carried out by steam assisting alcohol-hydrothermal method under the action of structure directed agents tetrapropylammonium hydroxide to obtain, method particularly includes: by ruler
Very little is 40-60nm, and the mesoporous silicon oxide bead that inside has 2-3nm mesoporous adds water to be thoroughly mixed uniformly to obtain suspension,
Then suspension is dried to obtain solid powder, tetrapropylammonium hydroxide dipping is then added dropwise on powder, is set after dry
Enter in beaker, in which: mesoporous silicon oxide bead and tetrapropylammonium hydroxide mass ratio are 0.9 ~ 1.3:1, are then placed in reaction
The water for the sufficient amount that air pressure in kettle can be made to reach saturated pressure is added in kettle liner, in inner liner of reaction kettle outside beaker, installs reaction
Steam is carried out after kettle and assists hydro-thermal reaction, and steam auxiliary hydrothermal reaction condition is；130-150 DEG C of 1 ~ 3d of isothermal reaction, reaction knot
It filtered, washed, be dried after beam, obtain mesoporous micro porous molecular sieve material；The mesoporous micro porous molecular sieve is monocrystalline knot
Structure has dual mesoporous and two kinds of pore structures of micropore, and dual mesoporous size is respectively 2-3nm and 40-60nm.
2. the preparation method of mesoporous micro porous molecular sieve material according to claim 1, it is characterised in that: the mesoporous micropore
Microporous molecular sieve is having a size of 0.45-0.47nm；The molecular sieve crystal is having a size of 700-900nm.
3. preparation method according to claim 1, it is characterised in that: the preparation method of the mesoporous silicon oxide bead:
By TEOS using second alcohol and water as primary solvent, then hydrolysis in the presence of auxiliary agent diethanol amine and pore creating material post-processes
Roasting obtains afterwards.
4. preparation method according to claim 3, it is characterised in that: in the preparation method of the mesoporous silicon oxide bead
TEOS: diethanol amine: the mass ratio of pore creating material is 30 ~ 35:1:10 ~ 15；
Hydrolysising reacting temperature is 20-60 DEG C, 3 ~ 6h of hydrolysis time.
5. preparation method according to claim 3, it is characterised in that: the concentration of TEOS is in the hydrolysis reaction system
0.3-0.4mol/L；
The pore creating material is hexadecyltrimethylammonium chloride；
The ratio that ethyl alcohol accounts for second alcohol and water total weight is 10% ~ 15%.
6. preparation method according to claim 1, it is characterised in that: be added as needed in the preparation of the suspension partially
Sodium aluminate, to synthesize Si/Al type molecular sieve, the mass ratio of mesoporous silicon oxide bead and sodium metaaluminate is 20-50:1.
7. preparation method according to claim 1, it is characterised in that: inside liner water content and liner capacity ratio be 4% ~
10%, so that air pressure in kettle is reached saturated vapour pressure.
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