CN107954438A - Lead directly to mesoporous FAU molecular sieves and preparation method thereof - Google Patents
Lead directly to mesoporous FAU molecular sieves and preparation method thereof Download PDFInfo
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- CN107954438A CN107954438A CN201610899052.6A CN201610899052A CN107954438A CN 107954438 A CN107954438 A CN 107954438A CN 201610899052 A CN201610899052 A CN 201610899052A CN 107954438 A CN107954438 A CN 107954438A
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- 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
- C01B39/04—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 using at least one organic template directing agent, e.g. an ionic quaternary ammonium compound or an aminated compound
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- 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
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
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- C—CHEMISTRY; METALLURGY
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
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Abstract
The present invention relates to one kind to lead directly to mesoporous FAU molecular sieves and preparation method thereof.The problems such as mainly solution conventional art can not connect in microporous mesoporous duct completely when preparation has mesoporous FAU molecular sieves, and mesopore orbit easily caves in.The present invention is by using secondary treatment method, microemulsion of the dipping rich in silicon/aluminium/FAU templates in mesopore molecular sieve, and by secondary crystallization, in mesopore molecular sieve inner surface epitaxial growth FAU molecular sieves, then generation has through-type mesoporous FAU molecular sieves.This method ideally solve the problems, such as it is mentioned above, its method can be used for prepare in a variety of straight-through mesopore molecular sieve industrial productions.
Description
Technical field
The present invention relates to one kind to lead directly to mesoporous FAU molecular sieves and preparation method thereof.
Background technology
FAU structure molecular screens belong to micro porous molecular sieve series, belong to octahedrite class, including the X-type of low silica-alumina ratio and Y types.Its
Skeleton is mainly made of alumino-silicate, has the secondary structure of double hexatomic rings and β cages, and β cages are connected by double hexatomic rings to be formed
Three-dimensional spaciousness skeleton structure.The Y types of high silica alumina ratio have high selectivity, high hydrothermal stability, suitable acidity.60 years 20th century
In generation, is used for catalytic cracking first by Linde companies, and shows excellent Catalytic Cracking Performance in FCC reactions behind, after
And it is widely used in major industrial enterprises and institutions.FAU molecular sieves use sodium hydroxide or 4-propyl bromide etc. to be used as structure directing
Agent, crystallization 6h-10d is prepared at 100-180 DEG C.The activated centre of micro porous molecular sieve is more inside duct.Molecular sieve master
The longer diffusional resistance that can increase molecule inside its duct in duct, prevents target product molecule from diffusing out in time inside duct
And secondary response finally occurs and generates other molecules.Therefore diffusion path is shortened, reduction diffusional resistance has great importance.
Introduced in one piece of micro porous molecular sieve crystal it is mesoporous come reduce diffusional resistance, accelerate diffusion：That is, synthetic microporous-composite mesoporous is more
The molecular screen material of level pore passage structure has become the hot spot studied at present.It is common synthesis multi-stage porous FAU molecular sieves method be
The micropore template agent for promoting FAU skeletons to be formed not only is added in synthetic system, is additionally added the mesoporous template for inducing mesoporous formation,
Including as the carbon black pellet of hard template, carbon nanotubes, charcoal-aero gel, polysaccharide compound etc. and as soft template sun from
Organosilan of sub- polymer and amphiphatic molecule etc.；J.Garcia-Martinez etc. (J.Garcia-Martinez et al.,
Catal.Sci＆tech, 2012,2,987) by introducing cetyl trimethylammonium bromide (CTAB), it is secondary with Y little crystal grains two
Length prepares mesoporous FAU molecular sieves；Song et al. is using the synthesising mesoporous FAU molecular sieves (Song Lijuan of method that starch is added in synthesis
Deng,《Petroleum technology and application》, 2015,33,288)；What (He Yilong etc.《Petrochemical industry Journal of Chinese Universities》, 2015,28,
Et al. 31) mesoporous FAU molecular sieves are prepared using etching alkaline solution method.Although above method can obtain mesoporous distribution,
The use of mesoporous template not only increases the complication that cost also results in synthesis step, is not appropriate for industrializing.Although on also,
The mesopore molecular sieve that various methods are prepared for FAU is stated, but the microporous mesoporous mesoporous FAU directly connected research hotspot and difficulty always
Point, otherwise the method preparation process reported is complicated, it is necessary to introduce the surfactant of price costly, complicated large scale
Template etc. make it that cost is high, and post processing is cumbersome and causes environmental pollution., the multi-stage porous of gained is not real meaning
On directly connect.Therefore, also there is very big challenge, conventional synthesis process for preparing with the mesoporous FAU directly connected
Limit development and the commercial Application of through-type mesoporous FAU molecular sieves.
The content of the invention
The technical problems to be solved by the invention, that is, of high cost, the mesoporous FAU molecular sieves knot of gained existing in the prior art
A kind of the problem of low, the straight-through property of crystalline substance is poor, there is provided preparation method of new straight-through mesoporous FAU molecular sieves.After this method has
Processing procedure is simple；Manufacturing cost is low (any mesopore molecular sieve can serve as directly connecting)；It is environmental-friendly that (microemulsion is whole
Dipping, has reached Zero discharge)；The mesoporous FAU of gained reaches the features such as real microporous mesoporous unbounded connection.
In order to solve the above technical problems, the technical solution adopted by the present invention is as follows：
One kind leads directly to mesoporous FAU molecular sieves, and the micropore in its structure is directly connected with mesoporous, and the micropore is in mesopore orbit
In.
In above-mentioned technical proposal, micropore in FAU molecular sieve structures is directly connected with mesoporous in mesoporous molecular sieve structure,
And the micropore is present in the mesopore orbit.
In above-mentioned technical proposal, mesopore molecular sieve is the mesopore molecular sieve with straight channels, is SBA more preferably
Or MCM series, it is further preferable that being SBA-15 or MCM-41 or MCM-48.
In above-mentioned technical proposal, the micropore is seamlessly connected with mesoporous wall, and micropore canals are parallel-oriented with mesopore orbit
It is again shorter than mesopore orbit, so as to form micro-~mesoporous part directly connected.
It is described to lead directly to mesoporous FAU molecular sieves by be soaked containing the microemulsion of FAU molecular sieve stostes in above-mentioned technical proposal
Stain is made into mesopore molecular sieve after crystallization, roasting.
The present invention also provides a kind of preparation method for leading directly to mesoporous FAU molecular sieves, comprise the following steps：
A) template, surfactant, water, silicon source, silicon source and organic solvent are mixed, prepares FAU molecular sieve microemulsions；
B) the FAU molecular sieve microemulsions of preparation are impregnated into mesopore molecular sieve and obtain precursor A；
C) at 90~260 DEG C, at autogenous pressures, FAU molecular sieve microemulsions in mesopore molecular sieve crystallization and be situated between
Hole FAU molecular sieves；
D) roasted under the conditions of 300~600 DEG C 0.5~72 it is small when through-type mesoporous FAU molecular sieves are made.
In above-mentioned technical proposal, the FAU molecular sieves microemulsion is water in oil microemulsion.
In above-mentioned technical proposal, in the FAU molecular sieves microemulsion, template, surfactant and water are mixed into water phase,
Silicon source, silicon source and organic solvent are mixed into oil phase, and mixing water phase and oil phase obtain microemulsion.
In above-mentioned technical proposal, the silicon source：Silicon source：The molar ratio of template is 10：1-10：1-3；Organic solvent and table
The molar ratio of face activating agent and water is 2-20：1-10：1.
In above-mentioned technical proposal, the FAU molecular sieves microemulsion is 1 in mass ratio with mesopore molecular sieve:0.5~5
In above-mentioned technical proposal, the mesopore molecular sieve is the mesopore molecular sieve with straight channels.
In above-mentioned technical proposal, the mesoporous molecular is screened from SBA or MCM series；More preferably, channel diameter 2
~8 nanometers.
In above-mentioned technical proposal, the mesopore molecular sieve is SBA-15 or MCM-41 or MCM-48.
In above-mentioned technical proposal, the mesopore molecular sieve can be synthesized by this area conventional technical means, its duct size
The big minor adjustment of surfactant can be passed through.
In above-mentioned technical proposal, the silicon source is included selected from ethyl orthosilicate, butyl silicate, white carbon, waterglass
It is at least one；Source of aluminium is included selected from aluminium isopropoxide, aluminum nitrate, at least one of boehmite；The organic solvent includes
Selected from benzene, toluene, carbon number be more than 6 alkane at least one, the present invention one specific embodiment in, organic solvent is
Toluene；The surfactant includes amphipathic molecule, amphipathic polyethers, the aminated compounds of C8~C18 selected from C8-C12
At least one, in an of the invention specific embodiment, surfactant is tri-n-octyl amine；The template is with Na2O,NaOH
Or quaternary ammonium salt, it is preferably sodium hydroxide or 4-propyl bromide.
In above-mentioned technical proposal, the crystallization temperature is 100-180 DEG C, is preferably, 110 DEG C；Crystallization time is 6-48h,
Preferably 24h.
The present invention allows the aqueous solution containing template completely into hydrophobic mesoporous hole using the method for microemulsion dipping
In road, micropore crystallization is set to be carried out completely in mesopore orbit.Specifically, using mesopore molecular sieve inner wall epitaxial growth
Method, during crystallization, a part of mesoporous wall serves as silicon source and enters microcellular structure, reaches micropore/mesoporous wall and is seamlessly connected；Crystallization
During, FAU is slowly grown in " circle " mesoporous inner wall in a manner of LBL, finally spontaneous in mesopore orbit to construct along Jie
The straight hole road in hole duct direction, the straight hole road in this direction is parallel-oriented with mesopore orbit and shorter than mesopore orbit, so form
Micro-~mesoporous part directly connected.The template containing N, O is removed by roasting, that is, produces highly uniform mesoporous/micropore and connects
Logical structure.Since whole process uses the method for complete wetting, the microemulsion of FAU is not unnecessary and needs the part of blowdown, greatly
The big cost for reducing reaction, at the same it is also environmentally friendly.Achieve preferable technique effect.
Attached drawing and explanation
Fig. 1 is the high-resolution-ration transmission electric-lens figure of the straight-through mesoporous FAU molecular sieves prepared in embodiment one under the conditions of 110 DEG C.
2. the micropore canals and the 1. of a relatively loose mesopore orbit parallel with apparent 2nm with apparent 0.8nm fine and close in figure
Row, and cover wherein, clearly disclose micropore and connected with the unbounded of mesoporous part.
Fig. 2 is the small angle X-ray diffraction spectrogram of the straight-through mesoporous FAU molecular sieves prepared in embodiment one under the conditions of 110 DEG C.
What the mesoporous part that XRD discloses the material was ordered into, the main spy of the main diffraction peak of celled portion and the standard spectrogram of FAU
It is consistent to levy peak.
Fig. 3 is the wide-angle X-ray diffraction curve of the straight-through mesoporous FAU molecular sieves prepared in embodiment one under the conditions of 110 DEG C.
What the mesoporous part that XRD discloses the material was ordered into, the main spy of the main diffraction peak of celled portion and the standard spectrogram of FAU
It is consistent to levy peak.
Below by embodiment, the invention will be further elaborated.
Embodiment
【Embodiment 1】
The preparation for leading directly to mesoporous FAU molecular sieves carries out according to the following steps：FAU water-in-oil microemulsions, hydroxide are prepared first
The aqueous solution that sodium and tri-n-octyl amine are matched somebody with somebody is micro emulsion water phase, and ethyl orthosilicate (TEOS) and the toluene solution of aluminium isopropoxide are oil phase,
Mixing water phase and an oil phase obtains clear microemulsion I.Si in microemulsion I：Al：The molar ratio of NaOH or TPABr is 10：1：10；First
Benzene is 2 with the molar ratio of tri-n-octyl amine and water：1：1；Lower microemulsion I of normal temperature condition and baked SBA-15 is in mass ratio
0.3：1 dipping obtains precursor II.After when aging 6 is small at 60 DEG C, precursor II is loaded stainless steel cauldron, in 110 DEG C of conditions
Under, crystallization 24 obtains the mesoporous FAU molecular sieves containing template when small.After product takes out, when roasting 6 is small under the conditions of 550 DEG C
Obtain straight-through mesoporous FAU molecular sieves.
The mesoporous SBA-15 can be synthesized by this area conventional technical means.
【Embodiment 2-3】
According to the type of the method for embodiment 1, simply change mesopore molecular sieve, you can to leading directly to mesoporous FAU molecular sieves
The distribution of mesoporous, micropore is adjusted, obtain different mesoporous/micropores than straight-through mesoporous FAU molecular sieves.
The mesoporous MCM series can be synthesized by this area conventional technical means.
【Embodiment 4】
According to the method for embodiment 1, simply change surfactant.
【Embodiment 5】
According to the method for embodiment 1, it is 4-propyl bromide simply to change template.
【Embodiment 6】
According to the method for embodiment 1, simply change the molar ratio of organic solvent and water.
【Comparative example 1-2】
According to the method for embodiment 1, simply change the water and oil balance of microemulsion, then can obtain mesoporous FAU molecular sieves, still
Duct is disconnected.
Specific embodiment result and comparative example result see the table below
Embodiment 1-6
| Embodiment | 1 | 2 | 3 | 4 | 5 | 6 |
| Synthesis temperature (DEG C) | 110 | 110 | 110 | 110 | 110 | 110 |
| Reaction time (h) | 24 | 24 | 24 | 24 | 24 | 24 |
| Calcination temperature (DEG C) | 550 | 550 | 550 | 550 | 550 | 550 |
| Mesopore molecular sieve type | SBA-15 | MCM-41 | MCM-48 | SBA-15 | SBA-15 | SBA-15 |
| Than surface (m2/g) | 310 | 310 | 300 | 290 | 330 | 280 |
| Whether lead directly to | It is | It is | It is | It is | It is | It is |
| It is situated between/micro- (void ratio) | 1.0 | 0.7 | 0.6 | 0.9 | 1.1 | 0.6 |
| Surfactant | Tri-n-octyl amine | Tri-n-octyl amine | Tri-n-octyl amine | Octyl phenol | Tri-n-octyl amine | Tri-n-octyl amine |
| Template | Sodium hydroxide | Sodium hydroxide | Sodium hydroxide | Sodium hydroxide | 4-propyl bromide | Sodium hydroxide |
| Organic solvent/water | 2:1 | 2:1 | 2:1 | 2:1 | 2:1 | 4:1 |
Comparative example 1-2
| Comparative example | 1 | 2 |
| Synthesis temperature (DEG C) | 110 | 110 |
| Reaction time (h) | 24 | 24 |
| Calcination temperature (DEG C) | 550 | 550 |
| Microemulsion type | Water oil is continuous | Oil-in-water |
| With the presence or absence of mesoporous and FAU | It is | It is |
| Whether connect | It is non- | It is non- |
Claims (10)
1. one kind leads directly to mesoporous FAU molecular sieves, it is characterised in that the micropore in its structure is directly connected with mesoporous, the micropore
In mesopore orbit.
2. a kind of preparation method for leading directly to mesoporous FAU molecular sieves, comprises the following steps：
A) template, surfactant, water, silicon source, silicon source and organic solvent are mixed, prepares FAU molecular sieve microemulsions；
B) the FAU molecular sieve microemulsions of preparation are impregnated into mesopore molecular sieve and obtain precursor A；
C) at 90~260 DEG C, at autogenous pressures, FAU molecular sieve microemulsions in mesopore molecular sieve crystallization and obtain mesoporous
FAU molecular sieves；
D) roasted under the conditions of 300~600 DEG C 0.5~72 it is small when through-type mesoporous FAU molecular sieves are made.
3. the preparation method according to claim 2 for leading directly to mesoporous FAU molecular sieves, it is characterised in that the FAU molecular sieves
Microemulsion is water in oil microemulsion.
4. the preparation method of the straight-through mesoporous FAU molecular sieves according to Claims 2 or 3, it is characterised in that the FAU points
In son sieve microemulsion, template, surfactant and water are mixed into water phase, and silicon source, silicon source and organic solvent are mixed into oil phase, mix
Heshui phase and oil phase obtain microemulsion.
5. the preparation method according to claim 2 for leading directly to mesoporous FAU molecular sieves, it is characterised in that the silicon source：Aluminium
Source：The molar ratio of template is 10：1-10：1-3；The molar ratio of organic solvent and surfactant and water is 2-20：1-10：1.
6. the preparation method according to claim 2 for leading directly to mesoporous FAU molecular sieves, it is characterised in that the FAU molecular sieves
Microemulsion is 1 in mass ratio with mesopore molecular sieve：0.5~5.
7. the preparation method according to claim 2 for leading directly to mesoporous FAU molecular sieves, it is characterised in that the mesoporous molecular
Sieve as the mesopore molecular sieve with straight channels.
8. the preparation method of the straight-through mesoporous FAU molecular sieves according to claim 2 or 7, it is characterised in that described mesoporous point
Son is screened from SBA or MCM series.
9. the preparation method for the straight-through mesoporous FAU molecular sieves stated according to claim 2, it is characterised in that the crystallization temperature is
100-180 DEG C, crystallization time 6-48h.
10. the preparation method according to claim 2 for leading directly to mesoporous FAU molecular sieves, it is characterised in that the silicon source includes
Selected from ethyl orthosilicate, butyl silicate, white carbon, waterglass at least one；Source of aluminium is included selected from aluminium isopropoxide, nitre
At least one of sour aluminium, boehmite；It is the alkane of more than 6 that the organic solvent, which is included selected from benzene, toluene, carbon number,
It is at least one；The surfactant includes amphipathic molecule, amphipathic polyethers, the amine of C8~C18 selected from C8-C 12
At least one of compound；The template is Na2O, NaOH or quaternary ammonium salt.
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