CN107954442A - Lead directly to mesoporous L-type molecular sieve and preparation method thereof - Google Patents
Lead directly to mesoporous L-type molecular sieve and preparation method thereof Download PDFInfo
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- CN107954442A CN107954442A CN201610898380.4A CN201610898380A CN107954442A CN 107954442 A CN107954442 A CN 107954442A CN 201610898380 A CN201610898380 A CN 201610898380A CN 107954442 A CN107954442 A CN 107954442A
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- 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
- C01B39/32—Type L
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- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P2006/16—Pore diameter
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Abstract
The present invention relates to one kind to lead directly to mesoporous L-type molecular sieve and preparation method thereof.The problems such as mainly solution conventional art can not connect in microporous mesoporous duct completely when preparation has mesoporous L-type molecular sieve, and mesopore orbit easily caves in.The present invention is by using secondary treatment method, microemulsion of the dipping rich in silicon/aluminium/L templates in mesopore molecular sieve, and by secondary crystallization, in mesopore molecular sieve inner surface epitaxial growth L-type molecular sieve, then generation has through-type mesoporous L-type molecular sieve.This method ideally solve the problems, such as it is mentioned above, in the industrial production available for a variety of straight-through mesopore molecular sieves.
Description
Technical field
The present invention relates to one kind to lead directly to mesoporous L-type molecular sieve and preparation method thereof.
Background technology
L-type molecular sieve belongs to chabasie series, is connected and formed with can cages by double hexatomic rings, 0.71 nanometer of aperture.The molecule
Sifter device has higher hydrothermal stability and stronger acid and hydrophobicity.Because of its unique pore passage structure and higher anti-carbon
Performance makes it play an important role in Subjective and Objective Material Field.L-type molecular sieve is developed first by linde companies, uses hydrogen
Potassium oxide is as structure directing agent, and crystallization is prepared for 6h-10 days at 100-175 DEG C.The activated centre of micro porous molecular sieve is more
Inside duct.The longer diffusional resistance that can increase molecule inside its duct in molecular sieve main aperture road, makes target product molecule not
It can in time diffuse out inside duct and secondary response finally occurs and generates other molecules.Therefore shorten diffusion path, reduce diffusion
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,
The molecular screen material of synthetic microporous-composite mesoporous multi-stage artery structure has become the hot spot studied at present.Common synthesis is more
The method of level porous molecular sieve is that the micropore template agent for promoting framework of molecular sieve to be formed not only is added in synthetic system, is additionally added and lures
Lead the mesoporous template of mesoporous formation, including the carbon black pellet as hard template, carbon nanotubes, charcoal-aero gel, polysaccharide compound
Deng and cationic polymer as soft template and the organosilan of amphiphatic molecule etc., but the use of mesoporous template not only increases
Add cost to also result in the complication of synthesis step, be not appropriate for industrializing.So far, there is the mesoporous L-type molecule directly connected
The preparation of sieve does not have been reported that illustrating conventional synthesis process, it is even more impossible to synthesize through-type mesoporous L-type molecular sieve also.
The content of the invention
The present invention provides a kind of new straight-through mesoporous L-type molecular sieve and preparation method thereof.This method, which has, to be post-processed
Journey is simple；Manufacturing cost is low (any mesopore molecular sieve can serve as directly connecting)；Environmental-friendly (microemulsion all impregnates,
Zero discharge is reached)；The mesoporous L-type molecular sieve 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 L-type molecular sieve, and the micropore of the L-type molecular sieve in its structure is directly connected with mesoporous, described micro-
Hole is in mesopore orbit.
In above-mentioned technical proposal, micropore in L-type molecular sieve structure 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 L-type molecular sieve by be soaked containing the microemulsion of L-type molecular sieve stoste 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 L-type molecular sieve, comprise the following steps：
A) template, surfactant, water, silicon source, silicon source and organic solvent are mixed, prepares L-type molecular sieve microemulsion；
B) the L-type molecular sieve microemulsion of preparation is impregnated into mesopore molecular sieve and obtains precursor A；
C) at 90~260 DEG C, at autogenous pressures, L-type molecular sieve microemulsion in mesopore molecular sieve crystallization and be situated between
Hole L-type molecular sieve；
D) roasted under the conditions of 300~600 DEG C 0.5~72 it is small when through-type mesoporous L-type molecular sieve is made.
In above-mentioned technical proposal, the L-type molecular sieve microemulsion is water in oil microemulsion.
In above-mentioned technical proposal, in the L-type molecular sieve 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 L-type molecular sieve 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-C 12
At least one, in an of the invention specific embodiment, surfactant is tri-n-octyl amine；The template is potassium hydroxide.
In above-mentioned technical proposal, the crystallization temperature is 100-180 DEG C, more preferably, 150 DEG C；Crystallization time is 6-
48h, more 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, L-type molecular sieve is slowly grown in " circle " mesoporous inner wall in a manner of LBL (layer by layer), is finally being situated between
The spontaneous straight hole road constructed along mesopore orbit direction in the duct of hole, the straight hole road in this direction is parallel-oriented with mesopore orbit and compares
Mesopore orbit is short, so form micro-~mesoporous part directly connected.The template containing N, O is removed by roasting, that is, is produced
Highly uniform mesoporous/microporous connectivity structure.Since whole process uses the method for complete wetting, the microemulsion of L-type molecular sieve
It is not unnecessary and need the part of blowdown, the cost of reaction is greatly reduced, and meanwhile it is also environmentally friendly.Achieve preferable skill
Art effect.
Attached drawing and explanation
Fig. 1 is the high-resolution-ration transmission electric-lens figure of the straight-through mesoporous L-type molecular sieve prepared in embodiment 1 under the conditions of 150 DEG C.Figure
In 2. fine and close micropore canals with apparent 0.8nm and the 1. of a relatively loose mesopore orbit parallel with apparent 2.1nm
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 L-type molecular sieve prepared in embodiment 1 under the conditions of 150 DEG C.
What the mesoporous part that XRD discloses the material was ordered into, the main diffraction peak of celled portion and the standard spectrogram of L-type molecular sieve
Principal character peak is consistent.
Fig. 3 is the wide-angle X-ray diffraction curve of the straight-through mesoporous L-type molecular sieve prepared in embodiment 1 under the conditions of 150 DEG C.
What the mesoporous part that XRD discloses the material was ordered into, the main diffraction peak of celled portion and the standard spectrogram of L-type molecular sieve
Principal character peak is consistent.
Below by embodiment, the invention will be further elaborated.
Embodiment
【Embodiment 1】
The preparation for leading directly to mesoporous L-type molecular sieve carries out according to the following steps：L-type molecular sieve water-in-oil microemulsion is prepared first,
The aqueous solution that potassium hydroxide is matched somebody with somebody with tri-n-octyl amine 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 obtain clear microemulsion I.Si in microemulsion I：Al：The molar ratio of KOH is 10：1：3；Toluene with
The molar ratio of tri-n-octyl amine and water is 2：1：1；Lower microemulsion I of normal temperature condition and baked SBA-15 in mass ratio 0.5：1
Dipping obtains precursor II.After when aging 6 is small at 60 DEG C, precursor II is loaded stainless steel cauldron, it is brilliant under the conditions of 150 DEG C
Change 48 it is small when obtain the mesoporous L-type molecular sieve containing template.After product takes out, obtained when roasting 6 is small under the conditions of 550 DEG C straight
Logical mesoporous L-type molecular sieve.
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 L-type molecular sieve
The distribution of mesoporous, micropore is adjusted, obtain different mesoporous/micropores than straight-through mesoporous L-type molecular sieve.
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, simply change organic solvent.
【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 L-type molecular sieve, still
Duct is disconnected.
Specific embodiment result and comparative example result see the table below
Embodiment 1-6
Comparative example 1-2
| Comparative example | 1 | 2 |
| Synthesis temperature (DEG C) | 150 | 150 |
| 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 L-type | It is | It is |
| Whether connect | It is non- | It is non- |
Claims (10)
1. one kind leads directly to mesoporous L-type molecular sieve, it is characterised in that the micropore of the L-type molecular sieve in its structure directly connects with mesoporous
Logical, the micropore is in mesopore orbit.
2. a kind of preparation method for leading directly to mesoporous L-type molecular sieve, comprises the following steps：
A) template, surfactant, water, silicon source, silicon source and organic solvent are mixed, prepares L-type molecular sieve microemulsion；
B) the L-type molecular sieve microemulsion of preparation is impregnated into mesopore molecular sieve and obtains precursor A；
C) at 90~260 DEG C, at autogenous pressures, L-type molecular sieve microemulsion in mesopore molecular sieve crystallization and obtain mesoporous L-type
Molecular sieve；
D) roasted under the conditions of 300~600 DEG C 0.5~72 it is small when through-type mesoporous L-type molecular sieve is made.
3. the preparation method according to claim 2 for leading directly to mesoporous L-type molecular sieve, it is characterised in that the L-type molecular sieve
Microemulsion is water in oil microemulsion.
4. the preparation method of the straight-through mesoporous L-type molecular sieve according to Claims 2 or 3, it is characterised in that the L-type point
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 L-type molecular sieve, 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 L-type molecular sieve, it is characterised in that the L-type molecular sieve
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 L-type molecular sieve, 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 L-type molecular sieve 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 according to claim 2 for leading directly to mesoporous L-type molecular sieve, it is characterised in that the crystallization temperature
For 100-180 DEG C, crystallization time 6-48h.
10. the preparation method according to claim 2 for leading directly to mesoporous L-type molecular sieve, 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 K2O or KOH.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1055344A (en) * | 1991-04-13 | 1991-10-16 | 南京大学 | The prescription of L-zeolite molecular sieve guiding agent and compound method |
| CN105668585A (en) * | 2016-01-04 | 2016-06-15 | 北京科技大学 | Methods for preparing L-type zeolite guiding agent and zeolite |
-
2016
- 2016-10-14 CN CN201610898380.4A patent/CN107954442B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1055344A (en) * | 1991-04-13 | 1991-10-16 | 南京大学 | The prescription of L-zeolite molecular sieve guiding agent and compound method |
| CN105668585A (en) * | 2016-01-04 | 2016-06-15 | 北京科技大学 | Methods for preparing L-type zeolite guiding agent and zeolite |
Non-Patent Citations (2)
| Title |
|---|
| NILESH P.TANGALE ET AL.: "Hierarchical K/LTL zeolites:Synthesis by alkali treatment,characterization and catalytic performance in Knoevenagel condensation reaction", 《JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY》 * |
| 石冈等: "ZSM-5分子筛的脱硅改性及加氢改质性能", 《燃料化学学报》 * |
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