CN107651693A - A kind of direct synthesis method of multi-stage ordered mesoporous molecular sieve - Google Patents
A kind of direct synthesis method of multi-stage ordered mesoporous molecular sieve Download PDFInfo
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- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
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- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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- C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
- C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D311/04—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
- C07D311/22—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 4
- C07D311/26—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 4 with aromatic rings attached in position 2 or 3
- C07D311/28—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 4 with aromatic rings attached in position 2 or 3 with aromatic rings attached in position 2 only
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- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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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
- C01P2006/16—Pore diameter
- C01P2006/17—Pore diameter distribution
Abstract
The invention discloses a kind of direct synthesis method of multi-stage ordered mesoporous molecular sieve, comprise the following steps：Template cetyl trimethylammonium bromide is put into water, is warming up to 65 75 DEG C, dissolving, add silicon source, alkali and silicon source, room temperature is cooled to, stirs 0.5 1.5 hours, obtains the coagulant liquid after aging, it is transferred in stainless steel water thermal synthesis reactor and seals, crystallization 34 days under the conditions of 90 110 DEG C, then it is warming up to 150 160 DEG C of crystallization 57 days, centrifugation, solid is washed with water, dries, calcined, and obtains multi-stage ordered mesoporous molecular sieve；Production cost of the present invention is low, technical process is simple, prepared molecular sieve has MFI micropores and the meso-hole structures of MCM 41, mesoporous order with height, high hydrothermal stability and mechanical stability and acid advantage, there is good catalytic activity, suitable for petrochemical industry, the separation fields such as the preparation of fine chemicals, adsorbing separation, UF membrane.
Description
Technical field
The invention belongs to porous material and catalytic field, more particularly to a kind of direct conjunction of multi-stage ordered mesoporous molecular sieve
Into method.
Background technology
The advantages of due to flexible skeleton structure, controllable framework ingredient and unified porosity, molecular sieve is shown
Unique physical/chemical properties.In the contrast with amorphous materials, they show preferably ion exchangeable, stronger
Acid and higher hydrothermal stability.Based on these characteristics, molecular sieve is having some including fields such as industry, aviations
Using, such as purifying, absorption, separation and catalysis in petroleum refining, petrochemical industry and chemical process.Inside molecular sieve structure
Hole, the size in hole, the size shape of passage and inherent connectedness may influence their practical application, because molecule needs
Enter in duct, be stored in duct or react and transform into other compounds.Molecular sieve is less than 0.8nm passage and is less than
1.3nm hole can provide the selectivity of size/shape.
MCM-41 mesopore molecular sieves can handle larger molecule and group, can be catalyzed macromolecular as catalyst
The reaction of participation, it is widely used in catalyst and catalyst carrier field.MCM-41 can load atom level as carrier
The hetero atom or oxide species of high dispersive, the metal of high degree of dispersion, metallic compound nano particle etc., can largely obtain ratio
Preferable catalytic effect.MCM-41 also has certain application in biology, separation absorption, photoelectric field, electrochemical field.
Mass transfer and limit can be largely affected by the industrial reaction process using molecular sieve.Therefore, numerous studies are directed to
Diffusion limitation is weakened by the microcellular structure of molecular sieve.A kind of method is related to nano-class molecular sieve microparticulate systems increase outer surface
Accumulate and shorten diffusion path length.However, the crystalline size of molecular sieve nanoparticle systems is less than 100nm, them are not only due to
Colloidal nature can cause filtration problem, and because the crystal structure of difference can cause reduction and the hydrothermally stable of micro pore volume
Property reduce.Another method is typically the diffusion for the macromolecular for improving main body porous material, is carried by synthesis by more than 12 T
The molecular sieve of the pretty plus in the duct that atom surrounds is realized.
Surfactant-template is the technology that a kind of most general most practical realization is changed into solid material from mesoporous system.
To produce new structure, the Different Strategies of the interphase interaction based on surfactant and solid precursor have begun to probe into.Point
Son sieve is a kind of important size and dimension selectivity solid acid catalyst.Many researchs are attempted by using surfactant
Assistance technology is limited to solve this problem to reduce diffusion.However, because the separation of micro/meso porous two-phase much makes great efforts all to fail
.Recently, it is a kind of can be with synthesising mesoporous molecular sieve using the new technology of cationic surfactant and weakly alkaline solution.These materials
Material maintains the characteristic (such as highly acid, crystallinity, microporosity and hydrothermal stability) of molecular sieve, adjustable microcellular structure and mesoporous
Degree.Mesopore molecular sieve can be used for business by Rive technologies now, and have very well in the cracking process of vacuum gas
Performance.But template to be present expensive for the above method, building-up process step is complicated, and exists and be separated etc. no
Foot.
(K.Na,C.Jo,J.Kim,K.Cho,J.Jung,Y.Seo,R.J.Messinger,B.F.Chmelka,R.Ryoo,
Directing Zeolite Structures into Hierarchically Nanoporous Architectures,
Science 333(2011)328.)
The content of the invention
The purpose of the present invention be overcome it is expensive during the existing synthesis multi-stage ordered mesoporous molecular sieve of prior art,
Process is complicated, the problem of effect difference, there is provided a kind of direct synthesis method of simple and effective multi-stage ordered mesoporous molecular sieve.
Technical scheme is summarized as follows：
A kind of direct synthesis method of multi-stage ordered mesoporous molecular sieve, comprises the following steps：By template cetyl three
Methyl bromide ammonium is put into water, is warming up to 65-75 DEG C, dissolving, is added silicon source, alkali and silicon source, be cooled to room temperature, stirs 0.5-
1.5 hours, the coagulant liquid after aging is obtained, is transferred in stainless steel water thermal synthesis reactor and seals, under the conditions of 90-110 DEG C
Crystallization 3-4 days, then it is warming up to 150-160 DEG C of crystallization 5-7 days, centrifugation, solid is washed with water, dries, calcined, obtains multilevel ordered
Mesopore molecular sieve；
The template cetyl trimethylammonium bromide, silicon source, the mol ratio of alkali and silicon source are 6:2-70:1-30:
0.1-10, the mass ratio of the template cetyl trimethylammonium bromide and water is 1：1000-1200；
Silicon source is preferably tetraethyl orthosilicate, waterglass, Silica hydrogel, sodium metasilicate or positive silicic acid propyl ester.
Alkali is preferably sodium hydroxide, potassium hydroxide or ammonium hydroxide.
Silicon source is preferably sodium aluminate, aluminum sulfate, tert-butyl group aluminium or aluminium isopropoxide.
Beneficial effect
The present invention uses traditional template cetyl trimethylammonium bromide (CTAB), is closed using simple and effective hydro-thermal
Into method, successfully synthesize multi-stage ordered mesoporous molecular sieve, reduce production cost, technical process is easy and effective, is adapted to industry
Metaplasia is produced.Prepared multi-stage ordered mesoporous molecular sieve has MFI micropores and MCM-41 meso-hole structures, and there is the mesoporous of height to have
Sequence, there is high hydrothermal stability and mechanical stability, there is acid advantage, there is good catalytic activity, can be catalyzed more
Kind macromolecular reaction, such as benzaldehyde and the reaction of 2- hydroxy acetophenones generate flavanones and the condensation of 2- hydroxylated chalcones is anti-
Should, reaction conversion ratio can reach 85%, substantially increase the conversion ratio of reaction.The multilevel ordered mesopore prepared simultaneously in the present invention
Porous molecular sieve can be applied to the field such as petrochemical industry, the preparation of fine chemicals.Its special pore passage structure can be wide
It is general to be applied to the separation field such as adsorbing separation, UF membrane.
Brief description of the drawings
The XRD of Fig. 1 multi-stage ordered mesoporous molecular sieves.
The N of Fig. 2 multi-stage ordered mesoporous molecular sieves2Adsorption/desorption curve and graph of pore diameter distribution.
The SEM figures of Fig. 3 multi-stage ordered mesoporous molecular sieves.
The TEM figures of Fig. 4 multi-stage ordered mesoporous molecular sieves
Embodiment
Below by specific embodiment, the present invention is further illustrated.
Embodiment 1
A kind of direct synthesis method of multi-stage ordered mesoporous molecular sieve, comprises the following steps：By template cetyl three
Methyl bromide ammonium (CTAB) is put into water, is warming up to 70 DEG C, dissolving, is added tetraethyl orthosilicate, sodium hydroxide and aluminum sulfate, drop
Warm to room temperature, stir 1 hour, obtain the coagulant liquid after aging, be transferred in stainless steel water thermal synthesis reactor and seal, 110
Crystallization 3 days under the conditions of DEG C, then be warming up to 160 DEG C of crystallization 5 days, centrifugation, solid is washed with water, dried, 550 DEG C of calcinings 6 hours, obtains
To multi-stage ordered mesoporous molecular sieve；
The template cetyl trimethylammonium bromide, tetraethyl orthosilicate, the mol ratio of sodium hydroxide and aluminum sulfate
For 6:2:1:1, the mass ratio of the template cetyl trimethylammonium bromide and water is 1：1100；See Fig. 1, Fig. 2, Fig. 3, figure
4。
The Aldol condensation reaction of flavanones and 2- hydroxylated chalcones is generated for benzaldehyde and the reaction of 2- hydroxy acetophenones, instead
It is 85% to answer conversion ratio.
Embodiment 2
A kind of direct synthesis method of multi-stage ordered mesoporous molecular sieve, comprises the following steps：By template cetyl three
Methyl bromide ammonium is put into water, is warming up to 65 DEG C, dissolving, is added sodium metasilicate, potassium hydroxide and sodium aluminate, be cooled to room temperature, stir
Mix 1.5 hours, obtain the coagulant liquid after aging, be transferred in stainless steel water thermal synthesis reactor and seal, it is brilliant under the conditions of 100 DEG C
Change 3 days, increase the temperature to 155 DEG C of crystallization 6 days, centrifugation, solid is washed with water, dried, 550 DEG C of calcinings 6 hours, and obtaining multistage has
Sequence mesopore molecular sieve；
The template cetyl trimethylammonium bromide, sodium metasilicate, the mol ratio of potassium hydroxide and sodium aluminate are 6:50:
20:0.1, the mass ratio of the template cetyl trimethylammonium bromide and water is 1：1000.
The Aldol condensation reaction of flavanones and 2- hydroxylated chalcones is generated for benzaldehyde and the reaction of 2- hydroxy acetophenones, instead
It is 83.2% to answer conversion ratio.
Embodiment 3
A kind of direct synthesis method of multi-stage ordered mesoporous molecular sieve, comprises the following steps：By template cetyl three
Methyl bromide ammonium is put into water, is warming up to 75 DEG C, dissolving, is added waterglass, ammonium hydroxide and tert-butyl group aluminium, be cooled to room temperature,
Stirring 0.5 hour, obtains the coagulant liquid after aging, is transferred in stainless steel water thermal synthesis reactor and seals, under the conditions of 90 DEG C
Crystallization 4 days, then be warming up to 150 DEG C of crystallization 7 days, centrifugation, solid is washed with water, dried, 550 DEG C of calcinings 6 hours, obtains multistage
Ordered mesoporous molecular sieve；
The template cetyl trimethylammonium bromide, waterglass, the mol ratio of ammonium hydroxide and tert-butyl group aluminium are 6:
70:30:10, the mass ratio of the template cetyl trimethylammonium bromide and water is 1：1200.
The Aldol condensation reaction of flavanones and 2- hydroxylated chalcones is generated for benzaldehyde and the reaction of 2- hydroxy acetophenones, instead
It is 82.1% to answer conversion ratio.
The waterglass of the present embodiment is substituted with Silica hydrogel or positive silicic acid propyl ester respectively, other same the present embodiment, is prepared a kind of
Multi-stage ordered mesoporous molecular sieve.
The tert-butyl group aluminium of the present embodiment is substituted with aluminium isopropoxide, other same the present embodiment, is prepared a kind of multilevel ordered mesoporous
Molecular sieve.
Claims (4)
- A kind of 1. direct synthesis method of multi-stage ordered mesoporous molecular sieve, it is characterized in that comprising the following steps：By template 16 Alkyl trimethyl ammonium bromide is put into water, is warming up to 65-75 DEG C, dissolving, is added silicon source, alkali and silicon source, be cooled to room temperature, stirs 0.5-1.5 hours, the coagulant liquid after aging is obtained, be transferred in stainless steel water thermal synthesis reactor and seal, in 90-110 DEG C of bar Crystallization 3-4 days under part, then it is warming up to 150-160 DEG C of crystallization 5-7 days, centrifugation, solid is washed with water, dries, calcined, and obtains multistage Ordered mesoporous molecular sieve；The template cetyl trimethylammonium bromide, silicon source, the mol ratio of alkali and silicon source are 6:2-70:1-30:0.1-10, The mass ratio of the template cetyl trimethylammonium bromide and water is 1：1000-1200.
- 2. according to the method for claim 1, it is characterized in that the silicon source is tetraethyl orthosilicate, waterglass, Silica hydrogel, silicon Sour sodium or positive silicic acid propyl ester.
- 3. according to the method for claim 1, it is characterized in that the alkali is sodium hydroxide, potassium hydroxide or ammonium hydroxide.
- 4. according to the method for claim 1, it is characterized in that source of aluminium is sodium aluminate, aluminum sulfate, tert-butyl group aluminium or isopropyl Aluminium alcoholates.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108448034A (en) * | 2018-02-05 | 2018-08-24 | 合肥国轩高科动力能源有限公司 | A kind of Low ESR lithium battery diaphragm and preparation method thereof |
| CN109482144A (en) * | 2018-12-29 | 2019-03-19 | 山东华泰纸业股份有限公司 | A kind of desulfurization removes the preparation method of carbon adsorbent |
| CN109482145A (en) * | 2018-12-29 | 2019-03-19 | 山东华泰纸业股份有限公司 | A kind of micro/nano level removes the preparation method of carbon adsorbent |
| CN115212732A (en) * | 2021-04-20 | 2022-10-21 | 大连理工大学 | Preparation method and application of MFI molecular sieve membrane with excellent gas separation performance |
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| CN1762806A (en) * | 2004-10-21 | 2006-04-26 | 中国石油天然气股份有限公司 | Method for mesoporous molecular sieve overgrowth on microporous molecular sieve surface |
| CN101873997A (en) * | 2007-10-26 | 2010-10-27 | 埃克森美孚化学专利公司 | The manufacture method of M41S family molecular sieve |
| CN103058216A (en) * | 2012-11-05 | 2013-04-24 | 新疆大学 | Method for preparing mesoporous molecular sieve having crystal microporous wall |
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- 2017-08-30 CN CN201710763659.6A patent/CN107651693B/en not_active Expired - Fee Related
Patent Citations (3)
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| CN1762806A (en) * | 2004-10-21 | 2006-04-26 | 中国石油天然气股份有限公司 | Method for mesoporous molecular sieve overgrowth on microporous molecular sieve surface |
| CN101873997A (en) * | 2007-10-26 | 2010-10-27 | 埃克森美孚化学专利公司 | The manufacture method of M41S family molecular sieve |
| CN103058216A (en) * | 2012-11-05 | 2013-04-24 | 新疆大学 | Method for preparing mesoporous molecular sieve having crystal microporous wall |
Non-Patent Citations (1)
| Title |
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| KYUNGSU NA ET AL.: "Directing Zeolite Structures into Hierarchically Nanoporous Architectures", 《SCIENCE》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108448034A (en) * | 2018-02-05 | 2018-08-24 | 合肥国轩高科动力能源有限公司 | A kind of Low ESR lithium battery diaphragm and preparation method thereof |
| CN109482144A (en) * | 2018-12-29 | 2019-03-19 | 山东华泰纸业股份有限公司 | A kind of desulfurization removes the preparation method of carbon adsorbent |
| CN109482145A (en) * | 2018-12-29 | 2019-03-19 | 山东华泰纸业股份有限公司 | A kind of micro/nano level removes the preparation method of carbon adsorbent |
| CN115212732A (en) * | 2021-04-20 | 2022-10-21 | 大连理工大学 | Preparation method and application of MFI molecular sieve membrane with excellent gas separation performance |
| CN115212732B (en) * | 2021-04-20 | 2024-02-06 | 大连理工大学 | Preparation method and application of MFI molecular sieve membrane with excellent gas separation performance |
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