CN100480183C - Mesoporous-microporous composite material and synthesis method thereof - Google Patents
Mesoporous-microporous composite material and synthesis method thereof Download PDFInfo
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- CN100480183C CN100480183C CNB2007100100813A CN200710010081A CN100480183C CN 100480183 C CN100480183 C CN 100480183C CN B2007100100813 A CNB2007100100813 A CN B2007100100813A CN 200710010081 A CN200710010081 A CN 200710010081A CN 100480183 C CN100480183 C CN 100480183C
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- molecular sieve
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- zeolite molecular
- zeolite
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Abstract
The invention discloses a dielectric hole-microhole composite material and synthesizing method in the inorganic porous material, adsorbing material and catalytic material technical domain, which comprises the following steps: adopting zeolite molecular sieve as raw material; reacting with sodium bisilicate solution under 30-60 deg.c for 10-300 min; disintegrating particle part of zeolite molecular sieve into piece with microhole structure; adding cetyl trimethyl ammonium bromide as molder; adjusting pH value of mother liquid to 10-12; aging 1-8h; adding in the high-pressure autoclave to do water heat synthesizing reaction at 80-130 deg.c for 24-72h; separating solid; washing; drying; sintering under 500-600 deg.c for 5-10h; obtaining the Si-Al porous material with dielectric hole and microhole composite structure.
Description
Technical field
The invention belongs to inorganic porous material, sorbing material and catalytic material technical field, relate to and have meso-hole structure and microvoid structure matrix material and synthetic method thereof.
Technical background
Porous material can be used as the carrier of sorbent material and solid catalyst owing to its specific pore passage structure and very high specific surface area, is widely used in fields such as chemical industry, light industry, the energy, environmental protection and space flight.Porous material is divided into macropore, mesoporous and poromerics according to the size in aperture.Zeolite molecular sieve has specific pore passage structure, and port size belongs to the category of micropore, is typical poromerics.Because zeolite molecular sieve can change the skeleton and the surface properties of molecular sieve by ion-exchange, it is having very important application aspect micromolecular catalysis and the absorption.Such as, sial type zeolite molecular sieve can form B acid and L acid on the surface through proton exchange, and formed solid acid can be used for many catalyzed reactions.Yet because the duct of zeolite molecular sieve is narrower, big reactant molecule is difficult to utilize the internal surface area of porous material, thereby is not suitable for the catalyzed reaction that macromole participates in.
Early 1990s, the scientist of Mobil company has synthesized the mesopore molecular sieve (as MCM-41) with uniform pore size distribution and ad hoc structure.The characteristics of this series mesoporous material are, even aperture distribution and can regulate very high (the about 1000m of its specific surface area within the specific limits
2/ g), thereby absorption and the bulky molecular catalysis field show good application prospects.The shortcoming of this material is that thermostability and hydrothermal stability are relatively poor, and hole wall is a non-crystalline state, thereby has limited its application.
In recent years, some investigators' propositions will have the hole wall of the micro-pore zeolite introducing mesoporous material of good hydrothermal stability, not only can improve the thermostability and the hydrothermal stability of mesoporous material, and can produce surperficial strong acid center by proton exchange.The method of introducing micro porous molecular sieve has two kinds: (1) obtains the crystal seed or the nano-cluster of zeolite under the synthesis condition of micro-pore zeolite, change the composition and the pH value of system then, add the synthetic template of using of mesoporous material, synthesis condition according to mesopore molecular sieve carries out hydrothermal synthesis reaction, thereby obtains mesoporous-microporous composite molecular screen; (2) will synthesize good zeolite molecular sieve its structure of NaOH aqueous solution partial destruction, obtain zeolite molecular sieve nano particle and structure fragment, the pH value of regulation system and mother liquor are formed then, synthesis condition at mesopore molecular sieve carries out hydrothermal synthesis reaction then, thereby obtains mesoporous-microporous composite molecular screen.
Summary of the invention
The synthetic method that the purpose of this invention is to provide mesoporous-microporous composite material, the synthetic method of being invented can be used for the matrix material of synthetic multiple zeolite structured and meso-hole structure, and institute's synthetic material can have stronger acidity through proton exchange.
Technical scheme of the present invention is to be raw material with the zeolite molecular sieve, the aqueous solution with Starso reacted 10～300 minutes at 30～60 ℃, the particulate fraction of zeolite molecular sieve is dissociated form fragment with microvoid structure, add template (cetyl trimethylammonium bromide), regulating mother liquor pH value then is 10～12, aging 1～8 hour, add autoclave then and carry out hydrothermal synthesis reaction in 80～130 ℃.React after 24～72 hours, isolate solid, washing, drying then in 500～600 ℃ of roastings 5～10 hours, obtain having mesoporous and the sial porous material micropore composite structure.
Zeolite molecular sieve is the porous material with specific micropore topological framework, comprises sial series zeolite (Y type, X type, A type, ZSM-5, β, mercerising), phosphorus aluminium series zeolite, other heteroatom zeolites.The content of zeolite molecular sieve is 0～80% (quality).
Effect of the present invention and benefit are the matrix materials that the synthetic method of being invented can be used for synthetic multiple zeolite structured and meso-hole structure, institute's synthetic material can have stronger acidity through proton exchange, and its mesoporous passage can reduce the diffusional resistance of reactant or adsorption molecule, thereby has wide application prospect in absorption and catalytic field.
Description of drawings
Fig. 1 a and 1b are the transmission electron microscope photos of institute's synthetic mesoporous-microporous composite material.
Embodiment
Below be described in detail the specific embodiment of the present invention.
Synthesizing of mesoporous-microporous composite material
Be mixed with the aqueous solution that concentration is 20.4% (quality) with the Starso powder, measure 14 milliliters of this aqueous solution.Take by weighing 1.0 gram ZSM-5 zeolite molecular sieve (SiO
2/ Al
2O
3=26, the about 400nm of particle diameter), adds in the Starso aqueous solution, in 55 ℃ of reactions 30 minutes and put it in the mixture of ice and water quenching 10 minutes.72 milliliters of the aqueous solution (concentration 3.8% (quality)) that add cetyl trimethylammonium bromide (CTAB) then, the pH value to 11 of regulating above-mentioned mixed solution with 6M sulfuric acid.Then, wore out 2 hours under the intense agitation, change in the band teflon-lined stainless steel autoclave in 120 ℃ of reactions 48 hours.The solid product that obtains is through washing, drying, then in air in 550 ℃ of roastings 6 hours, obtain the white solid powder.
The characterization result of X-ray powder diffraction (XRD) shows that resultant white powder has the structure similar to MCM-41.From the photo (as accompanying drawing) of transmission electron microscope, can see that the synthetic material has one-dimensional mesoporous structure.The skeleton infrared spectrum characterization is the result show, this material contains the skeleton structure of micro-pore zeolite.Above-mentioned characterization result explanation, institute's synthetic material is a mesoporous-microporous composite material.
The hydrothermal stability test
Institute's synthetic material was boiled in boiling water 120 hours, determine its crystallinity change with XRD then.The diffraction peak intensity that XRD locates 2 ° of 2 θ ≈ changes very little, shows that the hydrothermal stability of material is very high.Place 100% water vapour in 600 ℃ of processing 2 hours institute's synthetic material, determine its crystallinity change with XRD then.The diffraction peak intensity that XRD locates 2 ° of 2 θ ≈ changes very little, shows that once more the hydrothermal stability of material is very high.
The acid evaluation
The synthetic material NH of 1M
4NO
3The aqueous solution (1 gram sample/10 ml solns) 70 ℃ of ion-exchanges 2 hours, filter, exchange twice continuously, then 500 ℃ of roastings 3 hours, obtain the mesoporous-microporous composite material of proton exchange.This material is used for the dealkylation reaction of isopropyl benzene, and its activity is active 4 times of total silicon MCM-41, shows that this material has stronger surface acidity.
Claims (2)
1. the synthetic method of a mesoporous-microporous composite material, it is characterized in that with the zeolite molecular sieve being raw material, the aqueous solution with Starso reacted 10～300 minutes at 30～60 ℃, the particulate fraction of zeolite molecular sieve is dissociated form fragment with microvoid structure, add the template cetyl trimethylammonium bromide, regulating mother liquor pH value then is 10～12, aging 1～8 hour, adds autoclave then and carries out hydrothermal synthesis reaction in 80～130 ℃; React after 24～72 hours, isolate solid, washing, drying then in 500～600 ℃ of roastings 5～10 hours, obtain having mesoporous and the sial porous material micropore composite structure; Wherein zeolite molecular sieve is Y type, X type, A type, ZSM-5, β, mercerising, phosphorus aluminium series zeolite or other heteroatom zeolite.
2. the synthetic method of a kind of mesoporous-microporous composite material according to claim 1 is characterized in that it is greater than 0 to 80% that zeolite molecular sieve adds mass percent.
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| Application Number | Priority Date | Filing Date | Title |
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| CNB2007100100813A CN100480183C (en) | 2007-01-09 | 2007-01-09 | Mesoporous-microporous composite material and synthesis method thereof |
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| CNB2007100100813A CN100480183C (en) | 2007-01-09 | 2007-01-09 | Mesoporous-microporous composite material and synthesis method thereof |
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| CN100480183C true CN100480183C (en) | 2009-04-22 |
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101863491B (en) * | 2009-04-15 | 2011-09-07 | 中国石油天然气股份有限公司 | Preparation method of L/MCM-41 mesoporous composite molecular sieve |
| CN103100399B (en) * | 2011-11-11 | 2015-04-01 | 中国石油化工股份有限公司 | Preparation method of mesoporous-microporous composite molecular sieve |
| CN104843732B (en) * | 2015-05-12 | 2017-01-25 | 重庆理工大学 | Method for synthesizing high-hydrothermal-stability mesoporous MCM-41 molecular sieve by using MOR desiliconization |
| CN107686119B (en) * | 2016-08-03 | 2020-01-31 | 武汉理工大学 | hierarchical porous silicon-aluminum molecular sieve nanoclusters and preparation method thereof |
| WO2019010700A1 (en) * | 2017-07-14 | 2019-01-17 | 北京大学深圳研究生院 | Multi-pore zeolite having layered structure and preparation method therefor |
| CN114768748A (en) * | 2022-04-22 | 2022-07-22 | 山东亮剑环保新材料有限公司 | Preparation method of all-silicon micro-mesoporous composite molecular sieve VOCs adsorbent |
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