CN100480183C - Mesoporous-microporous composite material and synthesis method thereof - Google Patents
Mesoporous-microporous composite material and synthesis method thereof Download PDFInfo
- Publication number
- 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
- Authority
- CN
- China
- Prior art keywords
- molecular sieve
- mesoporous
- zeolite molecular
- zeolite
- composite material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000002131 composite material Substances 0.000 title claims abstract description 15
- 238000001308 synthesis method Methods 0.000 title 1
- 239000010457 zeolite Substances 0.000 claims abstract description 28
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 27
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000002808 molecular sieve Substances 0.000 claims abstract description 22
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000011148 porous material Substances 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 7
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims abstract description 5
- 238000001035 drying Methods 0.000 claims abstract description 4
- 239000007787 solid Substances 0.000 claims abstract description 4
- 238000005406 washing Methods 0.000 claims abstract description 4
- 230000032683 aging Effects 0.000 claims abstract description 3
- 239000002994 raw material Substances 0.000 claims abstract description 3
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 238000010189 synthetic method Methods 0.000 claims description 7
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 4
- 239000012634 fragment Substances 0.000 claims description 3
- 239000012452 mother liquor Substances 0.000 claims description 3
- 230000001105 regulatory effect Effects 0.000 claims description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- 150000001398 aluminium Chemical class 0.000 claims description 2
- 125000005842 heteroatom Chemical group 0.000 claims description 2
- 238000009992 mercerising Methods 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 230000002194 synthesizing effect Effects 0.000 abstract description 3
- 238000000034 method Methods 0.000 abstract description 2
- 239000002245 particle Substances 0.000 abstract description 2
- 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 abstract 1
- 229910002796 Si–Al Inorganic materials 0.000 abstract 1
- 239000007788 liquid Substances 0.000 abstract 1
- 238000005245 sintering Methods 0.000 abstract 1
- 229910052708 sodium Inorganic materials 0.000 abstract 1
- 239000011734 sodium Substances 0.000 abstract 1
- 229920002994 synthetic fiber Polymers 0.000 description 7
- 238000000634 powder X-ray diffraction Methods 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 4
- 239000013335 mesoporous material Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000006900 dealkylation reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 239000002594 sorbent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Landscapes
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Catalysts (AREA)
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.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CNB2007100100813A CN100480183C (en) | 2007-01-09 | 2007-01-09 | Mesoporous-microporous composite material and synthesis method thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CNB2007100100813A CN100480183C (en) | 2007-01-09 | 2007-01-09 | Mesoporous-microporous composite material and synthesis method thereof |
Publications (2)
Publication Number | Publication Date |
---|---|
CN101012061A CN101012061A (en) | 2007-08-08 |
CN100480183C true CN100480183C (en) | 2009-04-22 |
Family
ID=38699808
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CNB2007100100813A Expired - Fee Related CN100480183C (en) | 2007-01-09 | 2007-01-09 | Mesoporous-microporous composite material and synthesis method thereof |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN100480183C (en) |
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 and microporous 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 |
CN109790040B (en) * | 2017-07-14 | 2021-09-21 | 北京大学深圳研究生院 | Hierarchical structure hierarchical porous zeolite and preparation method thereof |
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 |
-
2007
- 2007-01-09 CN CNB2007100100813A patent/CN100480183C/en not_active Expired - Fee Related
Also Published As
Publication number | Publication date |
---|---|
CN101012061A (en) | 2007-08-08 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN104321280B (en) | Zeolite beta and manufacture method thereof | |
CN101186311B (en) | Y/MCM-48 composite molecular screen and preparation method thereof | |
CN100480183C (en) | Mesoporous-microporous composite material and synthesis method thereof | |
Hao et al. | n-Heptane catalytic cracking on ZSM-5 zeolite nanosheets: Effect of nanosheet thickness | |
CN101348262A (en) | Preparation of zeolite binderless ZSM-5 | |
CN105000573B (en) | Large block porous zeolite composed of nano-crystal grains and preparation method thereof | |
CN107519933B (en) | Y/EU-1/SBA-15/ASA/MOF composite material and preparation method thereof | |
CN104556125B (en) | A kind of isomorphous composite molecular screen and its preparation method and application | |
CN103030156B (en) | Preparation method of binderless ZSM-5 molecular sieve | |
Qi et al. | High activity in catalytic cracking of large molecules over a novel micro-micro/mesoporous silicoaluminophosphate | |
CN111333082A (en) | All-silicon H-Beta molecular sieve and preparation method and application thereof | |
CN103214006A (en) | Preparation method of composite zeolite with core/shell structure | |
Morawala et al. | TTAB mediated synthesis of Meso-H-BEA and its application in the production of n-butyl levulinate | |
CN108975349A (en) | A kind of compound ZSM-5 molecular sieve of macropore-micropore and its synthesis and application | |
Yang et al. | Preparation of nanocrystalline ZSM-5 and its catalytic performance in fast pyrolysis of cellulose to produce aromatic hydrocarbons | |
Król | Hydrothermal synthesis of zeolite aggregate with potential use as a sorbent of heavy metal cations | |
CN107021504B (en) | A kind of preparation method of mesoporous IM-5 molecular sieve | |
CN102060310B (en) | Preparation method of molecular sieve containing ZSM-5 zeolite secondary structure unit | |
CN104107719B (en) | Complex type molecular sieve containing metallic element and preparation method thereof | |
CN107519927B (en) | Y/ZSM-22/SAPO-34/ASA/MOF composite material and preparation method thereof | |
CN109775722A (en) | A kind of preparation method of multi-stage porous ZSM-5 nanometers of aggregates | |
CN105540605B (en) | A kind of method of synthesizing aluminum-enriched Beta zeolites | |
Jiao et al. | Nanocrystal zeolite Y assembly synthesized with CTAB under low gelling and aging temperature | |
CN102372278B (en) | Method for preparing binderless ZSM5/beta composite zeolite molecular sieve | |
Zhao et al. | Efficient and controllable synthesis of zeolite Beta nanospheres and hollow-boxes using a temperature-sensitive bifunctional additive |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C14 | Grant of patent or utility model | ||
GR01 | Patent grant | ||
C17 | Cessation of patent right | ||
CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20090422 Termination date: 20140109 |