CN1113811C - Preparation method of mesonic pore molecular sieve carrier material - Google Patents
Preparation method of mesonic pore molecular sieve carrier material Download PDFInfo
- Publication number
- CN1113811C CN1113811C CN01126476A CN01126476A CN1113811C CN 1113811 C CN1113811 C CN 1113811C CN 01126476 A CN01126476 A CN 01126476A CN 01126476 A CN01126476 A CN 01126476A CN 1113811 C CN1113811 C CN 1113811C
- Authority
- CN
- China
- Prior art keywords
- molecular sieve
- preparation
- carrier material
- sieve carrier
- poly
- 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
Landscapes
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The present invention relates to a method for preparing a mesoporous molecular sieve carrier material by using diblock high molecular polymers, which belongs to the technical field of inorganic nano materials. In the preparation method, a polyoxirene-polyepoxy butylene biblock high molecular surface active agent used as a template agent is hydrothermally synthesized at a temperature of 100 DEG C under the acid conditions. The method is suitable for being used for preparing mesoporous silicon oxide materials in a two-dimensional hexagonal structure with a high degree of order and a large specific surface area, and lamellar silicon oxide materials with a high degree of order. The new materials can be used as catalysts, catalyst carriers, adsorption thin films, organic-inorganic composite materials, sensors, chromatogram fillers, etc.
Description
Technical field
The invention belongs to technical field of polymer materials, be specifically related to the preparation method of mesonic pore molecular sieve carrier material.
Technical background
By tensio-active agent as template direction synthetic mesoporous material in macromole conversion, catalysis, have a wide range of applications as fields such as the microminiaturization of the separation and purification of support of the catalyst, biomacromolecule, electron device and chromatogram weighting agents.
People have been template with various poly-oxyethylene-poly-propylene oxide-poly-oxyethylene (PE0-PPO-PEO) three block macromoleculars, synthesize a series of novel mesoporous materials.This is comprising six side (H
1), stratiform (L
α) and cube phase (I
1) symmetrical structure.But but do not appear in the newspapers in the literature as template synthetic silica nano-catalytic agent carrier with two block macromoleculars.Before do not succeed with the trial of PEO-PPO two block macromolecular synthetic silica hole materials.Tracing it to its cause, may be that the hydrophilic gender gap between two block macromolecular tensio-active agent blocks is too little, and synthetic medium acidity too high due to.
Summary of the invention
The objective of the invention is to use two block macromoleculars-poly-oxyethylene-poly-epoxy butylene (PEO-PBO) as template, synthesize the mesonic pore molecular sieve carrier material that the aperture is big, the degree of order is high.
The preparation method of the mesonic pore molecular sieve carrier material that the present invention proposes, be in strong acid media, with poly-oxyethylene-poly-epoxy butylene diblock polymer tensio-active agent is template, the method for synthetic silica mesopore molecular sieve under hydrothermal condition, and its concrete step is as follows:
1, the acquisition of mesopore molecular sieve gel: with the poly-oxyethylene of a certain amount of two block macromolecular tensio-active agents-poly-epoxy butylene (EO
mBO
n) join in the solution of acid, fully stirring, used tensio-active agent is 1 with the mol ratio of acid: 1500-1: 60000, stirring can be adopted magnetic stirring apparatus; After treating that it dissolves fully, add silicon source or aluminium source, the mol ratio of silicon source or aluminium source and tensio-active agent is 240: 1-5000: 1; Continue to stir, until there being a large amount of white precipitates to generate; The temperature of this moment remains on 15-80 ℃, specifically looks the difference of synthetic materials and changes;
2, hydrothermal treatment consists: will transfer in the water heating kettle of tetrafluoroethylene by the mixture that step 1 obtains, and leave standstill 8-72 hour at 80-150 ℃;
3, the acquisition of mesonic pore molecular sieve carrier material: the mixture that step 2 is obtained cools off under room temperature, filters then, washing, drying at room temperature; In 450-650 ℃ of roasting 4-6 hour, promptly obtain the solid support material of white powder again.
The solid support material of the present invention's preparation can be that silicon oxide changes reaction source, also can prepare aluminum oxide etc.
Among the present invention, the diblock polymer tensio-active agent that is adopted is EO
mBO
nThe tensio-active agent of class, m/n can change within the 5-0.5 scope, and molecular weight from 1000 to 100000 does not wait.
The silicon source of being adopted among the present invention can be for tetraethoxy, methyl silicate, just silicic acid propyl ester, sodium metasilicate and silicon sol is a kind of.
The acidic medium that is adopted among the present invention can be in hydrochloric acid, sulfuric acid, nitric acid and the hydrobromic aqueous solution a kind of.
Gained mesoporous material of the present invention is two dimension six side (H
1) and laminate structure (L
α).
The pore size of gained mesoporous material of the present invention is modulation by the m/n value that changes tensio-active agent, and scope can be from 3nm to 40nm.
Embodiment
Embodiment 1, a kind of preparation of SiO 2 mesoporous materials of hexagonal structure, and concrete steps are as follows: with 0.4 gram EO
16BO
10(BL50-1500) be dissolved in the hydrochloric acid of 30 gram 2M, at room temperature stir, treat that its dissolving back adds 3 gram tetraethoxysilances.After stirring 24 hours under the condition of room temperature, put into 100 ℃ baking oven, ageing 24 hours.Take out postcooling, filtration, washing, promptly obtain white solid, at room temperature dry; In retort furnace, just obtain final product after 6 hours at last in 550 ℃ of calcinations.Learn that through sign this material is that the duct has the Metaporous silicon dioxide material that two-dimentional hexagonal structure is arranged, unit cell parameters is 9.26 nanometer (d
100Value is 8.02 nanometers), have single aperture, the 902m that distributes of 6.0nm
2The high-specific surface area of/g and 1.03cm
3The pore volume of/g.Product after the roasting also has the macro morphology of spherical shape.These balls have unified diameter, about 3 microns.
Embodiment 2, a kind of preparation of stratiform earth silicon material: with 7 gram EO
16BO
10(BL50-1500) join in the 30 gram 2M sulfuric acid, at room temperature stir, treat that its dissolving back adds 3 gram tetraethoxysilances.After at room temperature stirring 24 hours, form uniform solution.This solution is transferred to air-dry a couple of days in the watch-glass.Its X-ray diffraction of product (XRD) collection of illustrative plates of this moment demonstrates three sharp-pointed diffraction peaks, and corresponding d value is respectively 8.82,4.41 and 3.01 nanometers, is typical laminate structure.With the solid collected in retort furnace in 600 ℃ of calcinations after 5 hours because polymer is removed, laminate structure is caved in, and causes the disappearance of all diffraction peaks then.
Embodiment 3, a kind of preparation of SiO 2 mesoporous materials of hexagonal structure, and concrete steps are as follows: with 0.4 gram EO
16BO
10(BL50-1500) be dissolved in the hydrochloric acid of 30 gram 2M, at room temperature stir, treat that its dissolving back adds 2.5 gram tetramethoxysilances.After stirring 15 hours under the condition of room temperature, put into 100 ℃ baking oven, ageing 24 hours.Take out postcooling, filtration, washing, promptly obtain white solid, at room temperature dry; In retort furnace, just obtain final product after 6 hours at last in 450 ℃ of calcinations.Learn that through sign this material is that the duct has the Metaporous silicon dioxide material that two-dimentional hexagonal structure is arranged, unit cell parameters is 9.32 nanometer (d
100Value is 8.07 nanometers), have single aperture, the 884m that distributes of 6.0nm
2The high-specific surface area of/g and 1.01cm
3The pore volume of/g.Product after the roasting also has the macro morphology of spherical shape.These balls have unified diameter, about 2.5 microns.
Embodiment 4, a kind of preparation of SiO 2 mesoporous materials of fibrous hexagonal structure, and concrete steps are as follows: with 0.4 gram EO
16BO
10(BL50-1500) be dissolved in the hydrochloric acid of 30 gram 2M, at room temperature stir, treat that its dissolving back adds the positive silicic acid fourth fat of 3 grams.After stirring 24 hours under the condition of room temperature, put into 100 ℃ baking oven, ageing 24 hours.Take out postcooling, filtration, washing, promptly obtain white solid, at room temperature dry; In retort furnace, just obtain final product after 4 hours at last in 600 ℃ of calcinations.Learn that through sign this material is that the duct has the Metaporous silicon dioxide material that two-dimentional hexagonal structure is arranged, unit cell parameters is 9.28 nanometer (d
100Value is 8.03 nanometers), have single aperture, the 842m that distributes of 6.0nm
2The high-specific surface area of/g and 0.97cm
3The pore volume of/g.Product after the roasting also has fibrous macro morphology.These fibers have the diameter of homogeneous, about 4 microns, have the higher diameter of axle simultaneously than (＞10).
Claims (4)
1, a kind of preparation method of mesonic pore molecular sieve carrier material is characterized in that concrete synthesis step is as follows:
(1) the poly-oxyethylene of a certain amount of two block macromolecular tensio-active agents-poly-epoxy butylene is joined in the solution of acid, fully stir, tensio-active agent is 1 with the mol ratio of acid: 1500-1: 60000; After treating that it dissolves fully, add silicon source or aluminium source, the mol ratio of aluminium source or silicon source and tensio-active agent is 240: 1-5000: 1; Stir, until there being a large amount of white precipitates to generate, the temperature of this moment remains on 15-80 ℃, obtains the mesopore molecular sieve gel;
(2) will transfer in the water heating kettle by the mixture that step 1 obtains, leave standstill 8-72 hour at 80-150 ℃;
(3) mixture that step 2 is obtained cools off under room temperature, filters then, washing, drying at room temperature; In 450-650 ℃ of roasting 4-6 hour, promptly obtain the solid support material of white powder again.
2, the preparation method of mesonic pore molecular sieve carrier material according to claim 1 is characterized in that m/n is within the 5-0.5 scope in the poly-oxyethylene of the tensio-active agent of being represented by EOmBOn-poly-epoxy butylene, and molecular weight is 1000 to 100000.
3, the preparation method of mesonic pore molecular sieve carrier material according to claim 1 is characterized in that the silicon source of being adopted is a kind of of tetraethoxy, methyl silicate, positive silicic acid propyl ester, sodium metasilicate and silicon sol.
4, the preparation method of mesonic pore molecular sieve carrier material according to claim 1 is characterized in that the acidic medium that is adopted is a kind of in hydrochloric acid, sulfuric acid, nitric acid and the hydrobromic aqueous solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN01126476A CN1113811C (en) | 2001-08-14 | 2001-08-14 | Preparation method of mesonic pore molecular sieve carrier material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN01126476A CN1113811C (en) | 2001-08-14 | 2001-08-14 | Preparation method of mesonic pore molecular sieve carrier material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1341553A CN1341553A (en) | 2002-03-27 |
| CN1113811C true CN1113811C (en) | 2003-07-09 |
Family
ID=4666492
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN01126476A Expired - Fee Related CN1113811C (en) | 2001-08-14 | 2001-08-14 | Preparation method of mesonic pore molecular sieve carrier material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1113811C (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10035131B2 (en) | 2011-11-24 | 2018-07-31 | Indian Institute Of Technology | Multilayer organic-templated-boehmite-nanoarchitecture for water purification |
| US10041925B2 (en) | 2012-04-17 | 2018-08-07 | Indian Institute Of Technology | Detection of quantity of water flow using quantum clusters |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100715296B1 (en) | 2003-07-29 | 2007-05-08 | 가부시끼가이샤 도꾸야마 | Fine mesoporous silica particles and production process thereof |
| CN1314722C (en) * | 2004-09-30 | 2007-05-09 | 中国科学院金属研究所 | Method for improving property of thermoplastic polymer material |
| CN100335410C (en) * | 2005-06-15 | 2007-09-05 | 浙江大学 | Process for synthesizing mesic-porous molecular sieve SBA15 |
| CN100383043C (en) * | 2005-06-15 | 2008-04-23 | 浙江大学 | Process for synthesizing mesic porous molecular sieve SBA-15 |
| CN101638239B (en) * | 2008-07-30 | 2012-05-23 | 中国石油大学(北京) | Silicon aluminum based mesoporous-microporous composite molecular sieve and synthetic method thereof |
| CN105085757B (en) * | 2014-04-22 | 2017-12-19 | 中国石油化工股份有限公司 | A kind of ethylene-alpha-olefin non-conjugated diene hydrocarbon copolymer and preparation method thereof |
| CN104892874B (en) * | 2015-05-25 | 2017-06-30 | 上海师范大学 | Ordered mesoporous polymer nanosphere, its preparation method and application with flexure type duct |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1184699A (en) * | 1997-09-29 | 1998-06-17 | 天津大学 | Mesopore molecular sieve inorganic composite film used for water purification |
| CN1266019A (en) * | 1999-03-03 | 2000-09-13 | 中国科学院山西煤炭化学研究所 | Process for synthesizing hydrophobic medium porous molecular sieve |
-
2001
- 2001-08-14 CN CN01126476A patent/CN1113811C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1184699A (en) * | 1997-09-29 | 1998-06-17 | 天津大学 | Mesopore molecular sieve inorganic composite film used for water purification |
| CN1266019A (en) * | 1999-03-03 | 2000-09-13 | 中国科学院山西煤炭化学研究所 | Process for synthesizing hydrophobic medium porous molecular sieve |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10035131B2 (en) | 2011-11-24 | 2018-07-31 | Indian Institute Of Technology | Multilayer organic-templated-boehmite-nanoarchitecture for water purification |
| US10041925B2 (en) | 2012-04-17 | 2018-08-07 | Indian Institute Of Technology | Detection of quantity of water flow using quantum clusters |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1341553A (en) | 2002-03-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104248990B (en) | The preparation method of the composite mesoporous carrier of spherical attapulgite and loaded catalyst and its preparation method and application and ethyl acetate | |
| CN1113811C (en) | Preparation method of mesonic pore molecular sieve carrier material | |
| CN104248980B (en) | The preparation method of spherical diatomite mesoporous composite material and loaded catalyst and its preparation method and application and ethyl acetate | |
| JP5911953B2 (en) | Mesoporous silica and organic silica materials and methods for producing them | |
| WO2020228400A1 (en) | Method for preparing two-dimensional ordered mesoporous nanosheet by inorganic salt interface-induced assembly | |
| CN104248991B (en) | The preparation method of the composite mesoporous carrier of spherical montmorillonite and loaded catalyst and its preparation method and application and ethyl acetate | |
| WO2009101110A9 (en) | Method for manufacturing mesoporous materials, materials so produced and use of mesoporous materials | |
| KR101906792B1 (en) | Process for producing inorganic particulate material | |
| CN104248981A (en) | Spherical composite carrier of three dimensional cube tunnel and catalyst, preparation method and application thereof, and preparation method of ethyl acetate | |
| CN101531375A (en) | Method for synthesizing bimodal silicon-aluminum mesoporous material | |
| CN1273382C (en) | Method for preparing Nano silicon dioxide | |
| CN105435853A (en) | Illite mesoporous composite material, supported catalyst and preparation method and application thereof and preparation method of cyclohexanone glyceryl ketal | |
| CN105236417B (en) | Spherical mesoporous silica with controllable particle size and preparation method of spherical mesoporous silica | |
| JP5382700B2 (en) | Rod-shaped porous silica particles | |
| CN103864032A (en) | Method for preparing nano-material | |
| CN106829992B (en) | A kind of method that green prepares SBA-15 mesopore molecular sieve | |
| CN101298335B (en) | Hollow mesopore molecular sieve big ball and preparation thereof | |
| CN110156038A (en) | A kind of micropore-mesopore-macropore multi-stage porous SBA-15 molecular sieve and its preparation method and application | |
| CN105435854B (en) | The preparation method of chlorite mesoporous composite material and loaded catalyst and its preparation method and application and cyclohexanone glycerol ketals | |
| CN110201718A (en) | A kind of preparation and application of red phosphorus/ferrous metals organic framework composite material | |
| CN109133144A (en) | A kind of preparation method of monodisperse ultra-small grain size ceria nano-crystalline | |
| CN104071802B (en) | The preparation method of the low silicone zeolite of a kind of multi-stage porous | |
| Yu et al. | Photocatalytic activity of different morphology BiPO4 supported on zeolite | |
| CN102285659B (en) | Ordered mesoporous silicon-dioxide material and preparation method thereof | |
| CN1169716C (en) | SiO2 molecular sieve with 3D pore canal and 2D mesopore structure and its synthesizing process |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |