CN1613764A - Preparation for SBA-15 molecular sieve - Google Patents
Preparation for SBA-15 molecular sieve Download PDFInfo
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- CN1613764A CN1613764A CN 200410096184 CN200410096184A CN1613764A CN 1613764 A CN1613764 A CN 1613764A CN 200410096184 CN200410096184 CN 200410096184 CN 200410096184 A CN200410096184 A CN 200410096184A CN 1613764 A CN1613764 A CN 1613764A
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- sba
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- molecular sieve
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Abstract
Production of SBA-15 molecular screen is characterized by big aperture, high order degree and small specific superficial area. It is adjusted in raw material choose, proportioning design and parameter determination etc. and can be used for functional material with high specific superficial area.
Description
Technical field
That the present invention relates to is a kind of mesoporous material preparation method, belongs to the fine chemistry industry manufacturing technology field of relevant inorganic functional material.
Background technology
Molecular sieve is that a class has the material of selecting adsorption property, and it comprises solid crystallne material and the amorphous material with various compositions and permeability, and said permeability is meant nano-scale duct and the hole with even aperture distribution.Be mainly used in the aspects such as mineralising, chromosorb and bioseparation of absorption, catalysis, molecule assembling, electron device.Chemical constitution is (SiO
2) the siliceous SBA-15 molecular sieve of n is that to adopt triblock copolymer be template, a class mesoporous material that in acid synthetic system, prepares, aperture size is the molecular screen material of current aperture maximum in 4.6～30nm scope, pore volume can reach 0.85cm
3More than/the g.A known technology relevant with the present invention sees publication at China's " SCI " 2000,21 (1): 21～23, one piece of article (author Sun Jinyu, Zhao Dongyuan) that is entitled as " the high degree of order big-pore mesoporous molecular sieve of ' bagel ' shape SBA-15 synthetic ".This is a SBA-15 molecular sieve preparation method that is called as the cosolvent method.In the method, use N, dinethylformamide (code name is DMF) is done cosolvent, and the triblock copolymer template that is adopted is poly-oxyethylene ether-poly-propylene oxide ether-poly-oxyethylene ether, and silicon source raw material is tetraethoxy (code name is TEOS).The example that its detailed process is described is, the 2g template is dissolved among 45g distilled water and the 30g HCl (4mol/L), add the 15g cosolvent down at 40 ℃, after stirring 1h, add the 4.45g tetraethoxy, behind 40 ℃ of following stirring reaction 1d, filter, at air drying, resulting white solid product is a kind of SBA-15 molecular screen material under room temperature.Can be 500 ℃ of following roastings, thoroughly to dispel template.Because the adding of cosolvent makes aperture, the duct d value of product increase to 11.0nm by 9.6nm, pore volume is also by 1.3cm
3/ g increases to 1.45cm
3/ g, but, specific surface area is by 710m
2/ g is reduced to 700m
2/ g.
Summary of the invention
Purposes such as catalysis wish that the molecular screen material specific surface area is the bigger the better, and so, SBA-15 molecular sieve its specific surface area prepared by above-mentioned known technology only has 700m
2/ g obviously can not fully satisfy the requirement of this respect.Have the SBA-15 molecular screen material that can satisfy the specific surface area of purposes needs such as catalysis in order to prepare, we have invented the preparation method of a kind of SBA-15 molecular sieve of the present invention.
The present invention realizes like this, select parents' triblock copolymer poly-1 for use, 2-ethylidene glycol-polypropylene glycol-poly-1,2-ethylidene glycol (being abbreviated as T) is a template, selecting positive tetraethyl orthosilicate (code name is TEOS) for use is silicon source raw material, be dissolved in deionized water and the hydrochloric acid soln template and stirring, simultaneously silicon source raw material added the formation homogeneous phase solution lentamente, the initial mol ratio of each material is T: TEOS: HCl: H
2O=1: 59: 348: 2417, in this mixing solutions, add acetic acid again, this mixing solutions is continued to stir 20～30 hours under 30～50 ℃ of temperature, it is 90～110 ℃ in temperature then, be covered with in the reactor of plastic crystallization 1～2 day, the crystalline product that obtains is filtered, use deionized water wash, at room temperature dry, then in the air of static state in 500～600 ℃ of temperature lower calcinations 20～30 hours, thoroughly remove template, promptly obtain the siliceous SBA-15 molecular screen material of white powder.
Different with known technology is that we select for use parents' triblock copolymer to gather 1,2 ethylene glycol-polypropylene glycol-poly-1,2 ethylene glycol is template, rather than poly-oxyethylene ether-poly-propylene oxide ether-poly-oxyethylene ether; Do not add cosolvent; Adopt deionized water, rather than distilled water; Added acetic acid in addition; Be provided with a special crystallization process; At last, determine a calcination stage.Because these all differences, and in the difference of concrete processing parameter such as proportioning, temperature, time, make that the molecular screen material by the present invention's method preparation has had our desired techniques parameter.After testing, compared to the prior art, the aperture is reduced to 8.14nm, than the also little 1.46nm of 9.6nm of known technology, and the corresponding 1.059cm that is reduced to of pore volume
3/ g, and specific surface area can reach 1035.7m
2/ g has increased 335.7m
2/ g, amplification reaches 48%.Obtain beyond thought effect, realized purpose of the present invention.This effect can be by the N of prepared SBA-15 sieve sample
2Attached thermoisopleth of absorption-desorption and corresponding calculation result thereof show, see shown in the accompanying drawing, it among the figure a kind of typical IV type thermoisopleth, representing the adsorpting type of typical mesoporous material, the mean pore size that can calculate the SBA-15 molecular sieve from absorption and desorption isotherm is 8.14nm, pore volume 1.059cm
3G
-1, specific surface area is 1035.7m
2/ g; Define IV class adsorption-desorption curve according to IUPAC, sample demonstrates H1 kind of hysteresis ring, illustrates that the SBA-15 molecular sieve that makes has the mesopore molecular sieve capillary adsorption phenomena that the homogeneous duct distributes, and has one dimension column pore passage structure.
Description of drawings
Accompanying drawing is represented is the N of prepared SBA-15 sieve sample
2The attached thermoisopleth of absorption-desorption, transverse axis is a relative pressure, i.e. P/P
0, vertical pivot is the adsorption volume under the standard pressure (STP), unit is cm
3/ g, curve 1 is an adsorption isothermal line among the figure, curve 2 is desorption thermoisopleths.
Embodiment
Illustrate the present invention's method below, triblock copolymer poly-(1 with the 2g parents, the 2-ethylidene glycol)-block-poly-(propylene glycol)-block-poly-(1,2 ethylene glycol) (molecular-weight average 5800 is abbreviated as T) is dissolved in the 15g deionized water and 60g concentration is 2molL
-1Hydrochloric acid soln in and stir, add the positive tetraethyl orthosilicate of 4.25g (TEOS) simultaneously lentamente, form homogeneous phase solution, the initial mol ratio of each material is T: TEOS: HCl: H
2O=1: 59: 348: 2417, in this mixing solutions, add 10g acetic acid again, as the guiding auxiliary agent, this mixing solutions continues to stir 24 hours under 40 ℃ of temperature, be 100 ℃ in temperature then, be covered with in the reactor of plastic crystallization 2 days, afterwards, the crystalline product that obtains is filtered, use deionized water wash, at room temperature dry, then in the air of static state in 550 ℃ of temperature lower calcinations 24 hours, thoroughly to remove triblock copolymer, promptly get siliceous SBA-15 molecular sieve white powder at last.
Claims (2)
1, a kind of preparation method of SBA-15 molecular sieve, the raw material that adopts comprises template, silicon source raw material, strong acid solution, preparation process comprises produces homogeneous phase solution, crystallization, calcining, processing parameter comprises proportioning, temperature, time, process means comprises mixing, stir, heating, washing, dry, calcining, it is characterized in that, select parents' triblock copolymer poly-1 for use, 2-ethylidene glycol-polypropylene glycol-poly-1,2-ethylidene glycol (being abbreviated as T) is a template, selecting positive tetraethyl orthosilicate (code name is TEOS) for use is silicon source raw material, be dissolved in deionized water and the hydrochloric acid soln template and stirring, simultaneously silicon source raw material is added the formation homogeneous phase solution lentamente, the initial mol ratio of each material is T: TEOS: HCl: H
2O=1: 59: 348: 2417, in this mixing solutions, add acetic acid again, this mixing solutions is continued to stir 20～30 hours under 30～50 ℃ of temperature, it is 90～110 ℃ in temperature then, be covered with in the reactor of plastic crystallization 1～2 day, the crystalline product that obtains is filtered, use deionized water wash, at room temperature dry, then in the air of static state in 500～600 ℃ of temperature lower calcinations 20～30 hours, thoroughly remove template, promptly obtain the siliceous SBA-15 molecular screen material of white powder.
2, the preparation method of SBA-15 molecular sieve according to claim 1 is characterized in that, concentration of hydrochloric acid solution is 2molL
-1
Priority Applications (1)
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| CN 200410096184 CN1613764A (en) | 2004-12-01 | 2004-12-01 | Preparation for SBA-15 molecular sieve |
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| CN 200410096184 CN1613764A (en) | 2004-12-01 | 2004-12-01 | Preparation for SBA-15 molecular sieve |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN102039177A (en) * | 2009-10-23 | 2011-05-04 | 中国石油化工股份有限公司 | Zinc trifluoromethanesulfonate-loaded spherical mesoporous material, and preparation method and application thereof |
| CN101862675B (en) * | 2009-04-17 | 2012-02-29 | 中国石油化工股份有限公司 | Catalyst loaded with zinc trifluoromethanesulfonate, preparation method and application |
| CN101837983B (en) * | 2009-03-18 | 2012-03-07 | 中国石油天然气股份有限公司 | Method for synthesizing macroporous netlike spherical silicon dioxide material having mesoscopic structure |
| CN108557837A (en) * | 2018-01-23 | 2018-09-21 | 福州大学 | A kind of preparation method of the SBA-15 porous membranes with vertical channel |
| CN110156038A (en) * | 2019-05-31 | 2019-08-23 | 中国科学院广州能源研究所 | A kind of micropore-mesopore-macropore multi-stage porous SBA-15 molecular sieve and its preparation method and application |
-
2004
- 2004-12-01 CN CN 200410096184 patent/CN1613764A/en active Pending
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN101837983B (en) * | 2009-03-18 | 2012-03-07 | 中国石油天然气股份有限公司 | Method for synthesizing macroporous netlike spherical silicon dioxide material having mesoscopic structure |
| CN101862675B (en) * | 2009-04-17 | 2012-02-29 | 中国石油化工股份有限公司 | Catalyst loaded with zinc trifluoromethanesulfonate, preparation method and application |
| CN102039177A (en) * | 2009-10-23 | 2011-05-04 | 中国石油化工股份有限公司 | Zinc trifluoromethanesulfonate-loaded spherical mesoporous material, and preparation method and application thereof |
| CN102039177B (en) * | 2009-10-23 | 2013-03-27 | 中国石油化工股份有限公司 | Zinc trifluoromethanesulfonate-loaded spherical mesoporous material, and preparation method and application thereof |
| CN108557837A (en) * | 2018-01-23 | 2018-09-21 | 福州大学 | A kind of preparation method of the SBA-15 porous membranes with vertical channel |
| CN108557837B (en) * | 2018-01-23 | 2021-09-28 | 福州大学 | Preparation method of SBA-15 porous film with vertical pore channels |
| CN110156038A (en) * | 2019-05-31 | 2019-08-23 | 中国科学院广州能源研究所 | A kind of micropore-mesopore-macropore multi-stage porous SBA-15 molecular sieve and its preparation method and application |
| CN110156038B (en) * | 2019-05-31 | 2020-09-08 | 中国科学院广州能源研究所 | Microporous-mesoporous-macroporous hierarchical pore SBA-15 molecular sieve and preparation method and application thereof |
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