CN103482634A - Preparation method of silicon-based dual mesoporous material - Google Patents
Preparation method of silicon-based dual mesoporous material Download PDFInfo
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- CN103482634A CN103482634A CN201310405194.9A CN201310405194A CN103482634A CN 103482634 A CN103482634 A CN 103482634A CN 201310405194 A CN201310405194 A CN 201310405194A CN 103482634 A CN103482634 A CN 103482634A
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Abstract
The invention discloses a preparation method of a silicon-based dual mesoporous material. The silicon-based dual mesoporous material is prepared by taking P123 and F127 as template agents through a respective reaction and common crystallization method. Compared with a colloidal sol-gel dual template method, the method provided by the invention has the advantages of being simple and convenient, strong in controllability and easy to operate, nearly one half of work hours is saved, and the combined efficiency is greatly improved; the silicon-based dual mesoporous material has double-peak pore size distribution, the pore diameter of a small mesoporous is about 5nm, the pore diameter of a large mesoporous is about 10-15nm, the silicon-based dual mesoporous material has great potential application values when being taken as a catalyst in the heavy oil processing and taken as an adsorbent in oil product rectification.
Description
One, technical field
The invention belongs to field of material synthesis technology, be specifically related to a kind of preparation method of silica-based double-mesoporous material.
Two, background technology
Silica-based double-mesoporous material has the special pore structure of different grades and individual aperture distribution, two trepannings are mesoporous, the larger mesoporous adsorbate that is conducive to guide, reactant more easily enters and is littlely mesoporously adsorbed or react (this be little mesoporous material can not and), less mesoporous provide larger specific surface area (this be mesoporous greatly, large pore material can not and), this structure is conducive to improve the dispersity of rate of diffusion and metal.Have and report after silica-based double-mesoporous material load C o reactive metal and can not only increase significantly the dispersiveness of Co, can also effectively accelerate the transmission of material in F-T building-up reactions system, thereby obtain the catalytic activity higher than single mesoporous catalyst.The Ni/SiO that utilizes the strong acid corrodibility of chloroazotic acid to prepare
2two mesoporous catalysts have very high catalytic activity to the alkylation of carbonic acid gas.The SiO that uses sol-gel method to prepare
2two mesoporous carriers show than the higher activity of business Pd catalyzer after load P d in the reaction of 2-Hydrogenation of butanol.Therefore silica-based double-mesoporous material has huge development potentiality at the producer mask of petrochemical complex, fine chemistry industry, pharmaceutical industry and extraordinary polymeric material.
About the research of silica-based double-mesoporous material, at present still in the desk study stage, studying more is sol-gel process, comprises single template and two template, single template is similar to single mesoporous material building-up process, but need to add auxiliary agent, and preparation condition is usually more responsive, wayward.Two template adopt the synthetic pair mesoporous silicons that obtain of two kinds of template two steps, at first adopt the single mesoporous silicon based material of traditional method preparation, then add the template Hydrothermal Synthesis mesoporous greatly, also can adopt solvent evaporation guiding to generate two mesoporous, there is the operating process complexity in these methods, the shortcomings such as difficult control.
Three, summary of the invention
The purpose of this invention is to provide a kind of simple and conveniently, controllability is strong, the preparation method of the silica-based double-mesoporous material of easy handling.
For achieving the above object, the technical solution used in the present invention is: the method comprises the steps:
1. get template P123 and deionized water, be stirred under 45 ℃ of waters bath with thermostatic control fully and dissolve, then in this solution, add concentrated hydrochloric acid, continue to stir 0.5 hour, dropwise drip tetraethyl orthosilicate, continue to stir, obtain the oyster white suspension liquid;
2. get template F127 and deionized water, be stirred under 40 ℃ of waters bath with thermostatic control fully and dissolve, then in this solution, add concentrated hydrochloric acid, continue to stir 0.5 hour, add Na
2sO
410H
2o, after 2 hours, dropwise drip tetraethyl orthosilicate, continues to stir, and obtains the oyster white suspension liquid;
3. by step 1. with step 2. two suspension liquids of gained be mixed in same crystallization bottle, after stirring by bottle sealing, 100 ℃ of lower crystallization 24 hours, take out and be cooled to room temperature after crystallization, then suction filtration repeatedly cleaning to neutrality with deionized water, by the sample after suction filtration under 100 ℃ dry 12 hours, 500 ℃ of lower roastings obtained silica-based double-mesoporous material product in 5 hours.
The mass ratio of above-mentioned template P123 and template F127 is 1:1-1:4.
Above-mentioned steps 1. middle quality of material ratio is template P123: deionized water: concentrated hydrochloric acid: tetraethyl orthosilicate=0.8-1:20-29:4-8:1.8-2.4.
Above-mentioned steps 2. middle quality of material ratio is template F127: deionized water: concentrated hydrochloric acid: tetraethyl orthosilicate: Na
2sO
410H
2o=0.8-1:18-24:6-8:3.5-4.5:3-5.
1. above-mentioned steps continues churning time with step in 2. is 16-24 hour.
Above-mentioned steps 3. in the mixed churning time of two suspension liquids be 0-10 hour.
The mass concentration of the concentrated hydrochloric acid that 1. above-mentioned steps adds in 2. with step is 36%.
The inventive method is that to take P123 and F127 be template, adopt reaction respectively, the method of common crystallization prepares silica-based two mesoporous villages material, with colloidal sol-gel bimodulus plate method, compare, have simple and convenient, controlled strong, the advantage of easy handling, and save the closely man-hour of half, combined coefficient is greatly improved.The silica-based double-mesoporous material of gained has bimodal pore size distribution, and little mesoporous aperture is in the 5nm left and right, and large mesoporous aperture is in the 10-15nm left and right, and it all has great potential using value as catalyzer with in oil purification as sorbent material in heavy oil upgrading.
Four, accompanying drawing explanation
The XRD characterization result figure that Fig. 1 is the standby two mesoporous silicons of eutectic legal system.
Five, embodiment
Embodiment 1
1. get 1 g template P123, deionized water 24.5 g, put into the crystallization bottle, be stirred under 45 ℃ of waters bath with thermostatic control and dissolve (approximately 4 hours) fully, then in this solution, add the concentrated hydrochloric acid that the 6.3g mass concentration is 36%, regulate ph value<1, continue to stir 0.5 hour, dropwise drip 2.12 g tetraethyl orthosilicates (TEOS), continue to stir 20 hours, obtain the oyster white suspension liquid.
2. get 1g template F127 and 22.5g deionized water, put into the crystallization bottle, be stirred under 40 ℃ of waters bath with thermostatic control and dissolve (approximately 1 hour) fully, then in this solution, add the concentrated hydrochloric acid that the 7.5g mass concentration is 36%, continue to stir 0.5 hour, add 4.85g Na
2sO
410H
2o, after 2 hours, dropwise drip 4.2g tetraethyl orthosilicate (TEOS), continues to stir after 20 hours, obtains the oyster white suspension liquid.
3. above-mentioned two suspension liquids are mixed in same crystallization bottle, stir after 2 hours bottle sealing, 100 ℃ of lower crystallization 24 hours, take out and be cooled to room temperature after crystallization, then suction filtration repeatedly cleaning to neutral (ph=7) with deionized water, by the sample after suction filtration under 100 ℃ dry 12 hours, 500 ℃ of lower roastings obtained silica-based double-mesoporous material product in 5 hours.
Embodiment 2
1. get 0.5 g template P123, deionized water 12.3 g, put into the crystallization bottle, be stirred under 45 ℃ of waters bath with thermostatic control and dissolve (approximately 4 hours) fully, then in this solution, add the concentrated hydrochloric acid that the 3.15g mass concentration is 36%, regulate P one hour value<1, continue to stir 0.5 hour, dropwise drip 1.06 g tetraethyl orthosilicates (TEOS), continue to stir 16 hours, obtain the oyster white suspension liquid.
2. get 1.5g template F127 and 33.7g deionized water, put into the crystallization bottle, be stirred under 40 ℃ of waters bath with thermostatic control and dissolve (approximately 1 hour) fully, then in this solution, add the concentrated hydrochloric acid that the 11.25g mass concentration is 36%, continue to stir 0.5 hour, add 7.3g Na
2sO
410H
2o, after 2 hours, dropwise drip 6.3g tetraethyl orthosilicate (TEOS), continues to stir after 16 hours, obtains the oyster white suspension liquid.
3. above-mentioned two suspension liquids are mixed in same crystallization bottle, stir after 5 hours bottle sealing, 100 ℃ of lower crystallization 24 hours, take out and be cooled to room temperature after crystallization, then suction filtration repeatedly cleaning to neutral (ph=7) with deionized water, by the sample after suction filtration under 100 ℃ dry 12 hours, 500 ℃ of lower roastings obtained silica-based double-mesoporous material product in 5 hours.
Embodiment 3
1. get 1 g template P123, deionized water 28.0 g, put into the crystallization bottle, be stirred under 45 ℃ of waters bath with thermostatic control and dissolve (approximately 4 hours) fully, then in this solution, add the concentrated hydrochloric acid that the 0.2g mass concentration is 36%, regulate ph value<3, continue to stir 0.5 hour, dropwise drip 2.12 g tetraethyl orthosilicates (TEOS), continue to stir 16 hours, obtain the oyster white suspension liquid.
2. get 1g template F127 and 24.0g deionized water, put into the crystallization bottle, be stirred under 40 ℃ of waters bath with thermostatic control and dissolve (approximately 1 hour) fully, then in this solution, add the concentrated hydrochloric acid that the 6.0g mass concentration is 36%, continue to stir 0.5 hour, add 4.85g Na
2sO
410H
2o, after 2 hours, dropwise be added dropwise to the tetraethyl orthosilicate (TEOS) of 4.2g, continues to stir after 16 hours, obtains the oyster white suspension liquid.
3. above-mentioned two suspension liquids are mixed in same crystallization bottle, stir after 10 hours bottle sealing, 100 ℃ of lower crystallization 24 hours, take out and be cooled to room temperature after crystallization, then suction filtration repeatedly cleaning to neutral (ph=7) with deionized water, by the sample after suction filtration under 100 ℃ dry 12 hours, 500 ℃ of lower roastings obtained silica-based double-mesoporous material product in 5 hours.
As shown in the figure, the eutectic sample two stronger diffraction peaks occur at 0.8 ° and 1 ° (2 θ), the characteristic peak of corresponding two kinds of mesoporous (100) crystal faces, locate to occur two little diffraction peaks at 1.6 ° and 1.9 ° simultaneously, show that synthetic sample has the characteristic diffraction peak of typical two-dimentional hexagonal hole road structure, skeleton structure keeps good order.
Claims (7)
1. the preparation method of a silica-based double-mesoporous material, the method comprises the steps:
1. get template P123 and deionized water, be stirred under 45 ℃ of waters bath with thermostatic control fully and dissolve, then in this solution, add concentrated hydrochloric acid, continue to stir 0.5 hour, dropwise drip tetraethyl orthosilicate, continue to stir, obtain the oyster white suspension liquid;
2. get template F127 and deionized water, be stirred under 40 ℃ of waters bath with thermostatic control fully and dissolve, then in this solution, add concentrated hydrochloric acid, continue to stir 0.5 hour, add Na
2sO
410H
2o, after 2 hours, dropwise drip tetraethyl orthosilicate, continues to stir, and obtains the oyster white suspension liquid;
3. by step 1. with step 2. two suspension liquids of gained be mixed in same crystallization bottle, after stirring by bottle sealing, 100 ℃ of lower crystallization 24 hours, take out and be cooled to room temperature after crystallization, then suction filtration repeatedly cleaning to neutrality with deionized water, by the sample after suction filtration under 100 ℃ dry 12 hours, 500 ℃ of lower roastings obtained silica-based double-mesoporous material product in 5 hours.
2. the preparation method of a kind of silica-based double-mesoporous material according to claim 1, it is characterized in that: the mass ratio of described template P123 and template F127 is 1:1-1:4.
3. the preparation method of a kind of silica-based double-mesoporous material according to claim 1 and 2 is characterized in that: described step 1. in quality of material than being template P123: deionized water: concentrated hydrochloric acid: tetraethyl orthosilicate=0.8-1:20-29:4-8:1.8-2.4.
4. the preparation method of a kind of silica-based double-mesoporous material according to claim 1 and 2 is characterized in that: described step 2. in quality of material than being template F127: deionized water: concentrated hydrochloric acid: tetraethyl orthosilicate: Na
2sO
410H
2o=0.8-1:18-24:6-8:3.5-4.5:3-5.
5. the preparation method of a kind of silica-based double-mesoporous material according to claim 1 and 2 is characterized in that: 1. described step continues churning time with step in 2. is 16-24 hour.
6. the preparation method of a kind of silica-based double-mesoporous material according to claim 1 and 2 is characterized in that: described step 3. in the mixed churning time of two suspension liquids be 0-10 hour.
7. the preparation method of a kind of silica-based double-mesoporous material according to claim 1 and 2 is characterized in that: the mass concentration of the concentrated hydrochloric acid that 1. described step adds in 2. with step is 36%.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114195164A (en) * | 2020-09-17 | 2022-03-18 | 中国石油天然气股份有限公司 | Composite material with step pore structure distribution and preparation method thereof |
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| CN1304875A (en) * | 2000-11-28 | 2001-07-25 | 中国科学院山西煤炭化学研究所 | Composite dual-pure Si-Al molecular sieve and its preparing process |
| CN101811702A (en) * | 2010-04-16 | 2010-08-25 | 太原理工大学 | Double-mesopore silicon dioxide transparent gel monolith and preparation method thereof |
| CN101857234A (en) * | 2010-06-10 | 2010-10-13 | 天津大学 | Monodisperse mesoporous silicon dioxide hollow nano-microsphere and preparation method |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1304875A (en) * | 2000-11-28 | 2001-07-25 | 中国科学院山西煤炭化学研究所 | Composite dual-pure Si-Al molecular sieve and its preparing process |
| CN101811702A (en) * | 2010-04-16 | 2010-08-25 | 太原理工大学 | Double-mesopore silicon dioxide transparent gel monolith and preparation method thereof |
| CN101857234A (en) * | 2010-06-10 | 2010-10-13 | 天津大学 | Monodisperse mesoporous silicon dioxide hollow nano-microsphere and preparation method |
Non-Patent Citations (2)
| Title |
|---|
| OZLEM SEL ET AL.: "Principles of Hierarchical Meso- and Macropore Architectures by Liquid Crystalline and Polymer Colloid Templating", 《LANGMUIR》, vol. 22, 28 January 2006 (2006-01-28), pages 2311 - 2322 * |
| 郭翠梨: "双介孔材料的合成与应用研究进展", 《化工进展》, vol. 29, no. 3, 31 December 2010 (2010-12-31) * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114195164A (en) * | 2020-09-17 | 2022-03-18 | 中国石油天然气股份有限公司 | Composite material with step pore structure distribution and preparation method thereof |
| CN114195164B (en) * | 2020-09-17 | 2023-09-26 | 中国石油天然气股份有限公司 | Composite material with step hole structure distribution and preparation method thereof |
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