CN102464321B - Preparation method for mesopore/macropore compound hole structure silica gel and silicon and aluminum oxide material - Google Patents
Preparation method for mesopore/macropore compound hole structure silica gel and silicon and aluminum oxide material Download PDFInfo
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- CN102464321B CN102464321B CN201010552101.1A CN201010552101A CN102464321B CN 102464321 B CN102464321 B CN 102464321B CN 201010552101 A CN201010552101 A CN 201010552101A CN 102464321 B CN102464321 B CN 102464321B
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Abstract
The invention relates to a preparation method for mesopore/macropore compound hole structure silica gel and silicon and aluminum oxide material, which mainly solves the problems of high gel temperature and long ageing time when the mesopore/macropore compound hole structure silica gel and silicon and aluminum oxide material is prepared in the prior art. The preparation method comprises the following steps: mixing phase separation inducer R1, structure-directing agent R2, acid catalyst and water; adding an organic silicon source or the mixture of the organic silicon source and an aluminum source to carry out full hydrolysis reaction at the temperature of 0-30DEG C, wherein the mass ratio of the mixture is as follows: R1/SiO2 is equal to 0.3-1.0, R2/SiO2 is equal to 0.3-2.0, H2O/SiO2 is equal to 4-7, H+/SiO2 is equal to 0.1-0.35, and Al2O3/SiO2 is equal to 0-0.85; pouring the mixture into a die; gelling the mixture at the room temperature; continuously standing and ageing for 0.1-10hours; demoulding an aged product; drying at the temperature of 20-100DEG C for 1-7 days; and then, after calcining at the temperature of 450-800DEG C for 0.5-24hours, preparing the macropore structure oxide material. The problems can be better solved by the technical scheme. The preparation method can be used for the industrial production of the mesopore/ macropore compound hole structure silica gel and silicon and aluminum oxide material.
Description
Technical field
The present invention relates to the preparation method of a kind of mesoporous/macroporous composite pore structural silicone and silicon-aluminum oxide material.
Background technology
In recent years organic molecule is combined with inorganic oxide, the synthetic novel porous material with special construction and character is subject to extensive concern.The composite holes material being comprised of mesoporous and macropore is also one of them study hotspot.Compare with common material, composite holes material is conducive to material transfer diffusion, thereby shows wide application prospect at absorption, separation and catalytic field.Patent CN 101525137A and CN 101723393A have reported respectively the preparation method of mesoporous/macroporous composite pore structural silicone and silicon-aluminum oxide material.Prepared material all has integrated macro morphology, has high specific surface area and flourishing gap structure.But also exist gelling temp high, the long problem of digestion time, we solve problems by changing the kind in silicon source.
Summary of the invention
Technical problem to be solved by this invention is that the gelling temp existing in prior art is high, and digestion time is grown problem, and the preparation method of a kind of new mesoporous/macroporous composite pore structural silicone and silicon-aluminum oxide material is provided.It is low that this mesoporous/macroporous composite pore structural silicone and silicon-aluminum oxide material have gelling temp, the advantage that digestion time is short.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is as follows: the preparation method of a kind of mesoporous/macroporous composite pore structural silicone and silicon-aluminum oxide material, comprises the following steps:
A) will be separated inductor R1, structure directing agent R2, acid catalyst and water mixes, and adds the mixture in organosilicon source or He Lv source, organosilicon source, at 0～30 ℃, sufficient hydrolysis reaction occurs, and mixture quality ratio consists of: R1/SiO
2=0.3～1.0; R2/SiO
2=0.3～2.0; H
2o/SiO
2=4～7; H
+/ SiO
2=0.1～0.35; Al
2o
3/ SiO
2=0～0.85;
B) said mixture is poured in mould, at room temperature gel, continues standing aging 0.1～10 hour;
C) by the aging after product demoulding, at 20～100 ℃, be dried, be 1～7 day time of drying, then 450～800 ℃ of roastings, makes macroporous structure oxide material after 0.5～24 hour, its specific surface is up to 750～1000 meters
2/ gram, pore volume is 0.9～1.8 meter
2/ gram, on three-dimensional space, there are two cover ducts: a set of is the co-continuous macroporous structure connecting, and aperture is at 0.05～8 micron; Another set of is to form in the inorganic skeleton of macropore to have regular mesopore orbit, is orderly six sides (P6mm) and distributes mutually, and aperture is adjustable continuously between 2～8 nanometers;
The inductor R1 that is wherein separated be selected from polyoxyethylene glycol, polyoxyethylene or polyethylene oxide at least one, its molecular-weight average is 3000～100000;
Structure directing agent R2 is selected from least one in triblock copolymer, chain alkyl trimethylammonium halogenation ammonia, citric acid, tartrate, oxysuccinic acid or lactic acid; Wherein triblock copolymer is polyoxyethylene-poly-oxypropylene polyoxyethylene, and its molecular-weight average is 1500～10000; The general formula of chain alkyl trimethylammonium halogenation ammonia is (CH
3)
nn
+(CH
3)
3x
-, n=8～18, X is Cl or Br.
In technique scheme, silicon source is selected from two (triethoxy is silica-based) methane, 1, at least one in two (trimethoxy the is silica-based) hexanes of 6-, Isosorbide-5-Nitrae-bis-(triethoxy is silica-based) benzene.Aluminium source is selected from least one in aluminum nitrate, aluminum chloride, Tai-Ace S 150, aluminum isopropylate or pseudo-boehmite.Acid catalyst is at least one in nitric acid, phosphoric acid, hydrochloric acid or acetic acid.Gel digestion time preferably 0.1～1 hour, continues to extend digestion time on reaction structure impact not quite.Ageing products is 450～800 ℃ of roasting time preferably 2～10 hours, continues to extend roasting time little on reaction structure impact.
In the present invention, adopted two template to control respectively mesoporous and generation macropore, the inductor R1 that is wherein separated plays and causes the effect that the co-continuous macropore that is separated and then leads generates in sol-gel process, and structure directing agent R2 mainly plays space occupy-place or by interacting and generate the lead effect of regular mesoporous generation of mesomorphic phase with silicon species.By the modulation to silicon source category, Template Types, add-on and reaction conditions, can to the meso/macroporous structure of product and pore size distribution, effectively regulate and control respectively.In experiment, our pleasantly surprised discovery adopts the alternative inorganic silicon of organosilicon source can make gelling temp from more than room temperature reducing to room temperature, and digestion time can reduce to 0.1 hour above by 24 hours.
Accompanying drawing explanation
Fig. 1 is the SEM photo of embodiment 1 sample.
Below by embodiment, the present invention is further elaborated.
Embodiment
[embodiment 1]
Weigh 15 grams of the hydrochloric acid solns of 1 mol/L, add 2.0 grams of polyoxyethylene-poly-oxypropylene polyoxyethylene (molecular weight 5000, P123) stirring and dissolving under room temperature adds 0.7 gram of polyoxyethylene glycol (molecular weight 10000) in mixing solutions, proceeds in frozen water mixing bath and continues to stir 5 minutes.In mixing solutions, add 5 gram 1, two (trimethoxy the is silica-based) hexanes of 6-, vigorous stirring, after 10 minutes, is poured mixed solution in mould into and is sealed, standing 0.1 hour of room temperature, the demoulding after taking out, drying at room temperature, finally 550 ℃ of roastings 5 hours.Fig. 1 is the SEM photo of product, shows that product has the co-continuous macroporous structure of perforation, and concrete texture parameter is: 951 meters of specific surface areas
2/ gram, pore volume is 1.5 centimetres 3/ gram, 0.2 micron of macropore diameter, mesoporous aperture 7 nanometers.
[embodiment 2]
Weigh 10 grams of the acetums of 0.5 mol/L, add 1.0 grams of polyoxyethylene-poly-oxypropylene polyoxyethylene (molecular weight 2000, P123) stirring and dissolving under room temperature, in mixing solutions, add 1.0 grams of polyoxyethylene glycol (molecular weight 10000), proceed in frozen water mixing bath and continue to stir 5 minutes.In mixing solutions, add 7 gram 1, two (trimethoxy the is silica-based) hexanes of 6-and 0.1 gram of aluminum isopropylate, vigorous stirring is after 10 minutes, mixed solution is poured in mould and sealed, standing 1 hour of room temperature, the demoulding after taking out, drying at room temperature, finally 6000 ℃ of roastings 7 hours.The pore structure of product is similar to embodiment 1 product.Concrete texture parameter is: 835 meters of specific surface areas
2/ gram, pore volume is 1.1 centimetres 3/ gram, 0.4 micron of macropore diameter, mesoporous aperture 4 nanometers.
[embodiment 3～9]
Synthetic method is identical with embodiment 1, just change the parameter such as kind, proportioning raw materials, gelling temp of silicon source (two (triethoxy is silica-based) methane, Isosorbide-5-Nitrae-bis-(triethoxy is silica-based) benzene), aluminium source (aluminum nitrate, aluminum chloride, Tai-Ace S 150, pseudo-boehmite), the inductor R1 that is separated (polyoxyethylene, polyethylene oxide) or structure directing agent R2 (chain alkyl trimethylammonium halogenation ammonia, citric acid, tartrate, oxysuccinic acid, lactic acid).
The concrete synthesis condition of embodiment 3～9, proportioning are in Table 1.Synthetic product has the composite pore structural similar to embodiment 1 product, and its concrete structural parameter are in Table 1.
Table 1
* press the theoretical SiO of generation in silicon source
2amount is calculated.
[comparative example 1]
Weigh 15 grams of the hydrochloric acid solns of 1 mol/L, add 2.0 grams of polyoxyethylene-poly-oxypropylene polyoxyethylene (molecular weight 5000, P123) stirring and dissolving under room temperature adds 0.7 gram of polyoxyethylene glycol (molecular weight 10000) in mixing solutions, proceeds in frozen water mixing bath and continues to stir 5 minutes.In mixing solutions, add 5 grams of methyl silicates, vigorous stirring, after 10 minutes, is poured mixed solution in mould into and is sealed, standing 6 hours of room temperature, and the demoulding after taking out, drying at room temperature, finally 550 ℃ of roastings 5 hours.Product is dense structure powder, is not mesoporous/macroporous composite pore structural silicone material.
[comparative example 2]
Weigh 15 grams of the hydrochloric acid solns of 1 mol/L, add 2.0 grams of polyoxyethylene-poly-oxypropylene polyoxyethylene (molecular weight 5000, P123) stirring and dissolving under room temperature adds 0.7 gram of polyoxyethylene glycol (molecular weight 10000) in mixing solutions, proceeds in frozen water mixing bath and continues to stir 5 minutes.In mixing solutions, add 5 grams of methyl silicates, vigorous stirring, after 10 minutes, is poured mixed solution in mould into and is sealed, standing 12 hours of room temperature, and the demoulding after taking out, drying at room temperature, finally 550 ℃ of roastings 5 hours.Product is dense structure powder, is not mesoporous/macroporous composite pore structural silicone material.
[comparative example 3]
Weigh 15 grams of the hydrochloric acid solns of 1 mol/L, add 2.0 grams of polyoxyethylene-poly-oxypropylene polyoxyethylene (molecular weight 5000, P123) stirring and dissolving under room temperature adds 0.7 gram of polyoxyethylene glycol (molecular weight 10000) in mixing solutions, proceeds in frozen water mixing bath and continues to stir 5 minutes.In mixing solutions, add 5 grams of methyl silicates, vigorous stirring, after 10 minutes, is poured mixed solution in mould into and is sealed, room temperature ℃ standing 24 hours, and the demoulding after taking out, drying at room temperature, finally 550 ℃ of roastings 5 hours.The pore structure of product is similar to embodiment 1 product.Concrete texture parameter is: the pore structure of product is similar to embodiment 1 product.Concrete texture parameter is: 435 meters of specific surface areas
2/ gram, pore volume is 0..1 centimetre
3/ gram, 5 microns of macropore diameters, without mesoporous.
[comparative example 4]
Weigh 15 grams of the hydrochloric acid solns of 1 mol/L, add 2.0 grams of polyoxyethylene-poly-oxypropylene polyoxyethylene (molecular weight 5000, P123) stirring and dissolving under room temperature adds 0.7 gram of polyoxyethylene glycol (molecular weight 10000) in mixing solutions, proceeds in frozen water mixing bath and continues to stir 5 minutes.In mixing solutions, add 5 grams of methyl silicates, vigorous stirring, after 10 minutes, is poured mixed solution in mould into and is sealed, 60 ℃ standing 24 hours, the demoulding after taking out, drying at room temperature, finally 550 ℃ of roastings 5 hours.The pore structure of product and embodiment 1 product are dissimilar.Concrete texture parameter is: 842 meters of specific surface areas
2/ gram, pore volume is 1.6 centimetres
3/ gram, 2 microns of macropore diameters, mesoporous aperture 6 nanometers.
Claims (1)
1. a preparation method for mesoporous/macroporous composite pore structural silicone, comprises the following steps:
15 grams of hydrochloric acid solns that weigh 1 mol/L, add 2.0 grams of polyoxyethylene-poly-oxypropylene polyoxyethylenes, and its molecular weight is 5000, stirring and dissolving under room temperature, in mixing solutions, add 0.7 gram of polyoxyethylene glycol, its molecular weight is 10000, proceeds in frozen water mixing bath and continues to stir 5 minutes; In mixing solutions, add 5 gram 1, two (trimethoxy the is silica-based) hexanes of 6-, vigorous stirring, after 10 minutes, is poured mixed solution in mould into and is sealed, standing 0.1 hour of room temperature, the demoulding after taking out, drying at room temperature, finally 550 ℃ of roastings 5 hours; Result shows that product has the co-continuous macroporous structure of perforation, and concrete texture parameter is: 951 meters of specific surface areas
2/ gram, pore volume is 1.5 centimetres
3/ gram, 0.2 micron of macropore diameter, mesoporous aperture 7 nanometers.
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|---|---|---|---|
| CN201010552101.1A CN102464321B (en) | 2010-11-17 | 2010-11-17 | Preparation method for mesopore/macropore compound hole structure silica gel and silicon and aluminum oxide material |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101525137A (en) * | 2008-03-06 | 2009-09-09 | 中国石油化工股份有限公司 | Method for preparing mesoporous/macroporous composite pore structural silicone monolith |
| CN101723393A (en) * | 2008-10-28 | 2010-06-09 | 中国石油化工股份有限公司 | Method for preparing silicon-aluminum oxide material with mesopore/macropore combined porous structure |
-
2010
- 2010-11-17 CN CN201010552101.1A patent/CN102464321B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101525137A (en) * | 2008-03-06 | 2009-09-09 | 中国石油化工股份有限公司 | Method for preparing mesoporous/macroporous composite pore structural silicone monolith |
| CN101723393A (en) * | 2008-10-28 | 2010-06-09 | 中国石油化工股份有限公司 | Method for preparing silicon-aluminum oxide material with mesopore/macropore combined porous structure |
Non-Patent Citations (2)
| Title |
|---|
| Beranger Toury et al..Synthesis of periodic mesoporous organosilica from bis(triethoxysilyl)methane and their pyrolytic conversion into porous SiCO glasses.《Journal of the European Ceramic Society》.2004,第25卷第266页第1栏最后一段. |
| Synthesis of periodic mesoporous organosilica from bis(triethoxysilyl)methane and their pyrolytic conversion into porous SiCO glasses;Beranger Toury et al.;《Journal of the European Ceramic Society》;20041012;第25卷;第266页第1栏最后一段 * |
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