CN102464321A - 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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- CN102464321A CN102464321A CN2010105521011A CN201010552101A CN102464321A CN 102464321 A CN102464321 A CN 102464321A CN 2010105521011 A CN2010105521011 A CN 2010105521011A CN 201010552101 A CN201010552101 A CN 201010552101A CN 102464321 A CN102464321 A CN 102464321A
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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
Combine organic molecule with inorganic oxide in recent years, synthetic novel porous material with special construction and character receives extensive concern.By the mesoporous composite holes material of forming with macropore also is one of them research focus.Compare with common material, the composite holes material helps the material transfer diffusion, thereby shows wide application prospect at absorption, separation and catalytic field.Patent CN 101525137A and CN 101723393A have reported the preparation method of mesoporous/macroporous composite pore structural silicone and silicon-aluminum oxide material respectively.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 this type of problem through the kind that changes the silicon source.
Summary of the invention
Technical problem to be solved by this invention is that the gelling temp that exists in the prior art is high, and the long problem of digestion time provides a kind of new mesoporous/macroporous composite pore structural silicone and the preparation method of silicon-aluminum oxide material.It is low that this mesoporous/macroporous composite pore structural silicone and silicon-aluminum oxide material have a gelling temp, the advantage that digestion time is short.
In order to solve the problems of the technologies described above, the technical scheme that the present invention adopts is following: the preparation method of a kind of mesoporous/macroporous composite pore structural silicone and silicon-aluminum oxide material may further comprise the steps:
A) will be separated inductor R1, structure directing agent R2, acid catalyst and water mixes, and the mixture that adds organosilicon source or organosilicon source and aluminium source is at 0~30 ℃ of sufficient hydrolysis reaction of generation, and the 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 the mould, at room temperature gel continued to leave standstill aging 0.1~10 hour;
C) the after product demoulding of will wearing out, 20~100 ℃ of dryings, be 1~7 day time of drying, makes the macroporous structure oxide material after 0.5~24 hour 450~800 ℃ of roastings then, its specific surface is up to 750~1000 meters
2/ gram, pore volume is 0.9~1.8 meter
2/ gram has two cover ducts on three-dimensional space: a cover is the co-continuous macroporous structure that connects, and the aperture is at 0.05~8 micron; Another set of is to constitute in the inorganic skeleton of macropore to have regular mesopore orbit, is orderly six sides (P6mm) and distributes mutually, and the aperture is adjustable continuously between 2~8 nanometers;
The inductor R1 that wherein is separated be selected from polyoxyethylene glycol, T 46155 or polyethylene oxide at least a, its molecular-weight average is 3000~100000;
Structure directing agent R2 is selected from least a in triblock copolymer, chain alkyl trimethylammonium halogenation ammonia, Hydrocerol A, tartrate, oxysuccinic acid or the lactic acid; Wherein triblock copolymer is a 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 the technique scheme, the silicon source is selected from two (triethoxy is silica-based) methane, 1, two (trimethoxy the is silica-based) hexanes, 1 of 6-, at least a in two (triethoxy the is silica-based) benzene of 4-.The aluminium source is selected from least a in aluminum nitrate, aluminum chloride, Tai-Ace S 150, aluminum isopropylate or the pseudo-boehmite.Acid catalyst is at least a in nitric acid, phosphoric acid, hydrochloric acid or the acetic acid.Preferred 0.1~1 hour of gel digestion time continues to prolong digestion time to the reaction structure influence not quite.Ageing products is preferred 2~10 hours of 450~800 ℃ of roasting time, and it is little to the reaction structure influence to continue to prolong roasting time.
Adopted two template to come to control respectively mesoporous and generation macropore among the present invention; The inductor R1 that wherein is separated plays in sol-gel process and causes the effect that the co-continuous macropore that is separated and then leads generates, and structure directing agent R2 mainly play the space occupy-place or through with the lead effect of regular mesoporous generation of silicon species interaction Generation Liquid crystalline phase.Through modulation, can regulate and control effectively the meso/macroporous structure and the pore size distribution of product respectively silicon source category, template kind, add-on and reaction conditions.Our pleasantly surprised discovery adopts the alternative inorganic silicon source of organosilicon can make gelling temp from reducing to room temperature more than the room temperature in experiment, and digestion time can be by reducing to 0.1 hour more than 24 hours.
Description of drawings
Fig. 1 is the SEM photo of embodiment 1 sample.
Through embodiment the present invention is done further elaboration below.
Embodiment
[embodiment 1]
Hydrochloric acid soln 15 grams of weighing 1 mol; Add 2.0 gram polyoxyethylene-poly-oxypropylene polyoxyethylene (molecular weight 5000; P123) stirring and dissolving under the room temperature adds polyoxyethylene glycol (molecular weight 10000) 0.7 gram in mixing solutions, change in the frozen water mixing bath and continue to stir 5 minutes.In mixing solutions, add 5 grams 1, two (trimethoxy the is silica-based) hexanes of 6-, vigorous stirring is after 10 minutes, mixed solution poured in the mould seal, and room temperature left standstill 0.1 hour, took out the back demoulding, and drying at room temperature is at last 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 are 1.5 centimetre of 3/ gram, 0.2 micron of macropore diameter, mesoporous aperture 7 nanometers.
[embodiment 2]
Acetum 10 grams of weighing 0.5 mol; Add 1.0 gram polyoxyethylene-poly-oxypropylene polyoxyethylene (molecular weight 2000; P123) stirring and dissolving under the room temperature adds polyoxyethylene glycol (molecular weight 10000) 1.0 grams in mixing solutions, change in the frozen water mixing bath and continue to stir 5 minutes.In mixing solutions, add 7 grams 1, two (trimethoxy is silica-based) hexanes of 6-and 0.1 gram aluminum isopropylate, vigorous stirring is after 10 minutes, mixed solution poured in the mould seal, and room temperature left standstill 1 hour, took out the back demoulding, and drying at room temperature is at last 6000 ℃ of roastings 7 hours.The pore structure of product is similar with embodiment 1 product.Concrete texture parameter is: 835 meters of specific surface areas
2/ gram, pore volume are 1.1 centimetre of 3/ gram, 0.4 micron of macropore diameter, mesoporous aperture 4 nanometers.
[embodiment 3~9]
Compound method is identical with embodiment 1; Just change the parameters such as kind, proportioning raw materials, gelling temp of silicon source (two (triethoxy is silica-based) methane, 1,4-two (triethoxy is silica-based) benzene), aluminium source (aluminum nitrate, aluminum chloride, Tai-Ace S 150, pseudo-boehmite), the inductor R1 that is separated (T 46155, polyethylene oxide) or structure directing agent R2 (chain alkyl trimethylammonium halogenation ammonia, Hydrocerol A, tartrate, oxysuccinic acid, lactic acid).
The concrete synthesis condition of embodiment 3~9, proportioning are seen table 1.The synthetic product has and the similar composite pore structural of embodiment 1 product, and its concrete structural parameter are seen table 1.
Table 1
* press the theoretical SiO of generation in silicon source
2Amount is calculated.
[comparative example 1]
Hydrochloric acid soln 15 grams of weighing 1 mol; Add 2.0 gram polyoxyethylene-poly-oxypropylene polyoxyethylene (molecular weight 5000; P123) stirring and dissolving under the room temperature adds polyoxyethylene glycol (molecular weight 10000) 0.7 gram in mixing solutions, change in the frozen water mixing bath and continue to stir 5 minutes.In mixing solutions, add 5 gram methyl silicates, vigorous stirring is after 10 minutes, mixed solution poured in the mould seal, and room temperature left standstill 6 hours, took out the back demoulding, and drying at room temperature is at last 550 ℃ of roastings 5 hours.Product is the dense structure powder, is not the mesoporous/macroporous composite pore structural silicone material.
[comparative example 2]
Hydrochloric acid soln 15 grams of weighing 1 mol; Add 2.0 gram polyoxyethylene-poly-oxypropylene polyoxyethylene (molecular weight 5000; P123) stirring and dissolving under the room temperature adds polyoxyethylene glycol (molecular weight 10000) 0.7 gram in mixing solutions, change in the frozen water mixing bath and continue to stir 5 minutes.In mixing solutions, add 5 gram methyl silicates, vigorous stirring is after 10 minutes, mixed solution poured in the mould seal, and room temperature left standstill 12 hours, took out the back demoulding, and drying at room temperature is at last 550 ℃ of roastings 5 hours.Product is the dense structure powder, is not the mesoporous/macroporous composite pore structural silicone material.
[comparative example 3]
Hydrochloric acid soln 15 grams of weighing 1 mol; Add 2.0 gram polyoxyethylene-poly-oxypropylene polyoxyethylene (molecular weight 5000; P123) stirring and dissolving under the room temperature adds polyoxyethylene glycol (molecular weight 10000) 0.7 gram in mixing solutions, change in the frozen water mixing bath and continue to stir 5 minutes.In mixing solutions, add 5 gram methyl silicates, vigorous stirring is after 10 minutes, mixed solution poured in the mould seal, and room temperature ℃ left standstill 24 hours, took out the back demoulding, and drying at room temperature is at last 550 ℃ of roastings 5 hours.The pore structure of product is similar with embodiment 1 product.Concrete texture parameter is: the pore structure of product is similar with 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, no mesoporous.
[comparative example 4]
Hydrochloric acid soln 15 grams of weighing 1 mol; Add 2.0 gram polyoxyethylene-poly-oxypropylene polyoxyethylene (molecular weight 5000; P123) stirring and dissolving under the room temperature adds polyoxyethylene glycol (molecular weight 10000) 0.7 gram in mixing solutions, change in the frozen water mixing bath and continue to stir 5 minutes.In mixing solutions, add 5 gram methyl silicates, vigorous stirring is after 10 minutes, mixed solution poured in the mould seal, and 60 ℃ left standstill 24 hours, took out the back demoulding, and drying at room temperature is at last 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 (6)
1. the preparation method of mesoporous/macroporous composite pore structural silicone and silicon-aluminum oxide material may further comprise the steps:
A) will be separated inductor R1, structure directing agent R2, acid catalyst and water mixes, and the mixture that adds organosilicon source or organosilicon source and aluminium source is at 0~30 ℃ of sufficient hydrolysis reaction of generation, and the 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 the mould, at room temperature gel continued to leave standstill aging 0.1~10 hour;
C) the after product demoulding of will wearing out, 20~100 ℃ of dryings, be 1~7 day time of drying, makes the macroporous structure oxide material after 0.5~24 hour 450~800 ℃ of roastings then, its specific surface is up to 750~1000 meters
2/ gram, pore volume is 0.9~1.8 meter
2/ gram has two cover ducts on three-dimensional space: a cover is the co-continuous macroporous structure that connects, and the aperture is at 0.05~8 micron; Another set of is to constitute in the inorganic skeleton of macropore to have regular mesopore orbit, is orderly six sides (P6mm) and distributes mutually, and the aperture is adjustable continuously between 2~8 nanometers;
The inductor R1 that wherein is separated be selected from polyoxyethylene glycol, T 46155 or polyethylene oxide at least a, its molecular-weight average is 3000~100000;
Structure directing agent R2 is selected from least a in triblock copolymer, chain alkyl trimethylammonium halogenation ammonia, Hydrocerol A, tartrate, oxysuccinic acid or the lactic acid; Wherein triblock copolymer is a 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.
2. according to the preparation method of said mesoporous/macroporous composite pore structural silicone of claim 1 and silicon-aluminum oxide material; It is characterized in that the organosilicon source is selected from two (triethoxy is silica-based) methane, 1; Two (trimethoxy the is silica-based) hexanes, 1 of 6-, at least a in two (triethoxy the is silica-based) benzene of 4-.
3. according to the preparation method of said mesoporous/macroporous composite pore structural silicone of claim 1 and silicon-aluminum oxide material, it is characterized in that the aluminium source is selected from least a in aluminum nitrate, aluminum chloride, Tai-Ace S 150, aluminum isopropylate or the pseudo-boehmite.
4. the preparation method of mesoporous/macroporous composite pore structural silicone according to claim 1 and silicon-aluminum oxide material is characterized in that acid catalyst is at least a in nitric acid, phosphoric acid, hydrochloric acid or the acetic acid.
5. the preparation method of mesoporous/macroporous composite pore structural silicone according to claim 1 and silicon-aluminum oxide material, preferred 0.1~1 hour of its gel digestion time continues to prolong digestion time to the reaction structure influence not quite.
6. the preparation method of mesoporous/macroporous composite pore structural silicone according to claim 1 and silicon-aluminum oxide material, its ageing products is preferred 2~10 hours of 450~800 ℃ of roasting time, and it is little to the reaction structure influence to continue to prolong roasting time.
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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 |
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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 (1)
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》 * |
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