CN103482634B - Preparation method of silicon-based dual mesoporous material - Google Patents
Preparation method of silicon-based dual mesoporous material Download PDFInfo
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- CN103482634B CN103482634B CN201310405194.9A CN201310405194A CN103482634B CN 103482634 B CN103482634 B CN 103482634B CN 201310405194 A CN201310405194 A CN 201310405194A CN 103482634 B CN103482634 B CN 103482634B
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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 different grades and the special pore structure of individual aperture distribution, two trepannings are mesoporous, larger mesoporous being conducive to guides adsorbate, reactant more easily enters and littlely mesoporously carries out adsorbing or react (this be little mesoporous material can not and), less is mesoporous, provide larger specific surface area (this be mesoporous greatly, large pore material can not and), this structure is conducive to the dispersity improving rate of diffusion and metal.There is the dispersiveness reporting and can not only increase Co after silica-based double-mesoporous material load C o active metal significantly, effectively can also accelerate the transmission of material in F-T building-up reactions system, thus obtain the catalytic activity higher than single mesoporous catalyst.Utilize Ni/SiO prepared by the strong acid corrodibility of chloroazotic acid
2the alkylation of two mesoporous catalyst to carbonic acid gas has very high catalytic activity.Use SiO prepared by sol-gel method
2two mesoporous supports, shows the activity higher than 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.
Research about silica-based double-mesoporous material is still in the desk study stage at present, and studying more is sol-gel process, comprises single template and double-template method, 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.Double-template method adopts two kinds of template two step synthesis to obtain two mesoporous silicon, first adopt the single mesoporous silicon based material of traditional method preparation, it is mesoporous greatly then to add template Hydrothermal Synthesis, solvent also can be adopted to evaporate guide generate two mesoporous, the shortcomings such as these methods exist operating process complexity, difficult control.
Three, summary of the invention
The object of this invention is to provide a kind of simple and convenient, 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 DEG C of waters bath with thermostatic control and dissolve completely, then in this solution, add concentrated hydrochloric acid, continue stirring 0.5 hour, dropwise drip tetraethyl orthosilicate, continue to stir, obtain oyster white suspension liquid;
2. get template F127 and deionized water, be stirred under 40 DEG C of waters bath with thermostatic control and dissolve completely, then in this solution, add concentrated hydrochloric acid, continue stirring 0.5 hour, add Na
2sO
410H
2o, after 2 hours, dropwise drips tetraethyl orthosilicate, continues to stir, and obtains oyster white suspension liquid;
3. 1. step is mixed in same crystallization bottle with two suspension liquids of step 2. gained, by bottle sealing after stirring, crystallization 24 hours at 100 DEG C, take out after crystallization and be cooled to room temperature, then suction filtration repeatedly cleaning to neutrality with deionized water, by the sample after suction filtration at 100 DEG C dry 12 hours, at 500 DEG C, namely roasting obtained silica-based double-mesoporous material product for 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.
Above-mentioned steps 1. with step 2. in continue churning time be 16-24 hour.
Above-mentioned steps 3. in the mixed churning time of two suspension liquids be 0-10 hour.
Above-mentioned steps 1. with step 2. in the mass concentration of concentrated hydrochloric acid that adds be 36%.
The inventive method is for template with P123 and F127, adopt and react respectively, the method of common crystallization prepares silica-based two mesoporous villages material, compared with colloidal sol-gel double-template method, have simple and convenient, controlling is strong, the advantage of easy handling, and save the man-hour of nearly half, combined coefficient is greatly improved.The silica-based double-mesoporous material of gained has bimodal pore size distribution, and little mesoporous aperture is at about 5nm, and aperture mesoporous is greatly at about 10-15nm, 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
Fig. 1 is the XRD characterization result figure of the standby two mesoporous silicons of eutectic legal system.
Five, embodiment
Embodiment 1
1. 1 g template P123 is got, deionized water 24.5 g, put into crystallization bottle, be stirred under 45 DEG C of waters bath with thermostatic control and dissolve (about 4 hours) completely, then in this solution, add the concentrated hydrochloric acid that 6.3g mass concentration is 36%, regulate ph value <1, continue stirring 0.5 hour, dropwise drip 2.12 g tetraethyl orthosilicates (TEOS), continue stirring 20 hours, obtain oyster white suspension liquid.
2. 1g template F127 and 22.5g deionized water is got, put into crystallization bottle, be stirred under 40 DEG C of waters bath with thermostatic control and dissolve (about 1 hour) completely, then in this solution, add the concentrated hydrochloric acid that 7.5g mass concentration is 36%, continue stirring 0.5 hour, add 4.85g Na
2sO
410H
2o, after 2 hours, dropwise drips 4.2g tetraethyl orthosilicate (TEOS), continues stirring after 20 hours, obtains oyster white suspension liquid.
3. above-mentioned two suspension liquids are mixed in same crystallization bottle, stir bottle sealing after 2 hours, crystallization 24 hours at 100 DEG C, take out after crystallization and be cooled to room temperature, then suction filtration repeatedly clean to neutral (ph=7) with deionized water, by the sample after suction filtration at 100 DEG C dry 12 hours, at 500 DEG C, namely roasting obtained silica-based double-mesoporous material product for 5 hours.
Embodiment 2
1. 0.5 g template P123 is got, deionized water 12.3 g, put into crystallization bottle, be stirred under 45 DEG C of waters bath with thermostatic control and dissolve (about 4 hours) completely, then in this solution, add the concentrated hydrochloric acid that 3.15g mass concentration is 36%, regulate P one hour value <1, continue stirring 0.5 hour, dropwise drip 1.06 g tetraethyl orthosilicates (TEOS), continue stirring 16 hours, obtain oyster white suspension liquid.
2. 1.5g template F127 and 33.7g deionized water is got, put into crystallization bottle, be stirred under 40 DEG C of waters bath with thermostatic control and dissolve (about 1 hour) completely, then in this solution, add the concentrated hydrochloric acid that 11.25g mass concentration is 36%, continue stirring 0.5 hour, add 7.3g Na
2sO
410H
2o, after 2 hours, dropwise drips 6.3g tetraethyl orthosilicate (TEOS), continues stirring after 16 hours, obtains oyster white suspension liquid.
3. above-mentioned two suspension liquids are mixed in same crystallization bottle, stir bottle sealing after 5 hours, crystallization 24 hours at 100 DEG C, take out after crystallization and be cooled to room temperature, then suction filtration repeatedly clean to neutral (ph=7) with deionized water, by the sample after suction filtration at 100 DEG C dry 12 hours, at 500 DEG C, namely roasting obtained silica-based double-mesoporous material product for 5 hours.
Embodiment 3
1. 1 g template P123 is got, deionized water 28.0 g, put into crystallization bottle, be stirred under 45 DEG C of waters bath with thermostatic control and dissolve (about 4 hours) completely, then in this solution, add the concentrated hydrochloric acid that 0.2g mass concentration is 36%, regulate ph value <3, continue stirring 0.5 hour, dropwise drip 2.12 g tetraethyl orthosilicates (TEOS), continue stirring 16 hours, obtain oyster white suspension liquid.
2. 1g template F127 and 24.0g deionized water is got, put into crystallization bottle, be stirred under 40 DEG C of waters bath with thermostatic control and dissolve (about 1 hour) completely, then in this solution, add the concentrated hydrochloric acid that 6.0g mass concentration is 36%, continue stirring 0.5 hour, add 4.85g Na
2sO
410H
2o, after 2 hours, is dropwise added dropwise to the tetraethyl orthosilicate (TEOS) of 4.2g, continues stirring after 16 hours, obtains oyster white suspension liquid.
3. above-mentioned two suspension liquids are mixed in same crystallization bottle, stir bottle sealing after 10 hours, crystallization 24 hours at 100 DEG C, take out after crystallization and be cooled to room temperature, then suction filtration repeatedly clean to neutral (ph=7) with deionized water, by the sample after suction filtration at 100 DEG C dry 12 hours, at 500 DEG C, namely roasting obtained silica-based double-mesoporous material product for 5 hours.
As shown in the figure, there are two stronger diffraction peaks in eutectic sample at 0.8 ° and 1 ° (2 θ), the characteristic peak of corresponding two kinds of mesoporous (100) crystal faces, simultaneously 1.6 ° and 1.9 ° of place's appearance, two little diffraction peaks, show that the sample synthesized has the characteristic diffraction peak of typical two-dimentional hexagonal hole road structure, skeleton structure keeps good order.
Claims (7)
1. a preparation method for silica-based double-mesoporous material, the method comprises the steps:
1. get template P123 and deionized water, be stirred under 45 DEG C of waters bath with thermostatic control and dissolve completely, then in this solution, add concentrated hydrochloric acid, continue stirring 0.5 hour, dropwise drip tetraethyl orthosilicate, continue to stir, obtain oyster white suspension liquid;
2. get template F127 and deionized water, be stirred under 40 DEG C of waters bath with thermostatic control and dissolve completely, then in this solution, add concentrated hydrochloric acid, continue stirring 0.5 hour, add Na
2sO
410H
2o, after 2 hours, dropwise drips tetraethyl orthosilicate, continues to stir, and obtains oyster white suspension liquid;
3. 1. step is mixed in same crystallization bottle with two suspension liquids of step 2. gained, by bottle sealing after stirring, crystallization 24 hours at 100 DEG C, take out after crystallization and be cooled to room temperature, then suction filtration repeatedly cleaning to neutrality with deionized water, by the sample after suction filtration at 100 DEG C dry 12 hours, at 500 DEG C, namely roasting obtained silica-based double-mesoporous material product for 5 hours.
2. the preparation method of a kind of silica-based double-mesoporous material according to claim 1, 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. 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.
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. 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.
5. 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. with step 2. in continue churning time be 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 2-10 hour.
7. the preparation method of a kind of silica-based double-mesoporous material according to claim 1 and 2, is characterized in that: described step 1. with step 2. in the mass concentration of concentrated hydrochloric acid that adds be 36%.
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