CN104096551A - Aluminum-titanium oxide aerogel bead with high specific surface area and acid amount and preparation method thereof - Google Patents
Aluminum-titanium oxide aerogel bead with high specific surface area and acid amount and preparation method thereof Download PDFInfo
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Abstract
The invention provides a preparation method for an aluminum-titanium two-component oxide aerogel bead which uses non-organic alkoxide as a precursor and water as a solvent, realizes adjustment of a pore structure through changing an aluminum-titanium ratio and has a high specific surface area and a high surface acid amount. The preparation method is characterized by comprising the following steps: A) respectively preparing alumina and titanium oxide hydrosols with high solid contents; B) mixing the two hydrosols, carrying out co-hydrolysis, preparing a wet gel ball by using a hydrocarbon-ammonia balling method and carrying out aging; C) washing the wet gel ball with water many times, then displacing water in pores with ethanol as a solvent and carrying out aging; and D) carrying out drying and roasting so as to obtain the aerogel bead. The invention further provides the aluminum-titanium two-component oxide aerogel bead with the high specific surface area and acid amount prepared by using any method disclosed in claim 1 to 8.
Description
Technical field
The present invention relates to catalyst preparation field, provide and there is high-specific surface area, the mesoporous aluminium titanium binary oxide gas gel small ball method for preparing catalyst of acid amount.
Background technology
Aluminium oxide-titanium oxide binary oxide can keep Al
2o
3whole skeleton, have higher specific area and heat endurance, there is again TiO
2good catalytic performance thereby be often used as solid acid and photochemical catalyst field.Current, preparation method is more for aluminium oxide-titanium oxide binary composite oxides, and different preparation methods have considerable influence to pore structure.Common preparation method has mechanical mixing, coprecipitation, chemical vapour deposition technique, template, sol-gel process etc.Wherein sol-gel process is on the one hand distributed to presoma in solvent and forms low viscous solution, makes its uniformity that can obtain in the short period of time molecular level, while forming gel like this, forms the mixing of molecular level between each component; On the other hand, by sol-gel technique, can form three-dimensional netted wet gel skeleton, control wet gel is dry can obtain aperture at the aerogel material of mesoporous scope, so it is also the common method of preparing bigger serface carrier.In addition, by different dry means, can make pore structure and porosity adjustable continuously within the specific limits.Yet the current sol precursor of selecting is mainly organic alkoxide, solvent is organic solvent, and these costs of material are high and harmful to environment and human body.Therefore keeping under the prerequisite of high-specific surface area, reducing presoma and solvent cost and toxicity is main direction prepared by current composite oxide catalysts.
Summary of the invention
According to an aspect of the present invention, provide a kind of preparation method who prepares aluminium titanium ternary oxide spheric catalyst.It is characterized in that; Aperture between 5-20nm, the small ball's diameter 0.5-3mm.This gas gel small ball can directly be used as catalyst or catalyst carrier, does not need post forming.
According to another aspect of the present invention, provide a kind of have high-specific surface area and acid amount and aperture regulatable binary bead preparation method, it is characterized in that comprising:
A) configure respectively aluminium oxide and the titanium oxide hydrosol;
B) under room temperature, mix two kinds of colloidal sols, then splashing into upper strata is kerosene, and middle level is surfactant, in the container that lower floor is ammonia spirit, forms hydrogel sphere ageing;
C) filter also water and repeatedly wash wet gel ball removal residual surface activating agent, then with ethanol, repeatedly wash bead and replace the water in bead space, then put into 60 ℃ of ethanol and soak;
D) by dry, make wet gel bead become gas gel small ball, then carry out roasting, obtain high-specific surface area tilalite gas gel small ball.
According to a further aspect of the present invention, said method is characterised in that above-mentioned steps A) solvent of two kinds of colloidal sols only has water, containing other organic solvents.
According to a further aspect of the present invention, said method is characterised in that above-mentioned steps A) in alumina sol presoma be boehmite powder, titania precursor body is titanyl sulfate.
According to a further aspect of the present invention, said method is characterised in that
The aluminium oxide solid content of above-mentioned colloidal sol is at 8-10%, and solute is pressed Al
2o
3the mass ratio that accounts for colloidal sol calculates, Al
2o
3concentration be 8-10%; The solid content of titanium oxide is 4-5%.
According to a further aspect of the present invention, said method is characterised in that above-mentioned steps B) container in surfactant be saturated aqueous surfactant solution, surfactant can be neopelex, TBAB or softex kw.
According to a further aspect of the present invention, said method is characterised in that above-mentioned drying steps D) a kind of in following:
1) ethanol carries out supercritical drying as medium;
2) be placed in that under the environment that is full of alcohol vapour, to make wet gel ball ethanol slowly put into drying box after volatilization dry;
3) wet gel ball is placed in to 60 ℃ of ethanolic solutions that contain ethyl orthosilicate aging, takes out and with ethanol, clean that repeatedly to put into afterwards drying box dry;
4) utilize hexane solution that the ethanol containing in wet gel ball is fully washed to displacement, the solution modification of the wetter bead after fully replacing being put into n-hexane, trim,ethylchlorosilane, isopropyl alcohol, puts into drying box dry after finally the bead of modification repeatedly being washed with n-hexane.
According to a further aspect of the present invention, above-mentioned steps D) in roasting process be: with programming rate 1-10 ℃/min, be warming up to final temperature, in final temperature, stop 1-3 hour, final temperature is 400-1000 ℃.
The specific embodiment
Embodiment 1
Get 8g boehmite powder (SB powder) and be dissolved in 50ml80 ℃ of water after strong agitation 1h, add 8ml1.6M HNO
3the aqueous solution, makes colloidal sol transparent, is cooled to room temperature and obtains aluminium colloidal sol.14.7g titanyl sulfate is dissolved in 350ml water, stir add dilute sulfuric acid be dissolved to transparent, dropwise add concentrated ammonia liquor to pH when the 6-7, titanium all precipitates, when normal temperature continues to stir 1h precipitation fully after, utilize deionized water filtering-depositing repeatedly, remove sulfate ion.Clean titanium oxide is deposited in after 50 ℃ of water-soluble solutions, puts into 70 ℃ of water-baths and add and dropwise add 23.4ml1.6M nitric acid peptization 2h to be cooled to room temperature, obtain clarifying titanium colloidal sol.Two kinds of colloidal sols are mixed with oxide mol ratio 1:1, stir to splash into after 3h and fill balling-up ageing 18h in the container that the ammoniacal liquor volume ratio of kerosene, cetyl benzene sulfonic acid sodium salt saturated aqueous solution and 12.5% is 400:20:120.Filter and by deionized water, repeatedly wash wet gel ball and remove after remaining surfactant, then with ethanol, repeatedly washing bead and replace the water in bead space, then putting into 60 ℃ of ethanol and soak 24h.Take out alcogel ball and be placed in and under the environment that is full of alcohol vapour, make in it ethanol 48h that slowly volatilizees, then natural drying, then put into 110 ℃ of oven drying 2h.Finally insert tube furnace and be warming up to 500 ℃ with 2 ℃/min of programming rates, stop and be naturally cooled to room temperature after 3 hours.Utilize this method can obtain specific area for 218m
2/ g, pore volume is 0.81cm
3/ g, average pore size 14.8nm, Surface acidity are 0.923mmol NH
3the homogeneous binary tilalite gas gel small ball of/g.
Embodiment 2
Change roasting final temperature into 700 ℃, other conditions are with embodiment 1, and obtaining specific area is 185m
2/ g, pore volume is 0.77cm
3/ g, average pore size 16.6nm, Surface acidity are 0.348mmol NH
3the homogeneous binary tilalite gas gel small ball of/g.
Embodiment 3
Change mixing mol ratio into Al/Ti=2, other conditions are with embodiment 1, and obtaining specific area is 219m
2/ g, pore volume is 0.89cm
3/ g, average pore size 17.0nm, Surface acidity are 1.058mmol NH
3the homogeneous binary tilalite gas gel small ball of/g.
Embodiment 4
Change mixing mol ratio into Al/Ti=4, other conditions are with embodiment 1, and obtaining specific area is 221m
2/ g, pore volume is 0.9cm
3/ g, average pore size 16.3nm, Surface acidity are 0.863mmol NH
3the homogeneous binary tilalite gas gel small ball of/g.
Embodiment 5
Change mixing mol ratio into Al/Ti=8, other conditions are with embodiment 1, and obtaining specific area is 213m
2/ g, pore volume is 0.36cm
3/ g, the homogeneous binary tilalite gas gel small ball of average pore size 6.6nm.
Claims (9)
1. a high-specific surface area is measured with acid, aluminium-titanium binary oxide gas gel small ball of homogeneous, it is characterized in that: utilize non-organic alkoxide for presoma, the colloidal sol of preparing respectively two kinds of oxides, by oxide sol mixing aftershaping, dry and roasting, obtain mixed uniformly binary oxide gas gel small ball on nano-scale; Little ball aperture is in 5-20nm scope, the small ball's diameter 0.5-3mm.
2. aluminium-titanium binary oxide gas gel small ball preparation method with high-specific surface area and acid amount, is characterized in that comprising:
A) configure respectively aluminium oxide, two kinds of high solids content hydrosols of titanium oxide;
B) under room temperature, mix two kinds of colloidal sols, then splashing into afterwards upper strata is kerosene, and middle level is surfactant, in the container that lower floor is ammonia spirit, forms hydrogel sphere ageing;
C) Separation of Water gel ball, and with deionized water repeatedly detergent gel ball remove residual surface activating agent, then with ethanol, repeatedly wash bead and replace the water in bead space, put into 60 ℃ of ethanol and soak;
D) dry wet gelled pill, and carry out roasting heat processing, obtain high-specific surface area silicon-aluminium-titanium ternary oxide gas gel small ball.
3. according to the method for claim 2, it is characterized in that above-mentioned steps A) in the solvent of aluminium oxide and titanium oxide sol only have water, containing other organic solvents.
4. according to the method for claim 2, it is characterized in that above-mentioned steps A) in alumina sol presoma be boehmite powder, titania precursor body is titanyl sulfate.
5. according to the method for claim 2, it is characterized in that
The aluminium oxide solid content of above-mentioned colloidal sol is at 8-10%, and solute is pressed Al
2o
3the mass ratio that accounts for colloidal sol calculates, Al
2o
3concentration be 8-10%; The solid content of titanium oxide is 4-5%.
6. according to the method for claim 2, it is characterized in that
Above-mentioned steps B) in the container in, surfactant is saturated aqueous surfactant solution, and surfactant can be neopelex, TBAB or softex kw.
7. according to the method for claim 2, it is characterized in that above-mentioned steps D) in drying means be a kind of in following:
1) ethanol carries out supercritical drying as medium;
2) be placed in that under the environment that is full of alcohol vapour, to make wet gel ball ethanol slowly put into drying box after volatilization dry;
3) wet gel ball is placed in to 60 ℃ of ethanolic solutions that contain ethyl orthosilicate aging, takes out and with ethanol, clean that repeatedly to put into afterwards drying box dry;
4) utilize hexane solution that the ethanol containing in wet gel ball is fully washed to displacement, the solution modification of the wetter bead after fully replacing being put into n-hexane, trim,ethylchlorosilane, isopropyl alcohol, puts into drying box dry after finally the bead of modification repeatedly being washed with n-hexane.
8. according to the method for claim 2, it is characterized in that step D) in roasting process be: with programming rate 1-10 ℃/min, be warming up to final temperature, in final temperature, stop 1-3 hour, final temperature is 400-1000 ℃.
9. use according to any one high-specific surface area that has of preparing in claim 2-8 and measure and aperture regulatable aluminium titanium binary aerogel bead with acid.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104475168A (en) * | 2014-11-12 | 2015-04-01 | 中国海洋石油总公司 | Preparation method of titanium-aluminum composite oxide with large specific surface and small aperture |
| CN108585798A (en) * | 2018-05-09 | 2018-09-28 | 安徽中航名坤新材料科技有限公司 | A kind of nano-porous alumina aeroge ceramic bead and preparation method thereof |
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| CN104475168A (en) * | 2014-11-12 | 2015-04-01 | 中国海洋石油总公司 | Preparation method of titanium-aluminum composite oxide with large specific surface and small aperture |
| CN108585798A (en) * | 2018-05-09 | 2018-09-28 | 安徽中航名坤新材料科技有限公司 | A kind of nano-porous alumina aeroge ceramic bead and preparation method thereof |
| CN108585798B (en) * | 2018-05-09 | 2022-02-18 | 安徽弘徽科技有限公司 | Nano porous alumina aerogel ceramic pellet and preparation method thereof |
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