CN104096551B - The tilalite gas gel small ball and preparation method thereof of high-specific surface area and acid amount - Google Patents
The tilalite gas gel small ball and preparation method thereof of high-specific surface area and acid amount Download PDFInfo
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Abstract
The present invention provides one kind using non-organic alkoxide as presoma, water as solvent, can adjust pore structure by modulation al-ti ratio, and has the aluminium titanium binary oxide gas gel small ball preparation method of high-specific surface area and Surface acidity.It is characterized by comprising：A）The aluminium oxide and the titanium oxide hydrosol of high solids content are prepared respectively；B）Wet gel ball is obtained using hydrocarbon ammonia spherical container shaping method and be aged after two kinds of colloidal sol mixing cohydrolysis；C）After wet gel ball is washed with water repeatedly, with water and aging in ethanol as solvent displacement hole；D）Gas gel small ball is obtained through dry and roasting.The present invention also provides have high-specific surface area and the sour aluminium titanium binary aerogel bead measured with what is prepared according to any one above method in claim 1-8.
Description
Technical field
The present invention relates to field of catalyst preparation, provide with high-specific surface area, the mesoporous aluminium titanium binary oxide of acid amount
Gas gel small ball method for preparing catalyst.
Background technology
Aluminium oxide-titanium oxide binary oxide can keep Al2O3Overall skeleton, possess higher specific surface area and
Thermal stability, and there is TiO2Excellent catalytic performance is thus often used as solid acid and photochemical catalyst field.Currently, it aoxidizes
Aluminium-titanium oxide binary composite oxides preparation method is more, and different preparation methods have larger impact to pore structure.Common system
Preparation Method has mechanical mixing, coprecipitation, chemical vapour deposition technique, template, sol-gel method etc..Wherein sol-gel
On the one hand presoma is distributed in solvent and forms the solution of low viscosity so that it can obtain molecule in a relatively short period of time by method
Horizontal uniformity when forming gel in this way, forms the mixing of molecular level between each component；On the other hand, solidifying by colloidal sol-
Glue technology can form three-dimensional netted wet gel skeleton, control wet gel drying can obtain aperture macropore range aeroge
Material, therefore it is also the common method for preparing bigger serface carrier.In addition, hole can be made to tie by different drying means
Structure and porosity are continuously adjusted in a certain range.However the sol precursor currently selected is mainly organic alkoxide, solvent is
Organic solvent, these costs of material are high and harmful to environment and human body.Therefore under the premise of keeping high-specific surface area, before reduction
Drive body and solvent cost and toxicity are Main ways prepared by current composite oxide catalysts.
Invention content
According to an aspect of the present invention, a kind of preparation method preparing aluminium titanium ternary oxide spheric catalyst is provided.
It is characterized in that；Aperture is between 5-20nm, the small ball's diameter 0.5-3mm.This gas gel small ball can be directly used as catalyst
Or catalyst carrier, do not need post forming.
According to another aspect of the present invention, provide it is a kind of with high-specific surface area and acid amount and aperture controllable two
First bead preparation method, it is characterised in that including：
A）Aluminium oxide and the titanium oxide hydrosol is respectively configured；
B）Two kinds of colloidal sols are mixed at room temperature, and it is kerosene then to instill upper layer, and middle level is surfactant, and lower layer is ammonium hydroxide
In the container of solution, forms hydrogel sphere and be aged；
C）Filter and simultaneously repeatedly wash wet gel ball removal residual surfactant with water, then repeatedly washed with ethyl alcohol bead come
The water in bead gap is replaced, is then placed in 60 DEG C of ethyl alcohol and impregnates；
D）By drying, so that wet gel bead is become gas gel small ball, then roasted, obtains high-specific surface area aluminium titanium
Oxide silica aerogel bead.
A further aspect according to the present invention, the above method are characterized in that above-mentioned steps A）Two kinds of colloidal sol it is molten
Agent only has water, is free of other organic solvents.
A further aspect according to the present invention, the above method are characterized in that above-mentioned steps A）Middle alumina sol
Presoma is boehmite powder, and titania precursor body is titanyl sulfate.
A further aspect according to the present invention, the above method are characterized in that
The aluminium oxide solid content of above-mentioned colloidal sol presses Al in 8-10%, i.e. solute2O3The mass ratio for accounting for colloidal sol calculates, Al2O3's
A concentration of 8-10%；The solid content of titanium oxide is 4-5%.
A further aspect according to the present invention, the above method are characterized in that above-mentioned steps B）Container in surface
Activating agent is the aqueous surfactant solution of saturation, and surfactant can be neopelex, tetrabutylammonium bromide
Or cetyl trimethylammonium bromide.
A further aspect according to the present invention, the above method are characterized in that above-mentioned drying steps D）In following
One kind：
1）Ethyl alcohol carries out supercritical drying as medium；
2）Being placed in the environment of being full of alcohol vapour makes ethyl alcohol in wet gel ball be put into drying box drying after slowly volatilizing；
3）Wet gel ball is placed in aging in 60 DEG C of ethanol solutions containing ethyl orthosilicate, taking-up is cleaned repeatedly with ethyl alcohol
After be put into drying box it is dry；
4）The ethyl alcohol contained in wet gel ball is fully washed into displacement using hexane solution, then wet after being sufficiently displaced from
Bead is put into the solution of n-hexane, trim,ethylchlorosilane, isopropanol and is modified, and finally repeatedly washes modified bead with n-hexane
It is put into after washing in drying box dry.
A further aspect according to the present invention, above-mentioned steps D）In roasting process be：With heating rate 1-10
DEG C/min it is warming up to final temperature, is stopped 1-3 hour in final temperature, final temperature is 400-1000 DEG C.
Specific implementation mode
Embodiment 1
Take 8g boehmite powder（SB powder）It is dissolved in after stirring 1h strongly in 50ml80 DEG C of water, 8ml1.6M HNO is added3Water
Solution keeps colloidal sol transparent, is cooled to room temperature to obtain Aluminum sol.14.7g titanyl sulfates are dissolved in 350ml water, stirring plus dilute sulfuric acid
Be dissolved to transparent, concentrated ammonia liquor be added dropwise to pH in 6-7, titanium all precipitates, when room temperature continues to stir 1h precipitation fully after, profit
It is repeatedly filtered and is precipitated with deionized water, remove sulfate ion.By clean titanium oxide precipitate after 50 DEG C of water dissolutions, it is put into 70
It is added in DEG C water-bath and 23.4ml1.6M nitric acid is added dropwise and peptization 2h is cooled to room temperature, obtain clarification titanium colloidal sol.It is molten by two kinds
Glue is with oxide mol ratio 1:1 mixing, stir 3h after instill fill kerosene, cetyl benzenesulfonic acid sodium saturated aqueous solution and
12.5% ammonium hydroxide volume ratio is 400:20:Balling-up and it is aged 18h in 120 container.It filters and is repeatedly washed with deionized water wet
After gel ball removes remaining surfactant, then with ethyl alcohol bead is repeatedly washed to replace the water in bead gap, then put
Enter and is impregnated for 24 hours in 60 DEG C of ethyl alcohol.Alcogel ball is taken out to be placed in full of making its interior ethyl alcohol slowly volatilize in the environment of alcohol vapour
Then 48h is spontaneously dried, place into 110 DEG C of oven drying 2h.Finally merging tube furnace is warming up to for 2 DEG C/min with heating rate
500 DEG C, room temperature is naturally cooling to after stopping 3 hours.It is 218m that specific surface area, which can be obtained, using this method2/ g, pore volume are
0.81cm3/ g, average pore size 14.8nm, Surface acidity are 0.923mmol NH3The homogeneous binary tilalite aeroge of/g is small
Ball.
Embodiment 2
Roasting final temperature is changed to 700 DEG C, for other conditions with embodiment 1, it is 185m to obtain specific surface area2/ g, pore volume are
0.77cm3/ g, average pore size 16.6nm, Surface acidity are 0.348mmol NH3The homogeneous binary tilalite aeroge of/g is small
Ball.
Embodiment 3
Mixing molar ratio is changed to Al/Ti=2, for other conditions with embodiment 1, it is 219m to obtain specific surface area2/ g, hole body
Product is 0.89cm3/ g, average pore size 17.0nm, Surface acidity are 1.058mmol NH3The homogeneous binary tilalite airsetting of/g
Glue bead.
Embodiment 4
Mixing molar ratio is changed to Al/Ti=4, for other conditions with embodiment 1, it is 221m to obtain specific surface area2/ g, hole body
Product is 0.9cm3/ g, average pore size 16.3nm, Surface acidity are 0.863mmol NH3The homogeneous binary tilalite airsetting of/g
Glue bead.
Embodiment 5
Mixing molar ratio is changed to Al/Ti=8, for other conditions with embodiment 1, it is 213m to obtain specific surface area2/ g, hole body
Product is 0.36cm3The homogeneous binary tilalite gas gel small ball of/g, average pore size 6.6nm.
Claims (5)
1. aluminium-titanium binary oxide gas gel small ball preparation method with high-specific surface area and acid amount, it is characterised in that including：
A two kinds of aluminium oxide, titanium oxide high solids content hydrosols) are prepared respectively；
B two kinds of colloidal sols) are mixed at room temperature, and it is kerosene then to instill upper layer, and middle level is surfactant, and lower layer is ammonia spirit
Container in, formed hydrogel sphere simultaneously be aged；
C hydrogel sphere) is detached, the multiple detergent gel ball removal residual surfactant of deionized water is used in combination, then multiple with ethyl alcohol
Bead is washed to replace the water in bead gap, is put into 60 DEG C of ethyl alcohol and impregnates；
D) dry wet gel bead, and roasting heat processing is carried out, obtain aluminium-titanium binary oxide gas of high-specific surface area and acid amount
Gelled pill,
Wherein：
Above-mentioned steps A) in the solvent of aluminium oxide and titanium oxide sol there was only water, be free of other organic solvents,
Above-mentioned steps A) in alumina sol presoma be boehmite powder, titania precursor body be titanyl sulfate,
Above-mentioned steps D) in drying means be it is following in one kind：
Ethyl alcohol carries out supercritical drying as medium；
It is placed in full of making in wet gel ball ethyl alcohol slowly be put into drying box drying after volatilization in the environment of alcohol vapour；
Wet gel ball is placed in aging in 60 DEG C of ethanol solutions containing ethyl orthosilicate, taking-up is put after being cleaned repeatedly with ethyl alcohol
Enter dry in drying box；
The ethyl alcohol contained in wet gel ball is fully washed into displacement using hexane solution, then the wet bead after being sufficiently displaced from
It is put into the solution of n-hexane, trim,ethylchlorosilane, isopropanol and is modified, after finally repeatedly washing modified bead with n-hexane
It is put into drying box dry.
2. preparation method according to claim 1, it is characterised in that
Step A) in alumina sol aluminium oxide solid content in 8-10%, i.e., solute presses Al2O3Account for the mass ratio meter of colloidal sol
It calculates, Al2O3A concentration of 8-10%；
Step A) in titanium oxide sol titanium oxide solid content be 4-5%.
3. preparation method according to claim 1, it is characterised in that：
Above-mentioned steps B) in container in surfactant be saturation aqueous surfactant solution, surfactant is dodecane
Base benzene sulfonic acid sodium salt, tetrabutylammonium bromide or cetyl trimethylammonium bromide.
4. preparation method according to claim 1, it is characterised in that：
Step D) in roasting process be：It is warming up to final temperature for 1-10 DEG C/min with heating rate, is stopped 1-3 hours in final temperature, eventually
Temperature is 400-1000 DEG C.
5. with prepared by the preparation method according to any one in claim 1-4 there is high-specific surface area and acid to measure
Aluminium-titanium binary oxide gas gel small ball.
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| CN104475168B (en) * | 2014-11-12 | 2017-06-23 | 中海油天津化工研究设计院有限公司 | A kind of preparation method of Large ratio surface small-bore aluminum titanium composite oxide |
| 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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| CN101619177A (en) * | 2009-07-31 | 2010-01-06 | 孝感学院 | Preparation method of nano-titanium dioxide coated nano-aluminium oxide |
| CN101890371A (en) * | 2009-05-19 | 2010-11-24 | 中国石油化工股份有限公司 | Titanium dioxide-aluminum oxide composite carrier and preparation method thereof |
| CN102049247A (en) * | 2009-11-02 | 2011-05-11 | 中国石油化工股份有限公司 | Compound carrier for hydrofining catalyst, preparation method and purpose |
| CN102557670A (en) * | 2010-12-24 | 2012-07-11 | 中国科学院兰州化学物理研究所 | Preparation method of aluminum oxide and titanium oxide compound nanometer powder body |
| CN102921474A (en) * | 2012-10-30 | 2013-02-13 | 陕西高新能源发展有限公司 | Preparation method of TiO2/Al2O3 composite carrier |
| CN103055945A (en) * | 2011-10-21 | 2013-04-24 | 中国石油化工股份有限公司 | Synthesis method of titanium aluminum composite oxide carrier |
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101890371A (en) * | 2009-05-19 | 2010-11-24 | 中国石油化工股份有限公司 | Titanium dioxide-aluminum oxide composite carrier and preparation method thereof |
| CN101619177A (en) * | 2009-07-31 | 2010-01-06 | 孝感学院 | Preparation method of nano-titanium dioxide coated nano-aluminium oxide |
| CN102049247A (en) * | 2009-11-02 | 2011-05-11 | 中国石油化工股份有限公司 | Compound carrier for hydrofining catalyst, preparation method and purpose |
| CN102557670A (en) * | 2010-12-24 | 2012-07-11 | 中国科学院兰州化学物理研究所 | Preparation method of aluminum oxide and titanium oxide compound nanometer powder body |
| CN103055945A (en) * | 2011-10-21 | 2013-04-24 | 中国石油化工股份有限公司 | Synthesis method of titanium aluminum composite oxide carrier |
| CN102921474A (en) * | 2012-10-30 | 2013-02-13 | 陕西高新能源发展有限公司 | Preparation method of TiO2/Al2O3 composite carrier |
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