CN1834020A - Prepn. process of titania hydrosol having anatase type - Google Patents
Prepn. process of titania hydrosol having anatase type Download PDFInfo
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- CN1834020A CN1834020A CN 200610039319 CN200610039319A CN1834020A CN 1834020 A CN1834020 A CN 1834020A CN 200610039319 CN200610039319 CN 200610039319 CN 200610039319 A CN200610039319 A CN 200610039319A CN 1834020 A CN1834020 A CN 1834020A
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Abstract
This invention relates to a method to prepare photocatalytic and laser antifake materials and specifically refers to a method to prepare an anatase -type titanium dioxide hydrosol. In this method, titanium tetrachloride is adopted as raw materials and is diluted with a TiCl4/water volum ratio of 1:1~10 at a temperature of 0~20 deg. C. At 40~90 deg. C, the preceding solution is further diluted for a hydrolysis for 30~480 minutes. The hydrolyzed solution is then extracted with a mixed extracting system comprising trioctylamine as extractor and alkanes or aromatic hydrocarbons such as cyclohexane, benzene, toluene, etc as diluent. Aqueous phase and organic phase are separated, and organic phase is reextracted by room-temperature shaking with inorganic alkali so as to remove the chlorine ion in sol and obtain anatase-type titanium dioxide hydrosol. The reextractant for the hydrosol can be stably stored for over 1 month at room temperature. This invention has the advantages of simple technique and high efficiency, and the sprayable products can be sprayed onto kinds of inorganic and organic materials for photocatalytic or laser marking and antifake applications.
Description
Technical field
The present invention relates to a kind of photochemical catalysis and laser anti-counterfeit preparation methods, refer in particular to a kind of preparation method with anatase titanium dioxide water-sol, light-catalyzed reaction can take place in this material under the irradiation of UV-light, be applied to the environmental protection field.Simultaneously, the antiforge laser holographic imaging surface of making in mold pressing of can filming is made literal antiforge laser holographic film.
Background technology
At the beginning of the seventies, professor Fujishima of Japan finds TiO first
2Has photocatalysis performance.When titanium dioxide nanoparticle size during less than a certain critical size, it is remarkable that its quantum size effect becomes, charged particle carrier demonstrates the quantum behavior, conduction band becomes with valence band and separates energy level, energy gap broadens, the corrigendum that becomes of valence band current potential, and the conduction band current potential becomes more negative, thereby increased the redox ability in light induced electron and hole, improved nano-TiO
2The organic activity of photochemical catalytic oxidation.TiO
2Three kinds of crystal formations are arranged: anatase octahedrite (anatase), rutile (rutile) and brookite (brookite).It has been generally acknowledged that anatase octahedrite is the highest active a kind of crystal formation, secondly is rutile-type, and brookite and unformed TiO
2There is not tangible photocatalytic activity.Employing contains anatase TiO
2Can high-level efficiency be located in to fall airborne objectionable constituent such as NOx, formaldehyde etc. as photocatalyst.Surface plating one deck tens nanometers of conventional ceramic or the photocatalysis thin film of hundreds of nano titanium oxide, this film have deep oxidation one reducing power be subjected to activating signal activation under the ultraviolet wire spoke is shone after, thereby degradable organic pollutant keeps the cleaning of ceramic surface.When having avoided utilizing the adsorption of gac isoreactivity material to purify air with water in the past pollutent to another mutually from a phase transition, and the problem that pollutent self is difficult to handle.In air and water purification, especially, more and more be subjected to people's attention demonstrating huge application potential aspect the deep purifying of tap water and room air and the sterilization.Simultaneously, because TiO
2High refractive index (specific refractory power 2.6), it is coated in embossed hologram surface forms laser holographic anti counterfeiting label, can be used for the false proof of certificate passport card film, plastic wrapping and printing overlay film.
It is a kind of simple and important method in the photocatalytic applications process that the nano titanium oxide water-sol that will have the anatase octahedrite feature is sprayed directly on various inorganicss and the organism.The method for preparing the nano-titanium dioxide powder with anatase octahedrite feature is a lot, one of method is that the nano-titanium dioxide powder of anatase octahedrite feature is distributed in the aqueous solution by the method that adds dispersion agent, this method is almost unavoidable brings reunion, is difficult to guarantee the high dispersive of nano titanium oxide.Use the effect that often can not obtain in practice.And the method for preparing titania hydrosol usually all is a peptisation, promptly utilizes titaniferous inorganics (titanium tetrachloride, titanium sulfate) or organism (metatitanic acid tetrem fat, metatitanic acid four positive third fat etc.) to be hydrolyzed in acid, alkali or alcoholic solution.Obtain the titanic acid-sol, repetitive scrubbing goes out impurity, adds peptizing agent (normally mineral acid) then and carries out peptization.Form colloidal sol.Patent CN00127951.3, CN00110406.3, CN03119113.4, CN200410029904.3, CN200410043228.5, CN200510039171.6, CN200510012123.8 all takes the method for peptization to prepare the titania hydrosol of various performances, in above-mentioned preparation process, the contradiction that can't avoid is that the titanic acid-sol is too small owing to particle, causes washing impurity difficult unusually.In fact this limited the industrial applications of this method.In addition, titanium dioxide is unformed in the colloidal sol that aforesaid method obtains, and needs heating carry out crystallization (generally wanting more than 400 ℃) after filming, and this has also limited the application in practice of this method.
Summary of the invention
The purpose of this invention is to provide a kind of nano titanium oxide water-sol with anatase octahedrite feature.
Another object of the present invention provides a kind of high-level efficiency preparation and has the method for the nano titanium oxide water-sol of anatase octahedrite feature.
For achieving the above object, the technical scheme that the present invention takes is: with the titanium tetrachloride is raw material, presses titanium tetrachloride and water volume ratio 1: 1～10 0 ℃ ~ 20 ℃ down dilutions, under 40～90 ℃ temperature, above-mentioned diluent is added the water hydrolysis 30～480 minutes again.Make extraction agent with trioctylamine, comprise that alkane such as hexanaphthene, benzene, toluene or arene are that the hybrid extraction system of thinner extracts the solution that said hydrolyzed forms.Water phase separated and organic phase, organic phase is removed Cl in the colloidal sol with reverse-extraction agent in normal temperature concussion back extraction
-, the titania hydrosol that obtains having the anatase octahedrite feature.
Described reverse-extraction agent is the mineral alkali that comprises ammoniacal liquor, sodium hydroxide.
Because the technique scheme utilization, the present invention compared with prior art has following advantage:
(1), take extraction process to remove Cl in the colloidal sol
-Make colloidal sol stable, the titania hydrosol that can quick large batch of preparation has the anatase octahedrite feature.Be convenient to suitability for industrialized production.
(2), the water-sol that obtains of this method can be inorganic in difference, organic, spray on the macromolecule material, be coated with film forming, need not further heating crystallization.Enlarged the range of application of titania hydrosol.
(3), the titania hydrosol with anatase octahedrite feature that obtains of this method need not any stablizer, at room temperature can stablize more than one month.
Description of drawings
Fig. 1 is the uv-visible absorption spectra figure (ordinate zou is an absorb light intensity, and X-coordinate is the ultraviolet-visible wavelength) of the titania hydrosol with anatase octahedrite feature of 2 preparations of the embodiment of the invention;
Fig. 2 is the x-Ray diffraction light spectrogram (ordinate zou is a diffracted intensity, and X-coordinate is 2 θ diffraction angle) of the titania hydrosol smear with anatase octahedrite feature of the embodiment of the invention 2 preparations.
Embodiment
Below in conjunction with drawings and Examples the present invention is further described:
Embodiment 1: analytically pure titanium tetrachloride solution 112mL is put into there-necked flask, drip distilled water 388mL in ice bath, temperature is no more than 20 ℃.Obtaining concentration approximately is the titanium dioxide storing solution (solution I) of 2mol/L.Get solution I 20mL and add 140ml distilled water, 40 ℃ of following constant temperature hydrolysis 5 hours.Obtain clear solution.With the trioctylamine is extraction agent, and toluene is the clear solution of extraction system after normal temperature concussion extraction said hydrolyzed 15 minutes of thinner (volume ratio is 2: 1).Water phase separated and organic phase, organic phase is shaken back extraction with 10% sodium hydroxide 20mL at normal temperature, and the organic phase that obtains can be used repeatedly.Up to the pH of water value 6～7.This water is the titania hydrosol with anatase octahedrite feature, this colloidal sol TiO
2Weight percent be 2%, pH=6～7.Cl
-Content is 1 * 10
-6～1 * 10
-7Mol.L
-1
Embodiment 2: the solution I 20mL among the embodiment 1 is added 140ml distilled water, 70 ℃ of following constant temperature hydrolysis 1.5 hours, obtain clear solution.With toluene and trioctylamine (volume ratio is 2: 1) the mixed system clear solution that is extraction agent after normal temperature concussion extraction said hydrolyzed 15 minutes.Water phase separated and organic phase, organic phase is shaken back extraction 3～5 times with 10% sodium hydroxide 20mL at normal temperature, and the organic phase that obtains can be used repeatedly.Up to the pH of water value 6.5～7.This water is the titania hydrosol with anatase octahedrite feature, this colloidal sol TiO
2Weight percent be 2%, pH=6～7.Cl
-Content is 1 * 10
-6～1 * 10
-7Mol.L
-1
Embodiment 3: the solution I 20mL among the embodiment 1 is added 56ml distilled water, 70 ℃ of following constant temperature hydrolysis 1 hour, obtain clear solution.With toluene and trioctylamine (volume ratio is 2: 1) the mixed system clear solution that is extraction agent after normal temperature concussion extraction said hydrolyzed 15 minutes.Water phase separated and organic phase, organic phase is shaken back extraction 3～5 times with 10% sodium hydroxide 20mL at normal temperature, and the organic phase that obtains can be used repeatedly.Up to the pH of water value 6.5～7.This water is the titania hydrosol with anatase octahedrite feature.This colloidal sol TiO
2Weight percent be 5%, pH=6～7.Cl
-Content is 1 * 10
-6～1 * 10
-7Mol.L
-1
Embodiment 4: the solution I 20mL among the embodiment 1 is added 140ml distilled water, 90 ℃ of following constant temperature hydrolysis 0.5 hour, obtain clear solution.With hexanaphthene and trioctylamine (volume ratio is 2: 1) the mixed system clear solution that is extraction agent after normal temperature concussion extraction said hydrolyzed 15 minutes.Water phase separated and organic phase, organic phase is shaken back extraction 3～5 times with 10% ammonia soln 20mL at normal temperature, and the organic phase that obtains can be used repeatedly.Up to the pH of water value 6.5～7.This water is the titania hydrosol with anatase octahedrite feature.This colloidal sol TiO
2Weight percent be 2%, pH=6～7.Cl
-Content is 1 * 10
-6～1 * 10
-7Mol.L
-1
Embodiment 5: analytically pure titanium tetrachloride solution 100mL is put into there-necked flask, drip distilled water 100mL in ice bath, temperature is no more than 20 ℃.Get above-mentioned solution 20mL and add 48ml distilled water, 40 ℃ of following constant temperature hydrolysis 5 hours.Obtain clear solution.With benzene and trioctylamine (volume ratio is 2: 1) mixed system is the clear solution of extraction agent after normal temperature concussion extraction said hydrolyzed 15 minutes.Water phase separated and organic phase, organic phase is shaken back extraction 3～5 times with 10% ammoniacal liquor 20mL at normal temperature, and the organic phase that obtains can be used repeatedly.Up to the pH of water value 6～7.This water is the titania hydrosol with anatase octahedrite feature.This colloidal sol TiO
2Weight percent be 10%, pH=6～7.Cl
-Content is 1 * 10
-6～1 * 10
-7Mol.L
-1
Embodiment 6: analytically pure titanium tetrachloride solution 10mL is put into there-necked flask, drip distilled water 100mL in ice bath, temperature is no more than 20 ℃.Get above-mentioned solution 20mL and add 51ml distilled water, 50 ℃ of following constant temperature hydrolysis 4 hours.Obtain clear solution.With benzene and trioctylamine (volume ratio is 2: 1) mixed system is the clear solution of extraction agent after normal temperature concussion extraction said hydrolyzed 15 minutes.Water phase separated and organic phase, organic phase is shaken back extraction 3～5 times with 10% ammoniacal liquor 20mL at normal temperature, and the organic phase that obtains can be used repeatedly.Up to the pH of water value 6～7.This water is the titania hydrosol with anatase octahedrite feature, this colloidal sol TiO
2Weight percent be 1%, pH=6～7.Cl
-Content is 1 * 10
-6～1 * 10
-7Mol.L
-1
Claims (1)
1, the preparation method who has the anatase titanium dioxide water-sol, it is characterized in that: be raw material with the titanium tetrachloride, press titanium tetrachloride and water volume ratio 1: 1～10 0 ℃～20 ℃ down dilutions, under 40～90 ℃ temperature, above-mentioned diluent was added the water hydrolysis 30～480 minutes again, make extraction agent with trioctylamine, with comprising that alkane such as hexanaphthene, benzene, toluene or arene are that the hybrid extraction system of thinner extracts the solution that said hydrolyzed forms, water phase separated and organic phase, organic phase adopt reverse-extraction agent to remove Cl in the colloidal sol in normal temperature concussion back extraction
-, the titania hydrosol that obtains having the anatase octahedrite feature, described reverse-extraction agent are the mineral alkalis that comprises ammoniacal liquor, sodium hydroxide.
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| CN100513318C CN100513318C (en) | 2009-07-15 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102107907B (en) * | 2009-12-28 | 2012-11-28 | 中国科学院金属研究所 | Porous nano hydrated titanium dioxide dearsenifying material and preparation method thereof |
| CN104609469A (en) * | 2015-01-25 | 2015-05-13 | 北京化工大学 | Preparation method for mono-dispersed nano titanium dioxide sol |
| CN106263432A (en) * | 2016-08-30 | 2017-01-04 | 韦广 | Self-clean type Stationery bag |
| CN106542670A (en) * | 2016-10-31 | 2017-03-29 | 陕西蔚蓝节能环境科技集团有限责任公司 | A kind of wet desulphurization waste water zero discharge treatment process |
-
2006
- 2006-04-05 CN CNB2006100393190A patent/CN100513318C/en active Active
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102107907B (en) * | 2009-12-28 | 2012-11-28 | 中国科学院金属研究所 | Porous nano hydrated titanium dioxide dearsenifying material and preparation method thereof |
| CN104609469A (en) * | 2015-01-25 | 2015-05-13 | 北京化工大学 | Preparation method for mono-dispersed nano titanium dioxide sol |
| CN104609469B (en) * | 2015-01-25 | 2017-01-04 | 北京化工大学 | A kind of single dispersing, the preparation method of nano titanic oxide sol |
| CN106263432A (en) * | 2016-08-30 | 2017-01-04 | 韦广 | Self-clean type Stationery bag |
| CN106542670A (en) * | 2016-10-31 | 2017-03-29 | 陕西蔚蓝节能环境科技集团有限责任公司 | A kind of wet desulphurization waste water zero discharge treatment process |
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| Publication number | Publication date |
|---|---|
| CN100513318C (en) | 2009-07-15 |
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Effective date of registration: 20141204 Address after: Daitou town of Liyang City Ferry Street 213311 Jiangsu city of Changzhou province 8-2 No. 7 Patentee after: Liyang Chang Technology Transfer Center Co., Ltd. Address before: 213016 Baiyun road science and Technology Department, Jiangsu, Changzhou Patentee before: Jiangsu Polytechnic University |