CN1283555C - Method for preparing rutile nano titanium dioxide - Google Patents
Method for preparing rutile nano titanium dioxide Download PDFInfo
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- CN1283555C CN1283555C CN 200310106562 CN200310106562A CN1283555C CN 1283555 C CN1283555 C CN 1283555C CN 200310106562 CN200310106562 CN 200310106562 CN 200310106562 A CN200310106562 A CN 200310106562A CN 1283555 C CN1283555 C CN 1283555C
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Abstract
The present invention relates to a preparation method for rutile phase nanometer titanium dioxide powder. The method uses the technical scheme that carriers and dispersion media are selected; under the action of certain ultrasonic frequency and power, carriers in hydrolysate products and the dispersion media are coprecipitated by controlling the hydrolysis speed of titanium salt; the carriers are removed after water washing and alcohol washing, and the rutile phase nanometer titanium dioxide with the grain diameter of 7 to 40 nm is obtained. Reaction is carried out under normal temperature and normal pressure, and the obtain products do not need to be ground and are powder; therefore, the rutile phase nanometer titanium dioxide powder has the characteristics of controllable grain diameter, narrow distribution, high purity, no aggregation, simple manufacturing process, short process, low cost and easy large-scale production.
Description
Technical field
The present invention relates to a kind of preparation method of rutile-phase nano-titanium dioxide powder, belong to field of inorganic material preparing technology.
Background technology
Nano titanium oxide is the extremely wide nano material of a kind of application, and it has nanoparticle (1～100nm) distinctive small-size effect, quantum size effect, surface effects and macro quanta tunnel effect.Its extremely strong ultraviolet screener ability can make it make ultraviolet screening agent at makeup, field of textiles; Its high light oxidation capacity and chemical stability, nontoxicity make it be expected to become a kind of good photocatalyst material, are used to purify air, deodorizing, antifouling, antibiotic; Its good optical character can make coating and paint produce the effect of effect, improves coating and paint quality greatly; Can be used in addition in the emulsion paint, improve colour vividness, resistance to deterioration and the weathering resistance etc. of filming.
The above-mentioned performance of nano titanium oxide can be not fully exerted depend on size of particles, form, structure and use in agglomeration.Say that from crystal formation nano titanium oxide mainly contains anatase, rutile, plate attitude ore deposit.Because rutile has the impayable excellent properties of many other crystal formations (as good opacifying property, chemical stability, ultraviolet screener effect), application prospect is the most wide, is widely used in fields such as senior pigment, makeup, non-linear photon material.
The method that is used to prepare nano titanium oxide at present is a lot, but be used to produce amorphous or sharp attitude type mostly, produce the also few of high pure gold redrock phase nano-titanium dioxide, generally be rutile and sharp attitude and deposit, and, therefore be not easy to make the red schorl phase titanium dioxide of small particle size because sharp attitude type needs high temperature to the rutile-type transformation.Nanometer rutile phase titanic oxide preparation method generally is divided into vapor phase process and liquid phase method, relatively is typically the chloride oxidation method in the vapor phase process, powder purity height, and granularity is little, but technical equipment is had relatively high expectations, and energy consumption is big, the cost height.Liquid phase method relatively is typically sol-gel method, this method general using titanium alcohol ester is a raw material, cost is higher, and technical process is longer, easily produce hard aggregation in the powder last handling process, be not easy to obtain the rutile-phase nano-titanium dioxide of small particle size, and in the sol-gel building-up process, the factor that causes titanium dioxide crystal form to change is a lot, the nano titanium oxide that often obtains multiple crystal formation and deposit.Inorganic titanium salt hydrolysis direct precipitation method be the easiest also be most economical method, but because in the hydrolytic process, the subtle change of external conditions (as concentration, temperature, pH value etc.) all can produce very big influence to the result, and phase inversion at high temperature carries out, and therefore generally can only obtain micron order rutile-phase nano-titanium dioxide powder.Though hydrothermal method can directly generate gold redrock nano-titanium dioxide, its equipment requirements height, complicated operation, cost is higher.Publication number is in the Chinese patent " method of preparing titanic schorl phase titanium dioxide nanometer crystal under room temp " of CN1248550A, disclosing a kind of is main raw material with the titanium tetrachloride, adopt the method for prepared titanic schorl phase titanium dioxide nanometer crystals such as mineral acid hydrolysis, vacuum-drying, because it is relatively stricter that this method requires control of process condition, especially the concentration of titanium tetrachloride is bigger to the hydrolysis rate influence, and the required heavyization time is longer, therefore, productive rate is lower, is unfavorable for suitability for industrialized production.
Therefore explore that performance is good, cost is low, flow process is short and be convenient to the nanometer rutile phase titanic oxide powder preparing novel process of scale operation significant to the excellent properties of giving full play to nano titanium oxide.
Summary of the invention
The objective of the invention is to overcome the deficiencies in the prior art, provide a kind of titanium dioxide rutile phase content height, controlled, the narrowly distributing of particle diameter, and technology is simple, flow process short, the method for preparing the rutile-phase nano-titanium dioxide material of easy scale operation.
Its concrete technical process is as follows:
1. carrier is added in the solvent system that contains dispersion agent, the carrier consumption is 10～50g/L, under the ultrasonic wave effect carrier is fully disperseed;
2. the pH value with concentrated hydrochloric acid or concentrated nitric acid adjusting dispersion liquid is 1.0～2.0;
3. the titanium-containing compound aqueous solution that with strength of solution is 0.5～2.0mol/L slowly joins in the above-mentioned dispersion liquid, under the ultrasonic wave effect, slowly adds alkali lye, reacts 1～3 hour, and the mol ratio of alkali lye add-on and titanium-containing compound is 3～6: 1;
4. leave standstill after 2～3 hours filter, carrying out washing treatment, directly eliminate obtaining filter cake at 500～900 ℃ temperature lower calcination to carrier, make loose shape rutile-type nano titania powder.
In the preparation method of above-mentioned rutile-phase nano-titanium dioxide, described carrier is modified lignin mahogany sulfonate, cyclodextrin, powdered carbon, starch, algae, macromolecule network polymkeric substance or its mixture; Described titanium-containing compound is TiCl
4, Ti (SO
4)
2, titanic acid ester or its mixture; Described dispersion agent is ethylenediamine tetraacetic acid (EDTA), citric acid, T-80 or Yelkin TTS class, and the concentration of dispersion agent is 0.5～2.0g/L; Described solvent is ethanol, butanols, hexanaphthene, Virahol, water or its mixed solvent; Described alkali lye is urea, ammoniacal liquor, sodium hydroxide, potassium hydroxide, yellow soda ash, sodium bicarbonate, salt of wormwood, saleratus or its mixture; Described ultrasonic frequency is 20～50KHz, and power is 100～500W.
Outstanding advantage of the present invention is:
1. selected carrier has absorption and iris action, has avoided the reunion and the bonding of product, prevented growing up of crystal grain in the postorder phase inversion process, so the gained diameter of particle is little, and it is very narrow to distribute, in ± 1nm.
2. be reflected under the ultrasonic wave effect and carry out, the crystalline phase transformation ratio is more abundant, and therefore, the nano-powder rutile phase content of preparation is up to 99%.
3. products obtained therefrom need not milled and is nano-powder, and narrow diameter distribution, and therefore, powder has fabulous dispersiveness in the aqueous solution, places the long period and does not have obvious agglomeration.
4. reaction is carried out at normal temperatures and pressures, and technical process is short, easily suitability for industrialized production.
Description of drawings
Fig. 1 is the laser particle size analysis figure of the prepared rutile-phase nano-titanium dioxide powder of one embodiment of the invention;
Fig. 2 is the X diffraction analysis figure as a result of the prepared rutile-phase nano-titanium dioxide powder of one embodiment of the invention;
Fig. 3 is the transmission electron microscope picture of the prepared rutile-phase nano-titanium dioxide powder of one embodiment of the invention.
Embodiment
Below by embodiment also in conjunction with the accompanying drawings, technical scheme of the present invention is further elaborated.
Embodiment 1:
The 2g cyclodextrin is added to 100ml contains in the ethanol/water mixed solvent of Yelkin TTS 0.8g/L, under the ultrasonic wave effect, it is fully disperseed; PH value with concentrated hydrochloric acid adjusting dispersion liquid is 1.1 then; With concentration is that the titanium tetrachloride aqueous solution of 0.5mol/L slowly joins in the above-mentioned dispersion liquid, is 30KHz in frequency, and power is under the ultrasonic wave effect of 250W, drips concentration and be 30% ammoniacal liquor, and reaction is 1.5 hours under the room temperature; Leave standstill after 2 hours and filter, wash, 700 ℃ of temperature lower calcinations 1 hour, promptly getting particle diameter was the off-white powder shape rutile type nano titanic oxide of 9.5nm with the filter cake that obtains.
Referring to accompanying drawing 1, by the laser particle size analyzer analytical results as can be known, by the rutile-phase nano-titanium dioxide powder that embodiment 1 described preparation method makes, median size is 9.5nm, size distribution ± 0.1nm.
Referring to accompanying drawing 2, the rutile-phase nano-titanium dioxide powder that makes by embodiment 1 described preparation method, X diffraction analysis result shows: 2 corresponding respectively θ of main peaks are 27.39,36.03,41.19,54.28, and are in full accord with rutile material phase analysis normal data (JCPDF).
Referring to accompanying drawing 3, by the rutile-phase nano-titanium dioxide powder that embodiment 1 described preparation method makes, shown in the transmission electron microscope image, dispersion of particles and homogeneity are very good.
Embodiment 2:
The 2g modified lignin mahogany sulfonate is added to 150ml to be contained in ethanol/cyclohexane/water mixed solvent of ethylenediamine tetraacetic acid (EDTA) 2.0g/L, under the ultrasonic wave effect, carrier is fully disperseed, pH value with concentrated hydrochloric acid adjusting dispersion liquid is 1.5 then, with concentration is that the butyl (tetra) titanate aqueous solution of 1.5mol/L slowly joins in the above-mentioned dispersion liquid, in frequency is 30KHz, power is under the ultrasonic wave effect of 300W, dropping concentration is 30% ammoniacal liquor, other step gets 19.5nm off-white powder shape rutile type nano titanic oxide with embodiment 1.
1g powdered carbon and 1g starch are added to 150ml to be contained in ethanol/cyclohexane/water mixed solvent of citric acid 2.0g/L, under the ultrasonic wave effect, it is fully disperseed, pH value with concentrated nitric acid adjusting dispersion liquid is 1.0 then, with concentration is that the titanium tetrachloride aqueous solution of 0.5mol/L slowly joins in the above-mentioned dispersion liquid, in frequency is 30KHz, power is under the ultrasonic wave effect of 250W, dropping concentration is 30% ammoniacal liquor, reaction is after 1.5 hours under the room temperature, left standstill 2 hours, filter then, washing 700 ℃ of temperature lower calcinations 1 hour, promptly gets 24.5nm off-white powder shape rutile type nano titanic oxide with filter cake.
The 2g powdered carbon is added to 100ml contains in the ethanol/water mixed solvent of Yelkin TTS 0.8g/L, other step is with embodiment 1, and the gained diameter of particle is 25.2nm, the off-white powder shape.
The foregoing description shows, by changing kind of carrier and processing condition, can obtain the powder of different-grain diameter.
Claims (7)
1. the preparation method of a rutile-phase nano-titanium dioxide is characterized in that:
(1) carrier is added in the solvent system that contains dispersion agent, the carrier consumption is 10～50g/L, under the ultrasonic wave effect carrier is fully disperseed;
(2) the pH value with concentrated hydrochloric acid or concentrated nitric acid adjusting dispersion liquid is 1.0～2.0;
(3) be that the titanium-containing compound aqueous solution of 0.5～2.0mol/L slowly joins in the above-mentioned dispersion liquid with strength of solution, under the ultrasonic wave effect, slowly add alkali lye, reacted 1～3 hour, the mol ratio of alkali lye add-on and titanium-containing compound is 3～6: 1;
(4) leave standstill after 2～3 hours filter, carrying out washing treatment, directly eliminate obtaining filter cake at 500～900 ℃ temperature lower calcination to carrier, make loose shape rutile-type nano titania powder.
2. the preparation method of rutile-phase nano-titanium dioxide according to claim 1, it is characterized in that: described carrier is modified lignin mahogany sulfonate, cyclodextrin, powdered carbon, starch, algae, macromolecule network polymkeric substance or its mixture.
3. the preparation method of rutile-phase nano-titanium dioxide according to claim 1, it is characterized in that: described titanium-containing compound is TiCl
4, Ti (SO
4)
2, titanic acid ester or its mixture.
4. the preparation method of rutile-phase nano-titanium dioxide according to claim 1, it is characterized in that: described dispersion agent is ethylenediamine tetraacetic acid (EDTA), citric acid, T-80 or Yelkin TTS class, and the concentration of dispersion agent is 0.5～2.0g/L.
5. the preparation method of rutile-phase nano-titanium dioxide according to claim 1, it is characterized in that: described solvent is ethanol, butanols, hexanaphthene, Virahol, water or its mixed solvent.
6. the preparation method of rutile-phase nano-titanium dioxide according to claim 1, it is characterized in that: described alkali lye is urea, ammoniacal liquor, sodium hydroxide, potassium hydroxide, yellow soda ash, sodium bicarbonate, salt of wormwood, saleratus or its mixture.
7. the preparation method of rutile-phase nano-titanium dioxide according to claim 1, it is characterized in that: described ultrasonic frequency is 20～50KHz, power is 100～500W.
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| CN 200310106562 CN1283555C (en) | 2003-12-03 | 2003-12-03 | Method for preparing rutile nano titanium dioxide |
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| CN 200310106562 CN1283555C (en) | 2003-12-03 | 2003-12-03 | Method for preparing rutile nano titanium dioxide |
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Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1318307C (en) * | 2005-03-07 | 2007-05-30 | 李端 | Process for preparing titanic schorl titanium dioxide by adding powder reducing agent mode |
| CN101319405B (en) * | 2007-06-08 | 2011-05-18 | 中国科学院苏州纳米技术与纳米仿生研究所 | Production method of TiO2 nanotube and/or TiO2 nano-whisker |
| TWI487668B (en) * | 2009-02-19 | 2015-06-11 | Sakai Chemical Industry Co | Dispersion of rutile-type titanium oxide particles, method for producing the same, and use thereof |
| CN102145918A (en) * | 2011-04-18 | 2011-08-10 | 东华大学 | Method for preparing rutile titanium dioxide nanoparticles by using highly strong acid |
| CN103833377A (en) * | 2014-03-21 | 2014-06-04 | 景德镇陶瓷学院 | Particle size control method of ceramic powder prepared by wet chemical method |
| CN107324381A (en) * | 2017-07-14 | 2017-11-07 | 昆明理工大学 | A kind of preparation method of nano-titanium dioxide powder |
| CN107935035B (en) * | 2017-11-24 | 2019-08-02 | 河南科斗新材料研究院有限公司 | A kind of preparation method and applications of oil soluble nano titania particle |
| CN110787650A (en) * | 2019-11-22 | 2020-02-14 | 深圳市君脉膜科技有限公司 | Preparation method of porous nano antibacterial particles and composite hollow membrane |
| CN110813102A (en) * | 2019-11-22 | 2020-02-21 | 深圳市君脉膜科技有限公司 | Preparation method of porous nano antibacterial particles and composite tubular membrane |
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