CN1172993C - Process for preparing rutile phase nano titanium dioxide - Google Patents
Process for preparing rutile phase nano titanium dioxide Download PDFInfo
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- CN1172993C CN1172993C CNB021108498A CN02110849A CN1172993C CN 1172993 C CN1172993 C CN 1172993C CN B021108498 A CNB021108498 A CN B021108498A CN 02110849 A CN02110849 A CN 02110849A CN 1172993 C CN1172993 C CN 1172993C
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Abstract
The present invention relates to a method for preparing rutile phase nanometer titanium dioxide, which belongs to the field of fine chemical industry. The present invention is characterized in that a mixed water solution of TiCl3 and TiCl4 is used as initial raw material; the concentration ratio of TiCl3 to TiCl4 is from 1: 1 to 1: 30, and the concentration of TiCl4 is from 0.1 to 1 mol/l, and the concentration of TiCl3 is from 0.02 to 0.5 mol/l; the mixed water solution is warmed, hydrolyzed, aged, deposited and washed by inorganic carbonate to remove Cl<->; rutile phase TiO2 powder with the grain sizes of 6 to 10 nanometers is manufactured after drying; the secondary grain diameters are unequal from 100 to 500 nanometers; when the concentration ratio of TiCl3 to TiCl4 is 1: 1, the TiO2 powder entirely has a spherical rutile phase; when the concentration ratio of TiCl3 to TiCl4 is 1: 30, the TiO2 powder entirely has an acicular rutile phase. The method provided by the present invention is characterized in that the obtain powder has the rutile phase without heat treatment processing, and the powder has the characteristics of large specific surface area, simple manufacturing process and easy large-scale industrialized production.
Description
Technical field
The present invention relates to the preparation method of rutile-phase nano titanium oxide, belong to field of fine chemical.Use the nano-titanium oxide of present method preparation not need to be the rutile phase under the room temperature through high-temperature calcination or interpolation compound modifying agent, the control preparation condition, can obtain grain-size is the 6-10 nanometer, and the uniform rutile-phase nano titanium oxide powder of size distribution.
Technical background
Titanium oxide has three kinds of crystal formations: anatase octahedrite phase, rutile phase and brookite are mutually.Except that brookite mutually, anatase octahedrite all is widely used with rutile titanium oxide powder mutually mutually.The nano-titanium oxide powder can be used in the wastewater treatment, the objectionable constituent of degrading effectively, kill bacteria.As the second phase additive, can significantly improve the ultraviolet reflectivity and the light stability of materials such as paint, coating, plastics, rubber, can also improve its mechanical property.The titanium oxide powder of rutile phase is because its density is big, advantages such as specific refractory power is high, good stability are widely used in senior pigment, coating, paint and the makeup.At present, the production method of rutile phase oxidation titanium valve body mainly contains: the titanium tetrachloride vapour phase oxidation process can make rutile phase micro mist.Preparation process need at high temperature be finished, and equipment corrosion is serious.Another kind of preparation method is that it at first forms the stannic oxide of rutile phase in hydrolytic process, induce the formation of rutile phase oxidation titanium as crystal seed by interpolation crystal conversion agent such as tin tetrachloride in titanium tetrachloride.Contain a certain amount of stannic oxide in the titanium oxide powder that this method is prepared, generally about 5%～20% mole.
One of inventor is once with regard to preparation rutile phase TiO under the room temperature
2Nanocrystalline filing an application, though method technology is simple, constant product quality just can obtain the rutile phase without thermal treatment, can prepare the existing littler rutile-phase nano titanium oxide powder of method of particle diameter ratio.Regrettably be not suitable for the industrialization volume production, and the particle diameter of the rutile powder of producing, pattern are difficult for requiring and the TiO that changes and produce
2The difficult isolating shortcoming of powder.
Summary of the invention
The purpose of this invention is to provide a kind of production method that is applicable to batch preparations rutile phase oxidation nano-ti powder body, this method not only technology is simple, constant product quality, and do not need just can obtain the rutile phase through thermal treatment.Preparation method's schema of the present invention as shown in Figure 1.
Preparation method provided by the invention has 2 substantive distinguishing features and obvious improvement with previous application:
The one, aspect raw material, be raw material with titanous chloride and titanium tetrachloride, the two concentration ratio is controlled at certain limit.Introduce by trivalent titanium ion, play the effect of rutile phase crystal seed, induce the hydrolysis of titanic ionic, the speed of whole hydrolysis reaction and productive rate are improved; Control the add-on of trivalent titanium ion simultaneously, can obtain the rutile phase powder of different shapes, different-grain diameter, be particularly advantageous in the rutile phase of preparing about particle size 500 nanometers, the powder of this size has maximum scattering process to light, can be used in the high grade paint.
The 2nd, adopt the inorganic salt washing; the electrostatic double layer thickness of system is reduced; fine particle precipitates easily, thereby has improved separation greatly, detersive efficiency, has solved the shortcoming that preparation rutile phase powder under the room temperature of previous application difficultly separates, can't large-scale production.
Details are as follows for specific implementation process:
1. the selection of mineral acid: it is acid source that mineral acid can be selected concentrated hydrochloric acid or concentrated nitric acid, adds an amount of regulator solution acidity, and pH should play the effect of control hydrolysis between 0～1.
2. the concentration of titanium tetrachloride, titanous chloride: should be controlled at certain scope.Usually, titanium tetrachloride concentration is in 0.1～1 mol scope, and titanous chloride makes hydrolysis reaction carry out with moderate speed in 0.02～0.5 mol scope.Excessive concentration, hydrolysis rate are too fast, cause hard aggregation easily, and the product crystal formation is a mixed crystal.Concentration is low excessively, and hydrolysis rate is slow, and production efficiency is low.Titanous chloride and titanium tetrachloride concentration ratio are 1: 1-1: 30, can obtain difform rutile phase TiO by the two ratio
2Powder.Then all the spherical rutile phase when both ratios are 1: 1; 1: 30 o'clock all is needle-like rutile phase.
3. stirring, hydrolysis temperature and time: stirring, hydrolysis temperature and time all can influence the pattern of nano-titanium oxide greatly.Leave standstill and stir the pattern that influences powder.Different hydrolysis temperatures and hydrolysis time influence the hydrolysis productive rate.Can select as required to leave standstill or agitation condition, general hydrolysis temperature is 30～70 ℃, and the time is 2～6 hours, and is concrete relevant with the concentration of titanium tetrachloride, Titanium Trichloride Solution.
4. sedimentary ageing and washing: ageing helps obtaining the complete powder of grain growing, and helps next separating step.Digestion time is different with the difference of preparation condition, is generally 8～20 hours.Adopting a kind of concentration is that the method for the inorganic carbonate repetitive scrubbing of 0.02-0.5 mol is removed the chlorion in the precipitation, reduces the reunion degree in the powder drying process.
5. dry: can be dry in 30～70 ℃ baking oven, as reducing the specific surface area of powder greatly in the thermal treatment more than 450 ℃.
6. pulverize: the powder that the present invention obtains at room temperature is the rutile phase, and after washing and drying, powder is loose, without grinding or grinding a little and can pulverize.
In sum, the present invention proposes prepares the method that is rutile-phase nano-titanium dioxide under the room temperature, it is characterized in that:
(1) mixed aqueous solution with titanous chloride and titanium tetrachloride is a starting raw material; And the concentration ratio of titanous chloride and titanium tetrachloride is 1: 1～1: 30; Regulate the pH value of the aqueous solution between 0-1 with mineral acid;
(2) the aqueous hydrolysis temperature is 30-70 ℃, time 2-6 hour;
(3) the solution precipitation thing after the hydrolysis is the inorganic carbonate washing chlorion of 0.02-0.5 mol with concentration after ageing;
(4) the washing back is dry under 30-70 ℃ of temperature.
Use method provided by the invention can make the rutile phase oxidation titanium of grain-size as the 6-10 nanometer thus, its aggregate particle size does not wait in 100～500 nanometers.The outstanding feature of this method is that products obtained therefrom promptly obtains the rutile phase without heat treatment process, and very big specific surface area is arranged.This method has the advantages that technology is simple, be easy to large-scale industrial production.
In sum, the preparation method's of a kind of pure rutile-phase titanium dioxide nano-powder provided by the invention outstanding characteristics are:
1. preparation technology is simple, and processing parameter is controlled easily, is easy to large-scale industrial production.
2. do not need to be the rutile phase under the room temperature through Overheating Treatment and compound modifying agent, the specific surface area of powder is big.
3. preparation method provided by the invention, grain morphology and particle diameter can obtain needle-like and globular TiOx nano crystalline substance, the product purity height with regulating by processing parameter.
Description of drawings
Fig. 1 is a main technique schematic flow sheet of the present invention.
Fig. 2 is the X diffractogram with the TiOx nano crystalline substance of method provided by the invention preparation, among the figure main peaks 1,2,3,4 correspond respectively to rutile mutually 2 θ equal the characteristic diffraction peak of 27.45 °, 36.09 °, 41.23 ° and 54.32 °.
Fig. 3 is the X diffractogram of titanium oxide powder after 450 ℃ of calcinings with method provided by the invention preparation, among the figure main peaks 1,2,3,4 correspond respectively to rutile mutually 2 θ equal the characteristic diffraction peak of 27.45 °, 36.09 °, 41.23 ° and 54.32 °.Powder in the explanatory view one is the rutile phase all, does not have amorphous powder to exist.
Fig. 4, the 5th, the whole needle-likes of method preparation provided by the invention or the transmission electron microscope photo of whole spherical rutile phase oxidation nano-ti powders.Among Fig. 3, TiCl
3With TiCl
4Mol ratio be 1: 30, TiCl among Fig. 4
3With TiCl
4Mol ratio be 1: 1.Can obtain difform rutile phase oxidation titanium valve body by the ratio of controlling both.
Fig. 6 is the X diffractogram of powder before and after a kind of inorganic carbonate washing of 0.25 mol of method preparation provided by the invention, and the crystalline phase of powder does not change after washing as can be seen.
Fig. 7 provides the SEM photo of washing front and back powder, and the washing of inorganic salt hydrochlorate is very little to the pattern influence of powder as can be seen.
Fig. 8 is the measurement result of Zeta potential before and after the powder washing.Behind the inorganic carbonate solution washing under the identical pH condition Zeta potential of powder slightly descend, major cause is because the raising of salt concn makes the electrostatic double layer compression of powder, and the repulsive interaction between the particle reduces, and therefore helps the separation of powder.Abscissa is the pH value, and ordinate is the Zeta potential value, and unit is mV.
Embodiment
Further specify embodiment and effect with following indefiniteness embodiment.
Embodiment 1
Get 50 milliliters of 3 mol titanium tetrachloride solutions, 50 milliliters of the Titanium Trichloride Solutions of 1 mol add 300 milliliters of distilled water, 70 ℃ of hydrolysis 5 hours, and ageing 8 hours is filtered, inorganic carbonate washing after drying, diameter of particle is 10 nanometers.The X-ray diffraction analysis result is indicated as rutile phase powder, and Fig. 2 provides the diffractogram of X ray.X-ray diffractogram after 450 ℃ of calcinings all is the rutile phase still as shown in Figure 3, and the powder in the explanatory view 2 does not have amorphous existence.Pattern as shown in Figure 4.
Embodiment 2
Get 100 milliliters of 0.5 mol titanium tetrachloride solutions, 0.5 100 milliliters of mol Titanium Trichloride Solutions, 50 ℃ of hydrolysis 5 hours under the situation of magnetic agitation, ageing 8 hours, filtration, washing, drying, the inorganic carbonate salt concn of using during washing is 0.05 mol, and aggregated particle size is 200～500 nanometers.The X-ray diffraction analysis result is indicated as rutile phase powder.Figure four provides the transmission electron microscope photo of morphology microstructure.The powder glomeration is formed by the small grains gathering.
Get 100 milliliters of 0.3 mol titanium tetrachloride solutions, 100 milliliters of 0.3 mol Titanium Trichloride Solutions leave standstill hydrolysis in 70 ℃ of baking ovens, and ageing 8 hours behind the inorganic carbonate solution washing, is measured the X diffractogram, the results are shown in Fig. 5.The X-ray diffraction analysis result shows that powder is the rutile phase before and after the inorganic salt washing.
Claims (4)
1. method for preparing rutile-phase nano-titanium dioxide is characterized in that:
(1) mixed aqueous solution with titanous chloride and titanium tetrachloride is a starting raw material; And the concentration ratio of titanous chloride and titanium tetrachloride is 1: 1～1: 30; Regulate the pH value of the aqueous solution between 0-1 with mineral acid;
(2) the aqueous hydrolysis temperature is 30-70 ℃, time 2-6 hour;
(3) the solution precipitation thing after the hydrolysis is the inorganic carbonate washing chlorion of 0.02-0.5 mol with concentration after ageing;
(4) the washing back is dry under 30-70 ℃ of temperature.
2. by the described method for preparing rutile-phase nano-titanium dioxide of claim 1, it is characterized in that the concentration of described titanium tetrachloride aqueous solution is controlled at 0.1-1 mol scope, the concentration of titanium trichloride aqueous solution is controlled at 0.02-0.5 mol scope.
3. by the described method for preparing rutile-phase nano-titanium dioxide of claim 1, it is characterized in that used mineral acid is concentrated hydrochloric acid, concentrated nitric acid.
4. by the described method for preparing rutile-phase nano-titanium dioxide of claim 1, it is characterized in that described throw out digestion time is 8-20 hour.
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| Application Number | Priority Date | Filing Date | Title |
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| CNB021108498A CN1172993C (en) | 2002-02-09 | 2002-02-09 | Process for preparing rutile phase nano titanium dioxide |
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| CNB021108498A CN1172993C (en) | 2002-02-09 | 2002-02-09 | Process for preparing rutile phase nano titanium dioxide |
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| CN1172993C true CN1172993C (en) | 2004-10-27 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100334261C (en) * | 2005-12-01 | 2007-08-29 | 华中师范大学 | Rutile type structure TiO2 single dispersed nano-monocrystal and its synthesis method |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102675928B (en) * | 2012-05-22 | 2014-05-07 | 福州坤彩精化有限公司 | Rutile-type synthetic mica pearlescent pigment and preparation method thereof |
| CN103553124B (en) * | 2013-11-08 | 2015-03-11 | 中国科学技术大学 | Method for preparing blue titanium dioxide |
| CN106207146B (en) * | 2016-08-25 | 2019-10-01 | 北京化工大学 | A method of nano rutile-type titanium dioxide/carbon composite lithium ion battery negative electrode material is prepared in situ |
| CN111470531A (en) * | 2020-04-07 | 2020-07-31 | 福建富仕新材料有限责任公司 | Rutile type chemical fiber titanium dioxide, preparation method and application |
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2002
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100334261C (en) * | 2005-12-01 | 2007-08-29 | 华中师范大学 | Rutile type structure TiO2 single dispersed nano-monocrystal and its synthesis method |
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