CN108706630B - Preparation method of titanium dioxide special for lithium titanate - Google Patents
Preparation method of titanium dioxide special for lithium titanate Download PDFInfo
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- CN108706630B CN108706630B CN201810747056.1A CN201810747056A CN108706630B CN 108706630 B CN108706630 B CN 108706630B CN 201810747056 A CN201810747056 A CN 201810747056A CN 108706630 B CN108706630 B CN 108706630B
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- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
- C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
- C01G23/0536—Producing by wet processes, e.g. hydrolysing titanium salts by hydrolysing chloride-containing salts
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Abstract
A preparation method of titanium dioxide special for lithium titanate comprises the following steps: (1) dissolving titanium tetrachloride in deionized water to prepare a titanium tetrachloride water solution, and then stirring in an ice water bath; (2) adding sulfate into a titanium tetrachloride aqueous solution, and stirring to obtain a mixed solution; (3) adding liquid ammonia or ammonia gas into the mixed solution obtained in the step (2), heating, and carrying out hydrolysis reaction; (4) adding ammonia water or ammonium carbonate solution into the hydrolyzed product obtained in the step (3) for neutralization, stirring and standing, and washing the obtained feed liquid with deionized water to remove impurities to obtain a titanium dioxide material; (5) drying the titanium dioxide material, and then crushing and scattering to obtain the product. The preparation method provided by the invention has the advantages of simple production process, low production cost, easiness in industrial production and the like, and the titanium dioxide obtained by the method has the advantages of high purity, large specific surface area, small particle size, narrow particle size distribution, sphericity, difficulty in agglomeration and the like.
Description
Technical Field
The invention relates to a preparation method of titanium dioxide, in particular to a preparation method of titanium dioxide special for lithium titanate.
Background
At present, the battery-grade titanium dioxide mainly refers to nano-grade titanium dioxide used in lithium titanate batteries, and belongs to high-end titanium dioxide. The lithium titanate is a composite oxide of metal lithium and low-potential transition metal titanium, and the titanium dioxide is an important raw material in the preparation process of the lithium titanate. The demand of the lithium titanate battery for the titanium dioxide is expected to be doubled year by year to 2020 or reach the level of more than 20 ten thousand tons per year.
At present, the content of titanium dioxide in the market is basically less than 98%, and the titanium dioxide contains other impurity elements, so that the requirement of the titanium dioxide for the lithium titanate battery cannot be met.
Disclosure of Invention
The invention aims to provide a preparation method of titanium dioxide special for lithium titanate, and the titanium dioxide prepared by the method can meet the requirements of titanium dioxide for lithium titanate batteries.
In order to achieve the above object, the present invention adopts the following aspects.
A preparation method of titanium dioxide special for lithium titanate comprises the following steps:
(1) dissolving titanium tetrachloride in deionized water, preparing a 1-4M titanium tetrachloride water solution, and then stirring in an ice water bath for 4-8 hours;
(2) adding 0.1-1.5% of dispersant and 0.05-0.5% of sulfate into titanium tetrachloride water solution, and stirring for 15-45min to obtain mixed solution;
(3) adding liquid ammonia or ammonia gas with the mass fraction of 5-20% into the mixed solution obtained in the step (2), heating to 30-90 ℃, and carrying out hydrolysis reaction for 15-45 min;
(4) adding ammonia water or ammonium carbonate solution into the hydrolyzed product obtained in the step (3) to neutralize until the pH value is 7-8, stirring for 30min, standing to completely precipitate insoluble substances, and washing the obtained feed liquid with deionized water to remove impurities to obtain a titanium dioxide material;
(5) drying the titanium dioxide material, and then crushing and scattering to obtain the product.
The preparation method provided by the invention has the advantages of simple production process, low production cost, easiness in industrial production and the like, and the titanium dioxide obtained by the method has the advantages of high purity, large specific surface area, small particle size, narrow particle size distribution, sphericity, difficulty in agglomeration and the like.
In the above scheme, it is further preferable that the dispersant is one or more of monoisopropanolamine, acrylic acid, triethanolamine, and trimethylolpropane.
In the above scheme, it is further preferable that the sulfate is one or more of ammonium sulfate, sodium sulfate and potassium sulfate.
In the above scheme, it is further preferred that the hydrolysis reaction is started by hydrolysis at 30-60 ℃ for 5-20min, and then hydrolysis at 60-90 ℃ for 10-25 min.
In the above scheme, it is further preferable that, in the step (4), the feed liquid is washed with deionized water to remove impurities until the total ion content is less than 100 ppm.
In the above scheme, it is further preferable that, in the step (5), the drying temperature is 105-160 ℃, and the drying time is 8-12 hours.
Detailed Description
The invention is further illustrated by the following specific examples.
Example 1:
(1) dissolving titanium tetrachloride in deionized water to prepare a 1.5M titanium tetrachloride aqueous solution, and then stirring in an ice water bath for 4 hours;
(2) adding 0.5% of trimethylolpropane (dispersant) and 0.1% of ammonium sulfate into a titanium tetrachloride water solution, and stirring for 15min to obtain a mixed solution;
(3) adding 1M of liquid ammonia with the mass fraction of 8% into the mixed solution obtained in the step (2), and performing hydrolysis reaction at 30 ℃ for 20min and then at 75 ℃ for 20 min;
(4) adding ammonia water into the hydrolyzed product obtained in the step (3) to neutralize until the pH value is 7, stirring for 30min, standing for 15min to completely precipitate insoluble substances, washing the obtained feed liquid with deionized water in a filter press to remove impurities until the total ion content is less than 90ppm, and obtaining a titanium dioxide material;
(5) drying the titanium dioxide material in an oven at 120 ℃ for 10h, and then crushing and scattering the titanium dioxide material by a micro powder crusher to obtain a product with the particle size (average) of 5.2 nm.
Example 2:
(1) dissolving titanium tetrachloride in deionized water, preparing a 2.0M titanium tetrachloride water solution, and then stirring in an ice water bath for 5 hours;
(2) adding monoisopropanolamine (a dispersing agent) accounting for 1.0 percent and potassium sulfate accounting for 0.2 percent of the mass ratio into the titanium tetrachloride water solution, and stirring for 20min to obtain a mixed solution;
(3) adding 12% by mass of ammonia gas into the mixed solution obtained in the step (2), and performing hydrolysis reaction at 40 ℃ for 15min and then at 60 ℃ for 20 min;
(4) adding ammonium carbonate into the hydrolyzed product obtained in the step (3) to neutralize until the pH value is 8, stirring for 30min, standing for 20min to completely precipitate insoluble substances, washing the obtained feed liquid with deionized water in a filter press to remove impurities until the total ion content is less than 90ppm, and obtaining a titanium dioxide material;
(5) drying the titanium dioxide material in an oven at 130 ℃ for 9h, and then crushing and scattering the titanium dioxide material by a micro powder crusher to obtain a product with the particle size (average) of 5.5 nm.
Example 3:
(1) dissolving titanium tetrachloride in deionized water to prepare a 3.0M titanium tetrachloride aqueous solution, and then stirring in an ice water bath for 6 hours;
(2) adding 1.0 mass percent of acrylic acid (dispersant) and 0.2 mass percent of sodium sulfate into a titanium tetrachloride water solution, and stirring for 20min to obtain a mixed solution;
(3) adding 15% by mass of ammonia gas into the mixed solution obtained in the step (2), and performing hydrolysis reaction at 40 ℃ for 15min and then at 60 ℃ for 20 min;
(4) adding ammonium carbonate into the hydrolyzed product obtained in the step (3) to neutralize until the pH value is 7, stirring for 30min, standing for 15min, washing the obtained feed liquid with deionized water in a filter press to remove impurities until the total ion content is less than 95ppm, and obtaining a titanium dioxide material;
(5) drying the titanium dioxide material in an oven at 120 ℃ for 10h, and then crushing and scattering the titanium dioxide material by a micro powder crusher to obtain a product with the particle size (average) of 5.8 nm.
Example 4:
(1) dissolving titanium tetrachloride in deionized water to prepare a 4.0M titanium tetrachloride aqueous solution, and then stirring in an ice water bath for 8 hours;
(2) adding triethanolamine (dispersant) with the mass ratio of 1.0% and sodium sulfate with the mass ratio of 0.5% into a titanium tetrachloride water solution, and stirring for 30min to obtain a mixed solution;
(3) adding ammonia gas with the mass fraction of 20% into the mixed solution obtained in the step (2), performing hydrolysis reaction at 40 ℃ for 15min, and performing hydrolysis reaction at 60 ℃ for 20 min;
(4) adding ammonia water into the hydrolyzed product obtained in the step (3) to neutralize until the pH value is 7, stirring for 30min, standing for 15min, washing the obtained feed liquid in a filter press by deionized water to remove impurities until the total ion content is less than 95ppm, and obtaining a titanium dioxide material;
(5) drying the titanium dioxide material in an oven at 150 ℃ for 8h, and then crushing and scattering the titanium dioxide material by a micro powder crusher to obtain a product with the particle size (average) of 6.3 nm.
Example 5:
(1) dissolving titanium tetrachloride in deionized water to prepare a 3.5M titanium tetrachloride aqueous solution, and then stirring in an ice water bath for 7 hours;
(2) adding triethanolamine (dispersant) with the mass ratio of 1.5% and sodium sulfate with the mass ratio of 0.3% into a titanium tetrachloride water solution, and stirring for 20min to obtain a mixed solution;
(3) adding liquid ammonia with the mass fraction of 18% into the mixed solution obtained in the step (2), performing hydrolysis reaction at 50 ℃ for 15min, and performing hydrolysis reaction at 70 ℃ for 20 min;
(4) adding ammonia water into the hydrolyzed product obtained in the step (3) to neutralize until the pH value is 8, stirring for 30min, standing for 20min, washing the obtained feed liquid in a filter press by deionized water to remove impurities until the total ion content is less than 100ppm, and obtaining a titanium dioxide material;
(5) drying the titanium dioxide material in an oven at 160 ℃ for 8h, and then crushing and scattering the titanium dioxide material by a micro powder crusher to obtain a product with the particle size (average) of 5.5 nm.
The physical properties of the titanium dioxide produced in the above examples are shown in the following table:
as can be seen from the table above, the titanium dioxide prepared by the invention has the advantages of high purity, large specific surface area, small particle size and the like.
Claims (5)
1. A preparation method of titanium dioxide special for lithium titanate comprises the following steps:
(1) dissolving titanium tetrachloride in deionized water, preparing a 1-4M titanium tetrachloride water solution, and then stirring in an ice water bath for 4-8 hours;
(2) adding 0.1-1.5% of dispersant and 0.05-0.5% of sulfate into a titanium tetrachloride water solution, and stirring for 15-45min to obtain a mixed solution, wherein the dispersant is one or more of monoisopropanolamine, acrylic acid, triethanolamine and trimethylolpropane;
(3) adding liquid ammonia or ammonia gas with the mass fraction of 5-20% into the mixed solution obtained in the step (2), heating to 30-90 ℃, and carrying out hydrolysis reaction for 15-45 min;
(4) adding ammonia water or ammonium carbonate solution into the hydrolyzed product obtained in the step (3) to neutralize until the pH value is 7-8, stirring for 30min, standing to completely precipitate insoluble substances, and washing the obtained feed liquid with deionized water to remove impurities to obtain a titanium dioxide material;
(5) drying the titanium dioxide material, and then crushing and scattering to obtain the product.
2. The preparation method of titanium dioxide special for lithium titanate as claimed in claim 1, characterized by comprising: the sulfate is one or more of ammonium sulfate, sodium sulfate and potassium sulfate.
3. The preparation method of titanium dioxide special for lithium titanate as claimed in claim 1, characterized by comprising: when the hydrolysis reaction starts, the hydrolysis is carried out for 5-20min at 30-60 ℃ and then for 10-25min at 60-90 ℃.
4. The preparation method of titanium dioxide special for lithium titanate as claimed in claim 1, characterized by comprising: in the step (4), the feed liquid is washed by deionized water to remove impurities until the total ion content is less than 100 ppm.
5. The preparation method of titanium dioxide special for lithium titanate as claimed in claim 1, characterized by comprising: in the step (5), the drying temperature is 105-160 ℃, and the drying time is 8-12 hours.
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| CN108706630B true CN108706630B (en) | 2020-11-06 |
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| CN101074112B (en) * | 2007-06-27 | 2010-10-13 | 仙桃市中星电子材料有限公司 | Production of high-purity superfine titanic oxide |
| CN103803647B (en) * | 2014-03-19 | 2015-11-18 | 仙桃市展朋新材料有限公司 | A kind of preparation method of high purity electronic-grade rutile titanium dioxide |
| CN104150531B (en) * | 2014-06-27 | 2016-10-19 | 仙桃市中星电子材料有限公司 | The preparation method of high specific surface area titanic oxide |
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