Preparation method and application of anatase conductive titanium dioxide

Abstract

The invention provides a preparation method and application of anatase conductive titanium dioxide, and relates to the technical field of titanium dioxide production. The preparation method comprises the following steps: S1, adding deionized water into an anatase titanium dioxide base material, and stirring to form a white suspension; adding a dispersing agent and a precipitating agent into the white suspension, and carrying out ultrasonic treatment to obtain a titanium dioxide suspension; s2, dropwise adding an ethanol solution of tin chloride and antimony chloride into the titanium dioxide suspension to form an adsorption layer on the surface of titanium dioxide, then adjusting the pH value to 1.5-2.5, then transferring into a reaction kettle, reacting at 180 DEG C for 4 hours, and after the reaction is finished, carrying out suction filtration and drying to obtain anatase conductive titanium dioxide; according to the preparation method provided by the invention, anatase titanium dioxide is subjected to coating modification through a hydrothermal method, high-temperature treatment is not needed, the resistivity of the obtained titanium dioxide is about 22 omega.cm, the chromatic value is about 90.25, the average particle size is about 0.258 mu m, the particle size is uniform, the titanium dioxide is easily dispersed in various media, the high-temperature heat resistance is good, and meanwhile, the requirements of light-color appearance, low hardness and good dispersity are met; and the material has the characteristics of excellent conductivity and good stability at high temperature, and can be widely applied to chemical fiber products.

Description

Technical Field

[0001] This invention relates to the field of titanium dioxide production technology, specifically to a method for preparing anatase conductive titanium dioxide and its applications. Background Technology

[0002] Titanium dioxide, as a high-performance inorganic functional material, is known as "industrial MSG" due to its outstanding characteristics such as being non-toxic and harmless, having strong hiding power, excellent coloring power, and stable physicochemical properties. It is indispensable in many core areas of the national economy, such as coatings, plastics, papermaking, and chemical fibers, and has extremely wide application scenarios.

[0003] However, in the actual application of titanium dioxide, the surface of the material is prone to charge transfer and accumulation due to external forces such as friction, impact, and tearing, resulting in static electricity, which needs to be eliminated.

[0004] Currently, most conductive titanium dioxide products are rutile in crystal form. However, during the spinning process of chemical fibers, the high hardness of rutile conductive titanium dioxide can cause severe wear on the spinning nozzles, affecting spinning accuracy and equipment lifespan. Anatase titanium dioxide requires a high-temperature calcination process during modification to promote the crystallization and bonding of conductive active components. However, anatase titanium dioxide has poor crystal structure stability and is prone to irreversible crystal transformation under high temperatures, converting to the rutile form and failing to retain the low hardness required by the chemical fiber industry. Furthermore, conductive titanium dioxide in the chemical fiber field often uses carbon-based materials, leveraging the high conductivity of carbon-based materials to dissipate static electricity. The deep black color of carbon-based materials leads to a darker color in the composite conductive titanium dioxide, affecting the product's appearance.

[0005] Currently, there is a lack of conductive titanium dioxide that can simultaneously meet the three core requirements of "anatase crystal form (to meet the low hardness requirements of chemical fiber spinning), excellent conductivity (to eliminate static electricity problems), and light-colored appearance (to ensure the color of chemical fiber products)," which is an urgent problem to be solved. Summary of the Invention

[0006] To address the shortcomings of existing technologies, this invention provides a method for preparing anatase conductive titanium dioxide and its applications. The preparation method includes the following steps: S1, adding deionized water to anatase titanium dioxide base material and stirring to form a white suspension; adding a dispersant and a precipitant to the white suspension and ultrasonically treating it to obtain a titanium dioxide suspension; S2, adding an ethanol solution of tin chloride and antimony chloride dropwise to the titanium dioxide suspension to form an adsorption layer on the titanium dioxide surface, then adjusting the pH to 1.5–2.5, and then transferring it to a reaction vessel, reacting at 180°C for 4 hours. After the reaction is complete, the mixture is filtered and dried to obtain anatase conductive titanium dioxide. The preparation method provided by this invention uses a hydrothermal method to coat and modify anatase titanium dioxide, eliminating the need for high-temperature treatment. The resulting titanium dioxide has a resistivity of approximately 22 Ω·cm, a color value of approximately 90.25, and an average particle size of 0.258 μm. With a particle size of approximately μm, uniform particle size, easy dispersion in various media, good high-temperature heat resistance, and the characteristics of light-colored appearance, low hardness, good dispersibility, excellent electrical conductivity, and good stability at high temperatures, it can be widely used in chemical fiber products.

[0007] The objective of this invention is achieved through the following technical solution: In a first aspect, the present invention provides a method for preparing anatase conductive titanium dioxide, the method comprising the following steps: S1. Add deionized water to anatase titanium dioxide base material and stir to form a white suspension; add dispersant and precipitant to the white suspension and sonicate to obtain titanium dioxide suspension; S2. Add an ethanol solution of tin chloride and antimony chloride dropwise to the titanium dioxide suspension to form an adsorption layer on the surface of titanium dioxide. Then adjust the pH to 1.5-2.5, transfer it to a reaction vessel, and react at 180°C for 4 hours. After the reaction is completed, filter and dry to obtain anatase conductive titanium dioxide.

[0008] In some specific embodiments of the present invention, the dispersant in step S1 is polyvinylpyrrolidone, the precipitant is urea, and the mass ratio of the dispersant to the precipitant is 1 to 5.

[0009] In some specific embodiments of the present invention, the mass ratio of tin chloride to titanium dioxide in step S2 is 1 to 5.

[0010] In some specific embodiments of the present invention, the molar ratio of antimony chloride to tin chloride in step S2 is 1 to 10.

[0011] In some specific embodiments of the present invention, the method for preparing the ethanol solution of tin chloride and antimony chloride in step S2 is as follows: antimony chloride trihydrate is slowly added to ethanol and stirred until completely dissolved, then tin chloride pentahydrate is added and stirred continuously to obtain the ethanol solution of tin chloride and antimony chloride.

[0012] In some specific embodiments of the present invention, the pH adjustment solution in step S2 is a tartaric acid solution and an ammonia solution.

[0013] In some specific embodiments of the present invention, the power of the ultrasound in step S1 is 100-200W, and the duration of the ultrasound is 20-40 minutes.

[0014] In some specific embodiments of the present invention, the mass-to-volume ratio of the anatase titanium dioxide base material to the deionized water in step S1 is 1 to 2; and the stirring speed is 400 to 600 rpm.

[0015] In some specific embodiments of the present invention, the degree of filtration in step S2 is such that there is no chloride ion residue; the drying temperature is 90±5℃, the vacuum degree is -0.09MPa, and the time is 12 to 16 hours.

[0016] Secondly, the present invention provides an application of the anatase conductive titanium dioxide obtained by the preparation method described in the first aspect in chemical fiber products.

[0017] The beneficial effects achieved by this invention are as follows: The preparation method provided by this invention modifies anatase titanium dioxide by hydrothermal coating without high-temperature treatment. The resulting titanium dioxide has a resistivity of about 22 Ω·cm, a color value of about 90.25, an average particle size of about 0.258 μm, uniform particle size, is easy to disperse in various media, has good high-temperature heat resistance, and simultaneously meets the characteristics of light color, low hardness, good dispersibility, excellent electrical conductivity, and good stability at high temperatures. It can be widely used in chemical fiber products. Detailed Implementation

[0018] The present invention will be further described in detail below with reference to specific embodiments. The following embodiments are not intended to limit the present invention, but only to illustrate the present invention. Unless otherwise specified, the experimental methods used in the following embodiments are generally performed under conventional conditions. Unless otherwise specified, the materials and reagents used in the following embodiments are commercially available.

[0019] Example 1 A method for preparing anatase conductive titanium dioxide specifically includes the following steps: (1) Preparation of ethanol solution of tin chloride and antimony chloride: First, slowly add 0.02 mol / L SbCl3·3H2O to ethanol and stir at 300 rpm in a 25℃ water bath for 15 min until completely dissolved. Then, add 0.2 mol / L SnCl4·5H2O to the above solution in batches and continue stirring for 30 min to obtain a mixed ethanol solution of tin chloride and antimony chloride.

[0020] (2) Coating with titanium dioxide: Add anatase TiO2 base material to deionized water at a mass-volume ratio of 1:2 and continuously stir mechanically (500 rpm) to form a white suspension. Then add dispersant polyvinylpyrrolidone (PVP) and precipitant urea. The mass ratio of PVP to urea is 1:5. Continue stirring for 20 minutes to allow PVP to be fully adsorbed on the surface of TiO2 particles and urea to be uniformly dispersed. Ultrasonicate the above mixed suspension for 30 minutes to obtain TiO2 suspension. Ultrasonic power is 150W. PVP is used as a dispersant to ensure uniform dispersion of Sn and Sb sources. Urea slowly releases hydroxide ions to control the hydrolysis rate of Sn and Sb sources, resulting in more uniform particles. Ultrasonic treatment reduces secondary agglomeration of TiO2 particles.

[0021] A mixed solution of tin chloride and antimony chloride in ethanol was slowly added to a TiO2 suspension. The mass ratio of tin chloride to titanium dioxide was 1:5. Stirring was maintained throughout the addition process, and stirring continued for 60 minutes after the addition was complete. 4+ Sb 3+ It comes into full contact with the surface of TiO2 particles, forming a uniform adsorption layer.

[0022] (3) Hydrothermal reaction: The pH of the above solution is adjusted to 2 using tartaric acid solution and ammonia water, and then transferred into the reaction vessel. The reaction is carried out at 180°C for 4 hours. Tartaric acid, as a complexing agent, can reduce particle aggregation.

[0023] (4) Post-treatment: After the hydrothermal reaction is completed, the reaction product is taken out and the precipitate is transferred to a Buchner funnel. It is then washed with deionized water by suction filtration, adding 100 mL of deionized water each time and filtering until the filtrate is clear. The washing is repeated 4 times. Take 5 mL of the last washing filtrate and add 2 drops of 0.1 mol / L silver nitrate solution. No white precipitate is formed, indicating that there is no residual Cl ions in the precipitate (residual Cl ions will affect the conductivity and stability of the product). The washing is then stopped.

[0024] The washed precipitate was transferred to a vacuum drying oven, where the drying temperature was set to 90±5℃ and the vacuum degree to -0.09MPa for 12–16 hours to completely remove moisture. The dried solid product was then pulverized in an air jet mill to obtain a white, powdery anatase TiO2 conductive powder.

[0025] The titanium dioxide has a resistivity of 22 Ω·cm, a color value of 90.25, uniform particle size, an average particle size of 0.258 μm, is easy to disperse in various media, has good high-temperature heat resistance, and also meets the characteristics of light color, low hardness, good dispersibility, excellent electrical conductivity and good stability at high temperatures. It can be widely used in chemical fiber products.

[0026] Example 2 A method for preparing anatase conductive titanium dioxide specifically includes the following steps: (1) Preparation of ethanol solution of tin chloride and antimony chloride: First, slowly add 0.02 mol / L SbCl3·3H2O to ethanol and stir at 300 rpm in a 25℃ water bath for 15 min until completely dissolved. Then, add 0.2 mol / L SnCl4·5H2O to the above solution in batches and continue stirring for 30 min to obtain a mixed ethanol solution of tin chloride and antimony chloride.

[0027] (2) Coating with titanium dioxide: Add anatase TiO2 base material to deionized water at a mass-volume ratio of 1:2 and continuously stir mechanically (500 rpm) to form a white suspension. Then add dispersant polyvinylpyrrolidone (PVP) and precipitant urea. The mass ratio of PVP to urea is 1:5. Continue stirring for 20 minutes to allow PVP to be fully adsorbed on the surface of TiO2 particles and urea to be uniformly dispersed. Ultrasonicate the above mixed suspension for 30 minutes to obtain TiO2 suspension. Ultrasonic power is 150W. PVP is used as a dispersant to ensure uniform dispersion of Sn and Sb sources. Urea slowly releases hydroxide ions to control the hydrolysis rate of Sn and Sb sources, resulting in more uniform particles. Ultrasonic treatment reduces secondary agglomeration of TiO2 particles.

[0028] A mixed solution of tin chloride and antimony chloride in ethanol was slowly added to a TiO2 suspension. The mass ratio of tin chloride to titanium dioxide was 1:5. Stirring was maintained throughout the addition process, and stirring continued for 60 minutes after the addition was complete. 4+ Sb 3+ It comes into full contact with the surface of TiO2 particles, forming a uniform adsorption layer.

[0029] (3) Hydrothermal reaction: The pH of the above solution was adjusted to 1.5 using tartaric acid solution and ammonia water, and then transferred into the reaction vessel. The reaction was carried out at 180°C for 4 hours. Tartaric acid, as a complexing agent, can reduce particle aggregation.

[0030] (4) Post-treatment: After the hydrothermal reaction is completed, the reaction product is taken out and the precipitate is transferred to a Buchner funnel. It is then washed with deionized water by suction filtration, adding 100 mL of deionized water each time and filtering until the filtrate is clear. The washing is repeated 5 times. Take 5 mL of the last washing filtrate and add 2 drops of 0.1 mol / L silver nitrate solution. No white precipitate is formed, indicating that there is no residual Cl ions in the precipitate (residual Cl ions will affect the conductivity and stability of the product). The washing is then stopped.

[0031] The washed precipitate was transferred to a vacuum drying oven, where the drying temperature was set to 90±5℃ and the vacuum degree to -0.09MPa for 12–16 hours to completely remove moisture. The dried solid product was then pulverized in an air jet mill to obtain a white, powdery anatase TiO2 conductive powder.

[0032] The titanium dioxide has a resistivity of 25 Ω·cm, a chromaticity of 93.2, and an average particle size of 0.255 μm. It also meets the requirements of light color, low hardness, and electrical conductivity, and can be widely used in chemical fiber products.

[0033] Example 3 A method for preparing anatase conductive titanium dioxide specifically includes the following steps: (1) Preparation of ethanol solution of tin chloride and antimony chloride: First, slowly add 0.02 mol / L SbCl3·3H2O to ethanol and stir at 300 rpm in a 25℃ water bath for 15 min until completely dissolved. Then, add 0.2 mol / L SnCl4·5H2O to the above solution in batches and continue stirring for 30 min to obtain a mixed ethanol solution of tin chloride and antimony chloride.

[0034] (2) Coating with titanium dioxide: Add anatase TiO2 base material to deionized water at a mass-volume ratio of 1:2 and continuously stir mechanically (500 rpm) to form a white suspension. Then add dispersant polyvinylpyrrolidone (PVP) and precipitant urea. The mass ratio of PVP to urea is 1:5. Continue stirring for 20 minutes to allow PVP to be fully adsorbed on the surface of TiO2 particles and urea to be uniformly dispersed. Ultrasonicate the above mixed suspension for 30 minutes to obtain TiO2 suspension. Ultrasonic power is 150W. PVP is used as a dispersant to ensure uniform dispersion of Sn and Sb sources. Urea slowly releases hydroxide ions to control the hydrolysis rate of Sn and Sb sources, resulting in more uniform particles. Ultrasonic treatment reduces secondary agglomeration of TiO2 particles.

[0035] A mixed solution of tin chloride and antimony chloride in ethanol was slowly added to a TiO2 suspension. The mass ratio of tin chloride to titanium dioxide was 1:5. Stirring was maintained throughout the addition process, and stirring continued for 60 minutes after the addition was complete. 4+ Sb 3+ It comes into full contact with the surface of TiO2 particles, forming a uniform adsorption layer.

[0036] (3) Hydrothermal reaction: The pH of the above solution was adjusted to 2.5 using tartaric acid solution and ammonia water, and then transferred into the reaction vessel. The reaction was carried out at 180°C for 4 hours. Tartaric acid, as a complexing agent, can reduce particle aggregation.

[0037] (4) Post-treatment: After the hydrothermal reaction is completed, the reaction product is taken out and the precipitate is transferred to a Buchner funnel. It is then washed with deionized water by suction filtration, adding 100 mL of deionized water each time and filtering until the filtrate is clear. The washing is repeated 3 times. Take 5 mL of the last washing filtrate and add 2 drops of 0.1 mol / L silver nitrate solution. No white precipitate is formed, indicating that there is no residual Cl ions in the precipitate (residual Cl ions will affect the conductivity and stability of the product). The washing is then stopped.

[0038] The washed precipitate was transferred to a vacuum drying oven, where the drying temperature was set to 90±5℃ and the vacuum degree to -0.09MPa for 12–16 hours to completely remove moisture. The dried solid product was then pulverized in an air jet mill to obtain a white, powdery anatase TiO2 conductive powder.

[0039] The titanium dioxide has a resistivity of 23 Ω·cm, a chromaticity of 91.5, and an average particle size of 0.251 μm. It also meets the requirements of light color, low hardness, and electrical conductivity, and can be widely used in chemical fiber products.

[0040] Comparative Example 1 Titanium dioxide was obtained by referring to the preparation method of Example 1. The difference between the preparation method of Comparative Example 1 and Example 1 is that the hydrothermal reaction in step (3) was replaced by ultrasonication for 3 hours. The titanium dioxide obtained in Comparative Example 1 has a resistivity of 64 Ω·cm, a color value of 73.2, and an average particle size of 0.421 μm, which does not meet the requirements of light color appearance, low hardness, and electrical conductivity.

[0041] The above specific embodiments further illustrate the purpose, technical solution and beneficial effects of this application. It should be understood that the above are only specific embodiments of this application and are not intended to limit the scope of protection of this application. Any modifications, equivalent substitutions, improvements, etc., made on the basis of the technical solution of this application should be included within the scope of protection of this application.

Claims

1. A method for preparing anatase conductive titanium dioxide, characterized in that, The preparation method includes the following steps: S1. Add deionized water to anatase titanium dioxide base material and stir to form a white suspension; add dispersant and precipitant to the white suspension and sonicate to obtain titanium dioxide suspension; S2. Add an ethanol solution of tin chloride and antimony chloride dropwise to the titanium dioxide suspension to form an adsorption layer on the surface of titanium dioxide. Then adjust the pH to 1.5-2.5, transfer it to a reaction vessel, and react at 180°C for 4 hours. After the reaction is completed, filter and dry to obtain anatase conductive titanium dioxide.

2. The preparation method according to claim 1, characterized in that, The dispersant in step S1 is polyvinylpyrrolidone, the precipitant is urea, and the mass ratio of the dispersant to the precipitant is 1 to 5.

3. The preparation method according to claim 1, characterized in that, The mass ratio of tin chloride to titanium dioxide in step S2 is 1 to 5.

4. The preparation method according to claim 1, characterized in that, In step S2, the molar ratio of antimony chloride to tin chloride is 1 to 10.

5. The preparation method according to claim 4, characterized in that, The method for preparing the ethanol solution of tin chloride and antimony chloride in step S2 is as follows: slowly add antimony chloride trihydrate to ethanol, stir until completely dissolved, then add tin chloride pentahydrate, and continue stirring to obtain the ethanol solution of tin chloride and antimony chloride.

6. The preparation method according to claim 1, characterized in that, The pH adjustment solution mentioned in step S2 is a tartaric acid solution and an ammonia solution.

7. The preparation method according to claim 1, characterized in that, The ultrasonic power in step S1 is 100-200W, and the ultrasonic time is 20-40 minutes.

8. The preparation method according to claim 1, characterized in that, In step S1, the mass-to-volume ratio of the anatase titanium dioxide base material to the deionized water is 1 to 2; the stirring speed is 400 to 600 rpm.

9. The preparation method according to claim 1, characterized in that, The degree of filtration in step S2 is such that there is no residual chloride ions; the drying temperature is 90±5℃, the vacuum degree is -0.09MPa, and the time is 12 to 16 hours.

10. The use of anatase conductive titanium dioxide prepared by the method of claim 1 in chemical fiber products.