Method for producing TiO2 powder and TiO2 powder prepared thereby

Abstract

One aspect of the method for manufacturing TiO2 powder according to an embodiment of the present invention is a method for manufacturing TiO2 powder, comprising: obtaining NH3 and TiCl4 from a residue after formation of a Ti-N layer; dissolving NH3 and TiCl4 in a solvent to prepare a mixture; tiO2 and NH4Cl are obtained from the mixture; and separating the TiO2 powder from the obtained TiO2 and NH4Cl.

Description

Technical Field

[0001] The present invention relates to a TiO 2 Powder manufacturing method and TiO prepared by the method 2 powder. Background Art

[0002] Photocatalysts must be fundamentally stable and, in order to work, must have the ability to absorb light and oxidize other substances. 2 It is mainly used as a white paint, but it exhibits properties suitable for use as a photocatalyst, and when mixed with other dyes or colored organic substances, it can also exert photocatalytic effects using light in the visible range.

[0003] Meanwhile, in the manufacturing process of semiconductors forming Ti-N layers, NH 3 With TiCl 4 The Ti-N layer is formed on the wafer by reaction. However, the NH 3 and TiCl 4 The amount of NH3 is actually only about 10% of the supply, and the remaining 90% is discharged and discarded. Therefore, from the perspective of resource recovery, the remaining NH3 discharged needs to be recovered. 3 and TiCl 4 , but no technology has been proposed to solve such problems.

[0004] Prior Art Citations

[0005] Patent citations

[0006] Korean Patent No. 1872291 (Title: Method for manufacturing photocatalytic filter using titanium waste)

[0007] Korean Patent No. 2044380 (Title: Method for producing titanium dioxide nanoparticles)

[0008] Korean Patent Publication No. 2018-0008326 (Title: Method for producing surface-modified titanium dioxide) Summary of the invention

[0009] Technical issues

[0010] The present invention aims to solve the above-mentioned problems of the prior art. The purpose of the present invention is to provide a 3 With TiCl 4 The mixture discharged when the Ti-N layer is formed on the wafer is used to make TiO 2 Powder method.

[0011] Technical Solution

[0012] In order to achieve the above object, the TiO 2 One aspect of the method for producing a powder is a TiO 2 A method for producing a powder, comprising: obtaining NH from the residue after forming a Ti-N layer 3 and TiCl 4 ; NH 3 and TiCl 4 dissolving in a solvent to prepare a mixture; obtaining TiO from the mixture 2 and NH 4 Cl; and TiO 2 and NH 4 Separation of TiO from Cl 2 powder.

[0013] In one aspect of the embodiments of the present disclosure, wherein TiO 2 The powder is nanoparticles.

[0014] In one aspect of the embodiment of the present invention, vanadium carbide is formed by refining vanadium oxide and a carbon compound, then mixing to prepare a mixture of vanadium oxide and the carbon compound, and heat treating the mixture under vacuum and normal pressure.

[0015] In one aspect of the embodiments of the present disclosure, the molar ratio of vanadium to carbon in the vanadium carbide is 2:1, 3:2 or 4:3.

[0016] In one aspect of an embodiment of the present disclosure, wherein Max using vanadium carbide does not include using vanadium metal.

[0017] In one aspect of an embodiment of the present disclosure, wherein the carbon content in Max using vanadium carbide is 8 to 14 wt%.

[0018] In one aspect of the embodiments of the present disclosure, the solvent is selected from the group consisting of nitric acid, ammonia, hydrogen peroxide, hydrochloric acid, and combinations thereof.

[0019] In one aspect of the embodiments of the present disclosure, in the step of preparing the mixture, NH 3 and TiCl 4 Dissolve in a solvent and react at a temperature of 25°C to 350°C.

[0020] In one aspect of the embodiments of the present disclosure, in the step of preparing the mixture, NH 3 and TiCl 4 Dissolve in a solvent and react at a pressure of 1 bar to 10 bar.

[0021] In one aspect of the embodiments of the present disclosure, wherein, in obtaining TiO 2 and NH 4 In the step of Cl, TiO is obtained from the mixture at a temperature of 200°C to 1000°C. 2 and NH 4 Cl.

[0022] In one aspect of the embodiments of the present disclosure, the method further comprises treating the obtained TiO 2 The powder is subjected to an additional heat treatment.

[0023] In one aspect of the embodiments of the present disclosure, wherein, in the case of TiO 2 The powder is subjected to another heat treatment step to obtain TiO 2 The powder is heat treated at a temperature between 200°C and 1000°C.

[0024] TiO according to an embodiment of the present invention 2 Another aspect of the powder manufacturing method is a TiO 2 A method for producing a powder, wherein the NH obtained from the residue after forming the Ti-N layer is 3 and TiCl 4 Dissolve in a solvent to prepare a mixture, and obtain TiO from the mixture 2 and NH 4 Cl, and separate TiO from it 2 powder.

[0025] TiO according to an embodiment of the present invention 2 In one aspect of the method for producing a powder, the TiO 2 The powder is prepared by the method according to any one of claims 1 to 13.

[0026] In the TiO 2 Powder manufacturing method and TiO prepared therefrom 2 In the powder, the unreacted residual NH 3 and TiCl 4 Get TiO 2 and NH 4 Cl, and separate TiO from it 2 Therefore, according to the embodiment of the present invention, the residual NH 3 and TiCl 4 To produce TiO 2 powder.

[0027] Effects of the Invention

[0028] In the TiO 2 Powder manufacturing method and TiO prepared therefrom 2 In the powder, the unreacted residual NH 3 and TiCl 4 Get TiO 2 and NH 4 Cl, and separate TiO from it 2 Therefore, according to the embodiment of the present invention, the residual NH 3 and TiCl 4 To produce TiO 2 powder. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] Figure 1-5 It shows that TiO 2 SEM image of the particle size of powder particles.

[0030] Figure 6 The temperature of TiO 2 Plot of the particle size of powder particles.

[0031] Figure 7 A graph showing the crystal structure ratio of anatase and a mixed phase of anatase and rutile according to pH control.

[0032] Figure 8 The TiO 2 Powder diagram.

[0033] Fig. 9 A graph of solubility as a function of temperature is shown. DETAILED DESCRIPTION

[0034] Hereinafter, TiO2 according to an embodiment of the present invention will be described in conjunction with the accompanying drawings. 2 The method for producing the powder will be described in more detail.

[0035] In order to achieve the above object, the TiO 2 The powder manufacturing method includes obtaining NH from the residue after forming the Ti-N layer. 3 and TiCl 4 ; NH 3 and TiCl 4 dissolving in a solvent to prepare a mixture; reacting the mixture to obtain TiO 2 and NH 4 Cl; and TiO 2 and NH 4 TiO was separated from Cl 2 powder.

[0036] In the manufacturing process of semiconductors forming Ti-N layers, NH 3 With TiCl 4 A Ti-N layer is formed on the wafer. The NH released after the layer is formed is obtained. 3 With TiCl 4 , to make TiO 2 powder.

[0037] In the step of preparing the mixture, the solvent can be used to dissolve NH 3 and TiCl 4 TiO 2 Specifically, the ratio of anatase or a mixed phase of anatase and rutile in the crystal structure can be determined by heating TiO having a rutile structure at a temperature ranging from 200°C to 800°C. 2 Heat treatment is performed to control the obtained TiO 2 The color of the powder. When the temperature range is 1000℃ or higher, the final TiO 2 The powder structure can be changed to rutile structure. In addition, NH 3 and TiCl 4 The molar ratio of the solvent can be controlled between 0.01:1 and 0.13:1, and the solvent includes one selected from the group consisting of nitric acid, ammonia, hydrogen peroxide, hydrochloric acid and a combination thereof.

[0038] The step of preparing the mixture may include solid-liquid separation using a hydration reaction or a high pressure reaction. The hydration reaction may be performed at a temperature of 25°C to 100°C. TiO produced within the room temperature range 2 The particle size of the particles ranges from 2nm to 10nm. 4 The particle size of the particles produced in the Cl solution is actually very small, because the NH 4 Cl inhibits the growth of particles. 2 When generated, the particle size of the crystal particles maintains a nanometer size. However, the generated crystal particles may form aggregates and be filtered according to the heating temperature. Therefore, if the aggregates are formed to a certain size and then filtered and crushed to form particles, the particle size of the particles may be formed to about 10nm. The ammonia generated in the present invention may inhibit the TiO 2 The growth of particles is therefore based on NH 4 The Cl is recovered.

[0039] At the same time, since the particle size of the particles prepared in the hydration reaction is very small, a high pressure reaction can be used as a coagulation method to facilitate filtration. The temperature range of the high pressure reaction can be 25°C to 350°C, and the pressure range can be 1 bar to 10 bar. TiO with large particle size prepared by controlling the above temperature and pressure conditions 2 The powder can be filtered and separated into solid and liquid.

[0040] The particle size may be controlled to be 10 nm to 500 nm by heat-treating the mixture subjected to the hydration reaction or the high pressure reaction at a temperature of 300° C. to 1100° C. for 10 to 120 minutes.

[0041] In addition, by heating TiO at 300°C to 1000°C 2 After additional heat treatment, TiO with a 100% rutile crystal structure can be 2 Yellow dye is produced. Specifically, yellow dyes of different concentrations can be obtained according to the temperature range.

[0042] The TiO prepared by the above preparation method 2 The powder may be obtained in the form of nanoparticles, and the particle size of the nanoparticle powder may be in the range of 10 nm to 20 nm.

[0043] Hereinafter, preparation examples and experimental examples of the present invention are listed, but these preparation examples and experimental examples are only intended to more specifically illustrate the configuration and effects of the present invention, and the scope of the present invention is not limited thereto.

[0044] Example

[0045] <Preparation Example 1: TiO 2 Powder Preparation>

[0046] After the Ti-N layer is formed, the NH 3 and TiCl 4 It was condensed in a trap and obtained as a mixture. Ultrapure water was added as a solvent at a molar ratio of 1:0.01-0.13 to the condensed NH 3 and TiCl 4 The mixture was dissolved by heating at 45°C for 2 hours. TiO 2 and NH 4 Cl to obtain a dissolved mixture. First, filter the formed TiO 2 and NH 4 Cl separation, and then TiO 2 Powder and NH 4 Cl undergoes a second solid-liquid separation.

[0047] <Preparation Example 2: TiO2 Powder Preparation>

[0048] TiO was prepared in the same manner as in Preparation Example 1 2 The powder was obtained by heating at 70°C for 1.5 hours.

[0049] <Preparation Example 3: TiO 2 Powder Preparation>

[0050] TiO was prepared in the same manner as in Preparation Example 1 2 The powder was obtained by heating at 90°C for 2 hours.

[0051] <Preparation Example 4: TiO 2 Powder Preparation>

[0052] TiO was prepared in the same manner as in Preparation Example 1 2 The first heating condition was 70°C for 1 hour and 20 minutes, and the second heating condition was 90°C for 2 hours.

[0053] <Preparation Example 5: TiO 2 Powder Preparation>

[0054] TiO was prepared in the same manner as in Preparation Example 1 2 The first heating condition was 50°C for 1 hour and 20 minutes, and the second heating condition was 90°C for 2 hours.

[0055] <Preparation Example 6: TiO 2 Powder Preparation>

[0056] TiO was prepared in the same manner as in Preparation Example 1 2 The powder was heated at 800°C for 0.5 hours.

[0057] <Preparation Example 7: TiO 2 Powder Preparation>

[0058] TiO was prepared in the same manner as in Preparation Example 1 2 The heating condition was changed to 600°C for 1 hour.

[0059] <Preparation Example 8: TiO under high temperature and high pressure 2 Powder Preparation>

[0060] After the Ti-N layer is formed, the NH 3 and TiCl 4 It was condensed in a trap and obtained as a mixture. Ultrapure water was added as a solvent at a molar ratio of 1:0.01-0.13 to the condensed NH3 and TiCl 4 The mixture was dissolved by reaction at 150°C and 4 bar. The dissolved mixture was heated at 150°C and 4 bar for 180 minutes to form TiO 2 and NH 4 Cl. First, use a filter to make the formed TiO 2 With NH 4 Cl separation, and then TiO 2 Powder and NH 4 Cl undergoes a second solid-liquid separation.

[0061] <Preparation Example 9: TiO 2 Powder particle size changes with heat treatment conditions>

[0062] After the Ti-N layer is formed, the NH 3 and TiCl 4 It was condensed in a trap and obtained as a mixture. Ultrapure water was added as a solvent at a molar ratio of 1:0.01-0.13 to the condensed NH 3 and TiCl 4 and mixed. 2 and NH 4 The conditions of Cl were the same as those in Preparation Examples 1 to 3, 6 and 7. The TiO 2 The particle size of TiO 2 .

[0063] [Table 1]

[0064] Heating conditions 1 2 3 4 5 Temperature(℃) 200 400 600 800 1000

[0065] <Preparation Example 10: TiO with rutile crystal structure 2 Powder Preparation>

[0066] After the Ti-N layer is formed, NH 3 and TiCl 4 It was condensed in a trap and obtained as a mixture. Ultrapure water was added as a solvent at a molar ratio of 1:0.1-0.25 to the condensed NH 3 and TiCl 4 The mixture is reacted at 25 to 130°C and 1 to 4 bar for 30 to 180 minutes to obtain TiO 2 and NH 4 Cl. Then, NH 4 Cl and TiO 2 Separate and then TiO2 The powder is separated into solid and liquid. 2 The powders were additionally heat treated at a temperature ranging from 300°C to 800°C for 30 to 120 minutes to prepare yellow dyes having different concentrations.

[0067] <Preparation Example 11: TiO with rutile and anatase crystal structures 2 Powder Preparation>

[0068] After the Ti-N layer is formed, the NH 3 and TiCl 4 The mixture was condensed in the trap and obtained as a mixture. Ultrapure water was added as a solvent at a molar ratio of 0.02:1 to the condensed NH 3 and TiCl 4 The mixture was heated at 25 to 130°C and 1 to 3 bar for 120 minutes to obtain TiO 2 and NH 4 Cl. TiO formed at this time 2 and NH 4 Cl is first separated by a filter, and then TiO 2 Powder and NH 4 Cl was subjected to a second solid-liquid separation. The obtained TiO 2 The powder is further heat-treated at a temperature range of 200°C to 1000°C for 30 to 120 minutes to stabilize the crystal structure and control the crystal structure of the anatase phase and the mixed phase of anatase and rutile to prepare TiO 2 powder.

[0069] Table 2 below shows the results of analyzing the particle diameters (nm) of the X-RD particles of Preparation Examples 1 to 5 according to the Scherrer equation.

[0070] [Table 2]

[0071] condition Preparation Example 1 Preparation Example 2 Preparation Example 3 Preparation Example 4 Preparation Example 5 Particle size (nm) 8.49 9.54 10.05 9.38 8.96

[0072] NH 4 The particle size of the particles prepared in the Cl solution is actually very small, because the NH 4 Cl inhibits the growth of particles, and thus, aggregates are formed to a certain size and then broken to prepare particles so that the particle size is about 10 nm.

[0073] Figure 1-5 The TiO obtained in Preparation Example 9 according to the heat treatment temperature is shown. 2 SEM image of the particle size of powder particles. Figure 6 As shown, the particle size of the powder particles can be controlled according to the heat treatment temperature to produce TiO 2 powder.

[0074] Figure 7 A graph showing the crystal structure ratios of anatase and a mixed phase of anatase and rutile according to pH control in Preparation Examples 10 and 11. Different crystal structures can be obtained by controlling the pH value by adding a solvent.

[0075] Figure 8 The TiO with 100% rutile structure obtained in Preparation Example 10 is shown. 2 The heat treatment temperature of the powder is adjusted to 200°C to 1000°C and the time is adjusted to 10 to 120 minutes to obtain the powder. By adjusting the temperature and time, various concentrations of yellow dye TiO 2 powder.

[0076] Fig. 9 The solubility is shown as a function of temperature. It can be determined that as the temperature increases, the solubility increases.

Claims

1. A method for producing TiO2 powder, comprising: Obtaining NH3 and TiCl4 from the residue after the formation of the Ti-N layer; dissolving NH3 and TiCl4 in a solvent to prepare a mixture; TiO2 and NH4Cl are obtained from the mixture; as well as TiO2 powder was separated from the obtained TiO2 and NH4Cl.

2. The method for producing TiO2 powder according to claim 1, in, The TiO2 powder is nanoparticles.

3. The method for producing TiO2 powder according to claim 1, in, The TiO2 powder is nanoparticles with a particle size of 10nm to 20nm.

4. The method for producing TiO2 powder according to claim 1, in, The crystalline phases of the TiO2 powder are anatase and a mixed phase of anatase and rutile.

5. The method for producing TiO2 powder according to claim 1, in, In the step of preparing the mixture, The molar ratio of the solvent to NH3 and TiCl4 is 1:0.01 to 1:0.

13.

6. The method for producing TiO2 powder according to claim 1, in, In the step of preparing the mixture, The pH range is -0.02 to 1.

7. The method for producing TiO2 powder according to claim 1, in, The solvent is selected from the group consisting of nitric acid, ammonia, hydrogen peroxide, hydrochloric acid and combinations thereof.

8. The method for producing TiO2 powder according to claim 1, in, In the step of preparing the mixture, NH3 and TiCl4 are dissolved in a solvent and reacted at a temperature of 25°C to 350°C.

9. The method for producing TiO2 powder according to claim 1, in, In the step of preparing the mixture, NH3 and TiCl4 are dissolved in a solvent and reacted at a pressure of 1 bar to 10 bar.

10. The method for producing TiO2 powder according to claim 1, in, In the step of obtaining TiO2 and NH4Cl, TiO2 and NH4Cl are obtained from the mixture at a temperature of 200°C to 1000°C.

11. The method for producing TiO2 powder according to claim 1, in, The method further comprises subjecting the obtained TiO2 powder to an additional heat treatment.

12. The method for producing TiO2 powder according to claim 11, in, In a further step of heat treating the TiO2 powder, The obtained TiO2 powder is heat-treated at a temperature of 200°C to 1000°C.

13. A method for producing TiO2 powder, in, NH 3 and TiCl 4 obtained from the residue after forming the Ti-N layer are dissolved in a solvent to prepare a mixture, TiO 2 and NH 4 Cl are obtained from the mixture, and TiO 2 powder is separated therefrom.

14. TiO2 powder prepared by the method of any one of claims 1 to 13.

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