CN114591635B - Preparation method of high-weather-resistance high-gloss titanium dioxide - Google Patents
Preparation method of high-weather-resistance high-gloss titanium dioxide Download PDFInfo
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Abstract
The application discloses a preparation method of high-weather-resistance high-gloss titanium dioxide, which comprises the following steps: s1, preparing titanium white slurry, adding a zirconium source and a phosphorus source, and regulating the pH value to 6-7 by ammonia water; s2, performing a first hydrothermal reaction, and sanding after the reaction; s3, simultaneously adding an aluminum source and a phosphorus source, and keeping the pH value of the slurry to be 5-6; s4, regulating the pH value of the slurry to be 5-9, and simultaneously adding a zinc source and a phosphorus source to maintain the pH value of the slurry to be 5-9; s5, performing a second hydrothermal reaction, and sanding after the reaction; s6, coating an aluminum film; s7, calcining. According to the application, zirconium phosphate coating is firstly carried out on the surface of titanium dioxide, so that not only can the adhesive force of the titanium dioxide be improved, but also the zirconium phosphate prepared by a hydrothermal method is more complete in crystal form, and after sanding, the film layer is more uniform, so that the glossiness and weather resistance of the titanium dioxide can be remarkably improved. Then aluminum phosphate, zinc phosphate coating and alumina coating are carried out, so that the coating has the effects of improving glossiness and weather resistance.
Description
Technical Field
The application belongs to the technical field of titanium dioxide preparation, and particularly relates to a preparation method of high-weather-resistance high-gloss titanium dioxide.
Background
The rutile type titanium dioxide has higher weather resistance and tinting strength, and is widely applied to paint, plastics, papermaking and printing ink. Since the titanium dioxide crystal has lattice defects in the formation and growth processes, a plurality of light activation points exist on the surface of the titanium dioxide crystal, and the titanium dioxide is aged in an application system at a high speed under the irradiation of ultraviolet light, the titanium dioxide must be subjected to inorganic surface treatment, the light activation points are blocked, and the photocatalysis caused by the ultraviolet light is shielded.
The surface treatment of titanium dioxide has been a popular research area at home and abroad, and many research results have been applied to production practice. However, at present, domestic titanium dioxide is difficult to enter the high-grade titanium dioxide market due to quality reasons, so that research on surface treatment, especially inorganic surface treatment, is important to improve the performance of titanium dioxide in an application system.
At present, the main method for improving the weather resistance and the glossiness of the titanium dioxide is to carry out silicon aluminum coating and zirconium aluminum coating under the slurry temperature condition of 80-90 ℃, wherein the silicon aluminum coating amount is large, especially the silicon coating amount is large, and the inherent high Mohs hardness is difficult to grind and crush, so that the particle size is larger and the glossiness is reduced; the coating amount of zirconium and aluminum is small, the weather resistance and glossiness required by the target are difficult to reach, the coating amount of zirconium and aluminum is large, and the production cost of titanium pigment is high due to the high cost of zirconium element. Therefore, there is a need to develop a titanium dioxide with low cost, high gloss and high weather resistance.
Disclosure of Invention
The application aims to provide a preparation method of high-weather-resistance high-gloss titanium dioxide for solving the defects in the prior art.
The application aims at realizing the following technical scheme:
a preparation method of high weather-resistant high-gloss titanium dioxide comprises the following steps:
s1, preparing titanium white slurry, adding a zirconium source and a phosphorus source, and regulating the pH value to 6-7 by ammonia water;
s2, performing a first hydrothermal reaction at a reaction temperature of 300-500 ℃ for 3-5 hours, and sanding after the reaction;
s3, adjusting the temperature of the slurry to 80-90 ℃, adjusting the pH value to 5-6 by using citric acid, and simultaneously adding an aluminum source and a phosphorus source to keep the pH value of the slurry to 5-6;
s4, regulating the pH value of the slurry to 5-9 by using citric acid or ammonia water, and simultaneously adding a zinc source and a phosphorus source to maintain the pH value of the slurry to 5-9;
s5, performing a second hydrothermal reaction at 200-300 ℃ for 3-6 hours, and sanding after the reaction;
s6, regulating the pH value of the slurry to 8-8.5, controlling the temperature to 80-90 ℃, and adding an aluminum source to coat an aluminum film;
s7, calcining for 1.5-2.5 h at the temperature of 650-750 ℃ to obtain the titanium dioxide.
Preferably, the zirconium source is added in an amount of ZrO as described in step S1 2 The meter is TiO in the slurry 2 0.1 to 1 percent of the total mass; the addition amount of the phosphorus source is P 2 O 5 The meter is TiO in the slurry 2 0.1 to 1 percent of the total mass.
Preferably, the adding time of the zirconium source and the phosphorus source in the step S1 is 10-20 min.
Preferably, the aluminum source is added in an amount of Al in step S3 2 O 3 The meter is TiO in the slurry 2 0.5 to 2 percent of total mass; the phosphorus source is added in an amount to maintain the pH of the cocurrent flow at 5 to 6.
Preferably, in the step S3, the aluminum source and the phosphorus source are added simultaneously for 40-60 min, and the homogenization is carried out for 15-25 min after the addition.
Preferably, the zinc source in step S4 is added in an amount calculated by ZnO, which is TiO in the slurry 2 0.5 to 3 percent of the total mass; the phosphorus source is added in an amount to maintain the pH of the cocurrent flow at 5 to 9.
Preferably, after the slurry temperature is regulated to 80-90 ℃ in the step S6, acid aluminum salt and alkaline aluminum salt are added simultaneously within 30-50 min to maintain the slurryThe pH value is 8-8.5, and then homogenizing is carried out for 15-25 min; the total addition amount of the acidic aluminum salt and the alkaline aluminum salt is TiO in the slurry 2 1.5 to 3 percent of the total mass.
Preferably, the sanding is carried out in step S2 and step S5 to an average particle size of < 0.35. Mu.m.
Preferably, a step of adjusting the pH of the slurry to 5.5-5.8 is further included between the step S6 and the step S7.
The high weather-proof high-gloss titanium dioxide is prepared by adopting the method.
According to the application, zirconium phosphate coating is firstly carried out on the surface of titanium dioxide, because zirconium and titanium are fourth-subgroup elements, the structure and the properties are similar, not only can the adhesive force of the titanium dioxide be improved, but also the zirconium phosphate prepared by a hydrothermal method is more complete in crystal form, and after sanding, the film layer is more uniform, so that the glossiness and weather resistance of the titanium dioxide can be remarkably improved. Then aluminum phosphate, zinc phosphate coating and alumina coating are carried out, so that the coating has the effects of improving glossiness and weather resistance.
Drawings
FIG. 1 is the gloss results for the products of examples 1-3 and comparative examples 1-5;
FIG. 2 shows the hiding power results of the products of examples 1 to 3 and comparative examples 1 to 5.
Detailed Description
The preparation method of the high weather-resistant high-gloss titanium dioxide provided by the application comprises the following steps:
s1, preparing titanium white slurry, adding a zirconium source and a phosphorus source, and regulating the pH value to 6-7 by ammonia water;
s2, performing a first hydrothermal reaction at a reaction temperature of 300-500 ℃ for 3-5 hours, and sanding after the reaction;
s3, adjusting the temperature of the slurry to 80-90 ℃, adjusting the pH value to 5-6 by using citric acid, and simultaneously adding an aluminum source and a phosphorus source to keep the pH value of the slurry to 5-6;
s4, regulating the pH value of the slurry to 5-9 by ammonia water or citric acid, and simultaneously adding a zinc source and a phosphorus source to maintain the pH value of the slurry to 5-9;
s5, performing a second hydrothermal reaction at 200-300 ℃ for 3-6 hours, and sanding after the reaction;
s6, regulating the pH value of the slurry to 8-8.5, controlling the temperature to 80-90 ℃, and adding an aluminum source to coat an aluminum film;
s7, calcining for 1.5-2.5 h at the temperature of 650-750 ℃ to obtain the titanium dioxide.
According to the application, zirconium phosphate coating is firstly carried out on the surface of titanium dioxide, because zirconium and titanium are fourth-subgroup elements, the structure and the properties are similar, not only can the adhesive force of the titanium dioxide be improved, but also the zirconium phosphate prepared by a hydrothermal method is more complete in crystal form, and after sanding, the film layer is more uniform, so that the glossiness and weather resistance of the titanium dioxide can be remarkably improved. Then aluminum phosphate, zinc phosphate coating and alumina coating are carried out, so that the coating has the effects of improving glossiness and weather resistance.
The phosphate ions in the zinc phosphate synthesized by the hydrothermal method react with iron atoms in steel to generate the iron phosphate complex salt, the complex salt is firmly attached to the surface of the steel, a firm protective film taking the iron phosphate as a main body can be formed, and the compact passivation film is insoluble in water, high in hardness and strong in adhesive force, and has excellent antirust performance, so that the weather resistance is improved.
The applicant finds that zirconium phosphate and zinc phosphate are coated by adopting a conventional method, deposited zirconium phosphate and zinc phosphate have no crystal forms, so that the coating is uneven. In addition, the pH of the system is adjusted by adopting weak acid ammonia water and weak base citric acid in the coating process, so that the dispersibility of the system can be improved compared with common strong inorganic acid or strong inorganic base, the film layer is slowly deposited, the binding force of the film layer and titanium dioxide is enhanced, the weather resistance and glossiness are improved, and the formula applicability is also improved. After the coating is finished, the high-temperature calcination is carried out at about 700 ℃, so that bound water in the film can be removed, the integrity of the crystal form of the film is fully improved, and the weather resistance of the titanium dioxide is further improved. Therefore, the titanium dioxide product obtained by the method provided by the application has high weather resistance and glossiness.
Preferably, the titanium white slurry can be sulfuric acid method slurry or chloridizing method slurry, and the slurry concentration is TiO 2 The total weight is 300-700 g/L.
Preferably, the zirconium source in the step S1 adopts zirconium oxychloride with the addition amount of ZrO 2 The meter is TiO in the slurry 2 0.1 to 1 percent of the total mass; the phosphorus source adopts sodium hexametaphosphate, and the addition amount is P 2 O 5 The meter is TiO in the slurry 2 0.1 to 1 percent of the total mass. The zirconium source and the phosphorus source are added in the form of solution with the concentration of 80-200 g/L (ZrO 2 Calculated by P) of 20 to 80g/L 2 O 5 Meter).
Preferably, the adding time of the zirconium source and the phosphorus source in the step S1 is 10-20 min.
Preferably, the aluminum source is added in the amount of Al in step S3 2 O 3 The meter is TiO in the slurry 2 0.5 to 2 percent of total mass; the amount of the phosphorus source added is such that the pH of the co-current flow is maintained at 5 to 6. The aluminum source can be NaAlO 2 Or Al 2 (SO 4 ) 3 Is also added in the form of a solution with a concentration of 80-200 g/L (Al 2 O 3 Meter). The phosphorus source can be phosphoric acid or sodium hexametaphosphate.
Preferably, in the step S3, the aluminum source and the phosphorus source are added simultaneously for 40-60 min, and the homogenization is carried out for 15-25 min after the addition.
Preferably, the zinc source in the step S4 is added in the amount of ZnO as TiO in the slurry 2 0.5 to 3 percent of the total mass; the amount of the phosphorus source to be added is such that the pH of the co-current flow is maintained at 5 to 9. The zinc source is preferably ZnSO 4 Preferably in solution at a concentration of 80 to 200g/L (calculated as ZnO).
Preferably, after the temperature of the slurry is regulated to 80-90 ℃ in the step S6, acid aluminum salt and alkaline aluminum salt are added simultaneously within 30-50 min, the pH value of the slurry is maintained to 8-8.5, and then homogenization is carried out for 15-25 min; the total addition of the acidic aluminum salt and the alkaline aluminum salt accounts for TiO in the slurry 2 1.5 to 3 percent of the total mass. The acidic aluminum salt can be selected from aluminum or aluminum 2 (SO 4 ) 3 The alkaline aluminum salt can be NaAlO 2 Preferably in the form of a solution, concentratedThe degree is 80-200 g/L (Al is used 2 O 3 Meter).
Preferably, step S2 and step S5 are sanded to an average slurry particle size of < 0.35 μm. Further preferably, the sand mill is filled with zirconium-aluminum composite balls, the filling rate is 50-90%, the rotating speed is 800-1000 rpm, and the speed of slurry passing through the sand mill is 5.5-7 m 3 /h。
Preferably, the step S6 and the step S7 also comprise the step of adjusting the pH value of the slurry to 5.5-5.8, and finally adjusting the pH value of the slurry to be slightly acidic in the coating process, neutralizing the excessive alkali in the coating process, and simultaneously ensuring that the finished titanium dioxide is nearly neutral.
Example 1
Uncoated rutile titanium dioxide slurry with the concentration of 400g/L; adding 0.5% zirconium oxychloride and 0.3% sodium hexametaphosphate into the titanium white slurry while stirring within 15min, and then adding ammonia water to adjust the pH of the slurry to 6.8; transferring the slurry to a polytetrafluoroethylene reaction kettle for hydrothermal reaction at the reaction temperature of 400 ℃ for 4 hours; the slurry is guided into a sand mill for sand milling, and the sand milling flow is 7m 3 And/h, sanding until the average grain diameter is less than 0.35 mu m; the temperature of the slurry is adjusted to 90 ℃ after sanding, the pH value is adjusted to 5 by citric acid, 1.5 percent of sodium metaaluminate and phosphoric acid are added in parallel flow, the adding amount of the phosphoric acid is kept to be parallel flow pH=5, the parallel flow time is 50min, and the homogenization is carried out for 20min; adjusting the pH of the slurry to 8 by ammonia water, adding 1% of zinc sulfate and sodium hexametaphosphate, maintaining the parallel flow pH=8 by the addition amount of the sodium hexametaphosphate, and carrying out hydrothermal reaction at 200 ℃ for 3h; the slurry is guided into a sand mill for sand milling with the sand milling flow of 5.5m 3 And/h, sanding until the average grain diameter is less than 0.35 mu m; adjusting the temperature of the slurry to 90 ℃, adjusting the pH value of the slurry to 8.5 by sodium hydroxide, simultaneously adding 1.19% sodium metaaluminate and 0.81% aluminum sulfate solution within 40min, maintaining the pH value of the slurry to 8.5, and homogenizing for 20min; the pH value of the slurry is adjusted to 5.7 by dilute sulfuric acid; washing with water and calcining at 700 ℃ for 2 hours, and obtaining the titanium white finished product.
Example 2
Uncoated rutile titanium dioxide slurry with the concentration of 300g/L; adding 0.8% zirconium oxychloride and 0.5% sodium hexametaphosphate into the titanium white slurry while stirring within 15min, and then adding ammonia water to regulate the materialThe pH of the slurry was 6.3; transferring the slurry to a polytetrafluoroethylene reaction kettle for hydrothermal reaction at 500 ℃ for 3 hours; the slurry is guided into a sand mill for sand milling, and the sand milling flow is 5.5m 3 And/h, sanding until the average grain diameter is less than 0.35 mu m; the temperature of the slurry is regulated to 80 ℃ after sanding, the pH value is regulated to 6 by citric acid, 1% sodium metaaluminate and phosphoric acid are added in parallel flow, the parallel flow time is 40min, and the homogenization is 20min; the pH value of the slurry is adjusted to 5 by citric acid, and 3 percent of zinc sulfate and sodium hexametaphosphate are added for hydrothermal reaction at 200 ℃ for 6 hours; the slurry is guided into a sand mill for sand milling with the sand milling flow of 6.5m 3 And/h, sanding until the average grain diameter is less than 0.35 mu m; adjusting the temperature of the slurry to 80 ℃, adjusting the pH value of the slurry to 8 by sodium hydroxide and maintaining the pH value of the slurry to 8, simultaneously adding 1.78% sodium metaaluminate and 1.22% aluminum sulfate solution within 40min, and homogenizing for 20min; the pH value of the slurry is adjusted to 5.5 by dilute sulfuric acid; washing with water and calcining at 700 ℃ for 2 hours, and obtaining the titanium white finished product.
Example 3
Uncoated rutile titanium dioxide slurry with the concentration of 600g/L; adding 0.3% zirconium oxychloride and 0.2% sodium hexametaphosphate into the titanium white slurry while stirring within 15min, and then adding ammonia water to adjust the pH of the slurry to 6.5; transferring the slurry to a polytetrafluoroethylene reaction kettle for hydrothermal reaction at the reaction temperature of 300 ℃ for 5 hours; the slurry is guided into a sand mill for sand milling, and the sand milling flow is 6.5m 3 And/h, sanding until the average grain diameter is less than 0.35 mu m; the temperature of the ground slurry is adjusted to 85 ℃, the pH value is adjusted to 5.5 by citric acid, 2 percent of sodium metaaluminate and phosphoric acid are added in parallel flow, the parallel flow time is 60min, and the homogenization is carried out for 20min; ammonia water is used for regulating the pH value of the slurry to 7, and 2% zinc sulfate and sodium hexametaphosphate are added for hydrothermal reaction at 300 ℃ for 4 hours; the slurry is guided into a sand mill for sand milling with the sand milling flow of 7m 3 And/h, sanding until the average grain diameter is less than 0.35 mu m; adjusting the temperature of the slurry to 85 ℃, adjusting the pH of the slurry to 8.5 by sodium hydroxide and maintaining the pH of the slurry to 8.5, simultaneously adding 0.9% sodium metaaluminate and 0.6% aluminum sulfate solution within 40min, and homogenizing for 20min; the pH value of the slurry is adjusted to 5.8 by dilute sulfuric acid; washing with water and calcining at 700 ℃ for 2 hours, and obtaining the titanium white finished product.
Comparative example 1
Foreign standard sample product S.
Comparative example 2 (silica alumina coated)
Diluting the non-coated titanium white slurry to 300g/L, heating to 75 ℃, adding sodium silicate Solution (SiO) accounting for 5.0% of the titanium dioxide in the slurry by mass 2 The concentration is 100 g/L), meanwhile, dilute hydrochloric acid solution with the concentration of 80g/L is added to keep the pH value between 7.0 and 8.0, the adding time is 30min, and the homogenization is carried out for 30min; cooling to 65deg.C, adding 3.0% sodium metaaluminate (as Al) 2 O 3 160 g/L) solution and 80g/L dilute hydrochloric acid solution, keeping the pH of the slurry unchanged at 8.0+/-0.2, adding for 120min, and homogenizing for 30min; adjusting the pH to 6.0 with 80g/L dilute hydrochloric acid; the slurry is washed with water, dried and crushed.
Comparative example 3 (zirconium phosphate, aluminum phosphate, alumina coating)
Diluting non-coated titanium white slurry into 300g/L, heating to 75 ℃, adjusting the pH of the slurry to 6.5-7.0, adding 0.4% sodium hexametaphosphate within 10min, and homogenizing for 5min; adding 0.6% zirconium oxychloride within 20min, homogenizing for 20min; naOH is used for adjusting the pH value to 8, the adjustment time is 10min, and the homogenization is 10min;2.0% sodium metaaluminate and phosphoric acid are parallel-flow, the parallel-flow pH is 8, the parallel-flow time is 40min, and the homogenization is 30min;1.0% sodium metaaluminate and sulfuric acid are in parallel flow, the parallel flow pH is 8, the parallel flow time is 30min, and the homogenization is 20min; adjusting the pH to 5.8 with dilute sulfuric acid; and (5) washing, drying and steam-pulverizing the slurry.
Comparative example 4 (Zinc phosphate, aluminum phosphate, alumina coating)
Diluting non-coated titanium white slurry to 300g/L, heating to 75 ℃, regulating the pH of the slurry to 5-6, adding 1% phosphoric acid within 10min, and homogenizing for 10min; adding 1.5% zinc sulfate solution (concentration 100 g/L) within 30min, homogenizing for 20min; naOH is used for adjusting the pH value to 8, the adjustment time is 10min, and the homogenization is 10min;2.0% sodium metaaluminate and phosphoric acid are parallel-flow, the parallel-flow pH is 8, the parallel-flow time is 40min, and the homogenization is 30min;1.0% sodium metaaluminate and sulfuric acid are in parallel flow, the parallel flow pH is 8, the parallel flow time is 30min, and the homogenization is 20min; adjusting the pH to 5.8 with dilute sulfuric acid; and (5) washing, drying and steam-pulverizing the slurry.
Comparative example 5
Uncoated rutileThe concentration of the titanium dioxide slurry is 600g/L; adding 0.3% zirconium oxychloride into the titanium white slurry while stirring within 15min, counting the time for 10min, and homogenizing for 5min; adding 0.2% sodium hexametaphosphate within 10min, homogenizing for 10min; adjusting the pH value of the slurry to 6.5 by ammonia water; the slurry is guided into a sand mill for sand milling, and the sand milling flow is 6.5m 3 And/h, sanding until the average grain diameter is less than 0.35 mu m; the temperature of the ground slurry is adjusted to 85 ℃, the pH value is adjusted to 5.5 by citric acid, 2 percent of sodium metaaluminate and phosphoric acid are added in parallel flow, the parallel flow time is 60min, and the homogenization is carried out for 20min; ammonia water is used for regulating the pH value of the slurry to 7, 2% zinc sulfate and sodium hexametaphosphate are simultaneously added for reaction within 30min, the pH value of the slurry is maintained to 7, and the slurry is homogenized for 15min; the slurry is guided into a sand mill for sand milling with the sand milling flow of 7m 3 And/h, sanding until the average grain diameter is less than 0.35 mu m; adjusting the temperature of the slurry to 85 ℃, adjusting the pH of the slurry to 8.5 by sodium hydroxide and maintaining the pH of the slurry to 8.5, simultaneously adding 0.9% sodium metaaluminate and 0.6% aluminum sulfate solution within 40min, and homogenizing for 20min; the pH value of the slurry is adjusted to 5.8 by dilute sulfuric acid; washing with water and calcining at 700 ℃ for 2 hours, and obtaining the titanium white finished product.
Product and control application Properties comparison
The products obtained in examples 1 to 3 and comparative examples 1 to 5 were evaluated for application properties by a conventional high-gloss emulsion paint system method. The results are shown in fig. 1-2 and table 1, and it can be seen from fig. 1-2 and table 1 that the titanium pigment prepared by the present application has significant advantages in gloss, hiding power and weather resistance as compared with the comparative examples.
TABLE 1 light retention results for the products of examples 1-3 and comparative examples 1-5
| 0h | 8h | 16h | 24h | 32h | 40h | |
| Example 1 | 100.0 | 92.4 | 75.5 | 60.7 | 53.1 | 48.1 |
| Example 2 | 100.0 | 88.2 | 72.2 | 61.6 | 57.1 | 48.4 |
| Example 3 | 100.0 | 89.8 | 75.2 | 66.8 | 59.5 | 53.4 |
| Comparative example 1 | 100.0 | 83.0 | 69.1 | 52.6 | 41.4 | 31.6 |
| Comparative example 2 | 100.0 | 80.1 | 66.3 | 50.0 | 39.2 | 33.2 |
| Comparative example 3 | 100.0 | 82.4 | 65.9 | 52.3 | 38.4 | 34.3 |
| Comparative example 4 | 100.0 | 84.1 | 68.2 | 55.9 | 43.0 | 36.2 |
| Comparative example 5 | 100.0 | 78.8 | 64.5 | 48.4 | 36.9 | 31.6 |
While preferred embodiments of the present application have been described, additional variations and modifications in those embodiments may occur to those skilled in the art once they learn of the basic inventive concepts. It is therefore intended that the following claims be interpreted as including the preferred embodiments and all such alterations and modifications as fall within the scope of the application. It will be apparent to those skilled in the art that various modifications and variations can be made to the present application without departing from the spirit or scope of the application. Thus, it is intended that the present application also include such modifications and alterations insofar as they come within the scope of the appended claims or the equivalents thereof.
Claims (9)
1. The preparation method of the high weather-resistant high-gloss titanium dioxide is characterized by comprising the following steps of:
s1, preparing titanium white slurry, adding a zirconium source and a phosphorus source, and regulating the pH value to 6-7 by ammonia water; the zirconium source is added in the amount of ZrO 2 The meter is TiO in the slurry 2 0.1 to 1 percent of the total mass; the addition amount of the phosphorus source is P 2 O 5 The meter is TiO in the slurry 2 0.1 to 1 percent of the total mass;
s2, performing a first hydrothermal reaction at a reaction temperature of 300-500 ℃ for 3-5 hours, and sanding after the reaction;
s3, adjusting the temperature of the slurry to 80-90 ℃, adjusting the pH value to 5-6 by using citric acid, and simultaneously adding an aluminum source and a phosphorus source to keep the pH value of the slurry to 5-6;
s4, regulating the pH value of the slurry to 5-9 by using citric acid or ammonia water, and simultaneously adding a zinc source and a phosphorus source to maintain the pH value of the slurry to 5-9;
s5, performing a second hydrothermal reaction at 200-300 ℃ for 3-6 hours, and sanding after the reaction;
s6, regulating the pH value of the slurry to 8-8.5, controlling the temperature to 80-90 ℃, and adding an aluminum source to coat an aluminum film;
s7, calcining for 1.5-2.5 h at the temperature of 650-750 ℃ to obtain the titanium dioxide.
2. The method for preparing the high-weather-resistance high-gloss titanium dioxide according to claim 1, which is characterized in that,
and (2) adding the zirconium source and the phosphorus source in the step S1 for 10-20 min.
3. The method for preparing the high-weather-resistance high-gloss titanium dioxide according to claim 1, which is characterized in that,
the addition amount of the aluminum source in the step S3 is Al 2 O 3 The meter is TiO in the slurry 2 0.5 to 2 percent of total mass; the phosphorus source is added in an amount to maintain the pH of the cocurrent flow at 5 to 6.
4. The method for preparing the high-weather-resistance high-gloss titanium dioxide according to claim 1, which is characterized in that,
and step S3, simultaneously adding an aluminum source and a phosphorus source for 40-60 min, and homogenizing for 15-25 min after adding.
5. The method for preparing the high-weather-resistance high-gloss titanium dioxide according to claim 1, which is characterized in that,
the addition amount of the zinc source in the step S4 is calculated by ZnO and is TiO in the slurry 2 0.5 to 3 percent of the total mass; the phosphorus source is added in an amount to maintain the pH of the cocurrent flow at 5 to 9.
6. The method for preparing the high-weather-resistance high-gloss titanium dioxide according to claim 1, which is characterized in that,
after the temperature of the slurry is regulated to 80-90 ℃ in the step S6, acid aluminum salt and alkaline aluminum salt are added simultaneously within 30-50 min, the pH value of the slurry is maintained to 8-8.5, and then homogenization is carried out for 15-25 min; the total addition amount of the acidic aluminum salt and the alkaline aluminum salt is TiO in the slurry 2 1.5 to 3 percent of the total mass.
7. The method for preparing the high-weather-resistance high-gloss titanium dioxide according to claim 1, which is characterized in that,
and (3) sanding the mixture to the average particle size of less than 0.35 mu m in the step S2 and the step S5.
8. The method for preparing the high-weather-resistance high-gloss titanium dioxide according to claim 1, which is characterized in that,
the step S6 and the step S7 also comprise the step of adjusting the pH value of the slurry to be 5.5-5.8.
9. A highly weatherable high gloss titanium dioxide powder prepared by the method of any one of claims 1 to 8.
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Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101857736A (en) * | 2010-07-16 | 2010-10-13 | 四川龙蟒钛业股份有限公司 | Production method of high-light-fastness rutile type titanium dioxide |
| CN103112891A (en) * | 2013-02-25 | 2013-05-22 | 南京钛白化工有限责任公司 | Preparation method of high-performance rutile titanium white |
| CN103224717A (en) * | 2013-03-18 | 2013-07-31 | 中国科学院宁波材料技术与工程研究所 | Preparation method of composite coating titanium dioxide pigment |
| CN109705630A (en) * | 2018-12-21 | 2019-05-03 | 中信钛业股份有限公司 | A kind of preparation method of high fast light laminated paper titanium dioxide pigment |
| CN110903681A (en) * | 2019-12-18 | 2020-03-24 | 龙蟒佰利联集团股份有限公司 | Preparation method of super-weather-resistant titanium dioxide |
| CN111019402A (en) * | 2019-12-18 | 2020-04-17 | 龙蟒佰利联集团股份有限公司 | Preparation method of high-weather-resistance titanium dioxide |
| CN111019401A (en) * | 2019-12-18 | 2020-04-17 | 龙蟒佰利联集团股份有限公司 | Method for preparing slurry titanium dioxide by hydrothermal method |
| CN111334093A (en) * | 2020-04-14 | 2020-06-26 | 河南佰利联新材料有限公司 | Titanium dioxide for high-light-resistance laminated paper and preparation method thereof |
| CN113583480A (en) * | 2021-07-30 | 2021-11-02 | 龙佰集团股份有限公司 | Preparation method of high-end universal titanium dioxide |
| CN114031956A (en) * | 2021-12-01 | 2022-02-11 | 龙佰集团股份有限公司 | Preparation method of titanium dioxide with high light resistance and low cost |
| CN114085554A (en) * | 2021-12-01 | 2022-02-25 | 龙佰集团股份有限公司 | Preparation method of high-gloss high-weather-resistance titanium dioxide |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10153640A1 (en) * | 2001-10-31 | 2003-05-15 | Inst Neue Mat Gemein Gmbh | Coated titanium dioxide particles |
-
2022
- 2022-03-04 CN CN202210212189.5A patent/CN114591635B/en active Active
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101857736A (en) * | 2010-07-16 | 2010-10-13 | 四川龙蟒钛业股份有限公司 | Production method of high-light-fastness rutile type titanium dioxide |
| CN103112891A (en) * | 2013-02-25 | 2013-05-22 | 南京钛白化工有限责任公司 | Preparation method of high-performance rutile titanium white |
| CN103224717A (en) * | 2013-03-18 | 2013-07-31 | 中国科学院宁波材料技术与工程研究所 | Preparation method of composite coating titanium dioxide pigment |
| CN109705630A (en) * | 2018-12-21 | 2019-05-03 | 中信钛业股份有限公司 | A kind of preparation method of high fast light laminated paper titanium dioxide pigment |
| CN110903681A (en) * | 2019-12-18 | 2020-03-24 | 龙蟒佰利联集团股份有限公司 | Preparation method of super-weather-resistant titanium dioxide |
| CN111019402A (en) * | 2019-12-18 | 2020-04-17 | 龙蟒佰利联集团股份有限公司 | Preparation method of high-weather-resistance titanium dioxide |
| CN111019401A (en) * | 2019-12-18 | 2020-04-17 | 龙蟒佰利联集团股份有限公司 | Method for preparing slurry titanium dioxide by hydrothermal method |
| CN111334093A (en) * | 2020-04-14 | 2020-06-26 | 河南佰利联新材料有限公司 | Titanium dioxide for high-light-resistance laminated paper and preparation method thereof |
| CN113583480A (en) * | 2021-07-30 | 2021-11-02 | 龙佰集团股份有限公司 | Preparation method of high-end universal titanium dioxide |
| CN114031956A (en) * | 2021-12-01 | 2022-02-11 | 龙佰集团股份有限公司 | Preparation method of titanium dioxide with high light resistance and low cost |
| CN114085554A (en) * | 2021-12-01 | 2022-02-25 | 龙佰集团股份有限公司 | Preparation method of high-gloss high-weather-resistance titanium dioxide |
Non-Patent Citations (1)
| Title |
|---|
| 装饰层压纸用钛白粉技术现状的研究;吴婷婷等;《宁波化工》;20111231(第02期);22-26 * |
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