CN111662574A - Preparation method of high-durability anti-pulverization rutile type superfine titanium dioxide - Google Patents
Preparation method of high-durability anti-pulverization rutile type superfine titanium dioxide Download PDFInfo
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Abstract
The invention discloses a preparation method of high-durability anti-pulverization rutile type ultrafine titanium dioxide, belonging to the field of preparation of inorganic metal compounds. The impurities in the reduced titanium liquid A are fully separated out by adopting a method of mixing and settling the flocculating agent and the impurity removing agent in the preparation process, so that the prepared titanium dioxide has extremely high glossiness, extraordinary covering power and tinting strength and is easy to disperse.
Description
Technical Field
The invention belongs to the field of preparation of inorganic metal compounds, and particularly relates to a preparation method of high-durability anti-pulverization rutile type ultrafine titanium dioxide.
Background
Titanium dioxide, also called titanium dioxide, is a non-toxic white inorganic pigment with optimal whiteness and brightness, has stable chemical properties, excellent covering power, stronger coloring capability and higher melting point, and is widely applied to the fields of paint, plastics, printing ink, ceramics, paper industry, cosmetics and the like. Titanium dioxide generally comprises three crystal forms of rutile type, brookite type and anatase type, wherein the anatase type can be converted into the rutile type at high temperature, so that the two crystal forms have high commercial production values, and the rutile type (R type) has the advantages of compact structure, large refractive index, ultraviolet irradiation resistance, small photochemical activity, weather resistance and the like.
General production methods of titanium dioxide mainly include a sulfuric acid process and a chlorination process. The raw materials used in the chlorination process must be natural or artificial rutile, the technical requirement is high, and rutile titanium white is mainly produced, so that the method is not favorable for marketing popularization. The sulfuric acid method is widely applied, has low requirements on raw materials, is rich in raw material resources, is mature in technical method, and mainly comprises the procedures of acidolysis, reduction, crystallization filtration, hydrolysis, bleaching, calcination and post-treatment to obtain anatase type or rutile type titanium dioxide.
CN100545216C discloses a method for preparing titanium dioxide with high weather resistance, which uses rutile titanium dioxide of sulfuric acid method without surface treatment as raw material, adds sodium hexametaphosphate and isopropanolamine as dispersing agent, adjusts pH of the solution with dilute sulfuric acid, and then coats ZrO respectively2And Al2O3Then adding zirconium sulfate solution and sodium hydroxide solution, then adding aluminum sulfate solution and sodium hydroxide solution, then adding trimethylolpropane treating agent, and making air-flow pulverization so as to obtain the invented titanium dioxide with weatherability. The titanium dioxide samples prepared were tested for performance, the comparative example being a preparation without isopropanolamine addition, the average powdering rating of the examples prepared was around 1.9 and the comparative example was around 3.0 compared to the samples prepared with isopropanolamine additionWhen the samples of examples and comparative examples were subjected to the yellowing property index test, it was found that the yellowing resistance of titanium dioxide prepared using isopropanolamine was higher.
CN109266049A discloses a preparation method of a special titanium dioxide pigment for a high weather-resistant coating, which comprises the steps of firstly preparing a rutile type titanium dioxide primary product by a chlorination process, pulping by deionized water, preparing titanium dioxide slurry from the primary product, adding an inorganic alkali solution to adjust the pH value of the slurry, adding a water-soluble silicate solution as a dispersing agent, grinding, then adding a water-soluble silicate solution and an inorganic acid solution to adjust the pH value to form a first layer of compact silicon film, adding a water-soluble alkaline aluminate solution, adjusting the pH value by an inorganic acid solution to form a second layer of compact aluminum film, adding a water-soluble alkaline aluminate solution, and controlling the pH value by an inorganic acid solution to form a third layer of loose aluminum film; finally, washing, drying and carrying out vapor powder treatment to obtain the special titanium dioxide pigment for the high weather-resistant paint. The prepared product is subjected to related performance tests, and the weather resistance is found to be about 1.25, and the covering power is found to be about 83%, but the preparation process conditions are harsh, and industrial production is not easy to perform.
CN103265069A discloses a method for preparing rutile titanium dioxide, which comprises the specific steps of adding sulfuric acid into titanium slag to obtain acidolysis product, leaching with dilute sulfuric acid, filtering, adding ammonia water into the obtained filtrate, adding a reducing agent to obtain titanium liquid, hydrolyzing the obtained titanium liquid, filtering to obtain white hydrated titanium dioxide solid and hydrolysis mother liquor, calcining to obtain rutile titanium dioxide. The purity of the rutile type titanium dioxide prepared by the method is higher than 98%, but other physicochemical properties of the rutile type titanium dioxide are not tested, so that the corrosion resistance and other performances of the prepared titanium dioxide cannot be known.
In order to research rutile type titanium dioxide with excellent various properties, research and development personnel have conducted a lot of research, and the existing rutile type titanium dioxide has the problems of complicated preparation method, poor corrosion resistance, poor cohesive force and the like, so that the rutile type titanium dioxide with simple production method, low cost, good dispersibility and high durability is needed to be provided.
Disclosure of Invention
In view of the above-mentioned drawbacks of the background art, the present invention provides a method for preparing high-durability anti-pulverization rutile type ultrafine titanium dioxide, which has the advantages of low cost, good binding power performance, excellent high durability, alkali resistance, wear resistance and optical performance.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of high-durability anti-pulverization rutile type ultrafine titanium dioxide comprises the following steps:
(1) drying the titanium concentrate, grinding and sieving with a 325-mesh sieve to obtain dried titanium concentrate powder; quantitatively transferring the obtained powder into a mixing tank filled with concentrated sulfuric acid, uniformly mixing to obtain slurry, then sending the slurry into a continuous acidolysis reactor, and adding waste acid for acidolysis to obtain a solid-phase substance; dissolving the solid phase, adding iron powder for reduction to obtain reduced titanium liquid A;
(2) adding a flocculating agent and an impurity removing agent into the reduced titanium solution A obtained in the step (1) to settle insoluble impurities in the titanium solution; then removing solid impurities through filtration to obtain a titanium liquid B, crystallizing the titanium liquid B, filtering to remove ferrous sulfate heptahydrate generated by crystallization, and filtering and concentrating the filtrate to obtain a titanium liquid C;
(3) adding rutile calcined seed crystals into the titanium liquid C obtained in the step (2) for hydrolysis to obtain a hydrolysate, washing and carrying out salt treatment on the hydrolysate, and filtering to obtain a filter cake;
(4) calcining, crushing, pulping, grinding, sieving and the like the filter cake obtained in the step (3) to obtain a material C;
(5) and (5) coating the material C obtained in the step (4), drying and crushing to obtain the target product.
The mass ratio of the sulfuric acid to the titanium concentrate in the step (1) is 1.4-1.6:1, and the acidolysis temperature is 180-200 ℃; the mass ratio of the iron chips to the solid phase substances is (according to TiO)2Calculated) is 0.05-0.1:1, theThe reduction temperature is 60-70 ℃ and the time is 1-3 h.
The mass ratio of the flocculating agent is 1-2: 1 starch and modified polyacrylamide;
preferably, the mass ratio of the flocculating agent is 2: 1 and a modified polyacrylamide.
The impurity removing agent is prepared from the following components in a mass ratio of 1:1 antimony white and ferrous sulfide;
the addition ratio of the flocculating agent to the impurity removing agent is 1: 2-3.
The adding steps of the flocculating agent and the impurity removing agent are as follows: and (2) adding a flocculating agent into the reduced titanium liquid obtained in the step (1), standing until the precipitate is completely precipitated, filtering, then adding an impurity removing agent into the filtrate, standing until the precipitate is completely precipitated, and filtering to obtain a titanium liquid B.
TiO in the seed crystal described in the above step (3)2The mass of (A) is TiO in the titanium liquid C22-4.5% of the total amount.
The calcination in the step (4) adopts a gradient calcination mode, and the rotation speed of the brick kiln is 5-15 minutes/revolution; the calcination temperature from the kiln tail to the kiln head is 400-950 ℃, the final calcination temperature is 950-1000 ℃, and the retention time of the materials in the kiln body is 10-16 hours.
The filling coefficient of the materials in the kiln body is ensured to be 20-60% in the rotating process.
In the implementation process of the invention, the fact that the performance of the obtained titanium dioxide is affected by controlling the residence time of the materials in the kiln body and the filling coefficient of the materials in the kiln body is unexpectedly found, namely when the filling coefficient of the materials in the kiln body is controlled to be 20-60%, the durability and the pulverization resistance of the rutile type ultrafine titanium dioxide can be effectively improved.
The coating step in the step (5) is zinc-zirconium-aluminum coating;
the zinc coating is prepared by adding ammonium dihydrogen phosphate or sodium hexametaphosphate and zinc sulfate, wherein the slurry concentration of the zinc sulfate is ZnO/TiO2Calculated as 0.3-1.2%, the mass ratio of the ammonium dihydrogen phosphate or the sodium hexametaphosphate to the zinc sulfate is 3-8:1, and the pH value is 2.5-10;
the zirconium coating is prepared by using zirconium sulfate or zirconium chloride, the concentration of coating slurry is controlled to be 260-320g/L, the pH value of the coating is 3.5-5.5, and the addition amount is 0.3-0.8%;
the aluminum coating is prepared by using sodium metaaluminate and aluminum sulfate, the coating amount is controlled to be 2.5-4%, the pH value of the coating is 2.5-10, and the temperature in the coating process is 50-80 ℃.
The steps of crushing, pulping, grinding, sieving and the like in the step (5) are conventional methods in the field.
Compared with the prior art, the invention has the beneficial effects that:
(1) according to the preparation method of the rutile type superfine titanium dioxide, impurities in the reduced titanium liquid A are fully separated out by adopting a method of mixing and settling the flocculating agent and the impurity removing agent in the production process, so that the prepared titanium dioxide has extremely high glossiness, extraordinary covering power and tinting strength and is easy to disperse.
(2) In the preparation process, the rotation speed of the kiln body, the calcination temperature and the calcination time of the material in the kiln body in the calcination process are controlled, so that the prepared rutile type titanium dioxide has better weather resistance, and can not be pulverized, yellowed and glazed after being placed for a long time.
(3) According to the method for preparing rutile titanium dioxide, provided by the invention, the zinc-zirconium-aluminum coating is used in the preparation process, so that the durability of the rutile titanium dioxide can be improved, and the produced rutile titanium dioxide has better anti-pulverization performance.
Detailed Description
For a better understanding of the present invention, the present invention is further described in conjunction with the following specific examples, wherein the terminology used in the examples is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention.
The raw materials used in the following examples are all common commercial products, and the rotary kiln used is available from Nanning Guangfu heavy industry group, Inc., type
Example 1
A preparation method of high-durability anti-pulverization rutile type ultrafine titanium dioxide comprises the following steps:
(1) drying the titanium concentrate, grinding and sieving with a 325-mesh sieve to obtain dried titanium concentrate powder; quantitatively transferring the obtained powder into a mixing tank filled with concentrated sulfuric acid, uniformly mixing to obtain slurry, then sending the slurry into a continuous acidolysis reactor, and adding waste acid for acidolysis to obtain a solid-phase substance; dissolving the solid phase, adding iron powder for reduction to obtain reduced titanium liquid A;
(2) adding the reduced titanium solution A obtained in the step (1) into the reduced titanium solution A according to the mass ratio of 1:1, standing the starch and the modified polyacrylamide for complete precipitation, filtering, and adding a mixture of the starch and the modified polyacrylamide in a mass ratio of 1:1, standing antimony white and ferrous sulfide, filtering after complete precipitation to obtain a titanium liquid B, crystallizing the titanium liquid B, filtering to remove ferrous sulfate heptahydrate generated by crystallization, and filtering and concentrating filtrate to obtain a titanium liquid C;
(3) adding rutile calcined seed crystals into the titanium liquid C obtained in the step (2) for hydrolysis to obtain a hydrolysate, washing and carrying out salt treatment on the hydrolysate, and filtering to obtain a filter cake;
(4) calcining, crushing, pulping, grinding, sieving and the like the filter cake obtained in the step (3) to obtain a material C;
(5) and (5) coating the material C obtained in the step (4), drying and crushing to obtain the target product.
The mass ratio of the sulfuric acid to the titanium concentrate in the step (1) is 1.4:1, and the acidolysis temperature is 180 ℃; the mass ratio of the iron chips to the solid phase substances is (according to TiO)2Calculated) is 0.05:1, the temperature of the reduction is 60 ℃, and the time is 1 h.
The adding amount ratio of the flocculating agent to the impurity removing agent in the step (2) is 1: 2.
TiO in the seed crystal described in the above step (3)2The mass of (A) is TiO in the titanium liquid C22% of the total amount.
The calcination in the step (4) adopts a gradient calcination mode, and the rotation speed of the brick kiln is 5 minutes per revolution; the calcination temperature from the kiln tail to the kiln head is 400-950 ℃, the final calcination temperature is 950 ℃, and the retention time of the materials in the kiln body is 10 hours.
The filling coefficient of the materials in the kiln body is ensured to be 20 percent during the rotation process.
The coating step in the step (5) is zinc-zirconium-aluminum coating, wherein the zinc-zirconium-aluminum coating is to add ammonium dihydrogen phosphate and then add zinc sulfate; the slurry concentration of the zinc sulfate is ZnO/TiO2Calculated as 0.3 percent, the mass ratio of the ammonium dihydrogen phosphate to the zinc sulfate is 3:1, the pH value is 2.5, and the temperature in the coating process is 50 ℃.
The zirconium coating is prepared by using zirconium sulfate or zirconium chloride, the concentration of coating slurry is controlled to be 260g/L, the pH value of the coating is 3.5, and the addition amount is 0.3%;
the aluminum coating is prepared by coating sodium metaaluminate, the coating amount is 2.5%, the pH value of the coating is 2.5, and the temperature in the coating process is 50 ℃.
Example 2
A preparation method of high-durability anti-pulverization rutile type ultrafine titanium dioxide comprises the following steps:
(1) drying the titanium concentrate, grinding and sieving with a 325-mesh sieve to obtain dried titanium concentrate powder; quantitatively transferring the obtained powder into a mixing tank filled with concentrated sulfuric acid, uniformly mixing to obtain slurry, then sending the slurry into a continuous acidolysis reactor, and adding waste acid for acidolysis to obtain a solid-phase substance; dissolving the solid phase, adding iron powder for reduction to obtain reduced titanium liquid A;
(2) adding the reduced titanium solution A obtained in the step (1) into the reduced titanium solution A according to the mass ratio of 2: 1, standing the starch and the modified polyacrylamide for complete precipitation, filtering, and adding a mixture of the starch and the modified polyacrylamide in a mass ratio of 1:1, standing antimony white and ferrous sulfide, filtering after complete precipitation to obtain a titanium liquid B, crystallizing the titanium liquid B, filtering to remove ferrous sulfate heptahydrate generated by crystallization, and filtering and concentrating filtrate to obtain a titanium liquid C;
(3) adding rutile calcined seed crystals into the titanium liquid C obtained in the step (2) for hydrolysis to obtain a hydrolysate, washing and carrying out salt treatment on the hydrolysate, and filtering to obtain a filter cake;
(4) calcining, crushing, pulping, grinding, sieving and the like the filter cake obtained in the step (3) to obtain a material C;
(5) and (5) coating the material C obtained in the step (4), drying and crushing to obtain the target product.
The mass ratio of the sulfuric acid to the titanium concentrate in the step (1) is 1.5:1, and the acidolysis temperature is 190 ℃; the mass ratio of the iron chips to the solid phase substances is (according to TiO)2Calculated) is 0.08:1, the temperature of the reduction is 70 ℃, and the time is 2 h.
The adding amount ratio of the flocculating agent to the impurity removing agent in the step (2) is 1: 2.5.
TiO in the seed crystal described in the above step (3)2The mass of (A) is TiO in the titanium liquid C23% of the total amount.
The calcination in the step (4) adopts a gradient calcination mode, and the rotation speed of the brick kiln is 8 minutes per revolution; the calcination temperature from the kiln tail to the kiln head is 400-950 ℃, the final calcination temperature is 980 ℃, and the retention time of the materials in the kiln body is 12 hours.
The filling coefficient of the materials in the kiln body is ensured to be 30 percent in the rotating process.
The coating step in the step (5) is zinc-zirconium-aluminum coating, wherein the zinc-zirconium-aluminum coating is to add sodium hexametaphosphate and then add zinc sulfate; the slurry concentration of the zinc sulfate is ZnO/TiO2Calculated as 0.5 percent, the mass ratio of the sodium hexametaphosphate to the zinc sulfate is 5:1, the pH value is 5, and the temperature in the coating process is 60 ℃.
The zirconium coating is prepared by using zirconium sulfate or zirconium chloride, the concentration of coating slurry is controlled to be 300g/L, the pH value of the coating is 4.0, and the addition amount is 0.5%;
the aluminum coating is prepared by using sodium metaaluminate or aluminum sulfate, the coating amount is controlled to be 3.0 percent, the pH value of the coating is 10, and the temperature in the coating process is 60 ℃.
Example 3
A preparation method of high-durability anti-pulverization rutile type ultrafine titanium dioxide comprises the following steps:
(1) drying the titanium concentrate, grinding and sieving with a 325-mesh sieve to obtain dried titanium concentrate powder; quantitatively transferring the obtained powder into a mixing tank filled with concentrated sulfuric acid, uniformly mixing to obtain slurry 1, then sending the slurry 1 into a continuous acidolysis reactor, and adding waste acid for acidolysis to obtain a solid-phase substance; dissolving the solid phase, adding iron powder for reduction to obtain reduced titanium liquid A;
(2) adding the reduced titanium solution A obtained in the step (1) into the reduced titanium solution A according to the mass ratio of 2: 1, standing the starch and the modified polyacrylamide for complete precipitation, filtering, and adding a mixture of the starch and the modified polyacrylamide in a mass ratio of 1:1, standing antimony white and ferrous sulfide, filtering after complete precipitation to obtain a titanium liquid B, crystallizing the titanium liquid B, filtering to remove ferrous sulfate heptahydrate generated by crystallization, and filtering and concentrating filtrate to obtain a titanium liquid C;
(3) adding rutile calcined seed crystals into the titanium liquid C obtained in the step (2) for hydrolysis to obtain a hydrolysate, washing and carrying out salt treatment on the hydrolysate, and filtering to obtain a filter cake;
(4) calcining, crushing, pulping, grinding, sieving and the like the filter cake obtained in the step (3) to obtain a material C;
(5) and (5) coating the material C obtained in the step (4), drying and crushing to obtain the target product.
The mass ratio of the sulfuric acid to the titanium concentrate in the step (1) is 1.6:1, and the acidolysis temperature is 200 ℃; the mass ratio of the iron chips to the solid phase substances is (according to TiO)2Calculated) is 0.1:1, the temperature of the reduction is 70 ℃, and the time is 3 h.
The adding amount ratio of the flocculating agent to the impurity removing agent in the step (2) is 1: 2.
TiO in the seed crystal described in the above step (3)2The mass of (A) is TiO in the titanium liquid C24.5% of the total amount.
The calcination in the step (4) adopts a gradient calcination mode, and the rotation speed of the brick kiln is 10 minutes per revolution; the calcination temperature from the kiln tail to the kiln head is 400-950 ℃, the final calcination temperature is 1000 ℃, and the retention time of the materials in the kiln body is 16 hours.
The filling coefficient of the materials in the kiln body is ensured to be 60 percent in the rotating process.
The coating step in the step (5) is zinc-zirconium-aluminum coating, wherein the zinc-zirconium-aluminum coating is to add sodium hexametaphosphate and then add zinc sulfate; the slurry concentration of the zinc sulfate is ZnO/TiO2Calculated by 1.2 percent, the mass ratio of the sodium hexametaphosphate to the zinc sulfate is 8:1, the pH value is 10, and the temperature in the coating process is 80 ℃;
the zirconium coating is prepared by using zirconium sulfate or zirconium chloride, the concentration of coating slurry is controlled to be 320g/L, the pH value of the coating is 5.5, and the addition amount is 0.8%;
the aluminum coating is prepared by using sodium metaaluminate or aluminum sulfate, the coating amount is controlled to be 4%, the pH value of the coating is 10, and the temperature in the coating process is 80 ℃.
Comparative example 1
The difference from example 2 is that: only an impurity removing agent is used in the step (2), namely the mass ratio of 1:1 antimony white and ferrous sulfide, and other operations and steps were the same as in example 2.
Comparative example 2
The difference from example 2 is that: adding modified polyacrylamide into the reduced titanium solution A obtained in the step (1), standing for complete precipitation, filtering, then adding ferrous sulfide into the filtrate, standing for complete precipitation, and filtering to obtain a titanium solution B; the other operations and steps are the same as in example 2.
Comparative example 3
The difference from example 2 is that: the mass ratio of the flocculating agent to the impurity removing agent is 0.5: 1, the other operations and steps are the same as in example 2.
Comparative example 4
The difference from example 2 is that: the mass ratio of the flocculating agent to the impurity removing agent is 5:1, the other operations and steps are the same as in example 2.
Comparative example 5
The difference from example 3 is that: the brick kiln rotation speed in the step (4) is 20 minutes/revolution, the filling factor is 80%, and other operations are the same as those in the example 3.
Comparative example 6
The difference from example 3 is that: the brick kiln rotation speed in the step (4) is 20 minutes/revolution, the filling factor is 10%, and other operations are the same as those in the example 3.
Test experiments:
the rutile type titanium dioxides prepared in the above examples 1 to 3 and comparative examples 1 to 6 were subjected to specific surface area, particle size, yellowing property and TiO2The purity and other performance tests show that the test results are shown in table 1:
the related performance detection method comprises the following steps: the average chalking grade and yellowing performance test method comprises the following steps: and (3) naturally drying the sample in a paint spraying plate made of an alkyd resin system, and measuring the chalking grade and the yellow index of the paint spraying plate after accelerating aging for 320h by using an ultraviolet accelerating aging instrument (aging parameters are UV 8h-Spray 2min-Cond 4h in a circulating manner).
Table 1:
from the test data in Table 1 above, it can be seen that the rutile form of titanium dioxide prepared using only the disclosed components in the preferred ratio ranges of the present invention has excellent properties and better meets the customer requirements. In table 1, comparative examples 1-2 only use the impurity removing agent or use a flocculating agent or impurity removing agent, comparative examples 3-4 change the weight ratio of raw materials, and comparative examples 5-6 change the calcination conditions in the invention, so that the calcination conditions are not in the preferable range, and the detection result shows that the change of the weight ratio or the types of raw materials or the calcination conditions can affect the performance of the titanium dioxide, but from the general view, the titanium dioxide prepared by the method provided by the application has proper particle size range, good consistency and TiO2The purity of the product can reach more than 94%, and the average pulverization grade and the decolorization are better.
The above detailed description is specific to one possible embodiment of the present invention, and the embodiment is not intended to limit the scope of the present invention, and all equivalent implementations or modifications without departing from the scope of the present invention should be included in the technical scope of the present invention.
Claims (10)
1. A preparation method of high-durability anti-pulverization rutile type ultrafine titanium dioxide comprises the following steps:
(1) drying the titanium concentrate, grinding and sieving with a 325-mesh sieve to obtain dried titanium concentrate powder; quantitatively transferring the obtained powder into a mixing tank filled with concentrated sulfuric acid, uniformly mixing to obtain slurry, then sending the slurry into a continuous acidolysis reactor, and adding waste acid for acidolysis to obtain a solid-phase substance; dissolving the solid phase, adding iron powder for reduction to obtain reduced titanium liquid A;
(2) adding a flocculating agent and an impurity removing agent into the reduced titanium liquid A obtained in the step (1) to settle insoluble impurities in the titanium liquid A, removing solid impurities through filtration to obtain a titanium liquid B, then crystallizing the titanium liquid B, filtering to remove ferrous sulfate heptahydrate generated by crystallization, filtering and concentrating the filtrate to obtain a titanium liquid C;
(3) adding rutile calcined seed crystals into the titanium liquid C obtained in the step (2) for hydrolysis to obtain a hydrolysate, washing and carrying out salt treatment on the hydrolysate, and filtering to obtain a filter cake;
(4) calcining, crushing, pulping, grinding, sieving and the like the filter cake obtained in the step (3) to obtain a material C;
(5) and (5) coating the material C obtained in the step (4), drying and crushing to obtain the target product.
2. The method of claim 1, wherein: the mass ratio of the sulfuric acid to the titanium concentrate in the step (1) is 1.4-1.6:1, and the acidolysis temperature is 180-; the mass ratio of the scrap iron to the solid phase is 0.05-0.1:1, the reduction temperature is 60-70 ℃, and the time is 1-3 h.
3. The method of claim 1, wherein: the mass ratio of the flocculating agent is 1-2: 1 starch and modified polyacrylamide; the impurity removing agent is prepared from the following components in a mass ratio of 1:1 antimony white and ferrous sulfide.
4. The method of claim 1, wherein: the addition ratio of the flocculating agent to the impurity removing agent is 1: 2-3.
5. The method of claim 1, wherein: TiO in the seed crystal in the step (3)2The mass of (A) is TiO in the titanium liquid C22-4.5% of the total amount.
6. The method of claim 1, wherein: and (4) adopting a gradient calcination mode in the rotary kiln for calcination.
7. The method of claim 6, wherein: the rotating speed of the brick kiln is 5-15 minutes/revolution; the calcination temperature from the kiln tail to the kiln head is 400-950 ℃, and the final calcination temperature is 950-1000 ℃.
8. The method of claim 7, wherein: the residence time of the filter cake in the kiln body is 10-16 hours.
9. The method of claim 7, wherein: the filling coefficient of the materials in the kiln body is ensured to be 20-60% in the rotary kiln rotating process.
10. The method of claim 1, wherein: the coating step in the step (5) is zinc-zirconium-aluminum coating;
the zinc coating is prepared by adding ammonium dihydrogen phosphate or sodium hexametaphosphate and zinc sulfate, wherein the slurry concentration of the zinc sulfate is ZnO/TiO2Calculated as 0.3-1.2%, the mass ratio of the ammonium dihydrogen phosphate or the sodium hexametaphosphate to the zinc sulfate is 3-8:1, and the pH value is 2.5-10;
the zirconium coating is prepared by using zirconium sulfate or zirconium chloride, the concentration of coating slurry is controlled to be 260-320g/L, the pH value of the coating is 3.5-5.5, and the addition amount is 0.3-0.8%;
the aluminum coating is prepared by using sodium metaaluminate or aluminum sulfate, the coating amount is controlled to be 2.5-4%, the pH value of the coating is 2.5-10, and the temperature in the coating process is 50-80 ℃.
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