CN107935038B - Preparation process of special titanium dioxide for plastic color master batch - Google Patents
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Abstract
A preparation process of special titanium dioxide for color master batches has the following characteristics: 1. crushing raw ore, 2, acidolysis, 3, leaching, 4, reduction, 5, sedimentation, 6, concentration of titanium liquid, 7, hydrolysis, 8, water washing and bleaching, 9, salt treatment, 10, filtering, calcining, surface treatment, 11, drying and dedusting.
Description
Technical Field
The invention belongs to the field of titanium dioxide production, and particularly relates to a preparation process of special titanium dioxide for color master batches for plastic manufacturing.
Background
Titanium dioxide (TiO) with titanium dioxide name2) Mainly has two crystal forms of rutile type and anatase type. The pigment has the advantages of excellent whiteness, tinting strength, hiding power and the like, has the highest refractive index among all white pigments, is considered to be the best white pigment, and is widely applied to the industries of coatings, plastics, printing, rubber and the like. Plastics as the second largest consumer of titanium dioxide, except for its high hiding power, high tinting strength and its useBesides the pigment performance, the pigment can also improve the heat resistance, light resistance and weather resistance of plastic products. The titanium dioxide powder of the color master batch is positioned in the core layer of the color master batch, so the requirements on whiteness, dispersibility, covering power, processing torque performance and the like are higher, the titanium dioxide powder obtained by the traditional process is often difficult to meet the requirements, and the technical problem of how to improve the prior process to obtain the titanium dioxide powder product with higher whiteness, better dispersibility, stronger covering power and processing torque is urgently needed to be solved.
Disclosure of Invention
Aiming at the technical problems in the prior art, the invention provides an improved sulfuric acid method for preparing titanium dioxide, provides a titanium dioxide product with higher whiteness, better dispersibility, stronger covering power and processing torque, and can well meet the special requirements of the plastic industry, particularly ABS plastics, on the performance of the titanium dioxide.
The preparation method comprises the following specific steps: 1. crushing raw ore, 2, acidolysis, 3, leaching, 4, reduction, 5, sedimentation, 6, concentration of titanium liquid, 7, hydrolysis, 8, water washing and bleaching, 9, salt treatment, 10, filtering, calcining, surface treatment, 11, drying and dedusting.
1) Crushing raw ores:
raw ore selection needs to meet a certain titanium content, preferably the Ti content (all mass percentages are TiO)2In terms of the content of the titanium component, the acid solubility of the titanium component is required to be good, namely the content of rutile in the ilmenite is required to be low and is preferably less than or equal to 3%, meanwhile, the content of ferrous iron and high iron in the ilmenite is required to be more than or equal to 94%, the content of high iron is required to be less than 13%, and the content of colloidal impurities such as Cr, Co and the like is required to be low and is preferably less than or equal to 3%. The selected ilmenite sand generally has relatively coarse and uneven particles, is not easy to react with sulfuric acid and completely reacts, and needs to be crushed in order to improve the acidolysis rate, the optimized raw ore is crushed to the fineness of 320 meshes by a horizontal ball mill, the screen residue is less than or equal to 3.5 percent, and the crushed ore powder is fed to an acidolysis pot in batches by a pulse pneumatic conveying pump.
2) Acid hydrolysis:
firstly adding 93-95% sulfuric acid under strong compressed air stirring in an acidolysis pot, then adding mineral powder, controlling the acid-mineral ratio to be 1.52-1.55, after the mineral powder is completely added, using stronger compressed air to mix and homogenize for 8-15 minutes, preferably 10-12 minutes, so that the mineral powder and the sulfuric acid are fully mixed, after the stirring homogenization is finished, closing an acidolysis pot cover and fixing firmly to prevent the main reaction from turning the pot cover up, adding dilution water into the acidolysis pot for not more than 5 minutes generally, preferably not more than 3 minutes, stirring for about 5-10 minutes to initiate the main reaction, simultaneously opening a main reaction warning lamp, opening an acidolysis tail gas spray pump, after the main reaction is finished, closing the tail gas spray pump, closing the compressed air for curing, controlling the curing time to be 20-45 minutes, preferably 25-35 minutes, simultaneously introducing steam to directly heat to 80-100 ℃, so that the acidolysis reaction is smoothly carried out.
3) Leaching
After the aging is finished, opening a large compressed air valve, introducing compressed air for 25-30 minutes to assist cooling, adding about 3000ml of waste acid, then adding enough water, controlling the adding speed to ensure that the whole process is 30-40 minutes, controlling the temperature of the titanium liquid to be 60-75 ℃ after the leaching is finished, controlling the leaching volume during the leaching, adding enough water once, and generally not supplementing water during the leaching. After the leaching water is added, continuously stirring the solution by using compressed air to continuously dissolve the solid-phase substance, along with the continuous dissolution of the solid-phase substance, an operator measures the specific gravity and the temperature of the solution once every 20 minutes, keeps the temperature of the solution at 65-75 ℃, and indicates that the solid-phase substance is completely dissolved when the temperature of the solution is not increased after about 60 minutes of adding the water, wherein the final concentration of the solution generally contains TiO2120-135 g/l, the specific gravity of the solution is about 48-51, the F value (the ratio of effective acid to total titanium content) of the leaching solution is controlled to be 1.85-2.05, and the leaching time is generally 5-12 hours.
4) Reduction of
When the reduction operation is carried out, the solution temperature must be less than or equal to 65 ℃ to allow the addition of the iron powder, the addition time of the reduced iron powder should be controlled to be about 25 minutes, the first 15 minutes is faster and the last 10 minutes is slower, the maximum reaction temperature of the solution does not exceed 75 ℃, and meanwhile, in the reduction starting stage, the flow of the compressed air is controlled to be 0.8NM3One minute to prevent the oxidation of the trivalent titanium from boiling overThe phenomenon occurs, and the content of the trivalent titanium in the reducing solution is kept to be 1.5-3.0 g/l.
5) Sedimentation
The insoluble impurities, especially colloids, in the titanium liquid are removed for the purpose of sedimentation. When the trivalent titanium in the reducing liquid is detected to be about 3g/L, a well-dissolved and well-measured settling agent can be added, wherein the settling agent is 1-1.5 kg/L of Sb2O3Adding 1-2 kg/L ferrous sulfide into the hydrochloric acid solution, controlling the time of adding the settling agent within 5-8 minutes, and compressing air in the adding process to uniformly mix the prepared solution, the ferrous sulfide and the titanium solution, wherein the settling treatment is ensured to be more than 2 hours.
Pumping the clear solution obtained by settling out to the next stage for vacuum crystallization, filtering the residue containing a certain amount of titanium solution with a filter press, recovering the filtrate, and collecting the residue (containing TiO on a dry basis)240-50% Fe 10-25%) and can be recycled. 6) Concentration of titanium solution
In order to ensure that the particles of the hydrated titanium dioxide obtained after hydrolysis are fine and uniform, the concentration of the titanium liquid needs to be increased to the titanium dioxide content of more than 190g/l, the titanium liquid is concentrated continuously by adopting a vacuum film concentrator, the vacuum degree is controlled to be 0.09MPa, and the temperature of the titanium liquid is controlled to be 50-55 ℃.
7) Hydrolysis
The purpose of hydrolysis is to obtain metatitanic acid, and the basic process comprises the formation of crystal centers, the growth of crystal nuclei and the formation of precipitates, the coagulation and precipitation of metatitanic acid particles and the change of solution composition. Anatase seed crystals need to be added during the hydrolysis process.
The hydrolysis process comprises the following steps:
7.1) metering the prepared titanium liquid according to the process requirements, respectively pumping the titanium liquid into a hydrolysis preheating pot and a seed crystal titanium liquid tank, starting the preheating pot to stir when the liquid level reaches a stirring paddle, metering the prepared ammonia water with the concentration, and pumping the ammonia water into a seed crystal ammonia water tank for later use;
7.2) after the material is beaten, waiting for adding seed crystals. Starting the seed crystal manufacturing tank for stirring, opening a discharge valve of an ammonia water tank to quickly discharge ammonia water into the seed crystal manufacturing tank, then opening a discharge valve of a seed crystal titanium liquid tank to neutralize the seed crystal titanium liquid and the ammonia water in the seed crystal manufacturing tank, neutralizing with the ammonia water with the mass percentage concentration of 18-20% until the pH value is 9-10, keeping the neutralization process for 1 hour, and stirring while neutralizing. After the neutralization, the temperature of the material is raised to 90 ℃, the temperature raising rate is 1 ℃/min, and the temperature is kept for 1 hour. Then cooling to 75 ℃, rapidly detecting the stability of the crystal seed, rapidly opening an outlet valve of a crystal seed manufacturing groove when the stability is 90ml, and rapidly putting the manufactured crystal seed into a preheating pot titanium liquid preheated to 96 ℃; the temperature of the titanium liquid in the preheating pot must be raised to 96 ℃ and the seed crystal is ready, the temperature of the prepared seed crystal can not be raised, otherwise, the stability of the seed crystal is rapidly reduced, and the quality of the whole pot is affected.
7.3) stirring for 10 minutes after the seed crystal is added, opening an inlet valve of the hydrolysis pot, opening a discharge valve of the preheating pot, putting the titanium liquid in the preheating pot into the hydrolysis pot, and simultaneously starting the hydrolysis pot to stir.
7.4) after the titanium liquid in the preheating pot is put into the hydrolysis pot, opening a direct steam inlet valve of the hydrolysis pot, and starting hydrolysis and temperature rise.
7.5) after the titanium liquid hydrolysate is boiled for one time, the time from heating to boiling is required to be less than or equal to 28 minutes, and steam is reduced to prevent transitional boiling; when the hydrolysis reaches 1: 1 and the hair turns white, stopping steam, stopping stirring and preserving heat for 30 minutes.
7.6) after the heat preservation is finished, stirring and steam are started again for secondary heating, and the titanium hydrolysate is boiled for the second time within 20 minutes.
7.7) washing the titanium liquid preheating pot and the seed crystal manufacturing pot, discharging the washing liquid into the hydrolysis pot to be used as dilution water, and closing the valve after washing.
7.8) closing the direct steam valve to keep the micro-boiling state, and keeping the pressure in the cooker at 90-120 mmH2O, 150 minutes.
7.9) after the pressure maintaining is finished, opening an emptying valve of the hydrolysis kettle, adding quantitative dilution water, reducing the concentration to 140-155 g/l, and adding water to obtain a volume of 13.5m3And continuously heating to boil, and keeping slight boiling for 50 minutes.
7.10) the hydrolysis is finished, the steam valve is closed.
7.11) adding a certain amount of lignocellulose into the hydrolyzed metatitanic acid, and stirring for 10 minutes to discharge the material.
7.12) opening a discharge valve at the bottom of the pot to send the hydrolyzed metatitanic acid to a cooling system.
7.13) after the emptying, washing the inner wall of the clean hydrolysis kettle until no white water flows out.
8) Washing and bleaching
The hydrated titanium dioxide slurry obtained by hydrolyzing the titanium sulfate solution contains a large amount of impurities such as free sulfuric acid, ferrous sulfate and the like, and the hue of the finished titanium dioxide product is directly influenced by the content of the impurity ions. It is therefore necessary to further wash it with water and bleach it.
9) Salt treatment
The salt treatment process specifically comprises the following steps: step 1, adding 3-6%, preferably 4-5% of calcined rutile type seed crystal into bleached metatitanic acid solution; and step 2, adding ZnO with the addition amount of 0.05-0.25%, preferably 0.10%, and stirring for 30 minutes after adding. Then adding NH4H2PO40.5-0.7% of powder, preferably 0.55-0.65%, stirring for 10-15 min, preferably 12 min, adding 0.85-1.1% of KOH solution, preferably 0.9-1.0%, and finally adding Al2(SO4)30.1-0.8%, preferably 0.2-0.5%, and then stirring for 100-160 minutes, preferably 150 minutes. Pumping into a kiln tail storage tank.
However, the addition ratio of the above five types of substances needs to be strictly controlled, and the mass ratio between the rutile type seed crystal and the zinc, ammonium, potassium and aluminum salts needs to satisfy the following relationship, wherein each salt is calculated by the mass of the oxide, the rutile seed crystal: ZnO: P2O5∶K2O∶Al2O3The mass percentage of the components is controlled to be (9-18): (1-2): (1.3-2.5): (1-8).
Wherein, the preparation method of the rutile type seed crystal for salt treatment comprises the following steps:
A. preparation of sodium orthotitanate: filtering and washing TiO with qualified iron content lower than 50ppm by a double-washing filter press2Pumping hydrate into metatitanic acid heating and metering tank, measuring NaOH in alkali heating and metering tank, heating to 60 deg.C and 90 deg.C, and mixing with TiO2And (3) putting the hydrate NaOH into an alkali melting tank for reaction with 50% NaOH solution to generate sodium orthotitanate. Warp beamAfter cooling, pumping the solution into a filter press by a pump, loading the solution on a plate, washing, discharging the solution, pulping a filter cake, separating sodium orthotitanate from filtrate containing a large amount of free NaOH solution, enabling 15% NaOH filtrate to flow into an ammonia water collecting tank, and spraying tail gas by using an external pumping system. Washing NaOH in the sodium orthotitanate filter cake by using a filter press, discharging the filter liquor into a pulping tank after the NaOH content of the filter liquor is measured to be less than 1500ppm, then neutralizing the filter liquor by using 10% hydrochloric acid until the pH value is within the range of 3.5-4.0, pumping the filter liquor into the filter press by using a pump, then loading the filter liquor on a plate, washing until the pH value of the washing filtrate is more than 7, discharging the filter cake, and pulping to obtain TiO2The concentration is controlled to be 200-220 g/l, and the method is used for preparing an orthotitanic acid intermediate product from seed crystals. B. Preparing seed crystals: and D, reacting the sodium orthotitanate prepared in the step A with 30% hydrochloric acid to generate rutile type calcining seed crystals, and pumping the prepared seed crystals into a storage tank by using a pump.
10) Filtering, calcining and surface treating
Filtering the metatitanic acid mixture after salt treatment, and then feeding the metatitanic acid mixture into a rotary kiln for calcination, wherein the calcination temperature is controlled to be 800-980 ℃, and preferably 850-900 ℃. Adding kaolin powder with the particle size of 1.5-2.5 mu m and Al2O3The powders were subjected to a conventional inorganic coating surface treatment together.
11) Drying and dedusting
11.1) washing again, keeping the washing time for 1 hour, and ensuring that the sulfur content of the filter cake is less than 0.3 percent at the washing end point.
11.2) pulping the washed qualified filter cake with 30 ten thousand omega cm deionized water, controlling the concentration of the pulp to be 300g/L, and then pressing and drying the pulp by a filter press, wherein the water content of the filter cake is controlled to be 50%.
11.3) after cake removal, conveying the filter cake to a flash drying main machine, simultaneously inputting hot air into the flash drying main machine, and keeping the temperature of the filter cake to reach 95 ℃ after the filter cake is contacted with the hot air. Set up high speed stirrer in flash dryer main machine bottom, break up the filter cake rapidly, under hot-air flow and draught fan combined action, the material is dried by the in-process that rises to the desicator top rapidly by the desicator bottom in 3 ~ 5 seconds. A cyclone classifier is arranged at the top, and the unqualified materials are returned to the bottom of the flash dryer for re-drying; qualified dried materials are pumped into the pulse dust collector by the draught fan and attached to the surface of a filter bag of the dust collector, the materials fall into the bottom of the pulse dust collector through the impact of the electromagnetic vibration device and compressed air flow, the materials are collected into a storage bin through a spiral conveyor and a star-shaped discharge valve, and the materials are crushed by a micron crusher to obtain a titanium dioxide product with a high specific surface area.
The technical effects are as follows:
1. the preparation method effectively improves the performance of the titanium dioxide by strictly controlling the parameters of each step of the whole titanium dioxide preparation process:
2. the invention adds the novel salt treating agent mixed with the crystal seeds, and the rutile crystal seeds can improve the decoloring force of the product and the shape of primary particles of titanium dioxide during calcination, so that the particles are smooth, regular, soft and easy to crush; zinc salts are very strong rutile promoters. The addition of zinc salt can improve the weather resistance and the pulverization resistance of the product, and the sylvite is an indispensable crystal form stabilizer of rutile titanium dioxide. The potassium salt can inhibit the conversion rate of rutile type, reduce the calcination desulfurization temperature, avoid the sintering growth of particles, improve the performance of pigment and improve the achromatism. Ammonium dihydrogen phosphate can also be used for neutralizing free acid in metatitanic acid during salt treatment, so that product is neutral during calcination, and CO generated by reaction2And H2When O volatilizes, the product can be loosened, and the whiteness of the product can be improved. And the addition of aluminum sulfate is beneficial to the decomposition of sulfide and the reduction of the starting temperature of the transformation of rutile crystal form.
3. The salt treating agent used in the invention is a compound formula of a plurality of different types of treating agents, so the proportion is a main key technology, for example, if the zinc salt is added independently, the pigment performance of the product is reduced due to the fact that particles grow too fast and are easy to sinter, and the bottom phase of the product is yellow, the particles are hard, and the dispersing performance is reduced. The whiteness of the primary titanium white product is easy to reduce by adding excessive aluminum sulfate. The crystal seed consumption is large, although the conversion speed is high, the production cost is increased, and the metatitanic acid is difficult to be converted into rutile type in a short time if the crystal seed consumption is too small; and too much potassium salt can affect the transformation of the crystal form. The proportion of the invention not only can effectively reduce the calcination temperature, but also can ensure that
4. The final product of the invention has the following good performances:
titanium oxide TiO2The content range is 95-97%, wherein the rutile content is not lower than 99.7%; the content of the S element is not more than 3 ppm;
the specific surface area is 350-370 m2(ii)/g; agglomerate particle diameter D500.10 to 0.20 μm; agglomerate particle diameter D90≤0.5μm；
The volatile matter (105 ℃, 2h) is less than or equal to 1.5 percent; the ignition loss (after drying at 105 ℃ for 2h, the sample is ignited at 600 ℃ for 1h) is less than or equal to 8 percent;
the pH value of the aqueous suspension is 6.5-7.5; the water absorption capacity (30-35) g/50 g; 45 mu m screen residue is less than or equal to 0.04 percent; an oil absorption of 23 to 25(g/100 g); fe2O3≤0.005％；(K2O+Na2O)≤0.008％。
Color CIE properties:
luminance L: 98.5-98.8; hue a: (0.9 to 1.0); hue b: 1.4 to 1.5
Detailed Description
The present invention will be described in detail by the following exemplary embodiments, but the spirit of the present invention and the scope of the claims are not limited by these embodiments.
Example 1
7) Hydrolysis
The purpose of hydrolysis is to obtain metatitanic acid, and the basic process comprises the formation of crystal centers, the growth of crystal nuclei and the formation of precipitates, the coagulation and precipitation of metatitanic acid particles and the change of solution composition. Anatase seed crystals need to be added during the hydrolysis process.
The hydrolysis process comprises the following steps:
7.1) metering the prepared titanium liquid according to the process requirements, respectively pumping the titanium liquid into a hydrolysis preheating pot and a seed crystal titanium liquid tank, starting the preheating pot to stir when the liquid level reaches a stirring paddle, metering the prepared ammonia water with the concentration, and pumping the ammonia water into a seed crystal ammonia water tank for later use;
7.2) after the material is beaten, waiting for adding seed crystals. Starting the crystal seed preparation tank for stirring, opening a discharge valve of an ammonia water tank to quickly discharge ammonia water into the crystal seed preparation tank, then opening a discharge valve of a crystal seed titanium liquid tank to neutralize the crystal seed titanium liquid and the ammonia water in the crystal seed preparation tank, neutralizing with the ammonia water with the mass percentage concentration of 20% until the pH value is 9.5, keeping the neutralization process for 1 hour, and stirring while neutralizing. After the neutralization, the temperature of the material is raised to 90 ℃, the temperature raising rate is 1 ℃/min, and the temperature is kept for 1 hour. Then cooling to 75 ℃, rapidly detecting the stability of the crystal seed, rapidly opening an outlet valve of a crystal seed manufacturing groove when the stability is 90ml, and rapidly putting the manufactured crystal seed into a preheating pot titanium liquid preheated to 96 ℃; the temperature of the titanium liquid in the preheating pot must be raised to 96 ℃ and the seed crystal is ready, the temperature of the prepared seed crystal can not be raised, otherwise, the stability of the seed crystal is rapidly reduced, and the quality of the whole pot is affected.
9) Salt treatment
The salt treatment process specifically comprises the following steps: step 1, adding 4% of calcined rutile type crystal seeds into bleached metatitanic acid solution; and step 2, adding ZnO with the addition amount of 0.10%, and stirring for 30 minutes after adding. Then adding NH4H2PO40.65% of powder, stirring for 12 min, adding 1.0% of KOH solution, and finally adding Al2(SO4)3Powder 0.5%, then stirred for another 150 minutes. Pumping into a kiln tail storage tank. The mass ratios between the rutile seed and the zinc, ammonium, potassium and aluminum salts need to satisfy the following relationship, where each salt is based on the mass of the oxide, the rutile seed: ZnO: P2O5∶K2O∶Al2O3The mass percentage of the components should be controlled to be 9: 1: 1.3: 1.
Example 2
7) Hydrolysis
The purpose of hydrolysis is to obtain metatitanic acid, and the basic process comprises the formation of crystal centers, the growth of crystal nuclei and the formation of precipitates, the coagulation and precipitation of metatitanic acid particles and the change of solution composition. Anatase seed crystals need to be added during the hydrolysis process.
The hydrolysis process comprises the following steps:
7.1) metering the prepared titanium liquid according to the process requirements, respectively pumping the titanium liquid into a hydrolysis preheating pot and a seed crystal titanium liquid tank, starting the preheating pot to stir when the liquid level reaches a stirring paddle, metering the prepared ammonia water with the concentration, and pumping the ammonia water into a seed crystal ammonia water tank for later use;
7.2) after the material is beaten, waiting for adding seed crystals. Starting the crystal seed preparation tank for stirring, opening a discharge valve of an ammonia water tank to quickly discharge ammonia water into the crystal seed preparation tank, then opening a discharge valve of a crystal seed titanium liquid tank to neutralize the crystal seed titanium liquid and the ammonia water in the crystal seed preparation tank by using the ammonia water with the mass percentage concentration of 18 percent until the pH value is 9.8, keeping the neutralization process for 1 hour, and stirring while neutralizing. After the neutralization, the temperature of the material is raised to 90 ℃, the temperature raising rate is 1 ℃/min, and the temperature is kept for 1 hour. Then cooling to 75 ℃, rapidly detecting the stability of the crystal seed, rapidly opening an outlet valve of a crystal seed manufacturing groove when the stability is 90ml, and rapidly putting the manufactured crystal seed into a preheating pot titanium liquid preheated to 96 ℃; the temperature of the titanium liquid in the preheating pot must be raised to 96 ℃ and the seed crystal is ready, the temperature of the prepared seed crystal can not be raised, otherwise, the stability of the seed crystal is rapidly reduced, and the quality of the whole pot is affected.
9) Salt treatment
The salt treatment process specifically comprises the following steps: step 1, adding 5 percent of calcined rutile type seed crystal into bleached metatitanic acid solution; and step 2, adding ZnO with the addition amount of 0.10%, and stirring for 30 minutes after adding. Then adding NH4H2PO40.55% of powder, stirring for 12 minutes, adding 0.9% of KOH solution, and finally adding Al2(SO4)3Powder 0.2%, then stirred for another 150 minutes. Pumping into a kiln tail storage tank. The mass ratios between the rutile seed and the zinc, ammonium, potassium and aluminum salts need to satisfy the following relationship, where each salt is based on the mass of the oxide, the rutile seed: ZnO: P2O5∶K2O∶Al2O3The mass percentage of the components should be controlled to be 18: 1: 2: 2.5: 8.
The above-mentioned embodiments are merely illustrative of the preferred embodiments of the present invention, and do not limit the scope of the present invention, and various modifications and improvements made to the technical solution of the present invention by those skilled in the art without departing from the spirit of the present invention should be included in the protection scope defined by the claims of the present invention.
Claims (2)
1. The preparation method of the special titanium dioxide for the color master batch has the following characteristics: 1. crushing raw ore, 2, acidolysis, 3, leaching, 4, reduction, 5, sedimentation, 6, concentration of titanium liquid, 7, hydrolysis, 8, water washing and bleaching, 9, salt treatment, 10, filtering, calcining, surface treatment, 11, drying and dedusting;
the process of step 7 comprises: 7.1) metering the prepared titanium liquid according to the process requirements, respectively pumping the titanium liquid into a hydrolysis preheating pot and a seed crystal titanium liquid tank, starting the preheating pot to stir when the liquid level reaches a stirring paddle, metering the prepared ammonia water with the concentration, and pumping the ammonia water into a seed crystal ammonia water tank for later use; 7.2) after the material is beaten, waiting for adding seed crystals; starting a crystal seed production tank for stirring, opening a discharge valve of an ammonia water tank to quickly discharge ammonia water into the crystal seed production tank, then opening a discharge valve of a crystal seed titanium liquid tank to neutralize the crystal seed titanium liquid and the ammonia water in the crystal seed production tank, neutralizing with the ammonia water with the mass percentage concentration of 18-20% until the pH value is 9-10, keeping the neutralization process for 1 hour, and stirring while neutralizing; after the neutralization is finished, heating the material to 90 ℃, wherein the heating rate is 1 ℃/min, and keeping the temperature for 1 hour; then cooling to 75 ℃, rapidly detecting the stability of the crystal seed, rapidly opening an outlet valve of a crystal seed manufacturing groove when the stability is 90ml, and rapidly putting the manufactured crystal seed into a preheating pot titanium liquid preheated to 96 ℃; the titanium liquid in the preheating pot is heated to 96 ℃ and then the seed crystal is prepared, the prepared seed crystal can not be heated at all, otherwise, the stability of the seed crystal is rapidly reduced, and the quality of the whole pot is influenced;
the process of step 9 comprises: the salt treatment process specifically comprises the following steps: step 1, adding 3-6% of calcined rutile type seed crystal into bleached metatitanic acid solution; step 2, adding ZnO with the addition amount of 0.05-0.25%, and stirring for 30 minutes after adding; then adding NH4H2PO40.5-0.7% of powder, stirring for 10-15 minutes, adding 0.85-1.1% of KOH solution, and finally adding Al2(SO4)30.1-0.8% of powder, and then stirring for 100-160 minutes; pumping into a kiln tail storage tank;
step 9 further comprises: rutile seed crystal ZnO P2O5∶K2O∶Al2O3The mass percentage of the components should be controlled to be (9 to 18): (1 to 2): (1.3 to 2.5)∶(1～8)。
2. The preparation method of the titanium dioxide special for color masterbatch according to claim 1, wherein the step 9 further comprises: the preparation method of the rutile type seed crystal for salt treatment comprises the following steps: A. preparation of sodium orthotitanate: filtering and washing TiO with qualified iron content lower than 50ppm by a double-washing filter press2Pumping hydrate into metatitanic acid heating and metering tank, measuring NaOH in alkali heating and metering tank, heating to 60 deg.C and 90 deg.C, and mixing with TiO2The hydrate NaOH is put into an alkali melting tank to react with 50 percent NaOH solution to generate sodium orthotitanate; pumping the cooled sodium orthotitanate into a filter press by a pump, loading the sodium orthotitanate into a plate, washing, unloading, pulping a filter cake, separating sodium orthotitanate from filtrate containing a large amount of free NaOH solution, enabling 15% NaOH filtrate to flow into an ammonia water collecting tank, and spraying tail gas by using an external pumping system; washing NaOH in the sodium orthotitanate filter cake by using a filter press, discharging the filter liquor into a pulping tank after the NaOH content of the filter liquor is measured to be less than 1500ppm, then neutralizing the filter liquor by using 10% hydrochloric acid until the pH value is within the range of 3.5-4.0, pumping the filter liquor into the filter press by using a pump, then loading the filter liquor on a plate, washing until the pH value of the washing filtrate is more than 7, discharging the filter cake, and pulping to obtain TiO2The concentration is controlled to be 200-220 g/l, and the product is used as an orthotitanic acid intermediate product for preparing seed crystals; B. preparing seed crystals: and D, reacting the sodium orthotitanate prepared in the step A with 30% hydrochloric acid to generate rutile type calcining seed crystals, and pumping the prepared seed crystals into a storage tank by using a pump.
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