CN108410214B - Superfine ultraviolet-resistant rutile titanium dioxide for cosmetics and preparation process thereof - Google Patents

Superfine ultraviolet-resistant rutile titanium dioxide for cosmetics and preparation process thereof Download PDF

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CN108410214B
CN108410214B CN201810299153.9A CN201810299153A CN108410214B CN 108410214 B CN108410214 B CN 108410214B CN 201810299153 A CN201810299153 A CN 201810299153A CN 108410214 B CN108410214 B CN 108410214B
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titanium dioxide
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cosmetics
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CN108410214A (en
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张修臻
张本发
孙斌
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ANHUI VENUS TITANIUM DIOXIDE (GROUP) CO LTD
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ANHUI VENUS TITANIUM DIOXIDE (GROUP) CO LTD
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Abstract

The invention discloses superfine ultraviolet-resistant rutile titanium dioxide for cosmetics and a preparation process thereof, belonging to the technical field of titanium dioxide preparation. The method comprises the following steps: 1) crushing and grinding the crude rutile titanium dioxide into slurry, and adding an alkaline dispersant; 2) adding the primarily ground slurry into two sand mills connected in series to continuously grind for two times; 3) transferring the ground slurry into an inorganic surface treatment tank for dilution and heating; 4) adding cerium salt solution, curing, and adjusting pH with dilute alkali; 5) adding an alkaline aluminum solution and a dilute sulfuric acid solution in a concurrent flow manner under a stable pH value, and curing; 6) after adjusting the pH value, transferring the mixture into a filter press for washing; 7) drying the washed filter cake to obtain powder; 8) and (3) performing jet milling on the powder, and simultaneously adding an organic treating agent to obtain the finished product of the ultrafine ultraviolet-resistant rutile titanium dioxide for cosmetics. The titanium white obtained by the invention has superfine fineness and ultraviolet light intensity resistance, is suitable for cosmetic series, and the standard of the titanium white accords with European and American standards.

Description

Superfine ultraviolet-resistant rutile titanium dioxide for cosmetics and preparation process thereof
Technical Field
The invention belongs to the technical field of titanium dioxide preparation, and particularly relates to ultrafine ultraviolet-resistant rutile titanium dioxide for cosmetics and a preparation process thereof.
Background
TiO2Commonly known as titanium dioxide, is the most widely applied high-grade white pigment in the world and is mainly applied to the fields of coating, plastics, papermaking, chemical fibers, food, daily chemicals and the like. The crystal forms of the titanium dioxide comprise the following three types: rutile, anatase and brookite types. Among them, rutile type is the most stable crystalline form of titanium dioxide, and its structure is dense, and it is crystallized with other crystalsThe rutile type titanium dioxide pigment has wider application range and better public praise, is the best white pigment due to the excellent optical property of the rutile type titanium dioxide, and is used as a common additive of the existing cosmetics.
Titanium dioxide, as a wide band gap metal oxide semiconductor material, can absorb in the ultraviolet region, thereby causing the titanium dioxide to be easily degraded. Since cosmetics are mainly used for beautifying, enhancing charm, changing appearance, etc., it is required that the raw materials for cosmetics have beautiful appearance and lasting effect. However, the existing titanium dioxide is easy to turn yellow and dark after being irradiated under ultraviolet light for a period of time, so that the durability of the titanium dioxide is poor, and meanwhile, nano particles are easy to agglomerate during photodegradation, so that the transparency of the titanium dioxide is poor, and the using effect of cosmetics is influenced. Therefore, the improvement of the light resistance of the titanium dioxide has important significance for ensuring the using effect of the cosmetics.
Through retrieval, the prior art discloses a related technical scheme on how to improve the light resistance of titanium dioxide. For example, patent publication nos.: CN 102532952 a, published: on the year 2012, month 07, day 04, the name of the invention creation is: the application discloses a preparation method of a titanium dioxide pigment special for laminated paper, which comprises the following steps: preparing a slurry from a rutile titanium dioxide primary product, dispersing the slurry by using a solution of a phosphorus-containing compound, and grinding the dispersion; heating and preserving heat of the ground slurry; adding a water-soluble cerium salt solution, adjusting the pH value of the slurry, and curing to form a first coating; adding a solution of a phosphorus-containing compound and a zirconium salt solution, adjusting the pH value of the slurry, and curing to form a second coating; adding an aluminum salt solution, adjusting the pH value of the slurry, and curing to form a third layer of coating; adding an aluminum salt solution, adjusting the pH value of the slurry, and curing to form a third layer of coating; filtering and washing the filter cake with deionized water, drying, treating with gas powder, and separating gas from solid to obtain the final product. The titanium dioxide pigment prepared by the application has the advantages of high light resistance, high covering power and good retention rate, is low in isoelectric point, and has excellent dispersing performance in a weak alkaline application system. However, the titanium dioxide prepared by the preparation method of the application still cannot meet the requirement of the titanium dioxide for cosmetics.
In conclusion, how to overcome the defect that the light resistance of the existing titanium dioxide used as a cosmetic raw material is not ideal is a technical problem which needs to be solved in the prior art.
Disclosure of Invention
1. Technical problem to be solved by the invention
The invention aims to overcome the defect of poor light resistance of the existing titanium dioxide for cosmetics, and provides superfine ultraviolet-resistant rutile titanium dioxide for cosmetics and a preparation process thereof. The preparation process can effectively improve the light resistance of the titanium dioxide, thereby meeting the use requirements of cosmetics and ensuring the use effect of the cosmetics.
2. Technical scheme
In order to achieve the purpose, the technical scheme provided by the invention is as follows:
the invention relates to superfine ultraviolet-resistant rutile titanium dioxide for cosmetics, which has the particle size meeting the following requirements: d10: <0.15 μm, D50: <0.30 μm, D90: <0.55 μm, D99: <0.70 μm, the ratio of diameters between 0.2 and 0.6 μm is greater than 85 wt%.
The invention relates to a preparation process of superfine ultraviolet-resistant rutile titanium dioxide for cosmetics, which comprises the following steps:
step one, crushing
Taking a rutile crude product as a raw material, adding desalted water into the rutile crude product to prepare slurry, and then adding an alkaline dispersant to grind and crush the slurry;
step two, grinding
Further grinding the obtained slurry to obtain finer titanium dioxide slurry;
step three, primary aging
Transferring the ground slurry into an inorganic surface treatment tank, and treating with TiO2The solution is diluted to 280-340 g/L, then the temperature is raised to 40-45 ℃, and cerium salt solution is added into the solution for primary aging treatment;
step four, pH adjustment
Adjusting the pH value of the slurry obtained after primary aging to 6.8-7.2 by using dilute alkali, and then continuously heating to 85-90 ℃;
step five, secondary aging
Adding alkaline aluminum and dilute sulfuric acid into the slurry obtained in the fourth step in a concurrent flow manner for secondary aging treatment;
step six, curing
Adding dilute sulfuric acid to adjust the pH value of the slurry to 5.5-6.0, and curing for 40 min;
and seventhly, sequentially cooling, washing, drying and crushing the clinker obtained after curing, and then carrying out organic coating to obtain the finished product of the titanium dioxide for cosmetics.
Furthermore, in the step one, a rod press mill, a colloid mill and a ball mill are sequentially adopted to carry out serial crushing on the crude rutile, and TiO in the slurry obtained after crushing and grinding2The content of the second component is 800-1000 g/L, two sand mills are adopted to carry out serial grinding on the slurry in the second step to obtain slurry with 325 meshes and the residue less than 0.01 percent, and TiO is used for2The flow rate of the slurry is controlled to be 3.5-4.0t/h by the meter.
Further, the alkaline dispersant used in the first step is sodium polyacrylate or sodium silicate, the addition amount of the alkaline dispersant is 0.1-1.0% of the mass of the crude rutile, and the pH value of the obtained slurry is controlled to be 10.0-11.5.
Further, the cerium salt in the third step is preferably CeCl3Solution of Ce2O3The concentration is 90-110 g/L, the adding amount is 0.1-0.5% of the total titanium, and the time of one-time aging treatment is 30 min.
Further, the effective component of the alkaline aluminum used in the secondary aging treatment is Al2O3With Al2O3The measured mass concentration is 1.5-2.0%, the coating amount is 2.0-2.5%, and the pH of the slurry is controlled to be 6.0-7.0 during the secondary aging treatment, and the aging time is 60 min.
Further, the alkaline aluminum used in the secondary aging treatment is preferably NaAlO2And NaAlO2The concentration of the solution is Al2O3The content of 90-110 g/L is 200-220 g/L, the mass fraction of dilute sulfuric acid used in the secondary aging treatment is 12 percent, and NaAlO is controlled2The addition amount and the flow ratio of the diluted sulfuric acid to the diluted sulfuric acid are 1: (2.0-2.15).
Furthermore, the organic coating agent in the seventh step is preferably TMP, organic silicon or TME, and the adding amount of the organic coating agent is controlled to be 0.3-0.5% of the mass of the crushed clinker.
Furthermore, the dilute alkali solution in the fourth step adopts NaOH solution with the mass fraction of 12-14%; step seven, cooling the obtained clinker to 50-60 ℃, transferring the clinker to a filter press, and washing the clinker with desalted water at 40-55 ℃ until the resistivity is more than 300 omega-m, and controlling the washing water end point to be below 40 mu S/cm; then the obtained filter cake is dried at the temperature of 300-350 ℃, and the moisture of the powder is controlled to be less than 0.5 percent.
Furthermore, in the seventh step, a jet milling mode is adopted, the steam temperature is controlled at 290-310 ℃, the pressure is controlled at 1.4-1.5MPa, and the gas-solid ratio is controlled at 1.4 t/ton of titanium dioxide.
3. Advantageous effects
Compared with the prior art, the technical scheme provided by the invention has the following remarkable effects:
(1) compared with the existing titanium dioxide product, the ultrafine ultraviolet-resistant rutile titanium dioxide for cosmetics has finer and more uniform particle size distribution, thereby being beneficial to ensuring the dispersion uniformity of the ultrafine ultraviolet-resistant rutile titanium dioxide in cosmetics and being convenient for the cosmetics to be uniformly smeared. Meanwhile, compared with the existing titanium dioxide product, the titanium dioxide of the invention has better light resistance, thereby effectively preventing the titanium dioxide from decomposing under long-term illumination and influencing the glossiness and the use effect of the cosmetics.
(2) The invention relates to a preparation process of superfine ultraviolet-resistant rutile titanium dioxide for cosmetics, which sequentially carries out Ce on the titanium dioxide2O3Cladding, Al2O3Coating and organic coating, through the mutual cooperation and combined action of the three coating films, and simultaneously through the optimization design of specific process parameters of coating treatment in the production process of the titanium dioxide, the light resistance of the obtained titanium dioxide can be effectively improved, the decomposition in the long-term use process is prevented, and the use effect of cosmetics is further ensured.
(3) The invention relates to a preparation process of ultrafine ultraviolet-resistant rutile titanium dioxide for cosmetics, which takes a rutile crude product as a raw material and alkaline sodium polyacrylate or sodium silicate as a dispersing agent, sequentially adopts a rolling mill, a colloid mill and a ball mill to carry out serial grinding on slurry, then adopts two sand mills connected in series to carry out grinding, and simultaneously optimizes the grinding specific process, thereby being beneficial to improving the grinding and grinding effects of the slurry, effectively reducing the particle size of the titanium dioxide and improving the dispersion uniformity of the titanium dioxide. Meanwhile, when the titanium dioxide is subjected to jet milling, the invention is favorable for further reducing the particle size of the titanium dioxide by optimizing the milling steam pressure and the gas-solid ratio, so as to obtain the superfine titanium dioxide product.
(4) The invention relates to a preparation process of superfine ultraviolet-resistant rutile titanium dioxide for cosmetics, wherein inorganic coating is firstly carried out on the innermost layer of the titanium dioxide, and the inorganic coating agent adopts Ce2O3Envelope, Ce3+The outermost layer has vacancies which can absorb ultraviolet light and improve the glossiness and whiteness of the titanium dioxide, thereby ensuring that the cosmetic is more beautiful after being used.
(5) The invention relates to a preparation process of superfine ultraviolet-resistant rutile titanium dioxide for cosmetics, which is characterized in that the outermost layer of the titanium dioxide is coated with an organic film, wherein TMP, organic silicon or TME can be selected as the organic film coating agent. Meanwhile, the TME has excellent high temperature stability, can further improve the heat resistance, light resistance, hydrolysis resistance and oxidation resistance of the obtained titanium dioxide, and has excellent weather resistance, glossiness and chemical resistance.
(6) According to the preparation process of the rutile titanium dioxide for the superfine ultraviolet-resistant cosmetics, disclosed by the invention, the harmful ion content of the titanium dioxide finished product is ensured to meet the standard requirement of cosmetics by selecting the crude titanium dioxide and mainly screening the harmful ion content of Pb, Cr, As and the like.
(7) The invention relates to a preparation process of rutile titanium dioxide for superfine ultraviolet-resistant cosmetics, which is used for Ce2O3After the coating treatment, before adding alkaline aluminum and dilute sulfuric acid for parallel flow, adjusting the pH of the slurry to6.8-7.2, thereby being beneficial to ensuring that the cerium oxide can be fully settled and coated and ensuring the coating effect; meanwhile, a neutral environment is provided for the beginning of the alumina coating treatment through the regulation and control of the pH value, and then the pH is regulated to be 6.0-7.0 by adding alkaline aluminum and dilute sulfuric acid, so that the subsequent alumina coating is carried out under the condition of weak acid, and the flowing property and the ultraviolet resistance of the obtained titanium dioxide can be effectively improved. And after the end point of the cocurrent flow of the alkaline aluminum and the dilute sulfuric acid is finished, the pH value is finely adjusted to 5.5-6.0, so that the washing efficiency of the product can be improved.
Drawings
FIG. 1 is a flow chart of the preparation process of the rutile titanium dioxide for the ultrafine ultraviolet light resistant cosmetics.
Detailed Description
The invention relates to a preparation process of rutile titanium dioxide for superfine ultraviolet-resistant cosmetics, which comprises the following steps:
(1) crushing the crude rutile titanium dioxide, preparing titanium dioxide slurry by desalted water, adding alkaline sodium polyacrylate or sodium silicate As a dispersing agent, controlling the pH value to be between 10 and 11.5, and then performing subsequent dispersion, wherein the concentration of the obtained slurry is 800-1000 g/L, and the mass ratio of the added alkaline dispersing agent to the slurry is 0.2 to 1.0 percent.
(2) 3.5-4.0t/h (by TiO) of the slurry dispersed in the step (1) per hour2Measured) is added into two sand mills connected in series for grinding to obtain slurry with 325 mesh sieve residue less than 0.01 percent. Two sand mills are adopted for serial grinding before coating, so that the particle size of the titanium dioxide before coating is effectively reduced, and a better coating effect can be achieved; meanwhile, the titanium dioxide particles are smaller, so that the titanium dioxide is more exquisite in a cosmetic application system and better in aesthetic effect.
(3) Transferring the slurry ground in the step (2) into an inorganic surface treatment tank, and diluting to 280-340 g/L (by TiO)2Meter), heating to 40-45 deg.C, and keeping the temperature.
(4) Adding the mixture within 30minThe concentration is 90-110 g/L (as Ce)2O3Metering) cerium salt solution into the slurry obtained in the step (3), and curing for 30 min; effective content of cerium salt (Ce)2O3) The addition amount is 0.1-0.5% of the total titanium. The cerium salt in the present invention is preferably CeCl3And CeCl3Has a concentration of 135-150 g/L3Effective component Ce in solution2O3The concentration of (A) is 90-110 g/L.
(5) Adjusting the pH of the obtained clinker to 6.8-7.2 by adopting a NaOH solution with the mass fraction of 12-14%, and stirring for 10 min; the temperature is increased to 85-95 ℃.
(6) Adding alkaline aluminum and dilute sulfuric acid simultaneously within 0.5-1h, controlling the pH value at 6.0-7.0, and aging for 60 min. The effective component of the alkaline aluminum is Al2O3The coating amount is 2.0-2.5% (in percentage of TiO)2) The mass fraction of the dilute sulfuric acid is 12%, and the adding amount and flow rate ratio of the alkaline aluminum to the dilute sulfuric acid is 1: (2.0-2.15). The preferred basic aluminum of the present invention is NaAlO2，NaAlO2Al in solution2O3The concentration is 90-110 g/L, and the content is 200-220 g/L.
(7) Adding dilute sulfuric acid into the slurry obtained in the step (6) to adjust the pH value to 5.5-6.0, and curing for 40 min;
(8) and (3) cooling the clinker obtained in the step (7) to 50-60 ℃, transferring the clinker to a filter press, and washing the clinker with desalted water at the temperature of 40-55 ℃ until the resistivity is more than 300 omega-m, wherein the end point of washing water is controlled to be below 40 mu S/cm. And drying the obtained filter cake at the temperature of 300-350 ℃, and controlling the moisture of the powder to be less than 0.5 percent so as to ensure the stability of the trivalent cerium.
(9) And (3) performing jet milling on the obtained powder, and adding an organic coating agent for organic coating to obtain a titanium dioxide finished product for cosmetics. The steam temperature is controlled at 290-310 ℃, the pressure is controlled at 1.4-1.5MPa, the gas-solid ratio is controlled at 1.4 t/ton of titanium dioxide, the organic coating agent is TMP, organosilicon or TME, preferably TME, and the adding amount of the organic coating agent is controlled at 0.3-0.5% of the crushed clinker mass. The invention carries out TME coating in the air flow crushing process and optimizes the specific process of air flow crushing, thereby further increasing the dispersibility of the titanium dioxide in a cosmetic application system and being beneficial to ensuring the service performance of the obtained titanium dioxide. In addition, the obtained titanium dioxide product can be effectively prevented from yellowing under ultraviolet irradiation by coating the TME on the surface of the titanium dioxide, and the titanium dioxide coating has the advantages of better performance, higher absorptivity, less pollution and good environmental protection performance in the titanium dioxide coating process.
The titanium dioxide finished product prepared by the invention is as follows: (1) d10 <0.15 μm, D50 <0.30 μm, D90 <0.55 μm, D99 <0.70 μm, and the ratio of the diameter between 0.2 and 0.6 μm is more than 85%; (2) content of heavy metal ions: pb <0.8PPm, As <0.1PPm, Cr <0.1PPm, and Hg <0.1 PPm.
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The preparation process of the rutile titanium dioxide for the superfine ultraviolet-resistant cosmetics comprises the following steps:
(1) crushing the rutile titanium dioxide crude product by a rolling mill, feeding the crushed rutile titanium dioxide crude product into a beating tank, stirring the crushed rutile titanium dioxide crude product by desalted water to prepare a material, simultaneously adding alkaline sodium polyacrylate, controlling the pH to be 10.91, and carrying out series grinding and dispersion on the rutile titanium dioxide crude product by the rolling mill, a colloid mill and a ball mill, wherein the concentration of the obtained titanium dioxide slurry is 802 g/L, and the mass ratio of the added alkaline dispersing agent to the slurry is 0.2%.
(2) The dispersed slurry was added at 3.5t/h per hour (in TiO)2Meter) is added into two sand mills connected in series for grinding, and the 325-mesh screen residue is measured to be 0.004 percent.
(3) Transferring the ground slurry in the step 2) into an inorganic surface treatment tank, diluting the slurry to 284 g/L (by TiO) with the net content of titanium dioxide of 1000g2Meter), heating to 45 ℃, and keeping the temperature.
(4) CeCl is added in 30min3Adding 10m L solution into the slurry obtained in the step 3), and aging for 30minIn the examples CeCl3Has a concentration of 135.3 g/L3Effective component Ce in solution2O3Has a concentration of 90 g/L and an effective content of cerium salt (Ce)2O3) The amount added was 0.2% of the total titanium.
(5) Adjusting the pH value to 6.9 by using a NaOH solution with the mass fraction of 12%, stirring for 10min, and heating to 85 ℃.
(6) Simultaneously adding sodium metaaluminate solution and dilute sulfuric acid within 0.5h, controlling the pH to be 6.0-7.0, wherein the adding amount of the sodium metaaluminate solution is 200m L, the adding amount of the dilute sulfuric acid is 412m L, aging for 60min, and measuring the pH to be 6.8.
(7) And (4) adding dilute sulfuric acid into the slurry obtained in the step (6) to adjust the pH value to 5.6, and curing for 40 min.
(8) Cooling the clinker obtained in the step (7) to 53 ℃, and then transferring the clinker to a filter press to wash the clinker with desalted water at 45 ℃; drying the obtained filter cake at 310 deg.C, controlling water content of the powder to 0.3%, and resistivity to 352 Ω · m; the obtained powder is pulverized by air flow, the pulverizing steam pressure is controlled at 1.45MPa, the temperature is 292 deg.C, and simultaneously organic coating agent TME (optionally TMP or organosilicon) is added in an amount of about 0.35%. Data monitoring is performed on the titanium dioxide obtained in the embodiment, as shown in tables 1 and 2.
Example 2
The preparation process of the rutile titanium dioxide for the superfine ultraviolet-resistant cosmetics comprises the following steps:
(1) crushing the rutile titanium dioxide crude product by a rolling mill, feeding the crushed rutile titanium dioxide crude product into a beating tank, stirring the crushed rutile titanium dioxide crude product by desalted water to prepare a material, simultaneously adding alkaline sodium polyacrylate, controlling the pH to be 11.01, carrying out series grinding and dispersion by the rolling mill, a colloid mill and a ball mill, measuring the concentration of the titanium dioxide to be 859 g/L, and controlling the mass ratio of the added alkaline dispersing agent to the slurry to be 0.25%.
(2) 3.5t/h (in TiO) of the slurry dispersed in the step (1) per hour2Metering) is added into two sand mills connected in series for grinding; the 325 mesh sieve residue was found to be 0.005%.
(3) Transferring the slurry ground in the step (2) into an inorganic surface treatment tank, diluting the slurry to 310 g/L (by TiO), wherein the net content of titanium dioxide is 2000g2Meter), heating to 45 ℃, andpreserving heat;
(4) CeCl is added in 30min3Adding solution 40m L into the slurry obtained in step (3), aging for 30min, in this example, CeCl3Has a concentration of 142 g/L3Effective component Ce in solution2O3Has a concentration of 94.48 g/L and an effective content of cerium salt (Ce)2O3) The amount added was 0.3% of the total titanium.
(5) Adjusting the pH value to 7.2 by using a NaOH solution with the mass fraction of 13%, and stirring for 10 min; heating to 85 ℃;
(6) adding sodium metaaluminate solution and dilute sulfuric acid within 0.5h, controlling pH at 6.0-7.0, adding sodium metaaluminate solution at 400m L, adding dilute sulfuric acid at 833m L, aging for 60min, and measuring pH to 6.6.
(7) Adding dilute sulfuric acid into the slurry obtained in the step (6) to adjust the pH value to 5.7, and curing for 40 min;
(8) cooling the clinker obtained in the step (7) to 55 ℃, and then transferring the clinker to a filter press to wash with desalted water at 46 ℃; drying the obtained filter cake, wherein the drying temperature is 318 ℃, the moisture content of the powder is controlled to be 0.2 percent, and the resistivity is 398 omega.m; and (3) carrying out jet milling on the obtained powder, controlling the pressure of the milling steam to be 1.48MPa and the temperature to be 310 ℃, and simultaneously adding an organic coating agent TME, wherein the adding amount is about 0.30%. Data monitoring is performed on the titanium dioxide obtained in the embodiment, as shown in tables 1 and 2.
Example 3
The preparation process of the rutile titanium dioxide for the superfine ultraviolet-resistant cosmetics comprises the following steps:
(1) crushing the rutile titanium dioxide crude product by a rolling mill, feeding the crushed rutile titanium dioxide crude product into a beating tank, stirring the crushed rutile titanium dioxide crude product by desalted water to prepare a material, simultaneously adding alkaline sodium silicate, controlling the pH to be 11.20, carrying out series grinding and dispersion on the rutile titanium dioxide crude product by the rolling mill, a colloid mill and a ball mill, wherein the concentration of the titanium dioxide is measured to be 810 g/L, and the mass ratio of the added alkaline dispersing agent to the slurry is 0.90%.
(2) 3.8t/h (in TiO) of the slurry dispersed in the step (1) per hour2Metering) is added into two sand mills connected in series for grinding; the 325-mesh screen residue is measured to be 0.007%;
(3) the slurry ground in the step (2) is converted intoThe titanium white powder net content is 1000g, and the titanium white powder net content is diluted to 319 g/L (by TiO)2Metering), heating to 41 ℃, and keeping the temperature;
(4) CeCl is added in 30min3Adding 30m of solution L into the slurry obtained in the step (3), and aging for 30min, wherein CeCl is adopted in the embodiment3Has a concentration of 150 g/L3Effective component Ce in solution2O3Has a concentration of 99.8 g/L and an effective content of cerium salt (Ce)2O3) The amount added was 0.5% of the total titanium.
(5) Adjusting the pH value to 7.1 by using a NaOH solution with the mass fraction of 14%, and stirring for 10 min; heating to 87 ℃;
(6) adding sodium metaaluminate solution and dilute sulfuric acid simultaneously within 0.5h, controlling pH at 6.0-7.0, adding sodium metaaluminate solution at 220m L, adding dilute sulfuric acid at 462m L, aging for 60min, and measuring pH to 6.3.
(7) And (4) adding dilute sulfuric acid into the slurry obtained in the step (6) to adjust the pH value to 5.8, and curing for 40 min.
(8) Cooling the clinker obtained in the step (7) to 56 ℃, and then transferring the clinker to a filter press to wash with desalted water at 49 ℃; drying the obtained filter cake, wherein the drying temperature is 330 ℃, the moisture content of the powder is controlled to be 0.3 percent, and the resistivity is 412 omega m; and (3) carrying out jet milling on the obtained powder, controlling the pressure of the milling steam to be 1.50MPa and the temperature to be 300 ℃, and simultaneously adding the organic coating agent TME, wherein the adding amount is about 0.50%. Data detection is performed on the titanium dioxide obtained in the embodiment, as shown in tables 1 and 2.
Example 4
The preparation process of the rutile titanium dioxide for the superfine ultraviolet-resistant cosmetics comprises the following steps:
(1) crushing the rutile titanium dioxide crude product through a rolling mill, feeding the crushed rutile titanium dioxide crude product into a beating tank, stirring the crushed rutile titanium dioxide crude product with desalted water to prepare a material, simultaneously adding alkaline sodium silicate, controlling the pH to be 11.30, carrying out series grinding and dispersion on the rutile titanium dioxide crude product through a rolling mill, a colloid mill and a ball mill, wherein the concentration of the titanium dioxide is 810 g/L, and the mass ratio of the added alkaline dispersing agent to the slurry is 1.0%;
(2) 4.0t/h (in TiO) of the slurry dispersed in the step (1) per hour2Metering) is added into two sand mills connected in series for grinding; measuringThe 325-mesh screen residue is 0.008 percent;
(3) transferring the slurry ground in the step (2) into an inorganic surface treatment tank, diluting the slurry to 305 g/L (by TiO), wherein the net content of titanium dioxide is 2000g2Meter), heating to 43 ℃, and keeping the temperature;
(4) CeCl is added in 30min3Adding 80m of solution L into the slurry obtained in the step (3), and aging for 30min, wherein CeCl is adopted in the embodiment3Has a concentration of 147.3 g/L3Effective component Ce in solution2O3Has a concentration of 98 g/L and an effective content of cerium salt (Ce)2O3) The amount added was 0.1 of the total titanium.
(5) Adjusting the pH value to 6.9 by using a NaOH solution with the mass fraction of 13%, and stirring for 10 min; heating to 89 ℃;
(6) simultaneously adding sodium metaaluminate solution and dilute sulfuric acid within 0.5h, controlling the pH to be 6.0-7.0, wherein the adding amount of the sodium metaaluminate solution is 460m L, the adding amount of the dilute sulfuric acid is 980m L, aging for 60min, and measuring the pH to be 6.0.
(7) Curing the slurry obtained in the step (6) for 40min, wherein the pH value is 6.0;
(8) cooling the clinker obtained in the step (7) to 52 ℃, and then transferring the clinker to a filter press to wash the clinker with desalted water at 55 ℃; drying the obtained filter cake, wherein the drying temperature is 350 ℃, the moisture content of the powder is controlled to be 0.2 percent, and the resistivity is 423 omega m; and carrying out jet milling on the obtained powder, controlling the pressure of the milling steam to be 1.50MPa and the temperature to be 310 ℃, and simultaneously adding an organic coating agent TME, wherein the adding amount is about 0.40%. Data detection is performed on the titanium dioxide obtained in the embodiment, as shown in tables 1 and 2.
Example 5
The preparation process of the rutile titanium dioxide for the superfine ultraviolet-resistant cosmetics comprises the following steps:
(1) crushing the rutile titanium dioxide crude product through a rolling mill, adding the crushed rutile titanium dioxide crude product into a beating tank, stirring the crushed rutile titanium dioxide crude product with desalted water to prepare a material, simultaneously adding sodium polyacrylate, controlling the pH to be 10.78, carrying out series connection grinding and dispersion of the rolling mill, a colloid mill and a ball mill, measuring the concentration of the titanium dioxide to be 925 g/L, and controlling the mass ratio of an added alkaline dispersing agent to the slurry to be 0.23%;
(2) dispersing the slurry dispersed in the step (1) in small volumeAt 3.5t/h (in TiO)2Metering) is added into two sand mills connected in series for grinding; the residue of 325 meshes is measured to be 0.004%;
(3) transferring the slurry ground in the step (2) into an inorganic surface treatment tank, diluting the slurry to 306 g/L (by TiO), wherein the net content of titanium dioxide is 1000g2Metering), heating to 45 ℃, and keeping the temperature;
(4) CeCl is added in 30min3Adding 50m of solution L into the slurry obtained in the step (3), and aging for 30min, wherein CeCl is adopted in the embodiment3Has a concentration of 137 g/L3Effective component Ce in solution2O3Has a concentration of 91.15 g/L and an effective content of cerium salt (Ce)2O3) The amount added was 0.4% of the total titanium.
(5) Adjusting the pH value to 7.2 by using a NaOH solution with the mass fraction of 14%, and stirring for 10 min; heating to 87 ℃;
(6) adding sodium metaaluminate solution and dilute sulfuric acid within 0.5h, controlling pH at 6.0-7.0, adding sodium metaaluminate solution at 250m L, adding dilute sulfuric acid at 516m L, aging for 60min, and measuring pH to 6.4.
(7) And (4) adding dilute sulfuric acid into the slurry obtained in the step (6) to adjust the pH value to 505, and curing for 40 min.
(8) Cooling the clinker obtained in the step (7) to 52 ℃, and then transferring the clinker to a filter press to wash with desalted water at 52 ℃; drying the obtained filter cake at the drying temperature of 300 ℃, controlling the water content of the powder to be 0.5 percent and the resistivity to be 395 omega m; and (3) carrying out jet milling on the obtained powder, controlling the pressure of the milling steam to be 1.40MPa and the temperature to be 290 ℃, and simultaneously adding an organic coating agent TME, wherein the adding amount is about 0.360%. Data detection is performed on the titanium dioxide obtained in the embodiment, as shown in tables 1 and 2.
Example 6
The preparation process of the rutile titanium dioxide for the superfine ultraviolet-resistant cosmetics comprises the following steps:
(1) crushing the rutile titanium dioxide crude product through a rolling mill, adding the crushed rutile titanium dioxide crude product into a beating tank, stirring the crushed rutile titanium dioxide crude product with desalted water to prepare a material, simultaneously adding sodium polyacrylate, controlling the pH to be 11.5, carrying out serial grinding and dispersion on the rutile titanium dioxide crude product through a rolling mill, a colloid mill and a ball mill, wherein the concentration of the titanium dioxide is measured to be 1000 g/L, and the mass ratio of an added alkaline dispersing agent to the slurry is 0.97%;
(2) 4.0t/h (in TiO) of the slurry dispersed in the step (1) per hour2Metering) is added into two sand mills connected in series for grinding; the residue of 325 meshes is measured to be 0.004%;
(3) transferring the slurry ground in the step (2) into an inorganic surface treatment tank, diluting the slurry to 337 g/L (by TiO), wherein the net content of titanium dioxide is 1000g2Meter), heating to 44 ℃, and keeping the temperature;
(4) CeCl is added in 30min3Adding 50m of solution L into the slurry obtained in the step (3), and aging for 30min, wherein CeCl is adopted in the embodiment3Has a concentration of 135.3 g/L3Effective component Ce in solution2O3Has a concentration of 90 g/L and an effective content of cerium salt (Ce)2O3) The amount added was 0.3% of the total titanium.
(5) Adjusting the pH value to 7.2 by using a NaOH solution with the mass fraction of 14%, and stirring for 10 min; heating to 95 ℃;
(6) simultaneously adding sodium metaaluminate solution and dilute sulfuric acid within 0.5h, controlling the pH to be 6.0-7.0, wherein the adding amount of the sodium metaaluminate solution is 270m L, the adding amount of the dilute sulfuric acid is 520m L, aging for 60min, and measuring the pH to be 6.6.
(7) And (4) adding dilute sulfuric acid into the slurry obtained in the step (6) to adjust the pH value to 5.7, and curing for 40 min.
(8) Cooling the clinker obtained in the step (7) to 52 ℃, and then transferring the clinker to a filter press to wash with desalted water at 52 ℃; drying the obtained filter cake at the drying temperature of 300 ℃, controlling the water content of the powder to be 0.5 percent and the resistivity to be 395 omega m; and (3) carrying out jet milling on the obtained powder, controlling the pressure of the milling steam to be 1.40MPa and the temperature to be 290 ℃, and simultaneously adding an organic coating agent TME, wherein the adding amount is about 0.360%.
Data for the measurements on the samples prepared in examples 1-6:
the products of examples 1-5 were subjected to conventional testing and QUV aging testing, wherein the values of L, a, and b were tested using oil phase, pH was tested according to GB/T1717-1986, resistivity was tested using GB/T5211.12, rutile conversion was tested using XDF, particle size was tested using a Malvern 2000 particle sizer, heavy metal content was tested using ICP food grade standard, gloss was tested using a 60 ° angle, comparative sample was the current commercial product of titanium dioxide for cosmetics, and the specific data are shown in tables 1, 2, and 3.
TABLE 1 general data
Numbering L a b pH Resistivity/Ω · m Percent on sieve basis% Rutile content/%)
Example 1 95.42 -1.11 1.75 6.98 352 0.002 99.5
Example 2 95.46 -1.14 1.73 6.99 398 0.003 99.6
Example 3 95.56 -1.08 1.75 7.12 412 0.006 99.5
Example 4 95.52 -1.1 1.74 7.02 423 0.004 99.4
Example 5 95.6 -1.12 1.76 7.05 395 0.004 99.5
Example 6 95.50 -1.12 1.78 7.25 405 0.005 99.5
As can be seen from the table above, the conventional data of the product prepared by the five embodiments of the invention is better, and the product meets the requirements of cosmetics on the conventional indexes of titanium dioxide.
TABLE 2 particle size, gloss, heavy Metal content
Figure BDA0001619395600000101
As can be seen from the above table, the detection of the product prepared by the five examples of the invention and the comparison sample has the following particle size: the data of d10, d50, d90 and d99 are all better than those of products in the current market, the small particle size can ensure that the particle size of the titanium dioxide in a titanium dioxide application system is small, and the cosmetics are uniformly coated after being used; the gloss is better, and the appearance is better after the application; the heavy metal content also meets the requirements of cosmetics.
TABLE 3 QUV aging data
100hΔE 200hΔE 300hΔE 600hΔE 900hΔE 1200hΔE
Control sample 0.95 1.26 2.73 3.77 4.75 6.81
Example 1 0.31 0.52 1.54 2.06 2.41 2.51
Example 2 0.29 0.45 1.44 2.13 2.87 2.85
Example 3 0.28 0.51 1.66 2.08 2.39 2.59
Example 4 0.31 0.42 1.6 2.11 2.56 2.36
Example 5 0.22 0.43 1.44 2.01 2.26 2.76
Example 6 0.27 0.46 1.51 2.13 2.64 2.71
The titanium dioxide is put into a QUV ultraviolet aging box (Accelled weather tester) according to the industrial standard to carry out ultraviolet irradiation in different time periods, and then the color difference is measured, and the data shows that the product of the five embodiments of the invention has better gas color difference than products on the market after 100h, 200h, 300h, 600h, 1200h and 1500h of ultraviolet irradiation, and particularly the effect is more obvious when the irradiation time is longer, so the preparation method can effectively improve the ultraviolet resistance of the obtained titanium dioxide product, thereby meeting the use requirement of cosmetics and ensuring the use effect of the cosmetics.

Claims (6)

1. A preparation process of superfine ultraviolet-resistant rutile titanium dioxide for cosmetics is characterized by comprising the following steps:
step one, pulping and crushing raw materials
Taking a rutile crude product as a raw material, adding desalted water into the rutile crude product to prepare slurry, and then adding an alkaline dispersant to grind and crush the slurry;
step two, grinding
Further grinding the obtained slurry to obtain finer titanium dioxide slurry;
step three, primary aging
Transferring the ground slurry into an inorganic surface treatment tank, and treating with TiO2Diluting to 280-340 g/L, heating to 40-45 deg.C, adding cerium salt solution as CeCl, and aging3Solution of Ce2O3The concentration is 90-110 g/L, the adding amount is 0.1-0.5% of the total titanium, and the time of one-time aging treatment is 30 min;
step four, pH adjustment
Adjusting the pH value of the slurry obtained after primary aging to 6.8-7.2 by using dilute alkali, and then continuously heating to 85-90 ℃;
step five, secondary aging
Adding alkaline aluminum and dilute sulfuric acid into the slurry obtained in the fourth step in a concurrent flow manner for secondary aging treatment, wherein the alkaline aluminum used in the secondary aging treatment is NaAlO2And NaAlO2The concentration of the solution is Al2O3Calculated as 90-110 g/L, the coating amount is 2.0-2.5%, the pH value of the slurry is controlled to be 6.0-7.0 during the secondary aging treatment, and the aging time is 60 min;
step six, curing
Adding dilute sulfuric acid to adjust the pH value of the slurry to 5.5-6.0, and curing for 40 min;
step seven, sequentially cooling, washing, drying and crushing clinker obtained after curing treatment, and then carrying out organic coating to obtain a finished product of titanium dioxide for cosmetics; the organic coating agent is TMP, organic silicon or TME, and the addition amount of the organic coating agent is controlled to be 0.3-0.5% of the mass of the crushed clinker; the particle size of the obtained titanium dioxide is as follows: d10: <0.15 μm, D50: <0.30 μm, D90: <0.55 μm, D99: <0.70 μm, the ratio of diameters between 0.2 and 0.6 μm is greater than 85 wt%.
2. The preparation process of the cosmetic ultra-fine ultraviolet-resistant rutile titanium dioxide according to claim 1, which is characterized in that: in the first step, a roller press mill, a colloid mill and a ball mill are sequentially adopted to carry out serial grinding dispersion on the slurry, and TiO in the slurry obtained after grinding is carried out2The content of the slurry is 800-1000 g/L, two sand mills are adopted in the second step to sequentially carry out serial grinding on the dispersed slurry to obtain slurry with 325 meshes and the residual of less than 0.01 percent, and TiO is used for2The flow rate of the slurry is controlled to be 3.5-4.0t/h by the meter.
3. The preparation process of the cosmetic ultra-fine ultraviolet-resistant rutile titanium dioxide according to claim 1, which is characterized in that: the alkaline dispersant used in the first step is sodium polyacrylate or sodium silicate, the addition amount of the alkaline dispersant accounts for 0.1-1.0% of the mass of the slurry, and the pH value of the obtained slurry is controlled to be 10.0-11.5.
4. The preparation process of the cosmetic ultra-fine ultraviolet-resistant rutile titanium dioxide according to any one of claims 1-3, wherein the preparation process comprises the following steps: the mass fraction of dilute sulphuric acid used in the secondary aging treatment is 12 percent, and NaAlO is controlled2The addition amount and the flow ratio of the diluted sulfuric acid to the diluted sulfuric acid are 1: (2.0-2.15).
5. The preparation process of the cosmetic ultra-fine ultraviolet-resistant rutile titanium dioxide according to any one of claims 1-3, wherein the preparation process comprises the following steps: the dilute alkali solution in the fourth step adopts NaOH solution with the mass fraction of 12-14%; step seven, cooling the obtained clinker to 50-60 ℃, transferring the clinker to a filter press, and washing the clinker with desalted water at 40-55 ℃ until the resistivity is more than 300 omega-m, and controlling the washing water end point to be below 40 mu S/cm; then the obtained filter cake is dried at the temperature of 300-350 ℃, and the moisture of the powder is controlled to be less than 0.5 percent.
6. The preparation process of the cosmetic ultra-fine ultraviolet-resistant rutile titanium dioxide according to claim 5, wherein the preparation process comprises the following steps: in the seventh step, a jet milling mode is adopted, the steam temperature is controlled at 310 ℃, the pressure is controlled at 1.4-1.5MPa, and the gas-solid ratio is controlled at 1.4 t/ton of titanium dioxide.
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