CN111117297A - Surface coating process of submicron-grade high-purity titanium dioxide - Google Patents
Surface coating process of submicron-grade high-purity titanium dioxide Download PDFInfo
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Abstract
The invention discloses a surface coating process of submicron high-purity titanium dioxide, which comprises the following steps: step S1, adding the titanium dioxide primary product into deionized water of chitosan and dodecyl betaine to prepare a titanium dioxide base material; step S2, sequentially adding sodium hexametaphosphate and sodium silicate into the titanium dioxide base material to prepare silicon-coated titanium dioxide slurry; step S3, adding sodium metaaluminate into the titanium dioxide slurry to prepare silicon-aluminum coated titanium dioxide. According to the invention, the chitosan and the cyclodextrin are introduced, so that the stability and firmness of the oxide film coated on the surface of the titanium dioxide are improved, the lattice defect of the titanium dioxide can be blocked and covered well, the direct contact of the titanium dioxide and light is reduced to the greatest extent, and the performances of the titanium dioxide such as weather resistance, stability, brightness, acid solubility and the like are greatly improved.
Description
Technical Field
The invention relates to the technical field of titanium dioxide processing. More particularly, the invention relates to a surface coating process of submicron high-purity titanium dioxide.
Background
Titanium dioxide has the scientific name of titanium dioxide, has the reputation of 'king of white pigment', and is widely applied to fine chemical industries such as coating, papermaking, chemical fiber, cosmetics, plastics and the like due to the properties of higher covering power, weather resistance, decoloring power and the like. The titanium dioxide needs to be coated on the surface before application, mainly because untreated titanium dioxide primary particles have a strong photocatalytic effect, a film-forming agent of a titanium dioxide base material can be degraded under the irradiation of sunlight, particularly ultraviolet rays, so that a paint film is discolored and pulverized, and finally the performance of a titanium dioxide pigment is greatly weakened. Therefore, before titanium dioxide is used as a pigment, the surface of titanium dioxide needs to be subjected to a repolarization treatment, and an inorganic coating process is mainly used at present.
The inorganic coating on the surface of the titanium dioxide specifically comprises the following steps: the surface of the titanium dioxide primary product particles is coated with one or more layers of metal oxides, wherein the metal oxides comprise silicon oxide, aluminum oxide, zirconium oxide and the like. In the coating treatment process, firstly, titanium dioxide is uniformly dispersed in a solvent to prepare a stable and uniform suspension, then different metal salts are sequentially added into the suspension, and various metals are converted into metal oxide precipitates and adsorbed on the surface of the titanium dioxide by respectively adjusting the pH value. The existing surface coating process of titanium dioxide comprises the following steps: because the particle size of titanium dioxide particles is small, the surface of the particles has large surface energy, and agglomeration phenomenon is easy to occur in a solvent, the uniformity and stability of the prepared suspension are poor, and then the coating effect is influenced.
Disclosure of Invention
An object of the present invention is to solve at least the above problems and to provide at least the advantages described later.
The invention also aims to provide a surface coating process of submicron-grade high-purity titanium dioxide, which improves the stability and firmness of an oxide film coated on the surface of the titanium dioxide by introducing chitosan and cyclodextrin, so that the crystal lattice defects of titanium dioxide can be blocked and covered well, the direct contact of the titanium dioxide and light is reduced to the greatest extent, and the performances of the titanium dioxide, such as weather resistance, stability, brightness, acid solubility and the like, are greatly improved.
To achieve these objects and other advantages in accordance with the present invention, there is provided a surface coating process of submicron-sized high purity titanium dioxide, which coats silicon aluminum on the surface of titanium dioxide, comprising the steps of:
s1, dispersing chitosan and dodecyl betaine in deionized water, adding a titanium dioxide primary product under stirring, and placing the mixture in a wet ball mill for treatment for 20-30 min after the addition is finished to obtain a titanium dioxide base material, wherein the dosage of the chitosan and the dodecyl betaine is 0.05-0.1% and 0.005-0.008% of the total amount of the titanium dioxide respectively, and the mass concentration of the titanium dioxide in the titanium dioxide base material is 180-300 g/L;
step S2, heating the titanium dioxide base material obtained in the step S1 to 80-100 ℃, adding sodium hexametaphosphate accounting for 0.1% of the mass of the titanium dioxide into the titanium dioxide base material, adjusting the pH value to 11, stirring for two hours to obtain titanium dioxide slurry, adding sodium silicate into the titanium dioxide slurry, wherein the adding amount of the sodium hexametaphosphate is 2.5-5.8% of the total amount of the titanium dioxide, the adding time is 40-60 min, after the adding is finished, adjusting the pH value to 9, and stirring and curing for 0.5-2 hours to obtain silicon-coated titanium dioxide slurry;
and S3, adding the silicon-coated titanium dioxide slurry obtained in the step S2 to 60-90 ℃, adjusting the pH value to 6.0-7.5, adding cyclodextrin into the silicon-coated titanium dioxide slurry, wherein the addition amount of the cyclodextrin is 0.01-0.05% of the total amount of the titanium dioxide, fully stirring for 20-30 min, adding sodium metaaluminate into the silicon-coated titanium dioxide slurry, the addition amount of the sodium metaaluminate is 2.0-4.0% of the total amount of the titanium dioxide, the addition time is 40-60 min, adjusting the pH value of the slurry to 6.8-7.5, stirring and curing for 0.5-1 h, and performing suction filtration and drying to obtain the silicon-aluminum coated titanium dioxide.
Preferably, in the surface coating process of the submicron high-purity titanium dioxide, the chitosan in the step S1 is subjected to modification pretreatment, specifically: mixing 5-10 parts by weight of chitosan and 400-450 parts by weight of acetic acid to obtain a first mixed solution, fully stirring the mixed solution, dropwise adding 25-50 parts by weight of 20% maleic anhydride acetone solution into the mixed solution under stirring, and continuously stirring for 18-24 hours at room temperature after the addition is finished to obtain a second mixed solution; and pouring the mixed solution II into 500-1000 parts of potassium hydroxide solution with the mass concentration of 1000g/L, stirring and reacting for 1-2 hours to obtain a mixed solution III, placing the mixed solution III in a centrifuge for centrifugal treatment, collecting the lower-layer precipitate, and performing spray drying to obtain the compound I.
Preferably, in the surface coating process of the submicron high-purity titanium dioxide, the cyclodextrin in the step S3 is subjected to modification pretreatment, specifically: taking 1-5 parts of cyclodextrin, mixing the cyclodextrin with 10-50 parts of absolute ethyl alcohol, adjusting the pH value to 8.5 to obtain a mixed solution IV, heating the mixed solution IV in a water bath at 80-90 ℃, adding 1-5 parts of dimethyldiallylammonium chloride into the mixed solution IV under stirring, continuously stirring for reaction for 2-4 h, standing, naturally cooling to room temperature, pouring the cooled mixed solution into 20-100 parts of absolute ethyl alcohol, standing for 1-2 h, filtering, collecting a filter cake, drying and crushing to obtain the cyclodextrin-containing water dispersible granule.
Preferably, in the surface coating process of the submicron high-purity titanium dioxide, an inorganic acid solution or an inorganic alkali solution is adopted for adjusting the pH value, the inorganic acid solution is a dilute hydrochloric acid solution with the mass concentration of 9-10%, and the inorganic alkali solution is a sodium hydroxide aqueous solution with the concentration of 0.5 mol/L.
Preferably, in the surface coating process of the submicron high-purity titanium dioxide, the particle size of the titanium dioxide base material treated by the wet ball mill in the step S1 is 0.26-0.35 μm, and the particle size distribution is less than or equal to 1.38%.
Preferably, in the surface coating process of the submicron high-purity titanium dioxide, the wet ball mill in the step S1 has zirconium silicate beads as a grinding medium, the particle size of the grinding medium is 0.5-0.8 μm, and the filling amount is 60-75%.
Preferably, in the surface coating process of the submicron-grade high-purity titanium dioxide, the rotating speed of a centrifugal spray head in spray drying is 380-450 r/min, the feeding amount is 45-50 mL/min, and the temperatures of an air inlet and an air outlet are 78-90 ℃ and 60-68 ℃ respectively.
The invention at least comprises the following beneficial effects:
1. the chemical structure of the chitosan is a high-molecular alkaline polysaccharide polymer with cations, the chitosan has better coating performance, and has more adsorption sites, and the dodecyl betaine can increase the dispersibility of the chitosan in deionized water; before the silicon-aluminum material is coated by titanium dioxide, the titanium dioxide is added into deionized water in which chitosan is dispersed, titanium dioxide particles can be quickly coated by the chitosan when the titanium dioxide is added into the deionized water, the chitosan can prevent the titanium dioxide particles from agglomerating, so that the titanium dioxide can be uniformly dispersed in the deionized water, the surface of the titanium dioxide can be uniformly coated with a layer of chitosan, a titanium dioxide suspension liquid with good uniformity and stability is prepared, and a plurality of adsorption sites on the outer surface of the chitosan lay a good foundation for the subsequent silicon coating material for silicon precipitation;
2. after the surface of titanium dioxide is coated with chitosan, coating metal silicon, adjusting the pH value of a base material by adding soluble silicon to generate silicon dioxide precipitate, wherein the outer surface of the chitosan has more adsorption sites, so that the silicon dioxide can be uniformly and firmly adsorbed on the outer surface of the chitosan, and further the technical effect of uniformly coating the silicon metal outside the titanium dioxide is realized;
3. in the conventional technology, after the surface of titanium dioxide is directly coated with metal silicon, the coating of metal aluminum is also carried out by a precipitation method, because the two times of precipitation are both precipitation modes, the surface attached with the metal silicon is subjected to precipitation coating again, the metal aluminum has poor adsorbability, and in the process of precipitation adsorption of the metal aluminum, the metal silicon originally adsorbed on the surface of silicon dioxide can be extruded, so that the utilization rates of silicon salt and aluminum salt are greatly reduced, and the weather resistance and the color of the coated titanium dioxide product are influenced; the invention aims to solve the technical problems, a layer of cyclodextrin is coated on the surface of titanium dioxide coated with silicon, then the precipitation of metal aluminum is carried out, the cyclodextrin has a slightly conical hollow cylinder three-dimensional annular structure, can be coated on the surface of the titanium dioxide coated with silicon in a net structure, limits an inorganic silicon oxide film on the surface of the titanium dioxide, prevents the silicon oxide film from falling off, provides a place for the precipitation of the metal aluminum by virtue of a cavity structure of the cyclodextrin, improves the adsorption performance of the metal aluminum on the surface of titanium dioxide particles, improves the coating rate of the metal aluminum, improves the utilization rate of aluminum salt, and accelerates the coating rate of the metal aluminum;
the introduction of the chitosan and the cyclodextrin improves the stability and firmness of the oxide film coated on the surface of the titanium dioxide, so that the lattice defect of the titanium dioxide can be blocked and covered well, the direct contact of the titanium dioxide and light is reduced to the greatest extent, and the performances of the titanium dioxide such as weather resistance, stability, brightness, acid solubility and the like are greatly improved;
4. the untreated titanium dioxide white surface is provided with a large number of hydroxyl groups, and the chitosan is subjected to modification pretreatment by introducing carboxyl groups before being coated on the titanium dioxide surface, so that the chitosan and groups on the titanium dioxide particle surface can form chemical bonds and hydrogen bonds, and the coating stability of the chitosan is improved; the further cyclodextrin is also subjected to modification pretreatment before being coated, the dimethyl diallyl ammonium chloride of a cationic monomer is grafted on the outer surface of the cyclodextrin, cationic macromolecules are polymerized and adsorbed to the surface of the silicon-coated titanium dioxide particles through a bridging effect, water molecules are hydrated with the titanium dioxide particles under the action of cationic static electricity, a hydrated layer is formed on the surface of the titanium dioxide particles, the titanium dioxide to be coated with the metal aluminum can be stably suspended in deionized water, and the precipitation adsorption efficiency of the subsequent metal aluminum is prevented from being influenced by the precipitation of the titanium dioxide particles after the cyclodextrin is coated.
Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention.
Detailed Description
The present invention is further described in detail below with reference to examples so that those skilled in the art can practice the invention with reference to the description.
It will be understood that terms such as "having," "including," and "comprising," as used herein, do not preclude the presence or addition of one or more other elements or groups thereof.
It is to be noted that the experimental methods described in the following embodiments are all conventional methods unless otherwise specified, and the reagents and materials are commercially available unless otherwise specified.
< example 1>
The invention provides a surface coating process of submicron high-purity titanium dioxide, which comprises the following steps:
s1, dispersing chitosan and dodecyl betaine in deionized water, adding a titanium dioxide primary product under stirring, placing the mixture into a wet ball mill after the addition is finished, and treating for 20min to obtain a titanium dioxide base material, wherein the particle size of the titanium dioxide base material is 0.26 mu m, the particle size distribution of the titanium dioxide base material is less than or equal to 1.38%, the grinding medium in the wet ball mill is zirconium silicate beads, the particle size of the grinding medium is 0.5 mu m, and the filling amount of the grinding medium is 60%; wherein the dosage of the chitosan and the dodecyl betaine is respectively 0.05 percent and 0.005 percent of the total amount of the titanium dioxide, and the mass concentration of the titanium dioxide in the titanium dioxide base material is 180 g/L;
step S2, heating the titanium dioxide base material obtained in the step S1 to 80 ℃, adding sodium hexametaphosphate accounting for 0.1% of the mass of the titanium dioxide into the titanium dioxide base material, adjusting the pH value to 11, stirring for two hours to obtain titanium dioxide slurry, adding sodium silicate into the titanium dioxide slurry, wherein the adding amount of the sodium hexametaphosphate is 2.5% of the total amount of the titanium dioxide, the adding time is 40min, adjusting the pH value to 9 after the adding is finished, and stirring and curing for 0.5 hour to obtain silicon-coated titanium dioxide slurry;
and S3, adding the silicon-coated titanium dioxide slurry obtained in the step S2 to 60 ℃, adjusting the pH value to 6.0, then adding cyclodextrin, the addition amount of which is 0.01 percent of the total amount of the titanium dioxide, into the silicon-coated titanium dioxide slurry, fully stirring for 20min, then adding sodium metaaluminate, the addition amount of which is 2.0 percent of the total amount of the titanium dioxide, the addition time is 40min, adjusting the pH value of the slurry to 6.8, stirring and curing for 0.5h, and then carrying out suction filtration and drying to obtain the silicon-aluminum-coated titanium dioxide.
Wherein, the pH value is adjusted by adopting an inorganic acid solution or an inorganic alkali solution, the inorganic acid solution is a dilute hydrochloric acid solution with the mass concentration of 9%, and the inorganic alkali solution is a sodium hydroxide aqueous solution with the concentration of 0.5 mol/L.
< example 2>
The invention provides a surface coating process of submicron high-purity titanium dioxide, which comprises the following steps:
s1, dispersing chitosan and dodecyl betaine in deionized water, adding a titanium dioxide primary product under stirring, placing the mixture into a wet ball mill after the addition is finished, and treating for 30min to obtain a titanium dioxide base material, wherein the particle size of the titanium dioxide base material is 0.35 mu m, the particle size distribution of the titanium dioxide base material is less than or equal to 1.38, a grinding medium in the wet ball mill is zirconium silicate beads, the particle size of the grinding medium is 0.8 mu m, and the filling amount of the grinding medium is 75%; wherein the dosage of the chitosan and the dodecyl betaine is respectively 0.1 percent and 0.008 percent of the total amount of the titanium dioxide, and the mass concentration of the titanium dioxide in the titanium dioxide base material is 300 g/L;
step S2, heating the titanium dioxide base material obtained in the step S1 to 100 ℃, adding sodium hexametaphosphate accounting for 0.1% of the mass of the titanium dioxide into the titanium dioxide base material, adjusting the pH value to 11, stirring for two hours to obtain titanium dioxide slurry, adding sodium silicate into the titanium dioxide slurry, wherein the adding amount of the sodium hexametaphosphate is 5.8% of the total amount of the titanium dioxide, the adding time is 60 minutes, adjusting the pH value to 9 after the adding is finished, and stirring and curing for 2 hours to obtain silicon-coated titanium dioxide slurry;
and S3, adding the silicon-coated titanium dioxide slurry obtained in the step S2 to 90 ℃, adjusting the pH value to 7.5, then adding cyclodextrin into the silicon-coated titanium dioxide slurry, wherein the addition amount of the cyclodextrin is 0.05 percent of the total amount of the titanium dioxide, fully stirring for 30min, then adding sodium metaaluminate into the silicon-coated titanium dioxide slurry, wherein the addition amount of the sodium metaaluminate is 4.0 percent of the total amount of the titanium dioxide, the addition time is 60min, adjusting the pH value of the slurry to 7.5, stirring and curing for 1h, and then carrying out suction filtration and drying to obtain the silicon-aluminum-coated titanium dioxide.
Wherein, the pH value is adjusted by adopting an inorganic acid solution or an inorganic alkali solution, the inorganic acid solution is a dilute hydrochloric acid solution with the mass concentration of 10%, and the inorganic alkali solution is a sodium hydroxide aqueous solution with the concentration of 0.5 mol/L.
< example 3>
The invention provides a surface coating process of submicron high-purity titanium dioxide, which comprises the following steps:
s1, dispersing chitosan and dodecyl betaine in deionized water, adding a titanium dioxide primary product under stirring, and after the addition is finished, placing the mixture in a wet ball mill for treatment for 25min to obtain a titanium dioxide base material, wherein the particle size of the titanium dioxide base material is 0.30 mu m, the particle size distribution of the titanium dioxide base material is less than or equal to 1.38%, the grinding medium in the wet ball mill is zirconium silicate beads, the particle size of the grinding medium is 0.7 mu m, and the filling amount of the grinding medium is 60-75%; wherein the dosage of the chitosan and the dodecyl betaine is respectively 0.08 percent and 0.007 percent of the total amount of the titanium dioxide, and the mass concentration of the titanium dioxide in the titanium dioxide base material is 240 g/L;
step S2, heating the titanium dioxide base material obtained in the step S1 to 90 ℃, adding sodium hexametaphosphate accounting for 0.1% of the mass of the titanium dioxide into the titanium dioxide base material, adjusting the pH value to 11, stirring for two hours to obtain titanium dioxide slurry, adding sodium silicate into the titanium dioxide slurry, wherein the adding amount of the sodium hexametaphosphate is 4.1% of the total amount of the titanium dioxide, the adding time is 50min, adjusting the pH value to 9 after the adding is finished, and stirring and curing for 1.3 hours to obtain silicon-coated titanium dioxide slurry;
and S3, adding the silicon-coated titanium dioxide slurry obtained in the step S2 to 75 ℃, adjusting the pH value to 6.8, adding cyclodextrin into the silicon-coated titanium dioxide slurry, wherein the addition amount of the cyclodextrin is 0.03 percent of the total amount of the titanium dioxide, fully stirring for 25min, then adding sodium metaaluminate into the silicon-coated titanium dioxide slurry, wherein the addition amount of the sodium metaaluminate is 3.0 percent of the total amount of the titanium dioxide, the addition time is 50min, adjusting the pH value of the slurry to 7.3, stirring and curing for 0.8h, and performing suction filtration and drying to obtain the silicon-aluminum-coated titanium dioxide.
Wherein, the pH value is adjusted by adopting an inorganic acid solution or an inorganic alkali solution, the inorganic acid solution is a dilute hydrochloric acid solution with the mass concentration of 9.5%, and the inorganic alkali solution is a sodium hydroxide aqueous solution with the concentration of 0.5 mol/L.
< example 4>
The invention provides a surface coating process of submicron-grade high-purity titanium dioxide, which is different from the embodiment 1 in that the chitosan in the step S1 is subjected to modification pretreatment, and specifically comprises the following steps: mixing 5 parts of chitosan and 400 parts of acetic acid according to parts by weight to obtain a first mixed solution, fully stirring the mixed solution, dropwise adding 25 parts of 20% by mass of maleic anhydride in acetone solution under stirring, and continuously stirring at room temperature for 18 hours after the addition is finished to obtain a second mixed solution; pouring the mixed solution II into 500 parts of potassium hydroxide solution with the mass concentration of 1000g/L, stirring and reacting for 1h to obtain mixed solution III, placing the mixed solution III in a centrifugal machine for centrifugal treatment, collecting lower-layer precipitates, and performing spray drying to obtain the compound I; in spray drying, the rotating speed of a centrifugal nozzle is 380r/min, the feeding amount is 45mL/min, and the temperatures of an air inlet and an air outlet are 78 ℃ and 60 ℃ respectively. The other conditions and parameters were the same as in example 1.
< example 5>
The invention provides a surface coating process of submicron-grade high-purity titanium dioxide, which is different from the embodiment 2 in that the chitosan in the step S1 is subjected to modification pretreatment, and specifically comprises the following steps: mixing 10 parts by weight of chitosan and 450 parts by weight of acetic acid to obtain a first mixed solution, fully stirring the mixed solution, dropwise adding 50 parts by weight of 20% maleic anhydride acetone solution into the mixed solution under stirring, and continuously stirring for 24 hours at room temperature after the addition is finished to obtain a second mixed solution; pouring the mixed solution II into 1000 parts of potassium hydroxide solution with the mass concentration of 1000g/L, stirring and reacting for 2 hours to obtain mixed solution III, placing the mixed solution III in a centrifugal machine for centrifugal treatment, collecting lower-layer precipitates, and performing spray drying to obtain the potassium hydroxide solution I; in spray drying, the rotating speed of a centrifugal nozzle is 450r/min, the feeding amount is 50mL/min, and the temperatures of an air inlet and an air outlet are respectively 90 ℃ and 68 ℃. The remaining conditions and parameters were the same as in example 2.
< example 6>
The invention provides a surface coating process of submicron-grade high-purity titanium dioxide, which is different from the embodiment 3 in that the chitosan in the step S1 is subjected to modification pretreatment, and specifically comprises the following steps: mixing 8 parts of chitosan and 430 parts of acetic acid in parts by weight to obtain a first mixed solution, fully stirring the mixed solution, dropwise adding 38 parts of 20% by mass of maleic anhydride in acetone solution while stirring, and continuously stirring at room temperature for 21 hours after the addition is finished to obtain a second mixed solution; pouring the mixed solution II into 750 parts of potassium hydroxide solution with the mass concentration of 1000g/L, stirring and reacting for 1.5 hours to obtain mixed solution III, placing the mixed solution III in a centrifuge for centrifugal treatment, collecting lower-layer precipitates, and performing spray drying to obtain the potassium hydroxide solution I; in spray drying, the rotating speed of a centrifugal nozzle is 415r/min, the feeding amount is 48mL/min, and the temperatures of an air inlet and an air outlet are respectively 84 ℃ and 64 ℃. The remaining conditions and parameters were the same as in example 3.
< example 7>
The invention provides a surface coating process of submicron-grade high-purity titanium dioxide, which is different from the process of embodiment 1 in that cyclodextrin in step S3 is subjected to modification pretreatment, and specifically comprises the following steps: taking 1 part of cyclodextrin, mixing the cyclodextrin with 10 parts of absolute ethyl alcohol, adjusting the pH value to 8.5 to obtain a mixed solution IV, heating the mixed solution IV in a water bath at 80 ℃, adding 1 part of dimethyl diallyl ammonium chloride into the mixed solution IV under stirring, continuously stirring for reacting for 2 hours, standing, naturally cooling to room temperature, pouring the mixture into 20 parts of absolute ethyl alcohol, standing for 1 hour, filtering, collecting a filter cake, drying and crushing to obtain the cyclodextrin-containing water-soluble chitosan/chitosan. The other conditions and parameters were the same as in example 1.
< example 8>
The invention provides a surface coating process of submicron-grade high-purity titanium dioxide, which is different from the embodiment 2 in that cyclodextrin in the step S3 is subjected to modification pretreatment, and specifically comprises the following steps: taking 5 parts of cyclodextrin, mixing the cyclodextrin with 50 parts of absolute ethyl alcohol, adjusting the pH value to 8.5 to obtain a mixed solution IV, heating the mixed solution IV in a 90 ℃ water bath, adding 5 parts of dimethyl diallyl ammonium chloride into the mixed solution IV under stirring, continuously stirring for reacting for 4 hours, standing, naturally cooling to room temperature, pouring the mixture into 100 parts of absolute ethyl alcohol, standing for 2 hours, filtering, collecting a filter cake, drying and crushing to obtain the cyclodextrin-containing water-soluble chitosan/chitosan. The remaining conditions and parameters were the same as in example 2.
< example 9>
The invention provides a surface coating process of submicron-grade high-purity titanium dioxide, which is different from the embodiment 3 in that cyclodextrin in the step S3 is subjected to modification pretreatment, and specifically comprises the following steps: taking 3 parts of cyclodextrin, mixing the cyclodextrin with 30 parts of absolute ethyl alcohol, adjusting the pH value to 8.5 to obtain a mixed solution IV, heating the mixed solution IV in a water bath at 85 ℃, adding 3 parts of dimethyl diallyl ammonium chloride into the mixed solution IV under stirring, continuously stirring for reacting for 3 hours, standing, naturally cooling to room temperature, pouring the mixture into 60 parts of absolute ethyl alcohol, standing for 1.5 hours, filtering, collecting a filter cake, drying and crushing to obtain the cyclodextrin-containing water-soluble chitosan/chitosan. The remaining conditions and parameters were the same as in example 3.
< example 10>
The invention provides a surface coating process of submicron-grade high-purity titanium dioxide, which is different from the embodiment 4 in that cyclodextrin in the step S3 is subjected to modification pretreatment, and specifically comprises the following steps: taking 1 part of cyclodextrin, mixing the cyclodextrin with 10 parts of absolute ethyl alcohol, adjusting the pH value to 8.5 to obtain a mixed solution IV, heating the mixed solution IV in a water bath at 80 ℃, adding 1 part of dimethyl diallyl ammonium chloride into the mixed solution IV under stirring, continuously stirring for reacting for 2 hours, standing, naturally cooling to room temperature, pouring the mixture into 20 parts of absolute ethyl alcohol, standing for 1 hour, filtering, collecting a filter cake, drying and crushing to obtain the cyclodextrin-containing water-soluble chitosan/chitosan. The remaining conditions and parameters were the same as in example 4.
< example 11>
The invention provides a surface coating process of submicron-grade high-purity titanium dioxide, which is different from the embodiment 5 in that cyclodextrin in the step S3 is subjected to modification pretreatment, and specifically comprises the following steps: taking 5 parts of cyclodextrin, mixing the cyclodextrin with 50 parts of absolute ethyl alcohol, adjusting the pH value to 8.5 to obtain a mixed solution IV, heating the mixed solution IV in a 90 ℃ water bath, adding 5 parts of dimethyl diallyl ammonium chloride into the mixed solution IV under stirring, continuously stirring for reacting for 4 hours, standing, naturally cooling to room temperature, pouring the mixture into 100 parts of absolute ethyl alcohol, standing for 2 hours, filtering, collecting a filter cake, drying and crushing to obtain the cyclodextrin-containing water-soluble chitosan/chitosan. The remaining conditions and parameters were the same as in example 5.
< example 12>
The invention provides a surface coating process of submicron-grade high-purity titanium dioxide, which is different from the embodiment 6 in that cyclodextrin in the step S3 is subjected to modification pretreatment, and specifically comprises the following steps: taking 3 parts of cyclodextrin, mixing the cyclodextrin with 30 parts of absolute ethyl alcohol, adjusting the pH value to 8.5 to obtain a mixed solution IV, heating the mixed solution IV in a water bath at 85 ℃, adding 3 parts of dimethyl diallyl ammonium chloride into the mixed solution IV under stirring, continuously stirring for reacting for 3 hours, standing, naturally cooling to room temperature, pouring the mixture into 60 parts of absolute ethyl alcohol, standing for 1.5 hours, filtering, collecting a filter cake, drying and crushing to obtain the cyclodextrin-containing water-soluble chitosan/chitosan. The remaining conditions and parameters were the same as in example 6.
< example 13>
The present invention provides a surface coating process for submicron high purity titanium dioxide, which is different from the embodiment 3 in that in step S1, titanium dioxide is dispersed in deionized water, and then chitosan and dodecyl betaine are added. The other conditions and parameters were the same as in example 3.
< example 14>
The invention provides a surface coating process of submicron high-purity titanium dioxide, which is different from the embodiment 3 in that in the step S1, titanium dioxide is dispersed in deionized water, and wet ball mill treatment is carried out to obtain a titanium dioxide base material, namely chitosan and dodecyl betaine are not added. The other conditions and parameters were the same as in example 3.
< example 15>
The present invention provides a surface coating process for submicron high purity titanium dioxide, which is different from embodiment 3 in that in step S3, after the pH of the silicon-coated titanium dioxide slurry is adjusted to 6.8, sodium metaaluminate, i.e., cyclodextrin is not added, is directly added to the silicon-coated titanium dioxide slurry. The other conditions and parameters were the same as in example 3.
< example 16>
The present invention provides a surface coating process for submicron-sized high-purity titanium dioxide, which is different from example 3 in that chitosan and dodecyl betaine are not added in step S1, and cyclodextrin is not added in step S3. The other conditions and parameters were the same as in example 3.
In examples 1 to 16, the materials used:
and (3) chitosan: the brand is T0060, the degree of deacetylation is > 90%, the manufacturer is Jiangxi province Sankang health products Limited;
dodecyl betaine: the manufacturer is Wuhan far-becoming a co-creation science and technology company Limited;
cyclodextrin: selecting gamma-cyclodextrin with the brand of 17465-86-0, and powder, wherein the manufacturer is Shenzhen Sendi Biotech Co., Ltd;
primary titanium dioxide products: the untreated rutile type titanium dioxide has the titanium dioxide content of 98 percent and the standard serial number of Q/LXGX J3-01-2009, and a manufacturer is blue star chemical new material company Limited;
the manufacturers of sodium hexametaphosphate, sodium silicate, sodium metaaluminate, maleic anhydride, inorganic acid, inorganic base, acetic acid, acetone and potassium hydroxide are Hubei Xingying Galaxy chemical Co
The manufacturer of the dimethyl diallyl ammonium chloride is Wuhan Jianghun fine chemical industry, Limited liability company.
< comparative example 1>
Titanium white R-706 from DuPont, USA, was selected as a control group.
The titanium dioxide products obtained by the surface coating process in the embodiments 1-16 of the invention are tested for performance in the following manner:
photocatalytic decomposition rate: the better the weather resistance of the titanium dioxide, the lower the photocatalytic activity of the titanium dioxide, and the correspondingly lower the photocatalytic decomposition rate of the titanium dioxide, the invention tests the ratio of the reduction of the concentration of the organic matter to the original concentration by mixing the titanium dioxide finished product with the organic matter and irradiating ultraviolet rays for a certain time, and further tests the photocatalytic decomposition rate of the titanium dioxide finished product; the specific test method comprises the following steps: weighing a titanium dioxide finished product prepared by a coating process, adding the titanium dioxide finished product and rhodamine B into water to prepare a sample to be measured in an aqueous solution, wherein the concentration of the rhodamine B is 3g/L, and the concentration of the titanium dioxide finished product is 2 g/L; measuring the transmittance T of a sample to be measured in an aqueous solution at the wavelength of 552nm1Then placing the samples to be measured in the water solution under the ultraviolet lamp with the same condition for irradiation, after irradiating for a certain time, measuring the transmittance T of the samples to be measured in the water solution at the wavelength of 552nm again2(ii) a The aqueous solution isThe photocatalytic decomposition rate of the sample (T ═2-T1)/(1-T1) (ii) a According to the method, the photocatalytic decomposition rate of the titanium dioxide finished product prepared by the coating process in the embodiments 1-16 is respectively, any test sample is tested for three times in parallel, and the average value of the three times is taken; the measurement results are shown in table 1;
brightness: the titanium dioxide finished products prepared by the coating process in the embodiments 1-16 of the invention are measured by a method specified in GB/T5211.20-1999, any test sample is tested in parallel for three times, and the average value of the three times is taken; the measurement results are shown in table 1;
conductivity of the washing water: the method specified in GB/T5211.12 is adopted to measure (20 times of washing water) of the titanium dioxide finished product prepared by the coating process in the embodiments 1-16 of the invention; testing any test sample in parallel for three times, and taking the average value of the three times; the measurement results are shown in table 1;
oil absorption: the acid solubility of the titanium dioxide finished product prepared by the coating process in the embodiments 1-16 of the invention is tested by adopting a method specified in GB/T1706-2006, the density of a film layer of the titanium dioxide pigment is represented by oil absorption, the smaller the oil absorption is, the higher the density of the coated film layer is, any test sample is tested in parallel for three times, and the average value of the three times is taken; the measurement results are shown in table 1;
water dispersibility: selecting two drying products with mass m1The glass bottle is numbered as a first glass bottle and a second glass bottle, a titanium dioxide finished product prepared by a coating process and distilled water are added into a first conical bottle according to the weight ratio of 1:19, the first conical bottle is sealed and placed on an oscillator for oscillation and dispersion for 30min to obtain a sample slurry to be measured, 10mL of the sample slurry is transferred into the first glass bottle by a transfer pipette, and the weight is m2Standing the residual slurry in the first conical flask, naturally settling for 5h, taking supernatant of the first conical flask with the volume of 1/3 of the original volume after settling is finished, placing the supernatant in a second conical flask, placing a seal of the second conical flask on an oscillator for oscillation, dispersing for 30min, then transferring 10mL into a second glass bottle from the second conical flask, and weighing the glass bottle into m3Putting the first glass bottle and the second glass bottle into a drying oven at 150 ℃ for drying, and taking out the two glass bottles after 2.5 hoursPutting the sample in the bottle into a drying oven again for drying, taking out the sample after 30min, naturally cooling, weighing, and respectively counting as m4And m5(ii) a Water-dispersibility [ (m) ]5-m1)×(m2-m1)]/[(m3-m1)×(m4-m1)]X is 100%; according to the method, the water dispersibility of the titanium dioxide finished product prepared by the coating process in the embodiments 1-16 is respectively, any test sample is tested for three times in parallel, and the average value of the three times is taken; the measurement results are shown in table 1;
TABLE 1 measurement results
As can be seen from table 1, the titanium dioxide finished products prepared in the embodiments 10 to 12 of the present invention have the most excellent performance, the brightness and the water dispersibility of the titanium dioxide finished products are far higher than those of products sold in the market, the oil absorption is low, which indicates that the titanium dioxide finished products of the embodiments 10 to 12 have good coating property, high film density, low photocatalytic decomposition rate, strong weather resistance, low washing water conductivity, and can greatly save water resources; the difference between the embodiments 7 to 9 and the embodiments 10 to 12 is that chitosan is not pretreated, the difference between the embodiments 4 to 6 and the embodiments 10 to 12 is that cyclodextrin is not pretreated, the difference between the embodiments 1 to 3 and the embodiments 10 to 12 is that both chitosan and cyclodextrin are not pretreated, and the determination results in table 1 show that both chitosan and cyclodextrin are pretreated to have the effect of improving the performance of the finished titanium dioxide product; example 13 differs from example 3 in the order of addition of titanium dioxide, and it can be seen from the measurement results in table 1 that the effect of improving the performance of the finished product of titanium dioxide can be achieved by preparing the base material of chitosan and adding titanium dioxide to the base material; the differences between example 14, example 15 and example 16 and example 3 are that no chitosan, no cyclodextrin, and no chitosan and cyclodextrin are added, and the determination results in table 1 show that the introduction of chitosan and cyclodextrin greatly improves various performance indexes of the titanium dioxide finished product.
The number of apparatuses and the scale of the process described herein are intended to simplify the description of the present invention. Applications, modifications and variations of the present invention will be apparent to those skilled in the art.
While embodiments of the invention have been disclosed above, it is not limited to the applications listed in the description and the embodiments, which are fully applicable in all kinds of fields of application of the invention, and further modifications may readily be effected by those skilled in the art, so that the invention is not limited to the specific details without departing from the general concept defined by the claims and the scope of equivalents.
Claims (7)
1. The surface coating process of the submicron high-purity titanium dioxide is characterized by coating silicon and aluminum on the surface of the titanium dioxide and comprises the following steps:
s1, dispersing chitosan and dodecyl betaine in deionized water, adding a titanium dioxide primary product under stirring, and placing the mixture in a wet ball mill for treatment for 20-30 min after the addition is finished to obtain a titanium dioxide base material, wherein the dosage of the chitosan and the dodecyl betaine is 0.05-0.1% and 0.005-0.008% of the total amount of the titanium dioxide respectively, and the mass concentration of the titanium dioxide in the titanium dioxide base material is 180-300 g/L;
step S2, heating the titanium dioxide base material obtained in the step S1 to 80-100 ℃, adding sodium hexametaphosphate accounting for 0.1% of the mass of the titanium dioxide into the titanium dioxide base material, adjusting the pH value to 11, stirring for two hours to obtain titanium dioxide slurry, adding sodium silicate into the titanium dioxide slurry, wherein the adding amount of the sodium hexametaphosphate is 2.5-5.8% of the total amount of the titanium dioxide, the adding time is 40-60 min, after the adding is finished, adjusting the pH value to 9, and stirring and curing for 0.5-2 hours to obtain silicon-coated titanium dioxide slurry;
and S3, adding the silicon-coated titanium dioxide slurry obtained in the step S2 to 60-90 ℃, adjusting the pH value to 6.0-7.5, adding cyclodextrin into the silicon-coated titanium dioxide slurry, wherein the addition amount of the cyclodextrin is 0.01-0.05% of the total amount of the titanium dioxide, fully stirring for 20-30 min, adding sodium metaaluminate into the silicon-coated titanium dioxide slurry, the addition amount of the sodium metaaluminate is 2.0-4.0% of the total amount of the titanium dioxide, the addition time is 40-60 min, adjusting the pH value of the slurry to 6.8-7.5, stirring and curing for 0.5-1 h, and performing suction filtration and drying to obtain the silicon-aluminum coated titanium dioxide.
2. The surface coating process of sub-micron high purity titanium dioxide as claimed in claim 1, wherein the chitosan in step S1 is subjected to a modification pretreatment, specifically: mixing 5-10 parts by weight of chitosan and 400-450 parts by weight of acetic acid to obtain a first mixed solution, fully stirring the mixed solution, dropwise adding 25-50 parts by weight of 20% maleic anhydride acetone solution into the mixed solution under stirring, and continuously stirring for 18-24 hours at room temperature after the addition is finished to obtain a second mixed solution; and pouring the mixed solution II into 500-1000 parts of potassium hydroxide solution with the mass concentration of 1000g/L, stirring and reacting for 1-2 hours to obtain a mixed solution III, placing the mixed solution III in a centrifuge for centrifugal treatment, collecting the lower-layer precipitate, and performing spray drying to obtain the compound I.
3. The surface coating process of sub-micron high purity titanium dioxide as claimed in claim 1, wherein the cyclodextrin of step S3 is subjected to a modification pretreatment, specifically: taking 1-5 parts of cyclodextrin, mixing the cyclodextrin with 10-50 parts of absolute ethyl alcohol, adjusting the pH value to 8.5 to obtain a mixed solution IV, heating the mixed solution IV in a water bath at 80-90 ℃, adding 1-5 parts of dimethyldiallylammonium chloride into the mixed solution IV under stirring, continuously stirring for reaction for 2-4 h, standing, naturally cooling to room temperature, pouring the cooled mixed solution into 20-100 parts of absolute ethyl alcohol, standing for 1-2 h, filtering, collecting a filter cake, drying and crushing to obtain the cyclodextrin-containing water dispersible granule.
4. The surface coating process for submicron order high purity titanium dioxide according to any one of claims 1 to 3, wherein the pH value is adjusted by using an inorganic acid solution or an inorganic alkali solution, the inorganic acid solution is a dilute hydrochloric acid solution with a mass concentration of 9 to 10%, and the inorganic alkali solution is a sodium hydroxide aqueous solution with a concentration of 0.5 mol/L.
5. The surface coating process of submicron order high purity titanium dioxide according to claim 1, wherein the particle size of the titanium dioxide base material treated by the wet ball mill in step S1 is 0.26-0.35 μm, and the particle size distribution is less than or equal to 1.38%.
6. The surface coating process for submicron high purity titanium dioxide according to claim 5, wherein the wet ball mill in step S1 has zirconium silicate beads as the grinding medium, the particle size of the grinding medium is 0.5-0.8 μm, and the loading is 60-75%.
7. The surface coating process of submicron order high purity titanium dioxide according to claim 2, wherein the rotation speed of the centrifugal nozzle in spray drying is 380-450 r/min, the feeding amount is 45-50 mL/min, and the temperatures at the air inlet and the air outlet are 78-90 ℃ and 60-68 ℃ respectively.
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