WO2022007763A1 - Preparation method for titanium dioxide material - Google Patents

Preparation method for titanium dioxide material Download PDF

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WO2022007763A1
WO2022007763A1 PCT/CN2021/104593 CN2021104593W WO2022007763A1 WO 2022007763 A1 WO2022007763 A1 WO 2022007763A1 CN 2021104593 W CN2021104593 W CN 2021104593W WO 2022007763 A1 WO2022007763 A1 WO 2022007763A1
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titanium
titanium dioxide
solid powder
powder compound
dioxide material
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PCT/CN2021/104593
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French (fr)
Chinese (zh)
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梁先华
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宁波极微纳新材料科技有限公司
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/063—Titanium; Oxides or hydroxides thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J35/39—
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G23/00—Compounds of titanium
    • C01G23/04—Oxides; Hydroxides
    • C01G23/047—Titanium dioxide
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G23/00—Compounds of titanium
    • C01G23/04—Oxides; Hydroxides
    • C01G23/047—Titanium dioxide
    • C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
    • C01P2004/16—Nanowires or nanorods, i.e. solid nanofibres with two nearly equal dimensions between 1-100 nanometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer

Definitions

  • the invention particularly relates to a preparation method of titanium dioxide material.
  • Nano-titanium dioxide refers to titanium dioxide with a particle size of less than 100 nanometers. It has special effects such as small particle size, high specific surface area, excellent photocatalytic activity, stable chemical and thermal properties, and super affinity. Self-cleaning materials, sunscreen skin care products and other fields have irreplaceable application advantages.
  • the preparation methods of nano-titanium dioxide can be divided into two categories: physical and chemical methods.
  • the physical method only controls the particle size and crystal form through physical mechanics or solid phase re-precipitation, and the chemical composition of the prepared powder does not change before and after.
  • the commonly used methods are gas-phase condensation method and pulverization method.
  • the gas-phase condensation method is not suitable for the preparation of oxides with high melting point and high boiling point.
  • the pulverization method uses the huge energy of mechanical rotation and vibration to pulverize the raw materials into nano-sized particles.
  • the obtained powder has irregular shape and wide particle size distribution, which is difficult to achieve. A uniform nano-powder was obtained.
  • the chemical method can be divided into solid phase method, gas phase method and liquid phase method according to the form of the reactant system.
  • the solid-phase method is not suitable for the preparation of nanoparticles because the reaction only occurs between solid particles, and the degree of mixing between solids is very uneven.
  • the gas phase method is a method of directly using gas or changing substances into gases by various means, making them undergo physical or chemical changes in the gaseous state, and finally condensing and growing to form nanoparticles during the cooling process.
  • the gas phase method mainly includes gas condensation method, sputtering method, active hydrogen-molten metal reaction method, vacuum evaporation method on flowing liquid surface, mixed plasma method and electric heating evaporation method.
  • the gas phase method usually has high reaction temperature, complex process technology, high requirements on equipment and technology, and large investment, so the product cost is high.
  • the liquid phase synthesis method has the advantages of easy control of the reaction, simple equipment, and low energy consumption, and is widely used in the laboratory and industry to prepare titanium dioxide materials.
  • Liquid phase methods mainly include precipitation method, hydrothermal method, sol-gel method, microemulsion method, hydrolysis method, etc.
  • the nano-titania materials obtained by these methods have low yields, generally non-uniform particle size distribution, and long process flow.
  • nano-TiO2 powders on the market are large particles formed by agglomeration of nano-scale particles, not nano-TiO2 materials in the true sense. These materials have poor dispersibility in water, are opaque, It is easy to settle, resulting in great defects in practical applications; at the same time, the price of nano-titanium dioxide materials is generally high, and its price is tens to hundreds of times that of micron and sub-micron titanium dioxide materials.
  • an object of the present invention is to provide a preparation method of nano-titanium dioxide material, which can develop low-cost, high-performance nano-titanium dioxide material on a large scale.
  • the technical method uses titanium oxychloride solid powder as the precursor, and controls the diffusion path of the solute during the conversion process by controlling the moisture content of the material, and finally obtains a small-scale, uniform particle size, and monodisperse nanomaterial product.
  • a preparation method of titanium dioxide material comprising the steps:
  • step 2 The moisture content of the titanium oxychloride solid powder compound described in step 1 is controlled so that the mass fraction of water is 1% to 50%; the preferred mass fraction of water is 5% to 100% Thirty percent.
  • step 2 The titanium oxychloride solid powder compound described in step 2 is heated at a low temperature in a closed environment to obtain a titanium dioxide material.
  • the titanium dioxide material is a colloidal solution that can spontaneously disperse in water to form a stable suspension of nano titanium dioxide particles; the nano titanium dioxide particles are crystalline nano titanium dioxide particles.
  • the chemical formula of the titanium oxychloride solid powder compound is TiOxCly; the x value is 1.7 to 2.3; the y value is 0.01 to 0.5.
  • the titanium oxychloride solid powder compound in step 1 may also contain hydrogen; the number ratio of the contained hydrogen to titanium is 1:100 to 1:10.
  • the number ratio of oxygen to titanium is 1.8 to 2.2.
  • the number ratio of chlorine to titanium is 0.03 to 0.2.
  • the temperature of the low-temperature heating in step 3 is 100 degrees Celsius to 200 degrees Celsius; the low-temperature heating time is 2 hours to 24 hours.
  • the preparation of the titanium oxychloride solid powder compound in step 1 is obtained by contacting titanium chloride with water or water vapor; the titanium chloride is selected from titanium tetrachloride, titanium tetrachloride aqueous solution , one or a combination of titanium trichloride and titanium dichloride.
  • the preparation of the titanium oxychloride solid powder compound in step 1 is obtained by the direct hydrolysis of titanium alkoxide in an aqueous solution containing hydrochloric acid.
  • the preparation of the titanium oxychloride solid powder compound described in step 1 is obtained by reacting the titanium oxide compound with one or more combinations of hydrochloric acid, hydrochloric acid solution, chlorine gas, and chlorine gas solution; the The titanium oxide compound is selected from one or a combination of low-crystalline titanium dioxide, amorphous titanium dioxide, titanic acid, titanium oxide, titanium monoxide, metatitanic acid, titanium hydroxide, and hydrated titanic acid.
  • the synthesized titanium dioxide particles have uniform size and controllable particle size, and can spontaneously disperse in water to form a colloidal solution in which nano titanium dioxide particles are stably suspended.
  • the titanium dioxide photocatalyst has excellent photocatalytic activity.
  • Fig. 1 is the SEM image obtained after the product obtained in Example 1 is dispersed in water and applied on a silicon wafer, and observed after drying;
  • Fig. 2 is the X-ray diffraction pattern of the titanium dioxide product prepared in Example 1, and the main crystal phase is rutile phase;
  • Fig. 3 is the water dispersion liquid whose mass fraction obtained after adding water to the nano titanium dioxide product obtained in Example 1 is one thousandth, and has a stable colloidal dispersion state;
  • Fig. 4 is the SEM image obtained by drip-coating the product obtained in Example 4 on a silicon wafer after being dispersed in water, and observed after drying;
  • Figure 5 is a scanning electron microscope image of the product obtained in Comparative Example 1, and the product is a petal-shaped large particle agglomerate.
  • titanium tetrachloride liquid Take 10 grams of titanium tetrachloride liquid and slowly drop it into 200 ml of water, continue to stir for 7 days after the dropwise addition, obtain a white precipitate and centrifuge, and dry at room temperature to obtain a titanium oxychloride solid powder compound; measure and control the above titanium oxychloride solid The moisture content in the powder compound is 20%; then, the above powder is put into a reactor to seal, and then placed in an oven to be heated at 140 degrees Celsius for 20 hours to obtain a titanium dioxide product.
  • the main components are determined by energy spectrum to be titanium, oxygen and chlorine; wherein the number ratio of oxygen to titanium is about 2.1, and the number ratio of chlorine to titanium is about 2.1. about 0.16.
  • Example 1 Take a small amount of the product obtained in Example 1 and disperse it in deionized water, then take a small amount and drop it on the silicon wafer, air dry it naturally, and adhere the dried silicon wafer to the sample stage of the scanning electron microscope with a conductive adhesive for the observation of the scanning electron microscope.
  • the morphology of the sample is shown in Figure 1. It can be seen from Figure 1 that the product titanium dioxide nanoparticles are in the shape of nanorods, the length of the particles is 50 to 100 nanometers, the particle size of the particles is mainly 15 to 20 nanometers, and the uniformity is very good.
  • Figure 2 is the X-ray diffraction pattern of the titanium dioxide product prepared in Example 1. It can be seen from Figure 2 that the crystal phase of the nano-titanium dioxide prepared in Example 1 is a rutile phase and has good crystallinity.
  • the nano-titanium dioxide product obtained in Example 1 is added to water to obtain a nano-titanium dioxide dispersion with a mass fraction of one thousandth. As shown in Figure 3, the dispersion has good monodispersity and can be formed in an aqueous solution. Stable colloidal dispersion, nano-particles are stably suspended, not agglomerated and not easy to settle, and the solution has not been delaminated for 3 months.
  • the nano-titania obtained in Example 1 was dispersed in water to form an aqueous dispersion with a concentration of 5/10,000, and then the above-mentioned dispersion liquid was taken in a quartz cuvette with a thickness of 1 cm, and the UV-Vis absorption curve of the sample was tested.
  • the dispersion can completely absorb ultraviolet light less than 380 nanometers, has strong ultraviolet absorption ability, and has good light transmittance in the visible light region greater than 400 nanometers, and the transmittance is more than 60%.
  • the transparency of the product obtained in this example is increased by 40 times, which greatly expands the application of titanium dioxide materials in the fields of ultraviolet absorption and aesthetics.
  • the development of transparent coatings for No white spots are formed on the surfaces of doors and windows, leather goods, glass, mirrors, etc., and skin care and sunscreen products with transparent and natural skin tone are developed, and transparent film products, transparent durable topcoats, fine ceramics and other products are developed.
  • the advantages of the present invention are: (1) the technical synthesis is universal, the price is low, the technological process is simple, and it can be synthesized and applied on a large scale. (2)
  • the synthesized titanium dioxide particles have uniform size and controllable particle size, and can spontaneously disperse in water to form a colloidal solution in which nano titanium dioxide particles are stably suspended.
  • (3) The dispersion of this product has extremely high transparency and can be used for the development of transparent coating products, such as spraying on doors and windows, leather goods, glass, mirrors and other surfaces without forming white spots; it can also be used to make transparent and natural skin care, Sunscreen products; also conducive to the development of transparent film products, transparent durable topcoats, fine ceramics and other products.
  • titanium trichloride liquid Take 10 grams of titanium trichloride liquid and slowly drop it into 100 ml of water. After the addition is completed, the temperature is raised to 50 degrees Celsius and stirred continuously for 6 hours to obtain a white precipitate and centrifuged. After drying at 60 degrees Celsius, titanium oxychloride solid powder compound is obtained; Measure and control the moisture content in the above titanium oxychloride solid powder compound to be 10%; then, put the above powder in a reaction kettle to seal, and then put it in an oven and heat at 180 degrees Celsius for 8 hours to obtain a titanium dioxide product.
  • the main components are determined by energy spectrum as titanium, oxygen and chlorine; wherein the number ratio of oxygen to titanium is about 1.9, and the number ratio of chlorine to titanium is about 1.9. about 0.1.
  • Example 2 Take a small amount of the product obtained in Example 2 and disperse it in deionized water, then take a small amount and drop it on a silicon wafer for scanning electron microscopy to observe the morphology of the sample.
  • the product titanium dioxide nanoparticles are in the shape of nanorods, and the length of the particles is 60 to 150. Nano, the particle size of the particles is mainly 20 to 30 nanometers, and the uniformity is better.
  • X-ray diffraction confirmed that the main crystal phase of the nano-titania obtained in Example 2 was a rutile phase with good crystallinity.
  • the titanium dioxide material product obtained in Example 2 into pure water, it can be seen that the titanium dioxide material product spontaneously "dissolves" and is dispersed in the pure water to form a colloidal water dispersion in which nano-scale titanium dioxide particles are stably suspended.
  • the particles are stably suspended and do not agglomerate, with obvious Tyndall phenomenon, and the dispersion liquid will not appear obvious stratification if it is placed for half a month.
  • the nano-titania obtained in Example 2 was dispersed in water to form an aqueous dispersion with a concentration of 5/10,000, and then the above-mentioned dispersion was taken in a 1 cm thick quartz cuvette to test the UV-Vis absorption curve of the sample.
  • the dispersion can completely absorb ultraviolet light less than 380 nanometers, has strong ultraviolet absorption ability, and has good light transmittance in the visible light region greater than 400 nanometers, and the transmittance is more than 30%.
  • the transparency of the product obtained in this example is increased by 20 times, which expands the application of titanium dioxide materials in the fields of ultraviolet absorption and aesthetics, such as the development of transparent coatings for doors and windows.
  • leather goods, glass, mirrors and other surfaces do not form white spots, develop skin care and sunscreen products with transparent and natural skin tone, develop transparent film products, transparent durable topcoats, fine ceramics and other products.
  • water vapor and titanium dichloride gas were mixed to form a white precipitate and centrifuged, and dried at room temperature to obtain a solid powder compound of titanium oxychloride; measure and control the above titanium oxygen
  • the moisture content of the chlorine solid powder compound is 50%; then, the above powder is placed in a reaction kettle and sealed, and then placed in a microwave oven and heated in a microwave at 160 degrees Celsius for 3 hours to obtain a titanium dioxide product.
  • the main components are determined by energy spectrum as titanium, oxygen and chlorine; wherein the number ratio of oxygen to titanium is about 1.8, and the number ratio of chlorine to titanium is about 1.8. about 0.2.
  • Example 3 A small amount of the product obtained in Example 3 was dispersed in deionized water, and then a small amount was dropped on a silicon wafer for scanning electron microscopy to observe the morphology of the sample. It can be seen that the product titanium dioxide nanoparticles are in the shape of nanorods, and the length of the particles is 100 to 200 mm. Nano, the particle size of the particles is mainly 15 to 20 nanometers, and the uniformity is better. X-ray diffraction confirmed that the main crystal phase of the nano-titania obtained in Example 2 was a rutile phase with good crystallinity.
  • Example 3 Put a small amount of the titanium dioxide material product obtained in Example 3 into pure water, it can be seen that the titanium dioxide material product spontaneously "dissolves" and is dispersed in the pure water to form a colloidal water dispersion in which nano-titanium dioxide particles are stably suspended. The particles are stably suspended and not agglomerated, with obvious Tyndall phenomenon, and the dispersion liquid will not appear obvious stratification after being placed for 1 month.
  • the nano-titania obtained in Example 3 was dispersed in water to form an aqueous dispersion with a concentration of 5/10,000, and then the above-mentioned dispersion was taken in a 1 cm thick quartz cuvette to test the UV-Vis absorption curve of the sample.
  • the dispersion can completely absorb ultraviolet light less than 380 nanometers, has strong ultraviolet absorption ability, and has good light transmittance in the visible light region greater than 400 nanometers, and the transmittance is more than 40%.
  • the transparency of the product obtained in this example is increased by 30 times, which expands the application of titanium dioxide material in the fields of ultraviolet absorption and aesthetics, such as the development of transparent coatings for doors and windows.
  • leather goods, glass, mirrors and other surfaces do not form white spots, develop skin care and sunscreen products with transparent and natural skin tone, develop transparent film products, transparent durable topcoats, fine ceramics and other products.
  • the main components are determined by energy spectrum to be titanium, oxygen and chlorine; wherein the number ratio of oxygen to titanium is about 1.8, and the number of chlorine and titanium is about 1.8. The ratio is about 0.18.
  • Example 4 A small amount of the product obtained in Example 4 was dispersed in deionized water, and then a small amount was dropped on the silicon wafer, dried naturally, and the dried silicon wafer was adhered to the sample stage of the scanning electron microscope with a conductive adhesive for the observation of the scanning electron microscope.
  • the morphology of the sample is shown in Figure 4. It can be seen from FIG. 4 that the particle size of the product titanium dioxide nanoparticles is 5 nanometers to 10 nanometers, which further indicates that the nano titanium dioxide obtained in this example has a small particle size and good monodispersity.
  • the main crystal phase of the nano-titanium dioxide prepared in this example is anatase phase, which has good crystallinity.
  • the nano-titanium dioxide product obtained in this example is added to water to obtain a nano-titanium dioxide dispersion with a mass fraction of 5/1000.
  • the dispersion has good monodispersity and can form a stable colloidal dispersion in an aqueous solution. Nanoparticles are stable in suspension, do not agglomerate and are not easy to settle, and the solution has not been delaminated for more than 6 months.
  • the nano-titania material obtained in this example has good photocatalytic activity, and the catalytic efficiency is 8 times that of commercial P25 material.
  • the specific comparison method is to weigh the product obtained in this example 1 and P25 (Degussa) sample 2 respectively. g was dispersed in 100 ml of Rhodamine B solution with a concentration of 2.0 ⁇ 10-5 moles per liter, and was placed in a dark place with magnetic stirring for 30 minutes to achieve temperature equilibrium and adsorption equilibrium.
  • titanium isopropoxide was slowly added dropwise to 200 milliliters of aqueous hydrochloric acid with a concentration of 0.5 mol per liter. After the dropwise addition, stirring was continued for 2 hours to obtain a white precipitate and centrifuged. After drying at room temperature, a solid titanium oxychloride was obtained. powder compound; measure and control the water content in the above-mentioned titanium oxychloride solid powder compound to be 30%; then, put the above-mentioned powder into a reaction kettle to seal, and then place it in an oil bath and heat at 160 degrees Celsius for 20 hours, Titanium dioxide product is obtained.
  • the main components are determined by energy spectrum to be titanium, oxygen and chlorine; wherein the number ratio of oxygen to titanium is about 2.0, and the number ratio of chlorine to titanium is about 2.0. about 0.12.
  • Example 5 A small amount of the product obtained in Example 5 was dispersed in deionized water, and then a small amount was dropped on a silicon wafer for scanning electron microscopy to observe the morphology of the sample. It can be seen that the particle size of the product titanium dioxide nanoparticles is 8 nanometers to 20 nanometers.
  • the nano-titanium dioxide obtained in this example has a small particle size and good monodispersity. X-ray diffraction confirmed that the main crystal phase of the nano-titania obtained in Example 5 was anatase phase with good crystallinity.
  • Example 5 Put a small amount of the titanium dioxide material product obtained in Example 5 into pure water, it can be seen that the titanium dioxide material product spontaneously "dissolves" and is dispersed in the pure water to form a colloidal water dispersion in which the nanometer titanium dioxide particles are stably suspended.
  • the particles have stable suspension and no agglomeration, with obvious Tyndall phenomenon, and the dispersion liquid will not appear obvious layering phenomenon after being placed for 8 months.
  • the nano-titania obtained in Example 5 was dispersed in water to form an aqueous dispersion with a concentration of 5/10,000, and then the above-mentioned dispersion was taken in a 1 cm thick quartz cuvette to test the UV-Vis absorption curve of the sample.
  • the dispersion can completely absorb ultraviolet light less than 370 nanometers, has strong ultraviolet absorption capacity, and has good light transmittance in the visible light region greater than 400 nanometers, and the transmittance is more than 90%.
  • the transparency of the product obtained in this example is increased by 60 times, which expands the application of titanium dioxide material in the fields of ultraviolet absorption and aesthetics, such as the development of transparent coatings for doors and windows.
  • leather goods, glass, mirrors and other surfaces do not form white spots, develop skin care and sunscreen products with transparent and natural skin tone, develop transparent film products, transparent durable topcoats, fine ceramics and other products.
  • the nano-titania material obtained in Example 5 has good photocatalytic activity, and the catalytic efficiency is 9 times that of the commercial P25 material.
  • the specific comparison method is as described in Example 4.
  • the main components are determined by energy spectrum to be titanium, oxygen and chlorine; wherein the number ratio of oxygen to titanium is about 2.1, and the number ratio of chlorine to titanium is about 2.1. about 0.14.
  • Example 6 A small amount of the product obtained in Example 6 was dispersed in deionized water, and then a small amount was dropped on a silicon wafer for scanning electron microscopy to observe the morphology of the sample. It can be seen that the particle size of the product titanium dioxide nanoparticles is 20 nanometers to 50 nanometers.
  • the nano-titanium dioxide obtained in this example has a small particle size and good monodispersity. X-ray diffraction confirmed that the main crystal phase of the nano-titania obtained in Example 6 was anatase phase with good crystallinity, and contained a trace amount of rutile crystal phase.
  • Example 6 Put a small amount of the titanium dioxide material product obtained in Example 6 into pure water, it can be seen that the titanium dioxide material product is spontaneously "dissolved” and dispersed in the pure water, forming a colloidal water dispersion in which nano titanium dioxide particles are stably suspended. The particles have stable suspension and no agglomeration, with obvious Tyndall phenomenon, and the dispersion liquid will not appear obvious stratification after being placed for 3 months.
  • the nano-titania obtained in Example 6 was dispersed in water to form an aqueous dispersion with a concentration of 5/10,000, and then the above-mentioned dispersion was taken in a 1 cm thick quartz cuvette to test the UV-Vis absorption curve of the sample.
  • the dispersion liquid can completely absorb ultraviolet light less than 370 nanometers, has strong ultraviolet absorption ability, and has good light transmittance in the visible light region greater than 400 nanometers, and the transmittance is more than 70%.
  • the transparency of the product obtained in this example is increased by 45 times, which expands the application of titanium dioxide material in the fields of ultraviolet absorption and aesthetics, such as the development of transparent coatings for doors and windows.
  • leather goods, glass, mirrors and other surfaces do not form white spots, develop skin care and sunscreen products with transparent and natural skin tone, develop transparent film products, transparent durable topcoats, fine ceramics and other products.
  • the nano-titania material obtained in Example 6 has good photocatalytic activity, and the catalytic efficiency is 7.3 times that of the commercial P25 material.
  • the specific comparison method is as described in Example 4.
  • titanium tetrachloride liquid Take 10 grams of titanium tetrachloride liquid and slowly drop it into 200 ml of water, continue to stir for 7 days after the dropwise addition, obtain a white precipitate and centrifuge, and dry at room temperature to obtain a titanium oxychloride solid powder compound; measure and control the above titanium oxychloride solid The moisture content in the powder compound is 90%, and a mud-like titanium oxychloride solid suspension is obtained; then, the above-mentioned titanium oxychloride solid suspension is placed in a reaction kettle to seal, and then placed in an oven at 140 degrees Celsius Under heating for 20 hours, a titanium dioxide product was obtained.
  • the main components are determined by energy spectrum to be titanium, oxygen and chlorine; wherein the number ratio of oxygen to titanium is about 2.1, and the number ratio of chlorine to titanium is about 2.1. about 0.16.
  • the product obtained in this comparative example contains a large number of large petal-shaped particles, as shown in Fig. 5 of the scanning electron microscope; at the same time, the product cannot be dispersed in water to form a stable and transparent dispersion, and the obtained product is a suspension liquid, which will disappear within a few hours. Precipitation and stratification occurred; in addition, the comparative product was in the rutile phase, and the photocatalytic performance was poor. In this comparative example, the invention effect of the product of the embodiment cannot be obtained in terms of product morphology, dispersibility, crystal phase, catalytic efficiency and other structures and properties.
  • titanium tetrachloride liquid Take 10 grams of titanium tetrachloride liquid and slowly drop it into 200 ml of water, and continue to stir for 7 days after the dropwise addition to obtain a white precipitate and centrifuge it.
  • the moisture content in the above titanium oxide solid powder compound is controlled to be 20%; then, the above powder is placed in a reactor to seal, and then placed in an oven and heated at 140 degrees Celsius for 20 hours to obtain a titanium dioxide product.
  • the main components are determined by energy spectrum to be titanium and oxygen; wherein the number ratio of oxygen to titanium is about 2.0, and the number ratio of chlorine to titanium is less than 0.01 .
  • the product obtained in this comparative example contains a large number of large petal-shaped particles; at the same time, the product cannot be dispersed in water to form a stable and transparent dispersion, and the obtained product is a suspension liquid, and precipitation and stratification will appear within a few hours.
  • the invention effect of the product of the embodiment cannot be obtained in terms of product morphology, dispersibility and other structures and properties.
  • any numerical value recited herein includes all values of the lower value and the upper value in one unit increments from the lower value to the upper value, where there is an interval of at least two units between any lower value and any higher value, i.e. Can.
  • the number of components or process variables eg, temperature, pressure, time, etc.
  • the intent is to illustrate that the The specification also explicitly lists values such as 15 to 85, 22 to 68, 43 to 51, 30 to 32, and the like.
  • one unit is appropriately considered to be 0.0001, 0.001, 0.01, 0.1.

Abstract

Provided is a preparation method for a titanium dioxide material, comprising the following steps: (1) preparing a titanium oxychloride solid powder compound; (2) controlling the water content of the titanium oxychloride solid powder compound in step (1) to be 1% to 50% by mass of water; preferably, the water content being 5% to 30%; and (3) heating the titanium oxychloride solid powder compound in step (2) at a low temperature in a closed environment, so as to obtain the titanium dioxide material. The preparation method for the nano titanium dioxide material can be used for large-scale development of low-cost, high-performance nano titanium dioxide materials.

Description

一种二氧化钛材料的制备方法A kind of preparation method of titanium dioxide material
交叉参考相关引用Cross-reference related references
本申请要求2020年7月6日递交的申请号为202010642921.3、发明名称为“一种二氧化钛材料的制备方法”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。This application claims the priority of the Chinese Patent Application No. 202010642921.3 filed on July 6, 2020 and the title of the invention is "a method for preparing a titanium dioxide material", the entire contents of which are incorporated into this application by reference.
技术领域technical field
本发明特别涉及一种二氧化钛材料的制备方法。The invention particularly relates to a preparation method of titanium dioxide material.
背景技术Background technique
纳米二氧化钛是指粒径小于100纳米的二氧化钛，具有小的粒径、高的比表面积、优异的光催化活性、稳定的化学与热性能、超亲性等特殊效应，在空气治理、杀菌消毒、自清洁材料、防晒护肤品等领域具有不可替代的应用优势。Nano-titanium dioxide refers to titanium dioxide with a particle size of less than 100 nanometers. It has special effects such as small particle size, high specific surface area, excellent photocatalytic activity, stable chemical and thermal properties, and super affinity. Self-cleaning materials, sunscreen skin care products and other fields have irreplaceable application advantages.
目前，纳米二氧化钛的制备方式可以分为物理法化学法两大类。物理法由于只是通过物理力学或固相重新析出来控制粒径和晶型，制成的粉体前后化学组成没有发生变化，常用的有气相冷凝法和粉碎法。气相冷凝法不适用于制备高熔点和高沸点的氧化物，粉碎法是利用机械转动和震动的巨大能量，将原料粉碎为纳米级颗粒，得到的粉体形状不规则，颗粒尺寸分布宽，难以得到均匀的纳米粉体。At present, the preparation methods of nano-titanium dioxide can be divided into two categories: physical and chemical methods. The physical method only controls the particle size and crystal form through physical mechanics or solid phase re-precipitation, and the chemical composition of the prepared powder does not change before and after. The commonly used methods are gas-phase condensation method and pulverization method. The gas-phase condensation method is not suitable for the preparation of oxides with high melting point and high boiling point. The pulverization method uses the huge energy of mechanical rotation and vibration to pulverize the raw materials into nano-sized particles. The obtained powder has irregular shape and wide particle size distribution, which is difficult to achieve. A uniform nano-powder was obtained.
化学法根据反应物系的形态，可以分为固相法、气相法和液相法。其中固相法由于反应只发生在固体颗粒之间，而固体间的混合程度很不均匀，因而不适合纳米微粒的制备。气相法是直接利用气体或通过各种手段将物质变为气体，使之在气态下发生物理或化学变化，最后在冷却过程中凝聚长大形成纳米粒子的方法。气相法主要包括气体冷凝法、溅射法、活性氢-熔融金属反应法、流动液面上真空蒸发法、混合等离子法和通电加热蒸发法等。气相法通常反应温度高，工艺技术复杂，对设备和技术的要求高，投资大，因此产品成本高。液相合成法具有反应易控制、设备简单、能耗少等优点，是目实验室和工业上广泛采用制备二氧化钛材料的方法。液相法主要包括沉淀法、水热法、溶胶-凝胶法、微乳液法、水解法等。这些方法获得的纳米二氧化钛材料产率低、颗粒大小分布通常不均匀，工艺流程也较长。The chemical method can be divided into solid phase method, gas phase method and liquid phase method according to the form of the reactant system. Among them, the solid-phase method is not suitable for the preparation of nanoparticles because the reaction only occurs between solid particles, and the degree of mixing between solids is very uneven. The gas phase method is a method of directly using gas or changing substances into gases by various means, making them undergo physical or chemical changes in the gaseous state, and finally condensing and growing to form nanoparticles during the cooling process. The gas phase method mainly includes gas condensation method, sputtering method, active hydrogen-molten metal reaction method, vacuum evaporation method on flowing liquid surface, mixed plasma method and electric heating evaporation method. The gas phase method usually has high reaction temperature, complex process technology, high requirements on equipment and technology, and large investment, so the product cost is high. The liquid phase synthesis method has the advantages of easy control of the reaction, simple equipment, and low energy consumption, and is widely used in the laboratory and industry to prepare titanium dioxide materials. Liquid phase methods mainly include precipitation method, hydrothermal method, sol-gel method, microemulsion method, hydrolysis method, etc. The nano-titania materials obtained by these methods have low yields, generally non-uniform particle size distribution, and long process flow.
受制备技术与合成工艺等影响，当前市场上所谓的纳米二氧化钛粉体都是由纳米级颗粒团聚而成的大颗粒，并不是真正意义上的纳米二氧化钛材料，这些材料在水中分散 性差、不透明、易于沉降，造成在实际应用中具有很大的缺陷；同时，纳米二氧化钛材料的价格普遍较高，其价格是微米、亚微米二氧化钛材料的几十到上百倍。因此，发达国家如美国、日本和欧洲等国在纳米二氧化钛方面的研究工作十分活跃，前后投入了大量人力、物力，但性能优异的纳米二氧化钛材料始终没有被低成本、大规模的开发出来。Affected by preparation technology and synthesis process, the so-called nano-TiO2 powders on the market are large particles formed by agglomeration of nano-scale particles, not nano-TiO2 materials in the true sense. These materials have poor dispersibility in water, are opaque, It is easy to settle, resulting in great defects in practical applications; at the same time, the price of nano-titanium dioxide materials is generally high, and its price is tens to hundreds of times that of micron and sub-micron titanium dioxide materials. Therefore, developed countries such as the United States, Japan and Europe are very active in the research of nano-titanium dioxide, and a lot of manpower and material resources have been invested before and after, but nano-titanium dioxide materials with excellent performance have not been developed at low cost and on a large scale.
发明内容SUMMARY OF THE INVENTION
鉴于上述不足，本发明的一个目的是提供一种纳米二氧化钛材料的制备方法，该方法可大规模开发低成本、高性能的纳米二氧化钛材料。In view of the above deficiencies, an object of the present invention is to provide a preparation method of nano-titanium dioxide material, which can develop low-cost, high-performance nano-titanium dioxide material on a large scale.
该技术方法采用钛氧氯固体粉末为前驱物，通过控制材料的含水率来控制转化过程中溶质的扩散路径，最终获得小尺度、粒径均匀、单分散的纳米材料产物。The technical method uses titanium oxychloride solid powder as the precursor, and controls the diffusion path of the solute during the conversion process by controlling the moisture content of the material, and finally obtains a small-scale, uniform particle size, and monodisperse nanomaterial product.
为达到上述目的，本申请采用如下技术方案：To achieve the above object, the application adopts the following technical solutions:
一种二氧化钛材料的制备方法，包括如下步骤：A preparation method of titanium dioxide material, comprising the steps:
(1)制备钛氧氯固体粉末化合物；(1) prepare titanyl chloride solid powder compound;
(2)将步骤1中所述的钛氧氯固体粉末化合物的含水率控制在水的质量分数为百分之一到百分之五十；优选的水的质量分数为百分之五到百分之三十。(2) The moisture content of the titanium oxychloride solid powder compound described in step 1 is controlled so that the mass fraction of water is 1% to 50%; the preferred mass fraction of water is 5% to 100% Thirty percent.
(3)将步骤2中所述的钛氧氯固体粉末化合物在密闭环境中低温加热，获得二氧化钛材料。(3) The titanium oxychloride solid powder compound described in step 2 is heated at a low temperature in a closed environment to obtain a titanium dioxide material.
作为一种优选的实施方式，所述二氧化钛材料为在水中可自发分散形成纳米二氧化钛粒子稳定悬浮的胶体溶液；所述纳米二氧化钛粒子为结晶性纳米二氧化钛粒子。As a preferred embodiment, the titanium dioxide material is a colloidal solution that can spontaneously disperse in water to form a stable suspension of nano titanium dioxide particles; the nano titanium dioxide particles are crystalline nano titanium dioxide particles.
作为一种优选的实施方式，所述钛氧氯固体粉末化合物的化学式为TiOxCly；所述x值为1.7至2.3；所述y值为0.01至0.5。As a preferred embodiment, the chemical formula of the titanium oxychloride solid powder compound is TiOxCly; the x value is 1.7 to 2.3; the y value is 0.01 to 0.5.
作为一种优选的实施方式，步骤1中所述钛氧氯固体粉末化合物中还可以含有氢；所述含有的氢与钛的个数比为1:100至1:10。As a preferred embodiment, the titanium oxychloride solid powder compound in step 1 may also contain hydrogen; the number ratio of the contained hydrogen to titanium is 1:100 to 1:10.
作为一种优选的实施方式，步骤1中所述钛氧氯固体粉末化合物中，氧与钛的个数比为1.8至2.2。As a preferred embodiment, in the titanium oxychloride solid powder compound in step 1, the number ratio of oxygen to titanium is 1.8 to 2.2.
作为一种优选的实施方式，步骤1中所述钛氧氯固体粉末化合物中，氯与钛的个数比为0.03至0.2。As a preferred embodiment, in the titanium oxychloride solid powder compound in step 1, the number ratio of chlorine to titanium is 0.03 to 0.2.
作为一种优选的实施方式，步骤3中所述低温加热的温度为100摄氏度至200摄氏度；所述低温加热的时间为2小时至24小时。As a preferred embodiment, the temperature of the low-temperature heating in step 3 is 100 degrees Celsius to 200 degrees Celsius; the low-temperature heating time is 2 hours to 24 hours.
作为一种优选的实施方式，步骤1中所述钛氧氯固体粉末化合物的制备由氯化钛与水或水汽接触后获得；所述氯化钛选自四氯化钛、四氯化钛水溶液、三氯化钛、二氯化钛 中的一种或者几种的组合。As a preferred embodiment, the preparation of the titanium oxychloride solid powder compound in step 1 is obtained by contacting titanium chloride with water or water vapor; the titanium chloride is selected from titanium tetrachloride, titanium tetrachloride aqueous solution , one or a combination of titanium trichloride and titanium dichloride.
作为一种优选的实施方式，步骤1中所述钛氧氯固体粉末化合物的制备由钛醇盐在含有盐酸的水溶液中直接水解获得。As a preferred embodiment, the preparation of the titanium oxychloride solid powder compound in step 1 is obtained by the direct hydrolysis of titanium alkoxide in an aqueous solution containing hydrochloric acid.
作为一种优选的实施方式，步骤1中所述钛氧氯固体粉末化合物的制备由钛氧化合物与盐酸、盐酸溶液、氯气、氯气溶液中的一种或几种的组合进行反应获得；所述钛氧化合物选自低结晶性二氧化钛、无定型二氧化钛、钛酸、亚氧化钛、一氧化钛、偏钛酸、氢氧化钛、水合钛酸中的一种或者几种的组合。As a preferred embodiment, the preparation of the titanium oxychloride solid powder compound described in step 1 is obtained by reacting the titanium oxide compound with one or more combinations of hydrochloric acid, hydrochloric acid solution, chlorine gas, and chlorine gas solution; the The titanium oxide compound is selected from one or a combination of low-crystalline titanium dioxide, amorphous titanium dioxide, titanic acid, titanium oxide, titanium monoxide, metatitanic acid, titanium hydroxide, and hydrated titanic acid.
本发明的优点在于：The advantages of the present invention are:
1.该技术合成具有普适性，价格低廉，工艺过程简单，可规模化合成应用。1. The synthesis of this technology is universal, low in price, simple in process, and can be used in large-scale synthesis.
2.合成的二氧化钛粒子尺寸均一，粒径大小可控，在水中可自发分散形成纳米二氧化钛粒子稳定悬浮的胶体溶液。2. The synthesized titanium dioxide particles have uniform size and controllable particle size, and can spontaneously disperse in water to form a colloidal solution in which nano titanium dioxide particles are stably suspended.
3.该二氧化钛光催化剂具有优异的光催化活性。3. The titanium dioxide photocatalyst has excellent photocatalytic activity.
参照后文的说明和附图，详细公开了本发明的特定实施方式，指明了本发明的原理可以被采用的方式。应该理解，本发明的实施方式在范围上并不因而受到限制。With reference to the following description and drawings, specific embodiments of the invention are disclosed in detail, indicating the manner in which the principles of the invention may be employed. It should be understood that embodiments of the present invention are not thereby limited in scope.
针对一种实施方式描述和/或示出的特征可以以相同或类似的方式在一个或更多个其它实施方式中使用，与其它实施方式中的特征相组合，或替代其它实施方式中的特征。Features described and/or illustrated for one embodiment may be used in the same or similar manner in one or more other embodiments, in combination with, or instead of features in other embodiments .
应该强调，术语“包括/包含”在本文使用时指特征、整件、步骤或组件的存在，但并不排除一个或更多个其它特征、整件、步骤或组件的存在或附加。It should be emphasized that the term "comprising/comprising" when used herein refers to the presence of a feature, integer, step or component, but does not exclude the presence or addition of one or more other features, integers, steps or components.
附图说明Description of drawings
为了更清楚地说明本发明实施例或现有技术中的技术方案，下面将对实施例或现有技术描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本发明的一些实施例，对于本领域技术人员来讲，在不付出创造性劳动性的前提下，还可以根据这些附图获得其他的附图。In order to explain the embodiments of the present invention or the technical solutions in the prior art more clearly, the following briefly introduces the accompanying drawings that need to be used in the description of the embodiments or the prior art. Obviously, the accompanying drawings in the following description are only These are some embodiments of the present invention, and for those skilled in the art, other drawings can also be obtained from these drawings without any creative effort.
图1为实施例1获得的产物经水分散后滴涂在硅片上，干燥后观察得到的扫描电镜图；Fig. 1 is the SEM image obtained after the product obtained in Example 1 is dispersed in water and applied on a silicon wafer, and observed after drying;
图2为实施例1制备得到的二氧化钛产物的X射线衍射图，主要晶相为金红石相；Fig. 2 is the X-ray diffraction pattern of the titanium dioxide product prepared in Example 1, and the main crystal phase is rutile phase;
图3为实施例1得到的纳米二氧化钛产物加水后获得的质量分数为千分之一的水分散液，具有稳定的胶体状分散状态；Fig. 3 is the water dispersion liquid whose mass fraction obtained after adding water to the nano titanium dioxide product obtained in Example 1 is one thousandth, and has a stable colloidal dispersion state;
图4为实施例4获得的产物经水分散后滴涂在硅片上，干燥后观察得到的扫描电镜图；Fig. 4 is the SEM image obtained by drip-coating the product obtained in Example 4 on a silicon wafer after being dispersed in water, and observed after drying;
图5为对比例1获得的产物的扫描电镜图，产物为花瓣状的大颗粒团聚体。Figure 5 is a scanning electron microscope image of the product obtained in Comparative Example 1, and the product is a petal-shaped large particle agglomerate.
具体实施方式detailed description
为了使本技术领域的人员更好地理解本发明中的技术方案，下面将结合本发明实施例中的附图，对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动的前提下所获得的所有其他实施例，都应当属于本发明保护的范围。In order to make those skilled in the art better understand the technical solutions of the present invention, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention. Obviously, the described The embodiments are only some of the embodiments of the present invention, but not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by persons of ordinary skill in the art without creative work shall fall within the protection scope of the present invention.
除非另有定义，本文所使用的所有的技术和科学术语与属于本发明的技术领域的技术人员通常理解的含义相同。本文中在本发明的说明书中所使用的术语只是为了描述具体的实施方式的目的，不是旨在于限制本发明。本文所使用的术语“和/或”包括一个或多个相关的所列项目的任意的和所有的组合。Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terms used herein in the description of the present invention are for the purpose of describing specific embodiments only, and are not intended to limit the present invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
实施例1Example 1
取10克四氯化钛液体缓慢滴加到200毫升水中，滴加后持续搅拌7天，获得白色沉淀并离心分离，常温干燥后获得钛氧氯固体粉末化合物；测定并控制上述钛氧氯固体粉末化合物中的含水率在百分之二十；随后，将上述粉末放入反应釜中密封，后放入烘箱中于140摄氏度下加热20小时，获得二氧化钛产物。上述钛氧氯固体粉末化合物前驱物完全干燥后，在真空下，经能谱测定出主要成分为钛、氧、氯；其中氧与钛的个数比约为2.1，氯与钛的个数比约为0.16。Take 10 grams of titanium tetrachloride liquid and slowly drop it into 200 ml of water, continue to stir for 7 days after the dropwise addition, obtain a white precipitate and centrifuge, and dry at room temperature to obtain a titanium oxychloride solid powder compound; measure and control the above titanium oxychloride solid The moisture content in the powder compound is 20%; then, the above powder is put into a reactor to seal, and then placed in an oven to be heated at 140 degrees Celsius for 20 hours to obtain a titanium dioxide product. After the above-mentioned titanium oxychloride solid powder compound precursor is completely dried, under vacuum, the main components are determined by energy spectrum to be titanium, oxygen and chlorine; wherein the number ratio of oxygen to titanium is about 2.1, and the number ratio of chlorine to titanium is about 2.1. about 0.16.
取少量实施例1获得产物分散于去离子水中后取少量滴在硅片上，自然晾干，将晾干后的硅片用导电胶粘附在扫描电镜的样品台上，用于扫描电镜观察样品的形貌，如图1所示。从图1可以看出产物二氧化钛纳米粒子为纳米棒形状，颗粒的长度为50至100纳米，颗粒的粒径主要为15至20纳米，均一度很好。图2是实施例1制备得到的二氧化钛产物的X射线衍射图，从图2可以看出本实施例1制得的纳米二氧化钛晶相为金红石相，具有很好的结晶性。Take a small amount of the product obtained in Example 1 and disperse it in deionized water, then take a small amount and drop it on the silicon wafer, air dry it naturally, and adhere the dried silicon wafer to the sample stage of the scanning electron microscope with a conductive adhesive for the observation of the scanning electron microscope. The morphology of the sample is shown in Figure 1. It can be seen from Figure 1 that the product titanium dioxide nanoparticles are in the shape of nanorods, the length of the particles is 50 to 100 nanometers, the particle size of the particles is mainly 15 to 20 nanometers, and the uniformity is very good. Figure 2 is the X-ray diffraction pattern of the titanium dioxide product prepared in Example 1. It can be seen from Figure 2 that the crystal phase of the nano-titanium dioxide prepared in Example 1 is a rutile phase and has good crystallinity.
将本实施例1得到的纳米二氧化钛产物加入到水中，获得质量分数为千分之一的纳米二氧化钛分散液，如图3所示，该分散液具有很好的单分散性，在水溶液中可以形成稳定的胶体状分散液，纳米粒子悬浮稳定、不团聚也不易沉降，放置3个月溶液未发生分层现象。将实施例1得到的纳米二氧化钛分散于水中，形成浓度为万分之五的水分散液，后取上述分散液体于1厘米厚的石英比色皿中，测试样品的紫外-可见光吸收曲线。该分散液可完全吸收小于380纳米的紫外光，紫外线吸收能力强，同时在大于400纳米的可见光区域具有很好的透光性，透光度大于百分之六十以上。同P25纳米二氧化钛材料相比，以550纳米波长为例，本实施例获得的产品透明度提高了40倍，大大拓展了二 氧化钛材料在紫外吸收、美观等产品领域的添加应用，如开发透明涂料用于门窗、皮具、玻璃、镜子等表面不形成白色斑点，开发透明、自然肤色的护肤、防晒产品，开发透明薄膜制品、透明耐用面漆、精细陶瓷等产品等。综上，本发明的优点在于：(1)该技术合成具有普适性，价格低廉，工艺过程简单，可规模化合成应用。(2)合成的二氧化钛粒子尺寸均一，粒径大小可控，在水中可自发分散形成纳米二氧化钛粒子稳定悬浮的胶体溶液。(3)本产品的分散液具有极高的透明度，可用于透明涂料产品的开发，如喷涂于门窗、皮具、玻璃、镜子等表面不形成白色斑点；也可用于制造透明、自然肤色的护肤、防晒产品；还有利于开发透明薄膜制品、透明耐用面漆、精细陶瓷等产品等。The nano-titanium dioxide product obtained in Example 1 is added to water to obtain a nano-titanium dioxide dispersion with a mass fraction of one thousandth. As shown in Figure 3, the dispersion has good monodispersity and can be formed in an aqueous solution. Stable colloidal dispersion, nano-particles are stably suspended, not agglomerated and not easy to settle, and the solution has not been delaminated for 3 months. The nano-titania obtained in Example 1 was dispersed in water to form an aqueous dispersion with a concentration of 5/10,000, and then the above-mentioned dispersion liquid was taken in a quartz cuvette with a thickness of 1 cm, and the UV-Vis absorption curve of the sample was tested. The dispersion can completely absorb ultraviolet light less than 380 nanometers, has strong ultraviolet absorption ability, and has good light transmittance in the visible light region greater than 400 nanometers, and the transmittance is more than 60%. Compared with the P25 nanometer titanium dioxide material, taking the wavelength of 550 nanometers as an example, the transparency of the product obtained in this example is increased by 40 times, which greatly expands the application of titanium dioxide materials in the fields of ultraviolet absorption and aesthetics. For example, the development of transparent coatings for No white spots are formed on the surfaces of doors and windows, leather goods, glass, mirrors, etc., and skin care and sunscreen products with transparent and natural skin tone are developed, and transparent film products, transparent durable topcoats, fine ceramics and other products are developed. To sum up, the advantages of the present invention are: (1) the technical synthesis is universal, the price is low, the technological process is simple, and it can be synthesized and applied on a large scale. (2) The synthesized titanium dioxide particles have uniform size and controllable particle size, and can spontaneously disperse in water to form a colloidal solution in which nano titanium dioxide particles are stably suspended. (3) The dispersion of this product has extremely high transparency and can be used for the development of transparent coating products, such as spraying on doors and windows, leather goods, glass, mirrors and other surfaces without forming white spots; it can also be used to make transparent and natural skin care, Sunscreen products; also conducive to the development of transparent film products, transparent durable topcoats, fine ceramics and other products.
实施例2Example 2
取10克三氯化钛液体缓慢滴加到100毫升水中，滴加完成后升温至50摄氏度并持续搅拌6小时，获得白色沉淀并离心分离，60摄氏度下干燥后获得钛氧氯固体粉末化合物；测定并控制上述钛氧氯固体粉末化合物中的含水率在百分之十；随后，将上述粉末放入反应釜中密封，后放入烘箱中于180摄氏度下加热8小时，获得二氧化钛产物。上述钛氧氯固体粉末化合物前驱物完全干燥后，在真空下，经能谱测定出主要成分为钛、氧、氯；其中氧与钛的个数比约为1.9，氯与钛的个数比约为0.1。Take 10 grams of titanium trichloride liquid and slowly drop it into 100 ml of water. After the addition is completed, the temperature is raised to 50 degrees Celsius and stirred continuously for 6 hours to obtain a white precipitate and centrifuged. After drying at 60 degrees Celsius, titanium oxychloride solid powder compound is obtained; Measure and control the moisture content in the above titanium oxychloride solid powder compound to be 10%; then, put the above powder in a reaction kettle to seal, and then put it in an oven and heat at 180 degrees Celsius for 8 hours to obtain a titanium dioxide product. After the above-mentioned titanium oxychloride solid powder compound precursor is completely dried, under vacuum, the main components are determined by energy spectrum as titanium, oxygen and chlorine; wherein the number ratio of oxygen to titanium is about 1.9, and the number ratio of chlorine to titanium is about 1.9. about 0.1.
取少量实施例2获得产物分散于去离子水中后取少量滴在硅片上，用于扫描电镜观察样品的形貌，可以看出产物二氧化钛纳米粒子为纳米棒形状，颗粒的长度为60至150纳米，颗粒的粒径主要为20至30纳米，均一度较好。X射线衍射证实本实施例2获得的纳米二氧化钛主要晶相为结晶性良好的金红石相。Take a small amount of the product obtained in Example 2 and disperse it in deionized water, then take a small amount and drop it on a silicon wafer for scanning electron microscopy to observe the morphology of the sample. It can be seen that the product titanium dioxide nanoparticles are in the shape of nanorods, and the length of the particles is 60 to 150. Nano, the particle size of the particles is mainly 20 to 30 nanometers, and the uniformity is better. X-ray diffraction confirmed that the main crystal phase of the nano-titania obtained in Example 2 was a rutile phase with good crystallinity.
将少量本实施例2获得的二氧化钛材料产物放入纯净水中，可以看到二氧化钛材料产物自发的“溶解”分散在纯净水中，形成纳米二氧化钛粒子稳定悬浮的胶体状水分散液，该分散液中纳米粒子悬浮稳定、不团聚，具有明显的丁达尔现象，分散液放置半个月也不会出现明显分层现象。将实施例2得到的纳米二氧化钛分散于水中，形成浓度为万分之五的水分散液，后取上述分散液体于1厘米厚的石英比色皿中，测试样品的紫外-可见光吸收曲线。该分散液可完全吸收小于380纳米的紫外光，紫外线吸收能力强，同时在大于400纳米的可见光区域具有很好的透光性，透光度大于百分之三十以上。同P25纳米二氧化钛材料相比，以550纳米波长为例，本实施例获得的产品透明度提高了20倍，拓展了二氧化钛材料在紫外吸收、美观等产品领域的添加应用，如开发透明涂料用于门窗、皮具、玻璃、镜子等表面不形成白色斑点，开发透明、自然肤色的护肤、防晒产品，开发透明薄膜制品、透明耐用面漆、精细陶瓷等产品等。Put a small amount of the titanium dioxide material product obtained in Example 2 into pure water, it can be seen that the titanium dioxide material product spontaneously "dissolves" and is dispersed in the pure water to form a colloidal water dispersion in which nano-scale titanium dioxide particles are stably suspended. The particles are stably suspended and do not agglomerate, with obvious Tyndall phenomenon, and the dispersion liquid will not appear obvious stratification if it is placed for half a month. The nano-titania obtained in Example 2 was dispersed in water to form an aqueous dispersion with a concentration of 5/10,000, and then the above-mentioned dispersion was taken in a 1 cm thick quartz cuvette to test the UV-Vis absorption curve of the sample. The dispersion can completely absorb ultraviolet light less than 380 nanometers, has strong ultraviolet absorption ability, and has good light transmittance in the visible light region greater than 400 nanometers, and the transmittance is more than 30%. Compared with the P25 nanometer titanium dioxide material, taking the wavelength of 550 nanometers as an example, the transparency of the product obtained in this example is increased by 20 times, which expands the application of titanium dioxide materials in the fields of ultraviolet absorption and aesthetics, such as the development of transparent coatings for doors and windows. , leather goods, glass, mirrors and other surfaces do not form white spots, develop skin care and sunscreen products with transparent and natural skin tone, develop transparent film products, transparent durable topcoats, fine ceramics and other products.
实施例3Example 3
按水和二氯化钛质量比为20:1的量，将水汽和二氯化钛气体混合，形成白色沉淀并离心分离，常温干燥后获得钛氧氯固体粉末化合物；测定并控制上述钛氧氯固体粉末化合物中的含水率在百分之五十；随后，将上述粉末放入反应釜中密封，后放入微波炉中于160摄氏度下微波加热3小时，获得二氧化钛产物。上述钛氧氯固体粉末化合物前驱物完全干燥后，在真空下，经能谱测定出主要成分为钛、氧、氯；其中氧与钛的个数比约为1.8，氯与钛的个数比约为0.2。According to the mass ratio of water and titanium dichloride to be 20:1, water vapor and titanium dichloride gas were mixed to form a white precipitate and centrifuged, and dried at room temperature to obtain a solid powder compound of titanium oxychloride; measure and control the above titanium oxygen The moisture content of the chlorine solid powder compound is 50%; then, the above powder is placed in a reaction kettle and sealed, and then placed in a microwave oven and heated in a microwave at 160 degrees Celsius for 3 hours to obtain a titanium dioxide product. After the above-mentioned titanium oxychloride solid powder compound precursor is completely dried, under vacuum, the main components are determined by energy spectrum as titanium, oxygen and chlorine; wherein the number ratio of oxygen to titanium is about 1.8, and the number ratio of chlorine to titanium is about 1.8. about 0.2.
取少量实施例3获得产物分散于去离子水中后取少量滴在硅片上，用于扫描电镜观察样品的形貌，可以看出产物二氧化钛纳米粒子为纳米棒形状，颗粒的长度为100至200纳米，颗粒的粒径主要为15至20纳米，均一度较好。X射线衍射证实本实施例2获得的纳米二氧化钛主要晶相为结晶性良好的金红石相。A small amount of the product obtained in Example 3 was dispersed in deionized water, and then a small amount was dropped on a silicon wafer for scanning electron microscopy to observe the morphology of the sample. It can be seen that the product titanium dioxide nanoparticles are in the shape of nanorods, and the length of the particles is 100 to 200 mm. Nano, the particle size of the particles is mainly 15 to 20 nanometers, and the uniformity is better. X-ray diffraction confirmed that the main crystal phase of the nano-titania obtained in Example 2 was a rutile phase with good crystallinity.
将少量本实施例3获得的二氧化钛材料产物放入纯净水中，可以看到二氧化钛材料产物自发的“溶解”分散在纯净水中，形成纳米二氧化钛粒子稳定悬浮的胶体状水分散液，该分散液中纳米粒子悬浮稳定、不团聚，具有明显的丁达尔现象，分散液放置1个月也不会出现明显分层现象。将实施例3得到的纳米二氧化钛分散于水中，形成浓度为万分之五的水分散液，后取上述分散液体于1厘米厚的石英比色皿中，测试样品的紫外-可见光吸收曲线。该分散液可完全吸收小于380纳米的紫外光，紫外线吸收能力强，同时在大于400纳米的可见光区域具有很好的透光性，透光度大于百分之四十以上。同P25纳米二氧化钛材料相比，以550纳米波长为例，本实施例获得的产品透明度提高了30倍，拓展了二氧化钛材料在紫外吸收、美观等产品领域的添加应用，如开发透明涂料用于门窗、皮具、玻璃、镜子等表面不形成白色斑点，开发透明、自然肤色的护肤、防晒产品，开发透明薄膜制品、透明耐用面漆、精细陶瓷等产品等。Put a small amount of the titanium dioxide material product obtained in Example 3 into pure water, it can be seen that the titanium dioxide material product spontaneously "dissolves" and is dispersed in the pure water to form a colloidal water dispersion in which nano-titanium dioxide particles are stably suspended. The particles are stably suspended and not agglomerated, with obvious Tyndall phenomenon, and the dispersion liquid will not appear obvious stratification after being placed for 1 month. The nano-titania obtained in Example 3 was dispersed in water to form an aqueous dispersion with a concentration of 5/10,000, and then the above-mentioned dispersion was taken in a 1 cm thick quartz cuvette to test the UV-Vis absorption curve of the sample. The dispersion can completely absorb ultraviolet light less than 380 nanometers, has strong ultraviolet absorption ability, and has good light transmittance in the visible light region greater than 400 nanometers, and the transmittance is more than 40%. Compared with the P25 nanometer titanium dioxide material, taking the wavelength of 550 nanometers as an example, the transparency of the product obtained in this example is increased by 30 times, which expands the application of titanium dioxide material in the fields of ultraviolet absorption and aesthetics, such as the development of transparent coatings for doors and windows. , leather goods, glass, mirrors and other surfaces do not form white spots, develop skin care and sunscreen products with transparent and natural skin tone, develop transparent film products, transparent durable topcoats, fine ceramics and other products.
实施例4Example 4
搅拌下，将10克钛酸四丁酯缓慢滴加到200毫升浓度为1摩尔每升的盐酸水溶液中，滴加后持续搅拌2小时，获得白色沉淀并离心分离，常温干燥后获得钛氧氯固体粉末化合物；测定并控制上述钛氧氯固体粉末化合物中的含水率在百分之四十；随后，将上述粉末放入反应釜中密封，后放入烘箱中于120摄氏度下加热24小时，获得二氧化钛产物。Under stirring, 10 grams of tetrabutyl titanate was slowly added dropwise to 200 ml of an aqueous hydrochloric acid solution with a concentration of 1 mol per liter. After the dropwise addition, stirring was continued for 2 hours to obtain a white precipitate and centrifuged. After drying at room temperature, titanium oxychloride was obtained. solid powder compound; measure and control the moisture content in the above-mentioned titanium oxychloride solid powder compound to be 40%; then, put the above-mentioned powder into a reaction kettle to seal, and then put it into an oven and heat it at 120 degrees Celsius for 24 hours, Titanium dioxide product is obtained.
上述钛氧氯固体粉末化合物前驱物完全干燥后，在真空下，经能谱测定出主要成分为为钛、氧、氯；其中氧与钛的个数比约为1.8，氯与钛的个数比约为0.18。After the above-mentioned titanium oxychloride solid powder compound precursor is completely dried, under vacuum, the main components are determined by energy spectrum to be titanium, oxygen and chlorine; wherein the number ratio of oxygen to titanium is about 1.8, and the number of chlorine and titanium is about 1.8. The ratio is about 0.18.
取少量实施例4获得产物分散于去离子水中后取少量滴在硅片上，自然晾干，将晾 干后的硅片用导电胶粘附在扫描电镜的样品台上，用于扫描电镜观察样品的形貌，如图4所示。从图4可以看出产物二氧化钛纳米粒子的粒径为5纳米至10纳米，进而说明本实施例获得的纳米二氧化钛具有小的粒径，单分散性较好。A small amount of the product obtained in Example 4 was dispersed in deionized water, and then a small amount was dropped on the silicon wafer, dried naturally, and the dried silicon wafer was adhered to the sample stage of the scanning electron microscope with a conductive adhesive for the observation of the scanning electron microscope. The morphology of the sample is shown in Figure 4. It can be seen from FIG. 4 that the particle size of the product titanium dioxide nanoparticles is 5 nanometers to 10 nanometers, which further indicates that the nano titanium dioxide obtained in this example has a small particle size and good monodispersity.
本实施例制得的纳米二氧化钛主要晶相为锐钛矿相，具有较好的结晶性。将本实施例得到的纳米二氧化钛产物加入到水中，获得质量分数为千分之五的纳米二氧化钛分散液，该分散液具有很好的单分散性，在水溶液中可以形成稳定的胶体状分散液，纳米粒子悬浮稳定、不团聚也不易沉降，放置6个月以上溶液未发生分层现象。The main crystal phase of the nano-titanium dioxide prepared in this example is anatase phase, which has good crystallinity. The nano-titanium dioxide product obtained in this example is added to water to obtain a nano-titanium dioxide dispersion with a mass fraction of 5/1000. The dispersion has good monodispersity and can form a stable colloidal dispersion in an aqueous solution. Nanoparticles are stable in suspension, do not agglomerate and are not easy to settle, and the solution has not been delaminated for more than 6 months.
本实施例获得纳米二氧化钛材料具有很好的光催化活性，催化效率是商业P25材料的8倍，具体的比较方式为，分别称取本实施例1获得的产物和P25(德固萨)样品2克分散于100毫升浓度为2.0×10-5摩尔每升的罗丹明B溶液中，放置在暗处磁搅拌30分钟，使其达到温度平衡和吸附平衡。后开启模拟太阳光灯，搅拌，每隔固定时间取出3毫升样品，离心分离颗粒，用紫外-可见光谱仪在550纳米处测量溶液的吸光度，计算罗丹明B的剩余浓度。The nano-titania material obtained in this example has good photocatalytic activity, and the catalytic efficiency is 8 times that of commercial P25 material. The specific comparison method is to weigh the product obtained in this example 1 and P25 (Degussa) sample 2 respectively. g was dispersed in 100 ml of Rhodamine B solution with a concentration of 2.0 × 10-5 moles per liter, and was placed in a dark place with magnetic stirring for 30 minutes to achieve temperature equilibrium and adsorption equilibrium. Then turn on the simulated sunlight lamp, stir, take out 3 ml of samples at regular intervals, separate the particles by centrifugation, measure the absorbance of the solution at 550 nm with a UV-Vis spectrometer, and calculate the remaining concentration of Rhodamine B.
实施例5Example 5
搅拌下，将10克异丙醇钛缓慢滴加到200毫升浓度为0.5摩尔每升的盐酸水溶液中，滴加后持续搅拌2小时，获得白色沉淀并离心分离，常温干燥后获得钛氧氯固体粉末化合物；测定并控制上述钛氧氯固体粉末化合物中的含水率在百分之三十；随后，将上述粉末放入反应釜中密封，后置于油浴中于160摄氏度下加热20小时，获得二氧化钛产物。上述钛氧氯固体粉末化合物前驱物完全干燥后，在真空下，经能谱测定出主要成分为钛、氧、氯；其中氧与钛的个数比约为2.0，氯与钛的个数比约为0.12。Under stirring, 10 grams of titanium isopropoxide was slowly added dropwise to 200 milliliters of aqueous hydrochloric acid with a concentration of 0.5 mol per liter. After the dropwise addition, stirring was continued for 2 hours to obtain a white precipitate and centrifuged. After drying at room temperature, a solid titanium oxychloride was obtained. powder compound; measure and control the water content in the above-mentioned titanium oxychloride solid powder compound to be 30%; then, put the above-mentioned powder into a reaction kettle to seal, and then place it in an oil bath and heat at 160 degrees Celsius for 20 hours, Titanium dioxide product is obtained. After the above-mentioned titanium oxychloride solid powder compound precursor is completely dried, under vacuum, the main components are determined by energy spectrum to be titanium, oxygen and chlorine; wherein the number ratio of oxygen to titanium is about 2.0, and the number ratio of chlorine to titanium is about 2.0. about 0.12.
取少量实施例5获得产物分散于去离子水中后取少量滴在硅片上，用于扫描电镜观察样品的形貌，可以看出产物二氧化钛纳米粒子的粒径为8纳米至20纳米，进而说明本实施例获得的纳米二氧化钛具有小的粒径，单分散性较好。X射线衍射证实本实施例5获得的纳米二氧化钛主要晶相为结晶性良好的锐钛矿相。A small amount of the product obtained in Example 5 was dispersed in deionized water, and then a small amount was dropped on a silicon wafer for scanning electron microscopy to observe the morphology of the sample. It can be seen that the particle size of the product titanium dioxide nanoparticles is 8 nanometers to 20 nanometers. The nano-titanium dioxide obtained in this example has a small particle size and good monodispersity. X-ray diffraction confirmed that the main crystal phase of the nano-titania obtained in Example 5 was anatase phase with good crystallinity.
将少量本实施例5获得的二氧化钛材料产物放入纯净水中，可以看到二氧化钛材料产物自发的“溶解”分散在纯净水中，形成纳米二氧化钛粒子稳定悬浮的胶体状水分散液，该分散液中纳米粒子悬浮稳定、不团聚，具有明显的丁达尔现象，分散液放置8个月也不会出现明显分层现象。将实施例5得到的纳米二氧化钛分散于水中，形成浓度为万分之五的水分散液，后取上述分散液体于1厘米厚的石英比色皿中，测试样品的紫外-可见光吸收曲线。该分散液可完全吸收小于370纳米的紫外光，紫外线吸收能力强，同 时在大于400纳米的可见光区域具有很好的透光性，透光度大于百分之九十以上。同P25纳米二氧化钛材料相比，以550纳米波长为例，本实施例获得的产品透明度提高了60倍，拓展了二氧化钛材料在紫外吸收、美观等产品领域的添加应用，如开发透明涂料用于门窗、皮具、玻璃、镜子等表面不形成白色斑点，开发透明、自然肤色的护肤、防晒产品，开发透明薄膜制品、透明耐用面漆、精细陶瓷等产品等。Put a small amount of the titanium dioxide material product obtained in Example 5 into pure water, it can be seen that the titanium dioxide material product spontaneously "dissolves" and is dispersed in the pure water to form a colloidal water dispersion in which the nanometer titanium dioxide particles are stably suspended. The particles have stable suspension and no agglomeration, with obvious Tyndall phenomenon, and the dispersion liquid will not appear obvious layering phenomenon after being placed for 8 months. The nano-titania obtained in Example 5 was dispersed in water to form an aqueous dispersion with a concentration of 5/10,000, and then the above-mentioned dispersion was taken in a 1 cm thick quartz cuvette to test the UV-Vis absorption curve of the sample. The dispersion can completely absorb ultraviolet light less than 370 nanometers, has strong ultraviolet absorption capacity, and has good light transmittance in the visible light region greater than 400 nanometers, and the transmittance is more than 90%. Compared with the P25 nanometer titanium dioxide material, taking the wavelength of 550 nanometers as an example, the transparency of the product obtained in this example is increased by 60 times, which expands the application of titanium dioxide material in the fields of ultraviolet absorption and aesthetics, such as the development of transparent coatings for doors and windows. , leather goods, glass, mirrors and other surfaces do not form white spots, develop skin care and sunscreen products with transparent and natural skin tone, develop transparent film products, transparent durable topcoats, fine ceramics and other products.
本实施例5获得纳米二氧化钛材料具有很好的光催化活性，催化效率是商业P25材料的9倍，具体的比较方式如实施例4所述。The nano-titania material obtained in Example 5 has good photocatalytic activity, and the catalytic efficiency is 9 times that of the commercial P25 material. The specific comparison method is as described in Example 4.
实施例6Example 6
取2克偏钛酸，分散于50毫升浓度为1摩尔每升的盐酸水溶液中，后升温至50摄氏度并持续搅拌24小时，分离产物，50摄氏度下干燥后获得钛氧氯固体粉末化合物；测定并控制上述钛氧氯固体粉末化合物中的含水率在百分之三十；随后，将上述粉末放入反应釜中密封，后置于微波炉中于140摄氏度下微波加热5小时，获得二氧化钛产物。上述钛氧氯固体粉末化合物前驱物完全干燥后，在真空下，经能谱测定出主要成分为钛、氧、氯；其中氧与钛的个数比约为2.1，氯与钛的个数比约为0.14。Take 2 grams of metatitanic acid, disperse it in 50 milliliters of aqueous hydrochloric acid with a concentration of 1 mole per liter, then heat up to 50 degrees Celsius and continue to stir for 24 hours, separate the product, and dry it at 50 degrees Celsius to obtain a titanium oxychloride solid powder compound; determine And control the water content in the above titanium oxychloride solid powder compound to be 30%; then, put the above powder in a reaction kettle to seal, and then place it in a microwave oven and microwave at 140 degrees Celsius for 5 hours to obtain a titanium dioxide product. After the above-mentioned titanium oxychloride solid powder compound precursor is completely dried, under vacuum, the main components are determined by energy spectrum to be titanium, oxygen and chlorine; wherein the number ratio of oxygen to titanium is about 2.1, and the number ratio of chlorine to titanium is about 2.1. about 0.14.
取少量实施例6获得产物分散于去离子水中后取少量滴在硅片上，用于扫描电镜观察样品的形貌，可以看出产物二氧化钛纳米粒子的粒径为20纳米至50纳米，进而说明本实施例获得的纳米二氧化钛具有小的粒径，单分散性较好。X射线衍射证实本实施例6获得的纳米二氧化钛主要晶相为结晶性良好的锐钛矿相，含有微量的金红石晶相。A small amount of the product obtained in Example 6 was dispersed in deionized water, and then a small amount was dropped on a silicon wafer for scanning electron microscopy to observe the morphology of the sample. It can be seen that the particle size of the product titanium dioxide nanoparticles is 20 nanometers to 50 nanometers. The nano-titanium dioxide obtained in this example has a small particle size and good monodispersity. X-ray diffraction confirmed that the main crystal phase of the nano-titania obtained in Example 6 was anatase phase with good crystallinity, and contained a trace amount of rutile crystal phase.
将少量本实施例6获得的二氧化钛材料产物放入纯净水中，可以看到二氧化钛材料产物自发的“溶解”分散在纯净水中，形成纳米二氧化钛粒子稳定悬浮的胶体状水分散液，该分散液中纳米粒子悬浮稳定、不团聚，具有明显的丁达尔现象，分散液放置3个月也不会出现明显分层现象。将实施例6得到的纳米二氧化钛分散于水中，形成浓度为万分之五的水分散液，后取上述分散液体于1厘米厚的石英比色皿中，测试样品的紫外-可见光吸收曲线。该分散液可完全吸收小于370纳米的紫外光，紫外线吸收能力强，同时在大于400纳米的可见光区域具有很好的透光性，透光度大于百分之七十以上。同P25纳米二氧化钛材料相比，以550纳米波长为例，本实施例获得的产品透明度提高了45倍，拓展了二氧化钛材料在紫外吸收、美观等产品领域的添加应用，如开发透明涂料用于门窗、皮具、玻璃、镜子等表面不形成白色斑点，开发透明、自然肤色的护肤、防晒产品，开发透明薄膜制品、透明耐用面漆、精细陶瓷等产品等。Put a small amount of the titanium dioxide material product obtained in Example 6 into pure water, it can be seen that the titanium dioxide material product is spontaneously "dissolved" and dispersed in the pure water, forming a colloidal water dispersion in which nano titanium dioxide particles are stably suspended. The particles have stable suspension and no agglomeration, with obvious Tyndall phenomenon, and the dispersion liquid will not appear obvious stratification after being placed for 3 months. The nano-titania obtained in Example 6 was dispersed in water to form an aqueous dispersion with a concentration of 5/10,000, and then the above-mentioned dispersion was taken in a 1 cm thick quartz cuvette to test the UV-Vis absorption curve of the sample. The dispersion liquid can completely absorb ultraviolet light less than 370 nanometers, has strong ultraviolet absorption ability, and has good light transmittance in the visible light region greater than 400 nanometers, and the transmittance is more than 70%. Compared with the P25 nanometer titanium dioxide material, taking the wavelength of 550 nanometers as an example, the transparency of the product obtained in this example is increased by 45 times, which expands the application of titanium dioxide material in the fields of ultraviolet absorption and aesthetics, such as the development of transparent coatings for doors and windows. , leather goods, glass, mirrors and other surfaces do not form white spots, develop skin care and sunscreen products with transparent and natural skin tone, develop transparent film products, transparent durable topcoats, fine ceramics and other products.
本实施例6获得纳米二氧化钛材料具有很好的光催化活性，催化效率是商业P25材 料的7.3倍，具体的比较方式如实施例4所述。The nano-titania material obtained in Example 6 has good photocatalytic activity, and the catalytic efficiency is 7.3 times that of the commercial P25 material. The specific comparison method is as described in Example 4.
对比例1Comparative Example 1
取10克四氯化钛液体缓慢滴加到200毫升水中，滴加后持续搅拌7天，获得白色沉淀并离心分离，常温干燥后获得钛氧氯固体粉末化合物；测定并控制上述钛氧氯固体粉末化合物中的含水率在百分之九十，获得泥浆状钛氧氯固体悬浊液；随后，将上述钛氧氯固体悬浊液放入反应釜中密封，后放入烘箱中于140摄氏度下加热20小时，获得二氧化钛产物。上述钛氧氯固体粉末化合物前驱物完全干燥后，在真空下，经能谱测定出主要成分为钛、氧、氯；其中氧与钛的个数比约为2.1，氯与钛的个数比约为0.16。本对比例获得产物中含有大量的花瓣状大颗粒，如扫描电镜图5所示；同时产品无法分散在水中形成稳定、透明的分散液，得到的产物为悬浊液体，几个小时内便会出现沉淀分层；此外，本对比产物为金红石相，光催化性能不佳。本对比例在产物形貌、分散性、晶相、催化效率等结构、性能上均无法获得实施例产物的发明效果。Take 10 grams of titanium tetrachloride liquid and slowly drop it into 200 ml of water, continue to stir for 7 days after the dropwise addition, obtain a white precipitate and centrifuge, and dry at room temperature to obtain a titanium oxychloride solid powder compound; measure and control the above titanium oxychloride solid The moisture content in the powder compound is 90%, and a mud-like titanium oxychloride solid suspension is obtained; then, the above-mentioned titanium oxychloride solid suspension is placed in a reaction kettle to seal, and then placed in an oven at 140 degrees Celsius Under heating for 20 hours, a titanium dioxide product was obtained. After the above-mentioned titanium oxychloride solid powder compound precursor is completely dried, under vacuum, the main components are determined by energy spectrum to be titanium, oxygen and chlorine; wherein the number ratio of oxygen to titanium is about 2.1, and the number ratio of chlorine to titanium is about 2.1. about 0.16. The product obtained in this comparative example contains a large number of large petal-shaped particles, as shown in Fig. 5 of the scanning electron microscope; at the same time, the product cannot be dispersed in water to form a stable and transparent dispersion, and the obtained product is a suspension liquid, which will disappear within a few hours. Precipitation and stratification occurred; in addition, the comparative product was in the rutile phase, and the photocatalytic performance was poor. In this comparative example, the invention effect of the product of the embodiment cannot be obtained in terms of product morphology, dispersibility, crystal phase, catalytic efficiency and other structures and properties.
对比例2Comparative Example 2
取10克四氯化钛液体缓慢滴加到200毫升水中，滴加后持续搅拌7天，获得白色沉淀并离心分离，经多次洗涤分离，后经常温干燥获得钛氧固体粉末化合物；测定并控制上述钛氧固体粉末化合物中的含水率在百分之二十；随后，将上述粉末放入反应釜中密封，后放入烘箱中于140摄氏度下加热20小时，获得二氧化钛产物。上述钛氧氯固体粉末化合物前驱物完全干燥后，在真空下，经能谱测定出主要成分为钛、氧；其中氧与钛的个数比约为2.0，氯与钛的个数比小于0.01。本对比例获得产物中含有大量的花瓣状大颗粒；同时产品无法分散在水中形成稳定、透明的分散液，得到的产物为悬浊液体，几个小时内便会出现沉淀分层。本对比例在产物形貌、分散性等结构、性能上均无法获得实施例产物的发明效果。Take 10 grams of titanium tetrachloride liquid and slowly drop it into 200 ml of water, and continue to stir for 7 days after the dropwise addition to obtain a white precipitate and centrifuge it. The moisture content in the above titanium oxide solid powder compound is controlled to be 20%; then, the above powder is placed in a reactor to seal, and then placed in an oven and heated at 140 degrees Celsius for 20 hours to obtain a titanium dioxide product. After the above-mentioned titanium oxychloride solid powder compound precursor is completely dried, under vacuum, the main components are determined by energy spectrum to be titanium and oxygen; wherein the number ratio of oxygen to titanium is about 2.0, and the number ratio of chlorine to titanium is less than 0.01 . The product obtained in this comparative example contains a large number of large petal-shaped particles; at the same time, the product cannot be dispersed in water to form a stable and transparent dispersion, and the obtained product is a suspension liquid, and precipitation and stratification will appear within a few hours. In this comparative example, the invention effect of the product of the embodiment cannot be obtained in terms of product morphology, dispersibility and other structures and properties.
本文引用的任何数值都包括从下限值到上限值之间以一个单位递增的下值和上值的所有值，在任何下值和任何更高值之间存在至少两个单位的间隔即可。举例来说，如果阐述了一个部件的数量或过程变量(例如温度、压力、时间等)的值是从1到90，优选从20到80，更优选从30到70，则目的是为了说明该说明书中也明确地列举了诸如15到85、22到68、43到51、30到32等值。对于小于1的值，适当地认为一个单位是0.0001、0.001、0.01、0.1。这些仅仅是想要明确表达的示例，可以认为在最低值和最高值之间列举的数值的所有可能组合都是以类似方式在该说明书明确地阐述了的。Any numerical value recited herein includes all values of the lower value and the upper value in one unit increments from the lower value to the upper value, where there is an interval of at least two units between any lower value and any higher value, i.e. Can. For example, if the number of components or process variables (eg, temperature, pressure, time, etc.) are stated to have values from 1 to 90, preferably from 20 to 80, more preferably from 30 to 70, the intent is to illustrate that the The specification also explicitly lists values such as 15 to 85, 22 to 68, 43 to 51, 30 to 32, and the like. For values less than 1, one unit is appropriately considered to be 0.0001, 0.001, 0.01, 0.1. These are merely examples of what is intended to be express, and all possible combinations of numerical values recited between the lowest value and the highest value are considered to be expressly set forth in this specification in a similar fashion.
除非另有说明，所有范围都包括端点以及端点之间的所有数字。与范围一起使用的 “大约”或“近似”适合于该范围的两个端点。因而，“大约20到30”旨在覆盖“大约20到大约30”，至少包括指明的端点。Unless otherwise stated, all ranges include the endpoints and all numbers between the endpoints. "About" or "approximately" used with a range applies to both endpoints of the range. Thus, "about 20 to 30" is intended to cover "about 20 to about 30," including at least the indicated endpoints.
应该理解，以上描述是为了进行图示说明而不是为了进行限制。通过阅读上述描述，在所提供的示例之外的许多实施方式和许多应用对本领域技术人员来说都将是显而易见的。因此，本教导的范围不应该参照上述描述来确定，而是应该参照所附权利要求以及这些权利要求所拥有的等价物的全部范围来确定。出于全面之目的，所有文章和参考包括专利申请和公告的公开都通过参考结合在本文中。在前述权利要求中省略这里公开的主题的任何方面并不是为了放弃该主体内容，也不应该认为发明人没有将该主题考虑为所公开的发明主题的一部分。It should be understood that the above description is for purposes of illustration and not limitation. From reading the above description, many embodiments and many applications beyond the examples provided will be apparent to those skilled in the art. The scope of the present teachings should, therefore, be determined not with reference to the above description, but should instead be determined with reference to the appended claims, along with the full scope of equivalents to which such claims are entitled. The disclosures of all articles and references, including patent applications and publications, are incorporated herein by reference for the purpose of being comprehensive. The omission of any aspect of the subject matter disclosed herein in the preceding claims is not intended to disclaim such subject matter, nor should it be construed that the inventor did not consider such subject matter to be part of the disclosed subject matter.

Claims (10)

  1. 一种二氧化钛材料的制备方法，其特征在于，包括如下步骤：A method for preparing a titanium dioxide material, comprising the steps of:
    (1)制备钛氧氯固体粉末化合物；(1) prepare titanyl chloride solid powder compound;
    (2)将步骤(1)中所述的钛氧氯固体粉末化合物的含水率控制在水的质量分数为百分之一到百分之五十；优选的水的质量分数为百分之五到百分之三十；(2) The moisture content of the titanium oxychloride solid powder compound described in the step (1) is controlled to be 1% to 50% by mass fraction of water; the preferred mass fraction of water is 5% to thirty percent;
    (3)将步骤(2)中所述的钛氧氯固体粉末化合物在密闭环境中低温加热，获得二氧化钛材料。(3) The titanium oxychloride solid powder compound described in the step (2) is heated at a low temperature in a closed environment to obtain a titanium dioxide material.
  2. 如权利要求1所述的一种二氧化钛材料的制备方法，其特征在于：所述二氧化钛材料为在水中可自发分散形成纳米二氧化钛粒子稳定悬浮的胶体溶液；所述纳米二氧化钛粒子为结晶性纳米二氧化钛粒子。The method for preparing a titanium dioxide material according to claim 1, wherein the titanium dioxide material is a colloidal solution that can spontaneously disperse in water to form a stable suspension of nano-titanium dioxide particles; the nano-titanium dioxide particles are crystalline nano-titanium dioxide particles .
  3. 如权利要求1所述的一种二氧化钛材料的制备方法，其特征在于：所述钛氧氯固体粉末化合物的化学式为TiOxCly；其中，所述x值为1.7至2.3；所述y值为0.01至0.5。The method for preparing a titanium dioxide material according to claim 1, wherein the chemical formula of the titanium oxychloride solid powder compound is TiOxCly; wherein the x value is 1.7 to 2.3; the y value is 0.01 to 0.5.
  4. 如权利要求1所述的一种二氧化钛材料的制备方法，其特征在于：步骤(1)中所述钛氧氯固体粉末化合物中还含有氢；所述钛氧氯固体粉末化合物含有的氢与钛的个数比为1:100至1:10。The method for preparing a titanium dioxide material according to claim 1, characterized in that: in step (1), the titanium oxychloride solid powder compound further contains hydrogen; the titanium oxychloride solid powder compound contains hydrogen and titanium The number ratio is 1:100 to 1:10.
  5. 如权利要求1所述的一种二氧化钛材料的制备方法，其特征在于：步骤(1)中所述钛氧氯固体粉末化合物中，氧与钛的个数比为1.8至2.2。The method for preparing a titanium dioxide material according to claim 1, wherein in the titanium oxychloride solid powder compound in step (1), the number ratio of oxygen to titanium is 1.8 to 2.2.
  6. 如权利要求1所述的一种二氧化钛材料的制备方法，其特征在于：步骤(1)中所述钛氧氯固体粉末化合物中，氯与钛的个数比为0.03至0.2。The method for preparing a titanium dioxide material according to claim 1, wherein in the titanium oxychloride solid powder compound in the step (1), the number ratio of chlorine to titanium is 0.03 to 0.2.
  7. 如权利要求1所述的一种二氧化钛材料的制备方法，其特征在于：步骤(3)中所述低温加热的温度为100摄氏度至200摄氏度；所述低温加热的时间为2小时至24小时。The method for preparing a titanium dioxide material according to claim 1, wherein the temperature of the low-temperature heating in step (3) is 100 degrees Celsius to 200 degrees Celsius; and the time of the low-temperature heating is 2 hours to 24 hours.
  8. 如权利要求1所述的一种二氧化钛材料的制备方法，其特征在于：步骤(1)中所述钛氧氯固体粉末化合物的制备由氯化钛与水或水汽接触后获得；所述氯化钛选自四氯化钛、四氯化钛水溶液、三氯化钛、二氯化钛中的一种或者几种的组合。The method for preparing a titanium dioxide material according to claim 1, wherein the preparation of the titanium oxychloride solid powder compound in step (1) is obtained by contacting titanium chloride with water or water vapor; Titanium is selected from one or a combination of titanium tetrachloride, titanium tetrachloride aqueous solution, titanium trichloride, and titanium dichloride.
  9. 如权利要求1所述的一种二氧化钛材料的制备方法，其特征在于：步骤(1)中所述钛氧氯固体粉末化合物的制备由钛醇盐在含有盐酸的水溶液中直接水解获得。The method for preparing a titanium dioxide material according to claim 1, wherein the preparation of the titanium oxychloride solid powder compound in step (1) is obtained by direct hydrolysis of titanium alkoxide in an aqueous solution containing hydrochloric acid.
  10. 如权利要求1所述的一种二氧化钛材料的制备方法，其特征在于：步骤(1)中所述钛氧氯固体粉末化合物的制备由钛氧化合物与盐酸、盐酸溶液、氯气、氯气溶液 中的一种或几种的组合进行反应获得；所述钛氧化合物选自低结晶性二氧化钛、无定型二氧化钛、钛酸、亚氧化钛、一氧化钛、偏钛酸、氢氧化钛、水合钛酸中的一种或者几种的组合。The method for preparing a titanium dioxide material according to claim 1, characterized in that: the preparation of the titanium oxychloride solid powder compound described in the step (1) is composed of titanium oxychloride and hydrochloric acid, hydrochloric acid solution, chlorine gas, and chlorine gas solution. One or more combinations are obtained by reaction; the titanium oxide compound is selected from low-crystalline titanium dioxide, amorphous titanium dioxide, titanic acid, titanium oxide, titanium monoxide, metatitanic acid, titanium hydroxide, and hydrated titanic acid. one or a combination of several.
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