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CN112374523A - Preparation method of nano cerium oxide with strong ultraviolet ray shielding performance - Google Patents

Preparation method of nano cerium oxide with strong ultraviolet ray shielding performance Download PDF

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CN112374523A
CN112374523A CN202011207340.3A CN202011207340A CN112374523A CN 112374523 A CN112374523 A CN 112374523A CN 202011207340 A CN202011207340 A CN 202011207340A CN 112374523 A CN112374523 A CN 112374523A
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cerium oxide
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hydrogen peroxide
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杨应亚
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Changzhou Geoquin Nano New Materials Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F17/00—Compounds of rare earth metals
    • C01F17/20—Compounds containing only rare earth metals as the metal element
    • C01F17/206—Compounds containing only rare earth metals as the metal element oxide or hydroxide being the only anion
    • C01F17/224—Oxides or hydroxides of lanthanides
    • C01F17/235—Cerium oxides or hydroxides
    • 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
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    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
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    • C01P2004/51—Particles with a specific particle size distribution
    • C01P2004/52—Particles with a specific particle size distribution highly monodisperse size distribution
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    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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    • C01—INORGANIC CHEMISTRY
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    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/22—Rheological behaviour as dispersion, e.g. viscosity, sedimentation stability

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Abstract

The invention belongs to the technical field of preparation of rare earth compounds, and particularly relates to a preparation method of nano cerium oxide with strong ultraviolet ray shielding performance. By precipitation, Ca is added to cerium solution2+Precipitating with alkaline precipitant, adding anionic surfactant as additive to precipitate rare earth ions, oxidizing, washing with water, washing with alcohol, drying, firing, and jet pulverizing to obtain nanometer cerium oxide doped with Ca with ultraviolet shielding property2+The primary particle size is 10-30nm, the particle size distribution is uniform, the dispersion time in water is up to 30 days, no sedimentation exists, and the solid content is large. The invention has the advantages of simple process conditions, low production cost and easy realization of industrial production, and the whole process meets the environmental protection requirements.

Description

Preparation method of nano cerium oxide with strong ultraviolet ray shielding performance
Technical Field
The invention belongs to the technical field of preparation of rare earth compounds, and particularly relates to a preparation method of nano cerium oxide with strong ultraviolet ray shielding performance.
Background
In recent years, ultraviolet resistant products have been rapidly developed due to the high ability of ultraviolet rays to damage skin. The anti-ultraviolet agent mainly used at present comprises TiO, ZnO and CeO 2And the like, wherein TiO has a larger refractive index, ZnO has a larger forbidden band width, both of which have better ultraviolet ray shielding capability, and CeO2The refractive index and the forbidden band width of the film are both larger, so that the ultraviolet shielding capability of the film is better than that of TiO and ZnO. Therefore, the development of cerium-based functional materials is of great significance.
Nano cerium oxideHas stronger ultraviolet absorption performance and good visible light absorption, but because the pure nano cerium oxide has stronger oxidation catalytic activity, the Ce is easy to be led to4+Conversion to Ce3+Limiting its use.
Patent No. CN103013180B discloses a nano ultraviolet-resistant microcapsule and a preparation method thereof, which only performs a surface treatment on nano cerium oxide to improve its dispersibility, thereby improving the ultraviolet resistance. The dispersion of the treated nano cerium oxide in water is stable for about 10 days, and the solid content is low.
Disclosure of Invention
During the precipitation, certain amount of calcium chloride solution is first added into cerium chloride solution to make CeO precipitate2Ce in (1)4+More stable, thereby reducing the oxidation catalytic activity of the catalyst and improving the ultraviolet shielding performance of the catalyst. The dispersant is washed by alcohol and added in the preparation process, so that the self dispersibility of the powder is good, the primary particle size is lower and is 10-30nm, the powder can be directly depolymerized only by simple airflow crushing without complicated subsequent links such as ultrasonic treatment, emulsification and the like, the dispersion effect in water is very good, the powder can be kept in a stable state for about 30 days without sedimentation, the particle size of the crushed nano cerium oxide measured by a Malvern laser particle sizer is 1-1.2um, and the distribution interval is narrow, so that the nano cerium oxide doped with Ca has very strong ultraviolet shielding performance.
The specific process comprises the following steps:
(1) preparing a cerium chloride solution with the concentration of 0.2-0.8mol/l by taking rare earth cerium chloride as a raw material;
(2) adding a calcium chloride solution into the cerium chloride solution, uniformly mixing, adding an anionic surfactant, and uniformly stirring;
the adding amount of the calcium chloride is 5-8% of the mass of the metered cerium oxide, and the adding amount of the anionic surfactant is 2-5% of the mass of the metered cerium oxide; the anionic surfactant is sodium dodecyl benzene sulfonate or sodium dodecyl sulfate.
(3) Preparing a precipitator into a precipitator solution with the concentration of 1.0-3.0mol/l, then dropwise adding the precipitator solution into the rare earth cerium chloride solution obtained in the step (2), controlling the PH of the precipitate to be 10-12 after dropwise adding, and dropwise adding hydrogen peroxide to oxidize the precipitate.
Wherein, the precipitant comprises: sodium carbonate, sodium bicarbonate, sodium hydroxide, and the like;
the metered cerium oxide and the precipitating agent are as follows according to the molar ratio: 1:3-4.5, and carrying out coprecipitation;
the bottom water is pure water;
dropwise adding equipment: diaphragm pump, dropping speed: 120-150ml/min, ensuring the dropping constant speed.
The molar ratio of the cerium oxide to the hydrogen peroxide is 1:0.5-1.5, the concentration of the hydrogen peroxide is 2-5mol/l, and the dropping speed is 30-50 ml/min.
(4) Stirring for 1h after the hydrogen peroxide is added, aging for 2h, performing suction filtration and water washing until no precipitate is generated in the wastewater after the wastewater is titrated with silver nitrate, and performing alcohol washing with ethanol to completely replace free water in the precipitate.
Wherein, the water washing temperature is as follows: 50-80 deg.C
(5) And (4) pumping the slurry obtained in the step (4) to dryness, adding n-butanol accounting for 1-3% of the total mass of the cerium oxide, fully stirring, drying, firing to obtain Ca-doped nano cerium oxide, and then carrying out jet milling.
The drying temperature is 90-120 ℃, the firing temperature is 600-750 ℃, the firing heat preservation time is 1-3 hours, and the primary particle size measured by a scanning electron microscope is as follows: 10-30nm, spherical shape, uniform size, good dispersion, particle diameter of 1-1.2um measured by Malvern 2000, and narrow distribution interval. 10g of cerium oxide powder is added into 6L of pure water, stirred for 0.5h and then kept stand, the powder is uniformly dispersed in water, and a small amount of precipitate appears after about 30 days.
Advantageous effects
1. After Ca is doped in nano cerium oxide, CeO is made2Ce in (1)4+Is more stable and not easy to be converted into Ce3+Reacting CeO2The oxidation catalytic activity of (2) is lowered, the forbidden band width is narrowed, and the ultraviolet absorption performance and the visible light transmittance are enhanced.
2. The Ca-doped nano cerium oxide prepared by the coprecipitation method has small and uniform particles.
3. By alcohol washing, the Ce (OH) is added3Removing free water in the cerium oxide powder, using n-butanol as final dispersant to improve the dispersibility of the cerium oxide nanoparticles and reduce particle agglomeration, and directly using jet milling to depolymerize the cerium oxide nanoparticles, wherein the particle size of the depolymerized cerium oxide powder is smaller than that of the surface-treated cerium oxide powder, the distribution is narrower, the particle size is 1-1.2um, the dispersion effect in water is better, the cerium oxide nanoparticles do not settle in about 30 days, and the solid content is higher and is 15-20%
Drawings
FIG. 1 shows the calcium-doped nano-CeO of example 12SEM picture of (1);
FIG. 2 shows the calcium-doped CeO nanoparticles of example 12A particle size map of (a);
FIG. 3 shows comparative example 1 calcium-doped nano-CeO2A particle size map of (a);
FIG. 4 shows the calcium-doped nano-CeO of example 12A photograph of the dispersibility of the powder uniformly dispersed in water for 30 days;
FIG. 5 comparative example 4 calcium-doped nano-CeO2Photograph of dispersibility of the powder uniformly dispersed in water for 5 days.
Detailed Description
The present invention is further described below with reference to examples, but is not limited thereto.
Example 1
(1) Preparing a cerium chloride solution with the concentration of 0.6mol/l by taking rare earth cerium chloride as a raw material;
(2) adding a calcium chloride solution with the concentration of 0.2mol/l accounting for 6 percent of the mass of the cerium oxide into the cerium chloride solution, uniformly mixing, adding sodium dodecyl sulfate accounting for 4 percent of the mass of the cerium oxide, and uniformly stirring.
(3) Preparing sodium carbonate into a precipitator solution with the concentration of 2.0mol/l, dropwise adding the solution into the rare earth calcium cerium chloride solution obtained in the step (2) at the speed of 140ml/min by using a diaphragm pump, controlling the pH of the precipitate to be 10-12 after dropwise adding, and dropwise adding hydrogen peroxide with the concentration of 4mol/l at the speed of 40ml/min to oxidize the precipitate.
Wherein the molar ratio of the metered cerium oxide to the precipitating agent is as follows: 1:4, wherein the molar ratio of the metered cerium oxide to the hydrogen peroxide is 1: 1.
(4) After the dropwise addition of the hydrogen peroxide, stirring for 1h, aging for 2h, performing suction filtration and washing, wherein the washing temperature is as follows: washing at 60 deg.C until the waste water is titrated with silver nitrate and no precipitate is formed, washing with ethanol, and replacing the free water in the precipitate.
(5) And (4) pumping the slurry obtained in the step (4) to dryness, adding n-butanol accounting for 2% of the total amount of the cerium oxide, fully stirring, drying at 100 ℃, keeping the temperature at 700 ℃ and firing for 2 hours to obtain Ca-doped nano cerium oxide, and then carrying out jet milling.
The primary particle size measured by a scanning electron microscope is as follows: 10-30nm, spherical shape, uniform size, good dispersion, particle diameter of 1-1.2um measured by Malvern 2000, and narrow distribution interval. The forbidden band width measured by ultraviolet visible spectrum is 2.8ev, 10g cerium oxide powder is added into 6L pure water, the mixture is stirred for 0.5h and then stands, the powder is uniformly dispersed in water, and a small amount of precipitate appears after about 30 days.
Example 2
(1) Preparing a cerium chloride solution with the concentration of 0.6mol/l by taking rare earth cerium chloride as a raw material;
(2) adding a metered calcium chloride solution with the concentration of 0.2mol/l and the mass of 8 percent of cerium oxide into the cerium chloride solution, uniformly mixing, adding sodium dodecyl sulfate with the mass of 2 percent of the cerium oxide, and uniformly stirring.
(3) Preparing sodium carbonate into a precipitator solution with the concentration of 2.0mol/l, dripping the solution into a rare earth cerium calcium chloride solution at the speed of 140ml/min by using a diaphragm pump, controlling the PH of a precipitate to be 10-12 after dripping, and dripping hydrogen peroxide with the concentration of 4mol/l at the speed of 40ml/min to oxidize the precipitate.
Wherein the molar ratio of the metered cerium oxide to the precipitating agent is as follows: 1:4, wherein the molar ratio of the metered cerium oxide to the hydrogen peroxide is 1: 1.
(4) After the dropwise addition of the hydrogen peroxide, stirring for 1h, aging for 2h, performing suction filtration and washing, wherein the washing temperature is as follows: washing at 60 deg.C until the waste water is titrated with silver nitrate and no precipitate is formed, washing with ethanol, and replacing the free water in the precipitate.
(5) And (4) pumping the slurry obtained in the step (4) to dryness, adding n-butanol accounting for 2% of the total amount of the cerium oxide, fully stirring, drying at 100 ℃, keeping the temperature at 700 ℃ and firing for 2 hours to obtain Ca-doped nano cerium oxide, and then carrying out jet milling.
The primary particle size measured by a scanning electron microscope is as follows: 10-30nm, spherical shape, uniform size, good dispersion, particle diameter of 1-1.2um measured by Malvern 2000, and narrow distribution interval. The forbidden band width measured by ultraviolet visible spectrum is 2.85ev, 10g cerium oxide powder is added into 6L pure water, the mixture is stirred for 0.5h and then stands, the powder is uniformly dispersed in water, and a small amount of precipitate appears after about 30 days.
Example 3
(1) Preparing rare earth cerium chloride with the concentration of 0.8mol/l as a raw material;
(2) adding a metered calcium chloride solution with the concentration of 0.3mol/l and the mass of 8 percent of cerium oxide into the cerium chloride solution, uniformly mixing, adding sodium dodecyl benzene sulfonate with the mass of 2 percent of the cerium oxide, and uniformly stirring.
(3) Preparing sodium hydroxide into a precipitator solution with the concentration of 1.0mol/l, dropwise adding the precipitator solution into a rare earth cerium chloride solution at the speed of 120ml/min by using a diaphragm pump, controlling the PH of a precipitate to be 10-12 after dropwise adding, and dropwise adding hydrogen peroxide with the concentration of 2mol/l at the speed of 30ml/min to oxidize the precipitate.
Wherein the molar ratio of the metered cerium oxide to the precipitating agent is as follows: 1:3.8, and the molar ratio of the cerium oxide metered by oxygen to the hydrogen peroxide is 1: 1.
(4) After the dropwise addition of the hydrogen peroxide, stirring for 1h, aging for 2h, performing suction filtration and washing, wherein the washing temperature is as follows: and (4) washing at 80 ℃ until the waste water is titrated by silver nitrate without sediment, and then washing by alcohol by using ethanol to completely replace free water in the sediment.
(5) And (4) drying the slurry obtained in the step (4), adding n-butyl alcohol accounting for 2% of the total amount of the cerium oxide, fully stirring, drying at 90 ℃, keeping the temperature at 650 ℃ and firing for 3 hours to obtain Ca-doped nano cerium oxide, and then carrying out jet milling.
The primary particle size measured by a scanning electron microscope is as follows: 10-30nm, spherical shape, uniform size, good dispersion, particle diameter of 1-1.2um measured by Malvern 2000, and narrow distribution interval. The forbidden band width measured by ultraviolet visible spectrum is 2.78ev, 10g cerium oxide powder is added into 6L pure water, the mixture is stirred for 0.5h and then stands, the powder is uniformly dispersed in water, and a small amount of precipitate appears after about 30 days.
Example 4
(1) Preparing rare earth cerium chloride with the concentration of 0.4mol/l as a raw material;
(2) adding a calcium chloride solution with the concentration of 0.2mol/l accounting for 7 percent of the mass of the cerium oxide into the cerium chloride solution, uniformly mixing, adding sodium dodecyl benzene sulfonate accounting for 5 percent of the mass of the cerium oxide, and uniformly stirring.
(3) Preparing 3mol/l precipitator solution from sodium hydroxide, dripping into the rare earth cerium chloride solution at a speed of 130ml/min by using a diaphragm pump, controlling the PH of the precipitate to be 10-12 after dripping, and dripping 4mol/l hydrogen peroxide at a speed of 40ml/min to oxidize the precipitate.
Wherein the molar ratio of the metered cerium oxide to the precipitating agent is as follows: 1:4.5, and the molar ratio of the metered cerium oxide to the hydrogen peroxide is 1: 1.5.
(4) After the dropwise addition of the hydrogen peroxide, stirring for 1h, aging for 2h, performing suction filtration and washing, wherein the washing temperature is as follows: and (3) washing at 90 ℃ until the waste water is titrated by silver nitrate without sediment, and then washing by alcohol by using ethanol to completely replace free water in the sediment.
(5) And (4) pumping the slurry obtained in the step (4) to dryness, adding n-butanol accounting for 3% of the total mass of the cerium oxide, fully stirring, drying at 100 ℃, keeping the temperature at 650 ℃ and firing for 3 hours to obtain Ca-doped nano cerium oxide, and then carrying out jet milling.
The primary particle size measured by a scanning electron microscope is as follows: 10-30nm, spherical shape, uniform size, good dispersion, particle diameter of 1-1.2um measured by Malvern 2000, and narrow distribution interval. The forbidden band width measured by ultraviolet visible spectrum is 2.803ev, 10g cerium oxide powder is added into 6L pure water, stirred for 0.5h and then kept stand, the powder is uniformly dispersed in water, and a small amount of precipitate appears after about 30 days.
Example 5
(1) Preparing rare earth cerium chloride with the concentration of 0.4mol/l as a raw material;
(2) adding a calcium chloride solution with the concentration of 0.2mol/l accounting for 7 percent of the mass of the cerium oxide into the cerium chloride solution, uniformly mixing, adding sodium dodecyl benzene sulfonate accounting for 5 percent of the mass of the cerium oxide, and uniformly stirring.
(3) Preparing 3mol/l precipitator solution from sodium hydroxide, dripping into the rare earth cerium chloride solution at a speed of 130ml/min by using a diaphragm pump, controlling the PH of the precipitate to be 10-12 after dripping, and dripping 4mol/l hydrogen peroxide at a speed of 40ml/min to oxidize the precipitate.
Wherein the molar ratio of the metered cerium oxide to the precipitating agent is as follows: 1:4.5, and the molar ratio of the metered cerium oxide to the hydrogen peroxide is 1: 0.5.
(4) After the dropwise addition of the hydrogen peroxide, stirring for 1h, aging for 2h, performing suction filtration and washing, wherein the washing temperature is as follows: and (3) washing at 90 ℃ until the waste water is titrated by silver nitrate without sediment, and then washing by alcohol by using ethanol to completely replace free water in the sediment.
(5) And (4) pumping the slurry obtained in the step (4) to dryness, adding n-butanol accounting for 3% of the total mass of the cerium oxide, fully stirring, drying at 100 ℃, keeping the temperature at 650 ℃ and firing for 3 hours to obtain Ca-doped nano cerium oxide, and then carrying out jet milling.
The primary particle size measured by a scanning electron microscope is as follows: 10-30nm, spherical shape, uniform size, good dispersion, particle diameter of 1-1.2um measured by Malvern 2000, and narrow distribution interval. The forbidden band width measured by ultraviolet visible spectrum is 2.829ev, 10g cerium oxide powder is added into 6L pure water, stirred for 0.5h and then kept stand, the powder is uniformly dispersed in water, and a small amount of precipitate appears after about 30 days.
Comparative example 1
(1) Preparing a solution with the concentration of 0.6mol/l by taking rare earth cerium chloride as a raw material; adding sodium dodecyl sulfate accounting for 4% of the mass of the cerium oxide into the cerium chloride solution, and uniformly stirring;
(2) preparing sodium carbonate into a precipitator solution with the concentration of 2.0mol/l, dripping the solution into a rare earth cerium calcium chloride solution at the speed of 140ml/min by using a diaphragm pump, controlling the PH of a precipitate to be 10-12 after dripping, and dripping hydrogen peroxide with the concentration of 4mol/l at the speed of 40ml/min to oxidize the precipitate.
Wherein the molar ratio of the metered cerium oxide to the precipitating agent is as follows: 1:4, wherein the molar ratio of the metered cerium oxide to the hydrogen peroxide is 1: 1.
(3) After the dropwise addition of the hydrogen peroxide, stirring for 1h, aging for 2h, performing suction filtration and washing, wherein the washing temperature is as follows: washing at 60 deg.C until the waste water is titrated with silver nitrate and no precipitate is formed, washing with ethanol, and replacing the free water in the precipitate.
(4) And (3) pumping the slurry obtained in the step (3) to dryness, adding n-butanol accounting for 2% of the total mass of the cerium oxide, fully stirring, drying at 100 ℃, firing at 700 ℃ and preserving heat for 2 hours to obtain nano cerium oxide, and then carrying out jet milling.
The primary particle size measured by a scanning electron microscope is as follows: 10-50nm, spherical shape, uniform size, good dispersion, particle diameter of 1-1.5um measured by Malvern 2000, and narrow distribution interval. The forbidden band width measured by ultraviolet visible spectrum is 3.15ev, which is consistent with that of common cerium oxide. 10g of cerium oxide powder is added into 6L of pure water, stirred for 0.5h and then kept stand, the powder is uniformly dispersed in water, and a small amount of precipitate appears after about 10 days.
Comparative example 2
(1) Preparing a solution with the concentration of 0.6mol/l by taking rare earth cerium chloride as a raw material;
(2) adding a metered calcium chloride solution with the concentration of 0.2mol/l and the mass of 8 percent of cerium oxide into the cerium chloride solution, uniformly mixing, adding sodium dodecyl sulfate with the mass of 2 percent of the cerium oxide, and uniformly stirring.
(3) Preparing sodium carbonate into a precipitator solution with the concentration of 2.0mol/l, dripping the solution into a rare earth cerium calcium chloride solution at the speed of 140ml/min by adopting a diaphragm pump, and controlling the PH of a precipitate to be 10-12 after dripping.
Wherein, the molar ratio of cerium oxide to precipitant is: 1:4.
(4) Stirring the precipitate for 1h, aging for 2h, performing suction filtration and washing with water at the temperature of: washing at 60 deg.C until the waste water is titrated with silver nitrate and no precipitate is formed, washing with ethanol, and replacing the free water in the precipitate.
(5) And (4) pumping the slurry obtained in the step (4) to dryness, adding n-butanol accounting for 2% of the total mass of the cerium oxide, fully stirring, drying at 100 ℃, keeping the temperature at 700 ℃ and firing for 2 hours to obtain Ca-doped nano cerium oxide, and then carrying out jet milling.
The primary particle size measured by a scanning electron microscope is as follows: 20-50nm, spherical, uniform in size, and generally dispersed, and has a particle diameter of 1-1.6um measured by Malvern 2000, and a narrow distribution interval. The forbidden band width measured by ultraviolet visible spectrum is 3.23ev, which is consistent with that of common cerium oxide. 10g of cerium oxide powder is added into 6L of pure water, stirred for 0.5h and then kept stand, the powder is uniformly dispersed in water, and a small amount of precipitate appears after about 5 days.
Comparative example 3
(1) Preparing rare earth cerium chloride with the concentration of 0.8mol/l as a raw material;
(2) Adding a calcium chloride solution with the concentration of 0.3mol/l accounting for 8 percent of the mass of the cerium oxide into the cerium chloride solution, uniformly mixing, adding sodium dodecyl benzene sulfonate accounting for 2 percent of the mass of the cerium oxide, and uniformly stirring.
(3) Preparing sodium hydroxide into a precipitator solution with the concentration of 1.0mol/l, dropwise adding the precipitator solution into a rare earth cerium chloride solution at the speed of 120ml/min by using a diaphragm pump, controlling the PH of a precipitate to be 10-12 after dropwise adding, and dropwise adding hydrogen peroxide with the concentration of 2mol/l at the speed of 30ml/min to oxidize the precipitate.
Wherein the molar ratio of the metered cerium oxide to the precipitating agent is as follows: 1:3.8, and the molar ratio of the metered cerium oxide to the hydrogen peroxide is 1: 1.
(4) After the dropwise addition of the hydrogen peroxide, stirring for 1h, aging for 2h, performing suction filtration and washing, wherein the washing temperature is as follows: and (4) washing at 80 ℃ until the waste water is titrated by silver nitrate without sediment, and then washing by alcohol by using ethanol to completely replace free water in the sediment.
(5) And (4) pumping the slurry obtained in the step (4), drying at 90 ℃, keeping the temperature at 650 ℃ and firing for 3 hours to obtain Ca-doped nano cerium oxide, and then carrying out jet milling.
The primary particle size measured by a scanning electron microscope is as follows: 30-100nm, spherical, uniform in size, and generally dispersed, and the particle diameter is 1-2um measured by Malvern 2000. The forbidden band width measured by ultraviolet visible spectrum is 2.98ev, 10g cerium oxide powder is added into 6L pure water, the mixture is stirred for 0.5h and then stands, the powder is uniformly dispersed in water, and a small amount of precipitate appears after about 5 days.
Comparative example 4
(1) Preparing rare earth cerium chloride with the concentration of 0.4mol/l as a raw material;
(2) adding a barium chloride solution with the concentration of 0.2mol/l and the weight of 7 percent of the measured cerium oxide into the cerium chloride solution, uniformly mixing, adding sodium dodecyl benzene sulfonate with the weight of 5 percent of the measured cerium oxide, and uniformly stirring.
(3) Preparing 3mol/l precipitator solution from sodium hydroxide, dripping into the rare earth cerium chloride solution at a speed of 130ml/min by using a diaphragm pump, controlling the PH of the precipitate to be 10-12 after dripping, and dripping 4mol/l hydrogen peroxide at a speed of 40ml/min to oxidize the precipitate.
Wherein, the molar ratio of cerium oxide to precipitant is: 1:4.5, and the molar ratio of the cerium oxide to the hydrogen peroxide is 1: 1.5.
(4) After the dropwise addition of the hydrogen peroxide, stirring for 1h, aging for 2h, performing suction filtration and washing, wherein the washing temperature is as follows: and (3) washing at 90 ℃ until the waste water is titrated by silver nitrate without sediment, and then washing by alcohol by using ethanol to completely replace free water in the sediment.
(5) And (4) drying the slurry obtained in the step (4), adding n-butyl alcohol accounting for 3% of the total amount of the cerium oxide, fully stirring, drying at 100 ℃, keeping the temperature at 650 ℃ and firing for 3 hours to obtain Ca-doped nano cerium oxide, and then carrying out jet milling.
The primary particle size measured by a scanning electron microscope is as follows: 30-100nm, spherical, and generally dispersed, and has a particle diameter of 1-2um measured by Malvern 2000. The forbidden band width measured by ultraviolet visible spectrum is 3.01ev, 10g cerium oxide powder is added into 6L pure water, the mixture is stirred for 0.5h and then stands, the powder is uniformly dispersed in water, and a small amount of precipitate appears after about 5 h.
The present invention is not limited to the above-described embodiments, and any obvious improvements, substitutions or modifications can be made by those skilled in the art without departing from the spirit of the present invention.

Claims (8)

1. The preparation method of the nano cerium oxide is characterized by comprising the following steps:
(1) preparing a cerium chloride solution with the concentration of 0.2-0.8mol/l by taking rare earth cerium chloride as a raw material;
(2) adding a calcium chloride solution into the cerium chloride solution, uniformly mixing, adding an anionic surfactant, and uniformly stirring;
(3) preparing a precipitator into a precipitator solution with the concentration of 1.0-3.0mol/l, then dropwise adding the precipitator solution into the rare earth cerium chloride solution obtained in the step (2), controlling the PH of the precipitate to be 10-12 after dropwise adding, and dropwise adding hydrogen peroxide to oxidize the precipitate;
(4) Stirring for 1h after the hydrogen peroxide is added dropwise, aging for 2h, performing suction filtration and water washing until no precipitate is generated in the wastewater after the wastewater is titrated with silver nitrate, and performing alcohol washing with ethanol to completely replace free water in the precipitate;
(5) and (4) pumping the slurry obtained in the step (4) to dryness, adding n-butanol accounting for 1-3% of the total amount of the cerium oxide, fully stirring, drying, firing to obtain Ca-doped nano cerium oxide, and then carrying out jet milling.
2. The method for preparing nano cerium oxide according to claim 1, wherein the calcium chloride is added in an amount of 5-8% by mass of the metered cerium oxide in step (2), and the anionic surfactant is added in an amount of 2-5% by mass of the metered cerium oxide; the anionic surfactant is sodium dodecyl benzene sulfonate or sodium dodecyl sulfate.
3. The method for preparing nano cerium oxide according to claim 1, wherein the precipitating agent in step (3) is: sodium carbonate, sodium bicarbonate, sodium hydroxide.
4. The method for preparing nano cerium oxide according to claim 1, wherein the molar ratio of the metered cerium oxide to the precipitating agent in the step (3) is as follows: 1:3-4.5.
5. The method for preparing nano cerium oxide according to claim 1, wherein the bottom water in step (3) is pure water; dropwise adding equipment: diaphragm pump, dropping speed: 120-150 ml/min.
6. The method for preparing nano cerium oxide according to claim 1, wherein the molar ratio of the metered cerium oxide to the hydrogen peroxide in the step (3) is 1:0.5-1.5, the concentration of the hydrogen peroxide is 2-5mol/l, and the dropping speed is 30-50 ml/min.
7. The method for preparing nano cerium oxide according to claim 1, wherein the water washing temperature in step (4) is as follows: 50-80 ℃.
8. The method for preparing nano cerium oxide as claimed in claim 1, wherein the drying temperature in step (5) is 90-120 ℃, the ignition temperature is 600-750 ℃, and the ignition and heat preservation time is 1-3 hours.
CN202011207340.3A 2020-11-03 2020-11-03 Preparation method of nano cerium oxide with strong ultraviolet ray shielding performance Pending CN112374523A (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1308240C (en) * 1999-05-25 2007-04-04 株式会社高丝 Metal oxide doping cesium oxide, its prepn. and composition thereof
CN105502467A (en) * 2014-09-22 2016-04-20 常州市卓群纳米新材料有限公司 Nanometer dysprosium oxide preparation method
CN110104682A (en) * 2019-05-29 2019-08-09 常州市卓群纳米新材料有限公司 A kind of nano zirconium dioxide of high-specific surface area and preparation method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1308240C (en) * 1999-05-25 2007-04-04 株式会社高丝 Metal oxide doping cesium oxide, its prepn. and composition thereof
CN105502467A (en) * 2014-09-22 2016-04-20 常州市卓群纳米新材料有限公司 Nanometer dysprosium oxide preparation method
CN110104682A (en) * 2019-05-29 2019-08-09 常州市卓群纳米新材料有限公司 A kind of nano zirconium dioxide of high-specific surface area and preparation method thereof

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