CN110104671B - Induced crystallization method of flaky cerium carbonate - Google Patents
Induced crystallization method of flaky cerium carbonate Download PDFInfo
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- CN110104671B CN110104671B CN201910396955.6A CN201910396955A CN110104671B CN 110104671 B CN110104671 B CN 110104671B CN 201910396955 A CN201910396955 A CN 201910396955A CN 110104671 B CN110104671 B CN 110104671B
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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
- C01F17/247—Carbonates
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- C—CHEMISTRY; METALLURGY
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/20—Particle morphology extending in two dimensions, e.g. plate-like
Abstract
The invention belongs to the technical field of powder material preparation, and discloses an induced crystallization method of flaky cerium carbonate. The method comprises the following steps: preparing a cerium salt solution with the concentration of 0.02-0.5 mol/L and the pH value of 3.5-5.0; adding a needle-shaped cerium carbonate crystal serving as a seed crystal into a cerium salt solution, and performing ultrasonic dispersion; and then dropwise adding the precipitant solution, continuously stirring in the process, continuously stirring after dropwise adding is finished until all the amorphous cerium carbonate is transformed into crystals, and sequentially filtering, washing and drying the precipitate to obtain the flaky cerium carbonate crystal product. The reaction product obtained by the method is flaky, and has the advantages of high settling speed, small precipitation volume, easiness in filtration and the like.
Description
Technical Field
The invention belongs to the technical field of powder material preparation, and particularly relates to an induced crystallization method of flaky cerium carbonate.
Background
Cerium carbonate is a precursor for preparing various cerium products such as various cerium salts and cerium dioxide, and is a relatively important light rare earth product, wherein the cerium dioxide is widely applied to the fields of three-way catalysts, fuel cells, photocatalysis, wastewater and exhaust gas treatment, glass polishing agents, electronic ceramics and the like.
The preparation method of cerium carbonate mainly comprises a hydrothermal method and a liquid-phase precipitation method. The hydrothermal method has high energy consumption, long production period and low production efficiency. And the liquid phase precipitation method has mild reaction conditions and low cost, and is more suitable for industrial large-scale production. The crystallization process for preparing cerium carbonate by the liquid-phase precipitation method comprises the steps of firstly reacting to generate amorphous precipitate, and aging to obtain crystalline cerium carbonate. The crystal transformation time of the amorphous substance determines the preparation period of the crystalline cerium carbonate, the amorphous precipitate has larger volume, is not easy to separate from water and is difficult to filter, and the crystal transformation control process is a key step for preparing the cerium carbonate crystal. CN 102060319A obtains a cerium carbonate intermediate with narrow particle size distribution through two-step precipitation by adding 3-5% of crystalline cerium carbonate, but the process steps are complicated, and the influence of the crystal seed appearance on the crystal transformation is not examined.
Disclosure of Invention
In view of the above disadvantages and shortcomings of the prior art, the present invention is directed to a method for inducing crystallization of a sheet-shaped cerium carbonate. The method of the invention obviously shortens the crystal transformation time and realizes the rapid preparation of the cerium carbonate crystal by adding the cerium carbonate crystal seed with a specific shape to induce the amorphous crystal transformation.
The purpose of the invention is realized by the following technical scheme:
a method for inducing crystallization of a sheet-shaped cerium carbonate comprises the following steps:
(1) preparing a cerium salt solution with the concentration of 0.02-0.5 mol/L and the pH value of 3.5-5.0;
(2) adding needle-shaped cerium carbonate crystals serving as seed crystals into the cerium salt solution obtained in the step (1), and performing ultrasonic dispersion;
(3) and (3) dropwise adding the precipitant solution into the cerium salt solution obtained in the step (2), continuously stirring in the process, continuously stirring after dropwise adding is finished until all the amorphous cerium carbonate is crystallized, and sequentially filtering, washing and drying the precipitate to obtain the flaky cerium carbonate crystal product.
Preferably, the cerium salt solution in step (1) is a cerium nitrate or cerium chloride solution.
Preferably, the addition amount of the seed crystal in the step (2) is 3-9% of the mass of the flake cerium carbonate crystal product finally obtained theoretically.
Preferably, the precipitant solution in step (3) is a sodium bicarbonate solution with a concentration of 0.02-1.2 mol/L.
Preferably, the time for dripping the precipitant solution in the step (3) is 1-4 min.
The method of the invention has the following advantages and beneficial effects:
(1) the method only needs to add a proper amount of the crystal seeds with specific morphology at normal temperature to induce the crystal transformation of the cerium carbonate amorphous substance, thereby changing the process crystallization power, shortening the crystal transformation time and realizing the rapid preparation of the cerium carbonate crystal.
(2) The reaction product obtained by the method is flaky, and has the advantages of high settling speed, small precipitation volume, easiness in filtration and the like.
Drawings
FIG. 1 is a 50-fold microscopic image of the cerium carbonate crystal product obtained in comparative example 1;
FIG. 2 is a 50-fold microscopic image of the cerium carbonate crystal product obtained in comparative example 2;
FIG. 3 is a 50-fold microscopic image of the cerium carbonate crystal product obtained in comparative example 3;
FIG. 4 is a 50-fold microscope image of a needle-shaped morphology seed crystal used in examples 1 to 3;
FIGS. 5 to 7 are 50-fold microscopic images of the cerium carbonate crystal products obtained in examples 1 to 3, respectively;
FIG. 8 is a graph comparing the particle size distributions of crystalline products obtained by adding seeds of different morphologies in the comparative example and example.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the present invention is not limited thereto.
Comparative example 1
In this comparative example, cerium carbonate particles were prepared without seeding, as a comparative experiment:
(1) preparing a cerium nitrate solution, weighing 5.43g of cerium nitrate hexahydrate, dissolving in 125mL of deionized water to obtain a cerium nitrate solution with the concentration of 0.10mol/L, and controlling the pH value to be 3.5-5.0.
(2) And (2) dropwise adding a sodium bicarbonate precipitator solution with the concentration of 1.0mol/L into the cerium nitrate solution obtained in the step (1), and continuously stirring in the dropwise adding process for 3 min. After the dropwise adding, continuously stirring until all the cerium carbonate amorphous substances are subjected to crystal transformation (observing the time for finishing the crystal transformation of the amorphous substances by using a microscope), sequentially filtering the precipitates, and collecting filter cakes; washing the filter cake for 3 times by using deionized water, and then washing for 3 times by using alcohol; and drying the filter cake after the alcohol washing at 40 ℃ for 4h to obtain a cerium carbonate crystal product, wherein a 50-fold microscope image of the obtained product is shown in figure 1.
The end time of crystallization in this comparative example was 29min and the volume of precipitate was 115 mL.
Comparative example 2
In this comparative example, bulk morphology seed crystals were added to prepare cerium carbonate particles as comparative experiments:
(1) preparing a cerium nitrate solution, weighing 5.43g of cerium nitrate hexahydrate, dissolving in 125mL of deionized water to obtain a cerium nitrate solution with the concentration of 0.10mol/L, and controlling the pH value to be 3.5-5.0.
(2) And (3) adding 5% of blocky cerium carbonate crystals serving as seed crystals into the cerium nitrate solution obtained in the step (1), and performing ultrasonic dispersion.
(3) And (3) dropwise adding a sodium bicarbonate precipitator solution with the concentration of 1.0mol/L into the cerium nitrate solution obtained in the step (2), and continuously stirring in the dropwise adding process for 3 min. After the dropwise adding, continuously stirring until all the cerium carbonate amorphous substances are subjected to crystal transformation (observing the time for finishing the crystal transformation of the amorphous substances by using a microscope), sequentially filtering the precipitates, and collecting filter cakes; washing the filter cake for 3 times by using deionized water, and then washing for 3 times by using alcohol; and drying the filter cake after the alcohol washing at 40 ℃ for 4h to obtain a cerium carbonate crystal product, wherein a 50-fold microscope image of the obtained product is shown in figure 2.
In this comparative example, the time for completion of crystallization was 31min and the volume of precipitate was 120 mL.
Comparative example 3
In this comparative example, a lamellar crystal seed was added to prepare cerium carbonate particles as a comparative experiment:
(1) preparing a cerium nitrate solution, weighing 5.43g of cerium nitrate hexahydrate, dissolving in 125mL of deionized water to obtain a cerium nitrate solution with the concentration of 0.10mol/L, and controlling the pH value to be 3.5-5.0.
(2) And (2) adding 5% of cerium carbonate crystals with a flaky shape as seed crystals into the cerium nitrate solution obtained in the step (1), and performing ultrasonic dispersion.
(3) And (3) dropwise adding a sodium bicarbonate precipitator solution with the concentration of 1.0mol/L into the cerium nitrate solution obtained in the step (2), and continuously stirring in the dropwise adding process for 3 min. After the dropwise adding, continuously stirring until all the cerium carbonate amorphous substances are subjected to crystal transformation (observing the time for finishing the crystal transformation of the amorphous substances by using a microscope), sequentially filtering the precipitates, and collecting filter cakes; washing the filter cake for 3 times by using deionized water, and then washing for 3 times by using alcohol; and drying the filter cake after the alcohol washing at 40 ℃ for 4h to obtain a cerium carbonate crystal product, wherein a 50-fold microscope image of the obtained product is shown in figure 3.
In this comparative example, the time for completion of crystallization was 30min and the volume of precipitate was 120 mL.
Example 1
In this example, 3% of needle-shaped crystal seeds were added to prepare cerium carbonate particles:
(1) preparing a cerium nitrate solution, weighing 5.43g of cerium nitrate hexahydrate, dissolving in 125mL of deionized water to obtain a cerium nitrate solution with the concentration of 0.10mol/L, and controlling the pH value to be 3.5-5.0.
(2) And (3) adding the 3% acicular cerium carbonate crystal serving as a seed crystal into the cerium nitrate solution obtained in the step (1), and performing ultrasonic dispersion.
(3) And (3) dropwise adding a sodium bicarbonate precipitator solution with the concentration of 1.0mol/L into the cerium nitrate solution obtained in the step (2), and continuously stirring in the dropwise adding process for 3 min. After the dropwise adding, continuously stirring until all the cerium carbonate amorphous substances are subjected to crystal transformation (observing the time for finishing the crystal transformation of the amorphous substances by using a microscope), sequentially filtering the precipitates, and collecting filter cakes; washing the filter cake for 3 times by using deionized water, and then washing for 3 times by using alcohol; and drying the filter cake subjected to alcohol washing at 40 ℃ for 4h to obtain a cerium carbonate crystal product.
In this example, the time for completion of crystallization was 11min and the volume of precipitate was 25 mL.
Example 2
In this example, 5% of needle-shaped crystal seeds were added to prepare cerium carbonate particles:
(1) preparing a cerium nitrate solution, weighing 5.43g of cerium nitrate hexahydrate, dissolving in 125mL of deionized water to obtain a cerium nitrate solution with the concentration of 0.10mol/L, and controlling the pH value to be 3.5-5.0.
(2) And (2) adding 5% of needle-shaped cerium carbonate crystals serving as seed crystals into the cerium nitrate solution obtained in the step (1), and performing ultrasonic dispersion.
(3) And (3) dropwise adding a sodium bicarbonate precipitator solution with the concentration of 1.0mol/L into the cerium nitrate solution obtained in the step (2), and continuously stirring in the dropwise adding process for 3 min. After the dropwise adding, continuously stirring until all the cerium carbonate amorphous substances are subjected to crystal transformation (observing the time for finishing the crystal transformation of the amorphous substances by using a microscope), sequentially filtering the precipitates, and collecting filter cakes; washing the filter cake for 3 times by using deionized water, and then washing for 3 times by using alcohol; and drying the filter cake subjected to alcohol washing at 40 ℃ for 4h to obtain a cerium carbonate crystal product.
The end time of crystallization in this example was 7min and the volume of precipitate was 23 mL.
Example 3
In this example, 9% of needle-shaped crystal seeds were added to prepare cerium carbonate particles:
(1) preparing a cerium chloride solution, weighing 4.66g of cerium chloride heptahydrate, and dissolving in 125mL of deionized water to obtain a cerium chloride solution with the concentration of 0.10mol/L, wherein the pH value is controlled to be 3.5-5.0.
(2) And (2) adding 9% of needle-shaped cerium carbonate crystals serving as seed crystals into the cerium nitrate solution obtained in the step (1), and performing ultrasonic dispersion.
(3) And (3) dropwise adding a sodium bicarbonate precipitator solution with the concentration of 1.0mol/L into the cerium nitrate solution obtained in the step (2), and continuously stirring in the dropwise adding process for 1 min. After the dropwise adding, continuously stirring until all the cerium carbonate amorphous substances are subjected to crystal transformation (observing the time for finishing the crystal transformation of the amorphous substances by using a microscope), sequentially filtering the precipitates, and collecting filter cakes; washing the filter cake for 3 times by using deionized water, and then washing for 3 times by using alcohol; and drying the filter cake subjected to alcohol washing at 40 ℃ for 4h to obtain a cerium carbonate crystal product.
The end time of crystallization in this example was 9min and the volume of precipitate was 25 mL.
The 50-fold microscope images of the needle-shaped seeds used in examples 1-3 above are shown in FIG. 4.
The 50-fold microscope images of the cerium carbonate crystal products obtained in examples 1 to 3 are shown in FIGS. 5 to 7, respectively.
The particle size distribution of the crystal products obtained by adding the crystal seeds with different morphologies in the above comparative examples and examples is shown in a comparative graph in FIG. 8.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (3)
1. A method for inducing crystallization of a sheet-like cerium carbonate, characterized by comprising the steps of:
(1) preparing a cerium salt solution with the concentration of 0.02-0.5 mol/L and the pH value of 3.5-5.0;
(2) adding needle-shaped cerium carbonate crystals serving as seed crystals into the cerium salt solution obtained in the step (1), and performing ultrasonic dispersion;
(3) dropwise adding a precipitator solution into the cerium salt solution obtained in the step (2), continuously stirring in the process, continuously stirring after the dropwise adding is finished until all the amorphous cerium carbonate is crystallized, and sequentially filtering, washing and drying the precipitate to obtain a sheet cerium carbonate crystal product;
the adding amount of the seed crystal in the step (2) is 3-9% of the mass of the sheet cerium carbonate crystal product finally obtained theoretically;
and (4) in the step (3), the precipitant solution is a sodium bicarbonate solution with the concentration of 0.02-1.2 mol/L.
2. The method for induced crystallization of a sheet-like cerium carbonate according to claim 1, wherein: in the step (1), the cerium salt solution is cerium nitrate or cerium chloride solution.
3. The method for induced crystallization of a sheet-like cerium carbonate according to claim 1, wherein: and (4) dropwise adding the precipitant solution in the step (3) for 1-4 min.
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| CN112126977B (en) * | 2020-08-11 | 2021-11-19 | 南昌大学 | Method for preparing high-purity flaky single crystal and flaky crystal dense aggregated cerium carbonate |
| CN113830817B (en) * | 2021-10-22 | 2023-06-20 | 南昌大学 | Preparation method of cerium-based oxide material and precursor thereof |
| CN115159558B (en) * | 2022-07-05 | 2023-10-03 | 冕宁县新盛源新材料科技有限公司 | Precipitation method of rare earth carbonate |
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