CN114436312A - Preparation method of nano rare earth oxide and nano rare earth oxide - Google Patents
Preparation method of nano rare earth oxide and nano rare earth oxide Download PDFInfo
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Abstract
The invention provides a preparation method of a nanometer rare earth oxide, which comprises the following specific steps: s1, adding a certain amount of molten salt into a certain amount of water, stirring and dissolving, adding a certain amount of polyethylene glycol and a surfactant, gradually adding the mixed solution into a certain amount of water-insoluble rare earth salt, and uniformly stirring and dispersing to obtain slurry; s2, adding a certain amount of water into the slurry obtained in the step S1, ball-milling, and filtering to obtain uniform emulsion/suspension; s3, stirring the emulsion/suspension obtained in S2 and spray drying to obtain powder; and S4, calcining the powder obtained in the step S3 in a furnace body at the temperature of between room temperature and 900 ℃ for a period of time, and cooling the calcined powder along with the furnace body to obtain the nano rare earth oxide. The invention takes an insoluble rare earth salt as a raw material, and adopts a special high-temperature calcination process means, so that the obtained nano rare earth oxide has the characteristics of small particle size, uniform particle size distribution, high purity and the like.
Description
Technical Field
The invention relates to the field of rare earth oxide preparation, in particular to a preparation method of a nanometer rare earth oxide, and further relates to a nanometer rare earth oxide.
Background
The rare earth resources are scarce all over the world, and China has advantages in the aspects of the reserves and the yield of the rare earth resources all over the world. Due to the unique 4f electronic structure, the rare earth element brings excellent physical and chemical performances of electricity, light, magnetism, heat and the like, and is widely applied to the traditional industries and high-tech fields of petroleum, chemical engineering, metallurgy, ceramics, textiles, glass, permanent magnet materials and the like, such as the preparation of metal matrix composite materials, polishing materials, luminescent materials, laser materials, fibers, ceramic materials and the like.
The rare earth oxide can be used as a doping component of the material, a sintering aid, catalysis, magneto-optical storage and the like, and is a key basic material in the field of high and new materials at present. With the progress of science and technology, the value of rare earth oxide will be greater and greater.
The nano rare earth oxide has the excellent properties of the original rare earth oxide, simultaneously has the unique properties of a nano material, has larger specific surface area and surface energy and better fluidity and dispersibility, presents unique physical and chemical comprehensive characteristics, improves the performances of the nano rare earth oxide qualitatively and has wider application prospect.
With the inextensible expansion of the application field and the range of the rare earth, the quality requirements of the high-new material on the consideration of physical property control such as crystal form, granularity, morphology, specific surface and the like of the nano rare earth oxide are higher and higher.
At present, the method for preparing the nano rare earth oxide is a precipitation method, and the precipitation method is prepared by reacting rare earth metal salt with a precipitator, washing, drying and calcining.
There are two main cases in the preparation process by precipitation: one is to add surface modifier such as dispersant, surfactant, template agent, etc. for setting agglomeration to promote the formation of dispersed powder, for example, Chinese patent with application No. CN201910230266.8 mixes dispersant such as polyethylene glycol with rare earth nitrate solution, and pre-freezes and freezes-dries at-20-50 deg.C, then grinds, calcines to obtain 10-50nm superfine nanometer rare earth oxide; the Chinese patent with the application number of CN201010623570.8 takes rare earth oxide coarse powder as a raw material, urea is added as a precipitator and a surfactant, and the monodisperse 60-320nm rare earth oxide nanospheres are prepared by a hydrothermal method. The rare earth oxide nanospheres obtained by the method have uneven diameter size distribution, the method not only increases the cost, but also has certain influence on the purity of the product.
Alternatively, the surface modifier is not added, but by increasing the molar amount of urea. For example, in chinese patent application No. CN201010623570.8, coarse powder of rare earth oxide is used as a raw material, urea is added as a precipitating agent and a surfactant, and monodisperse rare earth oxide nanospheres of 60-320nm are prepared by a hydrothermal method; the method has the advantages that the concentration of rare earth ions is reduced to realize the preparation of the nano rare earth oxide, the preparation time is long, the yield is low, and the particle size distribution range of the obtained nano rare earth oxide is wide.
In addition, the nano rare earth oxide prepared by the hydrothermal method has serious agglomeration phenomenon, needs a large amount of solvent, is difficult to separate, has influence on purity, and has multiple processes, low yield and high cost. The sol-gel method usually uses metal organic matters or organic matter auxiliaries as raw materials, and has the advantages of high cost, easy hardening and long labor consumption time. Is not suitable for industrial mass production.
Disclosure of Invention
In order to solve the problems of high purity and cost, long preparation time and the like of products in the prior art, the invention provides a preparation method of nano rare earth oxide, which adopts insoluble rare earth salt as a raw material, adds molten salt and adopts a special high-temperature calcination process means, and the obtained nano rare earth oxide has the characteristics of small particle size, uniform particle size distribution, high purity and the like.
Another technical problem to be solved by the present invention is to provide a corresponding nano rare earth oxide according to the above preparation method of nano rare earth oxide.
A preparation method of nano rare earth oxide comprises the following steps:
s1: adding a certain amount of molten salt into a certain amount of water, stirring and dissolving, adding a certain amount of polyethylene glycol and a surfactant, gradually adding the mixed solution into a certain amount of water-insoluble rare earth salt, and uniformly dispersing by stirring to obtain slurry;
s2: adding a certain amount of water into the slurry obtained in the step S1, ball-milling, and filtering to obtain uniform emulsion/suspension;
s3: spray-drying the emulsion/suspension obtained in S2 while stirring to obtain powder;
s4: and calcining the powder obtained in the step S3 in a furnace body at the temperature of between room temperature and 900 ℃ for a period of time, and cooling the powder along with the furnace body to obtain the nano rare earth oxide.
Further, in S1, the surfactant is at least one of cetyltrimethylammonium bromide, polyethylene glycol, stearic acid, and quaternary ammonium compound.
Further, in S1, the mass ratio of the rare earth salt to the molten salt is 1: 0.01-5; the mass ratio of the rare earth salt to the water is 1: 0.1-5.
Further, in S1, the rare earth salt is at least one of carbonate, acetate and oxalate.
Further, in S1, the rare earth salt is praseodymium oxalate, thulium oxalate, erbium oxalate, holmium oxalate, terbium oxalate, samarium oxalate, gadolinium carbonate, lanthanum carbonate, or neodymium carbonate.
Further, in S1, the molten salt is at least one of ammonium chloride, sodium chloride, potassium chloride, sodium fluoride, ammonium carbonate, ammonia water, sodium carbonate, potassium carbonate, ammonium citrate, sodium citrate, and potassium citrate.
Further, in S2, the ball milling time is 5-10 min, preferably 8 min; wherein the mass ratio of the slurry to the water is 1: 0.5 to 4.
Further, in S3, the spray drying temperature is 100-200 ℃, and preferably 115 ℃; wherein the water content of the powder after spray drying is not higher than 20 wt%.
Further, in S1, the stirring mode is mechanical stirring.
Furthermore, the invention also claims a nano rare earth oxide which is prepared by adopting the preparation method of the nano rare earth oxide.
Further, the nanometer rare earth oxide is selected from nanometer praseodymium oxide, nanometer gadolinium oxide, nanometer thulium oxide, nanometer lanthanum oxide, nanometer erbium oxide, nanometer holmium oxide, nanometer terbium oxide, nanometer samarium oxide and nanometer neodymium oxide.
The technical scheme of the invention has the following beneficial effects:
1. the invention provides a method for preparing nanometer rare earth oxide, which takes insoluble rare earth salt as raw material, adds molten salt, and adopts special high-temperature calcination process means, and the obtained nanometer rare earth oxide has the characteristics of small particle size, uniform particle size distribution, high purity and the like.
2. The preparation method of the nanometer rare earth oxide is simple and stable, has less working procedures, low requirements on equipment, less varieties of used raw materials, no toxicity or pollution, low production cost and easy industrial production, and generates tail gas easy to absorb and treat.
3. The stirring and dispersing mode used by the invention is mechanical stirring at room temperature, and the mechanical stirring and dispersing function is to fully mix and uniformly disperse the molten salt and the rare earth salt which is not dissolved in water so that the molten salt is adsorbed on the surface of the rare earth salt which is not dissolved in water.
4. The ball milling of the invention has the following functions: firstly, the molten salt is more uniformly and comprehensively adsorbed on the surface of the rare earth salt which is insoluble in water; secondly, because the rare earth salt which is not dissolved in water is dissociated under the action of mechanical force, free electrovalence bonds can be generated on the new section, and the particle molecules are aggregated, so that the rare earth oxide obtained after calcination is more seriously aggregated, and positive and negative ions generated by the dissociation of the salt solution in the aqueous solution can be adsorbed on the surface of a ball-milled product, thereby preventing the aggregation phenomenon of the particles.
5. The invention aims to refine and homogenize the precursor material by adopting spray drying, so that the molten salt can be adsorbed on the surface of the rare earth salt which is insoluble in water more uniformly and effectively.
6. The invention promotes the crystallization of the nanometer rare earth oxide and controls the grain size of the nanometer rare earth oxide by controlling the calcining temperature, the time for raising the temperature to the maximum temperature and the heat preservation time of the maximum temperature.
7. The nano rare earth oxide produced by the invention has high purity, small particle size and narrow particle size distribution range; large specific surface area and high surface activity.
Detailed Description
Example 1
The invention provides a preparation method of a nanometer rare earth oxide, which comprises the following specific steps:
s1: adding a certain amount of molten salt into a certain amount of water, stirring and dissolving, adding a certain amount of polyethylene glycol and a surfactant, gradually adding the mixed solution into a certain amount of water-insoluble rare earth salt, and uniformly dispersing by stirring to obtain slurry;
s2: adding a certain amount of water into the slurry obtained in the step S1, ball-milling, and filtering to obtain uniform emulsion/suspension;
s3: spray-drying the emulsion/suspension obtained in S2 while stirring to obtain powder;
s4: and calcining the powder obtained in the step S3 in a furnace body at the temperature of between room temperature and 900 ℃ for a period of time, and cooling the powder along with the furnace body to obtain the nano rare earth oxide.
The invention provides a method for preparing nanometer rare earth oxide, which takes insoluble rare earth salt as raw material, adds molten salt, and adopts special high-temperature calcination process means, and the obtained nanometer rare earth oxide has the characteristics of small particle size, uniform particle size distribution, high purity and the like.
The preparation method of the nanometer rare earth oxide is simple and stable, has less working procedures, low requirements on equipment, less varieties of used raw materials, no toxicity, no pollution, low production cost and easy industrial production, and generates tail gas easy to absorb and treat.
In this embodiment, the molten salt in step S1 is one or more of ammonium chloride, sodium chloride, potassium chloride, sodium fluoride, ammonium carbonate, ammonia water, sodium carbonate, potassium carbonate, ammonium citrate, sodium citrate, and potassium citrate; among them, the molten salt is preferably ammonium chloride or sodium chloride.
In this embodiment, the surfactant or dispersant in step S1 may be one or more of cetyltrimethylammonium bromide, polyethylene glycol, stearic acid, quaternary ammonium compound; among these, as a preferable embodiment, cetyl trimethyl ammonium bromide and polyethylene glycol are used as the surfactant or the dispersant.
In this example, the mass of the dispersant and the surfactant is one to ten thousandths of the solid mass of the raw material, respectively, and in a preferred embodiment, the mass of the dispersant and the surfactant is three thousandths of the solid mass of the raw material, respectively.
In this embodiment, the rare earth salt insoluble in water in step S1 is one or more of carbonate, acetate and oxalate;
in this example, the rare earth salt is praseodymium oxalate, thulium oxalate, erbium oxalate, holmium oxalate, terbium oxalate, samarium oxalate, gadolinium carbonate, lanthanum carbonate, or neodymium carbonate.
In the present embodiment, the stirring dispersion method used in step S1 is mechanical stirring at room temperature.
The mechanical stirring and dispersing function of the invention is to fully mix and disperse the molten salt and the rare earth salt which is insoluble in water uniformly, so that the molten salt is adsorbed on the surface of the rare earth salt which is insoluble in water.
In the embodiment, the mass ratio of the rare earth salt to the molten salt is 1: 0.01-5; the mass ratio of the rare earth salt to the water is 1: 0.1-5.
In this embodiment, as a preferred embodiment, deionized water is used as water.
The deionized water can ensure the purity of the material and avoid the material from being polluted, thereby improving the purity of the nano rare earth oxide.
In the present embodiment, the mass ratio of the slurry to the water in step S2 is 1: 0.5 to 4.
In this embodiment, as a preferred embodiment, the filter sieve in step S2 is an 80-mesh filter sieve.
In this embodiment, the ball milling time in step S2 is 5-10 min, wherein the ball milling time is set to 8min as a preferred implementation manner; the invention can be used for ball milling treatment in a ball mill.
The ball milling of the invention has the following functions: 1. so that the molten salt is more uniformly and comprehensively adsorbed on the surface of the rare earth salt which is insoluble in water; 2. because the water-insoluble rare earth salt is dissociated under the action of mechanical force, free electrovalence bonds can be generated on the new section, and particle molecules are aggregated with each other, so that the agglomeration of the calcined rare earth oxide is more serious, and positive and negative ions generated by the dissociation of the salt solution in the aqueous solution can be adsorbed on the surface of a ball-milled product, thereby preventing the agglomeration of particles.
In this embodiment, the spray drying temperature in step S3 is 100 to 200 ℃, wherein, as a preferred embodiment, the spray drying temperature is 115 ℃, and the water content of the dried powder obtained after spray drying is not higher than 20 wt%.
The invention aims to refine and uniformly distribute the precursor, so that the fused salt can be uniformly and effectively adsorbed on the surface of the rare earth salt which is insoluble in water.
In this embodiment, the furnace body used for calcination in step S4 may be a muffle furnace, a tube furnace, a rotary furnace, a crucible resistance furnace, a box furnace, a lift furnace, a shaft furnace, a trolley furnace, a mesh belt furnace, a roller kiln, a pusher kiln, a tunnel furnace, a rotary kiln, a suspension calciner, or a calcination apparatus of the type with atmosphere; among these, in a preferred embodiment, the furnace body used for the calcination is a muffle furnace.
In this embodiment, the temperature of the calcination in step S4 is from room temperature to 900 ℃, and the calcination process is specifically as follows:
the first stage is in the preheating process, the preheating temperature is from room temperature to 400 ℃, the heating rate is 0.1-50 ℃/min, the front material, particularly molten salt, can be activated in the stage, and part of the molten salt begins to dissolve or decompose;
the second stage is in the heating process, the heating temperature is 400-600 ℃, wherein the heating rate is 0.1-50 ℃/min, and the molten salt in the stage accelerates the decomposition kinetic rate of the rare earth salt which is insoluble in water and promotes the crystallization of cerium oxide; the generated hot ascending air flow can break partial agglomeration or rare earth salt or rare earth oxide with agglomeration tendency to a certain extent by the decomposition of the molten salt at high temperature; effectively preventing the growth and agglomeration of rare earth oxide crystal nuclei, and keeping the dispersion function of the particles of the rare earth oxide by the molten salt through a grinding aid mechanism;
the third stage is in a high-temperature heating process, the high-temperature heating temperature is 600-900 ℃, the temperature rise rate is 0.1-50 ℃/min, the stage aims at the rapid forming of product rare earth oxide crystal nuclei and the growth of crystal grains, the crystal nuclei of the product rare earth oxide are rapidly formed due to the high temperature, the growth and agglomeration of the crystal nuclei of the rare earth oxide are effectively organized due to the existence of molten salt, and the grain size of the grains is controlled to a certain extent;
the fourth stage is in the heat preservation process, when the highest temperature is reached, heat preservation treatment is carried out, the crystallization of the rare earth oxide is promoted through the constant temperature and the time, and the size of the product rare earth oxide crystal grains is controlled; wherein the heat preservation time is 0-300 min;
the fifth stage is in the process of temperature reduction, and the purpose of the fifth stage is to prepare the nano rare earth oxide by cooling to room temperature along with the furnace body.
In this embodiment, in step S4, the crystallization of the nano rare earth oxide can be promoted by the high/low calcination temperature, the time for raising the temperature to the maximum temperature, and the maximum temperature holding time, and the grain size of the nano rare earth oxide can be controlled.
Example 2
The invention also provides a nano rare earth oxide which is prepared by adopting the preparation method of the nano rare earth oxide.
In this embodiment, the nano rare earth oxide includes nano praseodymium oxide, nano gadolinium oxide, nano thulium oxide, nano lanthanum oxide, nano erbium oxide, nano holmium oxide, nano terbium oxide, nano samarium oxide, and nano neodymium oxide.
The nanometer rare earth oxide obtained by the invention has the characteristics of small particle size, uniform particle size distribution, high purity and the like.
Example 3
Firstly, adding 1.75g of ammonium chloride into 7.5g of deionized water at 90 ℃, stirring and dissolving, adding 0.025g of polyethylene glycol and 0.025g of hexadecyl trimethyl ammonium bromide to obtain a mixed solution, gradually adding the mixed solution into 25g of praseodymium oxalate, and uniformly stirring and dispersing to obtain slurry;
secondly, adding 7.5g of deionized water into the obtained slurry, uniformly stirring, putting the slurry into a ball mill, ball-milling for 8min at a rotating speed of about 400r/min, sieving the ball-milled slurry by a filter sieve of 80 meshes, washing and sieving the slurry by using a proper amount of deionized water, and controlling the mass fraction of the obtained emulsion/suspension to be 40%;
thirdly, spraying and drying the emulsion/suspension while stirring, controlling the temperature of the spraying and drying to be 115 ℃, and feeding the mixture at 550ml/h to obtain mixture dry powder; wherein, the water content of the powder after spray drying is not higher than 20 wt%;
fourthly, placing the mixture dry powder into a ceramic crucible, placing the ceramic crucible into a muffle furnace for calcination treatment, setting the calcination temperature to be from room temperature to 800 ℃ and setting the calcination time to be 60 min;
fifthly, performing heat preservation treatment when the temperature reaches 800 ℃, wherein the heat preservation time is 90 min; and (4) cooling after heat preservation, and cooling the furnace body to room temperature for 40min to obtain the nano praseodymium oxide with the particle size of about 50nm and uniform distribution.
Example 4
Firstly, adding 1.75g of ammonium chloride into 7.5g of deionized water at 90 ℃, stirring and dissolving, adding 0.025g of polyethylene glycol and 0.025g of hexadecyl trimethyl ammonium bromide to obtain a mixed solution, gradually adding the mixed solution into 25g of gadolinium carbonate, and uniformly stirring and dispersing to obtain slurry;
secondly, adding 7.5g of deionized water into the obtained slurry, uniformly stirring to obtain slurry, putting the slurry into a ball mill, ball-milling for 8min at a rotating speed of about 400r/min, sieving the ball-milled slurry by using a filter sieve of 80 meshes, washing and sieving the slurry by using a proper amount of deionized water, and controlling the mass fraction of the obtained emulsion/suspension to be 40%;
thirdly, spraying and drying the emulsion/suspension while stirring, controlling the temperature of the spraying and drying to be 115 ℃, and feeding the mixture at 550ml/h to obtain mixture dry powder; wherein, the water content of the powder after spray drying is not higher than 20 wt%;
fourthly, placing the mixture dry powder into a ceramic crucible, placing the ceramic crucible into a muffle furnace for calcination treatment, setting the calcination temperature to be from room temperature to 800 ℃ and setting the calcination time to be 60 min;
fifthly, performing heat preservation treatment when the temperature reaches 800 ℃, wherein the heat preservation time is 90 min; and cooling after heat preservation, and cooling to room temperature along with the furnace body for 40min to obtain the nano gadolinium oxide with the particle size of about 50nm and uniform distribution.
Example 5
Firstly, adding 1.75g of ammonium chloride into 7.5g of deionized water at 90 ℃, stirring and dissolving, adding 0.025g of polyethylene glycol and 0.025g of hexadecyl trimethyl ammonium bromide to obtain a mixed solution, gradually adding the mixed solution into 25g of thulium oxalate, and uniformly stirring and dispersing to obtain slurry;
secondly, adding 7.5g of deionized water into the obtained slurry, uniformly stirring to obtain slurry, putting the slurry into a ball mill, ball-milling for 8min at a rotating speed of about 400r/min, sieving the ball-milled slurry by using a filter sieve of 80 meshes, washing and sieving the slurry by using a proper amount of deionized water, and controlling the mass fraction of the obtained emulsion/suspension to be 40%;
thirdly, spraying and drying the emulsion/suspension while stirring, controlling the temperature of the spraying and drying to be 115 ℃, and feeding the mixture at 550ml/h to obtain mixture dry powder; wherein, the water content of the powder after spray drying is not higher than 20 wt%;
fourthly, placing the mixture dry powder into a ceramic crucible, placing the ceramic crucible into a muffle furnace for calcination treatment, setting the calcination temperature to be from room temperature to 800 ℃ and setting the calcination time to be 60 min;
fifthly, performing heat preservation treatment when the temperature reaches 800 ℃, wherein the heat preservation time is 90 min; and (3) cooling after heat preservation, and cooling the furnace body to room temperature for 40min to obtain the nano thulium oxide with the particle size of 100-200nm and uniform distribution.
Example 6
Firstly, adding 1.75g of ammonium chloride into 7.5g of deionized water at 90 ℃, stirring and dissolving, adding 0.025g of polyethylene glycol and 0.025g of hexadecyl trimethyl ammonium bromide to obtain a mixed solution, gradually adding the mixed solution into 25g of lanthanum carbonate, and uniformly stirring and dispersing to obtain slurry;
secondly, adding 7.5g of deionized water into the obtained slurry, uniformly stirring to obtain slurry, putting the slurry into a ball mill, ball-milling for 8min at a rotating speed of about 400r/min, sieving the ball-milled slurry by using a filter sieve of 80 meshes, washing and sieving the slurry by using a proper amount of deionized water, and controlling the mass fraction of the obtained emulsion/suspension to be 40%;
thirdly, spraying and drying the emulsion/suspension while stirring, controlling the temperature of the spraying and drying to be 115 ℃, and feeding the mixture at 550ml/h to obtain mixture dry powder; wherein, the water content of the powder after spray drying is not higher than 20 wt%;
fourthly, placing the mixture dry powder into a ceramic crucible, placing the ceramic crucible into a muffle furnace for calcination treatment, setting the calcination temperature to be from room temperature to 800 ℃ and setting the calcination time to be 60 min;
fifthly, performing heat preservation treatment when the temperature reaches 800 ℃, wherein the heat preservation time is 90 min; and (4) cooling after heat preservation, and cooling to room temperature along with the furnace body for 40min to obtain the nano lanthanum oxide with the particle size of 50nm and uniform distribution.
Example 7
Firstly, adding 1.75g of ammonium chloride into 7.5g of deionized water at 90 ℃, stirring and dissolving, adding 0.025g of polyethylene glycol and 0.025g of hexadecyl trimethyl ammonium bromide to obtain a mixed solution, gradually adding the mixed solution into 25g of erbium oxalate, and uniformly stirring and dispersing to obtain slurry;
secondly, adding 7.5g of deionized water into the obtained slurry, uniformly stirring to obtain slurry, putting the slurry into a ball mill, ball-milling for 8min at a rotating speed of about 400r/min, sieving the ball-milled slurry by using a filter sieve of 80 meshes, washing and sieving the slurry by using a proper amount of deionized water, and controlling the mass fraction of the obtained emulsion/suspension to be 40%;
thirdly, spraying and drying the emulsion/suspension while stirring, controlling the temperature of the spraying and drying to be 115 ℃, and feeding the mixture at 550ml/h to obtain mixture dry powder; wherein, the water content of the powder after spray drying is not higher than 20 wt%;
fourthly, placing the mixture dry powder into a ceramic crucible, placing the ceramic crucible into a muffle furnace for calcination treatment, setting the calcination temperature to be from room temperature to 800 ℃ and setting the calcination time to be 60 min;
fifthly, performing heat preservation treatment when the temperature reaches 800 ℃, wherein the heat preservation time is 90 min; and (4) cooling after heat preservation, and cooling to room temperature along with the furnace body for 40min to obtain the nano erbium oxide with the particle size of 50nm and uniform distribution.
Example 8
Firstly, adding 1.75g of ammonium chloride into 7.5g of deionized water at 90 ℃, stirring and dissolving, adding 0.025g of polyethylene glycol and 0.025g of hexadecyl trimethyl ammonium bromide to obtain a mixed solution, gradually adding the mixed solution into 25g of holmium oxalate, and uniformly stirring and dispersing to obtain slurry;
secondly, adding 7.5g of deionized water into the obtained slurry, uniformly stirring to obtain slurry, putting the slurry into a ball mill, ball-milling for 8min at a rotating speed of about 400r/min, sieving the ball-milled slurry by using a filter sieve of 80 meshes, washing and sieving the slurry by using a proper amount of deionized water, and controlling the mass fraction of the obtained emulsion/suspension to be 40%;
thirdly, spraying and drying the emulsion/suspension while stirring, controlling the temperature of the spraying and drying to be 115 ℃, and feeding the mixture at 550ml/h to obtain mixture dry powder; wherein, the water content of the powder after spray drying is not higher than 20 wt%;
fourthly, placing the mixture dry powder into a ceramic crucible, placing the ceramic crucible into a muffle furnace for calcination treatment, setting the calcination temperature to be from room temperature to 800 ℃ and setting the calcination time to be 60 min;
fifthly, performing heat preservation treatment when the temperature reaches 800 ℃, wherein the heat preservation time is 90 min; and (4) cooling after heat preservation, and cooling the furnace body to room temperature for 40min to obtain the nano holmium oxide with the particle size of 50nm and uniform distribution.
Example 9
Firstly, adding 1.75g of ammonium chloride into 7.5g of deionized water at 90 ℃, stirring and dissolving, adding 0.025g of polyethylene glycol and 0.025g of hexadecyl trimethyl ammonium bromide to obtain a mixed solution, gradually adding the mixed solution into 25g of terbium oxalate, and uniformly stirring and dispersing to obtain slurry;
secondly, adding 7.5g of deionized water into the obtained slurry, uniformly stirring to obtain slurry, putting the slurry into a ball mill, ball-milling for 8min at a rotating speed of about 400r/min, sieving the ball-milled slurry by using a filter sieve of 80 meshes, washing and sieving the slurry by using a proper amount of deionized water, and controlling the mass fraction of the obtained emulsion/suspension to be 40%;
thirdly, spraying and drying the emulsion/suspension while stirring, controlling the temperature of the spraying and drying to be 115 ℃, and feeding the mixture at 550ml/h to obtain mixture dry powder; wherein, the water content of the powder after spray drying is not higher than 20 wt%;
fourthly, placing the mixture dry powder into a ceramic crucible, placing the ceramic crucible into a muffle furnace for calcination treatment, setting the calcination temperature to be from room temperature to 800 ℃ and setting the calcination time to be 60 min;
fifthly, performing heat preservation treatment when the temperature reaches 800 ℃, wherein the heat preservation time is 90 min; and (3) cooling after heat preservation, and cooling to room temperature along with the furnace body for 40min to obtain the nano terbium oxide with the particle size of 50nm and uniform distribution.
Example 10
Firstly, adding 1.75g of ammonium chloride into 7.5g of deionized water at 90 ℃, stirring and dissolving, adding 0.025g of polyethylene glycol and 0.025g of hexadecyl trimethyl ammonium bromide to obtain a mixed solution, gradually adding the mixed solution into 25g of samarium oxalate, and uniformly stirring and dispersing to obtain slurry;
secondly, adding 7.5g of deionized water into the obtained slurry, uniformly stirring to obtain slurry, putting the slurry into a ball mill, ball-milling for 8min at a rotating speed of about 400r/min, sieving the ball-milled slurry by using a filter sieve of 80 meshes, washing and sieving the slurry by using a proper amount of deionized water, and controlling the mass fraction of the obtained emulsion/suspension to be 40%;
thirdly, spraying and drying the emulsion/suspension while stirring, controlling the temperature of the spraying and drying to be 115 ℃, and feeding the mixture at 550ml/h to obtain mixture dry powder; wherein, the water content of the powder after spray drying is not higher than 20 wt%;
fourthly, placing the mixture dry powder into a ceramic crucible, placing the ceramic crucible into a muffle furnace for calcination treatment, setting the calcination temperature to be from room temperature to 800 ℃ and setting the calcination time to be 60 min;
fifthly, performing heat preservation treatment when the temperature reaches 800 ℃, wherein the heat preservation time is 90 min; and (4) cooling after heat preservation, and cooling to room temperature along with the furnace body for 40min to obtain the nano samarium oxide with the particle size of 50nm and uniform distribution.
Example 11
Firstly, adding 1.75g of ammonium chloride into 7.5g of deionized water at 90 ℃, stirring and dissolving, adding 0.025g of polyethylene glycol and 0.025g of hexadecyl trimethyl ammonium bromide to obtain a mixed solution, gradually adding the mixed solution into 25g of neodymium carbonate, and uniformly stirring and dispersing to obtain slurry;
secondly, adding 7.5g of deionized water into the obtained slurry, uniformly stirring to obtain slurry, putting the slurry into a ball mill, ball-milling for 8min at a rotating speed of about 400r/min, sieving the ball-milled slurry by using a filter sieve of 80 meshes, washing and sieving the slurry by using a proper amount of deionized water, and controlling the mass fraction of the obtained emulsion/suspension to be 40%;
thirdly, spraying and drying the emulsion/suspension while stirring, controlling the temperature of the spraying and drying to be 115 ℃, and feeding the mixture at 550ml/h to obtain mixture dry powder; wherein, the water content of the powder after spray drying is not higher than 20 wt%;
fourthly, placing the mixture dry powder into a ceramic crucible, placing the ceramic crucible into a muffle furnace for calcination treatment, setting the calcination temperature to be from room temperature to 800 ℃ and setting the calcination time to be 60 min;
fifthly, performing heat preservation treatment when the temperature reaches 800 ℃, wherein the heat preservation time is 90 min; and (4) cooling after heat preservation, and cooling to room temperature along with the furnace body for 40min to obtain the nano neodymium oxide with the particle size of 50nm and uniform distribution.
Example 12
Firstly, adding 1.75g of ammonium chloride into 7.5g of deionized water at 90 ℃, stirring and dissolving, adding 0.025g of polyethylene glycol and 0.025g of hexadecyl trimethyl ammonium bromide to obtain a mixed solution, gradually adding the mixed solution into 25g of praseodymium oxalate, and uniformly stirring and dispersing to obtain slurry;
secondly, adding 7.5g of deionized water into the obtained slurry, uniformly stirring to obtain slurry, putting the slurry into a ball mill, ball-milling for 8min at a rotating speed of about 400r/min, sieving the ball-milled slurry by using a filter sieve of 80 meshes, washing and sieving the slurry by using a proper amount of deionized water, and controlling the mass fraction of the obtained emulsion/suspension to be 40%;
thirdly, spraying and drying the emulsion/suspension while stirring, controlling the temperature of the spraying and drying to be 115 ℃, and feeding the mixture at 550ml/h to obtain mixture dry powder; wherein, the water content of the powder after spray drying is not higher than 20 wt%;
fourthly, placing the mixture dry powder into a ceramic crucible, placing the ceramic crucible into a muffle furnace for calcination treatment, setting the calcination temperature to be 300-850 ℃ and setting the calcination time to be 30 min;
fifthly, performing heat preservation treatment when the temperature reaches 850 ℃, wherein the heat preservation time is 60 min; and cooling after heat preservation, and cooling the furnace body to room temperature for 40min to obtain the nano praseodymium oxide with the particle size of 100-200nm and uniform distribution.
Example 13
Firstly, adding 1.75g of sodium chloride into 7.5g of deionized water at 90 ℃, stirring and dissolving, adding 0.025g of polyethylene glycol and 0.025g of hexadecyl trimethyl ammonium bromide to obtain a mixed solution, gradually adding the mixed solution into 25g of praseodymium oxalate, and uniformly stirring and dispersing to obtain a slurry;
secondly, adding 7.5g of deionized water into the obtained slurry, uniformly stirring to obtain slurry, putting the slurry into a ball mill, ball-milling for 8min at a rotating speed of about 400r/min, sieving the ball-milled slurry by using a filter sieve of 80 meshes, washing and sieving the slurry by using a proper amount of deionized water, and controlling the mass fraction of the obtained emulsion/suspension to be 40%;
thirdly, spraying and drying the emulsion/suspension while stirring, controlling the temperature of the spraying and drying to be 115 ℃, and feeding the mixture at 550ml/h to obtain mixture dry powder; wherein, the water content of the powder after spray drying is not higher than 20 wt%;
fourthly, placing the mixture dry powder into a ceramic crucible, placing the ceramic crucible into a muffle furnace for calcination treatment, setting the calcination temperature to be from room temperature to 900 ℃ and setting the calcination time to be 90 min;
fifthly, performing heat preservation treatment when the temperature reaches 900 ℃, wherein the heat preservation time is 60 min; and cooling after heat preservation, and cooling the furnace body to room temperature for 40min to obtain the nano praseodymium oxide with the particle size of 300-400nm and uniform distribution.
Example 14
Firstly, adding 1.75g of ammonium chloride into 7.5g of deionized water at 90 ℃, stirring and dissolving, adding 0.025g of polyethylene glycol and 0.025g of hexadecyl trimethyl ammonium bromide to obtain a mixed solution, gradually adding the mixed solution into 25g of praseodymium oxalate, and uniformly stirring and dispersing to obtain slurry;
secondly, adding 7.5g of deionized water into the obtained slurry, uniformly stirring to obtain slurry, putting the slurry into a ball mill, ball-milling for 8min at a rotating speed of about 400r/min, sieving the ball-milled slurry by using a filter sieve of 80 meshes, washing and sieving the slurry by using a proper amount of deionized water, and controlling the mass fraction of the obtained emulsion/suspension to be 40%;
thirdly, spraying and drying the emulsion/suspension while stirring, controlling the temperature of the spraying and drying to be 115 ℃, and feeding the mixture at 550ml/h to obtain mixture dry powder; wherein, the water content of the powder after spray drying is not higher than 20 wt%;
fourthly, placing the mixture dry powder into a ceramic crucible, placing the ceramic crucible into a muffle furnace for calcination treatment, setting the calcination temperature to be from room temperature to 800 ℃ and setting the calcination time to be 90 min;
fifthly, performing heat preservation treatment when the temperature reaches 800 ℃, wherein the heat preservation time is 60 min; and (3) cooling after heat preservation, and cooling the furnace body to room temperature for 40min to obtain the nano praseodymium oxide with the particle size of 30nm and uniform distribution.
By comparing examples 3 to 11 with example 14, it can be seen that the particle size of the nano-oxide is smaller as the calcination time is longer in the case where the calcination maximum temperature and the calcination time are the same.
By comparing example 13 with example 14, it can be seen that the particle size of the nano-oxide is larger and the change is larger as the maximum temperature is increased under the condition that the calcination time and the holding time at the maximum temperature are the same.
By analyzing the examples 3 to 14, it can be seen that the particle size of the obtained nano oxide is 30nm at the maximum calcination temperature of 800 ℃, and the particle size of the obtained nano rare earth oxide is small and the particle size distribution is relatively uniform.
Although the present invention has been described with reference to a preferred embodiment, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (10)
1. The preparation method of the nanometer rare earth oxide is characterized by comprising the following steps of:
s1: adding molten salt into water, stirring until the molten salt is dissolved, adding a dispersing agent and a surfactant, mixing to obtain a mixed solution, gradually adding the mixed solution into water-insoluble rare earth salt, and stirring until the mixed solution is uniformly dispersed to obtain required slurry; wherein the mass ratio of the rare earth salt to the molten salt is 1: 0.01-5; the mass ratio of the rare earth salt to the water is 1: 0.1-5;
s2: adding water into the slurry, performing ball milling, and sieving by a 80-mesh filter sieve to obtain uniform emulsion/suspension; wherein the mass ratio of the slurry to the water is 1: 0.5 to 4;
s3: dripping the emulsion/suspension obtained in the step S2 into a drying device under the stirring state for spray drying, and obtaining dry powder with the water content not higher than 20 wt%;
s4: and (3) calcining the dried powder obtained in the step (S3) in a furnace body, wherein the calcining stage comprises the following steps: from room temperature to 400 ℃, the heating rate is 0.1-50 ℃/min, the heating rate is 400-600 ℃, the heating rate is 0.1-50 ℃/min, the heating rate is 600-900 ℃, the heating rate is 0.1-50 ℃/min, and the heat preservation time is 0-300 min; cooling to room temperature after calcining to obtain the nano rare earth oxide.
2. The method for preparing nano rare earth oxide according to claim 1, wherein: in S1, the molten salt is at least one of ammonium chloride, sodium chloride, potassium chloride, sodium fluoride, ammonium carbonate, ammonia water, sodium carbonate, potassium carbonate, ammonium citrate, sodium citrate, and potassium citrate.
3. The method for preparing nano rare earth oxide according to claim 1, wherein: in S1, the surfactant is at least one of cetyltrimethylammonium bromide, polyethylene glycol, stearic acid, and quaternary ammonium compound.
4. The method for preparing nano rare earth oxide according to claim 1, wherein: in S1, the rare earth salt is at least one of a carbonate, an acetate, and an oxalate.
5. The method for preparing nano rare earth oxide according to claim 1, wherein: in S2, the ball milling time is 5-10 min.
6. The method for preparing nano rare earth oxide according to claim 1, wherein: in S3, the spray drying temperature is 100-200 ℃.
7. The method for preparing nano rare earth oxide according to claim 4, wherein: the rare earth salt is praseodymium oxalate, thulium oxalate, erbium oxalate, holmium oxalate, terbium oxalate, samarium oxalate, gadolinium carbonate, lanthanum carbonate and neodymium carbonate.
8. The method for preparing nano rare earth oxide according to claim 1, wherein: in S1, the stirring is performed by mechanical stirring.
9. A nanometer rare earth oxide is characterized in that: which is prepared by the method for preparing the nano rare earth oxide as described in any one of claims 1 to 8.
10. The nano rare earth oxide according to claim 9, wherein: the nanometer rare earth oxide is selected from nanometer praseodymium oxide, nanometer gadolinium oxide, nanometer thulium oxide, nanometer lanthanum oxide, nanometer erbium oxide, nanometer holmium oxide, nanometer terbium oxide, nanometer samarium oxide and nanometer neodymium oxide.
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| CN118125491A (en) * | 2024-05-06 | 2024-06-04 | 赣州湛海新材料科技有限公司 | Preparation method of superfine rare earth oxide powder |
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| CN118125491A (en) * | 2024-05-06 | 2024-06-04 | 赣州湛海新材料科技有限公司 | Preparation method of superfine rare earth oxide powder |
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