WO2020062954A1 - Method for preparing submicron scandium oxide - Google Patents

Abstract

Disclosed is a method for preparing submicron scandium oxide, comprising: subjecting a mixed solution of a first carboxylic acid extractant and an organic solvent to a first saponification reaction with ammonia water to obtain a first water-oil emulsion; using the first water-oil emulsion to extract a scandium ion-containing solution to obtain a scandium-supported organic phase; subjecting a mixed solution of a second carboxylic acid extractant and an organic solvent to a second saponification reaction with an aqueous sodium hydroxide solution to obtain a second water-oil emulsion, wherein the aqueous sodium hydroxide solution is added in excess relative to the mixed solution of a second carboxylic acid extractant and an organic solvent; subjecting the scandium-supported organic phase to a precipitation reaction in the second water-oil emulsion to obtain a scandium hydroxide precipitate; and calcining the scandium hydroxide precipitate to obtain the submicron scandium oxide. The dimensions and morphology of scandium hydroxide microparticles are effectively controlled in the present method so as to obtain the submicron scandium oxide.

Description

Preparation method of submicron erbium oxide Technical field

The present invention relates to the field of materials chemistry, and in particular, to a method for preparing submicron erbium oxide.

Background technique

The sub-micron material refers to fine particles having a particle diameter of 0.1 to 1.0 μm. Hafnium oxide (Sc ₂ O ₃ ) powder, especially sub-micron grade hafnium oxide, can be used in the preparation of high-efficiency lasers, solid electrolytes, superconducting materials, etc., and has a significant effect on improving material properties.

At present, the method for preparing thorium oxide is mainly a hydrometallurgical method. After thorium ions are dissolved with an acid, thallium ions are directly precipitated with a precipitating agent. For example, Chinese patent 201110186520.2 discloses a method for preparing high-purity thorium oxide, which mainly uses hydrochloric acid to dissolve thallium ions, and the filtrate is added with ammonia water to precipitate to pH 7-8, and then filtered and washed to obtain thorium oxide products. However, the particle size of the products produced by this method is relatively large, and it is impossible to obtain submicron erbium oxide.

Summary of the Invention

The main purpose of the present invention is to provide a method for preparing submicron erbium oxide to solve the problem that the submicron erbium oxide cannot be effectively prepared in the prior art.

In order to achieve the above object, according to an aspect of the present invention, a method for preparing submicron ytterbium oxide is provided, which includes the following steps: a first saponification reaction of a first carboxylic acid extractant-organic solvent mixed solution and ammonia water, A first water-oil emulsion is obtained; a thallium ion-containing solution is subjected to extraction treatment using the first water-oil emulsion to obtain a tritium-supported organic phase; a second carboxylic acid extractant-organic solvent mixed solution and an alkaline solution are subjected to a second saponification reaction To obtain a second water-oil emulsion in which an alkali liquid phase is added in excess to a second carboxylic acid extractant-organic solvent mixed solution, and the alkali liquid is selected from the group consisting of an aqueous sodium hydroxide solution, an aqueous potassium hydroxide solution, an aqueous sodium carbonate solution, and an aqueous potassium carbonate solution. The rhenium-supported organic phase is subjected to a precipitation reaction with a second water-oil emulsion to obtain a rhenium hydroxide precipitate; the rhenium hydroxide precipitate is calcined to obtain a submicron-level rhenium oxide.

Further, the step of the first saponification reaction includes: after the first carboxylic acid extractant-organic solvent mixed solution is mixed with the first phase regulator, ammonia water is added thereto to perform the first saponification reaction; preferably, the second saponification reaction The steps include: after the second carboxylic acid extractant-organic solvent is mixed with the second phase regulator, an alkaline solution is added thereto to perform a second saponification reaction.

Further, the first phase regulator and the second phase regulator are independently selected from alkane-based organic alcohols, preferably the first phase regulator and the second phase regulator are independently selected from n-butanol, n-hexanol, and n-octyl, respectively. One or more of alcohol and isooctanol; preferably, the volume of the first phase regulator relative to the total volume of the first carboxylic acid extractant-organic solvent mixed solution mixed with the first phase regulator The content is 5-25%; preferably, the volume content of the second phase conditioner is 5-25% relative to the total volume of the second carboxylic acid extractant-organic solvent mixed solution and the second phase conditioner. .

Further, the carboxylic acid extractant in the first carboxylic acid extractant-organic solvent and the second carboxylic acid extractant-organic solvent mixed solution is independently selected from the group consisting of aliphatic alkane carboxylic acids, aromatic carboxylic acids, and naphthenic acids. One or more of them; preferably the aliphatic alkane carboxylic acid is one or more of n-hexanoic acid, n-pentanoic acid, n-butyric acid and n-propionic acid; preferably the aromatic hydrocarbon carboxylic acid is sec-octylphenoxy Acetic acid and / or secondary nonylphenoxyacetic acid; preferably naphthenic acid is selected from one or more of carboxylic acids containing cyclopentyl or cyclohexyl.

Further, the organic solvents in the mixed solution of the first carboxylic acid extractant-organic solvent and the second carboxylic acid extractant-organic solvent are each independently selected from alkane solvents, and the alkane solvents are preferably n-octane, n-heptane, One or more of n-hexane, cyclohexane and kerosene.

Further, in the first saponification reaction, the saponification degree of the carboxylic acid extractant in the first carboxylic acid extractant-organic solvent mixed solution is 30 to 70%, and more preferably, the endpoint pH of the first saponification reaction is 2 to 4; In the second saponification reaction, the saponification degree of the carboxylic acid extractant in the second carboxylic acid extractant-organic solvent mixed solution is 50-90%.

Further, the concentration of the carboxylic acid extractant in the first carboxylic acid extractant-organic solvent mixed solution is 0.01 to 3.5 mol / L; preferably, the concentration of the carboxylic acid extractant in the second carboxylic acid extractant-organic solvent mixed solution It is 0.01 to 3.5 mol / L.

Further, the molar ratio between the carboxylic acid extractant in the first water-oil emulsion and the europium ions in the europium ion-containing solution is 3 to 20: 1; preferably, between the europium-loaded organic phase and the second water-oil emulsion The volume ratio is 0.1 to 10: 1.

Further, the thorium ion-containing solution is a thallium chloride-containing aqueous solution, wherein the thallium ion concentration is 0.001 to 1.0 mol / L; more preferably, the thallium ion-containing solution further includes Ca ²⁺ , Mg ²⁺ , Zn ²⁺ , Ni One or more of ²⁺ and Co ²⁺ .

Further, after the step of subjecting the tritium-loaded organic phase to a second water-oil emulsion to perform a precipitation reaction, the preparation method further includes: holding the system after the precipitation reaction at a temperature of 90 to 150 ° C. for precipitation and solid-liquid separation , And further to obtain a rhenium hydroxide precipitate; preferably, the heat preservation precipitation time is 2 to 8 hours.

Further, in the step of calcining the rhenium hydroxide precipitate, the calcination temperature is 400 to 800 ° C.

The invention provides a method for preparing sub-micron ytterbium oxide, which comprises the following steps: performing a first saponification reaction with a first carboxylic acid extractant-organic solvent mixed solution and ammonia water to obtain a first water-oil emulsion; A water-oil emulsion extracts a thorium ion-containing solution to obtain a tritium-supported organic phase; a second carboxylic acid extractant-organic solvent mixed solution and a sodium hydroxide aqueous solution are subjected to a second saponification reaction to obtain a second water-oil emulsion Where the aqueous sodium hydroxide solution is added in excess to the second carboxylic acid extractant-organic solvent mixed solution; the rhenium-supported organic phase is subjected to a precipitation reaction with the second water-oil emulsion to obtain a rhenium hydroxide precipitate; the rhenium hydroxide precipitate is subjected to Calcination to obtain submicron erbium oxide.

In the above preparation method provided by the present invention, the extraction effect of a carboxylic acid extractant and a saponified extractant, the saponification effect of an aqueous ammonia solution and a sodium hydroxide aqueous solution, and a microreactor provided by a water-oil emulsion are used to effectively control thallium hydroxide The size and morphology of the microparticles were further calcined to obtain submicron ytterbium oxide powder. In addition, the method for preparing sub-micron ytterbium oxide powder provided by the present invention also has simple and efficient characteristics. Rhenium is extracted and enriched from the solution and separated from impurity ions, and then the precipitation reaction is completed in the microreactor, which is more conducive to application. For industrial production.

detailed description

It should be noted that, in the case of no conflict, the embodiments in the present application and the features in the embodiments can be combined with each other. The present invention will be described in detail with reference to the following embodiments.

The following further describes the present application in detail with reference to specific embodiments, which cannot be understood as limiting the scope of protection claimed by the present application.

As described in the background section of the present invention, there is a problem in the prior art that the submicron erbium oxide cannot be efficiently prepared.

In order to solve the above problems, the present invention provides a method for preparing sub-micron ytterbium oxide, which includes the following steps: a first saponification reaction of a mixed solution of a first carboxylic acid extractant-organic solvent and ammonia water to obtain a first water- Oil emulsion; the first water-oil emulsion is used to extract the thorium ion-containing solution to obtain the thallium-supported organic phase; the second carboxylic acid extractant-organic solvent mixed solution and the sodium hydroxide aqueous solution are subjected to a second saponification reaction to obtain the first A two-water-oil emulsion; wherein an aqueous solution of sodium hydroxide is added in excess to a second carboxylic acid extractant-organic solvent mixed solution; a tritium-supported organic phase is subjected to a precipitation reaction with a second water-oil emulsion to obtain a tritium hydroxide precipitate; The europium hydroxide precipitate is calcined to obtain submicron erbium oxide.

The carboxylic acid extractant has a similar surface structure of the surfactant and has strong surface activity. After saponification treatment, the obtained saponified extractant has stronger surface activity. Therefore, in the present invention, after the first saponification reaction of the first carboxylic acid extractant-organic solvent mixed solution and ammonia water (the second carboxylic acid extractant-organic solvent mixed solution and the sodium hydroxide aqueous solution are subjected to the second saponification reaction, it has the same principle ), A relatively stable water-oil emulsion can be formed. The carboxylic acid extractant and the saponified extractant formed after saponification are located at the water-oil interface in the emulsion. The carboxylic acid extractant and saponified extractant at the water-oil interface and the water phase enclosed therein constitute a plurality of microreactors, and the plurality of microreactors are stably dispersed in the surrounding organic phase. Secondly, the carboxylic acid extractant and the corresponding saponified extractant have a good extraction effect on thallium ions, which can be enriched and extracted from thallium ion-containing solutions. Therefore, after the above extraction treatment, thallium ions can be extracted and supported in each of the above microreactors to form a thallium-supported organic phase to separate thallium ions from other impurity ions in the thallium ion-containing solution. Subsequently, during the precipitation reaction between the tritium-supported organic phase and the excess sodium hydroxide in the second water-oil emulsion, the tritium ions and sodium hydroxide in the microreactor can form a smaller-sized hydroxide through the precipitation reaction. Rhenium microparticles, Rhenium hydroxide microparticles will be dispersed in the organic phase, and a part of water will be formed in the process. Furthermore, it should be noted that the use of ammonia water in the first saponification reaction of the present invention can not only form a stable first water-oil emulsion, but also be beneficial to control its pH conditions and make the size of the formed microreactor smaller. The use of an aqueous sodium hydroxide solution during the second saponification reaction can also stabilize the second water-oil emulsion and make the precipitation reaction proceed more stably.

The principles of the above steps are as follows:

The first saponification reaction: HA _(o) + NH ₄ OH → NH ₄ A _(o) + H ₂ O; (Subscript _(o) represents organic phase, the same applies hereinafter)

The extraction process is based on the principle of cation exchange, specifically: Sc ³⁺ + 3NH ₄ A _(o) → ScA _{3 (o)} + 3NH ₄ ⁺ ; (NH ₄ A stands for ammonium saponified carboxylic acid extractant)

Precipitation reaction: ScA _{3 (o)} + 3NaOH → Sc (OH) ₃ ↓ + 3NaA _(o) ;

Calcination: 2Sc (OH) ₃ → Sc ₂ O ₃ + 3H ₂ O ↑.

In the above preparation process, the size of the micro-reactor of the water-oil emulsion is in the range of micrometers and nanometers, the middle is a 'small pool', and the shape is spherical, nearly spherical or ellipsoidal. During the saponification reaction, the lipophilic end (ie, alkane chain) of the carboxylic acid extractant extends to the oil phase, and the hydrophilic end (ie, carboxyl group) extends to the pool and gathers on the surface of the small pool. The carboxylic acid is stronger after reacting with the alkali. The surface activity makes the microreactor formed more stable. The purpose of adjusting the particle size of thorium oxide can be achieved by the capacity inside the microreactor.

It should be noted that the carboxylic acid extractant and the saponified extractant formed by the saponification reaction can be separated along with the precipitation of thorium hydroxide after the precipitation reaction is completed. It also helps to prevent the agglomeration of the precipitation and can stabilize the powder form. effect.

In summary, in the above-mentioned preparation method provided by the present invention, the extraction effect of carboxylic acid extractant and saponified extractant, the saponification effect of aqueous ammonia and sodium hydroxide solution, and the microreactor provided by water-oil emulsion are used to effectively control hydrogen. The size and morphology of the holmium oxide microparticles were further calcined to obtain submicron holmium oxide powder. In addition, the method for preparing sub-micron ytterbium oxide powder provided by the present invention also has simple and efficient characteristics. Rhenium is extracted and enriched from the solution and separated from impurity ions, and then the precipitation reaction is completed in the microreactor, which is more conducive to application. For industrial production.

In a preferred embodiment, the step of the first saponification reaction includes: after mixing the first carboxylic acid extractant-organic solvent mixed solution with the first phase regulator, ammonia water is added thereto to perform the first saponification reaction. Adding a first phase modifier to the first carboxylic acid extractant-organic solvent mixed solution is beneficial to further improving the stability of the first water-oil emulsion. In the same way, preferably, the second saponification step includes: after the second carboxylic acid extractant-organic solvent is mixed with the second phase conditioner, an aqueous sodium hydroxide solution is added to the second saponification reaction. It should be noted that the added first phase regulator and the second phase regulator can also be separated along with the precipitation of thorium hydroxide after the precipitation reaction is completed, which is also beneficial to prevent precipitation agglomeration and can further stabilize the powder form. effect.

In a preferred embodiment, the first phase regulator and the second phase regulator are each independently selected from alkane-based organic alcohols, preferably the first phase regulator and the second phase regulator are independently selected from n-butanol Or n-hexanol, n-octanol, and isooctanol. The above-mentioned phase regulator has a stronger stabilizing effect, which is beneficial to further improve the stability of the water-oil emulsion, maintain the stability of the shape and particle size of the microreactor, and then more effectively control the shape and size of the rhenium hydroxide microparticles.

Preferably, relative to the total volume of the first carboxylic acid extractant-organic solvent mixed solution mixed with the first phase regulator, the volume content of the first phase regulator is 5-25%; preferably, relative to the first In terms of the total volume of the mixed solution of the dicarboxylic acid extractant-organic solvent mixed with the second phase regulator, the volume content of the second phase regulator is 5-25%.

The carboxylic acid itself has good surface activity, and can form a more stable water-oil emulsion after saponification with ammonia or sodium hydroxide aqueous solution. In a preferred embodiment, the carboxylic acid extractant in the first carboxylic acid extractant-organic solvent and the second carboxylic acid extractant-organic solvent mixed solution is independently selected from the group consisting of an aliphatic alkane carboxylic acid and an aromatic hydrocarbon group. One or more of carboxylic acids and naphthenic acids. Preferably, the aliphatic alkane carboxylic acid is one or more of n-hexanoic acid, n-pentanoic acid, n-butyric acid, n-propionic acid, and the like; preferably, the aromatic hydrocarbon-based carboxylic acid is secondary octylphenoxyacetic acid and / or secondary nonyl Phenoxyacetic acid; Preferably, the cyclic alkanecarboxylic acid is selected from one or more of carboxylic acids containing cyclopentyl or cyclohexyl. The saponified extractant formed by the saponification reaction of the carboxylic acid described above has stronger surface activity, which is beneficial to further improve the stability of the water-oil emulsion.

The organic solvent in the mixed solution of the first carboxylic acid extractant-organic solvent and the second carboxylic acid extractant-organic solvent only needs to dissolve the carboxylic acid extractant. In a preferred embodiment, the organic solvents in the mixed solution of the first carboxylic acid extractant-organic solvent and the second carboxylic acid extractant-organic solvent are each independently selected from alkane solvents, and the alkane solvents are preferably n-octyl One or more of alkane, n-heptane, n-hexane, cyclohexane and kerosene.

The research by the inventors of the present invention has found that the lower the acidity of the solution, that is, the higher the pH, the more ammonia water is added, the higher the tritium extraction efficiency in the extraction process. In order to maximize the extraction efficiency while stabilizing the water-oil emulsion, in a preferred embodiment, in the first saponification reaction, the degree of saponification of the carboxylic acid extractant in the first carboxylic acid extractant-organic solvent mixed solution is 30. ∼70%, more preferably the end pH of the first saponification reaction is 2-4.

The higher the degree of saponification of the carboxylic acid extractant, the smaller the particle size of the erbium oxide powder produced. In order to stabilize the water-oil emulsion as much as possible to improve the efficiency and stability of the precipitation reaction, and to more effectively control the particle size of the hafnium oxide powder, preferably, in the second saponification reaction, the second carboxylic acid extractant-organic solvent is mixed The degree of saponification of the carboxylic acid extractant in the solution is 50-90%.

In a preferred embodiment, the concentration of the carboxylic acid extractant in the first carboxylic acid extractant-organic solvent mixed solution is 0.01-3.5 mol / L; preferably, the second carboxylic acid extractant-organic solvent mixed solution The concentration of the carboxylic acid extractant is 0.01 to 3.5 mol / L. This is more conducive to controlling the size and morphology of the microreactor, while improving the efficiency of the extraction process.

In order to further improve the extraction efficiency, in a preferred embodiment, the molar ratio between the carboxylic acid extractant in the first water-oil emulsion and the scandium ion in the scandium ion-containing solution is 3-20: 1. And in order to further improve the efficiency of the precipitation reaction, preferably, the volume ratio between the tritium-loaded organic phase and the second water-oil emulsion is 0.1 to 10: 1.

In a preferred embodiment, the thorium ion-containing solution is a thallium chloride-containing aqueous solution, wherein the thallium ion concentration is 0.001 to 1.0 mol / L. Generally, the rubidium ion-containing solution contains some impurity metal ions. Through the above-mentioned extraction process of the present invention, the rubidium ions and the impurity metal ions can be effectively separated. More preferably, the rhenium ion-containing solution further includes one or more of Ca ²⁺ , Mg ²⁺ , Zn ²⁺ , Ni ^2+, and Co ²⁺ . Preferably, the Ca ²⁺ concentration is 0.001 to 0.03 mol / L, the Mg ²⁺ concentration is 0.001 to 0.08 mol / L, the Zn ²⁺ concentration is 0.001 to 0.005 mol / L, and the Ni ²⁺ concentration is 0.001 to 0.1 mol / L. The Co ²⁺ concentration is 0.001 to 0.01 mol / L.

After the above precipitation reaction, thallium ions form thorium hydroxide microparticles. In order to further improve the separation effect of thorium hydroxide, in a preferred embodiment, the thorium-supported organic phase is subjected to a precipitation reaction with a second water-oil emulsion. After the step, the preparation method further includes: holding the system after the precipitation reaction at a temperature of 90 to 150 ° C. for precipitation, and then performing solid-liquid separation to obtain a rhenium hydroxide precipitate. The osmium oxide powder having the same particle size range is generated, and the higher the temperature of the heat preservation and precipitation, the shorter the time required. It is preferred that the heat-retaining time is 2 to 8 hours. The above solid-liquid separation method can be a method commonly used in the art, for example, a high-speed centrifuge can be used for centrifugation.

After the erbium hydroxide precipitate is obtained, it only needs to be calcined to obtain submicron erbium oxide powder. In a preferred embodiment, in the step of calcining the rhenium hydroxide precipitate, the calcination temperature is 400-800 ° C. At this temperature, the decomposition of thorium hydroxide is more complete, and the carboxylic acid extractants and phase regulators that precipitate with it can also be decomposed into CO ₂ and water vapor and removed, and the formed thorium oxide powder is more compact.

During the above-mentioned extraction process, in addition to the tritium-supported organic phase, a part of the aqueous phase may be formed. In an actual operation process, the product of the extraction treatment is preferably subjected to liquid-liquid separation to further obtain the tritium-supported organic phase. In addition, after the precipitation reaction is completed, it is preferable to return the filtrate obtained by the solid-liquid separation to the previous process for configuring the first water-oil emulsion and the second water-oil emulsion. In addition, the osmium extraction process can use mixing methods such as mechanical stirring to speed up the progress of the reaction.

The beneficial effects of the present invention are further illustrated by the following examples:

Example 1

In an extraction reactor, use 500 mL of a kerosene solution containing 1 mol / L CA-12 extractant (sec-nonylphenoxyacetic acid) -10% n-butanol (volume content), and add ammonia to make the degree of saponification of CA-12 to 30 %, The above-mentioned first water / oil microemulsion organic phase was mixed with 500 mL of a rhenium chloride solution containing 0.3 mol / L of rhenium to extract the rhenium in the rhenium-containing hydrochloric acid solution, and the pH of the hydrazone-containing solution was controlled to be 2.5 with ammonia water , Separating and removing the raffinate to obtain a supported organic phase containing tritium;

Use 500mL of kerosene solution containing 1mol / L CA-12 extractant and 10% n-butanol, add sodium hydroxide solution to make the degree of saponification of CA-12 to 70%, and form a translucent and stable second water / oil microemulsion type The organic phase;

Mixing the above-mentioned supported organic phase containing rhenium and the second water / oil microemulsion-type organic phase in a mixed reaction with a volume ratio of 1: 1;

The above-mentioned system containing the organic phase and the aqueous phase was subjected to heat preservation and precipitation at 200 ° C for 2 hours, and then centrifuged with a high-speed centrifuge and subjected to solid-liquid separation treatment to obtain a submicron erbium oxide powder having a surface adsorbed by an extractant and a phase modifier;

The above-mentioned submicron erbium hydroxide powder containing the extractant and the phase modifier was calcined at 500 ° C. in an air atmosphere to form a submicron erbium oxide powder, and the particle diameter of the powder was 0.1-0.4 μm as measured by a transmission electron microscope.

Example 2

In the extraction reactor, use 1000 mL of 3 mol / L naphthenic acid extractant (organic acid produced during the refining of petroleum products, which contains cyclopentyl and cyclohexyl naphthenic acid)-20% isooctanol Alkane solution, adding ammonia water to make the naphthenic acid extractant saponification degree of 50%, mixing the above first water / oil microemulsion organic phase with 500 mL of rhenium chloride solution containing 0.1 mol / L rhenium to extract the rhenium-containing hydrochloric acid solution The tritium in the tritium is controlled by using ammonia to control the pH of the tritium-containing solution to be 3.5, and the raffinate is separated and removed to obtain a supported organic phase containing the tritium;

Use 500mL of n-heptane solution containing 3mol / L naphthenic acid extractant-20% isooctanol, add sodium hydroxide solution to make the naphthenic acid extractant saponification degree of 50%, and form a translucent and stable second water / Oil microemulsion type organic phase;

Mixing the above-mentioned supported organic phase containing rhenium and the second water / oil microemulsion-type organic phase in a mixed reaction with a volume ratio of 1: 1;

The above-mentioned system containing the organic phase and the aqueous phase was subjected to heat preservation and sedimentation at 150 ° C for 4 hours, and then centrifuged with a high-speed centrifuge and subjected to solid-liquid separation treatment to obtain a submicron erbium oxide powder having a surface adsorbed by an extractant and a phase modifier;

The above-mentioned submicron erbium hydroxide powder containing the extractant and the phase modifier was calcined at 500 ° C. in an air atmosphere to form a submicron erbium oxide powder, and the particle size of the powder was 0.5-0.8 μm as measured by a transmission electron microscope.

Example 3

The process in this embodiment is the same as that in Example 1, except that 500 mL of a kerosene solution containing 3.5 mol / L CA-12 extractant and 5% n-butanol is added, and ammonia is added to make the degree of saponification of CA-12 to 70%. , Mixing the above first water / oil microemulsion type organic phase with 500 mL of a rhenium chloride solution containing 0.175 mol / L of rhenium to extract the rhenium in a rhenium-containing hydrochloric acid solution, and controlling the pH of the hydrazone-containing solution to an endpoint pH of 4 with ammonia water, Separating and removing the raffinate to obtain a supported organic phase containing tritium;

The submicron erbium oxide powder has a particle diameter of 0.05 to 0.2 μm as measured by a transmission electron microscope.

Example 4

The process in this example is the same as in Example 1, except that 500 mL of a kerosene solution containing 0.01 mol / L of CA-12 extractant and 25% n-butanol is added, and the degree of saponification of CA-12 is 50% by adding ammonia water. , Mixing the above-mentioned first water / oil microemulsion organic phase with 50 mL of a rhenium chloride solution containing 0.03 mol / L of rhenium to extract the rhenium in a rhenium-containing hydrochloric acid solution, and controlling the pH of the hydrazone-containing solution extraction endpoint pH to 2 with ammonia water, Separating and removing the raffinate to obtain a supported organic phase containing tritium;

Submicron erbium oxide powder has a particle diameter of 0.4-0.7 μm as measured by a transmission electron microscope.

Example 5

The process in this embodiment is the same as in Embodiment 1, except that:

Use 500mL of kerosene solution containing 3.5mol / L CA-12 extractant-5% n-butanol, add sodium hydroxide solution to make the degree of saponification of CA-12 to 90%, and form a translucent and stable second water / oil microemulsion Type organic phase; the above-mentioned supported organic phase containing rhenium and the second water / oil microemulsion type organic phase are mixed and reacted.

Submicron erbium oxide powder has a particle diameter of 0.1-0.3 μm as measured by a transmission electron microscope.

Example 6

The process in this embodiment is the same as in Embodiment 1, except that:

Use 500mL of kerosene solution containing 0.01mol / L CA-12 extractant and 25% n-butanol, add sodium hydroxide solution to make the degree of saponification of CA-12 to 80%, and form a translucent and stable second water / oil microemulsion Type organic phase; the above-mentioned supported organic phase containing rhenium and the second water / oil microemulsion type organic phase are mixed and reacted.

The submicron erbium oxide powder has a particle diameter of 0.3 to 0.5 μm as measured by a transmission electron microscope.

Example 7

The process in this embodiment is the same as in Example 1, except that the volume ratio of the supported organic phase containing rhenium and the second water / oil microemulsion organic phase is 10: 1 when the reaction is mixed;

The submicron erbium oxide powder has a particle diameter of 0.2-0.5 μm as measured by a transmission electron microscope.

Example 8

The process in this embodiment is the same as in Example 1, except that the volume ratio of the supported organic phase containing rhenium and the second water / oil microemulsion organic phase is 1:10 when the reaction is mixed;

The submicron erbium oxide powder has a particle diameter of 0.05 to 0.2 μm as measured by a transmission electron microscope.

From the above description, it can be seen that the foregoing embodiments of the present invention achieve the following technical effects:

In the above preparation method provided by the present invention, the extraction effect of a carboxylic acid extractant and a saponified extractant, the saponification effect of an aqueous ammonia solution and a sodium hydroxide aqueous solution, and a microreactor provided by a water-oil emulsion are used to effectively control thallium hydroxide The size and morphology of the microparticles were further calcined to obtain submicron ytterbium oxide powder. In addition, the method for preparing sub-micron ytterbium oxide powder provided by the present invention also has simple and efficient characteristics. Rhenium is extracted and enriched from the solution and separated from impurity ions, and then the precipitation reaction is completed in the microreactor, which is more conducive to application. For industrial production.

The above descriptions are merely preferred embodiments of the present invention and are not intended to limit the present invention. For those skilled in the art, the present invention may have various modifications and changes. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims (11)

1. A method for preparing sub-micron erbium oxide comprises the following steps:

   Performing a first saponification reaction with a first carboxylic acid extractant-organic solvent mixed solution and ammonia water to obtain a first water-oil emulsion;

   Using the first water-oil emulsion to perform an extraction treatment on a thorium ion-containing solution to obtain a thallium-supported organic phase;

   Performing a second saponification reaction with the second carboxylic acid extractant-organic solvent mixed solution and the alkaline solution to obtain a second water-oil emulsion, wherein the alkaline liquid phase is in excess of the second carboxylic acid extractant-organic solvent mixed solution Adding, the lye is selected from one or more of sodium hydroxide aqueous solution, potassium hydroxide aqueous solution, sodium carbonate aqueous solution, and potassium carbonate aqueous solution;

   Precipitating the tritium-supported organic phase with the second water-oil emulsion to obtain a tritium hydroxide precipitate;

   The ytterbium hydroxide precipitate is calcined to obtain the submicron ytterbium oxide.
2. The preparation method according to claim 1, wherein the step of the first saponification reaction comprises: after mixing the first carboxylic acid extractant-organic solvent mixed solution with a first phase regulator, adding it The ammonia water performs the first saponification reaction;

   Preferably, the step of the second saponification reaction comprises: after mixing the second carboxylic acid extractant-organic solvent and a second phase conditioner, adding the lye to the second saponification reaction.
3. The method according to claim 2, wherein the first phase regulator and the second phase regulator are independently selected from alkane-based organic alcohols, preferably the first phase regulator and the second phase regulator The second phase regulator is independently selected from one or more of n-butanol, n-hexanol, n-octanol and isooctanol;

   Preferably, relative to the total volume of the first carboxylic acid extractant-organic solvent mixed solution mixed with the first phase regulator, the volume content of the first phase regulator is 5-25%;

   Preferably, relative to the total volume of the second carboxylic acid extractant-organic solvent mixed solution and the second phase regulator, the volume content of the second phase regulator is 5-25%.
4. The preparation method according to any one of claims 1 to 3, wherein the carboxylic acid is extracted from a mixed solution of the first carboxylic acid extractant-organic solvent and the second carboxylic acid extractant-organic solvent. The agents are independently selected from one or more of aliphatic alkane carboxylic acids, aromatic carboxylic acids and naphthenic acids;

   Preferably, the aliphatic alkane-based carboxylic acid is one or more of n-hexanoic acid, n-valeric acid, n-butyric acid and n-propionic acid;

   Preferably, the aromatic hydrocarbon carboxylic acid is secondary octylphenoxyacetic acid and / or secondary nonylphenoxyacetic acid;

   Preferably, the naphthenic acid is selected from one or more of carboxylic acids containing cyclopentyl or cyclohexyl.
5. The preparation method according to claim 4, wherein the organic solvents in the first carboxylic acid extractant-organic solvent and the second carboxylic acid extractant-organic solvent mixed solution are independently selected from the group consisting of alkanes The solvent is preferably one or more of n-octane, n-heptane, n-hexane, cyclohexane and kerosene.
6. The preparation method according to any one of claims 1 to 5, wherein in the first saponification reaction, a saponification degree of the carboxylic acid extractant in the first carboxylic acid extractant-organic solvent mixed solution is 30 to 70%, more preferably the endpoint pH of the first saponification reaction is 2 to 4; preferably, in the second saponification reaction, the second carboxylic acid extractant-organic solvent mixed solution is a carboxylic acid extractant The degree of saponification is 50-90%.
7. The preparation method according to claim 6, wherein the concentration of the carboxylic acid extractant in the first carboxylic acid extractant-organic solvent mixed solution is 0.01 to 3.5 mol / L; preferably, the second carboxylic acid extractant The concentration of the carboxylic acid extractant in the acid extractant-organic solvent mixed solution is 0.01 to 3.5 mol / L.
8. The preparation method according to claim 6, wherein the molar ratio between the carboxylic acid extractant in the first water-oil emulsion and the europium ions in the europium ion-containing solution is 3 to 20: 1; preferably The volume ratio between the tritium-loaded organic phase and the second water-oil emulsion is 0.1 to 10: 1.
9. The preparation method according to any one of claims 1 to 5, wherein the thorium ion-containing solution is a thallium chloride-containing aqueous solution, wherein the thallium ion concentration is 0.001 to 1.0 mol / L; more preferably The samarium ion-containing solution further includes one or more of Ca ²⁺ , Mg ²⁺ , Zn ²⁺ , Ni ²⁺ and Co ²⁺ .
10. The preparation method according to any one of claims 1 to 5, wherein after the step of subjecting the tritium-supported organic phase to a second water-oil emulsion to perform a precipitation reaction, the preparation method further comprises: The system after the precipitation reaction is subjected to thermal precipitation at 90-150 ° C, and then solid-liquid separation is performed to further obtain the thorium hydroxide precipitation; preferably, the thermal precipitation time is 2-8 hours.
11. The method according to any one of claims 1 to 5, characterized in that in the step of calcining the rhenium hydroxide precipitate, the calcination temperature is 400 to 800 ° C.