阅读说明：本技术 一种高纯超细氧化锆的制备方法 (Preparation method of high-purity superfine zirconia ) 是由 张志峰 周海东 余瑶辰 于 2021-02-03 设计创作，主要内容包括：本发明公开了一种高纯超细氧化锆的制备方法,包括以下步骤：S1：配制锆盐水溶液,配制复合萃取剂；两者混合萃取,静置,分相,取有机相,得到含有Zr～(4+)的微乳液A；S2：将短链醇、氨水和复合萃取剂进行混合,配制得到微乳液B；S3：将微乳液A和微乳液B混合,静置陈化反应分层后,底层为沉淀物,中间层为含有铵根的水相,上层为含有复合萃取剂的油相；S4：水相外排,油相经过酸洗和水洗后重新返回进行微乳液A和微乳液B的配制,而沉淀物经过干燥,煅烧后,得到所述高纯超细氧化锆微粒。本发明的氧化锆制备方法,成本低、操作简单,易于批量化制备,所得到的产品纯度高,粒径分布理想,可满足各工业领域的使用。(The invention discloses a preparation method of high-purity superfine zirconia, which comprises the following steps: s1: preparing a zirconium salt aqueous solution and preparing a composite extracting agent; mixing the two, extracting, standing, separating phases, and taking an organic phase to obtain the Zr-containing solution 4+ The microemulsion A of (a); s2: mixing short-chain alcohol, ammonia water and a composite extracting agent to prepare a microemulsion B; s3: mixing the microemulsion A and the microemulsion B, standing, ageing, reacting and layering, wherein the bottom layer is a precipitate, the middle layer is a water phase containing ammonium groups, and the upper layer is an oil phase containing the composite extractant; s4: and discharging the water phase, returning the oil phase after acid washing and water washing to prepare the microemulsion A and the microemulsion B, and drying and calcining the precipitate to obtain the high-purity superfine zirconia particles. The preparation method of the zirconium oxide has the advantages of low cost, simple operation and easy batch preparation, and the obtained product has high purity and ideal particle size distribution and can meet the use requirements of various industrial fields.)

1. The preparation method of the high-purity superfine zirconia is characterized by comprising the following steps:

s1: preparing a zirconium salt aqueous solution, and adjusting the pH to 1-4; preparing a composite extracting agent, wherein the concentration of the composite extracting agent is 0.1-0.5 g/mL; mixing and extracting the prepared zirconium salt aqueous solution and the composite extractant, standing, splitting phases, and taking an organic phase to obtain the Zr-containing solution⁴⁺The microemulsion A of (a);

s2: mixing short-chain alcohol, ammonia water and the composite extracting agent in the step S1 to prepare a microemulsion B;

s3: stirring and mixing the microemulsion A and the microemulsion B in a reaction kettle, and then standing for aging reaction, wherein after the reaction kettle is layered, the bottom layer is a precipitate, the middle layer is a water phase containing ammonium radicals, and the upper layer is an oil phase containing a composite extracting agent;

s4: and discharging the water phase containing ammonium radicals, returning the oil phase containing the composite extracting agent to the steps S1 and S2 after acid washing and water washing to prepare the microemulsion A and the microemulsion B, and drying and calcining the precipitate obtained in the step S3 to obtain the high-purity superfine zirconia particles.

2. The method of preparing high purity ultrafine zirconia according to claim 1, wherein the zirconium salt is zirconium chloride or zirconium nitrate, and the concentration of the zirconium salt is 0.3 to 1 mol/L.

3. The method for preparing high-purity ultrafine zirconia according to claim 1, wherein the composite extractant is a mixed solution of di-n-octylamine, n-octanol and n-hexane, and the mass ratio of the di-n-octylamine, the n-octanol and the n-hexane is 1.2-5.6: 1.5-3.6: 10 to 20.

4. The method of preparing high purity ultrafine zirconia according to claim 1, wherein the volume ratio of the aqueous solution of zirconium salt to the composite extractant is 1: 2 to 8.

5. The method of preparing high purity ultrafine zirconia according to claim 1, wherein the short-chain alcohol is one of propanol, n-butanol or isobutanol.

6. The method for preparing high-purity ultrafine zirconia according to claim 1, wherein the volume ratio of the short-chain alcohol, the ammonia water and the composite extractant is 1: 3.2-5.5: 12 to 27.

7. The method of preparing high purity ultrafine zirconia according to claim 1, wherein in step S3, the microemulsion a and the microemulsion B are Zr-based⁴⁺And short-chain alcohol at a molar ratio of 1: 1-4, carrying out a mixing reaction.

8. The method for preparing high-purity ultrafine zirconia according to claim 1, wherein the aging reaction is carried out at a reaction temperature of 30 to 50 ℃ for 1 to 10 hours.

9. The method of claim 1, wherein the precipitate is dried at a temperature of 110 to 120 ℃ and calcined at a temperature of 750 to 950 ℃.

Technical Field

The invention relates to the technical field of preparation methods of zirconia, in particular to a preparation method of high-purity superfine zirconia.

Background

The nano zirconia has the characteristics of strong thermal shock resistance, high temperature resistance, good chemical stability, outstanding material composite property and the like. The ceramic material is widely applied to the fields of national defense, electronics, high-temperature structures, functional ceramics and the like, and particularly has important application value in the high-tech fields of surface coatings and the like. The nano zirconia material is generally synthesized by a hydrothermal method, a coprecipitation method, a microemulsion method and the like.

Microemulsion method in preparing nanoparticles, a microemulsion is generally composed of a surfactant, a co-surfactant, a solvent and water (or an aqueous solution). In the system, two continuous media which are not mutually soluble are divided into tiny spaces by surfactant amphiphilic molecules to form a micro-reactor, the size of the micro-reactor can be controlled in a nanometer range, and reactants react in the system to generate solid-phase particles. The microemulsion can accurately control the particle size and stability of the nano material, and limits the processes of nucleation, growth, coalescence, agglomeration and the like of the nano particles, so that the formed nano particles are wrapped by a layer of surfactant and have a certain condensed state structure. China CN01130825.7 discloses a method for preparing nano zirconia with controllable particle size, which adopts microemulsion method to prepare nano zirconia, but the method is at the cost of surfactant loss and can not be prepared in scale.

Accordingly, it is desirable to provide a method for preparing high purity ultrafine zirconia.

Disclosure of Invention

In view of the defects of the prior art, the invention aims to provide a preparation method of high-purity superfine zirconia, which aims to solve the problems that the high-purity superfine zirconia cannot be obtained, the high-purity superfine zirconia cannot be prepared in batches, the consumption of a surfactant is high and the like in the conventional zirconia preparation method.

In order to achieve the above purposes, the technical scheme adopted by the invention is as follows:

the preparation method of the high-purity superfine zirconia is characterized by comprising the following steps:

s1: preparing a zirconium salt aqueous solution, and adjusting the pH to 1-4; preparing a composite extracting agent, wherein the concentration of the composite extracting agent is 0.1-0.5 g/mL; mixing and extracting the prepared zirconium salt aqueous solution and the composite extractant, standing, splitting phases, and taking an organic phase to obtain the Zr-containing solution⁴⁺The microemulsion A of (a);

s2: mixing short-chain alcohol, ammonia water and the composite extracting agent in the step S1 to prepare a microemulsion B;

s3: stirring and mixing the microemulsion A and the microemulsion B in a reaction kettle, and then standing for aging reaction, wherein after the reaction kettle is layered, the bottom layer is a precipitate, the middle layer is a water phase containing ammonium radicals, and the upper layer is an oil phase containing a composite extracting agent;

s4: and discharging the water phase containing ammonium radicals, returning the oil phase containing the composite extracting agent to the steps S1 and S2 after acid washing and water washing to prepare the microemulsion A and the microemulsion B, and drying and calcining the precipitate obtained in the step S3 to obtain the high-purity superfine zirconia particles.

Preferably, the zirconium salt is zirconium chloride or zirconium nitrate, and the concentration of the zirconium salt is 0.3-1 mol/L.

Preferably, the composite extracting agent is a mixed solution of di-n-octylamine, n-octanol and n-hexane, and the mass ratio of the di-n-octylamine, the n-octanol and the n-hexane is 1.2-5.6: 1.5-3.6: 10 to 20.

Preferably, the volume ratio of the aqueous solution of the zirconium salt to the composite extractant is 1: 2 to 8.

Preferably, the short-chain alcohol is one of propanol, n-butanol or isobutanol.

Preferably, the volume ratio of the short-chain alcohol to the ammonia water to the composite extracting agent is 1: 3.2-5.5: 12 to 27.

Preferably, in the step S3, the microemulsion A and the microemulsion B are Zr⁴⁺And short-chain alcohol at a molar ratio of 1: 1-4, carrying out a mixing reaction.

Preferably, the reaction temperature of the aging reaction is 30-50 ℃, and the reaction time is 1-10 h.

Preferably, the drying temperature of the precipitate is 110-120 ℃, and the calcining temperature is 750-950 ℃.

The invention has the beneficial effects that:

the invention uses the mixed solution composed of di-n-octylamine, n-octanol and n-hexane as an extracting agent, wherein the di-n-octylamine contains nonpolar groups with alkyl chains and polar groups with amino groups, so that the mixed solution has the property of a surfactant, wherein the n-hexane is an oil phase substance, and the n-octanol plays a role in assisting surface activity, so that an organic phase after extraction balance and a solution after adding ammonia water and short-chain alcohol are all composed of the surfactant, an oil phase and a water phase, and the W/O type microemulsion is obtained. The microemulsion has the function of a micro-reactor, so that the prepared microemulsion A and microemulsion B are subjected to the reaction of zirconium ions, short-chain alcohol and ammonia water in the reactor to form zirconium alkoxide, the zirconium alkoxide is extremely unstable in water and is easy to decompose and condense, and high-purity zirconium dioxide particles are obtained after standing and aging; meanwhile, the microemulsion can also be used as a template, so that the particle size and the morphology of the zirconium dioxide particles generated by the reaction can be effectively controlled.

The preparation method of the zirconium oxide has the outstanding advantages that the preparation process is simple; the energy consumption is low, and the preparation can be carried out in batch; the product after reaction is easy to separate and control; the adopted extractant can be recycled, so that the cost is greatly reduced; the prepared material has stable performance, can meet the requirement of adding the ultra-pure nano zirconia for different purposes, and fully plays the role of the ultra-pure nano zirconia in different application systems.

Detailed Description

The following description is presented to disclose the invention so as to enable any person skilled in the art to practice the invention. The preferred embodiments in the following description are given by way of example only, and other obvious variations will occur to those skilled in the art.

Example 1

The preparation method of the high-purity ultrafine zirconia of the embodiment comprises the following steps:

s1: preparing a zirconium salt aqueous solution, wherein the zirconium salt is zirconium chloride, the concentration of the zirconium salt is 0.3mol/L, and the pH value is adjusted to 2; preparing a composite extracting agent, wherein the composite extracting agent is a mixed solution of di-n-octylamine, n-octanol and n-hexane, and the mass ratio of the di-n-octylamine, the n-octanol and the n-hexane is 1.2: 1.5: 10, the concentration of the composite extracting agent is 0.1 g/mL; mixing and extracting the prepared zirconium salt aqueous solution and the composite extracting agent, wherein the volume ratio of the zirconium salt aqueous solution to the composite extracting agent is 1: 2, standing, carrying out phase separation, taking an organic phase to obtain the Zr-containing material⁴⁺The microemulsion A of (a);

s2: mixing propanol, ammonia water and the composite extracting agent in the step S1 to prepare a microemulsion B; the volume ratio of the propanol to the ammonia water to the composite extractant is 1: 3.2: 12;

s3: stirring and mixing the microemulsion A and the microemulsion B in a reaction kettle, wherein the microemulsion A and the microemulsion B are Zr⁴⁺And propanol at a molar ratio of 1: 2, carrying out mixing reaction, standing and ageing reaction at the reaction temperature of 30 ℃ for 3 hours, wherein after the reaction kettle is layered, the bottom layer is a precipitate, the middle layer is a water phase containing ammonium radicals, and the upper layer is an oil phase containing the composite extractant;

s4: and discharging the water phase containing ammonium radicals, carrying out acid washing and water washing on the oil phase containing the composite extracting agent, returning to the steps S1 and S2 again to prepare the microemulsion A and the microemulsion B, drying and calcining the precipitate obtained in the step S3, wherein the drying temperature of the precipitate is 110 ℃, and the calcining temperature is 780 ℃, so that the high-purity superfine zirconia particles are obtained.

As a result of the examination, the zirconia fine particles obtained in this example had an average particle diameter of 10.4nm and a purity of 99.87%.

Example 2

The preparation method of the high-purity ultrafine zirconia of the embodiment comprises the following steps:

s1: preparing a zirconium salt aqueous solution, wherein the zirconium salt is zirconium chloride, the concentration of the zirconium salt is 0.7mol/L, and the pH value is adjusted to be 3; preparing a composite extracting agent, wherein the composite extracting agent is a mixed solution of di-n-octylamine, n-octanol and n-hexane, and the mass ratio of the di-n-octylamine, the n-octanol and the n-hexane is 3.5: 2.8: 15, the concentration of the composite extracting agent is 0.3 g/mL; mixing and extracting the prepared zirconium salt aqueous solution and the composite extracting agent, wherein the volume ratio of the zirconium salt aqueous solution to the composite extracting agent is 1: 6, standing, carrying out phase separation, taking an organic phase to obtain the Zr-containing material⁴⁺The microemulsion A of (a);

s2: mixing n-butanol, ammonia water and the composite extracting agent in the step S1 to prepare a microemulsion B; the volume ratio of the n-butyl alcohol to the ammonia water to the composite extracting agent is 1: 4.7: 18;

s3: stirring and mixing the microemulsion A and the microemulsion B in a reaction kettle, wherein the microemulsion A and the microemulsion B are Zr⁴⁺And n-butanol at a molar ratio of 1: 3, carrying out mixed reaction, then standing and aging for reaction at the reaction temperature ofThe reaction time is 6 hours at 50 ℃, after the reaction kettle is layered, the bottom layer is a precipitate, the middle layer is a water phase containing ammonium radicals, and the upper layer is an oil phase containing the composite extractant;

s4: and discharging the water phase containing ammonium radicals, carrying out acid washing and water washing on the oil phase containing the composite extracting agent, returning to the steps S1 and S2 again to prepare the microemulsion A and the microemulsion B, drying and calcining the precipitate obtained in the step S3, wherein the drying temperature of the precipitate is 115 ℃, and the calcining temperature is 900 ℃ to obtain the high-purity superfine zirconia particles.

As a result of the examination, the zirconia fine particles obtained in this example had an average particle diameter of 12nm and a purity of 99.77%.

Example 3

The preparation method of the high-purity ultrafine zirconia of the embodiment comprises the following steps:

s1: preparing a zirconium salt aqueous solution, wherein the zirconium salt is zirconium nitrate, the concentration of the zirconium salt is 1mol/L, and the pH value is adjusted to 4; preparing a composite extracting agent, wherein the composite extracting agent is a mixed solution of di-n-octylamine, n-octanol and n-hexane, and the mass ratio of the di-n-octylamine, the n-octanol and the n-hexane is 5.6: 3.6: 20, wherein the concentration of the composite extracting agent is 0.5 g/mL; mixing and extracting the prepared zirconium salt aqueous solution and the composite extracting agent, wherein the volume ratio of the zirconium salt aqueous solution to the composite extracting agent is 1: 8, standing, carrying out phase separation, taking an organic phase to obtain the Zr-containing material⁴⁺The microemulsion A of (a);

s2: mixing isobutanol, ammonia water and the composite extracting agent in the step S1 to prepare a microemulsion B; the volume ratio of the isobutanol to the ammonia water to the composite extracting agent is 1: 5.5: 27;

s3: stirring and mixing the microemulsion A and the microemulsion B in a reaction kettle, wherein the microemulsion A and the microemulsion B are Zr⁴⁺And isobutanol at a molar ratio of 1: 4, carrying out mixing reaction, standing and ageing reaction at the reaction temperature of 50 ℃ for 8 hours, wherein after the reaction kettle is layered, the bottom layer is a precipitate, the middle layer is a water phase containing ammonium radicals, and the upper layer is an oil phase containing the composite extractant;

s4: and discharging the water phase containing ammonium radicals, carrying out acid washing and water washing on the oil phase containing the composite extracting agent, returning to the steps S1 and S2 again to prepare the microemulsion A and the microemulsion B, drying and calcining the precipitate obtained in the step S3, wherein the drying temperature of the precipitate is 120 ℃, and the calcining temperature is 950 ℃, so that the high-purity superfine zirconia particles are obtained.

As a result of the examination, the zirconia fine particles obtained in this example had an average particle diameter of 12.4nm and a purity of 99.79%.

The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are merely illustrative of the principles of the invention, but that various changes and modifications may be made without departing from the spirit and scope of the invention, which fall within the scope of the invention as claimed.