CN110526272B - Micro-nano structure CeCO3Preparation process of OH - Google Patents

Abstract

The invention discloses a micro-nano structure CeCO₃The preparation process of OH is characterized in that cerium salt is used as a precursor, and the CeCO with the almond type or hollow spherical structure is synthesized and prepared by a hydrothermal method₃OH superfine powder material. The invention has CeCO₃The OH has the characteristics of adjustable appearance, uniform size, good dispersibility and simple preparation process.

Description

A kind of preparation technology of micro-nano structure CeCO3OH

technical field

The invention relates to a preparation process of CeCO ₃ OH, in particular to a preparation process of CeCO ₃ OH with a micro-nano structure.

Background technique

Cerium is the rare earth element with the largest reserves in the earth's crust, and the compound of cerium has a good functional application route. Cerium carbonate hydroxide (CeCO ₃ OH) is an important functional material, which not only provides unique optical properties related to its different structures and morphologies, but also possesses novel electronic and chemical properties, and CeCO ₃ OH microstructure exhibits Excellent electrochemical reversibility, an important feature for many applications such as Li-ion batteries. In particular, the different structures and morphologies of CeCO ₃ OH have different properties and can be used for different applications, and _{CeCO 3} OH with different morphologies can be prepared by simple thermal decomposition with the morphology unchanged. Realizing the controlled synthesis of nano-CeCO ₃ OH crystal structure and morphology, more applications and new functional materials may appear.

In recent years, nano _- CeCO3OH with different morphologies have been synthesized by different methods, such as self-assembly, sonochemical, hydrothermal and microwave-assisted hydrothermal methods. Among all the preparation methods, the hydrothermal method is considered to be an efficient and economical preparation method due to its advantages of low synthesis temperature, high powder reactivity and diversified morphology control. In hydrothermal systems, most reports on the synthesis of nanoscale CeCO ₃ OH crystals use CO(NH ₂ ) ₂ bases and carbon sources, and add surfactants or templates to modulate the nucleation and crystal growth of CeCO ₃ OH particles. prepared. This complicates the process and costs more raw materials.

At present, the morphologies of _{CeCO 3} OH reported in domestic and foreign literatures mainly include needle-like, rod-like and triangular shapes, while the preparation of almond-like and spherical CeCO ₃ OH has not been reported yet. The properties of the obtained CeO ₂ have important influences.

In addition, my country is a big country of rare earth, and a large amount of rare earth resources are exported to the country after mining and refining, and are processed into high value-added rare earth products. Rare earth resources are important resources, and it is very important for our country to develop the preparation process and products of high value-added rare earth products. As CeCO ₃ OH is an important and potential rare earth product, the research on the preparation process of high-quality CeCO ₃ OH is also of great significance to the comprehensive technology development and reserve of China's rare earth industry.

Therefore, the present invention develops a process for preparing and regulating CeCO ₃ OH of micro-nano structure. The prepared CeCO ₃ OH has uniform morphology and size, good dispersion performance, simple preparation process and good industrial application prospect.

SUMMARY OF THE INVENTION

The purpose of the present invention is to provide a preparation process of CeCO ₃ OH with a micro-nano structure. The invention has the characteristics of adjustable appearance of CeCO ₃ OH, uniform size, good dispersibility and simple preparation process.

The technical scheme of the present invention: a preparation process of CeCO ₃ OH with a micro-nano structure, using cerium salt as a precursor to synthesize an almond-shaped or hollow spherical structure CeCO ₃ OH ultrafine powder material by a hydrothermal method.

The preparation process of the aforementioned micro-nano structure CeCO ₃ OH, the specific steps are as follows:

1) Dissolve the cerium salt in distilled water, stir until a transparent solution is formed to obtain product A;

2) Dissolve ammonium bicarbonate in distilled water, add absolute ethanol, stir until a transparent solution is formed, and obtain product B;

3) Mix product A and product B, stir until a white milky slurry is formed, and then continue to stir the slurry for 0.1-1 h to obtain product C;

4) Put C product into the autoclave and seal, and pressurize and heat treatment, and naturally cool to room temperature after the treatment to obtain D product;

5) Wash product D and filter to obtain a white precipitate. After drying the white precipitate, a CeCO ₃ OH ultrafine powder material is obtained.

In the aforementioned preparation process of CeCO ₃ OH with a micro-nano structure, the cerium salt in step 1) is Ce(NO ₃ ) ₃ ·6H ₂ O or CeCl ₃ ·7H ₂ O.

In the aforementioned preparation process of CeCO ₃ OH with micro-nano structure, the molar ratio of ammonium bicarbonate and absolute ethanol in step 2) is 3:0.1-0.5.

In the aforementioned preparation process of CeCO ₃ OH with micro-nano structure, when product A and product B are mixed in step 3), the molar ratio of cerium salt in product A to ammonium bicarbonate in product B is 0.1-1:3.

In the aforementioned preparation process of CeCO ₃ OH with micro-nano structure, the white milky slurry in step 3) adopts magnetic stirring.

In the aforementioned preparation process of CeCO ₃ OH with a micro-nano structure, during the heating and pressure treatment in step 4), the pressure is 0.5-3 MPa, the temperature is 80-180° C., and the treatment time is 12-48 h.

In the aforementioned preparation process of CeCO ₃ OH with micro-nano structure, the washing in step 5) is to alternately wash with distilled water and anhydrous ethanol.

In the aforementioned preparation process of CeCO ₃ OH with a micro-nano structure, the drying in step 5) adopts vacuum drying, the drying temperature is 30-40° C., and the drying time is 10-15 h.

In the aforementioned preparation process of CeCO ₃ OH with a micro-nano structure, the average size of the CeCO ₃ OH ultrafine powder material is 0.2-1.5 μm.

The beneficial effects of the present invention

1. The present invention can realize the adjustment of the morphology of CeCO ₃ OH on the basis of adjusting different process parameters through the same process, and prepare the CeCO ₃ OH ultrafine powder material with almond-shaped or hollow spherical structure, which expands the CeCO 3 OH structure. The morphology and structure type of ₃ OH ultrafine powder material, the morphology remains unchanged after calcination, which fills the technical gap in the preparation of almond-shaped and hollow spherical CeCO ₃ OH micro-nano structure, and is very important for the development of rare earth materials in China and the development of high value-added rare earth products. are of significance;

2. The size of the CeCO ₃ OH ultrafine powder material prepared by the present invention is uniform, between 0.2-1.5 μm, and has good dispersion performance;

3. The present invention adopts the hydrothermal method, the method is simple, the operation is convenient, and has the characteristics and advantages of mass production.

Description of drawings

Accompanying drawing 1 is the SEM image of the almond-shaped CeCO ₃ OH ultrafine powder material prepared by the present invention;

Accompanying drawing 2 is the XRD pattern of the almond-shaped CeCO ₃ OH ultrafine powder material obtained by the present invention;

Accompanying drawing 3 is the SEM image of the hollow spherical CeCO ₃ OH ultrafine powder material prepared by the present invention;

Fig. 4 is the XRD pattern of the hollow spherical CeCO ₃ OH ultrafine powder material prepared by the present invention.

It can be seen from Figure 1 and Figure 3 that the almond-shaped and hollow spherical CeCO ₃ OH ultrafine powder materials prepared by the present invention are relatively uniform in shape and size, and have good dispersibility. The corresponding crystal phases can be seen from Figures 2 and 4.

Detailed ways

The present invention will be further described below in conjunction with the examples, but not as a basis for limiting the present invention.

Embodiments of the present invention

Embodiment 1: the preparation process of micro-nano structure CeCO ₃ OH, the specific steps are as follows:

1) Dissolve Ce(NO ₃ ) ₃ ·6H ₂ O in distilled water, stir until a transparent solution is formed, and obtain product A;

2) dissolving ammonium bicarbonate in distilled water, and adding absolute ethanol (the mol ratio of ammonium bicarbonate and absolute ethanol is 3:0.3), stirring to form a transparent solution to obtain product B;

3) Mix product A and product B (the molar ratio of Ce(NO ₃ ) ₃ 6H ₂ O in product A to ammonium bicarbonate in product B is 0.3:3), stir until a white milky slurry is formed, and then continue magnetic stirring Stir the slurry for 0.5h to obtain C product;

4) Put C product into an autoclave and seal it, process it at 2MPa and 130°C for 30h, and naturally cool it to room temperature after the treatment to obtain D product;

5) Wash product D with distilled water and anhydrous ethanol alternately, and then filter to obtain a white precipitate. The white precipitate is vacuum-dried at 35°C for 12 hours to obtain CeCO ₃ OH ultrafine powder material.

The morphology of the CeCO ₃ OH ultrafine powder material prepared in this example is almond-shaped.

Embodiment 2: the preparation process of micro-nano structure CeCO ₃ OH, the specific steps are as follows:

1) Dissolve Ce(NO ₃ ) ₃ ·6H ₂ O in distilled water, stir until a transparent solution is formed, and obtain product A;

2) dissolving ammonium bicarbonate in distilled water, and adding absolute ethanol (the mol ratio of ammonium bicarbonate and absolute ethanol is 3:0.1), stirring to form a transparent solution to obtain product B;

3) Mix product A and product B (the molar ratio of Ce(NO ₃ ) ₃ 6H ₂ O in product A to ammonium bicarbonate in product B is 0.1:3), stir until a white milky slurry is formed, and then continue magnetic stirring Stir the slurry for 0.1h to obtain C product;

4) Put C product into an autoclave and seal it, process it at 0.5MPa and 80°C for 12h, and naturally cool it to room temperature after the treatment to obtain D product;

5) Wash product D with distilled water and anhydrous ethanol alternately and then filter to obtain white precipitate, which is vacuum dried at 30°C for 10 hours to obtain CeCO ₃ OH ultrafine powder material.

The morphology of the CeCO ₃ OH ultrafine powder material prepared in this example is almond-shaped.

Embodiment 3: the preparation process of micro-nano structure CeCO ₃ OH, the specific steps are as follows:

1) Dissolve CeCl ₃ ·7H ₂ O in distilled water, stir until a transparent solution is formed to obtain product A;

2) dissolving ammonium bicarbonate in distilled water, and adding absolute ethanol (the mol ratio of ammonium bicarbonate and absolute ethanol is 3:0.5), stirring to form a transparent solution to obtain product B;

3) Mix product A and product B (the molar ratio of CeCl ₃ ·7H ₂ O in product A to ammonium bicarbonate in product B is 0.5:3), stir until a white milky slurry is formed, and then continue to magnetically stir the slurry for 1 h, get C grade;

4) Put C product into the autoclave to seal, process at 3MPa and 180 ° C for 48h, and naturally cool to room temperature after the treatment to obtain D product;

5) Wash product D with distilled water and anhydrous ethanol alternately and then filter to obtain white precipitate, which is vacuum dried at 40°C for 15 hours to obtain CeCO ₃ OH ultrafine powder material.

The morphology of the CeCO ₃ OH ultrafine powder material prepared in this example is almond-shaped.

Embodiment 4: the preparation process of micro-nano structure CeCO ₃ OH, the specific steps are as follows:

1) Dissolve Ce(NO ₃ ) ₃ ·6H ₂ O in distilled water, stir until a transparent solution is formed, and obtain product A;

2) dissolving ammonium bicarbonate in distilled water, and adding absolute ethanol (the mol ratio of ammonium bicarbonate and absolute ethanol is 3:0.3), stirring to form a transparent solution to obtain product B;

3) Mix product A and product B (the molar ratio of Ce(NO ₃ ) ₃ 6H ₂ O in product A to ammonium bicarbonate in product B is 0.9:3), stir until a white milky slurry is formed, and then continue magnetic stirring Stir the slurry for 0.5h to obtain C product;

4) Put C product into an autoclave and seal it, process it at 2MPa and 130°C for 30h, and naturally cool it to room temperature after the treatment to obtain D product;

5) Wash product D with distilled water and anhydrous ethanol alternately, and then filter to obtain a white precipitate. The white precipitate is vacuum-dried at 35°C for 12 hours to obtain CeCO ₃ OH ultrafine powder material.

The morphology of the CeCO ₃ OH ultrafine powder material prepared in this example is a hollow spherical shape.

Embodiment 5: the preparation process of micro-nano structure CeCO ₃ OH, the specific steps are as follows:

1) Dissolve Ce(NO ₃ ) ₃ ·6H ₂ O in distilled water, stir until a transparent solution is formed, and obtain product A;

2) dissolving ammonium bicarbonate in distilled water, and adding absolute ethanol (the mol ratio of ammonium bicarbonate and absolute ethanol is 3:0.1), stirring to form a transparent solution to obtain product B;

3) Mix product A and product B (the molar ratio of Ce(NO ₃ ) ₃ 6H ₂ O in product A to ammonium bicarbonate in product B is 0.8:3), stir until a white milky slurry is formed, and then continue magnetic stirring Stir the slurry for 0.1h to obtain C product;

4) Put C product into an autoclave and seal it, process it at 0.5MPa and 80°C for 12h, and naturally cool it to room temperature after the treatment to obtain D product;

5) Wash product D with distilled water and anhydrous ethanol alternately and then filter to obtain white precipitate, which is vacuum dried at 30°C for 10 hours to obtain CeCO ₃ OH ultrafine powder material.

The morphology of the CeCO ₃ OH ultrafine powder material prepared in this example is a hollow spherical shape.

Embodiment 6: the preparation process of micro-nano structure CeCO ₃ OH, the specific steps are as follows:

1) Dissolve CeCl ₃ ·7H ₂ O in distilled water, stir until a transparent solution is formed to obtain product A;

2) dissolving ammonium bicarbonate in distilled water, and adding absolute ethanol (the mol ratio of ammonium bicarbonate and absolute ethanol is 3:0.5), stirring to form a transparent solution to obtain product B;

3) Mix product A and product B (the molar ratio of CeCl ₃ ·7H ₂ O in product A to ammonium bicarbonate in product B is 1:3), stir until a white milky slurry is formed, and then continue to magnetically stir the slurry for 1 h, get C grade;

4) Put C product into the autoclave to seal, process at 3MPa and 180 ° C for 48h, and naturally cool to room temperature after the treatment to obtain D product;

5) Wash product D with distilled water and anhydrous ethanol alternately and then filter to obtain white precipitate, which is vacuum dried at 40°C for 15 hours to obtain CeCO ₃ OH ultrafine powder material.

The morphology of the CeCO ₃ OH ultrafine powder material prepared in this example is a hollow spherical shape.

The above description is only a preferred embodiment of the present invention, but the protection scope of the present invention is not limited to this. The equivalent replacement or modification of the created technical solution and its inventive concept shall be included within the protection scope of the present invention.

Claims (6)

1. Micro-nano structure CeCO₃The preparation process of OH is characterized by comprising the following steps: adopts cerium salt as a precursor, and prepares the almond-type or hollow spherical CeCO by hydrothermal synthesis₃OH superfine powder material; the method comprises the following specific steps:

1) dissolving cerium salt in distilled water, and stirring to form transparent solution to obtain product A;

2) dissolving ammonium bicarbonate in distilled water, adding anhydrous ethanol, and stirring to obtain transparent solution B; the molar ratio of the ammonium bicarbonate to the absolute ethyl alcohol is 3: 0.1-0.5;

3) mixing product A and product B, stirring to form white milky slurry, and stirring for 0.1-1 hr to obtain product C; when the product A and the product B are mixed, the molar ratio of the cerium salt in the product A to the ammonium bicarbonate in the product B is 0.1-1: 3;

4) sealing the product C in a high-pressure reaction kettle, pressurizing and heating, and naturally cooling to room temperature after the treatment is finished to obtain a product D; the pressure is 0.5-3MPa, the temperature is 80-180 ℃, and the treatment time is 12-48 h;

5) washing the product D, filtering to obtain white precipitate, and drying to obtain CeCO₃OH superfine powder material.

2. Micro-nano structure CeCO according to claim 1₃The preparation process of OH is characterized by comprising the following steps: step 1) the cerium salt is Ce (NO)₃)₃·6H₂O or CeCl₃·7H₂O。

3. Micro-nano structure CeCO according to claim 1₃The preparation process of OH is characterized by comprising the following steps: and 3) magnetically stirring the white milky slurry.

4. Micro-nano structure CeCO according to claim 1₃The preparation process of OH is characterized by comprising the following steps: and step 5), washing is alternately washing by using distilled water and absolute ethyl alcohol.

5. Micro-nano structure CeCO according to claim 1₃The preparation process of OH is characterized by comprising the following steps: and 5) drying in vacuum at 30-40 ℃ for 10-15 h.

6. Micro-nano structure CeCO according to claim 1₃The preparation process of OH is characterized by comprising the following steps: the CeCO₃The average size of the OH superfine powder material is 0.2-1.5 mu m.

Images