Preparation method of small-particle-size high-purity germanium dioxide

Abstract

The invention provides a preparation method of small-particle-size high-purity germanium dioxide, and relates to the technical field of new material preparation, and the preparation method comprises the following steps: S1, preparation of a hydrolysis solution, S2, spraying hydrolysis of germanium tetrachloride, S3, low-temperature aging, S4, solid-liquid separation and washing, and S5, high-temperature drying. The germanium dioxide production process is simple, low in cost and efficient, and the product is small in particle size and good in uniformity.

Description

Technical Field

[0001] This invention relates to the field of new material preparation technology, and in particular to a method for preparing high-purity germanium dioxide with small particle size. Background Technology

[0002] Currently, high-purity germanium dioxide is widely used in the production of high-purity metallic germanium, germanium compounds, chemical catalysts, PET resins, electronic devices, and healthcare industries. However, existing high-purity germanium dioxide methods all have certain problems. The precursor method requires conventional high-purity germanium dioxide as raw material and then reprocessing it to produce small-particle high-purity germanium dioxide, resulting in a long process, high cost, and waste of process and resources. The oxidation method requires germanium metal as raw material and then reprocessing it to produce small-particle high-purity germanium dioxide, which is even longer and more expensive than the precursor method, and has no prospect for industrial application. Summary of the Invention

[0003] The purpose of this invention is to address the shortcomings of existing technologies by proposing a method for preparing high-purity germanium dioxide with small particle size.

[0004] To achieve the above objectives, the present invention adopts the following technical solution: a method for preparing high-purity germanium dioxide with small particle size, comprising the following steps: S1: Preparation of hydrolysis solution: Mix polyacrylic acid and high-purity water thoroughly to obtain the hydrolysis solution; S2: Spray hydrolysis of germanium tetrachloride: The hydrolysis solution prepared in step S1 is sent to the hydrolysis tower for cooling. The hydrolysis solution in the hydrolysis tower is pumped to the ejector by an acid-resistant pump to form a negative pressure, and high-purity germanium tetrachloride is drawn into the ejector. The hydrolysis solution and high-purity germanium tetrachloride are fully emulsified and mixed in the ejector, and a hydrolysis reaction occurs to generate germanium dioxide, which then enters the hydrolysis tower. After all the germanium tetrachloride is drawn in, the acid-resistant pump emulsifies and mixes the solid-liquid mixture in the hydrolysis tower at the ejector and circulates it within a set circulation time. S3: Low-temperature aging: The solid-liquid mixture generated in step S2 is subjected to low-temperature settling and aging; S4: Solid-liquid separation and washing: The solid-liquid mixture obtained in step S3 is subjected to solid-liquid separation, and washed and separated with high-purity water. The solid obtained is germanium dioxide containing water. S5: High-temperature drying: Dry the aqueous germanium dioxide obtained in step S4 to obtain high-purity germanium dioxide with small particle size.

[0005] Preferably, in step S1, the volume ratio of polyacrylic acid to high-purity water is 0.01 to 0.06:1.

[0006] Preferably, in step S2, the acidic waste gas generated during the spray hydrolysis process is discharged to a waste gas treatment facility for compliant disposal.

[0007] Preferably, in step S2, the set temperature for cooling is -2 to -10°C, the volume ratio of high-purity germanium tetrachloride to hydrolysis solution is 1:6 to 8, and the cycle time is 50 to 180 min.

[0008] Preferably, in step S3, the solution obtained after solid-liquid separation is returned to germanium production for germanium recovery.

[0009] Preferably, in step S3, the settling and aging time is 30 to 120 minutes.

[0010] Preferably, in step S4, the washing is completed after the solution obtained by washing with high-purity water has a pH of 5-7.

[0011] Preferably, in step S5, the aqueous germanium dioxide is dried at a constant temperature of 300–500°C for 5–10 hours.

[0012] Preferably, the acid-resistant pump is connected to the ejector and the lower middle part of the hydrolysis tower via pipelines.

[0013] Compared with existing technologies, the beneficial effects of this invention are as follows: The process for producing germanium dioxide is simple, low-cost, and highly efficient, producing products with small particle size and good uniformity. The preparation of the hydrolysis solution utilizes polyacrylic acid, which is readily soluble in water and has a dispersing effect on germanium dioxide. This solves the problem of severe agglomeration during the crystal growth process after the reaction of high-purity water with germanium tetrachloride to produce germanium dioxide, leading to increased particle size. The hydrolysis solution and high-purity germanium tetrachloride undergo a continuous inhibitory effect, reducing the particle size of germanium dioxide. The hydrolysis reaction is completed in a jet hydrolysis device. The jet injector sprays the hydrolysis solution at high speed, driving and accelerating the surrounding gas, creating a negative pressure around the jet injector. This draws the high-purity germanium tetrachloride into the jet injector, where it is rapidly atomized or emulsified and thoroughly mixed with the hydrolysis solution, allowing for a reaction. Subsequent circulation ensures the complete completion of the hydrolysis reaction. Compared to... Traditional mechanical stirring hydrolysis reactions are superseded by high-speed jet hydrolysis, which offers advantages such as more thorough mixing and emulsification, and more complete and rapid hydrolysis of germanium tetrachloride. Furthermore, the continuous high-speed rinsing within the confined space of the jet effectively breaks down the agglomeration and mutual encapsulation of germanium dioxide, thereby effectively controlling the particle size of the germanium dioxide product to achieve a D50 of 2-4 μm and a D90 of 4-8 μm. Static aging ensures that the germanium dioxide crystals reach a stable state, facilitating subsequent solid-liquid separation. Washing and solid-liquid separation remove adsorbed HCl, polyacrylic acid, other impurities, and as much moisture as possible from the germanium dioxide particles, ensuring high purity. A relatively high drying temperature thoroughly removes moisture and any remaining polyacrylic acid from the germanium dioxide, ensuring that the germanium dioxide does not undergo crystallization. Attached Figure Description

[0014] Figure 1 This is a schematic diagram showing the distribution of the jet hydrolysis equipment used in the preparation method of high-purity germanium dioxide with small particle size according to the present invention.

[0015] Figure description: 1-Hydrolysis tower, 2-Outer jacket of hydrolysis tower, 3-Acid-resistant pump, 4-Ejector, 5-Hydrolysis solution inlet, 6-GeCl4 inlet, 7-Discharge port, 8-Tail gas outlet, 9-Hydrolysis solution inlet valve, 10-GeCl4 inlet valve, 11-Bottom valve of hydrolysis tower, 12-Discharge valve. Detailed Implementation

[0016] To provide a further understanding of the purpose, structure, features, and functions of the present invention, detailed descriptions are provided below with reference to specific embodiments. Example 1

[0017] Please refer to the reference. Figure 1 This invention provides a method for preparing high-purity germanium dioxide with small particle size, comprising the following steps: S1: Preparation of hydrolysis solution: Polyacrylic acid and high-purity water are thoroughly mixed to obtain a hydrolysis solution. Polyacrylic acid is easily soluble in water and has a dispersing effect on germanium dioxide. High molecular weight polyacrylic acid can form a protective layer on the surface of germanium dioxide particles through physical adsorption, which inhibits particle collision and agglomeration. S2: Spray hydrolysis of germanium tetrachloride: The hydrolysis solution prepared in step S1 is sent to the hydrolysis tower 1 for cooling. The hydrolysis solution in the hydrolysis tower 1 is pumped to the ejector 4 by the acid-resistant pump 3 to form a negative pressure, drawing high-purity germanium tetrachloride into the ejector 4. The hydrolysis solution and high-purity germanium tetrachloride are fully emulsified and mixed in the ejector 4, and a hydrolysis reaction occurs to generate germanium dioxide, which then enters the hydrolysis tower 1. After all the germanium tetrachloride is drawn in, the acid-resistant pump 3 emulsifies and mixes the solid-liquid mixture in the hydrolysis tower 1 at the ejector 4 and circulates it within a set circulation time. The ejector 4 sprays the hydrolysis solution at high speed to drive and accelerate the process. The surrounding gas creates a negative pressure around the ejector 4, which draws high-purity germanium tetrachloride into the power ejector 4 and rapidly atomizes or emulsifies it with the hydrolysis solution, ensuring thorough mixing and reaction. The subsequent circulation process ensures the complete completion of the hydrolysis reaction. Compared with the traditional mechanical stirring hydrolysis reaction, the hydrolysis reaction carried out by high-speed jetting has the advantages of more thorough mixing and emulsification, more thorough and rapid germanium tetrachloride hydrolysis reaction. Moreover, because it is constantly being high-speed flushed in the narrow space inside the ejector, it can effectively break the agglomeration and mutual encapsulation of germanium dioxide, thereby effectively controlling the particle size of the germanium dioxide product. S3: Low-temperature aging: The solid-liquid mixture generated in step S2 is subjected to low-temperature settling and aging; S4: Solid-liquid separation and washing: The solid-liquid mixture obtained in step S3 is subjected to solid-liquid separation, and washed and separated with high-purity water. The solid obtained is germanium dioxide containing water. S5: High-temperature drying: The aqueous germanium dioxide obtained in step S4 is dried to obtain high-purity germanium dioxide with small particle size. During the washing to neutralization and drying process, the carboxylic acid groups on the polyacrylic acid molecular chain dissociate into carboxylate ions under neutral or alkaline conditions. The ions stabilize the particle surface through electrostatic repulsion and prevent agglomeration. This solves the problem of severe agglomeration during the crystal growth process after high-purity water reacts with germanium tetrachloride to generate germanium dioxide, which leads to larger particle size. It inhibits the agglomeration of germanium dioxide and continues to play an inhibitory role, reducing the particle size of germanium dioxide.

[0018] In one embodiment, in step S1, the volume ratio of polyacrylic acid to high-purity water is 0.01 to 0.06:1.

[0019] In one embodiment, in step S2, the acidic waste gas generated during the spray hydrolysis process is discharged to a waste gas treatment facility for compliant disposal.

[0020] In one embodiment, in step S2, the temperature of the circulating cryosol is set to -2 to -10°C, the volume ratio of the high-purity germanium tetrachloride to the hydrolysis solution is 1:6 to 8, and the circulation time is 50 to 180 min.

[0021] In one embodiment, in step S3, the solution obtained after solid-liquid separation is returned to germanium production for germanium recovery.

[0022] In one embodiment, in step S3, the settling and aging time is 30 to 120 minutes. The settling and aging ensures that the germanium dioxide crystals reach a stable state, which is beneficial for subsequent solid-liquid separation.

[0023] In one embodiment, in step S4, the washing is completed after the solution obtained by washing with high-purity water has a pH of 5-7. The washing process removes HCl, polyacrylic acid, other impurities, and as much water as possible from the germanium dioxide particles through washing and solid-liquid separation, ensuring that the germanium dioxide has a high purity.

[0024] In one embodiment, in step S5, the aqueous germanium dioxide is dried at a constant temperature of 300-500°C for 5-10 hours to thoroughly remove moisture and a small amount of residual polyacrylic acid from the germanium dioxide, and to ensure that the germanium dioxide does not undergo crystallization.

[0025] In one embodiment, such as Figure 1 As shown, the acid-resistant pump 3 is connected to the ejector 4 and the lower middle part of the hydrolysis tower 1 through pipelines.

[0026] The specific steps for producing small-particle-size, high-purity germanium dioxide are as follows: S1: Preparation of hydrolysis solution: Mix polyacrylic acid and high-purity water thoroughly to obtain the hydrolysis solution; S2: Spray hydrolysis of germanium tetrachloride: In the spray hydrolysis equipment, the hydrolysis solution prepared in step S1 is pumped into the hydrolysis tower 1 through the hydrolysis solution inlet 5, and then the hydrolysis solution inlet valve 9 is closed. Circulating coolant is introduced into the outer jacket 2 of the hydrolysis tower to cool the solution inside the hydrolysis tower 1. The GeCl4 inlet valve 10 is opened, and the acid-resistant pump 3 is started to pump the hydrolysis solution in the hydrolysis tower 1 to the ejector 4. Due to the high-speed spray, a negative pressure is formed, drawing high-purity germanium tetrachloride from the GeCl4 inlet 6 into the ejector 4. The hydrolysis solution and high-purity germanium tetrachloride undergo thorough emulsification and... After mixing and undergoing hydrolysis to generate germanium dioxide, it enters the hydrolysis tower 1. After all the high-purity germanium tetrachloride in the GeCl4 inlet 6 is absorbed, the GeCl4 inlet valve 10 is closed and the bottom valve 11 of the hydrolysis tower is opened, allowing the solid-liquid mixture in the hydrolysis tower 1 to continue to emulsify, mix and circulate at the ejector 4 to ensure that the solid-liquid mixture in the hydrolysis tower 1 reacts fully and is evenly dispersed. After controlling a certain circulation time, the acid-resistant pump 3 and the bottom valve 11 of the hydrolysis tower are closed, and the jet hydrolysis process is completed. The acidic waste gas generated during the jet hydrolysis process is discharged to the waste gas treatment facility for compliant disposal through the tail gas outlet 8. S3: Low-temperature aging: The solid-liquid mixture generated in step S2 is subjected to low-temperature settling and aging in hydrolysis tower 1.

[0027] S4: Solid-liquid separation and washing: After opening the discharge valve 12, the solid-liquid mixture obtained in step S3 is discharged from the discharge port 7 and then subjected to solid-liquid separation. High-purity water is used for washing and solid-liquid separation. The obtained solid is germanium dioxide containing water, and the solution is returned to germanium production for germanium recovery.

[0028] S5: High-temperature drying: The aqueous germanium dioxide obtained in step S4 is placed in a drying device for drying to obtain high-purity germanium dioxide with small particle size, and D50: 2~4um, D90: 4~8um.

[0029] The GeCl4 inlet 6 is connected to the bottom of the ejector 4 and the hydrolysis tower 1 via pipelines, and the pipelines are equipped with a GeCl4 feed valve 10 and a hydrolysis tower bottom valve 11. The bottom of the hydrolysis tower 1 is connected to the discharge port 7 via pipelines, and the pipelines are equipped with a discharge valve 12. The top of the hydrolysis tower 1 is connected to the ejector 4, the hydrolysis solution inlet 5, and the tail gas outlet 8 via pipelines. The pipeline between the top of the hydrolysis tower 1 and the hydrolysis solution inlet 5 is equipped with a hydrolysis solution feed valve 9. The outer jacket 2 of the hydrolysis tower is fixed to the outer wall of the hydrolysis tower 1.

[0030] Usage: Combine Figure 1As shown, the ejector 4 sprays the hydrolysis solution at high speed, driving and accelerating the surrounding gas, creating a negative pressure state around the ejector 4. This draws high-purity germanium tetrachloride into the ejector 4, where it is rapidly atomized or emulsified with the hydrolysis solution, thoroughly mixed, and reacts. The subsequent circulation process ensures the complete completion of the hydrolysis reaction. Static aging ensures that the germanium dioxide crystals reach a stable state, which is beneficial for subsequent solid-liquid separation. By washing and solid-liquid separation, the HCl, polyacrylic acid, other impurities, and as much moisture as possible adsorbed in the germanium dioxide particles are removed. A relatively high drying temperature is used to thoroughly remove moisture and a small amount of residual polyacrylic acid from the germanium dioxide, while ensuring that the germanium dioxide does not undergo crystallization. Example 2

[0031] This invention provides a method for preparing high-purity germanium dioxide with small particle size, comprising the following steps: S1: Preparation of hydrolysis solution: Polyacrylic acid and high-purity water are thoroughly mixed at a volume ratio of 0.06:1 to obtain the hydrolysis solution; S2: Spray hydrolysis of germanium tetrachloride: In the spray hydrolysis equipment, the hydrolysis solution prepared in step S1 is pumped into the hydrolysis tower 1 through the hydrolysis solution inlet 5, and then the hydrolysis solution inlet valve 9 is closed. A circulating coolant is introduced into the outer jacket 2 of the hydrolysis tower to cool the solution inside the hydrolysis tower 1. The temperature of the circulating coolant is set to -10℃. The GeCl4 inlet valve 10 is opened, and the acid-resistant pump 3 is started to pump the hydrolysis solution in the hydrolysis tower 1 to the ejector 4. Due to the high-speed spray, a negative pressure is formed, drawing high-purity germanium tetrachloride from the GeCl4 inlet 6 into the ejector 4. The hydrolysis solution and high-purity germanium tetrachloride are fully emulsified and mixed in the ejector 4. After undergoing a hydrolysis reaction to generate germanium dioxide, it enters the hydrolysis tower 1. The volume ratio of high-purity germanium tetrachloride to the hydrolysis solution is 1:8. After all the high-purity germanium tetrachloride is drawn in through the GeCl4 inlet 6, the GeCl4 inlet valve 10 is closed and the bottom valve 11 of the hydrolysis tower is opened. The solid-liquid mixture in the hydrolysis tower 1 continues to emulsify, mix and circulate at the ejector 4 to ensure that the solid-liquid mixture in the hydrolysis tower 1 reacts fully and is evenly dispersed. After circulating for 150 minutes, the acid-resistant pump 3 and the bottom valve 11 of the hydrolysis tower are closed, and the jet hydrolysis process is completed. The acidic waste gas generated during the jet hydrolysis process is discharged to the waste gas treatment facility for compliant disposal through the tail gas outlet 8. S3: Low-temperature aging: The solid-liquid mixture generated in step S2 is subjected to low-temperature settling and aging in hydrolysis tower 1 for 45 minutes.

[0032] S4: Solid-liquid separation and washing: After opening the discharge valve 12, the solid-liquid mixture obtained in step S3 is discharged from the discharge port 7 and then subjected to solid-liquid separation. High-purity water is used for washing and solid-liquid separation until the pH of the washed solution reaches 6, after which the washing is completed. The obtained solid is germanium dioxide containing water. The solution is returned to germanium production for germanium recovery.

[0033] S5: High-temperature drying: The aqueous germanium dioxide obtained in step S4 is placed in a drying device and dried at a constant temperature of 480℃ for 6 hours to obtain high-purity germanium dioxide with small particle size, D50: 2.1um and D90: 4.5um. Example 3

[0034] This invention provides a method for preparing high-purity germanium dioxide with small particle size, comprising the following steps: S1: Preparation of hydrolysis solution: Polyacrylic acid and high-purity water are thoroughly mixed at a volume ratio of 0.01:1 to obtain the hydrolysis solution; S2: Spray hydrolysis of germanium tetrachloride: In the spray hydrolysis equipment, the hydrolysis solution prepared in step S1 is pumped into the hydrolysis tower 1 through the hydrolysis solution inlet 5, and then the hydrolysis solution inlet valve 9 is closed. Circulating coolant is introduced into the outer jacket 2 of the hydrolysis tower to cool the solution inside the hydrolysis tower 1. The temperature of the circulating coolant is set to -2℃. The GeCl4 inlet valve 10 is opened, and the acid-resistant pump 3 is started to pump the hydrolysis solution in the hydrolysis tower 1 to the ejector 4. Due to the high-speed spray, a negative pressure is formed, drawing high-purity germanium tetrachloride from the GeCl4 inlet 6 into the ejector 4. The hydrolysis solution and high-purity germanium tetrachloride are fully emulsified and mixed in the ejector 4. After undergoing a hydrolysis reaction to generate germanium dioxide, it enters the hydrolysis tower 1. The volume ratio of high-purity germanium tetrachloride to the hydrolysis solution is 1:6. After all the high-purity germanium tetrachloride is drawn in through the GeCl4 inlet 6, the GeCl4 inlet valve 10 is closed and the bottom valve 11 of the hydrolysis tower is opened. The solid-liquid mixture in the hydrolysis tower 1 continues to emulsify, mix and circulate at the ejector 4 to ensure that the solid-liquid mixture in the hydrolysis tower 1 reacts fully and is evenly dispersed. After circulating for 60 minutes, the acid-resistant pump 3 and the bottom valve 11 of the hydrolysis tower are closed, and the jet hydrolysis process is completed. The acidic waste gas generated during the jet hydrolysis process is discharged to the waste gas treatment facility for compliant disposal through the tail gas outlet 8. S3: Low-temperature aging: The solid-liquid mixture generated in step S2 is subjected to low-temperature settling and aging in hydrolysis tower 1 for 100 min.

[0035] S4: Solid-liquid separation and washing: After opening the discharge valve 12, the solid-liquid mixture obtained in step S3 is discharged from the discharge port 7 and then subjected to solid-liquid separation. High-purity water is used for washing and solid-liquid separation until the pH of the washed solution reaches 5, after which the washing is completed. The obtained solid is germanium dioxide containing water. The solution is returned to germanium production for germanium recovery.

[0036] S5: High-temperature drying: The aqueous germanium dioxide obtained in step S4 is placed in a drying device and dried at a constant temperature of 350℃ for 10 hours to obtain high-purity germanium dioxide with small particle size, D50: 3.5um and D90: 7.2um. Example 4

[0037] This invention provides a method for preparing high-purity germanium dioxide with small particle size, comprising the following steps: S1: Preparation of hydrolysis solution: Polyacrylic acid and high-purity water are thoroughly mixed at a volume ratio of 0.03:1 to obtain the hydrolysis solution; S2: Spray hydrolysis of germanium tetrachloride: In the spray hydrolysis equipment, the hydrolysis solution prepared in step S1 is pumped into the hydrolysis tower 1 through the hydrolysis solution inlet 5, and then the hydrolysis solution inlet valve 9 is closed. Circulating coolant is introduced into the outer jacket 2 of the hydrolysis tower to cool the solution inside the hydrolysis tower 1. The temperature of the circulating coolant is set to -6℃. The GeCl4 inlet valve 10 is opened, and the acid-resistant pump 3 is started to pump the hydrolysis solution in the hydrolysis tower 1 to the ejector 4. Due to the high-speed spray, a negative pressure is formed, drawing high-purity germanium tetrachloride from the GeCl4 inlet 6 into the ejector 4. The hydrolysis solution and high-purity germanium tetrachloride are fully emulsified and mixed in the ejector 4. After undergoing a hydrolysis reaction to generate germanium dioxide, it enters the hydrolysis tower 1. The volume ratio of high-purity germanium tetrachloride to the hydrolysis solution is 1:7. After all the high-purity germanium tetrachloride is drawn in through the GeCl4 inlet 6, the GeCl4 inlet valve 10 is closed and the bottom valve 11 of the hydrolysis tower is opened. The solid-liquid mixture in the hydrolysis tower 1 continues to emulsify, mix and circulate at the ejector 4 to ensure that the solid-liquid mixture in the hydrolysis tower 1 reacts fully and is evenly dispersed. After circulating for 120 minutes, the acid-resistant pump 3 and the bottom valve 11 of the hydrolysis tower are closed, and the jet hydrolysis process is completed. The acidic waste gas generated during the jet hydrolysis process is discharged to the waste gas treatment facility for compliant disposal through the tail gas outlet 8. S3: Low-temperature aging: The solid-liquid mixture generated in step S2 is subjected to low-temperature settling and aging in hydrolysis tower 1 for 80 minutes.

[0038] S4: Solid-liquid separation and washing: After opening the discharge valve 12, the solid-liquid mixture obtained in step S3 is discharged from the discharge port 7 and then subjected to solid-liquid separation. High-purity water is used for washing and solid-liquid separation until the pH of the washed solution reaches 6, after which the washing is completed. The obtained solid is germanium dioxide containing water. The solution is returned to germanium production for germanium recovery.

[0039] S5: High-temperature drying: The aqueous germanium dioxide obtained in step S4 is placed in a drying device and dried at a constant temperature of 400℃ for 7 hours to obtain high-purity germanium dioxide with small particle size, D50: 2.9um and D90: 5.1um.

[0040] The present invention has been described in the above-described embodiments; however, these embodiments are merely examples for implementing the present invention. It must be noted that the disclosed embodiments do not limit the scope of the present invention. Conversely, any modifications and refinements made without departing from the spirit and scope of the present invention are within the scope of patent protection of the present invention.

Claims

1. A method for preparing high-purity germanium dioxide with small particle size, characterized in that: Includes the following steps: S1: Preparation of hydrolysis solution: Mix polyacrylic acid and high-purity water thoroughly to obtain the hydrolysis solution; S2: Spray hydrolysis of germanium tetrachloride: The hydrolysis solution prepared in step S1 is sent to the hydrolysis tower (1) for cooling. The hydrolysis solution in the hydrolysis tower (1) is pumped to the ejector (4) by the acid-resistant pump (3) and a negative pressure is formed. High-purity germanium tetrachloride is drawn into the ejector (4). The hydrolysis solution and high-purity germanium tetrachloride are fully emulsified and mixed in the ejector (4) and undergo a hydrolysis reaction to generate germanium dioxide. Then it enters the hydrolysis tower (1). After all the germanium tetrachloride is drawn in, the acid-resistant pump (3) emulsifies and mixes the solid-liquid mixture in the hydrolysis tower (1) at the ejector (4) and circulates it within a set circulation time. S3: Low-temperature aging: The solid-liquid mixture generated in step S2 is subjected to low-temperature settling and aging; S4: Solid-liquid separation and washing: The solid-liquid mixture obtained in step S3 is subjected to solid-liquid separation, and washed and separated with high-purity water. The solid obtained is germanium dioxide containing water. S5: High-temperature drying: Dry the aqueous germanium dioxide obtained in step S4 to obtain high-purity germanium dioxide with small particle size.

2. The method for preparing small-particle-size high-purity germanium dioxide as described in claim 1, characterized in that: In step S1, the volume ratio of polyacrylic acid to high-purity water is 0.01 to 0.06:

1.

3. The method for preparing small-particle-size high-purity germanium dioxide as described in claim 1, characterized in that: In step S2, the acidic waste gas generated during the spray hydrolysis process is discharged to the waste gas treatment facility for compliant disposal.

4. The method for preparing small-particle-size high-purity germanium dioxide as described in claim 1, characterized in that: In step S2, the cooling temperature is set to -2 to -10°C, the volume ratio of high-purity germanium tetrachloride to hydrolysis solution is 1:6 to 8, and the cycle time is 50 to 180 min.

5. The method for preparing small-particle-size high-purity germanium dioxide as described in claim 1, characterized in that: In step S3, the solution obtained after solid-liquid separation is returned to germanium production for germanium recovery.

6. The method for preparing small-particle-size high-purity germanium dioxide as described in claim 1, characterized in that: In step S3, the settling and aging time is 30 to 120 minutes.

7. The method for preparing high-purity germanium dioxide with small particle size as described in claim 1, characterized in that: In step S4, the washing process is completed after the solution obtained by washing with high-purity water has a pH of 5-7.

8. The method for preparing small-particle-size high-purity germanium dioxide as described in claim 1, characterized in that: In step S5, the aqueous germanium dioxide is dried at a constant temperature of 300-500°C for 5-10 hours.

9. The method for preparing high-purity germanium dioxide with small particle size as described in claim 1, characterized in that: The acid-resistant pump (3) is connected to the lower middle part of the ejector (4) and the hydrolysis tower (1) through pipelines.

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