CN116199251A - Method for efficiently preparing gallium oxyhydroxide - Google Patents

Abstract

The invention belongs to the technical field of nonferrous metal metallurgy, and particularly relates to a method for efficiently preparing gallium oxyhydroxide. The technical scheme of the invention can solve the problems of long process flow, large reagent consumption, high requirement on equipment, difficult achievement of standards of product purity and physical specification and the like of the existing gallium oxyhydroxide preparation process, has the characteristics of low requirement on equipment, simple operation, low energy consumption, short process, high efficiency, low cost and the like, and can realize the high-efficiency short-process preparation of high-purity gallium oxyhydroxide powder materials.

Description

A method for efficiently preparing gallium oxyhydroxide

technical field

The invention belongs to the technical field of nonferrous metal metallurgy, and in particular relates to a method for efficiently preparing gallium oxyhydroxide.

Background technique

Gallium oxide (Ga ₂ O ₃ ) is an ultra-wide bandgap semiconductor, the latest fourth-generation semiconductor material, with a bandgap as high as 4.9-5.3eV. In contrast, semiconductors such as silicon carbide (SiC) and gallium nitride (GaN) have a bandgap of 3.25eV and 3.4eV, respectively, while the bandgap of silicon is only 1.1eV. The ultra-high band gap makes Ga ₂ O ₃ have high radiation resistance, high temperature resistance and high breakdown field strength. The prepared device can maintain stability in extreme environments such as high and low temperature, strong radiation, etc., and its power semiconductor performance data It is twice as much as Si, SiC and GaN, and it is the preferred material for the preparation of high-power semiconductor electronic devices. It has very important application value in high-power electronic devices, ultraviolet transparent conduction, solar blind detection, gas sensing, etc.

With the rapid development of high-tech industries such as information, energy, transportation, and national defense, the industry's demand for gallium oxide is increasing day by day. The production of high-purity gallium oxide usually uses high-purity metal gallium or gallium salt as raw materials. First, a gallium oxyhydroxide precursor with a purity and size that meets the requirements is prepared, and then high-purity gallium oxide is obtained by further high-temperature calcination. Therefore, the preparation of qualified gallium oxyhydroxide is the necessary condition and technical core for the production of gallium oxide.

After retrieval, the Chinese patent application No. 201810752162.9 discloses a method for preparing gallium oxide, which uses sulfuric acid and hydrogen peroxide as solvents to react with metal gallium to form a gallium sulfate solution, and then further crystallizes out gallium sulfate crystals, which are obtained by high-temperature calcination. Gallium oxide powder. Because this solution uses sulfuric acid with relatively low reactivity, it is necessary to add hydrogen peroxide to promote the dissolution process of metal gallium during leaching, the reagent cost is high, and the process of preparing gallium oxide by calcining gallium sulfate at high temperature will produce SO ₂ fume, which is environmentally friendly The pressure is high.

Chinese patent application numbers 201711418839.7 and 201710311705.9 disclose a method for preparing gallium oxyhydroxide using gallium metal as a raw material, preferably using nitric acid as a dissolving agent to react with gallium metal to form a gallium nitrate solution, and then further adding lye to the solution Neutralize and obtain gallium oxyhydroxide powder after aging; on this basis, the Chinese patent application number 202010436819.8 proposes to add surfactants such as dodecylbenzenesulfonic acid in the preparation of gallium nitrate solution to promote The next stage is the process of neutralizing and precipitating gallium oxyhydroxide; the above three applications are all based on the basic idea of metal gallium acid dissolution and alkali neutralization to prepare gallium oxyhydroxide, which involves the consumption of a large amount of reagents such as acid and alkali, not only the cost of reagents is high, It is easy to introduce impurities and affect the purity of the product, and the acid and alkali cannot be recovered, resulting in high-salt wastewater that is difficult to treat.

The Chinese patent application No. 201210542115.4 discloses a method for electrochemically preparing gallium oxyhydroxide, using metal gallium as the anode to conduct three-stage electrolysis in lye electrolyte to obtain sodium gallate solution, further neutralizing, washing and drying Gallium oxyhydroxide was obtained. Although this method can obtain high-purity products, the process of obtaining sodium gallate solution by electrolyzing metal gallium is not only long and complicated, but also requires high energy consumption and poor economic efficiency.

The Chinese patent application No. 201210313080.7 discloses a preparation method of gallium oxyhydroxide nanocrystals, using a benzene saturated solution of gallium chloride and cetyltrimethylammonium bromide as raw materials in a high-pressure reactor for 160 Gallium oxyhydroxide nanocrystals were successfully obtained by reacting at -200°C for 10-18 hours. However, this method requires high energy consumption, high equipment requirements, and is prone to produce difficult-to-treat organic wastewater, which poses a high pressure on environmental protection.

Chinese patent application numbers 201910971014.0 and 201510835364.6 disclose a short-process method for preparing gallium oxyhydroxide based on hydrothermal reaction. The gallium oxyhydroxide powder is obtained by direct reaction of metal gallium with water, but the reaction between metal gallium and water It needs to be carried out under high temperature and high pressure conditions above 150°C, which not only requires high energy consumption, but also requires the use of high-cost pressure reaction equipment, and the mechanical stirring method cannot fully disperse and stir the liquid gallium metal, resulting in water The thermal reaction is difficult to complete, and gallium oxyhydroxide powder materials with uniform shape and size cannot be obtained.

In summary, the existing gallium oxyhydroxide preparation process still has a lot of room for optimization and improvement. It is necessary to further develop a gallium oxyhydroxide preparation process technology with simple operation, short process, low cost and environmental friendliness to support the fourth High-quality development of the modern semiconductor industry.

Contents of the invention

The purpose of the present invention is to overcome the problems of the existing gallium oxyhydroxide preparation process, such as long process flow, large consumption of reagents, high requirements on equipment, difficulty in meeting product purity and physical specifications, etc., and provide a method for efficiently preparing gallium oxyhydroxide. The process technology of the present invention has the characteristics of low equipment requirements, simple operation, low energy consumption, short process, high efficiency, low cost, etc., and can realize efficient and short process preparation of high-purity gallium oxyhydroxide powder material.

In order to achieve the above-mentioned technical purpose and achieve the above-mentioned technical effect, the present invention is realized through the following technical solutions:

A method for efficiently preparing gallium oxyhydroxide. Under normal pressure, metal gallium is added to deionized water, and oxygen or air is blown into the system at the same time, and metal gallium is converted into gallium oxyhydroxide under mechanical stirring conditions to achieve high Efficient short-process preparation of pure gallium oxyhydroxide powder materials.

Further, the method for efficiently preparing gallium oxyhydroxide as described above, the specific process operation is:

1) adding metal gallium to deionized water in proportion;

2) under normal pressure, the system is heated to a predetermined temperature, and oxygen or air is blown into the system at the same time, and metal gallium is converted into gallium oxyhydroxide under mechanical stirring conditions;

3) After the reaction, the resulting mixed slurry is filtered to achieve solid-liquid separation;

4) drying the filter residue to obtain a high-purity gallium oxyhydroxide powder material.

Further, in the method for efficiently preparing gallium oxyhydroxide as described above, in step 1), the purity of gallium metal is above 4N, and the mass ratio of deionized water to gallium metal is controlled at 5-50:1.

Furthermore, in the method for efficiently preparing gallium oxyhydroxide as described above, in step 2), the reaction temperature is controlled at 25-95°C, and the reaction time is controlled at 2-12h.

Further, in the method for efficiently preparing gallium oxyhydroxide as described above, in step 2), the blowing rate of oxygen or air is controlled at 1-20 L/min.

Further, in the method for efficiently preparing gallium oxyhydroxide as described above, in step 2), the mechanical stirring speed is controlled at 300-1200r/min.

Further, in the method for efficiently preparing gallium oxyhydroxide as described above, in step 3), the solid-liquid separation temperature is consistent with the chemical reaction temperature in step 2), and the filter residue is washed 3-8 times with deionized water.

Further, in the method for efficiently preparing gallium oxyhydroxide as described above, in step 4), the filter residue is dried at 120-180° C. for 12-48 hours to obtain high-purity gallium oxyhydroxide powder material.

The beneficial effects of the present invention are:

1. The present invention uses gallium metal, deionized water, and oxygen or air as raw materials to prepare high-purity gallium oxyhydroxide powder materials in one step through gas-liquid reaction. The process is short and efficient, and no chemical reagents such as acids and alkalis are consumed. The risk of introducing impurities into raw materials is greatly reduced, which is conducive to obtaining high-purity products, and the production process is environmentally friendly and the production cost is low.

2. The present invention uses deionized water as the reaction medium to directly react with liquid metal gallium to generate gallium oxyhydroxide by bubbling oxygen or air, which greatly strengthens the thermodynamic and kinetic conditions of the reaction. Compared with the traditional gallium metal hydrothermal reaction without oxygen/air, the initial temperature of gallium oxyhydroxide is lowered from the original >150°C (preferably above 200°C) to below the boiling point of water (<100°C), making the reaction It can be carried out under normal pressure conditions, which not only greatly reduces the energy consumption required for the reaction, but also does not need to use high-pressure reaction equipment with high investment and maintenance costs, which can effectively reduce production costs and improve the economic benefits of production enterprises.

3. The present invention synergistically strengthens the conversion process of family gallium to gallium oxyhydroxide by bubbling oxygen/air and mechanical stirring, which can not only effectively reduce the temperature and pressure required for the reaction, but also fully disperse the liquid metal gallium during the reaction process, Stir well to form highly dispersed and uniform-sized nano-scale metal gallium particles. The particles have high surface activity and high reactivity, which is conducive to the efficient and thorough reaction process, and can form gallium oxyhydroxide with uniform microscopic morphology and particle size. Powder, so as to finally obtain the gallium oxyhydroxide precursor for the production of fourth-generation semiconductor materials that meet the requirements of chemical purity and physical specifications, and realize the efficient and short-process preparation of high-purity gallium oxyhydroxide.

Of course, implementing any product of the present invention does not necessarily need to achieve all the above advantages at the same time.

Detailed ways

The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some of the embodiments of the present invention, but not all of them. Based on the embodiments of the present invention, all other embodiments obtained by persons of ordinary skill in the art without creative efforts fall within the protection scope of the present invention.

The invention discloses a method for efficiently preparing gallium oxyhydroxide. Under normal pressure conditions, metal gallium is added to deionized water, and oxygen or air is blown into the system at the same time, and metal gallium is converted into oxyhydroxide under mechanical stirring conditions. gallium. The technical scheme of the invention has the characteristics of low equipment requirements, simple operation, low energy consumption, short process, high efficiency, low cost, etc., and can realize the efficient and short process preparation of high-purity gallium oxyhydroxide powder material.

Production technology of the present invention specifically comprises the following steps:

1) Add gallium metal with a purity of 4N or more into deionized water in proportion, and control the mass ratio of deionized water to gallium metal between 2:1 and 15:1.

2) Under normal pressure, heat the system to 25-95°C, and at the same time blow oxygen or air into the system at a speed of 1-20L/min, and react under the condition of mechanical stirring at a speed of 300-1200r/min. -12h, to convert gallium metal into gallium oxyhydroxide.

3) After the reaction is completed, filter the obtained mixed slurry at a temperature of 25-95° C. (consistent with the reaction temperature of the previous step) to realize solid-liquid separation, and wash the filter residue with deionized water for 3-8 times.

4) drying the filter residue at a temperature of 120-180° C. for 12-48 hours to obtain a high-purity gallium oxyhydroxide powder material.

The present invention will be further described below in conjunction with specific embodiments.

Example 1

This embodiment provides a method for efficiently preparing gallium oxyhydroxide, which specifically includes the following steps:

1) Add gallium metal with a purity of 4N to deionized water in proportion, and control the mass ratio of deionized water to gallium metal to be 2:1.

2) Under normal pressure, heat the system to 25°C, and at the same time blow oxygen into the system at a speed of 1L/min, and react for 12h under the condition of mechanical stirring at a speed of 300r/min, so that gallium metal is converted into oxyhydroxide gallium.

3) After the reaction, the obtained mixed slurry was filtered at a temperature of 25° C. to realize solid-liquid separation, and the filter residue was washed three times with deionized water.

4) Dry the filter residue at 120° C. for 48 hours to obtain a high-purity gallium oxyhydroxide powder material.

Using the processing method of the present embodiment, the conversion rate and product purity of gallium oxyhydroxide were analyzed by aqua regia dissolution combined with inductively coupled plasma mass spectrometer (ICP-MS), and the result was that the conversion rate of metal gallium to gallium oxyhydroxide was 99.71%. Gallium oxyhydroxide product has a purity of 99.995%.

Example 2

This embodiment provides a method for efficiently preparing gallium oxyhydroxide, which specifically includes the following steps:

1) Add gallium metal with a purity of 4N to deionized water in proportion, and control the mass ratio of deionized water to gallium metal to be 15:1.

2) Under normal pressure, heat the system to 95°C, and at the same time blow air into the system at a speed of 20L/min, and react for 2h under the condition of mechanical stirring at a speed of 1200r/min, so that gallium metal is converted into oxyhydroxide gallium.

3) After the reaction, the obtained mixed slurry was filtered at a temperature of 95° C. to realize solid-liquid separation, and the filter residue was washed 8 times with deionized water.

4) Dry the filter residue at 180° C. for 12 hours to obtain a high-purity gallium oxyhydroxide powder material.

Using the processing method of the present embodiment, the conversion rate and product purity of gallium oxyhydroxide were analyzed by aqua regia dissolution combined with inductively coupled plasma mass spectrometer (ICP-MS), and the result was that the conversion rate of metal gallium to gallium oxyhydroxide was 99.53%. Gallium oxyhydroxide product has a purity of 99.998%.

Example 3

This embodiment provides a method for efficiently preparing gallium oxyhydroxide, which specifically includes the following steps:

1) Add gallium metal with a purity of 4N to deionized water in proportion, and control the mass ratio of deionized water to gallium metal to be 4:1.

2) Under normal pressure, heat the system to 45°C, and at the same time blow oxygen into the system at a speed of 5L/min, and react for 4h under the condition of mechanical stirring at a speed of 450r/min, so that gallium metal is converted into oxyhydroxide gallium.

3) After the reaction, the obtained mixed slurry was filtered at a temperature of 45° C. to realize solid-liquid separation, and the filter residue was washed 4 times with deionized water.

4) Dry the filter residue at 130° C. for 18 hours to obtain a high-purity gallium oxyhydroxide powder material.

Using the processing method of the present embodiment, the conversion rate and product purity of gallium oxyhydroxide were analyzed by aqua regia dissolution combined with inductively coupled plasma mass spectrometer (ICP-MS), and the result was that the conversion rate of metal gallium to gallium oxyhydroxide was 99.23%. Gallium oxyhydroxide product has a purity of 99.996%.

Example 4

This embodiment provides a method for efficiently preparing gallium oxyhydroxide, which specifically includes the following steps:

1) Add gallium metal with a purity of 4N to deionized water in proportion, and control the mass ratio of deionized water to gallium metal to be 8:1.

2) Under normal pressure, heat the system to 55°C, and at the same time blow air into the system at a speed of 10L/min, and react for 8h under the condition of mechanical stirring at a speed of 600r/min, so that gallium metal is converted into oxyhydroxide gallium.

3) After the reaction, the obtained mixed slurry was filtered at a temperature of 55° C. to realize solid-liquid separation, and the filter residue was washed 5 times with deionized water.

4) Dry the filter residue at 140° C. for 24 hours to obtain a high-purity gallium oxyhydroxide powder material.

Using the processing method of the present embodiment, the conversion rate and product purity of gallium oxyhydroxide were analyzed by aqua regia dissolution combined with inductively coupled plasma mass spectrometer (ICP-MS), and the result was that the conversion rate of metal gallium to gallium oxyhydroxide was 99.37%. Gallium oxyhydroxide product has a purity of 99.997%.

Example 5

This embodiment provides a method for efficiently preparing gallium oxyhydroxide, which specifically includes the following steps:

1) Add gallium metal with a purity of 4N to deionized water in proportion, and control the mass ratio of deionized water to gallium metal to be 12:1.

2) Under normal pressure, heat the system to 70°C, and at the same time blow oxygen into the system at a speed of 15L/min, and react for 10h under the condition of mechanical stirring at a speed of 800r/min, so that gallium metal is converted into oxyhydroxide gallium.

3) After the reaction, the obtained mixed slurry was filtered at a temperature of 70° C. to realize solid-liquid separation, and the filter residue was washed 6 times with deionized water.

4) Dry the filter residue at 160° C. for 36 hours to obtain a high-purity gallium oxyhydroxide powder material.

Using the processing method of the present embodiment, the conversion rate and product purity of gallium oxyhydroxide were analyzed by aqua regia dissolution combined with inductively coupled plasma mass spectrometer (ICP-MS), and the result was that the conversion rate of metal gallium to gallium oxyhydroxide was 99.42%. Gallium oxyhydroxide product has a purity of 99.996%.

The preferred embodiments of the invention disclosed above are only to help illustrate the invention. The preferred embodiments do not exhaust all details nor limit the invention to specific implementations. Obviously, many modifications and variations can be made based on the contents of this specification. This description selects and specifically describes these embodiments in order to better explain the principle and practical application of the present invention, so that those skilled in the art can well understand and utilize the present invention. The invention is to be limited only by the claims, along with their full scope and equivalents.

Claims (8)

1. A method for efficiently preparing gallium oxyhydroxide is characterized in that: under normal pressure conditions, metal gallium is added to deionized water, and oxygen or air are blown into the system simultaneously, and metal gallium is converted into Gallium oxyhydroxide, realizing the efficient and short-process preparation of high-purity gallium oxyhydroxide powder materials. 2. a kind of method for efficiently preparing gallium oxyhydroxide according to claim 1, is characterized in that: specific process operation is: 1) adding metal gallium to deionized water in proportion; 2) under normal pressure conditions, the system is heated to a predetermined temperature, and oxygen or air is blown into the system at the same time, and metal gallium is converted into gallium oxyhydroxide under mechanical stirring conditions; 3) After the reaction, the resulting mixed slurry is filtered to achieve solid-liquid separation; 4) drying the filter residue to obtain a high-purity gallium oxyhydroxide powder material. 3. A method for efficiently preparing gallium oxyhydroxide according to claim 2, characterized in that: in step 1), the purity of gallium metal is above 4N, and the mass ratio of deionized water to gallium metal is controlled at 5-50 :1. 4. A method for efficiently preparing gallium oxyhydroxide according to claim 2, characterized in that: in step 2), the reaction temperature is controlled at 25-95°C, and the reaction time is controlled at 2-12h. 5. A method for efficiently preparing gallium oxyhydroxide according to claim 2, characterized in that: in step 2), the blowing speed of oxygen or air is controlled at 1-20L/min. 6. A method for efficiently preparing gallium oxyhydroxide according to claim 2, characterized in that: in step 2), the mechanical stirring speed is controlled at 300-1200r/min. 7. a kind of method for efficiently preparing gallium oxyhydroxide according to claim 2 is characterized in that: in step 3), the solid-liquid separation temperature is consistent with the chemical reaction temperature in step 2), and the filter residue is washed with deionized water for 3- 8 times. 8. A method for efficiently preparing gallium oxyhydroxide according to claim 2, characterized in that in step 4), the filter residue is dried at 120-180° C. for 12-48 hours to obtain high-purity gallium oxyhydroxide powder material.