Preparation method of hydroxyl gallium oxide

Abstract

The invention provides a preparation method of hydroxyl gallium oxide, and belongs to the technical field of nonferrous metallurgy. Comprising the following steps: mixing metal gallium and water according to a set mass ratio to obtain a mixture; placing the mixture in a closed reaction container; and under the action of a microwave external field, carrying out microwave treatment on the mixture in the closed reaction container, so that the metal gallium reacts with water and is converted into hydroxyl gallium oxide. Gallium metal and water are subjected to microwave treatment in a closed reaction container, the gallium oxyhydroxide powder can be efficiently prepared through one-step reaction, compared with a traditional autoclave reaction, parameters such as pressure and atmosphere in the reaction process do not need to be controlled, the dynamic process of the reaction does not need to be strengthened through mechanical stirring, and therefore the preparation efficiency of gallium oxyhydroxide is improved.

Description

Technical Field

[0001] The present application relates to the technical field of non-ferrous metallurgy, and in particular to non-ferrous metal metallurgy. Background Art

[0002] Gallium is a typical strategic rare and precious metal and an irreplaceable key raw material for strategic emerging industries such as semiconductors. In the iteration of semiconductors, gallium-based compound semiconductor materials are used throughout, including the second-generation gallium arsenide, the third-generation gallium nitride, and the latest generation of gallium oxide (Ga2O3). This is because gallium-based compounds have excellent semiconductor properties, especially the latest generation of semiconductor materials, gallium oxide, which has attracted widespread attention due to its ultra-wide bandgap characteristics. Its bandgap is as high as 4.9eV and has high temperature resistance, high pressure resistance, and radiation resistance. In addition, it has the advantages of higher absorption coefficient, high carrier mobility, and low manufacturing cost. It is expected to replace traditional semiconductor materials and become an ideal material for manufacturing high-performance optoelectronics and power devices.

[0003] Gallium oxyhydroxide (GaOOH) is a key precursor material for the production of gallium oxide. Therefore, the preparation of gallium oxyhydroxide that meets the requirements is a necessary condition for the production of gallium oxide. After searching, the application case with Chinese patent application number 201210542115.4 discloses a method for electrochemically preparing gallium oxyhydroxide, using metal gallium as an anode to perform three-stage electrolysis in an alkaline electrolyte, so that the metal gallium is converted into soluble sodium gallate and enters the solution, and the pH value of the solution is further adjusted to neutralize it, and gallium oxyhydroxide is precipitated. The application case with Chinese patent application number 201711418839.7 discloses a method for preparing gallium oxyhydroxide from metal gallium, firstly using nitric acid to react with metal gallium to completely dissolve it to obtain a gallium nitrate solution, and then further adjusting the pH value of the solution to neutralize it, and obtaining gallium oxyhydroxide powder by chemical precipitation. The application of Chinese patent application No. 201810752162.9 discloses a method for preparing gallium oxide, wherein metal gallium is completely dissolved in a sulfuric acid solution containing hydrogen peroxide to form a gallium sulfate solution, and then the conditions are further controlled to allow gallium sulfate to crystallize out of the solution, and gallium sulfate crystals are obtained after solid-liquid separation, and finally high-temperature calcination is performed to directly obtain gallium oxide powder. The application of Chinese patent application No. 201210313080.7 discloses a method for preparing gallium oxide hydroxyl nanocrystals, wherein gallium oxide hydroxyl nanocrystals are successfully prepared by a one-step reaction in an autoclave using a saturated solution of gallium chloride in benzene and hexadecyltrimethylammonium bromide as reaction raw materials. The application of Chinese patent application No. 201910971014.0 discloses a method for preparing gallium oxide hydroxyl based on a hydrothermal reaction, wherein metal gallium and water are reacted under high temperature, high pressure and strong mechanical stirring conditions to obtain gallium oxide hydroxyl powder. In summary, the existing gallium oxyhydroxide preparation methods generally have problems such as long process flow, low reaction efficiency, and high reagent consumption. It is necessary to further develop a greener, more efficient, and low-cost gallium oxyhydroxide preparation process technology to provide key raw material guarantees for the sustainable development of the strategic emerging semiconductor industry. Summary of the invention

[0004] The present application provides a method for preparing gallium oxyhydroxide to solve the following technical problem: how to improve the preparation efficiency of gallium oxyhydroxide.

[0005] In a first aspect, the present application provides a method for preparing gallium oxyhydroxide, the method comprising:

[0006] Mixing metallic gallium and water at a set mass ratio to obtain a mixture;

[0007] placing the mixture in a sealed reaction vessel; and

[0008] Under the action of a microwave external field, the mixture in the sealed reaction container is subjected to microwave treatment to allow metal gallium to react with water and be converted into gallium oxyhydroxide.

[0009] Optionally, the set mass ratio is 1:(5-100).

[0010] Optionally, the microwave power of the microwave treatment is 100W to 2500W.

[0011] Optionally, the reaction temperature is 120°C to 260°C, and the reaction time is 0.5h to 20h.

[0012] Optionally, after reacting the metal gallium with water and converting it into gallium oxyhydroxide, the method further comprises:

[0013] The microwave-treated reaction system is cooled to room temperature, and then the reaction system cooled to room temperature is sequentially subjected to solid-liquid separation, washing and drying to obtain gallium oxyhydroxide powder material.

[0014] Optionally, the washing is performed 3 to 15 times.

[0015] Optionally, the drying temperature is 120° C. to 160° C., and the drying time is 4 h to 72 h.

[0016] Optionally, the conversion rate of the metallic gallium to the gallium oxyhydroxide is ≥99%.

[0017] In a second aspect, the present application provides a gallium oxyhydroxide, wherein the gallium oxyhydroxide is prepared by the method described in any one of the embodiments of the first aspect.

[0018] The above technical solution provided by the embodiment of the present application has the following advantages compared with the prior art:

[0019] The present application provides a method for preparing gallium oxyhydroxide, comprising: mixing metal gallium and water at a set mass ratio to obtain a mixture; placing the mixture in a closed reaction vessel; and subjecting the mixture in the closed reaction vessel to microwave treatment under the action of a microwave external field, so that metal gallium reacts with water and is converted into gallium oxyhydroxide. Gallium oxyhydroxide powder can be efficiently prepared by microwave treatment of metal gallium and water in a simple closed reaction vessel in one step. Compared with the reaction in a traditional autoclave, there is no need to control the reaction process parameters such as pressure and atmosphere, nor is there a need to strengthen the reaction kinetics by mechanical stirring, thereby improving the preparation efficiency of gallium oxyhydroxide. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments consistent with the present application and, together with the description, serve to explain the principles of the present application.

[0021] In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, for ordinary technicians in this field, other drawings can be obtained based on these drawings without paying any creative labor.

[0022] Figure 1 A schematic flow chart of a method for preparing gallium oxyhydroxide provided in an embodiment of the present application. DETAILED DESCRIPTION

[0023] In order to make the purpose, technical solution and advantages of the embodiments of the present application clearer, the technical solution in the embodiments of the present application will be clearly and completely described below in conjunction with the drawings in the embodiments of the present application. Obviously, the described embodiments are part of the embodiments of the present application, not all of the embodiments. Based on the embodiments in the present application, all other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of this application.

[0024] Various embodiments of the present application may be presented in the form of a range; it should be understood that the description in the form of a range is only for convenience and brevity, and should not be understood as a rigid limitation on the scope of the present application; therefore, the range description should be considered to have specifically disclosed all possible sub-ranges and single numerical values ​​within the range. For example, the range description from 1 to 6 should be considered to have specifically disclosed sub-ranges, such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6, etc., as well as single numbers within the range, such as 1, 2, 3, 4, 5 and 6, which apply regardless of the range. In addition, whenever a numerical range is indicated herein, it is meant to include any cited number (fractional or integer) within the indicated range.

[0025] In addition, in the description of the specification of the present application, the terms "including", "comprising", etc. mean "including but not limited to". In this article, relational terms such as "first" and "second", etc. are only used to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply any such actual relationship or order between these entities or operations. In this article, "and / or" describes the association relationship of associated objects, indicating that three relationships may exist. For example, A and / or B can represent: A exists alone, A and B exist at the same time, and B exists alone. Wherein A and B can be singular or plural. In this article, "at least one" means one or more, and "plurality" means two or more. "At least one", "the following at least one item (items)" or similar expressions refer to any combination of these items, including any combination of single items (items) or plural items (items). For example, "at least one of a, b, or c", or "at least one of a, b and c", can both mean: a, b, c, ab (i.e. a and b), ac, bc or abc, where a, b, c can be single or plural, respectively.

[0026] Unless otherwise specified, various raw materials, reagents, instruments and equipment used in this application can be purchased from the market or prepared by existing methods.

[0027] Figure 1 A schematic flow chart of a method for preparing gallium oxyhydroxide provided in an embodiment of the present application.

[0028] See also Figure 1 The present application provides a method for preparing gallium oxyhydroxide, the method comprising:

[0029] S1, mixing metallic gallium and water at a set mass ratio to obtain a mixture;

[0030] In some embodiments, the set mass ratio is 1:(5-100).

[0031] The mass ratio is limited to metal gallium: water = 1: (5-100). In the reaction of metal gallium and water, an appropriate mass ratio can promote effective contact between the reactants, thereby improving the reaction rate and efficiency. A mass ratio that is too small (such as too little water) may cause the reaction to be too violent and difficult to control; while a mass ratio that is too large (such as too much water) may reduce the reaction rate and cause incomplete reaction. At the same time, a suitable mass ratio helps to reduce the formation of by-products and improve the purity of the product. Within this range, metal gallium can react more completely with water to generate the target product gallium oxyhydroxide while reducing the generation of other impurities. Exemplarily, the mass ratio of metal gallium to water can be 1:5, 1:10, 1:15, 1:25, 1:35, 1:55, 1:65, 1:85, 1:100, etc.

[0032] S2, placing the mixture in a closed reaction vessel; and

[0033] A closed environment helps reduce the evaporation of water during the reaction, ensuring the stability of the reaction system, while preventing harmful substances from entering the reaction system and affecting the quality of the product.

[0034] S3. Under the action of a microwave external field, subjecting the mixture in the sealed reaction container to microwave treatment to allow metallic gallium to react with water and convert the metal into gallium oxyhydroxide.

[0035] Microwave heating has the advantages of fast heating speed, high thermal efficiency and uniform heating, which can quickly increase the temperature of the reaction system and make the metal gallium react with water. This reaction method not only shortens the reaction time, but also improves the reaction efficiency, which is conducive to the formation of gallium oxyhydroxide.

[0036] The preparation method of gallium oxyhydroxide provided by the present invention has the characteristics of large polarity and excellent wave absorption performance. The raw water reacts with metal gallium under the action of microwave external field. During the process, microwaves are efficiently absorbed by water, and water molecules are stimulated to oscillate at high frequencies. On the one hand, metal gallium can be highly dispersed in the water medium in the form of fine liquid metal particles, which not only has high surface activity, but also has a large reaction specific surface area, so that gallium and water can have sufficient contact reaction and realize efficient conversion of gallium oxyhydroxide; on the other hand, after absorbing microwaves, water molecules collide violently with each other, and strong friction generates a large amount of heat, so that the system heats up rapidly, and the thermal intensity of the reaction is high. Therefore, under the action of microwave external field, the thermodynamic and kinetic synergistic enhancement of the reaction between gallium and water can be achieved, which is conducive to the efficient conversion of gallium oxyhydroxide.

[0037] In some embodiments, the microwave power of the microwave treatment is 100W to 2500W.

[0038] In some embodiments, the reaction temperature is 120° C. to 260° C., and the reaction time is 0.5 h to 20 h.

[0039] The selection of microwave power directly affects the heating rate and temperature distribution of the reaction system. The microwave power is limited to 100W to 2500W, the reaction temperature is 120°C to 260°C, and the reaction time is 0.5h to 20h, which is conducive to improving production efficiency and is conducive to complete reaction. At the same time, it reduces the risk of by-product generation and is conducive to maintaining the purity and structure of the product. Exemplarily, the microwave power can be 100W, 300W, 500W, 1000W, 1500W, 2000W, 2500W, etc., the reaction temperature can be 120°C, 150°C, 180°C, 200°C, 220°C, 250°C, 260°C, etc., and the reaction time can be 0.5h, 1h, 3h, 5h, 10h, 12h, 15h, 18h, 20h, etc.

[0040] In some embodiments, after reacting metallic gallium with water and converting it into gallium oxyhydroxide, the method further comprises:

[0041] S4, cooling the microwave-treated reaction system to room temperature, and then sequentially performing solid-liquid separation, washing and drying on the reaction system after cooling to room temperature to obtain gallium oxyhydroxide powder material.

[0042] The reaction product (solid gallium oxyhydroxide) is separated from the reaction liquid (which may contain unreacted metal gallium, water and other by-products). The solid product is then washed to remove impurities attached to the surface and residual reaction liquid. Finally, it is dried to obtain a pure gallium oxyhydroxide powder material.

[0043] In some embodiments, the washing is performed 3 to 15 times.

[0044] In some embodiments, the drying temperature is 120° C. to 160° C., and the drying time is 4 h to 72 h.

[0045] In some embodiments, the conversion rate of the metallic gallium to the gallium oxyhydroxide is ≥ 99%.

[0046] The conversion rate of gallium metal to gallium oxyhydroxide is an important indicator for measuring reaction efficiency. A conversion rate of ≥99% means that most of the gallium metal is successfully converted into gallium oxyhydroxide, and only a very small amount of gallium metal may not be converted due to various reasons (such as incomplete reaction, loss, etc.). A high conversion rate helps to improve the purity and economic benefits of the product.

[0047] Based on a general inventive concept, the present application provides a gallium oxyhydroxide, which is prepared by the method described in any one of the above embodiments.

[0048] The gallium oxyhydroxide is realized based on the preparation method of the gallium oxyhydroxide mentioned above. The specific steps of the preparation method of the gallium oxyhydroxide can refer to the above embodiment. Since the gallium oxyhydroxide adopts part or all of the technical solutions of the above embodiment, it at least has all the beneficial effects brought by the technical solutions of the above embodiment, which will not be repeated here one by one.

[0049] The present application will be further described below in conjunction with specific embodiments. It should be understood that these embodiments are intended only to illustrate the present application and are not intended to limit the scope of the present application. The experimental methods for which specific conditions are not specified in the following examples are usually measured according to industry standards. If there is no corresponding industry standard, then the conditions recommended by the manufacturer are followed.

[0050] Example 1

[0051] The method for efficiently preparing gallium oxyhydroxide from metal gallium in this embodiment specifically comprises the following steps:

[0052] (1) adding metallic gallium to deionized water, controlling the mass ratio of deionized water to metallic gallium to be 5:1, and further placing the mixture in a sealed reaction vessel;

[0053] (2) turning on the microwave external field, adjusting the microwave power to 100 W, and reacting at a temperature of 120° C. for 20 h, so that metallic gallium reacts with water in a closed reactor and is converted into gallium oxyhydroxide in one step;

[0054] (3) After the reaction is completed, the reaction is cooled to room temperature, and then solid-liquid separation is performed, and the resulting filter residue is washed three times with deionized water;

[0055] (4) The washed filter residue was dried at 120° C. for 72 h to obtain gallium oxyhydroxide powder material.

[0056] The obtained gallium oxyhydroxide powder was weighed and analyzed by inductively coupled plasma mass spectrometry (ICP-MS) using the treatment method of this embodiment. The results showed that the conversion rate of metallic gallium to gallium oxyhydroxide was 99.34%.

[0057] Example 2

[0058] The method for efficiently preparing gallium oxyhydroxide from metal gallium in this embodiment specifically comprises the following steps:

[0059] (1) adding metallic gallium to deionized water, controlling the mass ratio of deionized water to metallic gallium to be 100:1, and further placing the mixture in a sealed reaction vessel;

[0060] (2) turning on the microwave external field, adjusting the microwave power to 2500 W, and reacting at a temperature of 260° C. for 0.5 h, so that metallic gallium reacts with water in a closed reactor and is converted into gallium oxyhydroxide in one step;

[0061] (3) After the reaction is completed, the reaction is cooled to room temperature, and then solid-liquid separation is performed, and the resulting filter residue is washed 15 times with deionized water;

[0062] (4) The washed filter residue was dried at 160° C. for 4 h to obtain gallium oxyhydroxide powder material.

[0063] The obtained gallium oxyhydroxide powder was weighed and analyzed by inductively coupled plasma mass spectrometry (ICP-MS) using the treatment method of this embodiment. The results showed that the conversion rate of metallic gallium to gallium oxyhydroxide was 99.19%.

[0064] Example 3

[0065] The method for efficiently preparing gallium oxyhydroxide from metal gallium in this embodiment specifically comprises the following steps:

[0066] (1) adding metallic gallium to deionized water, controlling the mass ratio of deionized water to metallic gallium to be 30:1, and further placing the mixture in a sealed reaction vessel;

[0067] (2) turning on the microwave external field, adjusting the microwave power to 300 W, and reacting at a temperature of 140° C. for 16 h, so that metallic gallium reacts with water in a closed reactor and is converted into gallium oxyhydroxide in one step;

[0068] (3) After the reaction is completed, the reaction is cooled to room temperature, and then solid-liquid separation is performed, and the resulting filter residue is washed 6 times with deionized water;

[0069] (4) The washed filter residue was dried at 130° C. for 48 h to obtain gallium oxyhydroxide powder material.

[0070] The obtained gallium oxyhydroxide powder was weighed and analyzed by inductively coupled plasma mass spectrometry (ICP-MS) using the treatment method of this embodiment. The results showed that the conversion rate of metallic gallium to gallium oxyhydroxide was 99.26%.

[0071] Example 4

[0072] The method for efficiently preparing gallium oxyhydroxide from metal gallium in this embodiment specifically comprises the following steps:

[0073] (1) adding metallic gallium to deionized water, controlling the mass ratio of deionized water to metallic gallium to be 55:1, and further placing the mixture in a sealed reaction vessel;

[0074] (2) turning on the microwave external field, adjusting the microwave power to 500 W, and reacting at a temperature of 160° C. for 12 h, so that metallic gallium reacts with water in a closed reactor and is converted into gallium oxyhydroxide in one step;

[0075] (3) After the reaction is completed, the reaction is cooled to room temperature, and then solid-liquid separation is performed, and the resulting filter residue is washed 10 times with deionized water;

[0076] (4) Dry the washed filter residue at 140° C. for 24 h to obtain gallium oxyhydroxide powder material.

[0077] The obtained gallium oxyhydroxide powder was weighed and analyzed by inductively coupled plasma mass spectrometry (ICP-MS) using the treatment method of this embodiment. The results showed that the conversion rate of metallic gallium to gallium oxyhydroxide was 99.78%.

[0078] Example 5

[0079] The method for efficiently preparing gallium oxyhydroxide from metal gallium in this embodiment specifically comprises the following steps:

[0080] (1) adding metallic gallium to deionized water, controlling the mass ratio of deionized water to metallic gallium to be 80:1, and further placing the mixture in a sealed reaction vessel;

[0081] (2) turning on the microwave external field, adjusting the microwave power to 1000 W, and reacting at a temperature of 180° C. for 5 h, so that metallic gallium reacts with water in a closed reactor and is converted into gallium oxyhydroxide in one step;

[0082] (3) After the reaction is completed, the reaction is cooled to room temperature, and then solid-liquid separation is performed, and the resulting filter residue is washed 12 times with deionized water;

[0083] (4) The washed filter residue was dried at 150° C. for 10 h to obtain gallium oxyhydroxide powder material.

[0084] The obtained gallium oxyhydroxide powder was weighed and analyzed by inductively coupled plasma mass spectrometry (ICP-MS) using the treatment method of this embodiment. The results showed that the conversion rate of metallic gallium to gallium oxyhydroxide was 99.63%.

[0085] In addition, one or more technical solutions in the embodiments of the present invention have at least the following technical effects or advantages:

[0086] (1) In the embodiment of the present invention, metallic gallium and water are used as raw materials, and gallium oxyhydroxide powder can be efficiently prepared through a one-step reaction under the action of a microwave external field. This has the advantages of high reaction efficiency and a short process flow. In addition, the reaction process does not require the consumption of any acid, alkali or other chemical reagents, which can not only effectively reduce the cost of raw materials, but also minimize the risk of introducing impurities into the raw materials, thereby facilitating the acquisition of high-purity products.

[0087] (2) In the embodiment of the present invention, the reaction of metal gallium and water is carried out in a simple closed reaction vessel, and the reaction conditions are mainly controlled by the microwave external field power. Compared with the reaction in a traditional autoclave, there is no need to control the pressure, atmosphere and other parameters of the reaction process, nor is there any need to enhance the kinetic process of the reaction by mechanical stirring. Not only is the reaction efficiency higher, but the investment and maintenance costs of the equipment are also lower, which is a significant advantage.

[0088] (3) In the embodiments of the present invention, by precisely controlling the raw material ratio, using a closed reaction vessel and microwave heating technology, and strict post-processing steps, high-quality gallium oxyhydroxide powder material can be efficiently prepared, which has the potential for industrial production.

[0089] The above description is only a specific implementation of the present application, so that those skilled in the art can understand or implement the present application. Various modifications to these embodiments will be apparent to those skilled in the art, and the general principles defined herein can be implemented in other embodiments without departing from the spirit or scope of the present application. Therefore, the present application will not be limited to the embodiments shown herein, but will conform to the widest range consistent with the principles and novel features applied for herein.

Claims

1. A method for preparing gallium oxyhydroxide, characterized in that: The method comprises: Mixing metallic gallium and water at a set mass ratio to obtain a mixture; placing the mixture in a sealed reaction vessel; and Under the action of a microwave external field, the mixture in the sealed reaction container is subjected to microwave treatment to allow metal gallium to react with water and be converted into gallium oxyhydroxide.

2. The method according to claim 1, characterized in that The set mass ratio is 1:(5-100).

3. The method according to claim 1, characterized in that The microwave power of the microwave treatment is 100W to 2500W.

4. The method according to claim 1, characterized in that The reaction temperature is 120° C. to 260° C., and the reaction time is 0.5 h to 20 h.

5. The method according to claim 1, characterized in that After reacting the metal gallium with water and converting it into gallium oxyhydroxide, the method further comprises: The microwave-treated reaction system is cooled to room temperature, and then the reaction system cooled to room temperature is sequentially subjected to solid-liquid separation, washing and drying to obtain gallium oxyhydroxide powder material.

6. The method according to claim 5, characterized in that The washing is performed 3 to 15 times.

7. The method according to claim 5, characterized in that The drying temperature is 120° C. to 160° C., and the drying time is 4 h to 72 h.

8. The method according to claim 1, characterized in that The conversion rate of the metallic gallium to the gallium oxyhydroxide is ≥99%.

9. A gallium oxyhydroxide, characterized in that: The gallium oxyhydroxide is prepared by the method according to any one of claims 1 to 8.

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