阅读说明：本技术 一种利用ito废料制备氧化铟粉和氧化铟锡粉的方法 (Method for preparing indium oxide powder and indium tin oxide powder by using ITO waste material ) 是由 陆映东 黄作 张倍维 王凯 梁盈祥 宋春华 于 2021-02-01 设计创作，主要内容包括：本发明涉及一种利用ITO废料制备氧化铟粉和氧化铟锡粉的方法,该方法将收集的ITO废料进行干燥去除水分,然后进行煅烧,去除有机物,将所得物料用盐酸溶解,然后过滤得到溶液,再利用氯化铟在300℃即可挥发的原理,将所得溶液进行多次蒸馏,得到氯化铟,然后再以氯化铟为原料,采用沉淀法,制备氧化铟粉和氧化铟锡粉。本发明由ITO靶材生产过程中产生的废料制得氯化铟,不仅节约了成本,进行了废物利用,同时较传统的废料再利用,略去将废料转化成精铟的步骤,由废料直接制备出金属盐,再制备粉,能有效减少回收成本,进一步降低了生产成本。(The invention relates to a method for preparing indium oxide powder and indium tin oxide powder by utilizing ITO waste materials, which comprises the steps of drying the collected ITO waste materials to remove moisture, then calcining to remove organic matters, dissolving the obtained materials by hydrochloric acid, then filtering to obtain a solution, then distilling the obtained solution for multiple times by utilizing the principle that indium chloride can volatilize at 300 ℃ to obtain indium chloride, and then preparing the indium oxide powder and the indium tin oxide powder by taking the indium chloride as a raw material and adopting a precipitation method. The method for preparing indium chloride from the waste materials generated in the production process of the ITO target material saves cost, utilizes the waste materials, omits the step of converting the waste materials into refined indium compared with the traditional waste materials, directly prepares metal salt and then prepares powder from the waste materials, can effectively reduce the recovery cost, and further reduces the production cost.)

1. A method for preparing indium oxide powder by using ITO waste materials is characterized by comprising the following steps: the method comprises the following steps:

(1) collecting ITO waste materials generated in the production process of the ITO target material;

(2) heating the collected ITO waste to 80-120 ℃, drying moisture, and then calcining for 0.5-20 hours at 600-1400 ℃ in an oxidizing atmosphere to remove organic impurities and volatile and combustible impurities;

(3) dissolving the calcined ITO waste powder in hydrochloric acid with the concentration of 10-38%, and adding hydrogen peroxide with the weight of 0-5% of that of the ITO waste powder in the process to accelerate the dissolution rate;

(4) filtering the dissolved mixture, and reserving filtered clear liquid for later use;

(5) keeping the temperature of the clear liquid at 80-120 ℃ and evaporating the water to dryness, then heating to 280 ℃ at 200-;

(6) and completely dissolving the obtained indium chloride with water, adding alkali to control the pH value to be 8-10 to obtain indium hydroxide precipitate, cleaning, filtering and drying the precipitate, and calcining at the temperature of 600-.

2. The method for preparing indium oxide powder using ITO scrap according to claim 1, wherein: the ITO waste material in the step (1) comprises ITO waste powder and ITO waste slurry.

3. The method for producing indium oxide powder from ITO scrap according to claim 1 or 2, wherein: the alkali in the step (6) is one or more of ammonia water, sodium hydroxide, ammonium bicarbonate or urea.

4. The method for producing indium oxide powder from ITO scrap according to claim 1 or 2, wherein: the addition amount of the hydrochloric acid in the step (3) is 1.5-4 times of the required amount of the ITO waste powder and the hydrochloric acid after complete reaction.

5. A method for preparing indium tin oxide powder by using ITO waste materials is characterized by comprising the following steps: the method comprises the following steps:

(1) collecting ITO waste materials generated in the production process of the ITO target material;

(2) heating the collected ITO waste to 80-120 ℃, drying moisture, and then calcining for 0.5-20 hours at 600-1400 ℃ in an oxidizing atmosphere to remove organic impurities and volatile and combustible impurities;

(3) dissolving the calcined ITO waste powder in hydrochloric acid with the concentration of 10-38%, and adding hydrogen peroxide with the weight of 0-5% of that of the ITO waste powder in the process to accelerate the dissolution rate;

(4) filtering the dissolved mixture, and reserving filtered clear liquid for later use;

(5) keeping the temperature of the clear liquid at 80-120 ℃ and evaporating the water to dryness, then heating to 280 ℃ at 200-;

(6) and completely dissolving the obtained indium chloride with water, wherein the mass ratio of indium oxide: tin oxide is added in the calculation of (8-9.8) = (0.2-2), the tin oxide is dissolved and stirred evenly, alkali is added to control the pH value to be 8-11, indium tin hydroxide precipitate is obtained, then the precipitate is cleaned, filtered and dried, and is calcined for 0.5-15 hours at the temperature of 600 ℃ and 1000 ℃, and indium tin oxide powder is obtained.

6. The method for preparing ITO powder of claim 5, wherein the ITO scrap comprises: the ITO waste material in the step (1) comprises ITO waste powder and ITO waste slurry.

7. The method for preparing ITO powder according to claim 5 or 6, wherein the ITO scrap comprises: the alkali in the step (6) is one or more of ammonia water, sodium hydroxide, ammonium bicarbonate or urea.

8. The method for preparing ITO powder according to claim 5 or 6, wherein the ITO scrap comprises: the addition amount of the hydrochloric acid in the step (3) is 1.5-4 times of the required amount of the ITO waste powder and the hydrochloric acid after complete reaction.

Technical Field

The invention relates to a preparation method of a metal oxide target, in particular to a method for preparing indium oxide powder and indium tin oxide powder by utilizing ITO waste materials.

Background

Indium tin oxide target (ITO target) is an electronic ceramic material and is mainly used for magnetron sputtering coating of ITO films. The ITO film is a transparent conductive thin film, and is used for manufacturing electronic devices and components requiring transparent electrodes, such as displays, touch panels, and LEDs. The indium tin oxide target material is formed by molding ITO powder and sintering at high temperature. The preparation method of indium tin oxide powder mainly comprises two methods, one method is that indium salt and tin salt solution are added with alkali for coprecipitation to produce hydroxide, and then the hydroxide is calcined to obtain ITO powder; the other is formed by physically mixing indium oxide and tin oxide.

The ITO target has a large dimensional shrinkage rate, usually around 25%, from molding to sintering. The large shrinkage causes the sintering deformation of the target material to be large. In the production process of the ITO target, the deformed product needs to be machined so as to ensure that the overall dimension of the product meets the product requirement. In this process, 10-25% of ITO, even more, is processed into scraps (such as grinding scraps of a grinding machine and cutting scraps of cutting). The scraps are usually refined into refined indium again to be used as a production raw material of the ITO target. To reduce the production cost of the ITO target, on one hand, the sintering deformation is reduced, so that the generation of scraps is reduced, and on the other hand, the cost of scrap recycling is reduced. Therefore, it is necessary to develop a method for recycling ITO scrap at a lower cost.

Disclosure of Invention

The technical problem to be solved by the invention is as follows: a method for preparing indium oxide powder and indium tin oxide powder from ITO scrap is provided, the method directly prepares metal salt from the ITO scrap and then prepares the metal salt into powder, the step of converting the scrap into refined indium is omitted, and the production cost is reduced.

The technical scheme for solving the technical problems is as follows: a method for preparing indium oxide powder by using ITO waste materials comprises the following steps:

(1) collecting ITO waste materials generated in the production process of the ITO target material;

(2) heating the collected ITO waste to 80-120 ℃, drying moisture, and then calcining for 0.5-20 hours at 600-1400 ℃ in an oxidizing atmosphere to remove organic impurities and volatile and combustible impurities;

(3) dissolving the calcined ITO waste powder in hydrochloric acid with the concentration of 10-38%, and adding hydrogen peroxide with the weight of 0-5% of that of the ITO waste powder in the process to accelerate the dissolution rate;

(4) filtering the dissolved mixture, and reserving filtered clear liquid for later use;

(5) keeping the temperature of the clear liquid at 80-120 ℃ and evaporating the water to dryness, then heating to 280 ℃ at 200-;

(6) and completely dissolving the obtained indium chloride with water, adding alkali to control the pH value to be 8-10 to obtain indium hydroxide precipitate, cleaning, filtering and drying the precipitate, and calcining at the temperature of 600-.

Further, the ITO scrap in the step (1) comprises ITO waste powder and ITO waste slurry.

Further, the alkali in the step (6) is one or more of ammonia water, sodium hydroxide, ammonium bicarbonate or urea.

Further, the addition amount of the hydrochloric acid in the step (3) is 1.5-4 times of the amount required by the complete reaction of the ITO waste powder and the hydrochloric acid.

The other technical scheme of the invention is as follows: a method for preparing indium tin oxide powder by using ITO waste materials comprises the following steps:

(1) collecting ITO waste materials generated in the production process of the ITO target material;

(2) heating the collected ITO waste to 80-120 ℃, drying moisture, and then calcining for 0.5-20 hours at 600-1400 ℃ in an oxidizing atmosphere to remove organic impurities and volatile and combustible impurities;

(3) dissolving the calcined ITO waste powder in hydrochloric acid with the concentration of 10-38%, and adding hydrogen peroxide with the weight of 0-5% of that of the ITO waste powder in the process to accelerate the dissolution rate;

(4) filtering the dissolved mixture, and reserving filtered clear liquid for later use;

(5) keeping the temperature of the clear liquid at 80-120 ℃ and evaporating the water to dryness, then heating to 280 ℃ at 200-;

(6) and completely dissolving the obtained indium chloride with water, wherein the mass ratio of indium oxide: tin oxide is added in the calculation of (8-9.8) = (0.2-2), the tin oxide is dissolved and stirred evenly, alkali is added to control the pH value to be 8-11, indium tin hydroxide precipitate is obtained, then the precipitate is cleaned, filtered and dried, and is calcined for 0.5-15 hours at the temperature of 600 ℃ and 1000 ℃, and indium tin oxide powder is obtained.

Further, the ITO scrap in the step (1) comprises ITO waste powder and ITO waste slurry.

Further, the alkali in the step (6) is one or more of ammonia water, sodium hydroxide, ammonium bicarbonate or urea.

Further, the addition amount of the hydrochloric acid in the step (3) is 1.5-4 times of the amount required by the complete reaction of the ITO waste powder and the hydrochloric acid.

The method comprises the steps of drying the collected ITO waste (the waste generated in the production process of the ITO target, such as the waste generated in the working procedures of grinding, cutting and the like, including ITO waste powder and ITO waste slurry) to remove moisture, and then calcining to remove organic matters. The resulting material was dissolved with hydrochloric acid and then filtered to obtain a solution. Then, by utilizing the principle that indium chloride can volatilize at 300 ℃, distilling the obtained solution for many times to obtain indium chloride, then preparing indium oxide powder and indium tin oxide powder by taking the indium chloride as a raw material and adopting a precipitation method, namely dissolving the indium chloride by using water or directly adding an alkaline solution for precipitation, filtering, cleaning, drying and calcining the precipitate to obtain indium oxide powder; or adding a certain amount of tin chloride, adding an alkali solution for precipitation, filtering, cleaning, drying and calcining the precipitate to obtain the ITO powder.

The invention prepares indium chloride from waste materials generated in the production process of the ITO target material, and then prepares indium oxide powder and indium tin oxide powder by adopting a precipitation method. Not only practiced thrift the cost, carried out waste utilization, simultaneously than traditional waste material recycle, omit the step of changing the waste material into smart indium, directly prepare out metal salt by the waste material, the refabrication powder can effectively reduce the recovery cost, has further reduced manufacturing cost.

The technical features of one of the methods for producing indium oxide powder and indium tin oxide powder from ITO scrap according to the present invention will be further described with reference to the following examples.

Detailed Description

Example 1:

and collecting ITO waste powder and ITO waste slurry generated in the production process of the ITO target. And heating the collected ITO waste material to 80 ℃, and preserving heat and drying moisture. Then calcining for 20 hours at 600 ℃ in an air atmosphere to remove organic impurities and volatile and combustible impurities. And weighing the ITO waste powder calcined at the high temperature, and dissolving the ITO waste powder by using hydrochloric acid with the concentration of 10%, wherein the amount of the hydrochloric acid is 4 times of the amount of the ITO waste powder and the hydrochloric acid required by the theoretical calculation of the complete reaction. Adding analytically pure hydrogen peroxide accounting for 5 percent of the weight of the ITO waste powder to accelerate the dissolution rate. Filtering the dissolved mixture, and reserving filtered clear liquid for later use. And (3) preserving the heat of the clear liquid at 80 ℃ to dry out the water, then heating to 200 ℃, evaporating other volatile impurities, heating to 300 ℃ after the weight is not changed any more, evaporating and collecting the obtained substance to obtain the indium chloride. And completely dissolving the obtained indium chloride with water, adding ammonia water, controlling the pH value to be 8 to obtain indium hydroxide precipitate, cleaning, filtering and drying the precipitate, and calcining at 600 ℃ for 15 hours to obtain indium oxide powder. The detection proves that the purity of the indium oxide powder is more than 99.99 percent.

Example 2:

and collecting ITO waste powder and ITO waste slurry generated in the production process of the ITO target. And heating the collected ITO waste material to 120 ℃, and preserving heat and drying moisture. Then calcining for 0.5 hour at 1400 ℃ in an air atmosphere to remove organic impurities and volatile and combustible impurities. And weighing the ITO waste powder calcined at the high temperature, and dissolving the ITO waste powder by using hydrochloric acid with the concentration of 38%, wherein the amount of the hydrochloric acid is 1.5 times of the amount of the ITO waste powder and the hydrochloric acid required by the theoretical calculation of the complete reaction. Adding analytically pure hydrogen peroxide accounting for 1 percent of the weight of the ITO waste powder to accelerate the dissolution rate. Filtering the dissolved mixture, and reserving filtered clear liquid for later use. And (3) preserving the heat of the clear liquid at 100 ℃ to dry out the water, then heating to 250 ℃, evaporating other volatile impurities, heating to 305 ℃ after the weight is not changed any more, evaporating and collecting the obtained substance to obtain the indium chloride. Dissolving the obtained indium chloride with water, adding ammonia water, controlling the pH value to be 10 to obtain indium hydroxide precipitate, cleaning, filtering and drying the precipitate, and calcining at 1000 ℃ for 0.5 hour to obtain indium oxide powder. The detection proves that the purity of the indium oxide powder is more than 99.99 percent.

Example 3:

and collecting ITO waste powder and ITO waste slurry generated in the production process of the ITO target. And heating the collected ITO waste material to 120 ℃, and preserving heat and drying moisture. Then calcining for 10 hours at 1000 ℃ in an oxygen atmosphere to remove organic impurities and volatile and combustible impurities. And weighing the ITO waste powder calcined at the high temperature, and dissolving the ITO waste powder by using 28% hydrochloric acid, wherein the amount of the hydrochloric acid is 3 times of the amount of the ITO waste powder and the hydrochloric acid required by the theoretical calculation of complete reaction. Adding hydrogen peroxide accounting for 3 percent of the weight of the ITO waste powder to accelerate the dissolution rate. Filtering the dissolved mixture, and reserving filtered clear liquid for later use. And (3) preserving the heat of the clear liquid at 120 ℃ to dry out the water, then heating to 280 ℃, evaporating other volatile impurities, heating to 310 ℃ after the weight is not changed any more, evaporating, collecting a substance obtained by gasification and condensation, and obtaining the indium chloride. And completely dissolving the obtained indium chloride by using water, wherein the mass ratio of indium oxide to tin oxide is 9: 1, converting into the required tin chloride amount, adding tin chloride, dissolving and stirring uniformly, adding sodium hydroxide, controlling the pH value to be 11 to obtain indium tin hydroxide precipitate, cleaning, filtering and drying the precipitate, and calcining at 900 ℃ for 5 hours to obtain indium tin oxide powder. The detection proves that the purity of the indium tin oxide powder is more than 99.99 percent.

Example 4:

and collecting ITO waste powder and ITO waste slurry generated in the production process of the ITO target. And heating the collected ITO waste to 110 ℃, and preserving heat and drying moisture. Then calcining for 7 hours at 1200 ℃ in an air atmosphere to remove organic impurities and volatile and combustible impurities. And weighing the ITO waste powder calcined at the high temperature, and dissolving the ITO waste powder by using 22% hydrochloric acid, wherein the amount of the hydrochloric acid is 3.5 times of the amount of the ITO waste powder required by the theoretical calculation of the complete reaction of the ITO waste powder and the hydrochloric acid. Adding hydrogen peroxide accounting for 2.5 percent of the weight of the ITO waste powder to accelerate the dissolution rate. Filtering the dissolved mixture, and reserving filtered clear liquid for later use. And (3) preserving the heat of the clear liquid at 110 ℃ to dry out the water, then heating to 270 ℃, evaporating other volatile impurities, heating to 308 ℃ after the weight is not changed any more, evaporating, collecting a substance obtained by gasification and condensation, and obtaining the indium chloride. And completely dissolving the obtained indium chloride by using water, wherein the mass ratio of indium oxide to tin oxide is 9.8: and (3) converting the amount of the indium tin oxide powder into the required tin chloride amount by 0.2, adding the tin chloride, dissolving and stirring uniformly, adding ammonia water, controlling the pH value to be 9 to obtain an indium tin hydroxide precipitate, cleaning, filtering and drying the precipitate, and calcining at 800 ℃ for 7 hours to obtain indium tin oxide powder. The detection proves that the purity of the indium tin oxide powder is more than 99.99 percent.