METHOD FOR RECYCLING COPPER INDIUM GALLIUM SELENIUM MATERIALS

Abstract

A method for recycling copper indium gallium selenium materials comprises the steps of leaching by using sulfuric acid and hydrogen peroxide, reduction of selenium by using sulfur dioxide, separation of copper by using hydrolysis, alkali separation of indium and gallium, replacement of indium, hydrolysis of gallium, and the like. Leaching is carried out by using sulfuric acid in cooperation with hydrogen peroxide, so that the leaching rate is greatly improved, and acid gas pollution is reduced; PH differential copper is separated by using metal ion hydrolysis, so that costs are low; and in addition, alkali separation of gallium is carried out, separation between indium and gallium can be implemented by merely adjusting the PH of a solution, the separation effect is good, the purities of obtained indium and gallium products are high.

Claims

1. A method for recovering copper indium gallium selenide material, comprising the following steps: step A, in which the copper indium gallium selenide material is placed in a ball mill for ball milling; step B, in which the ball milled alloy powders obtained in step A are mixed with a diluted concentrated sulfuric acid and heated up, followed by introducing hydrogen peroxide for leaching; after the leaching is completed, the residue is filtered out to give a leachate; step C, in which the leachate is heated up, followed by introducing sulfur dioxide gas to reduce selenium; step D, in which a sodium hydroxide solution is directly added to the solution after selenium removal; the mixture is stirred at ambient temperature and then allowed to stand, followed by drawing the supernatant; gallium hydroxide and indium hydroxide precipitates and a copper sulfate supernatant are obtained by filtration; step E, in which the copper sulfate supernatant is directly evaporated and crystallized to give copper sulphate pentahydrate; step F, in which a sodium hydroxide solution is added to the gallium hydroxide and indium hydroxide precipitates; the mixture is heated while stirring at a constant temperature and then allowed to stand, followed by drawing the supernatant; indium hydroxide precipitate and a sodium gallate solution are obtained by direct filtration; step G, in which the sodium gallate solution is directly hydrolyzed to give gallium hydroxide precipitate; and step H, in which the indium hydroxide precipitate is reversely dissolved by hydrochloric acid, followed by heating up and stirring at a constant temperature; the mixture is replaced with a 4N zinc plate to give sponge indium.

2. The method for recovering copper indium gallium selenide material according to claim 1, further comprising in step A that the copper indium gallium selenide material is ball milled to powders of below 40 mesh, followed by drying at 100 C. for 4 hours.

3. The method for recovering copper indium gallium selenide material according to claim 1, further comprising in step B that concentrated sulfuric acid is diluted to 25%; 200 g of dried material is mixed with 25% concentrated sulfuric acid at a solid-liquid ratio of 1:5 and heated to 90 C., followed by introducing hydrogen peroxide at a rate of 8 ml/min at a stirring rate of 600 r/min and leaching at a constant temperature for 3 h.

4. The method for recovering copper indium gallium selenide material according to claim 1, further comprising in step C that the leachate is heated to 65 C., followed by introducing sulfur dioxide gas at a rate of 10 L/min and maintaining the temperature for 10 hours to reduce selenium.

5. The method for recovering copper indium gallium selenide material according to claim 1, further comprising in step D that an 8 mol/L sodium hydroxide solution is directly added to the solution after selenium removal to adjust the pH to 4.5; the mixture is stirred at ambient temperature for 20 minutes at a stirring rate of 200 r/min; after standing for 2 hours, the supernatant is drawn; the washing and drawing procedure is repeated three times, in which the amount of water used for each washing does not exceed 800 ml.

6. The method for recovering copper indium gallium selenide material according to claim 1, further comprising in step F that an 8 mol/L sodium hydroxide solution is added to the gallium hydroxide and indium hydroxide precipitates; the mixture is heated to 80 C. while stirring at a stirring rate of 200 r/min and at a constant temperature for 20 minutes; after standing for 2 hours, the supernatant is drawn; the washing and drawing procedure is repeated three times, in which the amount of water used for each washing does not exceed 800 ml.

7. The method for recovering copper indium gallium selenide material according to claim 1, further comprising in step G that a 1 mol/L sulfuric acid solution is added to the sodium gallate solution to adjust the pH to neutrality, followed by adding 20 ml diluted 10% polyacrylamide, maintaining the temperature at 80 C., and stirring at a stirring rate of 200 r/min and at a constant temperature for 10 min to allow flocculation and precipitation; after precipitation, the supernatant is drawn; the supernatant is drawn after repeating the washing and settling procedure three times, in which the amount of water used for each washing does not exceed 800 mL, and gallium hydroxide precipitate is finally obtained by direct filtration.

8. The method for recovering copper indium gallium selenide material according to claim 1, further comprising in step G that gallium hydroxide is placed in a drying oven and dried at a constant temperature of 80 C. for more than 8 hours to give gallium hydroxide.

9. The method for recovering copper indium gallium selenide material according to claim 1, further comprising in step H that the indium hydroxide precipitate is reversely dissolved by 600 ml of 10% hydrochloric acid, followed by adjusting the pH to 1.5, heating to 55 C. and stirring at a constant temperature and at a stirring rate of 200 r/min.

10. A method for recovering copper indium gallium selenide material, comprising the following steps: step A: in which the copper indium gallium selenide material is crushed; step B, in which the crushed material obtained in step A is mixed with a diluted sulfuric acid and heated up, followed by introducing hydrogen peroxide for leaching; step C, in which selenium in the leachate obtained in step B is reduced; step D, in which an alkali is added to the solution after selenium removal; and the mixture is separated to give gallium hydroxide and indium hydroxide precipitates and a copper sulfate supernatant; step E, in which the copper sulfate supernatant obtained in step D is evaporated and crystallized to give copper sulphate pentahydrate; step F, in which an alkali is added to the gallium hydroxide and indium hydroxide precipitates obtained in step D; the mixture is separated to give indium hydroxide precipitate and a sodium gallate solution; step G, in which the sodium gallate solution obtained in step F is hydrolyzed to give gallium hydroxide precipitate; and step H, in which the indium hydroxide precipitate obtained in step F is dissolved by hydrochloric acid; and the mixture is replaced with zinc to give sponge indium.

11. The method according to claim 10, wherein, in step C, selenium in the leachate obtained in step B is reduced by sulfur dioxide.

12. The method according to claim 10, wherein, in step H, the zinc is used in a form of 4N zinc plate.

13. The method for recovering copper indium gallium selenide material according to claim 7, further comprising in step G that gallium hydroxide is placed in a drying oven and dried at a constant temperature of 80 C. for more than 8 hours to give gallium hydroxide.

Description

BRIEF DESCRIPTION OF DRAWINGS

[0028] FIG. 1 is a schematic flowchart of the method for recovering copper indium gallium selenide material according to an example of the present invention.

SPECIFIC EMBODIMENTS

[0029] The embodiments of the present invention are further illustrated below with reference to the accompanying drawings.

[0030] As shown in FIG. 1, the method for recovering copper indium gallium selenide material according to an example of the present invention mainly includes the following steps.

[0031] In step A, 200 g of copper indium gallium selenide material was placed in a ball mill, ball milled to powders of below 40 mesh and dried at 100 C. for 4 hours.

[0032] In step B, concentrated sulfuric acid was diluted to 25%. 200 g of dried material was mixed with 25% concentrated sulfuric acid at a solid-liquid ratio of 1:5 and heated to 90 C., followed by introducing hydrogen peroxide at a rate of 8 ml/min at a stirring rate of 600 r/min and leaching at a constant temperature for 3 h. After the leaching was completed, the residues were filtered out to give a copper indium gallium selenium leachate.

[0033] In step C, the leachate was heated to 65 C., followed by introducing sulfur dioxide gas at a rate of 10 L/min and maintaining the temperature for 10 hours. During the reduction of selenium, it was observed that a brick red precipitate was formed in the container which gradually turned black, and black selenium was obtained after filtration.

[0034] In step D, an 8 mol/L sodium hydroxide solution was directly added to the solution after selenium removal to adjust the pH to 4.54.7. The mixture was stirred at ambient temperature for 20 minutes at a stirring rate of 200 r/min. After standing for 2 hours, the supernatant was drawn. The washing and drawing procedure was repeated three times, in which the amount of water used for each washing did not exceed 800 ml. Finally, gallium hydroxide and indium hydroxide precipitates and a copper sulfate supernatant were obtained by direct filtration.

[0035] In step E, the copper sulfate supernatant was directly evaporated and crystallized to give copper sulphate pentahydrate.

[0036] In step F, an 8 mol/L sodium hydroxide solution was added to the gallium hydroxide and indium hydroxide precipitates. The mixture was heated to 80 C. while stirring at a stirring rate of 200 r/min and at a constant temperature for 20 minutes. After standing for 2 hours, the supernatant was drawn. The washing and drawing procedure was repeated three times, in which the amount of water used for each washing did not exceed 800 ml. Finally, indium hydroxide precipitate and a sodium gallate solution were obtained by direct filtration.

[0037] In step G, a 1 mol/L sulfuric acid solution was added to the sodium gallate solution to adjust the pH to neutrality, followed by adding 20 ml diluted 10% polyacrylamide, maintaining the temperature at 80 C., and stirring at a stirring rate of 200 r/min and at a constant temperature for 10 min to allow flocculation and precipitation. After precipitation, the supernatant is drawn. Similar to the procedure in step F, the supernatant was drawn after repeating the washing and settling procedure three times, in which the amount of water used for each washing does not exceed 800 mL. Finally, a gallium hydroxide precipitate was obtained by direct filtration. Gallium hydroxide was placed in a drying oven and dried at a constant temperature of 80 C. for more than 8 hours to give gallium hydroxide.

[0038] In step H, the indium hydroxide precipitate was reversely dissolved by 600 ml of 10% hydrochloric acid, followed by adjusting the pH to 1.5, heating to 55 C. and stirring at a constant temperature and at a stirring rate of 200 r/min. The mixture was replaced with a 4N zinc plate for 6 hours, followed by washing and filtering to give sponge indium.

[0039] The above embodiments are only used to specifically illustrate the present invention. They do not impose any limit to the scope of protection of the present invention, which is determined by the claims. Many variants can be deduced or conceived according to well-known technologies in the art and the technical solution disclosed herein. All these variants should also be considered within the protection scope of the present invention.