WO2017124892A1

WO2017124892A1 - Method for recycling copper indium gallium selenium materials

Info

Publication number: WO2017124892A1
Application number: PCT/CN2016/112147
Authority: WO
Inventors: 高永涛; 刘军飞; 王冠; 吴国发
Original assignee: 汉能新材料科技有限公司
Priority date: 2016-01-21
Filing date: 2016-12-26
Publication date: 2017-07-27
Also published as: CN106987718B; CN106987718A

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 cuprous ammine complexation, alkali separation of indium and gallium, replacement of indium, hydrolysis of gallium, and the like. In the recycling method, 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; in addition, copper is separated by using cuprous ammine complexation, deposition is not generated, metal ions can be well separated;and in another aspect, in the method, 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.

Description

Method for recovering copper indium gallium selenide material

Technical field

The invention relates to a method for recovering a copper indium gallium selenide photovoltaic module, in particular to a method for recovering copper indium gallium selenide material.

Background technique

The copper indium gallium selenide thin film solar cell has many advantages and is favored by the market. It is the biggest hot spot in the research and development, scale production and application of thin film solar cells in recent years. The absorption layer of copper indium gallium selenide solar cell consists of copper, indium, gallium and selenium in the optimal proportion of chalcopyrite structure, which can absorb a wide range of wavelengths, except for the visible spectrum of light absorbed by amorphous silicon solar cells. It can also cover the near-infrared region with a wavelength between 700 and 2000 nm, that is, the longest power generation in one day. The copper indium gallium selenide thin film solar cell can exceed 20% per day compared with the same wattage level crystalline silicon solar cell. The total amount of electricity generated in proportion. Crystalline silicon cells are inherently photo-attenuating, and their power generation efficiency will gradually decrease after prolonged exposure to sunlight. The copper indium gallium selenide solar cell has no photo-induced attenuation characteristics and high power generation stability. Crystal silicon solar cells have hot spots after power generation for a long period of time, resulting in small power generation and increased maintenance costs. The copper indium gallium selenide solar cell can adopt an internal connection structure to avoid this phenomenon, and the maintenance cost is lower than that of the crystalline silicon solar cell.

Copper indium gallium selenide thin film solar cells are produced by vacuum sputtering, distillation and non-vacuum coating. No matter which manufacturing method is used, some materials of copper indium gallium selenide are produced during the production process. In addition to heavy metal copper, it also contains rare metals such as indium, gallium and selenium. In order to facilitate the continuous utilization of rare metals such as indium, gallium and selenium and heavy metal copper, it needs to be separated and separately recovered to facilitate further recycling to ensure the sustainable development of copper indium gallium selenide thin film solar cell materials. In the prior art, the method for recovering copper indium gallium selenide material mainly includes acid dissolution method, extraction method and oxidation distillation method. A combination of wet or fire refining methods.

A method for recovering copper indium gallium selenide is disclosed in Chinese Patent Application Publication No. CN102296178A, and specifically discloses a method of dissolving a metal powder containing copper indium gallium selenide using a mixed solution of hydrochloric acid and hydrogen peroxide. The method uses helium to reduce selenium, replaces copper with indium metal, and separates indium from gallium by a supported liquid membrane in combination with a dispersed stripping solution.

A method for recovering copper indium gallium selenide is disclosed in Chinese Patent Application Publication No. CN103184388A, which first breaks the copper indium gallium selenide thin film solar panel into pieces, and then uses the soaking process to use the sulphuric acid at a predetermined temperature by a soaking process. The soaking solution is obtained by immersing in a mixed system with hydrogen peroxide for a predetermined period of time, and then indium, gallium, and selenium are recovered by processes such as extraction, back extraction, and electrolysis.

U.S. Patent No. 5,779,877 discloses a method of recovering copper indium selenide solar cell materials. The method mainly comprises crushing, nitric acid leaching, electrolysis of copper, selenium and indium by two electrodes, followed by evaporation to obtain a mixture of indium and zinc oxides, and oxidative distillation to separate copper and selenium.

In the above prior art technique, the use of hydrochloric acid and hydrogen peroxide leaching consumes a large amount of oxidant, and hydrochloric acid is volatile, and is exothermic during the leaching reaction, causing a large amount of hydrochloric acid to volatilize and the pollution is serious. At the same time, the extractant used in the extraction of indium produces a co-extraction phenomenon of gallium, which makes separation of indium and gallium difficult, thereby reducing the recovery rate of gallium. On the other hand, the indium replacement copper treatment method is too expensive.

Summary of the invention

In order to solve the above-mentioned drawbacks in the prior art, an object of the present invention is to provide a method for recovering copper indium gallium selenide materials capable of reducing environmental pollution, high indium recovery rate, and low production cost.

The method for recovering copper indium gallium selenide material of the invention adopts sulfuric acid + hydrogen peroxide leaching to reduce the volatilization of acid gas during the leaching process, and is relatively environmentally friendly; separating copper by the principle of copper ammonia complexing greatly reduces the cost, the operation is simple, the equipment requirement is low, and at the same time Obtaining a high purity of the copper product; using the two sexes of gallium, that is, by adding excessive The lye directly obtains the sodium gallate solution, thereby achieving the purpose of separating indium and gallium, and the separation effect is good, and the obtained indium and gallium products have high purity.

The method for recovering copper indium gallium selenide material of the invention comprises the following steps:

In step A, the copper indium gallium selenide material is placed in a ball mill for ball milling, and then dried by ball milling.

In step B, the concentrated sulfuric acid is diluted, and the alloy powder obtained in the step A is mixed with the diluted concentrated sulfuric acid. After the temperature is raised, the hydrogen peroxide is introduced to carry out leaching, and after the leaching is completed, the residue is filtered to obtain a pure leachate. The process contains the following reactions:

In step C, after the temperature of the leachate is raised, sulfur dioxide gas is introduced to carry out selenium reduction. The process contains the following reactions:

During the process of reducing selenium, a red precipitate of bricks is formed in the container, which gradually turns black, and black selenium is obtained after filtration.

Step D, after removing the selenium, directly add concentrated ammonia water to adjust the pH value to neutral 7.0, and then stand at room temperature after stirring, then extract the supernatant, directly filter to obtain gallium hydroxide and indium hydroxide precipitate, and copper ammonia supernatant. The process contains the following reactions:

6OH ^- +In ₂ (SO ₄ ) ₃ →3Na ₂ SO ₄ +2In(OH) ₃

6OH ^- +Ga ₂ (SO ₄ ) ₃ →3Na ₂ SO ₄ +2Ga(OH) ₃

Cu ²⁺ +4NH ₃ →Cu(NH ₃ ) ₄ ²⁺

In step E, the copper ammonia supernatant is directly added with sodium sulfide, and the diluted polyacrylamide is added, and the copper sulfide precipitate is obtained by directly filtering after constant temperature stirring.

Step F, adding a solution of gallium hydroxide and indium hydroxide to the sodium hydroxide solution, stirring at a constant temperature, and then allowing to stand, and then extracting the supernatant, and directly filtering to obtain an indium hydroxide precipitate and a sodium gallate supernatant. The process contains the following reactions:

Ga(OH) ₃ +OH ^- →GaO ₂ ^- +2H ₂ O

In step G, the sodium gallate solution is directly electrolyzed under alkaline conditions to obtain a monolithic gallium. The process contains the following reactions:

GaO ₂ ^- +2H ₂ O→Ga+O ₂ +4OH ^-

In step H, the indium hydroxide precipitate is reverse-dissolved with hydrochloric acid, replaced with a zinc plate, and after displacement, washed and filtered to obtain sponge indium. The process contains the following reactions:

In(OH) ₃ +3Hcl→InCl ₃ +3H ₂ O

3Zn+2InCl ₃ →3ZnCl ₂ +2In

In the method for recovering the copper indium gallium selenide material of the present invention, the method further comprises: ball milling the copper indium gallium selenide material to 40 mesh or less in step A, and drying at 100 ° C for 4 hours after ball milling.

In the method for recovering the copper indium gallium selenide material of the present invention, the method further comprises: diluting the concentrated sulfuric acid to 25% in step B, mixing the drying material with 25% concentrated sulfuric acid according to a solid-liquid ratio of 1:5, and raising the temperature to At 90 ° C, hydrogen peroxide was introduced at a rate of 8 ml / min, the stirring rate was 600 r / min, and the temperature was leached for 3 h.

In the method for recovering the copper indium gallium selenide material of the present invention, the method further comprises: after the temperature of the leachate is raised to 65 ° C in step C, the sulfur dioxide gas is introduced at a rate of 10 L/min, and the temperature is maintained for 10 hours.

In the method for recovering the copper indium gallium selenide material of the present invention, the method further comprises: in step D, the ammonia water concentration is 20%, stirring at normal temperature for 20 minutes, stirring rate is 200r/min, and after standing for 2 hours, the supernatant is extracted, and the washing is performed three times repeatedly. The water consumption per wash water does not exceed 800ml.

In the method for recovering the copper indium gallium selenide material of the present invention, further comprising adding 10% of the diluted polyacrylamide 20 ml in step E, the temperature is 60 ° C, the stirring rate is 200 r/min, and the mixture is stirred at a constant temperature for 20 min.

In the method for recovering the copper indium gallium selenide material of the present invention, the method further comprises: adding the gallium hydroxide and the indium hydroxide precipitate in the step F to the 8 mol/L sodium hydroxide solution and heating to 80 ° C, stirring at a rate of 200 r/min, and stirring at a constant temperature for 20 min. After the reaction, the supernatant was taken for 2 hours, and washed repeatedly for three times. The water consumption per wash did not exceed 800 ml.

In the method for recovering the copper indium gallium selenide material of the present invention, the method further comprises: the sodium gallate solution in the step G is directly electrolyzed under alkaline conditions, and the electrolysis condition is a current of 1.5 A, a voltage of 4.0 V, a pole spacing of 25 mm, and a plate area. 50mm × 50mm, single cathode and double anode configuration, electrolysis for 6h, you can get gallium element.

In the method for recovering the copper indium gallium selenide material of the present invention, the method further comprises: in step H, pre-dissolving the indium hydroxide precipitate with 600 ml of 10% hydrochloric acid, dissolving and adjusting the pH to 1.5, and heating to 55 ° C, stirring at a constant temperature, stirring The rate was 200 r/min, and the replacement was carried out with a 4N zinc plate, and the replacement time was 6 hours. After the replacement, the sponge was infiltrated and filtered to obtain a sponge indium.

DRAWINGS

BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a schematic illustration of a process for recovering a copper indium gallium selenide material of the present invention.

detailed description

The embodiments of the present invention are further described below in conjunction with the accompanying drawings.

As shown in FIG. 1, the method for recovering copper indium gallium selenide material of the present invention mainly comprises the following steps:

In step A, 200 g of copper indium gallium selenide material was placed in a ball mill, ball-milled to a powder of 40 mesh or less, and dried at 100 ° C for 4 hours.

Step B, dilute concentrated sulfuric acid to 25%, mix 200g of dried material with 25% concentrated sulfuric acid according to a solid-liquid ratio of 1:5, raise the temperature to 90 ° C, and introduce hydrogen peroxide at a rate of 8 ml / min, stirring rate 600 r / Min, immersed at constant temperature for 3 h, and after the leaching is finished, the residue is filtered off to obtain a pure leachate.

In step C, after the leaching solution is heated to 65 ° C, sulfur dioxide gas is introduced at a rate of 10 L/min and the temperature is kept for 10 h. During the process of reducing selenium, a brick red precipitate is formed in the container, gradually becomes black, and black selenium is obtained after filtration.

Step D, after removing selenium, directly add 20% concentrated ammonia water to adjust the pH value to neutral 7.0, stir at normal temperature for 20 min, stir at a rate of 200 r/min, and after standing for 2 h, extract the supernatant, and wash it three times with each wash. The amount does not exceed 800 ml, and finally directly filtered to obtain a precipitate of gallium hydroxide and indium hydroxide, and a copper ammonia supernatant.

Step E, the copper ammonia supernatant is directly added with sodium sulfide, 20 ml of 10% diluted polyacrylamide is added, the temperature is 60 ° C, the stirring rate is 200 r / min, the temperature is stirred for 20 min, and the copper sulfide precipitate is obtained by direct filtration.

Step F, adding gallium hydroxide and indium hydroxide precipitate to 8 mol/L sodium hydroxide solution and heating to 80 ° C, stirring rate 200 r / min, stirring at a constant temperature for 20 min, after standing for 2 h, extracting the supernatant, repeatedly washing and extracting three times, each The secondary washing water does not exceed 800 ml, and finally directly filtered to obtain an indium hydroxide precipitate and a sodium gallate supernatant.

Step G, sodium gallate solution is directly electrolyzed under alkaline conditions. The electrolysis conditions are current 1.5A, voltage 4.0V, pole spacing 25mm, plate area 50mm×50mm, single cathode double anode configuration, electrolysis 6h, ie A single element of gallium is available.

Step H, the indium hydroxide precipitate is reversely dissolved with 600 ml of 10% hydrochloric acid, dissolved to adjust the pH to 1.5, and the temperature is raised to 55 ° C with constant temperature stirring, the stirring rate is 200 r / min, and the replacement is performed with 4N zinc plate, the replacement time is 6 h, and the replacement is performed. After washing and filtering, a sponge indium can be obtained.

The above embodiments are only intended to be illustrative of the invention, and are not intended to limit the scope of the invention, and the scope of the invention is defined by the claims. Many variations can be deduced or derived from the teachings of the present invention and the technical solutions disclosed herein, and all such modifications are also considered to be the scope of the present invention.

Claims

A method for recovering copper indium gallium selenide material, comprising the steps of:

Step A, placing the copper indium gallium selenide material in a ball mill for ball milling, and drying after ball milling;

Step B, the drying material obtained in the step A is mixed with the diluted concentrated sulfuric acid, and after heating, the hydrogen peroxide is introduced to perform leaching, and after the leaching is finished, the residue is filtered to obtain a leachate;

Step C, after the temperature of the leaching solution is raised, sulfur dioxide gas is introduced to perform selenium reduction;

Step D, the residual liquid after removing selenium is directly added with concentrated ammonia water to adjust the pH value to neutrality, and after standing at room temperature, the mixture is allowed to stand, and then the supernatant is extracted, and directly filtered to obtain a precipitate of gallium hydroxide and indium hydroxide, and a copper ammonia supernatant. ;

Step E, adding the copper ammonia supernatant to the sodium sulfide, adding the diluted polyacrylamide, stirring at a constant temperature, and filtering to obtain a copper sulfide precipitate;

Step F, the precipitate of the gallium hydroxide and the indium hydroxide obtained in the step E is added to the sodium hydroxide solution, and the mixture is stirred at a constant temperature, and then the supernatant is extracted, and the indium hydroxide precipitate and the sodium gallate solution are directly filtered.

Step G, electrolyzing the sodium gallate solution obtained in the step F under alkaline conditions to obtain a simple substance of gallium;

In step H, the indium hydroxide precipitate obtained in the step F is reversely dissolved with hydrochloric acid and replaced with a zinc plate to obtain a sponge indium.
The method for recovering a copper indium gallium selenide material according to claim 1, wherein in step A, the copper indium gallium selenide material is ball milled to 40 mesh or less, and dried at 100 ° C for 4 hours after ball milling.
The method for recovering a copper indium gallium selenide material according to claim 1 or 2, wherein in step B, the concentrated sulfuric acid is diluted to 25%, and the dried material and the 25% concentrated sulfuric acid are in a solid-liquid ratio. Mix 1:5, raise the temperature to 90 ° C, pass hydrogen peroxide at a rate of 8 ml / min, stir at 600 r / min, and immerse at constant temperature for 3 hours.
The method for recovering a copper indium gallium selenide material according to claim 1, wherein in the step C, the leaching liquid is heated to 65 ° C, and then sulfur dioxide gas is introduced at a rate of 10 L/min for 10 hours.
The method for recovering a copper indium gallium selenide material according to claim 1, wherein in the step D, the ammonia water concentration is 20%, the mixture is stirred at a normal temperature for 20 minutes or more, the stirring rate is 200 r/min, and the mixture is allowed to stand for 2 hours and then extracted. The clear liquid is washed repeatedly three times, and the water consumption of each wash water does not exceed 800 ml.
The method for recovering copper indium gallium selenide material according to claim 1, wherein in step E, 20 ml of 10% diluted polyacrylamide is added, the temperature is 60 ° C, the stirring rate is 200 r/min, and the mixture is stirred at a constant temperature for 20 minutes or more.
The method for recovering copper indium gallium selenide material according to claim 1, wherein in step F, the precipitation of gallium hydroxide and indium hydroxide is added to a solution of 8 mol/L sodium hydroxide to 80 ° C, and the stirring rate is 200 r/min. After stirring at a constant temperature for 20 minutes, the supernatant was taken after standing for 2 hours, and washed repeatedly three times, and the water consumption per washing did not exceed 800 ml.
The method for recovering copper indium gallium selenide material according to claim 1, wherein in step G, the sodium gallate solution is directly electrolyzed under alkaline conditions, and the electrolysis condition is a current of 1.5 A, a voltage of 4.0 V, and a pole spacing of 25 mm. The plate area is 50mm×50mm, single cathode and double anode configuration, and the electrolysis time is 6 hours, and the gallium element can be obtained.
The method for recovering copper indium gallium selenide material according to claim 1, wherein in step H, the indium hydroxide precipitate is dissolved in 600 ml of 10% hydrochloric acid, dissolved, adjusted to a pH of 1.5, and heated to 55 ° C. The mixture was stirred under constant temperature at a stirring rate of 200 r/min, and replaced with a 4N zinc plate for a replacement time of 6 hours.