TWI405855B - Method for recovery of copper, indium, gallium, and selenium - Google Patents

Abstract

A method for the recovery of copper, indium, gallium, and selenium is provided. The method includes steps of using a mixed solution containing a hydrochloric acid and hydrogen peroxide to dissolve the copper, indium, gallium, and selenium. After the selenium is separated by using the hydrazine, the copper is reduced by indium metal. After that, a combination of a supported liquid membrane (SLM) and a strip dispersion separates the indium from the gallium. The acid performed in all the steps of the method is hydrochloric acid. Therefore, the copper, indium, gallium, and selenium can be separated one by one without transforming the solution during the operation process thereby reducing the time and cost of the process.

Description

Method for recovering copper indium gallium selenide

The invention relates to a method for recovering copper indium gallium selenide, and in particular to a method for recovering copper indium gallium selenide combined with a supported liquid film.

Copper indium gallium selenide (CIGS) thin film solar cells are considered to have great potential for development due to their high photoelectric efficiency. The method of making copper indium gallium selenide thin film solar cells is vacuum reflow, evaporation or non-vacuum coating. In order to reduce cost and meet environmental requirements, copper, indium, gallium and selenium need to be recycled. Refining procedures. Therefore, how to separate and recover copper, indium, gallium and selenium from waste (liquid) is a technology that is currently being developed.

A method for recovering selenium is generally disclosed, for example, in U.S. Patent No. 3,954,951, which discloses the use of hydrazine to reduce selenous acid dissolved in methyl (ethyl) alcohol to an amorphous system at a low temperature (-20 ° C). Selenium. U.S. Patent No. 4,663,141 discloses the use of carbon monoxide and a primary or secondary amine to react a selenium-containing material to form a solvent-soluble compound which releases the elemental selenium by thermal decomposition. , to achieve the effect of selenium recovery.

In the recovery of gallium, the recovery of gallium from gallium arsenide waste by a supporting liquid film has been disclosed, for example, in the Republic of China Patent Publication No. I-268802. The use of the organic solvent 7(4-ethyl-1-methyloctyl)-8-hydroxyquinoline (Kelex10) and tricaprylmethyl-ammonium chloride (Aliquat 336) as an extractant for the recovery of gallium has been disclosed in U.S. Patent Publication No. US-20040042945A1. And purification.

However, in order to separately recover the copper indium gallium selenide in the waste (liquid), a relatively complicated process step is required. For example, after separating the selenium, the solution must be converted into a solution condition for appropriately separating the gallium, which is not only complicated in operation steps but also in the process time. It is lengthy and costs a lot in process costs. In addition, complex chemical processes generate a lot of wastewater.

Therefore, a method for removing and recovering high stability and high efficiency of copper, indium, gallium and selenium from industrial production processes and wastewater is a technology that is currently desired to be developed.

The method disclosed in the present invention can solve the problems of complicated recycling process of copper, indium, gallium and selenium and long process time in the prior art.

In one embodiment, the method of the present invention comprises the steps of first providing a plurality of metal powders comprising copper indium gallium selenide. These metal powders are then immersed in a hydrochloric acid solution. Further, a mixed solution containing hydrochloric acid and hydrogen peroxide is added to the above hydrochloric acid solution so that the metal powders are completely dissolved in the hydrochloric acid solution to form a first solution. The hydrazine solution is then added to the first solution, and the selenium in the metal powders is selectively separated from the first solution to form a second solution. The indium metal is placed in the second solution, the copper in the metal powder is displaced from the second solution, and a third solution is formed. A liquid film is provided, which is provided with a microporous support material. A dispersed stripping solution is provided, the dispersed stripping solution comprising a water counter-extracting solution dispersed in an organic solution, the organic solution comprising an extractant. The concentrated acid is added to the third solution such that the third solution contains an acid having an initial concentration greater than 8N. The third solution is treated on one side of the liquid film, and the other side of the liquid film is selectively removed from the gallium in the third solution by using the dispersed stripping solution. Part or all of the dispersed stripping solution is separated into an organic phase and water counter-extracted solution, wherein the water counter-extracting solution comprises a concentrated gallium solution, and the concentration of gallium ions in the third solution is less than 30 ppm. That is, the separation of copper indium gallium selenide is completed.

According to an embodiment of the invention, the proton concentration of the third solution is adjusted to 8N~10N by using concentrated acid before the third solution enters the liquid film.

According to another embodiment of the present invention, the volume ratio of hydrochloric acid to hydrogen peroxide in the mixed solution is from 10:1 to 10:3.

According to still another embodiment of the present invention, the hydrazine solution contains 1-3 equivalents of hydrazine.

According to still another embodiment of the present invention, the volume ratio of the above organic solution to the water counter-extraction solution is 2:1.

According to still another embodiment of the present invention, the water counter-extraction solution contains at least hydrochloric acid, wherein the equivalent concentration of hydrochloric acid is in the range of 1 N to 3 N.

According to still another embodiment of the present invention, after the dispersed stripping solution is separated into the organic phase and the water counter-extracted solution, at least the third solution is subjected to an electrolytic reaction to obtain indium.

According to still another embodiment of the present invention, wherein the third solution is treated on one of the liquid film sides, the shell side of the liquid film is selectively removed from the third solution by using the dispersed stripping solution.

According to still another embodiment of the present invention, wherein the third solution is treated on one of the shell sides of the liquid film, the tube side of the liquid film is selectively removed by using the dispersed stripping solution.

Compared with the conventional method for recovering copper indium gallium selenide, the present invention discloses The embodiment can be operated under a single production line, and the copper indium gallium selenium can be separated one by one without conversion of the process solution. Therefore, the process can be simplified, the process time is shortened, and the process cost is effectively reduced.

The invention discloses a method for recovering copper indium gallium selenide (copper, indium, gallium, and selenium). The acid used in each process step is hydrochloric acid, so copper indium can be transferred without conversion through solution during operation. Separation of gallium and selenium one by one.

In one embodiment, a method of recovering copper indium gallium selenide is disclosed. First, a plurality of metal powders are provided, and the metal powders include copper indium gallium selenide. These metal powders are then immersed in a hydrochloric acid solution. Further, a mixed solution containing hydrochloric acid and hydrogen peroxide is added to a hydrochloric acid solution in which these metal powders are soaked, so that the metal powders are completely dissolved in the hydrochloric acid solution to form a first solution. The hydrazine solution is then added to the first solution, and the selenium in the metal powder is selectively separated from the first solution to form a second solution. Indium metal is placed in the second solution, copper in the metal powder is displaced from the second solution, and a third solution is formed. A liquid membrane is provided which is provided with a microporous support. A strip dispersion solution is provided, the dispersion stripping solution comprising an aqueous aqueous solution solution dispersed in an organic solution, the organic solution comprising an extractant. The concentrated acid is added to the third solution such that the third solution contains an acid having an initial concentration greater than 8N. The third solution is treated on one side of the liquid film, and the other side of the liquid film is selectively removed from the gallium in the third solution by using the dispersed stripping solution. Part or all of the dispersed stripping solution is separated into organic phases The solution is counter-extracted with water, wherein the water counter-extraction solution contains a concentrated gallium solution. After the dispersed stripping solution is separated into the organic phase and the water counter-extracted solution, at least the third solution is subjected to an electrolytic reaction to obtain indium.

In the aforementioned step of adding the concentrated acid to the third solution, the initial concentration of the acid contained in the third solution will change with time after the start of recovery.

In some embodiments, the proton concentration of the third solution is adjusted to 8N~10N by using a concentrated acid before the third solution enters the liquid film.

In some embodiments, the volume ratio of hydrochloric acid to hydrogen peroxide in the mixed solution is from 10:1 to 10:3.

In some embodiments, the above hydrazine solution contains from 1 to 3 equivalents of hydrazine.

In some embodiments, the volume of the organic solution in the dispersed stripping solution is greater than the volume of the water stripping solution. In a particular embodiment, the volume ratio of the organic solution to the water counter-extracted solution in the above-described dispersed stripping solution is 2:1.

It is worth noting that the elemental selenium can be dissolved in a warm hydrochloric acid/hydrogen peroxide mixed solution or nitric acid, and its dissolved chemical formula is as shown in formulas (1), (2) and (3):

The hydrazine ion can reduce the tetravalent and hexavalent selenium to the elemental selenium, and its chemical formula is as shown in the formula (4):

In addition, it is worth noting that the above metal powder containing copper indium gallium selenide When the body is dissolved in a mixed solution of hydrochloric acid and hydrogen peroxide, since the gallium dissolves as an exothermic reaction, the temperature of the hydrochloric acid is increased when the gallium is dissolved, which is beneficial to the dissolution of the selenium, so that it is not necessary to additionally increase the process. The step of heating the solution.

It is worth noting that the above-mentioned indium metal is placed in the second solution to displace copper, and a metal having a lower standard electrode potential, such as indium, reduces and deposits a metal having a higher standard electrode potential, such as copper. Of course, if other noble metals having a high potential in the solution, such as tin, lead, nickel, and silver, may be replaced by indium metal. The indium metal is not limited to a shape, and may be, for example, an indium metal powder, an indium metal wire, an indium metal plate, and an indium metal plate.

Any supported liquid film (SLM) architecture can be used with the present invention. The liquid film structure used in one embodiment is a hollow fiber module. The hollow fiber module contains microporous hollow fibers to form a shell-and-tube structure. Referring to FIG. 1 , which is a schematic diagram of a device for recovering gallium combined with a supported liquid membrane technology and a dispersion stripping technique according to an embodiment of the present invention, the dispersed stripping solution 102 can flow through the shell side of the shell tube structure (shell) The side or tube side, while the third solution flows as the feed solution 104 through the other side of the shell structure (shell side or tube side). The supported liquid membrane with a hollow fiber structure provides a stable support for the dispersed stripping solution 102, thereby ensuring a stable process.

In one embodiment, the feed solution 104 flows through the tube side of the hollow fiber module by the feed pump 106, and the dispersed stripping solution flows through the shell of the hollow fiber module by the pump 108 system. side. In another embodiment, the fluid flow in the supported liquid film of the hollow fiber structure is in a countercurrent manner. That is, the flow direction of the dispersion stripping solution 102 flowing through the shell end is opposite to that of the feed solution 104 flowing through the tube end, whereby the contact time of the feed solution 104 and the dispersed stripping solution 102 becomes long, and the extraction efficiency is improved.

For the purposes of the present invention, a dispersed stripping solution is defined as a mixture of an aqueous phase and an organic phase. Wherein, the aqueous phase comprises an aqueous strip solution, and the organic phase comprises one or more extractants present in the organic solution. The dispersed stripping solution is formed by mixing the aqueous phase with the organic phase, for example, by mixing in a dispersion stripping tank 110 with a stirrer 112, as shown in FIG. This combination allows the water counter-extraction solution to be present in the form of droplets in the continuous organic phase. During the extraction process, the dispersed stripping solution flows through the hollow fiber membrane module to maintain the dispersed stripping solution. The organic phase of the dispersed stripping solution readily wets the hydrophobic pores of the porous hollow fibers to form a stable liquid film.

Figure 2 is an enlarged schematic view of a device for recovering gallium by a supported liquid membrane in combination with dispersion stripping in accordance with an embodiment of the present invention. The pressure at the dispersed stripping end of the supported liquid membrane is Po when the procedure is being carried out. At this time, at the feed solution end of the supported liquid membrane module (from the feed solution inflow direction 202 to the feed solution outflow direction 204), a low pressure Pa (usually around 2 psi) is applied, wherein the pressure Pa is greater than the pressure Po (Pa and Po are not shown). This pressure differential prevents the organic solution 212 in the dispersed stripping solution from seeping through the pores 208 of the hollow fibers to the feed solution end of the liquid membrane. The droplets 210 dispersed in the water counter-extraction solution have a size of about 80 micrometers to 800 micrometers. This size has been several orders of magnitude larger than the size of the aperture 208 of the microporous support structure, so that the droplets 210 at the dispersed stripping end of the supporting liquid film do not pass through the pores 208 of the microporous support structure. Arrived at the end of the feed solution.

In the supporting liquid film dispersion and stripping system disclosed in the present invention, organic The membrane solution, i.e., the organic phase from which the stripping solution is dispersed, is continuously supplied to the pores of the support. This continuous supply ensures stable and continuous operation of the supporting liquid film. In addition, by direct contact of the organic phase with the strip phase, an effective mass transfer is also provided for the stripping process. The organic phase and the stripping phase can even increase the contact area between the two by mixing, such as high-shearing mixing.

When the gallium is removed, the mixer (e.g., agitator 112) that disperses the stripping solution is stopped, and the dispersion is allowed to stand for phase separation until it is separated into two phases. Wherein, the two phases are respectively an organic solution and a concentrated strip solution, and the concentrated stripping solution is the product of the method disclosed in the present invention.

The metal powder containing copper indium gallium selenide may be a solution containing copper indium gallium selenide or the like from industrial process liquid or waste water, and is not limited to industrial process liquid and wastewater (material). In one embodiment, the metal powder containing copper indium gallium selenide may be derived from a copper indium gallium selenide target (Cu/In/Ga/Se spent target).

The dispersed stripping solution for recovering gallium disclosed in the present invention has an organic solution containing di(2-ethyl-hexyl) dialkyl phosphate (di(2-ethyl-hexyl) phosphate in a volume concentration of 10% to 70%. )phosphoric acid, D2EHPA) extractant. In one embodiment, the above-described dispersed stripping solution for recovering gallium has an organic solution comprising a D2EHPA extractant having a volume concentration of between 30% and 70%. In a particular embodiment, the above-described dispersed stripping solution for recovering gallium has an organic solution comprising a D2EHPA extractant having a volume concentration of 30% to 50%.

Compared to conventional supported liquid film technology, the present inventors have considerable advantages in applying a self-feeding solution to remove recovered gallium. These advantages include better film stability, lower cost, simplified program operation, and better The quality of the flux, and the preferred gallium recovery.

The disclosed technology stabilizes the supply of the organic film solution into the pores of the hollow fiber support for removal of gallium from the feed solution and recovery of gallium. This stable supply makes the supporting liquid film disclosed in the present invention more stable than the conventional liquid film, and the process is more stable and continuous. In addition, the present invention does not require the use of two sets of membrane modules for rotational operation and recharging. Therefore, the technology disclosed by the present invention can simultaneously reduce the cost of hardware and operation. At the same time, the removal technique disclosed in the present invention is easier to operate than conventional techniques.

In the techniques disclosed herein, the organic/extracted phase can be in direct contact with the stripped aqueous phase. The mixing of the two phases allows for more of the mass transfer surface area to be utilized in addition to the mass transfer surface area provided by the original hollow fiber, thereby increasing the efficiency of the target material from organic reverse extraction. The improved stripping efficiency further enhances the mass transfer flux when gallium is extracted.

The present invention may be embodied in various forms, and the embodiments shown in the drawings and the following description are examples of the invention, and it is understood that the disclosure herein is an example of the invention and is not It is intended that the invention be limited to the drawings and/or the particular embodiments described.

example

The supported liquid membrane used in the following examples was operated in a countercurrent mode. The feed solution flows through the tube side of the microporous polypropylene hollow fiber membrane group. The extracted gallium in the module and dispersion tank is stripped back into the dispersed stripping solution.

Example 1

Copper indium gallium selenide dissolution step

First, the metal powder prepared from the copper indium gallium selenide target is poured into a 10N hydrochloric acid solution, followed by slowly adding a mixed solution of hydrochloric acid and hydrogen peroxide in a volume ratio of 10:1 to dissolve the metal powder. The dissolution rate reached 98.5%. The solution in which the undissolved metal powder in the above solution having a dissolution rate of 98.5% is removed by filtration is the first solution.

Diamine reduction selenium step

A hydrazine solution is provided comprising from 1 to 3 equivalents of a hydrazine. After the hydrazine solution was slowly added to the first solution, the solution gradually changed from transparent to reddish brown and the solution was cloudy. After a further 21 hours of reaction, elemental selenium and a solution of copper indium gallium containing hydrochloric acid were filtered to separate selenium, and a second solution was prepared. After the separated selenium is analyzed by inductively coupled plasma emission spectrometer (ICP-OES), the selenium recovery rate is 99.1% after the converted selenium purity reaches 4N or higher, and the selenium content measured in the second solution is low. At 1ppm.

Indium replacement copper reduction step

The indium metal was placed in the second solution, and after an 8-hour replacement reaction, elemental copper and an indium gallium-containing hydrochloric acid solution were filtered to separate copper, and a third solution was prepared. After the separated copper was analyzed by inductively coupled plasma emission spectrometer (ICP-OES), the measured copper purity reached 2N or more, and the converted copper recovery rate was 99.2%, and the measured copper content in the third solution. Less than 0.5ppm.

Hollow fiber supporting liquid film column separation of indium and gallium steps

First, the volume ratio of the organic solution and the water counter-extracted solution in the dispersed stripping solution was 2:1. The organic solution is a mixture of the extractant D2EHPA and the dispersant kerosene, and the volume concentration of the D2EHPA is between 30% and 50%. The concentration of hydrochloric acid in the stripping solution was 1 N, and the concentration of the third solution was adjusted to 8 N with hydrochloric acid as a feed solution, and the operating temperature range was 20 ° C to 30 ° C.

Flowing through the tube side of the hollow fiber membrane group, when the tube side is filled with the third solution, the oil phase material containing the aqueous phase substance is sent to the shell side of the hollow fiber membrane group by the pump. To prevent the organic phase from entering the third solution through the pores of the hollow fiber, the tube side is subjected to a positive pressure, for example, about 4 to 5 psi above the shell side. When the system is in operation, the third solution and the dispersion solution are sent from the tank to the membrane membrane group by the pump, and then returned to the tank. The gallium ion concentration is sampled from the sampled third solution and the stripping solution at a fixed time. When the gallium ion concentration is less than 30 ppm, the reaction ends. The sample taken out of the dispersed stripping solution was allowed to stand for phase separation until phase separation occurred. Next, the aqueous phase sample in the dispersed stripping solution was analyzed by atomic absorption spectrometry (AAS) to determine the concentration of gallium therein, and the purity of gallium measured after subsequent electrolysis reached 4N or more, and the converted gallium recovery rate was about 99.1%. .

After the completion of the above reaction, the solution of the feed phase on the shell side is discharged and collected into a replacement tank. After the replacement, the purity of the indium obtained by electrolysis is 4N5 or more, and the converted indium ratio is about 99.2%.

Example 2

The experimental operation of this example was the same as that of Example 1, except that the volume ratio of hydrochloric acid to hydrogen peroxide in the mixed solution used was 10:2 instead of 10:1.

The recoveries of copper, indium, gallium and selenium recovered were approximately 99.4, 99.2, 99.2 and 99.4%, respectively.

Example 3

The experimental operation of this embodiment is the same as that of Embodiment 1, and the difference lies only in The volume ratio of hydrochloric acid to hydrogen peroxide in the mixed solution used was 10:3 instead of 10:1.

The recovered copper, indium, gallium and selenium recoveries were converted to approximately 99.5, 99.3, 99.2 and 99.9%, respectively.

Example 4

The experimental operation of this example is the same as that of Example 3, except that the hydrochloric acid concentration of the stripping solution in the step of separating the indium and gallium from the hollow fiber supporting liquid film column is 2N instead of 1N.

The recoveries of copper, indium, gallium and selenium recovered were approximately 99.4, 99.3, 99.4 and 99.9%, respectively, after conversion.

Example 5

The experimental operation of this example is the same as that of Example 3, except that the hydrochloric acid concentration of the stripping solution in the step of separating the indium and gallium from the hollow fiber supporting liquid film column is 3N instead of 1N.

The recovered copper, indium, gallium and selenium recoveries were converted to approximately 99.4, 99.3, 99.5 and 99.9%, respectively.

Example 6

The experimental operation of this example is the same as that of Example 5, except that the concentration of the third solution is adjusted to 9 N instead of 8N by hydrochloric acid in the step of separating the indium and gallium from the hollow fiber supporting liquid film column.

The recovered copper, indium, gallium and selenium recoveries were converted to approximately 99.4, 99.3, 99.5 and 99.9%, respectively.

Example 7

The experimental operation of this embodiment is the same as that of the embodiment 5, and the difference lies only in In the step of separating the indium and gallium from the hollow fiber supporting liquid film column, the concentration of the third solution is adjusted by using hydrochloric acid to be 10N instead of 8N.

The recovered copper, indium, gallium and selenium recoveries were converted to approximately 99.4, 99.2, 99.54 and 99.9%, respectively.

According to the above embodiment, it is known that the volume ratio of hydrochloric acid to hydrogen peroxide in the mixed solution, the hydrochloric acid concentration of the stripping solution, or the concentration of the third solution adjusted with hydrochloric acid can relatively increase the recovery rate of at least one metal of these noble metals. However, using the above method to recover copper, indium, gallium and selenium, the recovery rate can reach more than 99%, and the recovery rate is almost 100%. In addition, the disclosed embodiments can be operated under a single production line, and the copper indium gallium selenium can be separated one by one without conversion through the process solution. Therefore, the process can be simplified, the process time is shortened, and the process cost is effectively reduced.

Although the present invention has been disclosed in the above embodiments, it is not intended to limit the present invention, and the present invention can be modified and modified without departing from the spirit and scope of the present invention. The scope is subject to the definition of the scope of the patent application attached.

102‧‧‧Disperse stripping solution

104‧‧‧feed solution

106‧‧‧Feeding pump

108‧‧‧ pump

110‧‧‧Disperse counter extraction tank

112‧‧‧Agitator

202‧‧‧Incoming solution inflow direction

204‧‧‧ Feed solution outflow direction

208‧‧‧ hole

206‧‧‧ hollow fiber wall

212‧‧‧ organic solution

210‧‧‧ droplets

The above and other objects, features, advantages and embodiments of the present invention will become more apparent and understood.

1 is a schematic view of a device for recovering copper indium gallium selenide in combination with a supported liquid film technique and a dispersion stripping technique in accordance with an embodiment of the present invention.

Figure 2 is a construction according to an embodiment of the present invention, combined with support An enlarged schematic diagram of a liquid membrane technology and a dispersion stripping technique for recovering copper indium gallium selenide.

202. . . Feed solution inflow direction

204. . . Feed solution outflow direction

206. . . Hollow fiber wall

208. . . Hole

210. . . Droplet

212. . . Organic solution

Claims (12)

A method for recovering copper indium gallium selenide, comprising: providing a plurality of metal powders, the metal powders comprising copper indium gallium selenide; immersing the metal powders in a hydrochloric acid solution; providing a mixed solution, the mixing The solution comprises hydrochloric acid and hydrogen peroxide; the mixed solution is added to the hydrochloric acid solution soaked with the metal powder, so that the metal powder is completely dissolved in the hydrochloric acid solution to form a first solution; the hydrazine solution is added The first solution, wherein the selenium in the metal powder is selectively separated from the first solution to form a second solution; and an indium metal is placed in the second solution, from the second solution Displacement of copper in the metal powder to form a third solution; providing a liquid film provided with a microporous support; providing a dispersed stripping solution comprising a water opposite The extraction solution is dispersed in an organic solution, the organic solution comprises an extracting agent; a concentrated acid is added to the third solution, so that the third solution contains an acid having an initial concentration of at least 8N; and the first portion is treated on the side of the liquid film Three solution And causing the other side of the liquid film to selectively remove gallium from the third solution by using the dispersed stripping solution; and separating the partially or fully dispersed stripping solution into an organic phase opposite to the water The solution is extracted, wherein the water counter-extraction solution comprises a concentrated gallium solution, and the concentration of gallium ions in the third solution is less than 30 ppm. The method for recovering copper indium gallium selenide according to claim 1, wherein the proton concentration of the third solution is adjusted to 8 N to 10 N by using the concentrated acid before the third solution enters the liquid film. The method for recovering copper indium gallium selenide according to claim 1, wherein the mixed solution has a volume ratio of hydrochloric acid to hydrogen peroxide of 10:1 to 10:3. The method for recovering copper indium gallium selenide according to claim 1, wherein the hydrazine solution comprises 1-3 equivalents of hydrazine. The method for recovering copper indium gallium selenide according to claim 1, wherein the volume of the organic solution in the dispersed stripping solution is larger than the volume of the water stripping solution. The method for recovering copper indium gallium selenide according to claim 5, wherein the volume ratio of the organic solution to the water counter-extracted solution is 2:1. The method for recovering copper indium gallium selenide according to claim 1, wherein the extracting agent comprises di(2-ethyl-hexyl)phosphoric acid (D2EHPA). The volume concentration of the dialkyl 2-(2-ethyl-hexyl) diphosphate phosphate in the organic solution is between 10% and 70%. The method for recovering copper indium gallium selenide according to item 1 of the claim, wherein The extracting agent comprises di(2-ethyl-hexyl)phosphoric acid dialkyl phosphate, and the volume concentration of the dialkyl 2-(2-ethyl-hexyl)phosphoric acid in the organic solution is between 30% and 50%. The method for recovering copper indium gallium selenide according to claim 1, wherein the water counter-extraction solution comprises at least hydrochloric acid, and the equivalent concentration of the hydrochloric acid is in the range of 1N to 3N. The method for recovering copper indium gallium selenide according to claim 1, wherein the dispersed stripping solution is divided into the organic phase and the water counter-extracting solution, and at least comprises: performing an electrolytic reaction on the third solution to The indium is obtained. The method for recovering copper indium gallium selenide according to claim 1, wherein when the third solution is treated on one side of the liquid film, one side of the liquid film is made to use the dispersed stripping solution. The gallium in the third solution is selectively removed. The method for recovering copper indium gallium selenide according to claim 1, wherein when the third solution is treated on one of the shell sides of the liquid film, one side of the liquid film is made to use the dispersed stripping solution. The gallium in the third solution is selectively removed.