CN102296178A - Method for recovering copper, indium, gallium and selenium (CIGS) - Google Patents
Method for recovering copper, indium, gallium and selenium (CIGS) Download PDFInfo
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- CN102296178A CN102296178A CN2010102143938A CN201010214393A CN102296178A CN 102296178 A CN102296178 A CN 102296178A CN 2010102143938 A CN2010102143938 A CN 2010102143938A CN 201010214393 A CN201010214393 A CN 201010214393A CN 102296178 A CN102296178 A CN 102296178A
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Abstract
The invention relates to a method for recovering copper, indium, gallium and selenium (CIGS). The method comprises the following steps of firstly dissolving metal powder containing CIGS by utilizing mixed solution of hydrochloric acid and hydrogen peroxide; after separating out selenium using hydrazine, displacing copper by using indium metal; and finally separating indium and gallium through combining a support liquid membrane (SLM) with dispersed stripping liquor, wherein the acid used in all of the steps of the method is hydrochloric acid, thus, copper, indium, gallium and selenium can be separated one by one without being converted by solution during operation, and the process time and the process cost can be effectively reduced.
Description
Technical field
The invention relates to a kind of recovery method of copper-indium-galliun-selenium, and particularly relevant for a kind of recovery method in conjunction with the support type liquid film.
Background technology
Owing to have high photoelectric efficiency, so copper-indium-galliun-selenium (CIGS) thin film solar cell is considered to have very much the potentiality of development.No matter and the mode of making CIGS thin-film type solar cell is to adopt the technology of vacuum splashing and plating, evaporation or antivacuum coating, in order to reduce cost and the demand that meets environmental protection, copper, indium, gallium and selenium all need to reclaim and the refining program.Therefore, how by separating in the waste material (liquid) and reclaiming copper, indium, gallium and selenium, for desiring most ardently the technology of development at present.
Generally be used for reclaiming the method for selenium, for example in United States Patent (USP) notification number US-3954951 number, once disclosed (20 ℃) under the low temperature and utilize hydrazine will be dissolved in the selenium that selenous acid in first (second) alcohol restores amorphous.In United States Patent (USP) notification number US-4663141 number, once disclosed and utilize carbon monoxide and primary amine or secondary amine to form the compound that dissolves in solvent containing the reaction of selenium material, this selenium-containing compound discharges simple substance selenium in the pyrolysated mode again, reaches the effect that selenium reclaims.
And aspect the recovery of gallium, for example then have in TaiWan, China patent announcement number I-268802 number, once to disclose and utilize the supportive liquid film from the gallium arsenide waste, to carry out the recovery of gallium.In U.S. Patent Publication No. US-20040042945A1 number, once disclosed and utilized organic solvent 7 (4-ethyl-1-Methyl Octyl)-oxine (7 (4-ethyl-1-methyloctyl)-8-hydroxyquinoline; Kelex10) and three decanoyl methyl-ammonium chlorides (tricaprylmethyl-ammonium chloride, Aliquat 336) carry out the recovery and the purifying of gallium as extraction agent.
Yet, desire reclaim respectively copper-indium-galliun-selenium in the waste material (liquid) then must be quite complicated processing step, for example isolate selenium after, then solution must be changed into the solution condition that appropriate separation goes out gallium, not only complex operation step and process time tediously long, on the technology cost cost higher.In addition, Fu Za chemical process more can produce many waste water.
Therefore, a kind of high stability and high efficiency method that can remove and reclaim copper, indium, gallium and selenium from industrial manufacture process and waste water is the technology of desiring most ardently development at present.
Summary of the invention
The disclosed method of the present invention is the recovery complex process and the long problem of process time that can solve copper in the aforementioned known techniques, indium, gallium and selenium.
In an embodiment, method of the present invention comprises the following step: a plurality of metal-powders at first are provided, and these metal-powders comprise copper-indium-galliun-selenium.Then these metal-powders are soaked in the hydrochloric acid soln.The mixing solutions that will comprise hydrochloric acid and hydrogen peroxide again adds in the above-mentioned hydrochloric acid soln, makes these metal-powders be dissolved in fully in this hydrochloric acid soln, to form first solution.Then hydrazine solution is added first solution, selectivity goes out selenium in those metal-powders from first solution separating, to form second solution.Indium metal is inserted in second solution, and this second solution displaces the copper in those metal-powders certainly, and forms the 3rd solution.One liquid film is provided, and this liquid film is provided with micropore hole fid.The dispersion strip liquor is provided, and this dispersion strip liquor comprises the water stripping workshop and is scattered in the organic solution, and organic solution comprises extraction agent.Adding gelled acid to the three solution makes the 3rd solution contain the acid of starting point concentration greater than 8N.Side at liquid film is handled the 3rd solution, and makes the opposite side of liquid film disperse strip liquor by using, and the gallium in selective removal the 3rd solution.To partly or all disperse strip liquor to be divided into organic phase and water stripping workshop, wherein the water stripping workshop comprises spissated Gallium solution.Promptly finish the separation of copper-indium-galliun-selenium.
According to one embodiment of the invention, above-mentioned concentration of hydrochloric acid solution is 8N～10N.
According to another embodiment of the present invention, the hydrochloric acid of above-mentioned mixing solutions and the volume ratio of hydrogen peroxide are 10: 1～10: 3.
According to yet another embodiment of the invention, above-mentioned hydrazine solution comprises the normal hydrazine of 1-3.
According to further embodiment of this invention, the volume ratio of above-mentioned organic solution and this water stripping workshop is 2: 1.
According to further embodiment of this invention, above-mentioned water stripping workshop comprises hydrochloric acid at least, and wherein the equivalent concentration of hydrochloric acid is the scope between 1N to 3N.
Compared to the method for known recovery copper-indium-galliun-selenium, the disclosed embodiment of the present invention can operate under single product line, and must copper-indium-galliun-selenium can not separated one by one via the conversion of mill solution.Therefore can effectively simplify technology, shortened the process time and effectively reduce the technology cost.
Description of drawings
For above and other objects of the present invention, feature, advantage and embodiment can be become apparent, appended the description of the drawings is as follows:
Fig. 1 is for according to the construction of one embodiment of the invention institute, in conjunction with the support type liquid film technology and disperse reverse extraction technology to reclaim the schematic representation of apparatus of gallium;
Fig. 2 is for according to the construction of one embodiment of the invention institute, in conjunction with the support type liquid film technology and disperse the enlarged diagram of reverse extraction technology with the device that reclaims gallium;
Wherein, primary clustering nomenclature
102: disperse strip liquor 104: feedstock solution
106: fresh feed pump 108: pump
110: disperse back extraction groove 112: agitator
202: feedstock solution inflow direction 204: feedstock solution flows out direction
208: hole 206: hollow fiber walls
212: organic solution 210: drop
Embodiment
Therefore the present invention has disclosed a kind of recovery method of copper-indium-galliun-selenium, and the employed acid of each processing step is hydrochloric acid, must can be with copper-indium-galliun-selenium separation one by one via the conversion of solution in operating process.
In an embodiment, it discloses a kind of recovery method of copper-indium-galliun-selenium.A plurality of metal-powders at first are provided, and these metal-powders comprise copper-indium-galliun-selenium.Then these metal-powders are soaked in the hydrochloric acid soln.The mixing solutions that will comprise hydrochloric acid and hydrogen peroxide again adds to soak to be had in the hydrochloric acid soln of these metal-powders, makes these metal-powders be dissolved in fully in the hydrochloric acid soln, to form first solution.Then hydrazine solution is added first solution, selectivity goes out selenium in these metal-powders from first solution separating, to form second solution.Indium metal is inserted in second solution, displace copper in these metal-powders from second solution, and form the 3rd solution.One liquid film is provided, and this liquid film is provided with micropore hole fid.The dispersion strip liquor is provided, and this dispersion strip liquor comprises the water stripping workshop and is scattered in the organic solution, and organic solution comprises extraction agent.Adding gelled acid to the three solution makes the 3rd solution contain the acid of starting point concentration greater than 8N.Side at liquid film is handled the 3rd solution, and makes the opposite side of liquid film disperse strip liquor by using, and the gallium in selective removal the 3rd solution.To partly or all disperse strip liquor to be divided into organic phase and water stripping workshop, wherein the water stripping workshop comprises spissated Gallium solution.
In the step of aforementioned adding gelled acid to the three solution, the starting point concentration of the acid that the 3rd solution contains will change after reclaiming beginning in time.
In certain embodiments, above-mentioned concentration of hydrochloric acid solution is 8N～10N.
In certain embodiments, the volume ratio of the hydrochloric acid of above-mentioned mixing solutions and hydrogen peroxide is 10: 1～10: 3.
In certain embodiments, above-mentioned hydrazine solution comprises 1～3 normal hydrazine.
In certain embodiments, in the above-mentioned dispersion strip liquor volume of organic solution greater than the volume of water stripping workshop.In a particular embodiment, the volume ratio of organic solution and water stripping workshop is 2: 1 in above-mentioned dispersion strip liquor.
Selenium that it should be noted that element state is dissolvable in water in the mixing solutions or nitric acid of warm hydrochloric acid/hydrogen peroxide, and its dissolved chemical formula reaches (3) suc as formula (1), (2):
And the hydrazine ion can be reduced to tetravalence and hexavalent selenium the selenium of element state, its chemical formula such as formula (4):
In addition, it should be noted that, be dissolved in the process of mixing solutions of hydrochloric acid and hydrogen peroxide at the above-mentioned metal-powder that will contain copper-indium-galliun-selenium, during wherein owing to the gallium dissolving is a thermopositive reaction, therefore, during the gallium dissolving hydrochloric acid temperature is improved, and help the dissolving of selenium, so needn't increase step more in addition the mill solution heating.
It should be noted that above-mentioned indium metal inserts in second solution step with the displacement copper, the metal that standard potential is lower, indium for example, metal that can standard potential is higher, copper for example, reduction is deposition also.Certainly, if having the precious metal of other noble potential in the solution, for example tin, lead, nickel, silver also can be replaced by indium metal.Above-mentioned indium metal is not limited to body, can be for example indium metal powder, indium metal line, indium metal sheet and indium metal plate on the implementation.
The present invention can use any support type liquid film (SLM) framework.The liquid film framework that is adopted in an embodiment is to be tubular fibre (hollow fiber) module.The tubular fibre module comprises micropore (microporous) tubular fibre, to form a package (shell-and-tube) structure.Please refer to Fig. 1, its be one embodiment of the invention in conjunction with the support type liquid film technology and disperse reverse extraction technology to reclaim the schematic representation of apparatus of gallium, dispersion strip liquor 102 can flow through shell-side (shell side) or the pipe side (tube side) in the package structure, and the 3rd solution then flows through the opposite side (shell-side or pipe side) of package structure as feedstock solution 104.Adopt the support type liquid film of tubular fibre framework to provide to disperse the stable support of strip liquor 102, guarantee that in view of the above the stable of program carries out.
In one embodiment, feedstock solution 104 is the pipe sides of this tubular fibre formula module of flowing through by fresh feed pump 106, is the shell-sides of tubular fibre formula module of flowing through and disperse strip liquor by pump 108.In another embodiment, the mode of fluid flow is a reflux type in the support type liquid film of above-mentioned tubular fibre framework, just make the dispersion strip liquor 102 of the shell end of flowing through opposite with the flow direction of the feedstock solution 104 of the pipe end of flowing through, feedstock solution 104 is elongated with the duration of contact of disperseing strip liquor 102 by this, and has improved extraction efficiency.
For reaching purpose of the present invention, disperseing strip liquor is the mixture that is defined as water and organic phase.Wherein, water is to comprise a water stripping workshop (aqueous strip solution), and organic phase is to comprise one or more extraction agent (extractant) to be present in the organic solution.Disperseing strip liquor is by mixing this water with this organic phase forms, for example mixing formation with agitator 112 in disperseing back extraction groove 110, as shown in Figure 1.This kind combination makes the water stripping workshop be able to the drop form being present in the successive organic phase.In extraction process, disperse strip liquor to flow through the hollow-fibre membrane module, make and disperse strip liquor to be maintained.Disperse the organic phase of strip liquor very easily to bedew the hydrophobicity hole of porous hollow fiber, and form a stable liquid film.
Fig. 2 is for according to the construction of one embodiment of the invention institute, and the support type liquid film is in conjunction with disperseing back extraction to make enlarged diagram in order to the device that reclaims gallium.When program was carried out, the pressure of the dispersion strip liquor end of support type liquid film was Po.At this moment, the feedstock solution end (flow to feedstock solution by feedstock solution inflow direction 202 and flow out direction 204) at support type liquid film module applies a low pressure Pa (usually about 2psi), and wherein pressure Pa is greater than pressure P o.This pressure reduction can prevent to disperse the hole 208 of the organic solution 212 infiltrate tubular fibres in the strip liquor and arrive the feedstock solution end of liquid film.The size that is scattered in the drop 210 in the water stripping workshop is about 80 microns (micrometer) to 800 microns.This kind size is than big last several progression of hole 208 sizes of microporosity supporting structure, therefore, can not pass the hole 208 and the arrival feedstock solution end of microporosity supporting structure at the drop 210 of the dispersion strip liquor end of supportive liquid film.
Disperse in the back extraction system at the disclosed supportive liquid film of the present invention, organic membrane solution, that is the organic phase of disperseing strip liquor can continue to be supplied in the hole of fid.The supply of this kind persistence can guarantee that stable the continuing of supportive liquid film operates.In addition, by organic phase and the back extraction direct contact of (strip phase) mutually, also provide effective matter to pass and carried out for the back extraction program.Organic phase and back extraction mutually even can be by mixing, for example high shearing increases contact area between the two to mixing (high-shearing mixing).
When gallium be removed finish after, (for example: agitator 112) just stop, dispersion liquid leaves standstill phase-splitting till it is divided into two-phase to disperse the mixing tank of strip liquor.Wherein, institute is divided into two-phase and is respectively organic solution and concentrated stripping workshop (concentrated strip solution), and should concentrate the product that strip liquor is method that the present invention discloses.
The aforementioned metal-powder that contains copper-indium-galliun-selenium can be and comes from the solution that industrial procedure liquid or waste water etc. contain copper-indium-galliun-selenium, is not limited to industrial procedure liquid and waste water (material).In one embodiment, containing the metal-powder of copper-indium-galliun-selenium can be from the residual target of copper-indium-galliun-selenium (Cu/In/Ga/Se spent target).
The present invention is disclosed to be used to reclaim the organic solution inclusion body volume concentrations of dispersion strip liquor of gallium between 10% to 70% dialkyl group phosphoric acid, two (2-ethyl-hexyl) phosphoric acid (di (2-ethyl-hexyl) phosphoric acid, D2EHPA) extraction agent for example.In one embodiment, the organic solution inclusion body volume concentrations of the above-mentioned dispersion strip liquor that is used to reclaim gallium is between 30% to 70% D2EHPA extraction agent.In a particular embodiment, the above-mentioned organic solution inclusion body volume concentrations that is used to reclaim the dispersion strip liquor of gallium is 30%～50% D2EHPA extraction agent.
Compared to traditional supportive liquid film technology, the revealer of institute of the present invention has suitable advantage in application aspect removal recovery gallium in feedstock solution.These advantages comprise preferable membrane stability, lower cost, procedure operation simplification, preferable matter passes the flux (flux) and the preferable gallium rate of recovery.
But the disclosed technology stable supplying of the present invention organic film solution is to the hole of tubular fibre fid, for the usefulness that removes and reclaim gallium in feedstock solution.This kind stable supplying makes the more traditional liquid film of the disclosed supportive liquid film of the present invention stable, and more stable the continuing of program carried out.In addition, the present invention need not use two cluster film film groups so that wheel flow operation and live again (recharging).Therefore, the disclosed technology of the present invention can reduce the cost of hardware and operation simultaneously.Simultaneously, the disclosed operation that removes technology of the present invention is more easy than the conventional art person.
In the disclosed technology of the present invention, organic/extraction phase can directly contact strip aqueous.This biphase mixes makes the matter that is provided except the script tubular fibre pass the surface-area, and more matter passes surface-area and is utilized, and promotes the efficient of target substance from organic opposite collection in view of the above.Stripping efficiency that promotes and then the matter of having promoted when gallium is extracted pass flux.
Though the present invention can show as multi-form embodiment, but accompanying drawing those shown and be embodiments of the invention in exponent hereinafter, and please understand person disclosed herein and be thought of as one example of the present invention, and be not that intention is in order to be limited to the present invention in accompanying drawing and/or the described specific embodiment.
Example
The following employed support type liquid film of example is to operate with adverse current (countercurrent) pattern.The flow through pipe end (tube side) of micropore hole polypropylene (polypropylene) hollow-fibre membrane group of feedstock solution.The gallium that is extracted in module and dispersion slot can be by back extraction to disperseing in the strip liquor.
Embodiment 1
The copper-indium-galliun-selenium dissolving step
At first, will be poured in the hydrochloric acid soln of 10N by the made metal-powder of the residual target of copper-indium-galliun-selenium, the volume ratio that then slowly adds hydrochloric acid and hydrogen peroxide is that 10: 1 mixing solutions dissolves, and the dissolution rate of above-mentioned metal-powder reaches 98.5%.The solution that above-mentioned dissolution rate reaches after undissolved metal-powder is removed after filtration in 98.5% the solution is first solution.
Hydrazine reduction selenium step
Hydrazine solution is provided, comprises 1 to 3 normal hydrazine.After slowly hydrazine solution being added first solution, this moment, solution was transformed into reddish-brown and solution is cloudy state gradually by transparent.Again through after 21 hours the reaction, the hydrochloric acid soln of element state selenium and cupric indium gallium is filtered isolating selenium, and prepare second solution.The isolated selenium of institute is after inductively coupled plasma radiating light spectrometer (ICP-OES) is analyzed, and measured selenium purity reaches more than the 4N, and selenium recovery reaches 99.1% after converting, and measured selenium content is lower than 1ppm in second solution.
The native copper step is gone back in the indium displacement
Indium metal is inserted in second solution, after 8 hours replacement(metathesis)reaction, element state copper and the hydrochloric acid soln that contains the indium gallium are filtered separating copper, and prepare the 3rd solution.The isolated copper of institute is after inductively coupled plasma radiating light spectrometer (ICP-OES) is analyzed, and measured copper purity reaches more than the 2N, and copper recovery is 99.2% after converting, and measured copper content is lower than 0.5ppm in the 3rd solution.
Tubular fibre supportive liquid film tubing string separates indium and gallium step
At first, the volume ratio of organic solution and water stripping workshop is 2: 1 in the preparation dispersion strip liquor.Wherein organic solution is that extraction agent D2EHPA and dispersion agent kerosene mix, the volumetric concentration of D2EHPA is between 30% to 50%, and the concentration of hydrochloric acid of stripping workshop is 1N, utilize concentration that hydrochloric acid adjusts the 3rd solution for 8N with as feedstock solution, operating temperature range is 20 ℃ to 30 ℃.
The pipe side of the hollow-fibre membrane group of flowing through, after being full of the 3rd solution in the tubular fibre film, the oil phase substance that comprises aqueous phase substance promptly is pumped to the shell-side of hollow-fibre membrane group.For preventing that organic phase from passing the hole of tubular fibre and entering in the 3rd solution, pipe end can be subjected to positive pressure, for example: high by about 4 to 5psi than the shell end approximately.During System Operation, the 3rd solution and dispersion soln all are to be pumped to the film group in groove, and are recycled in the groove again.In taking a sample the 3rd solution certainly, a set time, then reacts end when treating gallium ion concentration less than 30ppm with stripping workshop sampling and measuring gallium ion concentration.Disperse the sample that strip liquor took out to be left standstill phase-splitting till the appearance that is separated.Then, analyze to disperse in the strip liquor aqueous sample determining the wherein concentration of gallium with Atomic Absorption Spectroscopy AAS (AAS), and measured gallium purity reaches more than the 4N after follow-up electrolysis, and the back gallium rate of recovery that converts is about 99.1%.
After above-mentioned reaction finishes, the solution of the charging phase of outer tube is discharged and is collected in the displacement slot, displacement is after the measured indium purity of electrolysis reaches more than the 4N, and indium recovery is about 99.2% after converting.
Embodiment 2
The experimental implementation of present embodiment is identical with embodiment 1, and its difference only is in the employed mixing solutions that the volume ratio of hydrochloric acid and hydrogen peroxide is 10: 2 but not 10: 1.
The copper that is reclaimed, indium, gallium and selenium recovery are about 99.4,99.2,99.2 and 99.4% respectively after converting.
Embodiment 3
The experimental implementation of present embodiment is identical with embodiment 1, and its difference only is in the employed mixing solutions that the volume ratio of hydrochloric acid and hydrogen peroxide is 10: 3 but not 10: 1.
The copper that is reclaimed, indium, gallium and selenium recovery are about 99.5,99.3,99.2 and 99.9% respectively after converting.
Embodiment 4
The experimental implementation of present embodiment is identical with embodiment 3, and its difference only is that concentration of hydrochloric acid that tubular fibre supportive liquid film tubing string separates stripping workshop in indium and the gallium step is 2N but not 1N.
The copper that is reclaimed, indium, gallium and selenium recovery are about 99.4,99.3,99.4 and 99.9% respectively after converting.
Embodiment 5
The experimental implementation of present embodiment is identical with embodiment 3, and its difference only is that concentration of hydrochloric acid that tubular fibre supportive liquid film tubing string separates stripping workshop in indium and the gallium step is 3N but not 1N.
The copper that is reclaimed, indium, gallium and selenium recovery are about 99.4,99.3,99.5 and 99.9% respectively after converting.
Embodiment 6
The experimental implementation of present embodiment is identical with embodiment 5, and its difference only is that tubular fibre supportive liquid film tubing string separates and utilizes concentration that hydrochloric acid adjusts the 3rd solution for 9N but not 8N in indium and the gallium step.
The copper that is reclaimed, indium, gallium and selenium recovery are about 99.4,99.3,99.5 and 99.9% respectively after converting.
Embodiment 7
The experimental implementation of present embodiment is identical with embodiment 5, and its difference only is that tubular fibre supportive liquid film tubing string separates and utilizes concentration that hydrochloric acid adjusts the 3rd solution for 10N but not 8N in indium and the gallium step.
The copper that is reclaimed, indium, gallium and selenium recovery are about 99.4,99.2,99.54 and 99.9% respectively after converting.
According to the foregoing description as can be known, the concentration of hydrochloric acid of the volume ratio of hydrochloric acid and hydrogen peroxide, stripping workshop or can increase the rate of recovery of at least a metal of these precious metals with the concentration that hydrochloric acid is adjusted the 3rd solution relatively in the inching mixing solutions.Yet, use aforesaid method to reclaim copper, indium, gallium and selenium, its rate of recovery all can reach the rate of recovery more than 99%, and its rate of recovery almost reaches absolutely.In addition, the disclosed embodiment of the present invention can operate under single product line, and must copper-indium-galliun-selenium can not separated one by one via the conversion of mill solution.Therefore can effectively simplify technology, shortened the process time and effectively reduce the technology cost.
Though the present invention discloses as above with embodiment; right its is not in order to limit the present invention; anyly have the knack of this skill person; without departing from the spirit and scope of the present invention; when can being used for a variety of modifications and variations, so protection scope of the present invention is as the criterion when looking the scope that the accompanying Claim book defined.
Claims (12)
1. the recovery method of a copper-indium-galliun-selenium, it comprises:
A plurality of metal-powders are provided, and described metal-powder comprises copper-indium-galliun-selenium;
Described metal-powder is soaked in the hydrochloric acid soln;
One mixing solutions is provided, and this mixing solutions comprises hydrochloric acid and hydrogen peroxide;
This mixing solutions is added the hydrochloric acid soln that immersion has metal-powder, make described metal-powder be dissolved in this hydrochloric acid soln fully, to form one first solution;
Hydrazine solution is added this first solution, use the selenium of in this first solution, optionally isolating in the described metal-powder, to form one second solution;
One indium metal is inserted in this second solution, and this second solution displaces the copper in those metal-powders certainly, to form one the 3rd solution;
One liquid film is provided, and this liquid film is provided with a micropore hole fid;
Provide one to disperse strip liquor, this dispersion strip liquor comprises a water stripping workshop and is scattered in the organic solution, and this organic solution comprises an extraction agent;
Add a gelled acid to the 3rd solution, make the 3rd solution contain the acid of starting point concentration greater than 8N;
Side at this liquid film is handled the 3rd solution, and makes the opposite side of this liquid film pass through to use this dispersion strip liquor, and the gallium in selective removal the 3rd solution; And
Should partly or all disperse strip liquor to be divided into an organic phase and water stripping workshop, this water stripping workshop comprises a spissated Gallium solution.
2. the recovery method of copper-indium-galliun-selenium as claimed in claim 1, wherein this concentration of hydrochloric acid solution is 8N～10N.
3. the recovery method of copper-indium-galliun-selenium as claimed in claim 1, wherein the volume ratio of the hydrochloric acid of this mixing solutions and hydrogen peroxide is 10: 1～10: 3.
4. the recovery method of copper-indium-galliun-selenium as claimed in claim 1, wherein this hydrazine solution comprises the normal hydrazine of 1-3.
5. the recovery method of copper-indium-galliun-selenium as claimed in claim 1, wherein said indium metal is indium metal powder, indium metal line, indium metal sheet and indium metal plate.
6. the recovery method of copper-indium-galliun-selenium as claimed in claim 1, the volume of organic solution is greater than the volume of water stripping workshop in the wherein said dispersion strip liquor.
7. the recovery method of copper-indium-galliun-selenium as claimed in claim 1, the volume ratio of wherein said organic solution and water stripping workshop is 2: 1.
8. the recovery method of copper-indium-galliun-selenium as claimed in claim 1, wherein this extraction agent is two (2-ethyl-hexyl) phosphoric acid.
9. the recovery method of copper-indium-galliun-selenium as claimed in claim 8, the volumetric concentration of wherein said two (2-ethyl-hexyl) phosphoric acid in organic solution is between 10% to 70%.
10. the recovery method of copper-indium-galliun-selenium as claimed in claim 9, the volumetric concentration of wherein said two (2-ethyl-hexyl) phosphoric acid in this organic solution is between 30%～50%.
11. the recovery method of copper-indium-galliun-selenium as claimed in claim 1, wherein said water stripping workshop comprises hydrochloric acid at least.
12. the recovery method of copper-indium-galliun-selenium as claimed in claim 11, the equivalent concentration of wherein said hydrochloric acid are the scopes between 1N to 3N.
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