CN108754126A - A kind of copper indium gallium selenide recovery method - Google Patents
A kind of copper indium gallium selenide recovery method Download PDFInfo
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Abstract
The present invention discloses a kind of copper indium gallium selenide recovery method, is related to technical field of solar batteries, to reduce the cost recovery of copper indium gallium selenide, and reduces discharge of wastewater.The copper indium gallium selenide recovery method includes that will contain copper indium gallium selenide material and concentrated sulfuric acid mixing, is roasted to the material dispersion system obtained, and selenium dioxide, sulfur dioxide and roasting residue are obtained；Utilize water sulfur dioxide absorption and selenium dioxide so that selenium dioxide is by sulphur dioxide reduction at elemental selenium；Roasting residue is post-processed, elemental copper, simple substance indium and Metallic Gallium are obtained.Copper indium gallium selenide recovery method provided by the invention is in the processing of the material containing copper indium gallium selenide.
Description
Technical field
The present invention relates to technical field of solar batteries more particularly to a kind of copper indium gallium selenide recovery methods.
Background technology
Copper-indium-galliun-selenium film solar cell is that a kind of performance is stable, capability of resistance to radiation is strong, high thin of photoelectric conversion efficiency
Film solar cell, it is much favored by the market, it is the maximum of thin-film solar cells research and development recent years, large-scale production and application
Hot spot product.
Currently, material containing copper indium gallium selenide caused by the manufacturing process of copper-indium-galliun-selenium film solar cell, wherein containing
There are a large amount of selenium, the metals such as copper, indium, gallium to need from the selenium of material recycle containing copper indium gallium selenide, then the metals such as copper, indium, gallium recycle
Using in the making to copper-indium-galliun-selenium film solar cell, in the production cost for reducing copper-indium-galliun-selenium film solar cell
While, improve the utilization rate of raw materials of copper-indium-galliun-selenium film solar cell.
Prior art discloses a kind of recovery methods of material containing copper indium gallium selenide, need to use during recycling selenium
Sodium sulfite restores selenium dioxide so that and the drug variety used in removal process increases, this increases not only cost recovery,
And more waste water is also created, it is unfavorable for environmental protection.
Invention content
The purpose of the present invention is to provide a kind of copper indium gallium selenide recovery methods, to reduce the cost recovery of copper indium gallium selenide, and
Reduce discharge of wastewater.
To achieve the goals above, the present invention provides the following technical solutions：
A kind of copper indium gallium selenide recovery method, the copper indium gallium selenide recovery method include：
Copper indium gallium selenide material and concentrated sulfuric acid mixing will be contained, obtain material dispersion system；
The material dispersion system is roasted, selenium dioxide, sulfur dioxide and roasting residue are obtained；
Utilize water to absorb the sulfur dioxide and the selenium dioxide so that the selenium dioxide by the sulfur dioxide also
Original is at elemental selenium；
The roasting residue is post-processed, elemental copper, simple substance indium and Metallic Gallium are obtained.
Optionally, the material dispersion system is roasted, obtains selenium dioxide, sulfur dioxide and roasting residue
Including：
The material dispersion system is once roasted, a calcining matter is obtained so that the primary roasting includes sulphur
Sour copper, indium sulfate, gallium sulfate and Selenium Sulphate；
After baking is carried out to a calcining matter, obtains selenium dioxide, sulfur dioxide and roasting residue.
Preferably, the temperature of the after baking is more than the temperature once roasted.
Preferably, the calcination temperature once roasted is 200 DEG C -250 DEG C, and the roasting time once roasted is
1h-2h；
The calcination temperature of the after baking is 450 DEG C -650 DEG C, and the roasting time of the after baking is 1h-4h.
Preferably, described that after baking is carried out to a calcining matter, obtain selenium dioxide, sulfur dioxide and roasting
Residue includes：
Calcining matter is mixed with the concentrated sulfuric acid, obtains mixture；
After baking is carried out to the mixture, obtains selenium dioxide, sulfur dioxide and roasting residue.
Specifically, the quality of the material containing copper indium gallium selenide is m1, the concentrated sulfuric acid mixed with the material containing copper indium gallium selenide
Quality be m2, the quality of concentrated sulfuric acid mix with a calcining matter is m3；Wherein, m1: (m2+m3)=1: (2.5~
4)。
Further, (2~5) m2: m3=: 1.
Optionally, described to be post-processed to the roasting residue, obtaining elemental copper, simple substance indium and Metallic Gallium includes：
Using residue is roasted described in water process, sulfate liquor is obtained；
It respectively is isolated by elemental copper, simple substance indium and Metallic Gallium from the sulfate liquor.
Preferably, described using residue is roasted described in water process, obtaining sulfate liquor includes：
According to 1kg: the roasting residue is distributed in water and is stirred so that institute by the solid-to-liquid ratio of (10-20) L
It states the sulfate that roasting residue contains to be dissolved into water, obtains roasting residue dispersion；
Sulfate liquor is isolated from the roasting residue dispersion.
Preferably, isolating elemental copper from the sulfate liquor includes：
The copper ion contained by the sulfate liquor is extracted using copper extractant, obtains cupric extraction phase；
The cupric extraction phase is stripped, cupric anti-stripping agent is obtained；
Using electrodeposition process elemental copper is isolated from the cupric anti-stripping agent.
Further, described to be stripped to the cupric extraction phase, obtaining cupric anti-stripping agent includes：
It is residual after electro-deposition using the aqueous sulfuric acid and/or cupric anti-stripping agent of a concentration of 150g/L-250g/L
Liquid is stripped the cupric extraction phase, obtains cupric anti-stripping agent.
Preferably, simple substance indium is isolated from the sulfate liquor includes：
The indium ion contained by the sulfate liquor is extracted using indium extractant, obtains extraction phase containing indium；
The extraction phase containing indium is stripped, anti-stripping agent containing indium is obtained；
Using metal ion displacement method, from thick indium is displaced in anti-stripping agent containing indium, thick indium is carried out using cell reaction
Refining obtains simple substance indium.
Further, the extraction phase containing indium is stripped, obtaining anti-stripping agent containing indium includes：
The extraction phase containing indium is stripped using the hydrochloric acid of 2mol/L-6mol/L, obtains anti-stripping agent containing indium.
Preferably, isolating Metallic Gallium from the sulfate liquor includes：
The gallium ion contained by the sulfate liquor is extracted using gallium extractant, obtains extraction phase containing gallium；
The extraction phase containing gallium is stripped, anti-stripping agent containing gallium is obtained；
Adjust pH value=11-14 of the anti-stripping agent containing gallium；
Using electrolysis Metallic Gallium is isolated from the anti-stripping agent containing gallium.
Further, the extraction phase containing gallium is stripped, obtaining anti-stripping agent containing gallium includes：
The extraction phase containing gallium is stripped using water, obtains anti-stripping agent containing gallium.
Preferably, isolating Metallic Gallium from the sulfate liquor includes：
It is extracted in the sulfate liquor using gallium extractant, obtains extraction phase containing gallium；
Using extraction phase containing gallium described in naoh treatment, gallium hydroxide precipitation is obtained；
Gallium hydroxide precipitation is added to the water, sodium hydroxide is then added so that gallium hydroxide is converted to gallic acid in water
Sodium obtains sodium solution gallate；
Adjust pH value=11-14 of the sodium solution gallate；
Metallic Gallium is isolated from the sodium solution gallate using electrolysis.
Compared with prior art, in copper indium gallium selenide recovery method provided by the invention, to containing copper indium gallium selenide material and dense sulphur
The material dispersion system that acid mixing obtains is roasted, and selenium dioxide and roasting residue are not only contained in the product obtained,
Also in roasting, the concentrated sulfuric acid reacts generated sulfur dioxide with copper indium gallium selenide, therefore, roasts preceding and material containing copper indium gallium selenide
The mixed concentrated sulfuric acid not only makes copper indium gallium sulphur hydrochlorate in material containing copper indium gallium selenide, but also due to dense in roasting process
Raw material of the sulfur dioxide that sulfuric acid and material reaction containing copper indium gallium selenide are generated also as reduction selenium dioxide so that before roasting and
Indirect material of the concentrated sulfuric acid also as reduction selenium dioxide mixed by material containing copper indium gallium selenide uses.And to material dispersion system
The selenium dioxide and sulfur dioxide obtained after being roasted is soluble easily in water, this make to roasting residue post-processed with
It recycles except copper and indium gallium, additionally it is possible to utilize water sulfur dioxide absorption and selenium dioxide so that sulfur dioxide molecule and selenium dioxide
Molecule comes into full contact in water, unnecessary this makes it possible to avoid selenium dioxide is reduced into elemental selenium using sulfur dioxide
Chemicals use, reduce production cost.Moreover, because selenium dioxide by sulphur dioxide reduction at elemental selenium after, dioxy
Change sulphur to be oxidized to sulfur trioxide and be dissolved in water to form sulfuric acid by selenium dioxide simultaneously, so, in selenium dioxide by titanium dioxide
Sulphur is reduced into elemental selenium, forms the aqueous sulfuric acid containing elemental selenium, and elemental selenium does not dissolve in aqueous sulfuric acid, therefore, only
Elemental selenium and aqueous sulfuric acid can need to be detached by way of filtering；Meanwhile aqueous sulfuric acid is widely used, it can be with
Preserving other, (such as aqueous sulfuric acid concentration is relatively low, can carry out enrichment processing, and it is required dense to generate roasting as other aspects
Sulfuric acid concentration, realize circular treatment), so, in copper indium gallium selenide recovery method provided by the invention, in roasting process the concentrated sulfuric acid with
Sulfur dioxide caused by material reaction containing copper indium gallium selenide can be oxidized and dissolved in water, generate aqueous sulfuric acid, be realized
The recycling and utilization of acidic materials avoids and generates unnecessary waste water.
Description of the drawings
Attached drawing described herein is used to provide further understanding of the present invention, and constitutes the part of the present invention, this hair
Bright illustrative embodiments and their description are not constituted improper limitations of the present invention for explaining the present invention.In the accompanying drawings：
Fig. 1 is the flow chart of copper indium gallium selenide recovery method provided in an embodiment of the present invention；
Fig. 2 is the flow chart roasted to material dispersion system in the embodiment of the present invention；
Fig. 3 is the flow chart post-processed to roasting residue in the embodiment of the present invention；
Fig. 4 is the flow chart for roasting residue in the embodiment of the present invention using water process；
Fig. 5 is respectively to be isolated by elemental copper, the flow of simple substance indium and Metallic Gallium from sulfate liquor in the embodiment of the present invention
Figure；
Fig. 6 is the flow chart for recycling elemental copper in the embodiment of the present invention from sulfate liquor；
Fig. 7 is the flow chart for recycling simple substance indium in the embodiment of the present invention from sulfate liquor；
Fig. 8 is a kind of flow chart recycling Metallic Gallium from sulfate liquor in the embodiment of the present invention；
Fig. 9 is the flow chart that another kind recycles Metallic Gallium from sulfate liquor in the embodiment of the present invention.
Specific implementation mode
Following will be combined with the drawings in the embodiments of the present invention, and technical solution in the embodiment of the present invention carries out clear, complete
Site preparation describes, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.It is based on
Embodiment in the present invention, those of ordinary skill in the art are obtained every other without creative efforts
Embodiment shall fall within the protection scope of the present invention.
Referring to Fig. 1, copper indium gallium selenide recovery method provided in an embodiment of the present invention includes the following steps：
Step S100：Copper indium gallium selenide material and concentrated sulfuric acid mixing will be contained, obtain material dispersion system, the quality of the concentrated sulfuric acid is dense
Degree is selected according to actual conditions, if the mass concentration of the concentrated sulfuric acid is 95%~98%.
Step S200：Material dispersion system is roasted, selenium dioxide, sulfur dioxide and roasting residue are obtained,
Specific reactional equation is as follows：
Step S300：Utilize water sulfur dioxide absorption and selenium dioxide so that selenium dioxide is by sulphur dioxide reduction Cheng Dan
Matter selenium, and sulfur dioxide is oxidized to sulfur trioxide and is reacted with water, forms aqueous sulfuric acid；It can be by way of filtering by selenium
It is separated from aqueous sulfuric acid.
SeO2+2SO2+2H2O→Se↓+2H2SO4Formula five
Step S400：Roasting residue is post-processed, elemental copper, simple substance indium and Metallic Gallium are obtained.
The process of the copper indium gallium selenide recovery method provided by above-described embodiment is it is found that containing copper indium gallium selenide material and the concentrated sulfuric acid
The material dispersion system that mixing obtains is roasted, and selenium dioxide and roasting residue is not only contained in the product obtained, also
There is the concentrated sulfuric acid in roasting to react generated sulfur dioxide with copper indium gallium selenide, and since selenium dioxide and sulfur dioxide are readily soluble
Yu Shui, this to post-process to recycle except copper and indium gallium roasting residue, additionally it is possible to using water sulfur dioxide absorption and
Selenium dioxide so that sulfur dioxide molecule and selenium dioxide molecule come into full contact in water, to utilize sulfur dioxide by titanium dioxide
Selenium is reduced into elemental selenium, this makes it possible to avoid unnecessary chemicals from using, reduces production cost.Moreover, because two
Selenium oxide by sulphur dioxide reduction at elemental selenium after, sulfur dioxide is oxidized to sulfur trioxide by selenium dioxide and is dissolved in water simultaneously
Middle formation sulfuric acid, so, in selenium dioxide by sulphur dioxide reduction at elemental selenium, it is water-soluble to form the sulfuric acid containing elemental selenium
Liquid, and elemental selenium does not dissolve in aqueous sulfuric acid, it therefore, only need to can be by elemental selenium and aqueous sulfuric acid by way of filtering
Separation；Meanwhile aqueous sulfuric acid is widely used, can preserving other, (such as aqueous sulfuric acid concentration compares as other aspects
It is low, enrichment processing can be carried out, generate and roast required concentrated sulfuric acid concentration, realize circular treatment), so, it is provided by the invention
In copper indium gallium selenide recovery method, the concentrated sulfuric acid can be weighed with sulfur dioxide caused by material reaction containing copper indium gallium selenide in roasting process
It is newly dissolved into water, generates aqueous sulfuric acid, realize the recycling and utilization of acidic materials, avoid and generate unnecessary give up
Water.
In addition, in copper indium gallium selenide recovery method provided by the invention, before roasting with it is dense mixed by material containing copper indium gallium selenide
Sulfuric acid is applied not only to so that copper indium gallium sulphur hydrochlorate in material containing copper indium gallium selenide, and due in roasting process the concentrated sulfuric acid with
Therefore raw material of the sulfur dioxide that material reaction containing copper indium gallium selenide is generated also as reduction selenium dioxide roasts preceding and cupric
Indirect material of the concentrated sulfuric acid also as reduction selenium dioxide mixed by indium gallium selenium material uses.
When it is implemented, the selectable type of material containing copper indium gallium selenide is relatively more in the embodiment of the present invention, can be photovoltaic
Copper indium gallium selenide waste material in cell production process can also be that other contain copper indium gallium selenide material, not limit herein.It is general and
Speech, for material containing copper indium gallium selenide other than trace impurity, the mass percent of the selenium contained is 45%~55%, described containing copper and indium
The mass percent of indium contained by gallium selenium material is 15%-20%, the quality percentage of the copper contained by material containing copper indium gallium selenide
Than for 15%-18%, the mass percent of the gallium contained by material containing copper indium gallium selenide is 12~15%.At this point, containing copper indium gallium selenide
The mass percent of selenium is maximum in material, by the way that the concentrated sulfuric acid is added into material containing copper indium gallium selenide and is roasted so that copper and indium
While gallium sulphation, selenium generates gaseous selenium dioxide with strong sulfuric acid response, meanwhile, it is acidified in copper indium gallium sulphur, selenium and dense sulphur
Sulfur dioxide can be generated when acid reaction, after the sulfur dioxide of selenium dioxide and these generations is absorbed with water so that titanium dioxide
Selenium is by sulphur dioxide reduction at elemental selenium, and sulfur dioxide is oxidized to sulfur trioxide and is reacted with water, obtains sulfuric acid；Thus
The most elemental selenium of content in material containing copper indium gallium selenide can be separated, be used to reduce subsequent recovery processing procedure
Amount of chemicals used.Moreover, from the above, it is seen that the concentrated sulfuric acid can not only as recycling selenium reactant, but also
It can be used as the lytic agent of copper and indium gallium；In other words, it in copper indium gallium selenide recovery method provided in an embodiment of the present invention, will return
The process and the process of dissolving copper and indium gallium for receiving selenium are combined into one, and not only reduce the use of unnecessary acid, oxidant, but also
Simplify the removal process of copper indium gallium selenide.
Optionally, as shown in Fig. 2, above-mentioned roast material dispersion system, obtain selenium dioxide, sulfur dioxide and
Roasting residue includes：
Step S210：Material dispersion system is once roasted, a calcining matter is obtained so that primary roasting includes sulphur
Sour copper, indium sulfate, gallium sulfate and Selenium Sulphate, specific reactional equation are as follows：
Step S220：After baking is carried out to a calcining matter, it is remaining to obtain selenium dioxide, sulfur dioxide and roasting
Object, in this process Selenium Sulphate aoxidized by the concentrated sulfuric acid, generate selenium dioxide, sulfur dioxide and water.
Double roasting processing is carried out to material dispersion system by above-mentioned so that material dispersion system is in the mistake once roasted
Cheng Zhong, the material containing copper indium gallium selenide contained by material dispersion system fully react with the concentrated sulfuric acid, make during after baking
The selenium for obtaining sulfation is further aoxidized by the concentrated sulfuric acid, generates selenium dioxide and sulfur dioxide.Therefore, by material dispersion body
System carries out double roasting, improves the rate of recovery from the copper indium gallium selenide of material recycle containing copper indium gallium selenide.
After calcining matter of above-mentioned acquisition, after baking is carried out to calcining matter, obtain selenium dioxide, sulfur dioxide with
And roasting residue further includes：
Calcining matter is mixed with the concentrated sulfuric acid, obtains mixture；After baking is carried out to mixture, obtains titanium dioxide
Selenium, sulfur dioxide and roasting residue.By the way that before after baking, a calcining matter is mixed with the concentrated sulfuric acid to be mixed
Object, to avoid the concentrated sulfuric acid decompose caused by the degree of sulfation of copper indium gallium selenide that contains of material containing copper indium gallium selenide not high ask
Topic.
In order to enable the copper indium gallium selenide sulphation contained by material containing copper indium gallium selenide, copper indium gallium selenide is contained in the embodiment of the present invention
The quality of material is m1, and the quality of the concentrated sulfuric acid mixed with material containing copper indium gallium selenide is m2, the dense sulphur mixed with a calcining matter
The quality of acid is m3；Wherein, m1: (m2+m3)=1: (2.5~4), under this ratio, material containing copper indium gallium selenide can with it is dense
Sulfuric acid contained by sulfuric acid fully reacts.
It as the mass ratio of sulfuric acid used in primary roasting and after baking, can be determined, but considered according to actual conditions
Relatively more to the sulfuric acid amount needed for primary roasting, the sulfuric acid amount needed for after baking is fewer, therefore, (2~5) m2: m3=: 1.
It is understood that when the temperature of above-mentioned after baking is more than the temperature once roasted, Selenium Sulphate quilt just can guarantee
Sulfuric acid oxidation generates selenium dioxide and sulfur dioxide.
In view of the concentrated sulfuric acid starts to decompose to give off part sulfur trioxide at 290 DEG C, this makes the concentrated sulfuric acid in roasting process
In be easy because decompose and generate certain loss.For this purpose, the calcination temperature once roasted is 200 DEG C -250 DEG C, it is primary to roast
Roasting time be 1h-2h, with ensure material containing copper indium gallium selenide contained by the abundant sulfation of copper indium gallium selenide, avoid the concentrated sulfuric acid
It causes sulfuric acid molecule to decompose the problem of caused concentrated sulfuric acid deficiency because calcination temperature is excessively high, and ensures copper indium gallium selenide sulfuric acid
Change complete；The temperature of after baking is 450 DEG C -650 DEG C, and the roasting time of after baking is 1h-4h, to ensure that Selenium Sulphate aoxidizes
Completely.
Optionally, as shown in figure 3, above-mentioned post-process roasting residue, elemental copper, simple substance indium and Metallic Gallium are obtained
Including：
Step S410：Residue is roasted using water process, obtains sulfate liquor, at this time copper sulphate, indium sulfate and sulfuric acid
Gallium is dissolved into water, obtains sulfate liquor.
Illustratively, as shown in figure 4, above-mentioned using residue is roasted described in water process, obtaining sulfate liquor includes：
Step S411：According to 1kg: roasting residue is distributed in water and is stirred, made by the solid-to-liquid ratio of (10-20) L
The sulfate that residue contains must be roasted to be dissolved into water, obtain roasting residue dispersion；Certainly roasting residue and water
Solid-to-liquid ratio can also be set according to actual conditions；
Step S412：Sulfate liquor is isolated from roasting residue dispersion, separation method can be filter type,
Filtering gained filtrate is sulfate liquor.
Step S420：It respectively is isolated by elemental copper, simple substance indium and Metallic Gallium from sulfate liquor.
In view of the copper indium gallium selenide that the prior art is recycled from material containing copper indium gallium selenide is largely hydrolysis copper ashes, sponge
The primary product such as copper, sponge indium, thick gallium, it is low to sell such primary product valuation coefficient, the added value compared with high pure metal product
It is low.Based on this, when sulfate liquor contains copper sulphate, indium sulfate and gallium sulfate；As shown in figure 5, dividing respectively from sulfate liquor
Separating out elemental copper, simple substance indium and Metallic Gallium includes：
Step S421：Elemental copper is isolated from the sulfate liquor using extraction, stripping process and electrodeposition process.Tool
For body, as shown in fig. 6, isolating elemental copper from sulfate liquor using extraction, stripping process and electrodeposition process and including：
Step S4211：Using the copper ion contained by copper extractant extraction sulfate liquor, cupric extraction phase is obtained；Extraction
What is taken is comparably 1: (1-5), extraction series be 3 grades -6 grades, copper extractant be M5640 copper extractants, Lix684 copper extractants,
It is one or more in N902 copper extractants.
Step S4212：Cupric extraction phase is stripped, cupric anti-stripping agent is obtained；Back extraction is comparably 1: (1-
5), the series of back extraction is 1 grade -2 grades, and extractant used in back extraction is that the sulfuric acid of a concentration of 150g/L-250g/L is water-soluble
The raffinate of liquid and/or cupric anti-stripping agent after electro-deposition；
Step S4213：Elemental copper is isolated from cupric anti-stripping agent using electrodeposition process, cupric anti-stripping agent is by electrolysis
Afterwards, it is used as cupric anti-stripping agent, to realize the purpose recycled.Electro-deposition voltage is 2V-3V, current density in electrodeposition process
For 200A/m2-300A/m2, electrodeposition time 12h-72h, electrodeposit reaction equation is as follows：
2CuSO4+4H2O→2Cu↓+2H2O+O2↑+2H2SO4Formula seven
Cathode reaction 2Cu2++ 4e=2Cu formulas eight
Anode reaction 2OH-+ 4e=2H2O+O2Formula nine
Step S422：Simple substance indium is isolated from the sulfate liquor using extraction, stripping process and electrolysis；Specifically
For, as shown in fig. 7, isolating simple substance indium from the sulfate liquor using extraction, stripping process and electrolysis and including：
Step S4221：Using the indium ion contained by indium extractant extraction sulfate liquor, extraction phase containing indium is obtained；Extraction
What is taken is comparably 1: (1-5), extraction series are 1 grade -6 grades, and indium extractant is P507D indiums extractant and/or butyl phosphoric acid
(HDBP)-butanol；
Step S4222：It is stripped to containing indium extraction phase, obtains anti-stripping agent containing indium；Back extraction is comparably 1: (1-
5), the series of back extraction is 1 grade -3 grades, and back extraction uses the hydrochloric acid of 2mol/L-6mol/L；
Step S4223：Using metal ion displacement method, from thick indium is displaced in anti-stripping agent containing indium, using cell reaction
Thick indium is refined, simple substance indium is obtained；Bath voltage 0.2V-0.5V, current density 50A/m2-300A/m2.Metal from
Displacement metal species used in sub- displacement method are relatively more, as long as its chemical activity is higher than indium, such as Zn or Al.Displacement
The thick indium gone out is needed by founding, then using thick indium as the anode of cell reaction, is refined to thick indium, purifying reaction equation
It is as follows：
In2(SO4)3+3Zn→2In↓+3ZnSO4Formula ten
Cathode reaction：In3+=In-3e formulas 11
Anode reaction：In=In3++ 3e formulas 12
Step S423：Metallic Gallium is isolated from the sulfate liquor using extraction, stripping process and electrolysis；Specifically
For, as shown in figure 8, isolating Metallic Gallium from sulfate liquor using extraction, stripping process and electrolysis and including：
Step S4231：Using the gallium ion contained by gallium extractant extraction sulfate liquor, extraction phase containing gallium is obtained；Extraction
What is taken is comparably 1: (1-5), extraction series are 1 grade -6 grades, and gallium extractant is gallium germanium extractant G315 and/or G8315 extractant；
Step S4232：It is stripped to containing gallium extraction phase, obtains anti-stripping agent containing gallium；Back extraction uses water, back extraction
Be comparably 1: (1-5), 1 grade -3 grades of the series of back extraction；
Step S4234：Using electrolysis Metallic Gallium is isolated from anti-stripping agent containing gallium；Bath voltage is 3V-5V, electric current
Density is 50A/m2-300A/m2。
It is above-mentioned to isolate Metallic Gallium from anti-stripping agent containing gallium using electrolysis to make anti-stripping agent containing gallium preferably be electrolysed
Before, after obtaining anti-stripping agent containing gallium, Metallic Gallium packet is isolated from sulfate liquor using extraction, stripping process and electrolysis
It includes：
Step S4233：PH value=11-14 of the anti-stripping agent containing gallium is adjusted, anti-stripping agent containing gallium is that gallic acid sodium is water-soluble at this time
Liquid.Above-mentioned electrolysis equation is as follows at this time：
4NaGaO2+2H2O→4Ga+3O2↑+4NaOH formulas 13
Anode reaction 2OH-+ 4e=2H2O+O2Formula 14
Cathode reaction Ga3+=Ga-3e formulas 15
Step S424：Divided from the sulfate liquor using extraction, chemical precipitation method, the anti-precipitation method of chemistry and electrolysis
Separate out Metallic Gallium.Specifically, as shown in figure 9, using extraction, chemical precipitation method, the anti-precipitation method of chemistry and electrolysis from sulphur
Acid salt solution isolates Metallic Gallium：
Step S4241：It is extracted in sulfate liquor using gallium extractant, obtains extraction phase containing gallium；Extraction is comparably 1:
(1-5), extraction series are 1 grade -6 grades, and gallium extractant is gallium germanium extractant G315 and/or G8315 extractant；
Step S4242：Using naoh treatment extraction phase containing gallium, gallium hydroxide precipitation is obtained；
Step S4243：Gallium hydroxide precipitation is added to the water, sodium hydroxide is then added so that sodium hydroxide is in water
It is converted to gallic acid sodium, obtains sodium solution gallate；Sodium hydroxide is reacted with gallium hydroxide as a solution, in sodium hydroxide solution
Gallium hydroxide containing 0.5kg-1kg, the water of 5L-10L, naturally it is also possible to sodium hydroxide solution be added according to actual conditions, only
Ensure that gallium hydroxide precipitation can be present in the form of gallic acid sodium in water.
Step S4245：Metallic Gallium is isolated from sodium solution gallate using electrolysis, bath voltage 3V-5V, electric current is close
Degree is 50A/m2-300A/m2。
In order to enable the electrolytic process of sodium solution gallate preferably carries out, it is described after acquisition sodium solution gallate described above
It is described anti-heavy using extraction, chemical precipitation method, chemistry using electrolysis before isolating Metallic Gallium in the sodium solution gallate
Shallow lake method and electrochemical process isolate Metallic Gallium from the sulfate liquor and further include：
Step S4244：PH value=the 11-14 for obtaining sodium solution gallate is adjusted, above-mentioned cell reaction at this time refers to formula 13
To formula 15.
As seen from the above, copper indium gallium selenide recovery method provided in an embodiment of the present invention is provided respectively from the sulfate
Elemental copper, the detailed process of simple substance indium and Metallic Gallium are isolated in solution, can be seen that from the separating technology of each elemental metals
Finally using electrochemical method sub-argument elemental metals, and the elemental metals compact structure that electrochemical method is recycled, it is not necessarily to
Using more oxidisability medicament and longer acidic leaching process is taken, the elemental metals generated are produced with high added value
Product.
It should be noted that in above-mentioned steps S421~step S424, step S421, step S422, step S423 be one by one
It carries out, is not limited then as sequencing, can be executed with the sequence of step S421, step S422, step S423, also may be used
Being executed with the sequence of step S422, step S421, step S423, specifically determined by actual conditions.And step S423 and step
Rapid S424 can be carried out at the same time, and can also carry out or select successively a progress；Flow it can be seen from the figure that step illustrated in fig. 5
S421, step S422, step S423 are sequentially executed, and either rapid S421, step S422, step S424 are sequentially carried out or rapid
S421, step S422, step S423, step S424 are sequentially carried out, or rapid S421, step S422, step S424, step S423
Sequentially carry out.
The specific implementation of copper indium gallium selenide recovery method provided in an embodiment of the present invention is provided below in conjunction with the accompanying drawings, below
Realization method is merely to illustrate effect possessed by the present invention, but does not constitute and limit to the scope of the present invention.
The first realization method, the copper indium gallium selenide recovery method that this realization method provides include：
The first step：Copper indium gallium selenide material and concentrated sulfuric acid mixing will be contained, obtain material dispersion system, so that containing copper indium gallium selenide
Material is slurried；Wherein, by percentage to the quality, this contain the selenium contained by copper indium gallium selenide material mass percent be 45%,
The mass percent of indium contained by material containing copper indium gallium selenide is 20%, the quality percentage of the copper contained by material containing copper indium gallium selenide
Than being 15%, the mass percent of the gallium contained by material containing copper indium gallium selenide is 15%, other are impurity.
Second step：Material dispersion system is once roasted, a calcining matter is obtained so that primary roasting includes sulfuric acid
Copper, indium sulfate, gallium sulfate and Selenium Sulphate；The calcination temperature once roasted is 200 DEG C, and the roasting time once roasted is 2h.
Third walks：Calcining matter is mixed with the concentrated sulfuric acid, obtains mixture, after baking then is carried out to mixture,
Obtain selenium dioxide, sulfur dioxide and roasting residue.Wherein, the calcination temperature of after baking is 450 DEG C, after baking
Roasting time is 4h；The quality of the material containing copper indium gallium selenide is m1, and the quality of the concentrated sulfuric acid mixed with material containing copper indium gallium selenide is m2,
The quality of the concentrated sulfuric acid mixed with a calcining matter is m3, and the unit of m1, m2, m3 are kg, wherein m1: (m2+m3)=1: 4, m2
: m3=1: 2；
4th step：According to 1kg: 10L solid-to-liquid ratio, roasting residue is distributed in water and is stirred so that roasting
The sulfate that residue contains is dissolved into water, obtains roasting residue dispersion；Roasting residue dispersion is carried out
Filtering, to isolate sulfate liquor from roasting residue dispersion, which contains copper sulphate, indium sulfate and sulfuric acid
Gallium.
5th step：Using M5640 copper extractants extraction sulfate liquor contained by copper ion, obtain cupric extraction phase and
The sulfate liquor of processing for the first time；Cupric extraction phase is stripped using the aqueous sulfuric acid of 150g/L, obtains cupric
Anti-stripping agent；Cupric anti-stripping agent is substantially the aqueous sulfuric acid of copper ions at this time.To the aqueous sulfuric acids of copper ions into
Row electro-deposition obtains the elemental copper that purity is 99.95%；
Wherein, extraction when extraction is comparably 1: 1, and extraction series is 3 grades；Back extraction when back extraction is comparably 1: 2, instead
It is 2 grades to extract series.Anode electrode used in electro-deposition is metal, and cathode electrode is stainless steel, and electro-deposition voltage is 2V, electricity
Current density is 300A/m2, electrodeposition time 36h；
6th step：The indium ion contained by the sulfate liquor of processing for the first time is extracted using P507D indium extractants, is obtained
Extraction phase containing indium and second of processing sulfate liquor；The extraction phase containing indium is stripped, anti-stripping agent containing indium is obtained；
It is stripped using the hydrochloric acid of 2mol/L to containing indium extraction phase, obtains anti-stripping agent containing indium, that is, contain indium salts acid；It will using zinc powder
Indium in acid containing indium salts cements out, and obtains thick indium, by thick indium founding at thick indium, is refined, is obtained to thick indium using electrolysis
Obtain the simple substance indium that purity is 99.995%.
Wherein, when extraction, extraction is comparably 1: 2, and extraction series is 3 grades；When back extraction, back extraction is comparably 1: 1,
The series of back extraction is 2 grades；When electrolysis, anode is the thick indium of founding, and cathode is high purity indium plate, bath voltage 0.5V, electricity
Current density is 300A/m2。
7th step：Using the gallium ion contained by gallium germanium extractant G315 extraction second processing sulfate liquors, contained
Gallium extraction phase and waste liquid；It is stripped using water to containing gallium extraction phase, obtains anti-stripping agent containing gallium, the i.e. aqueous solution of gallium；
The NaOH aqueous solutions of 1mol/L are added to the aqueous solution of gallium so that pH value=13 of the aqueous solution of gallium, at this time the aqueous solution change of gallium
For gallic acid sodium water solution；Gallic acid sodium water solution is electrolysed using electrolysis, obtains the Metallic Gallium that purity is 99.995%.
Wherein, when extraction, extraction is comparably 1: 1, and extraction series is 2 grades；When back extraction, back extraction is comparably 1: 2,
The series of back extraction is 1 grade；When isolating Metallic Gallium from anti-stripping agent containing gallium using electrodeposition process, bath voltage 3V, electricity
Current density is 100A/m2。
Second of realization method, the copper indium gallium selenide recovery method that this realization method provides include：
The first step：Copper indium gallium selenide material and concentrated sulfuric acid mixing will be contained, obtain material dispersion system, so that containing copper indium gallium selenide
Material is slurried；Wherein, by percentage to the quality, this contain the selenium contained by copper indium gallium selenide material mass percent be 55%,
The mass percent of indium contained by material containing copper indium gallium selenide is 15%, the quality percentage of the copper contained by material containing copper indium gallium selenide
Than being 16%, the mass percent of the gallium contained by material containing copper indium gallium selenide is 12%, other are impurity.
Second step：Material dispersion system is once roasted, a calcining matter is obtained so that primary roasting includes sulfuric acid
Copper, indium sulfate, gallium sulfate and Selenium Sulphate；The calcination temperature once roasted is 220 DEG C, and the roasting time once roasted is 1.5h.
Third walks：Calcining matter is mixed with the concentrated sulfuric acid, obtains mixture, after baking then is carried out to mixture,
Obtain selenium dioxide, sulfur dioxide and roasting residue.Wherein, the calcination temperature of after baking is 650 DEG C, after baking
Roasting time is 1h；The quality of the material containing copper indium gallium selenide is m1, and the quality of the concentrated sulfuric acid mixed with material containing copper indium gallium selenide is m2,
The quality of the concentrated sulfuric acid mixed with a calcining matter is m3, and the unit of m1, m2, m3 are kg, wherein m1: (m2+m3)=1: 2.5,
M2: m3=4: 1.
4th step：According to 1kg: 20L solid-to-liquid ratio, roasting residue is distributed in water and is stirred so that roasting
The sulfate that residue contains is dissolved into water, obtains roasting residue dispersion；Roasting residue dispersion is carried out
Filtering, to isolate sulfate liquor from roasting residue dispersion, which contains copper sulphate, indium sulfate and sulfuric acid
Gallium.
5th step：Using the copper ion contained by Lix684 copper extractants extraction sulfate liquor, cupric extraction phase is obtained
With the sulfate liquor of first time processing；Cupric extraction phase is stripped using the aqueous sulfuric acid of 200g/L, is contained
Copper anti-stripping agent；Cupric anti-stripping agent is substantially the aqueous sulfuric acid of copper ions at this time.To the aqueous sulfuric acid of copper ions
Electro-deposition is carried out, the elemental copper that purity is 99.95% is obtained；
Wherein, extraction when extraction is comparably 1: 2, and extraction series is 6 grades；Back extraction when back extraction is comparably 1: 4, instead
It is 1 grade to extract series.Anode electrode used in electro-deposition is metal, and cathode electrode is stainless steel, and electro-deposition voltage is 3V, electricity
Current density is 200A/m2, electrodeposition time 45h；
6th step：Using the indium contained by butyl phosphoric acid (HDBP)-the butanol, before immunoassay for the first time sulfate liquor of processing from
Son obtains extraction phase containing indium and second of processing sulfate liquor；It is stripped to containing indium extraction phase, obtains and be stripped containing indium
Liquid；It is stripped using the hydrochloric acid of 6mol/L to containing indium extraction phase, obtains anti-stripping agent containing indium, that is, contain indium salts acid；Utilize aluminium
Powder cements out the indium in acid containing indium salts, obtains thick indium, and by thick indium founding at thick indium, essence is carried out to thick indium using electrolysis
Refining obtains the simple substance indium that purity is 99.995%.
Wherein, when extraction, extraction is comparably 1: 1, and extraction series is 6 grades；When back extraction, back extraction is comparably 1: 5,
The series of back extraction is 1 grade；When electrolysis, anode is the thick indium of founding, and cathode is high purity indium plate, bath voltage 0.2V, electricity
Current density is 200A/m2。
7th step：Using the gallium ion contained by gallium germanium extractant G315 extraction second processing sulfate liquors, contained
Gallium extraction phase and waste liquid；It is stripped using water to containing gallium extraction phase, obtains anti-stripping agent containing gallium, the i.e. aqueous solution of gallium；
The NaOH aqueous solutions of 2mol/L are added to the aqueous solution of gallium so that pH value=11 of the aqueous solution of gallium, at this time the aqueous solution change of gallium
For gallic acid sodium water solution；Gallic acid sodium water solution is electrolysed using electrolysis, obtains the Metallic Gallium that purity is 99.995%.
Wherein, when extraction, extraction is comparably 1: 5, and extraction series is 1 grade；When back extraction, back extraction is comparably 1: 1,
The series of back extraction is 3 grades；When isolating Metallic Gallium from anti-stripping agent containing gallium using electrodeposition process, bath voltage 5V, electricity
Current density is 300A/m2。
The third realization method, the copper indium gallium selenide recovery method that this realization method provides include：
The first step：Copper indium gallium selenide material and concentrated sulfuric acid mixing will be contained, obtain material dispersion system, so that containing copper indium gallium selenide
Material is slurried；Wherein, by percentage to the quality, this contain the selenium contained by copper indium gallium selenide material mass percent be 50%,
The mass percent of indium contained by material containing copper indium gallium selenide is 16%, the quality percentage of the copper contained by material containing copper indium gallium selenide
Than being 18%, the mass percent of the gallium contained by the material containing copper indium gallium selenide is 13%, other are impurity.
Second step：Material dispersion system is once roasted, a calcining matter is obtained so that primary roasting includes sulfuric acid
Copper, indium sulfate, gallium sulfate and Selenium Sulphate；The calcination temperature once roasted is 250 DEG C, and the roasting time once roasted is 1h.
Third walks：Calcining matter is mixed with the concentrated sulfuric acid, obtains mixture, after baking then is carried out to mixture,
Obtain selenium dioxide, sulfur dioxide and roasting residue.Wherein, the calcination temperature of after baking is 500 DEG C, after baking
Roasting time is 3h；The quality of the material containing copper indium gallium selenide is m1, and the quality of the concentrated sulfuric acid mixed with material containing copper indium gallium selenide is m2,
The quality of the concentrated sulfuric acid mixed with a calcining matter is m3, and the unit of m1, m2, m3 are kg, wherein m1: (m2+m3)=1: 3, m2
: m3=2: 1.
4th step：According to 1kg: 15L solid-to-liquid ratio, roasting residue is distributed in water and is stirred so that roasting
The sulfate that residue contains is dissolved into water, obtains roasting residue dispersion；Roasting residue dispersion is carried out
Filtering, to isolate sulfate liquor from roasting residue dispersion, which contains copper sulphate, indium sulfate and sulfuric acid
Gallium.
5th step：The mixed liquor of the N902 copper extractants and M5640 copper extractants that are 1: 1 using mass ratio extracts sulfate
Copper ion contained by solution obtains cupric extraction phase and for the first time sulfate liquor of processing；Utilize the sulfuric acid water of 250g/L
Solution is stripped cupric extraction phase, obtains cupric anti-stripping agent；Cupric anti-stripping agent is substantially copper ions at this time
Aqueous sulfuric acid.Electro-deposition is carried out to the aqueous sulfuric acid of copper ions, obtains the elemental copper that purity is 99.95%；
Wherein, extraction when extraction is comparably 1: 1.5, and extraction series is 5 grades；Back extraction when back extraction is comparably 1: 5,
It is 1 grade to be stripped series.Anode electrode used in electro-deposition is metal, and cathode electrode is stainless steel, and electro-deposition voltage is
2.5V, current density 250A/m2, electrodeposition time 12h；
6th step：The P507D indiums extractant and butyl phosphoric acid (HDBP)-butanol mixed solution for being 3: 2 using mass ratio extract
The indium ion contained by the sulfate liquor handled for the first time is taken, extraction phase containing indium and second of processing sulfate liquor are obtained；
It is stripped to containing indium extraction phase, obtains anti-stripping agent containing indium；It is stripped using the hydrochloric acid of 4mol/L to containing indium extraction phase
It takes, obtains anti-stripping agent containing indium, that is, contain indium salts acid；The indium in acid containing indium salts is cemented out using zinc powder, obtains thick indium, it will be thick
Indium founding refines thick indium at thick indium, using electrolysis, obtains the simple substance indium that purity is 99.995%.
Wherein, when extraction, extraction is comparably 1: 5, and extraction series is 1 grade；When back extraction, back extraction is comparably 1: 3,
The series of back extraction is 3 grades；When electrolysis, anode is the thick indium of founding, and cathode is high purity indium plate, bath voltage 0.3V, electricity
Current density is 50A/m2。
7th step：Using mass ratio be 2: 1 gallium germanium extractant G315 and gallium germanium extractant G315 mixed solutions extraction the
Gallium ion contained by two processing sulfate liquors, obtains extraction phase containing gallium and waste liquid；It is carried out using water to containing gallium extraction phase
Back extraction obtains anti-stripping agent containing gallium, the i.e. aqueous solution of gallium；PH value=5 of the extraction phase containing gallium are adjusted using sodium hydroxide, are obtained
Gallium hydroxide precipitates；It is precipitated to gallium hydroxide and NaOH aqueous solutions (a concentration of 0.1kg/L) is added so that the pH value of the aqueous solution of gallium
=13, even gallic acid sodium water solution；Gallic acid sodium water solution is electrolysed using electrolysis, obtains the Metallic Gallium that purity is 99.995%.
Wherein, when extraction, extraction is comparably 1: 3, and extraction series is 6 grades；When back extraction, back extraction is comparably 1: 5,
The series of back extraction is 2 grades；When isolating Metallic Gallium from anti-stripping agent containing gallium using electrodeposition process, bath voltage 4V, electricity
Current density is 200A/m2。
4th kind of realization method, the copper indium gallium selenide recovery method that this realization method provides include：
The first step：Copper indium gallium selenide material and concentrated sulfuric acid mixing will be contained, obtain material dispersion system, so that containing copper indium gallium selenide
Material is slurried；Wherein, by percentage to the quality, this contain the selenium contained by copper indium gallium selenide material mass percent be 55%,
The mass percent of indium contained by material containing copper indium gallium selenide is 17%, the quality percentage of the copper contained by material containing copper indium gallium selenide
Than being 15%, the mass percent of the gallium contained by material containing copper indium gallium selenide is 12%, other are impurity.
Second step：Material dispersion system is once roasted, a calcining matter is obtained so that primary roasting includes sulfuric acid
Copper, indium sulfate, gallium sulfate and Selenium Sulphate；The calcination temperature once roasted is 200 DEG C, and the roasting time once roasted is 1.5h.
Third walks：Calcining matter is mixed with the concentrated sulfuric acid, obtains mixture, after baking then is carried out to mixture,
Obtain selenium dioxide, sulfur dioxide and roasting residue.Wherein, the calcination temperature of after baking is 600 DEG C, after baking
Roasting time is 2h；The quality of the material containing copper indium gallium selenide is m1, and the quality of the concentrated sulfuric acid mixed with material containing copper indium gallium selenide is m2,
The quality of the concentrated sulfuric acid mixed with a calcining matter is m3, and the unit of m1, m2, m3 are kg, wherein m1: (m2+m3)=1: 3.5,
M2: m3=5: 1.
4th step：According to 1kg: 12L solid-to-liquid ratio, roasting residue is distributed in water and is stirred so that roasting
The sulfate that residue contains is dissolved into water, obtains roasting residue dispersion；Roasting residue dispersion is carried out
Filtering, to isolate sulfate liquor from roasting residue dispersion, which contains copper sulphate, indium sulfate and sulfuric acid
Gallium.
5th step：Using N902 copper extractants extraction sulfate liquor contained by copper ion, obtain cupric extraction phase and
The sulfate liquor of processing for the first time；Cupric extraction phase is stripped using the aqueous sulfuric acid of 220g/L, obtains cupric
Anti-stripping agent；Cupric anti-stripping agent is substantially the aqueous sulfuric acid of copper ions at this time.To the aqueous sulfuric acids of copper ions into
Row electro-deposition obtains the elemental copper that purity is 99.95%；
Wherein, extraction phase when extraction extracts 4 grades of series than 1: 1；Back extraction when back extraction is comparably 1: 3, is stripped grade
2 grades of number.Anode electrode used in electro-deposition is metal, and cathode electrode is stainless steel, and electro-deposition voltage is 2.5V, and electric current is close
Degree is 270A/m2, electrodeposition time 72h；
6th step：Using the indium contained by butyl phosphoric acid (HDBP)-the butanol, before immunoassay for the first time sulfate liquor of processing from
Son obtains extraction phase containing indium and second of processing sulfate liquor；It is stripped to containing indium extraction phase, obtains and be stripped containing indium
Liquid；It is stripped using the hydrochloric acid of 3mol/L to containing indium extraction phase, obtains anti-stripping agent containing indium, that is, contain indium salts acid；Utilize aluminium
Powder cements out the indium in acid containing indium salts, obtains thick indium, and by thick indium founding at thick indium, essence is carried out to thick indium using electrolysis
Refining obtains the simple substance indium that purity is 99.995%.
Wherein, when extraction, extraction is comparably 1: 4, and extraction series is 2 grades；When back extraction, back extraction is comparably 1: 2,
The series of back extraction is 2 grades；When electrolysis, anode is the thick indium of founding, and cathode is high purity indium plate, bath voltage 0.4V, electricity
Current density is 150A/m2。
7th step：Using the gallium ion contained by gallium germanium extractant G315 extraction second processing sulfate liquors, contained
Gallium extraction phase and waste liquid；It is stripped using water to containing gallium extraction phase, obtains anti-stripping agent containing gallium, the i.e. aqueous solution of gallium；
The NaOH aqueous solutions of 1.5mol/L are added to the aqueous solution of gallium so that pH value=14 of the aqueous solution of gallium, the at this time aqueous solution of gallium
Become gallic acid sodium water solution；Gallic acid sodium water solution is electrolysed using electrolysis, obtains the Metallic Gallium that purity is 99.995%.
Wherein, when extraction, extraction is comparably 1: 2, and extraction series is 3 grades；When back extraction, back extraction is comparably 1: 4,
The series of back extraction is 2 grades；When isolating Metallic Gallium from the anti-stripping agent containing gallium using electrodeposition process, bath voltage is
3.5V, current density 50A/m2。
5th kind of realization method, the copper indium gallium selenide recovery method that this realization method provides include：
The first step：Copper indium gallium selenide material and concentrated sulfuric acid mixing will be contained, obtain material dispersion system, so that containing copper indium gallium selenide
Material is slurried；Wherein, by percentage to the quality, this contain the selenium contained by copper indium gallium selenide material mass percent be 50%,
The mass percent of indium contained by material containing copper indium gallium selenide is 20%, the quality percentage of the copper contained by material containing copper indium gallium selenide
Than being 15%, the mass percent of the gallium contained by material containing copper indium gallium selenide is 14%, other are impurity, material containing copper indium gallium selenide
Quality be m1, the quality of concentrated sulfuric acid mix with material containing copper indium gallium selenide is m2, and the unit of m1, m2 is kg, m1: m2=1:
3.5。
Second step：Material dispersion system is once roasted, a calcining matter is obtained so that primary roasting includes sulfuric acid
Copper, indium sulfate, gallium sulfate and Selenium Sulphate；The calcination temperature once roasted is 220 DEG C, and the roasting time once roasted is 1.8h.
Third walks：According to 1kg: 15L solid-to-liquid ratio, roasting residue is distributed in water and is stirred so that roasting
The sulfate that residue contains is dissolved into water, obtains roasting residue dispersion；Roasting residue dispersion is carried out
Filtering, to isolate sulfate liquor from roasting residue dispersion, which contains copper sulphate, indium sulfate and sulfuric acid
Gallium.
4th step：Using N902 copper extractants extraction sulfate liquor contained by copper ion, obtain cupric extraction phase and
The sulfate liquor of processing for the first time；Cupric extraction phase is stripped using the aqueous sulfuric acid of 200g/L, obtains cupric
Anti-stripping agent；Cupric anti-stripping agent is substantially the aqueous sulfuric acid of copper ions at this time.To the aqueous sulfuric acids of copper ions into
Row electro-deposition obtains the elemental copper that purity is 99.95%；
Wherein, extraction phase when extraction extracts 3 grades of series than 1: 1；Back extraction when back extraction is comparably 1: 5, is stripped grade
2 grades of number.Anode electrode used in electro-deposition is metal, and cathode electrode is stainless steel, and electro-deposition voltage is 2.5V, and electric current is close
Degree is 250A/m2, electrodeposition time 72h；
5th step：Using the indium contained by butyl phosphoric acid (HDBP)-the butanol, before immunoassay for the first time sulfate liquor of processing from
Son obtains extraction phase containing indium and second of processing sulfate liquor；It is stripped to containing indium extraction phase, obtains and be stripped containing indium
Liquid；It is stripped using the hydrochloric acid of 6mol/L to containing indium extraction phase, obtains anti-stripping agent containing indium, that is, contain indium salts acid；Utilize aluminium
Powder cements out the indium in acid containing indium salts, obtains thick indium, and by thick indium founding at thick indium, essence is carried out to thick indium using electrolysis
Refining obtains the simple substance indium that purity is 99.995%.
Wherein, when extraction, extraction is comparably 1: 3, and extraction series is 1 grade；When back extraction, back extraction is comparably 1: 2,
The series of back extraction is 3 grades；When electrolysis, anode is the thick indium of founding, and cathode is high purity indium plate, bath voltage 0.5V, electricity
Current density is 120A/m2。
6th step：Using the gallium ion contained by gallium germanium extractant G315 extraction second processing sulfate liquors, contained
Gallium extraction phase and waste liquid；It is stripped using water to containing gallium extraction phase, obtains anti-stripping agent containing gallium, the i.e. aqueous solution of gallium；
The NaOH aqueous solutions of 1.5mol/L are added to the aqueous solution of gallium so that pH value=13 of the aqueous solution of gallium, the at this time aqueous solution of gallium
Become gallic acid sodium water solution；Gallic acid sodium water solution is electrolysed using electrolysis, obtains the Metallic Gallium that purity is 99.995%.
Wherein, when extraction, extraction is comparably 1: 2, and extraction series is 3 grades；When back extraction, back extraction is comparably 1: 4,
The series of back extraction is 2 grades；When isolating Metallic Gallium from the anti-stripping agent containing gallium using electrodeposition process, bath voltage is
4.5V, current density 240A/m2。
By Atomic Absorption Spectrometry, elemental selenium, list are recycled from material containing copper indium gallium selenide in embodiment one to five
The rate of recovery of matter copper, simple substance indium and Metallic Gallium reaches 98% or more；Wherein, in embodiment one to four, from object containing copper indium gallium selenide
The rate of recovery that elemental selenium, elemental copper, simple substance indium and Metallic Gallium are recycled in material reaches 99% or more, it is seen then that relative to primary roasting
Method, the rate of recovery that copper indium gallium selenide is recycled in such a way that double roasting method roasts material containing copper indium gallium selenide are higher.
It should be noted that above-mentioned realization method has been merely given as recycling elemental selenium, simple substance from material containing copper indium gallium selenide
The process of copper, simple substance indium and Metallic Gallium, but elemental selenium, list can not be recycled by not representing the scheme given by the embodiment of the present invention
Matter copper, simple substance indium or Metallic Gallium.
In the description of the above embodiment, particular features, structures, materials, or characteristics can be at any one or more
It can be combined in any suitable manner in a embodiment or example.
The above description is merely a specific embodiment, but scope of protection of the present invention is not limited thereto, any
Those familiar with the art in the technical scope disclosed by the present invention, can easily think of the change or the replacement, and should all contain
Lid is within protection scope of the present invention.Therefore, protection scope of the present invention should be based on the protection scope of the described claims.
Claims (15)
1. a kind of copper indium gallium selenide recovery method, which is characterized in that including：
Copper indium gallium selenide material and concentrated sulfuric acid mixing will be contained, obtain material dispersion system；
The material dispersion system is roasted, selenium dioxide, sulfur dioxide and roasting residue are obtained；
Utilize water to absorb the sulfur dioxide and the selenium dioxide so that the selenium dioxide by the sulphur dioxide reduction at
Elemental selenium；
The roasting residue is post-processed, elemental copper, simple substance indium and Metallic Gallium are obtained.
2. copper indium gallium selenide recovery method according to claim 1, which is characterized in that roasted to the material dispersion system
It burns, obtaining selenium dioxide, sulfur dioxide and roasting residue includes：
The material dispersion system is once roasted, a calcining matter is obtained so that a calcining matter includes sulfuric acid
Copper, indium sulfate, gallium sulfate and Selenium Sulphate；
After baking is carried out to a calcining matter, obtains selenium dioxide, sulfur dioxide and roasting residue.
3. copper indium gallium selenide recovery method according to claim 2, which is characterized in that the temperature of the after baking is more than one
The temperature of secondary roasting.
4. copper indium gallium selenide recovery method according to claim 2, which is characterized in that the calcination temperature once roasted is
200 DEG C -250 DEG C, the roasting time once roasted is 1h-2h；
The calcination temperature of the after baking is 450 DEG C -650 DEG C, and the roasting time of the after baking is 1h-4h.
5. copper indium gallium selenide recovery method according to claim 2, which is characterized in that described to be carried out to a calcining matter
After baking obtains selenium dioxide, sulfur dioxide and roasting residue, including：
Calcining matter is mixed with the concentrated sulfuric acid, obtains mixture；
After baking is carried out to the mixture, obtains selenium dioxide, sulfur dioxide and roasting residue.
6. copper indium gallium selenide recovery method according to claim 5, which is characterized in that the quality of the material containing copper indium gallium selenide
For m1, the quality of the concentrated sulfuric acid mixed with the material containing copper indium gallium selenide is m2, the concentrated sulfuric acid mixed with a calcining matter
Quality be m3；Wherein, m1:(m2+m3)=1:(2.5~4).
7. copper indium gallium selenide recovery method according to claim 6, which is characterized in that m2：M3=(2~5)：1.
8. according to claim 1~7 any one of them copper indium gallium selenide recovery method, which is characterized in that described to the roasting
Residue is post-processed, and is obtained elemental copper, simple substance indium and Metallic Gallium and is included：
Using residue is roasted described in water process, sulfate liquor is obtained；
Elemental copper, simple substance indium and Metallic Gallium are isolated from the sulfate liquor.
9. copper indium gallium selenide recovery method according to claim 8, which is characterized in that isolated from the sulfate liquor
Elemental copper includes：
The copper ion contained by the sulfate liquor is extracted using copper extractant, obtains cupric extraction phase；
The cupric extraction phase is stripped, cupric anti-stripping agent is obtained；
Using electrodeposition process elemental copper is isolated from the cupric anti-stripping agent.
10. copper indium gallium selenide recovery method according to claim 9, which is characterized in that it is described to the cupric extraction phase into
Row back extraction, obtaining cupric anti-stripping agent includes：
Utilize raffinate pair of the aqueous sulfuric acid and/or cupric anti-stripping agent of a concentration of 150g/L-250g/L after electro-deposition
The cupric extraction phase is stripped, and cupric anti-stripping agent is obtained.
11. copper indium gallium selenide recovery method according to claim 8, which is characterized in that detached from the sulfate liquor
Going out simple substance indium includes：
The indium ion contained by the sulfate liquor is extracted using indium extractant, obtains extraction phase containing indium；
The extraction phase containing indium is stripped, anti-stripping agent containing indium is obtained；
Using metal ion displacement method, from thick indium is displaced in anti-stripping agent containing indium, thick indium is refined using cell reaction,
Obtain simple substance indium.
12. copper indium gallium selenide recovery method according to claim 11, which is characterized in that carried out to the extraction phase containing indium anti-
Extraction, obtaining anti-stripping agent containing indium includes：
The extraction phase containing indium is stripped using the hydrochloric acid of 2mol/L-6mol/L, obtains anti-stripping agent containing indium.
13. copper indium gallium selenide recovery method according to claim 8, which is characterized in that detached from the sulfate liquor
Going out Metallic Gallium includes：
The gallium ion contained by the sulfate liquor is extracted using gallium extractant, obtains extraction phase containing gallium；
The extraction phase containing gallium is stripped, anti-stripping agent containing gallium is obtained；
Adjust pH value=11-14 of the anti-stripping agent containing gallium；
Using electrolysis Metallic Gallium is isolated from the anti-stripping agent containing gallium.
14. copper indium gallium selenide recovery method according to claim 13, which is characterized in that carried out to the extraction phase containing gallium anti-
Extraction, obtaining anti-stripping agent containing gallium includes：
The extraction phase containing gallium is stripped using water, obtains anti-stripping agent containing gallium.
15. copper indium gallium selenide recovery method according to claim 8, which is characterized in that detached from the sulfate liquor
Going out Metallic Gallium includes：
It is extracted in the sulfate liquor using gallium extractant, obtains extraction phase containing gallium；
Using extraction phase containing gallium described in naoh treatment, gallium hydroxide precipitation is obtained；
Gallium hydroxide precipitation is added to the water, sodium hydroxide is then added so that gallium hydroxide is converted to gallic acid sodium in water, obtains
Obtain sodium solution gallate；
Adjust pH value=11-14 of the sodium solution gallate；
Metallic Gallium is isolated from the sodium solution gallate using electrolysis.
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| CN111378839A (en) * | 2018-12-28 | 2020-07-07 | 汉能新材料科技有限公司 | Method for preparing alloy powder by using copper indium gallium selenide-containing waste |
| CN111826527A (en) * | 2020-08-03 | 2020-10-27 | 矿冶科技集团有限公司 | Method for recovering copper indium gallium selenide material |
| CN113737221A (en) * | 2021-09-15 | 2021-12-03 | 中冶华天工程技术有限公司 | Method for continuously separating copper, indium and gallium from waste thin-film solar cells |
| CN117051267A (en) * | 2023-10-11 | 2023-11-14 | 矿冶科技集团有限公司 | Method for extracting and separating gallium by emulsion liquid film |
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| CN113737221B (en) * | 2021-09-15 | 2024-04-26 | 中冶华天工程技术有限公司 | Method for continuously separating copper, indium and gallium from waste thin film solar cell |
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| CN117051267B (en) * | 2023-10-11 | 2023-12-29 | 矿冶科技集团有限公司 | Method for extracting and separating gallium by emulsion liquid film |
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