CN108728655A - Copper indium gallium selenide material recycle method - Google Patents
Copper indium gallium selenide material recycle method Download PDFInfo
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- CN108728655A CN108728655A CN201810645536.7A CN201810645536A CN108728655A CN 108728655 A CN108728655 A CN 108728655A CN 201810645536 A CN201810645536 A CN 201810645536A CN 108728655 A CN108728655 A CN 108728655A
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/005—Separation by a physical processing technique only, e.g. by mechanical breaking
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03C—MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03C1/00—Magnetic separation
- B03C1/02—Magnetic separation acting directly on the substance being separated
- B03C1/30—Combinations with other devices, not otherwise provided for
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B19/00—Selenium; Tellurium; Compounds thereof
- C01B19/02—Elemental selenium or tellurium
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B15/00—Obtaining copper
- C22B15/0063—Hydrometallurgy
- C22B15/0084—Treating solutions
- C22B15/0089—Treating solutions by chemical methods
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B58/00—Obtaining gallium or indium
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- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
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- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/22—Electrolytic production, recovery or refining of metals by electrolysis of solutions of metals not provided for in groups C25C1/02 - C25C1/20
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Abstract
The present invention relates to copper indium gallium selenide material recycle methods.This method includes：Copper indium gallium selenide material is crushed, copper indium gallium selenide material powders are obtained；Magnetic separation is carried out to copper indium gallium selenide material powders, obtains irony material powders and magnetic separation copper indium gallium selenide material powders；Magnetic separation copper indium gallium selenide powder is handled, copper, indium, gallium, selenium are obtained.The technical solution can enter leachate to avoid ferro element, to reduce the difficulty of separating-purifying copper indium gallium selenide.
Description
Technical field
The present invention relates to technical field of solar batteries more particularly to copper indium gallium selenide material recycle methods.
Background technology
Start gradual to environmental problem with the high speed development and people's living standards continue to improve, people of science and technology
To pay attention to, environmental pollution is less or free of contamination new energy technology such as solar energy generation technology was quickly grown in recent years,
Solar cell directly can be converted to luminous energy by photoelectric effect the device of electric energy, to be improved more just for electrical equipment
Prompt energy supply, wherein copper indium gallium selenium solar cell has production cost is low, pollution is small, do not fail, dim light performance is good etc.
Feature.Copper indium gallium selenium solar cell contains the rare metals such as copper, indium, gallium and selenium, in order to recycle above-mentioned rare metal,
Copper, indium, gallium and selenium in waste and old copper indium gallium selenium solar cell can be separated and recovered from.In the related technology, exist
When recycling copper indium gallium selenide, extraction may be used, i.e., copper indium gallium selenium solar cell is crushed and is fragmentated, and is broken using Ore Leaching
Copper indium gallium selenide coating in piece, Reduced separating selenium, extraction and separation indium and gallium, then indium, gallium are extracted from separating liquid.Although above-mentioned side
Case can effectively extract copper indium gallium selenide from waste and old copper indium gallium selenium solar cell, but due to copper indium gallium selenium solar cell
Substrate is generally made of stainless steel, and in leaching process, is easy that a large amount of ferro elements is made to enter leachate, when extraction and separation indium, gallium
When, extractant can first extract iron, reduce the extraction efficiency of indium and gallium, increase indium gallium separating-purifying difficulty.
Invention content
To overcome in the copper indium gallium selenide cell recovery process at stainless steel lining bottom, since later separation carries caused by the leaching of iron
The big problem of pure difficulty, the present invention provide copper indium gallium selenide material recycle method.Technical solution is as follows：
It is according to an embodiment of the invention in a first aspect, provide a kind of copper indium gallium selenide material recycle method, including：
Copper indium gallium selenide material is crushed, copper indium gallium selenide material powders are obtained；
Magnetic separation is carried out to copper indium gallium selenide material powders, obtains irony material powders and magnetic separation copper indium gallium selenide material powders；
Magnetic separation copper indium gallium selenide powder is handled, copper, indium, gallium, selenium are obtained.
Optionally, magnetic separation is carried out to copper indium gallium selenide material powders, obtains irony material powders and magnetic separation copper indium gallium selenide material
Powder, including：
Selection by winnowing is carried out to copper indium gallium selenide material powders, obtains organic matter powder and metallic powder；
Magnetic separation is carried out to metallic powder, obtains irony material powders and magnetic separation copper indium gallium selenide material powders.
Optionally, magnetic separation copper indium gallium selenide powder is handled, obtains copper, indium, gallium, selenium, including：
Magnetic separation copper indium gallium selenide material powders sulfuric acid and hydrogen peroxide are leached, leachate is obtained；
It is filtered after leachate is passed through sulfur dioxide gas, obtains reduction extraction raffinate and selenium；
Extract liquor is added into reduction extraction raffinate to be extracted, and is separated after the extraction, obtains load indium organic phase
With raffinate；
Hydrochloric acid is added into load indium organic phase to be stripped, strip liquor is obtained；
Electro-deposition is carried out to strip liquor, obtains indium；
It sodium hydroxide is added into raffinate obtains Kocide SD precipitation and extract with gallium and solution；
Gallium is extracted and solution progress electro-deposition, obtains gallium.
Optionally, the granularity of copper indium gallium selenide material powders is greater than or equal to 200 mesh.
Optionally, the magnetic field intensity of magnetic separation is greater than or equal to 100000 peaces/rice and is less than or equal to 300000 peaces/rice,
Optionally, the magnetic separation time of magnetic separation is greater than or equal to 5 minutes and is less than or equal to 15 minutes.
Optionally, the wind pressure of selection by winnowing is greater than or equal to 1MPa and is less than or equal to 5MPa.
Optionally, the selection by winnowing time of selection by winnowing is greater than or equal to 1 minute and is less than or equal to 3 minutes.
Optionally, magnetic separation is carried out to copper indium gallium selenide material powders, obtains irony material powders and magnetic separation copper indium gallium selenide material
Powder, including：
Magnetic separator is added in copper indium gallium selenide material powders and carries out magnetic separation；
When the content of iron in the magnetic separation copper indium gallium selenide material powders obtained by magnetic separation is less than or equal to 0.5%, and magnetic separation
In copper indium gallium selenide material powders the ratio of the weight of the weight of copper indium gallium selenide and the copper indium gallium selenide in copper indium gallium selenide material be more than or
When equal to 97%, terminates magnetic separation, obtain irony material powders and magnetic separation copper indium gallium selenide material powders.
Optionally, selection by winnowing is carried out to copper indium gallium selenide material powders, obtains organic matter powder and metallic powder, including：
Winnowing machine is added in copper indium gallium selenide material powders and carries out selection by winnowing；
When the weight of copper indium gallium selenide in the metallic powder obtained by selection by winnowing and the copper indium gallium selenide in copper indium gallium selenide material
Weight ratio be greater than or equal to 99% when, terminate selection by winnowing, obtain organic matter powder and metallic powder.
In the technical solution that the embodiment of the present invention provides, by carrying out magnetic separation to copper indium gallium selenide material powders, iron is obtained
Matter material powders and magnetic separation copper indium gallium selenide material powders, then magnetic separation copper indium gallium selenide material powders sulfuric acid and hydrogen peroxide are leached,
Leachate is obtained, leachate can be entered to avoid ferro element, to reduce the difficulty of separating-purifying copper indium gallium selenide.
It should be understood that above general description and following detailed description is only exemplary and explanatory, not
It can the limitation present invention.
Description of the drawings
The drawings herein are incorporated into the specification and forms part of this specification, and shows the implementation for meeting the present invention
Example, and be used to explain the principle of the present invention together with specification.
Fig. 1 is the flow diagram according to the copper indium gallium selenide material recycle method shown in an exemplary embodiment；
Fig. 2 is the flow diagram according to the copper indium gallium selenide material recycle method shown in an exemplary embodiment；
Fig. 3 is the flow diagram according to the copper indium gallium selenide material recycle method shown in an exemplary embodiment；
Fig. 4 is the flow diagram according to the copper indium gallium selenide material recycle method shown in an exemplary embodiment；
Fig. 5 is the flow diagram according to the copper indium gallium selenide material recycle method shown in an exemplary embodiment；
Fig. 6 is the flow diagram according to the copper indium gallium selenide material recycle method shown in an exemplary embodiment.
Specific implementation mode
Example embodiments are described in detail here, and the example is illustrated in the accompanying drawings.Following description is related to
When attached drawing, unless otherwise indicated, the same numbers in different drawings indicate the same or similar elements.Following exemplary embodiment
Described in embodiment do not represent and the consistent all embodiments of the present invention.On the contrary, they be only with it is such as appended
The example of the consistent device and method of some aspects being described in detail in claims, of the invention.
A kind of copper indium gallium selenide material recycle method of the present invention, as shown in Figure 1, including the following steps 101 to step 103：
In a step 101, copper indium gallium selenide material is crushed, copper indium gallium selenide material powders are obtained.
Illustratively, copper indium gallium selenide material can be waste and old copper indium gallium selenium solar cell.Copper indium gallium selenide material is crushed, is obtained
To copper indium gallium selenide material powders, copper indium gallium selenide material can be crushed using crusher, and using grinder to after broken
Copper indium gallium selenide material be ground, obtain copper indium gallium selenide material powders.Wherein grinder can be ball mill, or its
His grinder.Copper indium gallium selenide material is crushed by using crusher, using grinder to broken copper indium gallium selenide object
Material is ground, and to obtain copper indium gallium selenide material powders, can make the finer of acquired copper indium gallium selenide material powders, to drop
The difficulty of low separating-purifying copper indium gallium selenide.
Milled processed to copper indium gallium selenide material is to be conducive to carry out magnetic separation, therefore object to copper indium gallium selenide material powders
The thinner feed powder end the more advantageous.But material powders are meticulous, not only increase milled processed process, also improve milled processed cost, it is excellent
The granularity of copper indium gallium selenide material powders is selected to be greater than or equal to 200 mesh.
In a step 102, magnetic separation is carried out to copper indium gallium selenide material powders, obtains irony material powders and magnetic separation copper indium gallium selenide
Material powders.
Illustratively, magnetic separation is carried out to copper indium gallium selenide material powders, can is that copper indium gallium selenide material powders are put into magnetic separation
Machine carries out magnetic separation, to obtain irony material powders and magnetic separation copper indium gallium selenide material powders.
Magnetic separator carry out magnetic separation process can be specially：Copper indium gallium selenide material powders are moved on on smooth support board,
With support board make magnetic separation copper indium gallium selenide material powders receiver (wherein the support board by non-magnetic material for example paper, wood, plastics,
Aluminium etc.), it is buckled to flat non-magnetic material container above copper indium gallium selenide material powder and sorts space to build, and disposes a magnet within
It is 100000 to generate magnetic field intensity in flat non-magnetic material container above the bottom surface of flat non-magnetic material container
Peace/rice controls magnet above the bottom surface of flat non-magnetic material container relative to flat non-to the magnetic field of 300000 peaces/rice
Magnetic material container moves, and since irony material powders can follow magnet movement, irony material powders can be by magnetic in movement
Body is adsorbed on the bottom surface of flat non-magnetic material container, and magnetic separation copper indium gallium selenide material powders rest on magnetic separation copper indium gallium selenide object
It in the receiver of feed powder end, carries out after the magnetic separation time is magnetic separation in 5 minutes to 10 minutes, by magnet by magnetic separation copper indium gallium selenide material
Powder adsorption is on the bottom surface of magnetic separation copper indium gallium selenide material powders receiver and removes, and is arranged via non-ferrous powder discharge port
Go out, the irony powder that will stay in magnetic separation copper indium gallium selenide material powders receiver is discharged by irony powder discharge port.
In step 103, magnetic separation copper indium gallium selenide powder is handled, obtains copper, indium, gallium, selenium.The processing of step 103
Process can refer to routine techniques progress.
The technical solution of aforementioned present invention separates irony material powder by carrying out magnetic separation to copper indium gallium selenide material powders
End and magnetic separation copper indium gallium selenide powder, then magnetic separation copper indium gallium selenide powder is handled, to reduce separating-purifying copper indium gallium selenide
Difficulty.
The preferred copper indium gallium selenide material recycle method of the present invention, as shown in Fig. 2, including the following steps 201 to step 204：
Step 201, copper indium gallium selenide material is crushed, copper indium gallium selenide material powders are obtained；
Step 202, selection by winnowing is carried out to copper indium gallium selenide material powders, obtains organic matter powder and metallic powder.
Step 203, magnetic separation is carried out to metallic powder, obtains irony material powders and magnetic separation copper indium gallium selenide material powders.
Step 204, magnetic separation copper indium gallium selenide powder is handled, obtains copper, indium, gallium, selenium.
Above-mentioned step 201, step 203 and step 204 can refer in abovementioned steps 101, step 103 and step 104
Content carries out, and details are not described herein.
In step 202, selection by winnowing is carried out to copper indium gallium selenide material powders, can is that copper indium gallium selenide material powders are put into wind
Machine is selected to carry out selection by winnowing, to obtain organic matter powder and metallic powder.
Specifically, the process that winnowing machine carries out selection by winnowing can be specially：By copper indium gallium selenide material powders by air classification cabin side
Feed inlet put into air classification cabin, carry out selection by winnowing when, wind regime is blown into air classification cabin by the air inlet of air classification cabin bottom, makes in air classification cabin
Wind pressure is 1MPa to 5MPa, and the copper indium gallium selenide material powders in air classification cabin seethe from lower to upper in winnowing process, lighter in weight
Organic matter powder be easy blown by wind, can in winnowing process by dust catcher from the top of air classification cabin suction inlet be discharged selection by winnowing
Cabin.After carrying out the selection by winnowing that the selection by winnowing time is 1 minute to 3 minutes, the air inlet of air classification cabin bottom is closed, due to the gold of heavier-weight
Belong to that matter powder is more difficult is blown by wind, therefore metallic powder stays in the bottom of air classification cabin, the discharge port from the bottom of air classification cabin can
Metallic powder to be discharged.
Since the content of organic matter in copper indium gallium selenide material is higher, if magnetic separation copper indium gallium selenide material powders contain it is more organic
Matter can increase the volume and weight of magnetic separation copper indium gallium selenide material powders, to improve the difficulty of separating-purifying copper indium gallium selenide.It is above-mentioned
In technical solution provided by the invention, by carrying out selection by winnowing to copper indium gallium selenide material powders, organic matter powder is detached, metal is obtained
Matter powder, and magnetic separation is carried out to metallic powder, irony material powders and magnetic separation copper indium gallium selenide material powders are obtained, can be reduced
The content of organic matter in magnetic separation copper indium gallium selenide material powders reduces the volume and weight of magnetic separation copper indium gallium selenide material powders, to
It further reduced the difficulty of separating-purifying copper indium gallium selenide.
Currently preferred copper indium gallium selenide material recycle method includes the following steps 301 to step as shown in Fig. 3 and Fig. 6
Rapid 309：
Step 301, copper indium gallium selenide material is crushed, copper indium gallium selenide material powders are obtained.
Step 302, selection by winnowing is carried out to copper indium gallium selenide material powders, obtains organic matter powder and metallic powder.
Step 303, magnetic separation is carried out to metallic powder, obtains irony material powders and magnetic separation copper indium gallium selenide material powders.
Step 301 to step 303 can refer to abovementioned steps 201 to the content in step 203, and details are not described herein.
Step 304, magnetic separation copper indium gallium selenide material powders acid is leached with hydrogen peroxide, obtains leachate.
Wherein, acid can use the inorganic acids such as sulfuric acid, hydrochloric acid, may be selected the sulfuric acid of a concentration of 10%-20%, copper in leachate
The ratio of the weight of indium gallium selenium and the weight of the copper indium gallium selenide in magnetic separation copper indium gallium selenide material powders can be greater than or equal to 99%.
Illustratively, reaction included in step 304 is as follows：
2CuIn0.6Ga0.4Se2+5H2SO4+H2O2=2CuSO4+0.6In2 (SO4) 3+0.4Ga2 (SO4) 3+
4H2SeO3+2H2O
Step 305, it is filtered after leachate being passed through sulfur dioxide gas, obtains reduction extraction raffinate and selenium.
Illustratively, reaction included in step 305 is as follows：
H2SeO3+2SO2+H2O=2H2SO4+Se
Wherein, the purity of obtained selenium can be greater than or equal to 98%, weight and the copper indium gallium selenide object of obtained selenium
The ratio of the weight of selenium can be greater than or equal to 97% in material.
Step 306, extract liquor is added into reduction extraction raffinate to be extracted, and is separated after the extraction, loaded
Indium organic phase and raffinate.
Illustratively, extract liquor can be P204 extract liquors.It is separated, can be to use liquid distributing device such as liquid separation
Funnel is separated, to obtain load indium organic phase and raffinate.
Step 307, hydrochloric acid is added into load indium organic phase to be stripped, obtains strip liquor.
Step 308, electro-deposition is carried out to strip liquor, obtains indium.
Illustratively, electrode reaction included in step 308 is as follows：
Cathode occur reaction be：In3++3e-=In
Anode occur reaction be：Cl--e-=Cl2
Wherein, the purity of obtained indium can be greater than or equal to 99%, weight and the copper indium gallium selenide object of obtained indium
The ratio of the weight of indium can be greater than or equal to 98% in material.
Step 309, it sodium hydroxide is added into raffinate obtains Kocide SD precipitation and extract with gallium and solution.
Step 310, Kocide SD precipitation is isolated, gallium is extracted and solution progress electro-deposition, obtains gallium.
Its electrode reaction is as follows：
Cathode occur reaction be：GaO2-+2H2O+3e-=Ga+4OH-
Anode occur reaction be：4OH--4e-=2H2O+O2
Wherein, the purity of obtained gallium can be greater than or equal to 99%, weight and the copper indium gallium selenide object of obtained gallium
The ratio of the weight of gallium can be greater than or equal to 96% in material.
By leaching magnetic separation copper indium gallium selenide material powders sulfuric acid and hydrogen peroxide, leachate is obtained；Leachate is passed through
It is filtered after sulfur dioxide gas, obtains reduction extraction raffinate and selenium；Extract liquor is added into reduction extraction raffinate to be extracted, and is extracting
It is separated after taking, obtains load indium organic phase and raffinate；Hydrochloric acid is added into load indium organic phase to be stripped, obtains
To strip liquor；Electro-deposition is carried out to strip liquor, obtains indium；Sodium hydroxide is added into raffinate and obtains Kocide SD precipitation and gallium
Extract and solution；Gallium is extracted and solution progress electro-deposition, gallium is obtained, the purity of obtained indium, gallium and selenium can be improved.
Currently preferred copper indium gallium selenide material recycle method, as shown in figure 4, including the following steps 401 to step 405：
Step 401, copper indium gallium selenide material is crushed, copper indium gallium selenide material powders are obtained.
Step 402, selection by winnowing is carried out to copper indium gallium selenide material powders, obtains organic matter powder and metallic powder.
Step 403, magnetic separation is carried out to metallic powder, obtains irony material powders and magnetic separation copper indium gallium selenide material powders.
Step 404, when the content of iron in the magnetic separation copper indium gallium selenide material powders obtained by magnetic separation is less than or equal to
0.5%, and the weight of the copper indium gallium selenide in magnetic separation copper indium gallium selenide material powders in the weight of copper indium gallium selenide and copper indium gallium selenide material
Ratio be greater than or equal to 97% when, terminate magnetic separation, obtain irony material powders and magnetic separation copper indium gallium selenide material powders.
It illustratively, can be after carrying out the magnetic separation that the magnetic separation time is 5 minutes, to discharging from the non-ferrous powder of magnetic separator
The magnetic separation copper indium gallium selenide material powders that mouth takes out are detected, when in determining magnetic separation copper indium gallium selenide material powders according to testing result
When the content of iron is 0.5%, terminate magnetic separation.
It can also be after carrying out the magnetic separation that the magnetic separation time is 5 minutes, to being taken out from the non-ferrous powder discharge port of magnetic separator
Magnetic separation copper indium gallium selenide material powders be detected, when determining copper and indium gallium in magnetic separation copper indium gallium selenide material powders according to testing result
The ratio of the weight of selenium is 97%, terminates magnetic separation.
Step 405, magnetic separation copper indium gallium selenide powder is handled, obtains copper, indium, gallium, selenium.
Above-mentioned steps 401, step 402, step 403 and step 405 can refer in abovementioned steps 201 to step 204
Hold, details are not described herein.
Magnetic separation is carried out by the way that magnetic separator is added in copper indium gallium selenide material powders, and when the magnetic separation copper and indium gallium obtained by magnetic separation
In selenium material powders the content of iron be less than or equal to 0.5%, and in magnetic separation copper indium gallium selenide material powders the weight of copper indium gallium selenide with
When the ratio of the weight of copper indium gallium selenide in copper indium gallium selenide material is greater than or equal to 97%, terminates magnetic separation, obtain irony material powder
End and magnetic separation copper indium gallium selenide material powders can improve the rate of recovery that copper indium gallium selenide is recycled from copper indium gallium selenide material.
Currently preferred copper indium gallium selenide material recycle method, as shown in figure 5, including the following steps 501 to step 505：
Step 501, copper indium gallium selenide material is crushed, copper indium gallium selenide material powders are obtained.
Step 502, winnowing machine is added in copper indium gallium selenide material powders and carries out selection by winnowing.
Step 503, when in the weight of copper indium gallium selenide in the metallic powder obtained by selection by winnowing and copper indium gallium selenide material
When the ratio of the weight of copper indium gallium selenide is greater than or equal to 99%, terminates selection by winnowing, obtain organic matter powder and metallic powder.
It illustratively, can be after carrying out the selection by winnowing that the magnetic separation time is 5 minutes, to the gold taken out from the discharge port of winnowing machine
Belong to matter powder to be detected, when in the weight and copper indium gallium selenide material of copper indium gallium selenide in determining metallic powder according to testing result
Copper indium gallium selenide weight ratio be equal to 99% when, terminate selection by winnowing, wherein organic matter powder in winnowing process by dust catcher
From the suction inlet discharge air classification cabin at the top of air classification cabin, air classification cabin is will be left in from the discharge port of the bottom of air classification cabin after end selection by winnowing
Whole metallic powder of bottom are discharged.
Step 504, magnetic separation is carried out to metallic powder, obtains irony material powders and magnetic separation copper indium gallium selenide material powders.
Step 505, magnetic separation copper indium gallium selenide powder is handled, obtains copper, indium, gallium, selenium.
Above-mentioned steps 501, step 502, step 504 and step 505 can refer in abovementioned steps 201 to step 204
Hold, details are not described herein.
Selection by winnowing is carried out by the way that winnowing machine is added in copper indium gallium selenide material powders, and when the metallic powder obtained by selection by winnowing
When the ratio of the weight of middle copper indium gallium selenide and the weight of the copper indium gallium selenide in copper indium gallium selenide material is greater than or equal to 99%, terminate wind
Choosing, obtains organic matter powder and metallic powder, can improve the rate of recovery that copper indium gallium selenide is recycled from copper indium gallium selenide material.
The technology of the present invention is given below by embodiment and is only illustrated to a step.
Embodiment 1
10 kilograms of waste and old copper indium gallium selenium solar cell, after crusher in crushing, is ground with ball mill, obtains granularity
For the copper indium gallium selenide material powders of 200 mesh.It is from the feeding port of magnetic separator input magnetic field intensity by the copper indium gallium selenide material powders
The magnetic separator of 300000 peaces/rice after carrying out the magnetic separation that the magnetic separation time is 5 minutes, takes out from the irony powder discharge port of magnetic separator
The irony material powders that weight is 8.5 kilograms, and take out the magnetic that weight is 1.5 kilograms from the non-ferrous powder discharge port of magnetic separator
Select copper indium gallium selenide material powders.
Copper indium gallium selenide is leached, the magnetic separation copper indium gallium selenide material powders sulfuric acid of (concentration 10%) is leached with hydrogen peroxide, is obtained
To leachate.
Copper and indium gallium selenium is separated and recovered, leachate is passed through sulphur dioxide reduction separation selenium, obtains impure selenium, thickness purity is
98%, the rate of recovery is more than 94%.The solution P204 extraction and separation indiums for detaching selenium, by obtaining 99.99% after back extraction, electro-deposition
Pure indium, the rate of recovery of indium is more than 95%.10%NaOH separation copper is added in raffinate and gallium obtains containing copper ashes and Gallium solution, and gallium is molten
Liquid electro-deposition obtains 99.99% pure gallium, the rate of recovery 94%.
Embodiment 2
By the condition of embodiment 1, it is the magnetic separator of 100000 peaces/rice only to select magnetic field intensity, carries out the magnetic separation time and is
Magnetic separation in 10 minutes, the obtained rate of recovery are 94.5%.
Embodiment 3
10 kilograms of waste and old copper indium gallium selenium solar cell, after crusher in crushing, is ground with ball mill, obtains granularity
For the copper indium gallium selenide material powders of 200 mesh.
Selection by winnowing in winnowing machine is added in copper indium gallium selenide material powders, and it is 1MPa to make the wind pressure in air classification cabin, carries out the selection by winnowing time
After 3 minutes selection by winnowing, the organic substance in copper indium gallium selenide material powders is removed.Obtain 9kg metal powders, 1kg organic substances,
It analyzes after testing, the rate of recovery of copper indium gallium selenide film plating layer is more than 99% in the metal powder that winnowing process obtains.
The copper indium gallium selenide material powders are put into the magnetic separation that magnetic field intensity is 300000 peaces/rice from the feeding port of magnetic separator
After carrying out the magnetic separation that the magnetic separation time is 5 minutes, the iron that weight is 8.5 kilograms is taken out from the irony powder discharge port of magnetic separator for machine
Matter material powders, and take out the magnetic separation copper indium gallium selenide material powder that weight is 0.5 kilogram from the non-ferrous powder discharge port of magnetic separator
End.
Copper indium gallium selenide is leached, the magnetic separation copper indium gallium selenide material powders sulfuric acid of (concentration 10%) is leached with hydrogen peroxide, is obtained
To leachate.
Copper and indium gallium selenium is separated and recovered, leachate is passed through sulphur dioxide reduction separation selenium, obtains impure selenium, thickness purity is
98%, the rate of recovery is more than 97%.The solution P204 extraction and separation indiums for detaching selenium, by obtaining 99.99% after back extraction, electro-deposition
Pure indium, the rate of recovery of indium is more than 98%.10%NaOH separation copper is added in raffinate and gallium obtains containing copper ashes and Gallium solution, and gallium is molten
Liquid electro-deposition obtains 99.99% pure gallium, the rate of recovery 96%.
Embodiment 4
By the condition of embodiment 3, only selecting makes the wind pressure in air classification cabin be 5MPa, and it is 1 minute to carry out the selection by winnowing time, is obtained
The rate of recovery arrived is 96.5%.
Comparing embodiment 1, embodiment 2 and embodiment 3, embodiment 4 can see, due in embodiment 2, embodiment 4
Wind election process is increased, organic substance of having gone out, identical in other treatment conditions, the rate of recovery improves 2%.
Comparative example
By the condition of embodiment 3, it is the copper indium gallium selenide material powders of 100 mesh only to select granularity, and the obtained rate of recovery is
81.5%.
It can see by the result of above-described embodiment and comparative example, be 200 purposes due to selecting granularity in embodiment
Copper indium gallium selenide material powders are identical in other treatment conditions compared with comparative example granularity is the copper indium gallium selenide material powders of 100 mesh
In the case of, the rate of recovery can be improved 10% or more.
Since the present invention uses following technologies：
1, be granularity with copper indium gallium selenide powder it is the above fine powder of 200 mesh；
2, selection by winnowing+magnetic separation detaches copper scrap indium gallium selenium powder, is effectively enriched copper indium gallium selenide raw material；
3, waste caused by detaching is iron powder and organic substance, also recyclable use.
Therefore compared with prior art, than with subzero treatment method is easy to operate, equipment investment is small；Than alkali soluble molybdenum layer stripping method
Separative efficiency is fast, and copper indium gallium selenide raw materials recovery rate is high.
Those skilled in the art after considering the specification and implementing the invention disclosed here, will readily occur to its of the present invention
Its embodiment.This application is intended to cover the present invention any variations, uses, or adaptations, these modifications, purposes or
Person's adaptive change follows the general principle of the present invention and includes undocumented common knowledge in the art of the invention
Or conventional techniques.The description and examples are only to be considered as illustrative, and true scope and spirit of the invention are by following
Claim is pointed out.
It should be understood that the invention is not limited in the precision architectures for being described above and being shown in the accompanying drawings, and
And various modifications and changes may be made without departing from the scope thereof.The scope of the present invention is limited only by the attached claims.
Claims (10)
1. a kind of copper indium gallium selenide material recycle method, which is characterized in that including：
Copper indium gallium selenide material is crushed, copper indium gallium selenide material powders are obtained；
Magnetic separation is carried out to the copper indium gallium selenide material powders, obtains irony material powders and magnetic separation copper indium gallium selenide material powders；
The magnetic separation copper indium gallium selenide powder is handled, copper, indium, gallium, selenium are obtained.
2. copper indium gallium selenide material recycle method according to claim 1, which is characterized in that described to the copper indium gallium selenide object
Feed powder end carries out magnetic separation, obtains irony material powders and magnetic separation copper indium gallium selenide material powders, including：
Selection by winnowing is carried out to the copper indium gallium selenide material powders, obtains organic matter powder and metallic powder；
Magnetic separation is carried out to the metallic powder, obtains the irony material powders and the magnetic separation copper indium gallium selenide material powders.
3. copper indium gallium selenide material recycle method according to claim 1 or 2, which is characterized in that described to the magnetic separation copper
Indium gallium selenium powder is handled, and copper, indium, gallium, selenium are obtained, including：
The magnetic separation copper indium gallium selenide material powders sulfuric acid and hydrogen peroxide are leached, leachate is obtained；
It is filtered after the leachate is passed through sulfur dioxide gas, obtains reduction extraction raffinate and selenium；
Extract liquor is added into the reduction extraction raffinate to be extracted, and is separated after the extraction, obtains load indium organic phase
With raffinate；
Hydrochloric acid is added into the load indium organic phase to be stripped, strip liquor is obtained；
Electro-deposition is carried out to the strip liquor, obtains indium；
It sodium hydroxide is added into the raffinate obtains Kocide SD precipitation and extract with gallium and solution；
The gallium is extracted and solution progress electro-deposition, obtains gallium.
4. copper indium gallium selenide material recycle method according to claim 1 or 2, which is characterized in that the copper indium gallium selenide material
The granularity of powder is greater than or equal to 200 mesh.
5. copper indium gallium selenide material recycle method according to claim 1 or 2, which is characterized in that the magnetic field of the magnetic separation is strong
Degree is more than or equal to 100000 peaces/rice and is less than or equal to 300000 peaces/rice.
6. copper indium gallium selenide material recycle method according to claim 1 or 2, which is characterized in that when the magnetic separation of the magnetic separation
Between be greater than or equal to 5 minutes and be less than or equal to 15 minutes.
7. copper indium gallium selenide material recycle method according to claim 2, which is characterized in that the wind pressure of the selection by winnowing be more than or
Equal to 1MPa and it is less than or equal to 5MPa.
8. copper indium gallium selenide material recycle method according to claim 2, which is characterized in that the selection by winnowing time of the selection by winnowing is big
In or equal to 1 minute and be less than or equal to 3 minutes.
9. copper indium gallium selenide material recycle method according to claim 1 or 2, which is characterized in that described to the copper and indium gallium
Selenium material powders carry out magnetic separation, obtain irony material powders and magnetic separation copper indium gallium selenide material powders, including：
Magnetic separator is added in the copper indium gallium selenide material powders and carries out magnetic separation；
When iron in the magnetic separation copper indium gallium selenide material powders obtained by the magnetic separation content be less than or equal to 0.5%, and
The weight of the weight of copper indium gallium selenide and the copper indium gallium selenide in the copper indium gallium selenide material in the magnetic separation copper indium gallium selenide material powders
Ratio be greater than or equal to 97% when, terminate the magnetic separation, obtain the irony material powders and the magnetic separation copper indium gallium selenide object
Feed powder end.
10. copper indium gallium selenide material recycle method according to claim 2, which is characterized in that described to the copper indium gallium selenide
Material powders carry out selection by winnowing, obtain organic matter powder and metallic powder, including：
Winnowing machine is added in the copper indium gallium selenide material powders and carries out selection by winnowing；
When in the weight of copper indium gallium selenide in the metallic powder obtained by the selection by winnowing and the copper indium gallium selenide material
When the ratio of the weight of copper indium gallium selenide is greater than or equal to 99%, terminates the selection by winnowing, obtain the organic matter powder and the gold
Belong to matter powder.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101121966A (en) * | 2007-06-19 | 2008-02-13 | 昆明理工大学 | Technique for reclaiming vanadium and iron from high-vanadium high-iron steel slag |
| CN102399997A (en) * | 2011-10-28 | 2012-04-04 | 中南大学 | Method for refining zinc through combination of dressing and smelting |
| CN103184338A (en) * | 2011-12-29 | 2013-07-03 | 广东先导稀材股份有限公司 | Recovery method of copper indium gallium selenide thin-film solar panel |
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2018
- 2018-06-21 CN CN201810645536.7A patent/CN108728655A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101121966A (en) * | 2007-06-19 | 2008-02-13 | 昆明理工大学 | Technique for reclaiming vanadium and iron from high-vanadium high-iron steel slag |
| CN102399997A (en) * | 2011-10-28 | 2012-04-04 | 中南大学 | Method for refining zinc through combination of dressing and smelting |
| CN103184338A (en) * | 2011-12-29 | 2013-07-03 | 广东先导稀材股份有限公司 | Recovery method of copper indium gallium selenide thin-film solar panel |
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