CN108359801B - The method of valuable metal is recycled from copper indium gallium selenide refuse battery chip - Google Patents
The method of valuable metal is recycled from copper indium gallium selenide refuse battery chip Download PDFInfo
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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
- C22B7/006—Wet processes
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- C—CHEMISTRY; METALLURGY
- 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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- 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
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/02—Roasting processes
- C22B1/06—Sulfating roasting
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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
- C22B15/00—Obtaining copper
- C22B15/0063—Hydrometallurgy
- C22B15/0065—Leaching or slurrying
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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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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- 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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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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Abstract
The present invention provides a kind of method that valuable metal is recycled from copper indium gallium selenide refuse battery chip, belongs to resource secondary and utilizes technical field.Copper indium gallium selenide (CIGS) refuse battery chip is carried out substrate desquamation by this method；Sulfating roasting is carried out to the valuable metal layer after removing and obtains impure selenium and slag；Pulp water soaks to obtain infusion and water logging slag；Copper sulphate is obtained containing zinc, cadmium, the slag of aluminium and filtrate, filtrate crystallisation by obtaining after infusion removal of impurities/separation；Alkali immersion liquid and alkali phase analysis are obtained after the leaching of water logging slag alkali；Acidleach obtains pickle liquor and acid leaching residue to alkali phase analysis again, and acid leaching residue returns to sulfating roasting；Pickle liquor restores to obtain thick indium, and purification of crude indium obtains slag and high purity indium containing aluminium, tin；The slag containing molybdenum, tin is isolated in alkali immersion liquid removal of impurities, and filtrate is obtained by filtration；Filtrate is electrolysed to obtain thick gallium, and thick gallium purifies to obtain high purity gallium.The present invention can be realized the efficient selective leaching of copper, indium, gallium, selenium, have a good application prospect.
Description
Technical field
The present invention relates to resource secondaries to utilize technical field, particularly relates to one kind and recycles from copper indium gallium selenide refuse battery chip
The method of valuable metal.
Background technique
Copper indium gallium selenide (CIGS) thin film solar cell has high photoelectric efficiency, has good development potentiality.Its
Production method has vacuum splashing and plating method, the way of distillation and an antivacuum rubbing method, no matter uses which kind of production method, in manufacturing process all
The waste material of some copper indium gallium selenide can be generated.From the angle of green economy environmental protection and sustainable development, to be conducive to indium, gallium
With the sustainable utilization of the rare metals and heavy metal copper such as selenium, need to be separated and be separately recovered, to facilitate further
It recycles, to guarantee the sustainable development of copper-indium-galliun-selenium film solar cell material.In the prior art, copper indium gallium selenide waste material
Recovery method mainly have the wet processes such as acid-soluble method, extraction, oxidation distillation method or pyro-refining combined method.
United States Patent (USP) US5779877 by discarded copper and indium Se solar cell broken, salt Ore Leaching, two electrode separation copper,
Selenium and indium, then evaporation, decomposition obtains the mixture of indium and zinc oxide, and oxidation distillation separates copper and selenium.But this method process
Long, selenium recovery is low, not can solve the recycling problem of gallium.
Chinese patent CN103184338A provides a kind of CIGS thin-film solar plate recovery method, comprising: broken,
H2SO4+H2O2System is leached, filtering, is extracted, HCl is stripped to obtain indium, restores to obtain selenium plus the processes such as alkali separation and electrolysis gallium.
This method long flow path, also toxicity is stronger for the hydrazine hydrate that reduction selenium uses, and operating process is relatively hazardous, also be easy to cause environmental pollution.
Chinese patent CN102296178A discloses a kind of recovery method of copper indium gallium selenide.This method first with hydrochloric acid with
The mixed solution of hydrogen peroxide dissolves the metal-powder comprising copper indium gallium selenide, after isolating selenium using hydrazine, is set with indium metal
Swap out copper, combines dispersion strip liquor to separate indium with gallium finally by brace type liquid film (SLM).However the leaching of this method metal
Rate is not high, while SLM liquid film technology separating gallium operation difficulty is big, and production procedure is complicated, at high cost, is not suitable for scale metaplasia
It produces.
Chinese patent CN105886767A is evaporated the selenium in CIGS waste material is first acidizing fired, then again to remaining
Three kinds of metals are separated, especially to divide the lye containing gallium generated in indium step and divide in gallium step solution of the gained containing gallium into
Row merging treatment, and electrodeposition extraction raffinate may return to electrodeposition containing circulation electrodeposition is carried out in Gallium solution, to realize the height of gallium
Effect, circulation and stress.
To sum up, copper indium gallium selenide waste material recovery method in the prior art that there are comprehensive recoveries is low, separation not exclusively,
The problems such as danger complicated for operation, high production cost, big environmental pollution, it would be highly desirable to it is useless to invent a kind of CIGS for being able to solve the above problem
Chip recovery method.
Summary of the invention
The technical problem to be solved in the present invention is to provide one kind recycled from copper indium gallium selenide (CIGS) refuse battery chip it is valuable
The method of metal.
This method comprises the following steps:
(1) stainless steel/glass substrate removing: copper indium gallium selenide refuse battery chip is removed, valuable metal layer is obtained；
(2) sulfating roasting: valuable metal layer obtained in step (1) is subjected to sulfating roasting and obtains impure selenium and slag；
(3) water logging: slag obtained in step (2) is subjected to water logging, obtains infusion and water logging slag；
(4) it removal of impurities/separation, crystallization: will obtain containing zinc, cadmium, aluminium after infusion removal of impurities/separation obtained in step (3)
Slag and filtrate one, the crystallization of filtrate one obtain copper sulphate；
(5) alkali soaks: water logging slag obtained in step (3) being carried out alkali leaching, obtains alkali immersion liquid and alkali phase analysis；
(6) acidleach: alkali phase analysis obtained in step (5) is subjected to acidleach again, obtains acid leaching residue and pickle liquor, acid leaching residue returns
It returns and carries out sulfating roasting in step (2)；
(7) it restores, purify: pickle liquor obtained in step (6) being restored to obtain thick indium, thick indium, which further purifies, to be contained
The slag and high purity indium of aluminium, tin；
(8) clean: the alkali immersion liquid removal of impurities that step (5) is obtained is isolated containing molybdenum, scruff, and filtrate two is obtained by filtration；
(9) it is electrolysed, purifies: the electrolysis of filtrate two obtained in step (8) being obtained into thick gallium, thick gallium purifies to obtain high purity gallium.
Wherein:
The copper indium gallium selenide refuse battery chip handled in step (1) containing Cu 15~25%, In 15~25%, Ga15~
25%, 40~60% Se, and a small amount of Zn, Cd, Mo, Al and Sn impurity.
Concentrated sulfuric acid amount added by sulfating roasting is 100~700kg/t- waste material in step (2), and maturing temperature is 200~700
DEG C, calcining time is 0.5~6h.
Water soaking temperature is 20~95 DEG C in step (3), and extraction time is 0.5~6h, and liquid-solid ratio is 1~10:1ml/g, is stirred
Mix 200~600rpm of revolving speed.
The NaOH or KOH that alkali leaching is 30%~80% with mass concentration in step (5) are leaching agent, in natural pressure condition
Lower alkali leaching, is not necessarily to impressed pressure.
Acidleach is inorganic acid with acid in step (6), includes sulfuric acid, hydrochloric acid, nitric acid etc..
It is iron powder, hydrazine hydrate, formaldehyde and both of which or three's arbitrary proportion that reducing agent used is restored in step (7)
Mixture；The method inclusion region smelting process of purifying crude indium, vacuum melting method, vacuum distillation method, Solid phase electrolysis method, segregation purification
Method, hydrogen plasma arc melting method.
The method of purification of thick gallium includes low-temperature electrolytic purification, area smelting refinement or both combined purifying in step (9).
The advantageous effects of the above technical solutions of the present invention are as follows:
This method comprehensive recovery is high, realizes the efficient selective leaching of copper, indium, gallium, selenium；Comprehensively consider in useless chip
The metal impurities of doping, separation are complete；It is easy to operate, it is environmental-friendly.
Detailed description of the invention
Fig. 1 is the method and process process of the invention that valuable metal is recycled from copper indium gallium selenide (CIGS) refuse battery chip
Figure.
Specific embodiment
To keep the technical problem to be solved in the present invention, technical solution and advantage clearer, below in conjunction with attached drawing and tool
Body embodiment is described in detail.
The present invention provides a kind of side that valuable metal is recycled from copper indium gallium selenide (CIGS) refuse battery chip for existing
Method.
As shown in Figure 1, this method comprises the following steps:
(1) stainless steel/glass substrate removing: copper indium gallium selenide refuse battery chip is removed, valuable metal layer is obtained；
(2) sulfating roasting: valuable metal layer obtained in step (1) is subjected to sulfating roasting and obtains impure selenium and slag；
(3) water logging: slag obtained in step (2) is subjected to water logging, obtains infusion and water logging slag；
(4) it removal of impurities/separation, crystallization: will obtain containing zinc, cadmium, aluminium after infusion removal of impurities/separation obtained in step (3)
Slag and filtrate one, the crystallization of filtrate one obtain copper sulphate；
(5) alkali soaks: water logging slag obtained in step (3) being carried out alkali leaching, obtains alkali immersion liquid and alkali phase analysis；
(6) acidleach: alkali phase analysis obtained in step (5) is subjected to acidleach again, obtains acid leaching residue and pickle liquor, acid leaching residue returns
It returns and carries out sulfating roasting in step (2)；
(7) it restores, purify: pickle liquor obtained in step (6) being restored to obtain thick indium, thick indium, which further purifies, to be contained
The slag and high purity indium of aluminium, tin；
(8) clean: the alkali immersion liquid removal of impurities that step (5) is obtained is isolated containing molybdenum, scruff, and filtrate two is obtained by filtration；
(9) it is electrolysed, purifies: the electrolysis of filtrate two obtained in step (8) being obtained into thick gallium, thick gallium purifies to obtain high purity gallium.
In order to more clearly from show technical solution provided by the present invention and generated technical effect, below with tool
The method provided by the present invention that valuable metal is recycled from CIGS refuse battery chip is described in detail in body embodiment.
Embodiment 1
As shown in Figure 1, the implementation steps of the embodiment include: that 50g CIGS refuse battery chip is taken to carry out substrate desquamation；It will
After the sulfuric acid of valuable metal layer 500kg/t- waste material after removing, sulfating roasting is carried out, maturing temperature is 200 DEG C, when roasting
Between be 3h, obtain impure selenium and slag；Slag carries out water logging, and water soaking temperature is 95 DEG C, extraction time 5h, liquid-solid ratio 10:1ml/g,
Speed of agitator 400rpm obtains infusion and water logging slag after water logging filtering；Infusion first removal of impurities/separation, filter out containing zinc, cadmium,
The slag of aluminium, filtrate recrystallize to obtain copper sulphate；Water logging slag is leaching agent in normal pressure item with the NaOH solution that mass concentration is 80%
Alkali soaks under part, and the extraction temperature of the dipped journey of alkali is 40 DEG C, extraction time 4.5h, and solid-to-liquid ratio is 1:10g/mL before leaching, and leaches
Alkali immersion liquid and alkali phase analysis are obtained by solid-liquor separation after complete；Alkali phase analysis is that leaching agent carries out acidleach with the concentrated sulfuric acid, acidleach process
Extraction temperature is 80 DEG C, extraction time 5h, and solid-to-liquid ratio is 1:1g/mL before leaching, and leaching obtains acid by solid-liquor separation after rolling
Immersion liquid and acid leaching residue, acid leaching residue return to sulfating roasting；Fe powder is added into pickle liquor can restore to obtain thick indium, and thick indium passes through again
Vacuum melting method purification can obtain being greater than containing aluminium, scruff and purity 99.9% high purity indium；Alkali immersion liquid removal of impurities may filter that out containing molybdenum,
The slag of tin, filtrate is electrolysed to obtain thick gallium, then area smelting refinement obtains high purity gallium.
Embodiment 2
The implementation steps of the embodiment include: that 100g CIGS refuse battery chip is taken to carry out substrate desquamation；By having after removing
After the sulfuric acid of 700kg/t- waste material is added in valence metal layer, sulfating roasting is carried out, maturing temperature is 700 DEG C, and calcining time is
0.5h obtains impure selenium and slag；Slag carries out water logging, and water soaking temperature is 20 DEG C, extraction time 5h, liquid-solid ratio 1:1ml/g, stirring
Revolving speed 200rpm obtains infusion and water logging slag after water logging filtering；Infusion first removal of impurities/separation is filtered out containing zinc, cadmium, aluminium
Slag, filtrate recrystallize to obtain copper sulphate；Water logging slag is the leaching of leaching agent alkali, the dipped journey of alkali with the KOH solution that mass concentration is 60%
Extraction temperature be 30 DEG C, extraction time 4.5h, leach before solid-to-liquid ratio be 1:5g/mL, leaching obtained after rolling by solid-liquor separation
To alkali immersion liquid and alkali phase analysis.Alkali phase analysis is that leaching agent carries out acidleach with a certain concentration hydrochloric acid, and the extraction temperature of acidleach process is 30
DEG C, extraction time 0.5h, solid-to-liquid ratio is 1:5g/mL before leaching, and leaching obtains pickle liquor and acidleach by solid-liquor separation after rolling
Slag, acid leaching residue return to sulfating roasting；Hydrazine hydrate solution is added into pickle liquor can restore to obtain thick indium, and thick indium passes through region again
Smelting process purification can obtain being greater than containing aluminium, scruff and purity 99.9% high purity indium；Alkali immersion liquid removal of impurities may filter that out containing molybdenum, tin
Slag, filtrate is electrolysed to obtain thick gallium, then low-temperature electrolytic purifies to obtain high purity gallium.
Embodiment 3
The implementation steps of the embodiment include: that 50g CIGS refuse battery chip is taken to carry out substrate desquamation；By having after removing
After the sulfuric acid of 100kg/t- waste material is added in valence metal layer, sulfating roasting is carried out, maturing temperature is 500 DEG C, and calcining time is
3.5h obtains impure selenium and slag；Slag carries out water logging, and water soaking temperature is 70 DEG C, extraction time 0.5h, liquid-solid ratio 5:1ml/g and stirs
Revolving speed 600rpm is mixed, obtains infusion and water logging slag after water logging filtering；Infusion first removal of impurities/separation, filters out containing zinc, cadmium, aluminium
Slag, filtrate recrystallizes to obtain copper sulphate；Water logging slag is leaching agent in condition of normal pressure with the NaOH solution that mass concentration is 50%
Lower alkali leaching, the extraction temperature of the dipped journey of alkali are 90 DEG C, extraction time 3h, and solid-to-liquid ratio is 1:5g/mL before leaching, and leaching is led to after rolling
It crosses solid-liquor separation and obtains alkali immersion liquid and alkali phase analysis.Alkali phase analysis is that leaching agent carries out acidleach, acidleach process with certain density nitric acid
Extraction temperature be 80 DEG C, extraction time 4h, leach before solid-to-liquid ratio be 1:1g/mL, leaching obtained after rolling by solid-liquor separation
Pickle liquor and acid leaching residue, acid leaching residue return to sulfating roasting；Formalin is added into pickle liquor can restore to obtain thick indium, thick indium
It can obtain being greater than containing aluminium, scruff and purity 99.9% high purity indium by segregation method of purification purification again；Alkali immersion liquid removal of impurities may filter that
Slag containing molybdenum, tin out, filtrate is electrolysed to obtain thick gallium, then area smelting refinement obtains high purity gallium.
Embodiment 4
The implementation steps of the embodiment include: that 100g CIGS refuse battery chip is taken to carry out substrate desquamation；By having after removing
After the sulfuric acid of 400kg/t- waste material is added in valence metal layer, sulfating roasting is carried out, maturing temperature is 600 DEG C, and calcining time is
2.5h obtains impure selenium and slag；Slag carries out water logging, and water soaking temperature is 50 DEG C, extraction time 6h, liquid-solid ratio 6:1ml/g, stirring
Revolving speed 400rpm obtains infusion and water logging slag after water logging filtering；Infusion first removal of impurities/separation is filtered out containing zinc, cadmium, aluminium
Slag, filtrate recrystallize to obtain copper sulphate；Water logging slag with the NaOH solution that mass concentration is 50% be leaching agent under an increased pressure
Alkali leaching, the extraction temperature of the dipped journey of alkali are 90 DEG C, extraction time 3h, and solid-to-liquid ratio is 1:5g/mL before leaching, and leaching passes through after rolling
Solid-liquor separation obtains alkali immersion liquid and alkali phase analysis.Alkali phase analysis is that leaching agent carries out acidleach, the extraction temperature of acidleach process with the concentrated sulfuric acid
It is 80 DEG C, extraction time 4h, solid-to-liquid ratio is 1:1g/mL before leaching, and leaching obtains pickle liquor and acid by solid-liquor separation after rolling
Phase analysis, acid leaching residue sulfating roasting；Fe powder is added into pickle liquor can restore to obtain thick indium, and thick indium passes through Solid phase electrolysis method again and mentions
The pure high purity indium for obtaining being greater than 99.9% containing aluminium, scruff and purity；Alkali immersion liquid removal of impurities may filter that out the slag containing molybdenum, tin, filtrate
Electrolysis obtains thick gallium, then low-temperature electrolytic purifies to obtain high purity gallium.
Embodiment 5
The implementation steps of the embodiment include: that 50g CIGS refuse battery chip is taken to carry out substrate desquamation；By having after removing
After the sulfuric acid of 300kg/t- waste material is added in valence metal layer, sulfating roasting is carried out, maturing temperature is 500 DEG C, and calcining time is
4.5h obtains impure selenium and slag；Slag carries out water logging, and water soaking temperature is 40 DEG C, extraction time 4h, liquid-solid ratio 3:1ml/g, stirring
Revolving speed 500rpm obtains infusion and water logging slag after water logging filtering；Infusion first removal of impurities/separation is filtered out containing zinc, cadmium, aluminium
Slag, filtrate recrystallize to obtain copper sulphate；Water logging slag is leaching agent alkali in atmospheric conditions with the KOH solution that mass concentration is 30%
Leaching, the extraction temperature of the dipped journey of alkali are 60 DEG C, extraction time 4h, and solid-to-liquid ratio is 1:1g/mL before leaching, and leaching passes through liquid after rolling
Gu isolated alkali immersion liquid and alkali phase analysis.Alkali phase analysis is that leaching agent carries out acidleach, acidleach with the concentrated nitric acid of certain mass concentration
The extraction temperature of journey is 90 DEG C, extraction time 3h, and solid-to-liquid ratio is 1:10g/mL before leaching, and leaching is obtained by solid-liquor separation after rolling
To pickle liquor and acid leaching residue, acid leaching residue returns to sulfating roasting；Hydrazine hydrate solution is added into pickle liquor can restore to obtain thick indium,
Thick indium passes through the purification of hydrogen plasma arc melting method again can obtain being greater than containing aluminium, scruff and purity 99.9% high purity indium；Alkali immersion liquid
Removal of impurities may filter that out the slag containing molybdenum, tin, and filtrate is electrolysed to obtain thick gallium, then area smelting refinement obtains high purity gallium.
The above is a preferred embodiment of the present invention, it is noted that for those skilled in the art
For, without departing from the principles of the present invention, several improvements and modifications can also be made, these improvements and modifications
It should be regarded as protection scope of the present invention.
Claims (5)
1. a kind of method for recycling valuable metal from copper indium gallium selenide refuse battery chip, characterized by the following steps:
(1) stainless steel/glass substrate removing: copper indium gallium selenide refuse battery chip is removed, valuable metal layer is obtained；
(2) sulfating roasting: valuable metal layer obtained in step (1) is subjected to sulfating roasting and obtains impure selenium and slag；
(3) water logging: slag obtained in step (2) is subjected to water logging, obtains infusion and water logging slag；
(4) removal of impurities/separation, crystallization: by after infusion removal of impurities/separation obtained in step (3) obtain containing zinc, cadmium, aluminium slag and
Filtrate one, the crystallization of filtrate one obtain copper sulphate；
(5) alkali soaks: water logging slag obtained in step (3) being carried out alkali leaching, obtains alkali immersion liquid and alkali phase analysis；
(6) acidleach: carrying out acidleach for alkali phase analysis obtained in step (5) again, obtains acid leaching residue and pickle liquor, and acid leaching residue returns to step
Suddenly sulfating roasting is carried out in (2)；
(7) restore, purify: pickle liquor obtained in step (6) is restored to obtain thick indium, thick indium further purify obtain containing aluminium,
The slag and high purity indium of tin；
(8) clean: the alkali immersion liquid removal of impurities that step (5) is obtained is isolated containing molybdenum, scruff, and filtrate two is obtained by filtration；
(9) it is electrolysed, purifies: the electrolysis of filtrate two obtained in step (8) being obtained into thick gallium, thick gallium purifies to obtain high purity gallium；
The copper indium gallium selenide refuse battery chip handled in the step (1) containing Cu 15~25%, In 15~25%, Ga 15~
25%, 40~60% Se；
Water soaking temperature is 20~95 DEG C in the step (3), and extraction time is 0.5~6h, and liquid-solid ratio is 1~10: 1mL/g, is stirred
Mix 200~600rpm of revolving speed；
The NaOH or KOH that alkali leaching is 30%~80% with mass concentration in the step (5) are leaching agent.
2. the method according to claim 1 for recycling valuable metal from copper indium gallium selenide refuse battery chip, it is characterised in that:
Concentrated sulfuric acid amount added by sulfating roasting is 100~700kg/t- waste material in the step (2), and maturing temperature is 200~700 DEG C,
Calcining time is 0.5~6h.
3. the method according to claim 1 for recycling valuable metal from copper indium gallium selenide refuse battery chip, it is characterised in that:
Acidleach is inorganic acid with acid in the step (6).
4. the method according to claim 1 for recycling valuable metal from copper indium gallium selenide refuse battery chip, it is characterised in that:
The mixing that reducing agent used is iron powder, hydrazine hydrate, formaldehyde and both of which or three's arbitrary proportion is restored in the step (7)
Object；The method inclusion region smelting process of purifying crude indium, vacuum melting method, vacuum distillation method, Solid phase electrolysis method, segregation method of purification,
Hydrogen plasma arc melting method.
5. the method according to claim 1 for recycling valuable metal from copper indium gallium selenide refuse battery chip, it is characterised in that:
The method of purification of thick gallium includes low-temperature electrolytic purification, area smelting refinement or both combined purifying in the step (9).
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|---|---|---|---|---|
| US8834818B2 (en) * | 2010-11-26 | 2014-09-16 | Molycorp Minerals Canada Ulc | Treatment of indium gallium alloys and recovery of indium and gallium |
| TW201540844A (en) * | 2014-04-28 | 2015-11-01 | Univ Nat Cheng Kung | Recovery method by heat-treating copper-indium-gallium-selenium residual target material |
| CN105886767A (en) * | 2014-12-16 | 2016-08-24 | 汉能新材料科技有限公司 | Recycling method for copper indium gallium selenide (CIGS) waste |
| CN106987718A (en) * | 2016-01-21 | 2017-07-28 | 汉能新材料科技有限公司 | A kind of recovery method of CIGS material |
| CN106987719A (en) * | 2016-01-21 | 2017-07-28 | 汉能新材料科技有限公司 | A kind of recovery method of CIGS material |
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2018
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| US8834818B2 (en) * | 2010-11-26 | 2014-09-16 | Molycorp Minerals Canada Ulc | Treatment of indium gallium alloys and recovery of indium and gallium |
| TW201540844A (en) * | 2014-04-28 | 2015-11-01 | Univ Nat Cheng Kung | Recovery method by heat-treating copper-indium-gallium-selenium residual target material |
| CN105886767A (en) * | 2014-12-16 | 2016-08-24 | 汉能新材料科技有限公司 | Recycling method for copper indium gallium selenide (CIGS) waste |
| CN106987718A (en) * | 2016-01-21 | 2017-07-28 | 汉能新材料科技有限公司 | A kind of recovery method of CIGS material |
| CN106987719A (en) * | 2016-01-21 | 2017-07-28 | 汉能新材料科技有限公司 | A kind of recovery method of CIGS material |
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