CN108715933A - The method of Treatment of Copper indium gallium selenium waste material - Google Patents
The method of Treatment of Copper indium gallium selenium waste material Download PDFInfo
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- CN108715933A CN108715933A CN201810507096.9A CN201810507096A CN108715933A CN 108715933 A CN108715933 A CN 108715933A CN 201810507096 A CN201810507096 A CN 201810507096A CN 108715933 A CN108715933 A CN 108715933A
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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
- C22B7/007—Wet processes by acid leaching
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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
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
- C22B3/08—Sulfuric acid, other sulfurated acids or salts thereof
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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
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/22—Treatment or purification of solutions, e.g. obtained by leaching by physical processes, e.g. by filtration, by magnetic means, or by thermal decomposition
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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
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
- C22B3/46—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes by substitution, e.g. by cementation
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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
- C25C1/12—Electrolytic production, recovery or refining of metals by electrolysis of solutions of copper
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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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The invention discloses a kind of methods of Treatment of Copper indium gallium selenium waste material, and this approach includes the following steps：1) copper indium gallium selenide waste material will be contained and carry out pre-treatment, obtain impure selenium and the first mixed liquor containing copper ion, indium ion, gallium ion；2) selective absorption copper ion desorbs the copper ion of selective absorption, copper electrowinning；3) indium ion of selective absorption is desorbed, thick indium is obtained by zinc dust precipitation founding by selective absorption indium ion, and thick indium is carried out electrolytic deposition indium；4) alkalization liquid making generates gallic acid sodium, electrolytic deposition gallium.Present invention introduces the different ion exchange resin having to metal compared with high separation capacity, separating-purifying is carried out into the copper ion of solution, indium ion and gallium ion after pre-treatment to waste material containing copper indium gallium selenide, high-purity copper, indium, the gallium metal product that the purity separated is mass percent 99.99% are electrolysed by subsequent.
Description
Technical field
The invention belongs to technical field of solar batteries, and in particular to a kind of method of Treatment of Copper indium gallium selenium waste material.
Background technology
Copper-indium-galliun-selenium film solar cell is referred to as the since theoretical efficiency is high, material consumption is few, prepares that low energy consumption etc.
Two generation solar battery technologies.The hull cell especially prepared on flexible substrates, have it is rollable fold, not fear of throwing touch,
It is light-weight, dim light performance is good etc., and advantages, future have a extensive future, be thin-film solar cells research and development recent years, scale
The maximum hot spot of production, application.The production method of copper-indium-galliun-selenium film solar cell has vacuum splashing and plating method, the way of distillation and non-real
Empty rubbing method, can all generate some waste materials containing copper indium gallium selenide in its manufacturing process of the above several method, in waste material containing copper,
Indium, gallium and selenium etc. is valuable and rare metal.To be conducive to the sustainable utilization of the rare metals such as indium, gallium and selenium and heavy metal copper, need
It is detached and is separately recovered, further recycled with facilitating, to ensure copper-indium-galliun-selenium film solar cell
The sustainable development of material.
In the recovery method of existing copper indium gallium selenide waste material, after copper indium gallium selenide is usually dissolved into solution, pass through displacement or water
The mode of solution detaches copper, indium and gallium, and since copper, indium, gallium dissolving are all higher into concentration after solution, displacement and hydrolysis all may
Causing copper, indium and gallium separation to be not thorough causes subsequently obtain the higher product of purity.
Invention content
In order to solve the higher copper of concentration that the prior art is segregated by way of replacing or hydrolyzing in solution from
The technical issues of son, indium ion and gallium ion, causing separation to be not thorough leads to subsequently obtain purity higher product, this hair
It is bright that a kind of method of Treatment of Copper indium gallium selenium waste material is provided.
Technical solution is to provide a kind of method of Treatment of Copper indium gallium selenium waste material used by solving present invention problem,
Include the following steps：
1) will contain copper indium gallium selenide waste material carry out pre-treatment, obtain impure selenium and containing copper ion, indium ion, gallium ion first
Mixed liquor；When copper ion, indium ion, gallium ion coexist in the first mixed liquor, the first chelating resin preferably adsorbs copper ion.
2) by the first mixed liquor carry out selective absorption copper ion, obtain the second mixed liquor, by the copper of selective absorption from
Subsolution is inhaled, and the first stripping liquid is obtained, and the first stripping liquid is carried out copper electrowinning；It is mixed when indium ion, gallium ion coexist in second
It closes in liquid, the second chelating resin preferably adsorbs indium ion.
3) by the second mixed liquor carry out selective absorption indium ion, obtain third mixed liquor, by the indium of selective absorption from
Subsolution is inhaled, and obtains the second stripping liquid, the second stripping liquid is obtained thick indium by zinc dust precipitation founding, and thick indium is carried out electrolytic deposition
Indium；Wherein, thick indium purity is less than mass percent 99.99%, and the indium of thick indium electrolytic deposition is high purity indium, and the purity of high purity indium is not
Less than mass percent 99.99%.
4) it will be passed through aqueous slkali into third mixing thing liquid and carries out alkalization liquid making generation gallic acid sodium, and obtain alkalization liquid making, it will
Liquid making of alkalizing carries out electrolytic deposition gallium.
Optionally, the step 1) specifically includes following steps：
M) copper indium gallium selenide waste material will be contained to mix with sulfuric acid, hydrogen peroxide is passed through after heating and is leached, is detached after leaching
Go out residue, obtains leachate；
N) reducing agent of selenium can be restored by, which being added to leachate, is restored, obtain impure selenium and containing copper ion, indium ion,
First mixed liquor of gallium ion.
Optionally, copper indium gallium selenide waste material will be contained in the step m) to mix with sulfuric acid, control ph 1-1.8, heated up
Hydrogen peroxide is passed through after to 80~95 DEG C to be leached.
Optionally, reducing agent is at least one of sulfur dioxide, sodium sulfite, thiocarbamide, urea.
Optionally, selective absorption copper ion and the condition of copper ion desorption are in the step 2)：By the first mixing
Liquid adjusts pH value to 0.5~1, is transferred to the first adsorption column selective absorption copper ion equipped with the first chelating resin, passes through first
The second mixed liquor is obtained after adsorption column, and the copper of the first adsorption column absorption is desorbed using the sulfuric acid solution of 20~25% mass percents
Ion obtains the first stripping liquid.
Optionally, the first chelating resin is carboxylic acid type chelating resin or phosphatic type chelating resin.
Optionally, the condition of copper electrowinning is in the step 2)：By the first stripping liquid decomposition voltage be 1~
3V, current density are 200~300A/m2, electrolytic deposition 12~72 hours, copper electrowinning.
Optionally, selective absorption indium ion and the condition of indium ion desorption are in the step 3)：By the second mixing
Liquid adjusts pH value to 1~3, is transferred to the second adsorption column selective absorption indium ion equipped with the second chelating resin, is inhaled by second
Third mixed liquor is obtained after attached column, using 20~25% mass percents sulfuric acid solution desorb the second adsorption column absorption indium from
Son obtains the second stripping liquid, and the second stripping liquid is obtained thick indium by zinc dust precipitation founding.
Optionally, the second chelating resin is carboxylic acid type chelating resin or phosphatic type chelating resin.
Optionally, the condition of electrolytic deposition indium is in the step 3)：By thick indium decomposition voltage be 1~5V, electric current
Density is 200~3000A/m2, electrolytic deposition indium.
Optionally, the step 4) is specially：By third mixed liquor be passed through aqueous slkali carry out alkalization liquid making to pH value extremely
10~14, the liquid making that will alkalize is 1~5V in decomposition voltage, and current density is 200~3000A/m2, electrolytic deposition gallium.
Optionally, further include before the step 1) step i) will contain copper indium gallium selenide waste material be crushed to granularity be 60~
100 mesh.
Present invention introduces the different ion exchange resin having to metal compared with high separation capacity, to containing copper indium gallium selenide waste material warp
It crosses after pre-treatment and enters the copper ion, indium ion and gallium ion of solution and carry out separating-purifying, detached by subsequent electrolysis
The purity opened is high-purity copper, indium, the gallium metal product of mass percent 99.99%.It is higher using having to metal in the present invention
The different ion exchange resin of separating capacity are detached, not only can be individually separated by copper ion, indium ion, gallium ion
It opens, and so that metallic copper, indium, gallium are completely separated out after electrolysis, solves in the prior art that displacement or hydrolysis can
Copper, indium and gallium separation can be caused to be not thorough the technical issues of leading to subsequently obtain purity higher product.
Specific implementation mode
To make those skilled in the art more fully understand technical scheme of the present invention, With reference to embodiment to this
Invention is described in further detail.
Embodiment 1
The present embodiment provides a kind of methods of Treatment of Copper indium gallium selenium waste material, include the following steps：
1) 5kg waste materials containing copper indium gallium selenide are mixed, control ph 1 with 20L sulfuric acid, theoretical amount is passed through after 90 DEG C of heating
1.2 times of hydrogen peroxide are leached, and residue is isolated after leaching, obtains leachate.
2) to leachate be added 1.5 times of theoretical amounts reducing agent sulfur dioxide restored, obtain impure selenium and containing copper from
First mixed liquor of son, indium ion, gallium ion.
3) the first mixed liquor is adjusted into pH value to 0.5, is transferred to the first adsorption column equipped with the first chelating resin and selectively inhales
Attached copper ion, 2R-H+Cu2+→2R-Cu+2H+, indium ion, gallium ion pass through the first absorption as solution is by the first adsorption column
The second mixed liquor is obtained after column, and the copper ion of the first adsorption column absorption, 2R- are desorbed using the sulfuric acid solution of 25% mass percent
Cu+2H+→2R-H+Cu2+, obtain the first stripping liquid, wherein the first chelating resin is carboxylic acid type chelating resin, carboxylic acid type chelating
Resin is best to the selectivity of copper and cheap.When copper ion, indium ion, gallium ion coexist in the first mixed liquor, first
Chelating resin preferably adsorbs copper ion.First stripping liquid is passed through copper electrolysis cells and carries out electrolytic deposition, the anode of electrolytic cell uses
Alloy lead anode, cathode use stainless steel cathode, and the decomposition voltage of copper electrolysis cells is 3V, current density 200A/m2, it is heavy to be electrolysed
Product 12 hours, cell reaction is as follows：Cathode：Cu2++ 2e=Cu；99.95% Cu-CATH-1 product is obtained from cathodic disbonding.
Residual electrolyte returns to desorption copper ion operation, for desorbing the copper ion of the first adsorption column absorption.
4) the second mixed liquor is adjusted into pH value to 1, is transferred to the second adsorption column selective absorption equipped with the second chelating resin
Indium ion, 3R-H+In3+→R-In+3H+, gallium ion is as solution is by the second adsorption column, by obtaining after the second adsorption column
Three mixed liquors desorb the indium ion of the second adsorption column absorption, 3R-In+3H using the sulfuric acid solution of 25% mass percent+→
3R-H+In3+, the second stripping liquid is obtained, the second stripping liquid is obtained into thick indium by zinc dust precipitation founding, Wherein, the second chelating resin is phosphatic type chelating resin.When indium ion, gallium ion coexist in
In two mixed liquors, the second chelating resin preferably adsorbs indium ion.Thick indium is passed through indium electrolytic cell and carries out electrolytic deposition, in electrolysis electricity
Pressure is 3V, current density 300A/m2, electrolytic deposition indium,
Anode：In=In3++3e；
Cathode：In3++ 3e=In.
5) third mixed liquor is passed through sodium hydroxide solution and carries out alkalization liquid making to pH value to 14, generate NaGaO2, by alkali
Change liquid making and be passed through gallium electrolytic cell progress electrolytic deposition, is 2V, current density 1000A/m in decomposition voltage2, electrolytic deposition gallium,
Anode：Ga=Ga3++3e；
Cathode：Ga3++ 3e=Ga.
The rate of recovery of the method for Treatment of Copper indium gallium selenium waste material in the present embodiment, copper and indium gallium is more than mass percent
99.5%, the rate of recovery of selenium is more than 99%.
Embodiment 2
The present embodiment provides a kind of methods of Treatment of Copper indium gallium selenium waste material, include the following steps：
1) 5kg waste materials containing copper indium gallium selenide are mixed, control ph 1.8 with 20L sulfuric acid, theoretical amount is passed through after 85 DEG C of heating
1.2 times of hydrogen peroxide are leached, and residue is isolated after leaching, obtains leachate.
2) to leachate be added 1.5 times of theoretical amounts reducing agent sulfur dioxide restored, obtain impure selenium and containing copper from
First mixed liquor of son, indium ion, gallium ion.
3) the first mixed liquor is adjusted into pH value to 1, is transferred to the first adsorption column selective absorption equipped with the first chelating resin
Copper ion, 2R-H+Cu2+→2R-Cu+2H+, indium ion, gallium ion pass through the first adsorption column as solution is by the first adsorption column
After obtain the second mixed liquor, use 20% mass percent sulfuric acid solution desorb the first adsorption column absorption copper ion, 2R-Cu
+2H+→2R-H+Cu2+, obtain the first stripping liquid, wherein the first chelating resin is phosphatic type chelating resin.By the first stripping liquid
It is passed through copper electrolysis cells and carries out electrolytic deposition, the anode of electrolytic cell uses alloy lead anode, cathode to use stainless steel cathode, cupric electrolysis
The decomposition voltage of slot is 1V, current density 250A/m2, electrolytic deposition 40 hours, cell reaction is as follows：Cathode：Cu2++ 2e=
Cu obtains 99.95% Cu-CATH-1 product from cathodic disbonding.Residual electrolyte returns to desorption copper ion operation, for desorbing
The copper ion of first adsorption column absorption.
4) the second mixed liquor is adjusted into pH value to 2, is transferred to the second adsorption column selective absorption equipped with the second chelating resin
Indium ion, 3R-H+In3+→R-In+3H+, gallium ion is as solution is by the second adsorption column, by obtaining after the second adsorption column
Three mixed liquors desorb the indium ion of the second adsorption column absorption, 3R-In+3H using the sulfuric acid solution of 30% mass percent+→
3R-H+In3+, the second stripping liquid is obtained, the second stripping liquid is obtained into thick indium by zinc dust precipitation founding, Wherein, the second chelating resin is phosphatic type chelating resin.Thick indium is passed through indium electrolytic cell to carry out
Electrolytic deposition is 1V, current density 200A/m in decomposition voltage2, electrolytic deposition indium,
Anode：In=In3++3e；
Cathode：In3++ 3e=In.
5) third mixed liquor is passed through sodium hydroxide solution and carries out alkalization liquid making to pH value to 10, generate NaGaO2, by alkali
Change liquid making and be passed through gallium electrolytic cell progress electrolytic deposition, is 1V, current density 200A/m in decomposition voltage2, electrolytic deposition gallium,
Anode：Ga=Ga3++3e；
Cathode：Ga3++ 3e=Ga.
Embodiment 3
The present embodiment provides a kind of methods of Treatment of Copper indium gallium selenium waste material, include the following steps：
1) 5kg waste materials containing copper indium gallium selenide are mixed, control ph 1.2 with 20L sulfuric acid, theoretical amount is passed through after 95 DEG C of heating
1.2 times of hydrogen peroxide are leached, and residue is isolated after leaching, obtains leachate.
2) to leachate be added 1.5 times of theoretical amounts reducing agent sulfur dioxide restored, obtain impure selenium and containing copper from
First mixed liquor of son, indium ion, gallium ion.
3) the first mixed liquor is adjusted into pH value to 0.8, is transferred to the first adsorption column equipped with the first chelating resin and selectively inhales
Attached copper ion, 2R-H+Cu2+→2R-Cu+2H+, indium ion, gallium ion pass through the first absorption as solution is by the first adsorption column
The second mixed liquor is obtained after column, and the copper ion of the first adsorption column absorption, 2R- are desorbed using the sulfuric acid solution of 22% mass percent
Cu+2H+→2R-H+Cu2+, obtain the first stripping liquid, wherein the first chelating resin is carboxylic acid type chelating resin.By the first desorption
Liquid is passed through copper electrolysis cells and carries out electrolytic deposition, and the anode of electrolytic cell uses alloy lead anode, cathode to use stainless steel cathode, copper electricity
The decomposition voltage for solving slot is 2V, current density 300A/m2, electrolytic deposition 72 hours, cell reaction is as follows：Cathode：Cu2++2e
=Cu；99.95% Cu-CATH-1 product is obtained from cathodic disbonding.Residual electrolyte returns to desorption copper ion operation, for solving
Inhale the copper ion of the first adsorption column absorption.
4) the second mixed liquor is adjusted into pH value to 3, is transferred to the second adsorption column selective absorption equipped with the second chelating resin
Indium ion, 3R-H+In3+→R-In+3H+, gallium ion is as solution is by the second adsorption column, by obtaining after the second adsorption column
Three mixed liquors desorb the indium ion of the second adsorption column absorption, 3R-In+3H using the sulfuric acid solution of 20% mass percent+→
3R-H+In3+, the second stripping liquid is obtained, the second stripping liquid is obtained into thick indium by zinc dust precipitation founding, Wherein, the second chelating resin is phosphatic type chelating resin.Thick indium is passed through indium electrolytic cell to carry out
Electrolytic deposition is 5V, current density 250A/m in decomposition voltage2, electrolytic deposition indium,
Anode：In=In3++3e；
Cathode：In3++ 3e=In.
5) third mixed liquor is passed through sodium hydroxide solution and carries out alkalization liquid making to pH value to 12, generate NaGaO2, by alkali
Change liquid making and be passed through gallium electrolytic cell progress electrolytic deposition, is 3V, current density 3000A/m in decomposition voltage2, electrolytic deposition gallium,
Anode：Ga=Ga3++3e；
Cathode：Ga3++ 3e=Ga.
Embodiment 4
The present embodiment provides a kind of methods of Treatment of Copper indium gallium selenium waste material, include the following steps：
1) 5kg waste materials containing copper indium gallium selenide are mixed, control ph 1.5 with 20L sulfuric acid, theoretical amount is passed through after 80 DEG C of heating
1.2 times of hydrogen peroxide are leached, and residue is isolated after leaching, obtains leachate.
2) to leachate be added 1.5 times of theoretical amounts reducing agent sulfur dioxide restored, obtain impure selenium and containing copper from
First mixed liquor of son, indium ion, gallium ion.
3) the first mixed liquor is adjusted into pH value to 0.6, is transferred to the first adsorption column equipped with the first chelating resin and selectively inhales
Attached copper ion, 2R-H+Cu2+→2R-Cu+2H+, indium ion, gallium ion pass through the first absorption as solution is by the first adsorption column
The second mixed liquor is obtained after column, and the copper ion of the first adsorption column absorption, 2R- are desorbed using the sulfuric acid solution of 23% mass percent
Cu+2H+→2R-H+Cu2+, obtain the first stripping liquid, wherein the first chelating resin is phosphatic type chelating resin.By the first desorption
Liquid is passed through copper electrolysis cells and carries out electrolytic deposition, and the anode of electrolytic cell uses alloy lead anode, cathode to use stainless steel cathode, copper electricity
The decomposition voltage for solving slot is 2.5V, current density 280A/m2, electrolytic deposition 60 hours, cell reaction is as follows：Cathode：Cu2++
2e=Cu；99.95% Cu-CATH-1 product is obtained from cathodic disbonding.Residual electrolyte returns to desorption copper ion operation, is used for
Desorb the copper ion of the first adsorption column absorption.
4) the second mixed liquor is adjusted into pH value to 2.5, is transferred to the second adsorption column equipped with the second chelating resin and selectively inhales
Attached indium ion, 3R-H+In3+→R-In+3H+, gallium ion is as solution is by the second adsorption column, by being obtained after the second adsorption column
Third mixed liquor desorbs the indium ion of the second adsorption column absorption, 3R-In+3H using the sulfuric acid solution of 28% mass percent+→
3R-H+In3+, the second stripping liquid is obtained, the second stripping liquid is obtained into thick indium by zinc dust precipitation founding, Wherein, the second chelating resin is carboxylic acid type chelating resin.Thick indium is passed through indium electrolytic cell to carry out
Electrolytic deposition is 4V, current density 280A/m in decomposition voltage2, electrolytic deposition indium,
Anode：In=In3++3e；
Cathode：In3++ 3e=In.
5) third mixed liquor is passed through sodium hydroxide solution and carries out alkalization liquid making to pH value to 11, generate NaGaO2, by alkali
Change liquid making and be passed through gallium electrolytic cell progress electrolytic deposition, is 5V, current density 2000A/m in decomposition voltage2, electrolytic deposition gallium,
Anode：Ga=Ga3++3e；
Cathode：Ga3++ 3e=Ga.
The rate of recovery of the method for Treatment of Copper indium gallium selenium waste material in the present embodiment, copper and indium gallium is more than mass percent
99.5%, the rate of recovery of selenium is more than 99%.
It is understood that the principle that embodiment of above is intended to be merely illustrative of the present and the exemplary implementation that uses
Mode, however the present invention is not limited thereto.For those skilled in the art, in the essence for not departing from the present invention
In the case of refreshing and essence, various changes and modifications can be made therein, these variations and modifications are also considered as protection scope of the present invention.
Claims (10)
1. a kind of method of Treatment of Copper indium gallium selenium waste material, which is characterized in that include the following steps：
1) copper indium gallium selenide waste material will be contained and carry out pre-treatment, obtain impure selenium and the first mixing containing copper ion, indium ion, gallium ion
Liquid；
2) the first mixed liquor is subjected to selective absorption copper ion, the second mixed liquor is obtained, by the copper ion solution of selective absorption
It inhales, obtains the first stripping liquid, the first stripping liquid is subjected to copper electrowinning；
3) the second mixed liquor is subjected to selective absorption indium ion, third mixed liquor is obtained, by the indium ion solution of selective absorption
It inhales, obtains the second stripping liquid, the second stripping liquid is obtained into thick indium by zinc dust precipitation founding, thick indium is subjected to electrolytic deposition indium；
4) it will be passed through aqueous slkali into third mixing thing liquid and carries out alkalization liquid making generation gallic acid sodium, and obtain alkalization liquid making, will alkalize
Liquid making carries out electrolytic deposition gallium.
2. the method for Treatment of Copper indium gallium selenium waste material according to claim 1, which is characterized in that the step 1) is specifically wrapped
Include following steps：
M) copper indium gallium selenide waste material will be contained to mix with sulfuric acid, hydrogen peroxide is passed through after heating and is leached, isolated after leaching residual
Slag obtains leachate；
N) reducing agent of selenium can be restored by, which being added to leachate, is restored, obtain impure selenium and containing copper ion, indium ion, gallium from
First mixed liquor of son.
3. the method for Treatment of Copper indium gallium selenium waste material according to claim 2, which is characterized in that will contain in the step m)
Copper indium gallium selenide waste material is mixed with sulfuric acid, control ph 1-1.8, and being passed through hydrogen peroxide after being warming up to 80~95 DEG C is leached.
4. the method for the Treatment of Copper indium gallium selenium waste material according to claims 1 to 3 any one, which is characterized in that described
Selective absorption copper ion and the condition of copper ion desorption are in step 2)：First mixed liquor is adjusted into pH value to 0.5~1, is turned
Enter the first adsorption column selective absorption copper ion of the first chelating resin is housed, by obtaining the second mixing after the first adsorption column
Liquid is desorbed the copper ion of the first adsorption column absorption using the sulfuric acid solution of 20~25% mass percents, obtains the first stripping liquid.
5. the method for Treatment of Copper indium gallium selenium waste material according to claim 4, which is characterized in that the first chelating resin is carboxylic
Acid type chelating resin or phosphatic type chelating resin.
6. the method for the Treatment of Copper indium gallium selenium waste material according to claims 1 to 3 any one, which is characterized in that described
The condition of copper electrowinning is in step 2)：By the first stripping liquid decomposition voltage be 1~3V, current density be 200~300A/
m2, copper electrowinning.
7. the method for the Treatment of Copper indium gallium selenium waste material according to claims 1 to 3 any one, which is characterized in that described
Selective absorption indium ion and the condition of indium ion desorption are in step 3)：Second mixed liquor is adjusted into pH value to 1~3, is transferred to
The second adsorption column selective absorption indium ion equipped with the second chelating resin, by obtaining third mixed liquor after the second adsorption column,
The indium ion that the absorption of the second adsorption column is desorbed using the sulfuric acid solution of 20~25% mass percents, obtains the second stripping liquid, will
Second stripping liquid obtains thick indium by zinc dust precipitation founding.
8. the method for Treatment of Copper indium gallium selenium waste material according to claim 7, which is characterized in that the second chelating resin is carboxylic
Acid type chelating resin or phosphatic type chelating resin.
9. the method for the Treatment of Copper indium gallium selenium waste material according to claims 1 to 3 any one, which is characterized in that described
The condition of electrolytic deposition indium is in step 3)：By thick indium decomposition voltage be 1~5V, current density be 200~3000A/m2, electricity
Solution deposition indium.
10. the method for the Treatment of Copper indium gallium selenium waste material according to claims 1 to 3 any one, which is characterized in that described
Step 4) is specially：Third mixed liquor is passed through aqueous slkali and carries out alkalization liquid making to pH value to 10~14, by alkalization liquid making in electricity
Solution voltage is 1~5V, and current density is 200~3000A/m2, electrolytic deposition gallium.
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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 |
| 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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