US20200277685A1 - Recovery method for copper-indium-gallium-selenium material - Google Patents
Recovery method for copper-indium-gallium-selenium material Download PDFInfo
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- US20200277685A1 US20200277685A1 US16/068,072 US201616068072A US2020277685A1 US 20200277685 A1 US20200277685 A1 US 20200277685A1 US 201616068072 A US201616068072 A US 201616068072A US 2020277685 A1 US2020277685 A1 US 2020277685A1
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- Prior art keywords
- solution
- copper
- gallium selenide
- indium gallium
- copper indium
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- 238000000034 method Methods 0.000 title claims abstract description 42
- 239000000463 material Substances 0.000 title claims abstract description 29
- 238000011084 recovery Methods 0.000 title abstract description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 40
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052802 copper Inorganic materials 0.000 claims abstract description 26
- 239000010949 copper Substances 0.000 claims abstract description 26
- 229910052738 indium Inorganic materials 0.000 claims abstract description 26
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims abstract description 26
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052733 gallium Inorganic materials 0.000 claims abstract description 22
- 229910052751 metal Inorganic materials 0.000 claims abstract description 18
- 239000002184 metal Substances 0.000 claims abstract description 18
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims abstract description 18
- 238000000605 extraction Methods 0.000 claims abstract description 17
- 238000002386 leaching Methods 0.000 claims abstract description 16
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052711 selenium Inorganic materials 0.000 claims abstract description 14
- 239000011669 selenium Substances 0.000 claims abstract description 14
- 235000010265 sodium sulphite Nutrition 0.000 claims abstract description 9
- KTSFMFGEAAANTF-UHFFFAOYSA-N [Cu].[Se].[Se].[In] Chemical compound [Cu].[Se].[Se].[In] KTSFMFGEAAANTF-UHFFFAOYSA-N 0.000 claims description 49
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 20
- 238000005868 electrolysis reaction Methods 0.000 claims description 20
- IGUXCTSQIGAGSV-UHFFFAOYSA-K indium(iii) hydroxide Chemical group [OH-].[OH-].[OH-].[In+3] IGUXCTSQIGAGSV-UHFFFAOYSA-K 0.000 claims description 11
- FZHLWVUAICIIPW-UHFFFAOYSA-M sodium gallate Chemical compound [Na+].OC1=CC(C([O-])=O)=CC(O)=C1O FZHLWVUAICIIPW-UHFFFAOYSA-M 0.000 claims description 11
- 239000002699 waste material Substances 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 9
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims description 8
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 7
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 7
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 6
- 239000003792 electrolyte Substances 0.000 claims description 6
- 229910052725 zinc Inorganic materials 0.000 claims description 6
- 239000011701 zinc Substances 0.000 claims description 6
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 5
- 229910001431 copper ion Inorganic materials 0.000 claims description 5
- 239000002244 precipitate Substances 0.000 claims description 5
- QYHFIVBSNOWOCQ-UHFFFAOYSA-N selenic acid Chemical compound O[Se](O)(=O)=O QYHFIVBSNOWOCQ-UHFFFAOYSA-N 0.000 claims description 5
- 239000006228 supernatant Substances 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 238000000498 ball milling Methods 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 239000004411 aluminium Substances 0.000 claims 1
- 229910052782 aluminium Inorganic materials 0.000 claims 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims 1
- 239000002253 acid Substances 0.000 abstract description 4
- 238000005273 aeration Methods 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 4
- 238000000926 separation method Methods 0.000 abstract description 4
- 239000003513 alkali Substances 0.000 abstract description 3
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000010248 power generation Methods 0.000 description 6
- 239000010409 thin film Substances 0.000 description 6
- 230000002045 lasting effect Effects 0.000 description 4
- 229910021419 crystalline silicon Inorganic materials 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- 238000010420 art technique Methods 0.000 description 1
- DVRDHUBQLOKMHZ-UHFFFAOYSA-N chalcopyrite Chemical group [S-2].[S-2].[Fe+2].[Cu+2] DVRDHUBQLOKMHZ-UHFFFAOYSA-N 0.000 description 1
- 238000000658 coextraction Methods 0.000 description 1
- HVMJUDPAXRRVQO-UHFFFAOYSA-N copper indium Chemical compound [Cu].[In] HVMJUDPAXRRVQO-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- QNWMNMIVDYETIG-UHFFFAOYSA-N gallium(ii) selenide Chemical compound [Se]=[Ga] QNWMNMIVDYETIG-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 238000001429 visible spectrum Methods 0.000 description 1
- 235000014692 zinc oxide Nutrition 0.000 description 1
- RNWHGQJWIACOKP-UHFFFAOYSA-N zinc;oxygen(2-) Chemical class [O-2].[Zn+2] RNWHGQJWIACOKP-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
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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
-
- 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
-
- 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
-
- 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
-
- 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
- C22B15/0067—Leaching or slurrying with acids or salts thereof
- C22B15/0071—Leaching or slurrying with acids or salts thereof containing sulfur
-
- 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
- C22B15/0084—Treating solutions
- C22B15/0089—Treating solutions by chemical methods
-
- 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
- C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
- C22B3/30—Oximes
-
- 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
-
- 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
-
- 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
Definitions
- the present invention relates to a method for recovering copper indium gallium selenide photovoltaic components, in particular to a method for recovering copper indium gallium selenide materials.
- Copper indium gallium selenide thin-film solar cells are favored by the market due to their many advantages. They have been the most interest in R&D, scaled production and application of thin-film solar cells in recent years.
- the absorption layer of copper indium gallium selenide solar cells has a chalcopyrite structure composed of four elements, i.e. copper, indium, gallium and selenium, in an optimum ratio.
- the absorbable spectrum has a broad wavelength range. In addition to the visible spectrum which can be absorbed by amorphous silicon solar cells, the spectrum can also cover the near-infrared region with a wavelength between 700 and 2000 nm, which means the longest duration in a day for power generation.
- the total power generation provided by copper indium gallium selenide thin-film solar cells per day is over 20% more than that provided by crystalline silicon solar cells of the same wattage level.
- Crystalline silicon cells are inherently characterized by light induced degradation: after a prolonged exposure to sunlight, their power generation performance will gradually diminish.
- copper indium gallium selenide solar cells are free from light induced degradation and have high power generation stability. Crystal silicon solar cells have hot spots after power generation for a long period of time, resulting in reduced power generation and increased maintenance costs.
- copper indium gallium selenide solar cells can adopt an internal connection structure, which can avoid the occurrence of this phenomenon and requires lower maintenance costs than crystalline silicon solar cells.
- the methods for manufacturing copper indium gallium selenide thin-film solar cells include vacuum sputtering, distillation and non-vacuum coating. No matter which manufacturing method is used, some copper indium gallium selenide waste materials may be produced during the manufacturing process. These waste materials contain rare metals such as indium, gallium and selenium, in addition to heavy metal copper. To help the continued use of rare metals such as indium, gallium and selenium and heavy metal copper, they need to be separated and separately recovered to facilitate further recycling, to ensure the sustainable development of copper indium gallium selenide thin-film solar cell materials. In the prior art, the main methods for recovering copper indium gallium selenide waste materials are combined wet or pyrometallurgical refining methods such as acid dissolution, extraction, oxidative distillation, etc.
- Chinese patent application publication No. CN102296178A discloses a method for recovering copper indium gallium selenide, and specifically discloses a method of dissolving metal powders containing copper indium gallium selenide by a mixture of hydrochloric acid and hydrogen peroxide. This method uses hydrazine to reduce selenium, uses metal indium to replace copper, and separates indium from gallium by a combination of a supported liquid membrane and a dispersed stripping solution.
- Chinese patent application publication No. CN103184388A discloses a method for recovering copper indium gallium selenide.
- the copper indium gallium selenide thin-film solar panels are first crushed into pieces, which are then soaked in a soaking process with a mixed system of sulfuric acid and hydrogen peroxide under a specified temperature for a specified time to give the soaking solution.
- Indium, gallium and selenium elements are then recovered by processes such as extraction, reverse extraction, electrolysis, and the like.
- U.S. Pat. No. 5,779,877 discloses a method for recovering copper indium selenide solar cell waste materials.
- the method mainly includes crushing, leaching with nitric acid, separating copper, selenium and indium with dual-electrode electrolysis, obtaining a mixture of indium and zinc oxides by evaporation and decomposition, and separating copper and selenium by oxidative distillation.
- the present invention aims to provide a method for recovering copper indium gallium selenide material which can reduce environmental pollution and has high indium recovery rate and lower production cost.
- the method for recovering copper indium gallium selenide waste material uses sulfuric acid in a high temperature aeration leaching to reduce acid gas pollution.
- a copper extractant is used for copper extraction.
- the separation effect is good and the cost is low.
- the extracted copper is directly electrolyzed to give high-purity copper metal.
- gallium is separated under basic conditions. Separation of indium from gallium can be achieved by merely adjusting the pH of the solution. The separation effect is good, and the resulted indium and gallium products have relatively high purities.
- the method for recovering copper indium gallium selenide material according to the present invention comprises the following steps.
- step A the copper indium gallium selenide waste material is placed in a ball mill for ball milling.
- step B the copper indium gallium selenide powders are added to a sulfuric acid solution and heated to 90 to 100° C., and air is introduced into the heated solution for leaching.
- step C sodium sulfite is added to the solution, and the solution is heated and stirred, during which sodium sulfite reacts with sulfuric acid to generate sulfur dioxide gas, which then reacts with selenic acid to produce selenium.
- step D sodium hydroxide is added to the solution to adjust the pH, followed by adding a copper extractant, preferably AD-100N (a high-efficiency copper extractant), to extract copper ions.
- a copper extractant preferably AD-100N (a high-efficiency copper extractant)
- the extract is then subjected to a reverse extraction to give a copper sulfate solution, which is electrolyzed to give copper metal.
- step E sodium hydroxide is added to the raffinate obtained in step D to adjust the pH to above 12. After standing, the supernatant is drawn, and the precipitate is filtered and washed with water. The obtained filter residue is indium hydroxide, and the obtained solution is a sodium gallate solution.
- step F the sodium gallate solution obtained in step E is electrolyzed to give gallium metal.
- step G indium hydroxide obtained in step E is dissolved by hydrochloric acid, and indium is replaced with zinc to give indium metal.
- the method for recovering copper indium gallium selenide material according to the present invention further comprises in step A that the copper indium gallium selenide waste material is ball milled to below 80 mesh.
- the method for recovering copper indium gallium selenide material according to the present invention further comprises in step B that a certain volume of a sulfuric acid solution having a molar concentration of 1.5 to 6 mol/L is taken, and the copper indium gallium selenide powders are added into the above sulfuric acid solution at a liquid-solid ratio of 2:1 to 8:1 and heated to 95° C. Air is introduced into the heated solution and the leaching lasts for 12 hours.
- the method for recovering copper indium gallium selenide material according to the present invention further comprises in step C that the solution is heated to above 60° C., and stirred to react for at least 2 hours.
- the method for recovering copper indium gallium selenide material according to the present invention further comprises in step D that the pH is adjusted to 1.2 to 2.2, and the ratio of the extractant and the solution phase is 1:1, and the extraction is conducted in two stages for 10 times, each extraction lasting for 6 min.
- the method for recovering copper indium gallium selenide material according to the present invention further comprises in step D that 1.5 mol/L sulfuric acid is taken under ambient temperature, and added to the extractant with a ratio of the extractant and sulfuric acid being 1:1 to conduct a 10-stage reverse extraction, each stage lasting for 6 min.
- the conditions for the electrolysis of the copper sulfate solution are as follows: electrolysis voltage, 1.8 V; current density, 250 A/m 2 ; electrolyte temperature controlled at about 45 to 60° C.; electrolysis time, 4 h.
- the method for recovering copper indium gallium selenide material according to the present invention further comprises in step E that sodium hydroxide is added to the raffinate to adjust the pH, followed by heating the solution to above 80° C. for 0.5 hours. After standing, the supernatant is drawn, and the precipitate is filtered and washed with water. The obtained filter residue is indium hydroxide and the obtained solution is a sodium gallate solution.
- the method for recovering copper indium gallium selenide material according to the present invention further comprises in step F that the conditions for the electrolysis of the sodium gallate solution are as follows: electrolysis voltage, 2.5 V; current density, 200 A/m 2 , electrolyte temperature controlled at about 45 to 60° C., electrolysis time, 6 h.
- the method for recovering copper indium gallium selenide material according to the present invention further comprises in step G that indium hydroxide is dissolved by 0.5 mol/L hydrochloric acid, and indium is replaced with zinc at a temperature of 50 to 60° C., in which a zinc plate is used for the replacement, and the replacement lasts for 8 h.
- FIG. 1 is a process flow chart of the present invention.
- the method for recovering copper indium gallium selenium material mainly comprises the following steps.
- Step 1 Ball milling and sample preparation: 400 g copper indium gallium selenide waste material was placed in a ball mill and ball milled to powders below 80 mesh.
- Step 2 Sieving: The ball milled powders were sieved. Powders above 80 mesh were returned to step 1 for further ball milling.
- Step 3 High temperature aeration leaching: 1600 ml of a sulfuric acid solution having a molar concentration of 3 mol/L was taken, and the copper indium gallium selenide powders were added to the above sulfuric acid solution and heated to 95° C. Air was introduced into the heated solution. The leaching lasted for 12 hours, and the leaching rate can reach above 95%.
- Step 4 Filtering: The filter residue was filtered out. In this step, the filter residue which is filtered out can also be returned to step 3 for secondary leaching.
- Step 5 Reducing: 500 g sodium sulfite was added to the solution, and the solution was heated to 70° C. and stirred to react for 2 hours, during which sodium sulfite reacted with sulfuric acid to generate sulfur dioxide gas, which then reacted with selenic acid to produce selenium.
- Step 6 Filtering: Selenium was obtained after filtration. The main elements remaining in the solution were only copper, indium and gallium.
- Step 7 Extracting copper: Sodium hydroxide was added to the solution to adjust the pH to 1.8, followed by adding the extractant AD-100 N (or lix984 extractant) to extract copper ions.
- the extraction conditions were as follows: 400 ml extractant was taken under ambient temperature, and the ratio of the extractant and the solution phase was 1:1, and the extraction was conducted in two stages for 10 times, each extraction lasting for 6 min.
- the extract was subjected to a reverse extraction to give a copper sulfate solution, during which 400 ml of 1.5 mol/L sulfuric acid was taken under ambient temperature and added to the extractant with a ratio of the extractant and the acid for the reverse extraction being 1:1 to conduct a 10-stage reverse extraction, each stage lasting for 6 min.
- Step 8 Electrolysis: The copper sulfate solution was electrolyzed under the following conditions: electrolysis voltage, 1.8 V; current density, 250 A/m 2 ; electrolyte temperature controlled at about 50 ° C.; electrolysis time, 4 h. High-purity copper metal was obtained with a purity of 99.95%.
- Step 9 Separating gallium with an alkali: NaOH was added to the raffinate obtained in Step 7 to adjust the pH to 13.5 (preferably making the pH above 13 ) and heated to 85° C. for 0.5 hour.
- Step 10 Standing and separating: After standing for 2 hours, the supernatant was drawn, and the precipitate was filtered and washed with water. The obtained filter residue was indium hydroxide and the obtained solution was a sodium gallate solution.
- Step 11 Electrolysis: The sodium gallate solution obtained in Step 10 was electrolyzed under the following conditions: electrolysis voltage, 2.5 V; current density, 200 A/m 2 , electrolyte temperature controlled at about 50° C., electrolysis time, 6 h. Gallium metal having a purity of 99.6% was obtained.
- Step 12 Leaching: Indium hydroxide obtained in step 10 was dissolved by 500 mL of 0.5 mol/L hydrochloric acid.
- Step 13 Replacing: Indium was replaced with zinc at a temperature of 55° C., in which a zinc plate was used for the replacement, and the replacement lasted for 8 h, to give indium metal having a purity of 99%.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
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- Electrolytic Production Of Metals (AREA)
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610039563.0 | 2016-01-21 | ||
| CN201610039563.0A CN106987720B (zh) | 2016-01-21 | 2016-01-21 | 一种铜铟镓硒物料的回收方法 |
| PCT/CN2016/112139 WO2017124890A1 (zh) | 2016-01-21 | 2016-12-26 | 一种铜铟镓硒物料的回收方法 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US20200277685A1 true US20200277685A1 (en) | 2020-09-03 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US16/068,072 Abandoned US20200277685A1 (en) | 2016-01-21 | 2016-12-26 | Recovery method for copper-indium-gallium-selenium material |
Country Status (9)
| Country | Link |
|---|---|
| US (1) | US20200277685A1 (zh) |
| EP (1) | EP3382044A4 (zh) |
| JP (1) | JP2019502828A (zh) |
| KR (1) | KR20180095931A (zh) |
| CN (1) | CN106987720B (zh) |
| AU (1) | AU2016388065A1 (zh) |
| CA (1) | CA3011905A1 (zh) |
| SG (1) | SG11201806234QA (zh) |
| WO (1) | WO2017124890A1 (zh) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107460341A (zh) * | 2017-08-04 | 2017-12-12 | 俞振元 | 从含铜金属废料中回收制备电镀级硫酸铜的方法 |
| CN108147375B (zh) * | 2017-12-27 | 2020-12-25 | 清远先导材料有限公司 | 一种硒锗硫系玻璃的回收方法 |
| CN108425015B (zh) * | 2018-03-16 | 2019-11-29 | 北京科技大学 | 从铜铟镓硒太阳能薄膜电池腔室废料回收有价金属的方法 |
| CN108425017B (zh) * | 2018-03-16 | 2019-10-18 | 北京科技大学 | 从铜铟镓硒废电池芯片中回收有价金属的方法 |
| CN108374091B (zh) * | 2018-03-30 | 2020-01-03 | 中国科学院过程工程研究所 | 一种从含难溶镓化合物的废料中回收镓的方法及由该方法得到的镓 |
| CN108611495A (zh) * | 2018-05-17 | 2018-10-02 | 汉能新材料科技有限公司 | 一种铜铟镓硒废料的回收方法 |
| CN108642522A (zh) * | 2018-05-17 | 2018-10-12 | 汉能新材料科技有限公司 | 一种含铟废料的回收方法 |
| CN108677017A (zh) * | 2018-05-23 | 2018-10-19 | 汉能新材料科技有限公司 | 一种铜铟镓硒废料的回收方法 |
| CN108754147A (zh) * | 2018-06-08 | 2018-11-06 | 汉能新材料科技有限公司 | 一种亚熔盐在分解回收铜铟镓硒物料和/或铜铟硒物料的用途 |
| CN108642290A (zh) * | 2018-06-15 | 2018-10-12 | 汉能新材料科技有限公司 | 一种铜铟镓硒废料的回收方法 |
| CN108754155A (zh) * | 2018-07-04 | 2018-11-06 | 汉能新材料科技有限公司 | 铜铟镓硒废物料的回收方法 |
| CN108796210A (zh) * | 2018-07-04 | 2018-11-13 | 汉能新材料科技有限公司 | 一种铜铟镓硒废物料的回收方法 |
| CN108929955B (zh) * | 2018-07-09 | 2020-07-31 | 顾帅 | 一种从铜铟镓硒靶材回收铜、硒单质、无水铟盐和无水镓盐的方法 |
| TWI792037B (zh) * | 2020-08-14 | 2023-02-11 | 國立清華大學 | 薄膜太陽能電池的回收方法 |
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| US5779877A (en) | 1997-05-12 | 1998-07-14 | Drinkard Metalox, Inc. | Recycling of CIS photovoltaic waste |
| JP3602329B2 (ja) * | 1998-03-20 | 2004-12-15 | 同和鉱業株式会社 | インジウム含有物からインジウムを回収する方法 |
| JP4169871B2 (ja) * | 1999-07-01 | 2008-10-22 | Ｄｏｗａホールディングス株式会社 | Ｉｎ含有酸化物からのＩｎ浸出方法 |
| US20100329970A1 (en) * | 2009-03-04 | 2010-12-30 | Solar Applied Materials Technology Corp. | Method for recovery of copper, indium, gallium, and selenium |
| JP5221608B2 (ja) * | 2009-09-18 | 2013-06-26 | 光洋応用材料科技股▲ふん▼有限公司 | 銅・インジウム・ガリウム・セレンの回収方法 |
| CN102296178A (zh) * | 2010-06-25 | 2011-12-28 | 光洋应用材料科技股份有限公司 | 铜铟镓硒的回收方法 |
| CA2721518C (en) * | 2010-11-26 | 2013-02-05 | Neo Material Technologies Inc. | Treatment of indium gallium alloys and recovery of indium and gallium |
| CN103184338B (zh) * | 2011-12-29 | 2015-04-01 | 广东先导半导体材料有限公司 | 铜铟镓硒薄膜太阳能板回收方法 |
| TWI458834B (zh) * | 2012-12-27 | 2014-11-01 | Univ Nat Cheng Kung | Recovery method of copper indium gallium selenium residual target |
| CN103184388A (zh) | 2013-03-08 | 2013-07-03 | 首钢贵阳特殊钢有限责任公司 | 一种凿岩钎杆用95CrMo钢整体正火工艺 |
| JP2015086436A (ja) * | 2013-10-30 | 2015-05-07 | 三菱マテリアル株式会社 | 有価物の回収方法 |
| CN105087935B (zh) * | 2014-05-22 | 2017-09-05 | 汉能新材料科技有限公司 | 一种从铜铟镓废靶材中分别回收铜、铟和镓的方法 |
| CN104017995B (zh) * | 2014-06-24 | 2016-01-13 | 株洲冶炼集团股份有限公司 | 一种从含铜铟镓硒废料中回收铜铟镓硒的方法 |
| CN104018186B (zh) * | 2014-06-24 | 2016-08-31 | 株洲冶炼集团股份有限公司 | 一种铜铟镓硒的回收方法 |
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| SG11201806234QA (en) | 2018-08-30 |
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