CN111826527A - Method for recovering copper indium gallium selenide material - Google Patents
Method for recovering copper indium gallium selenide material Download PDFInfo
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- CN111826527A CN111826527A CN202010769597.1A CN202010769597A CN111826527A CN 111826527 A CN111826527 A CN 111826527A CN 202010769597 A CN202010769597 A CN 202010769597A CN 111826527 A CN111826527 A CN 111826527A
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- 238000000034 method Methods 0.000 title claims abstract description 106
- KTSFMFGEAAANTF-UHFFFAOYSA-N [Cu].[Se].[Se].[In] Chemical compound [Cu].[Se].[Se].[In] KTSFMFGEAAANTF-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 239000000463 material Substances 0.000 title claims abstract description 43
- 229910052738 indium Inorganic materials 0.000 claims abstract description 148
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims abstract description 148
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 144
- 229910052802 copper Inorganic materials 0.000 claims abstract description 141
- 239000010949 copper Substances 0.000 claims abstract description 141
- 229910052733 gallium Inorganic materials 0.000 claims abstract description 91
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims abstract description 90
- 238000002386 leaching Methods 0.000 claims abstract description 69
- 229910052751 metal Inorganic materials 0.000 claims abstract description 60
- 239000002184 metal Substances 0.000 claims abstract description 60
- 229910052711 selenium Inorganic materials 0.000 claims abstract description 51
- 239000011669 selenium Substances 0.000 claims abstract description 51
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims abstract description 50
- 239000007788 liquid Substances 0.000 claims abstract description 47
- 238000000926 separation method Methods 0.000 claims abstract description 46
- 239000002253 acid Substances 0.000 claims abstract description 27
- 230000033116 oxidation-reduction process Effects 0.000 claims abstract description 26
- 230000003647 oxidation Effects 0.000 claims abstract description 12
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 12
- 150000003839 salts Chemical class 0.000 claims abstract description 12
- 239000002893 slag Substances 0.000 claims abstract description 12
- 239000007787 solid Substances 0.000 claims abstract description 6
- 238000000605 extraction Methods 0.000 claims description 41
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 23
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 18
- 238000005342 ion exchange Methods 0.000 claims description 15
- 238000000227 grinding Methods 0.000 claims description 14
- 230000001590 oxidative effect Effects 0.000 claims description 13
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 11
- 238000004070 electrodeposition Methods 0.000 claims description 11
- 229910021513 gallium hydroxide Inorganic materials 0.000 claims description 11
- DNUARHPNFXVKEI-UHFFFAOYSA-K gallium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[Ga+3] DNUARHPNFXVKEI-UHFFFAOYSA-K 0.000 claims description 11
- 238000004886 process control Methods 0.000 claims description 11
- 238000002425 crystallisation Methods 0.000 claims description 10
- 230000008025 crystallization Effects 0.000 claims description 10
- 238000003795 desorption Methods 0.000 claims description 10
- 238000011084 recovery Methods 0.000 claims description 10
- 239000007800 oxidant agent Substances 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 9
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 claims description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- 238000001704 evaporation Methods 0.000 claims description 7
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 6
- 230000008020 evaporation Effects 0.000 claims description 6
- 229910017604 nitric acid Inorganic materials 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
- 229910001449 indium ion Inorganic materials 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 claims description 5
- 229910001488 sodium perchlorate Inorganic materials 0.000 claims description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- 230000002378 acidificating effect Effects 0.000 claims description 3
- 150000001879 copper Chemical class 0.000 claims description 3
- 150000002471 indium Chemical class 0.000 claims description 3
- 238000006467 substitution reaction Methods 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 2
- 238000002203 pretreatment Methods 0.000 claims description 2
- 229910001195 gallium oxide Inorganic materials 0.000 claims 1
- 239000002699 waste material Substances 0.000 abstract description 18
- 238000004064 recycling Methods 0.000 abstract description 6
- 230000007613 environmental effect Effects 0.000 abstract description 4
- 238000009856 non-ferrous metallurgy Methods 0.000 abstract description 2
- 239000002910 solid waste Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 101
- 238000004519 manufacturing process Methods 0.000 description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 21
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 18
- 239000003795 chemical substances by application Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 238000001914 filtration Methods 0.000 description 8
- 150000002739 metals Chemical class 0.000 description 7
- 238000001556 precipitation Methods 0.000 description 7
- HVMJUDPAXRRVQO-UHFFFAOYSA-N copper indium Chemical compound [Cu].[In] HVMJUDPAXRRVQO-UHFFFAOYSA-N 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 229910052725 zinc Inorganic materials 0.000 description 6
- 239000011701 zinc Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000007670 refining Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- FZENGILVLUJGJX-NSCUHMNNSA-N (E)-acetaldehyde oxime Chemical compound C\C=N\O FZENGILVLUJGJX-NSCUHMNNSA-N 0.000 description 4
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 230000001376 precipitating effect Effects 0.000 description 4
- 229910000365 copper sulfate Inorganic materials 0.000 description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 3
- 238000006073 displacement reaction Methods 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 238000005868 electrolysis reaction Methods 0.000 description 3
- QNWMNMIVDYETIG-UHFFFAOYSA-N gallium(ii) selenide Chemical compound [Se]=[Ga] QNWMNMIVDYETIG-UHFFFAOYSA-N 0.000 description 3
- 230000003472 neutralizing effect Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- IRPLSAGFWHCJIQ-UHFFFAOYSA-N selanylidenecopper Chemical compound [Se]=[Cu] IRPLSAGFWHCJIQ-UHFFFAOYSA-N 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000003929 acidic solution Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000010440 gypsum Substances 0.000 description 2
- 229910052602 gypsum Inorganic materials 0.000 description 2
- PSCMQHVBLHHWTO-UHFFFAOYSA-K indium(iii) chloride Chemical compound Cl[In](Cl)Cl PSCMQHVBLHHWTO-UHFFFAOYSA-K 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 238000010979 pH adjustment Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- -1 selenium metals Chemical class 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- FZHLWVUAICIIPW-UHFFFAOYSA-M sodium gallate Chemical compound [Na+].OC1=CC(C([O-])=O)=CC(O)=C1O FZHLWVUAICIIPW-UHFFFAOYSA-M 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 230000003113 alkalizing effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- CABDFQZZWFMZOD-UHFFFAOYSA-N hydrogen peroxide;hydrochloride Chemical compound Cl.OO CABDFQZZWFMZOD-UHFFFAOYSA-N 0.000 description 1
- IGUXCTSQIGAGSV-UHFFFAOYSA-K indium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[In+3] IGUXCTSQIGAGSV-UHFFFAOYSA-K 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 150000003751 zinc Chemical class 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
-
- 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
-
- 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
-
- 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
- C22B15/0084—Treating solutions
- C22B15/0089—Treating solutions by chemical methods
- C22B15/0091—Treating solutions by chemical methods by cementation
-
- 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
-
- 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
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- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention provides a method for recovering a copper indium gallium selenide material, which relates to the technical field of non-ferrous metallurgy and resource recycling of solid wastes, and comprises the following steps: performing oxidation acid leaching on the pretreated material containing the copper, indium, gallium and selenium, wherein the oxidation-reduction potential of a system is controlled in the leaching process so that the copper, indium and gallium are dissolved in a solution, the selenium exists in the slag in a solid form, and performing solid-liquid separation on a leaching solution to obtain a solution containing the copper, the indium and the gallium and crude selenium; separating copper and indium in the solution containing copper, indium and gallium by using a metal replacement method or a wet separation method, and treating to obtain metal copper, indium or salts thereof; and adjusting the pH value of the solution after copper and indium are separated to precipitate gallium, and treating after solid-liquid separation to obtain the metal gallium. The invention has the advantages of strong reliability of each treatment process, less investment, low operation cost and convenient three-waste treatment, and meets the requirements of safety, environmental protection, economy and reliability.
Description
Technical Field
The invention relates to the technical field of non-ferrous metallurgy and resource recycling of solid wastes, in particular to a method for recovering a copper indium gallium selenide material.
Background
CIGS (Copper Indium Gallium selenide) thin-film type solar power generation cells have the characteristics of being light, thin, portable, high in energy conversion efficiency and the like, and are widely concerned. There are currently three main methods for its production: vacuum spraying, distillation, or non-vacuum spraying. By adopting any method, waste materials with high purity of copper, indium, gallium and selenium as main components are inevitably generated in the production process. The four metals have high values, and how to effectively separate and purify the four metals so as to be recycled as a CIGS battery production raw material or sold as pure metals has great economic and environmental significance.
At present, the development of the CIGS material separation process is still in a primary stage at home and abroad, and the process reliability, economy and safety reported in the prior art cannot be guaranteed. The safe, environment-friendly and economic separation and purification process of the copper indium gallium selenide material is expected to be sought.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The invention aims to provide a method for recovering copper indium gallium selenide from CIGS manufacturing waste materials, and solves the technical problem that the materials are free of safe, environment-friendly and economic separation processes at present.
The invention provides a method for recovering a copper indium gallium selenide material, which comprises the following steps:
performing oxidation acid leaching on the pretreated material containing the copper, indium, gallium and selenium, wherein the oxidation-reduction potential of a system is controlled in the leaching process so that the copper, indium and gallium are dissolved in a solution, the selenium exists in the slag in a solid form, and performing solid-liquid separation on a leaching solution to obtain a solution containing the copper, the indium and the gallium and crude selenium;
separating copper and indium in the solution containing copper, indium and gallium by using a metal replacement method or a wet separation method, and treating to obtain metal copper, indium or salts thereof;
and adjusting the pH value of the solution after copper and indium are separated to precipitate gallium, and treating after solid-liquid separation to obtain the metal gallium.
Further, the method for separating copper and indium in the solution containing copper, indium and gallium by using the metal replacement method comprises the following steps:
firstly, adding metal powder into a solution containing copper, indium and gallium to replace the copper in the solution, and adding an oxidation-reduction potential of a process control solution to separate out copper and no indium to obtain sponge copper;
and then adding metal powder into the solution after copper replacement to continuously replace indium in the solution, and adding the process control solution to control the oxidation-reduction potential so that indium is separated out and no gallium is separated out, thereby obtaining sponge indium.
Furthermore, the oxidation-reduction potential of the replacement copper process control solution is-100 to-220 mv;
the oxidation-reduction potential of the indium replacement process control solution is-220 to-500 mv.
Further, the copper and the indium in the solution containing copper, indium and gallium are respectively separated by using a wet separation method, wherein the wet separation method comprises extraction or ion exchange separation and comprises the following steps:
(a) separating copper ions in the solution by adopting an extraction or ion exchange method, carrying out back extraction or desorption on the separated copper-containing carrier to obtain a copper solution, and treating to obtain metal copper or salt thereof;
(b) separating indium ions in the solution by adopting an extraction or ion exchange method, performing back extraction or desorption on the separated indium-containing carrier to obtain an indium solution, and treating to obtain metal indium or salt thereof;
wherein, the step (a) and the step (b) are not in sequence.
Further, the extractant used in step (a) is an aldoxime extractant, preferably comprising lix984 and/or M5640;
preferably, the concentration of the extractant is 10-70 wt%.
Further, the extractant used in step (b) is a phosphoric acid-based extractant, preferably comprising P204;
preferably, the concentration of the extractant is 10-70 wt%.
Further, in the step (a), the copper solution is subjected to electrodeposition to obtain metal copper or evaporative crystallization to obtain a copper salt product;
preferably, in the step (b), the indium solution is electrolyzed and refined to obtain metal indium after sponge indium is obtained by replacement, or an indium salt product is obtained by evaporation and crystallization.
Further, the pretreatment comprises: and (3) carrying out ore grinding treatment on the material containing the copper, indium, gallium and selenium, wherein the granularity of the material after ore grinding is 80-500 meshes.
Further, the oxidizing agent used for oxidizing the acidic leaching comprises one or more of sodium chlorate, sodium perchlorate or hydrogen peroxide;
preferably, the acid used in the oxidative acidic leaching comprises one or more of sulfuric acid, hydrochloric acid or nitric acid;
preferably, the process conditions of the oxidative acid leaching comprise at least one of the following conditions:
the solid-liquid ratio of leaching is 1: 2-8, the leaching temperature is 16-100 ℃, the oxidation-reduction potential of a leaching process control system is kept at 300-500 mv, and the final acid concentration is 0.5-5 mol/L.
Further, adjusting the pH value of the solution after copper and indium are separated to 2-6 to precipitate gallium, and alkalifying gallium hydroxide obtained after solid-liquid separation to prepare solution and electrodepositing to obtain metal gallium;
preferably, the alkali concentration of the solution after alkalization liquid preparation is OH-The weight is 28-70 g/L.
The method for recovering the CIGS material has the advantages of short flow, less investment and low operation cost, comprehensively considers the convenience of three-waste treatment in the production practice process, and meets the requirements of safety, environmental protection, economy and reliability.
The replacement process flow is simple, the operation cost is low, the reduction by 20 percent is realized, the equipment investment is low, and the reduction by 40 percent is realized.
The method of the invention recovers the copper indium gallium selenide from the manufacturing waste materials generated in the production process of the CIGS solar thin film material, and can obtain high-purity copper, indium, gallium and selenium metals or corresponding salts thereof.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
Fig. 1 is a flowchart of a method for recovering a copper indium gallium selenide material according to an embodiment of the invention;
fig. 2 is a flowchart of a recycling method of a cigs material according to another embodiment of the present invention.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments, and it should be understood that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
At present, the reliability, the economy and the safety of the copper indium gallium selenide material separation process at home and abroad are still seriously insufficient.
The invention provides a method for recovering a copper indium gallium selenide material, which comprises the following steps:
s101: performing oxidation acid leaching on the pretreated material containing the copper, indium, gallium and selenium, wherein the oxidation-reduction potential of a system is controlled in the leaching process so that the copper, indium and gallium are dissolved in a solution, the selenium exists in the slag in a solid form, and performing solid-liquid separation on a leaching solution to obtain a solution containing the copper, the indium and the gallium and crude selenium;
s102: separating copper and indium in the solution containing copper, indium and gallium by using a metal replacement method or a wet separation method, and treating to obtain metal copper, indium or salts thereof;
s103: and adjusting the pH value of the solution after copper and indium are separated to precipitate gallium, and treating after solid-liquid separation to obtain the metal gallium.
S101
Raw materials: the material containing copper indium gallium selenide refers to copper indium gallium selenide containing waste materials, including but not limited to CIGS manufacturing waste materials.
In a preferred embodiment, the pre-treatment comprises: the method comprises the following steps of crushing and grinding a material containing copper, indium, gallium and selenium to form powder, wherein the granularity of the ground material is preferably 80-500 meshes. The material granularity is suitable for the leaching process treatment.
And (2) carrying out oxidation acid leaching on the pretreated material containing the copper, indium, gallium and selenium, wherein the oxidation acid leaching is to dissolve the pretreated powder into an acid solution containing an oxidant (an oxidizing substance).
During leaching (dissolving), the oxidation-reduction potential of the solution system needs to be controlled, so that copper, indium and gallium are dissolved in the solution, selenium is left in the slag in a solid form, and a solution containing copper, indium and gallium and a crude selenium product are obtained after solid-liquid separation (such as filtration, centrifugation and sedimentation).
The oxidant (oxidizing substance) includes, but is not limited to, sodium chlorate, sodium perchlorate, hydrogen peroxide, or the like.
Acidic solutions include, but are not limited to, sulfuric, hydrochloric, or nitric acid solutions, and the like.
In a preferred embodiment, the process conditions for the oxidative acid leaching include the following conditions:
the solid-liquid ratio of leaching is 1 kg: 2-8L (such as 1 kg: 2L, 1 kg: 3L, 1 kg: 4L, 1 kg: 5L, 1 kg: 6L, 1 kg: 7L or 1 kg: 8L), the leaching temperature is 16-100 ℃ (such as 20, 30, 40, 50, 60, 70, 80, 90 ℃), the oxidation-reduction potential of the leaching process control system is kept at 300-500 mv (such as 350, 400, 450mv), and the final acid concentration is 0.5-5 mol/L (such as 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5 mol/L).
Preferably, the solid-to-liquid ratio is controlled to be 1:3, the leaching temperature is 70 ℃, and the oxidation-reduction potential is controlled to be 400 mV.
By controlling the leaching conditions, controlling the solid-liquid ratio to be 1:3, the leaching temperature to be 70 ℃, and controlling the oxidation-reduction potential to be 400mV, the selenium product can be separated out better, and the separation rate of the selenium can reach 98.5%.
S102
And (3) separating copper and indium in the solution containing copper, indium and gallium by using a metal replacement method or a wet separation method, and treating to obtain metal copper, indium or salts thereof.
The metal replacement method is to replace other metal ions in the solution step by adopting active metals according to the order of metal activity.
The wet separation method is to recover valuable metals by extraction or ion exchange.
"metallic copper, indium or salts thereof" means metallic copper or copper salts, metallic indium or indium salts.
The copper and indium dissolved in the solution after the treatment in S101 can be separated by metal substitution or wet separation.
If the metal replacement method is adopted, stepwise replacement is required. Metals include, but are not limited to, zinc, iron, aluminum, but zinc is preferred in view of economy and operability and subsequent ease of wastewater treatment.
Firstly, a proper amount of zinc powder is slowly added into the solution, and the potential is controlled in the process, so that only copper is separated out from the solution, and the sponge copper is obtained.
And then, adding zinc powder into the solution after copper replacement, continuously replacing indium in the solution, controlling the potential in the process, and ensuring that no gallium is separated out in the process to obtain sponge indium.
In a preferred embodiment, the redox potential during copper displacement should be controlled to be in the range of-100 to-220 mv (e.g., -100, -120, -150, -160, -180, -200, -220 mv).
In a preferred embodiment, the redox potential during indium replacement is controlled to be between-220 and-500 mv (e.g., -240, -250, -260, -280, -300, -320, -350, -360, -380, -400, -420, -450, -460, -480 mv).
The metal replacement method has short process flow, reduces a large amount of solution pH adjustment and extraction processes, and has low operation cost and low equipment investment.
If extraction and ion exchange separation methods are adopted, copper and indium are separated respectively.
Separating copper ions in the solution (which can be the solution containing copper, indium and gallium, and can also be the raffinate after indium extraction) by adopting an extraction or ion exchange method, performing back extraction or desorption on the separated copper-containing carrier to obtain a copper solution with a certain concentration, and obtaining metal copper by electrodeposition or obtaining a copper sulfate product by evaporative crystallization.
The indium ions in the solution (which can be the solution containing copper, indium and gallium, and can also be the raffinate after copper extraction) are separated by adopting an extraction or ion exchange method, the separated indium-containing carrier is subjected to back extraction or desorption to obtain an indium solution with a certain concentration, sponge indium is obtained by displacement, and then metal indium is obtained by electrolytic refining or indium chloride products are obtained by evaporation crystallization.
It should be noted that the sequence of extracting copper and indium by extraction is adjustable, but extracting gallium needs to be performed after extracting copper and indium.
Electrodeposition refers to the process of depositing certain substances on electrodes by passing an electric current through an aqueous solution or suspension.
Electrorefining refers to a technique for extracting pure metals by utilizing differences in the degree of difficulty of anodic dissolution or cathodic precipitation of different elements.
Evaporative crystallization refers to a process in which the solvent is heated to evaporate, the solution becomes saturated from unsaturated, evaporation is continued, and excess solute is precipitated as crystals.
In a preferred embodiment, the extractant used to separate the copper using the extraction method comprises lix984, M5640, and the like, with the remainder of the aldoxime extractant.
Preferably, the extractant concentration is 10 to 70 wt% (e.g., 20, 30, 40, 50, 60 wt%).
In a preferred embodiment, the extractant used to separate the indium using an extraction method comprises the remaining phosphate-based extractant, such as P204.
Preferably, the extractant concentration is 10 to 70 wt% (e.g., 20, 30, 40, 50, 60 wt%).
S103
The solution after separating copper and indium is treated by adjusting pH value to precipitate gallium in the form of gallium hydroxide, and the gallium hydroxide obtained after solid-liquid separation (such as filtration, centrifugation and sedimentation) is alkalized to make liquid and then electrodeposited to obtain gallium metal.
The alkalization liquid making means that gallium hydroxide is subjected to alkaline leaching by using sodium hydroxide to produce a sodium gallate solution.
In a preferred embodiment, the precipitated gallium has an end point pH of 2 to 6 (e.g., 3, 4, 5).
In a preferred embodiment, the alkalized liquid-making is reduced in concentration by OH-The meter is 28-70 g/L (for example, 30, 35, 40, 45, 50, 55, 60, 65 g/L).
The process of gallium separation refers to the electrodeposition of sodium gallate solution obtained by alkalization liquid preparation to obtain gallium metal.
The copper indium gallium element is separated by adopting a wet separation technology to directly obtain metal salt or product-grade metal copper, indium and gallium are obtained after electrodeposition/electrolysis.
The recovery method has the advantages of short flow, less investment and low operation cost, comprehensively considers the convenience of three-waste treatment in the production practice process, and meets the requirements of safety, environmental protection, economy and reliability.
In one exemplary embodiment of the present invention, a method for recovering CIGS from CIGS manufacturing waste comprises the steps of: CIGS manufacturing waste is used as a raw material, and powder is formed after crushing and ore grinding treatment; the granularity of the ground material is 80-500 meshes.
Dissolving the powder in an acidic solution containing an oxidizing substance to form a solution containing copper, indium and gallium ions, wherein selenium does not dissolve in the process and exists in the form of solid slag. The leaching solid-liquid ratio is 1: 2-8, the leaching temperature is 16-100 ℃, the oxidation-reduction potential in the system needs to be controlled to be 300-500 mv all the time in the leaching process, and the final acid concentration is 0.5-5 mol/L.
And carrying out solid-liquid separation on the leaching solution to obtain crude selenium and copper, indium and gallium solutions.
The copper and indium in the copper-indium-gallium solution can be recovered by a zinc powder replacement, extraction or ion exchange method.
If a zinc powder replacement method is adopted, the oxidation-reduction potential of the process needs to be controlled, and copper and indium in the copper are replaced step by step. The oxidation-reduction potential in the copper replacement process should be controlled to-100 to-220 mv, and the oxidation-reduction potential in the indium replacement process should be controlled to-220 mv to-500 mv.
Firstly, adding a proper amount of zinc powder into the solution, and controlling the potential in the process to ensure that only copper is precipitated from the solution. Sponge copper is obtained. Then, zinc powder is added to the solution after copper replacement, and indium in the solution is continuously replaced. The potential is controlled in the process, and no gallium is separated out in the process. Obtaining the sponge indium.
For example, the copper ions in the solution are separated by adopting an extraction or ion exchange method, the separated copper-containing carrier is subjected to back extraction or desorption to obtain a copper solution with a certain concentration, and metal copper is obtained by electrodeposition or copper sulfate products are obtained by evaporation crystallization. The extractant comprises lix984, M5640 and other aldoxime extractants.
For example, an extraction or ion exchange method is adopted to separate indium ions in the solution, the separated indium-containing carrier is subjected to back extraction or desorption to obtain an indium solution with a certain concentration, sponge indium is obtained through displacement, and then metal indium is obtained through electrolytic refining or indium chloride products are obtained through evaporation crystallization. The extractant comprises P204 and other phosphoric acid extractants.
After separating copper and indium in the solution, adjusting the pH value of the solution to precipitate gallium in the form of gallium hydroxide, alkalifying the gallium hydroxide obtained after solid-liquid separation to make liquid, and then electrodepositing to obtain metal gallium. The final pH value of the precipitated gallium is 2-6. Alkalizing to make liquid and reducing concentration by OH-The weight is 28-70 g/L.
The method for recovering a copper indium gallium selenide material provided by an embodiment of the invention is shown in fig. 1, and specifically comprises the following steps:
1. and (3) crushing and grinding the chamber material (containing the copper indium gallium selenide), wherein the granularity of the ground material is 80-500 meshes.
2. Carrying out oxidation acid leaching: the leaching solid-liquid ratio is 1: 2-8, the leaching temperature is 16-100 ℃, the oxidation-reduction potential in the system needs to be controlled to be 300-500 mv all the time in the leaching process, and the final acid concentration is 0.5-5 mol/L. The acid can be one or more of sulfuric acid, hydrochloric acid and nitric acid, and the oxidant can be one or more of sodium chlorate, sodium perchlorate and hydrogen peroxide.
3. And carrying out solid-liquid separation to obtain a first solution containing copper, indium and gallium and crude selenium (a selenium product).
4. And (3) recovering the copper in the solution I by adopting a metal replacement zinc replacement method, slowly adding zinc powder, and controlling the oxidation-reduction potential to be-100-220 mv in the process to obtain a solution II and sponge copper. And pressing the sponge copper into a plate, and performing electrolytic refining to obtain the cathode copper.
5. And (3) recovering indium in the solution II by adopting a metal replacement zinc replacement method, slowly adding zinc powder, and controlling the oxidation-reduction potential to be-220 mv to-500 mv in the process. Obtaining solution III and sponge indium (crude indium), and obtaining an indium product after the crude indium is pressed into a ball, cast and electrolyzed.
6. And adjusting the pH value of the solution III (the solution after extracting copper and indium) to 2-6, precipitating gallium in the form of gallium hydroxide (neutralizing and precipitating gallium), alkalifying the gallium hydroxide obtained after solid-liquid separation to prepare a solution IV, and electrodepositing the solution IV to obtain the metal gallium. The alkaline reagent in the alkalization liquid-making and pH adjusting process can be one or more of sodium hydroxide, ammonia water and sodium carbonate. The concentration of the quaternary base in the solution is OH-The weight is 28-70 g/L.
7. And part of the gallium-precipitated liquid can be reused in the oxidation acid leaching process, and part of the gallium-precipitated liquid is sent to sewage treatment for neutralization to obtain gypsum slag.
Another embodiment of the present invention provides a method for recovering a cigs material, as shown in fig. 2, specifically including:
1. and (3) crushing and grinding the chamber material (containing the copper indium gallium selenide), wherein the granularity of the ground material is 80-500 meshes.
2. Carrying out oxidation acid leaching: the leaching solid-liquid ratio is 1: 2-8, the leaching temperature is 16-100 ℃, the oxidation-reduction potential in the system needs to be controlled to be 300-500 mv all the time in the leaching process, and the final acid concentration is 0.5-5 mol/L. The acid can be one or more of sulfuric acid, hydrochloric acid and nitric acid, and the oxidant can be one or more of sodium chlorate, sodium perchlorate and hydrogen peroxide.
3. And carrying out solid-liquid separation to obtain a first solution containing copper, indium and gallium and crude selenium (a selenium product).
4. And (3) separating copper ions in the solution by adopting an extraction or ion exchange method, wherein the extracting agent used for separating copper comprises lix984, M5640 and other aldoxime extracting agents, and the concentration of the extracting agent is 10-70%. And carrying out back extraction or desorption on the separated copper-containing carrier to obtain a copper solution V with a certain concentration, and obtaining metal copper through electrodeposition or obtaining a copper sulfate product through evaporative crystallization.
5. And (3) separating indium ions in the solution after copper extraction by adopting an extraction or ion exchange method, wherein an extracting agent used for separating indium comprises other phosphoric acid extracting agents such as P204 and the like, and the concentration of the extracting agent is 10-70%. And (2) carrying out back extraction or desorption on the separated indium-containing carrier to obtain an indium solution six with a certain concentration, adding one or more of zinc, aluminum and hydrogen into the solution six for replacement to obtain sponge indium (crude indium), briquetting, ingot casting, and carrying out electrolytic refining to obtain metal indium (indium product). After replacement, the solution can be evaporated and crystallized to obtain the zinc salt product.
The sequence of extracting copper and indium can be adjusted, but extracting gallium needs to be performed after extracting copper and indium.
6. And adjusting the pH value of the solution after copper and indium extraction to 2-6 to precipitate gallium in the form of gallium hydroxide, performing solid-liquid separation to obtain gallium hydroxide alkalization solution preparation to obtain solution IV, wherein the alkaline reagent in the alkalization solution preparation and pH adjustment process can be one or more of sodium hydroxide, ammonia water and sodium carbonate. The concentration of the quaternary base in the solution is OH-And (4) counting by 28-70 g/L, and then carrying out electrodeposition on the solution IV to obtain the gallium metal.
7. And part of the gallium-precipitated liquid can be reused in the oxidation acid leaching process, and part of the gallium-precipitated liquid is sent to sewage treatment for neutralization to obtain gypsum slag.
The present invention will be further specifically described below by way of specific examples.
Example 1
A method for recovering copper indium gallium selenide from CIGS manufacturing waste comprising the steps of:
1. and (3) carrying out crushing and ore grinding treatment on a CIGS chamber material sample, wherein the particle size after treatment is-150 meshes.
2. Adding sulfuric acid and hydrogen peroxide into the treated sample for leaching, wherein the temperature is 60 ℃, and the solid-to-liquid ratio is 1: end point pH 0.1, potential 450mv, leaching time 3 h. Filtering to obtain crude selenium.
3. The copper is extracted by lix984 with the concentration of 25 percent, the extraction temperature is room temperature (30 ℃), the mixing time is 3min, the clarification time is 3min, and the copper extraction rate is only 94.47 percent. And (4) after back extraction, electrodepositing copper to obtain cathode copper with the purity of 99.95 percent.
4. Adjusting the pH of the copper extraction residual liquid, and extracting indium, wherein the extracting agent is P204, and the concentration is 30%. The indium extraction rate was 99.88%. And (3) performing back extraction on indium by using 6mol/L hydrochloric acid, and replacing the indium by using a zinc plate after the back extraction, wherein the replacement rate is more than 99.8%. And the sponge indium after replacement is fused and cast to obtain 97 percent of crude indium.
5. The pH of indium raffinate is adjusted to 4.5 by sodium hydroxide, and the indium raffinate is stirred at constant temperature for reaction, so that the precipitation rate of gallium can reach 99.97% in the process of neutralizing and precipitating gallium. Taking gallium precipitation slag, using 150g/L sodium hydroxide to perform alkaline leaching on the gallium precipitation slag, controlling the reaction temperature to be 85 ℃, and the reaction time to be 2 hours, wherein the gallium leaching rate is more than 99.5 percent in the alkalization liquid-making process. Obtaining gallium after electrodeposition, wherein the purity is more than 99%.
According to the process, a set of production line for processing 1000t/a CIGS chamber material every year is built, the total construction investment is 9436 ten thousand yuan, and the operation cost is 58652 yuan/ton.
Example 2
A method for recovering copper indium gallium selenide from CIGS manufacturing waste comprising the steps of:
1. and (3) carrying out crushing and ore grinding treatment on a CIGS chamber material sample, wherein the particle size after treatment is-150 meshes.
2. Adding hydrochloric acid and sodium chlorate into the treated sample for leaching, wherein the temperature is 60 ℃, and the solid-liquid ratio is 1: end point pH 0.1, potential 450mv, leaching time 3 h. Filtering to obtain crude selenium.
3. Replacing the sponge copper by zinc powder, wherein the potential is-150 mv, and obtaining the sponge copper. And performing electrolytic refining after briquetting to obtain cathode copper with the purity of 99.95 percent.
4. And continuously adding zinc powder into the solution after copper replacement to replace indium, wherein the potential is-260 mv, and the replacement rate is more than 99.8%. And the sponge indium after replacement is fused and cast to obtain 97 percent of crude indium.
5. The pH of indium raffinate is adjusted to 4.5 by sodium hydroxide, and the indium raffinate is stirred at constant temperature for reaction, so that the precipitation rate of gallium can reach 99.97% in the process of neutralizing and precipitating gallium. Taking gallium precipitation slag, using 150g/L sodium hydroxide to perform alkaline leaching on the gallium precipitation slag, controlling the reaction temperature to be 85 ℃, and the reaction time to be 2 hours, wherein the gallium leaching rate is more than 99.5 percent in the alkalization liquid-making process. Obtaining gallium after electrodeposition, wherein the purity is more than 99%.
According to the process, a set of production line for processing 1000t/a CIGS chamber material every year is built, the total construction investment is 6939 ten thousand yuan, the operation cost is 38545 yuan/ton, the investment is further reduced by 26.5% compared with that of embodiment 1, and the operation cost is further reduced by 34.3%.
To further illustrate the present application, the following comparative tests were performed:
test example 1
A method for recovering copper indium gallium selenide from CIGS manufacturing waste comprising the steps of:
1. and (3) carrying out crushing and ore grinding treatment on a CIGS chamber material sample, wherein the particle size after treatment is-100 meshes.
2. Adding hydrochloric acid and hydrogen peroxide into the treated sample for leaching, wherein the temperature is 60 ℃, and the solid-liquid ratio is 1: and 3, controlling the oxidation potential to be 400mV and the leaching time to be 3h, wherein the end point pH is 0.1. The crude selenium is obtained by filtering, the leaching rate of the selenium is only 0.5 percent, the selenium basically cannot enter the solution, the purity of the selenium is 98 percent, and the separation of the selenium and the copper indium gallium is realized.
Comparative test example 1
A method for recovering copper indium gallium selenide from CIGS manufacturing waste comprising the steps of:
1. and (3) carrying out crushing and ore grinding treatment on a CIGS chamber material sample, wherein the particle size after treatment is-100 meshes.
2. Adding hydrochloric acid and hydrogen peroxide into the treated sample for leaching, wherein the temperature is 60 ℃, and the solid-liquid ratio is 1: and 3, controlling the oxidation potential and leaching for 3h, wherein the end point pH is 0.1. Crude selenium is obtained by filtering, the leaching rate of the selenium reaches 28.3 percent, a large amount of selenium also enters the solution, and the separation of the selenium and the copper indium gallium cannot be realized.
Test example 2
A method for recovering copper indium gallium selenide from CIGS manufacturing waste comprising the steps of:
1. and (3) carrying out crushing and ore grinding treatment on a CIGS chamber material sample, wherein the particle size after treatment is-100 meshes.
2. Adding hydrochloric acid and sodium chlorate into the treated sample for leaching, wherein the temperature is 60 ℃, and the solid-liquid ratio is 1: end point pH 0.1, potential 450mv, leaching time 3 h. Filtering to obtain crude selenium.
3. Replacing the sponge copper with zinc powder, and controlling the reduction potential to be-180 mV to obtain the sponge copper. The indium content in the sponge copper is only 0.8 percent, and the separation of copper and indium is realized.
Comparative test example 2
A method for recovering copper indium gallium selenide from CIGS manufacturing waste comprising the steps of:
1. and (3) carrying out crushing and ore grinding treatment on a CIGS chamber material sample, wherein the particle size after treatment is-100 meshes.
2. Adding hydrochloric acid and sodium chlorate into the treated sample for leaching, wherein the temperature is 60 ℃, and the solid-liquid ratio is 1: end point pH 0.1, potential 450mv, leaching time 3 h. Filtering to obtain crude selenium.
3. Replacing the sponge copper by zinc powder without controlling the reduction potential to obtain the sponge copper. The indium content in the sponge copper reaches 17.5 percent, and the separation of copper and indium cannot be realized.
Comparative example 1
Chinese patent CN 102296178A, a method for recovering copper indium gallium selenide, first uses hydrochloric acid and hydrogen peroxide to dissolve metal powder. Selenium is separated using hydrazine to replace copper with indium. The indium gallium is separated by using a supported liquid film in combination with a dispersion stripping solution.
Comparative example 2
US patent US 5779877 discloses a two-electrode electrolytic separation of copper, selenium and gallium using nitric acid as a leaching agent. Then evaporating and decomposing to form a mixture of indium and zinc oxides, and oxidizing, distilling and separating copper and selenium.
Comparative example 3
Chinese patent CN 104032136 a, a recycling method for recycling copper indium gallium selenium, which uses copper indium gallium selenium waste as an anode device to perform electrolysis for recycling gallium, reduces and separates indium from indium hydroxide and copper selenium mixture by acid dissolution, and reduces and obtains selenium and copper by steps after the remaining copper selenium solution is acid-dissolved.
Comparative example 1 the process used a hydrochloric acid hydrogen peroxide medium as a dissolving agent to leach all selenium, copper, indium and gallium into solution. Then, the production cost of reducing selenium by hydrazine is high, and copper is replaced by indium, so that the production process flow is long and the operation cost is overhigh.
Comparative example 2 the process flow is too long and only metal oxides can be obtained, the results of two electrode points are difficult to control, and the oxidative distillation separation is difficult to be carried out completely.
In the comparative example 3, the copper indium gallium selenium waste is loose in character and can be used as an anode to have electrolysis conditions after being melted and cast, the volatilization amount of selenium cannot be ensured in the process, and the possibility of selenium poisoning may exist. Gallium is in a liquid state at normal temperature in the electrolytic separation process, and the control difficulty of production operation conditions is high. The copper-selenium anode mud belongs to inert metal and is difficult to realize by using acid dissolution only.
Therefore, the method selectively leaches the copper, the indium and the gallium by controlling the reduction potential, and the selenium is not leached, so that the selenium reduction process is reduced; then, copper and indium are selectively replaced step by step, so that the extraction flow of copper and indium is saved; then "depositing gallium-making liquid-electrodepositing" to produce metal gallium. The invention greatly shortens the process flow, and has less equipment investment and low operation cost.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. A method for recovering a copper indium gallium selenide material is characterized by comprising the following steps:
performing oxidation acid leaching on the pretreated material containing the copper, indium, gallium and selenium, wherein the oxidation-reduction potential of a system is controlled in the leaching process so that the copper, indium and gallium are dissolved in a solution, the selenium exists in the slag in a solid form, and performing solid-liquid separation on a leaching solution to obtain a solution containing the copper, the indium and the gallium and crude selenium;
separating copper and indium in the solution containing copper, indium and gallium by using a metal replacement method or a wet separation method, and treating to obtain metal copper, indium or salts thereof;
and adjusting the pH value of the solution after copper and indium are separated to precipitate gallium, and treating after solid-liquid separation to obtain the metal gallium.
2. The recovery method according to claim 1, wherein the separating copper and indium in the solution containing copper, indium, and gallium by the metal substitution method comprises:
firstly, adding metal powder into a solution containing copper, indium and gallium to replace the copper in the solution, and adding an oxidation-reduction potential of a process control solution to separate out copper and no indium to obtain sponge copper;
and then adding metal powder into the solution after copper replacement to continuously replace indium in the solution, and adding the process control solution to control the oxidation-reduction potential so that indium is separated out and no gallium is separated out, thereby obtaining sponge indium.
3. The recovery method according to claim 2, wherein the oxidation-reduction potential of the replacement copper process control solution is-100 to-220 mv;
the oxidation-reduction potential of the indium replacement process control solution is-220 to-500 mv.
4. The recovery method according to claim 1, wherein the copper and indium in the solution containing copper, indium and gallium are separated respectively using a wet separation method, wherein the wet separation comprises extraction or ion exchange separation, comprising:
(a) separating copper ions in the solution by adopting an extraction or ion exchange method, carrying out back extraction or desorption on the separated copper-containing carrier to obtain a copper solution, and treating to obtain metal copper or salt thereof;
(b) separating indium ions in the solution by adopting an extraction or ion exchange method, performing back extraction or desorption on the separated indium-containing carrier to obtain an indium solution, and treating to obtain metal indium or salt thereof;
wherein, the step (a) and the step (b) are not in sequence.
5. The recovery process according to claim 4, characterized in that the extractant used in step (a) is an aldoxime-type extractant, preferably comprising lix984 and/or M5640;
preferably, the concentration of the extractant is 10-70 wt%.
6. The recovery process according to claim 4, wherein the extractant used in step (b) is a phosphoric acid-based extractant, preferably comprising P204;
preferably, the concentration of the extractant is 10-70 wt%.
7. The recovery method according to claim 4, wherein in step (a), the copper solution is subjected to electrodeposition to obtain metallic copper or evaporative crystallization to obtain a copper salt product;
preferably, in the step (b), the indium solution is electrolyzed and refined to obtain metal indium after sponge indium is obtained by replacement, or an indium salt product is obtained by evaporation and crystallization.
8. A recovery process according to any one of claims 1 to 7, characterized in that the pre-treatment comprises: and (3) carrying out ore grinding treatment on the material containing the copper, indium, gallium and selenium, wherein the granularity of the material after ore grinding is 80-500 meshes.
9. The recovery method according to any one of claims 1 to 7, wherein the oxidizing agent used for the oxidative acid leaching comprises one or more of sodium chlorate, sodium perchlorate or hydrogen peroxide;
preferably, the acid used in the oxidative acidic leaching comprises one or more of sulfuric acid, hydrochloric acid or nitric acid;
preferably, the process conditions of the oxidative acid leaching comprise at least one of the following conditions:
the solid-liquid ratio of leaching is 1: 2-8, the leaching temperature is 16-100 ℃, the oxidation-reduction potential of a leaching process control system is kept at 300-500 mv, and the final acid concentration is 0.5-5 mol/L.
10. The recovery method according to any one of claims 1 to 7, characterized in that the pH value of the solution after separating copper and indium is adjusted to 2-6 to precipitate gallium, and gallium hydroxide obtained after solid-liquid separation is alkalized to make liquid and electrodeposited to obtain metal gallium;
preferably, the alkali concentration of the solution after alkalization liquid preparation is OH-The weight is 28-70 g/L.
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| CN113667840A (en) * | 2021-08-24 | 2021-11-19 | 安徽工业大学 | A method for extracting metal gallium from gallium nitride waste by wet processing |
| CN115354174A (en) * | 2022-07-14 | 2022-11-18 | 广东中金岭南鑫晟技术投资有限公司 | Method for removing impurity zinc in crude gallium |
| CN116281912A (en) * | 2023-03-03 | 2023-06-23 | 安徽工业大学 | Comprehensive recycling method for indium phosphide waste |
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| CN113667840A (en) * | 2021-08-24 | 2021-11-19 | 安徽工业大学 | A method for extracting metal gallium from gallium nitride waste by wet processing |
| CN115354174A (en) * | 2022-07-14 | 2022-11-18 | 广东中金岭南鑫晟技术投资有限公司 | Method for removing impurity zinc in crude gallium |
| CN115354174B (en) * | 2022-07-14 | 2024-04-02 | 广东中金岭南鑫晟技术投资有限公司 | Method for removing impurity zinc in crude gallium |
| CN116281912A (en) * | 2023-03-03 | 2023-06-23 | 安徽工业大学 | Comprehensive recycling method for indium phosphide waste |
| CN116281912B (en) * | 2023-03-03 | 2025-02-07 | 安徽工业大学 | A comprehensive recovery method for indium phosphide waste |
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