CN115491494B - Method for efficiently recycling metal indium and tin oxide by treating ITO waste targets through eutectic solvent system - Google Patents
Method for efficiently recycling metal indium and tin oxide by treating ITO waste targets through eutectic solvent system Download PDFInfo
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- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 title claims abstract description 100
- 230000005496 eutectics Effects 0.000 title claims abstract description 62
- 239000002904 solvent Substances 0.000 title claims abstract description 59
- 239000002699 waste material Substances 0.000 title claims abstract description 59
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 53
- 239000002184 metal Substances 0.000 title claims abstract description 53
- 238000000034 method Methods 0.000 title claims abstract description 38
- 238000004064 recycling Methods 0.000 title claims abstract description 16
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 229910001887 tin oxide Inorganic materials 0.000 title claims abstract description 16
- 229910003437 indium oxide Inorganic materials 0.000 title claims abstract description 11
- 229910052738 indium Inorganic materials 0.000 claims abstract description 90
- 239000000047 product Substances 0.000 claims abstract description 35
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 26
- 238000002386 leaching Methods 0.000 claims abstract description 17
- 229910006404 SnO 2 Inorganic materials 0.000 claims abstract description 14
- 239000000843 powder Substances 0.000 claims abstract description 13
- 239000000706 filtrate Substances 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- 238000001914 filtration Methods 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims description 21
- 238000003756 stirring Methods 0.000 claims description 21
- 238000001035 drying Methods 0.000 claims description 18
- 239000003792 electrolyte Substances 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 10
- 238000005266 casting Methods 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 8
- 239000011268 mixed slurry Substances 0.000 claims description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 6
- 239000011521 glass Substances 0.000 claims description 6
- 239000010936 titanium Substances 0.000 claims description 6
- 229910052719 titanium Inorganic materials 0.000 claims description 6
- CWJZHEADHFAKAS-UHFFFAOYSA-M 2-hydroxyethyl(trimethyl)azanium;propanedioic acid;chloride Chemical compound [Cl-].C[N+](C)(C)CCO.OC(=O)CC(O)=O CWJZHEADHFAKAS-UHFFFAOYSA-M 0.000 claims description 5
- 229910002804 graphite Inorganic materials 0.000 claims description 4
- 239000010439 graphite Substances 0.000 claims description 4
- IYZAKYBKKQCJDI-UHFFFAOYSA-N propanedioic acid;thiourea Chemical compound NC(N)=S.OC(=O)CC(O)=O IYZAKYBKKQCJDI-UHFFFAOYSA-N 0.000 claims description 4
- ZGMRGXXFIUDSAJ-UHFFFAOYSA-N propanedioic acid;urea Chemical compound NC(N)=O.OC(=O)CC(O)=O ZGMRGXXFIUDSAJ-UHFFFAOYSA-N 0.000 claims description 4
- 238000010907 mechanical stirring Methods 0.000 claims description 3
- 239000010935 stainless steel Substances 0.000 claims description 3
- 229910001220 stainless steel Inorganic materials 0.000 claims description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 abstract description 12
- 238000000926 separation method Methods 0.000 abstract description 7
- 238000011084 recovery Methods 0.000 abstract description 5
- 238000004090 dissolution Methods 0.000 abstract description 4
- 238000005272 metallurgy Methods 0.000 abstract description 2
- 239000002893 slag Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 7
- RHZWSUVWRRXEJF-UHFFFAOYSA-N indium tin Chemical compound [In].[Sn] RHZWSUVWRRXEJF-UHFFFAOYSA-N 0.000 description 6
- 229910001128 Sn alloy Inorganic materials 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000004846 x-ray emission Methods 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000005265 energy consumption Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- -1 oxygen ions Chemical class 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- YWFJEGOSKAAABP-UHFFFAOYSA-N ethane-1,2-diol;propanedioic acid Chemical compound OCCO.OC(=O)CC(O)=O YWFJEGOSKAAABP-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 229910001338 liquidmetal Inorganic materials 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000011224 oxide ceramic Substances 0.000 description 1
- 229910052574 oxide ceramic Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000009853 pyrometallurgy Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G19/00—Compounds of tin
- C01G19/02—Oxides
-
- 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
- C22B25/00—Obtaining tin
- C22B25/04—Obtaining tin by 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
- C22B25/00—Obtaining tin
- C22B25/06—Obtaining tin from scrap, especially tin scrap
-
- 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
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C3/00—Electrolytic production, recovery or refining of metals by electrolysis of melts
- C25C3/34—Electrolytic production, recovery or refining of metals by electrolysis of melts of metals not provided for in groups C25C3/02 - C25C3/32
-
- 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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Metallurgy (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Electrochemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Electrolytic Production Of Metals (AREA)
Abstract
The invention discloses a method for efficiently recycling metallic indium and tin oxide by treating an ITO waste target through a eutectic solvent system, and belongs to the technical field of nonferrous metal metallurgy. The invention adopts the eutectic solvent to leach the ITO waste target powder, so that In the ITO waste target is obtained 2 O 3 Selective dissolution of SnO occurs 2 No reaction occurs and the reaction is enriched in leaching slag, so that the high-efficiency separation of indium and tin is realized. Filtering the leached pulp, wherein filter residues are pure SnO 2 A product; subjecting the filtrate to direct current electrolysis to dissolve In the solution 3+ Electrons are obtained at the cathode, and the metal indium product is obtained through reduction. The invention fully utilizes the eutectic solvent to make the In 2 O 3 Has the characteristics of high selective solubility and wide electrochemical window, and is used as a basic system for treating ITO waste targets to recover indium metal and SnO respectively 2 The product has the characteristics of short flow, high efficiency, low cost, high indium and tin recovery rate, high product purity and the like.
Description
Technical Field
The invention belongs to the technical field of nonferrous metal metallurgy, and particularly relates to a method for efficiently recycling metal indium and tin oxide by treating an ITO waste target through a eutectic solvent system.
Background
An Indium Tin Oxide (ITO) target is formed by In 2 O 3 And SnO 2 According to the mass ratio of 9:1, and an oxide ceramic sintered body comprising the sameThe prepared ITO film has good light transmittance and conductivity, and is an irreplaceable transparent electrode material of the flat panel display at present. At present, the ITO film is almost produced by an ITO target magnetron sputtering coating method, but the actual utilization rate of the ITO target in the coating process is only about 30%, the rest is a waste target, and the waste of indium resources is caused by scraps, chips and the like generated in the target preparation and forming process.
The ITO waste target contains a large amount of scattered metal indium, and is an important indium secondary resource. Currently, the global indium used to make ITO targets accounts for 40-50% of its total yield. According to statistics, the content of indium in the ITO waste targets produced in China every year reaches more than 300 tons, and the indium reserve which is currently ascertained in China is only about 8000 tons. Therefore, developing the technology of the high-efficiency short-flow ITO waste target recovery technology has important significance for guaranteeing the sustainable development of the indium industry in China.
Through retrieval, the application of Chinese patent application number 202010451276.7 discloses a method for recovering an ITO waste target by electrolyzing an aqueous solution, the method is characterized in that the ITO waste target is treated in a split type electrolytic tank connected by a salt bridge, indium is recovered by a two-stage electrolysis process, the ion composition and the pH value of a cathode region and an anode region are strictly controlled respectively in the electrolysis process, and an ultrasonic auxiliary electrolysis process is needed, so that the process flow is complex, the equipment requirement is high, and the high-efficiency recovery of the ITO waste target is difficult to realize. The application of Chinese patent application number 200910238428.9 discloses a method for preparing indium tin alloy by using ITO waste targets as cathodes in an aqueous solution through electrolysis, but an electrochemical window of an aqueous solution system is limited, the solubility of oxygen ions is small, and the high-efficiency deoxidization and reduction of the ITO waste targets at the cathodes are difficult to realize in theory. The application of Chinese patent application No. 202010967580.7 discloses an indium-tin alloy treatment method based on pyrometallurgy, which utilizes the difference of vapor pressures of indium and tin under high temperature conditions, and makes indium in the indium-tin alloy fully volatilize into a gas phase by controlling the vacuum degree and the temperature in a reactor, and further recovers in a condensation area, thereby realizing the high-efficiency separation of indium and tin; however, the process needs to be operated under high temperature and vacuum conditions, special vacuum metallurgical equipment is needed to realize the process, and the energy consumption required by the reaction is high. The application of the Chinese patent application number 201510896090.1 adopts an acidic aqueous solution system with pH=2.0-2.5 as electrolyte, and takes indium tin alloy as anode for electrolytic refining, so that the purity of the obtained metal indium product can reach more than 99.99 percent; however, the oxidation-reduction potential difference of indium and tin in the aqueous solution system is smaller, the anode residue rate of single electrolysis is higher, and multiple electrolysis is needed to realize effective separation of indium and tin. The application of Chinese patent application No. 201810528444.0 discloses a method for recovering crude indium from waste ITO powder by a molten salt electrochemical method, wherein graphite is used as an anode, molten metal indium or tin is used as a liquid cathode, ITO lump material obtained by high-temperature sintering is suspended in a mixed electrolyte of molten lithium chloride and potassium chloride for direct current electrolysis, indium tin alloy is obtained in the liquid metal cathode, but the solubility and dissolution speed of ITO in chloride molten salt are low, the efficiency of the electrolysis process is limited, the temperature of the electrolysis process is high, the corrosiveness is strong, the energy consumption is high, and the production cost is high.
Disclosure of Invention
1. Problems to be solved
Aiming at the problems of small electrochemical window, high indium-tin separation difficulty, low metal indium reduction efficiency and the like In the existing technology for recycling the ITO waste targets by using an aqueous solution electrolysis system, and the problems of high energy consumption, high corrosiveness, high equipment requirement, high production cost and the like In the fused salt electrolysis technology, the invention aims to provide a method for efficiently recycling the metal indium and the tin oxide In the ITO waste targets by using a eutectic solvent system, and leaching ITO waste target powder by using the eutectic solvent to ensure that In the ITO waste targets 2 O 3 Selective dissolution of SnO occurs 2 No reaction occurs, high-efficiency separation of indium and tin is realized, and SnO is obtained 2 A product; subjecting the filtrate to direct current electrolysis to dissolve In the solution 3+ Electrons are obtained at the cathode, and the metal indium product is obtained through reduction. The invention fully utilizes the eutectic solvent system to carry out the reaction on In 2 O 3 Has the characteristics of high selective solubility and wide electrochemical window, and is used as a basic system for treating ITO waste targets to recover indium metal and SnO respectively 2 The product has short flowHigh efficiency, low cost, high indium and tin recovery rate, high product purity, etc.
2. Technical proposal
In order to solve the problems, the technical scheme adopted by the invention is as follows:
the method for efficiently recovering the metallic indium and the tin oxide by treating the ITO waste target through the eutectic solvent system adopts the eutectic solvent to leach the ITO waste target powder, so that the In the ITO waste target is realized 2 O 3 Selective dissolution of SnO occurs 2 No reaction occurs, and the reaction is enriched in leaching slag, so that the high-efficiency separation of indium and tin is realized; filtering the leached pulp, wherein filter residues are pure SnO 2 A product; subjecting the filtrate to direct current electrolysis to dissolve In the solution 3+ Electrons are obtained at the cathode, and metal indium products are obtained through reduction, so that metal indium and SnO in the ITO waste target are realized 2 Is efficiently recovered.
Furthermore, the method for efficiently recycling the metal indium and the tin oxide by treating the ITO waste target through the eutectic solvent system is characterized by comprising the following steps of: the eutectic solvent system consists of malonic acid-choline chloride or malonic acid-urea or malonic acid-thiourea or malonic acid-glycol binary eutectic system.
Further, the specific process comprises the following steps:
s1, preparing a binary eutectic solvent system: uniformly mixing the raw materials, heating to obtain a liquid eutectic solvent system, and mechanically stirring the system to fully and uniformly mix the system;
specifically, preparing a binary eutectic solvent system consisting of malonic acid-choline chloride, malonic acid-urea, malonic acid-thiourea or malonic acid-glycol, uniformly mixing the raw materials, heating to 50-90 ℃ to obtain a liquid eutectic solvent system, and mechanically stirring the system at the stirring speed of 250-450rpm to fully and uniformly mix the eutectic solvent system;
s2, adding the ITO waste target powder into the prepared eutectic solvent system, and enabling In the ITO waste target to be under the condition of mechanical stirring 2 O 3 Fully dissolving to realize the selective leaching of indium;
specifically, adding ITO waste target powder with granularity smaller than 300 μm into the prepared eutectic solvent system, and mechanically stirring at 250-450rpm at 50-90deg.C to obtain In In the ITO waste target 2 O 3 Fully dissolving to realize the selective leaching of indium;
s3, filtering the solid-liquid mixed slurry obtained by leaching, fully washing and drying filter residues to obtain SnO 2 A product; drying at 120-150deg.C for 24-72 hr;
s4, carrying out direct current electrolysis on the filtrate to dissolve In the solution 3+ Electrons are obtained at the cathode, and metal indium is obtained through reduction;
specifically, the filtrate is used as electrolyte, graphite or glass carbon is used as anode, stainless steel plate or titanium plate is used as cathode to carry out direct current electrolysis under the condition that the tank voltage is 1.5-2.5V, the temperature of the electrolyte is 50-90 ℃ and the time is 8-24h, so that In dissolved In the solution 3+ Electrons are obtained at the cathode, and metal indium is obtained through reduction;
s5, washing and drying the metal indium collected by the cathode, further casting into ingots to obtain indium ingot products, specifically drying at 40-100 ℃ for 24-72h, and further casting the metal indium into ingots at 300-450 ℃.
The invention fully utilizes the eutectic solvent to make the In 2 O 3 Has the characteristics of high selective solubility and wide electrochemical window, and is used as a basic system for treating ITO waste targets to recover indium metal and SnO respectively 2 The product has the characteristics of short flow, high efficiency, low cost, high indium and tin recovery rate, high product purity and the like.
3. Advantageous effects
Compared with the prior art, the invention has the beneficial effects that:
(1) The invention relates to a method for efficiently recycling metallic indium and tin oxide In an ITO waste target treated by a eutectic solvent system, which adopts the eutectic solvent system based on malonic acid to treat and recycle the ITO waste target and aims at In the ITO waste target 2 O 3 Has extremely strong dissolving capacity, and SnO in the ITO waste target 2 In eutectic solventHas strong stability In the system and can realize In 2 O 3 Can realize the high-efficiency separation of indium and tin by one-step operation and obtain SnO at the same time 2 A product; the whole production process has short flow, high efficiency and SnO 2 The product has high purity.
(2) The method for efficiently recycling the metallic indium and the tin oxide by treating the ITO waste target through the eutectic solvent system has wider electrochemical window and higher conductivity compared with aqueous solution by taking the eutectic solvent system as electrolyte, can carry out electrolysis under the condition of high current density, and is beneficial to dissolving In the system 3+ The ions are quickly reduced into metal indium at the cathode, so that the electrolysis efficiency is high, and the purity of the metal indium product is high.
(3) According to the method for efficiently recycling the metal indium and the tin oxide by treating the ITO waste target through the eutectic solvent system, no impurities are accumulated in the whole electrolysis process, the eutectic solvent system can be recycled, the consumption of reagents is small, and the production cost is low; and the whole process does not produce pollutants such as waste water, waste residue and the like, and is environment-friendly.
Detailed Description
The invention is further described below in connection with specific embodiments.
Example 1
The method for efficiently recycling metallic indium and tin oxide by treating the ITO waste target through the eutectic solvent system in the embodiment specifically comprises the following steps:
s1, preparing a binary eutectic solvent system consisting of malonic acid-choline chloride, uniformly mixing raw materials, heating to 50 ℃ to obtain a liquid eutectic solvent system, and mechanically stirring the system at the stirring speed of 250rpm to fully and uniformly mix the eutectic solvent system;
s2, adding the ITO waste target powder with the granularity smaller than 300 mu m into the prepared eutectic solvent system, and mechanically stirring at 50 ℃ and 250rpm to enable In the ITO waste target to be In 2 O 3 Fully dissolving to realize the selective leaching of indium;
s3, carrying out treatment on the solid-liquid mixed slurry obtained by leachingFiltering, washing the filter residue, and drying at 120deg.C for 72 hr to obtain SnO 2 A product;
s4, using filtrate as electrolyte, using graphite as anode, using stainless steel plate as cathode to make direct current electrolysis under the condition of tank voltage of 1.5V, electrolyte temperature being 50 deg.C and time being 24 hr so as to make In dissolved In solution 3+ Electrons are obtained at the cathode, and metal indium is obtained through reduction;
s5, washing the metal indium collected by the cathode, drying the metal indium at the temperature of 40 ℃ for 72 hours, and further casting the metal indium into ingots at the temperature of 300 ℃ to obtain indium ingot products.
By the treatment method of this example, metallic indium and SnO were analyzed by X-ray diffraction and X-ray fluorescence spectroscopy, respectively 2 The phase composition and chemical composition of the product show that the purity of the obtained indium metal is 99.18 percent, and SnO 2 The purity was 99.23%.
Example 2
The method for efficiently recycling metallic indium and tin oxide by treating the ITO waste target through the eutectic solvent system in the embodiment specifically comprises the following steps:
s1, preparing a binary eutectic solvent system with a composition of malonic acid-urea, uniformly mixing raw materials, heating to 90 ℃ to obtain a liquid eutectic solvent system, and mechanically stirring the system at the stirring speed of 450rpm to fully and uniformly mix the eutectic solvent system;
s2, adding the ITO waste target powder with the granularity smaller than 300 mu m into the prepared eutectic solvent system, and mechanically stirring at the temperature of 90 ℃ and at the speed of 450rpm to enable In the ITO waste target to be In contact with the eutectic solvent system 2 O 3 Fully dissolving to realize the selective leaching of indium;
s3, filtering the solid-liquid mixed slurry obtained by leaching, fully washing filter residues, and drying at 150 ℃ for 24 hours to obtain SnO 2 A product;
s4, carrying out direct current electrolysis on the filtrate serving as an electrolyte and the glass carbon serving as an anode and a titanium plate serving as a cathode under the condition that the tank voltage is 2.5V, wherein the temperature of the electrolyte is 90 ℃ and the time is 8 hours, so that In dissolved In the solution 3+ Electrons are obtained at the cathode, and metal indium is obtained through reduction;
s5, washing the metal indium collected by the cathode, drying the metal indium at the temperature of 100 ℃ for 24 hours, and further casting the metal indium into ingots at the temperature of 450 ℃ to obtain indium ingot products.
By the treatment method of this example, metallic indium and SnO were analyzed by X-ray diffraction and X-ray fluorescence spectroscopy, respectively 2 The phase composition and chemical composition of the product show that the purity of the obtained indium metal is 99.33 percent, and SnO 2 The purity was 99.16%.
Example 3
The method for efficiently recycling metallic indium and tin oxide by treating the ITO waste target through the eutectic solvent system in the embodiment specifically comprises the following steps:
s1, preparing a binary eutectic solvent system with a composition of malonic acid-thiourea, uniformly mixing raw materials, heating to 60 ℃ to obtain a liquid eutectic solvent system, and mechanically stirring the system at a stirring speed of 300rpm to fully and uniformly mix the eutectic solvent system;
s2, adding the ITO waste target powder with the granularity smaller than 300 mu m into the prepared eutectic solvent system, and mechanically stirring at 60 ℃ and 300rpm to enable In the ITO waste target to be In 2 O 3 Fully dissolving to realize the selective leaching of indium;
s3, filtering the solid-liquid mixed slurry obtained by leaching, fully washing filter residues, and drying at 130 ℃ for 48 hours to obtain SnO 2 A product;
s4, carrying out direct current electrolysis on the filtrate serving as an electrolyte and the glass carbon serving as an anode and a titanium plate serving as a cathode under the condition that the tank voltage is 1.7V, wherein the temperature of the electrolyte is 60 ℃ and the time is 20h, so that In dissolved In the solution 3+ Electrons are obtained at the cathode, and metal indium is obtained through reduction;
s5, washing the metal indium collected by the cathode, drying the metal indium at 50 ℃ for 48 hours, and further casting the metal indium into ingots at 350 ℃ to obtain indium ingot products.
By the processing method of the embodiment, respectively by X-raysDiffraction and X-ray fluorescence spectroscopy analysis of indium metals and SnO 2 The phase composition and chemical composition of the product show that the purity of the obtained indium metal is 99.27 percent, snO 2 The purity was 99.21%.
Example 4
The method for efficiently recycling metallic indium and tin oxide by treating the ITO waste target through the eutectic solvent system in the embodiment specifically comprises the following steps:
s1, preparing a binary eutectic solvent system consisting of malonic acid-ethylene glycol, uniformly mixing raw materials, heating to 70 ℃ to obtain a liquid eutectic solvent system, and mechanically stirring the system at the stirring speed of 350rpm to fully and uniformly mix the eutectic solvent system;
s2, adding the ITO waste target powder with the granularity smaller than 300 mu m into the prepared eutectic solvent system, and mechanically stirring at the temperature of 70 ℃ and at the speed of 350rpm to enable In the ITO waste target to be In contact with the eutectic solvent system 2 O 3 Fully dissolving to realize the selective leaching of indium;
s3, filtering the solid-liquid mixed slurry obtained by leaching, fully washing filter residues, and drying at 140 ℃ for 36 hours to obtain SnO 2 A product;
s4, carrying out direct current electrolysis on the filtrate serving as an electrolyte and the glass carbon serving as an anode and a titanium plate serving as a cathode under the condition that the tank voltage is 1.9V, wherein the temperature of the electrolyte is 70 ℃ and the time is 16h, so that In dissolved In the solution 3+ Electrons are obtained at the cathode, and metal indium is obtained through reduction;
s5, washing the metal indium collected by the cathode, drying at the temperature of 60 ℃ for 36 hours, and further casting the metal indium into ingots at the temperature of 400 ℃ to obtain indium ingot products.
By the treatment method of this example, metallic indium and SnO were analyzed by X-ray diffraction and X-ray fluorescence spectroscopy, respectively 2 The phase composition and chemical composition of the product show that the purity of the obtained indium metal is 99.38%, snO 2 The purity was 99.04%.
Example 5
The method for efficiently recycling metallic indium and tin oxide by treating the ITO waste target through the eutectic solvent system in the embodiment specifically comprises the following steps:
s1, preparing a binary eutectic solvent system consisting of malonic acid-choline chloride, uniformly mixing raw materials, heating to 80 ℃ to obtain a liquid eutectic solvent system, and mechanically stirring the system at a stirring speed of 400rpm to fully and uniformly mix the eutectic solvent system;
s2, adding the ITO waste target powder with the granularity smaller than 300 mu m into the prepared eutectic solvent system, and mechanically stirring at 80 ℃ and 400rpm to enable In the ITO waste target to be In 2 O 3 Fully dissolving to realize the selective leaching of indium;
s3, filtering the solid-liquid mixed slurry obtained by leaching, fully washing filter residues, and drying at 135 ℃ for 40 hours to obtain SnO 2 A product;
s4, carrying out direct current electrolysis on the filtrate serving as an electrolyte and the glass carbon serving as an anode and a titanium plate serving as a cathode under the condition that the tank voltage is 2.3V, wherein the temperature of the electrolyte is 80 ℃ and the time is 12 hours, so that In dissolved In the solution 3+ Electrons are obtained at the cathode, and metal indium is obtained through reduction;
s5, washing the metal indium collected by the cathode, drying the metal indium at the temperature of 80 ℃ for 30 hours, and further casting the metal indium into ingots at the temperature of 420 ℃ to obtain indium ingot products.
By the treatment method of this example, metallic indium and SnO were analyzed by X-ray diffraction and X-ray fluorescence spectroscopy, respectively 2 The phase composition and chemical composition of the product show that the purity of the obtained indium metal is 99.46 percent, snO 2 The purity was 99.16%.
The invention and its embodiments have been described above by way of illustration and not limitation, but rather one of the embodiments of the invention is not limited thereto. Therefore, if one of ordinary skill in the art is informed by this disclosure, the structural mode and the embodiments similar to the technical scheme are not creatively designed without departing from the gist of the present invention.
Claims (1)
1. A method for efficiently recycling metallic indium and tin oxide by treating ITO waste targets through a eutectic solvent system is characterized by comprising the following steps of: the specific process comprises the following steps:
s1, preparing a binary eutectic solvent system: uniformly mixing the raw materials, heating to obtain a liquid eutectic solvent system, and mechanically stirring the system to fully and uniformly mix the system; the eutectic solvent system consists of a malonic acid-choline chloride or malonic acid-urea or malonic acid-thiourea or malonic acid-glycol binary eutectic system; heating at 50-90deg.C, and mechanically stirring at 250-450 rpm;
s2, adding the ITO waste target powder into the prepared eutectic solvent system, and enabling In the ITO waste target to be under the condition of mechanical stirring 2 O 3 Fully dissolving to realize the selective leaching of indium; the granularity of the ITO waste target powder is less than 300 mu m, the reaction temperature is 50-90 ℃, and the mechanical stirring speed is 250-450 rpm;
s3, filtering the solid-liquid mixed slurry obtained by leaching, fully washing and drying filter residues to obtain SnO 2 A product; the drying temperature of the filter residue is 120-150 ℃ and the time is 24-72h;
s4, carrying out direct current electrolysis on the filtrate to dissolve In the solution 3+ Electrons are obtained at the cathode, and metal indium is obtained through reduction; the electrolysis system adopts graphite or glass carbon as an anode, a stainless steel plate or a titanium plate as a cathode, the voltage of a direct current electrolytic tank is 1.5-2.5V, the temperature of electrolyte is 50-90 ℃ and the time is 8-24 h;
s5, washing and drying the metal indium collected by the cathode, and further casting into ingots to obtain indium ingot products; the drying temperature of the metal indium obtained by collecting the cathode is 40-100 ℃, the time is 24-72h, and the casting temperature of the indium ingot is 300-450 ℃.
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| CN104862482A (en) * | 2014-02-18 | 2015-08-26 | 纳米及先进材料研发院有限公司 | Method of selective recovery of valuable metals from mixed metal oxides |
| CN105483389A (en) * | 2016-01-13 | 2016-04-13 | 云南大学 | Leaching method for indium in waste liquid crystal panel and leaching agent |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104862482A (en) * | 2014-02-18 | 2015-08-26 | 纳米及先进材料研发院有限公司 | Method of selective recovery of valuable metals from mixed metal oxides |
| CN105483389A (en) * | 2016-01-13 | 2016-04-13 | 云南大学 | Leaching method for indium in waste liquid crystal panel and leaching agent |
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| Title |
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| 王晓民，南辉.《镁铝铟冶金及其复合材料轻量化》.冶金工业出版社,2018,229. * |
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