CN107513619A - A kind of method of recovery indium and tin in waste material from ito glass - Google Patents

A kind of method of recovery indium and tin in waste material from ito glass Download PDF

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CN107513619A
CN107513619A CN201710692579.6A CN201710692579A CN107513619A CN 107513619 A CN107513619 A CN 107513619A CN 201710692579 A CN201710692579 A CN 201710692579A CN 107513619 A CN107513619 A CN 107513619A
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solution
ito glass
solid
sno
indium
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CN107513619B (en
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田庆华
刘子康
郭学益
李栋
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Central South University
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/006—Wet processes
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • 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
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
    • C22B3/40—Mixtures
    • C22B3/409—Mixtures at least one compound being an organo-metallic compound
    • 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
    • C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
    • C25C1/22—Electrolytic production, recovery or refining of metals by electrolysis of solutions of metals not provided for in groups C25C1/02 - C25C1/20
    • 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)
  • Metallurgy (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Manufacturing & Machinery (AREA)
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  • Life Sciences & Earth Sciences (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Processing Of Solid Wastes (AREA)

Abstract

The invention provides a kind of method of recovery indium and tin in waste material from ito glass, comprise the following steps：(1) HCl and HNO is used3Mixed solution immersion ito glass powder, and add H2O2Solution；(2) using the mixed solution of P204 and kerosene as extractant, HCl solution is that strippant is extracted and is stripped to leachate；(3) NaOH solution is added dropwise into the aqueous phase after back extraction, then carries out separation of solid and liquid, obtains Na2SnO3Solution and In (OH)3Solid；(4)In(OH)3Solid obtains sponge indium with being electrolysed after dissolving with hydrochloric acid；To Na2SnO3NaHCO is added in solution3Solution, the precipitation of generation dry to obtain SnO through high temperature2Product.This method can realize that the high efficiency of indium and tin leaches simultaneously, also with the advantages of acid and alkali consumption amount is low, reaction efficiency is high, simple to operate, environmental pollution is small, suitable for industrialized production.

Description

A kind of method of recovery indium and tin in waste material from ito glass
Technical field
The invention belongs to a kind of method of recovery indium and tin in scrap concrete technical field, more particularly to waste material from ITO.
Background technology
Liquid crystal display device (Liquid Crystal Display, LCD) has work because its manufacturing cost constantly reduces Voltage is low, energy consumption is low, flicker free, total colouring function admirable, light portable, electromagnetic-radiation-free and is easily achieved big picture and shows The advantages that showing and rapidly become one of current most great-hearted electronic product, it is all kinds of aobvious to be widely used in computer, TV, mobile phone etc. Show equipment.
Liquid crystal display may enter the date of retirement after using 3-5, so as to cause to produce largely discarded liquid crystal Show device, the increase of learies will be to environment structure potential threat.ITO has good as nano indium tin metal oxide Electric conductivity and the transparency, harmful electron radiation, ultraviolet and far infrared can be cut off.Therefore, indium tin oxide Generally it is sprayed in glass, plastics and electronic display, as transparent conductive film, while reduces harmful electronics spoke Penetrate and ultraviolet, infra-red radiation.Indium is the rare precious metal that content is very low in a kind of earth's crust, there are about 60%~70% indium and is used for The making of tin indium oxide (ITO) glass in liquid crystal display.At present, the recycling technology of waste liquid crystal display is mainly Landfill and burning, operating procedure is simple, treating capacity is big, operating cost is cheap, is that most countries and area are very heavy in the world The municipal solid wastes processing mode wanted.In the case where indium, tin resource are rare, this mode can not effective recycling Indium, tin scarce resource, so as to accelerate the exploitation of indium, tin mineral, cause the destruction of ecological environment and accelerate the withered of mineral resources Exhaust.
The domestic patent literature on recovery indium is directed generally to exist from the recovery such as smeltery's slag, waste water content More than 0.5% high-grade indium.Patent document CN101133172A discloses a kind of method and dress of the recovery indium from useless LCD Put.This method has carried out the contrast experiment of 24h and 48h dissolutions using the hydrochloric acid of 1%, 3% and 10% 3 various concentrations respectively, It is oversize to there is extraction time, the problem of low production efficiency.
The method that patent document CN 101722169A disclose a kind of processing of liquid crystal display (LCD) harmless, this method is by liquid Heating and decomposition treatment after the glass substrate containing liquid crystal crushes in crystal display, caused organic gas is fully fired at high temperature Harmless discharge after burning processing, but without reference to the specific method of recovery indium.
Patent document CN1900770A discloses a kind of liquid crystal display panel resource processing method, and the invention is realized to useless Old glass panel harmless treatment, but gone in the step of removing light polarizing film using organic matter, inorganic acid or inorganic base immersion The method removed, resource consumption is big, and easily pollutes environment and be difficult to industrialization.
The content of the invention
The technical problems to be solved by the invention are to overcome the shortcomings of to mention in background above technology and defect, there is provided one Kind technique cleans, flow is short, the method for recovery indium and tin in easy to operate, the high waste material from ito glass of metal recovery rate.
In order to solve the above technical problems, technical scheme proposed by the present invention for one kind from ito glass waste material recovery indium with The method of tin, comprises the following steps：
(1) HCl solution and HNO are used3The mixed solution A of solution soaks ito glass powder, and H is added in immersion process2O2It is molten Liquid, leachate and leached mud are obtained after reaction；
(2) it is as extractant, HCl solution using the mixed solution B of di-(2-ethylhexyl)phosphoric acid ester (P204) and kerosene Strippant is extracted and is stripped to leachate；
(3) NaOH solution is added dropwise into the aqueous phase after back extraction, reaction carries out separation of solid and liquid after terminating, obtains Na2SnO3It is molten Liquid and In (OH)3Solid, with dissolving with hydrochloric acid In (OH)3Solid obtains containing In3+Solution；
(4) to containing In3+Solution is electrolysed, and sponge indium is obtained after separation of solid and liquid；To Na2SnO3NaHCO is added in solution3 Solution, obtain Sn (OH)4Precipitate, dry to obtain SnO through high temperature after separation of solid and liquid2Product.
Above-mentioned method, it is preferred that the mol ratio of hydrochloric acid and nitric acid is 8 in the mixed solution A of the step (1)：(3~ 7), H in mixed solution A+Molar concentration be 7~8mol/L.By Experimental Research, it has been found that hydrochloric acid to the leaching rate of indium compared with Height, nitric acid are higher to the leaching rate of tin, by controlling the ratio of hydrochloric acid and nitric acid appropriate, can simultaneously high efficiency leach indium with Tin.
Above-mentioned method, it is preferred that in the step (1), addition H per minute2O2The volume of solution accounts for mixed solution A body Long-pending 0.2%~1.5%；The H2O2The mass fraction of solution is 15%~45%.It is furthermore preferred that the H2O2The matter of solution It is 30% to measure fraction.The H of dropwise addition2O2Solution should not be excessive, H when excessive2O2Volume fraction is larger, and acid solution volume fraction is smaller, So as to pulp density increase, mass transfer rate is caused to reduce；If with constant flow pump by H2O2During being continuously added, it is molten that acid can be reduced Liquid concentration, causes metal leaching rate to reduce；Therefore, by H2O2The rate of addition control of solution within the scope of the invention, can enter one Step improves the oxidisability of solution, contributes to metal to be dissolved in acid, so as to further improve leaching efficiency, but also can avoid A large amount of oxygen generations are overflowed in course of reaction.
Above-mentioned method, in theory, H is added in mixed solution A2O2Following chemically react occurs after solution：
In2O3+6H+→2In3++3H2O；
2InO+6H++3H2O2→2In3++6H2O+O2↑；
2In2O+12H++6H2O2→4In3++12H2O+O2↑；
SnO+H2O2+4H+→Sn4++3H2O。
Above-mentioned method, it is preferred that the current density of electrolytic process is 100~250A/m in the step (4)2, use Aluminium sheet is as anode.It is furthermore preferred that current density is 150~200A/m2.It is rich by being electrolysed displacement using aluminium sheet as anode Indium in indium liquid, than traditional being directly added into, aluminium powder progress displacement efficiency is higher, and the rate of recovery of indium is higher, and additional power source causes sun Electronics in the aluminium sheet of pole faster flows to negative electrode, and Al loses electronics and becomes Al3+, In3+Electronics, which is obtained, in negative electrode becomes sponge indium.
Above-mentioned method, it is preferred that the NaHCO added in the step (4)3With Na in solution2SnO3Mol ratio be (1.5~2.5)：1.It is furthermore preferred that the NaHCO added in the step (4)3With Na in solution2SnO3Mol ratio for (1.8~ 2)：1.In the basic conditions, NaHCO is added when solution oxide current potential is higher3The pH of solution is adjusted, the SnO in precipitation solution3 2-, Prepare SnO2Product, avoid a large amount of consumption of soda acid, reduce the reaction time；Chemically reacted below the generation of the process： Na2SnO3+2NaHCO3+H2O→Sn(OH)4+2Na2CO3.Obtained Sn (OH)4After the filtered drying of colloid, you can obtain SnO2 Product：Sn(OH)4→SnO2+2H2O。
Above-mentioned method, it is preferred that first generate In (OH) after NaOH solution is added dropwise in the step (3)3With Sn (OH)4It is heavy Form sediment, continuing dropwise addition dissolves precipitation, stops being added dropwise when no longer reducing until precipitating, now pH value >=9, Ran Houjin of aqueous phase solution Row separation of solid and liquid obtains Na2SnO3Solution and In (OH)3Solid.This course of reaction, it is main that following chemically react occurs：
In3++3OH-→In(OH)3；
Sn2++4OH-→Sn(OH)4；
Sn(OH)4+2OH-→SnO3 2-+3H2O；
Above-mentioned method, it is preferred that the ratio of the volume of mixed solution A and the quality of ito glass powder in the step (1) For 20~30ml/g.
Above-mentioned method, it is preferred that in the step (1) soaking temperature be 30 DEG C~60 DEG C, soak time be 30~ 60min, H is added dropwise2O2The time of sustained response is 30~60min after solution.It is furthermore preferred that soaking temperature is 50 DEG C~60 DEG C.
Above-mentioned method, it is preferred that the preparation process of ito glass powder includes operating in detail below in the step (1) Step：Ito glass 30~60min of waste material first is soaked with n-hexane, then removes two layers of polarisation above and below ito glass waste material with blade Piece, waste material is finally crushed to 0.5~2.5mm, obtains ito glass powder.It is furthermore preferred that waste material is crushed to 0.5~ 1.0mm, obtain ito glass powder.By Task-size Controlling within the scope of the invention, be advantageous to improve ito glass in leaching process Powder participates in the surface area of reaction, while carries out mechanical activation, accelerates reaction speed.
Compared with prior art, using the present invention method from ito glass waste material recovery indium and tin, can realize simultaneously The high efficiency of indium and tin leaches, the rate of recovery up to more than 95% of indium and tin, sponge indium product and SnO2The purity of product is equal Up to more than 90%；The method of the present invention is also with acid and alkali consumption amount is low, reaction efficiency is high, cost is low, simple to operate, environment is dirty The advantages of small is contaminated, suitable for industrialized production.
Brief description of the drawings
In order to illustrate more clearly about the embodiment of the present invention or technical scheme of the prior art, below will be to embodiment or existing There is the required accompanying drawing used in technology description to be briefly described, it should be apparent that, drawings in the following description are the present invention Some embodiments, for those of ordinary skill in the art, on the premise of not paying creative work, can also basis These accompanying drawings obtain other accompanying drawings.
Fig. 1 is the process chart of the method for recovery indium and tin from ito glass waste material of the present invention.
Embodiment
For the ease of understanding the present invention, below in conjunction with Figure of description and preferred embodiment to invent herein do it is more complete Face, meticulously describe, but protection scope of the present invention is not limited to specific examples below.
Unless otherwise defined, all technical terms used hereinafter are generally understood that implication phase with those skilled in the art Together.Technical term used herein is intended merely to describe the purpose of specific embodiment, is not intended to the limitation present invention's Protection domain.
Unless otherwise specified, various raw material, reagent, the instrument and equipment etc. used in the present invention can pass through city Field is commercially available or can be prepared by existing method.
Embodiment 1：
A kind of method of recovery indium and tin in waste material of the invention from ito glass, its process chart is as shown in figure 1, bag Include following steps：
(1) waste liquid crystal display is disassembled, except decapsidate, support, takes out liquid crystal panel, remove circuit board, conductive plate, the back of the body After light source etc., ITO (Indium Tin Oxide) glass is obtained, ito glass 30min is soaked with n-hexane, removes liquid crystal, use knife Piece removes two layers of polaroid up and down, crushes the ito glass powder for obtaining that granularity is 1.5mm；
(2) HCl solution and HNO are used3The mixed solution A of solution soaks ito glass powder 60min at 30 DEG C, and mixing is molten The ratio of liquid A volume and the quality of ito glass powder be 20ml/g, and the mol ratio of hydrochloric acid and nitric acid is 8 in mixed solution A：3, H in mixed solution A+Concentration is 7mol/L, while in immersion process, using addition volume per minute as mixed liquor volume 0.2% speed adds the H that mass fraction is 30%2O2Solution, the sustained response time is 30min after addition, obtain leachate and Leached mud；
(3) using the mixed solution B of P204 and kerosene as extractant, HCl solution is that strippant extracts to leachate Take and be stripped；
(4) NaOH solution is added dropwise into the aqueous phase after back extraction, stops being added dropwise when no longer reducing to the precipitation generated, now The pH value of aqueous phase solution is 9, and reaction carries out separation of solid and liquid after terminating, and obtains Na2SnO3Solution and In (OH)3Solid, it is molten with hydrochloric acid Solve In (OH)3Solid obtains containing In3+Solution；
(5) using aluminium sheet as anode, to containing In3+Solution is electrolysed, and the current density of electrolytic process is 200A/m2, electrolysis Sponge indium is obtained after completion after separation of solid and liquid；To Na2SnO3NaHCO is added in solution3Solution, the NaHCO of addition3With solution Middle Na2SnO3Mol ratio be 2.5：1, obtain Sn (OH)4Precipitate, dry to obtain SnO through high temperature after separation of solid and liquid2Product.
Determined through detection means such as ICP, the recovery rate of indium is 95.2% in the method for the present embodiment, sponge indium product it is pure The recovery rate spent for 93.5%, Sn is 95.7%, purity 92.3%.
Embodiment 2
A kind of method of recovery indium and tin in waste material of the invention from ito glass, comprises the following steps：
(1) waste liquid crystal display is disassembled, except decapsidate, support, takes out liquid crystal panel, remove circuit board, conductive plate, the back of the body After light source etc., ITO (Indium Tin Oxide) glass is obtained, ito glass 60min is soaked with n-hexane, removes liquid crystal, use knife Piece removes two layers of polaroid up and down, and it is 1.5mm ito glass powder to crush and obtain granularity；
(2) HCl solution and HNO are used3The mixed solution A of solution soaks ito glass powder 60min at 30 DEG C, and mixing is molten The ratio of liquid A volume and the quality of ito glass powder be 25ml/g, and the mol ratio of hydrochloric acid and nitric acid is 2 in mixed solution A：1, H in mixed solution A+Concentration is 8mol/L, while in immersion process, using addition volume per minute as mixed liquor volume 0.5% speed adds the H that mass fraction is 30%2O2Solution, the sustained response time is 45min after addition, obtain leachate and Leached mud；
(3) using the mixed solution of P204 and kerosene as extractant, HCl solution is that strippant extracts to leachate And back extraction；
(4) NaOH solution is added dropwise into the aqueous phase after back extraction, stops being added dropwise when no longer reducing to the precipitation generated, now The pH value of aqueous phase solution is 9, and reaction carries out separation of solid and liquid after terminating, and obtains Na2SnO3Solution and In (OH)3Solid, it is molten with hydrochloric acid Solve In (OH)3Solid obtains containing In3+Solution；
(5) using aluminium sheet as anode, to containing In3+Solution is electrolysed, and the current density of electrolytic process is 200A/m2, electrolysis Sponge indium is obtained after completion after separation of solid and liquid；To Na2SnO3NaHCO is added in solution3Solution, the NaHCO of addition3With solution Middle Na2SnO3Mol ratio be 2：1, obtain Sn (OH)4Precipitate, dry to obtain SnO through high temperature after separation of solid and liquid2Product.
Determined through detection means such as ICP, the recovery rate of indium is 97.2% in the method for the present embodiment, sponge indium product it is pure The recovery rate spent for 96.4%, Sn is 96.8%, purity 93.5%.
Embodiment 3
A kind of method of recovery indium and tin in waste material of the invention from ito glass, comprises the following steps：
(1) waste liquid crystal display is disassembled, except decapsidate, support, takes out liquid crystal panel, remove circuit board, conductive plate, the back of the body After light source etc., ITO (Indium Tin Oxide) glass is obtained, ito glass 60min is soaked with n-hexane, removes liquid crystal, use knife Piece removes two layers of polaroid up and down, and it is 0.5mm ito glass powder to crush and obtain granularity；
(2) HCl solution and HNO are used3The mixed solution A of solution soaks ito glass powder 60min at 30 DEG C, and mixing is molten The ratio of liquid A volume and the quality of ito glass powder be 30ml/g, and the mol ratio of hydrochloric acid and nitric acid is 8 in mixed solution A：5, H in mixed solution A+Concentration is 8mol/L, while in immersion process, using addition volume per minute as mixed liquor volume 0.5% speed adds the H that mass fraction is 30%2O2Solutions Solution, the sustained response time is 45min after addition, is leached Liquid and leached mud；
(3) using the mixed solution B of P204 and kerosene as extractant, HCl solution is that strippant extracts to leachate Take and be stripped；
(4) NaOH solution is added dropwise into the aqueous phase after back extraction, stops being added dropwise when no longer reducing to the precipitation generated, now The pH value of aqueous phase solution is 9, and reaction carries out separation of solid and liquid after terminating, and obtains Na2SnO3Solution and In (OH)3Solid, it is molten with hydrochloric acid Solve In (OH)3Solid obtains containing In3+Solution；
(5) using aluminium sheet as anode, to containing In3+Solution is electrolysed, and the current density of electrolytic process is 200A/m2, electrolysis Sponge indium is obtained after completion after separation of solid and liquid；To Na2SnO3NaHCO is added in solution3Solution, the NaHCO of addition3With solution Middle Na2SnO3Mol ratio be 2：1, obtain Sn (OH)4Precipitate, dry to obtain SnO through high temperature after separation of solid and liquid2Product.
Determined through detection means such as ICP, the recovery rate of indium is 98.3% in the method for the present embodiment, sponge indium product it is pure The recovery rate spent for 96.2%, Sn is 95.5%, purity 94.9%.
Embodiment 4
A kind of method of recovery indium and tin in waste material of the invention from ito glass, comprises the following steps：
(1) waste liquid crystal display is disassembled, except decapsidate, support, takes out liquid crystal panel, remove circuit board, conductive plate, the back of the body After light source etc., ITO (Indium Tin Oxide) glass is obtained, ito glass 60min is soaked with n-hexane, removes liquid crystal, use knife Piece removes two layers of polaroid up and down, and it is 0.5mm ito glass powder to crush and obtain granularity；
(2) HCl solution and HNO are used3The mixed solution A of solution soaks ito glass powder 60min at 30 DEG C, and mixing is molten The ratio of liquid A volume and the quality of ito glass powder be 30ml/g, and the mol ratio of hydrochloric acid and nitric acid is 8 in mixed solution A：5, H in mixed solution A+Concentration is 8mol/L, while in immersion process, using addition volume per minute as mixed liquor volume 0.5% speed adds the hydrogenperoxide steam generator that mass fraction is 30%, and the sustained response time is 45min after addition, is soaked Go out liquid and leached mud；
(3) using the mixed solution B of P204 and kerosene as extractant, HCl solution is that strippant extracts to leachate Take and be stripped；
(4) NaOH solution is added dropwise into the aqueous phase after back extraction, stops being added dropwise when no longer reducing to the precipitation generated, now The pH value of aqueous phase solution is 9, and reaction carries out separation of solid and liquid after terminating, and obtains Na2SnO3Solution and In (OH)3Solid, it is molten with hydrochloric acid Solve In (OH)3Solid obtains containing In3+Solution；
(5) using aluminium sheet as anode, to containing In3+Solution is electrolysed, and the current density of electrolytic process is 200A/m2, electrolysis Sponge indium is obtained after completion after separation of solid and liquid；To Na2SnO3NaHCO is added in solution3Solution, the NaHCO of addition3With solution Middle Na2SnO3Mol ratio be 2.5：1, obtain Sn (OH)4Precipitate, dry to obtain SnO through high temperature after separation of solid and liquid2Product.
Determined through detection means such as ICP, the recovery rate of indium is 99.1% in the method for the present embodiment, sponge indium product it is pure The recovery rate spent for 97.7%, Sn is 96.3%, purity 93.7%.

Claims (9)

1. a kind of method of recovery indium and tin in waste material from ito glass, it is characterised in that comprise the following steps：
(1) HCl solution and HNO are used3The mixed solution A of solution soaks ito glass powder, and H is added in immersion process2O2Solution, instead Should after obtain leachate and leached mud；
(2) using the mixed solution B of di-(2-ethylhexyl)phosphoric acid ester and kerosene as extractant, HCl solution is strippant pair Leachate is extracted and is stripped；
(3) NaOH solution is added dropwise into the aqueous phase after back extraction, reaction carries out separation of solid and liquid after terminating, obtains Na2SnO3Solution with In(OH)3Solid, with dissolving with hydrochloric acid In (OH)3Solid obtains containing In3+Solution；
(4) to containing In3+Solution is electrolysed, and sponge indium is obtained after separation of solid and liquid；To Na2SnO3NaHCO is added in solution3Solution, Obtain Sn (OH)4Precipitate, dry to obtain SnO through high temperature after separation of solid and liquid2Product.
2. according to the method for claim 1, it is characterised in that hydrochloric acid and nitric acid in the mixed solution A of the step (1) Mol ratio is 8：(3~7), H in mixed solution A+Concentration be 7~8mol/L.
3. method according to claim 1 or 2, it is characterised in that in the step (1), addition H per minute2O2Solution Volume accounts for the 0.2%~1.5% of mixed solution A volume；The H2O2The mass fraction of solution is 15%~45%.
4. method according to claim 1 or 2, it is characterised in that the current density of electrolytic process is in the step (4) 100~250A/m2, using aluminium sheet as anode.
5. method according to claim 1 or 2, it is characterised in that the NaHCO added in the step (4)3With in solution Na2SnO3Mol ratio be (1.5~2.5)：1.
6. method according to claim 1 or 2, it is characterised in that first generated after NaOH solution is added dropwise in the step (3) Precipitation, continuing dropwise addition dissolves precipitation, stops being added dropwise when no longer reducing until precipitating, now pH value >=9 of aqueous phase solution.
7. method according to claim 1 or 2, it is characterised in that the volume and ITO of mixed solution A in the step (1) The ratio of the quality of glass powder is 20~30ml/g.
8. method according to claim 1 or 2, it is characterised in that soaking temperature is 30 DEG C~60 in the step (1) DEG C, soak time is 30~60min, and H is added dropwise2O2The time of sustained response is 30~60min after solution.
9. method according to claim 1 or 2, it is characterised in that the preparation of ito glass powder in the step (1) Journey includes operating procedure in detail below：Ito glass 30~60min of waste material first is soaked with n-hexane, then removes ITO glass with blade Two layers of polaroid above and below glass waste material, is finally crushed to 0.5~2.5mm by waste material, obtains ito glass powder.
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CN109628746A (en) * 2019-01-03 2019-04-16 江西铜业技术研究院有限公司 The extracting method of tin in a kind of silver separating residues
CN109868489A (en) * 2019-04-02 2019-06-11 柳州光华科技有限公司 A kind of refinement of tin and recovery method
CN110408958A (en) * 2019-08-28 2019-11-05 广东先导稀材股份有限公司 Method for separating and recovering tin and indium from indium-tin alloy
CN111996550A (en) * 2019-12-16 2020-11-27 青海西部铟业有限责任公司 Method for directly electrolyzing and extracting metal indium from indium back extraction solution
CN112591786A (en) * 2020-12-15 2021-04-02 株洲火炬安泰新材料有限公司 Method for recovering ITO powder from ITO target grinding waste liquid
KR20220030645A (en) * 2020-09-03 2022-03-11 고등기술연구원연구조합 Leaching Method of Indium from Waste Liquid Crystal Dispaly Panel

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CN108423867A (en) * 2018-03-06 2018-08-21 常州大学 A kind of tin indium oxide etching waste liquid processing unit
CN109628746A (en) * 2019-01-03 2019-04-16 江西铜业技术研究院有限公司 The extracting method of tin in a kind of silver separating residues
CN109868489A (en) * 2019-04-02 2019-06-11 柳州光华科技有限公司 A kind of refinement of tin and recovery method
CN110408958A (en) * 2019-08-28 2019-11-05 广东先导稀材股份有限公司 Method for separating and recovering tin and indium from indium-tin alloy
CN110408958B (en) * 2019-08-28 2021-08-13 广东先导稀材股份有限公司 Method for separating and recovering tin and indium from indium-tin alloy
CN111996550A (en) * 2019-12-16 2020-11-27 青海西部铟业有限责任公司 Method for directly electrolyzing and extracting metal indium from indium back extraction solution
KR20220030645A (en) * 2020-09-03 2022-03-11 고등기술연구원연구조합 Leaching Method of Indium from Waste Liquid Crystal Dispaly Panel
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CN112591786A (en) * 2020-12-15 2021-04-02 株洲火炬安泰新材料有限公司 Method for recovering ITO powder from ITO target grinding waste liquid

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