CN109957655A - A kind of give up from ITO extracts the process of indium and tin in target - Google Patents
A kind of give up from ITO extracts the process of indium and tin in target Download PDFInfo
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- CN109957655A CN109957655A CN201711428570.0A CN201711428570A CN109957655A CN 109957655 A CN109957655 A CN 109957655A CN 201711428570 A CN201711428570 A CN 201711428570A CN 109957655 A CN109957655 A CN 109957655A
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- indium
- tin
- ito
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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
- C22B25/00—Obtaining tin
- C22B25/02—Obtaining tin by dry 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
- 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
- C22B7/001—Dry processes
-
- 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
- C25C1/14—Electrolytic production, recovery or refining of metals by electrolysis of solutions of tin
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
A kind of give up from ITO extracts the process of indium and tin in target; the useless target of ITO that will be crushed and after ball milling using reducing substances; indium oxide and tin oxide are reduced into indium metal and tin respectively in reduction furnace; and indium stannum alloy anode is cast under the protective effect of alkali; it is electrolysed under alkaline condition; it is electrodeposited into tin on cathode and recycles refined tin, the earth of positive pole is indium hydroxide, and indium hydroxide extracts smart indium through leaching, purification and electrodeposition process.The present invention has process flow simple, and the cycling and reutilization period is short, and the indium tin rate of recovery is high, while solving the problems, such as that the filtering of stannic hydroxide is difficult, therefore the obvious advantages such as have cost recovery low with energy conservation and environmental protection.In the industrial production, the rate of recovery of tin is up to 98.5%, and 99% or more, the grade of smart indium and refined tin is more than 99.995% for the rate of recovery of indium.
Description
Technical field
The invention belongs to non-ferrous metallurgy fields more particularly to a kind of ITO to give up target through restoring the side of electroextraction indium tin
Method.
Background technique
ITO(Tin-dopedIndiumOxide) target is a kind of indium tin compound oxidate ceramic material, and ito film has saturating
The characteristics such as light, conduction and heat reflection are widely used in transparent electrode, top-grade building curtain wall, aircraft and the vehicle of flat panel display device
Antifrost antifogging glass, solar energy energy-gathering device and illuminator etc., be a kind of important photoelectric material.Industrial application
In, the utilization rate of ITO target sputter coating is only 20%~30%, and remaining part becomes waste target, adds target material moulding mistake
Leftover pieces, cutting, the waste product generated in journey.Whole world ITO target dosage is more than 1500 tons at present, annual to generate waste target about 2000
Ton；Domestic ITO target dosage is annual to generate 400 tons of waste target up to 300 tons.Indium is explored total in the world as rare precious metal
Reserves only have 1.6 ten thousand tons, and China is the maximum Chan Yin state in the whole world, are also the largest exported country, primary indium yield accounts for global indium
60% or more of total amount.Therefore, indium recycle it is particularly important, ITO give up target recycling be 85% or more for accounting for indium and recycling.
The composition of ITO target is generally indium oxide 90%, and tin oxide 10%, impurity is micro.Current published recycling skill
Art is mainly hydrometallurgic recovery, i.e., ITO gives up target strong acid dissolution, then electrolysis, hydrolytic precipitation, alkaline process separation, displacement etc..
Published application CN1487102A propose it is a kind of give up the method for recovery indium in target from indium tin oxide, specifically disclose
After granularity < 149 μm are milled to by the way that ITO is given up that target is broken, using leaching, removal of impurities, displacement, electrolysis Whote-wet method process from ITO
Recovery indium in useless target obtains the high purity indium containing indium up to 99.99%.
Publication number CN101701292A gives up the method for recovery indium tin in target using oxidizing process from ITO, specifically discloses
By the way that ITO is given up target after broken, ball milling, enriching dissolving with hydrochloric acid is leached, and by addition NaOH Oxidation Leaching liquid and pH value is adjusted to obtain
Tin separation is realized after obtaining leached mud, then washed, roasting, oxidation, obtains thick indium, and 4N indium, time of indium are obtained after once electrolytic
Yield can be stablized 97% or more.
Authorization Notice No. CN101701291B gives up the method for recovery indium tin in target using the way of distillation from ITO, specific public
It has opened by the way that ITO is given up target after broken, ball milling, by salt Ore Leaching, suitable oxidant is added, distillation stoste is made, by one
Fixed distillation technique separating indium, tin achieve the purpose that useless target recycling.
All there is the deficiencies of cumbersome process, inefficiency, high cost recovery in the above method, while conventional method need to reinforce acid
It is reacted, a large amount of acid waste liquid can be generated, seriously pollute environment.
In addition the patent of Publication No. CN101528988B discloses a kind of side that valuable metal is recycled from ITO waste material
Method is specifically disclosed by the way that ITO waste material to be electrolysed to the method to recycle indium metal.It is special that this method will use when being electrolysed
The electrolytic cell that diaphragm amberplex separates, indium recycling need to carry out in special indium accumulator tank, and electrolytic process is discontinuous, operation
Difficulty, investment and production cost are all higher；Anode scrap, fritter ITO waste material and useless ITO powder cannot be returned by this method simultaneously
It receives, needs to recycle using above-mentioned conventional hydrometallurgic recovery method, therefore also need mating conventional wet lay in this method industrial application
Recovery method, adaptability is not strong.
Publication number CN104032133A is specifically disclosed logical using a kind of method of the useless target recycling indium metal tin of ITO
It crosses and ITO gives up target surface cleaning, using reducing substances activated carbon or graphite in 1000 DEG C~1600 DEG C of high temperature and non-oxidizable
Under the conditions of gas shield, metal indium stannum alloy is generated.This method makes indium tin because using reducing substances activated carbon or graphite reason
The purity of alloy is only 99.99%, while needing 1000 DEG C~1600 DEG C of high temperature and the extreme item of non-oxidizing gas protection
Part, practical operation is difficult, and investment and production cost are all higher, and product purity is not high, and product is only alloy；It needs to make in this method
With organic solvent and pure dose of water supersound washing, the waste water of generation, useless organic phase is more and is difficult to handle, and there are the useless organic phases of waste water
Emission problem, while useless ITO powder is difficult to clean by this method, cannot be recycled or to recycle purity lower.
Therefore, how to give up and separate in target and high efficiente callback valuable metal indium, tin are the difficulties for needing further to be explored from ITO
Topic.
Summary of the invention
The present invention is complicated for the recovery process for solving the useless target of existing ITO, and the defect of higher cost, to provide
A kind of simple, at low cost, indium tin the rate of recovery of method high give up from ITO extracts the process of indium and tin in target.
The present invention provides a kind of useless method of the target through restoring electroextraction indium tin of ITO, method includes the following steps:
A kind of useless method of the target through restoring electroextraction indium tin of ITO, which is characterized in that method includes the following steps:
S1, broken and ball milling: ITO is given up, and target is broken and ball milling, obtains 80% or more granularity in -80 mesh powder below；
S2, the reduction of indium tin: the resulting powder of S1 is subjected to reduction reaction in reduction furnace using reducing substances, the reduction is anti-
The temperature control answered is 200-1000 DEG C, and indium oxide and tin oxide are reduced into indium metal and metallic tin respectively；
S3, anode casting mold: using indium metal obtained by step S2 and metallic tin as anode material casting mold at anode, indium stannum alloy is obtained
Anode；
S4, indium stannum alloy electrolysis: the resulting indium stannum alloy anode of step S3 is electrolysed, and tin electrolyte is that pH value is 11-14
Alkaline electrolyte, tin deposition forms the indium hydroxide earth of positive pole in recycling on cathode after electrolysis on anode；
S5, smart indium extract: the indium hydroxide earth of positive pole that step S4 is obtained carries out indium recycling, obtains smart indium.
As a further refinement of the present invention, the method that indium recycles in the S5 is: the indium hydroxide that S4 is obtained
The earth of positive pole successively carries out sulfuric acid leaching, filtering according to a conventional method, and the leachate obtained after filtering is purified through sponge indium or thick indium, obtained
To indium sulfate scavenging solution, indium sulfate scavenging solution is electrolysed, obtains smart indium.
As a further refinement of the present invention, the anode anode scrap formed in the S4 returns to the anode being added in the S3
In material.
As a further refinement of the present invention, the casting method of the anode material is: solid by being covered on anode material
Body sodium hydroxide or potassium hydroxide make its fusing, inject in anode mold, and with the salt acid soak of 8%-12% 3-5 minutes, then with 50
DEG C -80 DEG C of thermal distillation is washed 2-3 minutes, is put on acidproof bag, is obtained indium stannum alloy anode；
As a further refinement of the present invention, the reducing substances are in active carbon, graphite, H2 or CO in step S2
It is any.
As a further refinement of the present invention, the step S2 reduction reaction temperature is 200-400 DEG C, when reduction reaction
Between be 30-60 minutes.
As a further refinement of the present invention, electrolysis temperature is 15 DEG C -40 DEG C in step S4.
As a further refinement of the present invention, tin electrolyte described in step S4 is sodium hydroxide solution, potassium hydroxide
Any one of solution and Ammonia.
As a further refinement of the present invention, in step S1, the ITO target that gives up is crushed and is milled to its 80% or more grain
Degree is below -120 mesh.
As a further refinement of the present invention, in step S5, the material of the indium sulfate scavenging solution anode for electrolysis is
Any one of graphite, titanium plate or pb-ag alloy.
The beneficial effects of the present invention are:
Process route of the invention is first to be crushed ITO target waste material, carries out reduction treatment afterwards, makes indium tin from oxide shape
State is reduced into the solid alloy state of indium metal and metallic tin；It is electrolysed, is obtained by being cast indium stannum alloy anode again
The tin and the indium hydroxide earth of positive pole of high-purity, then the indium hydroxide earth of positive pole is recycled into smart indium, realize the recycling of indium tin.
The invention has the following advantages that
1, ITO target waste material is first crushed by S1, S2, carries out reduction treatment afterwards, make indium tin from oxide shape by the present invention
State is reduced into the solid alloy state of indium metal and metallic tin, in ITO waste target existing for the various forms such as powder, fragment
Indium tin electrolytic recovery creates condition, and can guarantee indium tin high conversion rate therein using reduction method processing ITO target waste material, is
The overall recovery for improving indium tin in ITO target waste material lays the foundation.
2, the present invention obtains indium stannum alloy anode by S3, condition needed for successfully making ITO waste target reach electrolysis.
With directly use in the prior art ITO waste target as anode electrolysis compared with, the present invention is without using special diaphragm ion exchange
The electrolytic cell equipment that film separates, and with continuous, the easy to operate advantage of electrolytic process, and such as anode scrap, fritter ITO waste material and useless
ITO powder can be recycled through the invention, guarantee the high-recovery of indium tin, while without separately building at conventional hydrometallurgic recovery
Reason method recyclable device, recovery process is adaptable, small investment, lower production costs.
3, the present invention obtains indium, the tin of high-purity by S4, S5, ensure that the purity of obtained product indium tin.It is specific former
Reason are as follows: the present invention is different using each metallics electrode potential to be recycled, and metal ion in the solution solubility because of pH value
Different and variation characteristic, realizes the separation of each substance.Specific separating step are as follows: in S4, due to the normal electrode of element In
The standard electrode EMF of potential ratio Sn is more negative, and in indium stannum alloy electrolytic process, indium metal tin all dissolves, and in the form of ion
Into in alkaline electrolyte, pH value be 11-14 when, indium ion anode formed indium hydroxide precipitating and separated with tin, tin with
The form of compound ion enters in electrolyte, then electrodeposition is smoothly precipitated on cathode, and above-mentioned electrolytic process of the invention can be continuous
It carries out；Indium hydroxide sink in anode formed the earth of positive pole and to recycle in next step.Applicant has found that indium tin is electrolysed under study for action
The acidity of liquid has a significant impact to the concentration of In3+ and Sn4+ generated in indium stannum alloy electrolysis and indium stannum alloy electrolytic process,
When pH value is lower than 11, tin also forms precipitating, and can not be successfully and be precipitated in cathode, and when pH value is higher than 14, indium also has part molten
Solution enters in electrolyte, and the effect of the two separation can not be successfully realization, therefore, in the present invention, in indium stannum alloy electrolysis step,
The pH value of electrolyte controls between 11-14, to ensure that electrolytically generated In3+ can generate indium hydroxide precipitating and separate with tin；
In subsequent step S5, indium hydroxide can be obtained indium by indium sulfate scavenging solution direct electrowinning or extract smart indium according to a conventional method.
4, present invention process step is few, it is only necessary to can complete above-mentioned technique using commonly used equipment in the prior art and walk
Suddenly, used crusher, ball mill, reduction furnace, electrolysis installation are commonly used equipment in the prior art, and in the prior art
Electrolysis method (patent " a method of from ITO waste material recycle valuable metal " of such as Publication No. CN101528988B) phase
Than equipment cost being greatly reduced, to reduce cost of investment.
5, smart indium and refined tin that grade is more than 99.995% can be obtained in the present invention, can directly return and do the raw material of ITO target and make
With so that the Matter Transfer realized in ITO target production utilizes.And in production process of the invention, tin electrolysis be with
Indium stannum alloy anode is anode, and anodic solution only occurs for when electrolysis, will not generate gas, and no exhaust gas generates, and tin electrolyte can follow
The Oxidation Leaching that ring use, no waste water generation, therefore this method overcome conventional method needs to reinforce in the process acid in strong oxidizer
Under the conditions of react brought by defect, avoid generating a large amount of acid waste liquid and exhaust gas, avoid pollution environment, obvious environment benefit.
In conclusion the present invention is being capable of excellent process that is extremely simple and efficiently recycling smart indium and refined tin.In industry
In production, the rate of recovery of tin is up to 98.5%, and 99% or more, the grade of smart indium and refined tin is more than 99.995% for the rate of recovery of indium.
Specific embodiment
In order to which the technical problems, technical solutions and beneficial effects solved by the present invention is more clearly understood, below in conjunction with
Embodiment, the present invention will be described in further detail.It should be appreciated that specific embodiment described herein is only to explain this
Invention, is not intended to limit the present invention.
The present invention provides a kind of useless method of the target through restoring electroextraction indium tin of ITO, method includes the following steps:
S1, broken and ball milling: ITO is given up, and target is broken and ball milling, obtains 80% or more granularity in -80 mesh powder below；
S2, the reduction of indium tin: the useless target of ITO after ball milling is distinguished indium oxide and tin oxide in reduction furnace using reducing substances
It is reduced into indium metal and tin；
S3, anode casting mold: using reducing metal indium obtained by step S2 and tin as anode material casting mold at anode, indium stannum alloy is obtained
Anode；
S4, indium stannum alloy electrolysis: the resulting indium stannum alloy anode of step S3 is electrolysed, and tin electrolyte is that pH value is 11-14
Alkaline electrolyte, tin deposition forms the indium hydroxide earth of positive pole in recycling on cathode after electrolysis on anode；
S5, smart indium extract: the indium hydroxide earth of positive pole that step S4 is obtained carries out indium recycling, obtains smart indium.
In a specific embodiment of the invention, it is preferable that in step S3, the casting method of the anode material is: will be positive
Solid sodium hydroxide or potassium hydroxide are covered on the material of pole makes its fusing, injects in anode mold, and with the salt acid soak of 8%-12%
3-5 minutes, then washed 2-3 minutes with 50 DEG C -80 DEG C of thermal distillation, acidproof bag is put on, indium stannum alloy anode is obtained.
The method that indium recycles in step S5 is: the indium hydroxide earth of positive pole successively carries out sulfuric acid leaching according to a conventional method
Out, it filters, the leachate obtained after filtering is purified through sponge indium or thick indium, indium sulfate scavenging solution is obtained, by indium sulfate scavenging solution
It is electrolysed, obtains smart indium.
In the present invention, in order to more effectively make indium oxide tin oxide be reduced into indium metal tin through reducing substances,
In S1, by ITO give up target be crushed and be milled to its 80% or more granularity -80(be preferably -120) mesh hereinafter, applicant test hair
Existing, after meeting above-mentioned requirements, in S2 reduction process, the contact area of reducing gas and the useless target of ITO is abundant, ensure that ITO powder
Abundant reduction, reduction rate up to 100%, while accelerate ITO give up target powder reduction rate and reduction efficiency.Going back in S2
Immunogenic substance can be any one of active carbon, graphite, H2 or CO, and the temperature of reduction reaction control is 200-1000 DEG C, reduction
The reaction controlling time is 30-60 minutes；The temperature of preferred reduction reaction control is 200-400 DEG C；In view of reducing substances
It is from a wealth of sources, price is low, and does not increase new impurity, preferably reducing substances be H2 or CO.The above-mentioned priority scheme of S1, S2
To guarantee that the overall recovery height of indium tin in entire production process is laid a good foundation.
In the present invention, in step S3, it is preferable that during the casting mold of anode material, in the indium metal and metallic tin of liquid
Solid sodium hydroxide or potassium hydroxide are covered, the indium metal and metallic tin of liquid are separated with air under alkali protection, avoided empty
Oxygen in gas is aoxidized；On the other hand, the impurity that the zinc in indium stannum alloy, aluminium etc. dissolve in high-temperature alkali is removed, and is played
The effect of purification.
In the present invention, in step S4, the electrolyte used when being electrolysed to indium stannum alloy is mainly sodium hydroxide, potassium hydroxide
Or the alkaline solutions such as ammonium hydroxide, in order to guarantee that the tin of anodic solution enters in electrolyte as far as possible, and indium is with the shape of indium hydroxide
Formula precipitates to form the earth of positive pole, and in tin electrolytic process, the pH value control of tin electrolyte is 11-14.Ox glue etc. can be added simultaneously
Known additive improves current efficiency, and additive additional amount is according to not improving production cost and do not reduce the purity of electrodeposition tin
Premise.It needs simultaneously and it is appreciated that the various the present invention using indium stannum alloy anode as anode, is carried out using titanium plate or graphite as cathode
Tin electrolysis, can recycle the opinion and judgement of valuable metal tin, belong to one of notable feature of the invention, it is necessary to further progress
A large amount of experiment can be realized.
In the present invention, in step S5, it is preferable that the indium hydroxide earth of positive pole leaching agent of recovery indium is selected as sulfuric acid, avoids
Using hydrochloric acid commonly used by the prior art, because ITO target has been the mixture of high-purity indium oxide and high-purity tin oxide, hydrogen-oxygen
Change the indium earth of positive pole after Ore Leaching, scavenging solution is purified through sponge indium or thick indium, the impurity such as removing tin, in gained sulfuric acid solution of indium
Impurity content is very low, it has been found that gained sulfuric acid solution of indium directly carries out the electrodeposition of indium (i.e. with the conjunction of graphite, titanium plate or lead silver
Gold is anode, is electrolysed using titanium plate or graphite as cathode), it can get higher indium recovery.Therefore molten for realization indium sulfate
The Direct Electrolysis of liquid, leaching agent must use sulfuric acid, applicants experimentally found that, the salt as commonly used by use in the prior art
When acid is used as leaching agent, then chlorine releasing is had in indium electrolytic deposition process, damages anode plate, influence the quality of product, while dirty
Contaminate environment.Meanwhile the electrodeposition parameter in indium electrolytic process is (such as acidity, electrolysis temperature, tank voltage, current strength, unit volume
Amount containing indium etc.) premised on reducing production cost, improve the rate of recovery and quality of indium.
In the present invention, in step S4, anode directly can be made when recycling tin with indium stannum alloy anode electrolysis with indium stannum alloy, with
Make cathodic master plate with corrosion-resistant electrodes such as titanium plates；In step S5, when indium sulfate scavenging solution Direct Electrolysis can be used titanium plate, graphite,
Anode is made in the materials such as pb-ag alloy, makees cathodic master plate with corrosion-resistant electrodes such as titanium plates, above-mentioned electrolysis to device without particular/special requirement,
General electrolysis installation can be used, without the electrolytic cell for being provided with amberplex, electrolytic process can be continuous, operation letter
Single, equipment cost is lower, can effectively avoid and increases or be mixed into impurity in finished product, improves the purity of product.
In the present invention, the electrolysis temperature in S4 is not particularly restricted, is preferably adjusted to 0-100 DEG C, improves electrolysis temperature, can drop
The viscosity of low electrolyte prevents anodic passivity, reduces tank voltage, improves the quality of electro-deposition tin；Electrolysis temperature is excessively high, hydrogen
Discharge potential reduces, and reduces the quality of electro-deposition tin, while increasing the evaporation loss of electrolyte, and electrolysis temperature is further preferred
It is 15 DEG C -40 DEG C.Above-mentioned preferred embodiment can more effectively improve the rate of recovery of tin, the grade of tin is made to be more than 99.995%.
The present invention can handle the useless target of various forms caused by ITO, and the pyrogenic process process only restored by indium tin is just
The anode material of indium stannum alloy anode is obtained, while anode scrap can also be recycled in the present invention, therefore, the present invention is can
Extremely simple, efficiently recovery indium tin excellent process.
In extracting method of the invention, a small amount of secondary composition also added in ITO sometimes, or lack certain element, but only
Will be substantially using ITO as fundamental component, then the present invention can also apply.
Reaction principle of the invention is:
In S2, the key reaction formula of hydrogen reducing:
The key reaction formula of metal indium stannum alloy electrolysis:
On anode: In-3e → In3+ ... ... ... ... ... ... ... ... ... ... (5)
Sn-2e→Sn2+……………………………………………………(6)
Sn-4e→Sn4+……………………………………………………(7)
On cathode: Sn2++2e → Sn ... ... ... ... ... ... ... ... ... ... (8)
Sn4++4e→Sn……………………………………………………(9)
In3++3NaOH→3Na++In(OH)3↓…………………………………………(10)
Sulfuric acid leaching: 3H2SO4+2In (OH) 3 → In2 (SO4) 3+6H2O ... ... ... ... ... (11)
Sponge indium purification: 4In+3Sn4+ → 3Sn+4In3+ ... ... ... ... ... ... ... (12)
2In+3Sn2+→3Sn+2In3+……………………………………(13)
The key reaction formula of indium electrolysis:
On anode: 4OH--4e → 2H2O+O2 ↑ ... ... ... ... ... ... ... ... (14)
On cathode: In3++3e → In ... ... ... ... ... ... ... ... ... ... (15)
Below by specific embodiment, invention is further explained.
Embodiment 1, using the useless target of 5 kilograms of ITO as raw material, the composition of the raw material are as follows: the weight percent of indium oxide is
90%, the weight percent of tin oxide is 10%.
1, it is crushed and ball milling step S1
By the raw material is broken and ball milling, 80% or more granularity is obtained in -120 mesh powder below.
2, indium tin reduction step S2
The useless target powder of smashed ITO is fitted into hydrogen reducing furnace, hydrogen is passed through, then controlling reduction temperature is 200 DEG C, reduction
Reaction time is 60 minutes, indium oxide and tin oxide is reduced into indium metal and metallic tin respectively, the rate of recovery of indium tin is above
99.5%。
3, anode casting mold step S3
Indium metal and tin are melted under the covering of solid potassium hydroxide, casting mold, with salt acid soak 5 minutes of 8%, then with 80 DEG C
Thermal distillation wash 2 minutes, put on acidproof bag, obtain indium stannum alloy anode, the purity of indium stannum alloy is more than 99.995%.
4, indium stannum alloy electrolysis step S4
Make anode with indium stannum alloy anode to be electrolysed in the electrolyte system of sodium hydroxide, the pH value of electrolyte is 11, electricity
Solving temperature is 15 DEG C, and ox glue is added by the condition of production, and in being recycled on cathode, indium forms the earth of positive pole and is able to tin deposition after electrolysis
Recycling, obtains the refined tin that stanniferous weight percent is 99.998%, and the overall recovery of tin is 98.5%.
5, the extraction step S5 of indium
The indium hydroxide earth of positive pole that S4 is obtained carries out sulfuric acid leaching, filtering, obtains indium sulfate leachate, indium sulfate leachate warp
Thick indium purifies to obtain indium sulfate scavenging solution.Using titanium plate as anode, graphite is that cathode is electrolysed indium sulfate scavenging solution, obtains essence
The grade of indium is 99.996%, and the overall recovery of indium is 99.3%.
Embodiment 2, using the useless target of 5 kilograms of ITO as raw material, the composition of the raw material are as follows: the weight percent of indium oxide is
90%, the weight percent of tin oxide is 10%.
1, it is crushed and ball milling step S1
By the raw material is broken and ball milling, 85% or more granularity is obtained in -120 mesh powder below.
2, indium tin reduction step S2
The useless target powder of smashed ITO is fitted into hydrogen reducing furnace, hydrogen is passed through, then controlling reduction temperature is 290 DEG C, reduction
Reaction time is 50 minutes, indium oxide and tin oxide is reduced into indium metal and metallic tin respectively, the rate of recovery of indium tin is above
99.5%。
3, anode casting mold step S3
Indium metal and tin are melted under the covering of solid potassium hydroxide, casting mold, with salt acid soak 4 minutes of 9%, then with 70 DEG C
Thermal distillation wash 3 minutes, put on acidproof bag, obtain indium stannum alloy anode, the purity of indium stannum alloy is more than 99.995%.
4, indium stannum alloy electrolysis step S4
Make anode with indium stannum alloy anode to be electrolysed in the electrolyte system of potassium hydroxide, the pH value of electrolyte is 12, electricity
Solving temperature is 20 DEG C, and ox glue is added by the condition of production, and in being recycled on cathode, indium forms the earth of positive pole and is able to tin deposition after electrolysis
Recycling, obtains the refined tin that stanniferous weight percent is 99.996%, and the overall recovery of tin is 99.3%.
5, the extraction step S5 of indium
The indium hydroxide earth of positive pole that S4 is obtained carries out sulfuric acid leaching, filtering, obtains indium sulfate leachate, indium sulfate leachate warp
Sponge indium purifies to obtain indium sulfate scavenging solution.Using pb-ag alloy plate as anode, titanium plate is that cathode carries out electricity to indium sulfate scavenging solution
Solution, the grade for obtaining smart indium is 99.998%, and the overall recovery of indium is 99.4%.
Embodiment 3, using the useless target of 5 kilograms of ITO as raw material, the composition of the raw material are as follows: the weight percent of indium oxide is
90%, the weight percent of tin oxide is 10%.
1, it is crushed and ball milling step S1
By the raw material is broken and ball milling, 88% or more granularity is obtained in -120 mesh powder below.
2, indium tin reduction step S2
The useless target powder of smashed ITO is fitted into hydrogen reducing furnace, hydrogen is passed through, then controlling reduction temperature is 400 DEG C, reduction
Reaction time is 30 minutes, indium oxide and tin oxide is reduced into indium metal and metallic tin respectively, the rate of recovery of indium tin is above
99.5%。
3, anode casting mold step S3
Indium metal and tin are melted under the covering of solid sodium hydroxide, casting mold, with salt acid soak 3 minutes of 12%, then with 50 DEG C
Thermal distillation wash 2 minutes, put on acidproof bag, obtain indium stannum alloy anode, the purity of indium stannum alloy is more than 99.995%.
4, indium stannum alloy electrolysis step S4
Make anode with indium stannum alloy anode to be electrolysed in the electrolyte system of ammonium hydroxide, the pH value of electrolyte is 13, electricity
Solving temperature is 40 DEG C, and ox glue is added by the condition of production, and in being recycled on cathode, indium forms the earth of positive pole and is able to tin deposition after electrolysis
Recycling, obtains the refined tin that stanniferous weight percent is 99.995%, and the overall recovery of tin is 99.4%.
5, the extraction step S5 of indium
The indium hydroxide earth of positive pole that S4 is obtained carries out sulfuric acid leaching, filtering, obtains indium sulfate leachate, indium sulfate leachate warp
Sponge indium purifies to obtain indium sulfate scavenging solution.Using graphite as anode, titanium plate is that cathode is electrolysed indium sulfate scavenging solution, is obtained
The grade of smart indium is 99.996%, and the overall recovery of indium is 99.5%.
Embodiment 4, using the useless target of 5 kilograms of ITO as raw material, the composition of the raw material are as follows: the weight percent of indium oxide is
90%, the weight percent of tin oxide is 10%.
1, it is crushed and ball milling step S1
By the raw material is broken and ball milling, 90% or more granularity is obtained in -120 mesh powder below.
2, indium tin reduction step S2
The smashed ITO target powder that gives up is fitted into reduction furnace, is passed through CO, then controlling reduction temperature is 350 DEG C, when reduction reaction
Between be 40 minutes, indium oxide and tin oxide are reduced into indium metal and metallic tin respectively, the rate of recovery of indium tin is above 99.5%.
3, anode casting mold step S3
Indium metal and tin are melted under the covering of solid potassium hydroxide, casting mold, with salt acid soak 4 minutes of 10%, then with 60 DEG C
Thermal distillation wash 3 minutes, put on acidproof bag, obtain indium stannum alloy anode, the purity of indium stannum alloy is more than 99.995%.
4, indium stannum alloy electrolysis step S4
Make anode with indium stannum alloy anode to be electrolysed in the electrolyte system of sodium hydroxide, the pH value of electrolyte is 14, electricity
Solving temperature is 30 DEG C, and ox glue is added by the condition of production, and in being recycled on cathode, indium forms the earth of positive pole and is able to tin deposition after electrolysis
Recycling, obtains the refined tin that stanniferous weight percent is 99.997%, and the overall recovery of tin is 98.8%.
5, the extraction step S5 of indium
The indium hydroxide earth of positive pole that S4 is obtained carries out sulfuric acid leaching, filtering, obtains indium sulfate leachate, indium sulfate leachate warp
Thick indium purifies to obtain indium sulfate scavenging solution.Using titanium plate as anode, titanium plate is that cathode is electrolysed indium sulfate scavenging solution, obtains essence
The grade of indium is 99.997%, and the overall recovery of indium is 99.2%.
Embodiment 5, using the useless target of 5 kilograms of ITO as raw material, the composition of the raw material are as follows: the weight percent of indium oxide is
90%, the weight percent of tin oxide is 10%.
1, it is crushed and ball milling step S1
By the raw material is broken and ball milling, 86% or more granularity is obtained in -120 mesh powder below.
2, indium tin reduction step S2
The smashed ITO target powder that gives up is fitted into reduction furnace, is passed through CO, then controlling reduction temperature is 380 DEG C, when reduction reaction
Between be 45 minutes, indium oxide and tin oxide are reduced into indium metal and metallic tin respectively, the rate of recovery of indium tin is above 99.5%.
3, anode casting mold step S3
Indium metal and tin are melted under the covering of solid potassium hydroxide, casting mold, with salt acid soak 3 minutes of 11%, then with 65 DEG C
Thermal distillation wash 2 minutes, put on acidproof bag, obtain indium stannum alloy anode, the purity of indium stannum alloy is more than 99.995%.
4, indium stannum alloy electrolysis step S4
To make anode with indium stannum alloy anode to be electrolysed in the electrolyte system of ammonium hydroxide, the pH value of electrolyte is 12.5,
Electrolysis temperature is 25 DEG C, and ox glue is added by the condition of production, and in being recycled on cathode, indium forms the earth of positive pole and obtains tin deposition after electrolysis
With recycling, the refined tin that stanniferous weight percent is 99.998% is obtained, the overall recovery of tin is 99.2%.
5, the extraction step S5 of indium
The indium hydroxide earth of positive pole that S4 is obtained carries out sulfuric acid leaching, filtering, obtains indium sulfate leachate, indium sulfate leachate warp
Sponge indium purifies to obtain indium sulfate scavenging solution.Using pb-ag alloy as anode, graphite is that cathode is electrolysed indium sulfate scavenging solution,
The grade for obtaining smart indium is 99.997%, and the overall recovery of indium is 99.4%.
Embodiment 6, using the useless target of 5 kilograms of ITO as raw material, the composition of the raw material are as follows: the weight percent of indium oxide is
90%, the weight percent of tin oxide is 10%.
1, it is crushed and ball milling step S1
By the raw material is broken and ball milling, 84% or more granularity is obtained in -120 mesh powder below.
2, indium tin reduction step S2
The smashed ITO target powder that gives up is fitted into reduction furnace, is passed through CO, then controlling reduction temperature is 240 DEG C, when reduction reaction
Between be 55 minutes, indium oxide and tin oxide are reduced into indium metal and metallic tin respectively, the rate of recovery of indium tin is above 99.5%.
3, anode casting mold step S3
Indium metal and tin are melted under the covering of solid sodium hydroxide, casting mold, with salt acid soak 4 minutes of 9%, then with 65 DEG C
Thermal distillation wash 2 minutes, put on acidproof bag, obtain indium stannum alloy anode, the purity of indium stannum alloy is more than 99.995%.
4, indium stannum alloy electrolysis step S4
To make anode with indium stannum alloy anode to be electrolysed in the electrolyte system of sodium hydroxide, the pH value of electrolyte is 13.5,
Electrolysis temperature is 36 DEG C, and ox glue is added by the condition of production, and in being recycled on cathode, indium forms the earth of positive pole and obtains tin deposition after electrolysis
With recycling, the refined tin that stanniferous weight percent is 99.997% is obtained, the overall recovery of tin is 99.3%.
5, the extraction step S5 of indium
The indium hydroxide earth of positive pole that S4 is obtained carries out sulfuric acid leaching, filtering, obtains indium sulfate leachate, indium sulfate leachate warp
Zinc powder purifies to obtain indium sulfate scavenging solution.To the displacement of indium sulfate scavenging solution and casting mold is at anode, and using thick indium as anode, graphite is yin
Pole is electrolysed, and the grade for obtaining smart indium is 99.995%, and the overall recovery of indium is 99%.
Comparative example 1, using " oxidizing process give up from ITO to the method for recovery indium tin in target " of Publication No. CN101701292A,
ITO is given up into target after broken, ball milling, enriching dissolving with hydrochloric acid leaches, and by addition NaOH Oxidation Leaching liquid and pH value is adjusted to obtain
Tin separation is realized after leached mud, then washed, roasting, oxidation, obtains thick indium, 4N indium, the recycling of indium are obtained after once electrolytic
Rate is only 97.3%, and the grade of smart indium is 99.992%, wherein tin can only be recycled in the form of tin oxide, and the rate of recovery is
95.8%, and production procedure is cumbersome, inefficiency, cost recovery height, specifically, in leaching step, leachate is needed through multiple oxygen
Change, the process of adjusting pH value, in washing step, washing material filtration difficulty causes cumbersome process, inefficiency, cost recovery
The deficiencies of high, in simultaneous oxidation step, leaching need to reinforce acid and be reacted under conditions of strong oxidizer, can generate a large amount of acid
Waste liquid and salt sour waste gas, seriously pollute environment.
Comparative example 2, using " a kind of method of the useless target recycling indium metal tin of ITO " of Publication No. CN104032133A, i.e.,
ITO is given up target surface cleaning, organic solvent and pure dose of water supersound washing are specially used, using reducing substances activated carbon in height
Under 1000 DEG C~1600 DEG C of temperature and non-oxidizing gas protective condition, metal indium stannum alloy is generated.It is only capable of producing the conjunction of indium tin
Gold cannot obtain indium metal tin product, and due to it uses reducing substances activated carbon etc., the purity of gained indium stannum alloy is only
It is 99.991%, because purity is too low, and is alloy, purposes is limited, cannot act as the raw material of preparation ITO target.On the other hand, should
The working condition of method is harsh, needs 1300 DEG C of high temperature and argon gas to make the extreme condition of protective gas, production cost is excessively high, practical
Operating difficulties needs waste discharge, useless organic phase, generates toxic gas CO, environmental pollution is serious, also can not be right with not avoiding
Useless ITO powder is recycled.
From embodiment 1-6 and comparative example 1, comparative example 2 comparison in find, physical form of the present invention to ITO waste target
Without limitation, the various useless ITO waste targets generated when ITO sputtering target or manufacture can be recycled, no matter it tiltedly expect or ITO gives up for corner
Target powder can recycle through the invention.The present invention is not necessarily to carry out material the heating of excessive temperature, and energy consumption is few, and no three wastes produces
Raw, the materials such as adopting electrolysis residual pole also can realize that in the present invention circulation is added, the present invention can simple and high efficiente callback tin and indium, and
Environmental benefit is good, at low cost, easy to operate, all has remarkable advantage in terms of resource reutilization, technical and economic feasibility.
Further, it is found from the comparison of embodiment 1-5 and embodiment 6, it, both can be routinely in indium removal process
Method recycling, as embodiment 6(is electrolysed using thick indium as anode), the overall recovery of indium is 99%.But the zinc of the embodiment
Piece is replaced in process, and zinc impurities etc. are inevitably mixed into thick indium, therefore is also needed in the processes such as briquetting, casting mold to being mixed into
Impurity removal of impurities, increase indium recycling step, there are about increases for production cost.And if in other embodiments in its leaching agent
It has carried chloride ion secretly, has then had chlorine releasing in indium electrolytic process, damage anode plate, influence the quality of product, pollute simultaneously
Environment.And embodiment 1-5 shortens indium recovery process according to the feature of indium hydroxide earth of positive pole purity is high obtained, improves indium
The rate of recovery, i.e., by indium sulfate Direct Electrolysis, and its solution is sulfuric acid system, avoids bringing chloride ion into, and anode region only generates oxygen,
It is generated without remaining toxic and harmful gas, no exhaust gas generates, and the overall recovery of indium is 99.2% or more.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Made any modifications, equivalent replacements, and improvements etc., should all be included in the protection scope of the present invention within mind and principle.
Claims (9)
1. a kind of give up from ITO extracts the process of indium and tin in target, which is characterized in that method includes the following steps:
S1, broken and ball milling: ITO is given up, and target is broken and ball milling, obtains 80% or more granularity in -80 mesh powder below；
S2, the reduction of indium tin: the resulting powder of S1 is subjected to reduction reaction in reduction furnace using reducing substances, the reduction is anti-
The temperature control answered is 200-1000 DEG C, and indium oxide and tin oxide are reduced into indium metal and metallic tin respectively；
S3, anode casting mold: using indium metal obtained by step S2 and metallic tin as anode material casting mold at anode, indium stannum alloy is obtained
Anode；
S4, indium stannum alloy electrolysis: the resulting indium stannum alloy anode of step S3 is electrolysed, and tin electrolyte is that pH value is 11-14
Alkaline electrolyte, tin deposition forms the indium hydroxide earth of positive pole in recycling on cathode after electrolysis on anode；
S5, smart indium extract: the indium hydroxide earth of positive pole that step S4 is obtained carries out indium recycling, obtains smart indium.
2. give up from ITO extracts the process of indium and tin in target according to claim 1, which is characterized in that indium in step S5
The method of recycling is: the indium hydroxide earth of positive pole successively carries out sulfuric acid leaching, filtering according to a conventional method, obtains after filtering
Leachate is purified through sponge indium or thick indium, obtains indium sulfate scavenging solution, indium sulfate scavenging solution is electrolysed, obtain smart indium.
3. give up from ITO extracts the process of indium and tin in target according to claim 1, which is characterized in that the step S4
The anode anode scrap of middle formation, which returns, to be added in the anode material in the S3.
4. giving up according to Claims 2 or 3 from ITO extracts the process of indium and tin in target, which is characterized in that step S3
In, the casting method of the anode material is: making its fusing for solid sodium hydroxide or potassium hydroxide is covered on anode material, infuses
Enter in anode mold, and with the salt acid soak of 8%-12% 3-5 minutes, then washed 2-3 minutes with 50 DEG C -80 DEG C of thermal distillation, is put on
Acidproof bag obtains indium stannum alloy anode.
5. give up from ITO extracts the process of indium and tin in target according to claim 1, which is characterized in that in step S2, institute
The reducing substances stated are any one of active carbon, graphite, H2 or CO.
6. give up from ITO extracts the process of indium and tin in target according to claim 1, which is characterized in that the step S2
Reduction reaction temperature is 200-400 DEG C, and the reduction reaction time is 30-60 minutes.
7. give up from ITO extracts the process of indium and tin in target according to claim 1, which is characterized in that in step S4, electricity
Solving temperature is 15 DEG C -40 DEG C.
8. give up from ITO extracts the process of indium and tin in target according to claim 1, which is characterized in that in step S4, institute
The tin electrolyte stated is any one of sodium hydroxide solution, potassium hydroxide solution and Ammonia.
9. give up from ITO extracts the process of indium and tin in target according to claim 1, which is characterized in that, will in step S1
ITO is useless, and target is crushed and is milled to its 80% or more granularity below -120 mesh.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN111809050A (en) * | 2020-05-25 | 2020-10-23 | 先导薄膜材料有限公司 | Method for recycling ITO waste target |
| CN114808036A (en) * | 2022-04-21 | 2022-07-29 | 柳州华锡有色设计研究院有限责任公司 | Method for recovering high-purity tin-indium alloy from ITO target waste |
| CN115522077A (en) * | 2022-09-27 | 2022-12-27 | 南京金美镓业有限公司 | Method for regenerating high-purity indium ingot from IZO waste target material |
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2017
- 2017-12-26 CN CN201711428570.0A patent/CN109957655A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN111809050A (en) * | 2020-05-25 | 2020-10-23 | 先导薄膜材料有限公司 | Method for recycling ITO waste target |
| CN114808036A (en) * | 2022-04-21 | 2022-07-29 | 柳州华锡有色设计研究院有限责任公司 | Method for recovering high-purity tin-indium alloy from ITO target waste |
| CN114808036B (en) * | 2022-04-21 | 2023-12-05 | 柳州华锡有色设计研究院有限责任公司 | Method for recycling high-purity tin-indium alloy from ITO target scrap |
| CN115522077A (en) * | 2022-09-27 | 2022-12-27 | 南京金美镓业有限公司 | Method for regenerating high-purity indium ingot from IZO waste target material |
| CN115522077B (en) * | 2022-09-27 | 2023-05-09 | 南京金美镓业有限公司 | Method for regenerating high-purity indium ingots from IZO waste targets |
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