CN105926022B - The electrolysis manufacture device and manufacture method of indium hydroxide or compound containing indium hydroxide - Google Patents

The electrolysis manufacture device and manufacture method of indium hydroxide or compound containing indium hydroxide Download PDF

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Publication number
CN105926022B
CN105926022B CN201610322530.7A CN201610322530A CN105926022B CN 105926022 B CN105926022 B CN 105926022B CN 201610322530 A CN201610322530 A CN 201610322530A CN 105926022 B CN105926022 B CN 105926022B
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indium hydroxide
electrolyte
hydroxide
plate
compound containing
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CN105926022A (en
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新藤裕朗
新藤裕一朗
竹本幸
竹本幸一
古仲充之
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JX Nippon Mining and Metals Corp
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JX Nippon Mining and Metals Corp
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Priority claimed from JP2011162813A external-priority patent/JP5711063B2/en
Priority claimed from JP2011171893A external-priority patent/JP5632340B2/en
Priority claimed from JP2011174662A external-priority patent/JP5557810B2/en
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
    • C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B15/00—Operating or servicing cells
    • C25B15/08—Supplying or removing reactants or electrolytes; Regeneration of electrolytes
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/34—Anodisation of metals or alloys not provided for in groups C25D11/04 - C25D11/32

Abstract

A kind of method that indium hydroxide or compound containing indium hydroxide are manufactured by electrolysis, its object is to, by making the electrical conductivity of electrolyte be electrolysed for more than 10mS/cm, indium hydroxide or the compound containing indium hydroxide is set to separate out in the electrolytic solution, and wash the indium hydroxide of precipitation or the compound containing indium hydroxide, until the electrical conductivity of cleaning solution is below 1mS/cm, thus suppress the decline of productivity ratio and the decline of quality.

Description

The electrolysis manufacture device and manufacture of indium hydroxide or compound containing indium hydroxide Method
It is on June 12nd, 2012, (the international application no PCT/ of Application No. 201280027688.1 applying date that the application, which is, The patent of invention Shen of JP2012/065013), entitled " manufacture method of indium hydroxide or the compound containing indium hydroxide " Divisional application please.
Technical field
The invention mainly relates to indium hydroxide or the compound containing indium hydroxide manufacture method, the indium hydroxide or hydrogeneous The compound of indium oxide is that the sputtering indium oxide of ITO targets or the compound powder containing indium oxide of ito film are formed for manufacturing Raw material.
Background technology
ITO (composite oxides using indium-tin as principal component) film is saturating as the display device based on liquid crystal display Prescribed electrode (film) and be widely used.It is generally general by vacuum vapour deposition or sputtering method etc. as the method for forming the ito film The method for being referred to as physical vapor deposition is carried out.Particularly consider from operability and the stability of film, mostly using magnetron sputtering method To be formed.
The formation of film based on sputtering method is carried out as follows：The cation physical bombardment such as Ar ions is set to be arranged on the target of negative electrode, And the material of target is formed using bombarding energy release, it is several with target material so as to be stacked on the substrate upper strata of opposed anode-side Identical film.
It is characterised by using the cladding process of sputtering method, can be with stabilization by adjusting processing time, output power etc. Film forming speed forms the thick film from the film to tens of μm of angstrom unit.
In general, ITO sintered body targets are entered by being pulverized and mixed indium oxide and tin oxide, and to the mixed-powder of gained Row shaping, sinter to manufacture.In indium oxide and when being pulverized and mixed of tin oxide, mixed using ball mill, V-Mixer or banding pattern Conjunction machine carries out dry type or wet mixed.
, can be by being calcined indium hydroxide to manufacture as the indium oxide powder of the raw material of ITO sintered body targets.Should The representative known technology of indium hydroxide manufacture method, disclosed in patent document 1.The method of the patent document 1 is with indium It is electrolysed for anode to manufacture indium hydroxide, then it is calcined to obtain indium oxide powder.It should be noted that, although should Patent document 1 causes applicant's title different from the application due to renaming, but it is also the application that the applicant proposes.
Manufacture method as indium oxide, it is also contemplated that neutralisation.However, as described in patent document 1, due to neutralisation Problems be present, therefore electrolysis is effective.
A) deviation of the various characteristics (average grain diameter, apparent density etc.) of gained indium oxide powder is big, and this is to hinder oxidation " reduction of quality deviation " of indium system display material, fluorophor etc. the or principal element of " high-quality ".
B) for by manufacturing condition (liquid temperature, reaction speed etc.) control for may not be easy for constant, and in order that manufacture Conditional stability, equipment cost rise.
C) when needing characteristic from the past different powder, this requirement can not neatly be tackled.
D) scale of device is bigger, therefore, if being constant by manufacturing condition control, needs sizable labor Power, from the side it is considered that may not be easy for volume increase.
E) waste liquid (such as ammonium nitrate) is neutralized due to can produce every time, it is therefore desirable to handled, this improves operation Cost.
Next, it is given by the typical example of electrolysis manufacture indium hydroxide.
In the ammonium nitrate (NH that concentration is 0.2~5mol/L, pH is 4~10, temperature is 10~50 DEG C4NO3) in the aqueous solution, Using indium as anode (anode), and with 100~1800A/m2Current density be powered, be electrolysed.Then, cell bottom is filtered The deposit in portion, wash and dry, obtain indium hydroxide.
When manufacturing indium oxide using the indium hydroxide as raw material, as long as being calcined at a temperature of 1100 DEG C or so. Thus, it is possible to obtain the indium oxide powder that average grain diameter is 1~5 μm.
When carrying out the electrolysis of above-mentioned indium hydroxide, it is conventional as anode (anode), configuration that indium plate is configured in a cell Stainless steel plate as negative electrode (cathode), and electrolyte is flowed between them to be electrolysed.However, the hydrogen of generation Indium oxide is attached to anode surface, and indium is electrodeposited in cathode surface and extended with branch (dendrite) shape, causes anode and the moon Short circuit occurs for pole, generates the problem of can not being electrolysed for a long time.
In addition, if continuous implement electrolysis, the dissolution current potential element higher than In remains in anode surface as impurity, ties The problem of impurity concentrates on surface be present in fruit.If continuing to be electrolysed in this case, impurity is also mixed into electrolyte, is led The purity for the indium hydroxide for causing to separate out before declines.In addition, locally losing indium metal in anode surface, the electric current of anode surface is close Degree becomes uneven.As a result following abnormal conditions are also created, i.e. hole is locally produced on the surface of anode, anode itself is de- Fall in electrobath.
Moreover, in the electrolysis of indium hydroxide, the indium hydroxide of generation is attached to anode surface, and indium is electrodeposited in negative electrode table Face is simultaneously extended with branch (dendrite) shape, the problem of generating anode and negative electrode short circuit.
When investigating prior art, following patent documents has been disclosed.
Patent document 2 is the manufacture method of indium oxide powder, and this method is stirring into indium hydroxide using indium as anode Precipitation is electrolysed in the state of suspending in the electrolytic solution.Specifically, when not being stirred, the pH near liquid level of electrolyzer For 8.5 or so, the pH near bottom land is 3.2 or so, and by stirring electrolyte, makes liquid level nearby and the electrolyte near bottom land Mixing, so that pH is homogenized.
Stirring extent is to reach the degree that electrolytically generated indium hydroxide precipitates the state in the electrolytic solution that suspends.If stir The degree of mixing is weaker than the degree, then the effect for homogenizing the pH of electrolyte is insufficient.Common electrolysis is usually to be in electrolyte Carried out in the state of stationary stream, will not carry out rolling the stirring of bottom land mud, and the electrowinning process of the present invention is characterised by, product Pole stirring electrolyte is electrolysed up to the degree that precipitation suspends.
Using ammonium nitrate or ammonium chloride as electrolyte, and the liquid temperature of electrolyte is set to be 40~80 DEG C (50~70 DEG C).Electricity The reagent concentration solved in liquid is 1~3mol/L, and voltage is 2~4V, and current density is 200~900A/m2(700A/m2Left and right), two Interpolar is 25m/m~50m/m, and the material of negative electrode can be carbon, but usually using indium plate.Calcining be typically in atmosphere and Carried out under 700~1100 DEG C (800~950 DEG C or so).
A kind of manufacture method of indium oxide-tin oxide powder has been recorded in patent document 3, and has been disclosed indium and tin point It is not electrolysed the technology of (PR formulas pulse electrifying) simultaneously as anode.It is disclosed that electrolyte uses NH4NO3, and in concentration It is 4~9.5 for 0.2~5mol/L, pH, bath temperature is 0~50 DEG C, current density is 100~1800A/m2Under conditions of carry out electricity Solution.Thus the powder of gained is calcined at 1100 DEG C, manufacture average grain diameter is 20 μm, apparent density 1.7g/cm3ITO Powder.And obtain SnO2Content ratio be 10 weight %, sintered density 6.70g/cm3、4.78g/cm3ITO targets.
Patent Document 4 discloses the manufacture method for the ITO targets that indium hydroxide is manufactured by electrolysis.Specifically, its Disclose and be electrolysed using indium as anode, and wash the indium hydroxide of generation, it is dispersed in the method in pure water.Wherein The ammonium nitrate as electrolyte is described, is had no problem in cost and in terms of maintaining purity, but due to the inclined tin as insulator Acid separates out in electrode surface, therefore can not be continuously electrolysed.Wherein also describe use be dispersed with particle diameter for less than 10 μm, The dispersion soln of 10~80 weight % indium hydroxide, and indium hydroxide dispersion soln and metastannic acid dispersion soln is mixed institute The pH for obtaining slurry is more than 5 and less than 9.
The method and electrolytic cell of the even concentration of electrolyte when making electrolysis for production have been recorded in patent document 5, wherein Disclose following method：Feed trough is configured in the end of electrolytic cell, when from feed trough to anode plate and cathode plate feed flow, supply Groove up has opening portion with lower section, and from upper opening portion feed flow, new electrolyte is provided from lower openings portion, simultaneously Side on the upside of the feed trough sets hole portion, and from the hole portion to anode plate and cathode plate feed flow, so that electrolyte is dense Degree homogenization.At this moment, with vertical direction to anode plate and cathode plate feed flow.
Patent document 6 discloses that electrorefining or electrowinning electrolytic cell, are being supplied wherein describing the electrolytic cell and having Multiple confession fluid apertures are set on the inwall of liquid side, same multiple outages are set on the inwall of discharge opeing side, so that liquid stream is in anode The construction of straight ahead between negative electrode.
In above-mentioned known document, the electrical conductivity that is not specified by electrolyte, and current efficiency is not recognized completely Density when the problem of variation and process (washing of indium hydroxide of precipitation etc.) afterwards can be to sintering has an impact, and Do not disclose for solving the specific method of these problems yet.
Moreover, when being all not disclosed in the electrolysis of indium hydroxide, the problem of impurity concentrates in anode surface, and anode comes off, And do not recognize and the high hydroxide of impurity content is also generated in addition to the indium hydroxide generated in electrolyte, so as to lead Cause the purity of indium hydroxide to decline, and do not disclose for solving the specific method of these problems.
Moreover, document known in the above does not all recognize that the indium hydroxide of generation is attached in the electrolysis of indium hydroxide Anode surface, indium be electrodeposited in cathode surface and with branch (dendrite) shape extend, so as to produce anode and negative electrode short circuit Problem, and do not disclose for solving the specific method of the problem.
Prior art literature
Patent document
Patent document 1：No. 2829556 publications of Japanese Patent Publication No.
Patent document 2：Japanese Unexamined Patent Publication 10-204669 publications
Patent document 3：No. 2736492 publications of Japanese Patent Publication No.
Patent document 4：Japanese Unexamined Patent Publication 2001-303239 publications
Patent document 5：Japanese Unexamined Patent Publication 2007-204779 publications
Patent document 6：Japanese Patent Publication 3-89166 publications
The content of the invention
Invent problem to be solved
It is produced when by electrolysis manufacture indium hydroxide or the compound containing indium hydroxide present invention aims at solving The problem of, i.e. generation current efficiency is excessively poor, and then sintering characteristic is deteriorated during sintering, the situation that density can not improve, so as to press down The decline of productivity ratio processed and the decline of quality.
The indium plate and negative electrode (cathode) plate that are used as anode (anode) are being configured at electrolysis in addition, also studying and having understood In groove, and when the electrolyte is flowed between them to be electrolysed, the oxide layer and impurity that are formed on the surface of anode The problem of the problem of being concentrated in the oxide layer, anode itself come off halfway, impurity content is also generated in addition to indium hydroxide High indium hydroxide, so as to cause the purity of indium hydroxide decline the problem of the reason for, and simultaneously propose solve these problems Some concrete countermeasures, its object is to suppress the decline of productivity ratio and the decline of quality.
Moreover, the present invention also research has been understood by electrolysis manufacture indium hydroxide or the compound when institute containing indium hydroxide The problem of generation, i.e. the indium or indium alloy plate and negative electrode (cathode) plate that are used as anode (anode) are being configured at electrolytic cell In, and when the electrolyte is flowed between them to be electrolysed, the indium hydroxide of generation or compound containing indium hydroxide are attached In anode surface, indium or indium alloy are electrodeposited in cathode surface and extended with branch (dendrite) shape so that anode and The reason for the problem of negative electrode short circuit, and some concrete countermeasures for solving the problem are proposed simultaneously, its object is to suppress productivity ratio Decline and the decline of quality.
For solving the method for problem
The present invention provides following methods to solve the above problems.
1) a kind of method by being electrolysed manufacture indium hydroxide or compound containing indium hydroxide, it is characterised in that make electricity The electrical conductivity of solution liquid is electrolysed for more than 10mS/cm, makes indium hydroxide or compound containing indium hydroxide in the electrolytic solution Separate out, and wash the indium hydroxide of precipitation or the compound containing indium hydroxide, until the electrical conductivity of the cleaning solution is 1mS/cm Below.
2) it is above-mentioned 1) as described in pass through the method for being electrolysed manufacture indium hydroxide or compound containing indium hydroxide, its feature It is, the electrical conductivity of the cleaning solution of compound of the washing to the indium hydroxide separated out or containing indium hydroxide is below 0.1mS/cm.
In addition, the present invention provides following methods to solve the above problems.
3) it is a kind of by being electrolysed the method for manufacturing indium hydroxide powder, the anode of the indium metal using minus plate and as raw material Plate is alternately arranged in a cell spacedly, to supplying electrolyte between the minus plate and positive plate, and passes through the system of electrolysis Make indium hydroxide powder, it is characterised in that indium hydroxide particle is separated out in the electrolytic solution, and reach sun in the weight of positive plate 20%~80% stage of pole initial weight stops electrolysis, takes out used positive plate, supplement new indium metal and with this Used positive plate is cast together, remakes positive plate, and the positive plate remake using this starts to be electrolysed, and makes Indium hydroxide particle separates out in the electrolytic solution.
4) it is above-mentioned 3) as described in by be electrolysed manufacture indium hydroxide powder method, it is characterised in that use stainless steel Plate or titanium plate are electrolysed as minus plate.
5) as it is above-mentioned 3)~4) any one of by being electrolysed the method for manufacturing indium hydroxide powder, its feature exists In further having：The process for taking out the indium hydroxide slurry separated out in the electrolytic solution；Concentrate the slurry and be separated into solid into Divide the process of concentrate and solid constituent thin liquid；Distributed with by the solid constituent thin liquid to the work of the electrolyte supply nozzle Sequence.
6) it is above-mentioned 5) as described in by be electrolysed manufacture indium hydroxide powder method, it is characterised in that have：Filtering institute State solid constituent concentrate and the process by its filtrate distribution to the electrolyte supply nozzle；With the dried solids filtered out Matter forms the process of indium hydroxide powder.
In addition, the present invention provides following methods to solve the above problems.
7) the electrolysis manufacture device of a kind of indium hydroxide or the compound containing indium hydroxide, it is characterised in that by minus plate With the indium as raw material or the positive plate of indium alloy it is spaced be alternately arranged in a cell, in the minus plate and positive plate Between and the position near a lateral edges between each minus plate and positive plate, configure another side to minus plate and positive plate Edge supplies the nozzle of electrolyte, make from the electrolyte each minus plate and positive plate in a cell of nozzle opening portion outflow it Between flow back, indium hydroxide or the compound containing indium hydroxide is separated out in the electrolytic solution.
8) it is above-mentioned 7) as described in indium hydroxide or compound containing indium hydroxide electrolysis manufacture device, its feature exists In minus plate is stainless steel plate or titanium plate.
9) it is above-mentioned 7) or 8) as described in indium hydroxide or compound containing indium hydroxide electrolysis manufacture device, its feature It is, configures one or more nozzles that electrolyte is supplied from the lateral edges between each minus plate and positive plate to another lateral edges, Flowed back between each minus plate and positive plate of the electrolyte for making to flow out from the opening portion of the nozzle in a cell, make indium hydroxide Or the compound containing indium hydroxide separates out in the electrolytic solution.
10) as it is above-mentioned 7)~9) any one of indium hydroxide or the electrolysis of compound containing indium hydroxide manufacture dress Put, it is characterised in that have：The device of the indium hydroxide that taking-up separates out in the electrolytic solution or the compound containing indium hydroxide；It is dense Contract and the hydroxide and be separated into the device of solid constituent concentrate and solid constituent thin liquid；Distributed with by the solid constituent thin liquid To the device of the electrolyte supply nozzle.
11) it is above-mentioned 7) as described in indium hydroxide powder or compound powder containing indium hydroxide electrolysis manufacture device, Characterized in that, possess：Filter the solid constituent concentrate and the dress by its filtrate distribution to the electrolyte supply nozzle Put；The device of indium hydroxide powder or compound powder containing indium hydroxide is manufactured with the dried solid matter filtered out.
12) a kind of method by being electrolysed manufacture indium hydroxide or compound containing indium hydroxide, it is characterised in that by the moon Pole plate and indium as raw material or the positive plate of indium alloy are alternately arranged in a cell spacedly, in the minus plate and sun The position between pole plate and near a lateral edges of each minus plate and positive plate, configure to the another of minus plate and positive plate Lateral edges supply the nozzle of electrolyte, adjust the liquid stream of the electrolyte from nozzle outflow, make its each negative electrode in a cell Flowed back between plate and positive plate, indium hydroxide or the compound containing indium hydroxide is separated out in the electrolytic solution.
13) it is above-mentioned 12) as described in pass through the method for being electrolysed manufacture indium hydroxide or compound containing indium hydroxide, it is special Sign is, is electrolysed using stainless steel plate or titanium plate as minus plate.
14) it is above-mentioned 12) or 13) as described in pass through and be electrolysed the side of manufacture indium hydroxide or compound containing indium hydroxide Method, it is characterised in that configure one or more and electrolysis is supplied from the lateral edges between each minus plate and positive plate to another lateral edges The nozzle of liquid, adjust each liquid stream of the electrolyte from the outflow of the opening portion of the nozzle, make its each minus plate in a cell and Flowed back between positive plate, indium hydroxide or the compound containing indium hydroxide is separated out in the electrolytic solution.
15) as it is above-mentioned 12)~14) any one of pass through and be electrolysed manufacture indium hydroxide or chemical combination containing indium hydroxide The method of thing, it is characterised in that further have：Take out the indium hydroxide separated out in the electrolytic solution or the chemical combination containing indium hydroxide The process of thing；The process for concentrating the hydroxide and being separated into solid constituent concentrate and solid constituent thin liquid；With by the solid Composition thin liquid is distributed to the process of the electrolyte supply nozzle.
16) it is above-mentioned 15) as described in by being electrolysed manufacture indium hydroxide powder or compound powder containing indium hydroxide Method, it is characterised in that have：Filter the solid constituent concentrate and by its filtrate distribution to the electrolyte supply nozzle Process；The work of indium hydroxide powder or compound powder containing indium hydroxide is formed with the dried solid matter filtered out Sequence.
17) as it is above-mentioned 12)~16) any one of indium hydroxide or compound containing indium hydroxide manufacturer Method, it is characterised in that make the feed speed of electrolyte relative to per unit current value, electrolysis area and time be 0.01~ 100.0L·m2/ A minutes flow electrolyte.
Invention effect
The present invention has following excellent results, i.e. is passing through electrolysis manufacture indium hydroxide or the chemical combination containing indium hydroxide During thing, indium hydroxide or the compound containing indium hydroxide can be efficiently manufactured, and thus improves agglutinating property when target manufactures.
In addition, being configured at by the indium plate and negative electrode (cathode) plate that are used as anode (anode) in electrolytic cell, and make electricity When solution liquid is flowed to be electrolysed between them, electrolytic anode is regenerated by the midway in electrolysis, can prevent impurity from existing Concentrated on the surface of anode, prevent anode to be shed in electrolytic process in electrobath, and can prevent from removing raw in electrobath Into indium hydroxide beyond be mixed into the high indium hydroxide of impurity content or impurity and cause indium hydroxide quality produce deviation.
But also there are following excellent results, i.e. passing through electrolysis manufacture indium hydroxide or the chemical combination containing indium hydroxide During thing, in order to not make indium hydroxide or compound containing indium hydroxide be attached to anode surface, and indium or indium alloy electricity are not made Cathode surface is deposited on, electrolyte is flowed back, so as to efficiently manufacture indium hydroxide or the compound containing indium hydroxide, thus may be used To improve productivity ratio.
Brief description of the drawings
Fig. 1 is the flow chart for representing the electrowinning process by indium manufacture indium hydroxide.
Fig. 2 is to represent that impurity is at indium anode (anode) when improving current density to improve the production efficiency of electrolysis Plate surface concentrates the figure of situation.
Fig. 3 is the outline figure of existing electrolysis unit, in the device, anode (anode) plate and negative electrode (cathode) Plate is configured in electrolytic cell spacedly, and the supply mouth for the nozzle for supplying electrolyte is configured with the top of electrolytic cell, Electrolyte is supplied into electrolytic cell.
Fig. 4 is the outline figure of electrolysis unit, and in the device, anode (anode) plate and negative electrode (cathode) plate leave Compartment of terrain is configured in electrolytic cell, meanwhile, downside in a cell and the lateral edges between each minus plate and positive plate, The supply mouth of the nozzle of configuration supply electrolyte, makes electrolyte flow back in a cell.
Fig. 5 is to show schematically the figure using liquid stream during Fig. 4 devices.
Fig. 6 is the outline figure of electrolysis unit, and in the device, anode (anode) plate and negative electrode (cathode) plate leave Compartment of terrain is configured in electrolytic cell, meanwhile, downside and upside in a cell and one between each minus plate and positive plate Lateral edges, the supply mouth of two sections of nozzles of configuration supply electrolyte, make electrolyte flow back in a cell.
Fig. 7 is to show schematically the figure using liquid stream during Fig. 6 devices.
Fig. 8 is to show schematically the figure using liquid stream when changing the device of upper nozzle position relative to Fig. 7.
Fig. 9 is the outline figure of electrolysis unit, and in the device, anode (anode) plate and negative electrode (cathode) plate leave Compartment of terrain is configured in electrolytic cell, meanwhile, downside, middle part and upside in a cell and between each minus plate and positive plate A lateral edges, configuration supply electrolyte three sections of nozzles supply mouth, electrolyte is flowed back in a cell.
Figure 10 is to show schematically the figure using liquid stream during Fig. 9 devices.
Embodiment
Fig. 1 represents to manufacture indium hydroxide (In (OH) by indium (In)3) electrowinning process flow chart.As shown in Figure 1, cast The affected indium for raw material, the positive plate being made up of indium is manufactured, and be configured in electrolytic cell.
In a cell, the minus plate that alternately configured in parallel multi-disc is made up of stainless steel plate or titanium plate.Into electrolytic cell Supply electrolyte.Electrolyte uses aqueous ammonium nitrate solution (NH4NO3).It should be noted that for electrolyte, not especially Specify, can arbitrarily use the nitric acid system aqueous solution, the sulfuric acid system aqueous solution, the hydrochloric acid system aqueous solution or other electrolyte etc., but from From the aspect of cost and maintenance product purity, it may be said that preferred aqueous ammonium nitrate solution.
Although what is enumerated in the following description is by indium (In) manufacture indium hydroxide (In (OH)3) example, but for Using the situation of compound of the indium alloy anode manufacture containing indium hydroxide, can similarly be applicable.The typical example of indium alloy is useful In ITO indium stannum alloy or indium kirsite etc..In addition, alloy of other elements etc. is also with the addition of, in generation and conduct What the representative of the present application exemplified manufactures indium hydroxide (In (OH) by indium (In)3) the same phenomenon of example situation Under, it can be applicable.
As addition element, in addition to above-mentioned tin (Sn), zinc (Zn), copper (Cu), silver-colored (Ag), antimony can also be enumerated (Sb), tellurium (Te), bismuth (Bi), thallium (Tl), gallium (Ga), germanium (Ge), cadmium (Cd) etc..It is big in these addition element in electrolysis Most and indium is identically formed hydroxide, but sometimes also with the simple substance or alloy of the oxide of addition element or addition element or The form of their mixture is present.The present application includes the complete of these compounds (containing mixture) contained in indium hydroxide Portion.
By electrolysis, indium dissolving, the fine particle of indium hydroxide separates out in the electrolytic solution.Take out what is separated out in the electrolytic solution Indium hydroxide, concentrated, be separated into solid constituent concentrate and solid constituent thin liquid.At this moment, solid constituent concentrate is entered Row washing, filtering, dry, obtain indium hydroxide powder.On the other hand, for solid constituent thin liquid, it is back to electrolyte In, carry out solution regulation and recycle.In addition, the filtrate for aforesaid solid composition concentrate to be filtered to gained, also by its time It flow in electrolyte, carries out solution regulation and recycle.
Problem can be turned into herein, current efficiency becomes excessively poor when being electrolysed.Moreover, in sintering separation of solid and liquid When rear indium hydroxide or its compound, there are sintered density can not improve, or that sintered density occurs is uneven in target The problem of such.
Therefore, the result after various researchs shows, if the electrical conductivity in electrolyte is too low, current efficiency becomes It is excessively poor, and be attached to the electrolyte on indium hydroxide and constitute the reason for sintered density is low.
In addition, with the progress of electrolysis, the impurity element of indium anode (anode) plate is remained and concentrated in indium anode surface. The situation is shown in Fig. 2.
Metallic element more inert than indium remains in surface, and ionization and dissolution occur for only indium.If impurity is in anode Surface concentrates, then ionization and dissolution also occur for the impurity, particularly metallic element more inert than indium, so as to be mixed into hydrogen In indium oxide slurry.Moreover, impurity comes off from anode surface, it is mixed into indium hydroxide slurry.
The present invention makes the electrical conductivity of electrolyte when by electrolysis manufacture indium hydroxide or the compound containing indium hydroxide For under conditions of more than 10mS/cm, and more preferably it is electrolysed under conditions of the upper limit is 500mS/cm, makes indium hydroxide or contain The compound of indium hydroxide separates out in the electrolytic solution.Thereby, it is possible to make current efficiency substantially 100%.
Moreover, the necessary condition of the present invention is the indium hydroxide that washing separates out or the compound containing indium hydroxide, until should The electrical conductivity of cleaning solution is below 1mS/cm.It is preferred that it is below 0.1mS/cm to wash to the electrical conductivity of cleaning solution.To thus gained Hydroxide be dried or reduce, as the raw materials for sintering of oxide, be then sintered again.Thereby, it is possible to will sintering The relative density of body is improved to more than 99%.
In addition, in the present application, above-mentioned aspect is improved, the starting weight at the beginning of the weight of positive plate reaches anode 20%~80% stage of amount stops electrolysis.When less than 20%, substantial amounts of impurity concentrates in anode surface, generates foregoing Problem.When more than 80%, service efficiency is poor, and productivity ratio is deteriorated.Then, used positive plate is taken out, it is used to this New indium metal is supplemented in positive plate and is cast, remakes positive plate, the melting casting is not particularly limited.Even if New indium metal is not supplemented, and is only cast with used positive plate, is had no problem yet.
The indium metal positive plate remake using this, starts to be electrolysed, and indium hydroxide particle can be made to analyse in the electrolytic solution Go out.The positive plate remake, same process can be passed through, reach anode initial weight using the weight of positive plate 20%~80% stage.After use, it can regenerate electrolytic anode by same method.The behaviour remake of the anode Make, can be repeatedly.
Workable anode scope is 20%~80% relative broad range of initial weight, and this depends primarily on the pure of anode Spend deviation.In general, the changes of contents of impurity is larger in the indium raw material of circulation.Moreover, in the production phase of anode, impurity Mixed volume also can according to circumstances change.If impurity is more, with continuous electrolysis, the impurity level concentrated on the anode surface is worked as So become more, service efficiency declines.On the other hand, it is few in the impurity level of anode surface concentration if impurity is few, therefore use effect Rate is high.
In electrolysis, anode surface is simultaneously anisotropically consumed, compared with the position more than impurity, portion that electric current easily flows through Faster, and the phenomenon that anode ingot comes off halfway also be present in the consumption of position (the few position of impurity).By upper it can be said that tendency is The service efficiency of the few anode of impurity content is high, and the service efficiency of the anode more than impurity content is low.
In addition, also sometimes not be all electrodeposited in as indium hydroxide, a part of In on negative electrode, and its grow so that Cause short circuit.At this moment, it is necessary to interrupt electrolysis.The short circuit can be read by voltage change.These factors are foregoing 20%~ The reason for 80% relative broad range.
Turn into problem herein, when being electrolysed, the indium hydroxide of generation adheres to what is be made up of in a cell indium The surface of positive plate, and indium is electrodeposited in the surface of minus plate, so as to continue to be electrolysed.Above-mentioned indium is with branch (dendrite) shape extends, the problem of so as to also create anode and negative electrode short circuit.
For this problem, when improving electrolytic current density to improve production efficiency, significantly there occurs hydrogen-oxygen Change the attachment of indium and the electro-deposition of indium.Although electro-deposition and attachment from indium hydroxide to positive plate of the indium to minus plate is not So firmly, but if attachment quantitative change is more, then have the tendency of to be difficult to gradually peel off.Therefore, the starting stage is being electrolysed, is making electrolyte Flowed back between each anode plate and cathode plate, carry out preventing indium to minus plate electro-deposition and hydrogen-oxygen by the backflow of electrolyte Change the method (experiment) that indium adheres to positive plate.
Illustrate existing electrolysis unit using Fig. 3.Left side shown in the Fig. 3 is the top view of electrolytic cell, and right side is anode The side view of the middle position of plate and minus plate.As shown in figure 3, anode (anode) plate and negative electrode (cathode) plate are reserved 10~500mm interval is configured in electrolytic cell, and configures the supply mouth for the nozzle for supplying electrolyte in upper part of the electrolytic cell.
Then, along the direction shown in the arrow of Fig. 3 right part of flg, electrolyte is supplied into electrolytic cell.Electrolyte will be supplied Flow strength (electrolyte supply speed) be set as 0.5Lm2/ A minutes.(electrolyte supplies the flow strength of the electrolyte To speed) represent relative to the male or female current density (A/dm of any one2Or A/m2) flow velocity (L/ minutes).Hereinafter, exist When representing flow strength (the electrolyte supply speed) of electrolyte, used with identical implication.
For the existing electrolyte supply method, there occurs electro-deposition of the indium to minus plate, indium hydroxide to face south The attachment of pole plate.Even if the flow strength (electrolyte supply speed) of electrolyte is risen above into above-mentioned numerical value, also obtain Same result.
In order to suppress the generation that indium adheres to minus plate electro-deposition, indium hydroxide to positive plate, it is contemplated that adjust liquid stream Direction, and carried out some experiments.
The outlining for electrolysis manufacture device of the indium hydroxide is illustrated in Fig. 4.It is viewed from above on the left of Fig. 4 Outline figure (top view), right side is the outline figure of the side of the middle position of anode plate and cathode plate.Except Beyond the configuration of nozzle, and structure shown in Fig. 3 is identical.
Then, along the direction shown in the arrow of Fig. 4 right part of flg, electrolyte is made to flow back.By the flow strength of the electrolyte (electrolyte supply speed) is set as 0.01~100.0Lm2/ A minutes.As shown in figure 4, liquid stream is formed from each anode, the moon The flowing of the lower direction center convolution of interpolar.
In addition, if electrolyte supply speed is less than 0.01Lm2/ A minutes, even then reflux type, can not yet Solve the above problems.If above 100.0Lm2/ A minutes, then the circulation rate of liquid stream accelerate, formed turbulent flow, be attached to The indium hydroxide of anode surface is peeled off with the state of oversize grain, come off, or the shape of the hydroxide of generation is very small, It can not use.The flow strength (electrolyte supply speed) of the electrolyte is preferably 0.1~10.0Lm2/ A minutes.
From Fig. 4 liquid stream control result, if using the nozzle shown in Fig. 4, electro-deposition of the indium to minus plate, hydrogen Attachment of the indium oxide to positive plate disappears.Its reason is understood in order to study, after the electrolyte in electrolytic cell is studied, confirmed Understand, as shown in Fig. 5 liquid stream schematic diagram, there occurs sufficient flowing in the central portion of minus plate and positive plate for electrolyte.
This as a result, the present invention reflow method it is extremely effective, improved by simple device, it is possible to effectively suppress The generation of attachment and electro-deposition from indium to minus plate of the indium hydroxide to positive plate, and in the whole of minus plate and positive plate The surface generation unconfirmed for arriving the attachment and electro-deposition.
From the foregoing, it will be observed that between each minus plate and positive plate, electrolyte is supplied from a lateral edges to another lateral edges, makes it Flowed back in a cell between each minus plate and positive plate, be that suppression indium is attached to minus plate electro-deposition, indium hydroxide to positive plate The effective ways, the present invention are completed based on above-mentioned experimental result.
That is, it is known that following methods are effective：10 are reserved using minus plate and as the positive plate of the indium of raw material~ 500mm's alternates arrangement in a cell, between the minus plate and positive plate and in each minus plate and positive plate Position near one lateral edges, the nozzle to another lateral edges of minus plate and positive plate supply electrolyte is configured, is made from the spray Flowed back between each minus plate and positive plate of the electrolyte of the opening portion outflow of mouth in a cell, make indium hydroxide in electrolyte Middle precipitation.
In addition, for supply electrolyte nozzle diameter (bore) for, according to the size of electrolytic cell, each minus plate and The gap size of positive plate, the quantity delivered of electrolyte, the configuration of nozzle and number etc. are suitably adjusted.Therefore, the diameter (mouth of nozzle Footpath) it is not particularly limited.
Can be wider gap, in such a case, it is possible to increase liquid for the interval of minus plate and positive plate Stream.That is, the nozzle of one or more supply electrolyte can be configured, as to the opposite side between minus plate and positive plate Edge supplies the nozzle of electrolyte, makes each minus plate and anode in a cell from the electrolyte of the opening portion of nozzle outflow Flowed back between plate, indium hydroxide is separated out in the electrolytic solution.
The electrolyte liquid stream from the outflow of the opening portion of lower nozzle, upper nozzle or intermediate noxzzle is effectively adjusted, is made Each liquid stream is returned between minus plate and positive plate in arc shaped from a lateral edges of each minus plate and positive plate to another lateral edges Flow (convolution).At this moment it is believed that the backflow of electrolyte needs the Uniform Flow between each minus plate and positive plate, and the stream A dynamic part contacts with the surface of minus plate and positive plate.If however, can be between minus plate and positive plate in negative electrode The whole surface of plate and positive plate flows back, then it may be said that it flows back, direction need not especially limit.
In the present invention, be effective using stainless steel plate or titanium plate as minus plate, as long as and do not pollute electrolyte, Can be other materials.
Following electrolysis manufacture device can also be formed, it is provided with：Take out the dress of the indium hydroxide separated out in the electrolytic solution Put；Concentrate the hydroxide and be separated into the device of solid constituent concentrate and solid constituent thin liquid；By the solid constituent Thin liquid is distributed to the device of aforementioned electrolyte supply nozzle, and is had：Filter aforesaid solid composition concentrate and by its filtrate Distribute to the device of aforementioned electrolyte supply nozzle；The device washed to the solid matter filtered out；And then to its carry out Dry to form the indium oxide powder manufacture device of indium oxide powder., can also be with this in order to reduce the cost of manufacture device The electrolysis unit of invention sets equipment for separating liquid from solid, filter, filtrate distribution device, water washing device, powder fabricating apparatus etc..
Embodiment
Hereinafter, embodiments of the invention are illustrated.It should be noted that the present embodiment is an example, this hair It is bright not limited by this.That is, the present invention is included beyond all embodiments in the technology of the present invention thought range Mode or deformation.
(embodiment 1)
Using indium plate as anode, using stainless steel plate as negative electrode, and aqueous ammonium nitrate solution is used to lead to as electrolyte Crossing electrolysis separates out hydroxide.At this moment electrolytic conductivity is set as that 10mS/cm is electrolysed, as a result current efficiency is 95%.
The hydroxide is further filtered, and is washed using pure water, until the electrical conductivity of cleaning solution is 0.1mS/cm. Then it is dried, forms indium oxide, then be sintered under conditions of 1500 DEG C, obtains the indium that relative density is 98% and sinter Body.
It should be noted that, although at this moment enumerate the example for separating out indium hydroxide using indium as anode and by electrolysis Son, but using the indium alloy such as indium stannum alloy, make the compound containing indium hydroxide (for example, indium hydroxide and stannic hydroxide Mixture) separate out when, same result can also be obtained.
That is, it has been confirmed that as being washed to the indium hydroxide obtained by any or the compound containing indium hydroxide Wash, relative density improves, and is used as its index, and controllable condition is the electrical conductivity of cleaning solution.
(embodiment 2)
The electrical conductivity of the electrolyte of embodiment 1 is changed to 100mS/cm, is electrolysed.At this moment current efficiency is 99%.Then, carry out repulping with pure water to wash, until the electrical conductivity of cleaning solution is 0.01mS/cm.Identical with embodiment 1 Under conditions of be sintered, as a result obtain sintered body relative density be 99.5% high-density sintered body.
It should be noted that, although at this moment enumerate the example for separating out indium hydroxide using indium as anode and by electrolysis Son, but using the indium alloy such as indium stannum alloy, make the compound containing indium hydroxide (for example, indium hydroxide and stannic hydroxide Mixture) separate out when, same result can also be obtained.
With embodiment 1 it is also possible to confirm, by indium hydroxide or the compound containing indium hydroxide is washed, phase Density is improved, and is used as its index, controllable condition is the electrical conductivity of cleaning solution.
(comparative example 1)
The electrical conductivity of the electrolyte of embodiment 1 is changed to 8.0mS/cm, is electrolysed.As a result, oxygen is produced from positive plate Gas, hydrogen is produced from minus plate, therefore current efficiency is poor, is about 80%.Reach the horizontal hydrogen of raw materials for sintering due to that can not manufacture Indium oxide, therefore the process after terminating.
(comparative example 2)
The electrical conductivity of the electrolyte of embodiment 1 is changed to 50mS/cm, is electrolysed.Current efficiency is good, reaches 99%, repulping then is carried out to hydroxide with pure water and washed, until the electrical conductivity of cleaning solution is 2mS/cm.And embodiment 1 is sintered under the same conditions, and as a result sintered density is poor, is 95%, and a part of sintered body cracks.It can recognize It is that the indium hydroxide of precipitation is not carried out caused by fully washing for the result.
It should be noted that, although at this moment enumerate the example for separating out indium hydroxide using indium as anode and by electrolysis Son, but using the indium alloy such as indium stannum alloy, make the compound containing indium hydroxide (for example, indium hydroxide and stannic hydroxide Mixture) separate out when, also obtained same result.
(comparative example 3)
The electrical conductivity of the electrolyte of embodiment 1 is changed to 1mS/cm, is electrolysed.As a result current efficiency is excessively poor, is 50%.But repulping is carried out to the hydroxide of precipitation with pure water and washed, until the electrical conductivity of cleaning solution is 0.01mS/cm.
Then, it is sintered under the same conditions with embodiment 1, as a result sintered density can reach 99%.Due to electricity Current efficiency during solution is poor, therefore is not the condition that can be used in practical operation, but it has been confirmed that indium hydroxide is washed Wash with the effect for improving sintered density.
It should be noted that, although at this moment enumerate the example for separating out indium hydroxide using indium as anode and by electrolysis Son, but using the indium alloy such as indium stannum alloy, make the compound containing indium hydroxide (for example, indium hydroxide and stannic hydroxide Mixture) separate out when, also obtained same result.
(embodiment 3)
Indium hydroxide (In (OH) is being manufactured by indium metal (In)3) electrowinning process in, the indium metal as raw material is entered Row casting, manufactures the positive plate being made up of indium metal, and configured in a cell.By what is be made up of stainless steel plate or titanium plate Minus plate alternately configures in a cell.These anode plate and cathode plate abreast configure multi-disc.Electricity is supplied into electrolytic cell Solve liquid.Use aqueous ammonium nitrate solution (NH4NO3) electrolyte is used as, start to be electrolysed.
Then, indium hydroxide particle is made to separate out in the electrolytic solution, and in 80% stage for reaching positive plate initial weight Stop electrolysis.Used positive plate is then taken out, and the used positive plate is melted.When melting, new indium is supplemented Metal, and cast, remake positive plate.
The indium metal positive plate that this can be used to remake, starts again at electrolysis, makes indium hydroxide particle in electrolyte Middle precipitation.For the positive plate that this remakes, same process can be passed through, reach anode initial weight using to it 20%~80% stage.After use, it can regenerate electrolytic anode by same method.
After electrolysis, the indium hydroxide slurry separated out in the electrolytic solution is suitably taken out, the slurry is concentrated, by its point From into solid constituent concentrate and solid constituent thin liquid.Then, the solid constituent thin liquid will be distributed to aforementioned electrolyte and supplied Nozzle.Also, aforesaid solid composition concentrate is filtered, it is on the other hand, right by its filtrate distribution to aforementioned electrolyte supply nozzle The solids filtered out is dried, and forms indium hydroxide powder.
(embodiment 4)
Equally operated with embodiment 1, indium hydroxide particle is separated out in the electrolytic solution, and reaching positive plate initial weight 20% stage stop electrolysis.Positive plate is similarly remake with embodiment 1, starts to be electrolysed.For the sun remake Pole plate, reach the 50% of anode initial weight using to it.After use, regenerate electrolytic anode by same method.
After electrolysis, the indium hydroxide slurry separated out in the electrolytic solution is suitably taken out, the slurry is concentrated, by its point From into solid constituent concentrate and solid constituent thin liquid.Then, the solid constituent thin liquid will be distributed to aforementioned electrolyte and supplied Nozzle.Also, aforesaid solid composition concentrate is filtered, it is on the other hand, right by its filtrate distribution to aforementioned electrolyte supply nozzle The solids filtered out is dried, and forms indium hydroxide powder.
(embodiment 5)
Equally operated with embodiment 1, indium hydroxide particle is separated out in the electrolytic solution, and reaching positive plate initial weight 60% stage stop electrolysis.Used positive plate is then taken out, is melted, and new indium gold is added when melting Category.
The positive plate remake using this, start to be electrolysed.For the positive plate remake, reach anode using to it The 30% of initial weight.After use, regenerate electrolytic anode by same method.
After electrolysis, the indium hydroxide slurry separated out in the electrolytic solution is suitably taken out, the slurry is concentrated, by its point From into solid constituent concentrate and solid constituent thin liquid.Then, the solid constituent thin liquid will be distributed to aforementioned electrolyte and supplied Nozzle.Also, aforesaid solid composition concentrate is filtered, it is on the other hand, right by its filtrate distribution to aforementioned electrolyte supply nozzle The solids filtered out is dried, and forms indium hydroxide powder.
(comparative example 4)
Indium hydroxide (In (OH) is being manufactured by indium metal (In)3) electrowinning process in, the indium metal as raw material is entered Row casting, manufactures the positive plate being made up of indium metal, and configured in a cell.By what is be made up of stainless steel plate or titanium plate Minus plate alternately configures in a cell.These anode plate and cathode plate abreast configure multi-disc.Electricity is supplied into electrolytic cell Solve liquid.Use aqueous ammonium nitrate solution (NH4NO3) it is used as electrolyte.
In order to improve the production efficiency of electrolysis, to continue to being reached 15% or so of anode initial weight.It is being electrolysed During, it is different on negative electrode (cathode) plate of indium anode (anode) plate and stainless steel to generate substantial amounts of indium oversize grain Thing, and anode plate and cathode plate are short-circuit because of these oversize grain foreign matters, can not be electrolysed.
Because impurity concentrates on the positive plate being made up of indium metal, therefore voltage uprises, the impurity dissolution.As a result impurity It is mixed into indium hydroxide, generates the problem of purity in electrolyte is deteriorated.
(comparative example 5)
Because the impurity concentration of anode is high, therefore stop electrolysis when reaching 85% or so of anode initial weight.This is Because although in purity of gained hydroxide etc., there is no problem, and more impurity concentrates on the anode surface, if It is further continued for being electrolysed, then the quality of indium hydroxide can produce deviation.
(comparative example 6)
In order to improve the production efficiency of electrolysis, to continue to being reached 5% or so of anode initial weight.It had been electrolysed Cheng Zhong, hole is produced in a part for positive plate, and dropped into electrobath, device damage, can not continue to be electrolysed.
In addition, the quality deviation of the hydroxide produced is big, can not use.
(embodiment 6)
Using the device shown in above-mentioned Fig. 4, separate out indium hydroxide by electrolysis.Specifically, replace in a cell Ground arrange 10 groups of 11 1000mm × 700mm × 5mmt stainless steel minus plate and 10 1000mm as raw material × The positive plate that 700mm × 50mmt is made up of indium, make the minus plate and positive plate at intervals of 50mm, and in each minus plate and The lower end position (chaotropic face 1000mm position) of a lateral edges between positive plate is configured to the another of minus plate and positive plate One lateral edges supply the nozzle of electrolyte.
Then, the direction shown in arrow of the electrolyte along Fig. 4 right part of flg is flowed back, make from the outflow of the opening portion of the nozzle Electrolyte flowed back in a cell between each minus plate and positive plate, indium hydroxide is separated out in the electrolytic solution.This is electrolysed The flow strength (electrolyte supply speed) of liquid is set as 0.1Lm2/ A (ampere) minutes.As shown in figure 4, liquid stream formed from The flowing that lower section is circled round upward.
It can be seen from the backflow direction shown in Fig. 4, the flowing of electrolyte does not produce blank between minus plate and positive plate Part, uniform backflow (swirling flow) is formd on the whole.As a result can suppress attachment of the indium hydroxide to positive plate and Electro-deposition of the indium to minus plate.It is and all unconfirmed to the generation attachment and electricity in the whole surface of minus plate and positive plate Deposition.
It should be noted that, although at this moment enumerate the example for separating out indium hydroxide using indium as anode and by electrolysis Son, but using indium alloys such as indium stannum alloys, when separating out the compound of the hydroxide containing indium, same show can also be obtained As.Below in an example and identical.
(embodiment 7)
In the method same with embodiment 1, the flow strength (electrolyte supply speed) of the electrolyte is set as 10L·m2/ A minutes.At this moment, equally operated with embodiment 1, can suppress electro-deposition of the indium to minus plate, indium hydroxide to The attachment of positive plate.It is and all unconfirmed heavy to the generation attachment and electricity in the whole surface of minus plate and positive plate Product.
(embodiment 8)
In the method same with embodiment 1, the flow strength (electrolyte supply speed) of the electrolyte is set as 0.01L·m2/ A minutes.At this moment, partly there occurs electro-deposition of the indium to minus plate, attachment of the indium hydroxide to positive plate, but It can also use.
(embodiment 9)
In the method same with embodiment 1, the flow strength (electrolyte supply speed) of the electrolyte is set as 50L·m2/ A minutes.At this moment, although slightly a little indium hydroxide oversize grains are peeled off from anode, can also use.
(embodiment 10)
In the method same with embodiment 1, the flow strength (electrolyte supply speed) of the electrolyte is set as 100L·m2/ A minutes.At this moment, indium hydroxide oversize grain in part is peeled off from anode, and generates a small amount of small hydrogen Oxide (average grain diameter after being calcined at 1100 DEG C is less than 0.5 μm).But itself it is not larger problem, it can use.
(embodiment 11)
Using the device shown in Fig. 6, separate out indium hydroxide by electrolysis.Specifically, using same with embodiment 1 Anode and negative electrode, the lower end of the lateral edges between the minus plate and positive plate and between each minus plate and positive plate Position (chaotropic face 1000mm position) and chaotropic face 155mm position configure another lateral edges to minus plate and positive plate Supply the lower nozzle and upper nozzle of electrolyte.
Then, the direction shown in arrow of 2 kinds of electrolyte along Fig. 6 right part of flg is flowed back, make from the lower nozzle and upper The electrolyte of the opening portion outflow of portion's nozzle flows back between each minus plate and positive plate in a cell, is being electrolysed indium hydroxide Separated out in liquid.The flow strength (electrolyte supply speed) of the electrolyte is set as 10Lm2/ A minutes.As shown in fig. 6, Liquid stream is formed from the flowing of upper direction center convolution and from below to this 2 kinds flowings of flowing of center convolution.
It can be seen from the backflow direction shown in Fig. 6, the flowing of electrolyte in the specific location of minus plate and positive plate not Blank parts are produced, form uniform backflow (swirling flow) on the whole.It is with the Main Differences of embodiment 1, in chaotropic Face 155mm opening position is provided with upper nozzle.As a result electro-deposition of the indium to minus plate, indium hydroxide can be suppressed to positive plate Attachment.It is and all unconfirmed to the generation attachment and electro-deposition in the whole surface of minus plate and positive plate.
It should be noted that as shown in Fig. 8 liquid stream schematic diagram, and embodiment 2 is same, uses the spray for being configured to two sections Mouth, and chaotropic face 322mm opening position configure epimere nozzle, carry out and the identical of embodiment 2 experiment when, can obtain and The same result of embodiment 2.
(embodiment 12)
Using the device shown in Fig. 9, separate out indium hydroxide by electrolysis.Specifically, using same with embodiment 1 Anode and negative electrode, the lower end of the lateral edges between the minus plate and positive plate and between each minus plate and positive plate Position (chaotropic face 1000mm position), chaotropic face 322mm position and upper end neighbouring position (chaotropic face 155mm position Put), configure lower nozzle, intermediate noxzzle and the upper nozzle to another lateral edges of minus plate and positive plate supply electrolyte.
Then, the direction shown in arrow of 3 kinds of electrolyte along Fig. 9 right part of flg is flowed back, make from the lower nozzle, centre The electrolyte of the opening portion of nozzle and upper nozzle outflow flows back between each minus plate and positive plate in a cell, makes hydroxide Indium separates out in the electrolytic solution.The flow strength (electrolyte supply speed) of the electrolyte is set as 10Lm2/ A minutes.Come Form the flowing circled round from the top to the bottom from the liquid stream of upper nozzle, the liquid stream from intermediate noxzzle is formed to diverging back up and down The flowing of rotation, this 3 kinds flowings of flowing that the liquid stream formation of nozzle is circled round upward from below from below.
It can be seen from the backflow direction shown in Fig. 9, the flowing of electrolyte does not produce in the central portion of minus plate and positive plate Blank parts, uniform backflow (swirling flow) is formd on the whole.It is with the Main Differences of embodiment 2, in chaotropic face 322mm opening position is provided with the opening portion of intermediate noxzzle, in this case, can also suppress indium and be sunk to the electricity of minus plate Product, attachment of the indium hydroxide to positive plate.It is and all unconfirmed to described in generation in the whole surface of minus plate and positive plate Attachment and electro-deposition.
(comparative example 7)
Using the device shown in Fig. 3, electrolyte is imported from the side ullage of electrolytic cell, and hydroxide is made by electrolysis Indium separates out.Specifically, using the anode and negative electrode same with embodiment 1.By the flow strength (electrolyte supply of the electrolyte Speed) it is set as 0.5Lm2/ A minutes.As a result substantial amounts of indium hydroxide is attached on the positive plate, and also has indium electricity heavy Accumulate onto minus plate, electrolysis becomes difficult.
(comparative example 8)
Using the device shown in Fig. 3, electrolyte supply speed is set as 10Lm2/ A minutes, it is electrolysed.As a result There occurs attachment of the indium hydroxide to positive plate, electro-deposition of the indium to minus plate.The attachment, electro-deposition occur mainly in minus plate Substantially central portion and bottom with positive plate.Even if the flow strength (electrolyte supply speed) of electrolyte is risen above Numerical value is stated, has also obtained same result.
(comparative example 9)
Electrolyte in contradistinction to is imported from 1 position of the side bottom of electrolytic cell one using electrolysis unit, and with Fig. 3, is led to Crossing electrolysis separates out indium hydroxide.At this moment, nozzle is configured not between each minus plate and positive plate to make electrolyte in these plates Between flow back, only in the same manner as Fig. 3 from the bottom of electrolytic cell (1 position) supply electrolyte situation.Electrolyte is supplied It is set as 0.5Lm to speed2/ A minutes.
As a result there occurs attachment of the indium hydroxide to positive plate, electro-deposition of the indium to minus plate.The attachment and electro-deposition Occur mainly in the substantially central portion of minus plate and positive plate.Even if the flow strength (electrolyte supply speed) of electrolyte is carried Up to it is more than above-mentioned numerical value, has also obtained same result.
(comparative example 10)
Under the same conditions, electrolyte supply speed is being set as 0.009Lm with embodiment 12/ A minutes.As a result Substantial amounts of indium hydroxide is attached on positive plate, and indium electro-deposition on minus plate, causes anode and negative electrode there occurs short circuit, It is difficult to continue to be electrolysed.The attachment and electro-deposition occur mainly in the substantially central portion of minus plate and positive plate.
(comparative example 11)
Under the same conditions, electrolyte supply speed is being set as 110Lm with embodiment 12/ A minutes.Though as a result So without occurring attachment, electro-deposition from indium to minus plate of the indium hydroxide to positive plate, but largely indium oversize grain from anode Upper stripping, and a large amount of small hydroxide (average grain diameter after being calcined at 1100 DEG C is less than 0.5 μm) are generated, can not Use.
Industrial applicability
A kind of method that indium hydroxide or compound containing indium hydroxide are manufactured by electrolysis, make the electrical conductivity of electrolyte It is electrolysed for more than 10mS/cm, indium hydroxide or the compound containing indium hydroxide is separated out in the electrolytic solution, and wash The indium hydroxide of precipitation or the compound containing indium hydroxide, until the electrical conductivity of cleaning solution is below 1mS/cm, thus there is suppression Productivity ratio processed declines and the excellent results of quality decline, therefore it is to have to form the sputtering of ito film etc. with ITO targets etc. for manufacture .
In addition, it is a kind of using minus plate and as the positive plate of the indium metal of raw material it is spaced be arranged alternately in electrolytic cell In, to electrolyte, and the method by being electrolysed manufacture indium hydroxide powder is supplied between the minus plate and positive plate, make hydroxide Indium particle separates out in the electrolytic solution, and the positive plate in electrolyte is impregnated in reaches 20%~80% stage of initial weight Stop electrolysis, take out used positive plate, new indium metal and progress are supplemented while the used positive plate is melted Casting, remakes positive plate, the positive plate remake using this starts to be electrolysed, and indium hydroxide particle is analysed in the electrolytic solution Go out, as a result can suppress the attachment by being electrolysed in the method for manufacture indium hydroxide powder, and can prevent in cathode surface Indium metal is generated, so as to suppress the decline of productivity ratio.It is to have that this method forms the sputtering of ito film with ITO targets for manufacture .
In addition, a kind of method by being electrolysed manufacture indium hydroxide or compound containing indium hydroxide, it is characterised in that will Minus plate and indium as raw material or the positive plate of indium alloy are alternately arranged in a cell spacedly, in the minus plate and The position between positive plate and near each minus plate and the lateral edges of positive plate one, configure to the another of minus plate and positive plate Lateral edges supply the nozzle of electrolyte, adjust the liquid stream of the electrolyte from the outflow of the opening portion of the nozzle, make it in a cell Each minus plate and positive plate between flow back, indium hydroxide or the compound containing indium hydroxide is separated out in the electrolytic solution.The party Method is when by electrolysis manufacture indium hydroxide or the compound containing indium hydroxide, because tool has the advantage that, you can to suppress Indium hydroxide or compound containing indium hydroxide are attached to anode surface, and can prevent from generating indium in cathode surface or indium closes Gold, so as to suppress the decline of productivity ratio, therefore it is useful to form the sputtering of ito film with ITO targets for manufacture.

Claims (18)

1. the electrolysis manufacture device of a kind of indium hydroxide or the compound containing indium hydroxide, it is characterised in that by minus plate and work The positive plate of indium or indium alloy for raw material is alternately arranged in a cell spacedly, between the minus plate and positive plate And in each minus plate and a lateral edges of positive plate, configure to another lateral edges of minus plate and positive plate supply electrolyte Nozzle, make to flow back between the electrolyte of the opening portion of nozzle outflow each minus plate and positive plate in a cell, make hydrogen Indium oxide or compound containing indium hydroxide separate out in the electrolytic solution.
2. the electrolysis manufacture device of indium hydroxide as claimed in claim 1 or the compound containing indium hydroxide, it is characterised in that Minus plate is stainless steel plate or titanium plate.
3. the electrolysis manufacture device of indium hydroxide as claimed in claim 1 or 2 or the compound containing indium hydroxide, its feature exist In configuring one or more nozzles that electrolyte is supplied from the lateral edges between each minus plate and positive plate to another lateral edges, make Flowed back between each minus plate and positive plate of the electrolyte flowed out from the opening portion of the nozzle in a cell, make indium hydroxide or Compound containing indium hydroxide separates out in the electrolytic solution.
4. the electrolysis manufacture device of indium hydroxide as claimed in claim 1 or 2 or the compound containing indium hydroxide, its feature exist In having：The device of the indium hydroxide that taking-up separates out in the electrolytic solution or the compound containing indium hydroxide；Concentrate the hydroxide And it is separated into the device of solid constituent concentrate and solid constituent thin liquid；Distributed with by the solid constituent thin liquid to the electrolyte The device of supply nozzle.
5. the electrolysis manufacture device of indium hydroxide as claimed in claim 3 or the compound containing indium hydroxide, it is characterised in that Have：The device of the indium hydroxide that taking-up separates out in the electrolytic solution or the compound containing indium hydroxide；Concentrate the hydroxide simultaneously It is separated into the device of solid constituent concentrate and solid constituent thin liquid；Supplied with the solid constituent thin liquid is distributed to the electrolyte Device to nozzle.
6. the electrolysis manufacture device of indium hydroxide as claimed in claim 4 or the compound containing indium hydroxide, it is characterised in that Possess：Filter the solid constituent concentrate and the device by its filtrate distribution to the electrolyte supply nozzle；With it is dried The solid matter filtered out manufactures the device of indium hydroxide powder or compound powder containing indium hydroxide.
7. the electrolysis manufacture device of indium hydroxide as claimed in claim 5 or the compound containing indium hydroxide, it is characterised in that Possess：Filter the solid constituent concentrate and the device by its filtrate distribution to the electrolyte supply nozzle；With it is dried The solid matter filtered out manufactures the device of indium hydroxide powder or compound powder containing indium hydroxide.
A kind of 8. method by being electrolysed manufacture indium hydroxide or compound containing indium hydroxide, it is characterised in that by minus plate With the indium as raw material or the positive plate of indium alloy it is spaced be alternately arranged in a cell, in the minus plate and positive plate Between and in the lower end of each minus plate and a lateral edges of positive plate, configure and supplied to another lateral edges of minus plate and positive plate To the nozzle of electrolyte, the liquid stream of the electrolyte from the outflow of the opening portion of the nozzle is adjusted, makes its each negative electrode in a cell Flowed back between plate and positive plate, indium hydroxide or the compound containing indium hydroxide is separated out in the electrolytic solution.
9. pass through electrolysis manufacture indium hydroxide or the method for the compound containing indium hydroxide, its feature as claimed in claim 8 It is, is electrolysed using stainless steel plate or titanium plate as minus plate.
10. the method by being electrolysed manufacture indium hydroxide or compound containing indium hydroxide as claimed in claim 8 or 9, its It is characterised by, configures one or more and supply electrolyte from a lateral edges to another lateral edges between each minus plate and positive plate Nozzle, the liquid stream of the electrolyte from the outflow of the opening portion of the nozzle is adjusted respectively, make its each minus plate and sun in a cell Flowed back between pole plate, indium hydroxide or the compound containing indium hydroxide is separated out in the electrolytic solution.
11. the method by being electrolysed manufacture indium hydroxide or compound containing indium hydroxide as claimed in claim 8 or 9, its It is characterised by also having：The process of the indium hydroxide that taking-up separates out in the electrolytic solution or the compound containing indium hydroxide；Concentration should Hydroxide and the process for being separated into solid constituent concentrate and solid constituent thin liquid；Distributed with by the solid constituent thin liquid to institute The process for stating electrolyte supply nozzle.
12. as claimed in claim 10 by electrolysis manufacture indium hydroxide or the method for the compound containing indium hydroxide, it is special Sign is also have：The process of the indium hydroxide that taking-up separates out in the electrolytic solution or the compound containing indium hydroxide；Concentrate the hydrogen Oxide and the process for being separated into solid constituent concentrate and solid constituent thin liquid；Distributed with by the solid constituent thin liquid to described The process of electrolyte supply nozzle.
13. as claimed in claim 11 by electrolysis manufacture indium hydroxide or the method for the compound containing indium hydroxide, it is special Sign is have：Filter the solid constituent concentrate and the process by its filtrate distribution to the electrolyte supply nozzle；With The dried solid matter filtered out forms the process of indium hydroxide powder or compound powder containing indium hydroxide.
14. as claimed in claim 12 by electrolysis manufacture indium hydroxide or the method for the compound containing indium hydroxide, it is special Sign is have：Filter the solid constituent concentrate and the process by its filtrate distribution to the electrolyte supply nozzle；With The dried solid matter filtered out forms the process of indium hydroxide powder or compound powder containing indium hydroxide.
15. the method by being electrolysed manufacture indium hydroxide or compound containing indium hydroxide as claimed in claim 8 or 9, its It is characterised by, makes the feed speed of electrolyte relative to per unit current density be 0.01~100.0Lm2/ Amin incomings Dynamic electrolyte.
16. as claimed in claim 10 by electrolysis manufacture indium hydroxide or the method for the compound containing indium hydroxide, it is special Sign is, makes the feed speed of electrolyte relative to per unit current density be 0.01~100.0Lm2/ Amin flows Electrolyte.
17. as claimed in claim 11 by electrolysis manufacture indium hydroxide or the method for the compound containing indium hydroxide, it is special Sign is, makes the feed speed of electrolyte relative to per unit current density be 0.01~100.0Lm2/ Amin flows Electrolyte.
18. pass through electrolysis manufacture indium hydroxide or the compound containing indium hydroxide as any one of claim 12~14 Method, it is characterised in that make the feed speed of electrolyte relative to per unit current density be 0.01~100.0Lm2/ Amin flows electrolyte.
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JP2011162813A JP5711063B2 (en) 2011-07-26 2011-07-26 Method for producing indium hydroxide
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JP2011171893A JP5632340B2 (en) 2011-08-05 2011-08-05 Electrolytic production apparatus and production method of indium hydroxide and compound containing indium hydroxide
JP2011-171893 2011-08-05
JP2011174662A JP5557810B2 (en) 2011-08-10 2011-08-10 Indium hydroxide and method for producing compound containing indium hydroxide
JP2011-174662 2011-08-10
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Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102129451B1 (en) * 2013-05-27 2020-07-03 스미토모 긴조쿠 고잔 가부시키가이샤 Method for producing indium hydroxide powder, method for producing indium oxide powder, and sputtering target
JP6201915B2 (en) * 2014-06-30 2017-09-27 住友金属鉱山株式会社 Cathode and method for producing metal hydroxide using the same
JP6222072B2 (en) * 2014-12-19 2017-11-01 住友金属鉱山株式会社 Electrolytic apparatus for indium hydroxide powder or tin hydroxide powder, method for producing indium hydroxide powder or tin hydroxide powder, and method for producing sputtering target
JP6222071B2 (en) * 2014-12-19 2017-11-01 住友金属鉱山株式会社 Electrolytic apparatus for indium hydroxide powder, method for producing indium hydroxide powder, and method for producing sputtering target
CN107935026B (en) * 2017-11-24 2021-01-15 郑州大学 Method and device for preparing nano indium oxide by electrolysis
CN109183057B (en) * 2018-11-13 2020-07-07 云南锡业集团（控股）有限责任公司研发中心 Method and device for preparing high-purity indium oxide powder by electrolytic method
CN111809050A (en) * 2020-05-25 2020-10-23 先导薄膜材料有限公司 Method for recycling ITO waste target
CN111979563A (en) * 2020-08-14 2020-11-24 郑州大学 Electrochemical recycling method of indium gallium zinc oxide target material

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06199522A (en) * 1992-12-28 1994-07-19 Japan Energy Corp Production of indium oxide-tin oxide powder
US5417816A (en) * 1992-12-09 1995-05-23 Nikko Kyodo, Ltd. Process for preparation of indium oxide-tin oxide powder
JPH10204669A (en) * 1997-01-16 1998-08-04 Mitsubishi Materials Corp Production of indium oxide powder
CN101104890A (en) * 2007-06-11 2008-01-16 华南师范大学 Method for recycling indium from waste mercury-free alkaline zinc-manganese dioxide battery
CN101528989A (en) * 2006-10-24 2009-09-09 日矿金属株式会社 Method for collection of valuable metal from ITO scrap
CN101528984A (en) * 2006-10-24 2009-09-09 日矿金属株式会社 Method for collection of valuable metal from ITO scrap

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1016366B (en) * 1988-02-24 1992-04-22 个旧市焊料厂 Process for producing high purity sn from raw soldering tin
CN1071714A (en) * 1991-10-14 1993-05-05 昆明工学院 A kind of electrolytic refining process of producing pure zinc by crude zinc
JP2783027B2 (en) * 1991-12-03 1998-08-06 住友金属鉱山株式会社 Quality control method in electrolytic refining of metals
JP2829556B2 (en) * 1992-12-09 1998-11-25 株式会社ジャパンエナジー Method for producing indium oxide powder
JPH10140384A (en) * 1996-09-15 1998-05-26 Yoshiya Okazaki Device for simultaneously generating strongly alkaline water and hypochlorous acid sterilizing water by electrolysis
JP3952766B2 (en) * 2001-12-19 2007-08-01 三井金属鉱業株式会社 High current density electrolysis of copper.
JP2003247089A (en) * 2002-02-25 2003-09-05 Nikko Materials Co Ltd Method of recovering indium
JP2004124115A (en) * 2002-09-30 2004-04-22 Nippon Mining & Metals Co Ltd Method of recovering copper from copper electrolytic solution, and liquid purification method
JP4844023B2 (en) 2005-07-01 2011-12-21 アタカ大機株式会社 Dimensional stabilization method for solid polymer electrolyte membrane
CN101611174B (en) * 2007-02-16 2011-03-02 日矿金属株式会社 Method of recovering valuable metal from scrap containing conductive oxide

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5417816A (en) * 1992-12-09 1995-05-23 Nikko Kyodo, Ltd. Process for preparation of indium oxide-tin oxide powder
JPH06199522A (en) * 1992-12-28 1994-07-19 Japan Energy Corp Production of indium oxide-tin oxide powder
JPH10204669A (en) * 1997-01-16 1998-08-04 Mitsubishi Materials Corp Production of indium oxide powder
CN101528989A (en) * 2006-10-24 2009-09-09 日矿金属株式会社 Method for collection of valuable metal from ITO scrap
CN101528984A (en) * 2006-10-24 2009-09-09 日矿金属株式会社 Method for collection of valuable metal from ITO scrap
CN101104890A (en) * 2007-06-11 2008-01-16 华南师范大学 Method for recycling indium from waste mercury-free alkaline zinc-manganese dioxide battery

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CN103857830B (en) 2016-09-21
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