WO2013015032A1 - 水酸化インジウム又は水酸化インジウムを含む化合物の製造方法 - Google Patents

水酸化インジウム又は水酸化インジウムを含む化合物の製造方法 Download PDF

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WO2013015032A1
WO2013015032A1 PCT/JP2012/065013 JP2012065013W WO2013015032A1 WO 2013015032 A1 WO2013015032 A1 WO 2013015032A1 JP 2012065013 W JP2012065013 W JP 2012065013W WO 2013015032 A1 WO2013015032 A1 WO 2013015032A1
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Prior art keywords
indium hydroxide
electrolysis
indium
plate
anode
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PCT/JP2012/065013
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English (en)
French (fr)
Japanese (ja)
Inventor
新藤　裕一朗
竹本　幸一
充之 古仲
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Jx日鉱日石金属株式会社
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Priority claimed from JP2011162813A external-priority patent/JP5711063B2/ja
Priority claimed from JP2011171893A external-priority patent/JP5632340B2/ja
Priority claimed from JP2011174662A external-priority patent/JP5557810B2/ja
Application filed by Jx日鉱日石金属株式会社 filed Critical Jx日鉱日石金属株式会社
Priority to KR1020137009735A priority Critical patent/KR101410187B1/ko
Priority to CN201280027688.1A priority patent/CN103857830B/zh
Publication of WO2013015032A1 publication Critical patent/WO2013015032A1/ja

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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

Definitions

  • the present invention relates to a method for producing indium hydroxide used as a raw material for indium oxide or a powder of a compound containing indium oxide, which is mainly used for producing an ITO target for sputtering for forming an ITO film, or a compound containing indium hydroxide. About.
  • ITO (complex oxide containing indium-tin as a main component) film is widely used as a transparent electrode (film) of a display device centering on a liquid crystal display.
  • a method of forming this ITO film it is usually performed by means generally called physical vapor deposition such as vacuum vapor deposition or sputtering.
  • the magnetron sputtering method is often used because of operability and film stability.
  • a film is formed by sputtering, in which positive ions such as Ar ions are physically collided with a target placed on the cathode, and the material constituting the target is released by the collision energy, and the substrate on the anode side facing the target is released. This is done by stacking films having the same composition as the target material.
  • the coating method by sputtering has a feature that a thin film in angstrom units to a thick film of several tens of ⁇ m can be formed at a stable film formation speed by adjusting the processing time, supply power, and the like.
  • the ITO sintered compact target is manufactured by grinding and mixing indium oxide and tin oxide, and molding and sintering the obtained mixed powder.
  • dry or wet mixing using a ball mill, a V-type mixer, or a ribbon-type mixer is performed.
  • Indium oxide powder as a raw material for the ITO sintered compact target can be produced by calcining indium hydroxide.
  • a representative known technique for producing this indium hydroxide is disclosed in Patent Document 1.
  • indium hydroxide is produced by electrolysis using indium as an anode, and this is calcined to obtain indium oxide powder.
  • this patent document 1 is an application by the present applicant although the name of the applicant is different due to the rename.
  • a neutralization method is also conceivable as a method for producing indium oxide.
  • the electrolytic method is effective because of the following problems. a) The resulting indium oxide powder has a large variation in various characteristics (average particle size, apparent density, etc.), and this is the “reduction in quality variation” or “higher quality” of indium oxide display materials, phosphors, etc. It is an impediment. b) It is not always easy to control the production conditions (liquid temperature, reaction rate, etc.) constantly, and the equipment cost increases to stabilize it. c) When a powder with different characteristics from the conventional one is required, it is not possible to respond flexibly to this requirement.
  • Neutralization waste liquid for example, ammonium nitrate
  • an indium plate is disposed as an anode (anode) and a stainless steel plate is generally disposed as a cathode (cathode) in an electrolytic bath, and an electrolytic solution is passed between them to perform electrolysis.
  • anode anode
  • cathode cathode
  • electrolytic solution is passed between them to perform electrolysis.
  • the generated indium hydroxide adheres to the surface of the anode, and indium is electrodeposited on the surface of the cathode, extending in a dendrite shape, the anode and the cathode are short-circuited, and electrolysis cannot be performed for a long time. There was a problem.
  • the generated indium hydroxide adheres to the surface of the anode, and indium is electrodeposited on the surface of the cathode, extending in a dendritic shape, and the anode and the cathode are short-circuited. The problem that occurred.
  • Patent Document 2 is a method for producing indium oxide powder, in which indium is used as an anode, and electrolysis is performed by stirring in a state in which an indium hydroxide precipitate is suspended in an electrolytic solution. Specifically, when stirring is not performed, the pH in the vicinity of the liquid level of the electrolytic cell is about 8.5, but the pH near the bottom of the cell is about 3.2. And the electrolyte near the bottom of the tank are mixed to make the pH uniform.
  • Stirring is performed so that the precipitate of indium hydroxide generated by electrolysis is suspended in the electrolyte. If the degree of stirring is weaker than this, the effect of making the pH of the electrolyte uniform will be insufficient.
  • the electrolyte is usually kept in a static flow state, and stirring is not performed so that the slime at the bottom of the tank is rolled up. However, in the electrolysis process of the present invention, it is aggressive to the extent that the precipitate is suspended.
  • the electrolysis is performed by stirring the electrolyte solution.
  • the electrolyte temperature is 40 to 80 ° C. (50 to 70 ° C.), and ammonium nitrate or ammonium chloride is used as the electrolyte.
  • Reagent concentration in electrolyte is 1 to 3 mol / L
  • voltage is 2 to 4 V
  • current density is 200 to 900 A / m 2 (about 700 A / m 2 )
  • distance between electrodes is 25 m / m to 50 m / m
  • cathode material may be carbon
  • an indium plate is used. Calcination is usually performed at 700 to 1100 ° C (about 800 to 950 ° C) in air.
  • Patent Document 3 describes a method for producing an indium oxide-tin oxide powder, and discloses a technique in which indium and tin are electrolyzed simultaneously (PR type pulse energization) using separate anodes. It is disclosed that the electrolytic solution uses NH 4 NO 3 and is electrolyzed at a concentration of 0.2 to 5 mol / L, a pH of 4 to 9.5, a bath temperature of 0 to 50 ° C., and a current density of 100 to 1800 A / m 2 . Has been. The powder thus obtained is roasted at 1100 ° C. to produce ITO powder having an average particle diameter of 20 ⁇ m and an apparent density of 1.7 g / cm 3 . An ITO target having a SnO 2 content of 10 wt% and a sintered body density of 6.70 g / cm 3 or 4.78 g / cm 3 is obtained.
  • Patent Document 4 discloses manufacturing indium hydroxide by an electrolytic method as a method for manufacturing an ITO target. Specifically, indium hydroxide generated by electrolysis using indium as an anode is washed and dispersed in pure water. Ammonium nitrate which is an electrolytic solution is satisfactory in terms of cost and purity maintenance, but it is described that electrolysis cannot be continuously performed because metastannic acid which is a nonconductor is deposited on the electrode surface.
  • the pH of the slurry obtained by mixing the indium hydroxide dispersion solution and the metastannic acid dispersion solution is 5 or more and 9 or less. It is described to do.
  • Patent Document 5 describes a method and an electrolytic cell for homogenizing the concentration of an electrolytic solution in electrolytic smelting, and a liquid supply pocket is disposed at an end of the electrolytic cell, and then fed toward an anode plate and a cathode plate.
  • the liquid supply pocket has upper and lower openings, and liquid is supplied from the upper opening, new electrolyte is supplied from the lower opening, and a hole is formed on the upper side surface of the liquid supply pocket.
  • a method of making the concentration of the electrolytic solution uniform by supplying the liquid toward the anode plate and the cathode plate is disclosed. In this case, the liquid is supplied in the vertical direction toward the anode plate and the cathode plate.
  • Patent Document 6 discloses an electrolytic tank for electrolytic purification or electrowinning, in which a large number of liquid supply holes are provided on the liquid supply side inner wall, and a number of similar drain holes are provided on the drain side inner wall. There is described an electrolytic cell having a structure in which the liquid flow goes straight in between.
  • the present invention is a problem that occurs when producing indium hydroxide or a compound containing indium hydroxide by electrolysis, that is, the current efficiency is very poor, and further, the sintering characteristics deteriorate during sintering and the density does not increase. Had occurred. Thus, it aims at suppressing the fall of productivity and the fall of quality.
  • an indium plate and a cathode (cathode) plate are disposed as an anode (anode) in an electrolytic cell, and an electrolysis is performed between them, an oxide layer formed on the surface of the anode and Causes of this concentration of impurities in the oxide layer, the problem of the anode itself dropping off in the middle, the generation of indium hydroxide with a high impurity content other than indium hydroxide, and the decrease in purity of indium hydroxide
  • a specific measure for solving this problem is proposed, and the purpose is to suppress the decrease in productivity and quality.
  • the present invention relates to a problem that occurs when producing indium hydroxide or a compound containing indium hydroxide by electrolysis, that is, an indium or indium alloy plate as an anode (anode) in an electrolytic cell,
  • electrolysis is performed by flowing an electrolyte solution between the cathode (cathode) plate and the generated indium hydroxide or a compound containing indium hydroxide adheres to the surface of the anode
  • the cathode surface Clarified the cause of the problem that indium or an indium alloy is electrodeposited and dendrites, and the anode and cathode are short-circuited, and at the same time, proposes a specific measure to solve this,
  • the purpose is to suppress a decrease in productivity and a decrease in quality.
  • the present invention provides the following method in order to solve the above problems.
  • a method for producing indium hydroxide or a compound containing indium hydroxide by electrolysis wherein electrolysis is performed with the conductivity of the electrolytic solution being 10 mS / cm or more, and indium hydroxide or a compound containing indium hydroxide is used as the electrolytic solution.
  • Indium hydroxide or hydroxide by electrolysis characterized in that the indium hydroxide or the compound containing indium hydroxide deposited is washed, and the washing liquid is washed until the conductivity becomes 1 mS / cm or less.
  • a method for producing a compound containing indium is produced by electrolysis, wherein electrolysis is performed with the conductivity of the electrolytic solution being 10 mS / cm or more, and indium hydroxide or a compound containing indium hydroxide is used as the electrolytic solution.
  • Indium hydroxide or hydroxide by electrolysis characterized in that the indium hydroxide or the compound containing
  • this invention provides the following method. 3) A cathode plate and an indium metal anode plate as a raw material are alternately arranged in the electrolytic cell at intervals, an electrolytic solution is supplied between the cathode plate and the anode plate, and indium hydroxide powder is electrolyzed. Indium hydroxide particles are precipitated in the electrolytic solution, and the electrolysis is stopped when the weight of the anode plate reaches 20% to 80% of the initial weight of the anode.
  • a method for producing indium hydroxide powder by electrolysis characterized by comprising:
  • this invention provides the following method. 7) An apparatus for producing an indium hydroxide or a compound containing indium hydroxide by an electrolytic method, in which an interval between a cathode plate and an indium or indium alloy anode plate as a raw material in an electrolytic cell The electrolyte solution is supplied alternately toward the other side edge of the cathode plate and the anode plate between the cathode plate and the anode plate and in the vicinity of one side edge between the cathode plate and the anode plate.
  • a nozzle is arranged, and the electrolytic solution flowing out from the nozzle opening is circulated between each cathode plate and anode plate in the electrolytic cell to deposit indium hydroxide or a compound containing indium hydroxide in the electrolytic solution.
  • An apparatus for taking out indium hydroxide precipitated in an electrolytic solution or a compound containing indium hydroxide, an apparatus for concentrating the hydroxide and separating it into a solid concentrate and a solid dilute liquid, the solid dilute liquid The apparatus for electrolytically producing indium hydroxide or a compound containing indium hydroxide according to any one of 7) to 9) above, further comprising a device for distributing the liquid to the electrolyte solution supply nozzle.
  • An apparatus for filtering the solid concentrate and distributing the filtrate to the electrolyte supply nozzle; and an apparatus for producing indium hydroxide powder or a compound powder containing indium hydroxide by drying the filtered solid The apparatus for electrolytically producing an indium hydroxide powder or a compound powder containing indium hydroxide as described in 7) above.
  • a method for producing indium hydroxide or a compound containing indium hydroxide by electrolysis wherein a cathode plate and an indium or indium alloy anode plate as a raw material are placed in an electrolytic cell at a distance.
  • the electrolyte solution is supplied between the cathode plate and the anode plate and in the vicinity of one side edge of each cathode plate and the anode plate toward the other side edge of the cathode plate and the anode plate.
  • a nozzle is arranged, and the liquid flow of the electrolyte flowing out from this nozzle is adjusted to circulate between each cathode plate and anode plate in the electrolytic cell, and indium hydroxide or a compound containing indium hydroxide is added to the electrolyte solution.
  • impurities are concentrated on the surface of the anode, the anode falls into the bath during electrolysis, indium hydroxide or impurities having a high impurity content are mixed in addition to the indium hydroxide generated in the electrolyte, It is possible to prevent variations in the quality of indium oxide.
  • indium hydroxide or a compound containing indium hydroxide when producing indium hydroxide or a compound containing indium hydroxide by electrolysis, indium hydroxide or a compound containing indium hydroxide is not attached to the surface of the anode, and indium is applied to the surface of the cathode.
  • the electrolytic solution can be circulated without electrodepositing the indium alloy to efficiently produce indium hydroxide or a compound containing indium hydroxide, thereby improving the productivity. Have.
  • FIG. 1 It is a figure which shows the flow of the electrolysis process which manufactures indium hydroxide from indium. It is a figure which shows a mode that an impurity concentrates on the surface of an indium anode (anode), when current density is raised in order to raise the production efficiency of electrolysis.
  • An anode (anode) plate and a cathode (cathode) plate are arranged in the electrolytic cell at an interval, and a nozzle supply port for supplying the electrolytic solution is arranged in the upper part of the electrolytic cell to supply the electrolytic solution to the electrolytic cell.
  • An anode (anode) plate and a cathode (cathode) plate are arranged in the electrolytic cell at an interval, and a nozzle supply port for supplying an electrolytic solution is located below the electrolytic cell, and each cathode plate
  • a schematic explanatory drawing of the electrolysis apparatus which arrange
  • An anode (anode) plate and a cathode (cathode) plate are arranged at intervals in the electrolytic cell, and the supply ports of the two-stage nozzle for supplying the electrolytic solution are the lower side and the upper side in the electrolytic cell, And it is a schematic explanatory drawing of the electrolyzer which arrange
  • FIG. 2 is a schematic explanatory diagram of an electrolysis apparatus that is arranged on one side edge between each cathode plate and anode plate and circulates an electrolyte in an electrolytic cell. It is the figure which showed typically the liquid flow at the time of using the apparatus of FIG.
  • FIG. 1 shows a flow of an electrolysis process for producing indium hydroxide (In (OH) 3 ) from indium (In).
  • indium as a raw material is cast to produce an anode plate made of indium, which is placed in an electrolytic cell.
  • An electrolytic solution is supplied to the electrolytic cell.
  • An aqueous ammonium nitrate solution (NH 4 NO 3 ) is used as the electrolytic solution.
  • the electrolytic solution is not particularly specified, and any of nitric acid aqueous solution, sulfuric acid aqueous solution, hydrochloric acid aqueous solution or other electrolytes may be used.
  • ammonium nitrate is used from the viewpoint of cost and product purity maintenance. It can be said that an aqueous solution is preferable.
  • indium hydroxide (In (OH) 3 ) from indium (In) is shown, but the same applies to the case of producing a compound containing indium hydroxide using an anode of an indium alloy.
  • Typical examples of indium alloys include indium tin alloys and indium zinc alloys used for ITO. These include alloys added with other elements, and examples of producing indium hydroxide (In (OH) 3 ) from indium (In), which are representative examples of the present invention, and all cases where the same phenomenon occurs Applicable to.
  • additive element in addition to the above tin (Sn) and zinc (Zn), copper (Cu), silver (Ag), antimony (Sb), tellurium (Te), bismuth (Bi), thallium (Tl), gallium (Ga), germanium (Ge), cadmium (Cd), and the like can be given.
  • copper (Cu) silver (Ag), antimony (Sb), tellurium (Te), bismuth (Bi), thallium (Tl), gallium (Ga), germanium (Ge), cadmium (Cd), and the like
  • Cu copper
  • silver Ag
  • antimony (Sb) tellurium
  • Te bismuth
  • Tl bismuth
  • Tl thallium
  • Ga gallium
  • germanium germanium
  • Cd cadmium
  • present invention includes all of these compounds (including mixtures) contained in indium hydroxide.
  • indium hydroxide precipitated in the electrolytic solution is taken out, concentrated, and separated into a solid concentrate and a solid dilute solution.
  • the solid content concentrate is washed, filtered, and dried to obtain indium hydroxide powder.
  • the dilute solid solution is circulated to the electrolytic solution, and the liquid is adjusted and reused.
  • the filtrate obtained by filtering the solid content concentrate is circulated to the electrolytic solution, and the liquid is adjusted and reused.
  • the problem here is that the current efficiency is very poor during electrolysis. Furthermore, when sintering solid-liquid separated indium hydroxide or a compound thereof, there is a problem that the sintering density does not increase or unevenness in the target of the sintering density occurs. Therefore, as a result of various studies, it was found that if the conductivity in the electrolyte is too low, the current efficiency becomes very poor, and the low sintering density is caused by the electrolyte attached to indium hydroxide. did.
  • the impurity element of the indium anode (anode) plate is concentrated on the surface of the indium anode. This is shown in FIG. A metal element nobler than indium remains on the surface, and only indium is ionized and eluted.
  • the impurities particularly metal elements that are more precious than indium, are ionized and eluted, and are mixed into the indium hydroxide slurry. Furthermore, impurities fall off from the anode surface and are mixed into the indium hydroxide slurry.
  • the electrolysis when producing indium hydroxide or a compound containing indium hydroxide by electrolysis, the electrolysis is conducted at an electric conductivity of 10 mS / cm or more, and a more preferable upper limit is 500 mS / cm. A compound containing indium oxide is deposited in the electrolytic solution. As a result, the current efficiency can be almost 100%.
  • the present invention requires that the deposited indium hydroxide or the compound containing indium hydroxide is washed and washed until the conductivity of the washing liquid becomes 1 mS / cm or less.
  • cleaning is performed until the electrical conductivity of the cleaning liquid is 0.1 mS / cm or less.
  • the hydroxide thus obtained was dried or reduced to obtain a sintered raw material for the oxide, which was further sintered. This makes it possible to improve the relative density of the sintered body to 99% or more.
  • the above point is improved, and electrolysis is stopped when the weight of the anode plate reaches 20% to 80% of the initial weight of the anode. If it is less than 20%, a large amount of impurities are concentrated on the anode surface, and the above-mentioned problems occur. If it exceeds 80%, the use efficiency is poor and the productivity deteriorates.
  • the used anode plate is taken out, and new indium metal is replenished and cast into the used anode plate to recreate the anode plate.
  • the melting / casting method is not particularly limited. There is no problem in casting only a used anode plate without replenishing new indium metal.
  • electrolysis can be started and indium hydroxide particles can be deposited in the electrolyte.
  • This regenerated anode plate can be used through the same process until the weight of the anode plate reaches 20% to 80% of the initial weight of the anode.
  • the electrolytic anode can be regenerated by the same method. This anode remanufacturing operation may be repeated many times.
  • the anodes that can be used range widely from 20% to 80% of the initial weight, mainly due to variations in the purity of the anode.
  • indium raw materials that are distributed may have a large variation in impurity content.
  • the amount of impurities mixed in varies depending on the situation even at the anode manufacturing stage. If the amount of impurities is large, the amount of impurities concentrated on the anode surface naturally increases when electrolysis is performed, and the use efficiency is lowered. On the other hand, when the amount of impurities is small, the amount of impurities concentrated on the anode surface is small, so the usage efficiency is high.
  • the anode surface is not evenly consumed, but there is also a phenomenon that the portion where current flows easily (where there are few impurities) is consumed faster than the portion where there are many impurities, and falls off from the middle of the anode ingot. From the above, it can be said that the anode having a low impurity content has a high use efficiency, and the anode having a high impurity content has a low use efficiency.
  • the anode having a low impurity content has a high use efficiency
  • the anode having a high impurity content has a low use efficiency.
  • not all is indium hydroxide, but some In is electrodeposited on the cathode, which may grow and short-circuit. In that case, the electrolysis must be interrupted. This short can be read by voltage change.
  • the problem here is that when electrolysis is performed, the indium hydroxide produced adheres to the surface of the anode plate made of indium in the electrolytic cell, and indium is electrodeposited on the surface of the cathode plate, There was a problem that electrolysis could not be continued. This indium also extended into a dendrite shape, causing a problem that the anode and the cathode were short-circuited. Such a problem is markedly caused by adhesion of indium hydroxide and electrodeposition of indium when the electrolytic current density is increased in order to increase production efficiency.
  • Electrodeposition of indium on the cathode plate and adhesion of indium hydroxide to the anode plate are not so strong, but when the amount of the adhesion increases, it tends to become difficult to peel off gradually. For this reason, in the initial stage of electrolysis, a method in which an electrolytic solution is circulated between the anode plate and the cathode plate, and the electrolytic solution circulates to prevent electrodeposition of indium on the cathode and adhesion of indium hydroxide to the anode. (Test) was performed.
  • FIG. 3 A conventional electrolysis apparatus will be described with reference to FIG.
  • the left side shown in FIG. 3 is a top view of the electrolytic cell
  • the right side is a side view at an intermediate position between the anode plate and the cathode plate.
  • an anode (anode) plate and a cathode (cathode) plate are placed in the electrolytic cell at a distance of 10 to 500 mm, and the nozzle supply port for supplying the electrolytic solution is connected to the top of the electrolytic cell. To place. Then, the electrolytic solution is supplied into the electrolytic cell in the direction indicated by the arrow in the right side of FIG.
  • the strength of the flow of the supplied electrolyte was 0.5 L ⁇ m 2 / A ⁇ min.
  • the strength of the electrolyte flow represents the flow rate (L / min) with respect to the current density (A / dm 2 or A / m 2 ) of either the anode or the cathode.
  • the strength of the electrolyte flow is expressed, it is used in the same meaning.
  • FIG. 4 shows a schematic explanatory diagram of this indium hydroxide electrolytic production apparatus.
  • 4 is a schematic explanatory view (top view) viewed from above, and the right side is a schematic explanatory view of a side surface at an intermediate position between the anode plate and the cathode plate. Except for the arrangement of the nozzles, the structure is the same as that shown in FIG. Then, the electrolytic solution was circulated in the direction indicated by the arrow in the diagram on the right side of FIG. The strength of the electrolyte flow (electrolyte supply rate) was 0.01 to 100.0 L ⁇ m 2 / A ⁇ min. As shown in FIG. 4, the liquid flow swirled from the bottom between each anode and cathode to the center.
  • the strength of the electrolyte flow is preferably 0.1 to 10.0 L ⁇ m 2 / A ⁇ min.
  • the circulation method of the present invention is extremely effective, and it is possible to effectively suppress the adhesion of indium hydroxide to the anode plate and the occurrence of indium electrodeposition on the cathode plate by improving the simple apparatus. This adhesion and electrodeposition was not observed on all surfaces of the cathode plate and the anode plate.
  • a cathode plate and an indium anode plate as a raw material are alternately arranged in an electrolytic cell with an interval of 10 to 500 mm, between the cathode plate and the anode plate, and between each cathode plate and anode plate.
  • a nozzle that supplies an electrolyte toward the other side edge of the cathode plate and the anode plate is disposed in the vicinity of one side edge, and the electrolyte that has flowed out from the opening of the nozzle is placed in each electrolytic cell. It has been found that it is effective to cause the indium hydroxide to precipitate in the electrolyte by circulating between the cathode plate and the anode plate.
  • the diameter (bore diameter) of the nozzle for supplying the electrolyte is appropriately adjusted according to the size of the electrolytic cell, the distance between each cathode plate and the anode plate, the amount of electrolyte supplied, the arrangement and number of nozzles, etc. To do. Therefore, the diameter (caliber) of the nozzle is not particularly limited.
  • the space between the cathode plate and the anode plate can be wide, but in such a case, the liquid flow can be increased. That is, as the nozzle that supplies the electrolyte toward the other side edge between the cathode plate and the anode plate, one or a plurality of nozzles that supply the electrolyte are arranged, and the electrolyte that has flowed out from the opening of the nozzle is disposed. Indium hydroxide can be deposited in the electrolyte by circulating between each cathode plate and anode plate in the electrolytic cell.
  • the liquid flow of the electrolyte flowing out from the opening of the lower nozzle, upper nozzle, or intermediate nozzle is adjusted, and each liquid flow is between the cathode plate and the anode plate, and one side edge of each cathode plate and anode plate. It is effective to circulate (turn) so as to draw an arc from one side edge to the other side edge.
  • the recirculation of the electrolyte flows uniformly between each cathode plate and the anode plate, and a part of the flow needs to contact the surface of the cathode plate and the anode plate.
  • the direction of the circulation is not particularly limited as long as the entire surface of the cathode plate and the anode plate can be circulated between the cathode plate and the anode plate.
  • the cathode plate it is effective to use a stainless steel plate or a titanium plate as the cathode plate, but other materials may be used as long as the electrolyte solution is not contaminated.
  • the solid content concentrate is filtered, the apparatus for distributing the filtrate to the electrolyte supply nozzle, the apparatus for washing the filtered solid matter with water, and further drying this to produce indium oxide powder.
  • It can also be set as the electrolytic manufacturing apparatus which has a powder manufacturing apparatus.
  • a solid-liquid separation device, a filtration device, a filtrate distribution device, a water washing device, a powder production device, and the like can be installed in association with the electrolysis device of the present invention in order to reduce the cost of the production device.
  • Example 1 An indium plate was used for the anode, a stainless plate was used for the cathode, and an aqueous ammonium nitrate solution was used as the electrolytic solution to deposit hydroxide by electrolysis.
  • the conductivity of the electrolytic solution in this case being 10 mS / cm 2
  • the current efficiency was 95%.
  • the hydroxide was filtered, washed with pure water, and washed until the electric conductivity of the washing liquid became 0.1 mS / cm 2. Thereafter, it was dried to form indium oxide, and further sintered at 1500 ° C. to obtain an indium sintered body having a relative density of 98%.
  • Example 2 Electrolysis was performed by changing the conductivity of the electrolytic solution of Example 1 to 100 mS / cm. In this case, the current efficiency was 99%. Thereafter, the pulp was washed with pure water and washed until the conductivity of the washing liquid became 0.01 mS / cm. As a result of sintering under the same conditions as in Example 1, a high-density sintered body having a relative density of 99.5% was obtained.
  • Example 1 an example in which indium was used for the anode and indium hydroxide was deposited by electrolysis was shown.
  • a compound containing indium hydroxide using an indium alloy such as indium-tin (for example, indium hydroxide and Similar results were obtained when a mixture of tin hydroxides) was precipitated.
  • the relative density is improved by cleaning indium hydroxide or a compound containing indium hydroxide, and the condition that can be controlled and controlled is the conductivity of the cleaning liquid. It could be confirmed.
  • Electrolysis was carried out by changing the conductivity of the electrolytic solution of Example 1 to 8.0 mS / cm. As a result, since oxygen gas was generated from the anode plate and hydrogen gas was generated from the cathode plate, the current efficiency was poor at about 80%. Since the level of indium hydroxide used as a sintering raw material could not be produced, the subsequent steps were stopped.
  • Example 2 Electrolysis was performed by changing the conductivity of the electrolytic solution of Example 1 to 50 mS / cm. The current efficiency was as good as 99%. Thereafter, the hydroxide was repulped with pure water and washed until the conductivity of the washing liquid reached 2 mS / cm. As a result of sintering under the same conditions as in Example 1, the sintered density was poor at 95%, and some sintered bodies were cracked. This was considered to be a result of insufficient cleaning of the deposited indium hydroxide.
  • Example 3 Electrolysis was performed by changing the conductivity of the electrolytic solution of Example 1 to 1 mS / cm. As a result, the current efficiency was very poor at 50%. However, the precipitated hydroxide was repulped with pure water and washed until the electrical conductivity of the cleaning liquid reached 0.01 mS / cm. And as a result of sintering on the same conditions as Example 1, the sintered density was able to be achieved to 99%. Although the current efficiency during electrolysis is poor, it is not a condition that can be used in actual operation, but it has been confirmed that cleaning of indium hydroxide improves the sintered density.
  • Example 3 In an electrolysis process for producing indium hydroxide (In (OH) 3 ) from metal indium (In), a metal indium as a raw material is cast to produce an anode plate made of metal indium, and this is placed in an electrolytic cell. In the electrolytic cell, cathode plates made of stainless steel plates or titanium plates were alternately arranged. A plurality of these anode plates and cathode plates were arranged in parallel. An electrolytic solution is supplied to the electrolytic cell. Electrolysis was started using an aqueous ammonium nitrate solution (NH 4 NO 3 ) as the electrolytic solution.
  • NH 4 NO 3 aqueous ammonium nitrate solution
  • indium hydroxide particles were precipitated in the electrolytic solution, and the electrolysis was stopped when it reached 80% of the initial weight of the anode plate. Then, the used anode plate was taken out, and this used anode plate was dissolved. In this melting, a new indium metal was replenished and cast to recreate the anode plate.
  • electrolysis can be started again to deposit indium hydroxide particles in the electrolyte solution.
  • This re-fabricated anode plate can be used through a similar process until it reaches a stage where it becomes 20% to 80% of the initial weight of the anode. After use, the electrolytic anode can be regenerated by the same method.
  • the indium hydroxide slurry precipitated in the electrolyte solution was taken out as appropriate, and the slurry was concentrated and separated into a solid content concentrate and a solid content dilute solution.
  • the solid dilute solution was distributed to the electrolyte supply nozzle.
  • the solid content concentrate was filtered, and the filtrate was distributed to the electrolyte solution supply nozzle.
  • the filtered solid material was dried to obtain indium hydroxide powder.
  • Example 4 In the same manner as in Example 1, indium hydroxide particles were precipitated in the electrolytic solution, and the electrolysis was stopped when it reached 20% of the initial weight of the anode plate. Reproduction was performed in the same manner as in Example 1, and electrolysis was started. The rebuilt anode plate was used until it was 50% of the initial weight of the anode. After use, the electrolytic anode was regenerated by the same method.
  • the indium hydroxide slurry precipitated in the electrolyte solution was taken out as appropriate, and the slurry was concentrated and separated into a solid content concentrate and a solid content dilute solution.
  • the solid dilute solution was distributed to the electrolyte supply nozzle.
  • the solid content concentrate was filtered, and the filtrate was distributed to the electrolyte solution supply nozzle.
  • the filtered solid material was dried to obtain indium hydroxide powder.
  • Example 5 In the same manner as in Example 1, indium hydroxide particles were precipitated in the electrolytic solution, and the electrolysis was stopped when it reached 60% of the initial weight of the anode plate. Then, the used anode plate was taken out and dissolved, and new indium metal was added at the time of dissolution.
  • Electrolysis was started using the remade anode plate.
  • the rebuilt anode plate was used until it was 30% of the initial weight of the anode.
  • the electrolytic anode was regenerated by the same method.
  • the indium hydroxide slurry deposited in the electrolyte was appropriately taken out, and the slurry was concentrated and separated into a solid concentrate and a solid dilute solution.
  • the solid dilute solution was distributed to the electrolyte supply nozzle.
  • the solid content concentrate was filtered, and the filtrate was distributed to the electrolyte solution supply nozzle.
  • the filtered solid material was dried to obtain indium hydroxide powder.
  • the anode plate made of indium metal had a high voltage due to concentration of impurities, and the impurities eluted. As a result, there was a problem that impurities were mixed in indium hydroxide and the purity in the electrolytic solution was deteriorated.
  • Example 6 Indium hydroxide was deposited by electrolysis using an apparatus as shown in FIG. Specifically, in an electrolytic cell, 10 pairs of 1000 mm ⁇ 700 mm ⁇ 5 mmt stainless steel cathode plates and 10 anode plates made of 1000 mm ⁇ 700 mm ⁇ 50 mmt of indium, which are raw materials, are arranged alternately.
  • the electrolyte solution is 50 mm between the cathode plate and the anode plate, and is located near the lower end of the one side edge between each cathode plate and the anode plate (position 1000 mm from the liquid level) toward the other side edge of the cathode plate and the anode plate.
  • the nozzle which supplies was arranged.
  • the electrolytic solution is circulated in the direction shown by the arrow in the right side of FIG. 4, and the electrolytic solution that has flowed out from the opening of the nozzle is circulated between each cathode plate and the anode plate in the electrolytic cell, and hydroxylated.
  • Indium was deposited in the electrolyte.
  • the strength of the electrolyte flow was 0.1 L ⁇ m 2 / A (ampere) ⁇ min. As shown in FIG. 4, the liquid flow swirled upward from the bottom.
  • Example 7 In the same manner as in Example 1, the strength of the electrolyte flow (electrolyte supply rate) was set to 10 L ⁇ m 2 / A ⁇ min. In this case, as in Example 1, indium electrodeposition on the cathode plate and indium hydroxide adhesion on the anode plate could be suppressed. Occurrence was not observed on all sides of the cathode and anode plates.
  • Example 8 In the same manner as in Example 1, the strength of the electrolyte flow (electrolyte supply rate) was set to 0.01 L ⁇ m 2 / A ⁇ min. In this case, indium electrodeposition on the cathode plate and indium hydroxide adhesion on the anode plate partially occurred, but they could not be used.
  • Example 9 In the same manner as in Example 1, the strength of the electrolyte flow (electrolyte supply rate) was set to 50 L ⁇ m 2 / A ⁇ min. In this case, the indium hydroxide coarse particles slightly peeled off from the anode, but were usable.
  • Example 10 In the same manner as in Example 1, the strength of the electrolyte flow (electrolyte supply rate) was set to 100 L ⁇ m 2 / A ⁇ min. In this case, a part of the coarse particles of indium hydroxide peeled off from the anode, and fine hydroxides (average particle size after baking at 1100 ° C. of 0.5 ⁇ m or less) were slightly generated. However, this was not a big problem and could be used.
  • Example 11 Indium hydroxide was deposited by electrolysis using an apparatus as shown in FIG. Specifically, using the same anode and cathode as in Example 1, the position between the cathode plate and the anode plate, and the vicinity of the lower end of one side edge between each cathode plate and the anode plate (position of 1000 mm from the liquid level) ) And a lower nozzle and an upper nozzle for supplying an electrolytic solution toward the other side edge of the cathode plate and the anode plate were arranged at a position of 155 mm from the liquid surface.
  • Example 1 According to the direction of the circulation as shown in FIG. 6, there is no blank portion of the electrolyte flow at a specific location on the cathode plate and the anode plate, and the circulation (swirl flow) is generated uniformly throughout. I understood.
  • the main difference from Example 1 is that an upper nozzle is provided at a position of 155 mm from the liquid level.
  • indium electrodeposition on the cathode plate and indium hydroxide adhesion on the anode plate could be suppressed. Occurrence was not observed on all sides of the cathode and anode plates.
  • Example 2 Similar to Example 2, nozzles arranged in two stages were used, and the upper nozzle was arranged at a position 322 mm from the liquid surface. When the same experiment was conducted, the same result as in Example 2 was obtained.
  • Example 12 Indium hydroxide was deposited by electrolysis using an apparatus as shown in FIG. Specifically, using the same anode and cathode as in Example 1, between the cathode plate and the anode plate, and near the lower end of one side edge of each cathode plate and anode plate (position of 1000 mm from the liquid level) ), A lower nozzle, an intermediate nozzle, and an upper nozzle that supply electrolyte toward the other side edge of the cathode plate and the anode plate are disposed at a position 322 mm from the liquid level and a position near the upper end (position 155 mm from the liquid level). did.
  • electrolytes are circulated in the direction indicated by the arrow on the right side of FIG. 9, and the electrolytes discharged from the openings of the lower nozzle, the intermediate nozzle, and the upper nozzle are connected to each cathode plate in the electrolytic cell.
  • Indium hydroxide was deposited in the electrolyte by circulating between the anode plates.
  • the strength of the electrolyte flow (electrolyte supply rate) was 10 L ⁇ m 2 / A ⁇ min.
  • Example 7 (Comparative Example 7) Using an apparatus as shown in FIG. 3, an electrolytic solution was introduced from one side of the electrolytic cell, and indium hydroxide was deposited by electrolysis. Specifically, the same anode and cathode as in Example 1 were used. The electrolytic solution supply rate of this electrolytic solution was 0.5 L ⁇ m 2 / A ⁇ min. As a result, a large amount of indium hydroxide adhered to the anode plate, and indium was electrodeposited onto the cathode plate, making electrolysis difficult.
  • Electrolysis was performed using an apparatus as shown in FIG. 3 at an electrolyte supply rate of 10 L ⁇ m 2 / A ⁇ min.
  • electrolyte supply rate 10 L ⁇ m 2 / A ⁇ min.
  • indium hydroxide adhered to the anode plate and indium electrodeposition occurred on the cathode plate.
  • This adhesion and electrodeposition mainly occurred at the central part and the lower part of the cathode plate and the anode plate. Even if the strength of the electrolyte flow (electrolyte supply rate) was made larger than the above, the same result was obtained.
  • a method for producing indium hydroxide or a compound containing indium hydroxide by an electrolysis method wherein electrolysis is performed with the conductivity of the electrolytic solution being 10 mS / cm or more, and indium hydroxide or a compound containing indium hydroxide is electrolyzed.
  • electrolysis is performed with the conductivity of the electrolytic solution being 10 mS / cm or more, and indium hydroxide or a compound containing indium hydroxide is electrolyzed.
  • the cathode plate and the indium metal anode plate as a raw material are alternately arranged in the electrolytic cell at intervals, and an electrolytic solution is supplied between the cathode plate and the anode plate.
  • Indium hydroxide particles are deposited in the electrolytic solution, and the electrolysis is stopped when the initial weight of the anode plate immersed in the electrolytic solution reaches 20% to 80%.
  • the used anode plate is taken out, the used anode plate is melted and indium metal is replenished and cast to recreate the anode plate.
  • electrolysis is started and water is added to the electrolyte.
  • the production method of indium hydroxide powder by electrolysis is prevented from adhering, and indium metal is prevented from being formed on the surface of the cathode. It was able to suppress the decrease of productivity through.
  • This method is useful for manufacturing an ITO target for sputtering to form an ITO film.
  • the cathode plate and the indium or indium alloy anode plate as the raw material are alternately arranged in the electrolytic cell at intervals.
  • a method for producing indium hydroxide by electrolysis or a compound containing indium hydroxide, characterized by being deposited in a liquid When producing indium hydroxide or a compound containing indium hydroxide by an electrolytic method, indium hydroxide or a compound containing indium hydroxide is prevented from adhering to the surface of the anode, and indium is applied to the surface of the cathode. Alternatively, it has an excellent effect of preventing the formation of an indium alloy and thereby suppressing a decrease in productivity, and thus is useful for producing an ITO target for sputtering for forming an ITO film.

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JP2016014163A (ja) * 2014-06-30 2016-01-28 住友金属鉱山株式会社 カソード及びこれを用いた金属水酸化物の製造方法
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JP2016117928A (ja) * 2014-12-19 2016-06-30 住友金属鉱山株式会社 水酸化インジウム粉又は水酸化スズ粉の電解装置、水酸化インジウム粉又は水酸化スズ粉の製造方法、及びスパッタリングターゲットの製造方法

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JP2016117928A (ja) * 2014-12-19 2016-06-30 住友金属鉱山株式会社 水酸化インジウム粉又は水酸化スズ粉の電解装置、水酸化インジウム粉又は水酸化スズ粉の製造方法、及びスパッタリングターゲットの製造方法

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