TW200538394A - Method for making a metal containing indium - Google Patents

Abstract

This invention provides a method for making a metal containing indium. An indium-containing substance can be efficiently obtained in high yield by recovering the indium scattered during the process of making an ITO thin film, dissolving the obtained indium-containing substance in an acid and then using the resulting indium-containing solution as a starting material. A metal containing indium is obtained by mixing the indium-containing solution with oxalic acid which is used as a precipitant to form indium oxalate precipitates, recovering the precipitates by a method of solid-liquid separation, dissolving the recovered precipitate in an acid to form an acidic solution, placing an aluminum plate in the acidic solution to form spongy indium through substitution reaction with aluminum and performing alkaline casting of the spongy indium.

Description

200538394 IX. Description of the invention: [Technical field to which the invention belongs] The present invention relates to a method for manufacturing a metal containing indium, which is made of ITO (indium tin oxide ·· indium tin oxide: (Recycling), waste ITO targets, scraps containing ITO, etc., are given: Dissolved indium-containing solution, to produce high-purity indium. [Previous technology] 'Indium is a metal that is used in various fields such as optical materials, optoelectronic materials, compound semiconducting conductors, and filter materials. Recently, it has been widely used as liquid crystal displays (LCD: liquid crystal display) and plasma displays ( For electrode materials such as PDP (plasma display panel), but steel has a high unit price, it is required to recover and reuse indium from indium-containing recycled materials or waste. ITO film made of indium-tin oxide (ITO) is used in solar cells, liquid crystal display devices, touch panels, and anti-condensation heating films for glass windows because of its high conductivity and visible light transmission. Various transparent conductive film applications. Examples of the method for manufacturing the ITO film include sputtering, vacuum evaporation, sol-gel method, cluster beam evaporation, and PLD. Among them, the sputtering method is widely used in industry because it can produce a low-resistance film on a large-area substrate at a relatively low temperature. When the ITO thin film is produced by a sputtering method, a ITO sintered body obtained by sintering a mixture of indium oxide and tin oxide is generally used as a target material, and plasma is irradiated to perform sputtering. In order to form an ITO thin film, the substrate is vapor-deposited on the substrate for 5 316907 200538394. At this time, ^, 叶, because the ITO that was sputtered was not evaporated on the substrate, ITO Fei Yutian took the political party; the surrounding situation, it is required to use the acid such as hydrochloric acid scattered ITO Yiling% to form an acid solution containing indium tin

The indium and tin-containing acid rolls were used to recover indium and tin in the A solution, and reused as IT0 materials. : Recipe 4 for recovering indigo from copper-containing materials has been known in the past in combination: wet-purification methods such as S 夂 cryolysis, parent ion exchange, and solvent extraction. In addition, several new methods have been proposed. # Example Shikou is disclosed in the following Patent Document 1: In electrolytic sludge (sHme) containing impurities such as Sn Pb, Cu, and Ag in addition to In, was eluted with hydrochloric acid, and adjusted to ρΗ〇 · with an alkaline agent. After 5 to 20, the residues are separated, followed by the addition of a reducing agent, and the resulting precipitate is separated, and then the original agent is added to recover crude indium for electrolysis. It is disclosed in the following Patent Document 2 that hydrogen peroxide water (commonly known as hydrogen peroxide, Η2202) and sulfuric acid are added to an Ιη containing substance that contains impurities such as heart and Mn in addition to Ιη, and metal Dissolve the salt, then add an alkali agent and adjust it to ρΗ4.5 to 6.0, and then perform a filtration treatment to obtain a gaseous substance coexisting with As and Ιη and move Mn and Zn to the neutralized solution, and then re-use the above Indium recovery method for removing As from Shen Dianwu. It is disclosed in the following Patent Document 3 that the indium-containing mass is subjected to a pulverization treatment, and the pulverized material is subjected to a dissolution treatment in an acidic aqueous solution in the presence of hydrogen peroxide, and then an aluminum plate is immersed in the dissolution solution. The sponge indium is precipitated on the plate by a substitution reaction, and then the sponge indium is subjected to alkali melting casting to obtain an indium recovery method of indium metal. 316907 6 200538394 is disclosed in the following Patent Document 4 *: The solution containing a scoop of hydrochloric acid is extracted with a solvent extraction type ⑽lngextract (ontype) extractant, and the second time it is recovered by dilute acid for back extraction The copper solution is electrolyzed or neutralized and the rhenium hydroxide is reused carbon or hydrogen for reduction or sulfuric acid: a method of dissolving and electrolyzing and recovering indium. ☆ The indium time method disclosed in the following Patent Document 5 includes the steps of: dissolving ITO containing osmium; and dissolving the waste material with hydrochloric acid to form a salted indium solution; adding nitrogen to the chlorinated solution A step of oxidizing the aqueous solution to form tin hydroxide contained in the #waste material and removing the tin hydroxide; and a step of removing the tin hydroxide, and then replacing zinc with zinc from the solution and recovering the tin hydroxide. Patent Literature 1: Japanese Patent Laid-Open No. 5_156381 Patent Literature 2: Japanese Patent Laid-Open No. 5_3 丨 丨 267 Patent Literature 3: Japanese Patent Laid-Open No. 9_268334 Patent Literature 4… Japanese Patent Laid-Open No. 2002-201026 Document 5 · • Japanese Unexamined Patent Publication No. 2002-69544 [Summary of the Invention] (The Green Problem to be Solved by the Invention) The object of the present invention is to provide a manufacturing method of a metal containing steel = indium scattered when the ITO film is manufactured. In the case of recovering and dissolving the obtained erbium-containing indium with an acid, etc., and using the indium-containing solution as the starting term, the indium can be obtained with good efficiency and indium yield. Method for manufacturing novel contained metals. (Means to solve the problem) In order to solve this problem, the inventors have chosen to mix 316907 7 200538394 with the marriage solution. According to this method, a precipitating agent can be used, and the method of precipitating and recovering indium can be performed with fewer operations. Obtain a metal containing indium. In terms of this simple method, when making this indium sink, it is necessary to prevent impurities from being collected (differently) in M as much as possible. The present inventors have targeted the case of indium sinking from an indium-containing solution. It can be discussed as “= the impure substance that does not cause 4 sinking agents, and the result = citric acid has a particularly superior indium separation ability, so the present invention is completed. In other words, the manufacturing method of the indium-containing metal of the present invention Is a method for manufacturing indium containing metal from 3 indium-containing indium-containing solution, which comprises: indium-containing solution, by mixing precipitating agent oxalic acid (.xalic ac) to generate indium oxalate (1ndium Gxalate) Shen Dian And the step of recovering the above indium oxalate precipitate by solid-liquid separation. Immediately after the indium oxalate precipitate recovered and obtained as described above, baking or mixing with & After contacting the oxidation test, the indium-containing metal can be formed by baking. After filling, the indium oxalate precipitate recovered as described above can be dissolved in the square and osmium to form an acid-dissolved solution. Acid soluble Metal is put into the liquid, and sponge indium is generated by the substitution reaction with the metal. From this sea, indium can be formed into a metal containing indium. In addition, at this time, passivation can be performed to form the original ion β washing process more than once. The cleaning process includes immersing the recovered grass & L indium precipitate in a liquid that does not dissolve indium, and dissolving ions forming the cause of metal surface passivation in the subsequent replacement precipitation step in the liquid. Remove the dissolving solution, and then dissolve the cleaning-treated substance obtained by the ion cleaning treatment of the passivation formation cause in the acid to form an acid-dissolving 8 316907 200538394 solution, and then put the metal in the dissolving solution and borrow i Generation of indium sponge, and from the orientation of the sea ^ ,. Shu from this sponge indium to form indium-containing indium. &Amp; According to such indium-containing metal manufacturers and other indium-containing waste to form an indium-containing solution, or The target temples can not only efficiently produce indium-containing metals, but also suppress intensive binji 'to produce high-purity indium-containing indium-containing metals.: The popularity of LCDs and PDPs has increased their use. The amount of use, and materialization of the attention of the material. Therefore, the present invention through the use of indium >: the use of 'can be achieved to reduce the cost of materials, and these low-priced I. In addition, the so-called in the present invention "Metal containing indium" refers to a metal lump material (80% by mass or more, preferably 90% by mass or more), and contains indium oxide. [Embodiment] The following is based on the embodiment. Although the description of the present invention is made, the present invention is not limited to the following embodiments. (First embodiment) The method for manufacturing an indium-containing metal according to the first embodiment is to produce the indium-containing metal through the following steps. Via:-a step of generating an indium oxalate precipitate by adding precipitating oxalic acid in an indium-containing solution (: indium oxalate precipitation step); and recovering the indium oxalate precipitate by performing solid-liquid separation Step (: Precipitation recovery step); 9 316907 200538394 According to needs, the step of contacting the recovered precipitate with ammonia, the alkali step (: alkali contact step); and after 'f, the recovered precipitate is executed The step of training (: Engineering baking) is performed like step of producing the metal-containing indium. Hereinafter, this embodiment will be described in detail. : (Raw material: indium-containing solution) The raw material used in this embodiment is an indium-containing solution containing indium. The female solution is a solution formed by dissolving 1 butyl, indium alloy waste, or LCD or DP waste with acid, and it also includes cleaning with: 2r The solution, etc., is only required to be a solution containing indium = there is no particular limitation on such an indium-containing solution. For the acid in which this indium-containing waste material is dissolved, consider, for example, nitric acid: fluoride, sulfuric acid, etc., and use the nitric acid solution formed by these acids, fluoric acid-based indium solution, and hydrochloric acid-based indium. The solution is targeted. Impurities may also be contained in rhenium indium-containing solutions. At this time, the impurity content phase, indium, and indium in the liquid may be a solution containing impure matter of 0.1% by weight or more: it may also be suitable for containing 1% by weight or more, 5% by weight or more, 10 li%, Even 20% by weight or more of an aqueous solution containing a large amount of impurities. As mentioned above, the indium-containing solution belongs to the waste and cleaning fluids: liquid, so it can be judged that the elements of impurities, magnesium, steel, iron, iron, aluminum, and aluminum will exist alone or contain multiple elements, but they can also be all Contained materials: Ranqing materials are mostly predicted to be tin-containing wastes (oxalate steel: material containing mash can also be treated. 316907 10 200538394 By adding oxalic acid to 3 indium ridge solution and mixing it ' From the indium-containing solution containing impurities, the copper can be selectively formed into indium oxalate and allowed to sink. The form of mixed oxalic acid can be in any form such as solid (including powder), aqueous solution,: body: f, and so on. When mixed The state of solid oxalic acid can be mixed, but anhydrate can be mixed, but in terms of cost, it is best to mix dihydrate. {It is A to make indium oxalate uniformly sink the temple and suppress the inclusion of impurities, it is best to win 1 friend aqueous solution When the oxalic acid is added in an aqueous solution, the oxalic acid concentration in the aqueous solution forms a low severity of more than 10% lower than the saturated concentration, so that even when the liquid temperature of the oxalic acid aqueous solution is generated, solid oxalic acid is produced. In addition, if the concentration of oxalic acid is excessively reduced, the amount of oxalic acid aqueous solution is increased due to the recovery of copper, and the amount of drainage is increased. The penalty for the above-mentioned 'early acid aqueous solution is preferably above 0 "m0L / L, especially It is better to be at least 0.2moL / L. Furthermore, the mixed oxalic acid can be ammonium oxalate or hydrogen oxalate. 'This compound is applicable because it contains oxalic acid, but according to the inventor's w, when using this In the case of compounds, the amount of indium remaining in the indium-containing solution after mixing with the steel-containing solution will be greater than that when oxalic acid is used, resulting in a lower recovery rate. Therefore, it is best to use grass si The mixed amount of oxalic acid (in other words, added oxalic acid :) 'is set to 1.2 to 5 times the equivalent of the amount of indium contained in the indium-containing solution (also known as "theory"). If less than 12 Times, the residual amount in the indium solution will increase and decrease the recovery rate; on the contrary, more than 5 times will not help to improve the recovery rate even if mixed. Therefore, the better mixing amount is contained in the indium-containing solution 316907 200538394 Steel equivalent In addition, the equivalent of oxalic acid to indium means that the average 1 moL of oxalic acid is 1.5 moL of oxalic acid. Therefore, the so-called "I · 2 to 5 times the equivalent of indium" refers to the average indium imoL, and The oxalic acid is i 8 to 75. In this embodiment, from the viewpoint of the purity of the recovered indium, the pH management of the indium-containing solution before and after oxalic acid mixing is best performed. Before the oxalic acid is mixed: the indium-containing solution The pH is preferably set below 2. The reason is that in the indium-containing solution whose pH exceeds 2, some of the indium will form hydroxide with the impurities and exist, resulting in an increase in impurities in the indium oxalate obtained by mixing with oxalic acid # In addition, by setting the solution containing oxalic acid before mixing oxalic acid to 2 or less, the pH after mixing with oxalic acid can be set to a preferable range described later. The lower the pH of this indium-containing solution, the better, and it is preferably below 10, especially below 0.5. · I Therefore, if the pH of the indium-containing solution is outside the above range, it is best to adjust the pH of the solution. This pH adjustment is preferably a method of lowering the pH by adding shirasmic acid, hydrochloric acid, hydrogen acid, sulfuric acid, etc. to the indium-containing solution. But "yes, from the lowering of pH ', it is better not to add excess acid. When the added excess acid concentration is converted into a large amount of acid whose monobasic acid is more than 3mOL / L (Nitrate, hydrochloric acid, hydrofluoric acid, etc. are added as more than 3mOL / L in terms of monobasic acid :: binary such as sulfuric acid When acid is added above UmoL / L), the recovery rate of tritium will decrease. Therefore, when pH adjustment is performed, it is best not to add more acid than the above amount. When it exceeds this value, it is best to add sodium hydroxide or potassium hydroxide to adjust the acid concentration to below this value. On the other hand, the pH of the indium-containing solution after mixing with oxalic acid is preferably set to 1.0 or less from the viewpoint of impurities of 316907 12 200538394 "bovine low sinking; temple objects φ & $ η < < a-U · 5 or less is preferred. The pH range of the solution after the oxalic acid is mixed is in this range, and it can be easily achieved by using the pH range before mixing to avoid the above range. • For the mixing method of indium-containing solution and precipitation agent (oxalic acid), in addition to the method of stirring the solution and adding a precipitating agent to it, there is also a method of using ridge solution or a polymeric sinking agent. The method of stirring and adding an indium-containing solution can be any method such as the method of simultaneously introducing the indium-containing solution and the Shen Dian agent into the heart (or Guwei). Mixing time of the indium-containing solution and oxalic acid It is best to set it to 5 minutes to 24 ^ ^ > especially 10 minutes to 12 hours. If less than 5 minutes, the amount of impurities mixed with grass indium will increase; otherwise, if it exceeds% hours, Even if this is the case, there is no difference in the reduction effect of impurities, but it only reduces the efficiency. — Moreover, the temperature of the liquid when the indium-containing solution is mixed with oxalic acid is preferably in the range of 0 to 9 (rc =, but in terms of energy costs, it is best to perform temperature adjustment without performing temperature adjustment =-Brewing in the pot仃 Mixed. In addition, if the liquid temperature during mixing is high to a certain range f, the situation of impurities is reduced, and it also affects the particle size of indium oxalate and indium oxide after baking, but the liquid temperature is not very important. Reason However, even if there is almost no difference in impure substances accompanying the impregnation and the particle size is almost the same, most of the recovered indium oxide is further purified. In this case, it is assumed that further purification is performed after dissolution. Indium compounds such as indium oxide or indium metal. I means that indium oxalate is precipitated by mixing the indium-containing solution and the precipitation agent as described above. 316907 13 200538394 / 'As mentioned above, this embodiment contains indium. The solution order is still effective for each situation, but most of the tin will be: Sui⑴er again in Shen; Dianwu. About this question with Cao Yi tin, because of the use of _ Right ττη — There is a case of ΤΤ, so it can be directly recovered and finally formed: indium oxide and tin oxide can be reused .: Furthermore, in this case, tin can be separated and only indium can be recovered in this embodiment. ^ Implementation mode In the tin separation method, the indium-containing solution is mixed with oxalic acid, and then the pH of the indium-containing solution is adjusted to 0.5 to 40 by using an acid or test, and the tin can be tinned by passing it through. Remove. In the solution containing tin right, in the solution above pHO.5, hydroxide will form and Shen Dian, so tin can be removed by filtering. In addition, if it exceeds 0, it will precipitate with tin. The increase in the amount of indium leads to a decrease in the recovery rate of indium, so it should be avoided. In addition, when pH adjustment is performed to remove tin, it is best to add sodium hydroxide or potassium hydroxide to the test. The reason is that even when ammonia is added for φ 4 Putian, the indium-containing solution after adding oxalic acid ^ the indium residual amount will increase. Then, the recovered precipitate (indium oxalate) can be recovered in a higher purity. It is best to use a cleaning step for cleaning. The cleaning solution at this time is preferably water or an oxalic acid aqueous solution, and the water includes pure water and ultrapure water. In addition, the oxalic acid underwater / hyaluronic acid solution is preferably an oxalic acid aqueous solution having a concentration of 0.5 m0L / L or less. . (Alkali contact step) The types of waste materials and acids that form the indium-containing grain liquid by tunneling may contain higher concentrations of copper in the indium-containing solution. This copper is easier to mix into the precipitate composed of 316907 14 200538394 indium oxalate. This copper is difficult to remove even if it is cleaned by using the above water and oxalic acid water " solution. ^ Therefore, in the recovery step from a copper-containing indium-containing solution, it is sufficient to contact the precipitate with ammonia (or ammonia and alkali hydroxide) (hereinafter, sometimes referred to as "ammonia: etc.") Remove copper. ~: The copper mixed in the indium oxalate of Shen Dianwu will react with ammonia to form copper ammonium ion ([CuWH3) 4] 2, which can be removed. = t 'Although this reaction can be directly performed from indium oxalate, the indium oxalate precipitated by the present invention has high crystallinity, and it is quite difficult to react copper mixed in the inside. In this contact treatment, by contacting ammonia (or ammonia and oxyhydroxide) with oxalic acid, the indium oxalate will be changed to steel hydroxide to destroy the crystal, and the reaction between ammonia and copper will proceed. This contact treatment can only be in contact with ammonia. Second, before and after (or at the same time) (including mixed = internal) contact between the milk and the sediments, it takes over the oxidation of alkali, promotes the conversion of indium oxalate to hydroxide, and performs copper. Reaction. "'," Bu = "alkali alkaloid" stated in the middle of the month refers to the metal's hydrogen and oxygen. Examples of this hydroxide test include: sodium hydroxide, Gongyang '· jiasi, it is best to use sodium hydroxide in terms of cost. Furthermore, 'the amount of ammonia or gas contacted by Shen Dianwu will be oxidized in the pi yi and the amount of nitrogen contacted by A will be at least equal to the average copper of the sinker, and it is best to set the required theoretical amount on. This amount is to make the steel react. Among them, it is best to set the average im0L of the steel, which is equivalent to the number of moL, and Shen Dianwu.

Marriage + average 1mOL is equivalent to 3mOL 316907 15 200538394 _ = the total number of moles or more. This is because indium oxalate will be fully converted to = indium, and copper will react with ammonia to be easily removed. On the other hand, regarding the upper limit of the amount of exposure to such ammonia, the copper level of the precipitate is best: lm0L is equivalent to the total number of moles of 4mQL, and the total number of moles of the average of the moles of the sinker. The number of moles b times the number is · ':. This upper limit is not from the point of view of copper removal: It is considered that, if an excessive amount of ammonia is used, a marriage will occur, and the recovery rate will decrease due to V. However, although the amount of ammonia used above is based on the di 'of the precipitate (indium oxalate): it is necessary to perform the analysis of Shen Dianwu based on the components in the precipitate, and then calculate the value based on this result. Performing this analysis will require waiting time to some extent, which will hinder efficient recycling operations. In addition, in the ordinary recycling operation, the component analysis of the indium-containing solution is performed at the operating cost. , Decision = In the form of official application, the best condition is based on the use of the indium-containing solution as the reference and then use of Lice Temple. —3 钔, the amount of ammonia and other components used in the mixture as the basis. Most of the copper in the test solution will be mixed with Shen Dianwu ’s copper in 2 indium-containing solution. = m〇L, and set to equivalent to 4moL Mo = especially the indium-containing solution, the average copper _ _ ear indium-containing solution indium average-for the heart II,. Count more than Mohr. The upper limit is preferably _ ^ y Two copper flat one is quite a mole: :: = the average indium in the two lm 〇 4 、, 3 marriage, together / night 0 [is equivalent to 3 m〇 The total mole number of L is 2 316907 16 200538394 or less. With this kind of setting, it is less than the use when it is based on the office: the lower limit of the amount of use, if not not greater than the sediment-based. Just-in-time limit 'and the upper limit of copper removal. )use! If the upper limit is 値, the connection to the Shen Dian Lake can be carried out under the condition of the valley liquid. It includes the steps of mixing Shen Dianwu with water, blowing ammonia gas, adding solid gas oxidation test, and finally forming the concentration of water to make the aqueous solution and hydrogen hydroxide solution. There are no special restrictions ^ as long as it contains the above necessary The amount of solution is sufficient. However, if the concentration is too low, the drainage volume will increase; conversely, if the concentration is too high, the amount of liquid relative to the amount of sediment will become too small and cause insufficient contact. Therefore, the wave length of these aqueous solutions is preferably set to 0.5 to 15 mL / L, especially i to ι〇_. Third, the number of treatments can be divided into a plurality of times to contact Shen Dianwu with the necessary amount of ammonia (aqueous solution) [or ammonia (water-soluble φ liquid) and hydroxide test (aqueous solution)], but from the point of view of efficiency, etc. , Preferably a single implementation. Furthermore, the temperature of the ammonia water and / valley liquid can be heated or normal temperature, but in order not to reduce the efficiency, the normal temperature is preferred. For the contact treatment with the ammonia, it is still best to know at this step and / or after (especially before), washing the precipitate with water or oxalic acid bath. This allows very high purity indium to be recovered. Then, by washing before the contact treatment, impurities other than hydroxides due to the contact treatment can be removed. 17 316907 200538394 Shen Dianwu's cleaning method and contact treatment method with ammonia, for example, immersing indium oxalate in an indium-containing solution and removing the supernatant, and then adding the cleaning solution or ammonia solution to the mixture ㈣ method; or pass indium-containing solution ~, and then _ cake to wash ㈣ ammonia material when mixing step, and apply = this step! Repulping and cleaning method for more than two times; or any method such as filtration and cleaning method in which a cleaning solution or an ammonia solution is passed into a filtering device that filters indium-containing solutions by using a vacuum filter or a filter press. In addition, when Shen Dianji was added, cleaning was not performed but immediately returned. In the case of indium oxalate, or Qingxian τ was performed by a method other than cleaning, although the indium oxalate can be separated from solid and liquid, but this will Adopt the filtration method. (Baking step)

"," And two mouthpieces are separated by a knife; the object (indium oxalate or indium hydroxide) can be converted into indium oxide by performing U. This baking preferably heats the Shen Dianwu f after the solid-liquid separation. Baking can also be performed after solid-liquid separation and drying, but from the standpoint of energy cost and efficiency, it is best to adopt direct baking. The baking temperature is best set to _ i let. c, especially 7GG i. 0 is. Also, baking time is up! To 48 hours, especially 2 to 24 hours. If the relevant feeding conditions are lower than the lower purity, it will not be fully formed. Conversely, even if baking is performed at a temperature and time exceeding the upper limit, only empty energy is wasted. (Second Embodiment) The second method for manufacturing a metal containing indium containing metal is performed through the following steps. 316907 200538394 Via :: The indium-containing material of the recovered raw material is dissolved in the indium-containing solution of the acid, six-force mouth sinking; the grass age of the agent _. /, J " The step of rolling to generate an indium oxalate precipitate. Temple steps) ;, early: Xiao You performed solid-liquid separation on the above indium oxalate sinking house: (: precipitation recovery step); the recovered sink; the house was immersed in a liquid that would not dissolve the marriage, and The passivation formation cause ions are dissolved in the liquid, and the passivation formation cause ion cleaning step (passivation ^ cause ion cleaning step) to remove the dissolved solution is performed more than once; (.passivation formation, the above passivation formation cause ion cleaning is performed) The cleaning process obtained in the process :) The step of dissolving the substance 'in acid to form an acid solution (: The step of acid dissolving in the step of leaching a metal plate and depositing sponge indium by reaction with the metallographic phase ( : Substituting the precipitation step "… a step of obtaining indium-containing metal from the sea_ (a metallization step and the like to produce indium-containing metal. In addition," the "sponge indium" refers to a porous state formed by contact with gold ( Sponge-like) indium-containing substances. The generation reaction is further, "the ionization cause of passivation is formed on the current Laita engineer /" mongolian plate "by replacing the precipitation step", also known as "passivation formation cause ion". The explanation in this embodiment.] The original 枓 and the steps are described in detail (indium-containing substances) 316907 19 200538394 The source of _ containing materials is not particularly ㈣. For example, thin films, recycled materials scattered during manufacturing, and discarded IT 〇 leather materials, ιτ〇 or marriage with Bangladesh, materials, or LCD and PDP waste, indium-containing semiconductor recyclables, or indium-containing substances recovered after use or departure from the original use: Among them From the marriage-containing substance scattered during the manufacturing of IT0 film, the recovered substance is, for example, a ITO sintered body obtained by sintering a mixture of indium oxide and tin oxide, and the ITO sintered body is used as a dry material. When the Zhaoqi Plasma TQ is mixed, the non-steamed rib substrate is scattered and scattered around the ΓΓΟ to recover, and the indium-containing substance obtained is an example of the raw material most suitable for this embodiment. (Including Copper solution) 3Indium / valley solution is preferably a solution in which the above-mentioned indium-containing substance is dissolved in an acid. Although the indium content in the indium-containing solution is not particularly limited, the indium content is preferably 10 g / L or more, especially 15 g / L or higher is preferred, and 2 or higher is more preferred. In addition, tin is preferably less than ι0% of the indium content. In addition, for metals other than indium and tin, if In place of precipitation, use metals other than metals (such as aluminum or zinc), and the total amount is preferably less than 10% of the indium content. Even if the content is more than 10% of the indium content, it is not impossible to apply this The morphology forming method is implemented. However, since the efficiency and the purity of indium in the silk deposition step will decrease, it is preferably less than 10% of indium. ▽ Although there is no particular limitation on the type of acid that dissolves indium-containing substances, those suitable for the second form are indium-containing solutions that are dissolved with inorganic acids such as hydrochloric acid, nitric acid, fluoric acid, and nitrofluoric acid. Among them, nitric acid is preferred. 316907 20 200538394 If you use nitric acid, you can easily dissolve indium-containing substances. When nitric acid is used, nitrate will form a passivation during substitution and precipitation, which may hinder substitution precipitation. However, if indium oxalate is precipitated when oxalic acid is added as in this embodiment, the compatibility between nitric acid and oxalic acid is good. And because the crystallization of oxalic acid (Shen Dianwu) becomes larger, so when the @liquid separation is performed, the separation performance will be improved, and the amount of mother liquid in the precipitate after solid-liquid separation can be reduced, thereby reducing nitrate ions. Residual amount, with the method of solid-liquid separation, may also omit the ion cleaning step for purification formation reasons.

When the indium-containing substance is dissolved in a nitric acid-containing nitric acid solution, the tin contained in the indium-containing nitric acid solution can be left standing for an appropriate time in a state of the nitric acid solution containing indium. Metastannic acid (酸 βηΟ3) is formed and removed by precipitation, which can reduce the burden of subsequent steps. The standing time at this time is preferably at least 24 hours, and more preferably at least 168 hours. (Indium oxalate precipitation step) By adding and mixing oxalic acid in an indium-containing solution, the indium can be selectively formed from the indium-containing solution to form indium oxalate and allowed to sink. The form of adding oxalic acid can be applied in any form such as solid (including powder), aqueous solution, and solid form in a dispersed form. In the case of solid oxalic acid, anhydrous hydrates can be mixed, but in terms of cost, it is a mixture of monohydrates. However, in order to uniformly sink copper oxalate and suppress impurities, it is best to mix with water> valley. When oxalic acid is added in an aqueous solution, f is obtained by changing the concentration of oxalic acid in the water to a saturation concentration that is lower than ⑽ / °. 'Even if the liquid temperature of the oxalic acid aqueous solution changes, it is still difficult to produce 316907 200538394. Condition of the sediment. In addition, if * is low, the amount of the oxalic acid aqueous solution recovered for the implementation of indium will be excessively reduced. In view of the above, the mushroom skin, and six 汸 汸 #, ^ and increase drainage

Above, especially the concentration of 22 is better than 1 L and more than UnoL / L. • Furthermore, the mixed oxalic acid can be recorded using oxalic acid ^ • Because both compounds contain oxalic acid and are suitable for both purposes: = In the case of the compound, it is left in the toiletry solution containing indium and Rongtian The amount of indium will be more than that of using oxalic acid:; Γ: lead: Γ The yield is reduced, and the best is oxalic acid. W causes the mixed amount of oxalic acid mixed with indium-containing solution (in other words, τ 'is preferably set to the equivalent of indium contained in the indium-containing solution (also = 1.2 to 5 times the spoon. If it is less than 2 times, indium, capacity) However, the recovery rate is reduced; on the other hand, even if it is _5 times plum = ^ = ::: = r. The mixing amount is 1 = 4 to 4 times that of 3 indium §. In addition, Equivalent is indium pingxiao lm〇L is oxalic acid 1: so / the so-called "up to 5 times the equivalent of marriage" means Ping: ·. Because ImoL 'early acid is 18 to 7 5m, the content recovered from increasing From the point of view of the domain degree of $, it is best to perform the pH management of the dihydrazone cold liquid before and after the oxalic acid mixing. The indium-containing solution before the oxalic acid mixing is preferably set to less than 3.5, especially preferably 2 or less. The reason is that in ρ3.5: Η on the day τ 'because the oxalic acid is not formed due to the formation of hydroxides in some steels, the recovery rate of indium will be reduced. In addition, the indium recovery rate can be improved by setting it below PH2 From this point of view, the lower the pH of the indium-containing solution, the better, 316907 200538394, so it is best to be below 1.0, especially 0.5 or less. Α When the pH of the indium-containing solution is over When it is out of the above range, it is best to perform pH adjustment on the solution. However, although it is desired to lower the pH, it is still better not to add excess acid. When the concentration of the added excess acid is converted into a monobasic acid, it is more than 3 mOL In the case of a large amount of acid / L (in the case of monoacids such as nitric acid, hydrochloric acid, hydrofluoric acid: more than 3mol / L, and the above acids in dibasic acids such as sulfuric acid), the recovery of indium will result Therefore, when pH adjustment is performed, the optimal acid addition amount is not more than the above number, and when it exceeds this value, it is best to add sodium hydroxide or potassium hydroxide to adjust the acid concentration to this On the other hand, for the pH of the indium-containing solution after mixing with oxalic acid, from the viewpoint of reducing impurities in Shen Dian, it is better to set it to below 20, especially to lower it to below 1.0 For the mixing method of the indium-containing solution and the precipitation agent (oxalic acid), in addition to the method of stirring the indium-containing liquid and adding a precipitating agent thereto, there is also a method of stirring the water valley solution or a slurry-like precipitating agent and adding indium. Solution method, or 2 in 1 Any method such as the method of simultaneously introducing an indium-containing solution and a precipitation agent into each tank (or container) can be used. Again, the liquid temperature when the indium-containing solution is mixed with oxalic acid is 0 to 90. (: == within the range is Yes. Because the liquid temperature at the time of mixing tends to lower the impurities and the impurities, but the influence is not large, so it is best to perform mixing at normal temperature without temperature adjustment from the aspect of energy cost. Δ I □ After adding oxalic acid to the solution, it is best to stir and mix at a moderate time, and it needs to stand properly. 316907 23 200538394 This% · search and mixing day can be set to 5 minutes to ^ hours, especially 10 Minutes to 12 hours are preferred. If it is less than 5 minutes, the amount of impurities mixed with oxalic acid may increase; on the contrary, if it is mixed for more than 24 hours, there is no difference in the effect of reducing impurities, but it only reduces the efficiency. (Sediment recovery step): ^ The above-mentioned method for performing solid-liquid separation of the indium oxalate Shen Dianwu can adopt a conventional solid-liquid separation method. For example, vacuum filtration such as suction filtration, pressurization filtration such as a dance machine, high speed _Solid-liquid separation methods such as centrifuges, separation methods such as centrifugation, separation, etc. In addition, depending on the degree of solid-liquid separation performed in this step, it is also possible to save each subsequent passivation formation cause ion cleaning step. Especially when using a nitric acid solution containing indium as the starting material, because nitrate ions are replacing the precipitation step! ^ Will form passivation formation cause ions and hinder the substitution of the precipitation reaction. Therefore, it is usually necessary to perform a passivation formation cause ion cleaning step, but by fully performing the solid-liquid separation of this step, for example, a solid-liquid separation method with good separation performance, Either lengthening the filtration time or increasing the filtration area will reduce the amount of mother liquor contained in the indium oxalate precipitate and reduce the amount of passivation formation cause ions. H This can omit the passivation formation cause ion cleaning step. Specifically, when the ion cleaning step for passivation formation reason is omitted, solid-liquid is applied in a manner that the concentration of the passivation formation cause ion in the dissolving solution prepared by dissolving the passivation towel is 10,000 Ppm or less (preferably 850,000 ppm or less). Dispensing can carry out the substitution reaction even if the passivation coin cleaning step is omitted. (Ion cleaning step for the cause of passivation formation) 316907 24 200538394 Second, the precipitate obtained by solid-liquid separation is immersed in a liquid that does not dissolve indium * (also known as "dipping solution"), so that it will be replaced in the subsequent In the precipitation step, the ions forming the passivation cause (passivation formation cause ions) on the metal plate are dissolved in the liquid towel, and the dissolving solution is removed more than once, and then the surface of the sinker can be removed. The attached mother liquor, or the mother liquor sucked into β in Shen Dianwu-Zhengcheng Cheng, is replaced with the dipping solution and washed to remove and purify the formation ions. By purging and removing the cause of passivation formation, the subsequent replacement precipitation step can be performed with high efficiency, and higher purity metals containing φ with indium can be recovered. Examples of metals other than In due to passivation formation include metal ions such as Fe.Fe Co Cr Nom, and anions such as tribasic acid ions (NCV) and fluoride ions (F ·) that form salts with these metal ions. #In the case of using a fine nitric acid solution as the starting material, the main reason is that the osmium acid ion (NCV) forms a passivation formation ion. In the case of using the indium-containing osmium solution, the main reason is that the fluoride ion (F ·) and Hydrogen ion (hf_) and other formation

Causes passivation to form ions. Although it does not dissolve indium, it can dissolve the immersion solution of passivation-forming ions, such as water, aqueous oxalic acid solution, lower alcohols such as ψ alcohol or ethanol, or a mixture of these. Most pregnant rabbits ☆. ^ ^ ▲ Take it for water. The water system includes pure water and ultrapure water, and the early acid solution is preferably, and the nc is poor, and the aqueous solution of oxalic acid is less than 05m0L / L. The cause of passivation is ion cleaning. For example, the recovered Shen Dianwu is thrown into the immersion solution, and the step of saki separation is performed at least once. When divided into two or more implementations, ^ and ^ show that the use of the dipping solution can be reduced. In addition to 316907 25 200538394. =, The cause of passivation can be removed in a short time. In addition, the most difficult thing is to put the precipitate into the dipping solution and then perform moderate stirring. . * #Formation cause There is no particular limitation on the amount of immersion solution or processing time used in the ion cleaning treatment. There is no particular limitation on the temperature of the immersion solution at the time of feeding. In terms of efficiency, the temperature can also be increased from room temperature. The cleaning target of the passivation formation ions is as follows. When 酉 = is used to dissolve and clean the finished product f, the _ ion in the acid solution is preferably below the deleter, especially _ Adjust the treatment time for the purpose or treatment. If the concentration of nitrate ions in the solution is less than 10_ah, instead of the precipitation step, the passivation phenomenon on the passivation formation can be suppressed. Sponge indium is precipitated by the metal ionization reaction of the plate. Jisenma: From this point of view, ‘If the concentration of the acid solution in the next step is less than 5000ppm, the ions of the animal husbandry will be better. As mentioned above, T will better promote the precipitation of sponge indium. The solid-liquid separation in the step, for example, is only to fully implement the sinking and killing material recovery step method, or to increase the flow time 2 to take a solid-liquid separation with good separation performance θ ^, I hope to reduce the content of indium oxalate precipitation And reduce the passivation and formation of the original 3 mother liquefaction formation cause ion cleaning step; the [error this is also omitted this step (pure (acid dissolution step) washing process is completed ==== caused by ion cleaning treatment) 316907 26 200538394 q The kind of towels that can be used in this A towel can be, for example, organic acids such as Lai, Tang acid, etc., but when the starting material contains ^, At the time, the use of hydrochloric acid is quite important. ". In the case of cereal fluids, the concentration of hydrochloric acid is not particularly limited at this time. As far as it is concerned, it is best to use m to 12N hydrochloric acid. 砚", again, the acid is dissolved In addition to the dissolving rail when acid is added, the temperature is preferably adjusted above the pit by temperature adjustment, and it is preferably 30 to 6 (TC range. Dry J Πι In addition, when the cleaning finished material is dissolved in the acid Residues will be tolerated after a moderate amount of time (eg 1 hour After the mixing, the mixture needs to stand for a moderate amount of time, and the dissolution and removal of the dissolve can be used to recover the acid solution. (Instead of the precipitation step) Next, the acid solution obtained in the above step is placed in the reaction tank. In the process, a metal plate (preferably an aluminum plate) is sub-impregnated, and a sponge indium is precipitated by performing a substitution reaction with a metal (such as aluminum) of the metal plate. If the pH of the acid solution during the substitution reaction is lower than 0.5 Or higher than 15 'because the substitution reactivity between indium and metals (such as aluminum) is reduced, so the pH of the acid > hydrolysate is adjusted to 0.5 · 1 · 1 by adding a test compound or water, etc. 5 (particularly in the range of 0.5 to 1 · 〇). At this time, the test compounds to be added may include, for example, sodium hydroxide, potassium hydroxide, hydroxide, ammonia, or an aqueous solution thereof. When adding water to adjust the pH, it is best not to reduce the indium concentration in the acid solution. The substitution reaction between indium and metals (such as Shao) will decrease sharply as the solution temperature falls below 27 316907 200538394.201 Tendency, the result of which makes sponge marriage The amount of precipitation is reduced *. Conversely, if the temperature is too high, it may cause problems in workability and thermal energy loss. Therefore, the temperature during the replacement reaction can be adjusted to 2 generations. Above, it is especially adjusted to the range of 2nd generation to 16th generation. Good. In addition to the method of impregnating the metal plate such as aluminum plate, the metal powder such as zinc powder (granular) can also be used. However, when metal powder such as powder (granular) is used, there will be sponge steel = title: to work hard to solve this problem, so in this embodiment = take good use as described above Method of metal plate. (Metalization step) The second method is to metallize the inferior seawater indium obtained in the above to form a block-shaped insoluble melt, but the specific method is not particularly limited, but it is best to take inspection ^ to >, Heat to surface melting point ⑴6. 〇The above test solution makes the implementation of the second anti-IS two sponge indium easier to oxidize, but by the implementation of alkali melting casting A, and can also be separated from the oxidation of the indium present on the surface of the indium by the pancreas and impurities in the sponge indium, Remove. ^ The test compound used in the casting is not particularly limited, but it is best to use sodium hydroxide in the industry. According to this test, the metal obtained will become a metal with higher indium quality. Now, the implementation form described in 2 'above is an example of the present invention, but the effect of the present invention depends on τ, and other steps are inserted in the above sequence. The order of the steps can also be reversed. Medium 316907 28 200538394 Examples-In the following, examples of the present invention will be described in comparison with comparative examples. (Examples 1 to 18 and Comparative Examples 1 to 5); The following two kinds of indium-containing solutions were prepared, and the indium was recovered. These indium-containing solutions are obtained by dissolving indium-containing waste with nitric acid. [Table 1]

In A1 — Mg Si Ca Sn Zn — pH 2.6 A Temperature (gA) 25.8 11.9 0.26 < 0.01 < 0.01 < 0.01 < 0 04 0.18 〇7〇 To In ratio (% by weight) 100 Γ46.1 1.0 bu < 0.04 < 〇y〇r B temperature (g / 1) 28.5 15.7 0.43 0.11 0.13 \ V / · 0.29 \ J · / \ J 0.35 ------- 0.1 to In ratio (weight 0 / 〇) 100 55.1 1.5 0.39 0.46 1.0 1.2 ------- According to the above two kinds of indium-containing solutions (A, B), change the various conditions to perform indium recovery. The basic flow of this step will be described using Figure 1. Prepare 10 L of either of the indium-containing solutions A and B (step (1)), adjust the pH by referring to the pH of this solution and adding appropriately (step (2)). Then, according to circumstances, the temperature is maintained at 60 C (step (3)), and the indium-containing solution is mixed with the precipitation agent (step (4)). The mixing step basically involves stirring the indium-containing solution and adding a precipitating agent (the example is oxalic acid 'and the comparative example is ammonia water), and some examples take the form of stirring the precipitating agent and adding the indium-containing solution thereto. In the case of adding Shen Dian agent to 4 to produce Shen Dian, the solution is subjected to vacuum filtration, (step (5)), and the precipitate is washed with pure water (step (6)). This washing step is performed with 100 mL of water The solution was passed four times. The indium oxalate (comparative example: indium hydroxide) obtained after the first month of the month was baked in a 316907 29 200538394 electric furnace at 1000 ° C for 5 hours (step (7)) to form indium oxide. Furthermore, in some of the examples, 4mOL / L of NaOH was added to adjust the pH to L8 before pH adjustment, and then the solution was filtered to remove tin in the indium-containing solution (step (8)). Following the steps described above, the conditions for recovery of multiple indium implemented in the examples are as follows. " [Table 2]

• > The amount of pediatric agent used is a multiple of the theoretical amount of indium * in the indium-containing solution 2: Excess acid concentration ... Example 6: 2 · 5_1Α, Example 7: 3.5 · ^ 16907 30 200538394 * 3: Indium-containing solution is mixed in the precipitant. * 4. After heating the solution to 60V, add 60V of precipitant. * 5. Perform de-tinning treatment. After de-tinning treatment, do not perform pH adjustment. In the case of adding a precipitant * 6 ·· de-tinning treatment is performed, and after the de-tinning treatment, nitric acid is added to form ρΗ〇ι, and a precipitating agent is added.

* 7: PH management ... Determine the pH after mixing, and add ammonia water to reach the pH value. Then, according to the conditions of Examples 丨 to 18 and Comparative Examples 丨 to 5 in Table 2, analyze the components of the recovered indium oxide.値, recovery rate is shown in Table 3.

316907 31 200538394 [Table 3] __Indium analysis rhenium (% by weight) In recovery (%) In A1 Si Ca Sn Zπ Example 1 82.6 &lt; 0.1 &lt; 0.1 &lt; 0.1 &lt; 0.1 &lt; 0.1 &lt; 0.1 95.3 Example 2 82.8 &lt; 0.1 &lt; 0.1 &lt; 0.1 &lt; 0.1 &lt; 0.1 &lt; 0.1 94.8 Example 3 82.5 0.2 &lt; 0.1 &lt; 0.1 &lt; 0.1 &lt; 0.1 &lt; 0.1 95.6 ~ Example 4 82.3 0.5 &lt; 0.1 &lt; 0.1 &lt; 0.1 &lt; 0.1 &lt; 0.1 &lt; 0.1 95.9 Example 5 Γδΐ. 3 1.5 r &lt; oT &lt; 0.1 &lt; 0.1 &lt; 0.1 &lt; 0.1 96.7 Example 6 82.7 &lt; 0.1 &lt; 0.1 &lt; 0.1 &lt; 0.1 &lt; 0.1 &lt; 0.1 93.8 Example 7 82.8 &lt; 0.1 &lt; 0.1 &lt; 0.1 &lt; 0.1 &lt; 0.1 &lt; 0.1 85.5 ~ Example 8 82.7 &lt; 0.1 &lt; 0.1 &lt; 0.1 &lt; 0.1 &lt; 0.1 &lt; 0.1 78.3 Example 9 82.8 &lt; 0.1 &lt; 0.1 &lt; 0.1 &lt; 0.1 &lt; 0.1 &lt; 0.1 90.3 Example 10 82.6 &lt; 0.1 &lt; 0.1 &lt; 0.1 &lt; 0.1 &lt; 0.1 &lt; 0.1 93.3 Example 11 82.6 &lt; 0.1 &lt; 0.1 &lt; 0.1 &lt; 0.1 &lt; 0.1 &lt; 0.1 98.2 Example 12 82.8 &lt; 0.1 &lt; 0.1 '' &lt; 0.1 &lt; 0.1 &lt; 0.1 &lt; 0.1 98.4 households, Example 13 11Ί; &lt; 0.1 &lt; 〇.Γ &lt; 0.1 &lt; 0.1 &lt; 0.1 &lt; 0.1 95.4 Through Target Example 14 82.6 &lt; 0.1 &lt; 0.1 &lt; 0.1 &lt; 0.1 &lt; 0.1 &lt; 0.1 95.3 Example 15 82.6 0.1 &lt; 0.1 -------- &lt; 0.1 &lt; 0.1 &lt; 0.1 &lt; 0.1 95.2 Example 16 / Α »juU / -r 1 1 82.0 &lt; ο · Γ &lt; 0.1-&lt; 0 · 1 &lt; 0.1 0.8 &lt; 0.1 95.1 Example 1 / Yingu; 柘il 1 8 82.6 0.3 〆η Γ &quot; &lt; 〇Τ ---—— &lt; 0.1 &lt; 0.1 &lt; 0.3 &lt; 0.1 94.2 ^ OvL Ir'J 1 Ο ο2.7 <0 · 1 &lt; 0.1 &lt; 0.1 &lt; 0.1 &lt; 0.1 &lt; 0.1 94.5 Than the car parent example 1 l ^^ 47.4 22.1 〇.48 ~ ------ &lt; 0.1 &lt; 0.1 &lt; 0.1 0.15 96.3 pG -fx ir'J L 49.3 20.9 〇47 &lt; 0.1 &lt; 0.1 &lt; 0.1 0.12 92.5 than the car parent example 3 48.4 21.4 0.48 ^ &lt; 0.1 &lt; 0.1 &lt; 0.1 0.11 95.8 than the Lee parent example 4 »1 I £ Τ 47.5 22.1 0.48 &lt; 0.1 &lt; 0.1 &lt; 0.1 0.12 98.2 Case example 5 * ΓΡΠ, 1 / r 48.7 -li ^ J ^ 〇Α6 ^ &lt; 0.1 &lt; 0.1 &lt; 0.1 0.10 96.0 、-, ... ~ 千 u 茨 四 里-龙爪, Tamping year%)} / {indium concentration (g / 1)} of the treatment solution (A, B) x the amount of the treatment solution ⑴} * Theoretical content of the indium content on the oxidized surface is 82.7 weight 0 / 〇. From the above results, it is known that the example is first compared with the comparative example using ammonia as the precipitation. The result shows that the indium oxide recovered in the comparative example is an impurity. It contains many impurities, especially aluminum. The situation with the precipitation is more obvious. 316907 32 200538394 In contrast, although the example contains a little aluminum, high-purity indium oxide with almost no impurities can be recovered. This phenomenon is considered to be due to the fact that the indium content in the recovered indium oxide is very close to the theoretical value. Furthermore, the differences in the recovery conditions will be discussed in each of the examples. First, from the viewpoint of mixing in impurities, in Examples 3 to 5, only a small amount of aluminum mixing was found. From this phenomenon, it is known that as the pH of the indium-containing solution increases when the precipitant is mixed, the aluminum content will also increase. Therefore, in the present invention, it is best to reduce the pH of the indium-containing solution as much as possible, especially 0. good. In addition, only the implementation of the indium recovery rate is below 80%. The reason is believed to be the mixing amount of the precipitating agent. In Example 8, compared to the indium content in the indium-containing solution, only a theoretical amount of precipitation W was added. Therefore, it is known that only 80% or more can be obtained. The recovery rate is the best method of mixing the precipitant in an amount more than L2 times as in Examples 9 to 12. However, when comparing Example 11 (adding 5 times the amount) with Example 12 (adding 6 times the amount), because the recovery rate of indium hardly changes, it is learned that the amount of Shen Lujue is best set to 5 Within the amount. Of the indium-containing solutions used in this example, Solution B contains a higher concentration of tin. Examples of recycling this solution B are Examples 16 and 17. As a result, it was found that in Example 17 in which tin removal (step (9)) was performed, it was confirmed that the tin in the recovered indium oxide was completely removed. Therefore, when a single metal of high purity indium is recovered from the recovered indium oxide, it is known that the step of removing tin is preferably performed. However, whether to implement the de-tinning step is determined by the purpose of using indium after the indium oxide is recovered. Even if the de-tinning step is not performed, both indium and tin can be recovered. Therefore, 316907 33 200538394 When I was making ιτοn brothers, I was more embarrassed. I also learned that the presence or absence of de-tinning treatment is a matter of use, not a matter of good or bad. (Examples 19 to 27) Herein, the following indium-containing solution (C) was prepared, and the indium-containing / synthetic liquid was used as the waste liquid when the liquid crystal substrate was washed with hydrofluoric acid in accordance with the indium recovery. [Table 4]

In A1

Mg c Temperature (g / l) Win 58.0 &lt; 0.01

Ratio (% by weight) &lt; 0.01

SiΈΪΤ

Ca &lt; 0.01

Sn

Zn

Cu

pH 19.7 100 &lt; 0.02 &lt; 0.02 0.36 &lt; 0.02 34.0 &lt; 0.01 &lt; 0.02 2.1 3.6 0.1 According to this indium-containing solution (0, change the conditions to perform indium recovery. For the basic flow of the steps in this embodiment, use Figure 2 Explain. Prepare 60L of indium-containing solution [indium content 3480g (30.3moL), copper containing rhenium 126g (1.98moL): Step (1), then mix the indium-containing solution with the precipitation agent (oxalic acid) (step (2)) The mixing system of this oxalic acid solution is to add 0,5m0L / L of oxalic acid aqueous bath solution to oxalic acid in a solution which is 2.5 times the theoretical amount of indium in the indium-containing solution, and add it in 10 minutes. Stir the indium-containing solution and add an oxalic acid aqueous solution. When the precipitation is added completely and the precipitate is completely generated, the solution is subjected to vacuum filtration (step (3)), and the precipitate is washed with pure water (step (sentence). This washing The steps were performed using HOOmL of water for 4 passes. After the cleaning was completed, the obtained indium oxalate (comparative example: indium hydroxide) was analyzed, and the result contained 3228g (28 lm0L) of indium and copper 1 〇8g (170m〇L). Secondly, the recovered grass Indium is divided into 12 equal parts. Among them, 9 316907 34 200538394 indium oxalates are changed in conditions and subjected to contact treatment (the following conditions are set to Examples 1 to 9: 27: step (5)). The contact treatment contents are shown in Table 5. For the sake of comparison, in this example, for the sake of comparison, the situation in which the Shendian is not subjected to ammonia contact treatment is also discussed (reference example).-[Table 5] Contact treatment content Contact treatment solution NaOH aqueous solution ammonia aqueous solution Total mol number of liquid concentration Mol number of liquids · temperature Mol number Example 19 Exposure to ammonia only--lmol / 1 0.5mol 0.5mol Example 20 Exposure to ammonia only--lmol / 1 0.66mol 0.66mol Saturation example 21 Exposure to ammonia only- -3 mol / l 7 mol 7 mol Example 22 exposure to ammonia only--3 mol / l 8.25 mol 8.25 mol example 23 exposure to ammonia only-3 mo 1/1 lOmol lOmol example 24 exposure to ammonia only-3 mol / l 16.5 mol 16.5 mol Example 25 Contact with ammonia only-3 mol / l 20 mol 20 mol Example 26 Contact with NaOH + ammonia 3 mol / l 9.34 mol 3 moi / l 0.66 mol 10 mol Example 27 Contact with NaOH + ammonia 3 mol / l 9.5 mol 3 mol / l 0.5 mol 10 mol Reference Example No contact treatment------

Note: From the amount of indium contained in the indium-containing solution (1/12) of the treatment object and the amount of indium contained in the precipitated indium oxalate (1/12), the lower limit of the amount of ammonia obtained, and The upper limit 値 and lower limit 値 of the amount of the contact treatment solution (ammonia + alkali hydroxide) are as follows. Lower limit of ammonia usage 下 Lower limit of contact treatment solution usage 値 Upper limit 基准 Indium-containing solution basis 0.66mol 8.25mol 16.5mol oxalate steel basis 0.57mol 7.59mol 1 8.97mol For the precipitate after contact treatment, vacuum filter the solution (step (6)), washing the recovered Shen Dianwu with pure water (step (7)). This washing step is performed by passing 100 mL of water once. Ran 35 316907 200538394 Precipitation of the β-washing precipitate (indium hydroxide) was performed in an electric furnace at 10001 for 5 hours and then baked (step ⑻) to form indium oxide. To confirm the recovery effect of indium on the indium oxide produced. At the time of confirmation: The estimation was performed by comparing the composition analysis of indium oxide and the scoop of indium oxide obtained from the experimental results with the obtained indium recovery ratios. The results are shown in Table ό. , Η [Table 6]

Regarding the results in Table 6, first of all, for the contact treatment with or without ammonia, after comparing each yoke example with the reference example, it was learned that the copper concentration in the recovered indium oxide will be removed by the majority of the ammonia contact treatment, and it was confirmed that The removal effect. On the other hand, the conditions of the contact treatment were discussed. The range of contact amount of ammonia (gas and IL oxidation test) was set within the optimal range (refer to the table in Table 5). Examples 22 to 24 surrounded by the lines, Examples 26, 27)) were compared with the results of the other examples, and the result was 36 316907 200538394. It is known that the amount of contact is small ...-"M 19 to 21 ), It is considered that the contact amount of ammonia (or ammonia and hydroxide) in indium oxide == indium has not been completely converted to indium oxychloride, and it is impossible to remove part of the mixed H Steel. On the other hand, when there is a large amount of contact (in the case of the example, the purity of the indium oxide collected can be met, but the recovery rate of A is poor. This phenomenon: tolerance is caused by the addition of excess inspection and oxidation. The dissolution phenomenon of steel. As mentioned above, the contact treatment of ammonia (or ammonia and alkali hydroxide) is an effective way to remove copper from indium oxide, and by setting the contact amount to an appropriate value, _ can be implemented more Effective indium recovery. Figure 3 is not for the precipitate immediately after precipitation (indium oxalate And the result of X-ray diffraction analysis of Shen Dianwu (indium hydroxide) which had been treated by ammonia contact. From the figure 0 (M), the precipitate immediately after precipitation (indium oxalate) belongs to Futami Rui The indium oxalate in the strong crystalline state of the wave peak. Therefore, by contacting the core steel crystal with ammonia ', the diffraction pattern of the precipitate will be formed in a wider shape This change can be judged that the Shen Dianwu composed of indium oxalate: 'by contact with ammonia, its crystal was destroyed and replaced with weakly crystalline indium hydroxide. Then, the In the process of destruction and replacement with indium hydroxide, the copper entrained in the precipitate will be removed. Moreover, the indium oxide diffraction pattern after baking the indium hydroxide is shown in Figure 3 (c). Examples 28 to 30) In this example, a mixture of indium oxide and tin oxide was sintered, 37 316907 200538394, and the obtained ITO sintered body was used as a target and plasma was irradiated. When the ITO was sputter-plated, it was scattered in ITO content in the surrounding and attached to the protective plate, ITO- It was dissolved with nitric acid, and the obtained indium-containing nitric acid solution (pHO. 12) was used as a raw material. The indium-containing nitric acid solution was analyzed by ion chromatography, and the results contained: In (30g / L), Sn (0.06g / L), • Al (10g / L), Mg (0.23g / L), Zn (0.03g / L), Fe (0.04g / L), Cr (less than 10ppm). Prepare the above contents 500mL of indium nitric acid solution (liquid temperature 27 ° C), 500mL of oxalic acid aqueous solution (liquid temperature 26 ° C, oxalic acid concentration 80g / L) was added to the solution, and after stirring for 30 minutes, it was left to stand for 1 hour and 30 minutes. Using filter paper of various sizes shown in Table 7 (manufactured by Toyo Filter Paper Co., Ltd. 4A), suction filtration was performed with a suction filter to obtain a precipitate (indium oxalate) and a filtrate (NCV concentration, pH, In concentration, as shown in Table 7). As shown). In addition, when the filter cake is cracked in the middle of filtering, the surface is smoothed first and then the filtering is continued. In either case, the nitric acid solution containing indium is put into the funnel, and the filtering ends after 15 minutes. . The obtained precipitate was put into 450 mL of water, and 50 mL of 12N hydrochloric acid was added to adjust the pH to 0.5, and 500 mL of an acid-dissolved solution (NO3 · concentration, pH, and In concentration, as shown in Table 7) was obtained after acid dissolution. Next, the temperature is controlled so that the acid-dissolved solution does not exceed 60 ° C, and the mixture is stirred for 1 hour. The residue (undissolved solids) is removed by filtration with a suction filter, and the acid-dissolved solution (ρ 在 0) is recovered. • In 7), the chain plate with a width of 100 mm, a length of 300 mm, and a thickness of 6 mm was immersed, and the substitution reaction was continued for 1 hour while the temperature was controlled to a liquid temperature of 50 ° C. 38 316907 200538394 Then, recover the sponge indium precipitated by the substitution reaction, remove the moisture and so on, and then use sodium hydroxide to perform alkali melting (30000), and then remove the metal containing indium from the mold. Sponge indium The amount obtained, the amount of metal containing indium, the In quality of the metal containing indium, and the amount of metal that can be recovered from an acid-soluble solution. • Recovery rate (In recovery rate (%) [in metals containing indium In content / In content in acid solution] χ 100, hereinafter referred to as "In recovery"}, are shown in Table 7. In addition, the In quality of metals containing indium was measured by lcp emission spectrometry _ lamp analysis The nitrate ion concentration was measured by ion chromatography (the same will be described later). (Examples 31 to 32) 500 mL of an indium-containing nitric acid solution was prepared as in Example 28, and an oxalic acid aqueous solution (liquid) was added to the solution. The temperature is 26 ° C, the concentration of oxalic acid is 500 mL, and after stirring for 30 minutes, it is allowed to stand for} hours% minutes. Next, filter papers of various sizes shown in Table 7 (manufactured by Toyo Filter Paper Co., Ltd. 4a) were used. Suction filter for suction filtration Obtain a precipitate (indium oxalate) and a filtrate (NO, concentration, pH, and In concentration, as shown in Table 7). In addition, when the filter and cake cracked in the middle of the process, first smooth the surface and then continue Filtration is performed. In either case, the nitric acid solution containing indium is put into the funnel, and the filtration is finished after 15 minutes. The obtained precipitate is put into 20 mL of water (2 (rc), and stirred) After 10 minutes, the mixing was stopped and the mixture was allowed to stand for 0.5 hours, and then the high-speed centrifugation was used to remove the aqueous phase. The cleaning process was performed i times in the example, and repeated in the example M two times to obtain the cleaning process. Finished substance and washing completed dissolving 316907 39 200538394 solution (NO3-concentration, pH, In concentrations, as shown in Table 7). Put the washing-treated finished substance into 450mL of water, and add 12N hydrochloric acid 500mL 'to pH Adjust to 0.5 and dissolve the acid to obtain 500 mL of acid-dissolved solution (NO, 3 concentration, pH, and In concentration, as shown in Table 7). • Secondly, the temperature should be controlled so that the acid-dissolved solution does not exceed 60 ° C. Under the condition of "quoting for 1 hour, filtering with suction filter Remove the residue (undissolved solids) and recover the acid solution. In this acid solution (ρΗ〇 · 7), immerse the aluminum plate 100mm, 300mm long, and 6mm thick, and control the temperature to 50 ° C. Stirring is performed in the state, and the substitution reaction is continued for one hour. Then, the sponge indium precipitated by the substitution reaction is recovered, and after removing water and the like, alkali casting (300t) is performed using sodium hydroxide, and then the mold is removed from the mold. The metal containing indium is taken out. The amount of sponge indium obtained (g), the quantity of metal containing indium), the In quality and In recovery of the metal containing the surface are shown in Table 7. (Comparative Example 6) • 500 mL of an indium-containing nitric acid solution was prepared as in Example 28, and 100 mL of room temperature (20 ° C) water was added thereto, and 25% ammonia water was further added, and adjusted to pH 4 · After 5 minutes, the mixture was stirred for 0.5 hours, and the indium hydroxide was precipitated by standing for 0.5 hours to obtain a slurry. Next, using various sizes of filter papers shown in Table 7 (manufactured by Toyo Filter Paper Co., Ltd. 4A), suction filtration was performed using a suction filter to obtain a precipitate (indium oxalate) and a filtrate (NO / concentration, ρΗ, Ιη concentration, As shown in Table 7). In addition, when the filter cake was cracked in the middle of filtration, the surface was smoothed first, and then the filtration was continued. After the nitric acid solution containing indium was added, the filtration was completed in 1 hour. 316907 40 200538394 Put 260g of neutralized Shen Dianwu into 360mL of water, and add concentrated sulfur-acid to adjust to pH 0.5. After acid dissolution, 500mL of acid dissolving solution is obtained. • (NO3 &gt; degree, pH, In concentration, As shown in Table 7). Next, control the temperature so that the acid solution does not exceed 60 ° C-Stir for 1 hour, filter with a suction filter to remove residues (undissolved solids), and recover the acid solution. Next, after adjusting this acid solution (pH 0.7), immerse the aluminum plate with a width of 100mm, a length of 300mm, and a thickness of 6mm, and control the temperature to a liquid temperature of 50 ° C. Stirring is performed, and the substitution reaction is continued for 24 hours. No precipitation of sponge marriage was found. (Comparative Example 7) 500 mL of an indium-containing nitric acid solution was prepared as in Example 28, and 100 mL of room temperature (20 ° C) water was added to the solution, and 25% ammonia water was added. After adjusting to ρΗ4.5, the mixture was stirred. 5 hours. Next, filter paper of various sizes shown in Table 7 (manufactured by Toyo Filter Paper Co., Ltd. 4A) was used to perform suction filtration with a suction filter to obtain a neutralized precipitate and filtrate (NO, concentration, ρΗ, 化 / 辰). Degrees, as shown in Table 7). In addition, when the filter cake was cracked in the middle of filtration, the surface was smoothed first, and then the filtration was continued. After the nitric acid solution containing indium was added, the filtration was completed in 1 hour. 260 g of neutralized sediment was put into 400 mL of water (20.0, after stirring for 10 minutes, the stirring was stopped, and the mixture was left to stand for 0.5 hours, and then the high-speed $ water-removing phase was cleaned and repeated twice to obtain Cleaning treatment of all substances and cleaning completion solution (NO3 · concentration, ρΗ, Ιη concentration, as shown in Table 7). 316907 41 200538394 Second, put this cleaning treatment completed substance into 360mL of water, and add concentrated sulfuric acid to adjust At pH 0.5, 500 mL of an acid-dissolved solution (N03 · concentration, pH, and In concentration, as shown in Table 7) was obtained after acid dissolution. Next, the temperature was controlled so that the acid-dissolved solution did not exceed 60 ° C. -Stir for 1 hour, filter with a suction filter to remove residues (undissolved solids), and recover the acid solution. Next, adjust the acid solution (pHO.7) and immerse it with a width of 100mm, a length of 300mm, and a thickness The 6mm nameplate was stirred while controlling the temperature to a liquid temperature of 50 ° C, and the substitution reaction was continued for 8 hours. Then, the sponge indium precipitated by the substitution reaction was recovered, and after removing moisture, it was used. Sodium hydroxide Alkali melting (300 ° C), and then remove the metal containing indium from the mold. The amount of sponge indium obtained (g), the amount of metal containing indium (g), the quality of In and the recovery of In , As shown in Table 7.

42 316907 200538394 [Table 7] Forming means Cleaning paper size (mm Φ) Filtration cleaning solution Acid dissolving solution sponge In (g) Metal NO containing In; (ppm) pH In concentration N03 · (ppm) pH In concentration _ ν〇3 · (ppm) PH In Concentration Obtained Amount (g) Quality (%) In Recovery (%) Example 28 Adding oxalic acid without 150 280000 0.6 3 — '— 3000 0.8 26 12.4 12.0 98 90 Example 29 Add oxalic acid 110 290000 0.7 3 — — 8500 0.8 26 12.2 11.8 98 89 Example 30 Likou oxalic acid 90 250000 0.7 3 — — 10000 0.8 29 13.0 12.0 98 85 Example 31 Likou oxalic acid 150 260000 0.7 3 16000 1.1 0.7 2700 0.8 26 12.7 12.3 98 93 Example 32 Timonic acid oxalic acid 110 230000 0.6 4 27000 1.1 0.6 6500 0.8 26 12.7 12.3 98 93 Comparative example 6 Ammonia neutral without 150 140000 4.0 0.1 Comparative example 7 Ammonia neutral with 150 140000 4.4 0.1 26000 5.2 &lt; 0.1 4600 0.6 27 11.9 11.6 97 83

In addition, the analysis result of the nitric acid solution containing indium will be as shown in Example 28. With the difference in In concentration of the nitric acid solution containing indium or the operation error, the In content in the acid solution will be found to be inconsistent (scattered). However, as shown in Table 7, it was found that if the content of nitric acid in the acid-dissolved solution concerning the In recovery rate is less than 1000 Oppm, In can be efficiently recovered. (Experiment 1: Relationship between the concentration of nitrate ions in the acid-dissolved solution and aluminum substitution precipitation) The effects of the concentration of nitrate ions in the acid-dissolved solution on the aluminum substitution precipitation reaction were examined. To 500 mL of the acid-dissolved solution obtained in the above Example 28, a predetermined amount of 14N nitric acid was added, and as shown in Table 8, the NCV concentration in the acid-dissolved solution was adjusted, and the substitution and precipitation were performed using an aluminum plate as in Example 28. However, 43 316907 200538394 was obtained by carrying out trials and prayers like 戸 and Example 28 to obtain a metal containing indium. At this time, the substitution precipitation reaction using ίLu plate was evaluated according to the following criteria. • ◎: Substitution precipitation is completed within 1 hour. -〇: Substitution precipitation was completed within 1 to 1.5 hours. △ ... Although replaced, the replacement has not been completed at the time of 2 hours. • X: Cannot be replaced. [Table 8] NO ^ (ppm) Replacement precipitation evaluation 3000 ◎ 4600 ◎ 7000 10000 15000 &quot; '--- 22000 29000 △ XV sponge In (g) 6.9 6.8 7 6.3 4.4 --------- 0 8 0 In contains metal (g) 6.7 6.4 6.8 5.5 2.7 0 0 As can be seen from Table 8, when a nitric acid solution containing indium is used as the starting material, in order to enable aluminum substitution precipitation reaction, nitric acid in the acid solution The ion concentration (ion concentration due to passivation formation) must be less than 220,000 ppm, preferably less than 15,000 ppm, and particularly preferably less than 10,000 ppm. [Brief description of the drawings] Fig. 1 is a flowchart illustrating the indium recovery steps in Examples 丨 to 18 and Comparative Examples 1 to 5. Fig. 2 is a flowchart illustrating the indium recovery steps in Examples i 9 to 27. Fig. 3 shows the X-ray diffraction pattern of the precipitate ⑷ immediately after precipitation, the precipitate b after the contact treatment (b), and the indium oxide (c) after baking. 316907 44

Claims (1)

200538394 X. The scope of Shenyin's patents ... 1. A method for making metals containing inscriptions] ▲ Also, clothing &amp; methods are used to make all ancient and earthy materials containing indium from an indium-containing solution containing indium. The mongolian method includes: forming indium saponate by cooperating oxalic acid as a precipitating agent in an indium-containing solution φ ,, e, and f; a step of cultivating; and The sinker of indium oxalate is subjected to a solid-liquid separation step. 2. If the method of manufacturing indium-containing metal in item 1 of the scope of patent application, the amount of oxalic acid when oxalic acid is mixed in indium ridge solution is 12 to 5 times the equivalent of the indium contained in the marriage solution . 3, the patent scope of the patent declaration! The method for producing a metal containing indium according to the item, wherein the pH of the indium-containing solution is adjusted to 2 or less before oxalic acid is mixed with 5 indium / mixture. 4. If you apply for patent 1¾ round! The method for producing a metal containing indium according to the item, wherein the indium solution is mixed before the oxalic acid is mixed in the indium solution. ) 11 Adjust below 0 · 5. _ 5. The manufacturing method of indium-containing metal according to the scope of the patent application, wherein the pH of the indium-containing solution after oxalic acid is mixed is set to 10 or less. 6. The method of manufacturing indium-containing metals such as the one in the scope of Shenyin patents is to preliminarily implement the dissolution of indium-containing materials in nitric acid to form a nitric acid solution containing indium, and to stand in the state of the nitric acid solution containing indium. Then, the tin precipitate contained in the nitric acid solution containing indium was removed. 7. The manufacturing method of indium-containing metal according to item 丨 of the application, wherein the indium-containing solution has a pH of 0.5 to 4.0, and the indium-containing solution is subjected to 316907 200538394 filtration to remove tin, and then in the indium-containing solution. Mix oxalic acid. 8. The method for manufacturing an indium-containing metal, as claimed in the scope of the patent, includes the step of baking the recovered indium oxalate. 9. The manufacturing method of indium-containing metal as stated in item 8 of the patent scope, wherein the baking temperature ranges from 0 to 120.00. 〇. .10. A method for producing a metal containing indium, comprising: a step of dissolving the recovered precipitate of indium oxalate in an acid to form an acid-dissolving solution; • putting a metal in the above-mentioned solution A step of generating sponge indium through a substitution reaction with the metal; and a step of obtaining a metal containing indium from the sponge indium. 11. The manufacturing method of indium-containing metal according to item 1G of the patent application scope, which includes the step of recovering the precipitation of indium oxalate by solid-liquid separation, ^ In the purification formation cause ion cleaning treatment step more than i times, the / step package 3 immersed the recovered grass indium in the liquid makeup which will not dissolve the button, so that it will be formed in the subsequent replacement precipitation step. The ionization reasons of the passivation +, and six jealousy> &amp; 丄 衣衣 ® Ion / combined in the liquid, and remove the dissolving solution; and the recovered indium oxalate sink is dissolved in the acid and The step of forming an acid-dissolving solution is replaced by a washing step: a step of forming a solution of the solution / purity obtained by ion cleaning treatment, and dissolving in an acid to form an acid-dissolving solution. 12 · If the manufacturer of the indium-containing metal in item 10 or 11 of the scope of patent application is 316907 46 200538394, ^, ^, ^ ',,,,,, indium-containing solution containing indium will be used. An indium-containing nitric acid solution in which an indium substance is dissolved in nitrate I, and hydrochloric acid is used in the preparation of an acid solution. 13. The manufacturing method of indium-containing metal according to item 1G or 11 of the scope of patent application, wherein the step of obtaining the metal containing caustic indium from sponge indium is passed, and the indium-containing metal is obtained by performing alkali melting casting of sea indium sponge. . 316907 47