JPS6219495B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention deals with Ge and (Ga and/or In) containing germanium (Ge) and gallium (Ga) and indium (In) at low concentrations, but also containing large amounts of metals other than Ge, Ga, and In. ) It relates to a method for recovering Ge, Ga, and In from trace amounts of substances (which may be solids, precipitates, or liquids) in a high yield and economically advantageous. Germanium, gallium, or indium may be distributed at low concentrations in sludge, smoke, or liquids from various metal smelting processes and other chemical processing processes, and these sludges and liquids may contain plays a major role as a source of germanium, gallium, or indium. However, this kind of sludge and liquid contains extremely large amounts of other metals, such as Fe, Al, Zn, As, Na, and other metals, compared to low concentrations of germanium, gallium, and indium. is normal. Ge and Ga, In sources such as Ge and
To give an overview of the industrial production methods that have been proposed and implemented in the past as methods for extracting Ga and In, they are metal smelting smoke, various residues after main metal collection, and solutions during the smelting process. The target raw materials are liquids and solids generated from other chemical processes.
When industrially extracting Ge, Ga, and In, which are mixed in small amounts in this, there are cases where all three of Ge, Ga, and In have an economical content, and sometimes only one or both of them have an economical content. In some cases, Ge is first separated (usually Ge is separated from Ga and In as sulfide from the leachate from which the raw material was leached, and this sulfide is recovered as germanium oxide by roasting or direct leaching distillation). After collecting this Ge, the following formulations were performed depending on whether the material was mainly Ga or In (and depending on the form of the raw material to be treated). First, industrial extraction of metallic gallium has mainly been carried out from aluminum smelting waste liquid or zinc smelting residue. In the case of waste liquid from aluminum smelting, alumina crystals are crystallized from a solution obtained by treating bauxite using the Bayer method, and after the alumina crystals are filtered out, the filtrate, which is a sodium aluminate solution, is treated. (1) A method of separating trace amounts of gallium contained in this solution in the form of crude hydroxide by blowing carbon dioxide gas into this solution (or by neutralizing it by adding an alkali agent). (2) A method has been implemented in which gallium is electrolyzed in this solution using a mercury cathode, and gallium is separated as a mixture with metallic mercury. In the case of zinc smelting residue, zinc leaching residue is obtained by leaching zinc burnt ore with sulfuric acid (in the case of wet zinc smelting method), or zinc concentrate is roasted with a reducing agent added to produce zinc. (3) Neutralize the gallium-containing solution obtained by acid leaching or alkali leaching of this residue in a strong acid or reducing atmosphere to obtain a solution containing gallium. A method has been used in which crude hydroxide is dissolved in concentrated hydrochloric acid to obtain a hydrochloric acid solution, and gallium is concentrated by performing liquid-liquid extraction from this solution using a solvent extraction method. However, the separation method using hydroxide (1) requires a very difficult filtration operation, and also requires a very difficult filtration operation.
When large amounts of Cu, Al, etc. coexist,
These hydroxides are produced in large quantities, making the processing operations complicated, and the resulting gallium also contains many other metals, making separation of these metals difficult. In addition, in the electrolysis method using a mercury cathode (2), in addition to the basic problem that this method cannot be used in solutions with a low gallium concentration or solutions mixed with organic matter due to the drop in current efficiency, there is also a loss of mercury. must also be taken into consideration. In the solvent extraction method (3), the solution to which this is applied is pretreated (neutralization method or concentrated alkali dissolution method).
Unless the gallium is concentrated, it will not be effective.
In the case of zinc smelting residue, which contains a large amount of Fe, Al, Cu, Zn, etc., it is difficult to use it industrially because the pretreatment is a heavy burden. On the other hand, industrial extraction of indium involves the use of weakly acidic solutions containing trace amounts of In generated from various processes. (3) A method in which metals such as Zn, Cd, Al, etc. are added to this weakly acidic solution to precipitate In as a hydroxide. (4) A method in which In is precipitated by displacement from this weakly acidic solution. There are methods to recover In by using sulfuric acid. A method has been implemented in which the resulting In-containing solution is subjected to hydrogen sulfide treatment and hydroxidation treatment, and then In is precipitated by substitution with metal Zn or Al. However, in methods (1) and (2), Cu, Fe, Zn,
If large amounts of As, Al, etc. coexist, a large amount of precipitates will be formed and the processing operations will be complicated, making it impossible to expect separation from other metals. Furthermore, in method (3), if a metal more noble than the additive metal coexists, it is impossible to separate the metal and In. In this respect, the solvent extraction method (4) has some advantages, as it can selectively separate In depending on the solvent used.
Although it is effective for separating certain metals from In,
There is no effective method for separating In from all metals, and when separating and concentrating In from a solution containing various metals, a large burden is placed on pretreatment in consideration of the properties of other metals. In addition, in the case of method (5), a trace amount of In is separated from a solution obtained by processing a substance containing a large amount of Cu, Fe, Zn, As, Al, etc., so there are many separation methods. It is no exaggeration to say that there was no economical method, as all conventional methods had complicated and complicated processes. The present invention was made with the aim of solving such problems in the conventional production of Ge, Ga, and In metals.For this purpose, the present inventors have conducted various tests and researches, and as a result, hereby, the above-mentioned findings have been made. Virtually all of the raw materials used in conventional industrial extraction of Ge, Ga, and In, as detailed in , can be used as target raw materials, and the problems mentioned above in various conventional methods can be solved at once. We were able to establish an industrial method for extracting Ge, Ga, and In from substances containing trace amounts of Ge and Ga or In. The present invention relates to a group of solid or liquid substances generated from various smelting processes and chemical processes, which contain Ge, Ga, and In, although in trace amounts.
This method targets virtually all substances containing trace amounts of Ge, Ga, and In that have been considered as sources of Ge, Ga, and In, but even if the source is the same, depending on the target substance, , Ge, Ga, and In may have an economic content, or even if Ge and Ga have an economic content, In may not reach the economic content, or vice versa. There are some raw materials that contain an economically sufficient amount of In but not enough Ga. In this way, since the present invention targets all raw materials whose contents vary in Ge, Ga, and In, in the following description of the present invention, Ge and Ga have economical contents, but In does not. The first invention is a method for recovering Ge and Ga from raw materials that do not reach an economical content, and uses raw materials that have an economical content of Ge and In but do not reach an economical content for Ga to be processed. The second invention is a method for recovering Ge and In as objects, and the second invention is a method for recovering Ge, Ga, and In from raw materials that have economic contents of Ge, Ga, and In as objects to be processed. This will be explained as 3 inventions. First, the first invention is a liquid obtained by dissolving a solid substance containing small amounts of Ge, Ga, and In in an acid, or a liquid generated from a metal smelting process or other chemical process.
A first step in which a solution containing Ge and trace amounts of Ga and In is used as a treatment stock solution, and this treatment stock solution is passed through a layer of chelating ion exchange resin at an acid concentration that can selectively adsorb Ge. The second step is to treat the resin that has passed through the process with an alkali to elute the resin-adsorbed substances.An acid is added to the eluate obtained in the second step to neutralize it, and the resulting precipitate is subjected to solid-liquid separation. In the third step, hydrochloric acid is added to the solid content, leaching distillation is carried out, and the distillate is hydrolyzed to recover germanium oxide. The fourth step is to pass the liquid through a layer of chelating ion exchange resin under a pH value that allows selective adsorption of Step, Ga electrowinning step of electrowinning Ga in this solution using the eluent obtained in the fifth step as a raw material. Ge consisting of Ge and Ga from substances containing trace amounts of In
and a method for recovering Ga and In. The second invention is a solution obtained by dissolving a solid substance containing a trace amount of Ge, Ga, and In with an acid, or a solution containing a trace amount of Ge, Ga, and In generated in a liquid form from a metal smelting process or other chemical process. year,
The first step is to pass this treated stock solution through a layer of chelating ion exchange resin at an acid concentration that allows Ge to be selectively adsorbed. In the second step, the eluent obtained in the second step is neutralized by adding acid, the resulting precipitate is separated into solid and liquid, hydrochloric acid is added to the separated solid content, leaching distillation is carried out, and The third step is to hydrolyze the effluent to recover germanium oxide, and the liquid that has passed through the chelating ion exchange resin layer in the first step is subjected to a pH value that allows Ga and In to be selectively adsorbed. a fourth step in which the liquid is passed through a layer of chelating ion exchange resin; a fifth step in which the resin after the fourth step is treated with mineral acid to elute the resin-adsorbed substance; Dissolved In,
A metal In precipitation step in which metal In is precipitated by substitution using a metal less base than In.
and a method for recovering Ga and In. Furthermore, the third invention is a solution obtained by dissolving a solid substance containing a trace amount of Ge, Ga, and In with an acid, or a solution containing a trace amount of Ge, Ga, and In generated in a liquid form from a metal smelting process or other chemical process as a raw solution. year,
The first step is to pass this treated stock solution through a layer of chelating ion exchange resin at an acid concentration that allows Ge to be selectively adsorbed. In the second step, the eluent obtained in the second step is neutralized by adding acid, the resulting precipitate is separated into solid and liquid, hydrochloric acid is added to the separated solid content, leaching distillation is carried out, and The third step is to hydrolyze the effluent to recover germanium oxide, and the liquid that has passed through the chelating ion exchange resin layer in the first step is subjected to a pH value that allows Ga and In to be selectively adsorbed. a fourth step in which the liquid is passed through a layer of chelating ion exchange resin; a fifth step in which the resin after the fourth step is treated with mineral acid to elute the resin-adsorbed substance; Dissolved In,
An In precipitation step in which In is precipitated by substitution using a metal less noble than In, and a Ga electrowinning step in which Ga is electrolytically extracted from the liquid using the liquid after collecting In in the above-mentioned In precipitation process as a raw material. Ge consisting of Ge and Ge from substances containing trace amounts of Ga and In
and a method for recovering Ga and In. In any of the first to third inventions, the first step to the fifth step are substantially the same. Therefore, the details of these common first to fifth steps will be explained first. [First step] This first step is performed using a liquid obtained by dissolving a solid material containing a small amount of Ge and Ga (and/or) In with an acid, or using Ge and Ga generated in liquid form from metal smelting and other chemical processes. (and/or) This is a step in which a solution containing a trace amount of In is used as a treatment stock solution, and this treatment stock solution is passed through a layer of chelating ion exchange resin at a free acid concentration that allows Ge to be selectively adsorbed. Here, the solid substance containing small amounts of Ge, Ga, and In is raw material minerals themselves such as bauxite, germanite, and zinc ore, or
Refers to smoke ash, smelting residue, coal ash, etc. generated from the smelting process of these or other minerals, including Zn,
It refers to a group of substances containing at least two or more of Fe, Al, As, Ni, Cd, etc., several tens to hundreds of times or more than Ge, Ga, and In.
In addition to those previously used as Ge, Ga, and In extraction sources, Ge, Ga, and In
This also includes those containing trace amounts of. In addition, liquids containing trace amounts of Ge, Ga, and In generated in liquid form from metal smelting processes and other chemical processes are used in metal smelting and chemical processes whose main purpose is not to extract Ge, Ga, or In. During the process, liquids that contain the main substance but also contain trace amounts of Ge, Ga, In, etc., such as electrolytic solutions for main metal electrolytic refining, or liquids that contain the main substance but contain other metal ions It refers to secondary liquids and waste liquids that contain large amounts of Ge, Ga, and In as well as trace amounts of Ge, Ga, and In. The present invention targets these substances containing trace amounts of Ge, Ga, and In (some solid and some liquid) that occur in various places.
If it is in solid form, it is treated with acid.
As this acid, it is preferable to use sulfuric acid, which is inexpensive. At that time, one step of leaching is performed at normal temperature and pressure so that the free sulfuric acid concentration after leaching with sulfuric acid is 10 (g/) or more, and the leachate (treated stock solution in the present invention) is collected by filtration. good. Furthermore, for solid materials containing a large amount of calcium, such as carbonate minerals, it is better to use hydrochloric acid. One step of leaching may be carried out, followed by filtration and separation to collect the leachate (the treated stock solution in the present invention). The processing stock solution used in the present invention is thus prepared.
A liquid containing a small amount of Ge, Ga, and In dissolved in an acid, or a liquid containing a small amount of Ge, Ga, and In that is generated in liquid form from metal smelting and other chemical processes, but in addition to a certain amount of Ge. contains about 0.01 to 1 (g/) of Ga or In, and this
Metal ions other than Ge, Ga, and In, such as Zn,
The treatment target is a liquid in which metal ions such as Fe, Al, As, Ni, Cd, etc. coexist alone or in total at 2 to 70 (g/) or more. If In in this treatment stock solution is 0.01 (g/) or less, the first
invention, when Ga in this treatment stock solution is 0.01 (g/) or less, the second invention, and when both Ga and In in this treatment stock solution are 0.01 (g/) or more, the third invention It is a good idea to carry out the following. In the first step, this treated stock solution is passed through a layer of chelating ion exchange resin at an acid concentration that allows Ge to be selectively adsorbed. The chelating ion exchange resin used here has the general formula, for example, However, M is an alkali metal or hydrogen, and R ₁ or R ₂ is hydrogen or an alkyl group having 1 to 3 carbon atoms. Can be used. Such a resin itself is known as an ion exchange resin capable of reducing the concentration of iron ions in an acidic electrogalvanizing bath, for example, in Japanese Patent Application Laid-Open No. 121241/1983, and is also known under the trade name Uniselect UR-50 (Unitika Co., Ltd.). It is commercially available as (manufactured by). It is known that such chelating ion exchange resins (particularly chelating ion exchange resins having aminocarboxylic acid groups) have the ability to selectively adsorb Ge from liquids containing extremely large amounts of various metal ions other than Ge. In this case, the concentration of free sulfuric acid in the treated stock solution should be adjusted to 10 (g/) or more and 100 (g/) or less, preferably 30 to 60 (g/). do. As mentioned above, when the sulfuric acid leachate is used as the processing stock solution, it is possible to obtain a solution that satisfies this free sulfuric acid concentration as it is, and the processing stock solution is originally an acidic solution with this acid concentration that can be used for metal smelting. If obtained from a process or chemical process, this acid adjustment may not be necessary. In addition, when trivalent iron ions coexist in this treatment stock solution, it is preferable to reduce the sulfur dioxide gas to divalent iron ions in advance using a reducing agent such as sodium bisulfite. When passing the treatment stock solution through the resin, the exchange tower filled with the resin must have a space velocity (hereinafter simply referred to as SV) of 5.0 or less,
Preferably, the liquid is passed at a rate of 1.0 to 3.0.
As a result, only Ge in the treatment stock solution is selectively adsorbed to this resin. At this time, the appropriate temperature for contacting the resin is 10 to 50°C, preferably 20 to 30°C. Figure 1 shows the relationship between the free sulfuric acid concentration of the treated stock solution and the amount of Ge adsorbed onto the resin. The data obtained when the solution was passed shows that Ge is well adsorbed when the free sulfuric acid concentration is 30 to 60 (g/). In addition, Fig. 2 contains 5 to 20 (g/) of each of zinc, iron, aluminum, and arsenic, and
Sulfur dioxide gas is blown into a sulfuric acid acidic solution (free sulfuric acid concentration: 50 g/) containing trace amounts of Ge, Ga, and In to reduce trivalent iron to divalent iron, and then the chelating ion exchange resin is heated at S.V2.0. This figure shows the relationship between the amount of liquid passed through and the flow-through point, and it can be seen from this that Ge is selectively adsorbed by the resin from this mixed solution under predetermined conditions. [Second Step] The second step is a step in which the resin that has undergone the first step is treated with an alkali to elute the resin-adsorbed substance.
As mentioned above, in the first step, this resin has
Ge is selectively adsorbed from other metal ions.
This can be easily eluted using an alkali such as sodium hydroxide. However, it is difficult to recover Ge by elution using mineral acids. When eluting with sodium hydroxide,
It is best to use 3N to 4N. At that time, it is possible to reduce the sodium hydroxide concentration by adding soda carbonate, sodium chloride, etc.
Industrially, it is preferable to use only sodium hydroxide. By this elution, it is possible to obtain a Ge-containing solution having a low concentration of metal ions other than Ge and containing about 0.01 to 1 (g/) or more of Ge. FIG. 3 shows an elution curve when Ge adsorbed on the resin was eluted from the treated stock solution with 4N-NaOH. This figure shows that Ge is well eluted. In addition, if 1N to 3N sulfuric acid is passed through the resin before elution with this alkali,
Impurities in the resin can be removed more effectively than water pressing, reducing impurities in the eluent and producing a purer product.
Ge can be recovered. [Third Step] This step is a step of recovering Ge as germanium oxide from the eluent obtained in the second step. In this case, it is advantageous to obtain an eluent with a high Ge concentration, but in accordance with the elution curve shown in Figure 3, the flow volume with a high Ge concentration is first collected, and the remaining thin portion is used as the re-eluent. It is preferable to adopt a formulation in which the resin is circulated through the resin. In this way, a Ge-containing alkaline solution with a Ge concentration of about 0.01 to 1 (g/) is obtained, but in order to recover the Ge in this alkaline solution, first add hydrochloric acid to neutralize it and form a precipitate. let Figure 4 shows the relationship between the pH of the liquid and the precipitation rate of sodium germanate (Na ₂ GeO ₃ ), and it can be seen that when the pH value is around 9, the solubility of sodium germanate is at its minimum and precipitation occurs well. I understand. Once this precipitate is generated, after solid-liquid separation, hydrochloric acid is added to the solid content, leaching distillation is carried out, and the distillate is hydrolyzed to recover high-purity germanium oxide as shown in the example below. be able to. Note that it is also possible to add hydrochloric acid to this alkaline solution to neutralize it and then distill it, but in this case, the amount of liquid will be large and the concentration of hydrochloric acid will be high, so the method described above, which involves first forming a precipitate and then concentrating it, is not suitable. This is what I want. [Fourth step] In the fourth step, the liquid that has passed through the resin layer in the first step (tail liquid) is used as a stock solution, and this stock solution is added to Ga and In.
This is a step in which the liquid is passed through a layer of chelating ion exchange resin similar to the first step under a pH value that allows selective adsorption of . The chelating ion exchange resin
It was discovered that this product has the ability to selectively adsorb Ga and In from a solution containing extremely large amounts of various metal ions other than Ga and In. ~4.0, preferably 1.5~
It is important to adjust it so that it is 3.0. This pH value can be easily adjusted by adding a necessary amount of a neutralizing agent to the resin passing through the first step. At this time, if a process of reducing trivalent iron ions using a reducing agent has already been performed in order to effectively recover Ge, this reduction process can be omitted in the fourth step. When passing the stock solution (tail liquid of the first step) through the resin, the rate is such that the space velocity (SV) is 5.0 or less, preferably 0.5 to 1.5 through the exchange tower filled with the resin. Pass the liquid through. This allows the concentration of
Only Ga and In are selectively adsorbed on this resin. The contact temperature to the resin at that time is 10 to 50.
℃, preferably 35 to 45℃ is suitable. Figure 5 shows the pH value of the stock solution and the concentration of Ga and resin in the resin.
This figure shows the relationship between the adsorption amount of In and the stock solution was put into an exchange column filled with the chelating ion exchange resin using S.
This is data when fluid was passed at V5.0 or lower, but the PH
It can be seen that both Ga and In are well adsorbed when the value is between 1.0 and 4.0. Also, Figure 6 shows that each contains about 5 to 20 (g/) of zinc, iron, aluminum, and arsenic.
After adjusting the sulfuric acid acidic solution containing trace amounts of Ga and In to PH2.8 and adding sodium bisulfite to maintain the reducing property of the solution, the solution was passed through the chelating ion exchange resin at S.V1.0. This shows the relationship between the amount of liquid passed and the flow-through point, and it can be seen from this that Ga and In are selectively adsorbed by the resin from this mixed solution under predetermined conditions. [Fifth Step] The fifth step is a step of treating the resin that has passed through the fourth step with a mineral acid to elute the resin-adsorbed substance. As mentioned above, in the fourth step, this resin contains
Ga and In ions are selectively adsorbed from other metal ions. This can be easily eluted using mineral acids such as sulfuric acid or hydrochloric acid. In the case of sulfuric acid, 1 to 6N, preferably 3 to 6N
4N, in the case of hydrochloric acid, 1 to 6N, preferably 2 to 3N
It is recommended to use one with a concentration of Due to this elution, the concentration of metal ions other than Ga and In is low, and Ga,
A Ga and In-containing solution containing In on the order of 0.01 to 1 (g/) or more can be obtained. Once this eluent is obtained, it is used in the adsorption step (fourth step) from the previously treated stock solution (tail liquid of the first step).
Similarly, the pH value of this eluent is adjusted to 1.0 to 4.0, preferably 1.5 to 3.0, and if necessary, trivalent iron ions are reduced to divalent iron ions with a reducing agent, and then By passing the liquid through a bed of the same chelating ion exchange resin (exchange tower filled with this resin) at an S.V of 5.0 or less, preferably S.V 1.0 to 3.0, Ga is added to this resin. By repeating the steps of re-adsorbing In and eluting it again with a mineral acid, the concentration of metal ions other than Ga and In in the eluent can be further reduced. The mineral acid used for this repeated elution is the same as in the previous case, for example, in the case of sulfuric acid, 1 to
6N preferably 3-4N, in the case of hydrochloric acid 1-6N
Preferably, a concentration of 2 to 3N can be used, and the concentration of Ga and In in this eluent is 0.1 to 50
(g/) can be achieved. The amount of metal ions other than Ga and In in this eluent becomes extremely small, and only Ga and In are separated and concentrated. Figure 7 shows the pH of the eluent obtained in the case of Figure 6.
The figure shows the relationship between the amount of liquid passed and the flow point when the liquid was passed through the layer of the chelating ion exchange resin at S.V2.0 after adjusting the value to 2.8. From the same figure, Ga, In
is selectively adsorbed by this resin, and in the eluent, Ga and In are concentrated, and the concentration of other metal ions is reduced. FIG. 8 shows an elution curve when gallium or indium adsorbed on the resin is eluted from the eluent with 2N hydrochloric acid. Ga obtained through the first, second, third, fourth and fifth steps as described above,
The eluent containing In may be used in subsequent steps slightly depending on the difference in the concentration of Ga and In in this eluent (and in turn, depending on the variation or difference in the Ga and In content in the stock solution in the first step). Processed under different manners. These will be explained individually below. "Case of the first invention" This is a case where the Ga concentration in the eluent obtained in the fifth step is sufficient, but the In concentration is so small that it has no economic value. Using the eluent obtained in the process as a raw material, metallic Ga is extracted from Ga in this liquid by electrowinning. At that time, although it is possible to directly subject this eluent to electrolysis (however, the pH should be adjusted appropriately), it is necessary to neutralize Ga ions and other metal ions in this eluent through neutralization treatment. It is also a good idea to adopt a method that separates waste. Figure 9 shows the relationship between the pH of the liquid and the precipitation rate of Ga hydroxide.
Ga precipitates well, but it can be seen that Ga dissolves even if the concentration is lower or higher than this. Therefore, for example, if iron ions coexist (as shown in the figure, since iron precipitates at a pH value of 5 or higher), an alkaline agent should be added to the eluent to raise the pH value to, for example, 10 or higher. (in the process, even if Ga precipitates once, it redissolves) to form a precipitate of iron hydroxide, which is filtered out, and then, for example, sulfuric acid is added to the solution to adjust the pH value to 5 to 8. When a precipitate of Ga hydroxide is formed by summing and the precipitate is filtered, iron ions entrained in the eluent can be separated and removed, and Ga can be concentrated. The obtained precipitate of Ga hydroxide may be redissolved by adding an alkaline agent such as sodium hydroxide, and the resulting solution may be provided as an electrolyte for Ga electrolysis. If there are not many metals other than Ga such as iron ions remaining in the eluent, add an alkaline agent to the eluent and directly adjust the pH value to 5 to 8 without performing reverse neutralization. Ga can be purified and concentrated by neutralization treatment to form a precipitate of Ga hydroxide, which can then be dissolved with an alkali and subjected to electrolysis. As a result, as shown in Examples below, highly purified metallic Ga can be collected at an extremely high yield. "In the case of the second invention" This is a process to be applied when the eluent obtained in the fifth step has a sufficient concentration of In. In, In
Indium sponge is collected by replacing and depositing metal In from a liquid using a more base metal. In other words, in the second invention, depending on the acid concentration of the eluent, the eluent is PH'd with a mineral acid, such as sulfuric acid or hydrochloric acid.
is 2.0 or less, and an indium sponge is obtained by adding powdered or plate-shaped metals less noble than In, such as zinc and aluminum, in an amount of 1 to 3 equivalents to In, to this acidic solution. At that time, before this displacement precipitation, more specifically, before pH adjustment, metals other than indium are precipitated by blowing hydrogen sulfide gas into the liquid, and this is filtered out from the liquid. If you use , you can easily purify the liquid,
This makes it possible to increase the purity of the indium sponge in the displacement precipitation step. This collected spongy indium can be melted and cast into an anode as needed, and if this is subjected to electrolytic refining, it is possible to produce In metal with even higher purity. “In the case of the third invention” This is because Ga in the eluent obtained in the fifth step
This process is applied when both In concentrations are sufficient. First, the In dissolved in this eluent is precipitated by displacement using a metal less noble than In, and an indium sponge is collected. The tail liquid (liquid after indium extraction) is used as a raw material to collect Ga in this liquid.
By going through the process of extracting metal Ga as metallic Ga using an electrowinning recipe, both metallic In and metallic Ga can be extracted at high yields. At that time, the collection process of the In sponge can be performed in the same manner as explained in the second invention, and the collected Indium sponge can be electrolytically refined to produce even higher purity metal In. .
In Ga electrolysis, the tail liquid after In substitution precipitation is used as the stock solution, and an alkaline agent is added to this liquid to raise the pH value to 5~5.
If the temperature is adjusted to 8, Ga hydroxide will precipitate as shown in Figure 9.
A formulation in which a precipitate of Ga hydroxide is generated, the precipitate is separated by filtration, and then this Ga hydroxide is dissolved in sodium hydroxide again to form a Ga electrolyte, or the PH of the tail liquid is 10 or more. Add an alkaline agent to produce a precipitate of metals other than Ga, such as iron, and filter this out, then reverse neutralize the filtrate with sulfuric acid to a pH of 5 to 8 to produce a precipitate of Ga hydroxide. Highly purified metallic Ga can be electrolytically extracted by filtering the Ga hydroxide and dissolving it again in sodium hydroxide to form a Ga electrolyte. In addition to the first to third inventions described above, methods A and B listed below can also be adopted as methods for separating and recovering Ga and In in the eluent obtained in the fifth step. [Method A] This method involves the steps of adding an alkaline agent to the eluent containing Ga and In obtained in the fifth step to adjust the pH to form a precipitate, and separating this solid-liquid. The solid content obtained in the liquid separation process is dissolved in acid, and a metal less base than In is added to this acidic solution to produce In.
The In precipitation step involves displacement precipitation of Ga. An acid is added to the liquid obtained in the solid-liquid separation step to form a precipitate, which is dissolved with an alkali to form Ga.
It consists of an electrolytic process of electrowinning. [Otsu method] In this Otsu method, the eluent containing Ga and In obtained in the fifth step is subjected to solvent extraction treatment using an organic solvent for Ga extraction, and then separated into an organic phase and an aqueous phase.
A Ga extraction step in which Ga in the organic phase is back-extracted into water; an electrolytic step in which the Ga aqueous solution obtained in this Ga extraction step is made alkaline to electrolytically collect metallic Ga; and an organic solvent for Ga extraction in the Ga extraction step. The aqueous phase separated after solvent extraction using an organic solvent is separated into an organic phase and an aqueous phase after solvent extraction using an organic solvent for In extraction, and the In ions in this organic phase are dissolved in water. This process consists of an In extraction step in which an In aqueous solution is obtained by back extraction, and an In substitution precipitation step in which a metal less noble than In is added to the In aqueous solution obtained in this In extraction step to precipitate metal In by displacement. As explained above, the present invention provides an economical and high-yield method that can be used to expand the range of raw materials to be processed, instead of the industrial production methods for Ge, Ga, and In, which have had various problems in the past. Methods for producing Ge, Ga, and In are provided. Examples are given below, and Example 1 corresponds to the third invention, Example 2 corresponds to the first invention, and
Example 3 corresponds to the second invention. The chelating ion exchange resin used in each example was a resin with the trade name Uniselect UR-50 (manufactured by Unitika Co., Ltd.). In addition, this compound has M, R ₁ and R ₂ as a compound of the above general formula.
It is obtained by three-dimensionally crosslinking a compound in which both are hydrogen with phenol as the phenol and formaldehyde as the aldehyde. Example 1 In this example, as the composition is shown in Table 1,
Contains a lot of Zn, Al, Fe, As, Ge, Ga, In
The following is an example in which Ge, Ga, and In were separated and recovered using a material from an intermediate smelting process that contains a small amount of Ge as a raw material.

[Table] Sulfuric acid was added to the raw materials shown in Table 1 to obtain a leachate whose composition is shown in Table 2. The free sulfuric acid concentration in this leachate was about 50 (g/).

[Table] After blowing sulfur dioxide gas into the leachate shown in Table 2 to reduce iron, the liquid was passed through a column filled with chelating ion exchange resin at SV = 2, and only germanium was selectively adsorbed to this resin. . Analysis of the passed-through liquid revealed that Ga, In, Zn, Al, Fe, and As were hardly adsorbed, and that Ge was adsorbed at almost 100%. Next, the Ge adsorbed on this resin was added to 160 (g/
)-NaOH at SV=1 to obtain an eluent having the composition shown in Table 3.

[Table] As shown in Table 3, when eluting with 160(g/)-NaOH, approximately 100% of the Ge adsorbed on the resin
% can be recovered. Next, hydrochloric acid was added to the eluent shown in Table 3 to adjust the pH to about 9, and the resulting precipitate was filtered out, and the filtered sodium germanate was leached and distilled with hydrochloric acid to obtain germanium chloride, which was further hydrolyzed. 99% purity
The above amount of germanium oxide was recovered. On the other hand, when the leachate shown in Table 2 was passed through the resin, the tail liquid that passed through the resin had the composition shown in Table 4.

[Table] This resin-filtered tail liquid was used as a treatment stock solution, which was neutralized with calcium carbonate to a pH value of 2.0. After filtering out the precipitate, an alkali agent was added to the solution again.
After adjusting the pH value to 2.5 and adding sodium bisulfite to maintain the reducibility of the solution, this solution was transferred to a column packed with a chelating ion exchange resin.
A liquid was passed through the resin at V1.0, thereby allowing Ga and In to be selectively adsorbed onto the resin. Next, 3N sulfuric acid was used to elute the gallium and indium adsorbed on the resin. The composition of the obtained eluent (referred to as separation liquid) is shown in Table 5.

[Table] Hydrogen sulfide gas was blown into the separated liquid shown in Table 5, and the resulting precipitate was filtered off. Zinc powder was added in an amount of 2 equivalents to indium to obtain an indium sponge. The collected indium sponge was melted to make an indium anode, and electrolytically purified to obtain metallic indium with a purity of 99.9% or higher. On the other hand, an alkaline agent was added to the indium sponge fractionated liquid to adjust the pH to 10 or higher, and the formed precipitate was filtered off. Sulfuric acid was added to the filtrate to reverse neutralize it, and the formed gallium hydroxide was collected by filtration. Sodium hydroxide is added and dissolved in this gallium hydroxide, and this is used as an electrolyte to perform electrowinning of Ga, and the purity is determined.
More than 99.9% metallic gallium was obtained. Example 2 In this example, carbonate minerals having the composition shown in Table 6 were used as raw materials, and trace amounts of germanium and gallium contained therein were recovered.

[Table] By leaching with the raw materials shown in Table 6 and hydrochloric acid, almost 100% of Ge and Ga were leached. The free hydrochloric acid concentration in the leachate was approximately 80 (g/). After blowing sulfur dioxide gas into this leachate to reduce iron, the liquid was passed through a column filled with a chelating ion exchange resin at SV = 2 to selectively adsorb only Ge. Analysis of the passing liquid revealed Ga, Cu, Zn, Fe, Pb,
It was found that almost no As was adsorbed, and almost 100% of Ge was adsorbed. Ge adsorbed on this resin is 160g/-NaOH
Elution was performed using SV=1. The composition of the obtained eluent is shown in Table 7.

[Table] From the results in Table 7, it can be seen that when elution is performed using 160 g/-NaOH, substantially all of the Ge adsorbed on the resin is eluted. Next, hydrochloric acid was added to the eluent shown in Table 7 to adjust the pH to about 9, and the resulting precipitate was filtered out. The filtered sodium germanate was leached and distilled with hydrochloric acid to obtain germanium chloride, which was further hydrolyzed. 99% purity
The above amount of germanium oxide was recovered. On the other hand, when the leachate of the raw materials listed in Table 6 was passed through the resin as described above, the tail liquid that had passed through the resin had the composition shown in Table 8.

[Table] Using this resin-filtered solution as a stock solution, neutralize it with calcium carbonate to make the pH value 2.0, filter out the precipitate, and then add sodium hydrogen sulfite to the solution to reduce its reducibility. After keeping this solution,
In a column packed with chelating ion exchange resin,
A liquid was passed through the resin at S.V 1.0, thereby allowing Ga to be selectively adsorbed onto the resin. Next, gallium adsorbed on this resin was eluted using 2N hydrochloric acid. The composition of the obtained eluent (referred to as separation liquid) is shown in Table 9.

[Table] Hydrogen sulfide gas is blown into the separated liquid in Table 9, and the resulting precipitate is filtered out. An alkaline agent is added to the liquid to adjust the pH value to 2.8, and sodium sulfite is added to this liquid. Maintained reducibility. Then, this solution was again passed through a column packed with a chelating ion exchange resin at SV=2, and Ga was selectively adsorbed onto this resin. Next, Ga adsorbed on the resin was eluted using 2N hydrochloric acid. The composition of the obtained eluent (concentrate) is shown in Table 10.

[Table] Add an alkaline agent to the concentrated liquid in Table 10 to adjust the pH.
10 or more, and the precipitate formed was filtered off, and sulfuric acid was added to the filtrate for reverse neutralization to form a precipitate of gallium hydroxide, which was collected by filtration. Sodium hydroxide was added and dissolved in this gallium hydroxide, and this solution was used as an electrolyte to perform electrowinning of Ga, yielding metallic Ga with a purity of 99.9% or higher. Example 3 In this example, germanium and indium were recovered from a solution discharged from a smelting process, the composition of which is shown in Table 11.

[Table] After reducing iron by blowing sulfur dioxide gas into the solution in Table 11, the solution is passed through a column packed with chelating ion exchange resin at SV=2, and only Ge is selectively adsorbed by this resin. I let it happen. Analysis of the passing liquid revealed that In, Zn, Al, Fe, and Cd were hardly adsorbed, and Ge
It was found that almost 100% of was adsorbed. Next, 120g/- of Ge adsorbed on the resin was added.
Elution was performed with NaOH at SV=1. The composition of the obtained eluent is shown in Table 12.

[Table] Next, hydrochloric acid was added to the eluent shown in Table 12, the pH was adjusted to about 9, and the precipitate formed was separated by filtration, and the filtered sodium germanate was leached and distilled with hydrochloric acid to obtain germanium chloride. Hydrolyzed to 99% purity
The above amount of germanium oxide was recovered. On the other hand, when the solution in Table 11 is passed through the resin as described above, the tail liquid that has passed through the resin is
It had the composition shown in the table.

[Table] Table 13 shows that calcium carbonate is added to the solution and the pH is 2.0.
After that, ammonia water was added to adjust the pH to 2.5. After adding sodium bisulfite to maintain the reducibility of the solution, this solution is passed through a column packed with a chelating ion exchange resin at S.V1.0, thereby removing indium from the resin. was selectively adsorbed to. The indium adsorbed on the resin was then eluted using 3N hydrochloric acid. The composition of the obtained eluent (this is called the separation liquid) is
I made 14 tables.

[Table] Add alkali to the separated liquid in Table 14 to adjust the pH.
2.5, add sodium bisulfite to maintain the reducibility of the solution, pass the solution through a column packed with the chelating ion exchange resin using S.V2 to selectively adsorb indium, and then add 3N of sulfuric acid to obtain an indium concentrate whose composition is shown in Table 15.

[Table] Add 2 equivalents of zinc dust to indium to the concentrated solution in Table 15 to obtain an indium sponge, collect it, melt it, make an indium anode, and use it for electrolytic refining to achieve a purity of 99.99%. Metallic indium was obtained.

[Brief explanation of the drawing]

Figure 1 is a diagram of the relationship between the acid concentration of the treated stock solution and the amount of Ge adsorbed onto the chelating ion exchange resin, and Figure 2 is
Contains high concentrations of Zn, Fe, Al, As, Ge and Ga,
Acidic sulfuric acid solution containing a trace amount of In (free sulfuric acid 50g/
) is passed through a chelating ion exchange resin after maintaining its reducing property.
Elution curve diagram when Ge is eluted with 4N-NaOH,
Figure 4 is a relationship diagram between the pH of the solution and the precipitation rate of sodium germanate, Figure 5 is a relationship diagram between the PH value of the treated stock solution and the amount of Ga and In adsorbed to the resin, Figure 6 is the amount of solution when a dilute solution of Ga and In containing high concentrations of zinc, iron, aluminum, and arsenic is passed through a chelating ion exchange resin after adjusting the pH and maintaining reducing properties. Figure 7 shows the relationship between the flow rate and flow point when a certain amount of eluent is passed through a chelating ion exchange resin after adjusting the pH of the eluent and maintaining reducing properties. , Figure 8 shows the adsorption-treated chelating ion exchange resin.
FIG. 9 is a diagram showing the relationship between the elution amount and Ga and In in the elution curve when eluting with 2N hydrochloric acid. FIG. 9 is a diagram showing the relationship between the pH value of the liquid and the hydrolysis of gallium and trivalent iron.

Claims (1)

[Claims] 1. A liquid obtained by dissolving a solid substance containing small amounts of Ge, Ga, and In in an acid, or Ge and Ga generated in liquid form from a metal smelting process or other chemical process,
The solution containing a trace amount of In is used as a processing stock solution, and this processing stock solution is
A first step in which the liquid is passed through a layer of chelating ion exchange resin at an acid concentration that allows Ge to be selectively adsorbed.A second step is in which the resin that has gone through the first step is treated with an alkali to elute the resin-adsorbed substances. Step: Add acid to the eluent obtained in the second step to neutralize it, separate the resulting precipitate into solid and liquid, add hydrochloric acid to the separated solid content, perform leaching distillation, and hydrolyze the distillate. The third step is to recover germanium oxide using a chelating ion exchange resin under a pH value that allows selective adsorption of Ga and In. a fourth step of passing the liquid through the layer; a fifth step of treating the resin after the fourth step with mineral acid to elute the resin-adsorbed substances; Ga electrowinning process where Ga is electrolytically extracted. Ge consisting of Ge and Ge from substances containing trace amounts of Ga and In
and Ga, In recovery methods. 2 Ge, Ga, and In liquids obtained by dissolving solid substances containing trace amounts of In in acid, or Ge and Ga generated in liquid form from metal smelting processes and other chemical processes;
The solution containing a trace amount of In is used as a processing stock solution, and this processing stock solution is
A first step in which the liquid is passed through a layer of chelating ion exchange resin at an acid concentration that allows Ge to be selectively adsorbed.A second step is in which the resin that has gone through the first step is treated with an alkali to elute the resin-adsorbed substances. Step: Add acid to the eluent obtained in the second step to neutralize it, separate the resulting precipitate into solid and liquid, add hydrochloric acid to the separated solid content, perform leaching distillation, and hydrolyze the distillate. The third step is to recover germanium oxide using a chelating ion exchange resin under a pH value that allows selective adsorption of Ga and In. a fourth step in which the liquid is passed through the layer; a fifth step in which the resin after the fourth step is treated with mineral acid to elute the resin-adsorbed substance; and In dissolved in the eluent obtained in the fifth step,
A metal In precipitation step in which metal In is precipitated by substitution using a metal less base than In.
and Ga, In recovery methods. 3 Ge, Ga, and liquids containing small amounts of In dissolved in acid, or Ge and Ga generated in liquid form from metal smelting processes and other chemical processes.
The solution containing a trace amount of In is used as a processing stock solution, and this processing stock solution is
A first step in which the liquid is passed through a layer of chelating ion exchange resin at an acid concentration that allows Ge to be selectively adsorbed.A second step is in which the resin that has gone through the first step is treated with an alkali to elute the resin-adsorbed substances. Step: Add acid to the eluent obtained in the second step to neutralize it, separate the resulting precipitate into solid and liquid, add hydrochloric acid to the separated solid content, perform leaching distillation, and hydrolyze the distillate. The third step is to recover germanium oxide using a chelating ion exchange resin under a pH value that allows selective adsorption of Ga and In. a fourth step in which the liquid is passed through the layer; a fifth step in which the resin after the fourth step is treated with mineral acid to elute the resin-adsorbed substance; and In dissolved in the eluent obtained in the fifth step,
An In precipitation step in which In is precipitated by substitution using a metal less noble than In, and a Ga electrowinning step in which Ga is electrolytically extracted from the liquid using the liquid after collecting In in the above-mentioned In precipitation process as a raw material. Ge consisting of Ge and Ge from substances containing trace amounts of Ga and In
and Ga, In recovery methods.