JPS59208031A - Production of metallic ga and in from material containing trace of ga and in - Google Patents

Abstract

PURPOSE:To obtain industrially Ga and In with a relatively simple stage by adsorbing a trace of Ga and In in an original liquid to be treated on an ion exchange resin and electrolyzing the eluate by the mineral acid thereof. CONSTITUTION:A liquid contg. a trace of Ga or In produced by dissolving a solid material with an acid or produced from metal refining or other chemical process is used as an original liquid to be treated and is passed through a chelate type ion exchange resin at the pH value at which Ga and In can be selectively adsorbed. The resin is then treated with a mineral acid to elute the materials adsorbed on the resin, by which the eluate contg. Ga and In is obtd. If the adsorption and elution are repeated, the other metallic ions are made slight. Said eluate is electrolyzed and Ga in the liquid is obtained as metallic Ga. A metal more base than In is otherwise added to the eluate and In in the liquid is deposited as metallic In. The liquid after the deposition is electrolyzed and metallic Ga is obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention is directed to the use of Ga and lnin-containing materials (solids and sludge) that contain gallium (Ga) and indium (In) at low concentrations, but also contain large amounts of metals other than gallium or indium. metal G
The present invention relates to a method for producing a and metal In in a high yield and economically advantageously.

Gallium or indium may be distributed at low concentrations in sludge, ash, or liquids from various metal smelting processes or other chemical processing processes, and these sludges or liquids may contain gallium or indium. It also plays a major role as a source of indium. However, this kind of sludge or liquid contains extremely large amounts of metals other than gallium or indium9, such as Fe, AI, Zn, As, Na, and other metals, compared to low concentrations of gallium or indium. There is a commuter seat.

As a method of extracting gallium or indium from such gallium or indium sources.

To give an overview of the industrial manufacturing methods that have been proposed and implemented in the past, they include metal smelting smoke, various residues after main metal recovery, solutions during the smelting process, and other liquids generated from chemical processes. When industrially extracting small amounts of Ga and In from solid materials, etc.,
Ga and In may both have an economical content, or one may have an economical content, and generally it depends on whether the content is mainly Ga or In (and depending on the form of the raw material to be processed). ) The main manufacturing method was as follows.

First, industrial extraction of metallic gallium is mainly done.

This was done from aluminum smelting waste liquid or zinc smelting residue. In the case of aluminum smelting waste liquid, alumina crystals are crystallized from a solution obtained by processing bauxite by the Bayer process, and the alumina crystals are filtered out. The target is a sodium aluminate solution, which is a liquid.

(1) A method of separating trace amounts of gallium contained in this solution in the form of crude hydroxide by blowing carbon dioxide into this solution (or by neutralizing it by adding an alkali agent).

(2) A method has been implemented in which this solution is subjected to Gallium J. electrolysis using a mercury cathode to separate gallium 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 and zinc is distilled. The target is the collected residue (in the case of pyrometallurgical zinc smelting).

(3) Neutralize the gallium-containing solution obtained by leaching or alkali leaching this residue in a strong acid or reducing atmosphere,
A method has been used in which the produced crude hydroxide containing gallium is dissolved with concentrated hydrochloric acid to form 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 hydroxides in (1) requires a very difficult filtration operation, and when large amounts of Fe, Cu, ^1, etc. coexist, these hydroxides A large amount of metal is produced, which complicates the processing operation, and the resulting aluminum also contains many other metals, making it difficult to expect separation of these metals. 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 contaminated with organic substances due to a drop in current efficiency, the loss of mercury must also be taken into consideration.

In addition, the solvent extraction method (3) is not effective unless the solution to which it is applied is pretreated (neutralization method or concentrated alkali melting method) to concentrate the gallium, and as such
In the case where a large amount of Fe, AI, Cu, Zn, etc. are present, such pretreatment requires a large burden and is difficult to employ industrially.

On the other hand, for industrial extraction of indium, weakly acidic solutions containing trace amounts of In generated from various processes are used.

(1) A method of precipitating In as a sulfide from this weakly acidic solution.

(2) A method in which In is precipitated as a hydroxide from this weakly acidic solution.

(3) A method in which metals such as Zn, Cd, and AI are added to this weakly acidic solution to precipitate In by displacement.

(4) Method 1 includes recovering In from this weakly acidic solution by solvent extraction.

Also, burnt ore produced in zinc smelting, copper smelting, etc.

Targeting In-containing solid raw materials such as smoke ash and crude lead alloys.

(5) After treating these with sulfuric acid and subjecting the resulting In-containing solution to hydrogen sulfide treatment and hydroxidation treatment.

A method of displacing and precipitating In with metal Zn or AI.

etc. are being implemented.

However, in methods (1) and (2), Cu, Fe,
Zn, As.

If a large amount of metals such as No. 81 coexists, a large amount of washed grains will be produced and the processing operation will be complicated, and separation from other metals cannot be expected. Furthermore, in the method (3), if a metal more harmful than the additive metal coexists, it is impossible to separate the metal and In. This point.

Depending on the solvent, the solvent extraction method described in (4) can selectively separate In and has its advantages, but although it is effective for separating In from a certain metal, it There is nothing effective to separate them.

When concentrating In from a solution containing various metals, a large burden is placed on pretreatment in consideration of the properties of other metals. Also, in the case of method (5).

Since trace amounts of In are separated from solutions obtained by processing substances containing large amounts of Cu, Fe, Zn, As + AI, etc., many separation methods must be combined, and in the end, conventional However, it is no exaggeration to say that there was no economical method, as the process was complicated and complicated.

The present invention was made with the aim of solving such problems in the conventional production of Ga and In metals. For this purpose, the present inventors have conducted various tests and researches, and hereby we have disclosed one or more details. Virtually all of the raw materials used in conventional industrial extraction of Ga or In as described above can be used as target raw materials, and the aforementioned problems of various conventional methods can be solved at once.

We were able to establish an industrial method for producing metal Ga and In from substances containing trace amounts of Ga or In.

The present invention relates to a group of solid or liquid substances generated from various smelting processes and chemical processes, and which contains a small amount of G
This method targets virtually all substances containing trace amounts of Ga and In that have traditionally been considered as sources of Ga and In, but even if their growth η is the same, Depending on the target substance, both Ga and In may be contained in an economical amount.

There are raw materials that contain an economical amount of Ga but do not reach an economical amount of In, or conversely, there are materials that contain an economical amount of In but do not reach that amount of Ga. .

As described above, the present invention targets all raw materials whose contents of Ga and In vary.

In the following description of the present invention, the first invention refers to a method for extracting Ga from a raw material that has an economical content of Ga but does not reach an economical content of In.
A second invention provides a method for extracting In from a raw material that has an economical content of n but does not reach an economical content of Ga, and a raw material that has an economical content of both Ga and In. A method for extracting Ga and In from a material to be processed will be described as a third invention.

The first invention is Ga, In? b. A solution obtained by dissolving a solid substance containing a small amount of Ga or In in an acid, or a solution containing a small amount of Ga or In generated in liquid form from metal smelting or other chemical processes is used as the processing stock solution, and this processing stock solution is used to select Ga and In. The first step is to flow the resin through a bed of chelating ion exchange resin at a pH value that allows it to be adsorbed.

A second step of treating the resin that has passed through the first step with vL acid to elute the resin-adsorbed substance.

Ga consisting of a Ga electrowinning process in which the obtained eluent is used as a raw material and Ga in this liquid is converted to metal Ga by electrowinning,
This is a method for producing metal Ga and In from a substance containing a trace amount of In.

The second invention uses a liquid obtained by dissolving a solid substance containing a trace amount of Ga + In with an acid, or a liquid containing a trace amount of Ga and In generated in a liquid form from a metal smelting process or other chemical process as a treatment stock solution, and the treatment stock solution is , Ga and In
The first step is to pass the liquid through a layer of chelating ion exchange resin directly under p1, which is capable of selectively adsorbing.

A second step of treating the resin that has passed through the first step with a mineral acid to elute the resin-adsorbed substance.

A metal In precipitation step in which In dissolved in the obtained eluent is precipitated by substitution using a metal less noble than In.

Ga consisting of, metallic Ga from a substance containing a trace amount of In,
This is a method for producing In.

Furthermore, the third invention is a liquid obtained by dissolving a solid substance containing a small amount of Ga or In with an acid, or Ga, In which is generated in liquid form from a chemical process such as metal smelting.
(The solution containing 7jl is used as the processing stock solution, and this processing stock solution is
A first step of passing liquid through a layer of chelating ion exchange resin at a pH value that allows Ga and In to be selectively adsorbed.

A second step of treating the resin that has passed through the first step with mineral acid to elute the resin-adsorbed substances.

A metal 10 precipitation step in which In dissolved in the obtained eluent is precipitated by substitution using a metal less noble than In.

In this metal In precipitation step, a Ga electrowinning step is performed in which Ga in this liquid is converted into metal Ga by electrowinning using the liquid after collecting metal [n] as a raw material.

Ga consisting of, metallic Ga from a substance containing a trace amount of In,
This is a method for producing In.

In any of the first to third inventions, the first step to the second step are substantially the same. Therefore, the details of these common first to second steps will be explained first.

[First step]

In this first step, a liquid obtained by dissolving a solid substance containing a small amount of Ga or In with an acid, or a liquid containing a small amount of Ga or In generated in a liquid form from a metal smelting process or other chemical process is used as the processing stock solution. This is a step in which the stock solution is passed through a layer of chelating ion exchange resin at a pH value that allows selective adsorption of Ga and In. Here, solid substances containing a small amount of Ga or In include raw material minerals themselves such as bauxite, germanite, and zinc ore, smoke ash generated from the smelting process of these or other minerals, and smelting residues 1 coal ash. 9 such as Zn, Fe,
Hel, hes, Ni.

Cd, etc. (2 or more types are Ga and In, number 10~
It refers to a group of substances that contain hundreds of times more or more of Ga, and includes not only those that have traditionally been used as Ga and In extraction sources, but also Ga and In that cannot be economically extracted using conventional techniques. This also includes those containing trace amounts of. In addition, a liquid containing a trace amount of Ga or In that is generated in liquid form from a metal smelting process or other chemical process is a liquid containing a small amount of Ga or In.
In metal smelting and chemical processes whose main purpose is not to extract a or indium.

A solution 1 that contains the main substance but also contains small amounts of Ga and In, such as an electrolytic solution for electrolytic refining of the main metal.

This refers to liquids similar to secondary liquids or waste liquids in which most of the main substances have been removed, but which contain large amounts of other metal ions and trace amounts of Ga and In.

In the present invention, such substances containing trace amounts of Ga+ In (some solid and some liquid) that are generated in various places are treated. Treat with acid. As this acid, it is preferable to use sulfuric acid, which is inexpensive. At that time, one stage of leaching is carried out at a seat temperature and pressure so that the free sulfuric acid concentration after leaching is 10 (g/ff) or more, and the leachate is separated by filtration.
What is necessary is to collect the processing stock solution (as used in the present invention).

The processing stock solution used in the present invention is 1 a solution obtained by decomposing a solid material containing a trace amount of Ga or In with an acid,
Or, it is a liquid containing a trace amount of Ga or In that is generated in liquid form from metal smelting process or other chemical process, but Ga or In is reduced by about 0.01 to 1 (g/j!), and this liquid other than Ga or In is Metal ions, e.g.

Zn, Fe+AI+8s It is a liquid in which metal ions such as Ni and Cd coexist singly or in total at 2 to 70 (g/ff) or more. When In in this treatment stock solution is 0.01 (g/l) or less, the first invention; when Ga in this treatment stock solution is 0.01 (g/β) or less, the second invention; When both Ga and In in this treatment stock solution are greater than or equal to 0.01 (g/j), it is preferable to implement the third invention.

In the first step, this treated stock solution is passed through a layer of clear ion exchange resin at a pH value that allows selective adsorption of Ga and In. The chelating ion exchange resin used here has the following formula, for example:

R, R where 1M is an alkali metal or hydrogen, R1 or R2
is hydrogen or an alkyl group having 1 to 3 carbon atoms.

A chelate resin obtained by three-dimensionally crosslinking the phenol compound represented by the above with phenols and aldehydes can be used. Such a resin itself is known as an ion exchange resin that can reduce the iron ion concentration in an acidic electrogalvanizing bath, for example, in Japanese Patent Application Laid-Open No. 54-121241, and is also available under the trade name UNICERESOC [IR-50].
(manufactured by Unideka Corporation). Such a chelating ion exchange resin (and a chelating ion exchange resin having an aminocarboxylic acid group) contains Ga,
It was discovered that it has the ability to selectively adsorb Ga and In from a solution containing extremely large amounts of various metal ions other than In, but in this case, the pH of the treated solution
The value is adjusted to 1.0 to 4.0, preferably 2.0 to 3.0. As mentioned above, when the sulfuric acid leachate is used as the processing stock solution, it is possible to obtain the solution that satisfies this pn value as is, and the processing stock solution can originally be used as an acidic solution with this pH value during the metal smelting process. When obtained from a chemical process, it is not necessary to carry out this pH value adjustment.

If trivalent iron ions coexist in this treatment stock solution, it is preferable to reduce them to divalent iron ions in advance using a reducing agent such as sulfur dioxide gas or sodium bisulfite. When passing the treatment stock solution through the resin, the space velocity (hereinafter sometimes simply referred to as S or V) of the exchange tower filled with the resin is 5.0 or less, preferably 0.5 to 1.5. The liquid is passed at a speed such that . As a result, G in the treatment stock solution
Only a and In are selectively adsorbed to this resin. At this time, the appropriate temperature for contacting the resin is 10 to 50°C, preferably 35 to 45°C.

Figure 1 shows the pH value of the treatment stock solution and the concentration of Ga and I to the resin.
This figure shows the relationship between the amount of adsorption of n and the treated stock solution is added to an exchange tower filled with the chelating ion exchange resin. O
The data below shows when the liquid is passed, but the pH value is 1.0 ~
It can be seen that both Ga and In are well adsorbed at 4.0.

In addition, Figure 2 shows 1 each of zinc, iron, and aluminum.
After adjusting the pH value of Galiu J1 containing 0 to 20 (g/A) or sulfuric acid/8m containing a trace amount of indium to a pH value of 2.8, and maintaining the reducing property of the /8 solution by adding sodium bisulfite, This graph shows the relationship between the amount of liquid passed through the clear ion exchange resin and the flow point when the liquid is passed through the clear ion exchange resin at S, V 1.0. It can be seen that the resin is selectively adsorbed from the solution.

[Second process]

The second step is a step of treating the resin that has undergone the first step with a mineral acid to elute the resin-adsorbed substance. As mentioned above, in the first step, Ga and In ions are selectively adsorbed to the resin, apart 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, it is 1 to 6N, preferably 3 to 4N.

In the case of hydrochloric acid, it is preferable to use one having a concentration of 1 to 6N, preferably 2 to 3N. With this elution.

The concentration of metal ions other than Ga and In is low, and Ga,
In.

0, O1 to 1 (g/liter or more)
a. An In-containing solution can be obtained.

Once this eluent has been obtained, it is used in the same way as in the previous adsorption step (first step) from the treated stock solution, with the pl (value of 1.0 to 4.0, preferably 2.0 to 3) of this eluent being obtained. After adjusting to S, V 5.0 or less, preferably S, V 1.0 to
By passing liquid at a temperature of 3.0, Ga, I
By repeating the process of adsorbing n again and eluting it again with mineral acid, Ga and In in the eluent are
The concentration of other metal ions 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 to 4N,
In the case of hydrochloric acid, a concentration of 1 to 6N, preferably 2 to 3N can be used, and the concentration of Ga in this solution is
The concentration of In can be extremely high, such as 0.1 to 50 (g/#). The amount of metal ions other than Ga and In in this eluent is extremely small, and the amount of Ga and In is small! 1ilt 9'! Shrunk.

Figure 3 shows that the pH of the eluent that was iM in the case of Figure 2 is 2.
．． 8 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, V 2.0. As shown in the figure, Ga and In are selectively adsorbed to this resin, and Ga is present in the eluent.

It can be seen that as In is concentrated, the concentrations of other metal ions are reduced.

FIG. 4 shows an elution curve when gallium or indium adsorbed on the resin is eluted from the molten liquid M with 2N hydrochloric acid.

The molten Flf containing Ga and In obtained through the first and second steps as described above. & indicates that the subsequent steps are slightly different depending on the difference in the Ga and In concentrations in the eluent (and in turn, depending on the fluctuation or difference in the Ga and In contents in the treatment stock solution in the first step). Processed under These will be explained individually below.

r In the case of the first invention J Was this obtained in the second step? Although the Gaa content in the 8Mtl solution is sufficient, the In concentration is so small that it has no economic value.In this case, the eluent obtained in the second step is used as the raw material, and the Ga in this solution is Metal Ga is extracted by electrowinning method. At that time, it is possible to directly apply the eluent to electrolysis (however, with appropriate PL+ adjustment), but the Ga ions and other metal ions in this eluent must be separated by neutralization treatment. It is also a good idea to take a prescription. Figure 5 shows the relationship between the pu of the liquid and the precipitation rate of Ga hydroxide. Ga precipitates well in the pH range of 4 to 8, but Ga precipitates well in the pH range of 4 to 8.
It can be seen that it melts. Therefore, for example, if iron ions coexist (as shown in the figure, iron has a pH value of 5 or higher).
), add an alkaline agent to the eluent and
By setting the H value to, for example, 10 or more (in the process, even if Ga precipitates once, it will decompose again), a precipitate of iron hydroxide is generated and this is filtered out, and then, for example, sulfuric acid is added to the liquid. By reverse neutralizing to a pH value of 5 to 8, a precipitate of ζGa hydroxide is generated, and this is filtered out. This makes it possible to remove a fraction of the iron ions entrained in the f6 syneresis, and at the same time remove Ga atI. ? I can do j. The iM precipitate of Ga hydroxide may be redissolved by adding an alkaline agent such as 1.lium hydroxide, and the resulting solution may be provided as an electrolyte for Ga electrolysis. If metals other than Ga, such as iron ions, do not remain in the eluent, add an alkaline agent to the eluent and directly adjust the pH value to 5 to 8 without performing any neutralization treatment. G
A can be purified and concentrated, which can be dissolved with an alkali and subjected to electrolysis.

As a result, as shown in Examples below, metallic Ga with crystal purity can be collected at an extremely high yield.

"In the case of the second invention" This is a process applied when the eluent obtained in the second step has a sufficient degree of Ina, but the concentration of Ina dissolved in the eluent obtained in the second step is An indium sponge is collected by displacing and precipitating In from a liquid using a metal less noble than In. However, in the second invention, depending on the acid concentration of the eluent, the dirt is treated with mineral acid 2, such as sulfuric acid or hydrochloric acid, to a pH value of 2.0 or less, and powdered or plate-shaped zinc or aluminum is added to this acidic solution. An indium sponge is obtained by adding a metal baser than In in an amount of 1 to 3 equivalents to In. At that time, before this displacement precipitation, more specifically, before adjusting the pH to 1 liter, hydrogen sulfide gas is blown into the liquid in advance to precipitate metals other than indium, and this is filtered out from the liquid. If you collect it, you can easily purify the liquid.

This makes it possible to increase the purity of the indium sponge that undergoes 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, even higher purity Indium can be obtained.
Metals can be manufactured.

r In the case of the third invention" This is a process applied when both the Ga and In concentrations in the /8 syneresis obtained in the second step are sufficient. In is substituted and precipitated using a metal less noble than In to collect an indium sponge, and then using the tailing liquid (liquid after indium collection) as a raw material, 68 in this liquid is converted into metal Ga using an electrowinning recipe. By going through the -X= process of extracting both metal In and metal Ga in a high yield.

In this case, the In sponge can be collected in the same manner as described in the second invention, and the collected Indium sponge can be electrolytically refined to produce even higher purity metal In. .

In the electrolysis of Ga, the tailing liquid after + lni exchange precipitation is
Make solution A, add an alkaline agent to this solution and adjust the pi (value from 5 to
When the temperature is adjusted to 8, Ga hydroxide precipitates as shown in FIG.
Precipitation of metals other than Ga such as iron by dissolving hydroxide in thorium hydroxide to form a Ga electrolyte, or by adding an alkaline agent so that the pH value of the tail liquid becomes 10 or more. After this is generated and filtered out, the filtrate is reverse neutralized with sulfuric acid to p115~8 to generate a precipitate of Ga hydroxide, and after this is filtered off, this Ga hydroxide is hydroxylated again. High purity metallic Ga can be electrolytically extracted by dissolving it in 1-lium to form a Ga electrolyte.

As explained above, according to the present invention, the industrial production methods of Ga and In, which have conventionally had various problems, can be replaced. Provided is an economical method for producing Ga and In in which a wide range of raw materials can be processed and a high yield.

Examples will be 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 clear ion exchange resin used in each example is a resin with the trade name ① UNISERESOKU UR-50 (manufactured by Unitika Co., Ltd.).

(Margins below this page) Example 1 In this example, as shown in Table 1, Zn.

AI + Using materials from intermediate smelting processes that contain a large amount of Fe and trace amounts of Ga and In as raw materials, Ga, I
An example of separately collecting n is shown below.

A leachate showing the composition was obtained.

The leachate in Table 2 was neutralized with calcium carbonate to a pH value of 2.
．． After adjusting the pH value to 2.5 by adding an alkaline agent to the solution and adding sodium bisulfite to maintain the reducing property of the solution.

This solution was passed through a column packed with a chelating ion exchange resin at S, V 1.0, thereby selectively adsorbing gallium and indium onto the resin. Then, 3N sulfuric acid was used to dissolve the gallium and indium adsorbed on this resin.

The composition of the obtained eluent (referred to as the separation liquid) is shown in Table 3.

Table 3 Composition of separated liquid (g/Il) Hydrogen sulfide gas is blown into the separated liquid shown in Table 3, and the resulting precipitate is filtered off. Zinc powder is added to the liquid in an amount of 2 equivalents to indium. I got a 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 more.

On the other hand, an alkaline agent is added to the liquid obtained by separating the indium sponge to adjust the pH to 10 or higher, and the precipitate formed is filtered out.
Sulfuric acid was added to the filtrate to reverse neutralize it, and the produced gallium hydroxide was collected by filtration. Sodium hydroxide was added and melted to this gallium hydroxide, and this was used as an electrolytic solution to perform electrowinning of Ga to obtain metallic gallium with a purity of 99.9% or more.

Example 2 In this example, an aluminum precipitate melt having the composition shown in Table 4 was used as a raw material, and a trace amount of gallium contained therein was recovered. The melt in Table 4 is.

Aluminum precipitate containing a small amount of gallium is dissolved with sulfuric acid, the pH value is adjusted to 2.8, and then sodium bisulfite is added to maintain reducing properties.

Table 4 Aluminum precipitate solution (g/2) The aluminum precipitate solution shown in Table 4 was passed through a column filled with a chelating ion exchange resin at S, V 1, and gallium was selectively removed from the column. Adsorbed onto resin. Next, i Mlf of gallium was performed using 2N hydrochloric acid, and the composition of the obtained eluent (this eluent is referred to as a separated solution) is shown in the fifth column.

Table 5 Composition of separated liquid (g/J) In addition, an alkaline agent is added to the separated liquid shown in Table 5.
The H value was adjusted to 2.8, and sodium bisulfite was added to maintain the reducing properties of this solution. This solution was again passed through a column filled with a chelating ion exchange resin at S, V2 to selectively adsorb gallium. Then, the gallium adsorbed on this resin was dissolved using 2N hydrochloric acid,
Eluent (this is called concentrate) whose composition is not shown in Table 6.
I got it.

Table 6 Composition of concentrated liquid (g/ff) Add an alkaline agent to the obtained concentrated liquid shown in Table 6 to adjust the pH value to 10 or more, filter out the formed precipitate, add sulfuric acid to the filtrate, and add sulfuric acid to the filtrate. The mixture was mixed to form a gallium hydroxide precipitate, which was collected by filtration. Sodium hydroxide was added and melted to this gallium hydroxide, and gallium was electrolytically extracted using this as an electrolyte to obtain metallic gallium with a purity of 99.9 or higher.

Example 3 In this example, indium was recovered from a solution produced from a zinc smelting process, the composition of which is shown in Table 7.

Table 7 Composition of solution (g/ff) Calcium carbonate was added to the solution in Table 7 to adjust the pH to 2.0, and then aqueous ammonia was added to adjust the pH to 2.5.

After adding sodium bisulfite to maintain the reducing properties of the melt, this solution was passed through a column filled with a chelating ion exchange resin at S, V 1.0, thereby removing indium. It was selectively adsorbed onto this resin. Then, indium adsorbed on this resin was eluted using 3N hydrochloric acid.

The composition of the obtained eluent (referred to as separation liquid) is shown in Table 8.

Table 8 ~ Composition of separated liquid (g/ff) Add an alkali to the separated liquid in Table 8 to adjust the pH to 2.5.
Sodium hydrogen sulfite was added to maintain the reducibility of the solution, and the solution was passed through a column packed with the chelating ion exchange resin at S, V 2 to selectively adsorb indium, and then 3N sulfuric acid to obtain an indium concentrate whose composition is shown in Table 9.

Table 9 Composition of concentrated solution (g/n) Zinc powder was added to the concentrated solution shown in Table 9 in an amount of 2 equivalents to indium to obtain an indium sponge, which was collected and melted to make an indium anode and electrolyzed. It was subjected to purification to obtain metallic indium with a purity of 99.99%.

[Brief explanation of drawings]

Figure 1 shows the p of the treatment solution for the chelating ion exchange resin.
A diagram showing the relationship between the H value and the adsorption amount of Ga and In. Figure 2 shows Ga containing high concentrations of zinc, iron, and aluminum.
, A relationship diagram between the amount of liquid passed and the flow point when a dilute solution of In is pH adjusted and reduced, and then a certain amount is passed through a chelating ion exchange resin. FIG. 3 is a diagram showing the relationship between the amount of eluent and the flow-through point when a certain amount of eluent is passed through a chelating ion exchange resin after adjusting the eluent to pl+ and maintaining reducing properties. Figure 4 shows the results when a clear ion exchange resin that has been adsorbed is melted with 2N hydrochloric acid. Figure 5 shows the relationship between the pH value of the solution and the hydrolysis of gallium and trivalent iron. Shi-5! ; To Figure 1: Temporary H Figure 2: Fluid flow < 1. /1-resin) 40 80 120 160 Amount of liquid passed (t/resin) Figure 4 1 23 Amount of solution <t, ・'t resin>

Claims (1)

[Claims] (11) A liquid obtained by dissolving a solid substance containing a trace amount of Ga or In with an acid, or a liquid containing a trace amount of Ga or In generated in a liquid form from a metal smelting process or other chemical process is used as a processing stock solution. , a first step in which this treated stock solution is passed through a layer of chelating ion exchange resin under a pH value that allows Ga and In to be selectively adsorbed.The resin that has undergone the first step is treated with mineral acid. A second step in which the resin-adsorbed substance is eluted using the obtained eluent as a raw material. A Ga electrowinning step in which Ga in this solution is converted into metals G and a by electrowinning using the obtained eluent as a raw material. metal Ga,
Method for producing In. (21. A solution obtained by dissolving a solid substance containing a trace amount of Ga and In with an acid, or a solution containing a trace amount of Ga and In generated in a liquid form from a metal smelting process or other chemical process is used as the treatment stock solution. A first step in which the liquid is passed through a layer of chelating ion exchange resin at a pH value that allows Ga and In to be selectively adsorbed.The resin that has gone through the first step is treated with a mineral acid to form a resin adsorbent. A second step of eluting the In dissolved in the obtained eluent. A metal In precipitation step of displacing and precipitating the metal In using a metal more base than In. Metal Ga from a substance containing a trace amount of In. ,
Method for producing In. (31. A liquid obtained by dissolving a solid substance containing a small amount of Ga and In with an acid, or a liquid containing a small amount of Ga and In generated in a liquid form from a metal smelting process or other chemical process 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 a pH value that can selectively adsorb Ga and In.The resin that has gone through the first step is treated with mineral acid to remove the resin-adsorbed substances from f4H1. A second step in which the In dissolved in the obtained eluent is precipitated by substitution using a metal less noble than In. After the metal In is collected in the above metal In precipitation step. Using the liquid as a raw material, Ga in the liquid is converted into metallic Ga by electrowinning.
Ga electrowinning process. Ga consisting of Ga, metal Ga from a substance containing a trace amount of In,
Method for producing In. (Margins below this page)