JP2019173041A - Method for refining copper, chelating resin, copper chelating agent and copper refiner - Google Patents

Abstract

To provide: a method for refining copper, capable of reducing the content of nickel being an impurity when separating and refining the copper from the nickel to collect a refined solution including high purity copper; a chelating resin; a copper chelating agent; and a copper refiner.SOLUTION: The method for refining copper comprises: the dissolution step of preparing a dissolved solution obtained by dissolving copper and nickel; the adsorption step of contacting the dissolved solution to the chelating resin to adsorb copper ions and nickel ions on the chelating resin; the cleaning step of passing a low concentration acid solution to discharge a solution including the nickel ions; and the collection step of passing a high concentration acid solution to obtain a solution including the copper ions. The chelating resin carries a chain chelating agent having four coordination groups selected from an amino group or a carboxyl group, and at least one of the four coordination groups is a primary amino group or a secondary amino group.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a copper purification method for separating and purifying radioactive copper produced in nickel from nickel, a chelate resin, a chelating agent for copper, and a copper purification apparatus.

  Conventionally, it is known that radioactive copper is an effective radioisotope for medical imaging and radiotherapeutic drugs. Therefore, establishment of the manufacturing method and purification method of radioactive copper is calculated | required. As a manufacturing method, a method of irradiating a nickel (Ni) target with a proton beam or the like is known. As a purification method for purifying radioactive copper from nickel in which a small amount of radioactive copper is generated, a method using an ion exchange resin or a chelate resin is known.

In the purification method using ion exchange resin, in order to obtain high-quality radioactive copper with few impurities such as nickel, it is necessary to extremely slow the flow rate of the solution in which copper and nickel are dissolved to the ion exchange resin. And there is a problem that it takes time for purification (for example, see Non-Patent Document 1). In Non-Patent Document 1, purification requires 12 hours or more, but ⁶⁴ Cu, which is a kind of radioactive copper, has a half-life of 12.7 hours. In the method of Non-Patent Document 1, ⁶⁴ Cu is not purified during purification. It will be halved.

  On the other hand, in a method using a chelate exchange resin having iminodiacetic acid as a coordinating group (see, for example, Patent Document 1), an acidic solution for washing only nickel without eluting radioactive copper is adsorbed on the chelate exchange resin. In order to obtain high-quality radioactive copper, strict concentration control of two types of acidic solutions is essential, and technical difficulty increases. .

Japanese Patent No. 4877863

Tomoyuki Ohya et al. “Efficient preparation of high-quality 64Cu for routine use”, Nucl. Med. Biol., 2016, 43, 685-691.

  This invention is made | formed in view of the above, Comprising: When separating and refine | purifying copper from nickel, the content rate of nickel which is an impurity can be reduced and the refinement | purification liquid containing high purity copper can be collect | recovered An object is to provide a purification method, a chelating resin, a chelating agent for copper, and a copper purifier.

  In order to shorten the purification time and improve the separation performance of copper and nickel, a chelating agent having high selectivity for copper and nickel is required. However, it has been known that copper and nickel have the same electric charge and have similar ionic radii, so that it is difficult to separate copper and nickel. On the other hand, the present inventor considers that the chelating agent having four coordination groups may exhibit high selectivity between copper and nickel based on the presence or absence of the yarn-teller effect of copper and nickel, The present invention has been completed.

In order to solve the above-described problems and achieve the object, the copper purification method according to the present invention includes a dissolution step of dissolving copper and nickel in an acidic solution for dissolution to prepare a solution, and chelating the solution. An adsorption step in which copper ions (Cu ²⁺ ) and nickel ions (Ni ²⁺ ) are adsorbed on the chelate resin by contacting the resin, and the nickel ions (Ni ²⁺ ) can be eluted in the chelate resin after the adsorption step. A washing step of passing a low concentration acidic solution and discharging the acidic solution containing nickel ions (Ni ²⁺ ), and a high concentration capable of eluting the copper ions (Cu ²⁺ ) into the chelate resin after the washing step was passed through the acidic solution comprises a recovery step of obtaining a purified solution containing the copper ions (Cu ^2+), the chelating resin is of selected from the amino or carboxyl group A chain chelating agent having four coordinating groups, wherein at least one of the four coordinating groups is a primary amino group or a secondary amino group. .

  The copper purification method according to the present invention is characterized in that, in the above invention, the pH of the low-concentration acidic solution is 2.5 or more and 3.5 or less.

  The copper purification method according to the present invention is characterized in that, in the above invention, the high-concentration acidic solution has a pH of -1 or more and 1.5 or less.

In the copper purification method according to the present invention, in the above invention, the stability constant of copper ions (Cu ²⁺ ) of the chain chelating agent is 10 ¹⁰ or more and 10 ³⁰ or less, and the stability constant of copper ions is characterized in that it is 10 ³ times or more the stability constant of the nickel ion.

  The chelate resin according to the present invention is a chelate resin in which the resin carries a chelating agent, and the chelating agent has four coordination groups selected from an amino group or a carboxyl group, and the four ligands At least one of these is a primary amino group or a secondary amino group.

  The chelate resin according to the present invention is characterized in that, in the above invention, the chelating agent is supported on the resin via the primary amino group or the secondary amino group.

In the chelate resin according to the present invention, in the above invention, the stability constant of copper ions (Cu ²⁺ ) of the chelating agent is 10 ¹⁰ or more and 10 ³⁰ or less, and the stability constant of copper ions is the stability of nickel ions. The frequency constant is 10 ³ times or more.

The chelate resin according to the present invention is characterized in that, in the above invention, the chelating agent is one selected from the group of compounds represented by the following formula (1), for example.

The chelate resin according to the present invention is characterized in that, in the above invention, the chelate resin is used for purification of copper ions (Cu ²⁺ ) in a solution containing copper ions (Cu ²⁺ ) and nickel ions (Ni ²⁺ ).

The chelating agent for copper according to the present invention is a chelating agent for copper that selectively binds to copper ions (Cu ²⁺ ) in a solution containing copper ions (Cu ²⁺ ) and nickel ions (Ni ²⁺ ). Having four coordination groups selected from a group or a carboxyl group, at least two of the four coordination groups are carboxyl groups, and the stability constant of the copper ion (Cu ²⁺ ) is 10 ^10. As described above, it is 10 ³⁰ or less, and the stability constant of copper ions is 10 ³ times or more of the stability constant of nickel ions.

The chelating agent for copper according to the present invention is characterized in that, in the above invention, the chelating agent for copper is one selected from the group of compounds represented by the following formula (2).

  The copper refining device according to the present invention comprises a dissolution tank for dissolving copper and nickel in a dissolution acidic solution to obtain a dissolution liquid, a dissolution acidic solution storage tank for storing the dissolution acidic solution, and a low concentration acidic solution. A low-concentration acidic solution storage tank for storing, a high-concentration acidic solution storage tank for storing a high-concentration acidic solution, a chelate resin container filled with a chelate resin, and supplying the dissolution acidic solution to the dissolution tank, And the chelate resin container, the solution, the low-concentration acid solution, or the high-concentration acid solution can be selectively supplied, and the solution, pure water, and the low-concentration discharged from the chelate resin container An acidic solution, or a piping system capable of discharging the high-concentration acidic solution, wherein the chelating resin is a chelating resin in which the resin carries a chelating agent, and the chelating agent has a chain shape. Has four coordinating group selected from amino or carboxyl group, at least one of the four coordinating groups is characterized by a primary amino group or secondary amino group.

  According to the copper purification method, the chelating resin, the copper chelating agent and the copper purification apparatus according to the present invention, when copper is separated and purified from nickel, the content of nickel as an impurity can be reduced, and high purity copper can be reduced. It becomes possible to collect the purified liquid contained.

FIG. 1 is a diagram showing the results of a solvent extraction test using ethylenediamine-N, N′-2-propanoic acid of the present invention. FIG. 2 is a diagram showing the results of a solvent extraction test using conventional iminodiacetic acid. FIG. 3 is a schematic diagram for explaining a method for purifying copper according to an embodiment of the present invention. FIG. 4 is a block diagram for explaining the copper refining apparatus according to the embodiment of the present invention.

  Embodiments of the present invention will be described below with reference to the drawings. In all the drawings of the following embodiments, the same or corresponding parts are denoted by the same reference numerals. The present invention is not limited to the embodiments described below.

  Conventionally, a method for purifying and separating radioactive copper from a solution containing radioactive copper and nickel using a chelate exchange resin having iminodiacetic acid as a coordinating group has been proposed, but copper and nickel of iminodiacetic acid. Therefore, it is technically difficult to selectively elute radioactive copper from a chelate exchange resin adsorbing radioactive copper and nickel.

It has been known that copper and nickel have the same charge and have similar ionic radii, so that it is difficult to separate them with high selectivity. For example, ethylenediaminetetraacetic acid (EDTA) having a structure represented by the following formula (3) forms an octahedral complex with six coordination groups with respect to copper and nickel, but the stability coefficient for copper is 10 ^{18. 80,} which is almost the same as nickel stability factor 10 ^18.62, and has no selectivity for copper and nickel.

  Copper and nickel together form an octahedral complex, but copper that produces the Yarn-Teller effect can be greatly stabilized even in a four-plane coordination. The present inventor considers that only the copper is strongly stabilized in the 4-coordination because nickel does not cause the yarn-teller effect, and is eager to purify and separate copper and nickel using a 4-coordinate chelating agent. Repeated examination.

  Separation of copper and nickel may be performed using a solvent extraction method, but in order to shorten the time required for the purification work and to perform it simply, it was considered preferable to use a solid phase extraction method. Also, considering loading on the resin, it was considered convenient and preferred to carry out via an amino group.

  The chelate resin according to the present invention is a chelate resin in which the resin carries a chelating agent, and the chelating agent has four coordination groups selected from an amino group or a carboxyl group. In addition, at least one of the four ligands is a primary amino group or a secondary amino group.

  The chelate resin of the present invention can improve the selectivity between copper and nickel when the chelating agent has four coordination groups selected from an amino group or a carboxyl group. In addition, when at least one of the four ligands is a primary amino group or a secondary amino group, the resin can be bonded to the resin via the primary amino group or the secondary amino group. Can be easily supported.

In the chelate resin according to the present invention, the stability constant of copper ion (Cu ²⁺ ) of the chelating agent is preferably 10 ¹⁰ or more and 10 ³⁰ or less. Further, by the stability constant of copper ions is more than 10 ³ times the stability constant of the nickel ion, thereby facilitating the separation of copper from a chelating agent.

A method of generating radioactive copper from zinc is also conceivable (Japanese Patent Laid-Open No. 2017-40653). However, the stability constant of the copper ion (Cu ²⁺ ) of the chelating agent is 10 ¹⁰ or more and 10 ³⁰ or less, and copper by selecting the chelating agent is 10 ³ times or more the stability constant of the stability constant of the ion zinc ions, it is possible to separate the radioactive copper zinc with the same technology as in the case of nickel.

In the chelate resin of the present invention, for example, one selected from the group of compounds represented by the following formula (1) can be suitably used as the chelating agent.

  In addition, in the chelate resin of the present invention, a weak acid cation exchange resin containing a carboxylic acid can be considered as the resin carrying the chelating agent. For example, as shown in the scheme of the following formula (6), a resin A having a carboxyl group as a functional group and a chelating agent (chelating agent B) having a primary amino group or a secondary amino group are appropriately dehydrated and condensed. A chelating resin E carrying the chelating agent B can be produced by amidation using an agent (for example, 1-ethyl-3- (3-dimethylaminopropyl) carbohydride hydride). As a resin carrying a chelating agent, for example, Sep-Pak Accel Plus CM manufactured by Waters can be used.

  Moreover, the chelate resin F carrying the chelating agent B can be produced simply by mixing the resin C having an epoxy group as a functional group and the chelating agent (chelating agent B) in an appropriate solvent not containing an amino group. it can. As the resin supporting the chelating agent, for example, Sepabead EC-EP manufactured by Mitsubishi Chemical Corporation can be used.

  In order to shorten and simplify the time required for the purification work, it is preferable to use a chelating resin with a chelating agent supported on the resin, but copper extraction can also be performed by solvent extraction using a chelating agent not supported on the resin. And nickel can be separated.

As the chelating agent used for solvent extraction, it is a chain and has four coordination groups selected from amino groups or carboxyl groups, and if two of the coordination groups are carboxyl groups Good. The stability constants of copper ions (Cu ²⁺ ) and nickel ions (Ni ²⁺ ) of the chelating agent used for solvent extraction are the same as those of the chelating agent used for the chelating resin.

As a chelating agent used for solvent extraction, 1 type selected from the compound group represented by following formula (2) can be used conveniently.

  The results of solvent extraction experiments using ethylenediamine-N, N′-2-propanoic acid, which is one of the chelating agents according to the present invention, and iminodiacetic acid, which is the prior art, are shown in FIGS. FIG. 1 is a diagram showing the results of a solvent extraction test using ethylenediamine-N, N′-2-propanoic acid of the present invention. FIG. 2 is a diagram showing the results of a solvent extraction test using conventional iminodiacetic acid. In FIG. 1 and FIG. 2, (circle) shows a copper ion and (square) shows a nickel ion.

In the experiment, ethylenediamine-N, N′-2-propanoic acid or iminodiacetic acid was added to an acidic solution (hydrochloric acid) containing copper ions (Cu ²⁺ ) and nickel ions (Ni ²⁺ ) in a predetermined ratio, and a solvent (benzene And the ratio of copper ions (II) and nickel ions (II) transferred to the oil phase after being shaken under a certain condition. The solvent extraction experiment is performed by changing the hydrogen ion concentration of the acidic solution.

As shown in FIG. 1, in the chelating agent according to the present invention, copper ions (Cu ²⁺ ) have a pH of 2.5 or more and a transfer rate to the oil phase of 80% or more, and nickel ions (Ni ²⁺ ) It turned out that the transfer rate to an oil phase will be 80% or more at pH 4.5 or more. Therefore, for example, when an acidic solution having a pH of 2.5 to 4.5 is passed through the chelating agent of the present invention that adsorbs copper ions (Cu ²⁺ ) and nickel ions (Ni ²⁺ ), it is nickel that is eluted. It can be seen that only ions (Ni ²⁺ ) and copper ions ((Cu ²⁺ ) are hardly eluted.

On the other hand, in the chelating agent (iminodiacetic acid) of the prior art, as shown in FIG. 2, the copper ion (Cu ²⁺ ) has a pH of 1.5 or more and a transfer rate to the oil phase of 80% or more. However, nickel ions (Ni ²⁺ ) have a transfer rate to the oil phase of 80% or more at pH 2.5 or more. In the prior art, the pH of an acidic solution that elutes only nickel ions (Ni ²⁺ ) is 1.5 to 2.5, and the selectivity between copper ions (Cu ²⁺ ) and nickel ions (Ni ²⁺ ) is low. It can be seen that the concentration management of the low concentration acidic solution eluting (Ni ²⁺ ) becomes severe.

  Subsequently, a copper purification method using the chelate resin described above will be described with reference to the drawings. FIG. 3 is a schematic diagram for explaining a method for purifying copper according to an embodiment of the present invention.

The method for purifying copper according to the present invention comprises a dissolution step of preparing a solution by dissolving copper and nickel in an acidic solution for dissolution, and contacting the solution with a chelate resin to obtain copper ions (Cu ²⁺ ) and nickel ions. An adsorption process for adsorbing (Ni ²⁺ ) to the chelate resin, and after the adsorption process, a low-concentration acidic solution capable of eluting nickel ions (Ni ²⁺ ) is passed through the chelate resin to produce an acid containing nickel ions (Ni ²⁺ ). A cleaning step for discharging the solution, and a recovery step for obtaining a purified liquid containing copper ions (Cu ²⁺ ) by passing a high concentration acidic solution capable of eluting the copper ions (Cu ²⁺ ) through the chelate resin after the cleaning step. It is characterized by including these.

First, radioactive copper ( ⁶⁴ Cu: hereinafter, copper or Cu) (not shown) is generated by irradiating the nickel target 1 of ⁶⁴ Ni with accelerated protons (proton beams). In the dissolution step, the nickel target 1 in which Cu is generated is dissolved in the dissolution acidic solution 3 in the dissolution tank 2 to prepare a solution (dissolution step).

In the adsorption step, a solution in which Cu ²⁺ and Ni ²⁺ are dissolved carries a chain chelating agent having four coordinating groups selected from amino groups or carboxyl groups. At least one of them is passed through a resin column 5 filled with a chelate resin 4 that is a primary amino group or a secondary amino group, and copper ions (Cu ²⁺ ) and nickel ions (Ni ²⁺ ) are allowed to flow through the chelate resin 4. Adsorb to. In the solution, the concentration of nickel ions (Ni ²⁺ ) is much higher than the concentration of copper ions (Cu ²⁺ ), but the chelate resin 4 selectively adsorbs copper ions (Cu ²⁺ ). The solution after passing through the resin column 5 is discharged from the drain port 5a.

In the washing step, a low-concentration acidic solution capable of eluting nickel ions (Ni ²⁺ ) is passed through the resin column 5 to discharge the solution containing nickel ions (Ni ²⁺ ). By passing a low concentration acidic solution through the resin column 5, nickel adsorbed on the chelate resin 4 is desorbed and eluted into the low concentration acidic solution. The low-concentration acidic solution after passing through the resin column 5 is discharged from the drain port 5a. In this embodiment, the concentration of the low-concentration acidic solution is set to a low concentration at which nickel ions (Ni ²⁺ ) are desorbed from the chelating agent 4 and copper ions (Cu ²⁺ ) are not desorbed from the chelating agent 4. . Specifically, for example, hydrochloric acid is used as the low-concentration acidic solution, and the pH is 2.5 or more, preferably 3.5 or more.

In the recovery step, a highly concentrated acidic solution is passed through the resin column 5 to obtain a solution containing copper ions (Cu ²⁺ ). By passing a high concentration acidic solution through the resin column 5, copper adsorbed on the chelate resin 4 is desorbed and eluted into the high concentration acidic solution. In the present embodiment, the concentration of the high-concentration acidic solution is set to a high concentration at which copper ions (Cu ²⁺ ) are desorbed from the chelating agent 5. Specifically, for example, hydrochloric acid is used as the high-concentration acidic solution, and the pH is from −1 to 1.5. The high-concentration acidic solution from which copper ions (Cu ²⁺ ) are eluted is discharged from the drain port 5a and collected as a purified solution. As described above, copper is purified by the purification method according to the present embodiment.

  Then, the copper refiner | purifier which concerns on this invention is demonstrated with reference to figures. FIG. 4 is a block diagram for explaining a copper refining device according to an embodiment of the present invention.

  As shown in FIG. 4, the copper purifier 10 includes a dissolution tank 2, a resin column 5 filled with a chelate resin 4, a purified liquid vial 11, a waste liquid vial 12, a reservoir tank group 13, and a valve group 14 and a valve group 15. A piping system having The reservoir tank group 13 includes reservoir tanks 13a, 13b, and 13c that constitute storage tanks that can store various solvents and various solutions.

The dissolution tank 2 is a tank for dissolving the nickel target 1 in which a very small amount of ⁶⁴ Cu is generated by proton beam irradiation. The dissolving tank 2 is supplied with the dissolving acidic solution from the reservoir tank 13a. For example, hydrochloric acid having a concentration of 1 mol / L is stored in the reservoir tank 13a as an acidic solution for dissolution. The nickel target 1 is dissolved by supplying the dissolved acidic solution from the reservoir tank 13 a to the dissolution tank 2. Thereby, a melt | dissolution process is performed and a solution is produced | generated. The supply of the acidic solution for dissolution from the reservoir tank 13a to the dissolution tank 2 is controlled by opening and closing the valve 15a.

  The resin column 5 filled with the chelate resin 4 is configured to be able to supply a solution from the dissolution tank 2. Supply of the solution from the dissolution tank 2 to the resin column 5 is controlled by a valve 2a. By supplying the solution from the dissolution tank 2 to the resin column 5, an adsorption process is performed, and copper is adsorbed to the chelate resin 4 filled therein. The resin column 5 is configured such that a low-concentration acidic solution and a high-concentration acidic solution can be supplied from the reservoir tanks 13b and 13c, respectively.

  In the reservoir tank 13b, a hydrochloric acid aqueous solution having a concentration of, for example, 1 mmol / L is stored as a low concentration acidic solution. By supplying the low concentration acidic solution from the reservoir tank 13b to the resin column 5, the cleaning process is executed. The supply of the low concentration acidic solution from the reservoir tank 13b to the resin column 5 is controlled by opening and closing the valve 15b.

  In the adsorption step and the washing step, the passing liquid discharged from the drain port 5a of the resin column 5 is supplied to the waste liquid vial 12 in accordance with the switching of the three-way valve 16b.

  In the reservoir tank 13c, hydrochloric acid having a concentration of, for example, 1 mol / L is stored as a highly concentrated acidic solution. The recovery step is executed by supplying the high-concentration acidic solution from the reservoir tank 13 c to the resin column 5. The supply of the high concentration acidic solution from the reservoir tank 13c to the resin column 5 is controlled by opening and closing the valve 15c. In the recovery step, the purified solution discharged from the drainage port 5a of the resin column 5 is supplied to the purified solution vial 11 in accordance with the switching of the three-way valve 16b.

The copper refining device 10 includes a mass flow controller (MFC) 17 as a supply amount control unit in order to supply an inert gas from an inert gas supply source to the dissolution tank 2 and the reservoir tank group 13. The inert gas is selectively supplied to the dissolution tank 2 and the reservoir tanks 13a to 13c through the MFC 17, respectively. The supply of the inert gas to the respective reservoir tanks 13a to 13c is controlled by opening and closing of the valve 2b and the valves 14a, 14b and 14c, respectively. Various solutions can be moved by the pressure of the supplied inert gas. For example, helium (He) or nitrogen (N ₂ ) is preferably used as the inert gas used for transferring various solutions, but is not necessarily limited to these gases. Further, the insides of the purified liquid vial 11 and the waste liquid vial 12 communicate with a vacuum pump via a valve 18. By opening and closing the valve 18, the inside of the purified solution vial 11 and the waste solution vial 12 can be evacuated to facilitate the inflow of various solutions.

  In the copper refining apparatus 10 configured as described above, a purified solution containing copper with high purity can be obtained by executing the dissolution step, the adsorption step, the washing step, and the recovery step. Further, in the copper refining device 10, a control unit that controls the respective components such as the valves 2 a, 2 b, 14 a to 14 c, 15 a to 15 c, 18, the three-way valve 16 b, the respective reservoir tanks 13 a to 13 c, and the MFC 17. You may prepare. In this case, when the control unit controls each component, the above-described copper purification method can be executed.

DESCRIPTION OF SYMBOLS 1 Nickel target 2 Dissolution tank 2a, 2b, 14a, 14b, 14c, 15a, 15b, 15c, 18 Valve 3 Acidic solution for dissolution 4 Chelate resin 5 Resin column 5a Drain outlet 10 Copper purification apparatus 11 Purified liquid vial 12 Waste liquid vial 13 Reservoir tank group 13a, 13b, 13c Reservoir tank 16b Three-way valve 17 Mass flow controller (MFC)

Claims (12)

A dissolving step of dissolving copper and nickel in a dissolving acidic solution to prepare a solution;
An adsorption step in which the solution is brought into contact with a chelate resin to adsorb copper ions (Cu ²⁺ ) and nickel ions (Ni ²⁺ ) to the chelate resin;
After the adsorption step, a washing step of passing a low concentration acidic solution capable of eluting the nickel ions (Ni ²⁺ ) through the chelate resin and discharging the acidic solution containing the nickel ions (Ni ²⁺ );
After the washing step, a recovery step of passing a highly concentrated acidic solution capable of eluting the copper ions (Cu ²⁺ ) through the chelate resin to obtain a purified solution containing the copper ions (Cu ²⁺ );
Including
The chelate resin carries a chelating agent having four coordination groups selected from an amino group or a carboxyl group, and at least one of the four coordination groups is a primary amino group or A method for purifying copper, which is a secondary amino group.   The method for purifying copper according to claim 1, wherein the pH of the low-concentration acidic solution is 2.5 or more and 3.5 or less.   The copper purification method according to claim 1 or 2, wherein the pH of the high-concentration acidic solution is -1 or more and 1.5 or less. The stability constant of copper ion (Cu ²⁺ ) of the chelating agent is 10 ¹⁰ or more and 10 ³⁰ or less, and the stability constant of copper ion is 10 ³ times or more of the stability constant of nickel ion, The method for purifying copper according to any one of claims 1 to 3. The resin is a chelating resin carrying a chelating agent,
The chelating agent is linear and has four coordination groups selected from an amino group or a carboxyl group, and at least one of the four ligands is a primary amino group or a secondary amino group. A chelate resin characterized by being a group.   6. The chelating resin according to claim 5, wherein the chelating agent is supported on the resin via the primary amino group or the secondary amino group. The stability constant of copper ion (Cu ²⁺ ) of the chelating agent is 10 ¹⁰ or more and 10 ³⁰ or less, and the stability constant of copper ion is 10 ³ times or more of the stability constant of nickel ion, The chelate resin according to claim 5 or 6. The chelating agent according to any one of claims 5 to 7, wherein the chelating agent is one selected from the group of compounds represented by the following formula (1).

The chelate resin according to claim 5, wherein the chelate resin is used for purification of copper ions (Cu ²⁺ ) in a solution containing copper ions (Cu ²⁺ ) and nickel ions (Ni ²⁺ ). A chelating agent for copper that selectively binds to copper ions (Cu ²⁺ ) in a solution containing copper ions (Cu ²⁺ ) and nickel ions (Ni ²⁺ ),
It has four coordination groups selected from an amino group or a carboxyl group, at least two of the four coordination groups are carboxyl groups, and the stability constant of copper ions (Cu ²⁺ ) is 10 ¹⁰ or more and 10 ³⁰ or less, for copper chelating agent characterized in that the stability constant of copper ions is 10 ³ times or more the stability constant of the nickel ion. The said chelating agent for copper is 1 type selected from the compound group represented by following formula (2), The chelating agent for copper of Claim 10 characterized by the above-mentioned.

A dissolution tank for dissolving copper and nickel in an acidic solution for dissolution to obtain a solution;
An acidic solution storage tank for storing the acidic solution for dissolution;
A low concentration acidic solution storage tank for storing a low concentration acidic solution;
A high concentration acidic solution storage tank for storing a high concentration acidic solution;
A chelate resin container filled with a chelate resin;
The dissolving acidic solution can be supplied to the dissolving tank, and the dissolving solution, the pure water, the low concentration acidic solution, or the high concentration acidic solution can be selectively supplied to the chelate resin container, A piping system capable of discharging the solution discharged from the resin container, the low-concentration acidic solution, or the high-concentration acidic solution;
With
The chelate resin is a chelate resin in which the resin carries a chelating agent, and the chelating agent has a chain shape and has four coordination groups selected from an amino group or a carboxyl group. The copper refining device, wherein at least one of the positional groups is a primary amino group or a secondary amino group.

Images