JP6491771B2 - Method for separating and recovering metal from plating media, and method for recycling plating media - Google Patents

Description

  The present invention relates to a plating medium used in a barrel plating method or the like, a method of separating and recovering metal from a plating medium for making the plating medium reusable while separating and recovering metal from a used plating medium, and The present invention relates to a method for recycling plating media.

  A barrel plating method is widely used as a method for conducting conductive plating on the surface of an object to be plated such as an electronic component. In general, in the barrel plating method, a small iron ball called a plating medium (dummy medium) is put into a polygonal barrel together with an object to be plated and stirred while energized (for example, see Patent Document 1). By using the plating media, the current flows uniformly to the object to be plated, so that the plating efficiency can be improved and the plating thickness can be made more uniform.

  By repeatedly using the plating media, a plating layer is gradually formed on the surface of the plating media. That is, the metal used for plating is laminated on the surface of the plating medium every time it is used, so that the plating medium grows (enlarges) every time it is used. As a result, the outer diameter and specific gravity of the plating media that have been optimized for barrel plating conditions change.

  When the plating media grows by repeated use, the gap between the object to be plated and the plating media increases in the barrel, resulting in a decrease in plating efficiency and variations in plating thickness. Conventionally, when a plating medium grows beyond a predetermined size, it is discarded as a used plating medium and replaced with a new plating medium. By discarding the plating media, the expensive metal used for plating laminated on the surface of the plating media is also discarded. When barrel plating is performed in this way, a large amount of used media is generated and discarded together with the plating metal. Therefore, in recent years, there has been a strong demand for recovering metal for plating laminated on the surface from used plating media to be discarded.

  In recent years, a plurality of metals are often plated on an object to be plated using a plating medium. In this case, since the plurality of types of metals are laminated on the used plating media, it is required to separate and collect the plurality of types of metals. As an example, when conductive plating is performed on capacitor electrodes or the like, nickel (Ni) and tin (Sn) are often used as the metal for plating. In this case, it is necessary to separate Ni and Sn with high accuracy from the used plating media in which the Ni component and the Sn component are stacked, and collect each of them.

  As a conventional method for individually separating and recovering a plurality of metals from a large amount of a metal mixture, a solvent extraction method, an adsorption method, or the like is used (for example, see Patent Document 2). In the case of the solvent extraction method, an organic solvent containing an extractant that selectively reacts with metal ions is brought into contact with an aqueous solution containing a plurality of metal ions, so that only the target metal ions are extracted into the organic solvent. And various metals can be isolate | separated and collect | recovered by back-extracting the metal ion extracted by the organic solvent to an aqueous phase.

  In the conventional ion exchange method, each metal ion is adsorbed on the ion exchange resin by passing a mixed aqueous solution of various metal ions obtained by dissolution using an acid or alkali through the ion exchange resin. Then, an eluent for desorbing specific metal ions is passed through the ion exchange resin that has adsorbed each metal ion.

  The desorption rate of the metal ions adsorbed on the ion exchange resin varies depending on the pH of the eluent. And the shape of the equilibrium curve which shows the change of the desorption rate according to pH changes with kinds of metal ion. That is, by utilizing the difference in the equilibrium curve of each metal ion at various pHs, and adjusting the pH of the eluent with an acid or alkali so as to achieve an appropriate desorption rate for each metal ion, Each metal ion is sequentially desorbed. Each metal ion is separated and recovered by appropriately fractionating the liquid passed through the ion exchange resin.

JP 61-15999 A JP-A-10-265863

However, the above conventional configuration has the following problems.
That is, in the conventional solvent extraction method, a large amount of organic solvent is required for extraction of metal ions, and a large amount of acid or alkali is required for back extraction. Therefore, enormous costs and labor are required for the treatment of these waste liquids. In addition, since part of the organic solvent and the extractant is mixed in the aqueous phase during back extraction, it is difficult to treat not only the organic solvent phase but also the solution in the aqueous phase.

  Further, the conventional ion exchange method has a poor adsorption selectivity, and there is a concern that the separation efficiency of each metal ion is low. That is, since metal ions generally become cations in an aqueous solution, a cation exchange resin is used in the conventional ion exchange method. In this case, all of the plurality of types of metal ions are adsorbed on the cation exchange resin.

  When a specific metal ion is desorbed from an ion exchange resin on which a plurality of types of metal ions are adsorbed, some of the other metal ions are desorbed together with the specific metal ion. That is, even when the pH of the eluent passing through the ion exchange resin is adjusted to a pH suitable for desorption of a specific metal ion, the desorption rate of other metal ions at that pH is generally not zero. .

  For this reason, not only the specific metal ions but also some other metal ions are easily mixed in the eluent passed through the ion exchange resin. Therefore, it is difficult to separate metal ions with high accuracy by a conventional metal separation method using an ion exchange method. In addition, since a large amount of acid or aqueous alkali solution is used for the purpose of pH adjustment during desorption, there is a concern that the waste liquid treatment requires cost and labor.

  The present invention has been made in view of such circumstances, and various metals can be separated and recovered from a metal mixture with high accuracy, and metals can be separated and recovered from plating media that can further reduce the generation of waste liquids that are difficult to process. The main object is to provide a method and a method for recycling plating media.

In order to achieve such an object, the present invention has the following configuration.
That is, the present invention is a method for separating and recovering metal from a plating medium comprising a spherical core made of Fe and a metal surface layer in which Ni and Sn are laminated on the surface of the core,
A dissociation step for dissociating the metal surface layer from the core with respect to the plating medium in a used state,
An ionization step of obtaining a mixed metal aqueous solution containing Ni ions and Sn ions by dissolving the metal surface layer dissociated from the core with an acid;
The Sn ion is separated from the metal mixed aqueous solution by bringing the metal mixed aqueous solution into contact with an anion exchange material having anion exchange property and selectively adsorbing the Sn ions on the anion exchange material, A separation step of obtaining a Ni ion aqueous solution containing only the Ni ions out of Sn ions and the Ni ions;
Water is brought into contact with the anion exchange material on which the Sn ions are adsorbed as an eluent, and the Sn ions are desorbed from the anion exchange material to the eluent to produce an Sn ion aqueous solution containing the Sn ions. A desorption process to be acquired;
It is characterized by providing.

  (Function / Effect) According to this method, in the ionization step, the metal surface layer made of Ni and Sn is dissolved with an acid to obtain a mixed metal aqueous solution containing Ni ions and Sn ions. In the separation step, when the metal mixed aqueous solution is brought into contact with the anion exchange material, Sn ions out of Sn ions and Ni ions are selectively adsorbed on the anion exchange material.

  By such selective adsorption, Sn ions are separated from the metal mixed aqueous solution, and an Ni ion aqueous solution containing only Ni ions out of Sn ions and Ni ions can be obtained. Thus, unlike the conventional ion exchange method, in the ion exchange method according to the present invention, specific metal ions can be selectively adsorbed from the metal mixed aqueous solution to the ion exchange material. Ni ions can be separated.

  Further, in the desorption step, water is brought into contact with the anion exchange material on which Sn ions are adsorbed as an eluent, and Sn ions are desorbed from the anion exchange material to the eluent. By this desorption, an Sn ion aqueous solution containing only Sn ions out of Sn ions and Ni ions can be recovered. In the conventional ion exchange method, since a metal ion is desorbed using an acid or alkali as an eluent, a large amount of acid or alkali is required. On the other hand, in the present invention, Sn ions can be desorbed with water, so that the cost and labor required for treatment of waste liquid and separation of metal ions can be greatly reduced.

  As described above, in the method for separating and collecting metal from the plating media according to the present invention, Fe constituting the core and Sn and Ni constituting the metal surface layer are separated and collected with high accuracy from the used plating media, respectively. it can. Therefore, it is possible to effectively use a plating metal such as Ni or Sn that is laminated on a used plating medium without being discarded.

  In the present invention, the metal can be separated and recovered from the plating medium by a relatively small amount of acid used for dissolving the metal surface layer and water used for desorption. That is, unlike the conventional metal separation and recovery step, the metal separation and recovery step according to the present invention does not require the use of an organic solvent or an alkaline solution. Therefore, even when Sn and Ni are separated and recovered from plating media in a plating factory, it is not necessary to newly provide an organic solvent treatment facility or an alkali treatment facility, and Sn and Ni can be obtained by diverting existing facilities. Separated and recovered.

  Therefore, the plating process and the process of separating and recovering the metal from the plating medium can be continuously performed inside the plating factory without transporting the plating medium and waste liquid from the plating factory to an external processing facility. As a result, the cost and time required for the process of separating and recovering metal from the plating media can be greatly reduced.

  In the above-described invention, the dissociation step includes a heat treatment step of heat-treating the plating medium in a used state at a temperature of 240 ° C. or higher and 1450 ° C. or lower, and physically polishing the plating medium after the heat treatment step. And a polishing step for peeling the metal surface layer from the core.

  (Function / Effect) According to this configuration, at least Sn contained in the metal surface layer is melted by the heat treatment, so that the adhesion between the core and the metal surface layer is lowered. Then, the metal surface layer can be reliably and easily peeled from the core by physically polishing the plating medium in a state where the adhesion is lowered. Therefore, each of Fe, Ni, and Sn can be separated from the plating media with higher accuracy.

  In the above-described invention, the anion exchange material is preferably a fibrous material. In this case, the specific surface area is large and the contact efficiency with the metal mixed aqueous solution can be improved. Moreover, the anion exchange material deteriorated by continuous use can be easily replaced with a new anion exchange material. Therefore, the separation accuracy in the separation step can be further improved, and a situation in which the efficiency of the separation step is reduced due to the trouble of newly exchanging the anion exchange material can be avoided.

  In the above-described invention, the Ni reduction step of reducing the Ni ions contained in the Ni ion aqueous solution to form a simple metal of Ni, and the Sn ions contained in the Sn ion aqueous solution are reduced to reduce the Sn metal. It is preferable to include an Sn reduction step for producing a simple substance.

  (Function / Effect) According to this configuration, after separating and recovering the Ni ion aqueous solution and the Sn ion aqueous solution by the separation step and the desorption step, the Ni ions are reduced to form a single metal of Ni and the Sn ions are reduced. To produce a single metal element of Sn. In this case, the Sn metal simple substance and the Ni metal simple substance can be collected separately from the used plating media. Since the Sn metal element and the Ni metal element can be used for a wider range of applications, the versatility of the process of separating and recovering metal from the plating media can be greatly improved.

In order to achieve such an object, the present invention may take the following configurations.
That is, the present invention is a recycling method of plating media comprising a spherical core made of Fe and a metal surface layer in which Ni and Sn are laminated on the surface of the core,
A dissociation step for dissociating the metal surface layer from the core with respect to the plating medium in a used state,
An ionization step of obtaining a mixed metal aqueous solution containing Ni ions and Sn ions by dissolving the metal surface layer dissociated from the core with an acid;
The metal ion solution is brought into contact with an anion exchange material having anion exchange properties, and the Sn ions are separated from the metal solution by selectively adsorbing the Sn ions to the anion exchange material, An ion separation step of obtaining a Ni ion aqueous solution containing only the Ni ions out of Sn ions and the Ni ions;
Water is brought into contact with the anion exchange material on which the Sn ions are adsorbed as an eluent, and the Sn ions are desorbed from the anion exchange material to the eluent to produce an Sn ion aqueous solution containing the Sn ions. A desorption process to be acquired;
A Ni plating step of reducing the Ni ions contained in the Ni ion aqueous solution and plating Ni on the surface of the core from which the metal surface layer has been dissociated;
After the Ni plating step, the Sn ion contained in the Ni ion aqueous solution is reduced, and a Sn plating step of plating Sn on the surface of the core in a state where Ni is plated;
It is characterized by providing.

  (Function / Effect) According to this method, by using an anion exchange material, Sn ions out of Sn ions and Ni ions contained in the metal mixed aqueous solution are selectively adsorbed to the anion exchange material. Therefore, Sn ions and Ni ions can be separated with higher accuracy.

  Further, in the desorption step, water is brought into contact with the anion exchange material on which Sn ions are adsorbed as an eluent, and Sn ions are desorbed from the anion exchange material to the eluent. Unlike the conventional method, the desorption step according to the present invention can desorb Sn ions from the ion exchange material with water without using acid or alkali, so that the cost and labor required for the treatment of waste liquid and separation of metal ions can be greatly reduced. .

  In this way, the Sn ion aqueous solution and the Ni ion aqueous solution can be separated and obtained by the separation step and the desorption step using the metal surface layer dissociated from the core in the dissociation step as a raw material. Then, by performing the Ni plating step and the Sn plating step on the core dissociated from the metal surface layer by the dissociation step, the Ni layer made of a single metal and the Sn layer are laminated on the surface of the core made of Fe. it can.

  In other words, the core has the same structure as that of a new plating medium by the Ni plating process and the Sn plating process. Accordingly, by using the core and the metal surface layer constituting the used plating medium, it is possible to regenerate the new plating medium without requiring a new metal. Therefore, the amount of plating media discarded can theoretically be zero.

  Moreover, in this invention, it can recycle from the used plating media to a new plating media with the comparatively small amount of acid used for melt | dissolution of a metal surface layer, and the water used for desorption. That is, the recycling method according to the present invention does not require the use of an organic solvent or an alkaline solution. Therefore, even when plating media is recycled in the plating plant, there is no need to newly install organic solvent treatment equipment and alkali treatment equipment, and it is possible to recycle plating media by diverting existing acid treatment equipment. Become.

  Therefore, the plating process and the plating media recycling process can be semipermanently repeated in the plating factory without transporting the plating media and waste liquid from the plating factory to an external processing facility. As a result, it is not necessary to discard the plating media, so that the usage efficiency of the plating media can be greatly improved.

In order to achieve such an object, the present invention may further have the following configuration.
That is, the present invention uses the first plating medium comprising a spherical core made of Fe and a metal surface layer in which Ni and Sn are laminated on the surface of the core, and Sn is laminated on the surface of the sphere made of Fe. A plating medium recycling method for producing a second plating medium having the above-described configuration,
A dissociation step for dissociating the metal surface layer from the core with respect to the first plating media in a used state;
An ionization step of obtaining a mixed metal aqueous solution containing Ni ions and Sn ions by dissolving the metal surface layer dissociated from the core with an acid;
The metal ion solution is brought into contact with an anion exchange material having anion exchange properties, and the Sn ions are separated from the metal solution by selectively adsorbing the Sn ions to the anion exchange material, An ion separation step of obtaining a Ni ion aqueous solution containing only the Ni ions out of Sn ions and the Ni ions;
Water is brought into contact with the anion exchange material on which the Sn ions are adsorbed as an eluent, and the Sn ions are desorbed from the anion exchange material to the eluent to produce an Sn ion aqueous solution containing the Sn ions. A desorption process to be acquired;
A Sn plating step of newly creating the second plating media by reducing the Sn ions contained in the Sn ion aqueous solution and plating Sn on the surface of the core from which the metal surface layer has been dissociated;
It is characterized by providing.

  (Function / Effect) According to this method, a first plating medium comprising a spherical core made of Fe and a metal surface layer in which Ni and Sn are laminated on the surface of the core is used to form a sphere made of Fe. The second plating media having a structure in which Sn is laminated on the surface can be easily reproduced at low cost. That is, by using an anion exchange material, Sn ions out of Sn ions and Ni ions contained in the metal mixed aqueous solution are selectively adsorbed on the anion exchange material. Therefore, Sn ions and Ni ions can be separated with higher accuracy.

  Further, in the desorption step, water is brought into contact with the anion exchange material on which Sn ions are adsorbed as an eluent, and Sn ions are desorbed from the anion exchange material to the eluent. Unlike the conventional method, the desorption step according to the present invention can desorb Sn ions from the ion exchange material with water without using acid or alkali, so that the cost and labor required for the treatment of waste liquid and separation of metal ions can be greatly reduced. .

  In this way, the Sn ion aqueous solution and the Ni ion aqueous solution can be separated and obtained by the separation step and the desorption step using the metal surface layer dissociated from the core in the dissociation step as a raw material. Then, by performing the Sn plating process on the core dissociated from the metal surface layer by the dissociation process, the Sn layer made of a single metal is laminated on the surface of the core made of Fe, and the second plating medium in a new state Can be played as.

  In other words, the core has the same structure as that of a new plating medium by the Ni plating process and the Sn plating process. Therefore, by using the core and the metal surface layer constituting the first plating medium in the used state, the new second plating medium can be regenerated without requiring a new metal.

  In the present invention, the first plating media in a used state is obtained by using a relatively small amount of acid used for dissolution of the metal surface layer constituting the first plating media and water used for desorption. It can be reused as the second plating medium in a new state. That is, the recycling method according to the present invention does not require the use of an organic solvent or an alkaline solution. Therefore, even when plating media is recycled in the plating plant, there is no need to newly install organic solvent treatment equipment and alkali treatment equipment, and it is possible to recycle plating media by diverting existing acid treatment equipment. Become.

  In the method for separating and recovering metal from the plating media according to the present invention and the method for recycling the plating media, dissociation of the metal surface layer from the used plating media, dissolution of the metal surface layer by acid treatment, Sn ion generation by the anion exchange material Sn ions and Ni ions are separated and recovered by a series of steps such as selective adsorption and desorption of Sn ions by water. In this case, various metals can be separated and recovered with high accuracy from the metal mixture of Ni and Sn dissociated from the plating media, and generation of waste liquid that is difficult to process can be further reduced.

2 is a cross-sectional view illustrating the structure of a plating medium according to Example 1. FIG. (A) is sectional drawing of the plating media in the new state before using for plating, (b) is sectional drawing of the plating media which grew by using for plating and became the used state. It is a flowchart explaining the outline | summary of the process which concerns on each Example. (A) is a flowchart of the first embodiment, and (b) is a flowchart of the second embodiment. It is a figure explaining step S1 and step S2 which concern on Example 1. FIG. (A) is a figure which shows the state of the plating media in step S1, (b) is a figure which shows the state of the plating media in step S2. It is a figure explaining step S4 which concerns on Example 1. FIG. (A) is a figure which shows the state before starting the flowing of metal mixed aqueous solution in step S4, (b) is a figure which shows the state after starting the flowing of metallic mixed aqueous solution in step S4. It is a figure explaining step S5 concerning Example 1. FIG. It is a figure explaining step S6 concerning Example 1. FIG. It is a figure which shows the density | concentration ratio of various metal ions in step S4 and step S5 in Example 1. FIG. (A) is a figure at the time of performing the liquid feeding speed to the column 17 in 1.0 ml / min in step S4, (b) is a figure in which the liquid feeding speed to the column 17 is 1.0 ml / min in step S5. (C) is a diagram in the case where the liquid feed rate to the column 17 is 2.0 ml / min in step S4, and (d) is a column 17 in the step S5. It is a figure at the time of performing the liquid feeding speed | rate to 2.0 ml / min. It is a figure which shows the process in which plating media are reproduced | regenerated in step S6 which concerns on Example 2. FIG. (A) is a figure which shows the core of the state which the metal surface layer dissociated in step S2, and the surface of Fe was exposed, (b) is the state which plated Ni with respect to the core of the state where the surface of Fe was exposed (C) is a figure which shows the state which plated Sn further with respect to the core in the state by which Ni was plated on the surface, and was reproduced | regenerated to the new plating medium. It is a figure explaining step S4 and step S5 which concern on a modification. (A) is a figure which shows the state before performing adsorption of Sn ion in step S4, (b) is a figure which shows the state after performing adsorption of Sn ion in step S4, (c) is step It is a figure which shows the state which has desorbed Sn ion in S5, (d) is a figure which shows the state from which desorption of Sn ion was completed in step S5, and Ni ion and Sn ion were isolate | separated. It is a figure which shows the process in which plating media are reproduced | regenerated in a modification. (A) is sectional drawing which shows the structure of the plating media reproduced | regenerated in a modification, (b) is a Ni layer from the plating media of the used state which Ni layer and Sn layer were laminated | stacked in multiple layers, and enlarged. It is a figure which shows the state of the plating media in each process for making it reproduce in the new plating media which do not have.

  Embodiment 1 of the present invention will be described below with reference to the drawings. In the first embodiment, a method for separating and recovering Ni and Sn from plating media used for plating Ni and Sn on an electronic component such as a capacitor will be described as an example.

  The plating media generally has a structure in which various metals used for plating are laminated around a core made of iron (Fe) or the like. FIG. 1A and FIG. 1B are cross-sectional views of a plating medium 1 used for plating Ni and Sn on a capacitor. In a new state before being used for barrel plating as shown in FIG. 1A, the plating medium 1 includes an iron core 3 and an Ni layer 5 and an Sn layer 7 laminated around the core 3. Yes. In the new state shown in FIG. 1A, each of the Ni layer 5 and the Sn layer 7 has a single-layer structure. In the new state, the diameter R of the plating medium 1 is about 0.1 mm to 3 mm as an example.

  Each time a new plating medium 1 shown in FIG. 1A is used for barrel plating and an object to be plated is plated with Ni and Sn, Ni and Sn are further laminated on the surface of the plating medium 1. That is, as a result of repeating barrel plating using the plating media 1, as shown in FIG. 1B, a large number of Ni layers 5 and Sn layers 7 (several to tens of layers as an example) are laminated on the plating media 1. As an example, the diameter R of the plating medium 1 grows (enlarges) to about 1 mm to 10 mm.

  In addition, the part which consists of the Ni layer 5 and the Sn layer 7 and is laminated on the surface of the plating medium 1 is referred to as a metal surface layer 4 and is distinguished from the core 3. In Example 1, as shown in FIG. 1B, Ni and Sn are separated and recovered from the plating medium 1 that has been grown by repeated use and is in a used state (conventional state of being discarded). . FIG. 2A is a flowchart illustrating the steps of the separation and recovery method according to the first embodiment. Hereafter, each process which concerns on Example 1 is demonstrated along the said flowchart.

Step S1 (Plating media heat treatment)
First, heat treatment is performed on the plating media 1 that has become enormous by repeated use in barrel plating and has been used. In the heat treatment according to step S1, it is particularly preferable to heat the plating medium 1 at 600 ° C. for 1 hour. Note that the temperature of the heat treatment may be appropriately applied as it is higher than the melting point of Sn and lower than the melting point of Fe. However, heating is preferably performed at 240 ° C. or higher and 1450 ° C. or lower. That is, it is more preferable that the temperature is higher than the melting point of Sn and lower than the melting point of Ni. Moreover, you may change a heating time suitably.

  The structure of the used media as shown in FIG. 1 (b) changes as shown in FIG. 3 (a) by the heat treatment. That is, the Sn layer 7 is melted by the heat treatment, and the Ni layer 5 is deformed and broken. As a result, the adhesion between the metal surface layer 4 and the core 3 is lowered, so that the metal surface layer 4 and the core 3 are easily separated in the subsequent step S2. The process of step S1 is complete | finished by returning the plating media 1 which heat-processed to normal temperature.

Step S2 (Separation of core and metal surface)
After returning the plating media 1 to room temperature, the core 3 and the metal surface layer 4 are separated. In Example 1, the core 3 and the metal surface layer 4 are separated by so-called co-rubbing, in which the plating media 1 are rubbed together. As an example, the plating medium 1 that has become room temperature after the heat treatment is transferred into a polygonal barrel. Then, the plating media 1 are polished by rotating the barrel, and the metal surface layer 4 is dissociated from the core 3 as a powder having a relatively small particle diameter as shown in FIG. The rotation speed of the barrel is preferably 40 rpm or more and 50 rpm or less, but may be appropriately changed according to various conditions such as the number and size of the plating media 1.

  After completion of co-grinding, the mixture of the core 3 and the metal surface layer 4 remaining in the barrel is transferred to a classifier (Otake fc2k, manufactured by Otake Manufacturing Co., Ltd.), and sorting is performed according to the particle size. As shown in FIG. 3B, the metal surface layer 4 is in the form of a powder having a particle size smaller than that of the core 3 by co-sliding. Therefore, by this sorting, the metal surface layer 4 made of Ni and Sn and the core 3 made of Fe can be completely separated. The step of sorting by the co-grinding and classifier according to step S2 is an example of a technique for separating the core 3 and the metal surface layer 4, and is not limited to the technique. By separating and recovering the core 3 and the metal surface layer 4, the step S2 is completed. A series of steps according to step S2 corresponds to the dissociation step in the present invention.

Step S3 (metal ionization)
After separating the metal surface layer 4 from the core 3, the metal is ionized. That is, an acid treatment is performed on the metal surface layer 4 to create an aqueous solution of metal ions. The metal surface layer 4, which is a mixture of Ni and Sn, is dissolved by acid treatment, and a metal mixed aqueous solution 13 containing Ni ions 9 and Sn ions 11 is obtained. In Example 1, the acid treatment is performed by adding 240 ml of 9% vol hydrochloric acid to 6.0 g of the metal surface layer 4 powder and reacting at 80 ° C. for 24 hours.

Each of the above conditions is a particularly preferable example, and the conditions for the acid treatment can be appropriately changed as long as Ni and Sn can be completely dissolved and ionized. As an example, conditions such as hydrochloric acid concentration and reaction time may be changed as appropriate. In addition, other acids such as sulfuric acid and nitric acid can be used as a substitute for hydrochloric acid. In the metal mixed aqueous solution 13 obtained by the acid treatment according to step S3, the concentration of Ni ions 9 is 129.5 mol / m ³ and the concentration of Sn ions 11 is 202.2 mol / m ³ . In each step of the present invention, the concentrations of Ni ions 9 and Sn ions 11 are measured using an ICP emission spectroscopic analyzer (ICP-8100, manufactured by SHIMADZU). A series of steps according to step S3 corresponds to an ionization step in the present invention.

Step S4 (ion exchange process)
After the acid treatment is completed and the metal mixed aqueous solution 13 is obtained, the ion exchange treatment according to step S4 is performed. As shown in FIG. 4A, the ion exchange treatment is performed by feeding the metal mixed aqueous solution 13 to the column 17 filled with the anion exchange fibers 15 with a pump (not shown). The anion exchange fiber 15 corresponds to the anion exchange material in the present invention.

  Various conditions relating to the ion exchange treatment are as follows. A commercially available anion exchange fiber 15 can be used as the anion exchange fiber 15, and in Example 1, a strong anion exchange fiber (IEF-SA, manufactured by Nichibi Corporation) having a trimethylammonium group as an ion exchange group is used. . The column 17 has an inner diameter of 1.0 cm and a length of 20 cm. The column 17 is filled with 2.0 g of anion exchange fiber 15. The liquid feed rate of the metal mixed aqueous solution 13 to the column 17 filled with the anion exchange fiber 15 is particularly preferably 1.0 ml / min or more and 2.0 ml / min or less.

As the metal mixed aqueous solution 13 fed to the column 17, the aqueous solution obtained in step S3 can be used as it is. That is, in the metal mixed aqueous solution 13 fed to the column 17, the concentration of Ni ions 9 is 129.5 mol / m ³ and the concentration of Sn ions 11 is 202.2 mol / m ³ . The pH of the metal mixed aqueous solution 13 to be fed is 0-1. The temperature of the liquid feeding is appropriately changed depending on the properties of the anion exchange fiber 15, but in Example 1, the liquid feeding is performed at room temperature (for example, 25 ° C.).

  By the ion exchange process according to step S4, the Ni ions 9 and the Sn ions 11 can be separated with high accuracy. That is, as shown in FIG. 4B, Sn ions 11 among the metal ions contained in the metal mixed aqueous solution 13 are selectively adsorbed to the anion exchange fiber 15. On the other hand, the Ni ions 9 are discharged through the column 17 without being adsorbed by the anion exchange fibers 15. As a result, an aqueous Ni ion solution 19 containing only Ni ions 9 among metal ions can be obtained. A series of steps according to step S4 corresponds to the separation step in the present invention.

Step S5 (desorption process)
After the Ni ions 9 and the Sn ions 11 are separated by the ion exchange process, a desorption process is performed. That is, as shown in FIG. 5, the Sn ion 11 is desorbed from the anion exchange fiber 15 by feeding the eluent 21 to the anion exchange fiber 15 that selectively adsorbs the Sn ions 11. Since the desorbed Sn ions 11 are discharged from the column 17 together with the eluent 21, an Sn ion aqueous solution 23 containing only the Sn ions 11 among the metal ions can be obtained.

  In the desorption process according to step S5, water can be used as the eluent 21. In Example 1, ultrapure water is used as the eluent 21, but distilled water or the like may be used. The liquid feeding speed of the eluent 21 is particularly preferably 1.0 ml / min or more and 2.0 ml / min or less. The liquid feeding temperature of the eluent 21 is performed at room temperature. Through the steps S1 to S5, the Ni ion aqueous solution 19, the Sn ion aqueous solution 23, and the spherical core 3 made of Fe can be obtained separately from the used plating media 1 respectively. A series of steps according to step S5 corresponds to a desorption step in the present invention.

Step S6 (collection process)
After each of the Ni ion aqueous solution 19 and the Sn ion aqueous solution 23 is obtained, each of the Ni ions and the Sn ions is reduced by a recovery process, and recovered in a state of being separated as a single metal of Ni and Sn, respectively. As an example of the recovery process, there is a method in which each metal ion is reduced by electrolysis and deposited as a simple metal on the electrode. When recovering the pure metal of Ni, as shown in FIG. 6, electrolysis is performed using the Ni ion aqueous solution 19 obtained in step S4 as an electrolytic solution. The Ni ions 9 in the Ni ion aqueous solution 19 are reduced by electrolysis, and a high-purity Ni metal simple substance 29 is deposited on the surface of the electrode 27 on the cathode side.

  The electrolysis in Example 1 is performed by flowing a current of 0.3 A for 10 minutes. Further, although Cu plates are used as the electrode 25 and the electrode 27, other materials may be appropriately used as long as they can deposit Ni. When the Sn ions 11 are reduced and the pure metal of Sn is recovered, electrolysis is performed using the Sn ion aqueous solution 23 obtained in step S5 as an electrolytic solution. Although the Fe plate is used as the electrode 25 and the electrode 27, other materials may be appropriately used as long as they can deposit Sn. Pure metals Ni and Sn can be recovered separately. A series of steps for separating and recovering Ni and Sn from the plating medium 1 is completed by the steps S1 to S6.

  Here, the separation and recovery efficiency of metal according to Example 1 will be described using the graphs of FIG. 7 while showing data of the concentration ratios (C / C0) of various metal ions in steps S4 and S5.

  The concentration ratio in step S4 (ion exchange treatment) is the liquid obtained from the outlet of the column 17, that is, the metal ion concentration (C) contained in the Ni ion aqueous solution 19, and the liquid sent to the inlet of the column 17, that is, the metal mixture It is determined by the ratio with the metal ion concentration (C0) contained in the aqueous solution 13.

  The concentration ratio (concentration rate) in step S5 (desorption treatment) is obtained by the liquid obtained from the outlet of the column 17, that is, the metal ion concentration (C) contained in the Sn ion aqueous solution 23, and the operation of step S3. It is obtained by the ratio with the metal ion concentration (C0) contained in the initial metal mixed aqueous solution 13.

  When the ion exchange process according to step S4 is performed at a liquid feed rate of 1.0 ml / min, as shown in FIG. 7A, the concentration ratio of Ni ions 9 indicated by rhombus symbols is approximately 1.0. . That is, the concentration of Ni ions 9 is substantially the same in the metal mixed aqueous solution 13 passed through from the inlet of the column 17 and the Ni ion aqueous solution 19 obtained as the liquid discharged from the outlet of the column 17. That is, it can be seen that the Ni ions 9 pass through the column 17 without being adsorbed by the anion exchange fibers 15 and are discharged from the outlet of the column 17.

  On the other hand, in the diagram of FIG. 7A, the concentration ratio of Sn ions 11 indicated by triangular symbols is initially zero. That is, it can be seen that the Sn ion 11 is not contained in the Ni ion aqueous solution 19 and the Sn ion 11 is all adsorbed on the anion exchange fiber 15. However, after about 30 minutes, the anion exchange fiber 15 breaks through, and the drained liquid of the column 17 contains Sn ions 11. When ion exchange treatment is performed at a liquid feed rate of 1.0 ml / min, the treatment time is preferably 25 minutes or less. Thus, it can be seen that the ion exchange treatment using the anion exchange fiber 15 according to Example 1 can separate the Ni ions 9 and the Sn ions 11 with very high accuracy.

  When the ion exchange process according to step S4 is performed at a liquid feed rate of 2.0 ml / min, as shown in FIG. 7B, the concentration ratio of Ni ions 9 is approximately 1.0, while the Sn ions 11 The concentration ratio is initially zero. That is, it can be seen that Sn ions 11 are selectively adsorbed on the anion exchange fiber 15 even under the condition of a liquid feeding rate of 2.0 ml / min. However, since breakthrough occurs after about 20 minutes, the treatment time is preferably 10 minutes or less when the ion exchange treatment is performed at a liquid feed rate of 2.0 ml / min.

When the desorption process according to step S5 is performed at a liquid feed rate of 1.0 ml / min, the concentration rate of Sn ions 11 is 3.5 times at the maximum as shown in FIG. That is, since the concentration of Sn ions 11 contained in the Sn ion aqueous solution 23 can be increased to about 700 mol / m ³ , it is possible to further improve the recovery efficiency of Sn in the metal simple substance state in Step S6.

  When the desorption process is performed at a liquid feed rate of 1.0 ml / min, it is preferable to recover the liquid discharged from the column 17 as the Sn ion aqueous solution 23 when the time of 30 minutes or less has elapsed after the process starts. It is particularly preferable to collect the effluent when a time of 5 minutes to 15 minutes has elapsed.

  When the desorption process according to step S5 is performed at a liquid feed rate of 2.0 ml / min, the concentration rate of Sn ions 11 is 1.8 times at the maximum as shown in FIG. When the desorption process is performed at a liquid feed rate of 2.0 ml / min, it is preferable to collect the liquid discharged from the column 17 as the Sn ion aqueous solution 23 when the time of 15 minutes or less has elapsed after the process starts. It is particularly preferable to collect the effluent when a time of 5 minutes to 10 minutes has elapsed.

  As a mechanism capable of separating the Ni ions 9 and the Sn ions 11 in the ion exchange process according to the first embodiment, the following hypothesis can be considered. That is, it is considered that the Sn ions 11 form complex ions having chloride ions or hydroxide ions as ligands under acidic conditions in which the metal surface layer 4 is dissolved, particularly under strong acidic conditions of pH 0 to 1. .

  In this case, since complex ions containing Sn exhibit a behavior as anions as a whole, it is considered that the complex ionized Sn ions 11 are selectively adsorbed by the anion exchange fibers 15. On the other hand, Ni ions 9 do not form complex ions under acidic conditions and behave as cations like general metal ions. Therefore, Ni ions 9 are not adsorbed on the anion exchange fiber 15. It is thought that the column 17 was passed.

<Effects of Configuration of Example 1>
With the configuration of Example 1, by repeatedly using it for plating operations, the plating metal stacked on the surface is separated and recovered with high efficiency from the plating media in which Ni and Sn, which are plating metals, are stacked and enlarged. And can be reused. Therefore, conventionally, a plating metal that can be disposed of together with the plating medium can be effectively used.

  In Example 1, the bonding between the core 3 and the metal surface layer 4 is weakened by performing the heat treatment according to Step S1 on the plating medium 1 that has become enlarging and used. Therefore, the core 3 and the metal surface layer 4 can be more easily dissociated at the time of physical polishing according to step S2. By the dissociation, the core 3 made of spherical Fe can be separated and recovered.

  By the acid treatment according to step S3, Ni and Sn forming the metal surface layer 4 are ionized, and a metal mixed aqueous solution in which a plurality of metal ions are mixed can be obtained. Even when a part of Ni and Sn is alloyed in the metal surface layer 4 during the heat treatment according to step S1, Ni and Sn alloyed by dissolving by acid treatment are surely Ni ions and It will be in the state isolate | separated into Sn ion. That is, by separating and recovering each of the plating metals after ionization, the problem of difficulty in separating and recovering due to alloying of the metals can be reliably avoided.

  In Example 1, Ni ions and Sn ions are separated by the ion exchange process according to step S4. In general, in a conventional metal separation and recovery method using a cation exchange resin as an ion exchange material, the selectivity of the ion exchange material with respect to metal ions is low, and a plurality of metal ions are all adsorbed on the ion exchange resin. Therefore, it is difficult to separate a plurality of metals with high accuracy.

  On the other hand, the inventor's diligent study revealed that Sn ions can be selectively adsorbed to the ion exchange material from a mixed aqueous solution of Ni ions and Sn ions by using strong anion exchange fibers as the ion exchange material. did. Ni ions are discharged without being adsorbed by the anion exchange fiber 15.

  That is, in Example 1, a plurality of metal ions (Ni ions and Sn ions) in the metal mixed solution can be completely separated at the stage of passing the metal mixed aqueous solution through the ion exchange material. Therefore, Ni ions and Sn ions can be separated with very high accuracy by the ion exchange treatment using the anion exchange fiber 15 and can be recovered as separate aqueous solutions.

  It has also been found that the selective adsorptivity of the anion exchange fiber 15 with respect to the Sn ions 11 is exhibited even under strong acidity. Therefore, Sn ions 11 can be selectively adsorbed by passing the metal mixed aqueous solution obtained by dissolving the metal surface layer 4 with a strong acid through the anion exchange fiber 15 as it is without performing any special treatment. Therefore, it is possible to suppress the labor and cost required for the selective adsorption of Sn ions 11.

  Further inventor's diligent study revealed that water can be surprisingly used as an eluent for desorbing Sn ion 11 from anion exchange fiber 15 adsorbing Sn ion 11. In the conventional ion exchange method, when metal ions are desorbed from an ion exchange material, it is necessary to feed a large amount of acid or alkali as an eluent and adjust pH appropriately. As a result, a large amount of acid and alkali waste liquid is generated, which increases the cost and labor required for waste liquid treatment.

  On the other hand, in the separation and recovery method according to Example 1, Sn ions 11 can be desorbed from the anion exchange fiber 15 by passing water, and an Sn ion aqueous solution 23 containing only Sn ions 11 can be obtained. Since water is used as an eluent in the desorption treatment according to Example 1, the solution required in the metal separation and recovery step is limited to an acid for dissolving the metal surface layer 4 in addition to water. Therefore, the cost required for waste liquid treatment can be reduced as compared with the conventional method, and deterioration of the anion exchange fiber 15 caused by passing a large amount of acid or alkali can be avoided.

  Further, unlike the conventional ion exchange treatment using a cation exchange material, the ion exchange treatment of Example 1 can avoid a situation where a plurality of metal ions are adsorbed on the anion exchange fiber 15 which is an ion exchange material. That is, in Example 1, out of the Ni ions 9 and the Sn ions 11, the Sn ions 11 are selectively adsorbed on the anion exchange fiber 15, and the Ni ions 9 pass without being adsorbed. Therefore, when the Sn ions 11 are desorbed from the anion exchange fiber 15, a situation in which the Ni ions 9 are desorbed together with the Sn ions 11 and the Ni ions 9 are mixed into the Sn ion aqueous solution 23 can be avoided.

  As a result, it is possible to reliably avoid the mixing of the Ni ions 9 into the Sn ion aqueous solution 23 obtained by the desorption of the Sn ions 11, so that the advantage of the ion exchange method that it is suitable for the treatment of a large volume metal mixed aqueous solution is utilized. The separation accuracy between the Sn ions 11 and the Ni ions 9 can be greatly improved.

  Further, as an advantageous feature of the separation and recovery method according to the present invention, it is possible to separate and recover Ni and Sn from the plating medium 1 using water and a relatively small amount of acid without requiring an organic solvent or an alkali. . Therefore, when a metal is separated and recovered from the plating media by the method according to the present invention in a plating factory, the existing equipment can be used to separate and recover the metal.

  In general, in a plating process using an electronic component or the like as an object to be plated, an acid treatment process for the purpose of removing an oxide film or the like is essential. Therefore, it is common for the plating factory to be equipped in advance with equipment for performing acid treatment. On the other hand, since the treatment with an organic solvent or alkali is not essential in the plating treatment, the organic solvent treatment equipment and the alkali treatment equipment are often not provided in the plating factory.

  Therefore, when separation / recovery is performed in a plating factory using a conventional ion exchange method or solvent extraction method, the conventional separation / recovery method requires an organic solvent or an alkali. In addition, it is necessary to prepare a new facility for the treatment of alkali and alkali, and further, the treatment of organic and alkaline waste. On the other hand, in the separation and recovery method according to the present invention, Ni and Sn can be separated and recovered from the plating medium with high accuracy using an existing acid treatment facility in the plating factory. Therefore, the barrel plating process and the process of separating and recovering the metal from the plating medium can be continuously performed in the plating factory without outsourcing.

  Next, a second embodiment of the present invention will be described. In the first embodiment, the present invention has been described by taking as an example a method for separating and recovering Ni and Sn from the plating medium 1 in a used state. In the second embodiment, a plating medium recycling method in which the plating medium 1 in a used state (FIG. 1B) is regenerated into a new plating medium 1 (FIG. 1A) will be described as an example. To do.

  Each step in the plating media recycling method according to Example 2 is as shown in FIG. That is, Example 1 and Example 2 are common about step S1 to S5. Therefore, description of each process of steps S1 to S5 according to the second embodiment will be omitted, and step S6 will be described.

Step S6 (reproduction process)
Through the steps S1 to S2, the metal surface layer 4 and the Fe core 3 are dissociated using the plating media 1 in a used state. And by the process from step S3 to S5, each of the Ni ion aqueous solution 19 and the Sn ion aqueous solution 23 is acquired in the separated state from the metal surface layer 4 which is a mixture of Ni and Sn. In step S6 according to the second embodiment, the plating media 1 is formed using the Ni ion aqueous solution 19 and the Sn ion aqueous solution 23 and the core 3 that is dissociated from the metal surface layer 4 in the step S2 and the surface of Fe is exposed. Perform the playback process.

  The regeneration process includes a Ni plating process for applying Ni plating to the core 3 and a Sn plating process for applying Sn plating to the core 3 subjected to Ni plating. Each plating process is performed by an electrolysis process as shown in FIG. First, the configuration of the Ni plating process will be described. Specifically, the Ni ion aqueous solution 19 obtained by passing through the column 17 in step S4 is used as the electrolytic solution. Electrolysis is performed using the core 3 with the Fe surface exposed as the cathode-side electrode 27. Other conditions are the same as step S6 according to the first embodiment.

  By passing an electric current, the Ni ions 9 in the Ni ion aqueous solution 19 are reduced, and pure Ni metal is deposited on the Fe surface of the core 3 constituting the cathode-side electrode 27. That is, Ni re-plating is performed on the core 3 (FIG. 8A) with the Fe surface exposed, and the Ni layer 5 is formed on the surface of the core 3 (FIG. 8B). ).

  After the Ni layer 5 is formed, the Sn layer 7 is subsequently formed by the Sn plating process. In Example 2, the Sn layer 7 is formed by electrolysis using the Sn ion aqueous solution 23 obtained by desorption in Step S5 as an electrolytic solution. The electrolysis is performed using the core 3 with the Ni layer 5 formed on the surface as the cathode-side electrode 27.

  By passing an electric current, Sn ions 11 in the Sn ion aqueous solution 23 are reduced, and a pure metal of Sn is deposited on the Ni surface of the core 3 constituting the electrode 27 on the cathode side. That is, Sn re-plating is performed on the core 3 (FIG. 8B) in a state where the Ni layer 5 is formed on the surface, and the Sn layer 7 is formed on the surface of the Ni layer 5 (FIG. 8). (C)). In step S6 according to the second embodiment, the thicknesses of the Ni layer 5 and the Sn layer 7 can be appropriately adjusted accurately depending on the strength of the current, the time during which the current flows, and the like.

  By forming the Ni layer 5 and the Sn layer 7 on the core 3 again, a new plating medium 1 is regenerated (FIG. 1A). The new plating medium 1 can be subjected to barrel plating again. When the reproduction of the plating media 1 is completed, each process related to the recycling method of the plating media 1 is completed.

<Effects of Configuration of Example 2>
In Example 2, similarly to Example 1, Ni ions 9 and Sn ions 11 are recovered in a separated state using the plating medium 1 that has become enlarging and used. That is, a metal mixed aqueous solution 13 obtained by dissolving the metal surface layer 4 made of Ni and Sn with a strong acid is passed through the anion exchange fiber 15 as it is to selectively adsorb Sn ions 11 to obtain a Ni ion aqueous solution 19. And Sn ion 11 is desorbed with respect to the said anion exchange fiber 15 by using water as an eluent, and Sn ion aqueous solution 23 is obtained.

  Therefore, in Example 2, the same effect as Example 1 can be acquired. That is, Ni and Sn constituting the metal surface layer 4 can be separated with high accuracy only by the acid required for dissolution of the metal surface layer 4 and the water required for desorption. That is, since the process according to the second embodiment does not require an organic solvent or an alkali, the recycling process according to the second embodiment can be performed by diverting an existing acid treatment facility or acid waste liquid treatment facility in a plating factory.

  Further, no special treatment is required for the metal mixed aqueous solution 13 and the water as the eluent, and the Sn ion 11 is adsorbed to the anion exchange fiber 15 or the Sn ion is desorbed from the anion exchange fiber 15. Each process is completed by passing one time. Therefore, the cost and labor required for the separation and recovery process of Ni and Sn can be greatly recommended, and the amount of waste liquid generated in the separation and recovery process can be greatly reduced.

  Furthermore, in Example 1, the separated Ni ions and Sn ions are separated and recovered as pure metals. On the other hand, in Example 2, in addition to the Ni ion aqueous solution 19 and the Sn ion aqueous solution 23 obtained in the separated state, the core 3 from which the metal surface layer 4 was peeled was used, and the Ni 3 and Sn plating were applied to the core 3 in a state where Fe was exposed. The plating media 1 is regenerated by applying the above again.

  With the configuration of Example 2, it is possible to easily recycle used plating media that have become enormous by repeated use in plating operations and can no longer be used in the plating plant where the plating operation is performed. That is, the use of the plating media by barrel plating and the regeneration of the used plating media can be semipermanently repeated inside the plating factory. By realizing such a semi-permanent plating media recycling process in the same plating factory, the efficiency of using the plating media can be greatly improved.

  The present invention is not limited to the above embodiment, and can be modified as follows.

  (1) In each of the above-described embodiments, the anion exchange fiber 15 may be any material that exhibits an anion exchange action, and may be in the form of a resin, gel, or the like in addition to the fiber. However, it is particularly preferable to use a fibrous material as the anion exchange material from the viewpoint that the specific surface area is large and the contact efficiency with the metal mixed aqueous solution 13 is high, and that it can be easily taken out from the column 17 and exchanged.

  (2) In each of the above-described embodiments, the metal mixed aqueous solution 13 containing Ni ions 9 and Sn ions 11 was obtained by dissolving the metal surface layer 4 of the plating media 1 with an acid. The method is not limited to this. As an example, the metal surface layer 4 of the used plating media may be dissolved by a method other than acid treatment. Moreover, it is not restricted to the method acquired from the metal surface layer 4 of a plating medium, You may obtain the metal mixed aqueous solution 13 as waste water containing Ni and Sn produced | generated by another work process.

  (3) In each of the embodiments described above, step S4 and step S5 are performed using a so-called column method in which the metal mixed aqueous solution 13 or the eluent 21 is pumped through the column 17 filled with the anion exchange fiber 15. It was broken. However, each process concerning this step S4 and step S5 is not restricted to the structure performed by the column method. That is, as an example, the steps S4 and S5 may be performed using a batch method or the like.

  FIGS. 9A and 9B show a configuration in which the process according to step S4 is performed by a batch method. That is, the metal mixed aqueous solution 13 obtained in step S <b> 3 is transferred to the container H, and the anion exchange fiber 15 is brought into contact with the metal mixed aqueous solution 13. By sufficiently stirring the anion exchange fiber 15 inside the container H, the Sn ions 11 out of the Ni ions 9 and the Sn ions 11 contained in the metal mixed aqueous solution 13 are selectively adsorbed on the anion exchange fibers 15. The As a result, as shown in FIG. 9B, Sn ions 11 are separated from the metal mixed aqueous solution 13, and the metal mixed aqueous solution 13 becomes a Ni ion aqueous solution 19.

  FIGS. 9C and 9D show a configuration in which the process according to step S5 is performed by the batch method. That is, the anion exchange fiber 15 on which Sn ions 11 are selectively adsorbed is removed from the container H and transferred to the container K filled with water as the eluent 21 (FIG. 9C). By bringing the anion exchange fiber 15 into contact with the water that is the eluent 21, the Sn ions 11 are desorbed from the anion exchange fiber 15 and mixed with the water that is the eluent 21. As a result, the water that is the eluent 21 becomes the Sn ion aqueous solution 23 containing the Sn ions 11. Finally, by removing the anion exchange fiber 15 from the container K, the Ni ion aqueous solution 19 and the Sn ion aqueous solution 23 can be obtained separately (FIG. 9D).

  (4) In Example 2 described above, iron (core 3), nickel (Ni ion aqueous solution 19), and tin (Sn ion aqueous solution 23) separated and recovered from the used plating media 1 by the method according to Example 1 As an example of a method for effectively using each of the above, a method for regenerating the plating media has been described. However, the new plating media 1 obtained by the regeneration process is a plating media in which the Ni layer 5 and the Sn layer 7 are laminated on the core 3 one by one as shown in FIG. There is no limit.

  That is, the structure of the plating media 1 used for the plating process may vary depending on the content of the plating process. As an example, as shown in FIG. 10A, a metal sphere in which a thin Sn layer 7 is laminated on the surface of an iron core 3 has recently been used as the plating medium 1a. The diameter of the plating medium 1a in a new state is the same as the diameter R of the plating medium 1 in a new state, and is about 0.1 mm to 3 mm as an example.

  Hereinafter, as a modified example of the plating medium recycling method, a method of regenerating a plating medium not including the Ni layer 5 as a new plating medium from a used plating medium including the Ni layer 5 and the Sn layer 7 will be described. In the following modification, the plating medium in which the Ni layer 5 and the Sn layer 7 are laminated on the core 3 corresponds to the first plating medium in the present invention. Moreover, the plating media in which the Sn layer 7 is laminated on the core 3 without including the Ni layer 5 corresponds to the second plating media in the present invention.

  The flowchart in the modification is basically the same as that in the second embodiment (FIG. 2B). However, the process of the reproduction process according to step S6 is different between the second embodiment and the second modification. That is, in step S6 according to the second embodiment, a Ni plating process for applying Ni plating to the core 3 and a Sn plating process for applying Sn plating to the core 3 subjected to Ni plating are performed. On the other hand, in step S6 according to the modification, only the step of Sn plating treatment for applying Sn plating to the core 3 is performed.

  In step S1 according to the modified example, similarly to step S1 according to the first and second embodiments, the multilayer Ni layer 5 and the Sn layer 7 are laminated on the core 3 as the used plating medium 1 to form a huge The plated media 1 in a converted state is used (FIG. 1 (b), FIG. 10 (b) left).

  Then, as in Example 1 and Example 2, the core 3 made of Fe, the Ni ion aqueous solution 19 and the Sn ion aqueous solution 23 are made from the used plating medium 1 as a raw material by the steps S1 to S5. It collect | recovers in the isolate | separated state (FIG.10 (b) center).

  In Step S6 according to the modification, Sn plating is performed on the core 3 obtained from the used plating medium 1 using the Sn ion aqueous solution 23 separated and recovered in Step S5. By the Sn plating process, a metal ball having a structure in which the Sn layer 7 is laminated on the core 3 is obtained as a new plating medium 1a (right in FIG. 10B). The Ni ion aqueous solution 19 separated and recovered in the modified example can be reused for other purposes in the state of an aqueous solution or the state reduced to a single metal of nickel. By recycling the plating medium 1a in the new state from the plating medium 1 in the used state, the recycling process of the plating medium according to the modification is completed.

  In such a modified example, the Ni layer 5 and the Sn layer 7 are stacked in multiple layers, and the plating medium 1 that has been used is used as a raw material, and another type of plating medium 1a that does not have the Ni layer 5 is used. Can be reproduced as new plating media. In the regeneration step, Ni ions and Sn ions can be separated by using the anion exchange fiber 15 and water, as in each example. Therefore, the solution required in the process according to the modified example is limited to an acid for dissolving the metal surface layer 4 in addition to water. Accordingly, it is possible to reduce the cost required for the waste liquid treatment, and it is also possible to avoid a situation in which the anion exchange fiber 15 is deteriorated due to passing a large amount of acid or alkali.

  (5) In Example 2 described above, the new plating media 1 was regenerated using all of the core 3, the Ni ion aqueous solution 19, and the Sn ion aqueous solution 23 separated and recovered from the used plating media 1. The method is not limited to using all the separated and recovered materials, and a new plating medium 1 may be regenerated using some materials. As an example, a newly manufactured iron ball is prepared as the core 3, and the Ni ion aqueous solution 19 separated and recovered from the used plating medium 1 and the Sn ion aqueous solution 23 are used to remove Ni from the iron ball. There is a method in which a plating medium 1 is newly created by performing plating and Sn plating.

  In the method according to (5), even if the core 3 separated in step S2 is not suitable for reuse due to reasons such as scratches and deformation, nickel and tin among the separated and recovered materials. The plating media 1 can be regenerated by reusing. The method of recycling the plating media using a part of the separated and recovered material can be applied to the modified example according to (4) in addition to the second embodiment.

  In each example and modification, the core 3 uses an iron metal sphere, but this is not limited to a metal sphere that does not contain any material other than iron. That is, in the present invention, the “spherical core made of Fe” and the “sphere made of Fe” include metal spheres mainly composed of Fe.

DESCRIPTION OF SYMBOLS 1 ... Plating medium 3 ... Core 4 ... Metal surface layer 5 ... Ni layer 7 ... Sn layer 9 ... Ni ion 11 ... Sn ion 13 ... Metal mixed aqueous solution 15 ... Anion exchange fiber (anion exchange material)
17 ... Column 19 ... Ni ion aqueous solution 21 ... Eluent 23 ... Sn ion aqueous solution 25 ... Electrode 27 ... Electrode

Claims (8)

A method of separating and recovering metal from a plating medium comprising a spherical core made of Fe and a metal surface layer in which Ni and Sn are laminated on the surface of the core,
A dissociation step for dissociating the metal surface layer from the core with respect to the plating medium in a used state,
An ionization step of obtaining a mixed metal aqueous solution containing Ni ions and Sn ions by dissolving the metal surface layer dissociated from the core with an acid;
The Sn ion is separated from the metal mixed aqueous solution by bringing the metal mixed aqueous solution into contact with an anion exchange material having anion exchange property and selectively adsorbing the Sn ions on the anion exchange material, A separation step of obtaining a Ni ion aqueous solution containing only the Ni ions out of Sn ions and the Ni ions;
Water is brought into contact with the anion exchange material on which the Sn ions are adsorbed as an eluent, and the Sn ions are desorbed from the anion exchange material to the eluent to produce an Sn ion aqueous solution containing the Sn ions. A desorption process to be acquired;
A method for separating and recovering metal from plating media, comprising: A method for separating and recovering metal from the plating media according to claim 1,
The dissociation step includes
A heat treatment step of heat-treating the plating media in a used state at a temperature of 240 ° C. or higher and 1450 ° C. or lower;
A polishing step of physically polishing the plating media after the heat treatment step and peeling the metal surface layer from the core;
A method for separating and recovering metal from plating media, comprising: A method for separating and recovering a metal from the plating media according to claim 1 or 2,
The method for separating and recovering metal from a plating medium, wherein the anion exchange material is a fibrous material. A method for separating and recovering metal from the plating media according to any one of claims 1 to 3,
A Ni reduction step in which the Ni ions contained in the Ni ion aqueous solution are reduced to form a single metal of Ni;
A Sn reduction step of reducing the Sn ions contained in the Sn ion aqueous solution to produce a Sn metal element;
A method for separating and recovering metal from plating media, comprising: A plating medium recycling method comprising a spherical core made of Fe and a metal surface layer in which Ni and Sn are laminated on the surface of the core,
A dissociation step for dissociating the metal surface layer from the core with respect to the plating medium in a used state,
An ionization step of obtaining a mixed metal aqueous solution containing Ni ions and Sn ions by dissolving the metal surface layer dissociated from the core with an acid;
The metal ion solution is brought into contact with an anion exchange material having anion exchange properties, and the Sn ions are separated from the metal solution by selectively adsorbing the Sn ions to the anion exchange material, An ion separation step of obtaining a Ni ion aqueous solution containing only the Ni ions out of Sn ions and the Ni ions;
Water is brought into contact with the anion exchange material on which the Sn ions are adsorbed as an eluent, and the Sn ions are desorbed from the anion exchange material to the eluent to produce an Sn ion aqueous solution containing the Sn ions. A desorption process to be acquired;
A Ni plating step of reducing the Ni ions contained in the Ni ion aqueous solution and plating Ni on the surface of the core from which the metal surface layer has been dissociated;
After the Ni plating step, the Sn ion contained in the Sn ion aqueous solution is reduced, and a Sn plating step of plating Sn on the surface of the core plated with Ni;
A method for recycling plating media, comprising: It is the recycling method of the plating media of Claim 5, Comprising:
The dissociation step includes
A heat treatment step of heat-treating the plating media in a used state at a temperature of 240 ° C. or higher and 1450 ° C. or lower;
A polishing step of physically polishing the plating media after the heat treatment step and peeling the metal surface layer from the core;
A method for recycling plating media, comprising: A plating media recycling method according to claim 5 or claim 6,
The plating media recycling method, wherein the anion exchange material is a fibrous material. A first plating medium comprising a spherical core made of Fe and a metal surface layer in which Ni and Sn are laminated on the surface of the core is used to provide a structure in which Sn is laminated on the surface of a sphere made of Fe. A plating media recycling method for creating the plating media of No. 2,
A dissociation step for dissociating the metal surface layer from the core with respect to the first plating media in a used state;
An ionization step of obtaining a mixed metal aqueous solution containing Ni ions and Sn ions by dissolving the metal surface layer dissociated from the core with an acid;
The metal ion solution is brought into contact with an anion exchange material having anion exchange properties, and the Sn ions are separated from the metal solution by selectively adsorbing the Sn ions to the anion exchange material, An ion separation step of obtaining a Ni ion aqueous solution containing only the Ni ions out of Sn ions and the Ni ions;
Water is brought into contact with the anion exchange material on which the Sn ions are adsorbed as an eluent, and the Sn ions are desorbed from the anion exchange material to the eluent to produce an Sn ion aqueous solution containing the Sn ions. A desorption process to be acquired;
A Sn plating step of newly creating the second plating media by reducing the Sn ions contained in the Sn ion aqueous solution and plating Sn on the surface of the core from which the metal surface layer has been dissociated;
A method for recycling plating media, comprising:

Images