JPH0694598B2 - Method for removing impure metal ions in copper electrolyte - Google Patents

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for removing impure metal ions from a copper electrolyte.

[0002]

2. Description of the Related Art As a method for refining copper, a method in which crude copper is used as an anode and pure copper is used as a cathode and a copper sulfate solution is used as an electrolytic solution for electrolysis is generally used. However, in the case of this refining method, bismuth contained in crude copper, antimony, arsenic, impurity ions other than copper such as iron are eluted into the electrolytic solution by the progress of electrolysis, and the concentration of these impurity ions becomes a certain concentration or more. It lowers the conductivity, lowers the electrolysis efficiency, and lowers the purity of the obtained electrolytic copper.

For this reason, it is necessary to purify the copper electrolytic solution, and as a conventional method for purifying the copper electrolytic solution, decopperization and dearsenic deelectrolysis (hereinafter referred to as decopperization and depyrogenization electrolysis) is mainly performed. It is being appreciated.

[0004]

However, although arsenic and iron can be removed by decopperization without copper removal, impure metal ions such as bismuth and antimony cannot be removed, and the purity of electrolytic copper can be improved. In addition to being difficult to hope for, there is a problem that the power efficiency of decopperization and depyrolysis is reduced when bismuth and antimony are present in the copper electrolytic solution.Therefore, a simple method for removing bismuth, antimony, etc. in the copper electrolytic solution Was desired.

The present invention has been made in view of the above points,
Bismuth contained in the copper electrolyte using a chelate resin,
It is an object of the present invention to provide a method for removing impure metal ions such as antimony.

The inventors of the present invention have conducted extensive studies to solve the above problems, and as a result, by using a chelating resin having a specific resin matrix and having an amidoxime group as a functional group, bismuth and antimony in a copper electrolytic solution can be obtained. The inventors have found that it is possible to effectively separate impurities such as impure metal ions, and have completed the present invention.

[0008]

That is, the method for removing impure metal ions in a copper electrolytic solution of the present invention uses a resin selected from divinylbenzene copolymer, epoxy resin, phenol resin, resorcin resin and vinyl chloride resin. It is characterized in that a copper electrolyte is brought into contact with a chelate resin which is a matrix and has an amidooxime group as a functional group, and impure metal ions are adsorbed to the chelate resin to be removed. In the present invention, the chelate resin is preferably a porous resin.

As the resin matrix of the chelate resin used in the present invention, any one of a divinylbenzene copolymer, an epoxy resin, a resorcin resin, a phenol resin and a vinyl chloride resin is used, and as the divinylbenzene copolymer, , Styrene-divinylbenzene copolymer,
Examples thereof include a methyl acrylate-divinylbenzene copolymer, a methyl methacrylate-divinylbenzene copolymer, an acrylonitrile-divinylbenzene copolymer and the like.

The chelate resin used in the present invention is a chelate resin having any of the above resins as a resin matrix and having an amidoxime group as a functional group. The chelate resin is preferably a porous type (MR type) rather than a gel type. If organic matter is present in the treated water,
This is because the gel-type chelate resin has a reduced ability to adsorb metals, whereas the MR-type chelate resin does not have a reduced ability to adsorb, and there is little loss of resin crushing due to volume changes that occur during resin regeneration.

Examples of the chelate resin include a chelate prepared by reacting chloromethylated styrene-divinylbenzene copolymer with ammonia or polyalkylene polyamine, then reacting with acrylonitrile and further reacting with hydroxylamine to introduce an amide oxime group. resin

A chelate resin having an amidoxime group introduced by reacting acrylonitrile-divinylbenzene copolymer with hydroxylamine

After reacting polyalkylenepolyamine with acrylonitrile, a bisepoxy compound is reacted with a curing agent to cure, and then hydroxylamine is reacted to obtain an amide oxime group as a functional group, and an epoxy resin is used as a resin. Chelating resin as a base

Acrylic acid alkyl ester-divinylbenzene copolymer such as methyl acrylate-divinylbenzene copolymer is reacted with polyalkylene polyamine, followed by reaction with acrylonitrile, and then with hydroxylamine to react with an amidoxime group. And a chelate resin into which is introduced.

In the method of the present invention, the method of bringing the copper electrolyte and the chelate resin into contact with each other includes, for example, immersing the chelate resin in the copper electrolyte solution, or a batch method in which the chelate resin is immersed and further stirred, and the chelate resin is filled. A column method in which a copper electrolytic solution is passed through the column is used.

In the case of the column type method, there are a passing method and a circulation method, but either method may be used, and as the liquid passing method, either an upward flow or a downward flow method can be adopted. In the column type, a method of slowly passing a liquid at a flow rate of SV 0.5 to 10 to adsorb impure metal ions, SV10
Various methods such as a method of rapidly passing and adsorbing at 50 or a method of circulating a copper electrolytic solution to adsorb impure metal ions can be adopted.

Impurity metal ions in the copper electrolyte adsorbed on the chelate resin as described above are 1 to 12N, preferably 5 to 8N hydrochloric acid, nitric acid using the chelate resin adsorbing the impure metal ions as an eluent. Although it can be recovered by treating with an acid such as phosphoric acid to elute and collect, hydrochloric acid is particularly preferably used as an eluent.

The method for eluting the impure metal ions adsorbed on the chelate resin with an eluent may be either a batch type or a column type. In the case of the column type, the eluent can be slowly passed through at an eluent flow rate of SV 0.5 to 5 or can be circulated through the eluent to elute. Further, if the obtained eluent is reused as the next eluent, the concentration of impure metal ions in the eluent can be increased.

The impure metal ions eluted from the chelate resin can be recovered as a metal by a method such as electrolysis. Further, the chelating resin after elution of the impure metal ions can be repeatedly used again for adsorbing the impure metal ions in the copper electrolytic solution.

[0020]

EXAMPLES The present invention will be described in more detail with reference to examples.

Example 1 Acrylonitrile (80 wt%) and divinylbenzene (2
0 wt%) was subjected to suspension polymerization in the presence of toluene to obtain an MR type spherical resin. Then, this resin was reacted with hydroxylamine to obtain a chelate resin having an amidoxime group as a functional group.

Of this resin, 0.5 g of 10-48 mesh resin was added to a pseudo copper electrolyte (copper: 50 g / liter, arsenic: 2.8 g / liter, iron: 0.52 g / liter, bismuth: 0.23 g). Per liter, antimony: 0.19 g / liter, free sulfuric acid: 200 g / liter) and added to 500 ml and stirred at 40 ° C. for 1.5 hours, and then the resin is separated and the pseudo copper electrolyte solution of iron, bismuth and antimony is added. Was measured by an atomic absorption method, and the adsorption amount (unit: g / kg-R) per 1 kg of the chelate resin was determined from this result.

The adsorption amount of the impure metal ions on the chelate resin is iron: 4.8 g / kg-R, bismuth: 13.5 g / kg.
-R, antimony: 21.2 g / kg-R.

Example 2 MR type spherical resin (10-60 mesh) consisting of styrene-divinylbenzene copolymer obtained by suspension polymerization of styrene (92 wt%) and divinylbenzene (8 wt%)
Was swollen in ethylene dichloride and reacted with chloromethyl ether in the presence of anhydrous zinc chloride to chloromethylate the spherical resin (chlorine content: 21.8 wt%).

Next, the chloromethylated resin was reacted with ethylenediamine (EDA) to obtain an EDA type resin.
Next, Michael was added to the obtained EDA type resin with acrylonitrile and further reacted with hydroxylamine to obtain a chelate resin having an amidoxime group as a functional group. A pseudo copper electrolytic solution similar to that used in Example 1 was treated with a resin of 10 to 48 mesh among these, under the same conditions.

The adsorption amount of the impure metal ions on the chelate resin is iron: 3.9 g / kg-R, bismuth: 14.5 g / kg.
-R, antimony: 22.8 g / kg-R.

Example 3 A product obtained by Michael-adding acrylonitrol to pentaethylenehexamine, bisphenol A diglycidyl ether and metaxylenediamine were subjected to suspension polymerization in polyvinyl alcohol to obtain a spherical cured resin.
Then, the obtained resin was reacted with hydroxylamine to obtain a chelate resin having an amidoxime group as a functional group. Using a 10 to 48 mesh resin classified from this chelate resin, the same pseudo copper electrolytic solution as in Example 1 was treated in the same manner.

The amount of impure metal ions adsorbed on this chelate resin is iron: 3.1 g / kg-R, bismuth: 11.8 g / kg.
-R, antimony: 17.9 g / kg-R.

Example 4 Methyl acrylate (90 wt%) and divinylbenzene (1
0 wt%) was suspension polymerized to obtain an MR type spherical resin. The obtained spherical resin was reacted with diethylenetriamine (DETA) to obtain a DETA type resin. Acrylonitrile was added to this DETA-type resin by Michael and further reacted with hydroxylamine to obtain a chelate resin having an amide oxime group as a functional group. Using 10 to 48 mesh of this resin, the same pseudo copper electrolytic solution as in Example 1 was treated in the same manner.

The amount of impure metal ions adsorbed on the chelate resin was iron: 2.2 g / kg-R, bismuth: 13.6 g / kg.
-R, antimony: 19.5 g / kg-R.

Comparative Example 1 A styrene-divinylbenzene copolymer was used as a resin matrix,
The same pseudo copper electrolytic solution as in Example 1 was treated in the same manner with 0.5 g of MR type chelate resin (10 to 48 mesh) having an iminodiacetic acid group as a functional group. Iron was adsorbed on this chelating resin at 1.5 g / kg-R, but bismuth,
Antimony was not adsorbed.

Example 5 100 ml of the chelate resin of 10 to 48 mesh used in the above Examples 1 to 4 and Comparative Example 1 was filled in each column (inner diameter 20 mmφ), and the pseudo copper electrolytic solution (copper:
45 g / liter, arsenic: 2.8 g / liter, iron: 0.5
4 g / liter, bismuth: 0.18 g / liter, antimony: 0.24 g / liter, free sulfuric acid: 200 g / liter) were passed through SV5 at 40 ° C. for 1 hour.

A predetermined amount of liquid to be passed through the column filled with each chelate resin (amount of liquid to be passed per liter of resin: unit is 1
/ L-R. Samples of the effluent were collected and the concentrations of iron, bismuth and antimony in the effluent were measured.
Table 1 shows the amount of each metal ion adsorbed on the chelate resin (unit: g / l-R) and the removal rate of the impure metal ions in the pseudo-copper electrolyte solution when the predetermined solution flow rate was reached.

[0034]

[Table 1]

[0035]

As described above, according to the method of the present invention, a chelate resin having a specific resin as a resin matrix and an amidoxime group as a functional group is brought into contact with a copper electrolytic solution, and the chelate resin is treated in a copper electrolytic solution. It is a method of adsorbing and separating impure metal ions, and according to the method of the present invention, bismuth in a copper electrolyte, antimony, etc., can be adsorbed and removed favorably by impure metal ions that could not be removed by conventional decopperization without copper removal. Therefore, the purity of electrolytic copper can be further improved. Further, as a result of removing the impure metal such as bismuth and antimony in the copper electrolytic solution, there is an effect that the power efficiency in the decoppering depyrogenization can be improved.

Claims (2)

[Claims] 1. A copper electrolyte is brought into contact with a chelate resin having a divinylbenzene-based copolymer, an epoxy resin, a phenol resin, a resorcin resin, or a vinyl chloride resin as a resin matrix and having an amidooxime group as a functional group. A method for removing impure metal ions in a copper electrolytic solution, which comprises removing impure metal ions by adsorbing them onto the chelate resin. 2. The method for removing impure metal ions in a copper electrolyte solution according to claim 1, wherein the chelate resin is a porous resin.