JPS61227190A - Method for removing impurity metallic ion in copper electrolyte - Google Patents

Abstract

PURPOSE:To adsorb away the impurities in an electrolyte for refining of electric copper in which the impurities accumulate by bringing a specifically composed porous type chelate resin into contact with said electrolyte. CONSTITUTION:The electrolyte consisting essentially of CuSO4 and H2SO4 is electrolyzed with blister copper as an anode and thin electric copper sheet as a cathode. The concn. of the impurities such as Bi, Sb, As and Fe contained in the blister copper of the anode increases in this stage. As a result, the electrolyzing efficiency decreases and the quality of the electric copper is deteriorated. The electrolyte is brought into contact with the chelate resin of the porous type consisting either of a divinyl benzene copolymer or epoxy resin or phenolic resin as a resin base material and contg. at least one of an amino alkylene phosphoric acid group or the salt thereof or iminoalkylene phosphoric acid group or the salt thereof and amidoxy group as a functional group in order to remove the above-mentioned impurities. Bi, Sb, As, Fe, etc., as the impurities except Cu are adsorbed away and the electrolyte is cleaned up.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for removing impure metal ions in a copper electrolyte.

[Prior Art] A commonly used method for refining copper is to use blister copper as an anode, pure copper as a cathode, and electrolyze copper sulfate solution as an electrolyte.However, in the case of this refining method, As the electrolysis progresses, impurity ions other than copper, such as bismuth, antimony, arsenic, and iron, contained in the blister copper elute into the electrolyte, and when the concentration of these impurity ions exceeds a certain concentration, the conductivity decreases and the electrolysis This results in a decrease in efficiency and a decrease in the purity of the obtained electrolytic copper.For this reason, it is necessary to purify the copper electrolyte, and traditionally, the main method for purifying copper electrolyte is decoppering and dearsenization (hereinafter referred to as decopper removal and dearsenization). (abbreviated as copper de-pin electrolysis) is being carried out.

[Problem that the invention seeks to solve]

However, although it is possible to remove arsenic and iron in decoppering and decoupling electrolysis, impurity metal ions such as bismuth and antimony cannot be removed, and it is difficult to expect to improve the purity of electrolytic copper. There is a problem in that their presence in the solution lowers the power efficiency of decoppering and decoppering electrolysis, and there has been a desire to develop a simple method that can remove bismuth, antimony, etc. from the copper electrolyte.

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

[Means for solving problems]

The present inventors have conducted intensive research to solve the above problems, and have found that the present inventors have a specific resin matrix, an aminoalkylene phosphate group or a salt thereof, an iminoalkylene phosphate group or a salt thereof,
Impure metal ions such as bismuth and antimony in copper electrolyte can be effectively separated by using a chelate resin having at least one of alkylene phosphate group or its salt, phosphoric acid group or its salt, or amidoxime group as a functional group. The inventors have discovered that it is possible to do this and have completed the present invention.

That is, the present invention uses any one of a divinylbenzene copolymer, an epoxy resin, a phenol resin, a resorcinol resin, and a vinyl chloride resin as a resin base, and an aminoalkylene phosphoric acid group or a salt thereof, an iminoalkylene phosphoric acid group or a salt thereof, an alkylene phosphoric acid The method is characterized in that a copper electrolyte is brought into contact with a chelate resin having at least one of a group or a salt thereof, a phosphoric acid group or a salt thereof, or an amidoxime group as a functional group, and impure metal ions are adsorbed onto the chelate resin and removed. The gist of this paper is a method for removing impure metal ions in a copper electrolyte.

As the resin base of the chelate resin used in the present invention, any one of divinylbenzene copolymer, epoxy resin, resorcinol resin, phenol resin, and vinyl chloride resin is used, and as the divinylbenzene copolymer, styrene-divinyl Benzene copolymer, methyl acrylate-divinylbenzene copolymer, methyl methacrylate-
Examples include divinylbenzene copolymer, acrylonitrile-divinylbenzene copolymer, and the like. The chelate resin in the present invention uses any of the above resins as a resin base, and contains an aminoalkylene phosphate group, an iminoalkylene phosphate group, an alkylene phosphate group, a phosphoric acid group, or a salt thereof, such as an alkali metal salt, an alkaline earth metal salt, etc. or a chelate resin having at least one kind of amidoxime group as a functional group, in particular a divinylbenzene copolymer such as a styrene-divinylbenzene copolymer as a resin matrix,
In addition, it is preferable to use a chelate resin having an aminoalkylene phosphate group or its salt and an iminoalkylene phosphate group or its salt as a functional group, which can selectively and efficiently adsorb impure metal ions in the copper electrolyte.
The resin is not easily attacked in acidic copper electrolytic P, making it possible to use the resin repeatedly. Further, the chelate resin having these functional groups is preferably of a porous type (MR type) rather than a gel type. This is because when organic matter is present in the treated water, the adsorption ability of gel-type chelate resins for metals decreases, whereas the adsorption ability of MR-type chelate resins tends to decrease (
This is because there is less loss due to resin crushing due to volume changes that occur during resin regeneration.

Examples of the above-mentioned chelate resin include: (1) After chloromethylation is performed by reacting styrene-divinylbenzene copolymer with chloromethyl ether, ammonia, ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexazine, etc. A primary or secondary amino group is introduced by reacting a polyalkylene polyamine, and then an aldehyde such as formaldehyde or acetaldehyde is reacted with phosphorous acid to introduce an aminoalkylene phosphoric acid group or an imino group into the primary or secondary amino group. Chelate resin with an alkylene phosphate group formed; ■ Phosphorous trichloride is applied to a di-lolomethylated styrene-divinylbenzene copolymer in the presence of aluminum chloride to form a methylene phosphate group (or Chelate resin with phosphoric acid group formed: ■Hvinyl chloride resin Polyalkylene polyamine is reacted with primary or secondary
Chelate resin in which an amino alkylene phosphate group or an iminoalkylene phosphate group is formed on the amino group by introducing a class amino group and then reacting with aldehyde and phosphorous acid; ■ Methyl acrylate-divinylbenzene copolymer or methyl methacrylate - After reacting a polyalkylene polyamine with the methyl ester group portion of the divinylbenzene copolymer, amino alkylene phosphoric acid is applied to the amino group portion of the polyalkylene polyamine introduced into the methyl ester group portion by acting with an aldehyde and phosphorous acid. chelate resin having an aminoalkylene phosphate group or an iminoalkylene phosphate group; ■ A polyalkylene polyamine is reacted with an aldehyde and phosphorous acid to obtain a compound having an aminoalkylene phosphate group or an iminoalkylene phosphate group, and this compound is treated with phenol in the presence of an aldehyde. Alternatively, a chelate resin having an aminoalkylene phosphate group or an iminoalkylene phosphate group and having a phenol resin or a resorcinol resin as a resin matrix obtained by reacting with resorcinol; A chelate resin in which a phosphoric acid group is introduced as a functional group into a benzene nucleus by the action of phosphorus chloride; ■ or an alkali metal salt such as sodium salt or potassium salt of the resins described in ■ to ■ above, or an alkaline earth salt such as a calcium salt or magnesium salt. Metal salt; ■ Chelate resin in which an amidoxime group is introduced by reacting a chloromethylated styrene-divinylbenzene copolymer with ammonia or polyalkylene polyamine, then reacting with acrylonitrile, and then reacting with hydroxylamine; ■ Acrylonitrile A chelate resin in which an amidosoxime group is introduced by reacting a divinylbenzene copolymer with hydroxylamine; [Phase] After reacting a polyalkylene polyamine with acrylonitrile,
Examples include chelate resins having an amide oxime group as a functional group obtained by reacting a bisepoxy compound with a curing agent for curing, and then reacting with hydroxylamine, and using an epoxy resin as a resin base. Among these chelate resins, the above-mentioned chelate resin (①) is preferable; in particular, a chloromethylated styrene-divinylbenzene copolymer is reacted with a polyalkylene polyamine, and then an aldehyde and a phosphorous acid are reacted to form a primary amino group. , chelate resins in which an aminoalkylene phosphate group or an iminoalkylene phosphate group is formed as a functional group in the secondary amino group portion are preferred.

In the present invention, methods for bringing the copper electrolyte and the chelate resin into contact include, for example, a batch method in which the chelate resin is immersed in the copper electrolyte, or is immersed and further stirred, and a copper electrolyte is placed in a column filled with the chelate resin. Column methods are available, and in the case of column methods, there are transient methods and circulation methods, but either method may be used.
In addition, either an upward flow method or a downward flow method can be adopted as a method for passing the liquid. In addition, in the column type, the liquid flow rate is set to S
Various methods are available, such as a method in which impure metal ions are adsorbed by passing the liquid slowly at V O of 5 to 10, a method in which the liquid is passed rapidly at V O to 50 to adsorb impure metal ions, or a method in which the copper electrolyte is circulated to adsorb impure metal ions. Can be used.

The impure metal ions in the copper electrolyte adsorbed to the chelate resin as described above are removed by using the chelate resin adsorbing the impure metal ions as an eluent of 1 to 12N, preferably 5 to 8N.
Although it can be treated and eluted and recovered using an acid such as hydrochloric acid, nitric acid, or phosphoric acid, it is particularly preferable to use hydrochloric acid as the eluent.

The elution method using the eluent 9 for impure metal ions adsorbed on the chelate resin may be either a batch method or a column method. In the case of a column type, the eluent flow rate S V 0.
Elution can be carried out by slowly passing the solution or by circulating the eluent. Moreover, 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 also be recovered as metal by a method such as electrolysis. Further, the chelate resin after eluting the impure metal ions can be used repeatedly to adsorb impure metal ions in the copper electrolyte.

〔Example〕

Hereinafter, the present invention will be explained in more detail with reference to Examples.

Example 1 An MR type spherical resin (10 to 60 mesh) made of a styrene-divinylbenzene copolymer obtained by suspension polymerization of 924% styrene and 8 wt% divinylbenzene was swollen in ethylene dichloride and anhydrous chlorinated. The spherical resin was chloromethylated by reacting chloromethyl ether in the presence of zinc (chlorine content: 21.8 wt%). Next, the obtained chloromethylated resin was reacted with diethylenetriamine (DETA) to obtain a DETA type resin having a primary amino group and a secondary amino group. This resin is reacted with orthophosphorous acid and paraformaldehyde in an aqueous hydrochloric acid solution, and the primary amino group and secondary amino group are converted into aminomethylene phosphate groups and iminomethylene phosphate groups. I got it. Of this chelate resin, 0.5 g of resin with 10 to 48 meshes was added to a simulated electrolyte solution (copper: 50 g, free sulfuric acid: 200 g/l, arsenic: 2.8 g.
/j! , iron 1.52 g/l bismuth: 0.23 g/i antimony: 0.19 g/l) was added to 500 ml, and after stirring at 40°C for 1.5 hours, the resin was separated and the bismuth in the simulated electrolyte was removed. Antimony, iron residual tM degree 1c
The amount of adsorption to the chelate resin was determined by measurement using atomic absorption spectrometry. The adsorption amount per kg of chelate resin is bismuth: 17.1 g/kg-R (the unit of adsorption amount per kg of resin is g/kg-R), antimony: 25
．． 6g/dazzle-R1 iron: 5.2 g/kg-R.

Example 2 The same chloromethylated resin as in Example 1 was reacted with ammonia to obtain an aminated resin. Next, this aminated resin was reacted with ortho-6M and trioxymethylene to obtain a chelate resin having an aminomethylene phosphate group as a functional group. 10 to 48 mesh resin classified from this resin 0
．． After adding 5 g to 500 ml of the same simulated electrolyte as in Example 1 and stirring under the same conditions as in Example 1, the amount of impure metal ions adsorbed to the chelate resin was determined. The adsorption amount to the chelate resin is bismuth: 15.3 g/kg-R, antimony: 23.8 g/kg-R, iron: 3.1 g/kg-R.
kg-R.

Comparative Example 1 Using styrene-divinylbenzene copolymer as a resin matrix,
MR type 10-4 having iminodiacetic acid group as a functional group
8 meshes of 0.5 g of chelate resin were added to 500 ml of the same simulated electrolyte as in Example 1, and after stirring under the same conditions as in Example 1, the amount of impure metal ions adsorbed to the chelate resin was determined. This chelate resin contains 1.5g/kg of iron.
R was adsorbed, but bismuth and antimony were not.

Example 3 Polyvinyl chloride pulverized into 10 to 50 meshes was swollen with perchlorethylene and then reacted with triethylenetetramine (TETA) to obtain a TETA type resin. This resin was reacted with acetaldehyde and orthophosphorous acid to obtain a chelate resin having aminoethylene phosphoric acid groups and iminoethylene phosphoric acid groups as functional groups. Using 10 to 48 meshes of this chelate resin, the same simulated electrolyte as used in Example 1 was treated under the same conditions. Impure metal ions adsorbed on the chelate resin are
Bismuth: 13.8 g/kg-R, Antimony:
19.2 g/kg-R1 iron: 3.8 g/kg-R.

Example 4 Acrylonitrile (80wt%) and divinylbenzene (
20%) was suspension polymerized in the presence of toluene to obtain an MR type spherical resin. This resin was then reacted with hydroxylamine to obtain a chelate resin having an amidoxime group as a functional group. Using 10 to 48 meshes of this resin, the same simulated electrolyte as used in Example 1 was treated under the same conditions. The adsorption amount to the chelate resin is bismuth: 13.5 g/kg-R, antimony: 21.
2g/kg-R1 iron: 4.8g/kg-R.

Example 5 An MR type spherical resin (particle size 10 to 60 mesh) made of the same styrene-divinylbenzene copolymer used in Example 1 was reacted with phosphorus trichloride in the presence of aluminum chloride to functionalize the phosphoric acid groups. A chelate resin having this as a base was obtained. Using 10 to 48 mesh of this resin,
The simulated electrolyte used in Example 1 was treated under the same conditions as in Example 1. The amount of bismuth adsorbed to the chelate resin is:
Og/kg-R, antimony: 10.8 g/kg
-R.

Iron: Og/kg-R, and antimony in the copper electrolyte was selectively adsorbed.

Example 6 The same chloromethylated resin as in Example 1 was reacted with phosphorus trichloride in the presence of aluminum chloride to obtain a chelate resin having phosphoric acid groups and methylene phosphoric acid groups as functional groups. Using 10 to 48 meshes of this resin, the simulated electrolyte used in Example 1 was treated in the same manner as in Example 1 to determine the amount of adsorption onto the chelate resin. Adsorption amount is bismuth: Og/kg-R, antimony 12.6g/kg-
R, iron: Og/kg-R, and antimony in the copper electrolyte was selectively adsorbed.

Example 7 The same chloromethylated resin as in Example 1 was reacted with ethylenediamine (EDA) to obtain an EDA type resin. Next, acrylonitrile was added to the obtained EDA type resin, and further reacted with hydroxylamine to obtain a chelate resin having an amidoxime group as a functional group. Of these, the simulated electrolyte solution used in Example 1 was treated in the same manner as in Example 1 using resins with 10 to 48 meshes, and the amount of adsorption to the chelate resin was determined. Bismuth:
14.5 g/kg-R, antimony: 22.8 g/
Dazzling-R, iron: 3.9 g/pupil-R.

Example 8 A reaction product obtained by reacting tetraethylenepentamine with orthophosphoric acid and formaldehyde was reacted with resorcinol and formaldehyde, and then suspension polymerized in a polyvinyl alcohol solution to form a product having an iminomethylene phosphate group as a functional group. A spherical chelate resin was obtained. Next, the same treatment as in Example 1 was performed on the simulated electrolyte solution used in Example 1 using a 10 to 48 mesh resin classified from the above chelate resin. The adsorption amount of impure metal ions to the chelate resin is bismuth: 13.5 g/ktr-R, antimony: 20.5 g/kg-R, iron: 3.2 g/kg-R
Met.

Example 9 A product obtained by Michael addition of acrylonitrile to pentaethylene hexazine and metaxylene diamine were suspension polymerized in polyvinyl alcohol to obtain a spherical cured resin. Next, the obtained resin was reacted with hydroxylamine to obtain a chelate resin having an amidoxime group as a functional group. 10~ classified from this chelate resin
The same treatment as in Example 1 was carried out using the same simulated electrolyte as used in Example 1 using 48 mesh resin.

The adsorption amount to the chelate resin is bismuth: 11.8g/k
g R, antimony: '17.9 g/kg-R, iron: 3.1 g/kg-R.

Example 10 Methyl acrylate (90wt%) and divinylbenzene (
(10 wt%) was subjected to suspension polymerization to obtain an MR type spherical resin.

Diethylenetriamine (DETA) was added to the obtained spherical resin.
were reacted to obtain a DETA type resin. Acrylonitrile was added to this DETA type resin, and hydroxylamine was further reacted to obtain a chelate resin having an amidoxime group as a functional group. Of these resins, 10 to 48 mesh resins were used and the same simulated electrolyte as used in Example 1 was subjected to the same treatment as in Example 1. The adsorption amount is bismuth: 13.6 g/kg-R, antimony: 19.
5g/kg-R1 iron: 2.2g/kg-R.

Example 11 A column (inner diameter 25 mφ) was filled with 10 to 48 meshes of the chelate resin obtained in Examples 1 to 10 and 100 ml of the chelate resin used in Comparative Example 1, and a simulated electrolyte solution (
Copper: 45g/It, free sulfuric acid: 200g/II, arsenic = 2.8g/it, antimony: 0.24g/l, bismuth: 0.18g/l iron: SV5 at 40°C The solution was passed for 1 hour. A predetermined amount of liquid passed through a column packed with each chelate resin (amount of liquid passed per 1 liter of resin:
The unit is 1/l-R. ) Samples of the effluent were collected and the concentrations of bismuth, antimony, and iron in the effluent were measured. Table 1 shows the adsorption amount of each metal ion on the chelate resin and the removal rate of impure metal ions in the simulated electrolyte when a predetermined amount of liquid is passed. FIG. 1 shows the relationship between the amount of a simulated electrolytic solution passed through a column filled with a chelate resin and the concentration of each metal ion in the effluent.

〔Effect of the invention〕

As explained above, the method of the present invention uses a specific resin as a resin base, and at least one of an aminoalkylene phosphate group, an iminoalkylene phosphate group, an alkylene phosphate group, a phosphoric acid group or a salt thereof, or an amidoxime group is added as a functional group. This is a method in which a copper electrolyte is brought into contact with a chelate resin having a copper electrolyte, and the impure metal ions in the copper electrolyte are adsorbed and separated by the chelate resin. It is possible to effectively adsorb and remove impurity metals that could not be removed by copper-removal film vinyl electrolysis, further improving the purity of electrolytic copper, and removing impurity metal ions such as bismuth and antimony in the copper electrolyte. As a result, it has effects such as being able to improve the power efficiency in copper-removal membrane electrolysis.

[Brief explanation of the drawing]

FIG. 1 is a graph showing the relationship between the amount of a simulated electrolytic solution passed through a column filled with the chelate resin of Example 1 and the concentration of impure metal ions in the effluent.

Claims (3)

[Claims] (1) Divinylbenzene copolymer, epoxy resin, phenol resin, resorcinol resin, or vinyl chloride resin as the resin base, and an aminoalkylene phosphate group or its salt, an iminoalkylene phosphate group or its salt, or an alkylene phosphate group or a salt thereof, a chelate resin having at least one of a phosphoric acid group, a salt thereof, or an amidoxime group as a functional group is brought into contact with a copper electrolyte, and impure metal ions are adsorbed to the chelate resin and removed. A method for removing impure metal ions from copper electrolyte. (2) The copper according to claim 1, wherein the chelate resin has a divinylbenzene copolymer as a resin base, and has an iminoalkylene phosphate group or a salt thereof and an aminoalkylene phosphate group or a salt thereof as functional groups. Method for removing impure metal ions in electrolyte. (3) The method for removing impure metal ions in a copper electrolyte according to claim 1 or 2, wherein the chelate resin is a porous resin.