JPH0524208B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for recovering copper from a copper-containing ore leachate. More specifically, the present invention relates to a method for economically recovering copper in a copper-containing ore leachate using a chelate resin. In recent years, in the field of copper smelting, resources have been depleted,
Even if it is low-grade ore that cannot be processed using conventional pyrometallurgical methods (hereinafter referred to as pyrometallurgical methods),
There is a need to process it. The development of extractants with superior performance for use in the extraction process of the hydrometallurgical smelting method (hereinafter referred to as the "wet method") spurred the switch from the dry method to the wet method of copper smelting. is being applied. Copper smelting by the wet method involves leaching a copper-containing ore with sulfuric acid or ammonia, and contacting the leachate containing the copper components from the copper ore with an organic extractant to extract the copper components from the leachate. Next, this copper-containing organic extract is brought into contact with a sulfuric acid aqueous solution of approximately 100 g/concentration to back-extract the copper component to the sulfuric acid aqueous solution side, and this extract is electrolyzed or reduced with a chemical to recover the copper by precipitation. This method is commonly used. However, in the wet method, since the oil extractant used in the extraction process is liquid, there is a problem that a part of the extractant and solvent is dissolved and lost to the leachate and reverse extraction solution, and dangerous organic solvents such as kerosene are used. There are safety problems due to the use of large amounts of silica, and the results are not necessarily completely satisfactory from an economic and pollution control perspective. On the other hand, in order to solve the above-mentioned disadvantages, attempts have been made to adsorb and recover copper in copper ore sulfuric acid leachate using aminocarboxylic acid type chelate resins [for example, Tsvet.Metal. 43 (10), 20- 22 (1970)].
However, chelate resins with aminocarboxylic acid groups do not have a very large ability to adsorb copper ions,
In addition, this method requires a large amount of chelate resin due to poor selective adsorption of copper ions, and is not fully satisfactory, so it has not been put into practical use. In view of these circumstances, the present inventors conducted intensive research to develop a wet copper smelting method that overcomes the above-mentioned disadvantages, and found that when extracting copper from a wet method copper-containing ore leachate, The inventors have discovered that the above disadvantages can be overcome by using a chelate resin, and have completed the present invention. That is, the present invention uses a copper-containing ore leachate in a hydrometallurgical process for recovering copper metal from a copper-containing ore to contain guanidino groups, amidoxime groups, oxime groups, amidino groups, formazan groups, diketone groups, and amino groups and their amino groups. Contact with a chelate resin having at least one functional group selected from groups having a hydroxyl group or a thiol group at the α- or β-position of the group,
The present invention provides a method for recovering copper from a copper-containing ore leachate, which comprises adsorbing copper ions to a chelate resin, and contacting the copper-adsorbing chelate resin with an eluent to elute copper. In the present invention, a copper-containing ore leachate from a hydrometallurgical process is treated. Generally, copper-containing ores are
0.1 to 0.1 obtained by elution treatment with a sulfuric acid aqueous solution with a pH of around 0.5 to 3 or an ammonia aqueous solution with a pH of 8 to 11.
A leachate containing 5 g/concentration of copper is preferably used. The chelate resin used in the present invention has a functional group that selectively adsorbs copper contained in the copper-containing ore leachate in the hydrometallurgical copper smelting process.
guanidino group, amidoxime group, oxime group,
It has an amidino group, a formazan group, a diketone group, or an amino group and its α-
Or it has a hydroxyl group or a thiol group at the β-position. Of course, it may have two or more types of functional groups among these. In particular, a chelate resin having at least one functional group selected from a guanidino group, an amidoxime group, and an oxime group, especially a chelate resin having a guanidino group, is preferably used. More specifically, the polymer having an amine-reactive group or a primary and/or secondary amino group includes hydroxylamine, guanidine, aminoguanidine, dicyandiamide, biguanide, ε-guanidinocaproic acid hexyl ester, guanidinoacetic acid, 2,4-diaminophenol, 2,2'-dihydroxy-5-diethylenetriamino-N,
N'-ethanediylidene dianiline, acetylacetone, oxalyl chloride, 4-aminobenzamidoxime, 4-diethylenetriaminobenzamidoxime, etc., or guanidino groups, amidoxime groups, oxime groups obtained by reacting derivatives thereof, A chelate resin having one or more functional groups that are a group consisting of an amino group and a hydroxyl group or a thiol group at its α- or β-position, or a diketone group is preferably used. Further, the resin substrate to which such a functional group is bonded is not particularly limited, but includes, for example, a polymer having a nitrile group such as an acrylonitrile-divinylbenzene copolymer, a styrene-divinylbenzene copolymer, a phenolic resin, and a polychloride. Examples include vinyl. Among these, for polymers having nitrile groups, the nitrile group itself can be an amine-reactive group, but other amine-reactive groups, primary and/or secondary amino groups can be prepared by known methods. , can be introduced into the resin substrate. Now, in the case of chelate resins having aminocarboxylic acid groups, which are conventionally known for adsorbing and collecting copper in copper-containing ore leachate, they have the disadvantage that their copper ion adsorption is not very high and their selective adsorption for copper is also low. It was hot. On the other hand, the chelate resin having the above-mentioned functional groups specified in the present invention exhibits almost no adsorption to cobalt, nickel, etc. in copper-containing ores, but has high adsorption to copper ions. In particular, compared to conventionally known chelate resins having aminocarboxylic acid groups, the copper ion adsorption property is approximately twice that of conventional chelate resins having aminocarboxylic acid groups. In carrying out the method of the present invention, the step of contacting the copper-containing ore leachate in the hydrometallurgical smelting process with the chelate resin having copper ion adsorption properties may generally be carried out at a temperature of 90°C or lower, preferably 10 to 60°C. If the temperature exceeds 90°C, the cost required for heating will increase, which is not preferable. The method of contacting the chelate resin with the copper-containing ore leachate in the hydrometallurgical process is not particularly limited, and examples include a method of immersing the chelate resin in the copper-containing ore leachate, and a method of contacting the copper-containing ore with the copper-containing ore leachate in the hydrometallurgical process. A method such as passing a leachate containing ore is generally adopted. Among these, a method in which the copper-containing ore leachate is passed through a column filled with a chelate resin is preferred in terms of processing operation. In this case, the liquid flow rate is generally preferably 1 to 500 parts by volume. The amount of chelate resin used is not particularly limited and varies depending on the copper concentration in the copper-containing ore leachate to be treated, the type of chelate resin used, etc., but this should be determined by conducting preliminary experiments as appropriate. be able to. Further, the contact time between the copper-containing ore leachate and the chelate resin is not particularly limited, but the contact time is usually several seconds or more, preferably in the range of 1 minute to 24 hours. Therefore, when using the chelate resin specified in the present invention, the effect of selectively adsorbing and separating copper ions in the copper-containing ore leachate is achieved. The chelate resin on which copper has been adsorbed as described above is separated from the treatment liquid. The chelate resin that has adsorbed and collected copper in this manner is then brought into contact with an eluent consisting of a mineral acid such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, etc. to elute the copper. The eluate containing the recovered copper can then be extracted using a known method, such as adding iron to the eluent and precipitating metallic copper using the difference in ionization tendency, or adding a reducing agent such as sulfur dioxide. Metallic copper can be recovered by performing a reduction treatment such as a method of precipitating metallic copper using a method of depositing metallic copper or a method of depositing metallic copper by electrolysis. Usually, from the viewpoint of processing operations and product purity, a method in which the eluent is directly electrolyzed is preferably employed. In this way, the eluent containing eluted and separated copper is preferably subsequently subjected to electrolytic treatment, but in this case, from the viewpoint of improving electrolysis current efficiency and productivity, electrolytic treatment is not performed. The eluent was 1
An aqueous sulfuric acid solution containing ~50 g/concentration of copper is preferred, more preferably an aqueous sulfuric acid solution containing 5 to 20 g/concentration of copper. In order to increase the copper concentration in the eluent, reusing such an electrolyte solution as an eluent is as follows.
More preferred. In addition, considering the selection of the material of the electrolytic cell, etc., the eluent should be sulfuric acid, which is also 0.5 to 3
Sulfuric acid at a defined concentration is preferably used. According to the method of the present invention as detailed above, the adsorption performance of copper ions from a copper-containing ore leachate is significantly higher than that of a method using a known aminocarboxylic acid type chelate resin, resulting in an extremely economical recovery process. Therefore, its economic value is extremely high. In addition, unlike the liquid extractant used in known wet extraction processes, the chelate resin used in the present invention is water-insoluble, flame retardant, and a solid polymer, so it can be used in copper-containing ore leachate. It has an excellent effect in that there is no dissolution loss to eluent or eluent. Therefore, the industrial value of the method of the present invention is great. EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited thereto. Example 1 1 part by weight of a chelate resin having a guanidino group obtained by reacting a copolymer of acrylonitrile and divinylbenzene with guanidine carbonate in a 10% by weight aqueous sodium hydroxide solution at 100 to 105°C for 4 hours, Cu1020mg/, Co115mg/,
Contains Cu, Co and Ni ions at Ni921mg/concentration
Immerse in 50 parts by volume of sulfuric acid-treated copper ore leachate with a pH of 2.1,
A shaking treatment was performed for 1 hour. Next, the chelate resin adsorbed with copper ions was over-separated, mixed with 4 parts by volume of a 10% by weight aqueous sulfuric acid solution at room temperature, and gently stirred for 1 hour to elute the copper ions. Cu, Co and Ni concentrations in the eluent are Cu12600
mg/, Co 25 mg/, and Ni 200 mg/, and the adsorption amount per chelate resin was 50.4 mg Cu/g resin, 0.1 mg Co/g resin, and 0.8 mg Ni/g resin. In addition, analysis of Cu, Co, and Ni ions remaining in the liquid revealed that Cu6mg/, Co111
mg/, and 901 mg/Ni. From the above, it can be seen that the chelate resin used in the present invention has excellent selective adsorption to copper. Examples 2 to 11 Chelate resin B: A resin having a guanidino group obtained by reacting a chloromethylated styrene-divinylbenzene copolymer with guanidine carbonate in a 10% by weight aqueous sodium hydroxide solution at 100 to 105°C for 4 hours. . Chelate resin C: A resin having guanidino groups and hydrazino groups obtained by reacting an acrylonitrile-polyethylene glycol dimethacrylate copolymer with guanidine nitrate and hydrazine in an aqueous solvent at 95 to 100°C for 8 hours. Chelate resin D: A resin having diethylenetriamino groups and amidino groups obtained by reacting an acrylonitrile-divinylbenzene copolymer with 4-diethylenetriaminobenzamidine in a water solvent under pressure at 120 to 130°C for 1 hour. Chelate resin E: A resin having a formazan group obtained by reacting a chloromethylated styrene-divinylbenzene copolymer with 3-phenylformazan in an aqueous N,N-dimethylformamide solution at 80 to 100°C for 2 hours. Chelate resin F: A resin having a guanidino group obtained by reacting a chloromethylated styrene-divinylbenzene copolymer with biguanide in an aqueous solvent at 90 to 100°C for 6 hours. Chelate resin G: A resin having an amidoxime group obtained by reacting an acrylonitrile-divinylbenzene copolymer with hydroxylamine sulfate and hydrazine in an aqueous solvent at 90 to 100°C for 2 hours. Chelate resin H: Diethylenetriamine was added to acrylonitrile-divinylbenzene copolymer in an aqueous solvent at 117-123°C.
Furthermore, to the aminated resin obtained by reacting for 4 hours with
5-bromo-2,2'-dihydroxy-N,N'-ethanediylidene dianiline in toluene solvent,
A resin having -N= of Schiff's base and a hydroxyl group at its β-position, obtained by reacting at 100 to 105°C for 6 hours in the presence of pyridine. Chelate Resin I: Aminomethylated styrene-divinylbenzene copolymer and 5-bromo-2-hydroxy-2'-mercapto-N,N'-succinyldianiline were mixed in a toluene solvent in the presence of pyridine to 97 to 103℃
A resin having -NH- of a Schiff base obtained by reacting for 3 hours with a hydroxyl group and a thiol group at its β-position, and a diketone group bonded to the -NH- by an amide bond. Chelate resin J: diethylenetriaminated acrylonitrile-divinylbenzene copolymer in ethanol solvent,
A resin containing diketone groups obtained by reacting ethyl acetoacetate in the presence of sodium ethoxide. Chelate resin K: A resin having an oxime group and an amide-bonded ketone group obtained by reacting chelate resin J with hydroxylamine in an aqueous solvent. Using 1 part by weight of each of the above chelate resins, contact treatment with 50 parts by volume of sulfuric acid-treated copper ore leachate was carried out in the same manner as in Example 1. As a result, in the liquid
The concentrations of Cu, Co, and Ni and the amounts of adsorption of Cu, Co, and Ni per chelate resin were as shown in Table 1.

[Table] Comparative Example 1 In the same manner as in Example 1, except that 1 part by weight of a commercially available aminocarboxylic acid type chelate resin was used instead of the chelate resin in Example 1, 50 parts by volume of sulfuric acid-treated copper ore leachate and Contact treatment was performed. the result,
The concentrations of Cu, Co, and Ni in the liquid and the adsorption amounts of Cu, Co, and Ni per chelate resin were as shown in Table 2.

[Table] Example 12 A column was filled with 20 ml of the chelate resin having the same guanidino group as used in Example 1, and from the top of the column, Cu1020mg/, Co115mg/, Ni921mg/
240ml of copper ore leachate with PH2.1, space velocity
When the solution was passed through the solution at SV10hr ^-1 , the metal concentration in the effluent was as shown in the column of "Chelate tower effluent of copper ore leachate" in Table 3. Next, 40 ml of an eluent mainly composed of a copper electrolyte solution with a concentration of 2.1N sulfuric acid containing 20 g of Cu was added.
When the eluent was run at SV2.5hr ^-1 , 10ml aliquots were collected, and the concentrations of Cu, Co, and Ni contained in each eluent fraction were analyzed, the results shown in Table 3 were obtained. .

[Table] From the above results, it is clear that the chelate resin used in the present invention exhibits excellent selective adsorption for copper.

Claims (1)

[Scope of Claims] 1. Copper-containing ore leachate in a hydrometallurgical process for recovering copper metal from copper-containing ore is treated with guanidino groups, amidoxime groups, oxime groups, amidino groups, formazan groups, diketone groups, and amino groups. α of amino group
Copper is brought into contact with a chelate resin having at least one functional group selected from groups having a hydroxyl group or a thiol group at the - or β-position to adsorb copper onto the chelate resin, and then the copper-adsorbing chelate resin is treated with an eluent. A method for recovering copper from a copper-containing ore leachate, which comprises contacting the solution to elute the copper. 2. Eluent contains 5-20g/concentration of copper
A method for recovering copper from a copper-containing ore leachate according to claim 1, characterized in that the sulfuric acid aqueous solution has a concentration of 0.5 to 3N. 3. Copper is extracted from a copper-containing ore leachate according to claim 1 or 2, wherein the chelate resin has at least one functional group selected from a guanidino group, an amidoxime group, and an oxime group. How to collect.