JP4406688B2 - Method for purifying electrolyte in monovalent copper electrowinning process - Google Patents

Description

The present invention relates to a method for purifying a solution containing monovalent copper used in a method for recovering metallic copper from a solution containing monovalent copper by electrolytic operation.

In recent years, interest in recycling has been increasing due to demands for preventing the depletion of various metal resources and reducing the environmental load, and when products are discarded after use, it is becoming a social request to use the original metal. Regarding metal copper or a copper compound, it is required to recover the original metal copper after being recovered in a waste state. From this point of view, the present inventors have prepared a cathode for depositing metallic copper in a solution containing monovalent copper ions in a copper recovery method for depositing metallic copper by electrolysis of a solution containing monovalent copper ions. An anode electrode in a ammonia alkaline solution containing monovalent copper ions, and a diaphragm between the cathode electrode and the anode electrode, and a current is passed through the electrode to move the solution from the cathode electrode side to the anode electrode side. A method for recovering metallic copper by electrolysis of a solution containing monovalent copper ions, characterized by electrolysis, has been developed (Patent Document 1, Non-Patent Document 1).
This method recovers metallic copper from an alkaline alkaline solution containing monovalent copper ions by electrolysis, and can significantly reduce power consumption as compared with the conventional method of electrolytic collection in a sulfuric acid state. Become. Further, by combining this electrowinning with a leaching method using an ammonia alkaline solution, there is a remarkable effect that it is possible to significantly reduce power consumption in the recovery of copper metal from copper-containing metal waste. In addition, since the divalent copper ions generated at the anode at this time can be circulated and used in the leaching tank, the material balance of the chemical necessary for generating the oxidant is maintained, and the closed circuit operation is possible. It has a great effect.
It is effective that the solution used in this method is a solution mainly containing monovalent copper ions. In the solution, copper is reacted with divalent copper ions, ammonium sulfate, and ammonia, thereby causing the above-mentioned 1 A valent copper ion complex is formed.
Here, the monovalent copper ion in the solution containing the monovalent copper ion is used as a complex ion state having a ligand. The _ligand, NH 3, Cl, Br, I, acetonitrile, cyan, phosphine _Lee emissions _{(PRH 2, PR 2 H,} PR 3: R is methyl, ethyl, alkyl groups such as propyl, phenyl, tolyl, Represents an aryl group such as a naphthyl group), arsine (AsH ₃ , As ₂ H ₄ , AsR ₃ , As ₂ R ₄ : R represents an alkyl group such as a methyl, ethyl, or propyl group; a phenyl, tolyl, or a naphthyl group; Represents an aryl group) and the like. Since leaching is performed with an alkaline solution, impurities are less dissolved than leaching with an acidic solution. Nevertheless, the target solution for recovering copper includes aluminum, manganese, iron, as well as silver, palladium, platinum and other precious metals. Each ion of metal such as cobalt, nickel, zinc and lead is contained. In order to perform the electrolysis operation, it is necessary to recover the noble metal and metal ions.
For this reason, it is desired to establish a systematic purification method for removing the noble metal and metal ions from the solution to be treated for copper recovery.

Although it is not the solution used for the said method, the prior art considered relevant is as follows.
There is a document that outlines a method for purifying copper leaching solution in an acidic region (Non-Patent Document 2). In this document, a multi-stage liquid purification method has been developed, and impurities are removed by precipitation operation by pH adjustment, substitution collection of silver by metallic copper, and separation of multivalent ions by ion exchange method.
There is a document related to the recovery of zinc from an alkaline solution using an oxine-based extractant (Patent Document 3). Zinc is separated by an extractant containing 8-hydroxyquinoline groups, back extracted with acid, and recovered as electrowinning or zinc carbonate.
There is also a document describing that an oxine-based extractant (Kelex 100) is used for extraction of Cu (II), Co, Ni, and Fe from an ammonia solution (Non-patent Document 3). In this method, in the range of pH 8.5 to 9.0, the ease of extraction decreases in the order of Cu (II)>Zn>Co> Ni. Back extraction of Co becomes difficult because the organic phase loaded with metal is oxidized from divalent to trivalent when exposed to air for a long time.
There is also a document describing a combination of various extractants regarding the extraction of nickel from an ammonia sulfate solution (Non-Patent Document 4). The nickel extraction rate reached 53% with the LIX64N / Kelex100 combination and 87% with the Kelex100 / DNNSA combination. On the other hand, these extractants alone did not exceed 43%.
There is also a patent that proposes a process for extracting and back-extracting cobalt from an ammonia leachate containing cobalt and other metals (Patent Document 3). After removing metals other than cobalt from the organic phase loaded with metal, cobalt in the organic phase is reduced to divalent before back extraction with dilute acid.
In any case, there is no literature suggesting a method for purifying a solution containing monovalent copper used in a method for recovering metallic copper from a solution containing monovalent copper by electrolytic operation as a prior art.
JP2003-105580, JP2003-253484, JP2003-105580 Canadian Patent No. 2234552 U.S. Pat.No. 4,083,915 K.Koyama, M. Tanaka and JC Lee, “Copper Recovery from Waste Printed CircuitBoard,” Hydrometallurgy 2003 -Fifth International Conference in Honor of Professor Ian Ritchie-Vol. 2: Electrometallurgy and Environmental Hydrometallurgy, CA Young, AM Alfantazi, CG Anderson, DBDreisinger, B. Harris and A. James, Eds., TMS, 2003, 1555-1563. M. Hamalainen, O. Hyvarinen and M. Jyrala, “SolutionPurification in the Outokumpu HydrocopperTM Process,” Hydrometallurgy 2003 -Fifth International Conference in Honor of Professor Ian Ritchie-Vol. 1: Leaching and SolutionPurification, CA Young, AM Alfantazi, CG Anderson , DB Dreisinger, B. Harris and A. James, Eds., TMS, 2003, 545-553. GM Ritcey and BH Lucas, “Extraction and Separationof Copper, Nickel, Zinc and Cobalt from Ammoniacal Solution Using Kelex 100,” Hydrometallurgy, 1975, 105-113. LR Penner, JH Russell and MJ Campbell, “TwoSynergic Pairs for the Extraction of Ammoniacal Ni,” Solvent Extraction 1990, T. Sekine (Editor), Elsevier Science Publishers BV, 1992, 423-428.

  The subject of this invention is related with the purification method of the solution containing monovalent copper used for the method of collect | recovering metallic copper from the solution containing monovalent copper by electrolysis operation. Silver, palladium which are noble metals contained in a solution, It is to provide a systematic method for selectively removing ions such as platinum, rhodium, etc., which are metals such as cobalt, nickel, zinc, lead, aluminum, manganese and iron.

The present inventors diligently investigated the above problems and found the following matters.
In a method of treating an aqueous solution containing copper (I) ions, noble metal ions, and metal ions other than copper (I) ions to extract an aqueous solution containing copper (I) ions, (a) copper (I) ions and noble metal ions And an aqueous solution containing metal ions other than copper (I) ions are brought into contact with metal copper to precipitate and remove noble metals, and (b) contact with an organic solvent to remove metal ions other than copper (I) ions. Selectively move it into an organic solvent, make an aqueous solution containing copper (I) ions into an aqueous phase, (c) separate the aqueous phase from the organic solvent, and then take it out as an aqueous solution containing copper (I) ions , (D) an organic solvent containing metal ions other than copper (I) ions is washed with water, and (e) an organic solvent containing metal ions other than copper (I) ions is optionally replaced with metal ions. After reduction, contact with the acid solution to remove other than copper (I) ions. Other than copper (I) ions, noble metal ions and copper (I) ions, characterized by back-extracting genus ions and regenerating organic solvents, and (f) recycling the regenerated organic solvents in the step (b) By removing the aqueous solution containing copper (I) ions by treating the aqueous solution containing the metal ions, noble metals silver, palladium, platinum, rhodium, etc. contained in the solution, such as cobalt, nickel, zinc, A systematic method for selectively removing ions such as lead, aluminum, manganese, and iron becomes possible.

According to the present invention, the following method is provided.
(1) In a method of removing an aqueous solution containing copper (I) ions by treating an aqueous solution containing copper (I) ions, noble metal ions and metal ions other than copper (I) ions, (a) copper (I) ions And an aqueous solution containing metal ions other than noble metal ions and copper (I) ions is brought into contact with copper metal, and the noble metal is precipitated and separated and removed, and then (b) is brought into contact with an organic solvent and other than copper (I) ions. Metal ions are selectively transferred into an organic solvent, an aqueous solution containing copper (I) ions is made into an aqueous phase, (c) the aqueous phase is separated from the organic solvent, and then contains copper (I) ions. Take out as an aqueous solution, (d) wash the organic solvent containing metal ions other than copper (I) ions with water, and (e) contact the organic solvent containing metal ions other than copper (I) ions with the acid solution And back-extracting metal ions other than copper (I) ions An aqueous solution containing copper (I) ions, noble metal ions and metal ions other than copper (I) ions, characterized in that the organic solvent is regenerated and (f) the regenerated organic solvent is recycled in the step (b). A method of removing an aqueous solution containing copper (I) ions by treatment.

  (2) For the organic solvent containing metal ions other than (e) copper (I) ions, after reducing the metal ions, the metal ions other than copper (I) ions are back-extracted by contacting with an acid solution. An aqueous solution containing copper (I) ions by treating an aqueous solution containing copper (I) ions, noble metal ions and metal ions other than copper (I) ions according to claim 1 How to take out.

(3) An aqueous solution containing metal ions other than the copper (I) ions, noble metal ions and copper (I) ions was obtained by leaching copper-containing waste or copper ore such as printed wiring boards and shredder dust. A method for removing an aqueous solution containing copper (I) ions by treating an aqueous solution containing copper (I) ions, noble metal ions and metal ions other than copper (I) ions according to (1), which is a solution .

(4) The solution obtained by leaching is an ammoniacal alkaline solution as a leaching agent, and is treated with an ammonium salt containing ammonium sulfate or ammonium chloride (3) A method of removing an aqueous solution containing copper (I) ions by treating an aqueous solution containing copper ions (I), noble metal ions and metal ions other than copper (I) ions.

(5) The noble metal ion is a noble metal ion selected from silver, palladium and platinum, and the metal ion other than the copper (I) ion and the noble metal ion and the copper (I) ion according to (1) A method of removing an aqueous solution containing copper (I) ions by treating an aqueous solution containing the aqueous solution.

(6) The copper (I) described in (1), wherein the metal ion other than the copper (I) ion is a metal ion selected from cobalt, nickel, zinc, lead, aluminum, manganese, and iron A method of removing an aqueous solution containing copper (I) ions by treating an aqueous solution containing metal ions other than ions, noble metal ions and copper (I) ions.

(7) The copper (I) ion and the noble metal ion according to (1), wherein the organic solvent (b) is 8-hydroxyquinoline substituted with 8-hydroxyquinoline, an alkyl group or an alkylene group And an aqueous solution containing copper (I) ions by treating an aqueous solution containing metal ions other than copper (I) ions.

(8) The organic solvent contains a modifier and is treated with an aqueous solution containing copper (I) ions, noble metal ions and metal ions other than copper (I) ions according to (7). A method for removing an aqueous solution containing copper (I) ions.

(9) In the method for removing an aqueous solution containing copper (I) ions by treating an aqueous solution containing copper (I) ions, noble metal ions, and metal ions other than copper (I) ions, containing copper (I) ions In the aqueous solution from which the aqueous solution is taken out, copper is mostly present in the form of copper (I) ions, except for copper (I) ions, noble metal ions and copper (I) ions described in (1) A method of removing an aqueous solution containing copper (I) ions by treating an aqueous solution containing metal ions.

(10) (d) The operation of washing an organic solvent containing metal ions other than copper (I) ions with water is performed with water or a dilute acidic aqueous solution to remove co-extracted ammonia. The method for removing an aqueous solution containing copper (I) ions by treating an aqueous solution containing copper (I) ions, noble metal ions and metal ions other than copper (I) ions according to (1).

(11) The copper (1) according to (1), wherein the reduction operation of the metal ion in the organic solvent containing a metal ion other than the copper (I) ion is performed with the metal copper in the ammonia solution. I) A method of treating an aqueous solution containing metal ions other than ions, noble metal ions and copper (I) ions to extract an aqueous solution containing copper (I) ions.

(12) After reducing metal ions in the organic solvent containing metal ions other than (e) copper (I) ions, the operation of bringing the organic solvent into contact with an acid solution is a mineral acid such as sulfuric acid. A method for removing an aqueous solution containing copper (I) ions by treating an aqueous solution containing copper (I) ions, noble metal ions and metal ions other than copper (I) ions as described in (1).

According to the method of this invention, the novel purification method of the solution containing monovalent copper used for the method of collect | recovering metallic copper from the solution containing monovalent copper by electrolysis operation is obtained. Specifically, a system for selectively removing ions such as cobalt, nickel, zinc, lead, aluminum, manganese, and iron, which are metals such as silver, palladium, platinum, and rhodium, which are noble metals contained in a solution The organic solvent used in this method can be regenerated and recycled.
Since the extractant used here does not extract monovalent copper ions, there is very little loss of copper in this purification step. By combining this method with a method of recovering metallic copper from a solution containing monovalent copper by electrolysis, it is possible to produce metallic copper with less energy, reducing costs in copper production and reducing greenhouse gas emissions. Leads to.

The liquid to be treated of the present invention is an aqueous solution containing copper (I) ions.
It is produced by a copper metal waste dissolution method in which a dissolution treatment is performed in a divalent copper ion solution in the presence of a copper metal waste and a complex compound. In supplying the copper metal waste, it may be a waste containing solid copper metal. When it is supplied in a solid state, it is necessary to make it easy to perform solution processing by pulverization before the dissolution processing. The size of the pulverized product varies depending on the processing amount of the dissolution processing apparatus. According to a relatively small test, an average of about 3 to 4 mm is sufficient. If pulverization is performed on an industrial scale, it can be performed using various pulverizers. When waste is supplied in the form of a solution, it needs to be monovalent copper ions. The dissolution reaction is performed in the presence of a divalent copper ion solution.

  A complexing agent is supplied to the solution. Examples of the complexing agent include ammonia, ammonium sulfate, acetonitrile, and cyan.

In the solution containing monovalent copper ions obtained by such dissolution treatment, the monovalent copper ions are in the form of complex ions having a ligand. Examples of the ligand include NH ₃ , Cl, Br, I, acetonitrile, and cyan. These can be produced by reacting copper ions with a complexing agent.

Next, the case where ammonia complex ions are used in relation to the production of monovalent copper ions from a divalent copper ion solution will be described. The resulting monovalent copper ion solution is an electrolyte complex and is dissociated into complex ions in the solution. The copper (I) ion in the ammonia alkaline solution forms a complex ion of ([Cu (NH ₃ ) ₂ ] ⁺ ). In the solution, the monovalent copper ion complex is formed by reacting copper with a divalent copper ion, ammonium sulfate and ammonia. The ammonia alkaline solution is a solution in a state where ammonia and an ammonium salt are present. Specific examples of ammonium salts include ammonium sulfate and ammonium chloride. Ammonia is due to the addition of aqueous ammonia. Alternatively, ammonia can be generated by adjusting the pH with sodium hydroxide or the like. The total concentration of ammonia concentration and ammonium salt concentration present in the monovalent copper ion solution is desirably 5 times or more with respect to the monovalent copper ion concentration. When this condition is satisfied, the copper ions can exist stably. This is because copper ions are not sufficiently formed when the amount is less than this range, and a monovalent copper precipitate may be generated. The pH of the solution is preferably between 8 and 12. This is because a precipitate may be formed when the range is exceeded. Further, monovalent copper ions having a concentration larger than 6.3 g / L are desirable. This is because when the copper concentration is low, hydrogen may be generated along with copper deposition, which causes a reduction in efficiency.

The dissolution treatment corresponds to the case where copper sulfate is used as the divalent copper ion, and by treating the solid copper waste in the presence of ammonium sulfate and ammonia, the ammine complex ion of monovalent copper is converted. It can be regarded as an operation by generating. The present inventors put 10 g of a waste printed board (multilayer board plated on four layers, containing 0.095 g of copper per 1 g of board) into a separable flask, pulverized to an average size of 3.4 mm. Then, 200 m ³ of a solution in which copper sulfate, ammonium sulfate, and ammonia were adjusted to a predetermined concentration was added, and stirring was performed at 400 rpm. After the completion, all the copper on the outermost surface of the substrate was eluted. The effect of copper sulfate concentration on copper leaching was examined. When divalent copper was not included, copper was hardly dissolved. As the divalent copper concentration increased, the initial leaching rate and the leaching rate at each time were It turned out to increase.

  When the solid copper waste contains noble metals such as silver, palladium, platinum, etc., each of the metals such as cobalt, nickel, zinc, lead, aluminum, manganese, iron, etc. A noble metal and a metal will be in the state contained in a solution in the state of an ion.

In the processing of the solution, the following processing operation is performed in the present invention (FIG. 1).
In a method of treating an aqueous solution containing copper (I) ions, noble metal ions, and metal ions other than copper (I) ions to extract an aqueous solution containing copper (I) ions, (a) copper (I) ions and noble metal ions And an aqueous solution containing metal ions other than copper (I) ions are brought into contact with metal copper to precipitate and remove noble metals, and (b) contact with an organic solvent to remove metal ions other than copper (I) ions. Selectively move it into an organic solvent, make an aqueous solution containing copper (I) ions into an aqueous phase, (c) separate the aqueous phase from the organic solvent, and then take it out as an aqueous solution containing copper (I) ions , (D) an organic solvent containing metal ions other than copper (I) ions is washed with water, and (e) an organic solvent containing metal ions other than copper (I) ions is optionally replaced with metal ions. After reduction, contact with the acid solution to remove other than copper (I) ions. The genus ions play an organic solvent with back-extracted, is recycled to (f) regenerated organic solvent the step (b).
This process will be described below.

(A) A step of bringing an aqueous solution containing copper (I) ions, noble metal ions and metal ions other than copper (I) ions into contact with metal copper, and precipitating and separating and removing the noble metal. The metal copper used in this step is It is granular. It is desirable that the particle size is fine considering the processing steps. The particle size is appropriately determined and added to the aqueous solution. In the examples, those having an average particle size of 30 μm were used. The amount of addition is appropriately determined according to the content of the noble metal to be removed contained in the aqueous solution. It is not preferable to add an unnecessarily large amount. The processing temperature may be room temperature. It is important that the treatment be performed in the absence of oxygen. The presence of oxygen is not preferable because copper (I) ions are oxidized.
As a result, noble metals such as silver, palladium, platinum, and rhodium are deposited and removed.
The deposited noble metal is removed by a filtration operation.

(B) A step of bringing an aqueous solution containing copper (I) ions into an aqueous phase by bringing metal ions other than copper (I) ions selectively into the organic solvent by contacting with an organic solvent, and ) Aqueous solution containing copper (I) ions containing various ions such as cobalt, nickel, zinc, lead, aluminum, manganese and iron after depositing and removing noble metals such as silver, palladium, platinum and rhodium It is a step of removing metal ions other than copper (I) ions from the inside, brought into liquid-liquid contact with the organic phase composed of the aqueous solution and the organic solvent, taking the metal ions into the organic phase, and removing metal ions from the aqueous solution Remove. The ratio at the time of liquid-liquid contact is determined suitably.
A known solvent can be appropriately acted on the organic solvent as long as it can remove the metal ions. Generally, an oxine extractant is used. Specifically, the organic solvent is 8-hydroxyquinoline substituted with 8-hydroxyquinoline, an alkyl group or an alkylene group.
These oxine extractants can be mixed with chelate extractants such as LIX63 and LIX64N, and acidic extractants such as VA10. As this extractant, a modifier can be appropriately used. An alcohol solution is used as the modifier. In the examples, 5 vol% of 1-decanol was used.

(C) After separating the aqueous phase from the organic solvent, the organic solvent and the aqueous phase are separated for the step of taking out as an aqueous solution containing copper (I) ions. The organic solvent is separated as an organic phase containing metal ions other than copper (I) ions. As a result, the aqueous phase does not contain precious metal and metal ions, and this aqueous phase is a method for recovering metallic copper by electrolytic operation as an aqueous solution containing copper (I) ions from which the precious metal and metal ions have been removed. Can be used.
For separation, stationary separation or the like is employed.

(D) In the step of washing an organic solvent containing metal ions other than copper (I) ions with water, the co-extracted ammonia is removed by washing the organic phase containing metal ions with water. As the water, an aqueous solution containing a dilute acid in addition to water usually used in industry is used. The acid is a mineral acid such as hydrochloric acid. Simultaneously with the treatment, the ammonia component is extracted and transferred to water. The amount and temperature of water are appropriately determined when washing with water.

(E) If necessary, after reducing metal ions in an organic solvent containing metal ions other than copper (I) ions, the organic solvent is brought into contact with an acid solution, and a metal other than copper (I) ions. Regarding the step of back-extracting ions and regenerating the organic solvent If necessary, a metal ion reduction treatment in an organic solvent containing metal ions other than copper (I) ions is performed. Copper powder is used as the reducing agent, and the treatment is performed in the presence of aqueous ammonia. An organic solvent is brought into contact with an acid solution to back-extract metal ions other than copper (I) ions. Sulfuric acid is used for the acid solution. Metal ions other than the copper (I) ions become metals and are treated with sulfuric acid to form sulfates that are separated from the organic solvent. Specifically, it is removed as Al ₂ (SO ₄ ) ₃ , MnSO ₄ , FeSO ₄ , CuSO ₄ , ZnSO ₄ , PbSO ₄ or the like. The concentration of sulfuric acid is appropriately determined.

(F) Regarding the step of recycling and using the regenerated organic solvent in the step (b) Since the regenerated organic solvent does not contain metal ions other than copper (I) ions, noble metal ions and copper (I) ions, The organic solvent (b) can be recycled.

Examples are shown below. These experiments are performed by a batch method, but can be performed using a continuous extraction apparatus such as an extraction column in actual operation.
Removal method of silver by substitution method using copper powder Silver removal experiment using 5M NH ₃ + 1M (NH ₄ ) ₂ SO ₄ solution containing silver (I) ion and copper powder with average particle size of 30 μm went.
All reaction operations were performed under a nitrogen atmosphere using a glove box. A trace amount of oxygen in the nitrogen gas was previously removed with a basic pyrogallol solution (a mixed solution of 15 wt% pyrogallol and 30 wt% KOH). 50 ml of the solution and copper powder were mixed at a predetermined temperature for a predetermined time. After filtration, the metal concentration in the filtrate was measured by ICP emission spectroscopy, and the results are shown in Table 1. From this, the substitution reaction of silver progresses as the amount of added copper powder increases, and the molar ratio at the time of supply (number of moles of metallic copper to 1 liter of solution) / (molar concentration of silver, mole / l) exceeds 6. It can be seen that the silver can be removed almost completely at 25 ° C. for 30 minutes.

Silver removal method using copper powder (when other metal ions are present)
The same operation as in Example 1 was performed under the condition that each ion of cobalt (II), nickel (II), zinc (II), and copper (I) coexisted. The substitution reaction was carried out at 25 ° C. for 45 minutes. The concentration of copper (II) was determined by the absorbance of visible light (wavelength 630 nm), and the copper (I) concentration was determined by subtracting the copper (II) concentration from the total copper concentration. The results are shown in Table 2. In addition, Table 3 shows the concentration and ratio of each copper ion in the solution.
From these, it can be seen that silver can be completely and selectively removed from an ammonia solution containing a plurality of metal ions, and that copper exists as copper (I) after the reaction.

Iron (II), cobalt (II), nickel and zinc, from _{5M NH 3 + 1M (NH 4} ) 2 SO 4 solution containing copper (I) in a large amount, the oxine extractant LIX26, the LIX63, LIX64N and VA10 It can be removed by solvent extraction with a small amount added as a cooperative effect reagent.
The experiment was performed in a nitrogen atmosphere as in the previous examples. The analysis method is also the same. As the aqueous phase, a 5M NH ₃ + 1M (NH ₄ ) ₂ SO ₄ solution containing iron (II), cobalt (II), nickel, zinc and copper (I) was used. For the organic phase, LIX26 solutions of various concentrations dissolved in Shellzol D70 were used. However, 5 vol% of 1-decanol was added as a modifier (hereinafter, the concentrations of the extractant and modifier in the organic phase all mean vol%). Cooperative effect reagents were also added as appropriate. The volume ratio of the organic phase to the aqueous phase was 1, the contact time was 10 minutes, and the reaction was performed at room temperature (25 ° C.).

About removal of iron The result about iron (II) is as showing in Table 4, and it turns out that iron is completely removed even if it uses any organic phase.

Regarding the removal of cobalt (II) The results for cobalt (II) are as shown in Table 5. It can be seen that cobalt is completely removed by using any organic phase.

About removal of nickel The result about nickel is as having shown in Table 6, and nickel extraction is greatly accelerated | stimulated by a cooperative effect, and it turns out that addition of carboxylic acid (VA10) is the most effective.

Zinc removal The results for zinc are shown in Table 7. The combination of LIX 26-LIX 64N (volume ratio 5: 1) has the highest zinc removal rate, and VA10 has no cooperative effect. I understand.

Regarding the behavior of copper The extraction behavior of copper was examined and the results are shown in Table 8, and the existence form of copper ions in the aqueous phase was examined and the results are shown in Table 9. From this, it can be seen that the copper loss is 5-9% in the cooperative extraction system, which is slightly lower than that when using LIX26 alone (3.7%). In addition, it is understood that copper is extracted from a trace amount of copper (II) ions present in the supply liquid, and copper (I) ions are not extracted.

Silver, cobalt (II), nickel and zinc are removed from ammonia alkaline solution containing a large amount of copper (I) ions by adding small amounts of extractants such as LIX 84I, DNNSA, PC88A, D2EHPA, VA10 to LIX 26 it can.
An equal volume (50 ml each) of the aqueous phase and the organic phase was mixed in a glove box under a nitrogen atmosphere, and 10 ml was collected by combining the aqueous phase and the organic phase at predetermined time intervals. After phase separation, the metal concentration in the aqueous phase was measured by ICP emission spectroscopy. The aqueous phase used is a 5M NH ₃ + 1M (NH ₄ ) ₂ SO ₄ solution containing silver, cobalt (II), nickel, zinc and copper (I), and the organic phase is 15% LIX26 and 5% 1− It was a solanol D70 solution of decanol, and various extractants were added as needed.

About removal of silver Table 10 shows the results for silver, and it can be seen that the removal of silver is complete.

Regarding the removal of cobalt Table 11 shows the results for cobalt and it can be seen that the removal of cobalt is complete.

Regarding the removal of nickel Table 12 shows the results for nickel. The removal of nickel is also completely performed, but it can be seen that the speed is slightly lower when using LIX 26 alone.

About Zinc Removal Table 13 shows the results for zinc. When LIX 84I was added to LIX 26 and shaken for 15 minutes, the maximum extraction rate of 76% was obtained. The zinc extraction rate tended to decrease slightly with time.

Regarding loss of copper in impurity removal step Table 14 shows the results for copper. It can be seen that about 10% of copper moves to the organic phase by the extraction operation.

When copper in a PCB is leached with an ammonium chloride solution, the concentration of each impurity metal ion is different from that of an ammonium sulfate solution system. These impurities are LIX
26 can be removed from the leachate containing a large amount of copper (I) ions.

Aluminum, manganese, iron (II), cobalt (II), nickel, copper _{(I), 5M NH 3 +} 4M NH 4 Cl solution and water phase feed solution containing zinc and lead, LIX 26 and 1-decanol and needs Accordingly, a solvent extraction experiment was conducted using Shellzol D70 solution in which other extraction reagents were dissolved as an organic phase supply solution. The impurity concentration was about 10 times the concentration obtained by actual leaching. However, since lead was not completely dissolved at this concentration, it was filtered before the experiment. An equal volume (20 ml) of the aqueous and organic phases were mixed at room temperature in a glove box filled with nitrogen. After phase separation, the metal concentration in the aqueous phase was quantified with an ICP emission spectroscopic analyzer.

About removal of aluminum Table 15 shows the results for aluminum, and it can be seen that aluminum can be completely removed.

Manganese removal:
Table 16 shows the results for manganese, and it can be seen that manganese can be completely removed.

Regarding the removal of iron Table 17 shows the results for iron. It can be seen that iron can be removed with high efficiency although the data varies.

Cobalt removal:
Table 18 shows the results for cobalt, and it can be seen that cobalt can be removed with high efficiency.

About removal of nickel Table 19 shows the results for nickel.In a 25% LIX 26 alone system, it can be removed with an efficiency of 90% or more by mixing for 60 minutes, and when an acidic extractant is added to LIX 26. It can be seen that it can be removed with an efficiency of 90% or more by mixing for 15 minutes.

Regarding extraction of copper Table 20 shows the results for copper, and Table 21 shows the presence of copper ions in the aqueous phase produced in Experiment No. 3 in Table 20. It can be seen from Table 20 that over 10% of copper has migrated to the organic phase, and this tendency is the same as that already described in the sulfate system. Table 21 also shows that most copper ions remain as copper (I).

About Zinc Removal Table 22 shows the results for zinc. The removal rate of zinc was low and the highest was 25% LIX
This was when extraction was performed for 10 to 15 minutes using 26, and the value was 66%. The addition of other extraction reagents has no effect in this system.

Regarding the removal of lead Table 23 shows the results for lead, and it can be seen that lead can be almost completely removed.

  Here, an impurity containing a large amount of copper (I) ions and impurities such as aluminum, manganese, iron (II), cobalt (II), nickel, zinc and lead is removed using a solvent extraction method, and impurities are removed. Attempts were made to wash and back-extract the organic phase loaded with metal ions. All experiments were performed in a nitrogen atmosphere using a glove box. After phase separation, the metal concentration in the aqueous phase was quantified by ICP emission spectroscopy.

1. Extraction Operation Impurities were extracted into the organic phase using LIX 26, and the resulting organic phase was washed with water to remove the co-extracted ammonia. The organic phase after washing was mixed with various concentrations of sulfuric acid and back extracted. Prior to back extraction, an attempt was made to reduce the metal ions by bringing the washed organic phase into contact with an ammonia solution containing copper metal.
The aqueous phase used in the extraction operation was a mixed solution of 5M NH ₃ and 4M NH ₄ Cl containing aluminum, manganese, iron, cobalt, nickel, zinc and lead. The organic phase used was 25% LIX 26 and 10% 1-decanol dissolved in Shellzol D70. Extraction was performed at room temperature for 30 minutes at a volume ratio of 1.
Table 24 shows the results of examining the extraction rate of each metal. It can be seen that impurities can be almost completely removed and the loss of copper is about 10%.

2. Washing of organic phase The organic phase produced in the above experiment and ion-exchanged water were mixed at a volume ratio of 1 at room temperature for 20 minutes for washing operation.
Table 25 shows the results. It can be seen that, depending on the washing operation, the metal ions hardly move to the aqueous phase.

3. Reduction of metals in the organic phase When cobalt (II) is extracted with an oxine-based extractant or hydroxyoxime-based extractant, once the extracted cobalt is oxidized to trivalent, back-extraction can be very difficult. Are known. It is known that when oxidized, it can be reduced to cobalt (II) when brought into contact with an aqueous solution containing copper powder. Therefore, it was investigated whether or not the metal extracted into the organic phase was back-extracted by this reduction operation. In the experiment, 50 ml of the organic phase after washing and 142 g / l ammonia solution containing 20 g / l copper powder (average particle size 30 μm) were contacted for 20 minutes at room temperature.
Table 26 shows the results, and it can be seen that the metal ions hardly move to the aqueous phase by the reduction operation.

4). Back extraction:
4.1 Back extraction of metal from the organic phase after reduction treatment 270
g / l sulfuric acid was mixed at a volume ratio of 1 in a separatory funnel for 15 minutes. After phase separation, the aqueous phase was extracted from the separatory funnel, and 270 g / l sulfuric acid was newly added and mixed in the same manner. This mixing operation was performed a total of four times.
Table 27 shows the results. All metals other than lead are completely back-extracted in the first stage. Each metal ion is also detected in the aqueous phase after the second stage, and this seems to be the effect of a small amount of the aqueous phase remaining on the inner wall of the separatory funnel (the same applies hereinafter). 73% of lead was back-extracted in 4 stages of back-extraction.

4.2 Back extraction of organic phase after washing
Under the same conditions as in 4.1, the washed organic phase was subjected to a back extraction experiment without performing a reduction operation. The results are shown in Table 28.
Table 28 shows the results, and all metals other than lead are completely back-extracted in the first stage. 43% of lead was back-extracted in 4 stages of back-extraction.

  Next, back extraction was performed under the same conditions as in the above experiment with a sulfuric acid concentration of 98 g / l. However, the number of repetitions of back extraction was set to 5. Table 29 shows the results. It can be seen that metals other than lead are completely back-extracted in up to three stages. The back extraction rate of lead was 47% in 5 stages.

4.3 Back extraction from mixed extractant Solvent extraction was performed using the mixed extractant to extract impurity metals, and the resulting organic phase was immediately subjected to a back extraction operation with sulfuric acid.
In the extraction operation, the aqueous phase after the substitution treatment was mixed with a Shellzol D70 solution containing 25% LIX 26, 3% VA10, 10% 1-decanol at room temperature at a volume ratio of 1 for 30 minutes. .
Table 30 shows the results. Impurities are removed with an efficiency of 70% or more by one-stage extraction. Copper loss is 10%.

Next, the organic phase produced by the above operation and 275 g / l sulfuric acid were mixed under the conditions of room temperature and volume ratio of 1. The mixing time was 15 minutes for the first stage and 30 minutes for the second stage.
Table 31 shows the results. Impurities other than lead are back-extracted with an efficiency of 95% or more by one-step back-extraction. The overall back extraction rate of lead after two stages of back extraction was 31%.

It is a flow sheet which shows the method of this invention.

Claims (8)

In a method of selectively removing metal ions other than noble metal ions and copper (I) ions and taking out an aqueous solution containing copper (I) ions,
(A) After contacting an aqueous solution containing metal ions other than copper (I) ions and noble metal ions and copper (I) ions with metal copper, the noble metal is precipitated and separated and removed;
(B) Contact with an organic solvent comprising 8-hydroxyquinoline or 8-hydroxyquinoline substituted with an alkyl group or an alkylene group to selectively transfer metal ions other than copper (I) ions into the organic solvent. An aqueous solution containing copper (I) ions is in an aqueous phase,
(C) After separating the aqueous phase from the organic solvent, taking it out as an aqueous solution containing copper (I) ions,
(D) After washing the organic solvent containing metal ions other than the copper (I) ions with water, (e) For organic solvents containing metal ions other than copper (I) ions, other than copper (I) ions Organic solvent is regenerated by back-extracting metal ions of
(F) A method of taking out an aqueous solution containing copper (I) ions, wherein the regenerated organic solvent is recycled in the step (b). The method according to claim 1, wherein the organic solvent contains a chelate extractant and / or an acidic extractant. The method according to claim 1, wherein the organic solvent contains an alcohol solution as a modifier. The method according to claim 1, wherein the back extraction of (e) is performed by reducing metal ions and then contacting with an acid solution. The method according to claim 3, wherein the acid solution is sulfuric acid. The aqueous solution containing the copper (I) ions, the noble metal ions and the metal ions other than the copper (I) ions is a copper- containing waste or copper ore as a leaching agent, and using an alkaline solution containing ammonium sulfate or ammonium chloride. The method according to claim 1, wherein the solution is obtained by treatment . The method according to claim 1 , wherein the noble metal ion is a noble metal ion selected from silver, palladium, and platinum . The method according to claim 1 , wherein the metal ions other than the copper (I) ions are metal ions selected from cobalt, nickel, zinc, lead, aluminum, manganese, and iron .

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