KR101723730B1 - High selective metals and acid recovery process from a multi-metallic solutio - Google Patents
High selective metals and acid recovery process from a multi-metallic solutio Download PDFInfo
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- KR101723730B1 KR101723730B1 KR1020150078493A KR20150078493A KR101723730B1 KR 101723730 B1 KR101723730 B1 KR 101723730B1 KR 1020150078493 A KR1020150078493 A KR 1020150078493A KR 20150078493 A KR20150078493 A KR 20150078493A KR 101723730 B1 KR101723730 B1 KR 101723730B1
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/22—Electrolytic production, recovery or refining of metals by electrolysis of solutions of metals not provided for in groups C25C1/02 - C25C1/20
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C55/00—Saturated compounds having more than one carboxyl group bound to acyclic carbon atoms
- C07C55/02—Dicarboxylic acids
- C07C55/06—Oxalic acid
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C59/00—Compounds having carboxyl groups bound to acyclic carbon atoms and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
- C07C59/235—Saturated compounds containing more than one carboxyl group
- C07C59/245—Saturated compounds containing more than one carboxyl group containing hydroxy or O-metal groups
- C07C59/265—Citric acid
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- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/06—Electrolytic production, recovery or refining of metals by electrolysis of solutions or iron group metals, refractory metals or manganese
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- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/06—Electrolytic production, recovery or refining of metals by electrolysis of solutions or iron group metals, refractory metals or manganese
- C25C1/10—Electrolytic production, recovery or refining of metals by electrolysis of solutions or iron group metals, refractory metals or manganese of chromium or manganese
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- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C3/00—Electrolytic production, recovery or refining of metals by electrolysis of melts
- C25C3/04—Electrolytic production, recovery or refining of metals by electrolysis of melts of magnesium
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Abstract
The present invention relates to a highly selective metal and an acid recovery method from a multi-component metal solution, and more particularly, to a high selectivity metal and acid recovery method using an electrodialysis system in which an anion exchange membrane is provided between a cathode electrolyzer and a cathode electrolyzer, , Water is added to the anode electrolytic cell and a cathode electrolytic bath is charged with a multi-component metal solution (aqueous solution of hydrochloric acid metal) and a polybasic acid solution containing iron (Fe), cobalt (Co), nickel (Ni), manganese (Mn) A primary electrodeposition process in which chloride ion (HCl) is generated by the transfer of chloride ions to the anode electrolytic bath through the anion exchange membrane and iron (Fe) is precipitated in the anode electrolytic bath when carboxylic acid is supplied and electricity is supplied; A step of synthesizing Co and Ni compounds in which a solution of a negative electrode electrolytic bath generated in the first electrodeposition step is heated to precipitate Co-carboxylic acid and Ni-carboxylic acid compound; A Co and Ni compound filtration step of subjecting the synthesized Co and Ni compound and the filtrate to solid-liquid separation; When water is supplied to the anode electrolytic cell and electricity is supplied to the cathode electrolytic cell while the filtrate recovered in the Co and Ni compound filtration process is supplied to the anode electrolytic cell, chlorine ions migrate to the anode electrolytic cell through the anion exchange membrane to generate hydrochloric acid (HCl) The electrolytic bath is characterized in that manganese (Mn) is initially precipitated and magnesium (Mg) is precipitated at the end of the electrolytic bath.
The high selectivity metal and acid recovery method from the multicomponent metal solution of the present invention is characterized by adding a polybasic carboxylic acid having strong bonding force with cobalt (Co) as an electrodeposition inhibitor to enhance the selectivity between iron (Fe) and cobalt (Co) The cobalt (Co) and nickel (Ni) are selectively separated and recovered by selective precipitation of iron (Fe) and chemical precipitation of cobalt (Co) and nickel (Ni) The recovery selection and recovery rate of all the metallic components are increased, and the acid recovery process of the solution can be simultaneously carried out through the anion exchange membrane.
The high selectivity metal and acid recovery method from the multicomponent metal solution of the present invention is a multistage process while preventing the generation of high concentration of wastewater, thereby reducing the cost of efficient facility operation and maintaining the pH and voltage of the solution appropriately (Mn) and magnesium (Mg) can be improved by improving the selectivity and purity of nickel (Ni), manganese (Mn) and magnesium (Mg)
Description
The present invention relates to a highly selective metal and an acid recovery method from a multi-component metal solution, and more particularly, to a method for recovering a highly selective metal and an acid from a multi- (Cobalt (Co)), which is strong enough to bind to cobalt (Co), that is, an electro-precipitation inhibitor, is added to the solution to maintain the pH and the voltage of the solution appropriately using an electrodialysis system. (Co) and nickel (Ni) are chemically precipitated and re-dissolved by selective precipitation of cobalt (Co) and nickel (Ni) The recovery of selectivity and recovery of all the metallic components can be increased and the acid recovery process of the solution can be carried out from a multicomponent metal solution which can be simultaneously carried out through an anion exchange membrane, And an acid recovery method.
In general, a method of recovering a selective metal from a waste liquid containing a metal component, particularly, a method of recovering iron, cobalt, nickel, and the like, includes an ion exchange method, a solvent extraction method, and a precipitation method.
The ion exchange method is a technology for separating and recovering acid and alkali by separately separating an acid or an alkali using an ion exchange membrane. It is possible to concentrate by removing water using a reverse osmosis membrane. Such a membrane separation method is energy saving because there is no heating operation . However, when a large amount of salt and metal ions are contained in the waste solution, ion exchange is inefficient and a large-capacity ion exchanger is required. A method of recovering spent acid by ion exchange membrane is a diffusion dialysis method in which a free acid is recovered only by a concentration difference using a fixed ion exchange membrane, a cation exchange membrane and an anion exchange membrane are used at the same time, a DC power is supplied from an anode electrode, There is an electrodialysis method.
The solvent extraction method is a method of extracting metal from a waste solution by using a selective extraction ability of a solvent. It is advantageous that a metal component can be recovered relatively purely from a mixed solution of various metals by controlling the composition of a solvent, The extraction performance is deteriorated due to the contamination of the solvent and the scale of the extraction equipment is large. On the other hand, the production of metal materials from minerals takes place through a series of processes such as leaching, separation, purification, and reduction. Recently, as the demand for high purity metal materials has increased, the development of more efficient separation and purification technology As the interest in environment and energy has increased, interest in environmentally friendly low-energy separation and purification technology is increasing.
The precipitation method is a purification technique in which a precipitant that forms a compound with a metal is added to precipitate a metal by selective precipitation. The precipitate is converted into an insoluble salt in an aqueous solution, precipitated, and then filtered to obtain a relatively small scale Since the process is relatively simple, it is the most widely used method in a small-scale unit factory. However, since it is difficult to recover as a high-purity product due to incorporation of impurities by coprecipitation, in order to obtain a metal having a certain degree of purity, There are fatal disadvantages that must be repeated.
A prior literature on a method for recovering a metal component from a waste solution is disclosed in Korean Patent Publication No. 1996-0010812, which relates to a method for recovering cobalt from a post-liquid generated in a malonic ester production process, A step of removing organic impurities by washing the solution of the precipitate generated in the process after the organic impurities are removed with petroleum; and a step of extracting and concentrating the cobalt in the post-liquid after removing the organic impurities at a pH of 2-5 by an organic solvent extraction method And cobalt extracted and concentrated in the organic solvent is washed with water and back extracted with an acid at a temperature of 30-60 to obtain concentrated cobalt or the reverse extract solution is neutralized with alkali and fired at a temperature of 300-400 for 2-4 hours And recovering it with cobalt oxide, thereby increasing the capacity, purity and economical efficiency of the cobalt recovery apparatus. A solvent extraction method is described.
Korean Patent Publication No. 1999-020593 discloses an economical and relatively simple precipitation method for recovering a cobalt compound waste catalyst which is a by-product in a malonic acid ester production plant to recover a cobalt compound, The present invention provides a method for recovering relatively pure cobalt compounds without any additional process such as recovery of cobalt hydroxide or cobalt carbonate. This is because the cobalt compound used as a catalyst in the malonic acid ester production process is recovered and recycled, And a method for recovering cobalt oxalate produced by adding a hydrate of oxalic acid or oxalic acid by precipitating selectively from impurities. The present invention recovers expensive cobalt compounds from various impurities in the waste liquid by a relatively simple method, thereby being economical and also preventing environmental pollution caused by heavy metals, because it can be recycled for use as pigments and dyes that do not need relatively high purity for their activity There is an effect that can be done.
Korean Patent Registration No. 10-0553311 discloses that when oxalic acid or oxalic acid dihydrate is added from an acid solution containing nickel, cobalt and iron elements, and in the precipitation and recovery thereof, the amount of the acid solution and the content of the metal element Wherein at least one of nickel, cobalt, and iron is recovered by progressing the reaction by supplying a DC voltage that is selected differently according to the amount of nickel and cobalt.
In addition, there is a precipitation of a metal hydroxide, precipitation trend Fe +3> Al +3> Cr +2 > Zn +2> Ni +2> Fe +2> Co +2> Mn +2> Mg +2> Ca + 2, and so on. However, Ni +2 , Fe +2 , Co + 2 and so on have very low selectivity due to the similar tendency of precipitation.
Until now, typical methods for selectively separating and recovering metals from multi-component metal mixed solutions include hydroxide precipitation method, sulfide precipitation method, solvent extraction method, etc. In the solvent extraction method, it is subdivided according to the kind of solvent, and ion exchange resin method, Acid extraction method, and amine resin method may be included in the solvent extraction method in a large range. These methods have disadvantages in that the purity is low due to the occurrence of coprecipitation when the recovery rate is good, and there are various problems that the purity is high but the reaction rate is slow and the apparatus cost is high.
Meanwhile, in order to improve the existing precipitation method, the present invention uses an electrodialysis system equipped with an anion exchange membrane to appropriately maintain the pH and the voltage of the solution, and repeated the electrodeposition experiments on the metal components contained in the acid solution. As a result, Nickel (Ni), manganese (Mn), and magnesium (Mg) in the solution can increase the selectivity by controlling the voltage and the pH. In order to increase the selectivity of iron (Fe) and cobalt (Co) The addition of this strong electrodeposition inhibitor enhances recovery and recovery of all the metallic components, and the acid recovery process of the mixed solution can be carried out simultaneously from a multicomponent metal solution that can be simultaneously conducted through an anion exchange membrane. Thereby completing the present invention.
It is an object of the present invention to provide a method and apparatus for adjusting the pH and voltage of a solution appropriately using an electrodialysis system from an acid solution containing iron (Fe), cobalt (Co), nickel (Ni), magnesium (Mg), manganese (Fe) can be selectively added by adding a polybasic carboxylic acid having a strong binding force with cobalt (Co) or the like as an electrodeposition inhibitor in order to enhance the selectivity of iron (Fe) and cobalt (Co) (Co) and nickel (Ni) which have been suppressed from precipitation are chemically precipitated and re-dissolved to selectively separate and recover cobalt (Co) and nickel (Ni) The recovery selectivity and recovery rate of the solution can be increased and the acid pickling process of the solution can provide a highly selective metal and acid recovery method from a multicomponent metal solution that can be simultaneously carried out through an anion exchange membrane.
In the method for recovering high selectivity metals and acids from a multi-component metal solution using an electrodialysis system in which an anion exchange membrane is provided between a cathode electrolyzer and a cathode electrolyzer, Water is added to the anode electrolyzer, and a multicomponent metal solution (aqueous solution of hydrochloric acid metal) containing iron (Fe), cobalt (Co), nickel (Ni), manganese (Mn), and magnesium (Mg) A first electrodeposition process in which chlorine ions migrate through the anion exchange membrane to the anode electrolytic cell to produce hydrochloric acid (HCl), and iron (Fe) precipitates in the anode electrolytic cell; A step of synthesizing Co and Ni compounds in which a solution of a negative electrode electrolytic bath generated in the first electrodeposition step is heated to precipitate Co-carboxylic acid and Ni-carboxylic acid compound; A Co and Ni compound filtration step of subjecting the synthesized Co and Ni compound and the filtrate to solid-liquid separation; When water is supplied to the anode electrolytic cell and electricity is supplied to the cathode electrolytic cell while the filtrate recovered in the Co and Ni compound filtration process is supplied to the anode electrolytic cell, chlorine ions migrate to the anode electrolytic cell through the anion exchange membrane to generate hydrochloric acid (HCl) The electrolytic bath is characterized in that manganese (Mn) is initially precipitated and magnesium (Mg) is precipitated at the end of the electrolytic bath.
According to a preferred embodiment of the present invention, the polybasic carboxylic acid used in the first electrodeposition step is any one selected from the group consisting of oxalic acid and citric acid, When the separated Co-carboxylic acid and Ni-carboxylic acid compound are re-dissolved in hydrochloric acid (HCl), water is added to the anode electrolytic bath, the solution is supplied to the anode electrolytic cell, and electricity is supplied. (HCl) is generated in the anode electrolytic cell, and cobalt (Co) is initially precipitated in the cathode electrolyzer and nickel (Ni) is precipitated at the end.
Also, the filtrate of the anode electrolytic cell generated in the third electrodeposition step is recovered and redissolved in hydrochloric acid (HCl), and then the third electrodeposition step is repeated one to three times, and the first to third electrodeposition The electricity supplied in the process is characterized by having a direct current voltage of 3 to 15V.
The high selectivity metal and acid recovery method from the multicomponent metal solution of the present invention is characterized by adding a polybasic carboxylic acid having strong bonding force with cobalt (Co) as an electrodeposition inhibitor to enhance the selectivity between iron (Fe) and cobalt (Co) (Co) and nickel (Ni) are chemically precipitated and re-dissolved by selectively removing iron (Fe), cobalt (Co) and nickel (Ni) are selectively separated and recovered, The recovery selection and recovery rate of all the metallic components are increased, and the acid recovery process of the solution can be simultaneously carried out through the anion exchange membrane.
The high selectivity metal and acid recovery method from the multicomponent metal solution of the present invention is a multistage process while preventing the generation of high concentration of wastewater, thereby reducing the cost of efficient facility operation and maintaining the pH and voltage of the solution appropriately (Mn) and magnesium (Mg) can be improved by improving the selectivity and purity of nickel (Ni), manganese (Mn) and magnesium (Mg)
BRIEF DESCRIPTION OF DRAWINGS FIG. 1 is a block diagram showing a highly selective metal and an acid recovery method from a multicomponent metal solution according to the present invention. FIG.
The present invention relates to a method for recovering a high selectivity metal and an acid from a multi-component metal solution using an electrodialysis system in which an anion exchange membrane is provided between a cathode electrolyzer and a cathode electrolyzer, water is supplied to the anode electrolyzer, When a multicomponent metal solution containing cobalt (Co), nickel (Ni), manganese (Mn) and magnesium (Mg) and polybasic carboxylic acid are supplied and electricity is supplied, chlorine ions migrate through the anion- A first electrodeposition process in which hydrochloric acid (HCl) is produced and iron (Fe) is precipitated in the anode electrolyzer; A step of synthesizing Co and Ni compounds in which a solution of a negative electrode electrolytic bath generated in the first electrodeposition step is heated to precipitate Co-carboxylic acid and Ni-carboxylic acid compound; A Co and Ni compound filtration step of subjecting the synthesized Co and Ni compound and the filtrate to solid-liquid separation; When water is supplied to the anode electrolytic cell and electricity is supplied to the anode electrolytic cell while the filtrate recovered in the Co and Ni compound filtration process is supplied to the anode electrolytic cell, chlorine ions migrate through the anion exchange membrane to the anode electrolytic cell to generate hydrochloric acid (HCl) The electrolytic cell is composed of a secondary electrodeposition process in which manganese (Mn) is initially precipitated and magnesium (Mg) is precipitated at the end.
In the present invention, the Co-carboxylic acid and the Ni-carboxylic acid compound separated in the Co and Ni compound filtration process are redissolved in hydrochloric acid (HCl), water is introduced into the anodic electrolytic bath, (Co) is precipitated in the cathode electrolytic cell and nickel (Ni) is precipitated in the cathode in the cathode electrolytic cell at the end of the electrochemical deposition process, in which chloride ions (HCl) are generated through the anion- .
Hereinafter, the process of each step of the present invention will be described in detail with reference to the drawings, which is intended to be illustrative of the invention so that those skilled in the art can easily carry out the invention, Quot; and " the "
1, a highly selective metal and acid recovery method from a multi-component metal solution according to the present invention includes a first electrodeposition process, an electrodeposition process in which an anion exchange membrane is provided between a positive electrode electrolysis tank and a negative electrode electrolysis tank, The compound synthesis step, the Co, the Ni compound filtration step, the second electrodeposition step, and the third electrodeposition step are carried out simultaneously.
First, in the first electrodeposition step, water is introduced into the anode electrolytic cell, and a multicomponent metal solution containing iron (Fe), cobalt (Co), nickel (Ni), manganese (Mn), and magnesium (Mg) When a polybasic carboxylic acid is supplied and electricity is supplied, chlorine ions migrate through the anion exchange membrane to the anode electrolytic cell to generate hydrochloric acid (HCl), and iron (Fe) precipitates in the cathode electrolyzer.
In the process of recovering a metal component from an acid solution using a conventional electrodialysis system, cobalt (Co) and nickel (Ni) are extracted first by an acid dissolution method or the like, and then iron (Fe) (Co) and nickel (Ni) are redissolved, it is difficult to separate iron (Fe) of high purity.
In order to solve such a problem, in the present invention, a process of separating cobalt (Co) and nickel (Ni) carboxylic acid precipitates is carried out by introducing a polybasic carboxylic acid such as oxalic acid as an electrodeposition inhibitor in a method of recovering cobalt from a conventional waste liquid And then precipitate iron (Fe) of high purity by electrochemical precipitation.
It is preferable that the polybasic carboxylic acid is any one selected from the group consisting of oxalic acid (C 2 H 2 O 4 ), citric acid (C 6 H 8 O 7 ), and their hydrates or anhydrides Type, which has the property of forming a complex with respect to a specific metal ion, and preferentially forms a complex with cobalt and nickel in a multi-component metal solution, thereby selectively precipitating them. The amount of the polybasic carboxylic acid is preferably 2 to 5 equivalents relative to the amount of cobalt ion. When the amount of the polybasic carboxylic acid is less than 2 equivalents, the recovery rate is lowered. When the amount is more than 5 equivalents, There is a problem and it is not desirable.
Next, the Co and Ni compound synthesis process is a process of precipitating a Co-carboxylic acid and a Ni-carboxylic acid compound by heating a filtrate of a negative electrode electrolytic bath generated in the first electrodeposition step, wherein cobalt and nickel are cobalt Oxalate, or nickel oxalate, or synthesized in the form of a carboxylic acid compound such as cobalt citrate or nickel citrate to recover Co or Ni compound, and continuously filtrate the solution and solid solution . The Co and Ni compounds are insoluble compounds in an aqueous solution, and can easily be filtered by a general filtration facility, and cleaning can be easily performed, so that incorporation of impurities can be minimized.
The solubility of the sodium salt, which is an impurity, is increased by performing the precipitation reaction in the state where the filtrate is heated to a temperature of 50 to 70, so that the selectivity to the cobalt compound can be further increased. When the reaction is performed at less than 50, There is a possibility that the purity of the compound is lowered. When it exceeds 70, the recovery rate is lowered, which is not preferable.
In the secondary electrodeposition process, when water is supplied to the anode electrolytic cell and electricity is supplied to the anode electrolytic cell while the filtrate recovered in the Co and Ni compound filtration process is supplied, chlorine ions migrate through the anion exchange membrane to the anode electrolytic cell and hydrochloric acid (Mn) is precipitated at the beginning and magnesium (Mg) is precipitated at the end. This is because the chloride ion moves to the anode electrolytic cell through the anion exchange membrane to generate hydrochloric acid (HCl) Manganese (Mn) having a large ionization tendency precipitates at an early stage and magnesium (Mg) having a small ionization tendency precipitates at a terminal stage depending on the electronegativity difference of a metal component.
Meanwhile, in the present invention, the Co-carboxylic acid and the Ni-carboxylic acid compound separated in the Co and Ni compound filtration process are redissolved in hydrochloric acid (HCl), water is introduced into the anode electrolytic cell, (Co) is precipitated in the cathode electrolytic cell and nickel (Ni) is precipitated in the cathode in the cathode electrolytic cell at the end of the electrochemical deposition process, in which chloride ions (HCl) are generated through the anion- And recovered cobalt (Co) and nickel (Ni). This is because, as in the first and second electrodeposition processes, chloride ions (HCl) are generated through the anion exchange membrane and the chloride ion (HCl) is generated through the anion exchange membrane, and the ionization tendency of cobalt ) Is precipitated at an early stage and nickel (Ni) having a small ionization tendency is precipitated at the end.
The filtrate of the anode electrolytic cell generated in the third electrodeposition process is recovered and redissolved in hydrochloric acid (HCl), and the third electrodeposition process is repeated one to three times to recover the metal components to the maximum, It is possible to realize a cost saving effect by efficiently operating the facility in accordance with the multistage continuous process while preventing the generation of waste water.
In the present invention, the electricity supplied to the primary to tertiary electrodeposition processes is maintained at a pH and a voltage of a solution by a constant voltage method in which the DC voltage is controlled in a range of 3 to 15 V, The selectivity and purity of manganese (Mn) and magnesium (Mg) can be improved.
Next, an example of the method for recovering a high selectivity metal and an acid from the multicomponent metal solution will be described. However, the present invention has been completed through a number of experiments. Hereinafter, The present invention will be described by way of preferred embodiments.
[Example 1] Fe electrodeposition step
Water is added to the anode electrolytic cell using an electrodialyzer, and a multicomponent metal solution containing oxides of iron (Fe), cobalt (Co), nickel (Ni), manganese (Mn), and magnesium (Mg) (HCl) was generated through the anion exchange membrane through the anion exchange membrane and iron (Fe) was precipitated in the anodic electrolyzer. The amount of the undiluted solution and the precipitated metal components were [ As shown in Table 1.
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[Example 2] Mn and Mg recovery process in a solution after Fe electrodeposition
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When precipitation of the Fe component is completed by the electrodeposition method, only Mn and Mg components of the metal components are present in the solution. When the chloride ion is moved to the anode electrolytic cell through the anion exchange membrane, the pH value of the solution cathode increases. At this time, Mn precipitates at a pH of 2 to 4, and Mg is precipitated at a pH of 4 or higher.
[Example 3] Ni and Co recovery process from Ni, Co-carboxylic acid compound
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In the Fe electrodeposition process, carboxylic acid was added to increase the selectivity of Fe and to inhibit precipitation of Ni and Co. At this time, Ni and Co precipitate as Ni, Co-carboxylic acid compound. It is recovered by filtration and redissolved, and Co electrodeposition is carried out at a pH of 0.5 ~ 1. At this time, Ni tends to be redissolved even if it is precipitated. After recovering all the Co, the pH can be raised to 2 or more, and when Ni electrodeposition is performed, all the Ni can be recovered. The results of the electrochemical precipitation process according to pH are shown in Table 2 below.
As shown in the above Table 2, when the pH value is lowered, the purity of Co, that is, the selectivity is increased but the rate of Co precipitation is slowed. For this reason, it is necessary to adjust the pH of the solution depending on the intended content or precipitation rate.
Claims (5)
Water is injected into the anode electrolytic cell and a multicomponent metal solution containing iron (Fe), cobalt (Co), nickel (Ni), manganese (Mn) and magnesium (Mg) A first electrodeposition process in which chlorine ions migrate to the anode electrolytic cell through an anion exchange membrane to produce hydrochloric acid (HCl), and iron (Fe) precipitates in a metallic state in the cathode electrolyzer;
A step of synthesizing a Co and Ni compound in which a solution of a negative electrode electrolytic bath generated in the first electrodeposition step is heated to a temperature of 50 to 70 ° C to precipitate a Co-carboxylic acid and a Ni-carboxylic acid compound;
A Co and Ni compound filtration step of subjecting the synthesized Co and Ni compound and the filtrate to solid-liquid separation;
When water is supplied to the anode electrolytic cell and electricity is supplied to the cathode electrolytic cell while the filtrate recovered in the Co and Ni compound filtration process is supplied to the anode electrolytic cell, chlorine ions migrate to the anode electrolytic cell through the anion exchange membrane to generate hydrochloric acid (HCl) A secondary electrodeposition process in which manganese (Mn) is initially precipitated in a metallic state and magnesium (Mg) is precipitated in a metallic state at the end of the electrolytic bath;
≪ RTI ID = 0.0 > 1, < / RTI >
Wherein the polybasic carboxylic acid used in the first electrodeposition step is any one selected from the group consisting of oxalic acid and citric acid.
After re-dissolving the Co-carboxylic acid and Ni-carboxylic acid compound separated in the Co and Ni compound filtration process into hydrochloric acid (HCl), water is added to the anode electrolytic bath, the solution is supplied to the anode electrolytic cell, The chloride ion is moved to the anode electrolytic cell through the exchange membrane to generate hydrochloric acid (HCl), and the cathode electrolytic cell is subjected to tertiary electrodeposition in which cobalt (Co) precipitates in a metallic state at the beginning and nickel (Ni) fair;
≪ RTI ID = 0.0 > 1, < / RTI >
Wherein the filtrate of the anode electrolytic cell generated in the third electrodeposition step is recovered and redissolved in hydrochloric acid (HCl), and the third electrodeposition step is repeated 1 to 3 times. Metal and acid recovery method.
Wherein the electricity supplied in the primary to tertiary electrodeposition step is a DC voltage of 3 to 15V.
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| JP2010504423A (en) | 2006-09-21 | 2010-02-12 | キュイテ−フェル エ チタン インコーポレイティド | Electrochemical method for recovery of metallic iron and chlorine values from iron-rich metal chloride waste |
| JP2009228030A (en) | 2008-03-19 | 2009-10-08 | Toda Kogyo Corp | Method for recovering residual nickel in electroless plating waste solution |
| JP2015081381A (en) | 2013-10-24 | 2015-04-27 | 栗田工業株式会社 | Method and apparatus for treating liquid containing iron-group metal ion |
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| KR20160142581A (en) | 2016-12-13 |
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