CA2732486C - Recovery method for cobalt - Google Patents
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- CA2732486C CA2732486C CA2732486A CA2732486A CA2732486C CA 2732486 C CA2732486 C CA 2732486C CA 2732486 A CA2732486 A CA 2732486A CA 2732486 A CA2732486 A CA 2732486A CA 2732486 C CA2732486 C CA 2732486C
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- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 69
- 239000010941 cobalt Substances 0.000 title claims abstract description 69
- 238000000034 method Methods 0.000 title claims abstract description 40
- 238000011084 recovery Methods 0.000 title claims abstract description 19
- 239000010949 copper Substances 0.000 claims abstract description 83
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 72
- 229910052802 copper Inorganic materials 0.000 claims abstract description 72
- 238000000638 solvent extraction Methods 0.000 claims abstract description 33
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 28
- 239000002253 acid Substances 0.000 claims abstract description 23
- 239000011347 resin Substances 0.000 claims abstract description 23
- 229920005989 resin Polymers 0.000 claims abstract description 23
- 239000007864 aqueous solution Substances 0.000 claims abstract description 18
- 238000001179 sorption measurement Methods 0.000 claims abstract description 18
- 125000002091 cationic group Chemical group 0.000 claims abstract description 12
- 239000013522 chelant Substances 0.000 claims abstract description 7
- 238000005363 electrowinning Methods 0.000 claims abstract description 7
- 125000003544 oxime group Chemical group 0.000 claims abstract 2
- 239000000243 solution Substances 0.000 claims description 55
- 229910052791 calcium Inorganic materials 0.000 claims description 29
- 239000011575 calcium Substances 0.000 claims description 29
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 25
- 239000011701 zinc Substances 0.000 claims description 21
- 229910052725 zinc Inorganic materials 0.000 claims description 20
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 16
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 238000011284 combination treatment Methods 0.000 claims description 2
- 238000002203 pretreatment Methods 0.000 claims description 2
- 238000000605 extraction Methods 0.000 description 25
- 229910052751 metal Inorganic materials 0.000 description 11
- 239000002184 metal Substances 0.000 description 11
- 238000005868 electrolysis reaction Methods 0.000 description 8
- 239000007788 liquid Substances 0.000 description 7
- 238000000926 separation method Methods 0.000 description 7
- 239000012535 impurity Substances 0.000 description 6
- 239000008346 aqueous phase Substances 0.000 description 5
- 230000002378 acidificating effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000012074 organic phase Substances 0.000 description 4
- 150000002923 oximes Chemical group 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910000365 copper sulfate Inorganic materials 0.000 description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- MJUVQSGLWOGIOB-GHRIWEEISA-N 2-[(E)-hydroxyiminomethyl]-4-nonylphenol Chemical compound [H]\C(=N/O)C1=CC(CCCCCCCCC)=CC=C1O MJUVQSGLWOGIOB-GHRIWEEISA-N 0.000 description 1
- ZDFBXXSHBTVQMB-UHFFFAOYSA-N 2-ethylhexoxy(2-ethylhexyl)phosphinic acid Chemical compound CCCCC(CC)COP(O)(=O)CC(CC)CCCC ZDFBXXSHBTVQMB-UHFFFAOYSA-N 0.000 description 1
- 229910020598 Co Fe Inorganic materials 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 229910009378 Zn Ca Inorganic materials 0.000 description 1
- SKYGTJFKXUWZMD-UHFFFAOYSA-N ac1l2n4h Chemical compound [Co].[Co] SKYGTJFKXUWZMD-UHFFFAOYSA-N 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- ALKZAGKDWUSJED-UHFFFAOYSA-N dinuclear copper ion Chemical compound [Cu].[Cu] ALKZAGKDWUSJED-UHFFFAOYSA-N 0.000 description 1
- 238000007714 electro crystallization reaction Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 125000000101 thioether group Chemical group 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Landscapes
- Electrolytic Production Of Metals (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
A recovery method for cobalt, wherein copper is removed from acid aqueous solution in which copper and cobalt are contained and concentration rate of Cu/Co is more or equal to 5, by a combination of a solvent extraction using cationic exchange extracting agent and a adsorption using cationic exchange resin, and then cobalt is recovered as electrolytic cobalt by a combination of a solvent extraction and an electrowinning, and (1) the acid aqueous solution contains more or equal to 10g/L of copper and less or equal to 5g/L of cobalt, (2) the cationic exchange extracting agent is an oxime series extract agent, and (3) the cationic exchange resin is an acid chelate resin.
Description
RECOVERY METHOD FOR COBALT
TECHNICAL FIELD OF THE INVENTION
(0001) The present invention relates to a recovery method for cobalt. The present invention relates to a recovery method for electrolytic cobalt from cobalt solution produced as a solution after removing copper from acid solution mainly containing copper by the combined method of solution extraction and adsorption.
BACKGROUND OF THE INVENTION
TECHNICAL FIELD OF THE INVENTION
(0001) The present invention relates to a recovery method for cobalt. The present invention relates to a recovery method for electrolytic cobalt from cobalt solution produced as a solution after removing copper from acid solution mainly containing copper by the combined method of solution extraction and adsorption.
BACKGROUND OF THE INVENTION
(0002) Cobalt is used in alloy material and lithium-ion battery. Though it is industrially important, the fact is that cobalt consumed in Japan is mostly imported. Accordingly, even if it is low-concentrated, a recovering metal cobalt from a cobalt-containing solution is significant.
(0003) Generally, cobalt is produced as a by-product of copper, nickel ore and the like, and it is in the oxide form or sulfide form and it contains impurity elements other than target metal. In the case of obtaining electrolytic cobalt by electrowinning, it is known that quality of the electrolytic cobalt deteriorates because of electrocrystallization of a metal, such as copper, being more base than cobalt if electrolysis solution contains the metal being more base than cobalt. Accordingly, in order to obtain high-quality electrolytic cobalt, it is necessary to remove impurity elements from electrolysis solution.
(0004) As a general method for removing copper from a cobalt-containing acid solution containing highly-concentrated copper, a method of sulfidizing treatment and then sulfidizing precipitation is used. Copper can be selectively removed by the method. However, in the method, toxic gas is i generated, medical agent is very expensive, recovering step for precipitated copper is necessary and then the method has disadvantages on the cost front.
As the other methods, there is a method in which metal iron and metal aluminum are added and copper in the solution is separated and removed as metal by cementation. In the method, copper can be removed because it reduces to metal easily. However, the solution is contaminated by added metals and then it is necessary to remove the added metals.
As the other methods, there is a method in which metal iron and metal aluminum are added and copper in the solution is separated and removed as metal by cementation. In the method, copper can be removed because it reduces to metal easily. However, the solution is contaminated by added metals and then it is necessary to remove the added metals.
(0005) Recently, copper can be-removed by solvent extraction as disclosed in Japanese Patent Application Laid-open Publication No.11-50167 (patent document 1).
(0006) However, the solvent extraction is used for a solution containing relatively low-concentrated copper as impurities and the document does not disclose a separation of copper from acid aqueous solution in which concentration rate of Cu/Co is more or equal to 5 and copper is contained in high concentration.
(Patent documents 1) Japanese Patent Application Laid-open Publication No.11-50167 SUMMARY OF THE INVENTION
(Patent documents 1) Japanese Patent Application Laid-open Publication No.11-50167 SUMMARY OF THE INVENTION
(0007) The present invention aims to recover highly-pure cobalt efficiently from acid aqueous solution in which at least copper and cobalt are contained.
(0008) The inventors have studied to cope with the requirements, and have found out the following inventions.
(1) A recovery method for cobalt, wherein copper is removed from acid aqueous solution in which copper and cobalt are contained and concentration ratio of Cu/Co is more or equal to 5, by a solvent extraction using cationic exchange extracting agent and a subsequent adsorption using cationic exchange resin, and then cobalt is recovered as electrolytic cobalt by a solvent extraction and a subsequent electrowinning, and (1) the acid aqueous solution contains more or equal to 10g/ L of copper and less or equal to 5g/L of cobalt, (2) the cationic exchange extracting agent is an oxime series extract agent, and (3) the cationic exchange resin is an acid chelate resin.
(1) A recovery method for cobalt, wherein copper is removed from acid aqueous solution in which copper and cobalt are contained and concentration ratio of Cu/Co is more or equal to 5, by a solvent extraction using cationic exchange extracting agent and a subsequent adsorption using cationic exchange resin, and then cobalt is recovered as electrolytic cobalt by a solvent extraction and a subsequent electrowinning, and (1) the acid aqueous solution contains more or equal to 10g/ L of copper and less or equal to 5g/L of cobalt, (2) the cationic exchange extracting agent is an oxime series extract agent, and (3) the cationic exchange resin is an acid chelate resin.
(0009) (2) The recovery method for cobalt of (1), wherein the acid aqueous solution derives from wet processing of copper ore and the solution contains more or equal to 15g/ L of chlorine.
(0010) (3) The recovery method for cobalt of (1) or (2), wherein the concentration of copper is reduced to a level in which the concentration ratio of Cu/Co is less than 1 / 10000 in the copper-removed solution by the combination treatment of the solvent extraction and the resin adsorption.
(0011) (4) The recovery method for cobalt of any one of (1) to (3), wherein the solvent extraction of copper is conducted at pH 1 to 3.
(0012) (5) The recovery method for cobalt of any one of (1) to (4), wherein the electrolytic copper is produced by an electrowinning of copper removed by the solvent extraction.
(0013) (6) The recovery method for cobalt of any one of (1) to (5), wherein the acid aqueous solution contains calcium and/or zinc and the calcium and/or zinc are removed by the solvent extraction at pH 1 to 3.
(0014) (7) The recovery method for cobalt of (6), wherein the solution is passed through the resin without extra pretreatments after the solvent extraction of copper or calcium and/or zinc.
ADVANTAGEOUS EFFECT OF THE INVENTION
ADVANTAGEOUS EFFECT OF THE INVENTION
(0015) The present invention can produce highly-pure cobalt at lower cost than ever before from previously little-used acid aqueous solution in which a concentration of copper is more or equal to 10g/L, a concentration of cobalt is less or equal to 5g/L and concentration rate of Cu/Co is more or equal to S.
Therefore, an industrial value of the present invention is very high.
BRIEF DESCRIPTION OF DRAWINGS
Fig. 1 indicates a process flow chart of one embodiment of the present invention.
Fig.2 indicates a process flow chart of another embodiment of the present invention.
Fig.3 indicates effects of pH on extraction performance of copper on the basis of results in example 1.
Fig.4 indicates effects of pH on extraction performance of calcium on the basis of results in example 3.
Fig.5 indicates effects of pH on extraction performance of zinc on the basis of results in example 4.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Therefore, an industrial value of the present invention is very high.
BRIEF DESCRIPTION OF DRAWINGS
Fig. 1 indicates a process flow chart of one embodiment of the present invention.
Fig.2 indicates a process flow chart of another embodiment of the present invention.
Fig.3 indicates effects of pH on extraction performance of copper on the basis of results in example 1.
Fig.4 indicates effects of pH on extraction performance of calcium on the basis of results in example 3.
Fig.5 indicates effects of pH on extraction performance of zinc on the basis of results in example 4.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
(0016) An intended solution of the present invention is an acid aqueous solution containing copper and containing cobalt in low concentration. More specifically, it is an acid aqueous solution in which a concentration of copper is more or equal to lOg/L, a concentration of cobalt is less or equal to 5g/L
and concentration rate of Cu/Co is more or equal to 5.
Removing copper by solvent extraction Procedures of the solvent extraction may comply with an ordinary method.
For example, the acid aqueous solution (aqueous phase) is contacted with an oxime series extract agent (organic phase), they are agitated and mixed with a mixer typically and then copper is reacted with the extract agent. In the case of using LIX984N as the extract agent, an extract pH is 1.0 to 3.0, preferably 2.0 to 3Ø The solvent extraction is preferably conducted in room temperature (15 to 25 C) to 60 C and in atmosphere pressure in terms of keeping qualities of the extract agent.
As the other extract agent, LIX84, LIX860, LIX984N and the like (trade names by Henkel corporation), Acorga OPT5510 (trade name) which is prepared by using 5-nonylsalicylaldoxime and the like can be used particularly.
and concentration rate of Cu/Co is more or equal to 5.
Removing copper by solvent extraction Procedures of the solvent extraction may comply with an ordinary method.
For example, the acid aqueous solution (aqueous phase) is contacted with an oxime series extract agent (organic phase), they are agitated and mixed with a mixer typically and then copper is reacted with the extract agent. In the case of using LIX984N as the extract agent, an extract pH is 1.0 to 3.0, preferably 2.0 to 3Ø The solvent extraction is preferably conducted in room temperature (15 to 25 C) to 60 C and in atmosphere pressure in terms of keeping qualities of the extract agent.
As the other extract agent, LIX84, LIX860, LIX984N and the like (trade names by Henkel corporation), Acorga OPT5510 (trade name) which is prepared by using 5-nonylsalicylaldoxime and the like can be used particularly.
(0017) Removing copper by adsorption In the solvent extraction, copper cannot be sufficiently removed and more or equal to a few mg/L of copper remains in the solution after extraction.
Copper is metal that is more base than cobalt. If a cobalt electrolysis is conducted to the solution after extraction, a low-grade electrolytic cobalt containing copper is produced. Accordingly, it is necessary to conduct adsorption after the solvent extraction and remove copper by the adsorption to a level in which the concentration rate of Cu/Co is less or equal to 1 / 10000 in order to improve quality of electrolytic cobalt.
Procedures of the adsorption may comply with an ordinary method. For example, column method may be used. An acidic chelate resin is filled in column, the acid aqueous solution containing metal ions is passed through the column and then copper is reacted with the resin. Contact temperature with the resin is room temperature (for example, 15 to 25 C) to 100 C.
The chelate resin may be, for example, UR-10S or UR-40H (trade names by Unitika corporation) that has iminodi acetic acid as functional group.
By the above method, copper can be recovered from the solution sufficiently.
Copper is metal that is more base than cobalt. If a cobalt electrolysis is conducted to the solution after extraction, a low-grade electrolytic cobalt containing copper is produced. Accordingly, it is necessary to conduct adsorption after the solvent extraction and remove copper by the adsorption to a level in which the concentration rate of Cu/Co is less or equal to 1 / 10000 in order to improve quality of electrolytic cobalt.
Procedures of the adsorption may comply with an ordinary method. For example, column method may be used. An acidic chelate resin is filled in column, the acid aqueous solution containing metal ions is passed through the column and then copper is reacted with the resin. Contact temperature with the resin is room temperature (for example, 15 to 25 C) to 100 C.
The chelate resin may be, for example, UR-10S or UR-40H (trade names by Unitika corporation) that has iminodi acetic acid as functional group.
By the above method, copper can be recovered from the solution sufficiently.
(0018) Recover of cobalt Cobalt solution can be produced as the solution after extraction of copper and it can be recovered by a combination of a solvent extraction and an electrowinning.
(0019) Recover of electrolytic copper Copper extracted into the organic phase by the solvent extraction is back-extracted with sulfuric acid via simple washing and then copper sulfate solution can be produced. Electrolytic copper can be produced by electrolysis of the copper sulfate solution. The organic phase in which copper is removed can be used in the solvent extraction repeatedly.
(0020) Removal of calcium and zinc If the solution of the present invention contains calcium, it can be removed by the solvent extraction. For example, the acid aqueous solution (aqueous phase) containing calcium is contacted with non-chelated extract agent (organic phase), they are agitated and mixed with a mixer typically and then calcium is reacted with the extract agent. In the case of using DP-8R
(Daihachi Chemicals) as the non-chelated extract agent, an extract pH of calcium is 1.0 to 3.0, preferably 1.5 to 3.0, and an extract pH of zinc is 1.0 to 3.0, preferably 2.0 to 3Ø In the light of degradation control of the extract agent, the solvent extraction is preferably conducted at room temperature (15 to 25 C) to 60 C in atmosphere pressure.
The non-chelated extract agent other than those above may be, for example, PC-88A (Daihachi Chemicals) that is an acidic phosphoric acid series extract agent.
Examples (0021) Examples of the present invention are described below. However, the present invention is not limited to these examples.
(Daihachi Chemicals) as the non-chelated extract agent, an extract pH of calcium is 1.0 to 3.0, preferably 1.5 to 3.0, and an extract pH of zinc is 1.0 to 3.0, preferably 2.0 to 3Ø In the light of degradation control of the extract agent, the solvent extraction is preferably conducted at room temperature (15 to 25 C) to 60 C in atmosphere pressure.
The non-chelated extract agent other than those above may be, for example, PC-88A (Daihachi Chemicals) that is an acidic phosphoric acid series extract agent.
Examples (0021) Examples of the present invention are described below. However, the present invention is not limited to these examples.
(0022) Example 1: Removal method of copper by oxime series extract agent The solvent extraction of copper, wherein LIX984N is used as the oxime series extract agent, is described below as an example.
A solution containing 20g/L of copper and 1.5g/L of cobalt was prepared and it was used as the solution before extraction.
LIX984N was diluted to 20 vol.% by adding Isoper M.
The solution before extraction and the extract agent were agitated together in volume rate 1:2 at room temperature in atmosphere pressure for 15 minutes with change in pH 0.5 to 3, and then they were left at rest for 15 minutes for solid-liquid separation.
After the solid-liquid separation, concentrations of copper and cobalt in the aqueous phase (the solution after extraction) were estimated. A result of this example is shown in Figure 3.
A solution containing 20g/L of copper and 1.5g/L of cobalt was prepared and it was used as the solution before extraction.
LIX984N was diluted to 20 vol.% by adding Isoper M.
The solution before extraction and the extract agent were agitated together in volume rate 1:2 at room temperature in atmosphere pressure for 15 minutes with change in pH 0.5 to 3, and then they were left at rest for 15 minutes for solid-liquid separation.
After the solid-liquid separation, concentrations of copper and cobalt in the aqueous phase (the solution after extraction) were estimated. A result of this example is shown in Figure 3.
(0023) As shown in Figure 3, cobalt was barely extracted and copper was selectively extracted and separated in each pH, and specifically in more or equal to pH 1.5, concentration of copper contained in the solution after extraction was less or equal to 100mg/L. Accordingly, it is understood that copper can be extracted and separated by controlling pH of the solution.
However, precipitates are produced in pH 4 or more and then copper can be removed more effectively, preferably in pH 2.0 to 3Ø
However, precipitates are produced in pH 4 or more and then copper can be removed more effectively, preferably in pH 2.0 to 3Ø
(0024) Example 2: Adsorption of copper by acidic chelate resin Two types of simulated solution, wherein one was conducted extraction of Ca and Zn and the other was not conducted the extraction, were prepared as the solution before adsorption. UR-10S (Unitika corporation) was used as an acidic chelate resin. The resin was deaerated and 20mL of the deaerated resin was filled in column, and then the solution was passed through the column in the condition of LV 1. Concentrations of the solution before and after adsorption are shown in Table 1.
(0025) Table 1 Cu Co Zn Ca Cu/Co m L m L m L m L
Solution before adsorption (without 800 1590 30.5 53.4 0.5 extraction of Ca and Zn) Solution after < 0.1 1310 28.6 53.2 < 0.0001 adsorption Solution before adsorption 60 1390 1.3 < 0.1 0.04 (with extraction of Ca and Zn) Solution after < 0.1 1110 0.8 < 0.1 < 0.0001 adsorption (0026) As shown in this example, copper was adsorbed to the resin and concentration ratio of Cu/Co was less than 1/10000. Accordingly, it is understood that cobalt solution can be produced by removing copper with resin adsorption even if the extraction of Ca and Zn is conducted.
Solution before adsorption (without 800 1590 30.5 53.4 0.5 extraction of Ca and Zn) Solution after < 0.1 1310 28.6 53.2 < 0.0001 adsorption Solution before adsorption 60 1390 1.3 < 0.1 0.04 (with extraction of Ca and Zn) Solution after < 0.1 1110 0.8 < 0.1 < 0.0001 adsorption (0026) As shown in this example, copper was adsorbed to the resin and concentration ratio of Cu/Co was less than 1/10000. Accordingly, it is understood that cobalt solution can be produced by removing copper with resin adsorption even if the extraction of Ca and Zn is conducted.
(0027) Example 3: Removal method of calcium by solvent extraction The solvent extraction of calcium, wherein DP-8R (Daihachi Chemicals) is used as the non-chelated extract agent, is described below as an example.
A solution containing lg/L of calcium, 100mg/L of copper and 1.5g/L of cobalt was prepared and it was used as the solution before extraction.
DP-8R was diluted to 20 vol.% by adding Isoper M. The solution before extraction and the extract agent were agitated together in volume rate 1:1 at room temperature in atmosphere pressure for 15 minutes with change in pH
0.5 to 3, and then they were left at rest for 15 minutes for solid-liquid separation.
After the solid-liquid separation, concentrations of calcium, copper and cobalt in the aqueous phase (the solution after extraction) were estimated. A
result of this example is shown in Figure 4.
A solution containing lg/L of calcium, 100mg/L of copper and 1.5g/L of cobalt was prepared and it was used as the solution before extraction.
DP-8R was diluted to 20 vol.% by adding Isoper M. The solution before extraction and the extract agent were agitated together in volume rate 1:1 at room temperature in atmosphere pressure for 15 minutes with change in pH
0.5 to 3, and then they were left at rest for 15 minutes for solid-liquid separation.
After the solid-liquid separation, concentrations of calcium, copper and cobalt in the aqueous phase (the solution after extraction) were estimated. A
result of this example is shown in Figure 4.
(0028) As shown in Figure 4, cobalt was barely extracted and calcium was selectively extracted and separated in each pH, and specifically in more or equal to pH 1.0, concentration of calcium contained in the solution after extraction was less or equal to 150mg/ L. Further, copper is also extracted with calcium. Accordingly, purer cobalt solution can be produced. Calcium can be removed more effectively, preferably in pH 1.5 to 3Ø
(0029) Example 4: Removal method of zinc by solvent extraction The solvent extraction of zinc, wherein DP-8R (Daihachi Chemicals) is used as the non-chelated extract agent, is described below as an example. A
solution containing 40mg/L of zinc, 400mg/L of calcium and 1OOmg/L of copper was prepared and it was used as the solution before extraction.
DP-8R was diluted to 10 vol.% by adding Isoper M. The solution before extraction and the extract agent were agitated together in volume rate 1:1 at room temperature in atmosphere pressure for 15 minutes with change in pH
0.5 to 3, and then they were left at rest for 15 minutes for solid-liquid separation. After the solid-liquid separation, concentrations of zinc, calcium and copper in the aqueous phase (the solution after extraction) were estimated. A result of this example is shown in Figure S.
solution containing 40mg/L of zinc, 400mg/L of calcium and 1OOmg/L of copper was prepared and it was used as the solution before extraction.
DP-8R was diluted to 10 vol.% by adding Isoper M. The solution before extraction and the extract agent were agitated together in volume rate 1:1 at room temperature in atmosphere pressure for 15 minutes with change in pH
0.5 to 3, and then they were left at rest for 15 minutes for solid-liquid separation. After the solid-liquid separation, concentrations of zinc, calcium and copper in the aqueous phase (the solution after extraction) were estimated. A result of this example is shown in Figure S.
(0030) As shown in Figure 5, zinc and calcium were extracted according to a rise of pH, and specifically in more or equal to pH 2.0, concentration of zinc contained in the solution after extraction was less or equal to 5mg/L, and concentration of calcium contained in the solution after extraction was less or equal to 1Omg/L. Accordingly, it is understood that zinc and calcium can be extracted and separated by controlling pH of the solution. Further, concentration of copper was less than 20mg/ L. In the case of recovering cobalt by electrolysis, an existence of copper is undesirable and then it is significant to remove copper in this step.
(0031) Example 5: Electrolysis method for cobalt The electrolysis method for cobalt, wherein energization for 40 hours in the condition of current density 200A/m2 to the solution produced by the method conducted according to the inventions of claims 1 to 7, is described below as an example. An assay result of electrolytic cobalt produced by the referential or experimental values of quality is shown in Table 2.
(0032) Table 2 Co Fe Cu Ni Zn Liquid composition 49.4 < 0.01 < 0.001 0.02 < 0.001 before electrolysis (g/L) Quality of electrolytic cobalt 99.8 < 0.01 < 0.01 < 0.15 < 0.005 referential Quality of electrolytic cobalt 99.9 < 0.01 < 0.01 < 0.01 < 0.001 (experimental) (The experimental value of cobalt was calculated by subtracting percentage of impurities from 100%.) (0033) As shown in this example 5, highly-pure electrolytic cobalt, wherein impurities are very few, was produced by removing impurities by conducting the method of the inventions of claims 1 to 7.
Claims (7)
1. A recovery method for cobalt, wherein copper is removed from acid aqueous solution in which copper and cobalt are contained and concentration ratio of Cu/Co is more or equal to 5, by a solvent extraction using cationic exchange extracting agent and a subsequent adsorption using cationic exchange resin, and then cobalt is recovered as electrolytic cobalt by a solvent extraction and a subsequent electrowinning, and (1) the acid aqueous solution contains more or equal to 10g/L of copper and less or equal to 5g/L of cobalt, (2) the cationic exchange extracting agent is an oxime series extract agent, and (3) the cationic exchange resin is an acid chelate resin.
2. The recovery method for cobalt of claim 1, wherein the acid aqueous solution derives from wet processing of copper ore and the solution contains more or equal to 15g/L of chlorine.
3. The recovery method for cobalt of claim 1 or 2, wherein the concentration of copper is reduced to a level in which the concentration ratio of Cu/Co is less than 1/10000 in the copper-removed solution by the combination treatment of the solvent extraction and the resin adsorption.
4. The recovery method for cobalt of any one of claims 1 to 3, wherein the solvent extraction of copper is conducted at pH 1 to 3.
5. The recovery method for cobalt of any one of claims 1 to 4, wherein the electrolytic copper is produced by an electrowinning of copper removed by the solvent extraction.
6. The recovery method for cobalt of any one of claims 1 to 5, wherein the acid aqueous solution contains calcium and/or zinc and the calcium and/or zinc are removed by the solvent extraction at pH 1 to 3.
7. The recovery method for cobalt of claim 6, wherein the solution is passed through the resin without extra pretreatments after the solvent extraction of copper or calcium and/or zinc.
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| JP2010-207262 | 2010-08-31 | ||
| JP2010207262A JP2011214132A (en) | 2010-03-17 | 2010-08-31 | Recovery method for cobalt |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AP3297A (en) * | 2011-10-09 | 2015-05-31 | Mintek | Direct electrowinning of cobalt |
| CN109022778A (en) * | 2018-07-13 | 2018-12-18 | 兰州金川新材料科技股份有限公司 | A kind of method that the leaching of ferro-cobalt high pressure prepares high-purity copper solution and high-purity cobalt liquor |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2013096070A1 (en) | 2011-12-20 | 2013-06-27 | Freeport-Mcmoran Corporation | Systems and methods for metal recovery |
| CN102603102B (en) * | 2012-03-30 | 2014-01-08 | 湖南万容科技股份有限公司 | Processing method of browning liquid |
| CN103468968B (en) * | 2013-09-04 | 2015-07-29 | 重庆材料研究院有限公司 | The extracting method of platinum rhodium in a kind of platinum rhodium mixed liquor |
| CN110468280A (en) * | 2019-09-12 | 2019-11-19 | 金川集团股份有限公司 | A kind of method that ion-exchange recycles valuable metal in waste and old cobalt acid lithium battery |
| CN115818868B (en) * | 2022-11-18 | 2023-06-23 | 科立鑫(珠海)新能源有限公司 | Deamination method for cobalt carbonate production wastewater |
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| AR012179A1 (en) * | 1997-03-27 | 2000-09-27 | Billiton Sa Ltd | A PROCEDURE FOR THE RECOVERY OF COPPER |
| CN101195861A (en) * | 2007-12-20 | 2008-06-11 | 金川集团有限公司 | Method for separating copper from nickel and cobalt solution |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AP3297A (en) * | 2011-10-09 | 2015-05-31 | Mintek | Direct electrowinning of cobalt |
| CN109022778A (en) * | 2018-07-13 | 2018-12-18 | 兰州金川新材料科技股份有限公司 | A kind of method that the leaching of ferro-cobalt high pressure prepares high-purity copper solution and high-purity cobalt liquor |
| CN109022778B (en) * | 2018-07-13 | 2020-04-07 | 兰州金川新材料科技股份有限公司 | Method for preparing high-purity copper solution and high-purity cobalt solution by high-pressure leaching of cobalt-iron alloy |
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| CN102191380A (en) | 2011-09-21 |
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