CN100554451C - A kind of from cobalt chloride solution the method for recovering copper - Google Patents
A kind of from cobalt chloride solution the method for recovering copper Download PDFInfo
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- CN100554451C CN100554451C CNB2007101644006A CN200710164400A CN100554451C CN 100554451 C CN100554451 C CN 100554451C CN B2007101644006 A CNB2007101644006 A CN B2007101644006A CN 200710164400 A CN200710164400 A CN 200710164400A CN 100554451 C CN100554451 C CN 100554451C
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- 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
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Abstract
The present invention relates to a kind of from cobalt chloride solution the method for recovering copper, it is characterized in that adopting the vinylformic acid nitrile is macroporous anion exchange resin, and copper in the cobalt chloride solution is removed recovery.Method of the present invention.Adopt a kind of ion exchange resin, under certain pH condition, exchange the bivalent cupric ion in the raw material, and then the copper wash-out that is adsorbed is come out to reclaim with certain density hydrochloric acid control condition.Thereby reach the copper in the raw material, purify raw material and reclaim the wherein purpose of copper.This method is easy to control, copper removes, rate of recovery height, and the Separation and Recovery process is pollution-free.
Description
Technical field
A kind of from cobalt chloride solution the method for recovering copper, relate in a kind of electrolysis, the electrodeposited cobalt production process, by the copper in the technological process Separation and Recovery chlorination cobalt liquors such as adjustment solution acidity, resins exchange, wash-out and resin regeneration, thus the method for raising electrolysis, electrodeposited cobalt quality product and efficient recovery valuable metal.
Technical background
At present, in electrolysis, in the production process of electrodeposited cobalt, cobalt chloride solution purifies copper removal 717 resins, but 717 resins can only adsorb univalent copper ion, can not adsorb bivalent cupric ion, decopper(ing) need add reductive agents such as S-WAT earlier in the production, cupric is reduced into monovalence copper, again by 717 resin copper removals, when the wash-out regeneration of resin, after elder generation is oxidized to cupric with oxygenant with the monovalence copper on the resin, use certain density hydrochloric acid elutriant flush away cupric again, this method reagent consumption is big, the cost height, complex process, technical process is long, and introduces other foreign ion easily in sepn process, causes the secondary pollution of cobalt chloride solution.
Summary of the invention
Purpose of the present invention is exactly the deficiency at above-mentioned technology, provide that a kind of reagent consumption is few, cost is low, technology is simple, and in sepn process, do not introduce hetero-ion, effectively improve the quality product of electrolysis, electrodeposited cobalt and can reclaim the method for recovering copper from cobalt chloride solution of copper.
The objective of the invention is to be achieved through the following technical solutions.
A kind of from cobalt chloride solution the method for recovering copper, it is characterized in that adopting the vinylformic acid nitrile is macroporous anion exchange resin, and copper in the cobalt chloride solution is removed recovery, its technological process is followed successively by:
A. adjust the acidity of cobalt chloride solution, control its pH value below 5;
B. the cobalt chloride solution that will adjust acidity is the large pore anion weakly basic exchange resin by the vinylformic acid nitrile, purifies the copper that removes in the solution;
C. the hydrochloric acid soln of using 1～3N is as elutriant, and the resin after the absorption is soaked 10～60min, then elutriant carried out wash-out by resin, to resin colourless till, the hydrochloric acid soln consumption is 1～5 times of resin volume;
D. the hydrochloric acid of using 0.5～2N is as regenerated liquid, and regenerated liquid hydrochloric acid is by eluted resins, and the time is 20～24 hours, and the regenerated liquid consumption is 1～1.5 times of resin, uses the water wash resin standby greater than 2 to pH at last.Method of the present invention adopts ion exchange process, with the copper Separation and Recovery in the cobalt chloride solution, by adjusting pH value of solution value, ion-exchange, wash-out, renovation process, with the copper Separation and Recovery in the solution, resin is regenerated in order to reusing.Method of the present invention is easy to control, copper removes, rate of recovery height, and the Separation and Recovery process is pollution-free.
Embodiment
A kind of from cobalt chloride solution the method for recovering copper, adopting the vinylformic acid nitrile is macroporous anion exchange resin, and copper in the cobalt chloride solution is removed recovery, its technological process is followed successively by: a. adjusts the acidity of cobalt chloride solution, controls its pH value below 5; B. the cobalt chloride solution that will adjust acidity is the large pore anion weakly basic exchange resin by the vinylformic acid nitrile, purifies the copper that removes in the solution; C. the hydrochloric acid soln of using 1～3N is as elutriant, and the resin after the absorption is soaked 10～60min, then elutriant carried out wash-out by resin, to resin colourless till, the hydrochloric acid soln consumption is 1～5 times of resin volume; D. the hydrochloric acid of using 0.5～2N is as regenerated liquid, and regenerated liquid hydrochloric acid is by eluted resins, and the time is 20～24 hours, and the regenerated liquid consumption is 1～1.5 times of resin, uses the water wash resin standby greater than 2 to pH at last.
During operation, for purifying cobalt chloride solution, remove copper wherein, the present invention selects the pH that adjusts solution to carry out under certain acidity, according to this resin properties, in the process of ion-exchange separating copper, rising with the pH value of solution value, exchange is more prone to carry out, but when the pH value greater than 5 the time, the cobalt in the solution begins to precipitate because of the too high form with cobaltous hydroxide of local pH value, carries impurity copper secretly, the cobalt loss amount is big, therefore the pH value should be controlled at below 5, can guarantee the copper effective elimination in the solution also can be prevented the precipitation of cobalt under this pH value, adopting the vinylformic acid eyeball is that large pore anion resin exchanges and need not cupric is reduced into monovalence copper, so neither increases cost and can not cause secondary pollution to cobalt chloride again.After the exchange, carry out wash-out, reclaim the copper after exchanging with certain density hydrochloric acid, the concentration of wash-out time control relieving haperacidity is between 1.5～2N, and directly wash-out goes out the cupric in the resin, and eluting rate can reach more than 98%, the copper recovery height is compared with original method, need not monovalence copper is oxidized to cupric.When resin being regenerated, the hydrochloric acid soln with 1N washed 20～24 hours earlier, used the water wash resin then again, and the pH value that makes resin is greater than 2, with standby.
Embodiment 1
A kind of from cobalt chloride solution the method for recovering copper, adopting HPA type vinylformic acid nitrile is macroporous anion exchange resin, and copper in the cobalt chloride solution is removed recovery, its technological process is followed successively by: a. adjusts the acidity of cobalt chloride solution, controls its pH value below 5; B. the cobalt chloride solution that will adjust acidity is the large pore anion weakly basic exchange resin by the vinylformic acid nitrile, purifies the copper that removes in the solution; C. the hydrochloric acid soln of using 1～3N is as elutriant, and the resin after the absorption is soaked 10～60min, then elutriant carried out wash-out by resin, to resin colourless till, the hydrochloric acid soln consumption is 1～5 times of resin volume; D. the hydrochloric acid of using 0.5～2N is as regenerated liquid, and regenerated liquid hydrochloric acid is by eluted resins, and the time is 20～24 hours, and the regenerated liquid consumption is 1～1.5 times of resin, uses the water wash resin standby greater than 2 to pH at last.
Embodiment 2
A kind of from cobalt chloride solution the method for recovering copper, adopting PA type vinylformic acid nitrile is macroporous anion exchange resin, and copper in the cobalt chloride solution is removed recovery, its technological process is followed successively by: a. adjusts the acidity of cobalt chloride solution, controls its pH value below 7; B. the cobalt chloride solution that will adjust acidity is the large pore anion weakly basic exchange resin by the vinylformic acid nitrile, purifies the copper that removes in the solution; C. use NaOH:1%; The HCl:2-3% mixing solutions is as elutriant, and the resin after the absorption is soaked 10～30min, then elutriant carried out wash-out by resin, to resin colourless till, the mixing solutions consumption be the resin volume 2-3 doubly; D. use NaOH:1%; The HCl:2-3% mixing solutions is as regenerated liquid, and regenerated liquid is by eluted resins, and the time is 30-60 minute, and the regenerated liquid consumption is 2-3 a times of resin, uses the water wash resin standby greater than 1 to pH at last.
Embodiment 3
A kind of from cobalt chloride solution the method for recovering copper, adopting D311 type vinylformic acid nitrile is macroporous anion exchange resin, and copper in the cobalt chloride solution is removed recovery, its technological process is followed successively by: a. adjusts the acidity of cobalt chloride solution, controls its pH value below 7; B. the cobalt chloride solution that will adjust acidity is the large pore anion weakly basic exchange resin by the vinylformic acid nitrile, purifies the copper that removes in the solution; C. use NaOH:1%; The HCl:2-3% mixing solutions is as elutriant, and the resin after the absorption is soaked 10～30min, then elutriant carried out wash-out by resin, to resin colourless till, the mixing solutions consumption be the resin volume 2-3 doubly; D. use NaOH:1%; The HCl:2-3% mixing solutions is as regenerated liquid, and regenerated liquid is by eluted resins, and the time is 30-60 minute, and the regenerated liquid consumption is 2-3 a times of resin, uses the water wash resin standby greater than 1 to pH at last.
Claims (1)
1. the method for a recovering copper from cobalt chloride solution, it is characterized in that adopting the vinylformic acid nitrile is macroporous anion exchange resin, and copper in the cobalt chloride solution is removed recovery, its technological process is followed successively by:
A. adjust the acidity of cobalt chloride solution, control its pH value below 5;
B. the cobalt chloride solution that will adjust acidity is the large pore anion weakly basic exchange resin by the vinylformic acid nitrile, purifies the copper that removes in the solution;
C. the hydrochloric acid soln of using 1～3N is as elutriant, and the resin after the absorption is soaked 10～60min, then elutriant carried out wash-out by resin, to resin colourless till, the hydrochloric acid soln consumption is 1～5 times of resin volume;
D. the hydrochloric acid of using 0.5～2N is as regenerated liquid, and regenerated liquid hydrochloric acid is by eluted resins, and the time is 20～24 hours, and the regenerated liquid consumption is 1～1.5 times of resin, uses the water wash resin standby greater than 2 to pH at last.
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| Application Number | Priority Date | Filing Date | Title |
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| CNB2007101644006A CN100554451C (en) | 2007-11-06 | 2007-11-06 | A kind of from cobalt chloride solution the method for recovering copper |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007101644006A CN100554451C (en) | 2007-11-06 | 2007-11-06 | A kind of from cobalt chloride solution the method for recovering copper |
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| CN101148704A CN101148704A (en) | 2008-03-26 |
| CN100554451C true CN100554451C (en) | 2009-10-28 |
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| CNB2007101644006A Active CN100554451C (en) | 2007-11-06 | 2007-11-06 | A kind of from cobalt chloride solution the method for recovering copper |
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102815763B (en) * | 2012-09-17 | 2013-11-06 | 工信华鑫科技有限公司 | Method for implementing copper-cobalt separation, enrichment and purification by using heavy metal adsorbing material |
| CN102978395B (en) * | 2012-12-03 | 2014-01-15 | 吉林大学 | Method for separating and enriching Cu and Co from sulfate diluted solution containing Co |
| CN109929999B (en) * | 2019-03-28 | 2020-09-22 | 中南大学 | Method for selectively recovering copper from chloride mixed liquor |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1065494A (en) * | 1992-05-16 | 1992-10-21 | 湖南省煤炭科学研究所 | A kind of novel method of from contain vanadium solution, extracting Vanadium Pentoxide in FLAKES |
| CN1141886A (en) * | 1996-06-11 | 1997-02-05 | 高大明 | Technology for treatment of waste liquid containing cyanogen by ion exchange method |
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2007
- 2007-11-06 CN CNB2007101644006A patent/CN100554451C/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1065494A (en) * | 1992-05-16 | 1992-10-21 | 湖南省煤炭科学研究所 | A kind of novel method of from contain vanadium solution, extracting Vanadium Pentoxide in FLAKES |
| CN1141886A (en) * | 1996-06-11 | 1997-02-05 | 高大明 | Technology for treatment of waste liquid containing cyanogen by ion exchange method |
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| CN101148704A (en) | 2008-03-26 |
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Address after: 737103 Jinchuan Road, Gansu, China, No. 98, No. Patentee after: Jinchuan Group Co., Ltd. Address before: 737103 Jinchuan Road, Gansu, China, No. 98, No. Patentee before: Jinchuan Group Corp., Ltd. |