CN103668322A - Method for recovering copper and nickel from copper-nickel based alloy waste - Google Patents
Method for recovering copper and nickel from copper-nickel based alloy waste Download PDFInfo
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- CN103668322A CN103668322A CN201310673020.0A CN201310673020A CN103668322A CN 103668322 A CN103668322 A CN 103668322A CN 201310673020 A CN201310673020 A CN 201310673020A CN 103668322 A CN103668322 A CN 103668322A
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 124
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 62
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 239000010949 copper Substances 0.000 title claims abstract description 58
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 55
- 238000000034 method Methods 0.000 title claims abstract description 43
- 239000002699 waste material Substances 0.000 title claims abstract description 34
- YOCUPQPZWBBYIX-UHFFFAOYSA-N copper nickel Chemical compound [Ni].[Cu] YOCUPQPZWBBYIX-UHFFFAOYSA-N 0.000 title claims abstract description 10
- 229910000570 Cupronickel Inorganic materials 0.000 title claims abstract description 8
- 229910045601 alloy Inorganic materials 0.000 title abstract description 10
- 239000000956 alloy Substances 0.000 title abstract description 10
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910001431 copper ion Inorganic materials 0.000 claims abstract description 22
- 238000004070 electrodeposition Methods 0.000 claims abstract description 20
- 239000010935 stainless steel Substances 0.000 claims abstract description 12
- 229910001220 stainless steel Inorganic materials 0.000 claims abstract description 12
- 239000003792 electrolyte Substances 0.000 claims abstract description 11
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000002131 composite material Substances 0.000 claims abstract description 6
- 229910000365 copper sulfate Inorganic materials 0.000 claims abstract description 6
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims abstract description 6
- 229910052741 iridium Inorganic materials 0.000 claims abstract description 6
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000010936 titanium Substances 0.000 claims abstract description 6
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 6
- 239000008151 electrolyte solution Substances 0.000 claims description 32
- 238000000151 deposition Methods 0.000 claims description 11
- 230000008021 deposition Effects 0.000 claims description 11
- 238000011084 recovery Methods 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 238000005868 electrolysis reaction Methods 0.000 claims description 6
- 238000009413 insulation Methods 0.000 claims description 5
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 claims description 5
- 238000010792 warming Methods 0.000 claims description 5
- 238000005266 casting Methods 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 3
- 238000004064 recycling Methods 0.000 abstract description 2
- 238000010438 heat treatment Methods 0.000 abstract 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 229910000881 Cu alloy Inorganic materials 0.000 description 4
- 229910000863 Ferronickel Inorganic materials 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000013459 approach Methods 0.000 description 2
- UMTMDKJVZSXFNJ-UHFFFAOYSA-N nickel;trihydrate Chemical compound O.O.O.[Ni] UMTMDKJVZSXFNJ-UHFFFAOYSA-N 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 239000002893 slag Substances 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000005363 electrowinning Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
Images
Classifications
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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
- Y02P10/20—Recycling
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- Electrolytic Production Of Metals (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention relates to a method for recovering copper and nickel from copper-nickel based alloy waste, and belongs to the technical field of comprehensive utilization of resources. The method comprises the following steps of: heating the copper-nickel based alloy waste to reach a molten state, and then casting to form a soluble anode plate; electrolyzing with the soluble anode plate as an anode, a stainless steel plate as a cathode, and copper sulfate as electrolyte until the concentration of copper ion in the electrolyte is reduced to 5 to 30g/L, thus obtaining copper on the cathode; recycling the obtained electrolyte to cyclone electrodeposition, namely, performing electrodeposition with an insoluble iridium film as an anode and an annular titanium plate as a cathode until the concentration of copper ion in the electrolyte reaches 1 to 5g/L, thus obtaining copper on the cathode; performing nickel electrodeposition by using the obtained copper-free electrolyte as the electrolyte, lead anode composite plate as an anode and another stainless steel plate as a cathode, thus obtaining nickel on the cathode after the cathode electrodeposition cycle is ended. The method enables the anode plate casting process and the alloy structure breaking process to be coupled and integrated, thus the energy-saving effect of the process is remarkable.
Description
Technical field
A kind of method that the present invention relates to steamalloy waste recovery copper, nickel, belongs to comprehensive utilization of resources technical field.
Background technology
China's nickel is supplied with and is comprised of two parts, and a part is newly to produce nickel ore concentrate supply, and this part accounts for 72.9% of nickel aggregate supply, and another part accounts for 27.1% from regeneration nickel, and along with the development of economic construction and Iron And Steel Industry, the demand of nickel constantly increases.Within 2010, estimate that Chinese nickel consumption reaches after 400,000 tons/year, China becomes nickel country of consumption the biggest in the world.Within 2010, Chinese nickel metal foundation reserves only have 2,300,000 tons of left and right, the Chinese nickel minerals exploration of 2010-2013 does not have major progress, if just gone down according to such consumption, after 10 years, the nickel ore resource of China is incited somebody to action approach exhaustion gradually, and copper resource situation is similar with it.Alleviate the resource pressure of China's copper, nickel resources, need to strengthen the utilising efficiency to secondary resource.
Corronel waste material material is increasing year by year simultaneously, the alloy components damaging in the waste material producing in the waste material producing while mainly comprising mechanical workout, smelting process, industrial sector and part etc.In addition, the nickel-copper alloy waste material major part circulating on domestic market is bought from the ground such as Taiwan of Japan, Korea S and China, it is the waste material of electronic component factory output, its chemical composition be take nickel, copper as main, and strengthening has comparatively positive effect to alleviation China nickel, copper resource pressure undoubtedly to this recycling.But at present about this alloyed scrap utilize mode for adding as alloying element additive in alloy manufacture craft after classifying, utilization ratio is on the low side and economy performance is poor.
Number of patent application provides " a kind of method that reclaims copper, nickel from ferronickel copper alloy scrap " for 201310455464.7, first the method heats up ferronickel copper alloy scrap to obtain molten state ferronickel copper alloy scrap, then add slag former and spray into oxidizing gas, obtaining molten metal and slag; Then molten metal is cast into soluble anode, final stage electrorefining reclaims copper, will reclaim electric deposition nickel after the electrolytic solution copper removal of copper.In the method in the process of one section of electrolytical refined copper for preventing nickel electrowinning out, need intermittent iron supplement Cu
2+, make electrolytic solution Cu
2+ionic concn maintains 20～80g/L, and must be by the Cu in electrolytic solution before electric deposition nickel
2+remove, so technique is more complicated and loaded down with trivial details, and final copper, the nickel product purity obtaining is not high.
Summary of the invention
For problem and the deficiency of above-mentioned prior art existence, the invention provides a kind of method of steamalloy waste recovery copper, nickel.The method is used for reference the thought of Complicated Copper raw material electrorefining, proposes three sections of electrorefinings of nickel copper-based alloy waste refusion destruction alloy structure and reclaims the wherein new approaches of nickel, copper.The present invention effectively destroys two techniques by positive plate casting and alloy structure and is coupled as one, energy saving technology effect is remarkable, and the mode by three sections of wet-process refinings reclaims wherein copper, nickel, and prepare high purity nickel, copper, waste resource overall availability is high, industry popularizing application prospect is good, and the present invention is achieved through the following technical solutions.
A method for steamalloy waste recovery copper, nickel, its concrete steps are as follows:
(1) first steamalloy waste material is warming up to after molten state insulation 0.5 ~ 2.5h, copper nickel molten metal is cast into soluble anode plate, then take soluble anode plate as anode, stainless steel plate is negative electrode, copper sulfate is electrolytic solution, at control flume voltage, is that 1.4 ~ 3.0V and while current density are 160 ~ 320A/m
2under condition, electrolysis to copper ion concentration in electrolytic solution is 5 ~ 30g/L, can on negative electrode, prepare copper;
(2) circulation of elecrolyte that copper ion concentration step (1) being obtained is 5 ~ 30g/L enters into eddy flow electrodeposition, and the insoluble iridium film of take is anode, and annular titanium plate is negative electrode, at control flume voltage, is that 2.0 ~ 3.0V and while current density are 300 ~ 700A/m
2, electrolyte flow rate is that under 0.1 ~ 2L/min condition, electrodeposition to copper ion concentration in electrolytic solution is 1 ~ 5g/L, can on negative electrode, prepare copper;
(3) after the electrolytic solution copper removal that copper ion concentration step (2) being obtained is 1 ~ 5g/L, as the electrolytic solution of electro deposited nickel, take plumbum anode composite board as anode, stainless steel plate is negative electrode, after electrodeposition cathode deposition period finishes, can on negative electrode, prepare nickel.
Described steamalloy waste material comprises the component of following mass percent: Cu30 ~ 98%, Ni2 ~ 70%.
The temperature of controlling electrolytic solution in above-mentioned steps (1), (2), (3) is 45 ~ 65 ℃.
In above-mentioned steps (1), steamalloy waste material holding temperature is 1500 ~ 1650 ℃.
In above-mentioned steps (3), in electro deposited nickel process, control flume voltage is 2.2 ~ 2.6V.
In above-mentioned steps (3), electro deposited nickel cathode deposition period is 7 ~ 10 days.
In above-mentioned steps (3), copper removal process is: nickel black method or sulfurization-precipitation method.
The invention has the beneficial effects as follows: (1) present method is effectively destroyed two techniques by positive plate casting and alloy structure and is coupled as one, energy saving technology effect is remarkable, and the mode by three sections of wet-process refinings reclaims wherein copper, nickel and prepares high purity nickel, copper, waste resource overall availability is high, and industrial popularizing application prospect is good; (2) present method technique is simple, and reagent is few, and cost is lower; (3) the copper products purity obtaining by electrolysis and eddy flow electrodeposition is all higher than 99.9%, and the final nickel product purity that electro deposited nickel obtains is also higher than 99.9%.
Accompanying drawing explanation
Fig. 1 is process flow sheet of the present invention.
Embodiment
Below in conjunction with the drawings and specific embodiments, the invention will be further described.
Embodiment 1
As shown in Figure 1, the method for this steamalloy waste recovery copper, nickel, its concrete steps are as follows:
(1) first steamalloy waste material is warming up to after molten state insulation 0.5h, copper nickel molten metal is cast into soluble anode plate, then take soluble anode plate as anode, stainless steel plate is negative electrode, copper sulfate is electrolytic solution, at control flume voltage, is that 1.4V and while current density are 160A/m
2under condition, electrolysis to copper ion concentration in electrolytic solution is 5g/L, can on negative electrode, prepare copper, wherein in steamalloy waste material, copper, nickel mass percent are respectively 98% and 2%, steamalloy waste material intensification temperature is 1500 ℃, soluble anode board size is 670 * 870 * 10mm, cell dimension is 871 * 1131mm, and homopolarity polar plate spacing is 80mm;
(2) circulation of elecrolyte that copper ion concentration step (1) being obtained is 5g/L enters into eddy flow electrodeposition, and the insoluble iridium film of take is anode, and annular titanium plate is negative electrode, at control flume voltage, is that 2.0V and while current density are 300A/m
2, electrolyte flow rate is that under 0.1L/min condition, electrodeposition to copper ion concentration in electrolytic solution is 1g/L, can on negative electrode, prepare copper;
(3) after the electrolytic solution copper removal that copper ion concentration step (2) being obtained is 1g/L as the electrolytic solution of electro deposited nickel, take plumbum anode composite board as anode, stainless steel plate is negative electrode, after electrodeposition cathode deposition period finishes, can on negative electrode, prepare nickel, wherein in electro deposited nickel process, control flume voltage is 2.2V; Electro deposited nickel cathode deposition period is 7 days.
The temperature of controlling electrolytic solution in above-mentioned steps (1), (2), (3) is 45 ℃; In step (3), copper removal process is: sulfurization-precipitation method.
Detect by analysis, the cathode copper purity obtaining in above-mentioned steps (1) is 99.994%, and the copper purity obtaining in above-mentioned steps (2) is 99.93%; The cathode nickel purity obtaining in step (3) is 99.91%.
Embodiment 2
As shown in Figure 1, the method for this steamalloy waste recovery copper, nickel, its concrete steps are as follows:
(1) first steamalloy waste material is warming up to after molten state insulation 2.5h, copper nickel molten metal is cast into soluble anode plate, then take soluble anode plate as anode, stainless steel plate is negative electrode, copper sulfate is electrolytic solution, at control flume voltage, is that 3.0V and while current density are 320A/m
2under condition, electrolysis to copper ion concentration in electrolytic solution is 30g/L, can on negative electrode, prepare copper, in steamalloy waste material, copper, nickel mass percent are respectively 30% and 70%, steamalloy waste material intensification temperature is 1650 ℃, soluble anode board size is 700 * 900 * 10mm, cell dimension is 871 * 1131mm, and homopolarity polar plate spacing is 85mm;
(2) circulation of elecrolyte that copper ion concentration step (1) being obtained is 30g/L enters into eddy flow electrodeposition, and the insoluble iridium film of take is anode, and annular titanium plate is negative electrode, at control flume voltage, is that 2.5V and while current density are 700A/m
2, electrolyte flow rate is that under 2L/min condition, electrodeposition to copper ion concentration in electrolytic solution is 5g/L, can on negative electrode, prepare copper;
(3) after the electrolytic solution copper removal that copper ion concentration step (2) being obtained is 5g/L as the electrolytic solution of electro deposited nickel, take plumbum anode composite board as anode, stainless steel plate is negative electrode, after electrodeposition cathode deposition period finishes, can on negative electrode, prepare nickel, wherein in electro deposited nickel process, control flume voltage is that 2.6V, electro deposited nickel cathode deposition period are 10 days.
The temperature of controlling electrolytic solution in above-mentioned steps (1), (2), (3) is 65 ℃; In above-mentioned steps (3), copper removal process is: nickel black method.
Detect by analysis, the cathode copper purity obtaining in above-mentioned steps (1) is 99.98%, and the copper purity obtaining in above-mentioned steps (2) is 99.93%; The cathode nickel purity obtaining in step (3) is 99.992%.
Embodiment 3
As shown in Figure 1, the method for this steamalloy waste recovery copper, nickel, its concrete steps are as follows:
(1) first steamalloy waste material is warming up to after molten state insulation 1h, copper nickel molten metal is cast into soluble anode plate, then take soluble anode plate as anode, stainless steel plate is negative electrode, copper sulfate is electrolytic solution, at control flume voltage, is that 2.5V and while current density are 250A/m
2under condition, electrolysis to copper ion concentration in electrolytic solution is 18g/L, can on negative electrode, prepare copper, wherein in steamalloy waste material, copper, nickel, weight of iron per-cent are respectively 45%, 35% and 20%, steamalloy waste material intensification temperature is 1600 ℃, soluble anode board size is 720 * 900 * 10mm, cell dimension is 940 * 1350mm, and homopolarity polar plate spacing is 90mm;
(2) circulation of elecrolyte that copper ion concentration step (1) being obtained is 18g/L enters into eddy flow electrodeposition, and the insoluble iridium film of take is anode, and annular titanium plate is negative electrode, at control flume voltage, is that 3.0V and while current density are 350A/m
2, electrolyte flow rate is that under 1.5L/min condition, electrodeposition to copper ion concentration in electrolytic solution is 3g/L, can on negative electrode, prepare copper;
(3) after the electrolytic solution copper removal that copper ion concentration step (2) being obtained is 3g/L as the electrolytic solution of electro deposited nickel, take plumbum anode composite board as anode, stainless steel plate is negative electrode, after electrodeposition cathode deposition period finishes, can on negative electrode, prepare nickel, wherein in step (3), in electro deposited nickel process, control flume voltage is 2.4V; Electro deposited nickel cathode deposition period is 8 days.
The temperature of controlling electrolytic solution in above-mentioned steps (1), (2), (3) is 50 ℃; In above-mentioned steps (3), copper removal process is: sulfurization-precipitation method.
Detect by analysis, the cathode copper purity obtaining in above-mentioned steps (1) is 99.98%, and the copper purity obtaining in above-mentioned steps (2) is 99.92%; The cathode nickel purity obtaining in step (3) is 99.94%.
Claims (2)
1. a method for steamalloy waste recovery copper, nickel, is characterized in that concrete steps are as follows:
(1) first steamalloy waste material is warming up to after molten state insulation 0.5 ~ 2.5h, copper nickel molten metal is cast into soluble anode plate, then take soluble anode plate as anode, stainless steel plate is negative electrode, copper sulfate is electrolytic solution, at control flume voltage, is that 1.4 ~ 3.0V and while current density are 160 ~ 320A/m
2under condition, electrolysis to copper ion concentration in electrolytic solution is 5 ~ 30g/L, can on negative electrode, prepare copper;
(2) circulation of elecrolyte that copper ion concentration step (1) being obtained is 5 ~ 30g/L enters into eddy flow electrodeposition, and the insoluble iridium film of take is anode, and annular titanium plate is negative electrode, at control flume voltage, is that 2.0 ~ 3.0V and while current density are 300 ~ 700A/m
2, electrolyte flow rate is that under 0.1 ~ 2L/min condition, electrodeposition to copper ion concentration in electrolytic solution is 1 ~ 5g/L, can on negative electrode, prepare copper;
(3) after the electrolytic solution copper removal that copper ion concentration step (2) being obtained is 1 ~ 5g/L, as the electrolytic solution of electro deposited nickel, take plumbum anode composite board as anode, stainless steel plate is negative electrode, after electrodeposition cathode deposition period finishes, can on negative electrode, prepare nickel.
2. the method for steamalloy waste recovery copper according to claim 1, nickel, is characterized in that: described steamalloy waste material comprises the component of following mass percent: Cu30 ~ 98%, Ni2 ~ 70%.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104278291A (en) * | 2014-10-24 | 2015-01-14 | 天津中色再生金属工程技术研究院 | Method of directly melting and molding scrap copper to extract copper by electrolysis |
| CN104724864A (en) * | 2015-03-31 | 2015-06-24 | 江苏地一环保科技有限公司 | Cyclone treatment technique of nickel-containing electroplating wastewater |
| CN105154919A (en) * | 2015-10-14 | 2015-12-16 | 池州西恩新材料科技有限公司 | Process for recycling copper and nickel from copper-nickel alloy |
| CN107268032A (en) * | 2017-06-27 | 2017-10-20 | 中国科学院过程工程研究所 | A kind of method of copper and zinc in Recycling of waste liquid |
| CN110983376A (en) * | 2019-12-31 | 2020-04-10 | 广西南国铜业有限责任公司 | Copper electrolyte purification process |
| CN114517309A (en) * | 2022-03-15 | 2022-05-20 | 金川镍钴研究设计院有限责任公司 | Method for supplementing nickel and removing copper in nickel electrolysis production system |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104278291A (en) * | 2014-10-24 | 2015-01-14 | 天津中色再生金属工程技术研究院 | Method of directly melting and molding scrap copper to extract copper by electrolysis |
| CN104724864A (en) * | 2015-03-31 | 2015-06-24 | 江苏地一环保科技有限公司 | Cyclone treatment technique of nickel-containing electroplating wastewater |
| CN105154919A (en) * | 2015-10-14 | 2015-12-16 | 池州西恩新材料科技有限公司 | Process for recycling copper and nickel from copper-nickel alloy |
| CN107268032A (en) * | 2017-06-27 | 2017-10-20 | 中国科学院过程工程研究所 | A kind of method of copper and zinc in Recycling of waste liquid |
| CN107268032B (en) * | 2017-06-27 | 2019-04-05 | 中国科学院过程工程研究所 | A kind of method of copper and zinc in Recycling of waste liquid |
| CN110983376A (en) * | 2019-12-31 | 2020-04-10 | 广西南国铜业有限责任公司 | Copper electrolyte purification process |
| CN114517309A (en) * | 2022-03-15 | 2022-05-20 | 金川镍钴研究设计院有限责任公司 | Method for supplementing nickel and removing copper in nickel electrolysis production system |
| CN114517309B (en) * | 2022-03-15 | 2023-09-26 | 金川镍钴研究设计院有限责任公司 | Nickel supplementing and decoppering method in nickel electrolysis production system |
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| CN103668322B (en) | 2016-09-14 |
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