CN103409773A - Method for extracting copper and cobalt from copper-cobalt alloy - Google Patents
Method for extracting copper and cobalt from copper-cobalt alloy Download PDFInfo
- Publication number
- CN103409773A CN103409773A CN2013103178181A CN201310317818A CN103409773A CN 103409773 A CN103409773 A CN 103409773A CN 2013103178181 A CN2013103178181 A CN 2013103178181A CN 201310317818 A CN201310317818 A CN 201310317818A CN 103409773 A CN103409773 A CN 103409773A
- Authority
- CN
- China
- Prior art keywords
- copper
- cobalt
- cobalt alloy
- alloy
- extracting
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
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
The invention discloses a method for extracting copper and cobalt from copper-cobalt alloy. The microstructure of the ferro-cobalt alloy phase in copper-cobalt alloy is similar to that of stainless steel NO. 400, so that the problem of reclaiming valuable metal from copper-cobalt alloy is always puzzled in the industry. The method is characterized in that 1), copper-cobalt alloy with low silicon content is electrolysed to obtain electrolyte, anode mud and cathode copper; 2), the electrolyte enters a leaching system through an open circuit, and cobalt is extracted after extraction and edulcoration; 3), acid leaching is performed on the anode mud under the condition of heating, pressurizing and adding oxygen, and obtained leachate returns to the leaching system. Through the method, the total recovery rate of valuable metal such as copper and cobalt is higher than 99.9%, and no residue is produced; copper can be transformed from the raw materials to a product through electrolytic reaction at one step, so that the intermediate links such as leaching and extraction can be saved; sulfuric acid is not consumed in the whole electrolysis process, so that the cost is lowered.
Description
Technical field
The invention belongs to the alloy treatment field, be specifically related to a kind of from copper-cobalt alloy, extracting the method for copper, cobalt.
Background technology
Copper-cobalt alloy (comprising red alloy and white metal) is one of principal mode of current Congo (Congo-Kinshasa) copper cobalt ore rough-wrought product, is also that China is from now on from one of main cobalt raw material of African import.Its outward appearance main manifestations of alloy that copper content is high is the copper red look, becomes red alloy; Its outward appearance performance of alloy that copper content is low is white in color slightly yellow, becomes white metal.Copper-cobalt alloy mainly is comprised of two portions, and a part be take Cu as main, contains the copper metallographic phase of a small amount of Si, Fe, Co; Another part be take Si, Fe, Co as main, contains the ferrocobalt phase of a small amount of Cu.Due to the microtexture of ferrocobalt phase and No. 400 stainless steel-likes seemingly, therefore from copper-cobalt alloy, reclaim the difficult problem that valuable metal is the puzzlement industry always.
Summary of the invention
The present invention is directed to deficiency and shortcoming that above-mentioned prior art exists, provide that a kind of flow process is short, cost is low, safety and environmental protection from copper-cobalt alloy, extracting the method that reclaims copper, cobalt.
For realizing purpose of the present invention, the present invention adopts following technical scheme: a kind of from copper-cobalt alloy, extracting the method for copper, cobalt, it is characterized in that comprising the following steps:
1) the copper-cobalt alloy electrolysis of silicon be will hang down, electrolytic solution, the anode sludge and cathode copper obtained;
2) described electrolytic solution open circuit enters leaching system, extracts and carries cobalt again after abstraction impurity removal;
3) the described anode sludge heat, pressurize and the condition of logical oxygen under carry out acidleach, the leach liquor obtained returns to leaching system.
Elucidated hereinafter reaction principle of the present invention, during the copper-cobalt alloy electrolysis, the negative and positive polarization response is as follows:
Anode: Me (Co, Fe, Cu)=Me
2+(Co, Fe, Cu)+2e, Cu
2S=2Cu
2++ S+4e
Negative electrode: Cu
2++ 2e=Cu
Main side reaction:
Anode: H
2O-2e=2H
++ 1/2O
2, SO
4 2--2e=SO
3+ 1/2O
2
Negative electrode: 2H
++ 2e=H
2, As
2+(Sb, Bi)+2e=As (Sb, Bi)
The anode sludge: Cu
2++ Co=Cu+Co
2+
React under the processing condition that keep suitable, the densification of gained copper coin, surface is without particle, and bath voltage is stable, can continuously produce the standard cathode copper that meets GB/T467-2010.
Further, step 1) the Hanging Basket electrolysis is adopted in the electrolysis in, regularly detecting electrolytic solution metal and acid concentration variation and bath voltage changes, according to the copper-cobalt alloy changing conditions, add copper-cobalt alloy in good time and upgrade electrolytic solution with circulation, and the anode sludge of cleaning bottom of electrolytic tank deposition, in reaction, control bath composition: Cu30-50g/L, H
2SO
4150-250g/L, temperature 60-65 ℃, current density 200-500A/m
2, circulation of elecrolyte speed 1-5m
3/ m
2H.
Further, described copper-cobalt alloy is red alloy.
Further, described copper-cobalt alloy is left intact, and directly as anode, carries out electrolysis.
Further, described copper-cobalt alloy is re-used as anode and carries out electrolysis to improve after copper grade with the acidleach of sulfuric acid High Temperature Pre.
Further, the Hanging Basket electrolysis of stating adopts the titanium basket to hold red alloy, and negative electrode adopts the 316L stainless steel plate; Described leaching system is the sulfuric acid leaching system for copper cobalt ore material.The present invention, in the copper-cobalt alloy electrolytic process, adopts copper-cobalt alloy to do anode, and stainless steel is done negative electrode, makes the metals such as copper, cobalt, iron from anode dissolution, and cupric ion is separated out as copper simple substance at negative electrode, directly obtains copper products.Cobalt in copper-cobalt alloy enters electrolytic solution and open circuit removes leaching system, makes cobalt salt solution by links such as deironing, extractions.
Further, step 2) in, electrolytic solution enters leaching system, adopts the LIX973 extracting copper, through P204 and P507 extraction, carries cobalt again after separation of iron in goethite form.
Further, step 3) the Anodic mud acid condition of soaking is temperature 150-300 ℃, oxygen partial pressure 0.1-2MPa, reaction times 0.5-4h, and the anode sludge can leach fully, and leach liquor enters leaching system, reclaims and extracts the copper cobalt.
Further, in electrolysis, add appropriate additive to improve the copper coin quality, described additive is one or more in gelatine, thiocarbamide, guar gum.
Further, in reaction process, with the carrying out of electrolysis, in electrolytic solution, Cu content reduces, and foreign matter content raises, and electrolytic solution is opened a way and supplementary CuSO continuously
4Liquid, guarantee that electrolytic solution metal and acid content remain stable substantially, and reaction process electrolytic solution turbidity is controlled at below 100mg/L.
Compared with prior art, the present invention has the following advantages:
1. energy consumption of reaction is low, produces ton the copper only about 400kWh of power consumption and a small amount of steam.
2. in reaction process, the total rate of recovery of the valuable metals such as copper, cobalt is greater than 99.9%, produces without slag.
3. electrolytic reaction has realized that copper expects that from former a step of product completes, and has saved the links such as middle leaching, extraction, in whole electrolytic process, does not consume sulfuric acid, has reduced cost.
4. electrolytic reaction is carried out under normal pressure, to production unit without particular requirement.
5. in reaction process, produce safety and environmental protection without obnoxious flavour.
The accompanying drawing explanation
Fig. 1 is process flow sheet of the present invention.
Embodiment
Below in conjunction with embodiment, more specific description content of the present invention.Be to be understood that enforcement of the present invention is not limited to the following examples, any pro forma accommodation and/or change that the present invention is made all will fall into protection scope of the present invention.
In the present invention, if not refer in particular to, all part, per-cents are weight unit, and all equipment and raw material all can be buied from market or the industry is commonly used.
In experimental example and embodiment, the every 100g composition of copper-cobalt alloy used sees the following form 1:
The red alloying constituent of table 1 (w%)
| Composition | Cu | Co | Fe | Ni | S | Mg、Mn、Ca、Zn、Pb、Al、C |
| (％) | 72.3 | 6.0 | 16.2 | 0.3 | 3.5 | Trace |
Experimental example 1
1. temperature condition experiment
Get 40 ℃, 50 ℃, 60 ℃ three temperature condition and investigate the impact of temperature on red alloy electrolysis.
The electrolytic experiment condition is: current density 200A/m
2, circulation of elecrolyte speed 1m
3/ m
2H, bath composition: Cu30g/L, H
2SO
4170g/L, with pole span 9cm, electrolysis time 15h.
The titanium basket is filled to completely red alloy, add electrolytic solution, after switching on power, open electrolysis, not timing detects bath voltage and changes, the gained cathode copper of weighing after the reaction end, and experimental result is in Table 2.
The impact of table 2 temperature on red alloy electrolysis
2. current density and the experiment of Cu concentration conditions
Current density, two conditions of Cu concentration are investigated to the impact of temperature on red alloy electrolysis.
The electrolytic experiment condition is: temperature 60 C, circulation of elecrolyte speed 1m
3/ m
2H, H
2SO
4170g/L, with pole span 9cm, electrolysis time 15h.
By in the titanium basket, filling completely red alloy, add electrolytic solution, after switching on power, open electrolysis, not timing detects bath voltage and changes, the gained cathode copper of weighing after the reaction end, experimental result is in Table 3.
The impact on red alloy electrolysis of table 3 current density and Cu concentration
3. impurity (Fe) content condition experiment
Current density, two conditions of Cu concentration are investigated to the impact of temperature on red alloy electrolysis.
The electrolytic experiment condition is: temperature 60 C, circulation of elecrolyte speed 1m
3/ m
2H, bath composition: Cu30g/L, H
2SO
4170g/L, with pole span 9cm, electrolysis time 15h.
The titanium basket is filled to completely red alloy, add electrolytic solution, after switching on power, open electrolysis, not timing detects bath voltage and changes, the gained cathode copper of weighing after the reaction end, and experimental result is in Table 4.
The impact of table 4 impurity (Fe) content on red alloy electrolysis
After testing, under above-mentioned different impurities (Fe) content, the gained cathode copper all reaches GB/T467-2010 Plays cathode copper index.
By above-mentioned experimental example, can be found out, in method of the present invention, electrolyte temperature 60-65 ℃ is advisable, current density 200A/m
2Left and right, the Cu30g/L left and right is suitable, electrolytic solution has no special requirements to foreign matter content.
Embodiment
Get the full titanium basket of the red alloy filling of 3kg, press following processing condition electrolysis: temperature 60 C, circulation of elecrolyte speed 1m
3/ m
2H, current density 250A/m
2, bath composition: Cu35-40g/L, H
2SO
4150-170g/L, Fe10-15g/L, with pole span 9cm.In electrolytic process, add in time mineral aggregate and the cleaning anode sludge, not timing detects bath voltage, and open a way in time electrolytic solution and supplementary copper sulfate, maintain electrolytic solution in above-mentioned processing range, electrolysis time 200h.
Electrolysis is dissolved altogether red alloy 13783g(and is not comprised that part drops to the red alloy of bottom land from the titanium basket), produce electrolytic copper 12055g, produce anode sludge 2168g.When reaction had just started, along with the carrying out of electrolysis, bath voltage had the trend of rising, but tends towards stability after for some time, and through constantly adding red alloy and upgrading electrolytic solution, bath voltage tends towards stability substantially, changes fluctuation little.Experimental result is in Table 5, and anode sludge composition is in Table 6.
The red alloy electrolytic experiment of table 5 result
Table 6 anode sludge composition
Although illustrated and described embodiments of the invention, those having ordinary skill in the art will appreciate that, do not breaking away from principle of the present invention and aim situation and can carry out multiple variation, modification, replacement and modification to embodiment, scope of the present invention is limited by claim and equivalent thereof.
Claims (10)
1. one kind from extracting the method for copper, cobalt copper-cobalt alloy, it is characterized in that comprising the following steps:
1) the copper-cobalt alloy electrolysis of silicon be will hang down, electrolytic solution, the anode sludge and cathode copper obtained;
2) described electrolytic solution open circuit enters leaching system, extracts and carries cobalt again after abstraction impurity removal;
3) the described anode sludge heat, pressurize and the condition of logical oxygen under carry out acidleach, the leach liquor obtained returns to leaching system.
2. according to claim 1 from copper-cobalt alloy, extracting the method for copper, cobalt, it is characterized in that, step 1) the Hanging Basket electrolysis is adopted in the electrolysis in, regularly detecting electrolytic solution metal and acid concentration variation and bath voltage changes, according to the copper-cobalt alloy changing conditions, add copper-cobalt alloy in good time and upgrade electrolytic solution with circulation, and the anode sludge of cleaning bottom of electrolytic tank deposition, bath composition: Cu30-50g/L, H in reaction, controlled
2SO
4150-250g/L, temperature 60-65 ℃, current density 200-500A/m
2, circulation of elecrolyte speed 1-5m
3/ m
2H.
3. according to claim 2ly from copper-cobalt alloy, extracting the method for copper, cobalt, it is characterized in that, described copper-cobalt alloy is red alloy.
4. according to claim 2ly from copper-cobalt alloy, extracting the method for copper, cobalt, it is characterized in that, described copper-cobalt alloy is left intact, and directly as anode, carries out electrolysis.
5. according to claim 2ly from copper-cobalt alloy, extracting the method for copper, cobalt, it is characterized in that, described copper-cobalt alloy is re-used as anode and carries out electrolysis to improve after copper grade with the acidleach of sulfuric acid High Temperature Pre.
6. according to claim 2ly from copper-cobalt alloy, extracting the method for copper, cobalt, it is characterized in that, described Hanging Basket electrolysis adopts the titanium basket to hold red alloy, and negative electrode adopts the 316L stainless steel plate; Described leaching system is the sulfuric acid leaching system for copper cobalt ore material.
7. according to claim 2 from copper-cobalt alloy, extracting the method for copper, cobalt, it is characterized in that step 2) in electrolytic solution enter leaching system, adopt the LIX973 extracting copper, after separation of iron in goethite form, through P204 and P507 extraction, carry cobalt again.
8. according to claim 2 from copper-cobalt alloy, extracting the method for copper, cobalt, it is characterized in that step 3) the Anodic mud acid condition of soaking is temperature 150-300 ℃, oxygen partial pressure 0.1-2MPa, reaction times 0.5-4h.
9. according to claim 2ly from copper-cobalt alloy, extracting the method for copper, cobalt, it is characterized in that, in electrolysis, add appropriate additive to improve the copper coin quality, described additive is one or more in gelatine, thiocarbamide, guar gum.
10. according to claim 2ly from copper-cobalt alloy, extracting the method for copper, cobalt, it is characterized in that, in reaction process, with the carrying out of electrolysis, in electrolytic solution, Cu content reduces, and foreign matter content raises, and electrolytic solution is opened a way and supplementary CuSO continuously
4Liquid, guarantee that electrolytic solution metal and acid content remain stable substantially, and reaction process electrolytic solution turbidity is controlled at below 100mg/L.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310317818.1A CN103409773B (en) | 2013-07-24 | 2013-07-24 | A kind of method extracting copper, cobalt from copper-cobalt alloy |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310317818.1A CN103409773B (en) | 2013-07-24 | 2013-07-24 | A kind of method extracting copper, cobalt from copper-cobalt alloy |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103409773A true CN103409773A (en) | 2013-11-27 |
| CN103409773B CN103409773B (en) | 2015-09-30 |
Family
ID=49602811
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310317818.1A Active CN103409773B (en) | 2013-07-24 | 2013-07-24 | A kind of method extracting copper, cobalt from copper-cobalt alloy |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103409773B (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103628088A (en) * | 2013-12-13 | 2014-03-12 | 深圳市新昊青科技有限公司 | Method for separating cobalt from cobalt-containing alloy and cobalt sulfate product |
| CN104152696A (en) * | 2014-07-14 | 2014-11-19 | 红板（江西）有限公司 | Process for recycling gold from waste circuit boards |
| CN104531988A (en) * | 2014-12-26 | 2015-04-22 | 昆明冶金研究院 | Recovery process of complex multi-metal ores difficult to treat |
| CN106400050A (en) * | 2016-09-21 | 2017-02-15 | 东莞市联洲知识产权运营管理有限公司 | Method for preparing high-quality electro-deposited copper from waste copper liquid |
| 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 |
| CN109706480A (en) * | 2019-03-08 | 2019-05-03 | 广东佳纳能源科技有限公司 | The separation method of corronil and its application |
| CN109825720A (en) * | 2019-01-23 | 2019-05-31 | 浙江工贸职业技术学院 | A kind of joint metallurgical technology of copper-cobalt alloy and cobalt salt mineral aggregate |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101086039A (en) * | 2007-06-22 | 2007-12-12 | 南通瑞翔新材料有限公司 | Copper cobalt alloy separation and recovery method |
| CN102560100A (en) * | 2012-02-21 | 2012-07-11 | 海南金亿新材料股份有限公司 | Process for preparing high-purity superfine cobalt powder from copper-cobalt-iron alloy |
-
2013
- 2013-07-24 CN CN201310317818.1A patent/CN103409773B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101086039A (en) * | 2007-06-22 | 2007-12-12 | 南通瑞翔新材料有限公司 | Copper cobalt alloy separation and recovery method |
| CN102560100A (en) * | 2012-02-21 | 2012-07-11 | 海南金亿新材料股份有限公司 | Process for preparing high-purity superfine cobalt powder from copper-cobalt-iron alloy |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103628088A (en) * | 2013-12-13 | 2014-03-12 | 深圳市新昊青科技有限公司 | Method for separating cobalt from cobalt-containing alloy and cobalt sulfate product |
| CN103628088B (en) * | 2013-12-13 | 2017-01-18 | 深圳市新昊青科技有限公司 | Method for separating cobalt from cobalt-containing alloy and cobalt sulfate product |
| CN104152696A (en) * | 2014-07-14 | 2014-11-19 | 红板（江西）有限公司 | Process for recycling gold from waste circuit boards |
| CN104531988A (en) * | 2014-12-26 | 2015-04-22 | 昆明冶金研究院 | Recovery process of complex multi-metal ores difficult to treat |
| CN106400050A (en) * | 2016-09-21 | 2017-02-15 | 东莞市联洲知识产权运营管理有限公司 | Method for preparing high-quality electro-deposited copper from waste copper liquid |
| 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 |
| CN109825720A (en) * | 2019-01-23 | 2019-05-31 | 浙江工贸职业技术学院 | A kind of joint metallurgical technology of copper-cobalt alloy and cobalt salt mineral aggregate |
| CN109825720B (en) * | 2019-01-23 | 2021-04-20 | 浙江工贸职业技术学院 | Combined metallurgy process for copper-cobalt alloy and cobalt salt mineral aggregate |
| CN109706480A (en) * | 2019-03-08 | 2019-05-03 | 广东佳纳能源科技有限公司 | The separation method of corronil and its application |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103409773B (en) | 2015-09-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103409773B (en) | A kind of method extracting copper, cobalt from copper-cobalt alloy | |
| CN104789783B (en) | Process for selective efficient copper extraction and comprehensive recovery from lead copper matte | |
| CN103014760B (en) | Production method of electrolytic manganese metal | |
| CN100554452C (en) | Method for extracting copper from copper-containing sulfide ore by wet process | |
| CN100594265C (en) | Method for producing electrolytic nickel by using various nickel-containing raw materials | |
| CN101575715B (en) | Method for extracting valuable metals from electronic waste | |
| CN102002594B (en) | Method for recycling tin | |
| CN105177307B (en) | Method for recycling copper-nickel-cobalt from low grade nickel matte through abrasive flotation separation | |
| CA2821042A1 (en) | Gold and silver electrorecovery from thiosulfate leaching solutions | |
| CN103668322B (en) | A kind of steamalloy waste recovery copper, the method for nickel | |
| CN101713028A (en) | Method for washing anode slime of electrolytic lead bismuth alloy | |
| CN104278291A (en) | Method of directly melting and molding scrap copper to extract copper by electrolysis | |
| CN107385219A (en) | Utilize the method for cyclone electrolytic cell processing nickel plated copper sludge recovery copper and mickel | |
| CN103194770A (en) | Process for extracting gold from low-grade, copper-containing and difficultly-treated goldmine ammonia cyanide leaching pulp via electrodeposition | |
| CN102690947A (en) | Smelting process of silver concentrate | |
| CN102839379A (en) | On-line treatment method of acidic etching solution | |
| CN102776527B (en) | Utilize cupric waste wet underwater welding higher-grade copper coin clean energy-saving environmental-protecting process | |
| KR20130125590A (en) | Method for recovering tin from waste-lead frame scrap | |
| CN104404262A (en) | Copper scum treatment technique | |
| CN105734293B (en) | A kind of high-grade lead copper matte resource comprehensive utilization technique | |
| CN105887118B (en) | A kind of method that Selective Separation from materials containing tellurium reclaims tellurium | |
| CN103060842A (en) | Method for preparing electrodeposited cobalt under large flow | |
| CN105821443A (en) | Production process of cathode copper | |
| CN102051635B (en) | Method for producing metal cobalt by adopting high-current density sulfuric acid electrolyte | |
| CN103397182A (en) | Method for efficiently recycling bismuth from monomer bismuth ore |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |