CN101608258B - Method for industrially extracting cobalt, copper and iron by taking cobalt-copper alloy as raw material - Google Patents
Method for industrially extracting cobalt, copper and iron by taking cobalt-copper alloy as raw material Download PDFInfo
- Publication number
- CN101608258B CN101608258B CN2008100722002A CN200810072200A CN101608258B CN 101608258 B CN101608258 B CN 101608258B CN 2008100722002 A CN2008100722002 A CN 2008100722002A CN 200810072200 A CN200810072200 A CN 200810072200A CN 101608258 B CN101608258 B CN 101608258B
- Authority
- CN
- China
- Prior art keywords
- cobalt
- copper alloy
- copper
- iron
- acid
- 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.)
- Active
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
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a method for industrially extracting cobalt, copper and iron by taking a cobalt-copper alloy as a raw material, which is characterized by comprising the following steps: (1) an oxidation leaching process, wherein water, concentrated sulfuric acid, concentrated nitric acid and a catalyst are prepared into mixed acid solution in a volume ratio of 10:0.5-6:0.5-6:0.1-10, and then a cobalt-copper alloy block is added to the mixed acid solution, so that the cobalt, the copper and the iron of the cobalt-copper alloy are leached into the solution; and (2) a solid-liquid separation process, wherein when the reaction is carried out to make the acidity of the solution reach 10-50g/L, liquid supernatant is sucked in a siphon mode to separate from the cobalt-copper alloy which is not completely dissolved, and the cobalt-copper alloy which is not completely dissolved is continuously leached according to a method in the process (1). The method has short process flow and low production cost, contributes to comprehensive recovery of metallic elements of the cobalt-copper alloy, and is suitable for industrial production.
Description
Technical field
The present invention relates to cobalt-copper alloy and make the method that primary industry extracts cobalt, copper, iron, is a kind of method that adopts fairly simple technology to leach cobalt, copper, iron from cobalt-copper alloy.
Background technology
Along with expanding economy, developing rapidly of battery material, superfine powdery material and superhard material particularly, also the consumption impetus in quick growth, particularly cobalt resource is swift and violent to cause the consumption of relevant nonferrous materials.And Chinese cobalt resource lacks relatively, and according to data statistics, China has 26 tame manufacturers to produce all kinds of cobalt products with cobalt concentrate approximately at present, and total annual production is 15000 tons of cobalt amounts of metal, and wherein Jinchuan output accounts for 27%.China has become world's second largest cobalt producing country, has very important effect in global cobalt market.
Cobalt-copper alloy is the important source material of producing cobalt metal and various finished products, is commonly called as cobalt white metal or cobalt red alloy or cobalt AB alloy, mainly originates from Africa.Cobalt-copper alloy makes by electric furnace reduction melting cupric oxide cobalt ore and the copper slag that contains cobalt, generally contain cobalt: contain cobalt Co:1%～50%, iron Fe:1%～50%, copper Cu:1%～50%, this alloy raw material intractability is bigger, subject matter is that the yield of cobalt, copper is low, and cost height, technical process are long.The method of handling at present cobalt-copper alloy mainly contains electro-dissolving, sulfuration lixiviation process, High Temperature High Pressure lixiviation process, ball milling machinery activated acids and soaks method, chlorine lixiviation process, direct leaching, melting atomizing lixiviation process etc., and leaching efficiency is low, equipment is complicated, cost is high, technical process is long, be difficult to realize technology but all exist.The treatment process patent of cobalt white metal also has report: the patent No. is 2005100620166, name is called " a kind of method of handling cobalt-copper alloy ", introduce a kind of treatment process of cobalt-copper alloy, have bad adaptability, equipment corrosion is serious, shortcomings such as ball milling Mechanical Crushing are volatilized, needed in acid easily; The patent No. is 200710069068.5, name is called " a kind of method for the treatment of cobalt-copper alloy by sulfuric acid ", and this method also exists needs the fragmentation of ball milling mechanical activation, speed of response to wait shortcoming more slowly; The patent No. is 200610032051.8, name is called the method for leaching valuable metal " a kind of from copper ferrocobalt alloy ", and this method leaching efficiency is low, equipment is complicated, cost is high, technical process is long, be difficult to realize technology.
The effectively comprehensive recovery technology of cobalt-copper alloy is the focus of everybody concern always, because cobalt-copper alloy hardness height, has certain ductility, be difficult to fragmentation with common disintegrating apparatus, and cobalt copper iron forms the eutectic Stability Analysis of Structures, under general condition be difficult to be dissolved in mineral acid commonly used, influenced the carrying out of leaching, cause in the leaching process metallic element rate of recovery low, the cobalt-copper alloy extract technology is not well broken through all the time, have not yet to see relevant industrial and produce report, the industrial production of cobalt-copper alloy reclaims significant to remedying domestic cobalt resource shortage.
Handle the industrial process of cobalt-copper alloy in order to seek ideal, it is in short supply to remedy domestic cobalt resource, it is core that the inventor has has independently researched and developed processing cobalt-copper alloy new technology, build up the metals such as cobalt, copper that a cover has good economic benefit and comprehensively reclaim production line, promote the comprehensive recovery of cobalt-copper alloy, and be developing direction with battery material and powder body material and non-ferrous metal functional materials, on the basis of existing work, further develop various high added value materials.
Summary of the invention
The objective of the invention is to overcome existing treatment process exists not enough, solve the problem that wet method industry high-level efficiency reclaims the cobalt-copper alloy difficulty, provide a kind of cobalt-copper alloy that adopts to make the method that primary industry extracts cobalt, copper, iron, its technical process is short, production cost is low, help the cobalt-copper alloy comprehensive recovery of metallic elements, is suitable for suitability for industrialized production.
The objective of the invention is to realize by following manner:
A kind of cobalt-copper alloy that adopts is made the method that primary industry extracts cobalt, copper, iron, and it is characterized in that: cobalt-copper alloy does not need fragmentation, ball-milling processing, directly adopts mixing acid heating by a certain percentage to leach under normal pressure, cobalt copper iron leach liquor is separated again.Mainly may further comprise the steps:
(1) operation is leached in oxidation: with water, the vitriol oil, concentrated nitric acid, catalyzer by volume the ratio of 10:0.5～6:0.5～6:0.1～10 make mixed acid solution; Add the cobalt-copper alloy piece then, make the cobalt copper iron leaching of cobalt-copper alloy enter into solution;
(2) solid-liquid separation process: when question response reaches 10～50g/L to solution acidity,, separate with not consoluet cobalt-copper alloy the supernatant liquor sucking-off by siphon mode, not consoluet cobalt-copper alloy continues to leach by the method for operation (1).
Described cobalt-copper alloy can be block, granular, powdery.
Described cobalt-copper alloy cobalt copper ferrous components is: Co:1%～50%, Fe:1%～50%, Cu:1%～50%.
When the mixing acid of described employing sulfuric acid and nitric acid carried out the oxidation leaching, the sulfuric acid in the mixing acid and the concentration of nitric acid were 50～500g/L respectively, sulfuric acid in the mixing acid and nitric acid mol ratio 1:0.2～2.
Described catalyzer has katalysis and anti-passivation, mainly is that fluorine-containing mineral acid (as HF) or inorganic salt are (as NH
4F, NaF, KF, MgF
2, CaF
2Deng) preparation the aqueous solution, compound concentration is 20～500g/L.
The preheating temperature of described leaching operation is controlled between 20 ℃～90 ℃, and temperature of reaction is controlled at 20～90 ℃.
Between the pH value control 1.0～5.0 of described leaching operation leach liquor terminal point.
Described leaching operation reaction times control 1～10 hour.
After adopting aforesaid method, the present invention has following characteristics:
One, adopt special leach liquor prescription, technical process is short, under condition of normal pressure, can easily make metal leachings such as cobalt copper iron, and cobalt, copper, iron leach and reaches 95～99.5%;
Two, solved the defective that traditional ball milling wet processing cobalt-copper alloy technology exists, the shape adaptability of cobalt-copper alloy is strong, does not need operations such as ball milling mechanical activation, fragmentation;
Three, simple to operate, be easy to control;
Four, the leaching speed of response is fast, leaches the operating efficiency height;
Five, the leaching yield height of cobalt and copper, the real height of receiving of cobalt and copper; Solve sulfuric acid and leached the inefficient problem of cobalt, helped the cobalt-copper alloy comprehensive recovery of metallic elements;
Six, can reduce investment significantly, reduce operator, production cost is low, has advantages such as energy-saving and environmental protection, safety, adaptability are strong, is suitable for suitability for industrialized production.
Embodiment
Below in conjunction with specific embodiments main processes of the present invention is sketched: it mainly may further comprise the steps:
(1) operation is leached in oxidation: with water, the vitriol oil, concentrated nitric acid, catalyzer by volume the ratio of 10:0.5～6:0.5～6:0.1～10 make mixed acid solution; The sulfuric acid in the mixing acid and the concentration of nitric acid are 50～500g/L respectively, sulfuric acid in the mixing acid and nitric acid mol ratio 1:0.2～2; Catalyzer has katalysis and anti-passivation, mainly is that fluorine-containing mineral acid (as HF) or inorganic salt are (as NH
4F, NaF, KF, MgF
2, CaF
2Deng) preparation the aqueous solution, compound concentration is 20～500g/L; Add the cobalt-copper alloy piece then, cobalt-copper alloy can be block, granular, powdery, and the cobalt copper ferrous components of cobalt-copper alloy is: Co:1%～50%, Fe:1%～50%, Cu:1%～50% make the cobalt copper iron leaching of cobalt-copper alloy enter into solution; The preheating temperature that leaches operation is controlled between 20 ℃～90 ℃, and temperature of reaction is controlled at 20～90 ℃, leaches between the pH value control 1.0～5.0 of operation leach liquor terminal point, leaches operation reaction times control 1～10 hour.
(2) solid-liquid separation process: when question response reaches 10～50g/L to solution acidity,, separate with not consoluet cobalt-copper alloy the supernatant liquor sucking-off by siphon mode, not consoluet cobalt-copper alloy continues to leach by the method for operation (1).
Following main component is that the cobalt-copper alloy of cobalt, copper, iron is illustrated.
Example one: the vitriol oil (concentration 98%) 2000ml, nitric acid (concentration 60%) 1500ml, hydrofluoric acid (concentration 55%) 1000ml mixes in the adding 6000ml water, is mixed with mixed acid solution.Take by weighing block cobalt-copper alloy 2000g, join one by one in the mixed acid solution, keep 85 ℃ of temperature of reaction, sustained reaction 5 hours.
The result: measure to show reaction end pH=2.5, the leaching filtrate that obtains contains cobalt 67.5g/L, cupric 54.3g/L, iron content 66.4g/L adopts the mode sucking-off of siphon with the supernatant liquor after leaching, with unreacted completely cobalt-copper alloy separate with leach liquor.
Unreacted cobalt-copper alloy completely continues to react with the mixed acid solution of new preparation, and cobalt-copper alloy has dissolved substantially, and the leaching yield of cobalt reaches 99.2%, and the leaching yield of copper reaches 98.5%, and the leaching yield of iron reaches 99.8%.
Example two: the vitriol oil (concentration 98%) 2000ml, nitric acid (concentration 60%) 2000ml, hydrofluoric acid (concentration 55%) 2000ml mixes in the adding 6000ml water, is mixed with mixed acid solution.Take by weighing block cobalt-copper alloy 2000g, join one by one in the mixed acid solution, keep 85 ℃ of temperature of reaction, sustained reaction 3 hours.
The result: measure to show reaction end pH=2.0, the leaching filtrate that obtains contains cobalt 60.4g/L, cupric 51.7g/L, iron content 63.6g/L adopts the mode sucking-off of siphon with the supernatant liquor after leaching, with unreacted completely cobalt-copper alloy separate with leach liquor.
Unreacted cobalt-copper alloy completely continues to react with the mixed acid solution of new preparation, and cobalt-copper alloy has dissolved substantially, and the leaching yield of cobalt reaches 99.4%, and the leaching yield of copper reaches 99.5%, and the leaching yield of iron reaches 99.8%.
Example three: the vitriol oil (concentration 98%) 1500ml, nitric acid (concentration 60%) 3000ml, hydrofluoric acid (concentration 55%) 800ml mixes in the adding 6000ml water, is mixed with mixed acid solution.Take by weighing block cobalt-copper alloy 2000g, join one by one in the mixed acid solution, keep 88 ℃ of temperature of reaction, sustained reaction 5 hours.
The result: measure to show reaction end pH=3.5, the leaching filtrate that obtains contains cobalt 64.2g/L, cupric 49.8g/L, iron content 67.3g/L adopts the mode sucking-off of siphon with the supernatant liquor after leaching, with unreacted completely cobalt-copper alloy separate with leach liquor.
Unreacted cobalt-copper alloy completely continues to react with the mixed acid solution of new preparation, and cobalt-copper alloy has dissolved substantially, and the leaching yield of cobalt reaches 98.5%, and the leaching yield of copper reaches 97.8%, and the leaching yield of iron reaches 99.7%.
Example four: the vitriol oil (concentration 98%) 2000ml, nitric acid (concentration 60%) 2200ml, hydrofluoric acid (concentration 55%) 1500ml mixes in the adding 6000ml water, is mixed with mixed acid solution.Take by weighing block cobalt-copper alloy 2000g, join one by one in the mixed acid solution, keep 80 ℃ of temperature of reaction, sustained reaction 5 hours.
The result: measure to show reaction end pH=4.0, the leaching filtrate that obtains contains cobalt 61.3g/L, cupric 48.9g/L, iron content 60.2g/L adopts the mode sucking-off of siphon with the supernatant liquor after leaching, with unreacted completely cobalt-copper alloy separate with leach liquor.
Unreacted cobalt-copper alloy completely continues to react with the mixed acid solution of new preparation, and cobalt-copper alloy has dissolved substantially, and the leaching yield of cobalt reaches 99.1%, and the leaching yield of copper reaches 98.7%, and the leaching yield of iron reaches 99.7%.
Claims (3)
1. one kind is adopted cobalt-copper alloy to make the method that primary industry extracts cobalt, copper, iron, it is characterized in that may further comprise the steps:
(1) operation is leached in oxidation: the ratio of water, the vitriol oil, concentrated nitric acid, catalyzer 10: 0.5 by volume～6: 0.5～6: 0.1～10 is made mixed acid solution; Add the cobalt-copper alloy piece then, make the cobalt copper iron leaching of cobalt-copper alloy enter into solution; Described cobalt-copper alloy cobalt copper ferrous components is: Co:1%～50%, Fe:1%～50%, Cu:1%～50%; Described catalyzer is the fluorine-containing mineral acid or the aqueous solution of inorganic salt preparation, and compound concentration is 20～500g/L; The preheating temperature of described leaching operation is controlled between 20 ℃～90 ℃, and temperature of reaction is controlled at 20～90 ℃; Between the pH value control 1.0～5.0 of described leaching operation leach liquor terminal point; Described leaching operation reaction times control 1～10 hour;
(2) solid-liquid separation process: when question response reaches 10～50g/L to solution acidity,, separate with not consoluet cobalt-copper alloy the supernatant liquor sucking-off by siphon mode, not consoluet cobalt-copper alloy continues to leach by the method for operation (1).
2. make the method that primary industry extracts cobalt, copper, iron according to the described employing cobalt-copper alloy of claim 1, it is characterized in that: described cobalt-copper alloy is block, granular, powdery.
3. employing cobalt-copper alloy according to claim 1 is made the method that primary industry extracts cobalt, copper, iron, it is characterized in that: when the mixing acid of described employing sulfuric acid and nitric acid carries out the oxidation leaching, the sulfuric acid in the mixing acid and the concentration of nitric acid are 50～500g/L respectively, sulfuric acid in the mixing acid and nitric acid mol ratio 1: 0.2～2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008100722002A CN101608258B (en) | 2008-11-20 | 2008-11-20 | Method for industrially extracting cobalt, copper and iron by taking cobalt-copper alloy as raw material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008100722002A CN101608258B (en) | 2008-11-20 | 2008-11-20 | Method for industrially extracting cobalt, copper and iron by taking cobalt-copper alloy as raw material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101608258A CN101608258A (en) | 2009-12-23 |
| CN101608258B true CN101608258B (en) | 2011-02-16 |
Family
ID=41482167
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2008100722002A Active CN101608258B (en) | 2008-11-20 | 2008-11-20 | Method for industrially extracting cobalt, copper and iron by taking cobalt-copper alloy as raw material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101608258B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102534658B (en) * | 2012-03-01 | 2014-07-23 | 崔海林 | Method for preparing electrolytic copper fast with copper ore |
| CN103898332B (en) * | 2012-12-28 | 2015-08-19 | 北京有色金属研究总院 | The technique that in copper scap metallurgical slag leaching process, copper zinc is separated with iron |
| CN109234545B (en) * | 2018-09-17 | 2020-12-11 | 广西银亿新材料有限公司 | Method for leaching cobalt matte or cobalt matte and cobalt ore mixture |
| CN111057846B (en) * | 2019-12-27 | 2021-03-16 | 四川顺应动力电池材料有限公司 | Method for separating and recovering cobalt, copper and iron in white alloy |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1912152A (en) * | 2006-08-04 | 2007-02-14 | 湖南瑞翔新材料有限公司 | Method for extracting valence metal from copper ferrocobalt alloy |
| 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 |
-
2008
- 2008-11-20 CN CN2008100722002A patent/CN101608258B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1912152A (en) * | 2006-08-04 | 2007-02-14 | 湖南瑞翔新材料有限公司 | Method for extracting valence metal from copper ferrocobalt alloy |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101608258A (en) | 2009-12-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102586600B (en) | Process for recycling valuable metal from lead copper matte | |
| CN106987728B (en) | A method of normal pressure phosphoric acid, which leaches nickel cobalt and synchronizes, from lateritic nickel ore prepares ferric phosphate | |
| CN102534255B (en) | Wet-fire combined smelting process for antimony or bismuth | |
| CN101481755A (en) | Method for leaching vanadium from vanadium-containing coal mine | |
| CN102925686B (en) | Method for selectively separating and extracting vanadium and chromium from solution containing vanadium and chromium | |
| CN101225476A (en) | Process for reclaiming copper from lead copper matte | |
| CN101463427A (en) | Method for recycling valuable metal from cobalt white alloy | |
| EP2683840B1 (en) | Gold and silver extraction technology | |
| CN104328284B (en) | A kind of method of Enrichment purification gold | |
| CN101003854A (en) | New method for soaking out enriched ores of high indium, high iron, and high sulfur zinc | |
| CN102828029A (en) | Method for preliminarily separating valuable metals from copper anode slime | |
| WO2012171481A1 (en) | Hydrometallurgical process for complete and comprehensive recovery with substantially no wastes and zero emissions | |
| CN104017991A (en) | Process for efficiently and selectively separating copper in lead copper matte | |
| CN101608258B (en) | Method for industrially extracting cobalt, copper and iron by taking cobalt-copper alloy as raw material | |
| CN104212976B (en) | The method reclaiming silver from wet method zinc abstraction waste residue | |
| CN106756069A (en) | A kind of method that valuable metal is reclaimed in the waste residue from zinc abstraction | |
| CN103498053A (en) | Method for separating base metals and noble metals in copper anode slime | |
| CN105110300A (en) | Method for extracting manganese and sulfur from composite manganese mine containing manganese sulfide | |
| CN117758080A (en) | Method for extracting scandium by combining titanium white waste acid and alkali precipitation waste residue | |
| CN107739841A (en) | A kind of method for separating arsenic from containing the high copper dross slag of arsenic, reclaiming copper | |
| CN110564961B (en) | Method for reducing leached hydrocobaltite | |
| CN104451169B (en) | The extraction process of agglomeration for iron mine smoke dust valuable element | |
| CN1115419C (en) | New process for treating electrolytic anode mud | |
| CN106756129A (en) | A kind of method that uranium is extracted from stone containing betafite | |
| CN103966433A (en) | Method for extracting copper, gold and silver from copper oxide 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 |