CN102206761B - Production method of high purity cobalt - Google Patents
Production method of high purity cobalt Download PDFInfo
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- CN102206761B CN102206761B CN 201010133634 CN201010133634A CN102206761B CN 102206761 B CN102206761 B CN 102206761B CN 201010133634 CN201010133634 CN 201010133634 CN 201010133634 A CN201010133634 A CN 201010133634A CN 102206761 B CN102206761 B CN 102206761B
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- cobalt
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- salt solution
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- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 61
- 239000010941 cobalt Substances 0.000 title claims abstract description 61
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 238000004519 manufacturing process Methods 0.000 title abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 31
- 150000001868 cobalt Chemical class 0.000 claims abstract description 26
- 239000012266 salt solution Substances 0.000 claims abstract description 26
- 239000000243 solution Substances 0.000 claims abstract description 18
- 238000005342 ion exchange Methods 0.000 claims abstract description 12
- 239000003456 ion exchange resin Substances 0.000 claims abstract description 12
- 229920003303 ion-exchange polymer Polymers 0.000 claims abstract description 12
- 239000011347 resin Substances 0.000 claims abstract description 7
- 229920005989 resin Polymers 0.000 claims abstract description 7
- 239000003792 electrolyte Substances 0.000 claims abstract description 3
- 238000002844 melting Methods 0.000 claims description 21
- 230000008018 melting Effects 0.000 claims description 21
- 238000004070 electrodeposition Methods 0.000 claims description 13
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 238000005266 casting Methods 0.000 claims description 6
- 238000010894 electron beam technology Methods 0.000 claims description 5
- 238000010521 absorption reaction Methods 0.000 claims description 4
- 239000003610 charcoal Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- XNZJTLSFOOXUAS-UHFFFAOYSA-N cobalt hydrochloride Chemical compound Cl.[Co] XNZJTLSFOOXUAS-UHFFFAOYSA-N 0.000 claims description 3
- 230000006698 induction Effects 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 2
- 230000008020 evaporation Effects 0.000 claims description 2
- 230000000630 rising effect Effects 0.000 claims description 2
- 241000220317 Rosa Species 0.000 claims 2
- 229910052799 carbon Inorganic materials 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 238000005363 electrowinning Methods 0.000 abstract description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 abstract 2
- 238000001179 sorption measurement Methods 0.000 abstract 2
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 abstract 1
- 238000003723 Smelting Methods 0.000 abstract 1
- 239000011259 mixed solution Substances 0.000 abstract 1
- 238000009849 vacuum degassing Methods 0.000 abstract 1
- 238000002360 preparation method Methods 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- RFYUQSQGLHNNOY-UHFFFAOYSA-N cobalt;sulfuric acid Chemical compound [Co].OS(O)(=O)=O RFYUQSQGLHNNOY-UHFFFAOYSA-N 0.000 description 4
- 239000008151 electrolyte solution Substances 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- INPLXZPZQSLHBR-UHFFFAOYSA-N cobalt(2+);sulfide Chemical compound [S-2].[Co+2] INPLXZPZQSLHBR-UHFFFAOYSA-N 0.000 description 2
- 238000005097 cold rolling Methods 0.000 description 2
- 238000007872 degassing Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 101100433727 Caenorhabditis elegans got-1.2 gene Proteins 0.000 description 1
- 229910001200 Ferrotitanium Inorganic materials 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hcl hcl Chemical compound Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000002198 insoluble material Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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Abstract
The invention relates to a production method of high purity cobalt. The method is characterized in the following steps that: (1) a CoSO4 solution or a mixed solution of CoSO4 and CoCl2 is purified through an ion exchange process and an active carbon adsorption process; (2) the purified cobalt salt solution is delivered to an electrolyte tank, and is subject to an electrowinning process; (3) the electrowon cobalt is subject to a vacuum degassing process and a vacuum smelting process, such that a high purity cobalt cast ingot is produced. Ion exchange resins used in the present invention at least comprise Diphonix resin which has a special effect in Fe removing, and M-4195 resin which has a special effect in Ni removing. The active carbon adsorption process is carried out after the ion exchange process. The high purity cobalt produced with the method provided by the present invention reaches a purity of 99.99% to 99.9999%, and has low gas content.
Description
Technical field
A kind of method of producing high-purity cobalt relates to ion-exchange and charcoal absorption purifying treatment, the electrodeposition of cobalt, the vacuum outgas of electrodeposited cobalt and the vacuum melting ingot casting of cobalt salt solution.
Background technology
High-purity cobalt is important electronic material.Purity is that 99.9～99.99% high-purity cobalt is widely applied in hard disc of computer.The cobalt that purity is higher as the cobalt of purity 99.99～99.9995%, is the contact layer material that plays very keying action in computer chip.
The production method of relevant high-purity cobalt, known patent has U.S. Patent number US6818119, US6843896, Japanese Patent No. JP11193483, China Patent Publication No. CN101538721, CN101302585.
US Patent No. 6818119 and US6843896 disclose a kind of method, with CoSO
4Solution and CoCl
2Solution is through ion-exchange, solvent extraction, Fe[OH]
3The methods such as precipitation recrystallize purify, and then electrolysis obtains high-purity electrolytic cobalt.Again high-purity electrolytic cobalt vacuum melting is obtained the high-purity cobalt ingot casting afterwards.Because during refining, dissolve as the low pure cobalt of anode and enter electrolytic solution, can pollute negative electrode electrolytic solution on every side, and then affect the purity of catholyte cobalt, the disclosed method of US6818119 and US6843896 adopts a kind of special film that electrolyzer is divided into cathode can and anode slot two portions.Metal ion comprises and the ion of Co and the impurity elements such as Ni, Fe can not pass through this film, but Cl
-And SO
4 2-Ion can pass through film, thereby has guaranteed the electrolyte conductivity that refining is necessary.In actual production, if the damage of film is not in time discovered, also cause the pollution of anodic dissolution anticathode electrolytic cobalt.In addition, the maintenance of film, renew also the inconveniences that have more.
The disclosed method of Japanese Patent JP11193483 is that two step electrodeposition add the method that the vacuum electron beam melting prepares high-purity cobalt.This method production cost is high, power consumption is large.
The disclosed method of China Patent Publication No. CN101538721 and CN101302585 adopts hydrochloric acid system, take 99.95% electrodeposited cobalt as anode, and the molten preparation CoCl of electricity
2Solution after the ion-exchange purifying treatment, passes into electrolyzer and carries out electrodeposition.High-purity electrodeposited cobalt prepares the high-purity cobalt ingot casting through the vacuum electron beam melting again.The method is because adopt the molten preparation CoCl of electricity
2Also there is the problem that production cost is high, power consumption is large in solution.In addition, CoCl
2Solution can produce corrodibility HCl fog in electrolytic process, cause badly damaged to equipment, instrument.These equipment and instruments that are corroded also may pollute electrolytic solution.
Summary of the invention
Purpose of the present invention is exactly the weak point for above-mentioned prior art, the scheme that proposition can effectively address these problems simultaneously.Detailed protocol is as follows: (1a) directly use the water-soluble CoSO of deionized water
4.7H
2O prepares the CoSO that cobalt concentration is 60-100g/L (grams per liter)
4Then solution add H
2SO
4Regulate the pH value of cobalt salt solution to 1-3.Perhaps (1b) directly uses the water-soluble CoSO of deionized water
4.7H
2O and CoCl
2.6H
2O prepares the cobalt salt solution that cobalt concentration is 60-100g/L (grams per liter), then adds H
2SO
4Or HCl regulates the pH value of cobalt salt solution to 1-3.CoSO
4And CoCl
2Ratio should be greater than 4: 1.Add a small amount of CoCl
2Can improve the electroconductibility of electrolytic solution.All use CoSO
4Solution or add a small amount of CoCl
2Solution can solve a large amount of HCl aerosols to the corrosion failure problem of equipment and instrument.(2) with CoSO
4Solution or CoSO
4Add CoCl
2Mixing solutions carry out purifying treatment with the method for ion-exchange and charcoal absorption.The ion exchange resin that the present invention uses comprises at least to the Diphonix resin (product of the Eichrom Technologies of u s company) that good result is arranged except Fe with to the M-4195 resin (the Dow Chemical of u s company product) of good result is arranged except Ni; Carrying out charcoal absorption after ion-exchange processes.(3) cobalt salt solution of purifying treatment passes into electrolyzer again and carries out electrodeposition, and the electrodeposition cathode current density is 100～300A/m
2(peace/square meter), cobalt salt solution temperature are 50～70 ℃.Because there is not the pollution problem of anolyte anticathode electrodeposited cobalt in the employing electrowinning with insoluble anode.(4) electrodeposited cobalt is carried out vacuum outgas and vacuum melting and obtain the high-purity cobalt ingot casting.Carry out in advance obtaining suitable vacuum tightness when vacuum outgas is conducive to vacuum melting afterwards, be conducive to reduce the elemental gas in the high-purity cobalt ingot casting, as the content of O, C, H, N, S etc.The particularly reduction of S content can avoid generating cobaltous sulfide (CoS, CoS when high temperature
2) brittle inclusion, this deformation processing to high-purity cobalt is favourable.The vacuum outgas temperature is usually below 800 ℃.Stove vacuum tightness changes when little, can think degassed end.The method of vacuum melting can be vacuum induction melting, vacuum electron beam melting and vacuum self-consumption electrode arc melting etc.
Further feature of the present invention is can be continuously, with suitable speed, add the variation of the cobalt concentration that purifying treatment, cobalt salt solution that concentration is suitable occurs with equilibrium system internal cause electrodeposition and moisture evaporation.Simultaneously can select suitable ion exchange resin volume, stabilize because adding continuously untreated cobalt salt solution to introduce the rising of the foreign matter content of system to reach.Through rationally controlling untreated cobalt salt solution concentration and interpolation speed and choose reasonable ion exchange resin volume and ion-exchange condition (flow velocity, temperature, pH etc.), can reach the interior stable cobalt concentration of electrolyzer and stable foreign matter content, and then guarantee the stable of high-purity cobalt quality product.
It is worthy of note, use ion-exchange techniques purifying treatment cobalt salt solution although all mention in the present invention and patent US6818119, US6843896, CN101538721, CN101302585, ion-exchange techniques of the present invention has essential distinction with these patents.US6818119 and US6843896 use M-4195 ion exchange resin; And the present invention also uses Diphonix resin and gac etc. except M-4195.CN101538721 and CN101302585 use 331,717, D201 and D301 ion exchange resin, and the present invention is fully different.
Description of drawings
Figure is the process drawing that high-purity cobalt is produced.
Embodiment
High-purity cobalt production craft step of the present invention is as follows:
(1) preparation of cobalt salt solution.(1a) preparation certain volume, target cobalt concentration are 60～100g/L CoSO
4Solution, calculate required high-purity sulfuric acid cobalt CoSO
4.7H
2The relative proportion of O and deionized water is with the high-purity sulfuric acid cobalt CoSO of gained weight
4.7H
2O and deionized water are put into container, stir until CoSO under room temperature
4.7H
2O dissolves fully.Then add sulfuric acid H
2SO
4Regulate the pH value of cobalt salt solution to 1-3.Perhaps (1b) preparation certain volume, target cobalt concentration are 60～100g/L, CoSO
4And CoCl
2The certain CoSO of ratio
4And CoCl
2Mixing solutions calculates required high-purity sulfuric acid cobalt CoSO
4.7H
2O, high-purity hydrochloric acid cobalt CoCl
2.6H
2The relative proportion of O and deionized water is with the high-purity sulfuric acid cobalt CoSO of gained weight
4.7H
2O, high-purity hydrochloric acid cobalt CoCl
2.6H
2O and deionized water are put into container, stir until CoSO under room temperature
4.7H
2O and CoCl
2.6H
2O dissolves fully.Then add sulfuric acid H
2SO
4Or hydrochloric acid HCl regulates the pH value of cobalt salt solution to 1-3.
(2) purifying treatment of cobalt salt solution.The cobalt salt solution of step (1) preparation is heated to 50～70 ℃, then pass into successively in the exchange column that Diphonix, M-4195, other ion exchange resin, gac are housed, flow velocity is got 1～2BV/h (bed volume per hour, namely solution throughput hourly is 1～2 times of ion exchange resin volume) usually.
(3) electrodeposition of cobalt.The cobalt salt solution importing electrolyzer of step (2) purifying treatment is carried out electrodeposition.Anode is with insoluble material such as titanium etc.The negative plate material is with high-purity cobalt or titanium, stainless steel etc.The electrodeposition cathode current density is 100～300A/m
2(peace/square meter), cobalt salt solution temperature remain on 50～70 ℃.If the negative plate material is the unlike materials such as titanium or stainless steel, the negative electrode electrodeposited cobalt need to be taken off from negative plate, then send into next process.If the negative plate material is high-purity cobalt, will both not separate.
(4) vacuum outgas of electrodeposited cobalt.The high-purity electrodeposited cobalt of negative electrode can be sent into the vacuum oven heat de-airing after surface washing.Heating temperature should be not too high, generates cobaltous sulfide CoS and/or CoS to prevent residual S and Co reaction
2Cobaltous sulfide fragility is very large, becomes at the cobalt ingot shape to add man-hour, can cause the cracking of cobalt when particularly cold rolling.And cold rolling be the effective means of preparation high magnetic spectroscopy susceptibility high-purity cobalt target.General vacuum outgas Heating temperature is no more than 800 ℃.When the variation of degasification furnace vacuum tightness is little, can finish degasification process.
(5) vacuum melting after degassed.Vacuum melting can be carried out in the stoves such as vacuum induction melting furnace, vacuum electron beam melting furnace, vacuum self-consumption electrode arc melting furnace.Under the high temperature high vacuum condition, some low melting point impurity can be removed by volatilization, thereby reaches the effect of further purification.High-purity cobalt that like this can production purity is 99.99～99.9999%, gas content is low.
Claims (5)
1. method of producing high-purity cobalt, it is characterized in that: (1) directly uses the water-soluble rose vitriol CoSO of deionized water
4.7H
2O prepares the cobalt salt solution that cobalt concentration is 60-100g/L, then adds H
2SO
4Regulate the pH value of cobalt salt solution to 1-3; Perhaps, directly use the water-soluble rose vitriol CoSO of deionized water
4.7H
2O and hydrochloric acid cobalt CoCl
2.6H
2O prepares the cobalt salt solution that cobalt concentration is 60-100g/L, then adds H
2SO
4Or the pH value that HCl regulates cobalt salt solution is to 1-3, wherein CoSO
4And CoCl
2Ratio greater than 4: 1; Then with CoSO
4Solution or CoSO
4Add CoCl
2Mixing solutions pass into special ion exchange resin and carry out purifying treatment, described ion exchange resin comprises at least to the Diphonix resin that good result is arranged except Fe with to the M-4195 resin of good result is arranged except Ni; Carrying out charcoal absorption after ion-exchange processes; (2) with the CoSO of purifying treatment
4Solution or CoSO
4+ CoCl
2Mixing solutions passes into electrolyzer to carry out electrodeposition and obtains the electrodeposition high-purity cobalt, and the electrodeposition cathode current density is 100～300A/m
2, the cobalt salt solution temperature is 50～70 ℃; (3) electrodeposited cobalt is carried out vacuum outgas and vacuum melting and obtain the high-purity cobalt ingot casting, wherein vacuum outgas temperature is below 800 ℃.
2. a kind of method of producing high-purity cobalt according to claim 1, it is characterized in that: the method for vacuum melting is vacuum induction melting, vacuum electron beam melting or vacuum self-consumption electrode arc melting.
3. a kind of method of producing high-purity cobalt according to claim 1 is characterized in that: the variation that adds continuously the cobalt concentration that cobalt salt solution appropriate, that concentration is suitable, not purifying treatment occurs with equilibrium system internal cause electrodeposition and moisture evaporation.
4. a kind of method of producing high-purity cobalt according to claim 3 is characterized in that: determine suitable ion exchange resin volume, to guarantee not causing because of the cobalt salt solution that adds the continuously purifying treatment not rising of electrolyzer electrolyte inside foreign matter content.
5. a kind of method of producing high-purity cobalt according to claim 3, it is characterized in that: rationally control not cobalt salt solution concentration and interpolation speed and choose reasonable ion exchange resin volume and the ion-exchange condition of purifying treatment, thereby reach the interior stable cobalt concentration of electrolyzer and stable foreign matter content, and then guarantee the stable of high-purity cobalt quality product.
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| CN 201010133634 CN102206761B (en) | 2010-03-29 | 2010-03-29 | Production method of high purity cobalt |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010133634 CN102206761B (en) | 2010-03-29 | 2010-03-29 | Production method of high purity cobalt |
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| CN102206761A CN102206761A (en) | 2011-10-05 |
| CN102206761B true CN102206761B (en) | 2013-05-22 |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103572224B (en) * | 2012-08-01 | 2016-03-16 | 宁波江丰电子材料股份有限公司 | The manufacture method of nickel target and nickel target material assembly |
| CN105154672A (en) * | 2015-09-08 | 2015-12-16 | 有研亿金新材料有限公司 | Method for removing nickel ions in cobalt chloride solution |
| CN105887137B (en) * | 2016-06-24 | 2018-04-06 | 有研亿金新材料有限公司 | One kind reduces the brittle method of electrolytic cobalt |
| CN106636638B (en) * | 2016-11-29 | 2018-12-07 | 河南科技大学 | A kind of method of deeply purifying and removing iron in cobalt liquor |
| CN112831802A (en) * | 2020-12-31 | 2021-05-25 | 格林美（江苏）钴业股份有限公司 | Production method of high-purity cobalt tablet with content of 99.999% |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5810983A (en) * | 1995-03-14 | 1998-09-22 | Japan Energy Corporation | High purity cobalt sputtering targets |
| CN1449457A (en) * | 2000-06-30 | 2003-10-15 | 霍尼韦尔国际公司 | Method and apparatus for processing metals, and the metals so produced |
| CN101532095A (en) * | 2009-04-01 | 2009-09-16 | 烟台凯实工业有限公司 | Method for producing electrodeposited cobalt by non-hydrochloric acid electrolyte |
| CN101538721A (en) * | 2009-03-19 | 2009-09-23 | 金川集团有限公司 | Method for preparing high-purity cobalt |
-
2010
- 2010-03-29 CN CN 201010133634 patent/CN102206761B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5810983A (en) * | 1995-03-14 | 1998-09-22 | Japan Energy Corporation | High purity cobalt sputtering targets |
| CN1449457A (en) * | 2000-06-30 | 2003-10-15 | 霍尼韦尔国际公司 | Method and apparatus for processing metals, and the metals so produced |
| CN101538721A (en) * | 2009-03-19 | 2009-09-23 | 金川集团有限公司 | Method for preparing high-purity cobalt |
| CN101532095A (en) * | 2009-04-01 | 2009-09-16 | 烟台凯实工业有限公司 | Method for producing electrodeposited cobalt by non-hydrochloric acid electrolyte |
Non-Patent Citations (4)
| Title |
|---|
| 崔薇.溶剂萃取-电积溶液除铁新工艺.《世界采矿快报》.1997,第13卷(第6期),18-19. |
| 溶剂萃取-电积溶液除铁新工艺;崔薇;《世界采矿快报》;19970630;第13卷(第6期);参见全文 * |
| 陈蓉.高纯钴制备技术.《稀有金属》.2005,第29卷(第5期),797-801. |
| 高纯钴制备技术;陈蓉;《稀有金属》;20051031;第29卷(第5期);第800页左栏第41-42行、右栏1-5 * |
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